CN101035832B - Method of producing modified polycarbonate using spray-crystallizing method - Google Patents

Method of producing modified polycarbonate using spray-crystallizing method Download PDF

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CN101035832B
CN101035832B CN2005800320969A CN200580032096A CN101035832B CN 101035832 B CN101035832 B CN 101035832B CN 2005800320969 A CN2005800320969 A CN 2005800320969A CN 200580032096 A CN200580032096 A CN 200580032096A CN 101035832 B CN101035832 B CN 101035832B
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modified polycarbonate
crystalline
molecular weight
crystalline state
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CN101035832A (en
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洪美贞
金钟勋
朴圣圭
禹富坤
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LG Electronics Inc
LG Corp
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LG Chemical Co Ltd
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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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • 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
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/085—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing silicon
    • 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
    • C08G64/1625—Aliphatic-aromatic or araliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
    • C08G64/1666—Aliphatic-aromatic or araliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing silicon
    • 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
    • C08G64/205—General preparatory processes characterised by the apparatus used
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying

Abstract

Provided is a method of producing a high-molecular weight modified polycarbonate resin. The method includes a melt condensation polymerization process in which transesterification and quick condensation polymerization are sequentially performed, a spray crystallization process, and a solid state polymerization process. When this method is used, solid state polymerization can be performed without additional drying, milling and fractionation processes so that the operation time and costs are highly reduced. In addition, crystallinity and size of crystallized modified polycarbonate particles can be efficiently controlled to produce a high-molecular weight modified polycarbonate having uniform physical properties in the solid state polymerization.

Description

Use the spray crystallization legal system to be equipped with the method for modified polycarbonate
Technical field
The present invention relates to a kind of method for preparing modified polycarbonate resin.Described method comprises that polycondensation and spray crystallization are to reduce the molecular fraction of aryl carbonates, described aryl carbonates is present in the unreacted diaryl carbonate and in the polymerization degree that melt condensation the obtains end group less than 3 byproduct of reaction, thereby, can make increase maximization through the modified polycarbonate resin molecular weight of solid state polymerization preparation.In this method, use the spray crystallization method, do not need independent grinding and drying process.Spray crystallization and solid state polymerization carry out in succession or simultaneously in a reactor and do not have other drying, grinding and classification process, therefore prepare the modified polycarbonate time necessary and obviously reduce.
Background technology
Polycarbonate resin has excellent thermotolerance, shock resistance, physical strength and the transparency.Because these advantages, polycarbonate resin is used for multiple application, as CD, transparent sheet, wrapping material and ultraviolet (UV) barrier film (blocking film), therefore, the demand of polycarbonate resin is being increased day by day.
Yet polycarbonate resin has low solvent resistance and low shock resistance at low temperatures.For example, do the time spent, crazing or crackle occur when polycarbonate is subjected to common solvent.Therefore, do many effort and overcome the problems referred to above, and developed multiple modified polycarbonate.Modified polycarbonate is meant that not only comprising carbonate group in its chemical structure also comprises other functional group, as the polycarbonate of ester group, ether, thioether group, sulfoxide group and siloxanes etc.Especially, silicone-modified polycarbonate shows excellent in low-temperature impact and workability.
The conventional manufacture method of preparation modified polycarbonate is divided into the interfacial polymerization that uses phosgene, and the melt phase polycondensation and the solid phase polymerization method that do not use phosgene.
At first, about the polycarbonate of ester group modification, we have found following document.
U.S. Patent number 4,983,706 disclosed interfacial polymerizations comprise makes aromatic dihydroxy compound such as bisphenol-A photoreactive gas and dicarboxylic acid reaction.Yet this method is accompanied by because use is harmful to chemical material phosgene and the caused danger of environmental pollutant chloride-based organic solvent, therefore, and equipment cost and production cost height.
U.S. Patent number 6,232,429 disclose a kind of method, wherein made modified polycarbonate through melt polymerization after following reaction: the esterification between transesterification reaction between aromatic dihydroxy compound and the carboxylic acid diesters and aromatic dihydroxy compound and the dicarboxylic acid compound, above-mentioned two reactions are carried out simultaneously and are used alkaline-earth metal catalyst and quaternary ammonium catalyzer.Owing to do not use toxic materials, described melt phase polycondensation is more stable.Yet, in order to prepare the high molecular modified polycarbonate that is used to extrude, must under high temperature and high vacuum, handle the high viscosity reactant, these conditions cause generating low-quality modified polycarbonate.
U.S. Patent No. 6,365,702 disclose a kind of solid phase polymerization method that is used for modified polycarbonate.More specifically, use antimony-based catalyst to make polycarbonate oligomer, carboxylic acid cpd and diaryl carbonate compound carry out esterification and transesterify, the product that cooling and grinding obtain.Make the product that ground carry out solid state polymerization.Grinding and drying independent in this method are essential.
Secondly, about silicone-modified polycarbonate, we have found following document.
U.S. Patent number 5,530,083 discloses a kind of interfacial polymerization method, and it comprises by using catalyzer that end capped diorganopolysiloxanecompositions of aromatic hydroxy compound, dihydroxy compound and hydroxyaryl and phosgene are reacted.In the case, the high-molecular-weight polycarbonate of continuous production silicone resin modification easily.Yet owing to use toxic gas and environmentally harmful chloride-based organic solvent, this method is dangerous.Therefore, equipment cost and production cost height.
As U.S. Patent number 6,252, disclosed a kind of melt phase polycondensation in 013, it comprises polymerization fused starting material.Because it is low dangerous not using deleterious material melt phase polycondensation.Yet, in order to prepare the modified high-molecular amount polycarbonate that is used to extrude, must under high temperature and high vacuum, handle the high viscosity reactant, these conditions cause generating low-quality modified polycarbonate.
Solid phase polymerization method is a kind of with the prepolymer crystallization of lower molecular weight modified polycarbonate and with crystalline prepolymer further polymeric method under the temperature of the fusing point that is lower than the crystalline prepolymer.In the case, do not use toxic materials, and owing to be aggregated in the quality of carrying out to guarantee resulting modified polycarbonate in the solid phase.Yet, generally speaking crystallization and solid state polymerization usually do not remove the polymerization degree less than 3 byproduct of reaction and with the situation of the unreacted diaryl carbonate of lower molecular weight prepolymer (weight-average molecular weight be 2000 to 20000g/mol) coexistence under carry out.Therefore, destroy the stoichiometric balance between hydroxyl and the aryl carbonates base, and prolonged the preparation time of high molecular modified polycarbonate.In this method, make the crystallization of non-crystalline state prepolymer by it being dissolved in precipitate then in the solvent.Therefore, the size of crystalline prepolymer and degree of crystallinity are irregular, thereby need independent drying, grinding and classification process.
Therefore, need more study to develop a kind of modified polycarbonate manufacture method of stablizing, ensuring the quality of products and only require a very short time and to prepare the high molecular modified polycarbonate.
Summary of the invention
Technical scheme
The invention provides a kind of method for preparing high molecular modified polycarbonate by effective crystallization control modified polycarbonate particulate degree of crystallinity and size with uniform physical properties.This method does not need other drying, grinding and classification process, therefore, can reduce operating time and running cost.
The present invention also provides a kind of modified polycarbonate that uses described method preparation.
According to an aspect of the present invention, provide a kind of method for preparing modified polycarbonate, its by in a reactor continuously or crystallization simultaneously and solid state polymerization have more low-molecular-weight modified polycarbonate, wherein do not have independent grinding and drying process.
According to a further aspect in the invention, provide a kind of modified polycarbonate that uses method for preparing.
In addition, effective crystallization control particulate degree of crystallinity and the big or small high molecular modified polycarbonate that has the homogeneous physicals with acquisition.
Beneficial effect
In the method for preparing modified polycarbonate resin of the present invention, under the situation that does not have other drying, grinding and classification process, carry out solid state polymerization, therefore can reduce operating time and running cost.In addition, crystallization control particulate degree of crystallinity and the size macromolecule modified polycarbonate that has the homogeneous performance with preparation effectively.
Description of drawings
By the exemplary embodiment that present invention will be described in detail with reference to the accompanying, above-mentioned and further feature of the present invention and advantage will be more apparent, and Fig. 1 is the device synoptic diagram that is used to strengthen the solid state polymerization modified polycarbonate.
Embodiment
Preparing by method for solid phase polymerization in the method for modified polycarbonate resin, should before solid state polymerization, make the non-crystalline state modified polycarbonate carry out crystallization in addition, thereby improve the fusing point of non-crystalline state modified polycarbonate and prevent modified polycarbonate fusion in solid state polymerization processes.
In an embodiment of the invention, spray crystallization and solid state polymerization can carry out in the described solid state polymerization reactor of Fig. 1 simultaneously.In yet another embodiment of the present invention, spray crystallization and solid state polymerization carry out in succession.Above-mentioned non-crystalline state modified polycarbonate can be the polycarbonate of ester group or siloxanes modification.
A kind of reinforcement method for solid phase polymerization is described now.
At first, the non-crystalline state modified polycarbonate is dissolved in the solvent.The non-crystalline state modified polycarbonate can pass through the transesterification reaction preparation of interfacial polymerization, dialkyl group (aryl) carbonic ether and aromatic dihydroxy compound.
The solvent that is used to prepare modified polycarbonate solution can be the mixture of methylene dichloride, chloroform, tetrahydrofuran (THF), meta-cresol (metacrezole), hexanaphthene, diox, dimethyl aldehyde (dimethylaldehyde), pyridine or above-mentioned solvent.
The concentration of final modified polycarbonate solution is 5.0～50.0 weight %, preferred 10.0～30.0 weight %.If the concentration of modified polycarbonate solution is less than 5.0 weight %, the degree of crystallinity of the modified polycarbonate of preparation is too high so that can not prepare high-molecular weight modified polycarbonate resin and needs and reclaim a large amount of solvents.On the contrary, if the concentration of modified polycarbonate solution greater than 50.0 weight %, then too high the so that modified polycarbonate solution of the viscosity of modified polycarbonate solution can not be sprayed well.
Then, the modified polycarbonate solution that makes is transferred to solid state polymerization reactor and in solid state polymerization reactor, sprays by nozzle.At this moment, modified polycarbonate solution can be sprayed through pressure nozzle or air-blast atomizer.If the use air-blast atomizer injects compressed carrier gas separately.
During the applying pressure nozzle, injection pressure is 2.0 to 51.0kgf/cm 2If injection pressure is less than 2.0kgf/cm 2, when the modified polycarbonate solution spray, the inlet of pressure nozzle blocks easily.On the contrary, if injection pressure greater than 51.0kgf/cm 2, then Pen Wu modified polycarbonate solution is excessive, causes part solution not evaporate and excessive solvent is retained in the subsequent process.
When using air-blast atomizer, the injection speed of pressurized gas is 200～800L/ hour, preferred 300～600L/ hour.If the injection speed of pressurized gas is less than 200L/ hour, unvaporized and quantity that therefore be present in the solvent in the crystalline modified polycarbonate pellets of preparation obviously increases.On the contrary, if the injection speed of pressurized gas greater than 800L/ hour, then Zhi Bei most of crystalline particle diameter less than 80 μ m and degree of crystallinity less than 5%.Pressurized gas can comprise at least a N of being selected from 2, air, CO 2And composition thereof gas.
Evaporate spray solution by the contact high-temperature gas, prepare crystalline modified polycarbonate thus.
As mentioned above, when preparing crystalline modified polycarbonate by spray crystallization, modified polycarbonate crystallization simultaneously and drying, and the particle diameter of crystalline modified polycarbonate is very regular.Therefore, do not need other drying, grinding and classification process, production technique is simplified and production cost reduces.
The hot gas that is used to evaporate modified polycarbonate solution can be N 2, air, CO 2Or its mixture.Gas has sufficiently high temperature with the solvent in can evaporating solns.For example, the temperature of gas is 40～250 ℃, preferred 60～150 ℃.
If the temperature of hot gas is lower than 40 ℃, solvent evaporation is slow and insufficient, can not be directly used in solid state polymerization processes.Therefore, need the other further evaporating solvent of drying process.If the temperature of hot gas is higher than 250 ℃, then the too fast therefore degree of crystallinity of solvent evaporation reduces.Therefore, the crystalline modified polycarbonate pellets that obtains can not be directly used in method for solid phase polymerization, because their fusions in solid state polymerization processes.
The mean diameter of crystalline modified polycarbonate pellets is 80～3000 μ m.The limit of error of particle diameter is less than 30%.
If particle diameter is less than 80 μ m or greater than 3000 μ m, its degree of crystallinity can be too low or too high.In addition, the particle with above-mentioned diameter range is unsuitable for necessary decompression of solid state polymerization or nitrogen injection condition.And, if the particle diameter limit of error that keeps after the solvent evaporation greater than 30%, the physicals of crystalline polyester carbonic ether is inhomogenous.
Referring now to the method for Fig. 1 detailed description as the crystalline modified polycarbonate of preparation of embodiment of the present invention.
In agitator 1 with non-crystalline state modified polycarbonate stirring and dissolving in solvent.
The solution that obtains is compressed gas 3 simultaneously by transfer pipeline 2 is transferred to solid state polymerization reactor 5 through nozzle 4 sprayings.The best injection speed of injecting the pressurized gas 3 of nozzle 4 changes with strength of solution.When the applying pressure nozzle replaces air-blast atomizer, do not use pressurized gas, as an alternative, the injection pressure of solution increases to 2.0kgf/cm 2Or it is higher.
Heat (high temperature) gas 8 injects along the opposite direction of solution spray through the hot gas injection tube, with the solvent of evaporating solns.The solvent and the hot gas 8 of evaporation are separated into liquid solvent and gas.Liquid solvent is back to agitator 1, and gas is heated and injects solid state polymerization reactor 5.
Collect modified polycarbonate in the distiller 12 below being installed in solid state polymerization reactor 5, in assembling cyclonic separator 6, collect the microsize particle of low-crystallinity.
In another embodiment, spray crystallization process and solid state polymerization processes are carried out in succession.That is to say that the present invention also comprises spray crystallization amorphous poly carbonic ether to prepare crystalline modified polycarbonate, the crystalline modified polycarbonate of solid state polymerization is with preparation high molecular modified polycarbonate then.
If the non-crystalline state modified polycarbonate is the polycarbonate of ester group modification, then this method can comprise:
(a) making number-average molecular weight is 3,000～20, and the non-crystalline state modification carbonic ether crystallization that comprises ester group of 000g/mol comprises the crystalline modified carbonic ether of ester group with preparation; With
(b) the solid state polymerization crystalline modified carbonic ether that comprises ester group is 15,000～200 with the preparation number-average molecular weight, the crystalline modified carbonic ether that comprises ester group of 000g/mol.
If the non-crystalline state modified polycarbonate is the non-crystalline state modified polycarbonate that comprises siloxanes, then this method can comprise:
(a ') makes weight-average molecular weight is 10,000～30, and the non-crystalline state modification carbonic ether crystallization that comprises siloxanes of 000g/mol comprises the crystalline modified carbonic ether of siloxanes with preparation; With
The crystalline modified carbonic ether that (b ') solid state polymerization comprises siloxanes is 20,000～200 with the preparation weight-average molecular weight, the modification carbonic ether that comprises siloxanes of 000g/mol.
The non-crystalline state modified polycarbonate can pass through interfacial polymerization, pass through dialkyl group (aryl) carbonic ether and the transesterify of aromatic dihydroxy compound or the transesterify and the condensation prepared of dialkyl group (aryl) carbonic ether and aromatic dihydroxy compound.
The spray crystallization method can be included in the solvent dissolving non-crystalline state modified polycarbonate with preparation solution, through nozzle spray solution, thereby and makes the solution of spraying contact evaporating solvent with hot gas to make crystalline modified polycarbonate except that desolvating.
Spray-crystallised condition can be identical with above-mentioned solid phase polymeric condition.
Solid state polymerization can carry out in the following manner, and the crystalline modified polycarbonate that is about to preparation is transferred to solid state polymerization reactor and provides hot gas to reactor continuously, thus preparation high molecular modified polycarbonate resin.Selectively, solid state polymerization can carry out in the following manner, and promptly the crystalline modified polycarbonate that will prepare in 0～50mmHg decompression is transferred to solid state polymerization reactor with preparation high molecular modified polycarbonate resin, removes by product simultaneously.If the modified polycarbonate resin through the solid state polymerization preparation is the modified polycarbonate resin that comprises ester group, then can make number-average molecular weight is 15,000～200, the modified polycarbonate resin that comprises ester group of 000g/mol.If the modified polycarbonate resin through the solid state polymerization preparation is the modified polycarbonate resin that comprises siloxanes, then can make weight-average molecular weight is 20,000～200, the modified polycarbonate resin that comprises siloxanes of 000g/mol.
Modified polycarbonate through the spray crystallization preparation does not need to use independent grinding and drying process.
Solid state polymerization processes is at solid phase polymerization temperature T pUnder carry out, it may be constant or increase in the temperature range shown in the following inequality:
T m-50≤T p≤T m.......(1)
T wherein mIt is fusing point.
In solid state polymerization processes, if desired, can also use the additive of powder, liquid or gaseous phase, as the quality with the modified polycarbonate resin of raising preparation such as terminator, branching agent, antioxidant.
If the modified polycarbonate resin through the above-mentioned steps preparation is the modified polycarbonate resin that comprises ester group, then its number-average molecular weight can be 15,000～200,000g/mol.If the modified polycarbonate resin through the above-mentioned steps preparation is the modified polycarbonate resin that comprises siloxanes, then its weight-average molecular weight can be 20,000～200,000g/mol.Described modified polycarbonate resin is suitable for extrusion molding and blowing.
If solid state polymerization is by the modified polycarbonate of conventional crystallization method preparation, then the polydispersity index of modified polycarbonate increases by 55～65% after the solid state polymerization.On the contrary, if the crystalline modified polycarbonate that solid state polymerization prepares according to the embodiment of the present invention, then the increase by 14.5% of the polydispersity index of modified polycarbonate is so low or lower, because crystalline modified polycarbonate has the degree of crystallinity of uniform grain sizes and homogeneous, therefore can prepare high molecular weight polycarbonate resin with even molecular weight and homogeneous physicals.
If the non-crystalline state modified polycarbonate that uses in the spray crystallization method as embodiments of the present invention is the non-crystalline state modified polycarbonate that comprises ester group, the method that then prepares the non-crystalline state modified polycarbonate that comprises ester group can comprise:
A) under the condition that has catalyzer to exist, carry out the esterification of dicarboxylic acid compound and aromatic dihydroxy compound and the transesterify between dialkyl group (aryl) carbonate products and the aromatic dihydroxy compound simultaneously, with the preparation number-average molecular weight is 1,500～15, the low molecular weight amorphous polyestercarbonate prepolymer of 000g/mol; With
B) polycondensation is by operating the low molecular weight amorphous modified polycarbonate prepolymer that comprises ester group that a) obtains.
Below, describe the method that preparation comprises the non-crystalline state modified polycarbonate of ester group in detail.
Step 1: transesterify and esterification
Based on the dihydroxy compound of 1mol as transesterify process starting material, according to the embodiment of the present invention, wherein the catalyst concentration of Cai Yonging is 10 -6To 10 -1Mol, preferred 10 -5To 10 -2Mol, more preferably 10 -4To 10 -3Mol.If based on the 1mol dihydroxy compound, catalyst concentration is less than 10 -6Mol, then catalyzer is difficult to give full play to its activity when the reaction beginning.If based on 1mol dihydroxy compound catalyst concentration greater than 10 -1Mol, then production cost height.
The catalyzer that uses in the specific embodiment of the invention can be a tin-based catalyst.Color, transparent and active aspect tin-based catalyst be more suitable for than alkaline-earth metal catalyst, quaternary ammonium salt catalyst and antimony-based catalyst.
Tin-based catalyst can be the tin compound that is selected from tri-chlorination dialkyl tin, Dutch loquid base tin, oxidation dialkyl tin, dioxane oxidation dialkyl tin, dialkyltin dicarboxylates and tetraalkyl tin, wherein alkyl can be C1～C20 alkyl, preferred C1～C10 alkyl, more preferably C1～C6 alkyl.
Tin-based catalyst can be a kind of in the compound of following chemical formulation:
And preferred dibutyl tin oxide.
According to the embodiment of the present invention, can represent by formula 1 as the dicarboxylic acid compound of one of starting material:
[formula 1]
HOOC-R 1-COOH
R wherein 1Be replace or unsubstituted C4～C30 aryl, C1～C10 alkyl or C5～C30 cycloalkyl.
Dicarboxylic acid compound can be the acid that is selected from oxalic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, sebacic acid (sebacic acid), sebacic acid (decandionic acid), dodecanedioic acid, terephthalic acid, m-phthalic acid and composition thereof.
For example, dicarboxylic acid can be 1, the 10-sebacic acid.
According to the embodiment of the present invention, making the aromatic dihydroxy compound of one of starting material can be by the compound of formula 2 expression:
[formula 2]
Figure G05832096920070514D000121
R wherein 2And R 3Be halogen atom or C1～C8 alkyl independently of one another, wherein halogen atom can be F, Cl, Br or I, and C1～C8 alkyl can be methyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, cyclohexyl, heptyl or octyl group;
Z be singly-bound, C1～C8 alkylidene group (alkylene group), C2～C8 alkylidene (alkylidengroup), C5～C15 ring alkylidene group (cycloalkylene group), C5～C15 ring alkylidene (cycloalkyliden group) ,-S-,-SO-,-SO 2-,-O-,-compound shown in the CO-, formula 3 or the compound shown in the formula 4, wherein C1～C8 alkylidene group or C2～C8 alkylidene can be methylene radical, ethylidene (ethylene group), propylidene, butylidene, pentylidene, hexylidene, ethidine (ethylidenegroup), isopropylidene (isopropylidene group) etc.; C5～C15 ring alkylidene group or C5～C15 ring alkylidene can be ring pentylidene, cyclohexylene, cyclopentylidene base (cyclopentylidene group) or cyclohexylidene base (cyclohexylidene group);
A and b are 0 to 4 integer independently of one another:
[formula 3]
Figure G05832096920070514D000122
[formula 4]
Figure G05832096920070514D000123
Aromatic dihydroxy compound shown in the formula 2 can be two (hydroxyaryl) alkane as two (4-hydroxyphenyl) methane,
Two (3-methyl-4-hydroxyphenyl) methane, two (3-chloro-4-hydroxyphenyl) methane,
Two (3,5-two bromo-4-hydroxyphenyl) methane, 1,1-two (4-hydroxyphenyl) ethane,
1,1-two (2-tertiary butyl-4-hydroxy-3-aminomethyl phenyl) ethane,
2,2-two (4-hydroxyphenyl) propane (dihydroxyphenyl propane),
2,2-two (3-methyl-4-hydroxyphenyl) propane,
2,2-two (2-methyl-4-hydroxyphenyl) propane,
2,2-two (3,5-dimethyl-4-hydroxyphenyl) propane,
1,1-two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propane,
2,2-two (3-chloro-4-hydroxyphenyl) propane,
2,2-two (3-fluoro-4-hydroxyphenyl) propane,
2,2-two (3-bromo-4-hydroxyphenyl) propane,
2,2-two (3,5-two fluoro-4-hydroxyphenyl) propane,
2,2-two (3,5-two chloro-4-hydroxyphenyl) propane,
2,2-two (3,5-two bromo-4-hydroxyphenyl) propane, 2,2-two (4-hydroxyphenyl) butane,
2,2-two (4-hydroxyphenyl) octane, 2,2-two (4-hydroxyphenyl) toluene,
2,2-two (4-hydroxyl-1-aminomethyl phenyl) propane, 1,1-two (4-hydroxyl-tert-butyl-phenyl) propane,
2,2-two (4-hydroxyl-3-bromophenyl) propane,
2,2-two (4-hydroxyl-3,5-3,5-dimethylphenyl) propane,
2,2-two (4-hydroxyl-3-chloro-phenyl-) propane,
2,2-two (4-hydroxyl-3,5-dichlorophenyl) propane,
2,2-two (4-hydroxyl-3,5-dibromo phenyl) propane,
2,2-two (3-bromo-4-hydroxyl-5-chloro-phenyl-) propane,
2,2-two (3-phenyl-4-hydroxyphenyl) propane, 2,2-two (4-hydroxyphenyl) butane,
2,2-two (3-methyl-4-hydroxyphenyl) butane,
1,1-two (2-butyl-4-hydroxy-5-methyl base phenyl) butane,
1,1-two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) butane,
1,1-two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) Trimethylmethane,
1,1-two (2-tert-pentyl-4-hydroxy-5-methyl base phenyl) butane,
2,2-two (3,5-two chloro-4-hydroxyphenyl) butane,
2,2-two (3,5-two bromo-4-hydroxyphenyl) butane, 4,4-two (4-hydroxyphenyl) heptane,
1,1-two (2-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) heptane, 2,2-two (4-hydroxyphenyl) octane,
1,1-(4-hydroxyphenyl) ethane etc.; Two (hydroxyaryl) naphthenic hydrocarbon as
1,1-two (4-hydroxyphenyl) pentamethylene, 1,1-two (4-hydroxyphenyl) hexanaphthene,
1,1-two (3-methyl-4-hydroxyphenyl) hexanaphthene,
1,1-two (3-cyclohexyl-4-hydroxyphenyl base) hexane,
1,1-two (3-phenyl-4-hydroxyphenyl) hexanaphthene,
1,1-two (4-hydroxyphenyl)-3,5,5-trimethyl-cyclohexane etc.; Two (hydroxyaryl) ether is as two (4-hydroxyphenyl) ether, two (4-hydroxy-3-methyl phenyl) ether etc.; Two (hydroxyaryl) thioether is as two (4-hydroxyphenyl) thioether, two (3-methyl-4-hydroxyphenyl) thioether etc.; Two (hydroxyaryl) sulfoxide is as two (hydroxyphenyl) sulfoxide, two (3-methyl-4-hydroxyphenyl) sulfoxide, two (3-phenyl-4-hydroxyphenyl) sulfoxide etc.; Two (hydroxyaryl) sulfone is as two (4-hydroxyphenyl) sulfone, two (3-methyl-4-hydroxyphenyl) sulfone, two (3-phenyl-4-hydroxyphenyl) sulfone etc.; Or dihydroxybiphenyl is as 4 ', 4 ' dihydroxybiphenyl, 4, and 4 '-dihydroxyl-2,2 '-dimethyl diphenyl, 4,4 '-dihydroxyl-3,3 '-dimethyl diphenyl, 4,4 '-dihydroxyl-3,3 '-dicyclohexyl biphenyl, 3,3 '-two fluoro-4,4 '-dihydroxybiphenyl etc.
Except the compound shown in the formula 2, aromatic dihydroxy compound can be by the dihydroxy-benzene of dihydroxy-benzene, halogen or alkyl replacement.This aromatic dihydroxy compound can be a Resorcinol, the 3-methylresorcinol, the 3-ethyl resorcinol, 3-propyl group Resorcinol, 3-butyl Resorcinol, the 3-tert-butyl resorcin, 3-phenyl Resorcinol, 3-cumyl Resorcinol, 2,3,4,6-tetrafluoro Resorcinol, 2,3,4,6-tetrabromo Resorcinol, pyrocatechol, Resorcinol, the 3-methyl hydroquinone, 3-ethyl Resorcinol, 3-propyl group Resorcinol, the 3-butylhydroquinone, the 3-Tert. Butyl Hydroquinone, 3-phenyl Resorcinol, 3-cumyl Resorcinol, 2,5-two chlorohydroquinones, 2,3,5, the 6-duroquinol, 2,3,5,6-tetra-tert Resorcinol, 2,3,5,6-tetrafluoro Resorcinol, 2,3,5,6-tetrabromo Resorcinol etc.
According to the embodiment of the present invention, aromatic dihydroxy compound can be a dihydroxyphenyl propane.
The diaryl carbonate that is used for one of transesterify starting material can be the compound shown in compound shown in the formula 5 or the formula 6:
[formula 5]
Figure G05832096920070514D000161
Ar wherein 1And Ar 2Be independently of one another aryl and
[formula 6]
Figure G05832096920070514D000162
Ar wherein 3And Ar 4Be independently of one another aryl and
D 1Be that the aromatic dihydroxy compound shown in the formula 2 is removed the residue that obtains behind two hydroxyls.
Diaryl carbonate shown in formula 5 or the formula 6 can be diphenyl carbonate, xylyl carbonate, two (chloro-phenyl-) carbonic ether, two (tolyl) carbonic ether, dinaphthyl carbonic ether, two (phenylbenzene) carbonic ether, dihydroxyphenyl propane-bis-phenol carbonic ether etc.
For example, according to the embodiment of the present invention, the diaryl carbonate that is used for one of transesterify starting material can be a diphenyl carbonate.
Based on 1mol diaryl carbonate compound, the concentration of dicarboxylic acid compound is 10 -4To 1mol, preferred 10 -3To 0.5mol, more preferably 0.05 to 0.1mol.If the concentration of dicarboxylic acid compound is outside above-mentioned scope, modified polycarbonate can not show gratifying physicals.
Based on the 1mol dihydroxy compound, the concentration of diaryl carbonate is in 1.0 to 1.5mol scopes, and preferred 1.0 to 1.3mol, and more preferably 1.0 to 1.2mol.If the concentration of diaryl carbonate is outside above-mentioned scope, the polymerization degree that is drawn by following formula is low:
[formula 1]
X ‾ n = 1 + r 1 + r - 2 rp
Wherein r is the mol ratio of oxy-compound and carbonate group, and Xn is the polymerization degree, and p is a level of response.When p was 1.0, formula 1 became formula 2.In the case, when r ten minutes near 1.0 the time, can make polymerization degree maximization at short notice:
[formula 2]
X ‾ n = 1 + r 1 - r
According to the embodiment of the present invention, when preparing modified polycarbonate resin, if desired, can use additive in addition, as terminator, antioxidant etc. by esterification and transesterify.
Terminator can be neighbour-normal-butyl phenol, between-normal-butyl phenol, right-normal-butyl phenol, neighbour-isobutyl-phenol, between-isobutyl-phenol, right-isobutyl-phenol, neighbour-tert.-butyl phenol, between-tert.-butyl phenol, p-tert-butylphenol, neighbour-n-pentyl phenol, between-n-pentyl phenol, right-n-pentyl phenol, neighbour-n-hexyl phenol, between-n-hexyl phenol, right-n-hexyl phenol, neighbour-cyclohexylphenol, between-cyclohexylphenol, right-cyclohexylphenol, neighbour-phenylphenol, between-phenylphenol, right-phenylphenol, neighbour-n-nonyl phenol, between-n-nonyl phenol, right-n-nonyl phenol, neighbour-cumyl phenol, between-cumyl phenol, right-cumyl phenol, neighbour-naphthyl phenol, between-naphthyl phenol, right-naphthyl phenol, 2,6-two-tert.-butyl phenol, 2,5-two-tert.-butyl phenol, 2,4-two-tert.-butyl phenol, 3,5-two-tert.-butyl phenol, 3,5-two-cumyl phenol, compound shown in the formula 7, compound shown in the formula 8, compound shown in the formula 9, compound shown in the formula 10, compound shown in the formula 11, compound shown in the formula 12, or monovalent phenol, suc as formula 13 or formula 14 shown in dimethylbiphenyl pyranyl phenol (croman) derivative:
[formula 7]
Figure G05832096920070514D000181
[formula 8]
Figure G05832096920070514D000182
[formula 9]
Figure G05832096920070514D000183
Wherein n is 7 to 30 integer,
[formula 10]
C nH 2n+1-OH
Wherein n is 7 to 30 integer,
[formula 11]
Figure G05832096920070514D000191
R wherein 13Be that C1～C12 alkyl and k are 1 to 3 integers,
[formula 12]
Figure G05832096920070514D000192
R wherein 13Be that C1～C12 alkyl and k are 1 to 3 integers,
[formula 13]
With
[formula 14]
Figure G05832096920070514D000201
What for example, terminator can be p-tert-butylphenol, right-cumyl phenol, right-phenylphenol and formula 11 to the compound shown in the formula 14 is a kind of.
Be used for the aromatic dihydroxy compound of transesterify process starting material based on 1mol, according to embodiment of the present invention, the concentration of terminator is 0.01 to 10mol%.
Can when beginning, transesterify add whole terminators.Selectively, in whole transesterify process, progressively add terminator in batches.Selectively, the specified time after aromatic dihydroxy compound and diaryl carbonate transesterify begin adds whole terminators.
Antioxidant can be the phosphino-antioxidant.The example of phosphino-antioxidant comprises trialkyl phosphite such as trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tricresyl phosphite monooctyl ester, tris(nonyl phenyl) phosphate, tridecyl phosphite, tricresyl phosphite (octadecyl) ester, diphosphorous acid distearyl pentaerythritol ester, tricresyl phosphite (2-chloroethyl) ester or tricresyl phosphite (2,3-two chloropropyls) ester etc.; Tricresyl phosphite cycloalkyl ester such as tricresyl phosphite cyclohexyl etc.; Triaryl phosphites such as triphenyl phosphite, tricresyl phosphite, tricresyl phosphite (ethylphenyl) ester, tricresyl phosphite (butyl phenyl) ester, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (hydroxyphenyl) ester etc.; Monoalkyl diaryl phosphorous acid ester such as 2-ethylhexyl phenylbenzene phosphorous acid ester etc.; Trialkylphosphate such as trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tricresyl phosphate (octadecyl) ester, bisphosphate distearyl pentaerythritol ester, tricresyl phosphate (2-chloroethyl) ester, tricresyl phosphate (2,3-two chloropropyls) ester etc.; Tricresyl phosphate cycloalkyl ester such as tricyclohexyl phosphate etc.; Or triaryl phosphate such as triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (nonyl phenyl) ester, phosphoric acid 2-ethylphenyl diphenyl etc.
According to the method for preparing modified polycarbonate resin of embodiment of the present invention, make aromatic dihydroxy compound and diaryl carbonate in the presence of polymerizing catalyst, carry out transesterify.In this case, can also add additive, as terminator, branching agent, antioxidant etc.
The temperature of transesterify without limits, transesterify can be carried out under 100 to 330 ℃, preferred 180 to 300 ℃, more preferably in the temperature that progressively rises to 300 ℃ from 180 ℃.If temperature of reaction is lower than 100 ℃, transesterify is carried out slowly.If temperature of reaction is higher than 330 ℃, the modified polycarbonate resin that side reaction or generation may occur may be painted.
The pressure of transesterify and can be controlled according to use monomeric vapour pressure and temperature of reaction without limits.When transesterify began, pressure can be for 1 to 10atm, and when transesterify finished, pressure can reduce to 0.1 to 100mbar.
The transesterification reaction time can prolong until obtaining desired molecular weight, and described molecular weight is 1,500 to 15,000g/mol.The reaction times of transesterify is in 0.2 to 10 hour scope.
Transesterify can be carried out under the condition of inert solvent not having.Yet if desired, transesterify can be carried out in the presence of the inert solvent that based on the modified polycarbonate all wts for preparing be 1～150% weight.Inert solvent can be an aromatic substance, as phenyl ether, halogenated diphenyl ether, benzophenone, polyphenylene ether, dichlorobenzene, methylnaphthalene etc.; Or naphthenic hydrocarbon is as three ring (5,2,10) decane, cyclooctane, cyclodecane etc.
In some cases, transesterify can be carried out in inert atmosphere.Rare gas element can be gas such as Ar 2, CO 2, N 2O or N 2Chlorofluorocarbon (chlorofluoro hydrocarbon); Alkane is as ethane or propane; Or alkene such as ethene or propylene.
The result of transesterify under the above-mentioned condition separates from reactor and the corresponding phenol of diaryl carbonate or its ester, water and the inert solvent that use.These isolating compositions can be separated, purifying and regeneration.Transesterify can be used predetermined equipment intermittence or carry out continuously.
Step 2: polycondensation
Making the weight-average molecular weight that is prepared from by transesterify is 1,500 to 20, and the lower molecular weight modified polycarbonate prepolymer that comprises ester group of 000g/mol under the high temperature reduced pressure, or carries out polycondensation in nitrogen atmosphere.Result as polycondensation, removed the diaryl carbonate that exists with the unreacted form in the transesterify process, the polymerization degree is less than the by product that generates in 3 byproduct of reaction and the reaction process, as phenol, make the intermediate molecular weight non-crystalline state modified polycarbonate that comprises ester group that molecular weight is higher than the low molecular weight amorphous polycarbonate prepolymer.
In polycondensation, because the relatively low unreacted diaryl carbonate that has neither part nor lot in reaction of its boiling point and the polymerization degree are evaporated to outside the reactor together less than 3 byproduct of reaction and byproduct of reaction phenol.Compare with ordinary method, this exclusion process in the solid state polymerization processes more helps increasing the molecular weight of modified polycarbonate.
In the method for routine, untapped excessive diaryl carbonate and the polymerization degree are not got rid of by polycondensation process less than 3 byproduct of reaction in the transesterify process before solid state polymerization.In addition, along with the growth of prepolymer molecular weight, the molecular fraction difference between aryl carbonates end group and the aromatic hydroxy end group increases.Therefore, the solid state polymerization processes that is used to prepare the high molecular modified polycarbonate that comprises ester group is extended.
The present embodiment according to the present invention, polycondensation can use conventional condensation reactor, as rotational circle disc type reactor or rotation cage reactor or film reactor.
Polycondensation can be at 180 to 330 ℃, carry out under preferred 200 to 300 ℃.
In polycondensation process, at 0～50mmHg, under the decompression of preferred 0～20mmHg and in above-mentioned high temperature range, remove unreacted dialkyl group (aryl) carbonic ether that exists after transesterify and the esterification, the polymerization degree less than 3 byproduct of reaction, the by-product phenol and the water of generation.
According to the specific embodiment of the present invention, can use nitrogen to inject and replace decompression to remove byproduct of reaction.In the case, the nitrogen amount of injection is 0.01 to 1.0Nm 3/ kgh.Reaction times is with change in reaction conditions, can be in 2 to 120 minutes scopes.
The intermediate molecular weight non-crystalline state modified polycarbonate that comprises ester group of said process preparation, its weight-average molecular weight can be 3,000 to 20,000g/mol.
According to the embodiment of the present invention, if the non-crystalline state modified polycarbonate that uses in the spray crystallization method is the non-crystalline state modified polycarbonate that comprises siloxanes, the method that then prepares the non-crystalline state modified polycarbonate that comprises siloxanes comprises:
A ') transesterify of carrying out under the condition of catalyzer between diaryl carbonate, dihydroxyl polysiloxane and the aromatic dihydroxy compound is being arranged, with the preparation weight-average molecular weight is 1,500～20, the non-crystalline state modification carbonic ether prepolymer that comprises siloxanes of 000g/mol; With
B ') polycondensation comprises the non-crystalline state modified polycarbonate prepolymer (a ' obtains by operation) of siloxanes
Below, describe the method that preparation comprises the non-crystalline state modified polycarbonate of siloxanes in detail.
Step 1: transesterify
The polymerizing catalyst that uses in the embodiments of the present invention can be metal compound as catalyst, nonmetallic compound catalyzer or the mixture of the two.Metal compound as catalyst can be a salt compound, as oxyhydroxide, acetate, alkoxide, carbonate, hydride, hydrate or the oxide compound of basic metal or alkaline-earth metal; Contain transition metal, as the organometallic compound of Zn, Cd, Ti or Pb; Aluminum hydride; Or hydroborate.
The nonmetallic compound catalyzer can be a quaternary ammonium salt, as tetramethylammonium hydroxide, acetic acid tetramethylammonium, tetramethyl-ammonium formate, carbonic acid tetramethylammonium, tetraethylammonium hydroxide, hydroxide tetrapropylammonium, tetrabutylammonium hydroxide, hydroxide four puratized agricultural sprays, hydroxide trimethylphenyl ammonium etc.; Quaternary alkylphosphonium salt such as Qing oxidation Si Jia Phosphonium, acetic acid Si Jia Phosphonium, formic acid Si Jia Phosphonium, carbonic acid Si Jia Phosphonium, Qing oxidation Si Yi Phosphonium, Qing oxidation Si Bing Phosphonium, hydroxide Si Ding Phosphonium, hydroxide Si Ben Phosphonium, hydroxide trimethyl Ben Ji Phosphonium etc.; The primary, the second month in a season or tertiary amine compound; Perhaps nitrogenous aromatic derivative is as pyridine.
Based on the dihydroxy compound that is used for transesterify process starting material, can be 10 according to the specific embodiment of the present invention nonmetallic compound catalyst concentration -6To 10 -1Mol, preferred 10 -5To 10 -2Mol, more preferably 10 -4To 10 -3Mol.If based on 1mol dihydroxy compound nonmetallic compound, catalyst concentration is less than 10 -6Mol, then the nonmetallic compound catalyzer is difficult to effectively bring into play its activity when the reaction beginning; If based on 1mol dihydroxy compound nonmetallic compound catalyst concentration greater than 10 -1Mol, then production cost height.
Comprising basic metal or alkaline earth metal compounds can be, but is not limited only to, and contains oxyhydroxide, carbonate, acetate, alkoxide or the borohydride compound of Li, Na, K, Ru, Cs, Be, Mg, Ca, Sr, Ba etc. separately.
According to the embodiment of the present invention, the concentration that comprises basic metal or alkaline earth metal compounds is 10 -8To 10 -3Mol, preferred 10 -7To 10 -4Mol, more preferably 10 -6To 10 -5Mol is used for the aromatic dihydroxy compound of transesterify process starting material based on 1mol.If based on the 1mol dihydroxy compound, the concentration that comprises basic metal or alkaline earth metal compounds is less than 10 -8Mol, then catalyzer is difficult to effectively bring into play its activity in the reaction later stage; If the concentration that comprises basic metal or alkaline earth metal compounds is greater than 10 -3Mol, production cost height then, and as the physicals of the modified polycarbonate that comprises siloxanes of the finished product, may be bad as thermotolerance and hydrolytic resistance.
According to the embodiment of the present invention, can be as the aromatic dihydroxy compound of one of transesterify starting material by formula 2 expressions.
The diaryl carbonate that is used for one of transesterify starting material can be the compound shown in compound shown in the formula 5 or the formula 6.
The polysiloxane compound that is used for the transesterify starting material can be the compound shown in the formula 15.
[formula 15]
Figure G05832096920070514D000251
Wherein n is 1 to 500 integer.
R 4, R 4 ', R 5And R 5 'Be hydrogen atom or C1～C20 alkyl independently of one another, wherein the part or all of hydrogen atom of alkyl can be replaced by halogen atom; With
R 6And R 7Be independently of one another C1-C20 alkylidene group, the monocycle of linearity or branching or encircle the C6-C30 arylidene more or-R 8-X-R 9-, R wherein 8And R 9Be to replace or unsubstituted C1-C20 alkylidene group or replacement or unsubstituted C6-C30 arylidene independently of one another; With
X is-O-,-S-,-SO-,-SO 2-or-CO-.
Polysiloxane compound shown in the formula 15 can be polydialkysiloxane～dialkoxy alcohol etc.
According to the embodiment of the present invention, the polysiloxane compound that is used for one of transesterify starting material can be the compound shown in the formula 16:
[formula 16]
Figure G05832096920070514D000252
Wherein x is 1 to 500 integer.
Based on the 1mol dihydroxy compound, the concentration of diaryl carbonate can be 1.0 to 1.5mol, and preferred 1.0 to 1.3mol, and more preferably 1.0 to 1.2mol.If the concentration of diaryl carbonate is outside above-mentioned scope, then the polymerization degree is low.Identical with the modified polycarbonate that comprises ester group, the polymerization degree is drawn by formula 1 and 2.
Based on dihydroxy compound, the concentration of the polysiloxane of interpolation is 0.01 to 20mol%, and preferred 0.1 to 15mol%, and more preferably 0.5 to 5mol%.If concentration is less than 0.01mol%, then the effect of modification is insignificant.If concentration is greater than 20mol%, then local increase of the concentration of polysiloxane and polysiloxane become gel.This gelation is unfavorable for reaction.
According to the embodiment of the present invention, when preparing modified polycarbonate resin, if desired, can use additive in addition, as terminator, oxidation inhibitor, branching agent etc. by transesterify.The example of additive, condition etc. are as mentioned above.
In addition, the reaction conditions of step of transesterification, as temperature of reaction, reaction pressure etc. as mentioned above.
Step 2: polycondensation
Making the weight-average molecular weight that is prepared from by transesterify is 1,500 to 20, and the lower molecular weight modified polycarbonate prepolymer that comprises siloxanes of 000g/mol under the decompression hot conditions, or carries out polycondensation in nitrogen atmosphere.Result as polycondensation, removed unreacted diaryl carbonate in the transesterify process, the polymerization degree is less than the by product that generates in 3 byproduct of reaction and the reaction process, as phenol, make the intermediate molecular weight non-crystalline state modified polycarbonate that comprises siloxanes that molecular weight is higher than the low molecular weight amorphous modified polycarbonate prepolymer that comprises siloxanes.
In polycondensation, have neither part nor lot in the unreacted diaryl carbonate of reaction and the polymerization degree owing to boiling point is lower and be evaporated to outside the reactor together less than 3 byproduct of reaction and byproduct of reaction phenol.With respect to ordinary method, this method for removing in the solid state polymerization processes more helps increasing the molecular weight of modified polycarbonate.
In the method for routine, untapped excessive diaryl carbonate and the polymerization degree are got rid of through polycondensation process less than 3 byproduct of reaction in the transesterify process before solid state polymerization.In addition, along with the growth of prepolymer molecular weight, the aryl carbonates end group of the prepolymer that makes and the molecular fraction difference between the aromatic hydroxy end group increase.Therefore, the solid state polymerization processes that is used to prepare the high molecular modified polycarbonate that comprises siloxanes is extended.
The present embodiment according to the present invention, polycondensation can use conventional condensation reactor, as rotational circle disc type reactor or rotation cage reactor or film reactor.
Polycondensation can be at 180 to 330 ℃, carry out under preferred 200 to 300 ℃.
In polycondensation process,, under the decompression of preferred 0～20mmHg and in above-mentioned high temperature range, remove unreacted dialkyl group (aryl) carbonic ether that exists after the transesterify, the polymerization degree less than 3 byproduct of reaction, the byproduct phenol of generation at 0～50mmHg.
According to the embodiment of the present invention, can use nitrogen injection to replace decompression to remove byproduct of reaction.In the case, the nitrogen amount of injection is 0.01 to 1.0Nm 3/ kgh.Reaction times is with change in reaction conditions, can be in 2 to 120 minutes scopes.
The weight-average molecular weight of the intermediate molecular weight non-crystalline state modified polycarbonate prepolymer that comprises siloxanes of said process preparation is 1,000 to 30,000g/mol.
Further describe the present invention with reference to the following example.Described embodiment only is an exemplary illustrated, is not used for limiting the scope of the invention.
Embodiment
Embodiment 1
(preparation comprises the non-crystalline state modified polycarbonate prepolymer of ester group)
With 1,500g (6.57mol) dihydroxyphenyl propane, 1,463g (6.83mol) diphenyl carbonate and 15.89g (6.9 * 10 -2Mol) 1, the 10-sebacic acid mixes, and mixture is joined in the reactor of nitrogen atmosphere.Add 2.5 * 10 based on every mol dihydroxyphenyl propane to reactor then -4The dibutyltin oxide of mol is as polymerizing catalyst.The reactant that obtains is mixed the jacket temperature that is incorporated in 230 ℃ to react 5 minutes down.Under 1 to 4mmHg decompression, carried out esterification and transesterification reaction 30 minutes then.As a result, having prepared number-average molecular weight is 3, the low molecular weight amorphous modified polycarbonate prepolymer that comprises ester group of 452g/mol.
(the non-crystalline state modified polycarbonate that comprises ester group by the polycondensation preparation)
The low molecular weight amorphous modified polycarbonate prepolymer that comprises ester group that makes is filled into temperature is 300 ℃, at 1mmHg or more in the film reactor under the low reaction pressure.Polycondensation was carried out 30 minutes.As a result, having prepared number-average molecular weight is 5, the intermediate molecular weight non-crystalline state modified polycarbonate that comprises ester group of 342g/mol.
(strengthening the high molecular modified polycarbonate that method for solid phase polymerization-preparation comprises ester group)
The number-average molecular weight that will make by melt phase polycondensation is 5, and the modified polycarbonate that comprises ester group of 342g/mol (polydispersity index (PDI)=2.69) stirring and dissolving obtains the solution of 15wt% in the 2L methylene dichloride.As shown in Figure 1, with solution with the compressed nitrogen that injects with 400L/h speed through nozzle spray to strengthening solid state polymerization reactor.The solution that makes spraying contact with the hot nitrogen of being supplied with by reactor bottom evaporating whole solvents, thus the crystalline modified polycarbonate that comprises ester group of collection dry particulate form in the coagulation vessel under reactor.
200 ℃ of hot nitrogens being supplied with by the polymerized unit bottom are cooled to 140 ℃ by temperature control unit, and refrigerative nitrogen contacts with solution then.After solvent that evaporates in the drying unit and nitrogen process were installed in the cyclonic separator of reactor upper end, the unit that is condensed again was divided into liquid solvent and gasiform nitrogen.Liquid solvent is back in the dissolving chamber that agitator is housed, and gasiform nitrogen is back to well heater by compressor.In drying unit, had on a small quantity less than 5% low-crystallinity with less than the particle of the diameter of 80 μ m, described particle is by collecting and be back to agitator in the cyclonic separator that is installed in reactor top.The size of the crystalline particle of bottom use scanning electron microscope and image dissector analysis reactor, collecting.As a result, find the crystalline particle size evenly, mean diameter is 400 μ m ± 35 μ m.In addition, use differential scanning calorimeter to measure the degree of crystallinity of crystalline particle, degree of crystallinity is 22.8%.
Crystalline particle after the solid state polymerization 12 hours, is measured molecular weight in reactor.As a result, the number-average molecular weight that comprises the high molecular modified polycarbonate of ester group is 20, and 463g/mol, PDI are 3.06.
Number-average molecular weight and the PDI of differential responses time are as shown in table 1.
The comparative example 1
(transesterify-preparation comprises the modified polycarbonate prepolymer of ester group)
With 1,500g (6.57mol) dihydroxyphenyl propane, 1,463g (6.83mol) diphenyl carbonate and 15.89g (6.9 * 10 ～2Mol) 1, the 10-sebacic acid mixes, and mixture is joined in the reactor of nitrogen atmosphere.Reactant mixed and under 230 ℃ jacket temperature the reaction 5 minutes.Under 1 to 4mmHg decompression, carried out esterification and transesterification reaction 30 minutes then.As a result, having prepared number-average molecular weight is 3, the low molecular weight amorphous modified polycarbonate prepolymer that comprises ester group of 452g/mol.
(crystallization～preparation comprises the crystalline modified polycarbonate of ester group)
To be dissolved in through the lower molecular weight modified polycarbonate prepolymer (PDI=2.38) that comprises ester group that transesterification reaction makes in the methylene dichloride to concentration be 0.1g/mL.Come the precipitated crystal particle by in solution, adding methyl alcohol as non-solvent.The amount of methyl alcohol is greater than 2 times of solution.In the case, the mean diameter that comprises the crystalline modified polycarbonate of ester group is 570 μ m, observes the crystalline particle of many diameters greater than 10mm.Therefore, in order to carry out solid state polymerization, the crystalline particle piece must grind and classification.Grinding and fractionated particle diameter are 200 μ m ± 42 μ m, and the degree of crystallinity of using differential scanning calorimeter to measure is 20.2%.
(solid state polymerization processes-preparation comprises the high molecular modified polycarbonate of ester group)
The modified polycarbonate that comprises ester group after the crystallization, grinding and the classification that make is added in the solid state polymerization reactor, from the bottom of reactor with the continuous nitrogen injection of the speed of 3L/min.Under 200 ℃ of constant temperature, carry out solid state polymerization processes and comprise the high molecular modified polycarbonate of ester group with preparation.The result is as shown in table 1.
Table 1
Figure G05832096920070514D000301
As shown in table 1, the non-crystalline state modified polycarbonate that comprises ester group among the embodiment 1 is melted polycondensation and spray crystallization, made the high molecular modified polycarbonate that comprises ester group through solid state polymerization then, after solid state polymerization 4 hours, the number-average molecular weight that comprises the modified polycarbonate of ester group surpasses 15,000g/mol.On the contrary, contrast implements to comprise in 1 the non-crystalline state modified polycarbonate of ester group by transesterify and by conventional non-solvent precipitated crystal, carry out solid state polymerization then, the number-average molecular weight that comprises the modified polycarbonate of ester group is difficult to reach 13,000g/mol is even the solid state polymerization time was above 10 hours.
Comparing embodiment 1 and comparative example 1, discovery is to be suitable for 20% to 30% of solid state polymerization according to the degree of crystallinity of the crystalline particle of the embodiment of the invention 1 preparation.In addition, different with comparative example 1 result, the crystalline particle of embodiment 1 preparation has deviation less than mean diameter 80～3, and 20% the narrow diameter of 000 μ m distributes, and this is to control by changing spray condition under the situation of not grinding.
And the present invention does not need the necessary other drying process of ordinary method and grinds classification process, and therefore, operating time and running cost obviously reduce.Finally, after 12 hours, the number-average molecular weight of the high molecular modified polycarbonate that comprises ester group of embodiment 1 preparation reaches 20,463g/mol at solid state polymerization.
After solid state polymerization, the polydispersity index that comprises the modified polycarbonate of ester group among the embodiment 1 only increases by 14.0%, its be among the comparative example 1 polydispersity index increasing value 61.3% 1/4th.Therefore, in embodiment 1, can prevent the formation of low-quality product, low-quality product is indicated by high polydispersity index, and can stablize the product that obtains having homogeneous molecular weight and physicals in a large number.
Embodiment 2
(preparation comprises the non-crystalline state modified polycarbonate prepolymer of siloxanes)
With 1,484g (6.50mol) dihydroxyphenyl propane, 1,478g (6.9mol) diphenyl carbonate and 5.08g (1.13 * 10 ～3Mol) dihydroxyl polysiloxane (Dow Corning 3058) mixes, and mixture is joined in the reactor of nitrogen atmosphere.Add 1 * 10 based on every mol dihydroxyphenyl propane to reactor then -6Mol sodium acetate and 2.5 * 10 ～4Mol hydroxide 4-butyl-phosphonium is as polymerizing catalyst.Reactant is mixed the jacket temperature that is incorporated in 230 ℃ to react 5 minutes down.Under 1 to 4mmHg decompression, carried out transesterification reaction 30 minutes then.As a result, having made weight-average molecular weight is 8, the non-crystalline state modified polycarbonate prepolymer that comprises siloxanes of 804g/mol.
(the non-crystalline state modified polycarbonate that comprises siloxanes by the polycondensation preparation)
It is film reactor under 300 ℃ of 1mmHg or the more decompression power that the low molecular weight amorphous modified polycarbonate prepolymer that will comprise siloxanes is filled into temperature.Polycondensation was carried out 30 minutes.As a result, having prepared weight-average molecular weight is 15, the non-crystalline state modified polycarbonate that has siloxanes of 578g/mol.
(strengthening the high molecular modified polycarbonate that method for solid phase polymerization～preparation comprises siloxanes)
The weight-average molecular weight that will make by melt phase polycondensation is 15, and the non-crystalline state modified polycarbonate (PDI=2.79) that comprises siloxanes of 578g/mol is dissolved in and obtains 15wt% solution in the 2L methylene dichloride.With reference to Fig. 1, with solution with the compressed nitrogen that injects with 400L/h speed through nozzle injection reinforcing solid state polymerization reactor.Spray solution is contacted with the hot nitrogen of being supplied with by reactor bottom evaporating whole solvents, thereby make the crystalline modified polycarbonate that comprises siloxanes of dry particulate form.
The size of the crystalline particle that use scanning electron microscope and image dissector measure.As a result, find the crystalline particle size evenly, mean diameter is 400 μ m ± 35 μ m.In addition, use differential scanning calorimeter to measure the degree of crystallinity of crystalline particle, degree of crystallinity is 23.2%.
Crystalline particle stopped 10 hours at polymerized unit, measured the resulting high molecular modified polycarbonate that comprises siloxanes.As a result, the weight-average molecular weight of high-molecular weight siloxanes Copolycarbonate is 39, and 500g/mol, PDI are 3.19.
Weight-average molecular weight and the PDI of differential responses time are as shown in table 2.
The comparative example 2
(transesterify-preparation comprises the modified polycarbonate prepolymer of siloxanes)
With 1,484g (6.50mol) dihydroxyphenyl propane, 1,478g (6.9mol) diphenyl carbonate and 5.08g (1.13 * 10 -3Mol) dihydroxyl polysiloxane (Dow Corning 3058) mixes, and mixture is joined in the reactor of nitrogen atmosphere.Reactant is mixed the jacket temperature that is incorporated in 230 ℃ to react 5 minutes down.Under 1 to 4mmHg decompression, carried out transesterification reaction 30 minutes then.As a result, making weight-average molecular weight is 8, the low molecular weight amorphous modified polycarbonate prepolymer that comprises siloxanes of 804g/mol.
(crystallization-preparation comprises the crystalline modified polycarbonate of siloxanes)
To be dissolved in through the lower molecular weight modified polycarbonate prepolymer (PDI=2.40) that comprises siloxanes that transesterification reaction makes in the methylene dichloride to concentration be 0.1g/mL.Make the crystalline solids precipitation by the methyl alcohol that adds as non-solvent.Quantity of methyl alcohol is greater than 2 times of solution.Thereby make the pulverous crystalline modified polycarbonate that comprises siloxanes.In the case, the mean diameter of crystalline particle is 570 μ m, and has generated the crystalline particle of many diameters greater than 10mm.Therefore, in order to carry out solid state polymerization, the crystalline particle piece must grind and classification.Grinding and fractionated particle diameter are 200 μ m+42 μ m, and the degree of crystallinity of using differential scanning calorimeter to measure is 20.5%.
(solid state polymerization processes-preparation comprises the high molecular modified polycarbonate of siloxanes)
The crystalline modified polycarbonate that will comprise siloxanes is filled in the typical solid state polymerization reactor, injects hot nitrogen from the bottom of reactor continuously with the speed of 3L/min.In the case, under 200 ℃ of constant temperature, carry out solid state polymerization comprises siloxanes with preparation high molecular modified polycarbonate.The result is as shown in table 2.
Table 2
6 38002 3.04 33324 3.23
8 38624 3.12 33996 3.52
10 39500 3.19 34523 3.8
As shown in table 2, according to embodiment 2, having made weight-average molecular weight in 4 hours is 35, the modified polycarbonate that comprises siloxanes of 000g/mol.On the contrary, according to comparative example 2, be 35 even be difficult to obtain weight-average molecular weight later in 10 hours in reaction, the modified polycarbonate that comprises siloxanes of 000g/mol.
Comparing embodiment 2 and comparative example 2 are found to compare with comparative example 2, are to be suitable for 20% to 30% of solid state polymerization according to the degree of crystallinity of the crystalline particle of embodiments of the invention 2 preparations.In addition, the crystalline particle of embodiment 2 preparation has deviation in mean diameter 80～3, and 20% the narrow diameter of 000 μ m distributes, this do not grind with the fractionated situation under control by changing spray condition.
And the present invention does not need the necessary other drying process of ordinary method, process of lapping and classification process, and therefore, operating time and running cost obviously reduce.Finally, after 10 hours, the weight-average molecular weight among the embodiment 2 is increased to 39,500g/mol at solid state polymerization.
In embodiment 2, after solid state polymerization, polydispersity index only increases by 14.5%, its be among the comparative example 2 polydispersity index increasing value 58.1% 1/4th.Therefore, in embodiment 2, can prevent the formation of low-quality product, low-quality product is indicated by high polydispersity index, and can stablize the product that obtains having homogeneous molecular weight and physicals in a large number.
Industrial applicibility
The invention provides and a kind ofly stablize, ensure the quality of products and only need the short time can prepare the modified polycarbonate preparation method of HMW modified polycarbonate.

Claims (14)

1. method for preparing the high molecular modified polycarbonate resin, it comprises: with modified polycarbonate be dissolved in obtain solution in the solvent after, spray crystallization and solid state polymerization non-crystalline state modified polycarbonate simultaneously,
Wherein, described non-crystalline state modified polycarbonate is that number-average molecular weight is 3,000-20, the non-crystalline state modified polycarbonate that comprises ester group of 000g/mol, and the modified polycarbonate of described solid state polymerization is that number-average molecular weight is 15,000-200, the modified polycarbonate that comprises ester group of 000g/mol; Perhaps described non-crystalline state modified polycarbonate is that weight-average molecular weight is 10,000-30, the non-crystalline state modified polycarbonate that comprises siloxanes of 000g/mol, and the modified polycarbonate of described solid state polymerization is that weight-average molecular weight is 20,000-200, the modified polycarbonate that comprises siloxanes of 000/mol.
2. method according to claim 1, wherein said non-crystalline state modified polycarbonate are the polycarbonate that comprises ester group or siloxanes in a kind of chemical structure.
3. method according to claim 1, wherein said solvent are the mixtures of methylene dichloride, chloroform, tetrahydrofuran (THF), meta-cresol, hexanaphthene, diox, dimethyl aldehyde, pyridine or above-mentioned solvent.
4. method according to claim 1, the concentration of wherein said non-crystalline state modified polycarbonate solution are 5.0 to 50 weight %.
5. method according to claim 1, the crystallization of wherein said non-crystalline state modified polycarbonate comprises by nozzle spray non-crystalline state modified polycarbonate solution, and it is contacted with evaporating solvent with high-temperature gas, and remove thus and desolvate, make crystalline modified polycarbonate.
6. method according to claim 5, wherein said nozzle are pressure nozzle or air-blast atomizer.
7. method according to claim 6, wherein nozzle is a pressure nozzle and at 2.0～51.0kgf/cm 2Spraying non-crystalline state modified polycarbonate solution under the injection pressure.
8. method according to claim 6, wherein said nozzle are air-blast atomizers and inject pressurized gas with 200～800L/ hour injection speed.
9. method according to claim 8, wherein said pressurized gas comprises at least a N of being selected from 2, air and CO 2Gas.
10. method according to claim 5, wherein said high-temperature gas are that temperature is 40～250 ℃ N 2, air or CO 2
11. method according to claim 5, the mean diameter of wherein said crystalline modified polycarbonate pellets are 80-3000 μ m, and its limit of error is less than 30%.
12. a method for preparing modified polycarbonate resin, this method comprises:
Spray crystallization non-crystalline state modified polycarbonate is to generate crystalline modified polycarbonate; With
The crystalline modified polycarbonate of solid state polymerization to be generating the high molecular modified polycarbonate,
Wherein, described non-crystalline state modified polycarbonate is that number-average molecular weight is 3,000-20, the non-crystalline state modified polycarbonate that comprises ester group of 000g/mol, and the modified polycarbonate of described solid state polymerization is that number-average molecular weight is 15,000-200, the modified polycarbonate that comprises ester group of 000g/mol; Perhaps described non-crystalline state modified polycarbonate is that weight-average molecular weight is 10,000-30, the non-crystalline state modified polycarbonate that comprises siloxanes of 000g/mol, and the modified polycarbonate of described solid state polymerization is that weight-average molecular weight is 20,000-200, the modified polycarbonate that comprises siloxanes of 000g/mol.
13. method according to claim 12, wherein said non-crystalline state modified polycarbonate forms by the transesterify of interfacial polymerization process, dialkyl carbonate or diaryl carbonate and aromatic dihydroxy compound or the transesterify and the condensation prepared of dialkyl carbonate or diaryl carbonate and aromatic dihydroxy compound.
14. method according to claim 12, the spray crystallization of wherein said non-crystalline state modified polycarbonate comprises: the non-crystalline state modified polycarbonate is dissolved in makes solution in the solvent; By nozzle spray solution; And the solution of spraying is contacted with evaporating solvent with high-temperature gas, and remove thus and desolvate, make crystalline modified polycarbonate.
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