Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/18—Block or graft polymers
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/18—Block or graft polymers
  • C08G64/183—Block or graft polymers containing polyether sequences
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
  • C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/305—General preparatory processes using carbonates and alcohols
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/307—General preparatory processes using carbonates and phenols

Definitions

• the present invention relates to a novel polycarbonate resin.
• Patent Document 1 discloses a ⁇ -ray irradiation resistant polycarbonate resin containing the same.
• Document 2 describes a thermoplastic resin composition blended with PMMA or the like, which has excellent antistatic properties and surface appearance.
• Patent Document 3 proposes to improve the transmittance and hue by blending a polyalkylene glycol composed of a linear alkyl group. By blending polytetramethylene ether glycol, the transmittance and the degree of yellowing (yellow index: YI) are improved.
• Patent Document 4 describes a method for producing a polycarbonate copolymer using a diol obtained by diesterizing polyalkylene glycol as a raw material (comonomer).
• this polycarbonate copolymer contains a diester diol of polyalkylene glycol. It is unstable, has insufficient impact resistance, and deteriorates hue and heat-resistant discoloration.
• High barrel temperature and high speed injection are required for molding optical parts. Along with this, there is a problem that the amount of gas generated during molding increases and mold contamination easily progresses. Therefore, the resin used for molding optical parts is required not only to have excellent optical properties, but also to have less mold contamination due to gas generation during injection molding at a high temperature and to have excellent impact resistance.
• Japanese Unexamined Patent Publication No. 1-22959 Japanese Unexamined Patent Publication No. 9-227785 Japanese Patent No. 5699188 Japanese Unexamined Patent Publication No. 2006-016497
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polycarbonate resin that generates less gas.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independent of hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, and carbon number 1 to 1.
• the alkyl is selected from the group consisting of an alkyl group of 7, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, and an aralkyl group having 7 to 17 carbon atoms.
• the group, the aryl group, the alkenyl group, the alkoxy group, and the aralkyl group may each have a substituent.
• X is represented by -O-, -S-, -SO-, -SO 2- , -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or the following general formula (2) or the following general formula (3).
• the cycloalkylene group may be substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms.
• R 9 and R 10 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 5 carbon atoms, and 6 to 12 carbon atoms, respectively. Selected from the group consisting of aryl groups, aralkyl groups having 7 to 17 carbon atoms, and alkoxy groups having 2 to 15 carbon atoms.
• the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group in R 9 and R 10 may each have a substituent.
• R 9 and R 10 may be bonded to each other to form a carbon ring having 3 to 20 carbon atoms or a heterocycle having 1 to 20 carbon atoms, and the carbon ring and the heterocycle each have a substituent. May be n represents an integer from 0 to 20.
• R 11 and R 12 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 7 carbon atoms, and 6 to 12 carbon atoms, respectively.
• the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group are selected from the group consisting of the aryl group, the aralkyl group having 7 to 17 carbon atoms, and the alkenyl group having 2 to 15 carbon atoms.
• R 11 and R 12 may be bonded to each other to form a carbon ring having 3 to 20 carbon atoms or a heterocycle having 1 to 20 carbon atoms, and the carbon ring and the heterocycle each have a substituent. You may be doing it. )]]
• R z and R x independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, i represents an integer of 3 to 10, and p represents 5 to 600. Indicates an integer of.
• R z and R x independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, i represents an integer of 3 to 10, and p represents 5 to 600. Indicates an integer of.
• ⁇ 4> The polycarbonate resin according to any one of ⁇ 1> to ⁇ 3> above, wherein the terminal hydroxyl group concentration of the polycarbonate resin is 1 ppm to 3000 ppm.
• ⁇ 6> The polycarbonate resin according to any one of ⁇ 1> to ⁇ 5> above, wherein the polystyrene-equivalent weight average molecular weight (Mw) of the polycarbonate resin is 1,000 to 60,000.
• Mw polystyrene-equivalent weight average molecular weight
• Tg glass transition temperature
• the polycarbonate resin of the present invention also has the effect of generating less gas and expanding the range of resin designs according to various uses.
• the first embodiment of the present invention is a polycarbonate resin containing a structural unit (A) represented by the following general formula (1) and a structural unit (B) represented by the following general formula (4).
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently hydrogen atom, fluorine atom, chlorine atom, bromine atom, respectively.
• Iodine atom alkyl group having 1 to 7 carbon atoms (preferably 1 to 3 carbon atoms), aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms), 2 to 7 carbon atoms (preferably 2 carbon atoms) It is selected from the group consisting of an alkenyl group having 5), an alkoxy group having 1 to 7 carbon atoms (preferably 1 to 4 carbon atoms), and an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 11 carbon atoms). Preferably, it is selected from the group consisting of a hydrogen atom, a phenyl group, and a methyl group.
• R 1 to R 8 represent a hydrogen atom
• R 1 or R 3 and R 6 or R 8 represent a phenyl group
• the others represent a hydrogen atom.
• the alkyl group, the aryl group, the alkenyl group, the alkoxy group, and the aralkyl group may each have a substituent, and the substituent is preferably a phenyl group.
• X is -O-, -S-, -SO-, -SO 2- , -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or the following general formula (2) or the following. It represents a divalent group represented by the general formula (3), and the cycloalkylene group may be substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms.
• X represents a divalent group represented by the following general formula (2) or a divalent group represented by the following general formula (3).
• R 9 and R 10 are independently each of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an alkyl having 1 to 20 carbon atoms (preferably 1 to 5 carbon atoms).
• alkoxy group having 1 to 5 carbon atoms preferably 1 to 3 carbon atoms
• aryl group having 6 to 12 carbon atoms preferably 6 to 8 carbon atoms
• 7 to 17 carbon atoms preferably 7 to 7 carbon atoms
• R 9 and R 10 represent a methyl group.
• the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group in R 9 and R 10 may each have a substituent.
• R 9 and R 10 are bonded to each other to form a carbon ring having 3 to 20 carbon atoms (preferably 5 to 15 carbon atoms) or a heterocycle having 1 to 20 carbon atoms (preferably 5 to 10 carbon atoms).
• the carbocycle and the heterocycle may each have a substituent.
• Preferred examples of the substituent include a cyclohexyl group, an adamantyl group, a cyclododecane group, and a norbornane group.
• n represents an integer of 0 to 20, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2.
• R 11 and R 12 are independently each of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an alkyl having 1 to 20 carbon atoms (preferably 1 to 3 carbon atoms).
• R 11 and R 12 represent a hydrogen atom.
• the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent, and the substituent is preferably a phenyl group.
• R 11 and R 12 are bonded to each other to form a carbon ring having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms) or a heterocycle having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms).
• the carbon ring and the heterocycle may each have a substituent.
• Examples of the monomer constituting the structural unit (A) represented by the general formula (1) are preferably poly-n-propylene glycol, polytetramethylene ether glycol and the like, and more preferably poly-n-propylene glycol. ..
• R z and R x each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably represent a hydrogen atom, a methyl group, or an ethyl group. More preferably, both R z and R x represent a hydrogen atom.
• i represents an integer of 3 to 10, preferably an integer of 3 to 6, and more preferably 3 or 4.
• p represents an integer of 5 to 600, preferably an integer of 5 to 550, and more preferably an integer of 5 to 500.
• Examples of the monomer constituting the structural unit (B) represented by the general formula (4) include bisphenol A, bisphenol S, 4,4'-oxydiphenol, 4,4'-biphenol, and 4,4'-thiodi. Phenol and the like are preferably mentioned, and bisphenol A and bisphenol S are more preferable.
• bisphenol A is preferable from the viewpoint of market availability because a polycarbonate resin having a small YI value and excellent heat resistance can be obtained.
• Bisphenol S is also preferable from the viewpoint of heat resistance.
• the polycarbonate resin of the present invention preferably has a mass ratio (A / B) of the structural unit (A) to the structural unit (B) of 1/99 to 50/50, and 5/95 to 50/50. It is more preferably 5/95 to 40/60, further preferably 5/95 to 35/65, and particularly preferably 10/90 to 30/70.
• the polycarbonate resin of the present invention is preferably a polycarbonate resin containing a carbonate bond derived from bisphenol A and a carbonate bond derived from poly-n-propylene glycol which may have a substituent.
• the mass ratio of bisphenol A and poly-n-propylene glycol constituting the polycarbonate resin is based on a total of 100% by mass of both, with bisphenol A in an amount of 5 to 50% by mass and poly-n-propylene glycol in an amount of 50 to 95% by mass. It is preferably 5 to 40% by mass of bisphenol A and 60 to 95% by mass of poly-n-propylene glycol, and more preferably 5 to 35% by mass of bisphenol A and poly-n-propylene glycol. Is 65 to 95% by mass. If the amount of poly-n-propylene glycol is less than 50% by mass, the hue of the polycarbonate resin deteriorates, and if it exceeds 95% by mass, it tends to become cloudy.
• the polycarbonate resin of the present invention is preferably represented by the following general formula (5), that is, a polycarbonate resin composed of a polycarbonate unit derived from bisphenol A and a polycarbonate unit derived from poly-n-propylene glycol.
• Ra , R b, and R c each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably represent a hydrogen atom, a methyl group, or an ethyl group.
• m represents an integer of 1 to 3000, and more preferably an integer of 1 to 2500.
• n represents an integer of 5 to 600, more preferably an integer of 5 to 550.
• l represents an integer of 1 to 3000, and more preferably an integer of 1 to 2500.
• the polycarbonate resin of the present invention can be produced by a conventional production method such as an interfacial polymerization method or a melt polymerization method, and for example, at least bisphenol A, poly n-propylene glycol, and a carbonate precursor such as phosgene or diphenyl carbonate can be produced. It can be produced by a method of reacting.
• poly-n-propylene glycol which may have a substituent
• various poly-n-propylene glycol can be used.
• the methylene group represented by the following general formula (6) has a substituent.
• good poly n-propylene glycol is preferred.
• Ra , R b and R c each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.
• n represents an integer of 6 to 600, more preferably an integer of 6 to 550.
• R b is a methyl group (2-methyl) -n-propylene glycol, an ethyl group (2-ethyl) -n-propylene glycol, or R.
• N-Propylene glycol in which all of a , R b and R c are hydrogen atoms is more preferable, and among them, n-propylene glycol in which all of Ra , R b and R c are hydrogen atoms (that is, trimethylene glycol). ) Is more preferable.
• the poly n-propylene glycol represented by the above general formula (6) is a homopolymer composed of a kind of Ra, R b , R c , or a copolymer composed of different Ra , R b , R c. There may be.
• the poly-n-propylene glycol represented by the general formula (6) is a copolymer with a linear polyalkylene glycol such as polyethylene glycol, polytetramethylene glycol, polypentamethylene glycol, and polyhexamethylene glycol.
• a homopolymer made of polytrimethylene glycol is preferable because the transparency of the obtained molded product is improved.
• Poly-n-propylene glycol is obtained from the units represented by the following general formulas (8-1) to (8-4) in addition to the n-propylene ether unit (P1) represented by the following general formula (7). It may contain a polyalkylene glycol copolymer having a branched alkylene ether unit (P2) of choice.
• Ra , R b and RC have the same meaning as the general formula (6).
• R 1 to R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and are respectively general formulas (8-1) to (8-1) to ( In 8-4), at least one of R 1 to R 10 represents an alkyl group having 1 to 3 carbon atoms.
• the branched alkylene ether unit represented by the general formulas (8-1) to (8-4) is composed of a branched alkylene ether unit having any one of the general formulas (8-1) to (8-4). It may be a homopolymer to be produced, or a copolymer composed of branched alkylene ether units having a plurality of structures.
• the n-propylene ether unit represented by the above general formula (7) is n-propylene glycol when it is described as glycol, and in addition to n-propylene glycol, ethylene glycol, tetramethylene glycol, pentamethylene glycol, etc. Any one or more of hexamethylene glycol and the like may be mixed, but it is preferable that only n-propylene glycol is used, and n-propylene glycol in which all of Ra , R b and RC described above are hydrogen atoms. More preferably, it is only (ie, trimethylene glycol).
• Trimethylene glycol industrially obtains 3-hydroxypropionaldehyde by hydroformylation of ethylene oxide and hydrogenates it, or hydrogenates 3-hydroxypropionaldehyde obtained by hydrating achlorine with a Ni catalyst. Manufactured by the method. Recently, glycerin, glucose, starch and the like have been reduced to microorganisms to produce trimethylene glycol by a biomethod.
• glycol As the branched alkylene ether unit represented by the above general formula (8-1), (2-methyl) ethylene glycol, (2-ethyl) ethylene glycol, (2,2-dimethyl) ethylene glycol, etc. These may be mixed, and (2-methyl) ethylene glycol and (2-ethyl) ethylene glycol are preferable.
• glycol As the branched alkylene ether unit represented by the above general formula (8-2), (2-methyl) trimethylene glycol, (3-methyl) trimethylene glycol, (2-ethyl) trimethylene glycol , (3-Eethyl) triethylene glycol, (2,2-dimethyl) trimethylene glycol, (2,2-methylethyl) trimethylene glycol, (2,2-diethyl) trimethylene glycol (ie, neopentyl glycol) , (3,3-dimethyl) trimethylene glycol, (3,3-methylethyl) trimethylene glycol, (3,3-diethyl) trimethylene glycol and the like, and these may be mixed.
• glycol as the branched alkylene ether unit represented by the above general formula (8-3)
• (3-methyl) tetramethylene glycol, (4-methyl) tetramethylene glycol, (3-ethyl) tetramethylene glycol , (4-Ethyl) tetramethylene glycol, (3,3-dimethyl) tetramethylene glycol, (3,3-methylethyl) tetramethylene glycol, (3,3-diethyl) tetramethylene glycol, (4,4-dimethyl) ) Tetramethylene glycol, (4,4-methylethyl) tetramethylene glycol, (4,4-diethyl) tetramethylene glycol, etc. may be mixed, and (3-methyl) tetramethylene glycol may be used. preferable.
• the units represented by the general formulas (8-1) to (8-4) constituting the branched alkylene ether unit have been described with glycol as an example for convenience, but the present invention is not limited to these glycols, and these alkylene oxides are not limited to these glycols. Alternatively, these polyether-forming derivatives may be used.
• a copolymer composed of an n-propylene ether unit and a unit represented by the general formula (8-2) is preferable, and a trimethylene ether unit and 3 are particularly preferable.
• -A copolymer composed of methyl trimethylene ether units is more preferable.
• the poly-n-propylene glycol copolymer may be a random copolymer or a block copolymer.
• the n-propylene ether unit (P1) represented by the general formula (7) and the branched alkylene ether represented by the general formulas (8-1) to (8-4) of the poly-n-propylene glycol copolymer is a molar ratio of (P1) / (P2), preferably 95/5 to 5/95, more preferably 93/7 to 40/60, and even more preferably. Is 90/10 to 65/35, and it is more preferable that the n-propylene ether unit (P1) is rich.
• the mole fraction is measured using a 1 H-NMR measuring device using deuterated chloroform as a solvent.
• a particularly preferable poly-n-propylene glycol is n-propylene glycol having no substituent, that is, a homopolymer of trimethylene glycol.
• the poly-n-propylene glycol may contain a structure derived from a polyol such as 1,4-butanediol, glycerol, sorbitol, benzenediol, bisphenol A, cyclohexanediol, and spiroglycol.
• a polyol such as 1,4-butanediol, glycerol, sorbitol, benzenediol, bisphenol A, cyclohexanediol, and spiroglycol.
• these organic groups can be added to the main chain.
• Particularly preferred are glycerol, sorbitol, bisphenol A and the like.
• poly-n-propylene glycol containing an organic group in the structure examples include, for example. Poly-n-Propylene Glycol Glyceryl Ether, Poly (2-methyl) -n-propylene glycol glyceryl ether, Poly-n-Propylene Glycol Glyceryl Ether, Poly-n-Propylene Glycol-Poly (2-Methyl) -n-Propylene Glycol Glyceryl Ether, Poly-n-Propylene Glycol-Poly (2-Ethyl) Poly-n-Propylene Glycol Glyceryl Ether, Poly-n-Propylene Glycol Solbityl Ether, Poly (2-methyl) -n-Propylene Glycol Solbityl Ether, Poly-n-Propylene Glycol Solbityl Ether, Poly-n-Propylene Glycol-Poly (2-Methyl) Ethylene Glycol Solbityl Ether, Bis
• the weight average molecular weight (Mw) of poly-n-propylene glycol is preferably 600 to 8,000, more preferably 800 or more, still more preferably 1,000 or more, still more preferably 6,000 or less, still more preferably. It is 5,000 or less, particularly preferably 4,000 or less. When the weight average molecular weight exceeds the above upper limit, the compatibility tends to decrease. If the weight average molecular weight is less than the above lower limit, the impact resistance of the polycarbonate resin may decrease.
• the weight average molecular weight (Mw) is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC) with the developing solvent THF.
• a high-speed GPC device "HLC-8320" manufactured by Tosoh Co., Ltd. is used as the GPC, column: manufactured by Tosoh Co., Ltd., HZ-M (4.6 mm x 150 mm) x 3 in series, eluent: chloroform, polystyrene-equivalent molecular weight. It is a value obtained as (weight average molecular weight).
• carbonate precursors examples of carbonate precursors.
• the carbonate precursor one kind may be used, or two or more kinds may be used in any combination and ratio.
• carbonyl halide examples include phosgene; a bischloroformate of a dihydroxy compound, a haloformate of a monochloroformate of a dihydroxy compound, and the like.
• carbonate ester examples include diaryl carbonates such as diphenyl carbonate and ditril carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate of dihydroxy compound, monocarbonate of dihydroxy compound, and cyclic carbonate. Examples thereof include carbonates of dihydroxy compounds such as.
• bisphenol A-poly-n-propylene glycol copolymerized polycarbonate represented by the following general formula (9) is particularly preferable.
• m, n and l are synonymous with the general formula (5).
• a second embodiment of the present invention is a polycarbonate resin containing only the structural unit (B) represented by the following general formula (4).
• R z , R x , i, and p are the same as those in the first embodiment described above.
• the method for producing the polycarbonate resin of the present invention is not particularly limited, and any known method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Among these, the molten transesterification method and the interfacial polymerization method are preferable, and the molten transesterification method is more preferable.
• the polystyrene-equivalent weight average molecular weight (Mw) of the polycarbonate resin of the present invention is preferably 1,000 to 60,000, and more preferably 5,000 to 40,000.
• the lower limit is more preferably 6,000 or more, particularly preferably 7,000 or more, and the upper limit is further preferably 37,000 or less, particularly preferably 35,000 or less.
• the weight average molecular weight (Mw) exceeds the above upper limit, the compatibility tends to decrease. If the weight average molecular weight is below the above lower limit, gas tends to be generated during molding.
• the weight average molecular weight (Mw) of the polycarbonate resin of the present invention can be adjusted by selecting Mw of polyalkylene glycol, which is one of the comonomer diol raw materials, adjusting the ratio of carbonate precursor, adding a terminator, and during polymerization. It is possible by adjusting the temperature and pressure of. For example, in order to increase Mw in the molten transesterification method, the monomer raw material ratio is adjusted so that the reaction ratio of the diphenyl carbonate, which is a carbonate precursor monomer, and the diol monomer is close to 1, and the by-product phenol is a polymerization system. This is possible by keeping the polymerization temperature high so that it can be easily removed from the inside, reducing the pressure as much as possible, and actively performing interface renewal by stirring.
• the weight average molecular weight (Mw) of the polycarbonate resin of the present invention is a polystyrene-equivalent molecular weight measured by GPC with the developing solvent chloroform.
• a high-speed GPC device "HLC-8320" manufactured by Tosoh Co., Ltd. is used as the GPC, column: manufactured by Tosoh Co., Ltd., HZ-M (4.6 mm x 150 mm) x 3 in series, eluent: chloroform, measurement temperature: It is a value obtained as a polystyrene-equivalent molecular weight (weight average molecular weight) at 25 ° C.
• the polycarbonate resin of the present invention preferably has a terminal hydroxyl group concentration of 1 ppm to 3000 ppm, preferably 1 to 1000 ppm, and particularly preferably 1 to 500 ppm, in order to maintain hydrolysis resistance.
• a terminal hydroxyl group concentration of 1 ppm to 3000 ppm, preferably 1 to 1000 ppm, and particularly preferably 1 to 500 ppm, in order to maintain hydrolysis resistance.
• the method for measuring the terminal hydroxyl group concentration the methods described in the following examples can be used.
• the polycarbonate resin of the present invention preferably has a glass transition temperature (Tg) of ⁇ 100 to 140 ° C. for easy handling, more preferably ⁇ 70 to 120 ° C., and preferably ⁇ 70 to 110 ° C. Is particularly preferable.
• Tg glass transition temperature
• the method for measuring the glass transition temperature the methods described in the following examples can be used.
• the polycarbonate resin of the present invention includes other additives other than those described above, such as antioxidants, mold release agents, ultraviolet absorbers, fluorescent whitening agents, pigments, dyes, polymers other than polycarbonate resins, and flame retardants. Additives such as impact resistance improvers, antistatic agents, plasticizers, and compatibilizers can be contained. These additives may be used alone or in combination of two or more.
• ⁇ Measuring method of terminal hydroxyl group concentration (ppm)> It was determined by dissolving 0.05 g of the resin sample in 1 ml of deuterium-substituted chloroform (containing 0.05 w / v% TMS) and measuring 1 H-NMR at 23 ° C. Specifically, the terminal hydroxyl group concentration (OH concentration) was calculated from the integral ratio of the peak related to the hydroxyl group and the peak contained in the other resin skeleton.
• Mw ⁇ (Wi x Mi) ⁇ ⁇ (Wi)
• i the i-th division point when the molecular weight M is divided
• Wi the i-th weight
• Mi the i-th molecular weight.
• the molecular weight M represents the polystyrene molecular weight value at the same elution time of the calibration curve.
• the measurement was performed using a thermogravimetric / differential thermal simultaneous measurement device (TG / TDA) (product name "TGDTA7300", manufactured by Hitachi High-Tech Science Corporation).
• the measurement sample was prepared by precisely weighing a 5 mg sample in a platinum pan (Pt open type sample container, cylindrical container having a diameter of 5.2 mm and a height of 5.0 mm). The measurement was carried out in a nitrogen atmosphere (nitrogen flow rate: 250 ml / min), and 5.52 mg of ⁇ -alumina was used as a reference substance in the reference cell. Then, the measurement sample was heated as described later and the weight was measured.
• TG / TDA thermogravimetric / differential thermal simultaneous measurement device
• the amount of gas generated (%) "120 ° C ⁇ 350 ° C” was calculated as follows.
• Gas generation amount (%) "120 ° C ⁇ 350 ° C” (weight at 350 ° C-weight at 120 ° C) / weight at 120 ° C x 100
• the amount of gas generated (%) "120 ° C ⁇ 320 ° C” was calculated as follows.
• Gas generation amount (%) "120 ° C ⁇ 320 ° C” (weight at 320 ° C-weight at 120 ° C) / weight at 120 ° C x 100
• the weight at 350 ° C. is the weight when the measurement sample is heated from 120 ° C.
• the weight at 120 ° C. is the weight after the measurement sample is heated from room temperature to 120 ° C. at 10 ° C./min and held at 120 ° C. for 2 hours.
• the weight at 320 ° C. is the weight when the measurement sample is heated from 120 ° C. to 10 ° C./min and reaches 320 ° C.
• Tg glass transition temperature
• DSC differential scanning calorimeter
• ⁇ Measurement of YI value> The measurement was performed using a spectrocolorimeter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. Specifically, 12 g of a resin sample was dissolved in 60 mL of dichloromethane, and the measurement was performed using a quartz cell having an optical path length of 6 cm. Dichloromethane was used as the blank.
• Example 1 In a polymerization apparatus equipped with a three-necked flask, 85% by mass of poly-n-propylene glycol manufactured by ALLESSA, Velvetol H500 (Mw: 1700) and 15% by mass of bisphenol A (hereinafter, BPA) are equivalent as raw materials. Amount, diphenyl carbonate (DPC) was added at a molar ratio of 1.16 to the diol. Further, as a catalyst, 11 ⁇ mol (as Cs) of Cs 2 CO 3 aqueous solution was added per 1 mol of the diol. After the inside of the system was dried for 1 hour, the inside of the polymerization apparatus was recompressed with nitrogen.
• DPC diphenyl carbonate
• the polymerization was started when the decompressed polymerization apparatus was immersed in the oil bath, and the polymerization was carried out according to the temperature raising / depressurizing program shown in Table 1.
• the physical characteristics of the obtained polycarbonate resin are shown in Table 5.
• the OH concentration of the polycarbonate resin obtained in Example 1 was 70 ppm.
• Examples 2 and 3 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 5.
• the physical characteristics of the obtained polycarbonate resin are shown in Table 5.
• the OH concentration of the polycarbonate resin obtained in Example 2 was 240 ppm, and the OH concentration of the polycarbonate resin obtained in Example 3 was 1100 ppm.
• Example 4 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 5 and the temperature raising / depressurizing program was replaced with Table 2. The physical characteristics of the obtained polycarbonate resin are shown in Table 5.
• Example 5 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 5 and the temperature raising / depressurizing program was replaced with Table 3.
• the physical characteristics of the obtained polycarbonate resin are shown in Table 5.
• the OH concentration of the polycarbonate resin obtained in Example 5 was 2200 ppm.
• Examples 6 and 7 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 5 and the temperature raising / depressurizing program was replaced with Table 4. The physical characteristics of the obtained polycarbonate resin are shown in Table 5.
• Example 8> The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 6. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• Example 9 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 7. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• Example 10 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 8. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• Example 11 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 9. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• Example 12 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 10. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• Example 13 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 11. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• Example 14 and 15 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 12. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• Example 16 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 13. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• Example 17 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 14. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• Example 18 The reaction was carried out in the same manner as in Example 1 except that the raw materials were replaced with the raw materials shown in Table 16 and the temperature raising / depressurizing program was replaced with Table 15. The physical characteristics of the obtained polycarbonate resin are shown in Table 17.
• BPA Bisphenol A
• BPS Bisphenol S
• BPO 4,4'-oxydiphenol BF: 4,4'-biphenol TDP: 4,4'-thiodiphenol
• PTMG polytetramethylene ether glycol
• P3MG poly-n-propylene glycol
• the polycarbonate resin of the present invention Since the polycarbonate resin of the present invention generates extremely little gas, it can be suitably used for various molded products.
• polycarbonate resin since polycarbonate resin has a high Tg, it is necessary to heat and melt it at a high temperature of 180 ° C. or higher when melt molding, and molding at a lower temperature has been desired in order to reduce the molding cost. .. Further, low Tg polycarbonate has been required as a material for various industrial products.
• the Tg of a generally widely known bisphenol A type polycarbonate resin is about 150 ° C., but a material having a Tg lower than that has been required.
• the copolymerized polycarbonate of polytetramethylene glycol and bisphenol A in the present invention and in particular, the copolymerized polycarbonate of poly-n-propylene glycol and bisphenol A have a low Tg and are widely and usefully used as materials for industrial products. be able to.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyesters Or Polycarbonates (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=75165741

Family Applications (1)

Country Status (7)

Cited By (2)

Families Citing this family (1)

Citations (7)

Family Cites Families (9)

• 2020
  • 2020-09-01 EP EP20868795.4A patent/EP4036146B1/en active Active
  • 2020-09-01 TW TW109129891A patent/TWI890694B/zh active
  • 2020-09-01 JP JP2021548724A patent/JP7687206B2/ja active Active
  • 2020-09-01 CN CN202080065530.8A patent/CN114423805A/zh active Pending
  • 2020-09-01 WO PCT/JP2020/033013 patent/WO2021059884A1/ja not_active Ceased
  • 2020-09-01 KR KR1020227010362A patent/KR102905002B1/ko active Active
  • 2020-09-01 US US17/761,102 patent/US20220389159A1/en not_active Abandoned

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events