Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUSRE27682 E
Publication typeGrant
Publication dateJun 19, 1973
Filing dateSep 9, 1971
Priority dateJan 15, 1965
Also published asUS3544514
Publication numberUS RE27682 E, US RE27682E, US-E-RE27682, USRE27682 E, USRE27682E
InventorsHermann Schnell
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for the production of thermo- plastic polycarbonates
US RE27682 E
Images(7)
Previous page
Next page
Description  (OCR text may contain errors)

United States Patent 27,682 PROCESS FOR THE PRODUCTION OF THERMO- PLASTIC POLYCARBONATES Hermann Schnell, Krefeld-Uerdingen, and Ludwig Bottenbruch, Kurt Weirauch, Wilhelm Hechelhammer, Hugo Streib, and Gerhard Fritz, Krefeld-Bockum, Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Original No. 3,544,514, dated Dec. 1, 1970,

Ser. No. 644,106, June 7, 1967, which is a continuationin-part of Ser. No. 520,653, Jan. 14, 1966. Application for reissue Sept. 9, 1971, Ser. No. 179,241 Claims priority, application Germany, Jan. 15, 1965,

44,973; June 8, 1966, F 49,420-

Int. Cl. C08g 17/13 U.S. Cl. 260-47 XA 16 Claims Matter enclosed in heavy brackets [II appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE Branched chain high molecular weight thermoplastic polycarbonates containing the residues of monohydric phenols and polyhydric phenols having more than two hydroxy groups in the molecule.

The present invention relates to polycarbonates and more particularly to a process for the production of soluble high molecular weight, thermoplastic polycarbonates and is a continuationin-part of copending application Ser. No. 520,653, filed Jan. 14, 1966, now abandoned and a reissue of U.S. Pat. No. 3,544,514.

Various types of polycarbonate resins are known, among which are those prepared by vinyl polymerization of unsaturated carbonate esters, such as allyl carbonates, etc., from the ester interchange of carbonate esters with glycols, and by the reaction of dihydroxy-monoaryl compounds such as hydroquinone and resorcinol with phosgene, carbonate esters or other carbonate precursors. In addition, it has been known that soluble high molecular weight linear thermoplastic polycarbonates can be obtained from the reaction of bisphenols with polycarbonate-forming derivatives of carbonic acid under polycarbonate forming reaction conditions, e.g., according to the processes of German patent specifications Nos. 971,- 790, 971,777, 959,497, 1,007,996, 1,031,512, 1,046,311, 1,047,430 and 1,317,030.

Therein, monohydric phenols have also been used as chain terminators in an attempt to inhibit the considerable variation of average molecular weight from batch to batch.

It is an object of this invention to provide novel polycarbonates having especially favorable properties and a method for making them.

Another object of this invention is to provide polycarbonates which have a certain degree of branching but which are substantially free of cross-linking.

Still another object of this invention is to provide polycarbonates the melts of which having increased form stability at elevated temperatures when extruded.

A further object of this invention is to provide a process for preparing branched polycarbonates which are substantially free of cross-linking and the melts of which have increased form stability at elevated temperatures when extruded.

A still further object of this invention is to provide a process for preparing branched chain polycarbonates ice which are suitable for forming molded articles, preferably by the extrusion process.

The foregoing objects and others which will become apparent from the following description are accomplished in accordance with this invention, generally speaking, by providing branched chain high molecular weight thermoplastic polycarbonates containing in addition to residues of dihydroxy compounds the residues of monohydric phenols and polyhydric phenols having more than two hydroxy groups in the molecule.

According to the present invention, branched chain high molcular weight polycarbonates substantially free of cross-linking are obtained by reacting dihydroxy compounds with carbonic acid derivatives in the presence of about 0.01 to about 2.0 mol percent of an organic poly (hydroxyphenyl) compound having more than two hydroxy groups in the molecule, and of about 0.1 to about 8 mol percent of monohydrie phenols, the mol percentages being based on the mols of the organic dihydroxy compounds. The organic poly(hydroxyphenyl) compounds are referred to hereinafter as polyhydric phenols.

Surprisingly, we have found that the thermoplastic polycarbonates thus obtained are completely soluble in the usual solvents and have relative viscosities of between about 1.20 and 1.55 when measured in solutions containing 0.5 gram of polycarbonate in milliliters of methylene chloride at 25 C. In addition, the polycarbonates have an average molecular weight of between about 30,000 and about 100,000 when measured by means of light dilfraction and have a melt viscosity of between 20,000 and about 300,000 poises when measured at 280 C. In addition, the melts exhibit an increased form stability to heat when extruded, while the extruded products show substantially no deterioration in their properties.

Any suitable polyhydric phenols having more than two hydroxy groups in the molecule may be used in this process such as, for example, .phloroglucinol, 4,6-dimethyl- 2,4,6 tri (4 hydroxyphenyDheptene 2, (trimeric isopropenyl-phenol, obtainable, for example by the proccess outlined in German patent specification No. 1,112,- 980; MP. 227228 C.), 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyhheptane (hydrogenated trimeric isopropenylphenol, obtainable by the hydrogenation of trimeric isopropenyl-phenol at 140 C. and 200 atmospheres hydrogen pressure in the presence of hydrogenation catalysis; M.P. 199-200 C.) 1,3,5-tri-(4-hydroxyphenyl)- benzene, 1, l l-tri- (4-hydroxyphenyl ethane, 2,2-bis- [4,4'- (dihydroxy diphenyl) cyclohexyl] propane 2,4-bis(4- hydroxy 1 isopropylidine) phenol, 2 (4 hydroxyphenyl) 2 [4,4 bis (4 hydroxyphenyl) cyclohexylJ-propane and the like as Well as the reaction products of any suitable alkyl, arylor halogen-substituted monophenols with formaldehyde or any suitable formaldehyde-yielding compounds. However, p-substituted monophenols are preferred. A representative example of this latter group of substances is the trisphenol obtained from p-cresol and formaldehyde, 2,6-bis(2'-hydr0xy-5'methylbenzyl)-4-methyl phenol; further examples include 2,6- bis (2' hydroxy 5' isopropyl benzyl) 4 isopropyl phenol, bis [2 hydroxy 3 (2' hydroxy 5' methylbenzyl) 5 methylphenyl] methane, 2,6 bis (2'- hydroxy 5 methylbenzyl) 4 chloroor bromophenol and 2,6 bis (2-hydroxy 5' chlorobenzyD- 4-methylphenol and the like.

Further examples of suitable products are described, for instance, in Houben-Weyl, Methoden d. org. Chemie 1963, pp. 193 if.

Furthermore, condensation products of phenols is described in the U.S. Pat. 2,885,385.

R is a divalent aliphatic, araliphatic or cycloaliphatic hydroxyl radical or the oxygen or sulphur atom or a sulphone group or a single bond, and

RI H

R iili wherein:

R is hydrogen, an alkyl group having 1 to 8 carbon 0 atoms or a cycloaliphatic hydrocarbon radical having to 10 carbon atoms, as described in the German Pat. 1,092,026.

Polyphenols of the type as described in the British specification No. 920,476.

Hence, any suitable alkyl-, arylor halogen-substituted monophenols with which the formaldehyde or formaldehyde-yielding compound may react can be used. Some such phenols include, for example, p-cresol, p-ethyl phenol, p-propyl phenol, p-isopropyl phenol, p-n-butyl-, and p-isobutyl phenol, p-tertiary butyl phenol, p-nonyl-phe-- nol, p-isoamyl phenol, 4,5-dimethyl phenol, 3-decyl-4- methyl phenol, p-cyclohexyl phenol, p-cyclodecyl phenol, 4-methyl-5-ethyl phenol, p phenyl-phenol, p phenylisopropyl phenol, oand p-chloro-bromoand methyl-phenol.

The polyhydric phenols may be composed of three or more molecules of the same kind or different kinds of monophenols and mixtures thereof and the like.

Further, any suitable formaldehyde-yielding compound may be used instead of or in addition to formaldehyde. Some such compounds include, for example, trioxane, methylal and hexamethylene tetramine and mixtures thereof and the like.

Any suitable monohydric phenols may be used to prepare the polycarbonate of this invention. Some such suitable compounds include, for example, phenol, lower alkyl phenols such as, for example, 4-methylphenol, 3-ethylphenol, S-propylphenol, 4-isopropylphenol, S-butylphenol, 3-isobutylphenol, 4-tertiary butylphenol, 4-pentylphenol and the like; aryl phenols such as, for example, 4-phenyl phenol, S-phenyl phenol and the like; cycloaliphatic phenols such as, for example, 4-cyclohexyl phenol, 3-cyclopentyl phenol and the like; monophenol alkanes such as, for example, 2,2-(4-hydroxyphenyl 4 methoxyphenyl) propane, 3-hydroxyphenyl ethane, as well as any of those referred to hereinbefore or hereinafter.

Further, the monohydric phenols may contain any suitable substituents which are inert with respect to the rest of the reactants as well as the polycarbonate product formed. Some such substituents include, for example, alkoxy groups such as, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy and the like; halogen groups such as, for example, chlorine, bromine, iodine and the like; and any of the hereinbefore described phenols may contain any of the foregoing substituents in any of the free positions on the aryl or alkyl groupings thereof. Examples of some such suitable substituted monohydric phenols include p-methoxy-phenol, p-ethoxy phenol, pchloro-phenol, 2,6-dichloro-phenol and the like.

High molecular weight thermoplastic polycarbonates may be produced from any suitable dihydroxy compounds including aliphatic, cycloaliphatic and aromatic dihydroxy compounds. Some such suitable aromatic dihydroxy compounds include, for example, the dimonohydroxy arylene alkanes and the dimonohydroxy arylene sulphones such as, for example,

4,4-dihydroxydiphenylene sulphone, 2,2-dihydroxydiphenylene sulphone, 3,3'-dihydroxydiphenylene sulphone, 4,4-dihydroxy-2,2'-dimethyldiphenylene sulphone, 4,4-dihydroxy-3,3'-dimethyldiphenylene sulphone, 2,2'-dihydroxy-4,4-dimethyldiphenylene sulphone, 4,4'-dihydroxy-2,2-diethyldiphenylene sulphone, 4,4-dihydroxy-3,3-diethyldiphenylene sulphone, 4,4'-dihydroxy-2,2'-ditert.-butyl-diphenylene sulphone, 4,4'-dihydroxy-3,3'-di-tert.-butyl-diphenylene sulphone and 2,2-dihydroxy-1,l'-dinaphthylene sulphone, 4,4'-dihydroxy-diphenylene-methane, l,l-(4,4-dihydroxy-diphenylene)-ethane, 1,1-(4,4'-dihydroxy-diphenylene)-propane, 1,1-(4,4'-dihydroxy-diphenylene)-butane, 1,1(4,4-dihydroxy-diphenylene)-2-methyl-propane, 1,1(4,4'-dihydroxy-diphenylene)-heptane, 1,1(4,4'-dihydroxydiphenylene)-1-phenyl-methane, (4,4'-dihydroxy-diphenylene)-(4-rnethyl-phenylene)- methane, (4,4'-dihydroxy-diphenylene)-(4-ethyl-phenylene)- methane, (4,4-dihydroxy-diphenylene (4-isopropy l-phenylene) methane, (4,4-dihydroxy-diphenylene)-(4-butyl-phenylene)- methane, (4,4'-dihydroxy-diphenylene -benzyl-methane, (4,4'-dihydroxy-diphenylene)-alpha-furyl-mcthane, 2,2-(4,4-dihydroxy-diphenylehe)-propane, 2,2-(4,4'-dihydroxy-diphenylene)-butane, 2,2-(4,4-dihydroxy-diphenylene)-pentane, 2,2-(4,4-dihydroxy-diphenylene)-4-methylpentane, 2,2(4,4'-dihydroxy-diphenylene)-heptane, 2,2-(4,4'-dihydroxy-diphenylene)-octane, 2,2-(4,4'-dihydroxy-diphenylene)-nonane, 1, l- (4,4'-dihydroxy-diphenylene -l-phenyl-ethane, (4,4-dihydroxy-diphenylene)-1-(alpha-furyl)-ethane, 3,3-(4,4'-dihydroxy-diphenylene)-pentane, 4,4-(4,4-dihydroxy-diphenylene)-heptane, 1,l-(4,4-dihydroxy-diphenylene)-cyclopentane, 1,1-(4,4-dihydroxy-diphenyleneJ-cyclohexane, 2,2-(4,4'-dihydroxy-diphenylene -decahydronaphthalene, 2,2-(4,4'-dihydroxy-3,3-dicyclohexyl-diphenylene)- propane, 2,2-(4,4-dihydroxy-3-methyl-diphenylene) pr0ane, 2,2-(4,4'-dihydroxy-3-isopropyl-diphenylene)-butane, 1,1-{4,4'-dihydroxy-3,3-dimeth'yl-diphenylene)- cyclohexane, 2,2-(4,4-dihydroxy-3,3-dibutyl-diphenylene)propane, 2,2-(4,4-dihydroxy-3,3-diphenyl-diphenylene)-propane, 2,2-(4,4'-dihydroxy-2,2'-dimethyl-diphenylene)-propane, 1,l(4,4'-dihydroxy-3,3'-dimethyl-6,6-ditert.-butyldiphenylene)-eth'ane, 1,1-(4,4-dihydroxy-3,3'-dimethyl-6,6'-ditert.-butyldiphenylene)-propane,

1,1-(4,4'-dihydroxy-3 ,3'-dimethyl-6,6-ditert.-butyldiphenylene butane,

1,1-(4,4'-dihydroxy-3 ,3'-dimethyl-6,6'-ditert.-butyldiphenylene -isobutane,

1,1-(4,4-dihydroxy-3,3 -dimethyl-6,6'-ditert.-butyldiphenylene -heptane,

1,1-(4,4-dihydroxy-3 ,3 '-dimethyl-6,6'-ditert.-bu .yldiphenylene 1 -phenyl-methane,

1,1-(4,4'-dihydroxy-3,3'-dimethyl-6,6'-ditert.-butyldiphenylene -2-methyl-2-pentane,

1, 1 (4,4'-dihydroxy- 3 ,3 -dirnethyl-6,6'-ditert.-butyldiphenylene -2-ethyl-2-hexane,

1,1-(4,4-dihydroxy-3 ,3-dimethyl-6,6'-ditert.-amyldiphenylene -butane,

the corresponding bis-hydroxyphenyl ethers, sulphides sulphoxides and the like.

Among the great number of suitable di-monohydroxy arylene alkanes which may be used are the 4,4'-dihydroxydiphenylene alkanes and it is preferred that of this class of compounds 2,2-(4,4'-dihydroxy-diphenylene)-propane and 1,1-(4,4-dihydroxy diphenylene)-cyclohexane be used.

Any suitable aliphatic dihydroxy compounds may be used including, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, thiodiglycol, ethylene dithiodiglycol, the diand poly-glycols pro duced from propylene oxide-1,2, o, m or p-xylene glycol, propanediol-1,3, butanediol-1,3, butanediol-1,4, 2-methyl propanediol-1,3- pentanediol-1,5, 2-ethylpropanediol-1,3, hexanediol-1,6, octanediol 1,8, 1-ethylhexanediol-1,3, decanediol-1,10 and the like.

Any other suitable aromatic dihydroxy compounds may also be used. Some such suitable compounds include hydroquinone, resorcinol, pyrocatechol, 4,4'-dihydroxydiphenyl, 2,2'-dihydroxydiphenyl, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,2-dihydroxynapl1thalene, 1,5-dihydroxynaphthalene, dihydroxy anthracene, 2,2'-dihydr0xynaphthalene, 1,1'-and o, m, and p-hydroxybenzyl alcohol and the like.

Any suitable cycloaliphatic dihydroxy compounds may be used including cyclohexanediol-1,4, cyclohexanediol- 1,2, 2,2-(4,4-dihydroxy dicyclohexylene)-propane, 2, 6-dihydroxy decahydronaphthalene, the corresponding bis-alkoxylated aromatic dihydroxy compounds thereof and the like.

In addition, any of those components and conditions described in Canadian Pats. 578,585, 578,795, 594,805 and US. Pats. 3,028,365, 2,999,846, 2,970,131, 2,991,273, 2,999,835 and 3,014,891 may also be used.

In some cases mixtures of various dihydroxy compounds especially those having at least one aromatic and at least one aliphatic dihydroxy compound can be used thereby providing for mixed polycarbonates.

The formation of the high molecular weight polycarbonates by the reaction of di-(monohydroxyaryl)-alkanes with derivatives of carbonic acid may be carried out by the conventional technique known in the art. For example phosgene can be introduced into a solution of di- (monohydroxyaryl)-alkanes in organic bases such as dimethylaniline, diethylaniline, trimethylamine and pyridine, or into solutions or di-(monohydroxyaryl)-alkanes in indifferent organic solvents such as benzene, ligroin, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chloroform, methylenechloride, carbon tetrachloride, trichloro-ethylene, trichloroethane, methyl acetate and ethyl acetate with the addition of an acid binding agent.

A process particularly suitable for producing polycarbonates consists of introducing phosgene into an aqueous solution of alkali metal salts such as lithium, sodium, potassium and calcium salts of the di-(monohydroxyaryU- alkanes, preferably in the presence of an excess of a base such as lithium, sodium, potassium and calcium hydroxide or carbonate. The polycarbonate precipitates out from the aqueous solution.

The conversion in the aqueous solution is promoted by the addition of indiflerent solvents of the kind mentioned above which are capable of dissolving phosgene and eventually the produced polycarbonate.

It is also possible to react the di-(monohydroxyaryl)- alkanes with equal molecular amounts of bis-chlorocarbonic acid esters of di(monohydroxyaryl)-alkanes under corresponding conditions.

Also the di-(monohydroxyaryl)-alkanes can be re-esterified with carbonic acid diesters, e.g. dimethyl, diethyl, dipropyl, dibutyl, diamyl, dioctyl, dicyclohexyl, diphenyl and di-, 0-, p-tolyl carbonate at elevated temperatures from about 50 C. to about 320 C. and especially from about 120 C. to about 280 C.

When using phosgene or bis-chlorocarbonic acid esters as derivatives of the carbonic acid in producing polycarbonates, catalysts may also be advantageous. Such catalysts are, for example, tertiary or quaternary organic bases or salts thereof such as, trimethylamine, triethylamine, dimethylaniline, diethylaniline, dimethylcyclohexylamine, and pyridine, or for instance, the corresponding hydrochlorides and tetramethylammonium hydroxide, triethyloctadecyl ammonium chloride, trimethylbenzylammonium fluoride, triethylbenzylammonium chloride, dimethyldodecyl ammonium chloride, dimethylbenzyl phenyl ammonium chloride, trimethylcyclohexyl ammonium bromide, and N-methyl-pyrodonium chloride in amounts of from about 0.002 to about 0.5% by weight. These compounds may be added to the reaction mixture before or during the reaction.

The reaction of dihydroxy compounds such as di- (monohydroxyaryl)alkanes with phosgene or the chlorocarbonic acid esters of di(monohydroxy)-alkanes in the presence of the polyhydric phenols and monohydric phenols may be carried out at room temperature or at lower or elevated temperatures, that is to say, at temperatures of from the freezing point up to about the boiling point of the mixture and preferably from about 0 C. to about C. The reaction conditions should be such that about one mo] of phosgene reacts with about one mol of the dihydroxy compounds.

By addition of from about 0.01 to about 2.0 and preferably from about 0.25 to about 1.5 mol percent of polyhydric phenols having more than two hydroxy groups in the molecule and from about 0.1 to about 8, and preferably from 1 to 6 mol percent of monohydric phenols based on the mols of dihydroxy compound, it is possible to produce thermoplastic polycarbonates which contain a certain degree of branching but which are substantially free of crosslinking. In addition, these polycarbonates have a relative viscosity ranging from about 1.20 to about 1.55, an average molecular weight of between 30,000 and about 100,000 and a melt viscosity of between 20,000 and about 300,000 poises.

In the formation of polycarbonates from either the solution polymerization reaction of the interfacial polycondensation reaction it is necessary to add both the polyhydric phenols and the monohydric phenols to the hydroxy compounds which are reacted with phosgene or bis-chlorocarbonic acid esters in order to obtain the desired polycarbonate product having the desired properties of this invention. However, in the transesterification reaction, i.e. in the case of the reaction of the bis-phenols with carbonic acid aryl esters in the melt, it is only necessary to add the polyhydric phenols in the above stated amounts and thus omit the addition of the monohydric phenols providing care is taken to prevent the monohydric phenol which is liberated by the reaction from the diary] carbonate from being completely removed from the reaction mixture. As long as the monohydric phenol is present in the amount specified above, it will automatically participate in the synthesis of the polycarbonates.

Furthermore, in some of these cases, it is preferred to add surface active agents such as alkali metal salts of higher fatty acids or of sulphonic acids or of higher aliphatic or aromatic hydrocarbons and polyoxyethylated alcohols and phenols. Greater amounts of the quaternary ammonium bases mentioned above act as surface active agents.

Additives of all kinds can be added before, during or after the production of the polycarbonates. For example, additives such as dyestuffs, pigments, stabilizing agents against the effect of moisture, heat, ultra-violet radiation, lubricants, fillers such as glass powder, quartz products, graphite, molybdenum disulphide, metal powders, powders of high melting synthetic resins, e.g., polytetrachloroethylene powder, natural fibers such as cotton and asbestos, as well as glass fibers of the most varied types, metal fibers as well as fibers which are stable during residence in the melt of the polycarbonate and do not markedly damage the polycarbonate may be added to the polycarbonate composition.

The polycarbonates produced according to the present invention are elastic thermoplastic materials which are soluble in a variety of organic solvents which can be worked up from solutions into shaped articles such as films, fibers or the like or into lacquer coatings. A polycarbonate which is substantiall free from decomposition at elevated temperatures such as is prepared by this invention, can be easily fabricated into useful articles, films, fibers, sheets, tubes, rods and the like from a melt or solution thereof by conventional shaping techniques such as molding, casting or extruding. Also, these polycarbonates can be used to make laminates such as safety glass, or to prepare protective or decorative coatings.

In order that those skilled in the art may better understand how the present invention may be practiced, the following examples are given by way of illustration and not by way of limitation. All parts are by weight unless otherwise specified, the relative viscosities being measured on solutions of 0.5 g. of the product in 100 ml. methylene chloride at C. and the melt viscosities being measured at 280 C.

EXAMPLE 1 To a mixture of about 137.6 parts of 2,2-(4,4'-dihydroxydiphenyl)-propane, about 2.55 parts of p-tert.-butylphenol, about 0.605 part of trimeric isopropenylphenol, about 112.5 parts of 45% sodium hydroxide solution, about 700 parts of distilled water and about 1336 parts of methylene chloride, are added over a period of about two hours at 20-25 C., with stirring in a nitrogen atmosphere, about 73 parts of phosgene, while adding simultaneously over a period of about 80 minutes an additional 48 parts of 45% sodium hydroxide solution dropwise. After the addition of phosgene is complete, about 0.24 part by weight triethylamine is added after which time the reaction mixture becomes more viscous. After about one hour, the reaction mixture is allowed to separate out; the organic phase, which contains the polycarbonate is separated off, and subsequently washed with 2% phosphoric acid, 2% sodium hydroxide solution, again twice with 2% phosphoric acid and, finally, 10 times with distilled water until the solution has a neutral reaction. After drying over anhydrous sodium sulphate, the methylene chloride solution can be worked up as follows:

(a) Via an evaporation extruder or simply by distilling off the solvent in a vacuum drying cambinet.

(b) By precipitation of the polymer with, for example, acetone, alcohol or aliphatic or cycloaliphatic hydrocarbons.

(c) By the addition of chlorobenzene and distilling off the methylene chloride. Upon cooling the chlorobenzene solution, it gels and can be further worked up in a granulating machine to a powdery-granular mixture. The products obtained are dried for 48 hours at 120 C. under water pump vacuum.

The relative viscosity of the product obtained by distilling olf the solvent is 1.341.

8 EXAMPLE 2 Into a mixture of approximately 137.6 parts of 2,2- (4,4-dihydroxy-diphenyl)-propane, about 2.55 parts of p-tert.-butylphenol, about 1.21 parts of trimeric isopropenylphenol, about 112.5 parts of 45% sodium hydroxide solution, about 700 parts of distilled water and about 1336 parts of methylene chloride, there are added over a period of about two hours at 2025 C. and with stirring in an atmosphere of nitrogen, about 73 parts of phosgene while, at the same time, over a period of about minutes an additional 48 parts of 45% sodium hydroxide solution are added dropwise.

After the phosgene addition is complete, about 0.24 part of triethylamine is added. The reaction mixture becomes viscous. After about one hour, the organic phase is separated off and the polycarbonate recovered by one of the methods described in Example 1. The relative viscosity of the product is 1.385.

EXAMPLE 3 Into a mixture of approximately 137.6 parts of 2,2- (4,4-dihydroxy-diphenyl)-pr0pane, about 2.55 parts of p-tert.-butylphenol, about 1.694 parts of trimeric isopropenylphenol, about 112.5 parts of sodium hydroxide solution, about 700 parts of distilled water and about 1336 parts of methylene chloride, there are added over a period of about two hours at 38 C. and with stirring in an atmosphere of nitrogen, about 73 parts of phosgene while, at the same time, over a period of about 80 minutes an additional 48 parts of 45% sodium hydroxide solution are added dropwise. After the phosgene addition is complete, about 0.24 part by weight triethylamine is added. The reaction mixture becomes viscous. The polycarbonate product is recovered by one of the methods described in Example 1. The relative viscosity of the product is 1.431.

EXAMPLE 4 Into a mixture of about 137.6 parts of 2,2-(4,4'-dihydroxydiphenyl)-propane, about 2.55 parts of p-tert.-butylphenol, about 2.42 parts of trimeric isopropenylphenol, about 112.5 parts of 45% sodium hydroxide solution, about 700 parts of distilled water and about 1336 parts of methylene chloride, there are added over a period of about two hours at 20-25 C. with stirring and in an atmosphere of nitrogen, approximately 73 parts of phosgene while, at the same time, adding about 48 parts of 45 sodium hydroxide solution dropwise over a period of about 80 minutes. Upon completion of the phosgene addition, about 0.24 part of triethylamine is added. The reaction mixture becomes viscous. The product is worked up in accordance with the procedure described in Example 1. The relative viscosity of the product is 1.539.

EXAMPLE 5 Into a mixture of about 161.5 parts of 1,1-(4,4'-dihydroxydiphenyl)-cyclohexane, about 2.7 parts of p-tert.- butylphenol, about 2.42 parts of trimeric isopropenylphenol, about 164.5 parts of 45% sodium hydroxide solution, about 700 parts of distilled water and about 1336 parts of methylene chloride, there are added over a period of about two hours at 20-25 C. with stirring and in an atmosphere of nitrogen, about 73 parts of phosgene. Approximately 0.24 part of triethylamine is thereafter added. After about one hour, the reaction mixture is allowed to separate out and the organic phase, which contains the polycarbonate, separated off and worked up in accordance with the procedure described in Example 1. The relative viscosity of the product is 1.522.

EXAMPLE 6 Into a mixture of about 161.5 parts of 1,1-(4,4-dihydroxydiphenyl)-cyclohexane, about 2.7 parts of p-tert.-

butylphenol, about 1.22 parts of hydrogenated trimeric isopropenylphenol, about 164.5 parts of 45% sodium hydroxide solution, about 700 parts of distilled water and about 1336 parts of methylene chloride, there are added over a period of about two hours at 20-25 C. with stirring and in an atmosphere of nitrogen, about 73 parts of phosgene. Thereafter about 0.24 part of triethylamine is added. After about one hour, the reaction mixture is allowed to separate out and the organic phase, which contains the polycarbonate, is separated oh and worked up in accordance with the method described in Example 1. The relative viscosity of the product is 1.321.

EXAMPLE 7 Into a mixture of about 161.5 parts of l,1-(4,4'-dihydroxydiphenyl)-cyclohexane, about 2.7 parts of p-tert.- butylphenol, about 1.22 parts of trimeric isopropenylphenol, about 166 parts of 45% sodium hydroxide solution, about 700 parts of distilled Water and about 1330 parts of chlorobenzlene, there are added over a period of about two hours at 60 C. with stirring and in an atmosphere of nitrogen, about 73.5 parts of phosgene. Thereafter about 0.25 part of triethylamine is added. After one hour, the reaction mixture is allowed to separate out and the organic phase, which contains the polycarbonate, is separated off and worked up by the method described in Example 1. The relative viscosity of the product is 1.325.

EXAMPLE 8 Into a mixture of about 137.6 parts of 2,2-(4,4-dihydroxycliphenyl)-propane, about 2.85 parts of p-tert.- butylphenol, about 1.067 parts of 1,3,5-tri-(4-hydroxyphenyl)-benzene, about 112.5 parts of 45% sodium hydroxide solution, about 700 parts of distilled water and about 1336 parts of methylene chloride, there are added over a period of about two hours at 20-25 C. with stirring and in an atmosphere of nitrogen, about 73 parts by weight phosgene while simultaneously adding dropwise for up to 80 minutes an additional 52 parts of 45% sodium hydroxide solution. Approximately 0.24 part of triethylamine is thereafter added. After about one hour, the reaction mixture is allowed to separate out, the organic phase is separated off and the polycarbonate isolated therefrom as described in Example 1. The relative viscosity of the product is 1.328.

EXAMPLE 9 Into a mixture of about 3440 parts of 2,2-(4,4'-dihydroxydiphenyl)-propane, about 82.5 parts of p-tert.- butylphenol, about 60.5 parts of trimeric isopropenylphenol, about 4113 parts of 45% sodium hydroxide solution, about 17,500 parts of distilled water and about 33,130 parts of methylene chloride, there are added at about 24-26 C. over a period of about two hours with stirring and in an atmosphere of nitrogen approximately 1825 parts of phosgene. Thereafter about 6 parts of triethylamine are added. After stirring for an additional hour, the organic phase is separated oif, washed several times with 2% sodium hydroxide solution, 2% phosphoric acid and distilled water and finally worked up according to the process (c) of Example 1. The polycarbonate has a relative viscosity of 1.322, the melt viscosity is about 129,500 poises and the average molecular weight determined by means of light diffraction is about 56,700.

EXAMPLE 10 Into a mixture of about 3,440 parts of 2,2-(4,4'-dihydroxydiphenyl)propane, about 71.25 parts of p-tert.- butylphenol, about 30.25 parts of trimeric isopropenylphenol, about 4,113 parts of 45% sodium hydroxide solution, about 17,500 parts of distilled water and about 33,130 parts of methylene chloride, there are added at about 24-25 C. over a period of about two hours with stirring and in an atmosphere of nitrogen, about 1825 parts of phosgene followed by the addition of about 6 parts triethylamine. The reaction mixture is stirred for an additional hour. The polymer is worked up to a granulate by means of an evaporation extruder. The relative viscosity of the product is about 1.322, the melt viscosity is about 59,370 poises and the average molecular weight, determined by means of light dilfraction, is about 43,200.

EXAMPLE 1 1 Into a mixture of about 3,440 parts of 2,2-(4,4-dihydroxydiphenyl)-propane about 60.0 parts of p-tert.- butylphenol, about 21.2 parts of trimeric isopropenylphenol, about 4,113 parts of 45% sodium hydroxide solution, about 17,500 parts of distilled water and about 33,130 parts of methylene chloride, there are added at about 2425 over a period of about two hours with stirring and in an atmosphere of nitrogen, approximately 1825 parts phosgene. Approximately 6 parts of triethylamine are subsequently added thereto. The reaction mixture is stirred for an additional hour. The polymer is worked up to a granulate by means of an evaporation extruder. The relative viscosity is about 1.359 and the average molecular weight, determined by light diffraction, is about 47,000.

The polymers obtained according to Examples 10 and 11 are, after drying for 6 hours in a vacuum drying cupboard at C., melted, homogenized and extruded to a thread in known manner by means of a worm press (heating zones: 290 0, 290 C., 290 C., 220 C.; 18 r.p.m.; current utilization 3.5 amps). The behavior of the thread thus obtained is investigated. The results are given in Table I wherein (a) and (b) represent the threads obtained from the instant process. For comparison, columns (c) and (d) illustrate two known polycarbonates which are synthesized only on the basis of bisphenol A. The polymer according to Example (c) was produced by transesterification and that according to Example (d) was produced in known manner by interfacial polycondensation process.

TABLE I a b c d Relative viscosity of starting material (25 0.111 methylene chloride; C=5 g./llter. 1. 323 1. 359 1.325 Extrusion of a 50 cm. long thread:

Time (seconds) 62 86 48 58 75 45 Weight (grams) 30 It is to be recognized that the new polycarbonates described under (a) and (b) possess a substantially more viscous melt tube. Furthermore, the test rods injection molded from (a) and (b) also show a lower degree of attack with regard to tension corrosion in comparison with (c) and (d). In addition, test rods from (a) and (b) show a reduced inflammability in comparison with those from (c) and (d).

The products produced according to Examples 10 and 11 are outstandingly suitable for the production of large containers and flasks. Thus, an 18 liter container with a weight of about 1.3 kg. could be produced without difiiculties.

EXAMPLE 12 Into a mixture of about 3,440 parts of 2,2-(4,4'-dihydroxydiphenyl)-propane about 88.5 parts of p-tert.- butylphenol, about 75,625 parts of (1.25 mol percent) trimeric isopropenylphenol, about 4,113 parts of 45 sodium hydroxide solution, about 17,500 parts of distilled water and about 33,130 parts of methylene chloride, there are added at temperatures of between about 24 and 25 C. over a period of about two hours with stirring and in an atmosphere of nitrogen, about 1825 parts of phosgene. Approximately 6 parts of triethylamine are thereafter 11 added. After stirring for an additional hour, the organic phase is separated off, washed several times with 2% sodium hydroxide solution, 2% phosphoric acid and dis tilled water and finally worked up by means of an evaporation extruder. The polycarbonate obtained has a viscosity of 1.316, the melt viscosity is 97,600 poises and the molecular weight, determined by light diffraction, is 57,300.

EXAMPLE 13 In a stainless steel 25 1. capacity, autoclave equipped with a stirrer, approximately 7000 parts of 2,2-(4,4- dihydroxy-diphenyl)propane, about 6,770 parts of diphenyl carbonate and about 0.01 part of a disodium salt of bisphenol are melted under a nitrogen atmosphere. Subsequently about 4,000 parts of phenol are distilled off, with agitation, at a pressure of about 100 mm. Hg while slowly increasing the melt temperature from 180 to 210 C. The pressure is then gradually reduced to about 2 mm. Hg and the temperature increased to 280 C.

An additional 1,700 parts of phenol is distilled. At this point, about 92.5 parts (0.75 mol percent) of trimeric isopropenylphenol are introduced into the melt and for about 30 minutes stirred at a pressure of about 50 mm. Hg. The pressure is subsequently reduced to about 0.3 mm. Hg and the polycondensation continued to the end at a melt temperature of between about 300 and 305 C. over a period of about 150 minutes.

A yellow colored melt is spun off from the autoclave as bristle and granulated. The polycarbonate has a relative viscosity of 1.320.

EXAMPLE 14 About 1825 parts of phosgene are introduced into a mixture of about 3440 parts of 2,2-(4,4-dihydroxydiphenyl)-propane, about 18 parts of 2,6 bis(2-hydroxy-5'-methyl-benzyl)-4-methyl-phenol, about 50 parts of p-tertiary-butylphenol, about 2813 parts of a 45% sodium hydroxide solution, about 17,500 parts of distilled water and about 33,130 parts of methylene chloride at about 24 to 25 C. in the course of about 2 hours while stirring in a nitrogen atmosphere. Simultaneously, from the th to,the 90th minute, about 1300 parts of a 45% sodium hydroxide solution are added dropwise. After the introduction of phosgene is completed, about 6 parts of triethylamine are added. Stirring is continued for about one hour. The organic phase is washed, consecutively, with 2% phosphoric acid, 2% sodium hydroxide solution, twice more with 2% phosphoric acid and finally with distilled water until the solution is neutral. About 7500 parts of chlorobenzene are then added to the methylene chloride solution. The bulk of the ethylene chloride is distilled off. After cooling, the polycarbonate gels and is comminuted to a powder/grain mixture in a granulating machine. The mixture is dried at about 120 C. for about 48 hours in a water jet vacuum. The relative viscosity of the polycarbonate is 1.38 (C=5 g./liter at 25 C. in methylene chloride). Under the conditions described in Examples 10 and 11, about 90 seconds are required to extrude the polycarbonate product into a 50 cm. long strand.

It is to be understood that any of the components and conditions mentioned as suitable herein can be substituted for its counterpart in the foregoing examples and that although the invention has been described in considerable detail in the foregoing, such detail is solely for the purpose of illustration. Variations can be made in the invention by those skilled in the art without departing from the spirit and scope of the invention except as is set forth in the claims.

What is claimed is:

1. A high molecular weight branched polycarbonate substantially free of crosslinking which comprises a polycarbonate polymer containing residues of an aromatic dihydroxy compound [having up to ten carbon atoms], about 0.01 to about 2 mol percent of an organic trihydric or tetrahydric phenol and about 0.1 to about 8 mol percent of monohydric phenol, the mol percentages being based on the mols of the organic dihydroxy compound, said branched polycarbonate having a relative viscosity of from about 1.2 to about 1.55 measured on a solution of 0.5 gram in ml. of methylene chloride at 25 C., an average molecular weight of between about 30,000 and about 100,000 measured by light diffraction and a melt viscosity of between about 20,000 and about 300,000 poises at 280 C.

2. The high molecular weight branched polycarbonate of claim 1 wherein the aromatic dihydroxy compound is a dihydric phenol.

3. The high molecular weight branched polycarbonate of claim 1 wherein the trihydric or tetrahydric phenol is trimeric isopropenylphenol.

4. The high molecular weight branched polycarbonate of claim 1 wherein the trihydric or tetrahydric phenol is 1,3,5-tri(4-hydroxyphenyl)benzene.

5. The high molecular weight branched polycarbonate of claim 1 wherein the trihydric or tetrahydric phenol is the reaction product of one or more alkyl, aryl, or halogen substituted monophenols with formaldehyde or a formaldehyde yielding compound.

6. The high molecular weight branched polycarbonate of claim 1, wherein the polycarbonate polymer contains residues of an aromatic dihydroxy compound [having up to ten carbon atoms], about 0.01 to about 2 mol percent of an orgaiic trihydric or tetrahydric phenol and about 1 to about 6 mol percent of monohydric phenol.

7. A process for the preparation of a high molecular weight branched polycarbonate substantially free of crosslinking which comprises reacting a carbonic acid derivative with an aromatic dihydroxy compound [containing up to about ten carbon atoms], from about 0.01 to about 2 mol percent of an organic trihydric or tetrahydric phenol and about 0.1 to about 8 mol percent of a monohydric phenol, the mol percentages being based on the mols of the organic dihydroxy compound.

8. The process of claim 7 wherein the trihydric or tetrahydric phenol is trimeric isopropenylphenol.

9. The process of claim 7 wherein the trihydric or tetrahydric phenol is the reaction product of an alkyl, aryl or halogen substituted monophenol with formaldehyde or a formaldehyde yielding compound.

10. The process of claim 7 wherein the carbonic acid derivative is phosgene or diphenyl carbonate.

11. Process of claim 7 wherein the aromatic dihydroxy compound is a dihydric phenol.

12. The high molecular weight branched polycarbonate of claim 1 wherein the aromatic dihydroxy compound is a dim onohydroxy arylene olkane or a dimonohydroxy arylene sulphone.

13. The high molecular weight branched polycarbonate of claim I wherein the aromatic dihydroxy compound is 2,2-(4,4'-dihydroxy-diphenylene)-propane.

14. The high molecular weight branched polycarbonate of claim I wherein the aromatic dihydroxy compound is 1,1-(4,4-dihydlroxy-diphenylene)-cyclohexanc.

15. A high molecular weight branched polycarbonate substantially free of crosslinking which comprises a polycarbonate polymer containing residues of an organic dihydroxy compound selected from the group consisting of aromatic dihydroxy compounds, aliphatic dihydroxy compounds and cycloaliphatic dihydroxy compounds, about 0.01 to about 2 mol percent of an organic trihydric or tetrahydric phenol and about 0.1 to about 8 mol percent of monohydric phenol, the mol percentages being based on the mols of the organic dihydroxy compound, said branched polycarbonate having a relative viscosity of from about 1.2 to about 1.55 measured on a solution of 0.5 gram in 100 ml. of methylene chloride at 25 C., an average molecular weight of between about 30,000 and about about 100,000 measured by light diffraction and a melt viscosity of between about 20,000 and about 300,000 poises at 280 C.

16. A process for the preparation of a high molecular weight branched polycarbonate substantially free of crosslinking which comprises reacting a carbonic acid derivative with an organic dihya'roxy compound selected from the group consisting of aromatic dihydroxy compounds, aliphatic dihydroxy compounds and cycloaliphatic dihydroxy compounds, from about 0.01 to about 2 mol percent of an organic trihydric or tetrahydric phenol and about 0.1 to about 8 mol percent of a monohydric phenol, the mo! percentages being based on the mols of the organic dihydroxy compound.

References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.

14 UNITED STATES PATENTS 3,240,756 3/1966 Deanin 26047 3,275,674 9/1966 Bottenbruch 260463 5 FOREIGN PATENTS 697,453 11/1964 Canada 26047 885,442 12/1961 Great Britain 26047 C. A. HENDERSON,

260-37 PC, 75.5 D 15 1a., Assistant Examiner US. Cl. X.R.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5021521 *Dec 22, 1989Jun 4, 1991General Electric CompanyProcess of reacting branched thermoplastic polycarbonate with polyhydric phenol having more than two hydroxy groups
US5037942 *Mar 28, 1990Aug 6, 1991The Dow Chemical CompanyContinuous motionless mixer reactor process for the production of branched polycarbonate
US5097002 *May 10, 1991Mar 17, 1992Ge Plastics Japan Ltd.Melt, catalytic process for preparing polycarbonates from carbonic acid diester
US5097008 *May 10, 1990Mar 17, 1992General Electric CompanyPreparation of branched polycarbonate from oligomeric cyclic polycarbonate and polyhydric phenol
US5142018 *Oct 30, 1991Aug 25, 1992Ge Plastics Japan Ltd.Process for preparing polycarbonates
US5151491 *Sep 21, 1989Sep 29, 1992Ge Plastics Japan, Ltd.Nitrogen compound, a boric acid compound and a dihydroxy compound terminated with a monoalcohol
US5276129 *Jun 19, 1992Jan 4, 1994Ge Plastics Japan, Ltd.Aromatic polycarbonates with excellent color tone, heat resistance and water resistance
US5473046 *Oct 5, 1994Dec 5, 1995Idemitsu Petrochemical Co., Ltd.Interfacial polymerization; heat resistance, corrosion resistance
US5521041 *Mar 3, 1993May 28, 1996Idemitsu Kosan Co., Ltd.Polycarbonate, method of preparing the same and electrophotographic photoreceptor produced by using the same
US5863992 *Dec 17, 1996Jan 26, 1999General Electric CompanyBisphenol a for polycarbonates
US6528612Mar 15, 2000Mar 4, 2003Bayer AktiengesellschaftHighly branched polycondensates
US7057005Jun 29, 2004Jun 6, 2006Dow Global Technologiessinc.mixing a dihydric phenol and a polyhydric phenol branching agent in basic solution; adding the carbonyl reagent and the water immissible organic solvent to polymerize; adding a monophenolic chain terminator and the coupling catalyst; improved branching and shear sensitivity
US7226985Jul 12, 2005Jun 5, 2007Eastman Chemical CompanyPolyester-polycarbonate compositions
US7230065Jul 12, 2005Jun 12, 2007Eastman Chemical CompanyBlends of polycarbonate and sulfone copolyesters
US7297736Oct 28, 2004Nov 20, 2007Eastman Chemical CompanyNeopentyl glycol containing polyesters blended with polycarbonates
US7342059Dec 16, 2003Mar 11, 2008Eastman Chemical Companyresultant blends are clear and do not produce problems with crystallization during the extrusion blow-molding process
US7345104Nov 5, 2004Mar 18, 2008Eastman Chemical CompanyPolyester-polycarbonate blends useful for extrusion blow-molding
US7425590Jul 12, 2005Sep 16, 2008Eastman Chemical CompanyTransparent two phase polyester-polycarbonate compositions
US7510768Mar 28, 2006Mar 31, 2009Eastman Chemical CompanyPolyester/aromatic polycarbonate blend
US7576171Mar 28, 2006Aug 18, 2009Eastman Chemical CompanyDicarboxylic acid component having terephthalic acid residues; optionally, aromatic dicarboxylic acid residues or aliphatic dicarboxylic acid residues high impact strengths, high glass transition temperature, toughness, certain inherent viscosities, low ductile-to-brittle transition temperatures
US7696297Jun 30, 2008Apr 13, 2010Sabic Innovative Plastics Ip B.V.Branched polycarbonates and processes for producing the same
US7704605Feb 4, 2009Apr 27, 2010Eastman Chemical Companypolyester containing terephthalic acid, optional other aromatic or aliphatic dicarboxylic acids, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cyclohexanedimethanol/1,4-/ , optional ethylene glycol; used in the construction industry as glazing for windows, in partitions and as decorative panels
US7737246Dec 7, 2006Jun 15, 2010Eastman Chemical CompanyPolyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor
US7740941Jan 29, 2009Jun 22, 2010Eastman Chemical CompanyThermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US7781562Mar 28, 2006Aug 24, 2010Eastman Chemical CompanyPolyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US7803439Mar 28, 2006Sep 28, 2010Eastman Chemical CompanyBlood therapy containers comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7803440Mar 28, 2006Sep 28, 2010Eastman Chemical CompanyContaining units of terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanol; a glass transition temperature of 100-130 degrees C.; izod impact strength of at least 7.5 ft-lbs/in at 23 degrees C.; melt viscosity is less than 10,000 poise; polycarbonate-free
US7803441Mar 28, 2006Sep 28, 2010Eastman Chemical CompanyTerephthalic acid; inherent viscosity of 0.60-0.75 dL/g; a glass transition temperature of 100-130 degrees C.; izod impact strength of at least 7.5 ft-lbs/in at 23 degrees C.; melt viscosity is less than 10,000 poise; polycarbonate-free
US7807774Mar 28, 2006Oct 5, 2010Eastman Chemical Companyglass transition temperature, density, slow crystallization rate, melt viscosity, and toughness but with melt processability; heat resistance, thermoforming
US7807775Mar 28, 2006Oct 5, 2010Eastman Chemical CompanyPoint of purchase displays comprising polyester compositions formed from 2,2,4,4-tetramethyl-1, 3,-cyclobutanediol and 1,4-cyclohexanedimethanol
US7812111Mar 28, 2006Oct 12, 2010Eastman Chemical CompanyLCD films comprising polyester compositions formed from 2,2,4,4-tetramethy1-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7812112Mar 28, 2006Oct 12, 2010Eastman Chemical Companyand terephthalic acid; melt processable with qualities of toughness, high impact strength, clarity, chemical resistance, high glass transition temperature Tg, hydrolytic stability, good color and clarity
US7834129Mar 28, 2006Nov 16, 2010Eastman Chemical CompanyRestaurant smallware comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7838620Mar 28, 2006Nov 23, 2010Eastman Chemical CompanyThermoformed sheet(s) comprising polyester compositions which comprise cyclobutanediol
US7842776Mar 28, 2006Nov 30, 2010Eastman Chemical Companycombination of two or more of properties: toughness, clarity, chemical resistance, Tg, and hydrolytic stability; no polycarbonate
US7855267Mar 28, 2006Dec 21, 2010Eastman Chemical CompanyFilm(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
US7868128Mar 28, 2006Jan 11, 2011Eastman Chemical CompanySkylights and windows comprising polyester compositions formed from 2,2,4,4,-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7893187Mar 28, 2006Feb 22, 2011Eastman Chemical CompanyGlass laminates comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7893188Mar 28, 2006Feb 22, 2011Eastman Chemical CompanyBaby bottles comprising polyester compositions which comprise cyclobutanediol
US7902320Mar 28, 2006Mar 8, 2011Eastman Chemical CompanyGraphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7906211Mar 16, 2010Mar 15, 2011Eastman Chemical CompanyThermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US7906212Mar 16, 2010Mar 15, 2011Eastman Chemical CompanyThermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US7906610Mar 28, 2006Mar 15, 2011Eastman Chemical CompanyFood service products comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7915376Mar 28, 2006Mar 29, 2011Eastman Chemical CompanyContainers comprising polyester compositions which comprise cyclobutanediol
US7951900Mar 28, 2006May 31, 2011Eastman Chemical CompanyDialysis filter housings comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7985827Mar 28, 2006Jul 26, 2011Eastman Chemical CompanyPolyester compositions which comprise cyclobutanediol having certain cis/trans ratios
US8063172Mar 28, 2006Nov 22, 2011Eastman Chemical CompanyFilm(s) and/or sheet(s) made using polyester compositions containing low amounts of cyclobutanediol
US8063173Mar 28, 2006Nov 22, 2011Eastman Chemical CompanyPolyester compositions containing low amounts of cyclobutanediol and articles made therefrom
US8067525Mar 28, 2006Nov 29, 2011Eastman Chemical CompanyFilm(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and high glass transition temperature
US8101705May 20, 2010Jan 24, 2012Eastman Chemical CompanyPolyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US8119761Mar 28, 2006Feb 21, 2012Eastman Chemical CompanyPolyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US8119762Nov 10, 2010Feb 21, 2012Eastman Chemical CompanyFilm(s) and/or sheet(s) comprising polyester compositions which comprise cyclobutanediol and have a certain combination of inherent viscosity and moderate glass transition temperature
US8133967Oct 7, 2010Mar 13, 2012Eastman Chemical CompanyRestaurant smallware comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US8193302Oct 27, 2006Jun 5, 2012Eastman Chemical CompanyPolyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof
US8198371Feb 23, 2009Jun 12, 2012Eastman Chemical CompanyBlends of polyesters and ABS copolymers
US8287970Nov 20, 2008Oct 16, 2012Eastman Chemical CompanyPlastic baby bottles, other blow molded articles, and processes for their manufacture
US8299204Oct 27, 2006Oct 30, 2012Eastman Chemical CompanyPolyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
US8354491Jan 28, 2011Jan 15, 2013Eastman Chemical CompanyContainers comprising polyester compositions which comprise cyclobutanediol
US8394997Dec 9, 2010Mar 12, 2013Eastman Chemical CompanyProcess for the isomerization of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8415450Jan 12, 2012Apr 9, 2013Eastman Chemical CompanyPolyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US8420868Dec 9, 2010Apr 16, 2013Eastman Chemical CompanyProcess for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8420869Dec 9, 2010Apr 16, 2013Eastman Chemical CompanyProcess for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8501287Sep 23, 2010Aug 6, 2013Eastman Chemical CompanyPlastic baby bottles, other blow molded articles, and processes for their manufacture
US8501292Aug 28, 2012Aug 6, 2013Eastman Chemical CompanyPlastic baby bottles, other blow molded articles, and processes for their manufacture
US8507638Aug 23, 2011Aug 13, 2013Eastman Chemical CompanyPolyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US8568860Nov 12, 2007Oct 29, 2013Sabic Innovative Plastics Ip B.V.Multiwall polymer sheet comprising branched polycarbonate
EP0327951A2 *Feb 2, 1989Aug 16, 1989Bayer AgPolycarbonates with aralkyl phenyl end groups, their preparation and their use
EP0387714A2 *Mar 9, 1990Sep 19, 1990Idemitsu Petrochemical Co., Ltd.Process for production of branched polycarbonate
EP0646613A2 *Oct 4, 1994Apr 5, 1995Idemitsu Petrochemical Co. Ltd.A branched polycarbonate and a process for producing the same
EP0819718A1 *Jul 7, 1997Jan 21, 1998General Electric CompanyTetraphenol polycarbonate branching agents
WO1990012059A1 *May 10, 1989Oct 18, 1990Gaf Chemicals CorpThermoplastic molding compositions
Classifications
U.S. Classification528/174, 528/202, 528/372, 528/199, 528/201, 528/204
International ClassificationC08G64/00, C08G64/14, C08G63/00
Cooperative ClassificationC08G64/14
European ClassificationC08G64/14