US20030139529A1 - Method of making block copolymers by solid state polymerization - Google Patents

Method of making block copolymers by solid state polymerization Download PDF

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Publication number
US20030139529A1
US20030139529A1 US10/000,913 US91301A US2003139529A1 US 20030139529 A1 US20030139529 A1 US 20030139529A1 US 91301 A US91301 A US 91301A US 2003139529 A1 US2003139529 A1 US 2003139529A1
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Prior art keywords
group
polycarbonate
starting material
partially crystalline
solid state
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US10/000,913
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Inventor
Gregory O'Neil
James Day
Daniel Brunelle
Joseph Suriano
Patrick McCloskey
Paul Smigelski
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General Electric Co
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General Electric Co
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Priority to US10/000,913 priority Critical patent/US20030139529A1/en
Assigned to GENERAL ELECTRIC COMPANY reassignment GENERAL ELECTRIC COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BRUNELLE, DANIEL J., DAY, JAMES, MCCLOSKEY, PATRICK J., SMIGELSKI, PAUL M., JR., SURIANO, JOSEPH A., O'NEIL, GREGORY A.
Priority to PCT/US2002/032085 priority patent/WO2003040208A1/en
Priority to DE60212172T priority patent/DE60212172T2/de
Priority to EP02778466A priority patent/EP1444288B1/en
Priority to AT02778466T priority patent/ATE328934T1/de
Priority to JP2003542251A priority patent/JP2005508419A/ja
Priority to CN02825545.3A priority patent/CN1286879C/zh
Publication of US20030139529A1 publication Critical patent/US20030139529A1/en
Priority to US10/743,241 priority patent/US6960641B2/en
Abandoned legal-status Critical Current

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    • 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
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation

Definitions

  • This invention relates to a method of copolymer preparation by solid state polymerization. More particularly the method relates to the preparation of block copolymers incorporating polycarbonate and polyester structural units by solid state polymerization.
  • Block copolymers are prized for the degree to which polymer physical properties are determined by polymer structure.
  • Block copolymer structure may be varied by adjusting the monomers constituting the blocks, the length of the blocks, and the number of blocks per copolymer molecule.
  • Block copolymers prepared from two different difunctional, mutually reactive oligomers, for example an oligomeric diacid chloride and an oligomeric diol, are referred to as multiblock copolymers and possess a structure in which there are multiple blocks comprising the structural units of the first oligomer alternating with blocks comprising the structural units of the second oligomer.
  • the physical properties of multiblock copolymers may be adjusted through careful control of the block length of the starting oligomers and the choice of a synthetic method which preserves the block length of the starting oligomers in the final multiblock copolymer.
  • Block copolymers incorporating polycarbonate and polyester structural units, block copolyestercarbonates have demonstrated effectiveness as UV resistant thermoplastics and hold promise as “weatherable” plastic materials for use in applications in which resistance to the elements is required.
  • Block copolyestercarbonates are typically prepared by reaction of at least one aromatic dihydroxy compound with at least one aromatic dicarboxylic acid dichloride in the presence of water and a solvent such as methylene chloride, an acid acceptor such as sodium hydroxide, and an amine catalyst such as triethylamine to produce a hydroxy-terminated oligomeric polyester.
  • the hydroxy-terminated oligomeric polyester is then further reacted with an additional source of carbonate units, for example phosgene, under interfacial conditions analogous to those used in making polycarbonates such as bisphenol A polycarbonate, in the presence of at least one dihydroxy aromatic compound.
  • an additional source of carbonate units for example phosgene
  • a block copolyestercarbonate having polyester blocks and polycarbonate blocks is produced.
  • SSP solid state polymerization
  • SSP offers several advantages over both melt phase and the interfacial polycondensation processes. SSP does not require the use of phosgene gas which forms an important element of the interfacial process. Additionally SSP utilizes considerably lower temperatures than those required for the preparation of high molecular weight polycarbonate by melt polymerization of a diaryl carbonate such as diphenyl carbonate and a bisphenol such as bisphenol A. Also, the SSP process, unlike the melt phase process, does not require handling highly viscous polymer melt at high temperatures and the special equipment capable of mixing polymer melt under vacuum at high temperature required in the melt process is not required to perform the SSP process.
  • This oligomerization reaction is typically carried out under reduced pressure to facilitate the orderly removal of the phenol by-product.
  • the reaction is terminated and the product oligomeric polycarbonate is isolated.
  • the oligomeric polycarbonate so produced is amorphous and must be partially crystallized in order to be suitable for solid state polymerization.
  • the oligomeric polycarbonate may be partially crystallized by one of several methods, such as exposure of powdered or pelletized oligomer to hot solvent vapors, or dissolution of the amorphous oligomer in a solvent such as methylene chloride and thereafter adding a solvent such as methanol or ethyl acetate to precipitate crystalline oligomeric polycarbonate.
  • solvent vapor or liquid solvent crystallization methods result in partially crystalline oligomeric polycarbonates having a percent crystallinity between about 20 and about 40 percent as measured by differential scanning calorimetry.
  • the partially crystalline oligomeric polycarbonate in a solid form such as a powder, particulate or pellet is then heated under solid state polymerization conditions at a temperature below the sticking temperature or melting point of the oligomeric polycarbonate, but above the glass transition temperature of the partially crystalline oligomeric polycarbonate, and the volatile by-products formed as chain growth occurs, phenol, diphenyl carbonate and the like, are removed.
  • the polycondensation reaction which converts the low molecular weight oligomer to high polymer is effected in the solid state under these conditions.
  • the solid state polymerization method suffers from several disadvantages.
  • the partially crystalline precursor polycarbonate and a partially crystalline oligomeric polyester precursor require two steps for their preparation; an oligomerization step and a crystallization step.
  • the solid state polymerization process itself is relatively slow, and affords a random distribution of ester and carbonate structural units within the product copolyestercarbonate.
  • the present invention provides a method of preparing block copolymers, said method comprising contacting a partially crystalline polycarbonate starting material (A) comprising activated terminal aryloxy groups with at least one polymeric species (B) comprising reactive terminal hydroxy groups under solid state polymerization conditions to afford a product block copolymer.
  • the block copolymer is a multiblock copolyestercarbonate.
  • polycarbonate refers to polycarbonates incorporating structural units derived from one or more dihydroxy aromatic compounds and includes copolycarbonates and polyester carbonates.
  • BPA is herein defined as bisphenol A and is also known as 2,2-bis(4-hydroxyphenyl)propane, 4,4′-isopropylidenediphenol and p,p-BPA.
  • bisphenol A polycarbonate refers to a polycarbonate in which essentially all of the repeat units comprise a bisphenol A residue.
  • partially crystalline polycarbonate starting material (A) comprising activated terminal aryloxy groups is used interchangeably with the terms “partially crystalline polycarbonate starting material (A)” and “starting material (A)”, each of said terms referring to a partially crystalline polycarbonate comprising activated terminal aryloxy groups.
  • polymeric species (B) comprising reactive terminal hydroxy groups is used interchangeably with the terms “polymeric species (B)” and “starting material (B)”, each of said terms referring to a polymeric species comprising reactive terminal hydroxyl groups.
  • polymeric species includes both polymeric and oligomeric materials.
  • Polymeric materials are defined as having weight average molecular weights, M w , greater than 15,000 daltons, and oligomeric materials are defined as having weight average molecular weights, M w , less than 15,000 daltons.
  • partially crystalline precursor polycarbonate refers to an oligomeric polycarbonate having a weight average molecular weight of less than 15000 daltons and percent crystallinity of at least about 15 percent based on differential scanning calorimetry.
  • partially crystalline precursor polycarbonate and “partially crystalline oligomeric polycarbonate” are used interchangeably.
  • oligomeric hydroxy-terminated polyester includes both aliphatic and aromatic oligomeric hydroxy-terminated polyesters.
  • oligomeric hydroxy-terminated polyesters includes oligomeric hydroxy-terminated polyarylates.
  • oligomeric hydroxy-terminated polyester refers to an oligomeric polyester having a weight average molecular weight (M w ) of less than 15,000 and having hydroxy groups at about 50 percent or more of its chain ends.
  • M w weight average molecular weight
  • a polyester prepared by the melt reaction of excess resorcinol with a 1:1 mixture of diphenyl isophthalate and diphenyl terephthalate, having a weight average molecular weight of 9,000 daltons and possessing hydroxy groups at 80 percent of the chain ends and phenoxy groups at 20 percent of the chain ends represents an oligomeric hydroxy-terminated polyester.
  • reactive terminal hydroxyl groups refers to hydroxy groups located at the chain ends of polymeric species, for example, the hydroxy groups found at the chain ends of an oligomer produced by the interfacial reaction of a 10 mole percent excess of bisphenol A with isophthaloyl dichloride.
  • bis(methyl salicyl) carbonate and bis(2-methoxycarbonylphenyl) carbonate have the same meaning and are used interchangeably.
  • percent endcap refers to the percentage of polycarbonate chain ends which are not hydroxyl groups.
  • a “percent endcap” value of about 75% means that about seventy-five percent of all of the polycarbonate chain ends comprise phenoxy groups while about 25% of said chain ends comprise hydroxyl groups.
  • percent endcap and percent endcapping are used interchangeably.
  • aromatic radical refers to a radical having a valence of at least one and comprising at least one aromatic ring.
  • aromatic radicals include phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl.
  • the term includes groups containing both aromatic and aliphatic components, for example a benzyl group.
  • aliphatic radical refers to a radical having a valence of at least one and consisting of a linear or branched array of atoms which is not cyclic.
  • the array may include heteroatoms such as nitrogen, sulfur and oxygen or may be composed exclusively of carbon and hydrogen.
  • Examples of aliphatic radicals include methyl, methylene, ethyl, ethylene, hexyl, hexamethylene and the like.
  • cycloaliphatic radical refers to a radical having a valance of at least one and comprising an array of atoms which is cyclic but which is not aromatic, and which does not further comprise an aromatic ring.
  • the array may include heteroatoms such as nitrogen, sulfur and oxygen or may be composed exclusively of carbon and hydrogen.
  • cycloaliphatic radicals include cyclopropyl, cyclopentyl cyclohexyl, 2-cyclohexylethy-1-yl, tetrahydrofuranyl and the like.
  • multilayer article refers to an article which comprises at least two layers.
  • the present invention relates to a method for preparing block copolymers, said method comprising contacting a partially crystalline polycarbonate starting material (A) comprising activated terminal aryloxy groups with at least one polymeric species (B) comprising reactive terminal hydroxy groups under solid state polymerization conditions to afford a product block copolymer.
  • the block copolymer is a multiblock copolyestercarbonate.
  • the partially crystalline polycarbonate starting material (A) according to the method of the present invention comprises activated terminal aryloxy groups having structure I
  • R 1 is independently at each occurrence a C 1 -C 20 aliphatic radical, C 4 -C 20 cycloaliphatic radical, C 4 -C 20 aromatic radical
  • R 2 is independently at each occurrence a halogen atom, nitro group, cyano group, C 1 -C 20 alkoxycarbonyl group, C 1 -C 20 acyl group, C 4 -C 20 cycloalkoxycarbonyl group, C 6 -C 20 aryoxycarbonyl group, C 1 -C 20 alkylaminocarbonyl group, C 2 -C 40 dialkylaminocarbonyl group, or a C 1 -C 20 perfluoroalkyl group; p is an integer having a value 0 to 4, and q is an integer having a value of 1 to 5.
  • Terminal groups having structure I are exemplified by the 2-methoxycarbonylphenoxy, 2-cyanophenoxy, 2-acetylphenoxy, 2-nitrophenoxy, 4-nitrpophenoxy, and 2,4,6-trifluorophenoxy groups.
  • the partially crystalline polycarbonate starting material (A) comprising activated terminal aryloxy groups is prepared by the melt reaction of at least one dihydroxy aromatic compound with at least one diaryl carbonate to provide an amorphous polycarbonate which is then crystallized in a second step.
  • the partially crystalline polycarbonate starting material (A) comprising activated terminal aryloxy groups may be obtained directly by reaction of a dihydroxy aromatic compound with a diaryl carbonate, for example the reaction of bisphenol A with bis(methyl salicyl) carbonate under reaction conditions promoting the crystallization of the polycarbonate product.
  • the partially crystalline polycarbonate starting material (A) comprising activated terminal aryloxy groups may be obtained by interfacial reaction of phosgene with at least one dihydroxy aromatic compound in the presence of an acid acceptor and a hydroxy aromatic compound chainstopper, said chain stopper comprising at least one “activating substituent”.
  • Activating substituents include alkoxycarbonyl groups; for example, the methoxycarbonyl group, the cyano group; the nitro group; and halogen atoms.
  • Chainstoppers incorporating at least one activating substituent are exemplified by methyl salicylate, 2-cyanophenol, 2,4,6-trifluorophenol and the like.
  • the partially crystalline polycarbonate starting material (A) comprising activated terminal aryloxy groups is prepared by a method comprising treatment under melt reaction conditions of a polycarbonate comprising reactive terminal hydroxy groups, with a diaryl carbonate comprising activating substituents, for example, diaryl carbonates having structure II.
  • a polycarbonate comprising reactive terminal hydroxy groups said polycarbonate having been prepared either by melt polymerization or interfacial polymerization, may be further reacted with a diaryl carbonate comprising activating substituents, thereby converting all or a portion of said reactive terminal hydroxy groups to endgroups comprising activated terminal aryloxy groups and affording a polycarbonate comprising said activated terminal aryloxy groups. Crystallization of said polycarbonate comprising activated terminal aryloxy groups affords starting material (A).
  • melt polymerization conditions is understood to mean those conditions necessary to effect reaction between a diaryl carbonate and a dihydroxy aromatic compound in the presence of a catalyst and optionally a co-catalyst.
  • the catalyst may be any one of a number of transesterification catalysts, such as alkali metal hydroxides, alkaline earth hydroxides and mixtures thereof.
  • Co-catalysts include tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide; tetraalkylphosphonium hydroxides, such as tetrabutylphosphonium hydroxide; and tetraalkylphosphonium carboxylates, such as tetrabutylphosphonium acetate.
  • the reaction temperature is typically in the range of about 100 to about 350° C., more preferably about 180 to about 310° C.
  • the pressure may be at atmospheric pressure, supraatmospheric pressure, or a range of pressures from atmospheric pressure to about 15 torr in the initial stages of the reaction, and at a reduced pressure at later stages, for example in the range of about 0.2 to about 15 torr.
  • the reaction time is generally about 0.1 hours to about 10 hours.
  • the partially crystalline polycarbonate starting material (A) is prepared by a method comprising reacting under melt polymerization conditions at least one dihydroxy aromatic compound with at least one diaryl carbonate II
  • R 1 , R 2 , p and q are defined as in structure I.
  • Diaryl carbonates II are exemplified by bis(2-methoxycarbonylphenyl) carbonate, bis(4-chloro-2-methoxycarbonylphenyl) carbonate, bis(2-ethoxycarbonylphenyl) carbonate, bis(2-butoxycarbonylphenyl) carbonate, bis(2,4,6-trifluorophenyl) carbonate, bis(2-nitrophenyl) carbonate, and bis(2-cyanophenyl) carbonate.
  • Dihydroxy aromatic compounds which may be employed to prepare said partially crystalline polycarbonate starting material (A) include bisphenols III
  • R 3 is independently at each occurrence a halogen atom, nitro group, cyano group, C 1 -C 20 alkyl group, C 4 -C 20 cycloalkyl group, or C 6 -C 20 aryl group; n and m are independently integers 0-4; and W is a bond, an oxygen atom, a sulfur atom, a SO 2 group, a C 1 -C 20 aliphatic radical, a C 6 -C 20 aromatic radical, a C 6 -C 20 cycloaliphatic radical or the group
  • R 4 and R 5 are independently a hydrogen atom, C 1 -C 20 alkyl group, C 4 -C 20 cycloalkyl group, or C 4 -C 20 aryl group; or R 4 and R 5 together form a C 4 -C 20 cycloaliphatic ring which is optionally substituted by one or more C 1 -C 20 alkyl, C 6 -C 20 aryl, C 5 -C 21 aralkyl, C 5 -C 20 cycloalkyl groups or a combination thereof.
  • Bisphenols having structure III are exemplified by bisphenol A; 2,2-bis(4-hydroxy-3-methylphenyl)propane; 2,2-bis(4-hydroxy-2-methylphenyl)propane; 2,2-bis(3-chloro-4-hydroxyphenyl)propane; 2,2-bis(3-bromo-4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-3-isopropylphenyl)propane; 1,1-bis(4-hydroxyphenyl)cyclohexane; 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane; 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 4,4′-dihydroxy-1,1-biphenyl; 4,4′-dihydroxy-3,3′-dimethyl-1,1-biphenyl; 4,4′-dihydroxy-3,3′-dioctyl- 1,1 -biphen
  • the partially crystalline polycarbonate starting material (A) will have a percent endcap of between about 50 and about 100 percent and a percent crystallinity as measured by differential scanning calorimetry of between about 15 and about 40 percent.
  • starting material (A) will have a weight average molecular weight between about 1000 and about 30,000 daltons.
  • the partially crystalline polycarbonate starting material (A) is a “partially crystalline precursor polycarbonate” as defined herein, said partially crystalline precursor polycarbonate having a weight average molecular weight less than 15000 daltons, preferably in a range between about 1000 and about 14000 daltons.
  • polymeric species (B) comprising reactive terminal hydroxy groups comprises structural units selected from the group consisting of
  • R 6 and R 7 are independently at each occurrence a halogen atom, C 1 -C 20 aliphatic radical, C 4 -C 20 cycloaliphatic radical, or a C 4 -C 20 aromatic radical, and r and s are independently integers having values from 0 to 4; and
  • R 3 , n, m, and W are defined as in structure III.
  • the polymeric species (B) comprising reactive terminal hydroxy groups is an oligomeric polyester comprising structural units VII and having a degree of polymerization of at least about 4.
  • resorcinol is reacted with a mixture of terephthaloyl dichloride and isophthaloyl dichloride under interfacial conditions such that the molar ratio of resorcinol to total moles of terephthaloyl dichloride and isophthaloyl dichloride is between about 1.01 and about 1.5, and the molar ratio of terephthaloyl dichloride to isophthaloyl dichloride is in a range between about 1 to about 10 and about 10 to about 1.
  • Polyesters comprising repeat units having structure V may also be prepared by contacting one or more dihydroxy aromatic compounds, such as resorcinol and hydroquinone, with one or more diaryl esters such as diphenyl terephthalate and diphenyl isophthalate, under melt polymerization conditions in the presence of a transesterification catalyst such as an alkali metal hydroxide and a co-catalysts, such as a tetraalkylammonium hydroxide.
  • a transesterification catalyst such as an alkali metal hydroxide and a co-catalysts, such as a tetraalkylammonium hydroxide.
  • polymeric species (B) is a polyester comprising repeat units VII and further comprising reactive terminal hydroxy groups is prepared by reacting resorcinol under melt polymerization conditions with a mixture of diphenyl terephthalate and diphenyl isophthalate in the presence of a transesterification catalyst. The reaction is carried out such that the molar ratio of moles of resorcinol to the combined number of moles of diphenyl terephthalate and diphenyl isophthalate is between about 1.01 and about 1.5, and the molar ratio of diphenyl terephthalate to diphenyl isophthalate is in a range between about 1 to about 10 and about 10 to about 1.
  • polymeric species (B) comprising repeat units VII and further comprising reactive terminal hydroxy groups is prepared by reacting resorcinol reacted under melt polymerization conditions with a mixture of diphenyl terephthalate and diphenyl isophthalate in the absence of any added catalyst.
  • the reaction is carried out such that the molar ratio of moles of resorcinol to the combined number of moles of diphenyl terephthalate and diphenyl isophthalate is between about 1.01 and about 1.5, and the molar ratio of diphenyl terephthalate to diphenyl isophthalate is in a range between about 1 to about 10 and about 10 to about 1.
  • Block copolymers are prepared according to the method of the present invention by contacting a partially crystalline polycarbonate starting material (A) comprising activated terminal aryloxy groups with at least one polymeric species (B) comprising reactive terminal hydroxy groups under solid state polymerization conditions.
  • the starting material (A) may be a partially crystalline “polymeric material” as defined herein, meaning a polycarbonate having a weight average molecular weight, M w , of greater than 15,000 daltons.
  • partially crystalline polycarbonate starting material (A) may be a partially crystalline oligomeric polycarbonate having M w , of less than 15,000 daltons.
  • Contacting the partially crystalline polycarbonate starting material (A) comprising activated terminal aryloxy groups with at least one polymeric species (B) comprising reactive terminal hydroxy groups under solid state polymerization conditions may be carried out by forming a mixture of starting materials (A) and (B) and subjecting the said mixture to solid state polymerization conditions.
  • the mixture may be formed by mixing the partially crystalline polycarbonate starting material (A) in powder form with polymeric species (B) in powder form. This mixing may be accomplished by dry mixing the two powders using a variety of mechanical devices, for example, a roller mixer, or a Henschel mixer.
  • crystalline polycarbonate starting material (A) is mixed together with at least one polymeric species (B) such that the weight ratio of starting material (A) to starting material (B) is in a range between about 0.01 to about 100 and about 100 to about 0.01.
  • the starting materials (A) and (B) are mixed in a weight ratio of between 0.01 grams and 100 grams starting material (A) per gram of starting material (B). More typically, the weight ratio of starting material (A) to starting material (B) is in a range between about 1 to about 5 and about 5 to about 1.
  • starting material (A) is partially crystalline and starting material (B) is amorphous it is desirable that starting material (A) be the major component present in the mixture.
  • the polymeric species (B) may be a partially crystalline material or may be amorphous.
  • the polymeric species (B) is a hydroxy terminated polyester such as polyethylene terephthalate or polybutylene terephthalate it may be a partially crystalline material.
  • polymeric species (B) is a hydroxy terminated polyarylate comprising structural units derived from resorcinol, diphenyl terephthalate and diphenyl isophthalate it will typically be an amorphous material.
  • Alternate methods of preparing mixtures of the starting materials (A) and (B) include preparing a solution containing a polycarbonate starting material comprising activated terminal aryloxy groups, and a polymeric species (B), and adding an anti solvent to precipitate the two materials as a mixture.
  • Suitable solvents include halogenated solvents such as methylene chloride.
  • Anti solvents include alcohols such as methanol, ketones such as acetone, and esters such as ethyl acetate.
  • the precipitate contains the polymeric species (B) admixed with the partially crystalline polycarbonate starting material (A).
  • the partially crystalline precursor polycarbonate (A) in powder form is mixed with at least two polymeric species (B), for example powdered forms of polyethylene terephthalate and a polyarylate oligomer comprising structural units VII, and the mixture of powders is then reacted under solid state polymerization conditions to afford a block copolyestercarbonate.
  • B polymeric species
  • the solid state polymerization conditions employed according to the method of the present invention comprise heating a mixture of the partially crystalline polycarbonate starting material (A) with at least one polymeric species (B) at a temperature between about 100° C. and about 240° C. for a period of from about 0.5 and about 10 hours, preferably between about 140° C. and about 220° C. for a period of from between about between about 2 and about 9 hours.
  • the solid state polymerization may be carried out in any reaction vessel adapted for contacting a stream of an inert gas with the solid undergoing solid state polymerization, and removal of the by-products of solid state polymerization.
  • the by-products of solid state polymerization are principally hydroxy aromatic compounds comprising at least one activating substituent, for example methyl salicylate.
  • the hydroxy aromatic compound by-products are formed in chain growth steps such as when the reactive hydroxy groups of starting material (B) react with the activated terminal groups of starting material (A).
  • the by-products of solid state polymerization may also include diaryl carbonates such as II and mixed carbonates, for example phenyl salicyl carbonate.
  • Mixed carbonates and phenol may be present in the by-products of solid state polymerization when starting material (A) comprises activated terminal aryloxy groups and starting material (B) comprises terminal phenoxy groups, as is the case when stating material (B) is made by the melt reaction of one or more diphenyl esters with a molar excess of a dihydroxy aromatic compound.
  • the solid state polymerization process may be carried out in either a batch or continuous mode.
  • the solid mixture undergoing solid state polymerization is configured as a fixed bed with an inert gas passing through it.
  • the block copolymer product made by the method of the present invention is typically a multi-block copolymer.
  • both starting material (A) and starting material (B) contain internal functional groups subject to attack by a reactive hydroxy group, for example the internal carbonate groups of starting material (A) or the internal ester linkages present when starting material (B) is an oligomeric polyester. Reactions between terminal reactive hydroxy groups and internal functional groups results in a reduction of the average block length of one or more of the blocks present in the product block copolymer. Under certain conditions a completely random distribution of the repeat units present in the product block copolymer may be obtained.
  • An important feature of the method of the present invention is the ability to control and limit the randomization of the structural units present in the block copolymer. This is achieved by favoring bond forming processes between starting material (A) and starting material (B) based upon the enhance reactivity of the terminal groups in starting material (A).
  • the method of the present invention preserves to a greater extent the block lengths of the starting materials than do other solid state polymerization methods in which the partially crystalline polycarbonate lacks activated terminal aryloxy groups I. This preservation of the block lengths is quantifiable by comparing the block lengths present in the product block copolymer with the block lengths which would be expected if the structural units of the copolymer were distributed randomly along the polymer chain.
  • the block lengths of the product block copolymer are at least 50 to about 90 percent longer, preferably at least 60 to about 90 percent longer than the corresponding random distribution of structural units in an identically constituted copolymer.
  • the block copolymers made by the method of the present invention may optionally be blended with any conventional additives, including but not limited to dyestuffs, UV stabilizers, antioxidants, heat stabilizers, and mold release agents, to form a molded article.
  • any conventional additives including but not limited to dyestuffs, UV stabilizers, antioxidants, heat stabilizers, and mold release agents, to form a molded article.
  • the blend may optionally comprise from about 0.0001 to about 10% by weight of the desired additives, more preferably from about 0.0001 to about 1.0% by weight of the desired additives.
  • Substances or additives which may be added to the block copolymers of this invention include, but are not limited to, heat-resistant stabilizer, UV absorber, mold-release agent, antistatic agent, slip agent, antiblocking agent, lubricant, anticlouding agent, coloring agent, natural oil, synthetic oil, wax, organic filler, inorganic filler and mixtures thereof.
  • heat-resistant stabilizers examples include, but are not limited to, phenol stabilizers, organic thioether stabilizers, organic phosphide stabilizers, hindered amine stabilizers, epoxy stabilizers and mixtures thereof.
  • the heat-resistant stabilizer may be added in the form of a solid or liquid.
  • UV absorbers include, but are not limited to, salicylic acid UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, cyanoacrylate UV absorbers and mixtures thereof.
  • mold-release agents include, but are not limited to natural and synthetic paraffins, polyethylene waxes, fluorocarbons, and other hydrocarbon mold-release agents; stearic acid, hydroxystearic acid, and other higher fatty acids, hydroxyfatty acids, and other fatty acid mold-release agents; stearic acid amide, ethylenebisstearamide, and other fatty acid amides, alkylenebisfatty acid amides, and other fatty acid amide mold-release agents; stearyl alcohol, cetyl alcohol, and other aliphatic alcohols, polyhydric alcohols, polyglycols, polyglycerols and other alcoholic mold release agents; butyl stearate, pentaerythritol tetrastearate, and other lower alcohol esters of fatty acid, polyhydric alcohol esters of fatty acid, polyglycol esters of fatty acid, and other fatty acid ester mold release agents; silicone oil and other silicone mold release agents, and mixtures of
  • the coloring agent may be either pigments or dyes. Inorganic coloring agents and organic coloring agents may be used separately or in combination in the invention.
  • the block copolymers prepared by the method of the present invention may transformed into desired articles by molding the block copolymer, or a blend of the block copolymer with a second polymer such as bisphenol A polycarbonate, by injection molding, compression molding, extrusion methods and solution casting methods. Injection molding is the more preferred method of forming the article.
  • the molded article formed from the block copolymer made by the method of the present invention is a multilayer article. Multilayer articles prepared from block copolymers comprising structural units V and VI, said block copolymers being prepared by the method of the present invention, are particularly well suited for use in such varied outdoor applications such as body parts for outdoor vehicles and the like.
  • Molecular weights are reported as number average (M n ) or weight average (M w ) molecular weight and were determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the first method employed polycarbonate molecular weight standards to construct a broad standard calibration curve against which polymer molecular weights were determined. This calibration method was used to determine the molecular weights of methyl salicylate endcapped polycarbonate oligomers used to prepare block copolycarbonates as described herein.
  • the second GPC calibration method relied upon a series of polystyrene standards of known molecular weight which were used to construct a calibration curve with which to determine the molecular weights of product copolyestercarbonates.
  • This second GPC calibration method was also used to determine the molecular weights of oligomeric polyesters described herein.
  • GPC When characterizing a polycarbonate by GPC, it is generally believed that the molecular weights obtained using polycarbonate standards are more accurate than those obtained using polystyrene standards.
  • polycarbonate molecular weights determined using a polystyrene standard based GPC method have M n and M w values which are about 1.5 to about 2.5 times higher than the same values measured using polycarbonate standards.
  • the degree of polymerization (DP) of polycarbonate and polyester oligomers was obtained using NMR.
  • Polycarbonate oligomer degree of polymerization values obtained by NMR generally correlate well with M n values obtained by GPC using polycarbonate molecular weight standards.
  • Gel permeation chromatography was carried out such that the temperature of the columns was about 25° C. and the mobile phase was chloroform.
  • Solid state polymerizations were carried out as follows. About 1 gram of the material being subjected to a “heating protocol under solid state polymerization conditions” was placed in a 10 mL fritted funnel positioned in a convection oven. The base of the oven was equipped with a nitrogen inlet. Nitrogen, preheated by passage through approximately 16 meters of copper tubing contained within the convection oven, was passed through the base of the funnel, through the material undergoing solid state polymerization and out through the top of the funnel. The nitrogen flow rate was about 2.5 liters per minute. Typically, over the course of the solid state polymerization reaction the temperature was raised in one or more steps from an initial temperature of about 140° C.
  • the course of the solid state polymerization reaction was followed by periodically sampling the material in the fritted funnel and subjecting the sample to differential scanning calorimetry (DSC).
  • the copolyestercarbonate product of solid state polymerization the product was characterized by DSC to determine the glass transition temperature, GPC using polystyrene standards to determine the values of M n and M w , and NMR to evaluate the composition and blockiness of the product copolyestercarbonate.
  • the product copolyestercarbonates are “multiblock copolyestercarbonates” which for convenience are referred to here simply as “block copolyestercarbonates”.
  • Amorphous methyl salicyl endcapped polycarbonate was prepared as follows. The reactor was charged with 150 grams (0.6571 mole) solid bisphenol-A (BPA) and 243.6 grams (0.7368 mole) solid bis(methyl salicyl) carbonate (BMSC) such that the molar ratio of BMSC to BPA was about 1.12 at the outset of the reaction. Tetrabutyl phosphonium acetate co-catalyst was added in an amount corresponding to 2.5 ⁇ 10 ⁇ 4 moles co-catalyst per mole BPA. The catalyst, EDTA magnesium disodium salt, was added in an amount corresponding to 1.0 ⁇ 10 ⁇ 6 mole catalyst per mole BPA.
  • the reactor was sealed and the atmosphere was exchanged with nitrogen three times. Following the final nitrogen exchange the pressure in the reactor was brought to between about 5 and about 15mmHg.
  • the reactor was submerged in the fluidized bath at 170° C. After five minutes, agitation was begun at a rate of 60 rpm. After an additional ten to fifteen minutes the reactants were fully melted and the agitator speed was increased to 200 rpm.
  • the reaction mixture was stirred and heated while liberated methyl salicylate was collected in the receiving vessel. Between about 90 and about 95 percent of the theoretical amount (based on complete reaction between BPA and the BMSC) of the methyl salicylate by-product was removed at 170° C.
  • the bath temperature was then raised through a series of temperature stages; 210° C., 240° C., and 270° C. and the reaction mixture was stirred for 20 minutes at each stage. During the last two stages (240° C. and 270° C.) the pressure over the reaction mixture was reduced to about 1 torr or less.
  • Examples 2-6 represent analogously prepared amorphous methyl salicyl endcapped polycarbonate oligomers. Data for oligomeric polycarbonates of Examples 2-6 are gathered in Table 1. TABLE 1 AMORPHOUS METHYL SALICYL ENCAPPED OLIGOMERS Example BMSC/BPA Mw Mn [OH] EC(%) 2 1.042 12906 5697 109 98.2 3 1.052 10853 4973 96 98.6 4 1.064 9547 3871 189 97.9 5 1.087 6885 3134 0 100 6 1.136 4376 2013 0 100
  • Crystalline oligomeric polycarbonates incorporating methyl salicyl endgroups were prepared analogously.
  • the reactor was charged with solid BPA (150 g or 300 g, 0.6571 or 1.3141 mole) and solid BMSC such that the molar ratio of BMSC to BPA was between about 1.00 and about 1.15 at the outset of the reaction.
  • Catalyst identities and amounts were the same as those used in Example 1.
  • the reactor was, sealed and the atmosphere was exchanged with nitrogen three times. Following the final nitrogen exchange the pressure in the reactor was brought to between about 5 and about 15 mmHg.
  • the reactor was submerged into the fluidized bath at 170° C. After five minutes, agitation was begun at a rate of 60 rpm.
  • methyl salicylate was distilled from the reaction vessel until between about 90 and about 95 percent of the theoretical amount (based on complete reaction between BPA and the BMSC) of the methyl salicylate by-product had been removed.
  • the reaction vessel was then removed from the sand bath and the vessel was gently purged with nitrogen gas. Upon cooling, the crystalline oligomeric product was observed to contract and fracture. The cooled crystalline product was easily poured from the reactor.
  • BMSC/BPA represents the mole ratio of bis(methyl salicyl) carbonate to bisphenol A employed.
  • [OH] is expressed in parts per million (ppm) and represents the concentration of free hydroxyl groups found in the product polycarbonate. The free hydroxyl group concentration was determined by quantitative infrared spectroscopy.
  • EC (%) represents the percentage of polymer chain ends not terminating in a hydroxyl group. Salicyl endgroups were determined by HPLC analysis after product solvolysis.
  • % Cryst represents the percent crystallinity of the product polycarbonate and was determined by differential scanning calorimetry.
  • Tg of this material was 112° C.
  • Oligomeric hydroxy-terminated polyesters comprising structural units derived from resorcinol, isophthalic acid, and terephthalic acid, or their derivatives, are referred to as “ITR oligomers”.
  • a series of oligomeric hydroxy-terminated polyesters comprising Examples 12-19 was prepared by the melt reaction of resorcinol with a 1:1 mixture of diphenyl isophthalate and diphenyl terephthalate according to the method described in Example 11. Data for the oligomeric hydroxy-terminated polyesters of Examples 11 -19 are gathered in Table 3. Values of weight average molecular weight, M w , were determined by GPC using polystyrene molecular weight standards. TABLE 3 HYDROXY TERMINATED POLYESTER OLIGOMERS Mw % excess % phenol Example oligomer a resorcinol removed Tg 11 8,026 10 80 112° C.
  • the product block copolyestercarbonate was analyzed by DSC, and shown to possess a T g of about 129° C. and two broad peaks corresponding to melting points at approximately 187° C. and 208° C., respectively.
  • Quantitative 13 C-NMR indicated a blocky copolymer with an average polycarbonate block length of about 4.05 and an average polyester block length of about 7.
  • Example 20 A portion of the powder mixture reserved for later use in Example 20 was subjected to the following heating protocol under solid state polymerization conditions. Step Temperature Time Total Time 1 140-160° C. 185 minutes 185 minutes 2 165° C. 25 minutes 210 minutes 3 170° C. 20 minutes 230 minutes
  • the product copolyestercarbonate had a T g of about 135° C. and two broad peaks corresponding to melting points at approximately 169° C. and 221° C. respectively.
  • Quantitative 13 C-NMR indicated a blocky copolymer with an average polycarbonate block length of about 6.7 and an average polyester block length of about 8.6.
  • the product copolyestercarbonate had a T g of about 143° C. and three corresponding to melting points at approximately 130° C., 161° C. and 243° C. respectively.
  • Quantitative 13 C-NMR indicated a blocky copolymer with an average polycarbonate block length of about 4.25 and an average polyester block length of about 6.4.
  • the product copolyestercarbonate had a T g of about 133° C. and two broad peaks corresponding to melting points at approximately 162° C. and 221° C. respectively.
  • Quantitative 13 C-NMR indicated a blocky copolymer with an average polycarbonate block length of about 5.65 and an average polyester block length of about 7.
  • the partially crystalline oligomeric polycarbonate had a percent endcapping of about 60 percent, meaning that 60 percent of the oligomer chain ends were phenoxy groups derived from diphenyl carbonate, and about 40 percent of the chain ends were hydroxy groups.
  • a portion of the partially crystalline oligomeric polycarbonate was mixed together in a laboratory mill mixer for several minutes with an equal weight of a fine powder of oligomeric hydroxy-terminated polyester (DP about 9.2 by 13 C-NMR) prepared using the methodology and proportions of Example 11. The mixture was then subjected to the following heating protocol under solid state polymerization conditions. Step Temperature Time Total Time 1 170-200° C. 75 minutes 75 minutes 2 200° C. 60 minutes 135 minutes
  • Example 20-24 illustrate the method of the present invention which provides blocky copolyestercarbonates under mild conditions.
  • Comparative Example 1 illustrates the limitations of conventional solid state polymerization technology for the preparation of copolyestercarbonates. Data for Example 20-24 and Comparative Example 1 is given in Table 4.
  • Examples 20-24 between about 70 and about 97 percent of the initial polyester block length is preserved in the product copolyestercarbonate.
  • the average block length of the hydroxy-terminated ITR oligomer also referred to as its degree of polymerization (DP)
  • DP degree of polymerization
  • the product copolyestercarbonate following solid state polymerization comprised polyester blocks (ITR blocks) having an average block length of about 7.
  • ITR blocks polyester blocks
  • CE-1 Comparative Example 1
  • the method of the present invention provides blocky copolyestercarbonates having substantial molecular weights (M w 's from about 19000 to about 79000 daltons) whereas a much more random copolyestercarbonate having low molecular weight (M w ⁇ 15000 daltons) was obtained using a conventional solid state polymerization technique (Comparative Example 1).

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DE60212172T DE60212172T2 (de) 2001-11-02 2002-10-07 Verfahren zur herstellung von blockcopolymeren durch festphasenpolymerisation
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