CA1331669C

CA1331669C - Carboxy-functionalized polycarbonates and method of preparation

Info

Publication number: CA1331669C
Application number: CA000598055A
Authority: CA
Inventors: Timothy Joseph Ullman; Ronald John Gambale; Susan Jane Hathaway; Kathryn Lynn Longley
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 1987-10-19
Filing date: 1989-04-27
Publication date: 1994-08-23
Anticipated expiration: 2011-08-23
Also published as: EP0312811A2; JPH01163213A; EP0312811A3; US4853458A

Abstract

CARBOXY-FUNCTIONALIZED POLYCARBONATES AND
METHOD OF PREPARATION
Abstract Carboxy-functionalized polycarbonates are prepared by incorporating a carboxylic acid-substituted phenol, preferably t-butyl p-hydroxybenzoate, as a chainstopper in a polycarbonate-forming reaction The products are capable of forming copolymers with other polymers such as polyamides and functionalized olefin polymers, by generation of a carboxy group which reacts therewith.

Description

133~ ~9 CARBOXY-FUNCTIONALIZED POLYCARBONATES
AND METHOD OF PREPARATION

This invention relates to the carboxy-functionalization of polycarbonates.
The superior physical properties of - i polycarbonates render them useful in a large number of application areas. However, polycarbonates are deficient in certain properties such as solvent resistance.
Therefore, there is considerable activity in the ~
development of blends of polycarbonates with other -polymers which modify their properties. Illustrative polymers of this type are polyamides and olefin polymers.
The blends thus prepared are, however, often themselves deficient in properties due to the ;-, incompatibility of the polymers comprising them. Thus, blends of polycarbonates and polyamides or olefin polymers tend to delaminate severely. It is expected --Z~ -that the compatibility of such blends could be improved ~ by incorpora*ing therein, in various proportions, a ii ; copolymer of the blend constituents. The formation of such copolymers requires the presence of functional groups on the polyca~rbonate~whioh are capable of undergoing reaction with~the~other polymer.~ Thus, the ;-;~
functionalization~of polycarbonates is a prime;~concern "~
relative to the preparation of copolymers;therefrom. -~
An illustrative method of functionalizing ~i 25 polyqar~onateol~s disclosed~and claimed in, U.S.,Patent 4,732,934, issued March 22, 1988. In this method, a hydroxy-terminated polycarbonate is caused to react with a tricarboxylic~acid derivative such as trimellitic ---~-;
anhydride acid chloride. Said method is, however, 30~ ~ dlsadvantageous~to~a certain extent because it ~ -` requires the use of~special procedures to prepare a - .

~ `

~ RD-17911 ~337 ~

hydroxy-terminated polycarbonate, followed by an additional reaction (usually in solution) with the tricarboxylic acid derivative to form the functionalized polycarbonate.
Intere~t continues, therefore, in simplifying the S procedures for preparing functionalized polycarbonates. One possible expedient is the employment of a functionalized chain termination agent in the preparation of the polycar-bonate. The use of chain termination agents such as phenol and t-butylphenol is known in the art~ Also known by way of disclosure in German Offenlegungsschrift 3,445,108 is the use as a chain termination agent o a phenol containing an olefinic functional group. However, methods for carboxy-functionalization of polycarbonates by means of chain termination agents have not been previously disclosed.
The present invention provides a class of car-boxy-functionalized polycarbonates. This class of poly-carbonates may be conveniently prepared by the incorporation of a carboxy-functionalized phenol as a chain termination ~gent in a conventional system for interfacial preparation o polycarbonates.
In one of its aspects, therefore, the present ~ invention includes carboxy-functionalized polycarbonates ; containing end groups of the formula ~, .
,-- .: O
r 25 (I) -o_Rl-o-C-O-Al wherein Rl is a divalent aliphatic, alicyclic or aromatic radical and A is a carboxylic acid-substituted phenyl group or a unctional derivative thereof.
The carboxy-functionalized polycarbonates of this ; 30 invention generally comprise structural units of the formula '~

:
~ -2-:::

r~ RD-17911 ,, 133~ ~9 ~II) _o_Rl_o-ll-wherein each Rl is independently as defined hereinabove.
The Rl values may be different but are usually the same, and may be aliphatic, alicyclic, aromatic or mixed; those which are aliphatic or alicyclic generally contain up to about 8 carbon atoms. Suitable Rl values include ethylene, pro-pylene, trimethylene, tetramethylene, hexamethylene, dodeca-methylene, poly-1,4-(2-butenylene), poly-1,10-(2-ethyldec-ylene), 1,3-cyclopentylene, 1,3-cyclohexylene, 1,4-cyclo- ~ ~
hexylene, m-phenylene, p-phenylene, 4,4'-biphenylene, ~ -2,2-bis(4-phenylene)propane, benzene-1,4-dimethylene (which ~ !
~; is a vinylog of the ethylene radical and has similar proper-~ ties) and similar radicals such.as those which correspond to ~-~
;~ 15 the dihydroxy compounds disclosed by name or formula (gener- -ic or specific) in U.S. Patent 4,217,438, issued ` August 12, 1980. ~ Also included `` are radicals containing non-hydrocarbon moietie~. These may . be Jubstituents such a~ chloro, nitro, alkoxy and the like, ~ -20 and al~o linking radicals such as thio, sulfoxy, sulfone, ;~
e~ter, amide, ether and carbonyl. Most often, however, all l radicals are hydrocarbon radicals.
Preferably at least about 60% and more preferably ~
at least~abo~t 80% of the total number of Rl values in the -~-polycarbonate, and most d;sirably all of said R values, are ~ aromatic. The aromatic R radicals preferably have the -~ formula III) -A2-Y-A3- , , -- ~ -3-. : ~
~` .
~:
~`~

133~

wherein each of A2 and A3 is a monocyclic divalent aromatic radical and Y is a bridging radical in which one or two atoms separate A2 from A3. The free valence bonds in for-mula III are usually in the meta or para positions of A2 and S A3 in relation to Y. Such Rl va}ues may be considered as being derived from bisphenols of tho formula Ho-A2-Y-A3-oH.
Frequent reference to bisphenols will be made hereinafter, but it should be understood that R1 values derived from suitable compounds other than bisphenols may be employed a~
appropriate.
In formula III, the A2 and A3 values may be unsub-stituted phenylene or substituted derivatives thereof, illustrative substituents ~one or more) being alkyl, alkenyl (e.g., crosslinkable-graftable moieties such as vinyl and ~- 15 allyl), halo (especially chloro and/or bromo), nitro, alkoxy and the like. Unsubstituted phenylene radicals are prefer- ~ ~
red. Both A2 and A3 are preferably p-phenylene, although -both may be o- or m-phenylene or one o- or m-phenylene and the other p-phenylene.
The bridging radical, Y, i~ one in which one or two atoms, preferably one, separate A2 from A3. It is most ` often a hydrocarbon radical and particularly a saturated radical such as methylene, cyclohexylmethylene, 2-[2.2.1]-bicycloheptylmethylene, ethylene, 2,2-propylene, 1,1-(2,2-dimethylpropylene), ~l,l-cyclohexylene, l,l-cyclopentadecyl-ene, l,l-cyclododecylene or 2,2-adamantylene, especially a `~; gem-alkylene radical. Also included, however, are unsatur-ated radicals and radicals which are entire,ly or parti!ally composed of atoms other than carbon and hydrogen. Example~
of such radicals are 2,2-dichloroethylidene, carbonyl, oxy, ~^` thio and sulfone. For reasons of availability and particu-- lar suitability for the purposes of this invention, the preferred radical of formula III is the --. ~
i~ 4 \i:

, .

1331 6~9 2,2-bis(4-phenylene)propane radica}, which is derived from bisphenol A and in which Y is isopropylidene and A2 and A3 are each p-phenylene.
As is apparent from formula I, the end groups on the carboxy-functionalized polycarbonates of this invention are Al values which are carboxylic acid-substituted phenyl \
groups or functional derivatives thereof. Both mono- and polycarboxylic acid-substituted phenyl groups are included, with mono- and dicarboxylic acid-substituted groups being preferred and monocarboxylic acid-substituted groups being especially preferred. The functional derivatives which are particularly contemplated are ester, anhydride and imide groups.
A particularly preferred class of Al values 15 consists of those having the formulas ~ -. `:
(IV) ~ COOR2 a*d ' ' (V) ~C-X , ,~''' l-x ~ 20 `i ~
wherein R2 is hydrogen, Cl 6 alkyl or pheny} and each X is independently OH,I,Cl_6 alkoxy or phenoxy or both X radicals ~ taken together are 0 or N-R2. Thus, the preferred end ; ~ groups are p-carboxylic acid-substituted groups or esters 2S thereof and 3,4-dicarboxylic acid-substituted groups or ~3'~ ~ esters, anhydrides or imides thereof. Especially desirable, for reasons described hereinafter, are end groups of formula ' ..

~- ~5~
~ ~ .
~ .

~331~

IV wherein R is a C4 6 tertiary alkyl radical containing at least one ~-hydrogen atom.
The carboxy-functionalized polycarbonates of this invention may be prepared by incorporating a carboxylated phenol o~ the formula Al-OH as a chainstoppor in a polycar-bonate-forming reaction between a carbonate source and at loast one dihydroxy compound of the formula Rl(OH)2. This method is another aspect of the invention.
Any known polycarbonate-forming reaction employing dihydroxy compounds, especially bisphenols, may be employed in the method of this invention. Typical reactions of this type include transesterification reactions, in which the ~ -dihydroxy compound is caused to react with a carbonate~ester such as diphenyl carbonate, and interfacial reactions, in 15 which said dihydroxy compound is caused to react with ~
phosgene in a two-phase liquid system comprising water and ~:-an inert organic solvent. The interfacial method is fre-quently preferred. It is well known in the art and i5 generally conducted under highly alkaline conditions, most ofton in the pre-ence of a catalytic amount o an amine such as triethylamine.
The proportion of chainstopper in the polycar- ---bonate-forming reaction mixture will depend to a consider-able extent on the molecular weight of the polycarbonate ~-~
desired. It is generally in the range of about l-10 mole percent, preferably about 2-7 mole percent, based on dihy-droxy compound.
- The preparatio,n of the carboxy-functionalized polycarbonates of this invention is illustrated by the following examples.
.
.

~ -6-: . .

1331~9 ~ .

Exam~les 1-6 Mixtures of 29.l grams (128 mmol.) of bisphenol A, 65 ml. of methylene chloride, 55 ml. of water, 2.58 ml. of trlethylamine in the form of a 5% w/v solution in methylene chloride, and various amounts of carboxylated phenols were stirred at room temperature and a 50% aqueou~ solution of sodium hydroxide was added to bring the pH to ll. Phosgene was then passed through the mixtures for 18-22 minutes at 0.8 gram per minute, with maintenance of the pH at ll, to provide a 2S% excess of phosgene. Additional methylene chloride was added as necessary to control the viscosity.
When the reaction was complete, the organic phase ;~
was removed and washed once with 7% aqueous hydrochloric ; ;
acid solution and three~times with water. The desired 15 carboxy-functionalized polycarbonates were precipitated into -methanol, filtered and dried in vacuum.
The products obtained are listed in the following table. Mole percentages of carboxylated phenol are based on bl phenol A. Molecular weightsi were determined by gel permeation chromatography.
: ~
.

- .

~ ~7~ ~

. - :

- ` ~

1 3 3 ~

Mole %
carboxylated Product Exam~le Al ~henol Mw Mw/Mn 1 ~ COOH 3.556,0005.6 2 ~ COOCH3 3.757,2005.4 ~;

3 ~ CoOC(CH3)3 3-562,600 3.6 4 ~ COOC6~5 3.050,7004.2 ` : ~
~` S ~ COOCH3 3.739,5006.2 ~` COOCH

~ ` ~
6~ , ~;)~C~ 4.0, 40,500, 4.0 ~ -r~ ~:

~ 3- ~

^ RD-17911 13~1~S~ :

The carboxy-functionalized polycarbonates of this invention may be made to react with nucleophilic polymers other than polycarbonates, such as amine-terminated poly-amides and functionalized olefin polymers, to form copoly-mer~ having desirable properties. Such copolymers are inturn useful as compatibilizers for blend~ of the same polymers. This method of copolymer formation is another aspect of the invention.
Copolymer formation may frequently be achieved by heating the carboxy-functionalized polycarbonate with the other polymer in solution or in the melt, at temperatures in ~-the range of about 150-300C. Following the reaction, non-copolymerized polycarbonate may be removed by dissolu-tion in a suitable solvent such as chloroform; the i~solu~le ; 15 material includes the desired copolymer.
The above-described procedure is particularly useful with polycarbonates containing carboxylic acid end groups, which may be produced from materials having ester or -imide end qroups or the like by conventional acid-catalyzed hydrolysis reaction~. Alkaline catalysis should be avoided bocau~e of its tondency to degrade the polycarbonate.
A more convenient method for generating car~oxylic acid-functionaLized polycarbonates employs compositions of this invention in which Al has formula IV and R2 is a 25 tertiary alkyl radical, especially t-butyl. Such polycar- -~
~; bonates may be thermally converted to carboxylic acid-ter-minated polycarbonates, under conditions similar to those ~ encountered in an extruder or similar conventional me~t `~ blending equipment. Thu~, copolymer formation is possible by melt blending, either in a two-step seguence $n which the first step produces the carboxylic acid-functionalized -~
polycarbonate and the second step produces the copolymer, or .: ~ , _g_ .:

~L331~9 in a single extrusion under conditions promoting both reactions.
The preparation o copolymers from the carboxy-late-functionalized polycarbonates of this invention is illustrated by the following exampl~s.

ExamPle 7 A solution of 6 grams of the product of Example 3 in 120 ml. of 1,2,3,4-tetrachlorobenzene was heated at 260C
for 2 hours, after which the polymer was precipitated 10 therefrom by pouring into an excess of methanol. The -product was slurried in methanol, filtered and dried under ; vacuum. It was shown by proton nuclear magnetic resonance to contain a substantial proportion of carboxylic acid end groups, and had a weight averagç molecular weight of 61,600.
A solution of 4 grams of the carboxylic acid-func-tionalized polycarbonate, 4 grams of a commercially avail-able glycidyl methacrylate-grafted EPDM copolymer and 0.17 ml. of triphcnyl phosphite in 80 ml. of 1,2,4-trichloroben-z~ne was heated under reflux for 2 hours and the polymer was 20 precipitated by pouring into an excess of methanol in a ~
blender. The polymer was wà hed with~methanol, slurried and ~-dried in a vacuum oven at 80C. A 7.494-gram portion ~ -~
théreof was continuously extracted with chloroform in a Soxhlet~extractor for 18~hours to remove polycarbonate ~" 25 homopolymer. A total of 41% of the polycarbonate was thus recovered, indicalt,ing a 59% conversion to copolymer. The ~~
residue was vacuum dried and pressed into a film which waQ
hown~by infrared spectro-copy to contain both polycarbonate and methacrylate moleties.

. . ~ ~ - , : ~, ~ RD-17911 1 3 3 ~

ExamDle_8 A product similar to that of Example 3, but having a weight average molecular weight of 74,700, was extruded in a twin- wrew extruder at temperaturos in the range of 115-274C. The extrudate was quenched in water, air dried, pelletized and dried in an oven at 100C. It had a molecu-lar weight of 62,600 and was shown by proton nuclear magnet-ic resonance to contain a substantial proportion of free : carboxylic acid groups.
A mixture of 350 grams of the carboxylic acid-functionalized polycarbonate, 350 grams of the glycidyl ~ .:
.ethacrylate-grafted EPDM copolymer of Example 7 and 5.91 ml. of triphenylphosphite was tumble mixed and extruded on a :
twin screw extruder at temperatures in the range of 115-268C. Upon workup and chloroform extraction as in : Example 7, 44% of the polycarbonate was recovered by dis-: solution, indicating 56% conversion to copolymer. The :: copolymer was spectroscopically analyzed, with results ~ lmllar to those of Example 7.

`"'~
` " I ! ' ~ ' '`'```~

~ ~ --11--~.: "~, .
. . _ , . .", ,.i ~

Claims

1. A carboxy-functionalized polycarbonate containing end groups of the formula , wherein each R1 is independently a divalent aliphatic, alicyclic or aromatic radical and A1 is a carboxylic acid-substituted phenyl group or an ester, anhydride or imide derivative thereof.

2. A polycarbonate according to claim 1 which comprises structural units of the formula

3. A polycarbonate according to claim 2 wherein A1 is a mono- or dicarboxylic acid-substituted phenyl group or an ester, anhydride or imide derivative thereof.

4. A polycarbonate according to claim 3 wherein at least about 60% of the total number of radicals are aromatic hydrocarbon radicals.

5. A polycarbonate according to claim 4 wherein each R1 has the formula -A2-Y-A3-, wherein each of A2 and A3 is a monocyclic divalent aromatic radical and Y is a bridging radical in which one or two atoms separate A2 from A3.

6. A polycarbonate according to claim 5 wherein A1 has the formula (IV) or (V) , wherein R2 is hydrogen, C1-6 alkyl or phenyl and each X
is independently OH, C1-6 alkoxy or phenoxy or both X
radicals taken together are O or N-R2.

7. a polycarbonate according to claim 6 wherein Y is isopropylidene and A2 and A3 are each p-phenylene.

8. A polycarbonate according to claim 7 wherein A1 has formula IV and R2 is a C4-6 tertiary alkyl radical containing at least one .beta.-hydrogen atom.

9. A method for preparing a carboxy-functionalized polycarbonate according to claim 1 which comprises incorporating a carboxylated phenol of the formula A1-OH as a chainstopper in a polycarbonate-forming reaction between a carbonate source and at least one dihydroxy compound of the formula R1(OH)2.

10. A method according to claim 9 wherein A1 is a mono- or dicarboxylic acid-substituted phenyl group or functional derivative thereof and at least about 60% of the total number of R1 radicals are aromatic hydrocarbon radicals.

11. A method according to claim 10 wherein the carbonate source is phosgene.

12. a method according to claim 11 wherein each R1 has the formula -A2-y-A3 wherein each of A2 and A3 is a monocyclic divalent aromatic radical and Y is a bridging radical in which one or two atoms separate A2 from A3.

13. A method according to claim 12 wherein A1 contains an ester, anhydride or imide group.

14. A method according to claim 13 wherein A1 has the formula (IV) or (V) , wherein R2 is hydrogen, C1-6 alkyl or phenyl and each X
is independently OH, C1-6 alkoxy or phenoxy or both X
radicals taken together are O or N-R2.

15. A method according to claim 14 wherein the proportion of chainstopper in the polycarbonate-forming reaction mixture is in the range of about 2-7 mole percent, based on dihydroxy compound.

16. A method according to claim 15 wherein Y is isopropylidene and A2 and A3 are each p-phenylene.

17. A method according to claim 16 wherein A1 has formula IV and R2 is a C4-6 tertiary alkyl radical containing at least one .beta.-hydrogen atom.

18. A method for forming a copolymer which comprises effecting reaction between an amine-terminated polyamide or epoxy-functionalized olefin polymer and a carboxy-functionalized polycarbonate containing end groups of the formula , wherein each R1 is independently a divalent aliphatic, alicyclic or aromatic radical and A1 is a carboxylic acid-substituted phenyl group or a functional derivative thereof.

19. A method according to claim 18 wherein the polycarbonate comprises structural units of the formula

20. A method according to claim 19 wherein A1 is a mono- or dicarboxylic acid-substituted phenyl group or functional derivative thereof.

21. A method according to claim 20 wherein at least about 60% of the total number of R1 radicals are aromatic hydrocarbon radicals.

22. A method according to claim 21 wherein each R1 has the formula -A2-Y-A3-, wherein each of A2 and A3 is a monocyclic divalent aromatic radical and Y is a bridging radical in which one or two atoms separate A2 from A3.

23. A method according to claim 22 wherein A1 contains an ester, anhydride or imide group.

24. A method according to claim 23 wherein A2 has the formula (IV) or (V) , wherein R2 is hydrogen, C1-6 alkyl or phenyl and each X
is independently OH, C1-6 alkoxy or phenoxy or both X
radicals taken together are O or N-R2.

25. A method according to claim 24 wherein Y is isopropylidene and A2 and A3 are each p-phenylene.

26. A method according to claim 25 wherein Al has formula IV and R2 is a C4-6 tertiary alkyl radical containing at least one .beta.-hydrogen atom.

27. A method according to claim 20 wherein the epoxy-functionalized olefin polymer is a glycidyl methacrylate-grafted copolymer of ethylene, propylene and a non-conjugated diene.