Journal of Coatings Technology and Research

Synthesis of BHET-based polyester polyols by introducing BHET moiety into polyester

polyols and application into as a PU coating and comparison study with industrial-
based polyester-based coating materials
--Manuscript Draft--

Manuscript Number:

Full Title: Synthesis of BHET-based polyester polyols by introducing BHET moiety into polyester
polyols and application into as a PU coating and comparison study with industrial-
based polyester-based coating materials

Article Type: Original Research

Keywords: BHET-based Polyester polyols; Glycolized product; polyurethane coating

applications; physico-mechanical and chemical properties; comparative evaluations
study; Two-pack coating system

Corresponding Author: Jigar V. Patel, Ph.D

ISTAR: Institute of Science and Technology for Advanced Studies and Research
Anand, Gujarat INDIA

Corresponding Author Secondary

Information:

Corresponding Author's Institution: ISTAR: Institute of Science and Technology for Advanced Studies and Research

Corresponding Author's Secondary

Institution:

First Author: KHODIDAS K BHANDERI, M.sc (Industrial Chemistry)

First Author Secondary Information:

Order of Authors: KHODIDAS K BHANDERI, M.sc (Industrial Chemistry)

Jeimin R. Joshi, M.sc industrial chemistry

Jigar V. Patel, P.hD

Order of Authors Secondary Information:

Funding Information: SHODH - ScHeme of Developing High Mr. KHODIDAS K BHANDERI

Quality Research
(202010820003)

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
 Click here to access/download;Manuscript;Final Paper-
PU.docx

Synthesis of BHET-based polyester polyols by introducing BHET moiety into

1
2 polyester polyols and application into as a PU coating and comparison study with
3
4 industrial-based polyester-based coating materials
5
6 Khodidas K. Bhanderi1, Jeimin R. Joshi2, Dr. Jigar V. Patel*
7
8 ORCID Id: 0000-0001-7769-48461, 0000-0001-5372-764X2, 0000-0002-8769-0299*
9
10
Department of Industrial Chemistry, Institute of Science & Technology for Advanced Studies and
11
12 Research (affiliated to The Charutar Vidya Mandal (CVM) University), Vallabh Vidyanagar,
13
14 Anand, 388120, Gujarat, India1, 2,*
15
16 Sophisticated Instrumentation Centre for Applied Research and Testing - SICART, Vallabh
17 Vidyanagar, Anand-388120, Gujarat, India*
18
19 [Emails: [email protected], [email protected], [email protected]*,
20 [email protected]*]
21
22
23
24
25 Abstract
26
27 Waste PET bottles were depolymerized via glycolysis using ethylene glycol in presence of bio-
28
29 catalysts. The obtained product Bis-(2-hydroxyethyl) terephthalate (BHET) was purified and then used to
30
synthesis of polyester polyols by using different chemical reagents by using Dibutyltin dilaurate (DBTDL) and
31
32 PTSA as a catalyst to get a long chain polyester polyol. Obtained polyester polyols were characterized by end
33
group analysis includes acid value, Hydroxyl value, as well as spectral analysis. characterization techniques
34
35 like Fourier-transform infrared spectroscopy (FT-IR) and Nuclear magnetic resonance (NMR) used for
36
structural elucidation of polyester polyols. The hydroxyl functional polyester polyols were reacted with
37
38 Hexamethylene diisocyanate trimer (HDI) to obtain polyurethane (PU) coatings. The prepared PUs was used
39
40 as coatings materials and their performance was checked by various laboratory physico-mechanical and
41 chemical properties such as transparency, gloss, hardness, impact resistance, cross-cut adhesion, flexibility, and
42
43 solvent & anticorrosion performance as well as instrumental analysis were also evaluated and found to be
44 useful for industrial coatings against industrial based polyols-based coating materials. The prepared PU coating
45
46 was also tested for their thermal stability using a Differential scanning calorimetry (DSC) and
47 Thermogravimetric analysis (TGA) analysis were carried out to analyse the glass transition temperature (Tg)
48
49 and thermal stability of the PU coatings. The developed coatings revealed excellent results with industrial based
50 coating materials which has already into market. So, we can say that the renewable sources used in the
51
52 preparation of PU coatings can be good substitutes over petroleum resources.
53
54 Keywords: BHET-based Polyester polyols, Glycolized product, polyurethane coating applications, physico-
55
mechanical and chemical properties, comparative evaluations study, Two-pack coating system
56
57
58
59
60 Abbreviations
61
62 Page 1 of 39
63
64
65
 AA – Adipic acid
1
2 AV - Acid value
3
ATR - Attenuated total reflection
4
5 BHET - Bis (2-hydroxyethyl) terephthalate
6
7 CDCL3 - Carbon tetrachloride
8
9 DA - Dimer Fatty Acid
10
11 DBTDL - Dibutyltin dilaurate
12
13 DI - Diisocyanate
14
15 DSC – Differential scanning calorimeter
16
17 FTIR – Fourier transform infrared spectroscopy
18
F-T - Freeze-Thaw
19
20 GPS – Gel permeation chromatography
21
22 HV - Hydroxyl value
23
24 HDI - Hexamethylene diisocyanate
25
26 IA - Isophthalic acid
27
28 MA - Maleic Anhydride
29
30 MS - Mild steel Plate/ Panels
31
32 MEK - Methyl Ethyl Ketone
33
NPG – Neopentyl glycol
34
35 NVM - Non-volatile matter
36
37 NMR - Nuclear Magnetic Resonance
38
39 PA – Phthalic anhydride
40
41 PG – Propylene glycol
42
43 PU/Pus - Polyurethane
44
45 PET – Poly ethylene terephthalate
46
47 PTSA - P-Toluene Sulfonic Acid Monohydrate
48
SA – Sebacic acid
49
50 Tg - Glass transition temperature
51
52 TGA - Thermogravimetric analysis
53
54
55
56
57
58
59
60
61
62 Page 2 of 39
63
64
65
 1.0 Introduction
1
2 Our daily tasks are becoming more dependent on polymers. Our bodies contain several essential
3
organs, and it is impossible to think about life without them. It would be impossible for us to think about living
4
5 or working without the use of any polymeric products in our daily routines; they are like organs. Furthermore,
6
petrochemical-derived chemicals were used to synthesize a wide range of polymer-based products.
7
8
9 However, the polymeric industries are dealing with rising expenses and new environmental issues as
10 a result of the ongoing shortage of fossil fuels and tightening environmental laws [1]. Finding renewable
11
12 resources that can substitute for instead of fossil fuels and be transformed into commercially viable polymeric
13 materials is therefore essential for the chemical industry. Green, sustainable, and economical bio-based
14
15 resources or waste materials may thus be used as a source for derived different building block chemicals for
16 the production of different kinds of product. An eco-friendly method of product development is offered by a
17
18 variety of bio-based raw materials and their derivatives, including vegetable oils [2], cellulose [3],
19 polysaccharides [4], carbohydrates [5], cashew nut shell liquid, eugenol, natural phenols, dimer acid (DA)
20
21 (which is obtained by the dimerization of unsaturated renewable acids), etc [6]. Therefore, efforts have been
22
initiated in recent years to replace petroleum-based constituents in polymeric materials with biomass-based
23
24 units [7]. Bio-based polymeric materials with a variety of applications such as coatings, composites, foams,
25
and elastomers, have been made from a number of biomass sources.
26
27
28 Due to its outstanding mechanical, chemical, and physical properties, PU is the most significant
29 polymeric products in polymeric coating materials. Because of this, they have been used in many different
30
31 kinds of applications, such as composites, foams, elastomers, coatings, and adhesives. Generally speaking, they
32 may be easily formed by adding and polymerizing petroleum derived components like diisocyanates and
33
34 polyester polyols. As a result, industry and academics are paying more attention to producing PU coatings
35 utilizing materials that come from waste materials or biomass/natural source [8].
36
37
38 A new kind of renewable resource called "best products out of waste products" is currently being
39 discovered by researchers. An investigation into the chemical recycling of plastic waste/waste materials led to
40
41 useful chemical compounds for building blocks. It has been utilized into to derived veluable products more
42 efficiently. The packaging industry utilizes polymers regularly, which leads to a substantial accumulation of
43
44 solid waste after use [9,10]. PET has become increasingly popular than the others polymeric materials due to
45 to its low cost, durability, and outstanding mechanical properties. The growing use of disposable soft drink
46
47 bottles is the main cause of PET waste materials. Recycling this kind of waste polymeric materials is a better
48 approach, even if it has the drawback of generating inferior products. Chemical recycling by waste
49
50 depolymerization is the only feasible future solution. Waste polymeric materials are chemically converted into
51 distant monomers, which can then be used as building blocks to produce new, relevant compounds. Proven
52
53 techniques for breaking down PET include glycolysis [11–14] hydrolysis [15,16], methanolysis [17], and
54 amionolysis [18,19]. Glycolysis is a better option for chemically recycling waste PET polymers. Polyester
55
56 resins [20], polyurethane resins, and alkyd resins [21] have all been produced using the intermediates that are
57 derived from waste PET glycolysis. The synthesis of oligomers and dimers, as well as the generation of a single
58
59 high-yield product, are benefits of glycolyzing PET waste. The development of BHET is one of the most
60 substantial outcomes of recycling PET waste with EG using a glycolytic chemical into recycling process.
61
62 Page 3 of 39
63
64
65
 Polyurethanes, which have several applications, including the development of different kinds of coatings, have
1 been synthesized using this chemical which are derived from waste materials [22]. In addition to offering
2
3 commercial resins with strong terephthalate backbone properties, these intermediates or the use of
4 obtained monomers can significantly reduce product prices.
5
6
The synthesis of hydroxyl functional polyester polyols from BHET and their utilization in the
7
8 development of PU coatings with batter transparency and anticorrosive properties are addressed in the work
9
10 that has been presented over hear. First, an Agri-waste-based catalyst was used to recovere BHET (full process
11 provided in my earlier work) from waste PET plastics, which was subsequently used to synthesize several
12
13 BHET-based polyester polyols [14,23]. The different physicomechanical, thermal, and anticorrosive
14 capabilities of the developed PU coatings were evaluated by various evaluaction methods. and all gathered
15
16 data will be compared with the results of PU coatings developed from industrial-grade polyester.
17
18 By turning waste materials into new building block chemicals that were then used to manufacture
19 various valued-added products, this method addressed two main issues: the first was minimizing waste material
20
21 from nature and reducing environmental pollution. and the second was to use recycled chemicals to convert
22
basic monomers into various products in order to reduce the cost of the reaction and raw materials while
23
24 maintaining the necessary chemical qualities of the final product. Additionally, it will lower the demand for
25
chemical compounds derived from petroleum. Waste polymeric materials were a new resource for coating
26
27 development segments among all the feedstocks addressed in the early phases because of their affordability
28
and accessibility.
29
30
31 1.2 Materials & Method
32
33
34 1.2.1 Materials
35
36 Using agri-waste-based catalysts, waste PET plastic was glycolyzed to produce BHET (detailed
37
38 process in my previous work) [23]. DA was provided by the surface coating department of ISTAR College,
39 Vallabh Vidyanagar, Andnd-388120, Gujarat. Glycerol, PG, AA, Sebacic Acid (SA), NPG, Maleic Anhydride
40
41 (MA), PA, Dibutyltin Dilaurate (DBTDL), Xylene, and p-Toluene Sulfonic Acid Monohydrate (PTSA) were
42 all purchased from Suvidhinath Laboratories, Chiti-Chem Corporation, Samir Tech-Chem, Loba Chemi. Pvt.
43
44 Ltd., Chemdyes Corporation. Mild steel (MS) panels with dimensions of 6 x 3 cm were provided by Packme
45 Industries Pvt. Ltd. Vithal Udyognagar, Anand. Desmodur N3390 (Aliphatic polyisocyanate (trimer) NCO
46
47 content = 19.6-19.8%) was supplied by Merigold Paints Pvt Ltd and Divine Paints Pvt Ltd, Vitthal Udyognagar
48 INA, Anand, Gujarat 388325. Ather Polyurethane Pvt. Ltd., Ahmedabad, Gujarat, and Vision Products Pvt.
49
50 Ltd., Vadodara, Gujarat 391410, respectively, provided the polyester polyols required for the comparative study
51 of the developed BHET-based coating material with industrial grade polyester polyols (VOY-8239 & B-95).
52
53
54 1.2.2 Methods
55
56 1.2.2.1 Synthesis of BHET-based polyester polyol
57
58
59 There was an explanation of the polyesterification reaction in detail. Glycols and diacids are
60 polymerized to create polyester polyols. To produce a uniform light-yellow liquid at the beginning of the
61
62 Page 4 of 39
63
64
65
 procedure, the all-solid reagent was melted in accordance with its melting temperature and properly blended
1 with each of the other reagents. A distillation column with Dean-Stark apparatus is used to remove water from
2
3 the reaction system at temperatures between 120-160°C. Water is rapidly removed and reflux drops occur as
4 the temperature reaches 160-170°C. Until no further water reflux appears, the reaction should be run
5
6 continually. To check the unreacted component in the reaction system and the reaction state, then periodically
7 collect the necessary amount of resin sample from the reaction system and titrate it with 0.1N alcoholic KOH
8
9 solution to measure the acid value. To calculate the amount of free OH in our resin sample measurement by
10 titration with a 0.5N alcoholic solution of KOH, we must concurrently determine the hydroxyl value of the
11
12 resin sample.
13
14 Fig. 1 shows the setup and synthesis plan for three different polyester polyols as well as the reaction
15
16 system. The product structure of the polyester polyols based on BHET is displayed in the reaction schemes 1,
17 2, and 3 (polyester-2) (left side polyester-3; right side polyester-1). As demonstrated in Table No. 1, the
18
19 synthesis of 3 distinct polyester polyols using BHET was carried out by utilizing different dibasic acids and
20 glycols that vary the molar ratio of each reagent in the presence of two completely different catalysts. All
21
22 reagents were blended and charged into Round bottom flask with xylene as a solvent along with PTSA and
23 DBTDL as catalysts. All components were charged into three-necked reaction vessels equipped with an
24
25 overhead stirrer and condenser. The whole reaction was conducted between 160-180° C in an Round bottom
26 flask placed into a heating metal. The acid value was used to monitor the process. Polyester polyol, a light
27
28 yellowish waxy product that was later utilized for the PU coating on the MS plate, was obtained by cooling the
29 reaction mass. The catalyst and unreacted reactants were then separated by washing the mixture with water,
30
31 passing it through a bed of sodium sulfate, removing the xylene by dissolving it in hexane, and then separating
32 it according to density into a separating funnel. The final product was then dissolved in diethyl ether and
33
34 evaporated solvent at room temperature to obtain the final desirable resin products.
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53 Fig. 1 : a) Reaction setup & b) workup process for polyester polyols synthesis
54
55
56 Table 1 : Molar ratio & reagent detail
57
58 Sr. Polyols Code with Reagent Code Molar ratio of reagent Catalyst ratio (%
59
60 no. w/w)
61
62 Page 5 of 39
63
64
65
 1 Polyester-1 (BHET: AA: SA: DA) 5:1:1:2 1 % (PTSA)
1 2 Polyester-2 (BHET: Glycerol: PA: AA: 1:2.79:2.99:1.49:1.49 1 % (DBTDL)
2
3 PG)
4 Polyester-3 (BHET: NPG: PA: AA: PG) 2.33:3.33:1.66:1.66:1 1 % (DBTDL)
3
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 Reaction scheme 1 & 2: Proposed reaction scheme of polyester polyols 3 & 1
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 Reaction scheme 3: Proposed reaction scheme of polyester polyols-2
61
62 Page 6 of 39
63
64
65
 1.2.2.2 Polyester Structural properties & colour
1
2 Hydroxyl groups present in BHET moiety react with the carboxylic end groups of organic acids, their
3
4 derivatives, and other glycols in a polycondensation process leading to BHET-based polyester polyols. Ester
5 interactions develop as a result, and a condensation product typically water is formed as a byproduct. In order
6
7 to develop materials with suitable chemistry and molecular properties for every requirement, emerging
8 applications of BHET-based polyester polyols require precise control over the polycondensation process [24].
9
10
11 The flexibility, chemical resistance, high thermal stability, and reduced flammability of polymers
12 containing ester bonds in their backbone structure are all benefits of ester linking in some kind of. To provide
13
14 these properties, organic acid anhydrides like MA and PA may be used. Ester monomers provide softness
15 without sacrificing stickiness because of their lower Tg value. The hydrolytic instability of ester bonds in the
16
17 ester polyol-based PU might result in the loss of its mechanical and physical properties. Polyesters were
18 effectively strengthened by aromatic dicarboxylic and other acids [25,26]. Long chain DA unique structure
19
20 provides the final compound with a number of desirable properties, such as hydrophobicity, low viscosity, high
21 impact strength, high stability, flexibility, and reduced film shrinking [27].
22
23
Because of these DA include many hydrocarbon isomers, their crystallinity is decreased. They
24
25 increase the flexibility of polymers made from them because they do not crystallize. 560 g/mol is the average
26
molecular weight of DA as in a natural structural foam. Apart from the fact that they come from renewable
27
28 resources, the main justification for using DA in polymer formulation is to give the finished product special
29
30 qualities like elasticity, flexibility, high impact strength, hydrolytic stability, hydrophobicity, and lower glass
31 transition temperatures [28].
32
33 When producing resins utilizing as a transparent resin in the surface coating field, the color, as well
34
35 as transparency of a polyester polyol based on BHET, maybe even more important. according to Fig. 2. A high
36 reaction temperature, foreign impurities, particularly iron, or an insufficient inert gas flow might be the reason
37
38 of the dark red color seen during resin synthesis in the presented work. The setting time of the resin may be
39 affected by several factors. Viscosity, which alters with color, may also be found during work.
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55 Fig. 2 : Color change of polyester polyols after reaction a). Polyester polyols-3 b). Polyester polyols-2
56
57
58
59
60 1.2.2.3 Gelation effect during reaction
61
62 Page 7 of 39
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20 Fig. 3 : Gelling effect observed during reaction
21
22
23 The system is reflected by the polycondensation process of BHET, glycerol, and diacids, where
24 glycerol can be either linear or branched on the polymer backbone, while BHET and other diacids contain the
25
26 linear chain portion. Glycerol's trifunctionality enables gel formation at high reactant conversion rates during
27 polymerization in bulk methods. It arises from hyperbranching and, ultimately, gelation brought on by the
28
29 esterification of the secondary hydroxyl groups on glycerol units. Controlling gelation is crucial in polymer
30 design and engineering as it indicates the start of the material's thermoset characteristic.
31
32
Gelation can be avoided by regulating esterification processes on the secondary hydroxyl group of
33
34 glycerol, controlling the monomer stoichiometry, quenching the reaction before gelation, and/or employing
35
36 diluted polymerization systems by incorporating solvent into the reaction system. While primary hydroxyl
37 groups are more reactive than secondary hydroxyl sites, BHET/diacids preferentially esterify glycerol units at
38
39 these positions. Hyperbranched polyesters are produced as a result of the monosubstituted glycerol units
40 becoming disubstituted and finally trisubstituted as the process continues. The degree of branching depends on
41
42 the temperature of the reaction as well as the molar ratio of the reactants. While too much diacid promotes
43 branching, too much glycerol inhibits it [29–31]. A lower degree of branching results from the esterification of
44
45 secondary hydroxyls in glycerol being reduced at lower reaction temperatures (~120°C) [24,32].
46
47 The polycondensation process usually stops when an exponential rise in medium viscosity appears in
48
order to prevent gelation. As a method of preventing gelation, reduced or prevented esterification processes on
49
50 the secondary hydroxyl groups of glycerol have also been used. Catalysts that are selective for primary alcohol
51
esterification are usually used to accomplish this. Commercially accessible Lipase B from Candida Antarctica
52
53 immobilized on a poly(methyl methacrylate cobutyl methacrylate) resin is the most often utilized catalyst for
54
this purpose [33–40]. As a selective catalyst substitute for lipases, dialylborinic acids were just recently
55
56 revealed [41]. Using solvents as a reaction medium is another method for preventing gelation in the
57
58 polycondensation of glycerol and diacids. These are commonly known as diluted reaction systems. Because
59
60
61
62 Page 8 of 39
63
64
65
 molecules are more separated in diluted reaction systems, there is a decreased probability of crosslinking
1 [24,42].
2
3
4
5
6 1.4 Development of PU coatings
7
8
Before being coated, MS panels were cleaned with acetone or another suitable solvent, scraped with
9
10 sandpaper, and allowed to dry at room temperature. Using BHET-based polyester polyol and diisocyanate (DI)
11
12 as curing chemicals, a two-pack polyurethane coating system was developed. The PU coatings are produced
13 by reacting polyols with HDI at a molar equivalent ratio of 1:1 (NCO: OH) with xylene/Acetone as a catalyst.
14
15 A predetermined amount of the curing agent was added to the solutions to the dissolved polyester polyol into
16 xylene, and they were left to react for 30 seconds at room temperature. Using a brush or bar applicator, the
17
18 prepared viscose solutions were applied to mild steel panels that were 6 x 3 inches. The PU films were also
19 prepared by pouring the mixtures onto a glass plate. A schematic representation of the coating procedure and
20
21 PU formulation is shown in Fig. 4.
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49 Fig. 4 : Process for developing PU coating panels
50
51 Following application, glass slides and MS panels were allowed to cure for 7-10 days at room
52
53 temperature. The panels' performance properties were assessed over curing. Usually, a polyester polyol and an
54 isocyanate undergo a polyaddition process to produce PU. Reaction Schemes 2 and 3 illustrate the proposed
55
56 experimental PU preparation approaches.
57
58
59
60
61
62 Page 9 of 39
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20 Reaction scheme 4 : Polyurethane bond formation reaction of polyester 1 (Left side) & 2 (Right side)
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46 Reaction scheme 5 : Polyurethane bond formation reaction polyester-3
47
48
49 1.5 Methods of Characterizations
50
51
52
1.5.1 characterizations for polyester
53
54 A condensation/esterification process is used to derive all BHET-based polyester polyols. The acid
55 value was used to track the reaction; a decrease signified the production of polyester polyol. Ultimately, the
56
57 reaction appeared to be finished and stopped right away when the acid value approached less than 20 mg KOH
58 per gram. Additionally, spectroscopic techniques were used to analyse the structural characteristics of the
59
60 derived polyols and quantify their hydroxyl value and other structural identification conformation data. The
61
62 Page 10 of 39
63
64
65
 amount of DI utilized in polyurethane formulations and the hydroxyl equivalent weight of the produced polyol
1 were both determined using the hydroxyl number.
2
3
4 1.5.1.1 Acid value
5
6 The unreacted acid moieties determine the acid value (AV). It was determined using DIN EN ISO 2114
7
by titrating the carboxylic acid groups of the sample with a alcoholic KOH solution. It was defined as the
8
9 milligrams of potassium hydroxide needed to neutralize one gram of sample. The following question is used
10
11 for determining the acid value:
12 𝐵𝑢𝑟𝑟𝑒𝑡𝑒 𝑟𝑒𝑎𝑑𝑖𝑛𝑔 × 𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝐾𝑂𝐻 × 56.1056
Acid value = × 100…………..(1.1)
13 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑡𝑎𝑘𝑒𝑛
14
15
16 1.5.1.2 Hydroxyl value
17
18
19 The amount of KOH milligrams required to neutralize the acetic acid produced following the acetylation
20 of one gram of a chemical molecule containing free hydroxyl groups is known as the hydroxyl value (HV).
21
22 The determination was made in compliance with DIN EN ISO 4629-1. Acetic anhydride in pyridine is used in
23 the process to acetylate the sample's hydroxyl groups. After acetylation, an aqueous potassium hydroxide
24
25 solution was used to titrate the remaining acetic anhydride after it had been hydrolyzed with water [43]. The
26 following equation was used to determine the hydroxyl value:
27
28 (𝐵𝑙𝑎𝑛𝑘−𝑆𝑎𝑚𝑝𝑙𝑒 𝑟𝑒𝑎𝑑𝑖𝑛𝑔) × 𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝐾𝑂𝐻 × 56.1056
29 Hydroxyl value = × 100..(1.2)
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑡𝑎𝑘𝑒𝑛
30
31
32
33 1.5.1.3 % Non-volatile matter (NVM)
34
35 A 1 gm sample was placed in a silica crucible that had been previously weighed, heated to 120°C in a
36
thermostat oven for 1 hr, cooled to 90°C, and then moved to desiccators in order to measure Non-volatile matter
37
38 (NVM). A sample's weight loss was converted to a percentage and related to the volatile matters contained
39
inside [44]. The following equation was used to calculate the % NVM:
40
41
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑎𝑓𝑡𝑒𝑟 𝑑𝑟𝑦𝑖𝑛𝑔
42 % NVM = × 100…..(1.3)
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑏𝑒𝑓𝑜𝑟𝑒 𝑑𝑟𝑦𝑖𝑛𝑔
43
44
45
46 1.5.1.4 Specific gravity & Density (Kg/m3)
47
48
49 All the BHET-based polyester polyols samples were measured. Specific gravity and density were
50
51 measured and calculated based on the questions provided below:
52
53
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
54 Density (Kg/m3) = ……………………………… (1.4)
55 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒

56
57 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑝𝑜𝑙𝑦𝑒𝑠𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒
58 Specific gravity = ………………………. (1.5)
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 referance 𝑠𝑎𝑚𝑝𝑙𝑒
59
60
61
62 Page 11 of 39
63
64
65
 1.5.2 Structural characterization of polyester polyols by instrumental analysis
1
2 1.5.2.1 FTIR
3
4
5 FTIR was used immediately to examine the dry, impurity-free PU film samples and BHET-
6 based polyester polyols. Spectra between 450-4000 cm-1 were detected. All samples' FTIR spectra were
7
8 recorded at 25°C using the Perkin Elmer Spectrum GX FTIR spectrometer. A universal attenuated total
9 reflection (ATR) probe was used to capture the spectra in the 10,000–370 cm-1 wavenumber range at a
10
11 resolution of 0.15 cm-1.
12
13 1.5.2.2 1H NMR
14
15
16 Avance Neo (Bruker) equipment, model AVANCE II, TOPSPIN software, and an automatic sample
17 changer operating at 500 MHz were used to record the 1H NMR spectra. A cryomagnet with an 11.7 T field
18
19 strength is part of the arrangement. TMS was used as an internal reference, and carbon tetrachloride (CDCL 3)
20 solutions were used as the solvent for the all BHET-based polyester polyol material to produce the spectra.
21
22 PPM is used to represent chemical shifts.
23
24
25 1.5.2.3 Thermal Analysis
26
27
28 For evaluating the thermal stability of every PU based coating film, a Perkin Elmer (Model No. STA-
29
30 8000) was utilized. 15–20 mg samples were placed in a platinum sample pan and heated from 25–800°C at a
31 rate of 10°C min-1 in a nitrogen atmosphere to assess the thermal resistance of PU films. Weight loss and
32
33 temperature change as a function of temperature were recorded throughout the heating phase.
34 All PU films' glass transition temperature (Tg) was determined using a Perkin Elmer STA-8000 DSC.
35
36 The sample was heated in a nitrogen atmosphere between 25–300◦C at a rate of 20◦C min-1. To identify the Tg,
37 the device was calibrated using indium and n-octane.
38
39 1.5.2.4 GPC
40
41
42
GPC (Perkin Elmer, Autosystem XL GC with Turbomass) was used to figure out the average
43
44 molecular weights and polydispersity of the BHET-based polyester polyols products. The reference material
45
was monodispersed polystyrene, and the solvent was analytical grade tetrahydrofuran (THF). GPC was used
46
47 to calculate Mw, and a series of monodisperse PS standards were used to calibrate the column.
48
49
50 1.6 Testing & Performance Evaluation of Coatings
51
52 1.6.1 Gloss (60◦)
53
54
55 Using a digital gloss meter (Model BYK Additive and Instruments, Germany), the gloss of coated
56 panels was tested at 60◦. The gloss meter was calibrated using a reference sample provided by the manufacturer
57
58 prior to starting testing actual samples.
59
60 1.6.2 Adhesion (%)
61
62 Page 12 of 39
63
64
65
 In according to ASTM D-3359-95B guidelines, the adhesion test was performed on a cross-hatch
1 cutter (Elcometer 107.1542) utilizing a die with a closed pair of parallel blades (11 teeth). The die was drawn
2
3 twice at a straight angle on the coated MS panels while under pressure to create the square design. A strip of
4 self-adhesive tape was then applied to the cross-cut region, lightly rubbed with a finger, and then cut off with
5
6 a sharp object. The number of squares that stayed adhered to the film was counted using the following
7 calculation to determine how adhesive the film was.
8
9 Number of squares intact in the tape applied area
10 Adhesion % = × 100……………..(1.6)
Total number of squares in the tape applied area
11
12
13
14
15 1.6.3 Flexibility
16
17 The EN ISO 6860 standard was used to assess the coatings' flexibility. A conical mandrel was used
18
19 for the test. A MS substrate was used to test the coatings. A Conical Mandrel Instrument (Khushboo Scientific
20 Pvt. Ltd., Mumbai, India) was used to assess each material at 45°-180° angles. The results are shown as "+" or
21
22 "-," where "+" denotes that the coating's surface remained intact and free of cracks and "-" denotes that the test
23 was failure because of chipping marks and cracks.
24
25
26 1.6.4 Water absorption
27
28 The purpose of the test was to evaluate the cured coatings' water permeability properties, which are
29
30 related to the coating's free volume proportion. Weighing was carried out simultaneously before and after the
31 coated panels were immersed in water for 24 hr. where W1 and W2 represent the sample's weights before and
32
33 following their submersion in water, accordingly.
34
W2−W1
35 % Water absorption = × 100……………………………. (1.7)
W1
36
37
38
39
40 1.6.5 Gel time
41
42
43 Gel time is critical for a two-pack coating system, it represents the longest period of time the
44 mixture system (Polyester & Isocyanide) may remain fluid like properties.
45
46
47 1.6.6 Chemical & Corrosion resistance
48
49 The ASTM-1308-02 method was used to conduct the chemical resistance tests. For 7 days, the PU
50
coating samples were immersed in water, xylene, acid (5 % by wt HCl), alkali (5 % by wt NaOH), and NaCl
51
52 (5 % by wt). Additionally, the Methyl Ethyl Ketone (MEK) and xylene rubbing tests, as described by ASTM
53
D-5402 and ASTM D-4752, were used to assess the solvent resistance process of the developed PU coatings.
54
55
56 1.6.7 Hardness
57
58
59
60
61
62 Page 13 of 39
63
64
65
 The term "hardness" describes a material's ability to withstand scratches and indentations. The three
1 most often used tests to evaluate a coating's hardness are (i) pencil, (ii) impact, and (iii) scratch. The results of
2
3 every coating material based on polyester are shown in Table No. 3.
4
5 1.6.7.1 Impact resistance
6
7
In accordance with ASTM D-2794, impact resistance was assessed. An impact tester with three
8
9 different heights (50, 75, and 100 cm) and a 900 kg load was used to test the coating's impact resistance.
10
11
1.6.7.2 Pencil hardness (B-H)
12
13
14 The hardness of coatings was measured using a pencil hardness gauge. The ASTM D-3363
15 specifications were followed when conducting the pencil hardness test. A range of pencils, from soft to hard,
16
17 were part of the instrument setup. The pencils were placed at a 45° angle to measure their hardness.
18
19 1.6.8 Freeze Thaw (F-T) & thermal/temperature stability
20
21
22 A PU-coated panel was put in a deep freeze (~-15-18◦C) for 24 hr and then thawed to room
23 temperature in order to evaluate its F-T stability. A PU coated film panel was placed in an oven at different
24
25 temperature at regular time intervals to evaluate the change in the coating film as part of another stability test
26 called thermal stability [45].
27
28
29 1.6.9 Swelling properties (S)
30
31 Using toluene, ethanol, and water as solvents, the cured films swelling characteristics (S) were
32
examined. After weighing the samples and dipping them in different solvents for 50 hr at room temperature,
33
34 they were dried and weighed once more. Using Eq. (1.8), the swelling performance with various solvents was
35
calculated. The weights of the film samples before and after their immersion in the solvent are denoted by W1
36
37 and W2.
38
39 W2−W1
%S= × 100………………………………… (1.8)
40 W2
41
42
43
44
45 1.7 Results and discussion
46
47 1.7.1 Basic test result
48
49
50 Table 2 : General laboratory testing result
51
52 Sr. Test name Polyester-1 Polyester-2 Polyester-3 VOY- B-95
53
54 No. 8239
55
56 1 AV (mg 13-15 10-15 5-7 0.6 0.6
57
58 KOH/gm)
59
60
61
62 Page 14 of 39
63
64
65
 2 HV (OH) 221 318 351 45-55 54
1
2 (mg
3
4 KOH/gm)
5
6
3 % NVM 55.5776 88.8376 91.2698 87.5247 97.1910
7 4 Specific 0.9601 1.5177 1.1359 1.1630 1.1269
8
9 gravity
10
11 5 Density 0.9530 1.5162 1.1386 1.166 1.1188
12
13 (Kg/m3)
14
15 6 Solubility Non-polar Polar solvent Non-polar solvent
16
17 solvent
18
19 7 Colour of Dark brown Orange Light yellow Transparent
20 the product to black (Slightly red Colourless
21
22 due to
23
24 temperature
25
26 variation)
27
28
29
30
31
32 1.7.2 1H NMR
33
34 polyols-1
1H_8scan CDCl3 {D:\Spectra} nmr 57 BRUKER
35 AVANCE NEO
500 MHz NMR
-0.0002
8.1084
7.2632
7.1283
7.1260
7.1184
7.1170
7.0988
7.0930
7.0904
7.0877
7.0806

4.6986
4.5357
4.4271
4.2668

2.3346
2.3197
2.3045
2.2615
1.6652
1.6165
1.3964
1.3820
1.3674
1.2551
0.9052
0.8906
0.8762

SPECTROMETER
36 SAIF, P.U.
CHANDIGARH
Current Data Parameters
37 NAME
EXPNO
Feb22-2023
570
PROCNO 1
38 F2 - Acquisition Parameters
Date_ 20230223
39 Time
INSTRUM
PROBHD
12.01 h
Avance Neo 500
Z119470_0333 (
40 PULPROG
TD
SOLVENT
zg30
65536
CDCl3
NS 128
41 DS
SWH
0
14705.883 Hz
FIDRES 0.448788 Hz
42 AQ
RG
2.2282240 sec
95.7854
DW 34.000 usec
43 DE
TE
6.79 usec
300.2 K
D1 1.00000000 sec
44 TD0
SFO1
1
500.1730885 MHz
NUC1 1H
45 P0
P1
PLW1
3.33 usec
10.00 usec
20.93000031 W
46 F2 - Processing parameters
SI 65536
SF 500.1700101 MHz
47 WDW
SSB
EM
0
LB 0.30 Hz
48 GB
PC
0
1.00

49
9.04

1.00
1.07

4.20
4.86
3.72
3.45
1.30
0.59

8.01
4.22
3.11
12.78
41.91

8.74

50
51 10 9 8 7 6 5 4 3 2 1 0 ppm
52
53 Fig. 5 : Proton NMR result of BHET-based Polyester polyol-1
54
55
56
57
58 Proton NMR was used to structurally assess and conform all BHET-based polyester polyol samples;
59
60 results are shown in Figs. 7-9. As a baseline, TMS was measured at 0 ppm. The proton of the core -CH2-groups
61
62 Page 15 of 39
63
64
65
 in the long fatty acid chain was detected at δ=1.25 ppm, whereas the proton of the terminal methyl groups (-
1 CH3) was detected at δ=0.87-0.90 ppm [49]. Two -CH2 proton peaks may be identified in the long fatty acid
2
3 chain at δ=2.26 and δ=1.61, respectively [50,51]. The methylene protons of SA are responsible for the results
4 found at δ=1.36-1.39, δ=1.61-1.66, and δ=2.30-2.33 ppm [52]. The ester methyl group next to the carbonyl
5
6 carbon appears by the peaks at δ=4.26 ppm, respectively. δ=7.0-7.12 ppm is a chemical shift attributed to
7 protons attached to an aromatic ring. The signals from the protons of the cyclic structure appear gradually
8
9 between δ=6.5 and δ=7.5 ppm. According to [53], protons attached to a cyclic ring can be detected by chemical
10 shifts of δ=6.5-8.0 ppm. The signal at δ=7.2632 ppm indicates the CDCL3 solvent peak. The presence of an
11
12 aromatic entity in the structure is indicated by the chemical shift at δ=8.1084 ppm.
13 polyester-2
1H_8scan CDCl3 {D:\Spectra} nmr 3 BRUKER
14 AVANCE NEO
500 MHz NMR
7.8436
7.8344
7.6941
7.4728
7.2960
7.2821
4.4054
4.3741
4.3559
4.3227
4.2491
4.1372
4.1304
4.0932
4.0748
4.0099
3.9964
3.9466
3.9025
3.8895
3.8823
3.7328
3.7223
3.7067
3.6208
3.5935
3.5595
3.5514
3.4694
3.4030
3.3962
3.3605
3.3451
3.3359
3.3128
3.3011
2.7207
2.6587
2.5669
2.4725
2.3372
2.1965
2.0839
1.3735
1.0708
1.0579
0.9685
0.9574
15 SPECTROMETER
SAIF, P.U.
16 CHANDIGARH
Current Data Parameters
NAME Jun21-2024
17 EXPNO
PROCNO
30
1
18 F2 - Acquisition Parameters
Date_ 20240621
19 Time 11.15 h
INSTRUM Avance Neo 500
20 PROBHD
PULPROG
Z119470_0333 (
zg30
TD 65536
21 SOLVENT
NS
CDCl3
64
22 DS
SWH
0
14705.883 Hz
FIDRES 0.448788 Hz
23 AQ
RG
2.2282240 sec
13.4726
24 DW
DE
34.000 usec
6.79 usec
TE 300.1 K
25 D1 1.00000000 sec
TD0 1
26 SFO1
NUC1
500.1730885 MHz
1H
P0 3.33 usec
27 P1 10.00 usec
PLW1 20.93000031 W
28 F2 - Processing parameters
SI 65536
29 SF 500.1700000 MHz
WDW EM
30 SSB
LB
0
0.30 Hz
GB 0
31 PC 1.00

32
33
1.04
1.92
2.00

2.21
3.53
1.59
1.20
2.11

0.27
0.32
10.80
2.08

2.05
1.20

34
35 11 10 9 8 7 6 5 4 3 2 1 ppm
36
37
38 Fig. 6 : Proton NMR result of BHET-based Polyester polyol-2
39
40 As shown in Fig. 8 the proton of the terminal methyl groups of BHET-based polyester polyols-2 (-
41
42 CH3) was detected at δ=0.9 ppm, but the proton of C-CH2 linked as a ꞵ--substitution to CH3 group present in
43 the long fatty acid chain was detected at δ=1.05 ppm [49]. The methylene protons of acid are responsible for
44
45 the peak signal at δ=1.37 and δ=2.33 ppm [52]. The BHET-based polyester sample existing acid group will
46 provide a pick at δ=2.19 ppm of 4H(CH2) acid [54]. The signal at δ=3.40-3.51 ppm is associated with the
47
48 proton of a carbon chain that is connected by a -CH2-group. At δ=3.70-3.73 ppm, the proton of the -CH2 group
49 connected to the terminal hydroxyl group was found. The frequency range of δ=3.9 - δ=4.1 ppm was where
50
51 the multiplate pick of (CH) was seen [55]. Multiplate with higher intensity appear by glycerol terminal units
52 in the 3.5–3.9 ppm range. However, between 3.5 and 4.5 ppm, all protons linked to glyceride repeating units
53
54 are found [56–58]. δ=4.07 & 4.09 ppm 4H (CH2) diol and δ=3.7 ppm polyester terminal OH groups were
55 identified to be the peak [54]. At δ=4.13 ppm 2H (CH2) diol, the pick of acid terminal was detected [54].
56
57 Between δ=4.13 and δ=4.24 ppm, another doublet signal of (CH2) was seen [55]. In this case, the PG/PA
58 molecular structure methylene proton signal is shifted from 4.15 ppm to 4.05 ppm. The methine protons
59
60 (CH) appear at 5.0 ppm if PG is secondary connected to PA, whereas they appear at 5.1 to 5.2 ppm in
61
62 Page 16 of 39
63
64
65
 prepolymers based on terephthalate (or isophthalate). The absorption of methine protons changes significantly
1 when two acid species protect the propyl moiety. The ester methyl group and the carbonyl carbon appear by
2
3 the peaks at δ=4.24 ppm, respectively. The protons in the cyclic structure emit signals gradually between δ=6.5
4 and δ=7.5 ppm. According to [53], protons attached to a cyclic ring are indicated by chemical shifts of δ=6.5-
5
6 8.0 ppm. The hydrogen from the aromatic ring was associated with the displacements at δ=7.69, 7.83, and 7.84
7 [58]. There
NMRisPOLYOLS-3
a signal at δ=7.28 ppm that indicates the CDCL3 solvent peak.
8 1H_8scan CDCl3 {D:\Spectra} nmr 14 BRUKER
9 AVANCE NEO
500 MHz NMR

-0.0002
8.1254
8.1161
8.1085
8.1010
8.0915
8.0874
8.0747
7.5620
7.5593
7.5549
7.5517
7.5476
7.5455
7.2820
4.4777
4.4733
4.2070
4.2031
4.1992
4.1658
4.1562
3.9672
3.9580
3.9312
3.9225
3.9188
3.9163
3.9105
3.8805
3.7099
3.4888
3.4252
3.3910
3.3150
3.0183
2.3788
2.3682
2.3538
2.3488
2.3109
2.2589
1.6773
1.6617
1.6553
1.2530
1.2378
1.2225
1.0762
1.0672
1.0429
1.0348
1.0210
1.0153
0.9904
0.9772
0.9722
0.9648
0.9534
0.9498
0.9430
0.9331
0.9143
0.9027
0.8995
0.8944
10 SPECTROMETER
SAIF, P.U.
11 CHANDIGARH
Current Data Parameters
12 NAME Jan26-2024
EXPNO 140
13 PROCNO 1
14 F2 - Acquisition Parameter
Date_ 20240126
15 Time 21.10 h
INSTRUM Avance Neo 500
16 PROBHD Z119470_0333 (
17 PULPROG zg30
TD 65536
18 SOLVENT CDCl3
NS 128
19 DS 0
SWH 14705.883 Hz
20 FIDRES 0.448788 Hz
AQ 2.2282240 se
21 RG
DW
40.3291
34.000 us
22 DE 6.79 us
TE 300.1 K
23 D1 1.00000000 se
TD0 1
24 SFO1 500.1730885 MH
NUC1 1H
25 P0 3.33 us
P1 10.00 us
26 PLW1 20.93000031 W
27 F2 - Processing parameters
SI 65536
28 SF 500.1700006 MH
WDW EM
29 SSB 0
LB 0.30 Hz
30 GB 0
PC 1.00
31
32
2.00
1.02
1.08
0.20
0.17
0.23
0.04

0.85
0.35
1.10
0.34
0.79
0.80
0.42
0.64
0.89
0.53
0.23
0.33
0.30
0.43
0.51
2.10
0.14
2.37
0.36
2.29
0.60
0.23
0.62
0.82
1.51
2.04
2.10
33
34
35 10 9 8 7 6 5 4 3 2 1 0 ppm
36
37
Fig. 7 : Proton NMR result of BHET-based Polyester polyol-3
38
39
40 TMS as Reference standard give peak at 0.0002 ppm. While the proton of C-CH2 attached as a ꞵ-
41 substitution to the CH3 group present in the long fatty acid chain was recorded at δ=1.22-1.25 ppm, the proton
42
43 of the terminal methyl groups (-CH3) was identified at δ=0.89-0.90 ppm [49]. The -CH2-linked carbonyl and
44
ester functionalities are exhibited by the peaks at δ=2.25 and δ=2.34 ppm, respectively. The primary -OH from
45
46 structure is represented by the signal at δ = 3.01 ppm [59]. The -CH2-group proton, which is present between
47
the ester functionality and -CH2, is the trigger of the signal at δ=3.4 ppm. A -CH2-OH group linked as a
48
49 substitution is indicated by the doublet at δ=3.4 ppm [60]. It was confirmed that the -CH2-OH unit was present
50
in the monomeric product both as a substituted segment of the NPG structure and as an attached methylene
51
52 group [60]. At δ=3.70-3.73 ppm, the proton of the -CH2 group connected to the terminal hydroxyl group was
53
54 identified. The range of δ=3.9 to δ=4.1 ppm was where the multiplate pick of (CH) occurred [55]. The presence
55 of an ethylene unit in the structure is shown by the chemical shift indicators at δ=4.0 and 4.5 ppm. In 2H (CH 2)
56
57 diol, an acid terminal was detected at δ=4.13 ppm [54]. The presence of a substituted neo pentyl group is
58 indicated by the C-CH2-O-CO signals at δ = 4.2 and 4.3 ppm that correspond to -CH2. Between δ=4.15 and
59
60 δ=4.25 ppm, another doublet signal of (CH2) was observed [55]. The -OH group relates to the strong signal
61
62 Page 17 of 39
63
64
65
 seen at δ=4.15 ppm [59]. The presence of an ester methyl group next to the carbonyl carbon is indicated by
1 signals at δ= 4.20 ppm that represent C-CH2-O-CO linked to -CH2 at position. The signals from the protons
2
3 of the cyclic structure appear gradually between δ=6.5 and δ=7.5 ppm. δ=7.0-7.12 ppm is a chemical shift
4 caused by protons attached to an aromatic ring. According to [53], protons attached to a cyclic ring are
5
6 indicated by chemical shifts of δ=6.5-8.0 ppm. An indication of the CDCL3 solvent peak may be seen at
7 δ=7.2820 ppm. The presence of an aromatic component in the structure is shown by the chemical shift evidence
8
9 at δ=8.0-8.1 ppm.
10
11
1.7.3 GPC
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41 Fig. 8 : GPC analysis results of prepared BHET-based polyesters polyols-1
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 Page 18 of 39
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26 Fig. 9 : GPC analysis results of prepared BHET-based polyesters polyols-2
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57 Fig. 10 : GPC analysis results of prepared BHET-based polyesters polyols-3
58
59
60
61
62 Page 19 of 39
63
64
65
 Table 3 : GPC analysis result
1
2
3 Sample ID Poly dispersity Molecular weight (Mn)
4
5
6 Polyester -1 2.7673 2665.5
7
8 Polyester -2 1.025 3018.9
9
10 Polyester -3 1.782 1972.6
11
12
13
14 1.7.4 FTIR
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34 Fig. 11 : FTIR result of polyester
35
36
37 Each of the characteristic peaks depicted in Fig.5 was present in the FTIR spectra of the BHET-
38 based polyester polyols. Transmission bands occurred by aliphatic and aromatic -C-H stretching at 1871.1,
39
40 1900.9, 1949.4 cm-1, as well as 1453.7, 2855.1, and 2922.2 cm-1. The transmission band at 1602.8 cm-1
41 corresponds with a C-C aromatic bond. Identical peak of -C-O bond was identified to be present in the
42
43 backbone structure at 1263.6 and 1166.7 cm-1. Peaks at 3015.4 and 3175.7 cm-1 verified C-H bending and
44 stretching, whereas 730.6 and 872.2 cm-1 demonstrate that alkane-C=C interactions are present in the backbone.
45
46 The existence of the carbonyl ester's -C=O group was demonstrated by the stretching band at 1722.0 cm-1. The
47 existence of pendant hydroxyl groups in BHET-based polyester polyol was demonstrated by the broad
48
49 transmission band at 3436.6 cm-1.
50
51 Fig. 6 exhibits the results of an FTIR analysis of another BHET-based polyester polyol and PU
52
53 Coating film for conforming the backbone structure as well as cured properties of PU film. An intramolecularly
54 attached hydroxyl group showed a weak starching band at 2964 and 2953 cm−1, 2876 and 2878 cm−1, and 3072
55
56 cm−1. At 3424 cm-1, two small starching bands of hydroxyl groups joined by intermolecular bonds were
57 observed. The presence of the carbonyl ester's -C=O group was confirmed by a prominent stretching band at
58
59 1718 cm-1. Conjugation of the -C=O- with the phenyl ring from PA & BHET is indicated by another signal at
60 1579 cm-1 [46]. The starching of alkane C=C bonds and aromatic C-C bonds relates to the transmission band
61
62 Page 20 of 39
63
64
65
 at 1599 cm-1.The aromatic and aliphatic -C-H stretching and bending, respectively, contributed for the
1 transmission bands at 1373 and 1386 cm-1, 1407 and 1409 cm-1, 1456 and 1447 cm-1, and 1474 and 1489 cm-
2
1
3 . For aromatic esters, the presence of -C-O linkages in the backbone was detected at 1251 & 1262 cm-1 and
4 1169 & 1170 cm-1.
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34 Fig. 12 : FTIR result of polyester & PU Film
35
36 The stretching vibration of C-O-C bond can be seen by the bands found at 1102, 1118, and 1120 cm-
37 1
38 , whereas the stretching vibration of the C-C-O bond of polyesters is represented by the two bands found at
39 1067, 1072, and 1041 cm-1, respectively [47]. Alkene -C=C- bond exhibited two strong bendings at 907 and
40
41 927 cm-1 and 973 and 986 cm-1. A minor bend was found at 771 and 774 cm-1, 793.68 cm-1, and 846.07 cm-1,
42 whereas a significant bend at 729 and 731 cm-1 indicated the presence of alkene-C=C linkages in the backbone.
43
44 At 874 and 876 cm-1, strong C-H bending was observed.
45
46 Peaks were observed at 3028-3064 cm−1, 1605 cm−1, 1697 cm−1, and 2252 cm−1, which correspond to
47
the NH and CN bonds of the isocyanate that make up the breakdown of PU films. The PU film's FTIR spectra
48
49 reveal two prominent stretching bands at 2930, 2926, and 2956 cm−1 and 2857, 2856, and 2861 cm−1, as well
50
as a small starching peak at 3345, 3355, and 3377 cm−1. These bands demonstrate the establishment of the N-
51
52 H bond in the urethane production. On the associated BHET-based polyester polyols, the OH band disappeared.
53
54 This was in accordance with the way that OH and N-C=O interact [46]. Peaks located at 1408-1410 cm−1,
55 1517-1519 cm−1, and 1638 cm−1 show that PU contains C-N bonds. The C-H asymmetrical bending band is
56
57 located at 1460-1471 cm−1 [48]. At 1720 cm−1, the C-O bond of ester and urethane compounds was found.
58
59
60
61
62 Page 21 of 39
63
64
65
 1.7.4 Thermal Analysis
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28 Fig. 13 : TGA analysis of PU Films
29
30
31
32
33 The amount of urethane moieties, the molecular weight of BHET-based polyester polyols, the physical
34 interactions of polymer chains to the curing agent, the presence of aromatic structures, the number of raw
35
36 materials as well as BHET moiety, and changes the physical properties of PU film materials with respect to
37 mole ratio change in during polyol synthesis, and other factors which influence the thermally stability PU Film
38
39 was measured by TGA.
40
41 Therefore, the heat stability properties of all created PU films were examined and Fig.10 displays
42
43 their TGA curves. The obtained results showed that all PU films had two stages of heat degradation. The solvent
44 and moisture present in the PU layer may be the cause of the initial 2-3% weight loss observed. The breakdown
45
46 of urethane linkages and urea bonds (hard segment) caused 8–10% weight loss throughout the thermal
47 degradation process, which started at 216–220°C and finished at 295–306°C. Alcohols, primary or secondary
48
49 amines, and isocyanates were formed as a result. The urethane moiety releases carbon dioxide. Deterioration
50 caused weight losses of 8.35–17.64% in the second stage, which started at 317–347°C and ended at 372–388°C.
51
52 The destruction of cycloaliphatic and aromatic moieties, as well as ester and aliphatic linkages, may be the
53 cause of the second stage of thermal degradation. At 745°C & 445°C, respectively, PU Films 1 & 2 completely
54
55 disintegrated out of all the PU Films. 12.5 gm of sample remained undecomposed foam when PU Film-3 was
56 heated up to 785°C, that was confirming that PU Film-3 had excellent cross linking between the polyester
57
58 moiety and cyanides allowed it to be more thermally stable than the other two films. This occurs because of by
59 the high crosslink density of the coating. Unsaturation, hydrocarbon structure, and hydroxyl functionality all
60
61
62 Page 22 of 39
63
64
65
 are responsible for higher crosslinking density present into final backbone structure, and it was directly
1 enhancing the thermal properties of materials. While raising heat stability, a higher crosslink density in the PU
2
3 coating decreases the mobility of polymer chain fragments.
4
5
6
7 1.7.5 DSC
8
9 The phase changes that take place when PU film samples are heated were examined using the DSC
10 apparatus. As seen in Fig.11, the DSC thermograms of every PU film showed a melting temperature of
11
12 around 175 to 200◦C and a glass transition temperature (Tg) of 0 to 75◦C. The Tg values for PU Films 1, 2, and
13 3 are 43.26◦C, 71◦C, and 52◦C, respectively. The lower Tg value were due to imparted by the presence of
14
15 structural moiety of AA. Tg and viscosity are decreased by its structure four linear methylene groups [61,62].
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36 Fig. 14 : DSC result of PU Films
37
38
39
40 In general, chain segment mobility and intermolecular interactions play a major role in determining a
41
42 polymaric materials Tg value. Additionally, the polymer cross-link density, which is directly influenced by the
43 polyol and hardener functionality, has the most impact on the Tg value. All PU film samples have lower glass
44
45 transition temperatures, which may be because of the glycol chain. The type of hardener used may have also an
46 impact on increasing Tg values in PU coatings. An HDI trimer aliphatic polyisocyanate is N-3390. As a result,
47
48 the films treated with it had higher Tg values. The lower cross-linked density of PU films may be the reason
49 for their significantly lower Tg values when compared to other films.
50
51
52 1.8 Testing results of coatings & Performance evaluation
53
54
55 1.8.1 General testing results
56
57 Table 4 : General results for coating materials
58
59
60
61
62 Page 23 of 39
63
64
65
 Sr. Test name Polyester-1 Polyester-2 Polyester-3 VOY 8239 B-95
1 No.
2
3 1 Gloss (60o) (GU) or % 94.93 90 113.6 100.2 110.4
4
5 2 Adhesion (Cross-hatch) 100 75-80 100 80-85 100
6 (%)
7
8 3 Flexibility Test Pass (+) Pass (+) Pass (+) Pass (+) Pass (+)
9
10 4 Water Absorption (%) 0.04844 0.00023 0.005829 0.04334 0.03317
11
12 5 Swelling properties (S) (%) 4.2 3.8 2.8 1.6 2.2
13
14 6 Surface drying(hr) 15-18 4-5 1.5 12-15 30-32
15
7 Tack free drying(hr) 22-23 6 2 30-32 34-36
16
17 8 Hard drying(hr) 36-37 10 3-3.5 36 37
18
19 9 Dry film thickness (μm) 225 150 225 300 300
20
21 10 Get time (hr) 10-12 2-2.5 1.5-2 10-12 29-30
22
23 11 Gardner color test 37 or 38 13 or 14 0 0 0
24
25
26
27 The various parameter outcomes of the PU coating films developed with BHET-based polyester
28
polyol scan be seen in Table No. 4. Because of the suitable reactivity of the curing agent led on by the presence
29
30 of an aromatic ring, the developed samples were cured at room temperature. all PU coatings developed with
31
BHET-based polyester polyols (Polyester-1-3) had gloss amounts between 94 -113, at a 60° angle. A long chain
32
33 of dicarboxylic acid may be the root cause of the high gloss values for BHET-based PU-3 coatings, whereas
34
the lack of a long fatty acid chain may be the cause of the lower gloss values for PU-1 coatings film. Gloss
35
36 values are improved by the smooth surface that was increase in with increasing crosslink density of PU film,
37
38 and it was also reflects more light due to smooth surface of coating film [63]. According to the results of the
39 study, the developed coatings film total gloss value was higher than that of industrial-grade polyester polyol
40
41 based coatings film [64].
42
43 The degree of interaction between a coated film and the underlying material which might be another
44 layer of paint or any other material or substrate is determined by the adhesion (cross-hatch) test. It is defined
45
46 as the amount of force required, under controlled circumstances, to remove the coating from the substrate.
47 Adhesion tests on BHET-based PU coatings revealed that all samples (except from Polyester-2 and VOY-8239)
48
49 adhered well to metal surfaces; this might be because of the polar urethane and fatty acid esters. Because
50
polyester-2 and VOY-8239 have a hard aromatic component in the form of PA and another aromatic moiety,
51
52 their adherence is reduced. Further applications of the new BHET-based coatings become possible by their
53
high adhesion rate in surface coating sectors by fulfilled the requirement of batter resisstance properties with
54
55 excellent adhesion to the substrate. In the case of industrial grade polyester-based generated PU coating, the
56
57 cross-cut adhesion test results indicated that part of the lattice squares were detached, which is around 25%. it
58
59
60
61
62 Page 24 of 39
63
64
65
 was comparable result to BHET-based coating systems. Therefore, it can be said that BHET-based polyester
1 polyol PU coatings have strong cross-cut adhesion [65]. Fig. 15 exhibits the results of the adhesion test.
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22 Fig. 15 : Adhesion (cross-hatch) test result a). BHET-based polyesters b). Industrial grade polyester-based
23
24 coating
25
26 The ability of a substance to bend or flex without breaking or failing is referred to as flexibility. A
27
28 conical mandrel device was used to evaluate the flexibility of each PU coating panel. A coated
29 MS panel was bent to 180° and evaluated the result of each panel. The panel is considered to have passed if
30
31 the surface isn't cracked or damaged. Because long chains of acids and dicarboxylic acid moieties were
32 incorporated into the final product structure, all BHET-based polyester polyol coated samples passed a
33
34 flexibility test [65]. Because the aromatic bond in the BHET structural moiety offered an appropriate amount
35
of hardness and flexibility, the coating exhibited good mechanical characteristics. Consequently, every panel
36
37 including the industrial-grade polyester-based coated panel displayed in Fig.16 passed the flexibility test.
38
However, the coatings were durable and passed the flexibility test due to each of them incorporated fatty acid
39
40 chains (CH2), which are in the role of imparting flexibility.
41
42
43
44
45
46
47
48
49
50
51
52
53
54 Fig. 16 : Flexibility test result a). BHET-based polyesters b). Industrial grade polyester-based coating
55
56 According to ASTM D1544, light-transmitting materials having colour properties ranging from light
57
58 yellow to brownish red can be evaluated using the Gardner Colour Scale, a single-number colour system. It is
59 commonly used in oils, paints, and chemicals such as fatty acids, lecithin, sunflower oil, linseed oil, lacquers,
60
61
62 Page 25 of 39
63
64
65
 varnishes, drying oils, and resins. The chromaticities of glass standards, which go from 1 for brightest to 18
1 for darkest, form the scale. Polyols with a more bright colour, from yellow to brown, are classified using the
2
3 Gardner colour scale. In addition to increasing their market value, polyol light colour shows that they weren't
4 affected during synthesis [66,67].
5
6
7
8
9 1.8.2 Hardness
10
11
Significant amounts of hydrogen bonding in polyester help to establish strong connections, increasing
12
13 the material's tensile strength and hardness [68].
14
15 Table 5: Performance properties of coating panel
16
17 PU film name Impact hardness/resistance Pencil hardness
18
19 (cm)
20 Polyester-1 100 pass 6H
21
22 Polyester-2 60 pass 8H
23 Polyester-3 50 pass 9H
24
VOY-8239 50 pass 8H
25
26 B-95 100 pass 8H
27
28
29
30 1.8.2.1 Impact hardness/resistance
31
32
The impact resistance test measured a coating's ability to withstand impact without breaking in the
33
34 event of a rapid deformation. It dropped with a weight of 900 kg from drop heights of 50, 60, 75, and 100 cm.
35
if the applied impact energy distributed evenly throughout the film that means it was good impact strength. At
36
37 this point, the free volume between two atom molecules in the chains is crucial. The impact resistance of the
38
39 BHET-based polyester polyol developed coating was outstanding, and that were comparable to the industrial
40 grade polyol-based coated film shown in Fig.17.
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57 Fig. 17 : Impact hardness results a). BHET-based polyesters b). Industrial grade polyester-based coating
58
59
60 1.8.2.2 Pencil hardness
61
62 Page 26 of 39
63
64
65
 All coating films are measured for pencil hardness using Mitsu-Bishi UNI 3H-9H pencils. Pencil
1 hardness is the term used to describe the pencil's ability to produce scratches. The softest pencil is represented
2
3 by the notation 1B, and up to 6B, the pencil becomes harder than the pencil with the previous value. The pencil
4 that represents 1H is harder than the one that represents 6B. The H pencil series has numbers, similar to the B
5
6 pencil series, and the harder the pencil, greater the number. Use the softest pencil to begin measuring coating
7 hardness. The following pencil is used for measuring if it does not leave a scratch on the coated surface. Until
8
9 the pencil doesn't scratch the coated surface, this process is repeated.
10
11 A significant difference in the measured pencil hardness values for the developed coatings were
12
13 generated by variations in the structural moieties in final backbone structural. The presence of an aromatic ring
14 in hard segments via curing agent/BHET and a high NCO/OH ratio may be responsible for the hardness
15
16 property of all PU coatings, which was determined in the 6–9H range. The hardness of coatings which included
17 PA and NPG was significantly higher than that of coatings containing other acids & hydroxyl containing raw
18
19 component. The presence of hard aromatic rings (BHET) and the higher cross-linking density imposed on by
20 the extra OH groups in PG and neopentyl may be the reason of this. According to this study, coatings developed
21
22 with BHET-based polyester polyol showed better pencil hardness characteristics than coatings developed with
23 industry-grade polyester polyols [65].
24
25
26
27
28 1.8.3 Chemical & Corrosion resistance
29
30
1.8.3.1 Chemical resistance
31
32
33 Water, acid, alkali, and organic solvents are just a few of the environmental factors that might be
34 affected or deteriorated the coated materials panels due to long term contact. To help understand or predict
35
36 how prepared PU coatings would behave against various types of substances & chemical resistance to check
37 the resistance testing is required. For seven to thirty days, the developed PU samples were submerged in water,
38
39 5% HCl acid, 5% NaOH alkali, and xylene (an organic solvent) respectively. Fig.18 &19 and Table No. 6.
40 was deliver images of the obtained result & data.
41
42
43 Table 6: Result solvent Resistance after 7 days
44
45 Chemical name Polyester-1 Polyester-2 Polyester-3 VOY 8239 B-35
46
47 5 % NaOH 2 2 2 1 2
48
5 % NaCl 1 2 1 1 1
49
50 5 % HCl 1 6 1 1 1
51
52 Water 2 2 1 1 1
53 Xylene 7 7 7 7 7
54
55 1= No effect, 2 = loss in gloss, 3 = Soften, 4 = Loss of adhesion, 5 = blistering, 6 = lifting or slightly peel out
56 , 7 = rupture
57
58
59
60
61
62 Page 27 of 39
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 Fig. 18 : Chemical resistance of PU coated panel immerged into solution a). For 7 days b). apply cross cut on
24 plate and immerged for another 7 days
25
26
27 Prior to the chemical resistance test, all PU-coated panels were sealed off on all side walls using
28 melted wax to prevent liquid from penetrating through. The chemical resistance test was then carry forward of
29
30 all developed panel. All PU coated panels were immersed in appropriate chemicals for seven days in order to
31 assess their chemical resistance. Panels were taken out from the medium at regular time interval and observed
32
33 visually; pictures of the panels taken before and after the testing are shown in Fig. 18 &19, respectively. Since
34 there was no change in appearance, it was concluded that all produced coatings had better solvent resistance.
35
36 All PU coatings displayed medium-level gloss loss, with the exception of the BHET-based polyester-3-based
37 coating panel. When tested against an acidic media, the PU coatings displayed slight change in color and a loss
38
39 of shine. The resulting PU foaming lesser long-chain fatty acid content may be the cause of the lower acid
40 resistance.
41
42
43 All of the coating alkali resistance was found to be ideal because PU-1 & 3, VOY-8239, and B-95
44 showed only slight gloss loss, whereas PU-2 showed greater gloss loss because of the hydrolysis of glycerol
45
46 and other OH function groups that were present in the final product Backbone structure [69,70]. With just a
47 slight gloss loss and color change all of the coatings exhibited good water resistance. Protecting metal surfaces
48
49 from corrosive environments like salt solutions, moisture, acids, or exposure to a variety of industrial or
50 environmental substances is known as anticorrosion.By immersing or dipping PU Coated MS panels in an
51
52 aqueous 5% NaCl solution, the anticorrosive performance of all developed PU coatings was evaluated. Typical
53 pictures and outcomes are displayed in Table No. 6 and Fig.18 & 19. The coatings impacted the film and lost
54
55 the gloss in the salt medium [69]. Almost all of the coating layer was stripped or separated from the panel
56 during a seven-day placing in xylene solvent. The greatest performance against acid, water, alkali, and NaCl
57
58 was achieved by the PU coating film based on BHET-based polyester polyols-3.
59
60
61
62 Page 28 of 39
63
64
65
 Because of the urethane moieties, aliphatic chain, and aromatic feature in the coating chemical
1 structure, the BHET-based polyester polyol-prepared coatings had exceptional chemical resistance [8,71]. This
2
3 behaviour may be addressed by the crosslinked structure of the coating, which depends on the polyol
4 unsaturation and hydroxyl groups. Higher crosslink density coatings are more acid and alkali resistant [65].
5
6 Additionally, polyester polyol's long fatty acid chains, which provide chemical stability, can be responsible for
7 of the improved chemical resistance [72]. Additionally, the hydrophobic qualities of the coated films enable
8
9 them to function as a barrier to absorb massive amounts of moisture. Likewise, coatings containing nitrogen
10 may have anticorrosive characteristics and attach to the substrate. The enhanced reactivity of the curing agent,
11
12 leading to a greater contribution to cross-linking, may have been the cause of PU superior adhesion to the metal
13 surface and good corrosion resistance [65]. The BHET-based PU coating -1 was found to be weekly resistant
14
15 to water and salt solutions up to specific limitations after a month of immersion in various chemicals to evaluate
16
chemical resistance. However, it was more resistant to HCl and NaOH chemical solutions than the BHET-
17
18 based PU coating -3 coated panel. The chemically resistant BHET-based PU coating -2 film was more resistant
19
to the NaCl salt solution than the BHET-based PU coating -3 & other polyols based coated panel, even if it was
20
21 weekly resistant to HCl, water, and NaOH solutions up to certain limits. It was found that the coating film was
22
23 peeling from the MS plate when the BHET-based PU coating-3 coated panel was placed in contact with HCL.
24 PA and NPG to deliver BHET-based PU coating-3 strong resistance to weak caustic solutions and the solvent
25
26 xylene.Moreover, NPG has two pendant methyl groups in its structure. The ester groups are protected from
27 water and other reactive substances by their pendant groups. For formulations that are resistant to hydrolysis,
28
29 NPG is therefore a helpful chemical for formulate this kind of materials [61,73]. The polyester polyols that
30 utilise PA deliver a unique balance of improved hydrolytic stability and adhesion properties, make formulation
31
32 simpler [74]. The findings were comparable to the industrial-grade polyester-based coated panels illustrated in
33 Fig. 19, with better resistance to a range of chemicals.
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 Page 29 of 39
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 Fig. 19 : Chemical resistance of PU coated panel immerged into solution for 30 days
31
32 1.8.3.2 Solvent resistance
33
34
35 Table 7 : Chemical resistance result
36
37 PU film code name Xylene MEK
38
39 Polyester-1 300 cycle pass 300 cycle pass
40 Polyester-2 300 cycle pass 185-190 cycle pass
41
42 Polyester-3 300 cycle pass 300 cycle pass
43
VOY 8239 300 cycle pass 300 cycle pass
44
45 B-35 300 cycle pass 300 cycle pass
46
47
48
49 Using the solvent rub test (200–300 cycles) with different solvents such xylene and MEK, the solvent
50 resistance of PU coatings was examined. Differences in coating appearance were observed as seen in Fig.20
51
52 (Table no.7). In the solvent rub test, every coating performed admirably and remained unaffected by 300 rub
53
cycles with methyl ethyl ketone and xylene. The greater crosslink density of BHET-based PU coating, which
54
55 has the most hydroxyl groups, might be the cause of this. Nevertheless, the BHET-based polyester-2 coating
56
gloss as well as some part of coating layer was somewhat reduced and the coated film vanished when treated
57
58 to the MEK rub test [72].
59
60
61
62 Page 30 of 39
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
14 Fig. 20 : solvent resistance result of Developed coating panels
15
16 1.8.3.3 Freeze thaw & thermal/temperature stability
17
18
19 All PU-based coated panels were successfully cleared in a deep freezer for 24 hours at a temperature
20 of about -18◦C, maintaining to freezing and thawing procedures. After being taken out of the frigid
21
22 temperatures, the panels showed no signs of damage or cracking. To find out how much heat the PU-coated
23 panel could withstand and what kinds of changes happened when it came into contact with elevated
24
25 temperatures, another test was carried out. Temperature affects colour, and appearance as shown in Fig. 21.
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50 Fig. 21 : Result of color appearance & properties changes to temperature
51
52 Absolutely no changes were seen in any PU-based coating panel upon at 165°C temperature. But the
53
54 PU film's colour switched from pale yellow to wine red at 165°C. During the test, none of the coated panels
55 had cracks or other damage. During testing, the material turned glossy and charcoal black at 225°C, but no
56
57 cracks or defects were found. However, as seen in Fig. 22, all of the coated panel sample burned and the
58 industrial polyol-based coated films spilt up at temperatures as high as 300◦C. However, the developed BHET-
59
60 based polyester-based coated film did not pill out of the MS plate.
61
62 Page 31 of 39
63
64
65
 1
2
3
4
5
6
7
8
9
10
11
12
13
Fig. 22 : Result of Overnight set up at higher temperature
14
15
16 1.9 Conclusion & Future aspects
17
18 An innovative technique to produce polyesters for coating applications was developed through mixing
19
20 the recovered chemicals from PET with the use of renewable resource-based components (DA, SA). The
21 production of polyester resin signified that one of the glycols in the resin chemical composition might be
22
23 effectively substituted by a glycolyzed PET product. It has been displayed that BHET, a glycolyzed PET waste
24 product, is a potential raw material for the synthesis of polyester, producing value-added compounds for coating
25
26 applications. In the presence of a catalyst such PTSA & DBTDL, BHET was esterified with many different
27 kinds of dicarboxylic acids and glycols, including DA, SA, AA, PA, glycerol, MA, NPG, and PG, to
28
29 successfully produce a BHET-based polyester polyol.
30
31 FTIR, GPC, and proton NMR spectroscopic techniques have been used to validate the structures of
32
33 the final product of BHET-based polyester polyols. During application, the contents of both coating ingredients
34 will influence the characteristics of the PU film. If the hardener content lowers, the curing of the PU film is
35
36 incomplete and remains uncured after a long period of curing. In addition, adding more hardener will reduce
37 the flexibility of the PU film. Excellent resistance to acids, alkalis, and organic solvents was shown by each
38
39 coating. When tested against a 5% salt solution, the produced PU coatings showed higher anticorrosive
40 performance. Overall, all polyurethane coatings showed good performance features, and the outcomes were on
41
42 comparable with coating panels created from industrial polyester. Therefore, when creating transparent
43 anticorrosive PU coatings, BHET can be used as an effective substitute for petroleum-based precursors. In
44
45 contrast to the current trend of using petroleum feedstock in the polymer industry, this study encourages the
46 use of PET waste as a novel sustainable source for the synthesis of polyester polyol. Thus, a novel, sustainable,
47
48 and eco-friendly approach to PET waste chemical recycling has been effectively explored.
49
50 Ester linkage improves the flexibility, thermal stability, and reduced flammability of polymeric
51
coating materials. Acid anhydrides, such as MA and PA, might be responsible for these characteristics.
52
53 Presence of DA contains several hydrocarbon isomers, which leads to decreased crystallinity. They do not
54
55 crystallize and hence add to the flexibility in polymeric coating materials film. Its purpose is to give unique
56 properties to the finished product, such as elasticity, flexibility, low viscosity, high impact strength, reduced
57
58 film shrinkage, hydrolytic stability, hydrophobicity, and lower glass transition temperatures. Aliphatic diacids
59 (e.g., AA & SA) provide softness and flexibility to coating films with little to no damage resistance.
60
61
62 Page 32 of 39
63
64
65
 Furthermore, the presence of SA in the coating materials demonstrated high gloss and hardness. Glycerol
1 increased the viscosity and strength of the coated layer due to its tri-OH functionality. Although the Polyester
2
3 polyols-3-based coating delivered outstanding outcomes and is equivalent to an industrial grade polyester-
4 based coating, all generated BHET-based polyester polyols have excellent properties. A combination of PA &
5
6 NPG has given BHET-based polyurethane coating -3 chemical resistance in addition to excellent hardness,
7 adhesion, and glossy behaviors. Moreover, NPG has two pendant methyl groups in its structure. The ester
8
9 groups are kept protected from water and other reactive substances by their pendant groups. For compositions
10 that are resistant to hydrolysis, NPG thus becomes a helpful chemical. The polyester polyols based on PA
11
12 provide a unique combination of improved hydrolytic stability and adhesion properties, making formulation
13 simpler. Good hardness and UV resistance properties are achieved by the presence of a BHET moiety in the
14
15 final structure of BHET-based polyester-3-based coating materials.
16
17 The world will soon be more environmentally conscious, with a focus on recycling wasted plastic
18
19 materials. One efficient and sustainable way to improve industrial and social sustainability is to recover, reuse,
20 and recycle waste materials like plastics, paper, and glass. Reducing the amount of solid waste on our world
21
22 and conserving natural resources are the main goals of for recycling plastic waste. Recycling plastic waste was
23 utilized to incorporate got chemicals or building blocks to develop a range of derivatives or value-added
24
25 products. About half of the world population will eventually consume value-added products as well as plastics
26 that are recycled or biodegradable. In this manner, we might potentially lower the global amount of plastic
27
28 garbage. It follows that the amount of BHET used in the manufacturing of resin will vary and will have a direct
29 impact on the hardness and, to a certain extent, chemical resistance features.
30
31
32
33
34
35
1.10 Declaration of Competing Interest
36
37  Consent to participate Not applicable.
38
39  Consent to publish Not applicable
40  The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
41
42 publication of this article, and the authors also declare that they have no known competing financial
43 interests or personal relationships that could have appeared to influence the work reported in this
44
45 paper.
46
47 1.11 Acknowledgements
48
49
50 The authors are grateful to the Institute of Science & Technology for Advanced Studies & Research
51 (ISTAR) College & The Charutar Vidya Mandal (CVM) University for providing the necessary infrastructure.
52
53 We would also like to thank the Sophisticated Instrumentation Centre for Applied Research and Testing
54 (SICART), the Sophisticated Analytical Instrument Facility (SAIF) at Punjab University & Indukaka Ipcowala
55
56 Center for Interdisciplinary Studies in Science and Technology (IICISST) for their support in conducting quick
57
and reliable evaluations of the synthesised products. The authors acknowledge financial assistance from
58
59 SHODH - ScHeme of Developing High Quality Research, Knowledge Consortium of Gujarat, Education
60
Department, Government of Gujarat.
61
62 Page 33 of 39
63
64
65
 1.12 Funding
1
2 SHODH - ScHeme of Developing High Quality Research, Knowledge Consortium of Gujarat,
3
4 (Education Department, Government of Gujarat. Letter Reference no: KCG/SHODH/2020-21/ & Grant
5 number: 202010820003.
6
7
8 1.13 Author Contributions
9
10 Dr. Jigar V. Patel have given guidance’s & idea about this work, and he have supervised, monitored,
11
12 and revised the manuscript. Khodidas K. Bhanderi & Jeimin R. Joshi have collected data, designed the
13 manuscript and written the main text and revised the manuscript. All authors have read and agreed to the
14
15 published version of the manuscript.
16
17 1.14 Ethical Approval
18
19
20 We hereby declare that this work is original and not copied from anywhere else. We approve that this
21 work is not submitted in this language or any other language to any other journal nor it is submitted for
22
23 simultaneous consideration.
24
25 1.15 Data Availability
26
27
28 The datasets generated during and/or analysed during the current study are not publicly available due
29 to privacy problem but are available from the corresponding author on reasonable request.
30
31
32
33
34 1.16 References
35
36
37
[1] E. Baştürk, T. İnan, A. Güngör, Flame retardant UV-curable acrylated epoxidized soybean oil
38 based organic–inorganic hybrid coating, Progress in Organic Coatings 76 (2013) 985–992.
39 https://doi.org/10.1016/j.porgcoat.2012.10.007.
40 [2] C. Li, H. Xiao, X. Wang, T. Zhao, Development of green waterborne UV-curable vegetable oil-
41 based urethane acrylate pigment prints adhesive: Preparation and application, Journal of
42
Cleaner Production 180 (2018) 272–279. https://doi.org/10.1016/j.jclepro.2018.01.193.
43
44 [3] Y. Tan, Y. Liu, W. Chen, Y. Liu, Q. Wang, J. Li, H. Yu, Homogeneous Dispersion of Cellulose
45 Nanofibers in Waterborne Acrylic Coatings with Improved Properties and Unreduced
46 Transparency, ACS Sustainable Chem. Eng. 4 (2016) 3766–3772.
47 https://doi.org/10.1021/acssuschemeng.6b00415.
48 [4] R.P. Babu, K. O’Connor, R. Seeram, Current progress on bio-based polymers and their future
49
50 trends, Prog Biomater 2 (2013) 8. https://doi.org/10.1186/2194-0517-2-8.
51 [5] S. Schmidt, B.S. Ritter, D. Kratzert, B. Bruchmann, R. Mülhaupt, Isocyanate-Free Route to
52 Poly(carbohydrate–urethane) Thermosets and 100% Bio-Based Coatings Derived from
53 Glycerol Feedstock, Macromolecules 49 (2016) 7268–7276.
54 https://doi.org/10.1021/acs.macromol.6b01485.
55
56
[6] C. Voirin, S. Caillol, N.V. Sadavarte, B.V. Tawade, B. Boutevin, P.P. Wadgaonkar,
57 Functionalization of cardanol: towards biobased polymers and additives, Polym. Chem. 5
58 (2014) 3142–3162. https://doi.org/10.1039/C3PY01194A.
59 [7] J.C. Khanderay, V.V. Gite, Vegetable oil-based polyurethane coatings: recent developments
60 in India, Green Materials (2017) 1–14. https://doi.org/10.1680/jgrma.17.00009.
61
62 Page 34 of 39
63
64
65
 [8] M.S. Mahajan, P.P. Mahulikar, V.V. Gite, Eugenol based renewable polyols for development
1 of 2K anticorrosive polyurethane coatings, Progress in Organic Coatings 148 (2020) 105826.
2 https://doi.org/10.1016/j.porgcoat.2020.105826.
3 [9] R. Atakan, USE OF RECYLED POLY(ETHYLENE TEREPHTALATE) FIBERS IN NEEDLEPUNCHED
4
5 AUTOMOTIVE CARPETS, (2014) 115.
6 [10] Khodidas K. Bhanderi, J. Joshi, V. Suthar, V. Shah, G.M. Patel, J. Patel, Eco-friendly polymer
7 nanocomposites based on bio-based fillers: preparation, characterizations and potential
8 applications, in: Biodegradable and Biocompatible Polymer Nanocomposites, Elsevier, 2023:
9 pp. 173–203. https://doi.org/10.1016/B978-0-323-91696-7.00015-5.
10
11
[11] R. López-Fonseca, I. Duque-Ingunza, B. de Rivas, S. Arnaiz, J.I. Gutiérrez-Ortiz, Chemical
12 recycling of post-consumer PET wastes by glycolysis in the presence of metal salts, Polymer
13 Degradation and Stability 95 (2010) 1022–1028.
14 https://doi.org/10.1016/j.polymdegradstab.2010.03.007.
15 [12] S.R. Shukla, A.M. Harad, Glycolysis of polyethylene terephthalate waste fibers, J. Appl.
16 Polym. Sci. 97 (2005) 513–517. https://doi.org/10.1002/app.21769.
17
18 [13] N.D. Pingale, V.S. Palekar, S.R. Shukla, Glycolysis of postconsumer polyethylene
19 terephthalate waste, Journal of Applied Polymer Science 115 (2010) 249–254.
20 https://doi.org/10.1002/app.31092.
21 [14] K.K. Bhanderi, J.R. Joshi, J.V. Patel, Recycling of polyethylene terephthalate (PET Or PETE)
22 plastics – An alternative to obtain value added products: A review, Journal of the Indian
23
24 Chemical Society 100 (2023) 100843. https://doi.org/10.1016/j.jics.2022.100843.
25 [15] D.S. Achilias, H.H. Redhwi, M.N. Siddiqui, A.K. Nikolaidis, D.N. Bikiaris, G.P. Karayannidis,
26 Glycolytic depolymerization of PET waste in a microwave reactor, Journal of Applied
27 Polymer Science 118 (2010) 3066–3073. https://doi.org/10.1002/app.32737.
28 [16] G.P. Karayannidis, D.S. Achilias, Chemical Recycling of Poly(ethylene terephthalate),
29
Macromolecular Materials and Engineering 292 (2007) 128–146.
30
31 https://doi.org/10.1002/mame.200600341.
32 [17] M.N. Siddiqui, D.S. Achilias, H.H. Redhwi, D.N. Bikiaris, K.G. Katsogiannis, G.P. Karayannidis,
33 Hydrolytic Depolymerization of PET in a Microwave Reactor, Macromolecular Materials and
34 Engineering 295 (2010) 575–584. https://doi.org/10.1002/mame.201000050.
35 [18] G. Mir Mohamad Sadeghi, R. Shamsi, M. Sayaf, From Aminolysis Product of PET Waste to
36
37 Novel Biodegradable Polyurethanes, J Polym Environ 19 (2011) 522–534.
38 https://doi.org/10.1007/s10924-011-0283-7.
39 [19] R.K. Soni, K. Dutt, A. Jain, S. Soam, S. Singh, A novel route of synthesis, characterization of
40 terephthalic dihydrazide from polyethylene terephthalate waste and it’s application in PVC
41 compounding as plasticizer, Journal of Applied Polymer Science 113 (2009) 1090–1096.
42
43
https://doi.org/10.1002/app.29842.
44 [20] Y. Öztürk, G. Güçlü, Unsaturated Polyester Resins Obtained from Glycolysis Products of
45 Waste PET, Polymer-Plastics Technology and Engineering 43 (2005) 1539–1552.
46 https://doi.org/10.1081/PPT-200030272.
47 [21] G.P. Karayannidis, D.S. Achilias, I.D. Sideridou, D.N. Bikiaris, Alkyd resins derived from
48
glycolized waste poly(ethylene terephthalate), European Polymer Journal 41 (2005) 201–
49
50 210. https://doi.org/10.1016/j.eurpolymj.2004.10.001.
51 [22] P.U. Kapadi, S.R. Shukla, S.T. Mhaske, A. More, M.N. Mali, Development of corrosion
52 resistant polyurethane coating from aminolytic depolymerization of pet bottle waste,
53 (2015).
54 [23] K.K. Bhanderi, J.R. Joshi, J.V. Patel, Optimization process for glycolysis of poly (ethylene
55
56 terephthalate) using bio-degradable & recyclable heterogeneous catalyst, Journal of the
57 Indian Chemical Society 100 (2023) 100904. https://doi.org/10.1016/j.jics.2023.100904.
58 [24] O. Valerio, M. Misra, A.K. Mohanty, Poly(glycerol- co -diacids) Polyesters: From Glycerol
59 Biorefinery to Sustainable Engineering Applications, A Review, ACS Sustainable Chem. Eng. 6
60 (2018) 5681–5693. https://doi.org/10.1021/acssuschemeng.7b04837.
61
62 Page 35 of 39
63
64
65
 [25] S.R. Mohanty, S. Mohanty, S.K. Nayak, S.K. Samal, Synthesis and evaluation of novel acrylic
1 and ester-based polyols for transparent polyurethane coating applications, Materials Today
2 Communications 27 (2021) 102228. https://doi.org/10.1016/j.mtcomm.2021.102228.
3 [26] J.S. Canaday, M.J. Skowronski, A Comparison of Aromatic Polyester Polyols for Rigid
4
5 Urethane and Isocyanurate Foam, Journal of Cellular Plastics 21 (1985) 338–344.
6 https://doi.org/10.1177/0021955X8502100507.
7 [27] P.M. Paraskar, V.M. Hatkar, R.D. Kulkarni, Facile synthesis and characterization of renewable
8 dimer acid-based urethane acrylate oligomer and its utilization in UV-curable coatings,
9 Progress in Organic Coatings 149 (2020) 105946.
10
11
https://doi.org/10.1016/j.porgcoat.2020.105946.
12 [28] de Março de, Study of the production of polyesters for polyurethanes at pilot plant scale,
13 (2005).
14 https://repositorio.ipl.pt/bitstream/10400.21/3933/1/Disserta%C3%A7%C3%A3o.pdf.
15 [29] J. Stumbé, B. Bruchmann, Hyperbranched Polyesters Based on Adipic Acid and Glycerol,
16 Macromol. Rapid Commun. 25 (2004) 921–924. https://doi.org/10.1002/marc.200300298.
17
18 [30] V.T. Wyatt, G.D. Strahan, Degree of Branching in Hyperbranched Poly(glycerol-co-diacid)s
19 Synthesized in Toluene, Polymers 4 (2012) 396–407.
20 https://doi.org/10.3390/polym4010396.
21 [31] T. Zhang, B.A. Howell, A. Dumitrascu, S.J. Martin, P.B. Smith, Synthesis and characterization
22 of glycerol-adipic acid hyperbranched polyesters, Polymer 55 (2014) 5065–5072.
23
24 https://doi.org/10.1016/j.polymer.2014.08.036.
25 [32] Y. Li, W.D. Cook, C. Moorhoff, W. Huang, Q. Chen, Synthesis, characterization and properties
26 of biocompatible poly(glycerol sebacate) pre‐polymer and gel, Polymer International 62
27 (2013) 534–547. https://doi.org/10.1002/pi.4419.
28 [33] Y. Yang, W. Lu, J. Cai, Y. Hou, S. Ouyang, W. Xie, R.A. Gross, Poly(oleic diacid- co -glycerol):
29
Comparison of Polymer Structure Resulting from Chemical and Lipase Catalysis,
30
31 Macromolecules 44 (2011) 1977–1985. https://doi.org/10.1021/ma102939k.
32 [34] P. Kallinteri, S. Higgins, G.A. Hutcheon, C.B. St. Pourçain, M.C. Garnett, Novel Functionalized
33 Biodegradable Polymers for Nanoparticle Drug Delivery Systems, Biomacromolecules 6
34 (2005) 1885–1894. https://doi.org/10.1021/bm049200j.
35 [35] A.S. Kulshrestha, W. Gao, R.A. Gross, Glycerol Copolyesters: Control of Branching and
36
37 Molecular Weight Using a Lipase Catalyst, Macromolecules 38 (2005) 3193–3204.
38 https://doi.org/10.1021/ma0480190.
39 [36] T. Naolou, V.M. Weiss, D. Conrad, K. Busse, K. Mäder, J. Kressler, Fatty Acid Modified
40 Poly(glycerol adipate) - Polymeric Analogues of Glycerides, in: C. Scholz, J. Kressler (Eds.),
41 ACS Symposium Series, American Chemical Society, Washington, DC, 2013: pp. 39–52.
42
43
https://doi.org/10.1021/bk-2013-1135.ch004.
44 [37] V. Taresco, R.G. Creasey, J. Kennon, G. Mantovani, C. Alexander, J.C. Burley, M.C. Garnett,
45 Variation in structure and properties of poly(glycerol adipate) via control of chain branching
46 during enzymatic synthesis, Polymer 89 (2016) 41–49.
47 https://doi.org/10.1016/j.polymer.2016.02.036.
48
[38] V. Taresco, J. Suksiriworapong, R. Creasey, J.C. Burley, G. Mantovani, C. Alexander, K.
49
50 Treacher, J. Booth, M.C. Garnett, Properties of acyl modified poly(glycerol-adipate) comb-
51 like polymers and their self-assembly into nanoparticles, J. Polym. Sci. Part A: Polym. Chem.
52 54 (2016) 3267–3278. https://doi.org/10.1002/pola.28215.
53 [39] T. Wersig, M.C. Hacker, J. Kressler, K. Mäder, Poly(glycerol adipate) – indomethacin drug
54 conjugates – synthesis and in vitro characterization, International Journal of Pharmaceutics
55
56 531 (2017) 225–234. https://doi.org/10.1016/j.ijpharm.2017.08.093.
57 [40] Y.-R. Zhang, S. Spinella, W. Xie, J. Cai, Y. Yang, Y.-Z. Wang, R.A. Gross, Polymeric triglyceride
58 analogs prepared by enzyme-catalyzed condensation polymerization, European Polymer
59 Journal 49 (2013) 793–803. https://doi.org/10.1016/j.eurpolymj.2012.11.011.
60
61
62 Page 36 of 39
63
64
65
 [41] E. Slavko, M.S. Taylor, Catalyst-controlled polycondensation of glycerol with diacyl chlorides:
1 linear polyesters from a trifunctional monomer, Chem. Sci. 8 (2017) 7106–7111.
2 https://doi.org/10.1039/C7SC01886J.
3 [42] H. Chen, J. Kong, Hyperbranched polymers from A 2 + B 3 strategy: recent advances in
4
5 description and control of fine topology, Polym. Chem. 7 (2016) 3643–3663.
6 https://doi.org/10.1039/C6PY00409A.
7 [43] I. Schoon, M. Kluge, S. Eschig, T. Robert, Catalyst Influence on Undesired Side Reactions in
8 the Polycondensation of Fully Bio-Based Polyester Itaconates, Polymers 9 (2017) 693.
9 https://doi.org/10.3390/polym9120693.
10
11
[44] C.M. Patel, A.A. Barot, V. Kumar Sinha, Sequential liquefaction of Nicotiana tabacum stems
12 biomass by crude polyhydric alcohols for the production of polyols and rigid polyurethane
13 foams, J of Applied Polymer Sci 133 (2016) app.43974. https://doi.org/10.1002/app.43974.
14 [45] Patil, R N, Kapadi, U R, Wani, Y R, Hundiwale, D G, PU Dispersions - Effect of Glycol in Polyol
15 Moiety on the Properties of PU Coatings, NISCAIR 62 (2003) 1020–1030.
16 [46] T.S. Velayutham, W.H.A. Majid, A.B. Ahmad, G.Y. Kang, S.N. Gan, Synthesis and
17
18 characterization of polyurethane coatings derived from polyols synthesized with glycerol,
19 phthalic anhydride and oleic acid, Progress in Organic Coatings 66 (2009) 367–371.
20 https://doi.org/10.1016/j.porgcoat.2009.08.013.
21 [47] D. Modra, G. Vlase, P. Albu, C. Bolcu, T. Vlase, Influence of the nature of the chain breaker
22 on the thermal stability of phthalic anhydride-based polyesters, J Therm Anal Calorim 121
23
24 (2015) 1021–1030. https://doi.org/10.1007/s10973-015-4764-0.
25 [48] D. Cevher, S. Sürdem, Polyurethane adhesive based on polyol monomers BHET and BHETA
26 depolymerised from PET waste, International Journal of Adhesion and Adhesives 105 (2021)
27 102799. https://doi.org/10.1016/j.ijadhadh.2020.102799.
28 [49] M.S. Gaikwad, V.V. Kusumkar, O.S. Yemul, D.G. Hundiwale, P.P. Mahulikar, Eco-friendly
29
waterborne coating from bio-based polyester amide resin, Polym. Bull. 76 (2019) 2743–
30
31 2763. https://doi.org/10.1007/s00289-018-2511-y.
32 [50] A. Lesbani, Fitriliana, R. Mohadi, Conversion of Cyclohexanone to Adipic Acid Catalyzed by
33 Heteropoly Compounds, Indonesian Journal of Chemistry 15 (2015) 64–69.
34 https://doi.org/10.22146/ijc.21225.
35 [51] T. Zhang, B.A. Howell, P.K. Martin, S.J. Martin, P.B. Smith, Synthesis and NMR
36
37 Characterization of Hyperbranched Polyesters from Trimethylolpropane and Adipic Acid, in:
38 H.N. Cheng, R.A. Gross, P.B. Smith (Eds.), ACS Symposium Series, American Chemical Society,
39 Washington, DC, 2013: pp. 281–290. https://doi.org/10.1021/bk-2013-1144.ch019.
40 [52] H. Park, J. Seo, H.-Y. Lee, H.-W. Kim, I.B. Wall, M.-S. Gong, J.C. Knowles, Synthesis of elastic
41 biodegradable polyesters of ethylene glycol and butylene glycol from sebacic acid, Acta
42
43
Biomaterialia 8 (2012) 2911–2918. https://doi.org/10.1016/j.actbio.2012.04.026.
44 [53] K.J. Park, M. Kim, S. Seok, Y.-W. Kim, D.H. Kim, Quantitative analysis of cyclic dimer fatty acid
45 content in the dimerization product by proton NMR spectroscopy, Spectrochimica Acta Part
46 A: Molecular and Biomolecular Spectroscopy 149 (2015) 402–407.
47 https://doi.org/10.1016/j.saa.2015.04.099.
48
[54] M. Sokolsky‐Papkov, R. Langer, A.J. Domb, Synthesis of aliphatic polyesters by
49
50 polycondensation using inorganic acid as catalyst, Polymers for Advanced Techs 22 (2011)
51 502–511. https://doi.org/10.1002/pat.1541.
52 [55] A.I. Hamad, PREPARATION AND CHARACTERIZATION OF SOME UNSATURATED POLYESTER
53 ALKYDS BASED ON TEREPHTHALIC AND ISOPHTHALIC ACIDS, (February 19).
54 [56] Á.S. Olalla, V.H. Talavera, D.L. García, E.G. Torres, M.F. García, Glycerol-based enzymatically
55
56 synthesized renewable polyesters: Control of molecular weight, degree of branching and
57 functional endgroups, European Polymer Journal 170 (2022) 111173.
58 https://doi.org/10.1016/j.eurpolymj.2022.111173.
59 [57] A.S. Amarasekara, A. Razzaq, P. Bonham, Synthesis and Characterization of All Renewable
60 Resources Based Branched Polyester: Poly(2,5-furandicarboxylic acid-co-glycerol),
61
62 Page 37 of 39
63
64
65
 International Scholarly Research Notices 2013 (2013) 645169.
1 https://doi.org/10.1155/2013/645169.
2 [58] C.V.R. de Moura, A.S.L. Nunes, J.M. Moita Neto, H.L.S. Neres, L.M.G. de Carvalho, E.M. de
3 Moura, Synthesis and characterization of polyesters from glycerol by-product of biodiesel
4
5 production, J. Braz. Chem. Soc. 23 (2012) 1226–1231. https://doi.org/10.1590/S0103-
6 50532012000700005.
7 [59] P.M. Paraskar, R.D. Kulkarni, Synthesis of Isostearic Acid/Dimer Fatty Acid-Based
8 Polyesteramide Polyol for the Development of Green Polyurethane Coatings, J Polym
9 Environ 29 (2021) 54–70. https://doi.org/10.1007/s10924-020-01849-x.
10
11
[60] M. Kathalewar, N. Dhopatkar, B. Pacharane, A. Sabnis, P. Raut, V. Bhave, Chemical recycling
12 of PET using neopentyl glycol: Reaction kinetics and preparation of polyurethane coatings,
13 Progress in Organic Coatings 76 (2013) 147–156.
14 https://doi.org/10.1016/j.porgcoat.2012.08.023.
15 [61] J.K. Fink, Reactive Polymers: Fundamentals and Applications: A Concise Guide to Industrial
16 Polymers, William Andrew, 2017.
17
18 [62] U. Edlund, A.-C. Albertsson, Polyesters based on diacid monomers, Advanced Drug Delivery
19 Reviews 55 (2003) 585–609. https://doi.org/10.1016/S0169-409X(03)00036-X.
20 [63] S. Pathan, S. Ahmad, Synthesis, characterization and the effect of the s-triazine ring on
21 physico-mechanical and electrochemical corrosion resistance performance of waterborne
22 castor oil alkyd, J. Mater. Chem. A 1 (2013) 14227. https://doi.org/10.1039/c3ta13126b.
23
24 [64] P.D. Meshram, R.G. Puri, A.L. Patil, V.V. Gite, High performance moisture cured poly(ether–
25 urethane) amide coatings based on renewable resource (cottonseed oil), J Coat Technol Res
26 10 (2013) 331–338. https://doi.org/10.1007/s11998-012-9449-z.
27 [65] C.K. Patil, S.D. Rajput, R.J. Marathe, R.D. Kulkarni, H. Phadnis, D. Sohn, P.P. Mahulikar, V.V.
28 Gite, Synthesis of bio-based polyurethane coatings from vegetable oil and dicarboxylic acids,
29
Progress in Organic Coatings 106 (2017) 87–95.
30
31 https://doi.org/10.1016/j.porgcoat.2016.11.024.
32 [66] J.M. Chajęcka, Synthesis of Biodegradable and Biocompostable Polyesters, (n.d.).
33 [67] Colour Grading according to the Gardner Colour Scale (ASTM D1544) Lovibond Gardner
34 Comparator 3000, AF 228, (n.d.).
35 http://www.ssco.com.tw/Tintometer/3000series_comparator/AF228GARDNER.pdf.
36
37 [68] A. Das, P. Mahanwar, A brief discussion on advances in polyurethane applications, Advanced
38 Industrial and Engineering Polymer Research 3 (2020) 93–101.
39 https://doi.org/10.1016/j.aiepr.2020.07.002.
40 [69] J.C. Khanderay, V.V. Gite, Fully biobased polyester polyols derived from renewable resources
41 toward preparation of polyurethane and their application for coatings, J of Applied Polymer
42
43
Sci 136 (2019) 47558. https://doi.org/10.1002/app.47558.
44 [70] D.P. Pfister, Y. Xia, R.C. Larock, Recent Advances in Vegetable Oil‐Based Polyurethanes,
45 ChemSusChem 4 (2011) 703–717. https://doi.org/10.1002/cssc.201000378.
46 [71] G.A. Phalak, D.M. Patil, S.T. Mhaske, Synthesis and characterization of thermally curable
47 guaiacol based poly(benzoxazine-urethane) coating for corrosion protection on mild steel,
48
European Polymer Journal 88 (2017) 93–108.
49
50 https://doi.org/10.1016/j.eurpolymj.2016.12.030.
51 [72] P.M. Paraskar, M.S. Prabhudesai, R.D. Kulkarni, Synthesis and characterizations of air-cured
52 polyurethane coatings from vegetable oils and itaconic acid, Reactive and Functional
53 Polymers 156 (2020) 104734. https://doi.org/10.1016/j.reactfunctpolym.2020.104734.
54 [73] M. Akbari, R. Najjar, Reactive and Functional Polyesters and Polyurethanes, in: T.J. Gutiérrez
55
56 (Ed.), Reactive and Functional Polymers Volume One, Springer International Publishing,
57 Cham, 2020: pp. 157–194. https://doi.org/10.1007/978-3-030-43403-8_8.
58 [74] J.A. Faunce, M.E. O’brien, D.K. Hillshafer, Phthalic anhydride based polyester polyols for
59 improved hydrolytic stability in urethane-based coatings, adhesives, sealants and
60
61
62 Page 38 of 39
63
64
65
 elastomers, WO1997030100A1, 1997.
1 https://patents.google.com/patent/WO1997030100A1/en (accessed July 5, 2024).
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62 Page 39 of 39
63
64
65
Graphical abstract Click here to access/download;Figure;Graphical Abstract for a research paper of coating material.pptx

1% w/w PTSA catalyst

1% w/w DBTDL at 160-180◦C
catalyst at 160-180◦C

BHET-based Polyester
Polyols

Curing with Isocyanates for

coating application