United States Patent [19]

Culbertson et a1.
[54] POLYMERS DERIVED FROM

[11]
[45]
3,280,148 10/1966 Pawloski et a1.

4,388,451
Jun. 14, 1983
............. .. 260/338

ALLYLPHENOL 0R SUBSTITUTED

4,100,140 7/1978 Abdul~Cader Zahrr et al.

526/90

ALLYLPHENOL AND MALEIC

[75]

ANHYDRIDE

Inventors: Billy M. Culbertson, Worthington; Larry K. Post, Columbus, both of

zsrgggles '

f gill-[ER PUBLIZCZTZONS 246-248 d

ymema m
. t. ,

n 6

pp

an

Ohio; Ann E- Alllaballgh, Madison,

Wi$~

Primary Examiner-Harold D. Anderson

Attorney, Agent, or Firm-Wood, Herron 8:; Evans

[73] Assignee: Ashland Oil, Inc., Ashland, Ky.

' [21] Appl- No.: 306,198

[57]

ABSTRACI

A copolymer formed by reacting maleic anhydride or a

_

[22] Filed;
' 5'2

_ sep. 23, 1981

malrlelirrilidle lor almixture if thesedwltllll 21m allylphelrggll, la

met a y p eno , or su stitute y or met y -

Cc]; """"""""""" " Cusp

phenol. The anhydride polymers are characterized as

525/1; 525/159:
528/159_ 528/322_ 526/262" 526/313

having a 1:1 molar ratio of maleic anhydride to phenol

525/161: 525/163: 528A: 528 49f 528/l52f

[58] Field of Search ....... .f ............. ..'. ..... .. 525/271, 313
_

or substituted phenol. The maleic anhydride copoly

mers are water soluble materials, useful as epoxy resin

wdi?ers a? curatives' as i" exchavge Si"s_mem

branes, laminates, and detergent additives and builders.

[56]

References Clted U_S_ PATENT DOCUMENTS 2 818 402 12/1957 D, Alelio

2,827,442 3/1958 DAlelio . . . . .

526A71
. . . .. 526/271

The maleimide containing copolymers are also useful as epoxy resin modi?ers and useful in the production of laminates, composites and coatings.

2,850,481

9/1958

D'Alelio ............................ .. 526/271

3 Claims, No Drawings

4,388,451

POLYMERS DERIVED FROM ALLYLPHENOL OR SUBSTITUTED ALLYLPHENOL AND MALEIC ANHYDRIDE

BACKGROUND OF THE INVENTION

The present invention relates to copolymers of maleic

anhydride or copolymers of maleimides. Speci?cally,

the present invention relates to copolymers formed

from allylphenols or substituted allylphenols and maleic

anhydride or maleimide.

Maleic anhydride does not homopolymerize easily.

However, due to its polar character and ability to hy drolyze as well as other physical characteristics, this molecule possesses a great deal of potential utility if

incorporated into polymers systems.

Despite the tendency of maleic anhydride not to homopolymerize, applicants have discovered that ma leic anhydride, as well as maleimides, readily copoly merize with allylphenols or substituted allylphenols. The maleic anhydride copolymers are characterized by
a 1:1 ratio of maleic anhydride moiety to allylphenol or

20

25

The novel maleic anhydride copolymers of the pres ent invention are characterized by having a high degree of water solubility due to the inclusion in one polymer of a phenol in combination with a maleic anhydride

substituted allylphenol moiety. In contrast, the malei mide copolymers are nonequimolar
SUMMARY OF THE INVENTION

moiety. The maleimide containing copolymers are readily soluble in polar organic solvents.
30

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a polymer derived The present invention comprises a copolymer formed from an allylphenol or derivative of allylphenol having 35 from a maleic anhydride, a maleimide, or a mixture of these two and an allylphenol or a substituted allyl one of the following general formulas:

phenol.

The allylphenols useful in the present invention are

0R3 Ia

represented by formulas (IVa) and (IVb):

IVa

R2

R1 CHZC=CHZ 4-allylphenol
0R3

45
lb

R1

CHz-C=CH2
R2 Z-allylphenol

reacted with a second compound having the general

55

formula (II):

wherein R1 represents hydrogen or -CH3 and R2 rep resents alkyl, aryl, substituted alkyl or substituted aryl. In addition to the allylphenols, also useful in the pres ent invention are substituted allylphenols having the

following general formulas (Va) and (Vb):

OR

R]

wherein R4 represents >NR5 or 0. The formed co

polymer is represented by the following general formu

las (Illa) or (IIIb):

3
-continued

4,388,451
Ri

Amines would not be suitable for the present invention

since they react with maleic anhydride. The'tempera ture at which the solution polymerization should be
conducted is also between 70l20 C. Whether conducted in bulk or solution, the time of

the reaction solution will varyF depending upon the

reagents, initiators and solvents, but generally will be between 4-24 hours. The completion of the reaction can

wherein R3 represents alkyl,- aryl, substituted alkyl,

substituted aryl, or a carbonyl.

be determined by analysis of the reagents for unreacted

ole?ns to determine when the reaction has stopped. 1

Primarily, the groups represented by any subscripted

Stoichiometrically, the reaction should be conducted

with a 1:1 molar proportion of allylphenol" to either

R do not represent any moiety which would interfere maleic anhydride or maleimide, or the mixture of maleic with the polymerization of the allylphenol and the anhydrideand maleimide. The polymerization should maleimide or maleic anhydride. Such interfering groups 15 be conducted in an inerLdry atmosphere to avoid con would include thiols, amines and strong acid groups. tamination or oxidation of the reagents. Suitable atmo The second component of the copolymer of the pres spheres include' helium and nitrogen which is preferred. ent invention comprises a maleimide, a'maleic anhy According to the preceding method, copolymers and ' dride or a mixture of both a maleimide and maleic anhy

dride which is represented by the following general

formula VI: '

20

terpolymers containing allylphenol and maleic anhy

R7

R5

VI

dride and/or a-maleimide having one --of the following two general formulas are prepared. When a 4-allyl phenol or a substituted 4-allylphenol is reacted with the
sented by formula IXa is formed.

' maleic anhydride or maleimide, the polymer repre

25

In the case of a maleimide R4represents >NR5 and

has the following general formula:

R7 ' R6 VII

30

-35

l
Rs

When a 2-allylphenol or a substituted 2-allylphenol is

wherein R5, R6, and R7 represent alkyl, aryl, substituted alkyl, substituted aryl and hydrogen. R6 and R7 may
also represent a halogen such as Cl,'Br or F. In the

reacted, a copolymer having the following formula IXb

40
is produced. ' '

alternative, R4 can represent 0 wherein formula VI

represents a maleic anhydride as shown in formula VIII:
45
R7 R6 VIII

Al
R; v n

50

wherein R5 and R6 represent the same moieties stated above. The formation of the copolymers according to the

present invention is accomplished by free radical poly

In each of the formulas IXa and IXb, A represents terminal groups of the polymer chain and n is an integer

either bulk or solution. Suitable initiators include azo

generally greater than 10. merization, in the presence of an initiator, conducted in 55 The preparation of these

polymers is furtherdillus

bisisobutyronitrile, di-tert butyl peroxide, lauryl perox

ide and benzoyl peroxide.

trated by the following non-limiting examples/

EXAMPLE I

Where a bulk process is used, the polymerization is

normally carried out at a temperature at which an initia 60

tor will perform and at which the phenol or maleic anhydride or maleimide will not decompose. It is pre ferred to effect polymerization at temperatures from about 70 C. to 120 C.

A copolymer of Z-allylphenol and maleic anhydride was formed by mixing 9.0 grams of anhydrous 2-allyl phenol together with 6.6 grams maleic anhydride and
0.2 grams azobisisobutyronitrile, the initiator, in 6.8 grams of methyl ethyl ketone. This mixture was heated

Where the polymerization is effected in solution, the 65 for seven hours at 7-578 C. under nitrogen. A booster of 0.22 grams azobisisobutyrlnitrile in 0.7 grams dichlo-. solvent should be substantially anhydrous. Suitable romethane was then added after 3.5 .hours. A solid solvents include ethyl acetate, 1,2 dichloroethane, tolu

ene, methyl ethyl ketone, cyclohexanone, and xylene.

formed and was separated and dissolved in acetone and

4,388,451

6.

precipitated into diethyLether. The solid was ?ltered and dried leaving 10 rams (75%) polymer.

tives and builders, photographic ?lm modi?ers, coat

ings, fungicidal polymers, medicinal carriers, resins, oil

additives, rubber additives and Portland cement modi? ers. The maleimide containing copolymers, which are
5

EXAMPLE II A copolymer of 2-ally1phenol and N-phenylmalei

mide were formed by mixing in solution 12.9 grams of

soluble in polar organic solvents, are also useful in plas

N-phenylmaleimide with 0.37 grams azobisisobutyroni

trile and 21.4 grams tetrahydrofuran. This was added dropwise over a period of two hours to a heated solu

tics, adhesives, composites, "and coating applications. The following examples demonstrate the utility of the
polymers formed according to the present invention in
use as additives to epoxy resins. '

tion of 10.0 grams of 2-allylpheno1 under nitrogen. 10 After four hours, a booster of 0.12 grams of azobisis
butyronitrile was added. The mixture was then main tained at 707l C.'foran additional 16 hours. A solid

EXAMPLE VI

Epoxy Cure Study

a A sample of- poly (2 allylphenol-co-maleicl- anhy dride), prepared in Example I, was dissolved in a 50:50
(w/w) mixture of acetone and cyclohexanone to form a

polymer formed which was separated and dissolved in

acetone. This in turn was precipitated out of solution by 15

mixing with diethyl ether. The precipitated polymer

was ?ltered and dried yielding 16.4 grams (72%) co
polymer.v 4

50% solids solution. A mixture of 4.0 grams (0.026

equivalent) of the polymer solution, 1.60 ~grains (0.0084

equivalent) Epon 828, an epoxy resin and 0.04 dimethyl benzylamine were combined and thoroughly mixed.
Three mil wet ?lms were cast onto glass and cold roll steel. The ?lms were cured in a forced air oven at 100

EXAMPLE III
A copolymer of 2-acetoxy allylbenzene and maleic anhydride was formed by mixing in solution 13.1 grams 2-acetoxy allylbenzene, 7.3 grams maleic anhydride,

0.24 ,grams azobisisobutyronitrile together with 13.6

grams methyl ethyl ketone. This solution was heated for 25

F. for 30 minutes and subsequently, 300 F. for 60 min utes. Properties of the cured' ?lms are outlined Table
, ' TABLE 1 ~ ..

6.5 hours at 75-7_8__ C. with constant stirring under

nitrogen bubbled through the reaction mixture. This
mixture was cooled and the formed solid was dissolved
%

'

in acetone and precipitated into diethyl ether. The solid

Sub-

Non-; vola-

Sward l-ylard- I .

100 Rub

Adhesion (Cross-

Y,

.. Impact 1 ,1

precipitate yielded 12.4 grams (61.2%) polymer.

EXAMPLE IV _ _ 5'

30 strate
Glass Cold I

tiles
65 g .

ness
58

MEK Test
v Pass 100
I

hatch)
I
.

>_ Front:
_ ' '

Reverse.

95%

A copolymer of 2-methallylphenol and maleic anhy

dride was formed by mixing 10.4 grams Z-methallyl

R011

Steel

65

Pass 100

100%

' ' 20

;0_

phenol with 6.9 grams of maleic anhydride together

35

with 0.26 grams azobisisobutyronitrile dissolved in 7.8 EXAMPLE VII grams methyl ethyl ketone. This mixture was heated Epoxy Cure Study I " under nitrogen forsev'en hours at 75-80 C. After three hours, a booster of 0.26 gram initiator dissolved in 3 A sample of poly (2-allylphenol-co-ma1eic i'anhy grams of methyl ethyl ketone was added to the reaction 40 dride), prepared in Example Ljwas dissolved in ya 50:50 mixture. A viscous solution formed which was diluted (w/w) mixture of acetone and cyclohexanoneto form a with acetone and slowlyadded to diethyl ether which 50% solid solution. A mixture of 3.0 grams (0.019 equiv: caused the copolymer to precipitate out of solution. The alent) of polymer solution 0.61 grams (0.0032 equiva precipitated copolymer was collected, washed with lent) Epon 828, 0.42 grams (0.0032Lequivalent) butyl diethyl ether, and dried obtaining a 15.7 gram. (88%) 45 glycidyl ether and 0.03 grams , dirne'thylben'zlylamine
yield of white copolymer.

steel. The ?lms were cured ,inya forced air oven at 100 A copolymer of 2-metha11y1phenol and N-phenyl F. for 30 minutes and subsequently, for60 minutes at maleimide was formed by mixing 7.4 grams of methal 50 300 F. The properties of the cured ?lms are outlined in lylphenol with 6.9 grams of N-phenylmaleimide to Table 2. I , ~ gether with an initiator 0.2 grams azobisisobutyronitrile , TABLE 2= ' .1 ~' in 14.3 grams of tetrohydrofuran. This mixture was heated under nitrogen with stirring for six hours at 70,-75 C. A viscous solution formed which was di 55 strate Sub-l ' Nonvolatiles .l-lardSward ness, - MEK 100 Rub Test , Adhesion (Crosshatch) .,- Front .Impact . Reverse luted with acetone and slowly added to diethyl ether to precipitate out a solid copolymer. The precipitate was Glass 63 64 Pass 100 ' 100% 1, I. i - . collected, washed with diethyl ether, and dried to ob tain a 12.3 ram (85%)_'yie1d of copolymer.
Cold ' . .

EXAMPLE v

. '

were combined and thoroughly. mixed. Three mil wet ?lms of this material were castonto glass and cold roll

The anhydride containing copolymers of the present

invention are useful generally as water soluble polymers

Roll

Steel:

63

'

Pass 100

100%

25

' 07

containing maleic anhydride and phenolic or substituted phenolic groups. Accordingly, the polymers of the present invention are' useful in an extremely wide vari
ety of areas including epoxy resin modi?ers and vcura 65

AEXAMPLE'VIII

; (Epoxy Cure Study

_ 1.

tives, biomedical applications, molding resins, ion 'ex- change resins, and membranes for ultra?ltration of dial

A 50% solid polymer solutionof poly (2-ally1phenol-i

co-N-phenylmaleimide), prepared in Example 11, with a
50:50 (w/w) mixture of acetone and cyclohexanone was

ysis, adhesives, laminates, foam plastics, detergent addi-

4,388,451

formed. 3.0 grams (0.0049 equivalent) of the polymer solution, 0.93 grams (0.0049 equivalent), Epon 828 and
0.02 grams of dimethylbenzylamine were combined and thoroughly mixed. This solution was cast in three mil wet ?lms onto glass and cold roll steel. The ?lms were
cured in a forced air oven at 100 F. for 20 minutes and 300. F. for 60 minutes. The properties of the cured ?lm are outlined in Table 3.

a glass chamber saturated with triethylamine vapor, cure catalyst. The ?lm was exposed for 15 seconds to 5} minutes. The ?lm was hard and tack-free to the touch after a couple of minutes. Adhesion to the glass in creased with increased exposure time. After one week,
the ?lrn was unaffected by 10 minute exposure to xylene

TABLE 3
%
Substrate
Glass,

and 95% ethanol, but there was a slight effect upon 10 minute exposure to acetone. A ?lm not exposed to
10 amine vapor disintegrated after 10 minute exposure to xylene, 95% ethanol, and acetone. -

Non- Sward vola- Hard- > 100 Rub=

tiles
62 .

Adhesion (Crosshatch)
100%

Impact
Front Reverse

ness .

MEK Test
Pass 100

EXAMPLE x1
15

Poly(2-allylphenol-co-N-phenylmaleimide) (2.92 g)
as prepared in Example X was dissolved in 3.78 g cel

Cold
Steel Pass 90 100% 20 0

lusolve acetate (polyurethane grade). The solution was blended with 1.00 g Pepset resin #9086, a polyether
phenolic resin. This mixture was blended 5.79 g
20 Mondur I-IC. Total solids content was 55% and the

EXAMPLE IX
' Cymel Cure Study

4040, a Strong acid catalyst. This mixture was thor oughly combined and cast onto glass and cold roll steel
in three mil wet ?lms. The ?lms were cured in a forced air oven at 100 F. for 30 minutes and 300 F. for 60 minutes. The properties of the cured ?lms are outlined
in Table 4. ' ' '

OH/NCO ratio was 2:1. Thin, wet ?lms of 1.5 mil thick ness were drawn on glass plates, then exposed to trieth ,A sample of poly (2-allylphenol-co-N-phenylmalei ylamine vapor for 30 to 150 seconds. The ?lm was hard mide), prepared in Example II, was dissolved in a 50:50 and tack-free'to the touch after a couple of minutes. (w/w) mixture of acetone and cyclohexanone to form a 50% polymer solution. A mixture of 4.0 grams (0.0065 25 Films exhibited 100% adhesion after 5 days. After one equivalent) of.the.polymer solution was combined with week, the ?lm exhibited good solvent resistance after 10 1.17 grams 0.0067 equivalent Cymel 303, a melamine minute exposures to xylene and 95% ethanol. A ?lm not formaldehyde resin material and 0.02 grams catalyst exposed to amine, showed some disintegration upon
exposure to the above solvents.

These examples are meant to illustrate the utility of the present invention, but in no way limit the present
invention to the uses shown. Polymers of the present .

TABLE 4
% ,

as soluble polymers and alsov show particular utility as

described in the preceding examples. .
Impact
Front Reverse

invention can be generally applied to the area of water

Non-

Adhesion

volaSubstrate " Glass Cold Roll Steel '

100 Rub
MEK Test
Pass 90

(Crosshatch)
100%

Having thus described our invention, we_claim: 1. A polymer consisting of one of the following two
general formulas: i

tiles
' 57 57

Pass 90

I00%

15

The following use examples X and XI demonstrate

the polyisocyanate crosslinking of the phenolic contain

ingrnaliemide copolymers. In the process, the phenolic (OH) groups react with the isocyanate (NCO) moiety, under the catalytic in?uence of an amine vapor, to
causev crosslinking and produce insoluble coatings or
?lms. .

45

50

EXAMPLE X

A 2-allylphenol-N-phenylmaleimide copolymer was prepared by conventional free radical solution polymer ization. A solutionof 51.60 g N-phenylmaleimide and
1.48 g azobisisobutyronitrile in 100 g THF was added over two hours to a heated (79 C.) solution of 0.76 g

55

naphthalene in 40.00 g 2-allylphenol under nitrogen.

The solution was heated an additional 24 hours at 74

C., then cooled, and added to diethyl ether. The poly

mer was ?ltered and dried. Conversion was to 73%.

Poly(2-allylphenol-co-N-phenylmaleimide) (4.50 g)
prepared above was dissolved in 4.19 g cellusolve ace tate (polyurethane grade). The solution was blended

wherein R2 represents H or CH3; A represents termi-_

greater than 10. I 1 ' Y

with 5.35 g Mondur HC, a poly (aliphatic/aromatic) 65 nal groups of a polymer chain; and _n is an integer

isocyanate. Total solids content was 56.8%, and the OH/NCO ration was 2:1. Thin, wet ?lms of 1.5 mil thickness were drawn on glass plates, then placed inside

2. An addition polymer having the following general

formula:

4,388,451
formula:

10

3. An addition polym'er having the following general

wherein R1 represents H or CH3; R2 represents alkyl, wherein R1 represents H or -CH3; R2 represents alkyl, substituted alkyl, aryl, substituted aryl, or H; R6 and R7 15 substituted alkyl, aryl, substituted aryl, or H; R6 and R7

represent alkyl, substituted alkyl, aryl, substituted aryl,

H, or a halogen; A represents terminal groups of the polymer chain; and n is an integer greater than 10.
2O

represent alkyl, substituted alkyl, aryl, substituted aryl,

H, or a halogen; A represents terminal groups of the polymer chain; and n is an integer greater than 10.
t t i i

25

30

35

50

55