CA1198248A - Process for preparing ester carbonate copolymers - Google Patents
Process for preparing ester carbonate copolymersInfo
- Publication number
- CA1198248A CA1198248A CA000427726A CA427726A CA1198248A CA 1198248 A CA1198248 A CA 1198248A CA 000427726 A CA000427726 A CA 000427726A CA 427726 A CA427726 A CA 427726A CA 1198248 A CA1198248 A CA 1198248A
- Authority
- CA
- Canada
- Prior art keywords
- carbonate
- ester
- oligomer
- dihydric
- ordered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
Abstract
ABSTRACT OF THE DISCLOSURE
This invention is directed to a process for making ordered ester/carbonate copolymers characterized by comprising the steps of (1) contacting in an organic liquid medium a dihydric organic compound such as bisphenol-A with a carbonate precursor such as phosgene and a diacid halide such as terephthaloyl chloride under conditions such that the carbonate moieties in the resultant intermediate oligomer are formed simultane-ously with or before the formation of ester moieties and (2) contacting this oligomer with additional carbo-nate precursor under conditions sufficient to form the desired ordered ester/carbonate copolymer.
This invention is directed to a process for making ordered ester/carbonate copolymers characterized by comprising the steps of (1) contacting in an organic liquid medium a dihydric organic compound such as bisphenol-A with a carbonate precursor such as phosgene and a diacid halide such as terephthaloyl chloride under conditions such that the carbonate moieties in the resultant intermediate oligomer are formed simultane-ously with or before the formation of ester moieties and (2) contacting this oligomer with additional carbo-nate precursor under conditions sufficient to form the desired ordered ester/carbonate copolymer.
Description
A PROCESS ~OR MAKING ORDERED
ESTER/CARBONATE COPOLYMERS
This invention relates to linear ester carbo-nate copolymers that contain both carbonate groups and ester gxoups in the linear chain.
Polycarbonate resins are known to be tough and rigid and have moderately high softening tempera-tures. Of particular interest are the polycarbonates of bisphenol A diols as described in U.S. Patent No. 3,028,365. On the other hand, polyesters such as those described ~rom terephthalic acid, isophthalic acid and/or 1,4-butane diol are well known as molding resins having high softening temperatures but poor impact resistance.
In the past, it has been a practice to make random linear copolymers containing ester and carbonate linkages in order to obtain polymers having heat distor-tion temperatures generally higher than those character-istic of polycarbonates. See, for example, U.S. Patent Nos. 3,129,121; 3,549,570; 3,053,810; 3,030,331 and 29,645-F -1- ~ ~
3,220,976. Unfortunately, however, the desired increase in heat distortion is often no-t as high as needed for many applications. More importantly, any increase in heat distortion is achieved only by sacrificing almost all of the high impact resistance that is characteristic of polycarbonate resins.
Recently, it has been found that, by alternat-ing or ordering the ester and carbonate linkages in the ester/carbonate copolymer molecule, improved thermal resistance is achieved without a corresponding sacrifice of physical strength. See, for e~ample, U.S. Patent Nos. 4,156,069; 4,105,633 and 4,278,787. Such copoly-mers are normally prepared in a two-step procedure wherein a dihydric phenol is reacted with a diacid chloride to form a hydroxy-terminated polyester oligomer, this oligomer is then reacted with phosgene to form the desired ordered ester/carbonate copolymer. In -the preparation of such copolymer having a high ester to carbonate ratio, the polyester intermediate often precipitates from solution. When this precipitation occurs, it causes problems in pol~mer purification, loss of mechanical and optical properties and an ester/-carbonate ratio different from that which is desired.
Therefore, it is highly desirable to provide an improved process for producing ordered ester carbo-nate copol~mers wherein the copolymer is easily purified and exhibits the desired optical and mechanical proper-ties at the desired ester to carbonate ratio.
29,645-F -2~
3 o This lnvention is directed to a process for making ordered ester/carbonate copolymers characterized by the steps of (1) contacting in an organic liquid medium a dihydric organic compound with a carbonate precursor and a diacid halide under conditions such that the carbonate moieties in the resultant interme-diate oligomer are formed simultaneously with or before formation of the ester moieties and (2~ contacting this oligomer with additional carbonate precursor under conditions sufficient to form the desired ordered ester/carbonate copolymer.
In one embodiment, this invention is a pre-phosgenation pxocess for making an ester/carbonate copolymer characterized by comprising the steps of (1) contacting in an organic liquid medium a dihydric organic compound with a carbonate precursor under conditions sufficient to form a dihydric carbonate,
ESTER/CARBONATE COPOLYMERS
This invention relates to linear ester carbo-nate copolymers that contain both carbonate groups and ester gxoups in the linear chain.
Polycarbonate resins are known to be tough and rigid and have moderately high softening tempera-tures. Of particular interest are the polycarbonates of bisphenol A diols as described in U.S. Patent No. 3,028,365. On the other hand, polyesters such as those described ~rom terephthalic acid, isophthalic acid and/or 1,4-butane diol are well known as molding resins having high softening temperatures but poor impact resistance.
In the past, it has been a practice to make random linear copolymers containing ester and carbonate linkages in order to obtain polymers having heat distor-tion temperatures generally higher than those character-istic of polycarbonates. See, for example, U.S. Patent Nos. 3,129,121; 3,549,570; 3,053,810; 3,030,331 and 29,645-F -1- ~ ~
3,220,976. Unfortunately, however, the desired increase in heat distortion is often no-t as high as needed for many applications. More importantly, any increase in heat distortion is achieved only by sacrificing almost all of the high impact resistance that is characteristic of polycarbonate resins.
Recently, it has been found that, by alternat-ing or ordering the ester and carbonate linkages in the ester/carbonate copolymer molecule, improved thermal resistance is achieved without a corresponding sacrifice of physical strength. See, for e~ample, U.S. Patent Nos. 4,156,069; 4,105,633 and 4,278,787. Such copoly-mers are normally prepared in a two-step procedure wherein a dihydric phenol is reacted with a diacid chloride to form a hydroxy-terminated polyester oligomer, this oligomer is then reacted with phosgene to form the desired ordered ester/carbonate copolymer. In -the preparation of such copolymer having a high ester to carbonate ratio, the polyester intermediate often precipitates from solution. When this precipitation occurs, it causes problems in pol~mer purification, loss of mechanical and optical properties and an ester/-carbonate ratio different from that which is desired.
Therefore, it is highly desirable to provide an improved process for producing ordered ester carbo-nate copol~mers wherein the copolymer is easily purified and exhibits the desired optical and mechanical proper-ties at the desired ester to carbonate ratio.
29,645-F -2~
3 o This lnvention is directed to a process for making ordered ester/carbonate copolymers characterized by the steps of (1) contacting in an organic liquid medium a dihydric organic compound with a carbonate precursor and a diacid halide under conditions such that the carbonate moieties in the resultant interme-diate oligomer are formed simultaneously with or before formation of the ester moieties and (2~ contacting this oligomer with additional carbonate precursor under conditions sufficient to form the desired ordered ester/carbonate copolymer.
In one embodiment, this invention is a pre-phosgenation pxocess for making an ester/carbonate copolymer characterized by comprising the steps of (1) contacting in an organic liquid medium a dihydric organic compound with a carbonate precursor under conditions sufficient to form a dihydric carbonate,
(2) contacting the dihydric carbonate with a diacid halide under conditions sufficien-t to form an ester/-carbonate oligomer and (3) contacting the oligomer witha carbonate precursor under conditions sufficie~t to form an ordered ester/carbonate copolymer.
In another embodiment, this invention is a con-add process for making an ester/carbonate copolymer characterized by comprising the steps of (1) concurrently contacting ln an organic li~uid medium a dihydric organic compound with a carbonate precursor and a diacid halide under conditions sufficient to form an ester/carbonate oligomer and (2) contacting the oligomer with addi.tional carbonate precursor under conditions sufficient to form an ordered ester/carbona-te copolymer.
29,645-F -3-w Practice of this inven-tion reduces the rate of precipitation from solution of the intermediate olig3mers which are characteristically produced in conventional post-phosgenation procedures. Thus, the reaction mixture can contain higher concentrations of reactants and the intermediate oligomers, thereby reducing the amount of solvent which must be recy~led for a given amount of copolymer. Surprisingly, the resulting ester/carbonate copolymers have physical properties equivalent to or better than those of the ester/carbonate copolymers prepared by the post--phosgenation process.
The copolymers prepared in the practice of this invention are useful in most applications in which polycarbonates, polyester and copolymers thereof are conventionally employed. In particular, such copolymers are useful for making transparent, tough films and molded articles having high heat resistance. In addi-tion, these copolymers may be blended with other poly-mers such as ABS resins, styrene/acrylonitrile copoly-mers and impact polystyrenes to provide moldable blends and/or they may be combined with reinforcing fibers, such as glass fibers in the production of various molded articles.
The dihydric organic compound employed in the practice of this invention is suitably any predominantly hydrocarbon compound containing at least two alcoholic hydroxyl groups wherein alcoholic hydroxyl includes phenolic hydroxyl. Included within the dihydric organic compounds are aliphatic diols including glycols and cycloalipha-tic diols, aromatic diols, including alkaryl 29,645-F -4-diols, dihydric phenols and aroma-tic diols having heterocyclic groups such as phenolphthalein. Of the dihydric organic compounds, the dihydric phenols are preferredO
The dihydric phenols preferably used in pre~
paring the copolymers of the present invention are suitably any aromatic compound having an aromatic hydrocarbylene group to which is aromatically bonded two hydroxyl groups. Most advantageously, the dihydric phenols are those aromatic diols represented by the formula:
(Y)m (R)p (Y)m HQ -~- [A~ E k~ A ~ _- OH
In the formula, A is an aromatic group such as, for example, phenylene, biphenylene, naphthenylene, and anthracenylene. E is alkylene or alkylidene such as methylene, ethylene, ethylidene, propylene, propylidene, isopro,pylidene, butylene, butylidene, isobutylidene, amylene, isoamylene, amylidene, and isoamylidene or E
may be cycloalkylene such as cyclopentylene, cyclohexy-lene; a sulfur-containing linkage such as sulfide, sulfoxide or sulfone, an ether linkage; a carbonyl group; a tertiary nitrogen group or a silicone-containing linkage such as silane or siloxy. R is hydrogen or a monovalent hydrocarbon group such as alkyl, aryl, aryla.lkyl or cycloaliphatic; Y is chlorine, bromine, fluorine or R wherein R is defined above. The letter m is any whole number from and including zero throuyh the number of positions on A available for substitution; p is any whole number from and including zero through the number of available positions on E; t is a whole number 29,645-F
~ 3~ ~
equal to at least one; s is either zero or one and u is any whole nu~ber including zero. Examples of such dihydric phenols include 2,2-bis-(4-hydroxyphenyl)-propane [bisphenol-A]; his-(4-hydroxyphenyl)methane;
1,1-bis~(4-hydroxyphenyl~ethane and others including dihydroxy aromatic ethers listed in U.S. Patent No.
In another embodiment, this invention is a con-add process for making an ester/carbonate copolymer characterized by comprising the steps of (1) concurrently contacting ln an organic li~uid medium a dihydric organic compound with a carbonate precursor and a diacid halide under conditions sufficient to form an ester/carbonate oligomer and (2) contacting the oligomer with addi.tional carbonate precursor under conditions sufficient to form an ordered ester/carbona-te copolymer.
29,645-F -3-w Practice of this inven-tion reduces the rate of precipitation from solution of the intermediate olig3mers which are characteristically produced in conventional post-phosgenation procedures. Thus, the reaction mixture can contain higher concentrations of reactants and the intermediate oligomers, thereby reducing the amount of solvent which must be recy~led for a given amount of copolymer. Surprisingly, the resulting ester/carbonate copolymers have physical properties equivalent to or better than those of the ester/carbonate copolymers prepared by the post--phosgenation process.
The copolymers prepared in the practice of this invention are useful in most applications in which polycarbonates, polyester and copolymers thereof are conventionally employed. In particular, such copolymers are useful for making transparent, tough films and molded articles having high heat resistance. In addi-tion, these copolymers may be blended with other poly-mers such as ABS resins, styrene/acrylonitrile copoly-mers and impact polystyrenes to provide moldable blends and/or they may be combined with reinforcing fibers, such as glass fibers in the production of various molded articles.
The dihydric organic compound employed in the practice of this invention is suitably any predominantly hydrocarbon compound containing at least two alcoholic hydroxyl groups wherein alcoholic hydroxyl includes phenolic hydroxyl. Included within the dihydric organic compounds are aliphatic diols including glycols and cycloalipha-tic diols, aromatic diols, including alkaryl 29,645-F -4-diols, dihydric phenols and aroma-tic diols having heterocyclic groups such as phenolphthalein. Of the dihydric organic compounds, the dihydric phenols are preferredO
The dihydric phenols preferably used in pre~
paring the copolymers of the present invention are suitably any aromatic compound having an aromatic hydrocarbylene group to which is aromatically bonded two hydroxyl groups. Most advantageously, the dihydric phenols are those aromatic diols represented by the formula:
(Y)m (R)p (Y)m HQ -~- [A~ E k~ A ~ _- OH
In the formula, A is an aromatic group such as, for example, phenylene, biphenylene, naphthenylene, and anthracenylene. E is alkylene or alkylidene such as methylene, ethylene, ethylidene, propylene, propylidene, isopro,pylidene, butylene, butylidene, isobutylidene, amylene, isoamylene, amylidene, and isoamylidene or E
may be cycloalkylene such as cyclopentylene, cyclohexy-lene; a sulfur-containing linkage such as sulfide, sulfoxide or sulfone, an ether linkage; a carbonyl group; a tertiary nitrogen group or a silicone-containing linkage such as silane or siloxy. R is hydrogen or a monovalent hydrocarbon group such as alkyl, aryl, aryla.lkyl or cycloaliphatic; Y is chlorine, bromine, fluorine or R wherein R is defined above. The letter m is any whole number from and including zero throuyh the number of positions on A available for substitution; p is any whole number from and including zero through the number of available positions on E; t is a whole number 29,645-F
~ 3~ ~
equal to at least one; s is either zero or one and u is any whole nu~ber including zero. Examples of such dihydric phenols include 2,2-bis-(4-hydroxyphenyl)-propane [bisphenol-A]; his-(4-hydroxyphenyl)methane;
1,1-bis~(4-hydroxyphenyl~ethane and others including dihydroxy aromatic ethers listed in U.S. Patent No.
3,169,121 at Col. 2, line 60 through Col~ 3, line 55.
Also included among the suitable dihydric phenols are those having an ar,ar'-dihydroxytrityl nucleus represented by the formula:
Ho~ C-@-oE~
wherein the aromatic rings beax, in addition to the hydroxy substituents, such substituents as, for example, H, F, Cl, Br, I, -NO2, -O-, alkyl, acyl, carboxylate ester, and sulfonate ester. Representative diols containing the ar,ar'-dihydroxytrityl nucleus include phenolphthalein nucleus compounds as described in U.S.
Patent No. 3,036,036; phenolsulfonephthalein nucleus compounds described in U.S. Patent No. 3,036,037;
phthalidene nucleus compounds as described in U.S.
Patent No. 3,036,038; fluorescein nucleus compounds as described in U.S. Patent No. 3,036,039 and phenol-phthalimidene nucleus compounds corresponding to the phenolphthalein nucleus compounds described in U.S.
Patent No. 3,036,036. Of the aforementioned dihydric phenols, the bis(ar-hydrox~phenyl~alkylidenes, particu-larly bisphenol-A, are most preferred.
29,645-F -6-The diacid halides that are suitably employed include both the acid halides of the aromatic and the saturated aliphatic dibaslc acids. The saturated aliphatic dibasic acids which can be employed are derived from straight chain paraffin hydrocarbons such as oxalic, malonic, dimethyl malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acid as well as the halogen substituted aliphatic dibasic acids. The aliphatic carboxylic acids containing heteroatoms in their aliphatic chain, such as thio-diglycollic or diglysollic acid can also be used as well as unsaturated diacids such as maleic or fumaric.
Examples of aromatic and aliphatic aromatic dicarboxylic acids which can be employed in their acid chloride form are phthalic, isophthalic, terephthalic, homophthalic, ortho-, meta- and para-phenylenediacetic acidi the polynuclear aromatic acids such as diphenic acid, 1,4-naphthalic acïd and 2,6-naphthalic acid. Of the foregoing diacid halides, prefexred are isophthaloyl chloride, terephthaloyl chloride, as well as mixtures thereof, with the mixtures being most preferred.
The carbonate precursor employed is suitably a carbonyl dihalide, a carbonate ester, a haloformate or other compound which will suitably react with terminal hydroxyl groups to form carbonate linkages. The carbonyl halides which may be employed are carbonyl bromide, carbonyl chloride (phosgene) and mixtures thereof.
Suitable caxbonate esters are diphenyl carbonate, di(halophenyl)carbonates such as, ~or example, di(chlorophenyl)carbonate, di-(bromophenyl)carbonate, di-(tri-chlorophenyl)carbonate, and di-(tri-bromophenyl)-carbonate; di-(alkylphenyl)carbonate such as di-(tolyl)-carbonate; di-(naphthyl)carbonate, di-(chloronaphthyl)-carbonate, phenyltolyl carbonate, chlorophenyl 29,64S-F
chloronaphthyl carbonate and mixtures thereof. Suitable haloformates include bishaloformates of dihydric phenols such as bischloroformates of hydroquinone or glycols such as, for example, bishaloformates of ethylene S glycol, neopentyl glycol, and polyethylene glycol. Of the foregolng carbonate precursors, phosgene is preferred.
The process of this invention is practiced in a manner such that a portion of the carbonate moieties are formed simultaneous with or before the formation of ester moieties in the intermediate oligomer. By achiev-ing this early carbonation in the in-termediate oligomer, undesirable precipitation of the oligomer from the liquid reaction mixture is minimized.
The process of this invention is normally carried out under an inert atmosphere such as nitrogen with the reactants dissolv~d in one or more solvents such that the reactants are totally miscible. While the concentration of the reactants in the solvents is not particularly critical, the conce~tration of the dihydric organic compound is preferably from 2 to 10 weight percent, and the concentration of the diacid chloride is preferably from 1 to 5 weight percent based on the total weight of the reaction mixture. As a result of practicing the present invention, the concen-tration of the ester/carbonate intermediate oligomer can be greater than the concentrations of the ester intermediate oligomer which are normally employed in conventional procedures. Accordingly, such concentra-tion of the ester/carbonate intermediate oligomer is inthe range from 3 to 15, most preferably from 5 to 12, weight percent based on the total weight of the reac-29,645-F -8-_9 tion mixture. It is preferreA that the solutions of the various reactants be totally miscible in each other. However, it is sufficient if such solutions are partially miscible, i.e., at least 10 weight percent.
Examples of suitable solvents for the reac tion mixture include chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, sym-tetrachloro-ethane, 1,1,2-trichloroethane and cis-1,2-dichloro-ethylene. Other solvents normally employed in the preparation of ester/carbonate copolymers may also be suitably employed.
The molar ratio of dihydric organic compound to diacid chloride varies proportionately with the ester:carbonate ratio desired in the ester/carbonate copolymer. The molar ratio of dihydric compound to diacid chloride is advantageously from 21:1 to 1.1:1, preferably from 21:1 to 1.3:1. The molar ra-tio of carbonate precursor to total moles of dihydric compound and diacid halide is advantageously from 0.05:1 to 0.91:1, preferably from 0.13:1 to 0.91:1.
In addition to the foregoing components, the process of the present invention is also carried out in the presence of a hydrogen chloride acceptor. Examples of such acceptors include pyridine, triethyl amine, N,N-trimethyl aniline and N,N-trimethylcyclohexyl amine, with pyridine being preferred. Such acceptors are advantageously employed in amounts sufficient to complex the hydrogen chloride liberated in the reaction and to catalyze both the ~orrnation o~ ester linkages and carbonate linkages. Since higher concentrations of acceptor produce higher molecular weight copolymers, 29,645-F -9-the concentration of acceptor employed will vary depend-ing on the molecular weight desired. Preferably, in order to prepare copolymers having weight average molecular weights ~Mw) from 25,000 to 60,000, the acceptor is employed in amounts from 100 to 160 mole percent based on moles of hydroxyl moiety in the monomers, more preferably from 120 to 140 mole percent.
Pre~Phos~enation Embodiment In one embodiment of this invention (the pre-phosgenation process), the dihydric organic compound and the carbonate precursor are combined in the first stage in any manner, preferably by bubbling phosgene or adding another suitable carbonate precursor with stirring into a solution of the dihydric organic compound and hydrogen chloride acceptor. The molecular weight of the resultant carbonate intermediate oligomer is advanta-geously controlled by maintaining the mole ratio of the carbonate precursor to dihydric organic compound at less than 1:1 in the first stage. Preferably, the ratio of the carbonate precursor to dihydric organic compound in the first stage is from 0.09:1 to 0.95:1, more preferably from 0.09:1 to 0.5:1. Although not critical, the reaction temperature of this stage is preferably maintained in the range from 10 to 35C, more preferably from 15 to 30C, and the reaction pressure is normally maintained at atmospheric to superatmospheric as a matter of convenience. The hydrogen chloride acceptor is generally employed in an amount sufficient to take up whatever hydrogen chloride is genera-ted ln this stage, preferably from l.0 to 1.6, more preferably from 1.2 to 1.4, moles of acceptor per mole of carbonate precursor. While -the carbonate intermediate oligomer may be recovered and puriied 29,645 F -lO-before continuing the pre-phosgenation process, it is generally not desirable to do so.
In the second stage of the pre phosgenation process, the aforementioned reactioIl m1xture containlng a carbonate intermediate oligomer is converted to an ester/carbonate intermediate oligomer having terminal hydroxy groups by combining a diacid halide with the reaction mixture in any manner, preferably by addlng the diacid chloride either neat or dissolved in a suitable solvent with stirring to the reaction mixture which contains sufficient hydrogen chloride acceptor to absorb hydrogen chloride of reaction. Similar to the first stage, the reaction temperature and pressure are not critical. Preferably, however, the reaction tempera-ture is mainkained in the range from lQ to 35C, morepreferably from 15 to 25C and the reaction pressure is atmospheric to superatmospheric. Advantageously, the amount of diacid chloride added to the reaction mixture is one which i5 sufficient to provide a molar ratio of ester moiety to carbonate moiety in the inter~
mediate oligomer in the range from 0.1:1 -to 20:1, more preferably from 4:1 to 20:1.
Finally, the ester/carbonate copolymer inter-mediate oligomer from the foregoing second stage is converted in the third stage of the pre-phosgenation process to the desired ordered ester/carbonate copoly-mer by bubbling phosgene or adding similar carbonate precuxsor into the reaction mixture. Advantageously, the reaction mixture contains an amount of monohydr:ic phenol or other suitable Ghain terminator to effec-t the desired control of molecular weight of the ordered ester/carbonake copolymer. While the amount of the 29,645-F
~L~ D4~
chain terminator employed varies with the efficacy of the terminator, the molecular weight desired and the final ester/carbonate ra-tio, beneficial amounts of chain terminator are normally in the range from 1 to 15 mole percent based on the mole5 of dihydric organic compound less moles of the diacid halide, preferably from 2 to 12 mole percent. As in the previous two s-tages, reaction temperature and pressure are not critical. However, the reaction temperature is prefer-ably in the range from 10 to 35C, most preferablyfrom 15 to 25C and the reaction pressure is preferably in the range from atmospheric to superatmospheric. In all three stages of the foregoing embodiment, the reaction mixtures are agitated sufficiently to effec-t intimate contact of the reactants and desirable heat transfer throughout the reaction medium. Following completion of the third stage of the embodiment, the desired ordered ester/carbonate copolymer is readily recovered from the reaction medium by conventional techniques as exemplified in the examples set forth hereinafter.
Concurrent Addition Embodiment In the first stage of this embodiment, the diacid halide and phosgene or other carbonate precursor are combined with the dihydric organic compound by continuously adding the diacid halide and carbonate precursor either neat or dissolved in a suitable solvent to a solution of the dihydric oryanic compound and a hydrogen chloride acceptor. While reaction temperature and reaction pressure are not critical for this stage of the con-add embodiment, the reaction -temperature is preferably maintained in -the range from 10 to 35C, most preferably from 15 to 25C and reaction pressure 29,645-F -12-is maintained at atmospheric to superatmospheric pressure as a matter of convenience. The amount of diacid halide added to the reaction mixture is that which produces the desired ester content in the copolymer.
Examples of such suitable amounts are described herein-before. The amount of carbonate precursor added in this stage is advantageously such that the mole ratio of carbonate precursor to dihydric organic compound is less than 1:1, preferably from 0.09:1 to 0.95:1. As stated before, the diacid chloride and the carbonate precursor are added continuously to the reaction mixture containing the dihydric organic compound. While the rates of addition of the components are not particularly critical, it is generally desirable -to add enough carbonate precursor early in the reaction in order to minimize the undesired precipitation that can occur ~hen the resulting ester/carbonate intermediate oligomer contains essentially all ester linkages and no carbonate linkages. Preferably, sufficient carbonate precursor is added to provide at least 50 mole percent of the theoretical carbonate moieties in the ester/carbonate copol~mer intermediate, most preferably from 75 to 95 mole percent. Advantageously, the carbonate precursor and diacid halide are added continuously at rates sufficient to provide the desired copolymer and will vary with reactor size and cooling capacity and the like.
While the ester/carbonate intermediate oligomer may be recovered and purified before proceeding to the second stage of this con-add process, it is generally not desir-able to do so.
In the second stage of the con-add process, the aforementioned reaction mixture containing the ester/carbonate oligomer is converted to the desired 29,645-F -13-mixed copolymer by bubbling phosgene or adding other suitable car~onate precursor into the reaction mixture.
Advantageously, the reaction mixture contains an amount of monohydric phenol or other suitable chain terminator to effect the desired control of molecular weight as is employed in the pre~phosgenation process. Although not critical, the reaction temperature of this stage is preferably maintained in the range from 10 to 35C, more preferably from 15 to 25C, and the reaction pressure is advantageously from atmospheric to super-atmospheric, with atmospheric being preferred. As in the pre-phosgenation process, the reaction mixture in the con-add process is agitated sufficiently to effect intimate contact of the reactants and to provide heat transfer throughout the reaction medium. The resulting ordered ester/carbonate copolymer is readily recovered by conventional techniques as shown in the following examples.
The ordered ester/carbonate copolymers produced in the preferred practices of this invention are advantageously represented by the formula:
o o o _.. " " " ~
Y - -~ROC-R1C0~xROCO In Z
wherein Y and Z are independently terminating groups common to polyesters or polycarbonates; each R is independently a divalent or~anic moiety derived from the dihydric organic compound as defined hereinbefore, especially aroma~ic hydrocarbylene or inertly substi-tuted aromatic hydrocarbylene; each R~ is a divalentorganic radical derived from a diacid halide as described hereinbefore, especially phenylene or other 29,645-F -14-divalent aromatic moiety; x is a number from 0.05 to 10 and n is a whole number from 5 to 300. Using the aforementioned formula, the ester/carbonate mole ratio in the copol~mer is de~ined by 2x/1. The process of this invention is particularly efective in the prepara-tion of ester/carbonate copolymers having (1) relatively high ester/carbonate mole ratios, e.g., wherein x is from 1 -to 10 in the foregoing structural formula, and (2) relatively high concentration of one ester, e.g., from 70 to 100 percent of terephthalate or isophthalate based on total ester.
In the foregoing formula, R1 is pxeferably para-phenylene, meta-phenylene or a combination of para-phenylene and meta-phenylene such that the molar ra-tio of para-phenylene to meta-phenylene is from 0.95:0.05 to 0.05:0.95, preferably from 0.95:0.05 to 0.2:0.8, most preferably from 0.9:0.1 to 0.5:0.5.
Illustratively, Y is O O O O O O O
~ ,~ ,. ....... .. .. .. .. ..
-OH, R2OCO~-, HOCR1CO~, R2OCR1CO- or HOROCR1CO-wherein R2 is hydrocarbyl such as alkyl, aryl or aralkyl;
and R and Rl are as defined herei~before. Representa-tive Z includes R2~ and HOR-wherein R2 and R are as defined hereinbefore.
More preferred are those copolymers represented by the formula:
29,645-F -15-O O o , Y _ (ROC-R1CO~xROCo n Z
wherein Y is -OH or ,, Z is R2 or -ROH; x is 0.05 to 10, preferably 0.05 to 3, and R, Rl, R2 and n are as defined hereinbefore.
Most preferred copol~mers are those represented by the foregoinc3 formula wherein R is ~ CH3 ~ CH
Y is ~oCOR2 i I-Z is -R2; R2 is hydrocarbyl, e.g., alkyl, aryl, alkaryl, cycloalkyl or aralkyl; x i5 1 to 3; and n is a whole number from 5 to 300, preferably from 10 to 200 and most preferably ~rom 30 to 100. For purposes of this invention, hydrocarbyl is a monovalent hydrocarbon radical.
While the molecular weight o~ khe copolymers is not particulaxly critical, those having weight average rnolec:ular weight ~Mw, determined by gel permea-tion chromatography using a bisphenol-A polycarbona-te 29,645-F -16-calibration curve) greater than 20,000 are of more significance. The copolymers of relatively high mole-cular weighk, e.g., those having an Mw of at leas-t 25,000 up -to and including those having an Mw of 60,000, are found to exhibi-t the properties and physical charac-texistics most desirable of molding resins. Most preferred for this purpose are those copol~mers having an Mw in the range from 25,000 to 40,000 and Mw/Mn (wher~in Mn is number average molecular weight) from 1.5 to 5. Preferred copolymers have inherent viscosi~
ties (~ inh) measured in methylene chloride at 0.5 grams/deciliter and 25C in the range from 0.35 to 1 deciliter/gram (dl/g), most preferably from 0.45 to 0.70 dl/g.
The following examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.
Examples 1, 2, and 3 and Comparative Runs A, B, C and D
~0 In step 1 of a three-step pre-phosgenation (PP) process, a 5-liter flask was charged with 268.73 grams ~1.177 moles) of bisphenol-A, 3.00 liters of methylene chloride and 242.1 grams (3.061 moles) of pyridine. Stirring began and when a clear solution of bisphenol~A was obtained, 38.8 grams (0.392 mole) of phosgene was added over a period of 20 minutes by bubbling the phosgene into the bisphenol-A solution a-t a temperature bet~een 23 and 25C while continuously stirring the corltents o~ the flask at 200 rpm.
In step 2., the aforementionec~ reaction mixture containing the dihydric carbonate intermediate oligomer 29,645-F -17-was combined with 159.32 grams (O.785 mole) of tereph-thaloyl chloride while the reaction mixture was main-tained at a temperature of 24C and continuously stirred at 200 rpm. This addition of diacid chloride occurred by a continuous addition over a period of 3 minutes after which time, the temperatuxe of the reaction mixture rose to 33C. The reaction mixture was then s~irred for an additional 5 minutes and 4.71 grams (0.031 mole) of t-butyl phenol (TBP) was added to the reaction mixture.
In step 3, the aforementioned reaction mixture containing a dihydric ester/carbonate intermediate oligomer was combined with 6.0 grams (O.061 mole) o~
phosgene by bubbling the phosgene into the reaction _15 mixture at a rate of 1 gram per minute over a period of 6 minutes while maintaining the reaction mixture at a temperature between 22 and 24C and stirring the mixture at 200 rpm.
The resulting ordered ester/carbonate copoly-mer was recove~ed from the reaction mixture by the following procedure:
0.5 liter of 3N HCl was added to neutralize excess pyridine. Following phase separation, the methylene chloride solution of copol~mer was washed consecutively with 0.5 liter of 0.5N HCl and 0.5 liter of water, with phase separation after each washing.
Following the final washing, the methylene chloride solution of copolymer was passed through a column packed with a cation exchange resin (sulfonic acid type, dead volume hetween 500 and 600 milliliters), giving a clear, almost water--white solution. The polymeric product was 29,645-F -18-~19--isolated by the slow addition of 1 volume of methylene chloride solution to 4 volumes of hexane with rapid stirring. The resulting white fibers were isolated by filtration, dried in air for 24 hou.rs and then dried in vacuo for 48 hours at 120C to yield 354.1 grams (92.9 percent of theory) of copolymer having an inherent viscosity of 0.551 deciliter per gram ~measured in methylene chloride at 25C, 0.5 gram per deciliter).
Analysis of the copolymer by IR and NMR analysis indi-cated that it was an ordered ester/carbonate copolymerrepresented by the structural formula:
~ O ~ ~ 3 CH3 ~ CH3 ~ \ ~ ~ " ~
OC0 ~ ~ -C~3 CH3 n CH3 The copolymer repeating unit had an ester/carbonate molar ratlo of 4:1.
This copolymer (Example 1) was compression molded at 300C using a compression molding press sold by Pasadena Hydraulics Inc. The physical properties fOL the compression molded specimens (0.32 cm thickness) are shown in Table I. Examples 2 and 3 were carried out in accordance with the foregoing procedure of Example 1 except that different amounts of phosgene 29,645~F -19-were added in the first stage of the process as indicated in Table I. The resulting copolymers were similarly compression molded and tested and the results are recorded in Table I.
S For Comparison Runs A-D, several copolymers were prepared using a conventional procedure similar to the foregoing procedure except that it was a standard 2-stage ~S2S) process wherein phosgene was added only in the second stage (so-called post~phosgenation process).
The resulting copolymers were similarly compression molded and tested for physical properties and the results are shown in Table I. The copolymer of Compara-tive Run A was not soluble in methylene chloride. Its inherent viscosity was not measured.
Examples 4, 5, 6, 7 and 8 In step 1 of a 2-step concurren-t addition ~CA~ process, a 5-litex flask was charged with 268.73 grams (1.177 moles) of bisphenol-A, 2.70 liters of methylene chloride and 242.1 grams (3.061 moles) of pyridine. Stirriny was begun and when a clear solution of bisphenol-A was obtained, 38.8 grams ~0.392 mole) of phosgene and a solution of 159.32 grams (0.785 mole) of terephthaloyl chloride dissolved in 0.30 liter of methylene chloride were added continuously to -the reactlon vessel over a period of 20 minutes while continuously stirring the contents of the flask at a -temperature between 21 and 25C and 200 rpm. The tereph~haloyl chloride was added ~o the reaction mixture via a liquid addition funnel and the phosgene was added by bubbling it into the liquid reaction mixture.
29,645-F -20-In step 2, the aforementloned reaction mixture containing the ester/carbonate intermediate oligomer was combined with 4.71 grams (O.031 mole) of t-bu-tyl phenol. The resulting solution was stirred at lO0 rpm and 8 grams (0.081 mole) of phosgene were added over a period of 6 minutes.
The resulting ordered ester/carbonate copoly-mer was recovered from the reaction mixture by the procedure of Example 1, analyzed and determined to have a structure similar to that of the ester/carbonate copolymer of Sample No. 1 in Example l. This copolymer ~Example 4) was compression molded and tested as in Example l and the results are recorded in Table I.
For Examples 5, 6, 7 and 8 copolymers were similarly prepared by the concurrent addition process except that the amount of phosgene added in the first stage of the process was varied as indicated in Table I.
The resulting copolymers were similarly compression molded and tested for physical properties and the results of these tests are reported in Table I.
In E~ample 5, the t-butyl phenol was added prior to the addition of phosgene and terephthaloyl chloride.
In Table I, the mole percen-t of the theore-ti-cal amount of phosgene added in the first stage of thepre-phosyenation process or the concurrently-added process is calculated from the theoretical moles of phosgene being equal to the moles of bisphenol-A minus the moles of terephthaloyl chloride. The abbreviation DPC stand for designed polymer concentration, w:hich is 29,645-F -21-defined as -the theoretical grams of polymer excluding terminator per liter of methylene chloride. The mole percent p-tertiary butyl phenol (TBP) is based on the moles of bisphenol-A minus the moles of terephthaloyl chloride. In Example 5, the p-tertiary butyl phenol was added prior -to the addition of phosgene and terephthaloyl chloride. It should be noted that in Examples 3 and 10, a slight haze due to an insoluble fraction was observed. The copolymer of Comparative Run A was not soluble in methylene chloride. Its inherent viscosity was not measured. It was also observed that the copolymer of Comparative Run A did not yield in the tensile and elongation tests. The tensile at break was 6877 psi (47.42 MPa).
Vicat softening point was measured according to ASTM D-1525. Izod impact was measured according to ASTM D-256. Tensile at yield and elongation at yield and break were measured according to ASTM D-638. Mole percent ester is defined as (moles of estex divided by moles of ester plus moles of carbonate) multiplied by 100. The moles of ester and moles of carbonate were determined by nuclear magnetic resonance spectroscopy.
The theoretical mole percent ester for all ~xamples and Comparative Runs is 80Ø Yellowness index was measuxed according to ASTM D-1925. Transmission and haze were measured according to ASTM D-1003.
29,645-F' 22-o l` d1 ~
~: O ~ 0~0 ~r~--1` ~i ~0~ ~ O
~ U Ir~ N 1~') N~ ~
0 (~ ~ ~('\1 r~l O
O N ~ (~
O LnO ^L~ r-l~ Ln ~, Ul ~ t:J~ N ON '~ Lr) 10 N U) r~ C~ ) N
~1 ~ ~ N ~) ~ ~ / N
o ~
o o O ~ ~~1 0N ~ ~(S` O (`~
t~ ~ N 1~) N~ ~`~ O
~ (~ ~ N N a~
o ~
-1~ ~-- ~-- N ~D O
fS o ~ co~ ~o ooo d~
u~ ~ O
rl ~ ~ 10 N rl ~ \ N ~1 o ~ ) N~ t`
-~ O ~` ~ao ot~
d~ U O N ~)N ~ O
H ~1 ~I ' d' ~1 ~ ' 00 ~ N ~1 OC~
O ~-0 ~ ~1 ~
~ ~ t~ ~ ~O "~
O ~ ~N 1~)N 0 ~ CO 00 CS~
I~') N ~O ,1 . ~ ~ 11 ~ . . . .
~1 ~ N~ NO ~ N ~1 o ~
O L/) O
~ L'l --` ~ N t` t` ~ ~
r-l ~N ~ ~1 ~ ~ ~1 -- [`
~1 ~
p~ O ~`oD In ~ ~ ^ -- ~ ~ ~ o dl r~t Pl C~N L0 ~ ~1 ~
~) ~ N O
O t`~
-~).,1 ,-1 (.
N 0 ~1 U~
O r~
u ~rl ~ ~
~ O ~ 1 h ~ ~ ~ t,~ OI
Zi ~ ~ ~ ~ ` r~ O (d ~ ~ O '~ ~ , O U~
O O U~r~ ~-rl r~l ~1 11~ 1 a.
V? ;~ ~ lO ~ H q ~ r~ d rl ~1 ~1 ~C ~
~ a) G ~n e ~ ~ ,~ e .r~ ~ tn~ m ,~ ~
.) ~ rl P~ r-l p I O
td o --~ O-rl ~.) p~ r~ O O ~ ~ ~ O ~ ~ ~ 7 r--l ~ ~1 0 q t~ P~ !q rl N ~1-- O ~ -- O
t~l ~ r~ 1 c ~> ~ E~
29, 645-F -23-2~
~4--O o ~ ~ o u~
CS~ U-! ~ O ~O~ ~ ~ ~D O ~
N r~ 0 ~ O
o ~ ~o:) o~ r~
~ ~ ~1 ~ ~1 0 O -- _ O O
~0 U) O ~ ~rl 0~ ~1 ~D 0 U~
N ~,--I,~ . .. ..
O ~ N ~ N
~ ^
u~ o o wo a~ o ^~ d1 ~ Ll~ O
N CO U') CS~ D 00 ll~ t~ C~
o ~f) ~1~) vl C~ N N
O
~n o r~
N N `I O ~ ~D I I ~ .
O
rl N
-- ~ N U
N O ~I tn O V ~ I~
o U ~ ~ ~ ~ U ~ f . O I -1 .~ f ~1 4~ 0 ~) r-l f,) fd f ~fd O ~ X ~ O U~
~) O Ul -1 fl~ ~ O .~rl -rl r-l ~ r~
d t~ ~ r-l ~i ~ al ~ a) ~ q) h U~ rl t:i~ O ` ~ (a rl h r-l X ~~
.~1fd a) ~ ) r~ rf ~l,f~ ~rl fl~
~Q U a) O ~ ~ ~a ~f I ~fn ,f Q, ~ f~, f~~ o ,~ f~ .~ u o ~ ~ f~ fJl ~ o ~ ~ f~ fn f~ ,~
O h O ~C ~1 f~ fCI rl N ~1 ~ I td a~ f~-- o f~ > 1-l E~ il ,f~ ~, 29, 645-F -24~--~5-Copolymers from Examples 2 and 5, and Compara-tive Runs A and B of Table I are tested for optical properties and the results are recorded in Table A.
These properties were measured using molded films having a thickness of 0.43 mm.
TABLE A
Examples and Comparative Runs 2 5 A B
Yellowness Index 1.5 2.3 5.8 1.7 Transmission, % 86.3 85.1 75.5 86.8 Haze, % 12.7 14.0 101.0 14.3 Example 9 and Comparative Runs E and F
In step 1 of a 2-step concurrent addition process, a 12-liter flask was charged with 716.60 grams (3.139 moles) of bisphenol-A/ 7.40 liters of methylene chloride and 645.6 grams (8.161 moles) of pyridine.
Stirring was be~un and when a clear solution of bisphenol-A was obtained, 77.6 grams (0.784 mole) of phosgene and a solution of 424.85 grams (2.093 moles~
of tereph-thaloyl chloride dissolved in 0.60 liter of methylene chloride were added continuously to the reaction vessel over a period of 39 minutes while con-tinuousl~y stirring the contents of the flask at a temperature betwee~ 22 and 26C and 200 rpm.
In step 2, the aforementioned reaction mixture was stirred for 10 minutes ~ollowing phosgene and terephthaloyl chloride addition, then 15.71 grams 29,645-F -25 -26~
(0.105 mole) of t-butylphenol was added. The resulting solution was stirred at 200 rpm and 42.0 grams (0.425 mole) of phosgene were added over a period of 28 minutes while maintaining the reaction mixture at a temperature between 24 and 25C.
The resulting ordered ester/carbonate copoly-mer was recovered from the reaction mixture by the general procedure of Example 1, analyzed, and determined to have a structure similar to that of the copolymer of Example 1. This copolymer (Example 9) was injection molded using a Newbury H1 30RS machine and the following molding conditions: barrel zone - 329C, noæzle - 338C, mold halves - 121C, injection time - lO seconds, cycle time - 40 seconds, feed setting - 2.5, and single stage injection mode. The physical and optical properties for the injection molded specimens having a 3.2 mm thickness are shown in Table II.
For the purpose of comparison, Comparative Runs E and F were prepared using a conventional proce-dure similar to the foregoing pracedure except that itwas a standard 2-stage process wherein phosgene was added only in the second step (post-phosgenation). The resulting copolymers were similarly injection molded and tested for physical and optical properties. The results are shown in Table II. The copolymer from Comparative Run E was not soluble in methylene chloride.
Its inherenk viscosity was not measured.
29,645-F -26-l~
~27-_BLE II
Example and Com~arative Runs 9 E F
c _ . _ Process Type CA S2S S2S
Mole % of Theoretical Amount of COC12 in First Stage 75 0 0 DPC, g/l in CH2Cl2 127 127 80 TBP mole % 10 8 9 0 ~ inh' dl/g 0.565 _ O.551 Vicat , C 215 196 214 Izod Impact, notched ft-lb/in, 5.20 0.67 5.05 (J/m) (277) ~36) (269) Tensile at Yield psi 8724 a864 8702 (MPa) (60.15)(61.12)(60.00) Elongation, %
at Yield 9.46 8.75 9.55 at Break 30.9 13.0 21.2 Tensile Mo~ulus, psi x lO 2.79 2.92 2.74 (GPa) (1-92) (2.01) (1-89) 25 Yellowness Index33.8 13.3 32.1 Transmission % 84.0 78.6 83.4 Haze % 2.6 18.2 2.2 Mole ~O ester 80.0 77.0 79.3 29,645-F -27~
As evidenced by the data in Tables I, A and II, copolymers prepared by the pre-phosgenation and concurrent addition processes (Examples 1-9) have improved properties including better solubility, higher notched Izod impact strength, -tensile strength, percent transmission, elongation and ester/carbonate ratios closer to theoretical compared to the same pol~mers prepared at e~uivalent designed polymer concentrations ~DPC) using the standard 2-stage (post-phosgenation) process (Comparative Runs A and E~. The data of Tables I, A and II also show that the copolymers pre-pared in the practice of this invention (Examples 1-9) have equivalent or better properties compared to the copolymers prepared by the post-phosgenation process using lower designed polymer concentrations (Comparative Runs B-D and F).
29,645 F -28-
Also included among the suitable dihydric phenols are those having an ar,ar'-dihydroxytrityl nucleus represented by the formula:
Ho~ C-@-oE~
wherein the aromatic rings beax, in addition to the hydroxy substituents, such substituents as, for example, H, F, Cl, Br, I, -NO2, -O-, alkyl, acyl, carboxylate ester, and sulfonate ester. Representative diols containing the ar,ar'-dihydroxytrityl nucleus include phenolphthalein nucleus compounds as described in U.S.
Patent No. 3,036,036; phenolsulfonephthalein nucleus compounds described in U.S. Patent No. 3,036,037;
phthalidene nucleus compounds as described in U.S.
Patent No. 3,036,038; fluorescein nucleus compounds as described in U.S. Patent No. 3,036,039 and phenol-phthalimidene nucleus compounds corresponding to the phenolphthalein nucleus compounds described in U.S.
Patent No. 3,036,036. Of the aforementioned dihydric phenols, the bis(ar-hydrox~phenyl~alkylidenes, particu-larly bisphenol-A, are most preferred.
29,645-F -6-The diacid halides that are suitably employed include both the acid halides of the aromatic and the saturated aliphatic dibaslc acids. The saturated aliphatic dibasic acids which can be employed are derived from straight chain paraffin hydrocarbons such as oxalic, malonic, dimethyl malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acid as well as the halogen substituted aliphatic dibasic acids. The aliphatic carboxylic acids containing heteroatoms in their aliphatic chain, such as thio-diglycollic or diglysollic acid can also be used as well as unsaturated diacids such as maleic or fumaric.
Examples of aromatic and aliphatic aromatic dicarboxylic acids which can be employed in their acid chloride form are phthalic, isophthalic, terephthalic, homophthalic, ortho-, meta- and para-phenylenediacetic acidi the polynuclear aromatic acids such as diphenic acid, 1,4-naphthalic acïd and 2,6-naphthalic acid. Of the foregoing diacid halides, prefexred are isophthaloyl chloride, terephthaloyl chloride, as well as mixtures thereof, with the mixtures being most preferred.
The carbonate precursor employed is suitably a carbonyl dihalide, a carbonate ester, a haloformate or other compound which will suitably react with terminal hydroxyl groups to form carbonate linkages. The carbonyl halides which may be employed are carbonyl bromide, carbonyl chloride (phosgene) and mixtures thereof.
Suitable caxbonate esters are diphenyl carbonate, di(halophenyl)carbonates such as, ~or example, di(chlorophenyl)carbonate, di-(bromophenyl)carbonate, di-(tri-chlorophenyl)carbonate, and di-(tri-bromophenyl)-carbonate; di-(alkylphenyl)carbonate such as di-(tolyl)-carbonate; di-(naphthyl)carbonate, di-(chloronaphthyl)-carbonate, phenyltolyl carbonate, chlorophenyl 29,64S-F
chloronaphthyl carbonate and mixtures thereof. Suitable haloformates include bishaloformates of dihydric phenols such as bischloroformates of hydroquinone or glycols such as, for example, bishaloformates of ethylene S glycol, neopentyl glycol, and polyethylene glycol. Of the foregolng carbonate precursors, phosgene is preferred.
The process of this invention is practiced in a manner such that a portion of the carbonate moieties are formed simultaneous with or before the formation of ester moieties in the intermediate oligomer. By achiev-ing this early carbonation in the in-termediate oligomer, undesirable precipitation of the oligomer from the liquid reaction mixture is minimized.
The process of this invention is normally carried out under an inert atmosphere such as nitrogen with the reactants dissolv~d in one or more solvents such that the reactants are totally miscible. While the concentration of the reactants in the solvents is not particularly critical, the conce~tration of the dihydric organic compound is preferably from 2 to 10 weight percent, and the concentration of the diacid chloride is preferably from 1 to 5 weight percent based on the total weight of the reaction mixture. As a result of practicing the present invention, the concen-tration of the ester/carbonate intermediate oligomer can be greater than the concentrations of the ester intermediate oligomer which are normally employed in conventional procedures. Accordingly, such concentra-tion of the ester/carbonate intermediate oligomer is inthe range from 3 to 15, most preferably from 5 to 12, weight percent based on the total weight of the reac-29,645-F -8-_9 tion mixture. It is preferreA that the solutions of the various reactants be totally miscible in each other. However, it is sufficient if such solutions are partially miscible, i.e., at least 10 weight percent.
Examples of suitable solvents for the reac tion mixture include chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, sym-tetrachloro-ethane, 1,1,2-trichloroethane and cis-1,2-dichloro-ethylene. Other solvents normally employed in the preparation of ester/carbonate copolymers may also be suitably employed.
The molar ratio of dihydric organic compound to diacid chloride varies proportionately with the ester:carbonate ratio desired in the ester/carbonate copolymer. The molar ratio of dihydric compound to diacid chloride is advantageously from 21:1 to 1.1:1, preferably from 21:1 to 1.3:1. The molar ra-tio of carbonate precursor to total moles of dihydric compound and diacid halide is advantageously from 0.05:1 to 0.91:1, preferably from 0.13:1 to 0.91:1.
In addition to the foregoing components, the process of the present invention is also carried out in the presence of a hydrogen chloride acceptor. Examples of such acceptors include pyridine, triethyl amine, N,N-trimethyl aniline and N,N-trimethylcyclohexyl amine, with pyridine being preferred. Such acceptors are advantageously employed in amounts sufficient to complex the hydrogen chloride liberated in the reaction and to catalyze both the ~orrnation o~ ester linkages and carbonate linkages. Since higher concentrations of acceptor produce higher molecular weight copolymers, 29,645-F -9-the concentration of acceptor employed will vary depend-ing on the molecular weight desired. Preferably, in order to prepare copolymers having weight average molecular weights ~Mw) from 25,000 to 60,000, the acceptor is employed in amounts from 100 to 160 mole percent based on moles of hydroxyl moiety in the monomers, more preferably from 120 to 140 mole percent.
Pre~Phos~enation Embodiment In one embodiment of this invention (the pre-phosgenation process), the dihydric organic compound and the carbonate precursor are combined in the first stage in any manner, preferably by bubbling phosgene or adding another suitable carbonate precursor with stirring into a solution of the dihydric organic compound and hydrogen chloride acceptor. The molecular weight of the resultant carbonate intermediate oligomer is advanta-geously controlled by maintaining the mole ratio of the carbonate precursor to dihydric organic compound at less than 1:1 in the first stage. Preferably, the ratio of the carbonate precursor to dihydric organic compound in the first stage is from 0.09:1 to 0.95:1, more preferably from 0.09:1 to 0.5:1. Although not critical, the reaction temperature of this stage is preferably maintained in the range from 10 to 35C, more preferably from 15 to 30C, and the reaction pressure is normally maintained at atmospheric to superatmospheric as a matter of convenience. The hydrogen chloride acceptor is generally employed in an amount sufficient to take up whatever hydrogen chloride is genera-ted ln this stage, preferably from l.0 to 1.6, more preferably from 1.2 to 1.4, moles of acceptor per mole of carbonate precursor. While -the carbonate intermediate oligomer may be recovered and puriied 29,645 F -lO-before continuing the pre-phosgenation process, it is generally not desirable to do so.
In the second stage of the pre phosgenation process, the aforementioned reactioIl m1xture containlng a carbonate intermediate oligomer is converted to an ester/carbonate intermediate oligomer having terminal hydroxy groups by combining a diacid halide with the reaction mixture in any manner, preferably by addlng the diacid chloride either neat or dissolved in a suitable solvent with stirring to the reaction mixture which contains sufficient hydrogen chloride acceptor to absorb hydrogen chloride of reaction. Similar to the first stage, the reaction temperature and pressure are not critical. Preferably, however, the reaction tempera-ture is mainkained in the range from lQ to 35C, morepreferably from 15 to 25C and the reaction pressure is atmospheric to superatmospheric. Advantageously, the amount of diacid chloride added to the reaction mixture is one which i5 sufficient to provide a molar ratio of ester moiety to carbonate moiety in the inter~
mediate oligomer in the range from 0.1:1 -to 20:1, more preferably from 4:1 to 20:1.
Finally, the ester/carbonate copolymer inter-mediate oligomer from the foregoing second stage is converted in the third stage of the pre-phosgenation process to the desired ordered ester/carbonate copoly-mer by bubbling phosgene or adding similar carbonate precuxsor into the reaction mixture. Advantageously, the reaction mixture contains an amount of monohydr:ic phenol or other suitable Ghain terminator to effec-t the desired control of molecular weight of the ordered ester/carbonake copolymer. While the amount of the 29,645-F
~L~ D4~
chain terminator employed varies with the efficacy of the terminator, the molecular weight desired and the final ester/carbonate ra-tio, beneficial amounts of chain terminator are normally in the range from 1 to 15 mole percent based on the mole5 of dihydric organic compound less moles of the diacid halide, preferably from 2 to 12 mole percent. As in the previous two s-tages, reaction temperature and pressure are not critical. However, the reaction temperature is prefer-ably in the range from 10 to 35C, most preferablyfrom 15 to 25C and the reaction pressure is preferably in the range from atmospheric to superatmospheric. In all three stages of the foregoing embodiment, the reaction mixtures are agitated sufficiently to effec-t intimate contact of the reactants and desirable heat transfer throughout the reaction medium. Following completion of the third stage of the embodiment, the desired ordered ester/carbonate copolymer is readily recovered from the reaction medium by conventional techniques as exemplified in the examples set forth hereinafter.
Concurrent Addition Embodiment In the first stage of this embodiment, the diacid halide and phosgene or other carbonate precursor are combined with the dihydric organic compound by continuously adding the diacid halide and carbonate precursor either neat or dissolved in a suitable solvent to a solution of the dihydric oryanic compound and a hydrogen chloride acceptor. While reaction temperature and reaction pressure are not critical for this stage of the con-add embodiment, the reaction -temperature is preferably maintained in -the range from 10 to 35C, most preferably from 15 to 25C and reaction pressure 29,645-F -12-is maintained at atmospheric to superatmospheric pressure as a matter of convenience. The amount of diacid halide added to the reaction mixture is that which produces the desired ester content in the copolymer.
Examples of such suitable amounts are described herein-before. The amount of carbonate precursor added in this stage is advantageously such that the mole ratio of carbonate precursor to dihydric organic compound is less than 1:1, preferably from 0.09:1 to 0.95:1. As stated before, the diacid chloride and the carbonate precursor are added continuously to the reaction mixture containing the dihydric organic compound. While the rates of addition of the components are not particularly critical, it is generally desirable -to add enough carbonate precursor early in the reaction in order to minimize the undesired precipitation that can occur ~hen the resulting ester/carbonate intermediate oligomer contains essentially all ester linkages and no carbonate linkages. Preferably, sufficient carbonate precursor is added to provide at least 50 mole percent of the theoretical carbonate moieties in the ester/carbonate copol~mer intermediate, most preferably from 75 to 95 mole percent. Advantageously, the carbonate precursor and diacid halide are added continuously at rates sufficient to provide the desired copolymer and will vary with reactor size and cooling capacity and the like.
While the ester/carbonate intermediate oligomer may be recovered and purified before proceeding to the second stage of this con-add process, it is generally not desir-able to do so.
In the second stage of the con-add process, the aforementioned reaction mixture containing the ester/carbonate oligomer is converted to the desired 29,645-F -13-mixed copolymer by bubbling phosgene or adding other suitable car~onate precursor into the reaction mixture.
Advantageously, the reaction mixture contains an amount of monohydric phenol or other suitable chain terminator to effect the desired control of molecular weight as is employed in the pre~phosgenation process. Although not critical, the reaction temperature of this stage is preferably maintained in the range from 10 to 35C, more preferably from 15 to 25C, and the reaction pressure is advantageously from atmospheric to super-atmospheric, with atmospheric being preferred. As in the pre-phosgenation process, the reaction mixture in the con-add process is agitated sufficiently to effect intimate contact of the reactants and to provide heat transfer throughout the reaction medium. The resulting ordered ester/carbonate copolymer is readily recovered by conventional techniques as shown in the following examples.
The ordered ester/carbonate copolymers produced in the preferred practices of this invention are advantageously represented by the formula:
o o o _.. " " " ~
Y - -~ROC-R1C0~xROCO In Z
wherein Y and Z are independently terminating groups common to polyesters or polycarbonates; each R is independently a divalent or~anic moiety derived from the dihydric organic compound as defined hereinbefore, especially aroma~ic hydrocarbylene or inertly substi-tuted aromatic hydrocarbylene; each R~ is a divalentorganic radical derived from a diacid halide as described hereinbefore, especially phenylene or other 29,645-F -14-divalent aromatic moiety; x is a number from 0.05 to 10 and n is a whole number from 5 to 300. Using the aforementioned formula, the ester/carbonate mole ratio in the copol~mer is de~ined by 2x/1. The process of this invention is particularly efective in the prepara-tion of ester/carbonate copolymers having (1) relatively high ester/carbonate mole ratios, e.g., wherein x is from 1 -to 10 in the foregoing structural formula, and (2) relatively high concentration of one ester, e.g., from 70 to 100 percent of terephthalate or isophthalate based on total ester.
In the foregoing formula, R1 is pxeferably para-phenylene, meta-phenylene or a combination of para-phenylene and meta-phenylene such that the molar ra-tio of para-phenylene to meta-phenylene is from 0.95:0.05 to 0.05:0.95, preferably from 0.95:0.05 to 0.2:0.8, most preferably from 0.9:0.1 to 0.5:0.5.
Illustratively, Y is O O O O O O O
~ ,~ ,. ....... .. .. .. .. ..
-OH, R2OCO~-, HOCR1CO~, R2OCR1CO- or HOROCR1CO-wherein R2 is hydrocarbyl such as alkyl, aryl or aralkyl;
and R and Rl are as defined herei~before. Representa-tive Z includes R2~ and HOR-wherein R2 and R are as defined hereinbefore.
More preferred are those copolymers represented by the formula:
29,645-F -15-O O o , Y _ (ROC-R1CO~xROCo n Z
wherein Y is -OH or ,, Z is R2 or -ROH; x is 0.05 to 10, preferably 0.05 to 3, and R, Rl, R2 and n are as defined hereinbefore.
Most preferred copol~mers are those represented by the foregoinc3 formula wherein R is ~ CH3 ~ CH
Y is ~oCOR2 i I-Z is -R2; R2 is hydrocarbyl, e.g., alkyl, aryl, alkaryl, cycloalkyl or aralkyl; x i5 1 to 3; and n is a whole number from 5 to 300, preferably from 10 to 200 and most preferably ~rom 30 to 100. For purposes of this invention, hydrocarbyl is a monovalent hydrocarbon radical.
While the molecular weight o~ khe copolymers is not particulaxly critical, those having weight average rnolec:ular weight ~Mw, determined by gel permea-tion chromatography using a bisphenol-A polycarbona-te 29,645-F -16-calibration curve) greater than 20,000 are of more significance. The copolymers of relatively high mole-cular weighk, e.g., those having an Mw of at leas-t 25,000 up -to and including those having an Mw of 60,000, are found to exhibi-t the properties and physical charac-texistics most desirable of molding resins. Most preferred for this purpose are those copol~mers having an Mw in the range from 25,000 to 40,000 and Mw/Mn (wher~in Mn is number average molecular weight) from 1.5 to 5. Preferred copolymers have inherent viscosi~
ties (~ inh) measured in methylene chloride at 0.5 grams/deciliter and 25C in the range from 0.35 to 1 deciliter/gram (dl/g), most preferably from 0.45 to 0.70 dl/g.
The following examples are given to illustrate the invention and should not be construed as limiting its scope. Unless otherwise indicated, all parts and percentages are by weight.
Examples 1, 2, and 3 and Comparative Runs A, B, C and D
~0 In step 1 of a three-step pre-phosgenation (PP) process, a 5-liter flask was charged with 268.73 grams ~1.177 moles) of bisphenol-A, 3.00 liters of methylene chloride and 242.1 grams (3.061 moles) of pyridine. Stirring began and when a clear solution of bisphenol~A was obtained, 38.8 grams (0.392 mole) of phosgene was added over a period of 20 minutes by bubbling the phosgene into the bisphenol-A solution a-t a temperature bet~een 23 and 25C while continuously stirring the corltents o~ the flask at 200 rpm.
In step 2., the aforementionec~ reaction mixture containing the dihydric carbonate intermediate oligomer 29,645-F -17-was combined with 159.32 grams (O.785 mole) of tereph-thaloyl chloride while the reaction mixture was main-tained at a temperature of 24C and continuously stirred at 200 rpm. This addition of diacid chloride occurred by a continuous addition over a period of 3 minutes after which time, the temperatuxe of the reaction mixture rose to 33C. The reaction mixture was then s~irred for an additional 5 minutes and 4.71 grams (0.031 mole) of t-butyl phenol (TBP) was added to the reaction mixture.
In step 3, the aforementioned reaction mixture containing a dihydric ester/carbonate intermediate oligomer was combined with 6.0 grams (O.061 mole) o~
phosgene by bubbling the phosgene into the reaction _15 mixture at a rate of 1 gram per minute over a period of 6 minutes while maintaining the reaction mixture at a temperature between 22 and 24C and stirring the mixture at 200 rpm.
The resulting ordered ester/carbonate copoly-mer was recove~ed from the reaction mixture by the following procedure:
0.5 liter of 3N HCl was added to neutralize excess pyridine. Following phase separation, the methylene chloride solution of copol~mer was washed consecutively with 0.5 liter of 0.5N HCl and 0.5 liter of water, with phase separation after each washing.
Following the final washing, the methylene chloride solution of copolymer was passed through a column packed with a cation exchange resin (sulfonic acid type, dead volume hetween 500 and 600 milliliters), giving a clear, almost water--white solution. The polymeric product was 29,645-F -18-~19--isolated by the slow addition of 1 volume of methylene chloride solution to 4 volumes of hexane with rapid stirring. The resulting white fibers were isolated by filtration, dried in air for 24 hou.rs and then dried in vacuo for 48 hours at 120C to yield 354.1 grams (92.9 percent of theory) of copolymer having an inherent viscosity of 0.551 deciliter per gram ~measured in methylene chloride at 25C, 0.5 gram per deciliter).
Analysis of the copolymer by IR and NMR analysis indi-cated that it was an ordered ester/carbonate copolymerrepresented by the structural formula:
~ O ~ ~ 3 CH3 ~ CH3 ~ \ ~ ~ " ~
OC0 ~ ~ -C~3 CH3 n CH3 The copolymer repeating unit had an ester/carbonate molar ratlo of 4:1.
This copolymer (Example 1) was compression molded at 300C using a compression molding press sold by Pasadena Hydraulics Inc. The physical properties fOL the compression molded specimens (0.32 cm thickness) are shown in Table I. Examples 2 and 3 were carried out in accordance with the foregoing procedure of Example 1 except that different amounts of phosgene 29,645~F -19-were added in the first stage of the process as indicated in Table I. The resulting copolymers were similarly compression molded and tested and the results are recorded in Table I.
S For Comparison Runs A-D, several copolymers were prepared using a conventional procedure similar to the foregoing procedure except that it was a standard 2-stage ~S2S) process wherein phosgene was added only in the second stage (so-called post~phosgenation process).
The resulting copolymers were similarly compression molded and tested for physical properties and the results are shown in Table I. The copolymer of Compara-tive Run A was not soluble in methylene chloride. Its inherent viscosity was not measured.
Examples 4, 5, 6, 7 and 8 In step 1 of a 2-step concurren-t addition ~CA~ process, a 5-litex flask was charged with 268.73 grams (1.177 moles) of bisphenol-A, 2.70 liters of methylene chloride and 242.1 grams (3.061 moles) of pyridine. Stirriny was begun and when a clear solution of bisphenol-A was obtained, 38.8 grams ~0.392 mole) of phosgene and a solution of 159.32 grams (0.785 mole) of terephthaloyl chloride dissolved in 0.30 liter of methylene chloride were added continuously to -the reactlon vessel over a period of 20 minutes while continuously stirring the contents of the flask at a -temperature between 21 and 25C and 200 rpm. The tereph~haloyl chloride was added ~o the reaction mixture via a liquid addition funnel and the phosgene was added by bubbling it into the liquid reaction mixture.
29,645-F -20-In step 2, the aforementloned reaction mixture containing the ester/carbonate intermediate oligomer was combined with 4.71 grams (O.031 mole) of t-bu-tyl phenol. The resulting solution was stirred at lO0 rpm and 8 grams (0.081 mole) of phosgene were added over a period of 6 minutes.
The resulting ordered ester/carbonate copoly-mer was recovered from the reaction mixture by the procedure of Example 1, analyzed and determined to have a structure similar to that of the ester/carbonate copolymer of Sample No. 1 in Example l. This copolymer ~Example 4) was compression molded and tested as in Example l and the results are recorded in Table I.
For Examples 5, 6, 7 and 8 copolymers were similarly prepared by the concurrent addition process except that the amount of phosgene added in the first stage of the process was varied as indicated in Table I.
The resulting copolymers were similarly compression molded and tested for physical properties and the results of these tests are reported in Table I.
In E~ample 5, the t-butyl phenol was added prior to the addition of phosgene and terephthaloyl chloride.
In Table I, the mole percen-t of the theore-ti-cal amount of phosgene added in the first stage of thepre-phosyenation process or the concurrently-added process is calculated from the theoretical moles of phosgene being equal to the moles of bisphenol-A minus the moles of terephthaloyl chloride. The abbreviation DPC stand for designed polymer concentration, w:hich is 29,645-F -21-defined as -the theoretical grams of polymer excluding terminator per liter of methylene chloride. The mole percent p-tertiary butyl phenol (TBP) is based on the moles of bisphenol-A minus the moles of terephthaloyl chloride. In Example 5, the p-tertiary butyl phenol was added prior -to the addition of phosgene and terephthaloyl chloride. It should be noted that in Examples 3 and 10, a slight haze due to an insoluble fraction was observed. The copolymer of Comparative Run A was not soluble in methylene chloride. Its inherent viscosity was not measured. It was also observed that the copolymer of Comparative Run A did not yield in the tensile and elongation tests. The tensile at break was 6877 psi (47.42 MPa).
Vicat softening point was measured according to ASTM D-1525. Izod impact was measured according to ASTM D-256. Tensile at yield and elongation at yield and break were measured according to ASTM D-638. Mole percent ester is defined as (moles of estex divided by moles of ester plus moles of carbonate) multiplied by 100. The moles of ester and moles of carbonate were determined by nuclear magnetic resonance spectroscopy.
The theoretical mole percent ester for all ~xamples and Comparative Runs is 80Ø Yellowness index was measuxed according to ASTM D-1925. Transmission and haze were measured according to ASTM D-1003.
29,645-F' 22-o l` d1 ~
~: O ~ 0~0 ~r~--1` ~i ~0~ ~ O
~ U Ir~ N 1~') N~ ~
0 (~ ~ ~('\1 r~l O
O N ~ (~
O LnO ^L~ r-l~ Ln ~, Ul ~ t:J~ N ON '~ Lr) 10 N U) r~ C~ ) N
~1 ~ ~ N ~) ~ ~ / N
o ~
o o O ~ ~~1 0N ~ ~(S` O (`~
t~ ~ N 1~) N~ ~`~ O
~ (~ ~ N N a~
o ~
-1~ ~-- ~-- N ~D O
fS o ~ co~ ~o ooo d~
u~ ~ O
rl ~ ~ 10 N rl ~ \ N ~1 o ~ ) N~ t`
-~ O ~` ~ao ot~
d~ U O N ~)N ~ O
H ~1 ~I ' d' ~1 ~ ' 00 ~ N ~1 OC~
O ~-0 ~ ~1 ~
~ ~ t~ ~ ~O "~
O ~ ~N 1~)N 0 ~ CO 00 CS~
I~') N ~O ,1 . ~ ~ 11 ~ . . . .
~1 ~ N~ NO ~ N ~1 o ~
O L/) O
~ L'l --` ~ N t` t` ~ ~
r-l ~N ~ ~1 ~ ~ ~1 -- [`
~1 ~
p~ O ~`oD In ~ ~ ^ -- ~ ~ ~ o dl r~t Pl C~N L0 ~ ~1 ~
~) ~ N O
O t`~
-~).,1 ,-1 (.
N 0 ~1 U~
O r~
u ~rl ~ ~
~ O ~ 1 h ~ ~ ~ t,~ OI
Zi ~ ~ ~ ~ ` r~ O (d ~ ~ O '~ ~ , O U~
O O U~r~ ~-rl r~l ~1 11~ 1 a.
V? ;~ ~ lO ~ H q ~ r~ d rl ~1 ~1 ~C ~
~ a) G ~n e ~ ~ ,~ e .r~ ~ tn~ m ,~ ~
.) ~ rl P~ r-l p I O
td o --~ O-rl ~.) p~ r~ O O ~ ~ ~ O ~ ~ ~ 7 r--l ~ ~1 0 q t~ P~ !q rl N ~1-- O ~ -- O
t~l ~ r~ 1 c ~> ~ E~
29, 645-F -23-2~
~4--O o ~ ~ o u~
CS~ U-! ~ O ~O~ ~ ~ ~D O ~
N r~ 0 ~ O
o ~ ~o:) o~ r~
~ ~ ~1 ~ ~1 0 O -- _ O O
~0 U) O ~ ~rl 0~ ~1 ~D 0 U~
N ~,--I,~ . .. ..
O ~ N ~ N
~ ^
u~ o o wo a~ o ^~ d1 ~ Ll~ O
N CO U') CS~ D 00 ll~ t~ C~
o ~f) ~1~) vl C~ N N
O
~n o r~
N N `I O ~ ~D I I ~ .
O
rl N
-- ~ N U
N O ~I tn O V ~ I~
o U ~ ~ ~ ~ U ~ f . O I -1 .~ f ~1 4~ 0 ~) r-l f,) fd f ~fd O ~ X ~ O U~
~) O Ul -1 fl~ ~ O .~rl -rl r-l ~ r~
d t~ ~ r-l ~i ~ al ~ a) ~ q) h U~ rl t:i~ O ` ~ (a rl h r-l X ~~
.~1fd a) ~ ) r~ rf ~l,f~ ~rl fl~
~Q U a) O ~ ~ ~a ~f I ~fn ,f Q, ~ f~, f~~ o ,~ f~ .~ u o ~ ~ f~ fJl ~ o ~ ~ f~ fn f~ ,~
O h O ~C ~1 f~ fCI rl N ~1 ~ I td a~ f~-- o f~ > 1-l E~ il ,f~ ~, 29, 645-F -24~--~5-Copolymers from Examples 2 and 5, and Compara-tive Runs A and B of Table I are tested for optical properties and the results are recorded in Table A.
These properties were measured using molded films having a thickness of 0.43 mm.
TABLE A
Examples and Comparative Runs 2 5 A B
Yellowness Index 1.5 2.3 5.8 1.7 Transmission, % 86.3 85.1 75.5 86.8 Haze, % 12.7 14.0 101.0 14.3 Example 9 and Comparative Runs E and F
In step 1 of a 2-step concurrent addition process, a 12-liter flask was charged with 716.60 grams (3.139 moles) of bisphenol-A/ 7.40 liters of methylene chloride and 645.6 grams (8.161 moles) of pyridine.
Stirring was be~un and when a clear solution of bisphenol-A was obtained, 77.6 grams (0.784 mole) of phosgene and a solution of 424.85 grams (2.093 moles~
of tereph-thaloyl chloride dissolved in 0.60 liter of methylene chloride were added continuously to the reaction vessel over a period of 39 minutes while con-tinuousl~y stirring the contents of the flask at a temperature betwee~ 22 and 26C and 200 rpm.
In step 2, the aforementioned reaction mixture was stirred for 10 minutes ~ollowing phosgene and terephthaloyl chloride addition, then 15.71 grams 29,645-F -25 -26~
(0.105 mole) of t-butylphenol was added. The resulting solution was stirred at 200 rpm and 42.0 grams (0.425 mole) of phosgene were added over a period of 28 minutes while maintaining the reaction mixture at a temperature between 24 and 25C.
The resulting ordered ester/carbonate copoly-mer was recovered from the reaction mixture by the general procedure of Example 1, analyzed, and determined to have a structure similar to that of the copolymer of Example 1. This copolymer (Example 9) was injection molded using a Newbury H1 30RS machine and the following molding conditions: barrel zone - 329C, noæzle - 338C, mold halves - 121C, injection time - lO seconds, cycle time - 40 seconds, feed setting - 2.5, and single stage injection mode. The physical and optical properties for the injection molded specimens having a 3.2 mm thickness are shown in Table II.
For the purpose of comparison, Comparative Runs E and F were prepared using a conventional proce-dure similar to the foregoing pracedure except that itwas a standard 2-stage process wherein phosgene was added only in the second step (post-phosgenation). The resulting copolymers were similarly injection molded and tested for physical and optical properties. The results are shown in Table II. The copolymer from Comparative Run E was not soluble in methylene chloride.
Its inherenk viscosity was not measured.
29,645-F -26-l~
~27-_BLE II
Example and Com~arative Runs 9 E F
c _ . _ Process Type CA S2S S2S
Mole % of Theoretical Amount of COC12 in First Stage 75 0 0 DPC, g/l in CH2Cl2 127 127 80 TBP mole % 10 8 9 0 ~ inh' dl/g 0.565 _ O.551 Vicat , C 215 196 214 Izod Impact, notched ft-lb/in, 5.20 0.67 5.05 (J/m) (277) ~36) (269) Tensile at Yield psi 8724 a864 8702 (MPa) (60.15)(61.12)(60.00) Elongation, %
at Yield 9.46 8.75 9.55 at Break 30.9 13.0 21.2 Tensile Mo~ulus, psi x lO 2.79 2.92 2.74 (GPa) (1-92) (2.01) (1-89) 25 Yellowness Index33.8 13.3 32.1 Transmission % 84.0 78.6 83.4 Haze % 2.6 18.2 2.2 Mole ~O ester 80.0 77.0 79.3 29,645-F -27~
As evidenced by the data in Tables I, A and II, copolymers prepared by the pre-phosgenation and concurrent addition processes (Examples 1-9) have improved properties including better solubility, higher notched Izod impact strength, -tensile strength, percent transmission, elongation and ester/carbonate ratios closer to theoretical compared to the same pol~mers prepared at e~uivalent designed polymer concentrations ~DPC) using the standard 2-stage (post-phosgenation) process (Comparative Runs A and E~. The data of Tables I, A and II also show that the copolymers pre-pared in the practice of this invention (Examples 1-9) have equivalent or better properties compared to the copolymers prepared by the post-phosgenation process using lower designed polymer concentrations (Comparative Runs B-D and F).
29,645 F -28-
Claims (10)
1. A process for making ordered ester/-carbonate copolymers characterized by comprising the steps of (1) contacting in an organic liquid medium a dihydric organic compound with a carbonate precursor and a diacid halide under conditions such that the carbonate moieties in the resultant intermediate oligomer are formed simultaneously with or before the formation of ester moieties and (2) contacting this oligomer with additional carbonate precursor under conditions sufficient to form the desired ordered ester/carbonate copolymer.
2. The process of Claim 1 characterized in that the amount of carbonate formed in the oligomer is sufficient to essentially prevent precipitation of the oligomer from the organic medium.
3. The process of Claim 2 characterized in that the amount of carbonate moiety formed in the oligomer is at least 50 mole percent of the total carbonate moiety of the ordered ester/carbonate copolymer.
4. The process of Claim 2 characterized in that the amount of carbonate moiety formed in the oligomer is from 75 to 95 mole percent of the total carbonate moiety of the ordered ester/carbonate copolymer.
5. The process of Claim 2, ? charac-terized by comprising the steps of (1) contacting in an organic liquid medium a dihydric organic compound with a carbonate precursor under conditions sufficient to form a dihydric carbonate, (2) contacting the dihydric carbonate with a diacid halide under conditions suffi-cient to form an ester/carbonate oligomer and (3) con-tacting the oligomer with a carbonate precursor under conditions sufficient to form an ordered ester/carbonate copolymer.
6. The process of Claim 5 characterized in that the dihydric organic compound is a dihydric phenol, the diacid halide is terephthaloyl halide, isophthaloyl halide or mixture thereof, and the carbonate precursor is phosgene.
7. The process of Claim 2, ? charac-terized by comprising the steps of (1) concurrently contacting in an organic liquid medium a dihydric organic compound with a carbonate precursor and a diacid halide under conditions sufficient to form an ester/carbonate oligomer and (2) contacting the oligomer with additional carbonate precursor under conditions sufficient to form an ordered ester/carbonate copolymer.
8. The process of Claim 7 characterized in that the dihydric organic compound is a dihydric phenol, the diacid halide is terephthaloyl halide, isophthaloyl halide or mixture thereof, and the carbonate precursor is phosgene.
9. The process of Claim 1, charac-terized in that the mole ratio of ester to carbonate in the resulting ordered ester/carbonate copolymer is from 0.1:1 to 20:1.
10. The process of Claim 9 characterized in that said ester:carbonate ratio is from 2:1 to 20:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/378,693 US4388455A (en) | 1982-05-17 | 1982-05-17 | Process for preparing ester carbonate copolymers |
| US378,693 | 1982-05-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1198248A true CA1198248A (en) | 1985-12-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000427726A Expired CA1198248A (en) | 1982-05-17 | 1983-05-09 | Process for preparing ester carbonate copolymers |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4388455A (en) |
| EP (1) | EP0094585B1 (en) |
| JP (1) | JPS58217519A (en) |
| KR (1) | KR860000593B1 (en) |
| AT (1) | ATE20594T1 (en) |
| AU (1) | AU561019B2 (en) |
| CA (1) | CA1198248A (en) |
| DE (1) | DE3364368D1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4465820A (en) * | 1983-06-03 | 1984-08-14 | General Electric Company | Copolyestercarbonates |
| US4487896A (en) * | 1983-09-02 | 1984-12-11 | General Electric Company | Copolyester-carbonate compositions exhibiting improved processability |
| DE3346945A1 (en) * | 1983-12-24 | 1985-07-04 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING AROMATIC POLYESTER CARBONATES |
| US4506065A (en) * | 1984-01-03 | 1985-03-19 | General Electric Company | Copolyestercarbonates |
| US4684678A (en) * | 1985-05-30 | 1987-08-04 | Minnesota Mining And Manufacturing Company | Epoxy resin curing agent, process, and composition |
| US4649180A (en) * | 1986-03-17 | 1987-03-10 | The Dow Chemical Company | Polyamide-poly-carbonate block copolymers |
| US5218078A (en) * | 1991-07-15 | 1993-06-08 | The Dow Chemical Company | Process for preparing halogenated polycarbonate from emulsified reaction mixture |
| US5614599A (en) * | 1994-10-31 | 1997-03-25 | The Dow Chemical Company | Stilbene-based polyester and polycarbonate compositions |
| US5714568A (en) * | 1996-09-26 | 1998-02-03 | Reichhold Chemicals, Inc. | Methods of preparing polyesters from cycle organic carbonates in the presence alkali metal-containing catalysts |
| US5679871A (en) * | 1996-09-26 | 1997-10-21 | Reichhold Chemicals, Inc. | Hydroxyalklylation of phenols |
| US5998568A (en) * | 1999-01-14 | 1999-12-07 | Reichhold, Inc. | Polyesters prepared from alkoxylated intermediates |
| US5969056A (en) * | 1999-01-14 | 1999-10-19 | Reichhold, Inc. | Process for preparing esterification products from cyclic organic carbonates using catalysts comprising quaternary ammonium salts |
| US6225436B1 (en) * | 2000-04-07 | 2001-05-01 | The Dow Chemical Company | Polycarbonate preparation process |
| US20090189321A1 (en) * | 2008-01-29 | 2009-07-30 | Dow Global Technologies Inc. | Thermoplastic composition and use for large parison blow molding applications |
| US10066102B2 (en) | 2013-11-22 | 2018-09-04 | Trinseo Europe Gmbh | Polycarbonate containing compositions |
| EP3071646A1 (en) | 2013-11-22 | 2016-09-28 | Trinseo Europe GmbH | Polycarbonate containing compositions |
| CN106715561B (en) | 2014-09-15 | 2020-05-19 | 盛禧奥欧洲有限责任公司 | Flame retardant polycarbonate with high total light transmittance |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4059565A (en) * | 1975-06-16 | 1977-11-22 | Mitsubishi Gas Chemical Company, Inc. | Process for producing a branched polycarbonate or poly(ester-carbonate) |
| US4156069A (en) * | 1976-04-02 | 1979-05-22 | Allied Chemical Corporation | Bisphenol-A/terephthalate/carbonate melt processable copolymers |
| JPS52150496A (en) * | 1976-06-09 | 1977-12-14 | Mitsubishi Gas Chem Co Inc | Preparation of polycaronate oligomers |
| US4278787A (en) * | 1978-06-19 | 1981-07-14 | The Dow Chemical Company | Alternating copolyestercarbonate resins |
| US4105633A (en) * | 1977-05-11 | 1978-08-08 | The Dow Chemical Company | Alternating copolyestercarbonate resins |
| US4260731A (en) * | 1978-09-11 | 1981-04-07 | Mitsubishi Chemical Industries, Ltd. | Aromatic polyester-polycarbonate |
| US4194038A (en) * | 1979-01-25 | 1980-03-18 | Allied Chemical Corporation | Poly(ester-carbonates) from dicarboxylic acid chlorides |
| US4238597A (en) * | 1979-04-26 | 1980-12-09 | General Electric Company | Process for producing copolyester-carbonates |
| US4310652A (en) * | 1980-03-24 | 1982-01-12 | Allied Chemical Corporation | Melt processable poly(ester carbonate) with high glass transition temperature |
| US4311822A (en) * | 1980-05-02 | 1982-01-19 | Allied Corporation | Interfacial production of poly(ester carbonate) or polyester including acid chloride synthesis |
| US4330662A (en) * | 1980-10-27 | 1982-05-18 | The Dow Chemical Company | Ordered copolyestercarbonate resins |
| EP0069157A1 (en) * | 1981-07-02 | 1983-01-12 | The Dow Chemical Company | Alternating copolyestercarbonate resins |
-
1982
- 1982-05-17 US US06/378,693 patent/US4388455A/en not_active Expired - Fee Related
-
1983
- 1983-05-09 CA CA000427726A patent/CA1198248A/en not_active Expired
- 1983-05-09 EP EP83104541A patent/EP0094585B1/en not_active Expired
- 1983-05-09 AT AT83104541T patent/ATE20594T1/en active
- 1983-05-09 AU AU14370/83A patent/AU561019B2/en not_active Ceased
- 1983-05-09 DE DE8383104541T patent/DE3364368D1/en not_active Expired
- 1983-05-16 KR KR1019830002126A patent/KR860000593B1/en not_active IP Right Cessation
- 1983-05-17 JP JP58086512A patent/JPS58217519A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0094585A3 (en) | 1984-03-28 |
| EP0094585A2 (en) | 1983-11-23 |
| KR860000593B1 (en) | 1986-05-17 |
| AU1437083A (en) | 1983-11-24 |
| DE3364368D1 (en) | 1986-08-07 |
| EP0094585B1 (en) | 1986-07-02 |
| US4388455A (en) | 1983-06-14 |
| ATE20594T1 (en) | 1986-07-15 |
| JPS58217519A (en) | 1983-12-17 |
| KR840004915A (en) | 1984-10-31 |
| AU561019B2 (en) | 1987-04-30 |
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