WO2019062428A1 - 一种聚酯嵌段共聚物及其制备方法与应用 - Google Patents

一种聚酯嵌段共聚物及其制备方法与应用 Download PDF

Info

Publication number
WO2019062428A1
WO2019062428A1 PCT/CN2018/102638 CN2018102638W WO2019062428A1 WO 2019062428 A1 WO2019062428 A1 WO 2019062428A1 CN 2018102638 W CN2018102638 W CN 2018102638W WO 2019062428 A1 WO2019062428 A1 WO 2019062428A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
polycondensation
acid
block copolymer
dicarboxylic acid
Prior art date
Application number
PCT/CN2018/102638
Other languages
English (en)
French (fr)
Inventor
崔晓文
汪永斌
庞小琳
姚君
黄华
胥保礼
戴伍国
Original Assignee
南通星辰合成材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南通星辰合成材料有限公司 filed Critical 南通星辰合成材料有限公司
Publication of WO2019062428A1 publication Critical patent/WO2019062428A1/zh

Links

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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and 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
    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/10—Applications used for bottles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • the invention belongs to the technical field of polymer synthetic materials, and particularly relates to a polyester block copolymer having cold resistance and hydrophobicity and a preparation method thereof.
  • Polyester material as one of the five major engineering plastics, mainly refers to PBT, the Chinese name polybutylene terephthalate, which is a semi-crystalline thermoplastic resin with high modulus, high strength, high elasticity and heat resistance.
  • Advantages mainly used in electronics, automotive, lighting, machinery, spinning, communications, film and instrumentation.
  • PET the Chinese name polyethylene terephthalate
  • PET is widely used in spinning, film, blow molding and other fields due to its good mechanical properties, high temperature resistance and scratch resistance. What we usually call polyester is the yarn spun from PET.
  • PTT the Chinese name polytrimethylene terephthalate, as a new star in the polyester family, has excellent resilience and dyeing properties, providing a new choice for the spinning industry.
  • PCT Chinese name poly(cyclohexanedimethylene terephthalate) and PEN, Chinese name polyethylene naphthalate is used in high temperature environment due to its high temperature resistance and mechanical properties. In the fields of electronics and automobiles.
  • polyester materials mentioned above have excellent mechanical properties, but are relatively brittle and have insufficient toughness, especially at low temperatures, which have substantially no toughness and are in a state of collision. This disadvantage limits the application of polyester.
  • China has a vast territory, and the temperature difference between different regions in the north and south is extremely great, especially in the winter, Hainan Island is still sunny and warm, and the temperature is over 20 °C; Heilongjiang is another scene, the cold wind, the cold weather, The minimum temperature can be as low as -40 ° C.
  • polyester fiber, PBT fiber and PTT fiber can no longer function in this environment. The clothes made with it are expected to break at the touch, which greatly limits the application of PET, PBT and PTT. .
  • PET and PBT films are prone to embrittlement and bursting at -40 ° C, posing a safety hazard for their applications and devices.
  • PBT injection molding grade materials are also limited in application due to their brittleness in the -20 ° C environment. Therefore, if a common substance can be found, the toughness of these materials, especially the low temperature toughness, can be improved, and the application field can be significantly broadened, which has very important practical significance.
  • the polyester is a high molecular polymer obtained by condensing a diacid and a diol to remove water molecules, and the presence of an ester bond imparts a certain polarity to the polyester material.
  • the higher the polarity the easier it is to absorb moisture, the easier it is to adsorb other small molecules or particulate impurities.
  • the lower the polarity the less likely it is to absorb moisture and the less likely it is to adsorb other small molecules or particulate impurities.
  • PET fiber, PBT fiber and PTT fiber have been widely used in various human garments. The fluffy fiber structure can better keep warm, clothes can be made more and more comfortable to wear. In East China, there is always rain and rain every winter.
  • Patent CN100551053C proposes to solve the problem of adhesiveness of the polyester film by coating a silicone anti-sticking liquid on one side of the polyester film and stably and uniformly coating the anti-sticking liquid on the polyester film to satisfy the field of electronic applications. Anti-sticking requirements.
  • Patent CN105538853A discloses a coextrusion process in which a silicone additive is added to the upper or lower layer material for coextrusion to give a film of low polarity.
  • Patent CN103042780B provides a co-extrusion method in which a polyester and a thermoplastic elastomer are co-extruded to form a composite film to achieve a low temperature resistance.
  • Patent CN104136534A discloses a low temperature resistant poly(alkylene carbonate) resin composition, which is prepared by copolymerization of an epoxy compound to prepare a low temperature resistant resin material, but the introduction of an epoxy compound fails to effectively reduce the resin. The polarity, which is not mentioned in the patent.
  • Patent CN102382307A discloses a preparation method for preparing a dihydroxyaryl siloxane for improving the compatibility of a polycarbonate with a polymer after copolymerization thereof, mainly by reacting with phosgene in a solution to form a polycarbonate copolymer.
  • U.S. Patent No. 5,132,392 A discloses the formation of a copolyester which exhibits better hydrophilic properties by introducing a polysilane having a polyether segment at the end, but the compound does not provide improved low temperature resistance and hydrophobic properties of the material.
  • 4,927,785 A improves the hydrolysis resistance of the material by introducing a copolyester obtained from a special polysiloxane.
  • the polysilane end group used is an alkyl epoxy group, which is bonded to the carboxyl group of the epoxy or polyester.
  • the terminal hydroxyl group reacts to form a copolymer, and the patent also does not mention improvements in low temperature resistance and hydrophobic properties.
  • U.S. Patent No. 4,894,427 A provides a polysilane-containing polyester copolymer which is mainly obtained by copolymerizing a polysilane having a hydroxyalkyl group at the end thereof with a dicarboxylic acid, and the resulting copolymer has improved hydrolysis resistance, but its low temperature resistance. Performance and hydrophobic properties are not mentioned.
  • silicone resin is often used to enhance the release properties of the final modified material, because the added silicone is a small molecular material, modified by blending and extrusion, organic Silicon molecules easily migrate to the surface of the material, reducing the surface tension of the material, making it easier to injection mold.
  • the disadvantage is that the amount of silicone resin added cannot be too high, otherwise the added silicone small molecules migrate to the surface of the part to form oil spots and defects.
  • other low surface energy additives such as extrusion and granulation, to melt and granulate silicone rubber and nylon resin to improve the low temperature impact resistance of the resin, but due to the difference between the two resins.
  • the property is too large to achieve uniform mixing, and the silicone rubber is unevenly dispersed in the nylon resin, and the performance fluctuates, which is often difficult to control in the production process, and cannot be applied to the application fields requiring relatively precise parts or spinning films. Achieving stable production limits its application. If a small molecule of silicone or oligomer and polyester are copolymerized by means of polymerization, the silicone can be uniformly dispersed in the polyester resin, and the new material will have a higher mechanical structure of the polyester resin at the same time. Properties and low temperature resistance and hydrophobicity of silicone, and silicone molecules are dispersed in the resin at the molecular level, the properties of the material become stable, the volatility becomes smaller, and the performance is superior, greatly expanding its application. field.
  • the object of the present invention is to provide a cold-resistant, hydrophobic polyester block copolymer by means of copolymerization in order to overcome the deficiencies in the prior art described above.
  • the novel polyester block polymer prepared by the invention simultaneously gives the new material a low surface tension and a high impact strength at a low temperature, which provides a possibility for the application of the material.
  • a polyester block copolymer is obtained by a method of copolymerization by introducing a polysilane molecule into a molecular structure of a polyester, and the prepared polyester block copolyester has the following formula (1). structure:
  • the A block is a polyester obtained by reacting a dibasic acid with a glycol; wherein the dibasic acid is selected from one or more of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid; The alcohol is selected from one or more of an aliphatic diol and an alicyclic diol;
  • the B block structure is as shown in formula (II):
  • R 4 and R 5 are each independently selected from methyl, ethyl, propyl, phenyl, ⁇ -methylphenyl or p-methylphenyl;
  • R 6 represents (CH 2 ) 2 , (CH 2 ) 3 , (CH 2 ) 4 , (CH 2 ) 6 , One or several of them; s is an integer greater than one;
  • n is an integer greater than 1
  • t is an integer greater than 1.
  • the polyester block copolymer of the present invention satisfies the percentage of the A block as a percentage of the total mass of the copolymer and the percentage of the B block to the total mass of the copolymer is 100%; preferably, the B block The mass is from 0.1% to 50%, more preferably from 0.5% to 30%, even more preferably from 3% to 20%, still more preferably from 10% to 15%, based on the total mass of the copolymer.
  • the aromatic dicarboxylic acid is selected from one or more of terephthalic acid, isophthalic acid, and naphthalic acid;
  • the metacarboxylic acid is selected from one or more of succinic acid, adipic acid, and suberic acid;
  • the alicyclic diol is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, and hexanediol.
  • the same structure as R 4, R 5 or different, preferably the same, more preferably R 4 and R 5 are methyl.
  • the polyester block copolymer provided by the present invention has an intrinsic viscosity of from 0.6 to 2.0 dL/g, preferably from 0.79 to 1.33 dL/g. Unless otherwise specified, the characteristic viscosities of the present invention are measured in accordance with the ASTM D445 standard method.
  • the polyester block copolymer is selected from one or more of the following structures:
  • the polyester block copolymer provided by the invention has excellent low-temperature resistance, good low-temperature impact property and small expression tension, and can be used in applications of cold resistance and hydrophobicity, such as fibers, films, bottles, engineering plastics and the like.
  • the invention also provides a preparation method of a polyester block copolymer, which comprises an esterification reaction, a pre-polycondensation reaction and a polycondensation reaction; further, a solid phase viscosity-increasing reaction can also be carried out as needed.
  • the method includes the following steps:
  • the dicarboxylic acid in this step is selected from one or more of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid;
  • the glycol in this step is selected from the group consisting of an aliphatic diol and an alicyclic two.
  • R 4 and R 5 are each independently selected from methyl, ethyl, propyl, phenyl, ⁇ -methylphenyl or p-methylphenyl; s is an integer greater than 1;
  • the glycol in this step is selected from one or more of an aliphatic diol and an alicyclic diol;
  • the pre-polycondensation product obtained in the step (3) is placed in a reaction vessel to carry out a polycondensation reaction to obtain a polyester block copolymer.
  • the process of the present invention may further comprise subjecting the product obtained in the step (4) to a solid phase thickening reaction.
  • the solid phase viscosity-increasing reaction can be carried out under a vacuum state (3-100 Pa) or an inert gas-protected state (a flow rate of the inert gas is 0.5-5 L/[min ⁇ KG tackifying particles]).
  • the temperature of the solid phase viscosity increasing reaction is from 100 to 260 ° C, and the general reaction time is from 4 to 36 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer is from 0.8 to 2.0 dL/g, preferably from 0.79 to 1.33 dL/g, by solid phase thickening reaction.
  • the specific reaction conditions can be determined according to actual needs.
  • the dicarboxylic acid may be selected from the group consisting of phthalic acid (PTA), isophthalic acid (PIA), 2,6-naphthalenedicarboxylic acid (NDA), and 1,4-butane. a mixture of one or more of acid (SA), adipic acid or suberic acid; the glycol is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6- A mixture of one or more of hexanediol and 1,4-cyclohexanedimethanol (CHDM).
  • PTA phthalic acid
  • PIA isophthalic acid
  • NDA 2,6-naphthalenedicarboxylic acid
  • SA acid
  • SA adipic acid or suberic acid
  • the glycol is ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6- A mixture of one or more of hexanediol and 1,
  • the present invention further optimizes the combination of the dicarboxylic acid and the diol in the step (1), specifically: the dicarboxylic acid is terephthalic acid, and the glycol is ethylene glycol; Alternatively, the dicarboxylic acid is terephthalic acid, the dihydric alcohol is 1,3-propanediol; or the dicarboxylic acid is terephthalic acid, and the dihydric alcohol is 1, 4-butanediol; or the dicarboxylic acid is terephthalic acid, the glycol is 1,4-cyclohexanedimethanol (CHDM); or the dicarboxylic acid is 2,6-naphthalenedicarboxylic acid (NDA), the diol is ethylene glycol; or the dicarboxylic acid is 2,6-naphthalenedicarboxylic acid, and the diol is 1,4-butyl a diol; or the dicarboxylic acid is 1,4-succinic acid (SA),
  • the compound represented by the formula (III) may be selected from ⁇ , ⁇ -dicarboxyethylpolydimethylsiloxane, ⁇ , ⁇ -dicarboxyethylpolydiethylsiloxane. , ⁇ , ⁇ -dicarboxyethylpolymethylphenylsiloxane, ⁇ , ⁇ -dicarboxyethylpolydiphenylsiloxane, and the like.
  • the diol is one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol (CHDM). mixture.
  • the present invention preferably optimizes the amount of the raw materials in each step to obtain a polyester block copolymer excellent in properties.
  • the molar ratio of the dicarboxylic acid to the diol is from 1:1 to 1:1.5.
  • the molar ratio of the compound represented by the formula (III) to the diol is from 1:1.2 to 1:1.5.
  • the ratio of the amount of the product obtained in the step (2) to the sum of the amounts of the products of the steps (1) and (2) is 0.1% to 50%, preferably 0.5% to 30%, more preferably 3 From 5% to 20%, more preferably from 10% to 15%.
  • the catalyst may be selected from the group consisting of cerium oxide, manganese acetate, zinc acetate, tetrabutyl titanate, antimony trioxide, ethylene glycol hydrazine, and ethylene glycol titanium.
  • the mass of the catalyst preferably ranges from 0.01% to 0.1% by weight based on the total mass of the reaction materials.
  • the method for preparing the catalyst mixed system comprises: placing the diol and the catalyst in a reaction kettle in a ratio, and heating and boiling under vacuum. 2-4 hours, the degree of vacuum is 20-30KPa, the temperature is 170-200 ° C, cooling, you can. Wherein the molar ratio of the glycol to the catalyst is 1:3 to 1:6.
  • the esterification reaction may be carried out under ordinary conditions.
  • the conditions of the esterification reaction in the step (1) are preferably: a temperature of 160 to 245 ° C, a degree of vacuum of 40 to 45 KPa; and an esterification reaction condition of the step (2): a temperature of 160 to 245 ° C, The degree of vacuum is 40 to 45 KPa.
  • the present invention adopts a pre-polycondensation reaction and then a polycondensation reaction, and optimizes the reaction conditions of the two-step polycondensation.
  • the pre-polycondensation reaction conditions in the step (3) are: a temperature of 180 to 310 ° C, a vacuum degree of 1.5 to 2.5 KPa, a general reaction time of 30 to 60 min; and a polycondensation reaction condition of the step (4): a temperature of 180 ⁇ 310 ° C, vacuum 100 ⁇ 200Pa, the general reaction time is 60-240min.
  • the polycondensation process which has begun in the esterification reaction is continued in the pre-polycondensation kettle, and the pre-polycondensation reaction produces a low molecular weight polyester copolymer, and the pre-polycondensation product passes through a pre-condensation discharge pump, a pre-condensation discharge filter, and a pre-condensation discharge. After the cooler, it enters the polycondensation reactor.
  • the polycondensation reaction produces a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the obtained polyester block copolymer has an intrinsic viscosity of 0.5 to 1.0 dL/g.
  • the temperature of the solid phase viscosity increasing reaction is 100 to 260 °C.
  • the method comprises the following specific steps:
  • the dicarboxylic acid and the diol are placed in a container (formulation tank), and stirred uniformly to obtain a mixture S1; wherein, the molar ratio of the dicarboxylic acid to the diol is 1:1 to 1:1.5;
  • the compound represented by the formula (III) and the diol are placed in a container (formulation tank) and stirred uniformly to obtain a mixture S2; wherein the molar ratio of the compound represented by the formula (III) to the diol is 1: 1.2 to 1:1.5;
  • the diol and the catalyst are added to a vessel (preparation tank) at a molar ratio of 1:3 to 1:6, and heated under vacuum for 2-4 hours, with a vacuum of 20-30 KPa and a temperature of 170. -200 ° C, cooling; preparing a catalyst mixing system;
  • the mixture S1 is placed in a reaction vessel (esterification kettle), and then the catalyst mixture system prepared in the step S2 is added to carry out an esterification reaction until the water is no longer produced; the oligomer OM1 is formed; wherein the catalyst is added
  • the mass ratio of the mass to the mixture S1 is 0.01%-0.1%; the esterification reaction conditions are: temperature 160-245 ° C, vacuum degree 40-45 KPa, reaction time 1-3 hours;
  • the mixture S2 is placed in a reaction vessel (esterification kettle), and then the catalyst mixture system prepared in the step S2 is added to carry out an esterification reaction until the water is no longer produced; the oligomer OM2 is produced, that is, the formula (III) Compound shown;
  • the mass ratio of the added catalyst to the mixture S2 is 0.01%-0.1%;
  • the esterification reaction conditions are: temperature 160-245 ° C, vacuum degree 40-45 KPa, reaction time 1-3 hours;
  • the oligomer OM1 and the oligomer OM2 are placed in a reaction vessel (pre-polycondensation kettle) to carry out a pre-polycondensation reaction to form a pre-polycondensation product (ie, a low molecular weight polyester copolymer); wherein the quality of the oligomer OM1 is The ratio of the sum of the masses of the oligomer OM1 and the oligomer OM2 is 0.1% to 50%; the precondensation reaction conditions are: a temperature of 180-310 ° C, a degree of vacuum of 1.5-2.5 KPa, and a reaction time of 30-60 min.
  • the pre-polycondensation product obtained in the step S4 is placed in a reaction vessel (polycondensation reactor) to carry out a polycondensation reaction to produce a compound represented by the formula (I) (that is, a high molecular weight polyester block copolymer);
  • the polycondensation reaction conditions are: temperature 180-310 ° C, vacuum degree 100-200Pa, reaction time is 60-240min; the intrinsic viscosity of the obtained polyester block copolymer is 0.5-1.0dL / g;
  • the polyester block copolymer particles obtained by the polycondensation reaction are fed into an adhesion-increasing kettle, and the flow rate of the inert gas is 0.5-5 L/[min ⁇ KG thickening particles in a vacuum state of 3-100 Pa or an inert gas protection state.
  • the solid phase reaction was carried out at a set temperature of 100 to 260 ° C for a reaction time of 4 to 36 hours; and the obtained polyester block copolymer had an intrinsic viscosity of 0.8 to 2.0 dL/g.
  • the present invention further optimizes the reaction conditions for the characteristics of the raw materials. in particular:
  • the precondensation reaction temperature ranges from 250 to 310 ° C
  • the polycondensation reaction temperature is from 250 to 310 ° C
  • the solid phase viscosity increasing reaction temperature is preferably 200. ⁇ 240 ° C.
  • the precondensation reaction temperature ranges from 280 to 310 ° C
  • the polycondensation reaction The temperature is 280 to 310 ° C
  • the solid phase viscosity increasing reaction temperature is preferably 240 to 260 ° C.
  • the glycol in the step (1) is terephthalic acid
  • the glycol is a glycol other than 1,4-cyclohexanedimethanol (CHDM) or two or more
  • the precondensation reaction temperature is in the range of 200 to 250 ° C
  • the polycondensation reaction temperature is 200 to 250 ° C
  • the solid phase viscosity increasing reaction temperature is preferably 180 to 220 ° C.
  • the pre-polycondensation reaction temperature ranges from 100 to 200 ° C
  • the polycondensation reaction temperature is from 100 to 200 ° C
  • the solid phase viscosity-increasing reaction temperature is from 100 to 110 ° C.
  • the invention simultaneously protects the polyester block copolymer or the polyester block copolymer prepared by the method for preparing fibers, films, bottles and engineering plastics.
  • the invention has the following advantages:
  • the polyester copolymer containing the silicon unit prepared by the invention has high intrinsic viscosity, which directly reflects the high molecular weight of the copolymer and excellent mechanical properties, and at the same time imparts excellent low temperature resistance and low surface tension to the material. Greatly expand the range of applications of existing polyester.
  • the polyester copolymer containing the silicon unit prepared by the invention is prepared by a direct polymerization method, and the silicon molecules in the prepared polyester copolymer are uniformly distributed in the molecular chain of the polyester resin.
  • the way of blending silicone rubber or silicone resin with polyester resin through a twin-screw extruder may cause delamination or incompatibility due to compatibility problems;
  • the small molecule of the reactive group-containing silicone molecule is blended with the polyester resin through a twin-screw extruder. Due to the short residence time in the twin screw, the reaction is insufficient, and more residual small molecules are finally blended. The volatiles are higher.
  • the silicon-containing monomer and the silicon-free monomer are separately esterified and then polymerized, so that the reaction is more easily controlled according to requirements, and it is convenient to obtain a polyester block copolymer having a certain degree of regularity.
  • the silicon-containing monomer is first esterified and the reaction is easier to control.
  • the preparation method provided by the present invention finally adopts a solid phase polymerization method with mild reaction conditions to synthesize a high molecular weight polyester copolymer which cannot be obtained by direct polycondensation, thereby not only achieving the intended effect, but also avoiding
  • the conventional polycondensation method consumes a large amount of energy, the reaction conditions are harsh, the requirements on the equipment are high, and it is difficult to control the defects of the product process conditions.
  • the preparation method of the polyester copolymer provided by the invention is optimized on the basis of the current production method of the polyester, and the method is simple and convenient, and is easy to control and realize industrial production.
  • Viscosity Measured according to ASTM D445.
  • Terminal carboxyl content measured according to GB/T 14190-2008 standard.
  • Solution constant temperature thermal weight loss Weigh the appropriate amount of sample, in the air atmosphere heating furnace, the initial temperature is room temperature, the heating rate is 20 ° C / min, the temperature is programmed to 260 ° C, for 120 min. The amount of volatiles in the sample is calculated by a curve change in the relationship between sample mass and temperature.
  • Slurry preparation 1) Putting terephthalic acid (PTA) and 1,4 butanediol (BDO) into the slurry preparation tank U1 through the metering system, and stirring evenly, which is recorded as slurry S1, wherein PTA is 773G (G The meaning is mass unit gram, the same below), BDO is 520G.
  • PTA terephthalic acid
  • BDO 1,4 butanediol
  • ⁇ , ⁇ -dicarboxyethylpolydimethylsiloxane and 1,4 butanediol (BDO) are respectively introduced into the slurry preparation tank U2 through a metering system, and stirred uniformly, and recorded as slurry S2, wherein ⁇ The ⁇ -dicarboxyethyl polydimethylsiloxane was 210 G, and the 1,4 butanediol (BDO) was 30 G.
  • Catalyst preparation 1,4 butanediol (BDO) 100G and catalyst C (tetrabutyl titanate) 158.9G were added to the preparation tank U3, and heated under vacuum for 2-3 hours, and the degree of vacuum was 20-30 KPa. The temperature was 180 ° C, and after cooling, the configured catalyst was transferred to a catalyst addition tank.
  • BDO butanediol
  • catalyst C tetrabutyl titanate
  • the esterification reaction the slurry S1 in the slurry tank U1 is pumped from the slurry into the esterification tank E1, and the configured catalyst C is pumped to the esterification tank E1 through a gear to produce an ester under the action of the catalyst.
  • the oligomerization reaction OM1 is formed by the esterification reaction until no more water is produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification rate of 99.2%.
  • Esterification reaction the slurry S2 in the slurry tank U2 is pumped from the slurry into the esterification kettle E2, and the configured catalyst is pumped to the esterification kettle E2 through a gear, and esterification occurs under the action of the catalyst.
  • the oligomer OM2 formed by the reaction and esterification reaction until water is no longer produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification ratio of 99%.
  • Pre-polycondensation reaction The oligomers in the esterification kettles E1 and E2 were separately fed into the pre-polycondensation kettle, wherein the ratio OM2/(OM1+OM2) of the OM2 added in the esterification kettle E2 was 10%.
  • the polycondensation process which has started in the esterification reaction is continued in the pre-condensation polymerization vessel, the pre-polycondensation reaction temperature is 245 ° C, the vacuum degree is -2 KPa, the reaction time is 40 min, and a low molecular weight polyester copolymer is formed, and the pre-polycondensation product is passed through The polycondensation discharge pump, the pre-condensation discharge filter, and the pre-condensation discharge cooler enter the polycondensation reactor.
  • Polycondensation reaction The pre-polycondensation product is sent from the pre-polycondensation unit to the polycondensation reactor, and the prepolymer is further reacted.
  • the polycondensation reaction temperature is 248 ° C
  • the vacuum degree is 120 Pa
  • the reaction time is 200 min to form a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.61 dL/g.
  • the structure of the obtained polyester block copolymer is as follows:
  • Solid phase viscosity-increasing reaction the polyester block copolymer particles obtained by the polycondensation reaction are sent to an adhesion-increasing kettle, and a solid phase reaction is carried out at a set temperature under a vacuum of 10 Pa or an inert gas protection state. The time is 20 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.92 dL/g.
  • the temperature is set to 200 °C.
  • Slurry preparation 1) Put terephthalic acid (PTA) and 1,4 butanediol (BDO) into the slurry preparation tank U1 through the metering system, stir evenly, and record it as slurry S1, where PTA is 773G, BDO It is 520G.
  • PTA terephthalic acid
  • BDO 1,4 butanediol
  • ⁇ , ⁇ -dicarboxyethylpolydimethylsiloxane and 1,4 butanediol (BDO) are respectively introduced into the slurry preparation tank U2 through a metering system, and stirred uniformly, and recorded as slurry S2, wherein ⁇ , ⁇ -dicarboxyethyl polydimethylsiloxane is 300 G, and 1,4 butanediol (BDO) is 45 G.
  • Catalyst preparation 1,4 butanediol (BDO) 100G and catalyst C (tetrabutyl titanate) 158.9G were added to the preparation tank U3, and heated under vacuum for 2-3 hours, and the degree of vacuum was 20-30 KPa. The temperature was 180 ° C, and after cooling, the configured catalyst was transferred to a catalyst addition tank.
  • BDO butanediol
  • catalyst C tetrabutyl titanate
  • the esterification reaction the slurry S1 in the slurry tank U1 is pumped from the slurry into the esterification tank E1, and the configured catalyst C is pumped to the esterification tank E1 through a gear to produce an ester under the action of the catalyst.
  • the oligomerization reaction OM1 is formed by the esterification reaction until no more water is produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification rate of 99.2%.
  • Esterification reaction the slurry S2 in the slurry tank U2 is pumped from the slurry into the esterification kettle E2, and the configured catalyst is pumped to the esterification kettle E2 through a gear, and esterification occurs under the action of the catalyst.
  • the oligomer OM2 formed by the reaction and esterification reaction until water is no longer produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification ratio of 99%.
  • Pre-polycondensation reaction The oligomers in the esterification kettles E1 and E2 were separately fed into the pre-polycondensation kettle, wherein the ratio OM2/(OM1+OM2) of the OM2 added in the esterification kettle E2 was 20%.
  • the polycondensation process which has started in the esterification reaction is continued in the pre-polycondensation kettle, the pre-polycondensation reaction temperature is 245 ° C, the vacuum degree is -2 KPa, the reaction time is 50 min, and a low molecular weight polyester copolymer is formed, and the pre-polycondensation product is passed through The polycondensation discharge pump, the pre-condensation discharge filter, and the pre-condensation discharge cooler enter the polycondensation reactor.
  • Polycondensation reaction The pre-polycondensation product is sent from the pre-polycondensation unit to the polycondensation reactor, and the prepolymer is further reacted.
  • the polycondensation reaction temperature is 248 ° C
  • the vacuum degree is 120 Pa
  • the reaction time is 200 min to form a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.6 dL/g.
  • the structure of the obtained polyester block copolymer is as follows:
  • Solid phase viscosity-increasing reaction the polyester block copolymer particles obtained by the polycondensation reaction are sent to an adhesion-increasing kettle, and a solid phase reaction is carried out at a set temperature under a vacuum of 10 Pa or an inert gas protection state. The time is 25 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.90 dL/g.
  • the temperature was set to 200 °C.
  • Slurry preparation 1) Put terephthalic acid (PTA) and 1,4 butanediol (BDO) into the slurry preparation tank U1 through the metering system, stir evenly, and record it as slurry S1, where PTA is 773G, BDO It is 520G.
  • PTA terephthalic acid
  • BDO 1,4 butanediol
  • ⁇ , ⁇ -dicarboxyethylpolydimethylsiloxane and 1,4 butanediol (BDO) are respectively introduced into the slurry preparation tank U2 through a metering system, and stirred uniformly, and recorded as slurry S2, wherein ⁇ , ⁇ -dicarboxyethyl polydimethylsiloxane is 420G, and 1,4 butanediol (BDO) is 60G.
  • Catalyst preparation 1,4 butanediol (BDO) 100G and catalyst C (tetrabutyl titanate) 158.9G were added to the preparation tank U3, and heated under vacuum for 2-3 hours, and the degree of vacuum was 20-30 KPa. The temperature was 180 ° C, and after cooling, the configured catalyst was transferred to a catalyst addition tank.
  • BDO butanediol
  • catalyst C tetrabutyl titanate
  • the esterification reaction the slurry S1 in the slurry tank U1 is pumped from the slurry into the esterification tank E1, and the configured catalyst C is pumped to the esterification tank E1 through a gear to produce an ester under the action of the catalyst.
  • the oligomerization reaction OM1 is formed by the esterification reaction until no more water is produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification rate of 99.2%.
  • Esterification reaction the slurry S2 in the slurry tank U2 is pumped from the slurry into the esterification kettle E2, and the configured catalyst is pumped to the esterification kettle E2 through a gear, and esterification occurs under the action of the catalyst.
  • the oligomer OM2 formed by the reaction and esterification reaction until water is no longer produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification ratio of 99%.
  • Pre-polycondensation reaction The oligomers in the esterification kettles E1 and E2 were separately fed into the pre-polycondensation kettle, wherein the ratio OM2/(OM1+OM2) of the OM2 added in the esterification kettle E2 was 30%.
  • the polycondensation process which has started in the esterification reaction is continued in the pre-polycondensation kettle, the pre-polycondensation reaction temperature is 245 ° C, the vacuum degree is -2 KPa, the reaction time is 50 min, and a low molecular weight polyester copolymer is formed, and the pre-polycondensation product is passed through The polycondensation discharge pump, the pre-condensation discharge filter, and the pre-condensation discharge cooler enter the polycondensation reactor.
  • Polycondensation reaction The pre-polycondensation product is sent from the pre-polycondensation unit to the polycondensation reactor, and the prepolymer is further reacted.
  • the polycondensation reaction temperature is 248 ° C
  • the vacuum degree is 120 Pa
  • the reaction time is 200 min to form a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.55 dL/g.
  • the structure of the obtained polyester block copolymer is as follows:
  • Solid phase viscosity-increasing reaction the polyester block copolymer particles obtained by the polycondensation reaction are sent to an adhesion-increasing kettle, and a solid phase reaction is carried out at a set temperature under a vacuum of 10 Pa or an inert gas protection state. The time is 30 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.88 dL/g.
  • the temperature was set to 200 °C.
  • Slurry preparation 1) Put terephthalic acid (PTA) and 1,4 butanediol (BDO) into the slurry preparation tank U1 through the metering system, stir evenly, and record it as slurry S1, where PTA is 773G, BDO It is 520G.
  • PTA terephthalic acid
  • BDO 1,4 butanediol
  • ⁇ , ⁇ -dicarboxyethylpolydimethylsiloxane and 1,4 butanediol (BDO) are respectively introduced into the slurry preparation tank U2 through a metering system, and stirred uniformly, and recorded as slurry S2, wherein ⁇ , ⁇ -dicarboxyethyl polydimethylsiloxane is 100 G, and 1,4 butanediol (BDO) is 20 G.
  • Catalyst preparation 1,4 butanediol (BDO) 100G and catalyst C (tetrabutyl titanate) 158.9G were added to the preparation tank U3, and heated under vacuum for 2-3 hours, and the degree of vacuum was 20-30 KPa. The temperature was 180 ° C, and after cooling, the configured catalyst was transferred to a catalyst addition tank.
  • BDO butanediol
  • catalyst C tetrabutyl titanate
  • the esterification reaction the slurry S1 in the slurry tank U1 is pumped from the slurry into the esterification tank E1, and the configured catalyst C is pumped to the esterification tank E1 through a gear to produce an ester under the action of the catalyst.
  • the oligomerization reaction OM1 is formed by the esterification reaction until no more water is produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification rate of 99.2%.
  • Esterification reaction the slurry S2 in the slurry tank U2 is pumped from the slurry into the esterification kettle E2, and the configured catalyst is pumped to the esterification kettle E2 through a gear, and esterification occurs under the action of the catalyst.
  • the oligomer OM2 formed by the reaction and esterification reaction until water is no longer produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification ratio of 99%.
  • Pre-polycondensation reaction The oligomers in the esterification tanks E1 and E2 were separately fed into the pre-polycondensation kettle, wherein the ratio OM2/(OM1+OM2) of the OM2 added in the esterification kettle E2 was 5%.
  • the polycondensation process which has started in the esterification reaction is continued in the pre-condensation polymerization vessel, the pre-polycondensation reaction temperature is 245 ° C, the vacuum degree is -2 KPa, the reaction time is 40 min, and a low molecular weight polyester copolymer is formed, and the pre-polycondensation product is passed through The polycondensation discharge pump, the pre-condensation discharge filter, and the pre-condensation discharge cooler enter the polycondensation reactor.
  • Polycondensation reaction The pre-polycondensation product is sent from the pre-polycondensation unit to the polycondensation reactor, and the prepolymer is further reacted.
  • the polycondensation reaction temperature is 248 ° C
  • the vacuum degree is 120 Pa
  • the reaction time is 200 min to form a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.65 dL/g.
  • the structure of the obtained polyester block copolymer is as follows:
  • Solid phase viscosity-increasing reaction the polyester block copolymer particles obtained by the polycondensation reaction are sent to an adhesion-increasing kettle, and a solid phase reaction is carried out at a set temperature under a vacuum of 10 Pa or an inert gas protection state. The time is 20 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.93 dL/g.
  • the temperature was set to 200 °C.
  • Slurry preparation 1) Put terephthalic acid (PTA) and 1,4 butanediol (BDO) into the slurry preparation tank U1 through the metering system, stir evenly, and record it as slurry S1, where PTA is 773G, BDO It is 520G.
  • PTA terephthalic acid
  • BDO 1,4 butanediol
  • Catalyst preparation 1,4 butanediol (BDO) 100G and catalyst C (tetrabutyl titanate) 158.9G were added to the preparation tank U3, and heated under vacuum for 2-3 hours, and the degree of vacuum was 20-30 KPa. The temperature was 180 ° C, and after cooling, the configured catalyst was transferred to a catalyst addition tank.
  • BDO butanediol
  • catalyst C tetrabutyl titanate
  • the esterification reaction the slurry S1 in the slurry tank U1 is pumped from the slurry into the esterification tank E1, and the configured catalyst C is pumped to the esterification tank E1 through a gear to produce an ester under the action of the catalyst.
  • the oligomerization reaction OM1 is formed by the esterification reaction until no more water is produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification rate of 99.2%.
  • Pre-polycondensation reaction the oligomer in the esterification kettle E1 is sent to the pre-polycondensation kettle, and the polycondensation process which has started in the esterification reaction is continued in the pre-polycondensation kettle, the pre-polycondensation reaction temperature is 245 ° C, and the degree of vacuum is - 2KPa, the reaction time is 40min, the low molecular weight polyester copolymer is formed, and the precondensed product enters the polycondensation reactor through the precondensation and discharge pump, the precondensation and discharge filter, and the precondensation and discharge cooler.
  • Polycondensation reaction The pre-polycondensation product is sent from the pre-polycondensation unit to the polycondensation reactor, and the prepolymer is further reacted.
  • the polycondensation reaction temperature is 248 ° C
  • the vacuum degree is 120 Pa
  • the reaction time is 200 min to form a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.75 dL/g.
  • Solid phase viscosity-increasing reaction the polyester block copolymer particles obtained by the polycondensation reaction are sent to an adhesion-increasing kettle, and a solid phase reaction is carried out at a set temperature under a vacuum of 10 Pa or an inert gas protection state. The time is 20 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.95 dL/g.
  • the temperature was set to 200 °C.
  • Slurry preparation 1) terephthalic acid (PTA) and 1,4-cyclohexanedimethanol (CHDM) were respectively introduced into the slurry preparation tank U1 through a metering system, and stirred uniformly, and recorded as slurry S1, wherein PTA was 773G, CHDM is 670G. 2)
  • the ⁇ , ⁇ -dicarboxyethylpolydimethylsiloxane and the 1,4-cyclohexanedimethanol (CHDM) used in the slurry 1) are separately fed into the slurry preparation tank U2 through a metering system, and stirred.
  • Uniform, referred to as slurry S2 wherein the ⁇ , ⁇ -dicarboxyethylpolydimethylsiloxane was 100 G and the 1,4-cyclohexanedimethanol (CHDM) was 30 G.
  • Catalyst preparation 1,4-cyclohexanedimethanol (CHDM) 128.89G and catalyst C (tetrabutyl titanate) 158.9G were added to the preparation tank U3, and slowly heated to 200 ° C, heated to boil under vacuum 2 -3 hours, the degree of vacuum is 20-30 KPa, and after cooling, the configured catalyst is transferred to the catalyst addition tank.
  • CHDM 1,4-cyclohexanedimethanol
  • catalyst C tetrabutyl titanate
  • the esterification reaction the slurry S1 in the slurry tank U1 is pumped from the slurry into the esterification tank E1, and the configured catalyst C is pumped to the esterification tank E1 through a gear to produce an ester under the action of the catalyst.
  • the oligomerization reaction OM1 is formed by the esterification reaction until no more water is produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 280 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification rate of 99.1%.
  • Esterification reaction the slurry S2 in the slurry tank U2 is pumped from the slurry into the esterification kettle E2, and the configured catalyst is pumped to the esterification kettle E2 through a gear, and esterification occurs under the action of the catalyst.
  • the oligomer OM2 formed by the reaction and esterification reaction until water is no longer produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 245 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification ratio of 99%.
  • Pre-polycondensation reaction The oligomers in the esterification tanks E1 and E2 were separately fed into the pre-polycondensation kettle, wherein the ratio OM2/(OM1+OM2) of the OM2 added in the esterification kettle E2 was 5%.
  • the polycondensation process which has started in the esterification reaction is continued in the pre-condensation polymerization vessel, the pre-polycondensation reaction temperature is 300 ° C, the vacuum degree is -2 KPa, the reaction time is 40 min, and a low molecular weight polyester copolymer is formed, and the pre-polycondensation product is passed through The polycondensation discharge pump, the pre-condensation discharge filter, and the pre-condensation discharge cooler enter the polycondensation reactor.
  • Polycondensation reaction The pre-polycondensation product is sent from the pre-polycondensation unit to the polycondensation reactor, and the prepolymer continues to react.
  • the polycondensation reaction temperature is 300 ° C
  • the vacuum degree is 120 Pa
  • the reaction time is 200 min to form a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.56 dL/g.
  • the structure of the obtained polyester block copolymer is as follows:
  • Solid phase viscosity-increasing reaction the polyester block copolymer particles obtained by the polycondensation reaction are sent to an adhesion-increasing kettle, and a solid phase reaction is carried out at a set temperature under a vacuum of 10 Pa or an inert gas protection state. The time is 20 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.82 dL/g.
  • the temperature was set to 260 °C.
  • Slurry preparation 1) terephthalic acid (PTA) and 1,4-cyclohexanedimethanol (CHDM) were respectively introduced into the slurry preparation tank U1 through a metering system, and stirred uniformly, and recorded as slurry S1, wherein PTA was 773G, CHDM is 670G.
  • PTA terephthalic acid
  • CHDM 1,4-cyclohexanedimethanol
  • Catalyst preparation 1,4-cyclohexanedimethanol (CHDM) 128.89G and catalyst C (tetrabutyl titanate) 158.9G were added to the preparation tank U3, and slowly heated to 200 ° C, heated to boil under vacuum 2 -3 hours, the degree of vacuum is 20-30 KPa, and after cooling, the configured catalyst is transferred to the catalyst addition tank.
  • CHDM 1,4-cyclohexanedimethanol
  • catalyst C tetrabutyl titanate
  • the esterification reaction the slurry S1 in the slurry tank U1 is pumped from the slurry into the esterification tank E1, and the configured catalyst C is pumped to the esterification tank E1 through a gear to produce an ester under the action of the catalyst.
  • the oligomerization reaction OM1 is formed by the esterification reaction until no more water is produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 280 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification rate of 99.1%.
  • Pre-polycondensation reaction the oligomer of the esterification kettle E1 is sent to the pre-polycondensation kettle, and the polycondensation process which has started in the esterification reaction is continued in the pre-polycondensation kettle, the pre-polycondensation reaction temperature is 300 ° C, and the degree of vacuum is -2 KPa.
  • the reaction time is 40 min, and a low molecular weight polyester copolymer is formed.
  • the precondensed product enters the polycondensation reactor through a precondensation discharge pump, a precondensation discharge filter, and a precondensation discharge cooler.
  • Polycondensation reaction The pre-polycondensation product is sent from the pre-polycondensation unit to the polycondensation reactor, and the prepolymer continues to react.
  • the polycondensation reaction temperature is 300 ° C
  • the vacuum degree is 120 Pa
  • the reaction time is 200 min to form a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.61 dL/g.
  • Solid phase viscosity-increasing reaction the polyester block copolymer particles obtained by the polycondensation reaction are sent to an adhesion-increasing kettle, and a solid phase reaction is carried out at a set temperature under a vacuum of 10 Pa or an inert gas protection state. The time is 20 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.85 dL/g.
  • the temperature was set to 260 °C.
  • NDA 2,6-naphthalene dicarboxylic acid
  • BDO 1,4 butanediol
  • ⁇ , ⁇ -dicarboxyethylpolydimethylsiloxane and 1,4 butanediol (BDO) are respectively introduced into the slurry preparation tank U2 through a metering system, and stirred uniformly, and recorded as slurry S2, wherein ⁇ , ⁇ -dicarboxyethyl polydimethylsiloxane is 80 G, and 1,4 butanediol (BDO) is 20 G.
  • Catalyst preparation 1,4 butanediol (BDO) 100G and catalyst C (tetrabutyl titanate) 158.9G were added to the preparation tank U3, and heated under vacuum for 2-3 hours, and the degree of vacuum was 20-30 KPa. The temperature was 180 ° C, and after cooling, the configured catalyst was transferred to a catalyst addition tank.
  • BDO butanediol
  • catalyst C tetrabutyl titanate
  • the esterification reaction the slurry S1 in the slurry tank U1 is pumped from the slurry into the esterification tank E1, and the configured catalyst C is pumped to the esterification tank E1 through a gear to produce an ester under the action of the catalyst.
  • the oligomerization reaction OM1 is formed by the esterification reaction until no more water is produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: temperature was 265 ° C, vacuum degree was 42 KPa, reaction time was 2 hours, and esterification rate was 99.2%.
  • Esterification reaction the slurry S2 in the slurry tank U2 is pumped from the slurry into the esterification kettle E2, and the configured catalyst is pumped to the esterification kettle E2 through a gear, and esterification occurs under the action of the catalyst.
  • the oligomer OM2 formed by the reaction and esterification reaction until water is no longer produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: a temperature of 265 ° C, a vacuum of 42 KPa, a reaction time of 2 hours, and an esterification ratio of 98.6%.
  • Pre-polycondensation reaction The oligomers in the esterification kettles E1 and E2 were separately fed into a pre-condensation vessel, wherein the ratio OM2/(OM1+OM2) of the OM2 added in the esterification kettle E2 was 5%.
  • the polycondensation process which has started in the esterification reaction is continued in the pre-polycondensation kettle, the pre-polycondensation reaction temperature is 265 ° C, the vacuum degree is -2 KPa, the reaction time is 40 min, and a low molecular weight polyester copolymer is formed, and the pre-polycondensation product is passed through The polycondensation discharge pump, the pre-condensation discharge filter, and the pre-condensation discharge cooler enter the polycondensation reactor.
  • Polycondensation reaction The pre-polycondensation product is sent from the pre-polycondensation unit to the polycondensation reactor, and the prepolymer continues to react.
  • the polycondensation reaction temperature is 268 ° C
  • the vacuum degree is 120 Pa
  • the reaction time is 200 min to form a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.66 dL/g.
  • the structure of the obtained polyester block copolymer is as follows:
  • Solid phase viscosity-increasing reaction the polyester block copolymer particles obtained by the polycondensation reaction are sent to an adhesion-increasing kettle, and a solid phase reaction is carried out at a set temperature under a vacuum of 10 Pa or an inert gas protection state. The time is 20 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.79 dL/g.
  • the temperature was set to 200 °C.
  • NDA 2,6-naphthalene dicarboxylic acid
  • BDO 1,4 butanediol
  • Catalyst preparation 1,4 butanediol (BDO) 100G and catalyst C (tetrabutyl titanate) 158.9G were added to the preparation tank U3, and heated under vacuum for 2-3 hours, and the degree of vacuum was 20-30 KPa. The temperature was 180 ° C, and after cooling, the configured catalyst was transferred to a catalyst addition tank.
  • BDO butanediol
  • catalyst C tetrabutyl titanate
  • the esterification reaction the slurry S1 in the slurry tank U1 is pumped from the slurry into the esterification tank E1, and the configured catalyst C is pumped to the esterification tank E1 through a gear to produce an ester under the action of the catalyst.
  • the oligomerization reaction OM1 is formed by the esterification reaction until no more water is produced.
  • the amount of the catalyst added was 0.05% by mass of the slurry.
  • the reaction conditions of the esterification kettle were as follows: temperature was 265 ° C, vacuum degree was 42 KPa, reaction time was 2 hours, and esterification rate was 99.2%.
  • Pre-polycondensation reaction the oligomer in the esterification kettle E1 is sent to the pre-polycondensation kettle, and the polycondensation process which has started in the esterification reaction is continued in the pre-polycondensation kettle, the pre-polycondensation reaction temperature is 265 ° C, and the degree of vacuum is - 2KPa, the reaction time is 40min, the low molecular weight polyester copolymer is formed, and the precondensed product enters the polycondensation reactor through the precondensation and discharge pump, the precondensation and discharge filter, and the precondensation and discharge cooler.
  • Polycondensation reaction The pre-polycondensation product is sent from the pre-polycondensation unit to the polycondensation reactor, and the prepolymer continues to react.
  • the polycondensation reaction temperature is 268 ° C
  • the vacuum degree is 120 Pa
  • the reaction time is 200 min to form a high molecular weight polyester block copolymer.
  • the polycondensation product enters the pelletizer system through a polycondensation discharge pump, a polymer viscometer, a polycondensation discharge filter, and a polycondensation discharge distribution valve.
  • a high molecular weight polyester block copolymer product is obtained after cooling dicing.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.75 dL/g.
  • Solid phase viscosity-increasing reaction the polyester block copolymer particles obtained by the polycondensation reaction are sent to an adhesion-increasing kettle, and a solid phase reaction is carried out at a set temperature under a vacuum of 10 Pa or an inert gas protection state. The time is 20 hours.
  • the intrinsic viscosity of the obtained polyester block copolymer was 0.85 dL/g.
  • the temperature was set to 200 °C.
  • the polyester block copolymer prepared by the invention has low surface tension and good low temperature impact resistance, and low heat weight loss rate, which compensates for the insufficient performance of the ordinary polyester resin. Expanded its application areas.
  • the invention provides a polyester block copolymer and a preparation method thereof.
  • the invention polymerizes the silicon-containing unit into the polyester molecular chain by the copolymerization method, and the obtained copolymer has excellent low temperature resistance and low surface tension, and improves the characteristics that the polyester resin is not resistant to low temperature, and expands the Its application space in the fields of fiber, film, blow molding and engineering plastics has good economic value and application prospects.

Landscapes

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

Abstract

本发明公开了一种聚酯嵌段共聚物，其特征在于，其结构如下式(I)所示；本发明同时公开了一种聚酯嵌段共聚物的制备方法。本发明通过共聚的方法，将含硅单元聚合至聚酯分子链中，所得到的共聚物具有优异的耐低温性能和较低的表面张力，改善了聚酯树脂不耐低温的特点，拓展了其在纤维、薄膜、吹塑和工程塑料领域的应用空间。 A n-B t (I)

Description

一种聚酯嵌段共聚物及其制备方法与应用
交叉引用
本申请要求2017年9月27日提交的第2017108891563号中国专利申请的优先权，其全部公开内容通过引用整体并入本文。
技术领域
本发明属于高分子合成材料技术领域，具体涉及一种具有耐寒性和疏水性的聚酯嵌段共聚物及其制备方法。
背景技术
随着社会的发展，科技的进步，人类对材料的需求日益扩大，高分子合成材料的生产和应用也得到了快速的发展。其中，工程塑料在各个领域的应用也是逐年扩大。聚酯材料，作为五大工程塑料之一，主要指PBT,中文名称聚对苯二甲酸丁二醇脂，为半结晶型热塑性树脂，因具有高模量、高强度、高弹性和耐热性等优点，主要应用于电子电器、汽车、照明、机械、纺丝、通信、薄膜及仪器仪表等领域。PET，中文名称聚对苯二甲酸乙二醇酯，由于其较好的力学性能、耐高温性能和耐刮擦性能，则广泛用于纺丝、薄膜、吹塑等领域。我们平常所说的涤纶就是使用PET材料所纺的丝。PTT，中文名称聚对苯二甲酸丙二醇酯，作为聚酯家族的新星，具有优异的回弹性和染色性能，为纺丝行业提供新的选择。PCT，中文名称聚对苯二甲酸环己烷二甲酯和PEN，中文名称聚对萘二甲酸乙二醇酯由于其较高的耐温性和力学性能，被用于高温环境中的机械、电子和汽车等领域。
上述所提到的这些聚酯材料，其力学性能都很优异，但是都比较脆，韧性不足，尤其是在低温下，其基本没有任何韧性，属于一碰即断的情况。这一缺点限制聚酯的应用。我国幅员辽阔，南北不同地域的温差极大，特别是在冬天，海南岛依然艳阳高照、暖风习习，温度超过20℃；黑龙江则是另外一番景象，凛冽的寒风，寒冷的天气，最低温度可低至-40℃。 作为御寒保暖的衣服，涤纶纤维、PBT纤维和PTT纤维在这种环境下已经无法起到作用，用其做的衣服预计一碰就破了，这极大的限制了PET、PBT和PTT的应用。再例如，PET和PBT薄膜，尤其是双向拉伸薄膜，在-40℃的环境下，容易出席变脆和爆裂现象，为其应用的设备和器件带来了安全隐患。在家电领域，由于冷冻室常年工作在-20℃的环境中，PBT注塑级材料由于其脆性也被限制了应用。因此，如能找到一种共性的物质，可以改善上述这些材料的韧性，尤其是低温韧性，能够明显拓宽其应用领域，具有非常重要的现实意义。
第二方面，聚酯是由二酸和二醇通过缩合，脱去水分子得到的高分子聚合物，酯键的存在，则赋予了聚酯材料一定的极性。极性越高，越容易吸潮、越容易吸附其它的小分子或者颗粒杂质，极性越低，则越不易吸潮、越不易吸附其它小分子或者颗粒杂质。目前，PET纤维、PBT纤维和PTT纤维已经广泛用于人类的各种服装上，蓬松的纤维结构，可以更好的保暖，衣服可以做的更博，穿起来更舒服。在华东地区，每年冬天总会阴雨连绵，人们所穿的衣服由于聚酯纤维的吸湿性，也会不如以前暖和，棉被也是又重又不暖和，一到天晴，变迫不及待的拿到室外让太阳晒干。PET和PBT树脂所制成的膜，为了方便运送，一般总是卷起来，但是由于PET和PBT分子的极性，卷起来的薄膜总是很难展开。最近几年，作为汽车车灯饰框的材料，免喷涂免底漆PBT材料发展也很快，但是为了保证较高的平整度和镜面要求，模具表面的光洁度是非常高，PBT材料也遇到了较难脱模的缺点。较高的极性，也带来了聚酯材料应用上的缺陷，如何降低聚酯的极性，提高其应用的便利性和使用的舒适性，也有非常重要的现实意义。
如何能够同时提高聚酯材料的耐低温性能和降低分子极性，拓展其应用领域，目前还未见公布。专利CN100551053C提出了解决聚脂薄膜的粘结性，通过在聚脂薄膜的一个面上涂覆有机硅防粘液，并且防粘液在聚脂薄膜上稳定均匀的涂覆的方法来满足电子应用领域的防粘要求。专利CN105538853A公布了一种共挤出的方法，在上表层或者下表层材料中添 加硅氧烷添加剂进行共挤而得到低极性的薄膜。专利CN103042780B提供了一种共挤的方法，将聚酯和热塑性弹性体共同挤出，形成复合膜，来达到耐低温的效果。专利CN104136534A公布了一种耐低温性的聚(碳酸亚烷基酯)树脂组合物，通过引入环氧化合物进行共聚制备了耐低温的树脂材料，但是环氧化合物的引入，并未能有效降低树脂的极性，这在专利中并未提及。专利CN102382307A公布了一种制备二羟基芳基硅氧烷的制备方法，用以提高聚碳酸酯与其共聚后聚合物的相容性，主要通过在溶液中与光气反应形成聚碳酸酯共聚物，但是并未用到本文所示的聚酯领域，以及纤维和薄膜领域。美国专利US5132392A通过引入含有末端是聚醚链段的聚硅烷，形成的共聚酯显现出较好的亲水性能，但是该化合物没有提供改善耐低温性能和材料的疏水性能。美国专利US4927895A通过引入特殊的聚硅氧烷所得的共聚酯，提高了材料的耐水解性，所使用的聚硅烷端基为烷基环氧基团，通过环氧与聚酯的端羧基或者端羟基反应形成共聚物，该专利也未有提及耐低温性能和疏水性能的改善。美国专利US4894427A提供了一种含有聚硅烷的聚酯共聚物，主要通过末端含有羟基烷基的聚硅烷与二元羧酸共聚所得，所得的共聚物的耐水解性能得到了改善，但是其耐低温性能和疏水性能并未提及。
在工程塑料的改性应用中，有机硅树脂经常被用来增强最终改性材料的脱模性，这是由于所加入的有机硅都是小分子材料，改性通过共混挤出之后，有机硅分子容易迁移至材料的表面，从而降低了材料的表面张力，使得其更容易注塑成型。但是其缺点就是，有机硅树脂的加入量不能过高，否则加入的有机硅小分子迁移至制件表面，形成油斑和缺陷。也有人提出添加其它低表面能助剂，比如通过共混挤出的方式，将有机硅橡胶和尼龙树脂进行挤出造粒，来达到提高树脂的耐低温冲击性能，但是由于两种树脂的差异性太大，无法达到均匀的混合，硅橡胶在尼龙树脂中分散不均匀，性能产生波动，在生产过程中往往也难以控制，对于要求比较精密的制件或者纺丝薄膜的应用领域，则无法达到稳定的生产，限制了其应用。如能 通过聚合的方式，将小分子的有机硅或者齐聚物和聚酯进行共聚，则有机硅能均匀的分散在聚酯树脂中，新的材料将同时具有聚酯树脂的较高的机械性能和硅树脂的耐低温性能和疏水性，并且有机硅分子是以分子的级别分散在树脂中，材料的性能就会变得稳定，波动性变小，性能更为优异，大大拓展了其应用领域。前述部分专利提到了含有聚硅烷的共聚物，但是并没有解决材料的耐低温性能和疏水性能。同时，所述的专利CN102382307A只研究了与光气反应形成聚碳酸酯共聚物；所述的专利US4927895A采用末端为环氧基团的聚硅烷与聚酯末端反应得到共聚物，该材料对环境要求苛刻，不能吸潮，严重影响了其使用；所述的专利US5132392A和US4894427A采用末端为羟基的聚硅烷进行共聚得到了新的聚合物，改善了亲水性能和耐水解性能，但是由于其采用的一步聚合，聚硅烷与二元醇的反应速率的差异，导致了聚硅烷在共聚物中的分布不均匀，材料的其它性能受到影响，故文中并未提及所得到的聚合物的耐低温性能和疏水性能。综上所述，在公开文献中，未能发现能够解决上述聚酯材料耐低温性能和疏水性能的公开报道。
发明内容
本发明的目的就是旨在克服上述现有技术中的不足，通过共聚方式，提供一种耐寒性、疏水性的聚酯嵌段共聚物。本发明制备的新型聚酯嵌段聚合物，同时赋予了新材料较低的表面张力和在低温下较高的冲击强度，为材料的应用拓展提供了可能。
本发明通过在聚酯的分子结构中引入了聚硅烷分子，通过共聚的方法得到一种聚酯嵌段共聚物，所制备的聚酯嵌段共聚酯具有如下通式(1)所示的结构：
A n-B t    (I)
式(I)中：
A嵌段是二元酸与二元醇反应得到的聚酯；其中，所述二元酸选自芳香族二元羧酸、脂肪族二元羧酸中的一种或者几种；所述二元醇选自脂肪 族二元醇、脂环族二元醇中的一种或者几种；
B嵌段结构如式(II)所示：
Figure PCTCN2018102638-appb-000001
式(II)中：R 4、R 5各自独立地选自甲基、乙基、丙基、苯基、α-甲基苯基或对甲基苯基；R 6表示(CH 2) 2、(CH 2) 3、(CH 2) 4、(CH 2) 6、
Figure PCTCN2018102638-appb-000002
中的一种或几种；s为大于1的整数；
所述嵌段共聚物中，n为大于1的整数，t为大于1的整数。
本发明所述聚酯嵌段共聚物满足A嵌段占所述共聚物总质量的百分比与B嵌段占所述共聚物总质量的百分比之和为100％；优选地，所述B嵌段的质量占所述共聚物总质量的百分比为0.1％～50％，更优选为0.5％～30％，进一步优选为3％～20％，更进一步优选为10％～15％。
所述聚酯嵌段共聚物的A嵌段中，所述芳香族二元羧酸选自对苯二甲酸、间苯二甲酸、萘二酸中的一种或几种；所述脂肪族二元羧酸选自丁二酸、己二酸、辛二酸中的一种或几种；所述脂环族二元醇选自乙二醇、丙二醇、丁二醇、己二醇、1,4-环己烷二甲醇中的一种或几种。
所述聚酯嵌段共聚物的B嵌段中，1≤s≤100；优选地，1≤s≤50；更优选地，1≤s≤30；进一步优选地，1≤s≤20。所述R 4、R 5的结构相同或不同，优选为相同，更优选R 4与R 5均为甲基。
本发明提供的聚酯嵌段共聚物的特性粘度为0.6～2.0dL/g，优选为0.79～1.33dL/g。如无特殊指明，本发明所述特征粘度均按照ASTM D445标准方法测得。
作为本发明的优选方案，所述聚酯嵌段共聚物选自如下结构的一种或多种：
Figure PCTCN2018102638-appb-000003
本发明提供的聚酯嵌段共聚物耐低温性能优异，低温冲击性好，表现张力小，可用于耐寒性和疏水性的应用领域，比如纤维、薄膜、瓶罐、工程塑料等领域。
本发明同时提供了一种聚酯嵌段共聚物的制备方法，包括酯化反应、预缩聚反应和缩聚反应；进一步地，还可以根据需要进行固相增粘反应。
具体而言，所述方法包括以下步骤：
(1)将二元羧酸与二元醇置于反应釜中，进行酯化反应；
本步骤所述二元羧酸选自芳香族二元羧酸、脂肪族二元羧酸中的一种或者几种；本步骤所述二元醇选自脂肪族二元醇、脂环族二元醇中的一种或者几种；
(2)将如式(III)所示的α,ω-二羧基聚硅烷与二元醇置于反应釜中，进行酯化反应；
Figure PCTCN2018102638-appb-000004
式(III)中，R 4、R 5各自独立地选自甲基、乙基、丙基、苯基、α-甲基苯基或对甲基苯基；s为大于1的整数；
本步骤所述二元醇选自脂肪族二元醇、脂环族二元醇中的一种或者几种；
(3)将步骤(1)所得产物和步骤(2)所得产物置于反应釜中，进行预缩聚反应，生成预缩聚产物；
(4)将步骤(3)所得预缩聚产物置于反应釜中，进行缩聚反应，得聚酯嵌段共聚物。
为了提高所述聚酯嵌段共聚物的粘度，本发明所述方法还可以包括将步骤(4)制得的产物进行固相增粘反应。所述固相增粘反应可在的真空状态(3-100Pa)或者惰性气体保护的状态(惰性气体的流速为0.5-5L/[min·KG增粘粒子])下进行。优选地，所述固相增粘反应的温度为100-260℃，一般反应时间为4-36小时。通过固相增粘反应使所得到的聚酯嵌段共聚物的特性粘度为0.8-2.0dL/g，优选为0.79～1.33dL/g。具体的反应条件可根据实际需要而定。
所述步骤(1)中，所述的二元羧酸可选自苯二甲酸(PTA)、间苯二甲酸(PIA)、2,6-萘二甲酸(NDA)、1,4-丁二酸(SA)、己二酸或者辛二酸其中的一种或者几种的混合物；所述二元醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇和1,4-环己烷二甲醇(CHDM)其中的一种或者几种的混合物。
本发明进一步对步骤(1)中二元羧酸与二元醇的组合方式进行优选，具体而言：所述的二元羧酸为对苯二甲酸、所述二元醇为乙二醇；或者，所述的二元羧酸为对苯二甲酸、所述二元醇为1,3-丙二醇；或者，所述的二元羧酸为对苯二甲酸、所述二元醇为1,4-丁二醇；或者，所述的二元羧酸为对苯二甲酸、所述二元醇为1,4-环己烷二甲醇(CHDM)；或者，所述的二元羧酸为2,6-萘二甲酸(NDA)、所述二元醇为乙二醇；或者，所述的二元羧酸为2,6-萘二甲酸、所述二元醇为1,4-丁二醇；或者，所述的二元羧酸为1,4-丁二酸(SA)、所述二元醇为1,4-丁二醇；或者，所述的二元羧酸为对苯二甲酸、所述二元醇为乙二醇和1,4-环己烷二甲醇。
所述步骤(2)中，式(III)所示的化合物可选自α,ω-二羧基乙基聚二甲基硅氧烷、α,ω-二羧基乙基聚二乙基硅氧烷、α,ω-二羧基乙基聚甲基 苯基硅氧烷、α,ω-二羧基乙基聚二苯基硅氧烷等。所述二元醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇和1,4-环己烷二甲醇(CHDM)其中的一种或者几种的混合物。
本发明对各步骤原料的用量进行优选，从而得到性能优异的聚酯嵌段共聚物。具体而言，所述步骤(1)中，二元羧酸与二元醇的摩尔比为1:1～1:1.5。所述步骤(2)中，式(III)所示的化合物与二元醇的摩尔比为1:1.2～1:1.5。所述步骤(3)中，步骤(2)所得产物的用量占步骤(1)、(2)产物用量之和的比例为0.1％～50％，优选为0.5％～30％，更优选为3％～20％，进一步优选为10％～15％。
所述步骤(1)、步骤(2)的酯化反应中，优选采用催化剂进行催化。所述催化剂可选自氧化锗、醋酸锰、醋酸锌、钛酸四丁酯、三氧化二锑、乙二醇锑、乙二醇钛中的一种或者几种的复合物。所述催化剂的质量优选占反应原料总质量的0.01％-0.1％。
本发明优选在酯化反应时采用上述催化剂与二元醇的混合体系，该催化剂混合体系的制备方法包括：将所述二元醇和所述催化剂按配比置于反应釜中，真空状态下加热沸腾2-4小时，真空度为20-30KPa，温度为170-200℃，降温，即可。其中，所述二元醇与所述催化剂的摩尔比为1:3～1:6。
所述酯化反应按照常规条件进行即可。作为一种优选方案：步骤(1)所述酯化反应的条件优选为：温度160～245℃，真空度40～45KPa；步骤(2)所述酯化反应条件为：温度160～245℃，真空度40～45KPa。
本发明为了提高所得产物的聚合效果以及综合性能，采用先进行预缩聚反应，再进行缩聚反应的方案，并对两步缩聚的反应条件进行优化。
具体而言：步骤(3)所述预缩聚反应条件为：温度180～310℃，真空度1.5～2.5KPa，一般反应时间为30-60min；步骤(4)所述缩聚反应条件为：温度180～310℃，真空度100～200Pa，一般反应时间为60-240min。
酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应生 成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后进入缩聚反应器。缩聚反应生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为0.5-1.0dL/g。
当所述方法还进一步进行固相增粘反应时，固相增粘反应的温度为100～260℃。
作为本发明的优选方案，所述方法包括以下具体步骤：
S1：浆料配制
将二元羧酸和二元醇置于容器(配制罐)中，搅拌均匀，制得混合物料S1；其中，二元羧酸与二元醇的摩尔比1:1～1:1.5；
将式(III)所示的化合物和二元醇置于容器(配制罐)中，搅拌均匀，制得混合物料S2；其中，式(III)所示的化合物与二元醇的摩尔比1:1.2～1:1.5；
S2：催化剂配制
将所述二元醇和所述催化剂按照摩尔比1:3～1:6的比例加入到容器(配制罐)中，真空状态下加热沸腾2-4小时，真空度为20-30KPa，温度为170-200℃，降温；制得催化剂混合体系；
S3：酯化反应
将混合物料S1置于反应釜(酯化釜)中，再加入步骤S2制备的催化剂混合体系进行酯化反应，反应至不再有水产生为止；生成低聚物OM1；其中，所加催化剂的质量与所述混合物料S1的质量比例为0.01％-0.1％；酯化反应条件为：温度160-245℃，真空度40-45KPa，反应时间为1-3小时；
将混合物料S2置于反应釜(酯化釜)中，再加入步骤S2制备的催化剂混合体系进行酯化反应，反应至不再有水产生为止；生成低聚物OM2，即式(III)所示的化合物；
其中，所加催化剂的质量与所述混合物料S2的质量比例为0.01％-0.1％；酯化反应条件为：温度160-245℃，真空度40-45KPa，反应时间为1-3小时；
S4：预缩聚反应
将低聚物OM1和低聚物OM2置于反应釜(预缩聚釜)中，进行预缩聚反应，生成预缩聚产物(即低分子量的聚酯共聚物)；其中，低聚物OM1的质量与低聚物OM1、低聚物OM2的质量之和的比例为0.1％-50％；预缩聚反应条件为：温度180-310℃，真空度1.5-2.5KPa，反应时间为30-60min。
S5：缩聚反应
将步骤S4所得预缩聚产物置于反应釜(缩聚反应器)中，进行缩聚反应，生成式(I)所示的化合物(即高分子量的聚酯嵌段共聚物)；缩聚反应条件为：温度180-310℃，真空度100-200Pa，反应时间为60-240min；所得聚酯嵌段共聚物的特性粘度为0.5-1.0dL/g；
S6：固相增粘反应
将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜中，在3-100Pa的真空状态或者惰性气体保护的状态下，惰性气体的流速为0.5-5L/[min·KG增粘粒子]，于设定的温度100-260℃下进行固相反应，反应时间为4-36小时；所得到的聚酯嵌段共聚物的特性粘度为0.8-2.0dL/g。
本发明进一步针对原料的特性对反应条件进行了优化。具体而言：
当步骤(1)所述二元羧酸为2,6-萘二甲酸时，预缩聚反应温度范围为250～310℃，缩聚反应温度为250～310℃，优选固相增粘反应温度为200～240℃。
当步骤(1)所述二元羧酸为对苯二甲酸、所述二元醇为1,4-环己烷二甲醇(CHDM)时，预缩聚反应温度范围为280～310℃，缩聚反应温度为280～310℃，优选固相增粘反应温度为240～260℃。
当步骤(1)所述二元羧酸为对苯二甲酸、所述二元醇为除1,4-环己 烷二甲醇(CHDM)之外的一种二元醇或为两种以上的二元醇的混合物时，预缩聚反应温度范围为200～250℃，缩聚反应温度为200～250℃，优选固相增粘反应温度为180～220℃。
当步骤(1)所述二元羧酸为丁二酸时，预缩聚反应温度范围为100～200℃，缩聚反应温度为100～200℃，固相增粘反应温度为100～110℃。
本发明采用的各原料均可市售购得。
本发明同时保护所述聚酯嵌段共聚物或所述方法制备而成的聚酯嵌段共聚物在制备纤维、薄膜、瓶罐、工程塑料方面的应用。
本发明与现有技术相比，具有以下优点：
第一、本发明制备的含有硅单元的聚酯共聚物，特性粘度高，直接反映出共聚物分子量较高，力学性能优异，同时赋予了材料优异的耐低温性能和较低的表面张力，可以极大的拓展现有聚酯的应用范围。
第二、本发明制备的含有硅单元的聚酯共聚物，是采用直接聚合的方法制备的，制备的聚酯共聚物中硅分子均匀的分布在聚酯树脂的分子链中。相比较采用共混的方式，将硅橡胶或者硅树脂与聚酯树脂通过双螺杆挤出机进行共混的方式，由于相容性问题产生会分层或者不相容的现象；另外，如果采用小分子的含有反应基团的有机硅分子与聚酯树脂通过双螺杆挤出机共混，由于在双螺杆中停留时间较短，反应不充分，将残留较多的小分子在最后的共混物中，挥发物较高。
第三、本发明所采用的制备方法，将含硅单体和不含硅单体分别进行酯化之后再聚合，使反应更易于按照要求进行控制，便于得到一定规整度的聚酯嵌段共聚物；同时，含硅单体先被酯化，反应更易于控制。
第四、本发明提供的制备方法，最后采用了反应条件温和的固相聚合方式来合成直接缩聚所不能制得的高分子量的聚酯共聚物，因而不仅达到了预期的效果，而且还避免了常规的缩聚方式耗能大，反应条件较为苛刻，对设备要求高，难以控制产品工艺条件的弊病。本发明所提供的聚酯共聚物的制备方法是在现行聚酯的生产方法的基础上进行优化，方法简单方 便，易于控制和实现工业化生产。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。
以下检测方法：
特征粘度：按照ASTM D445标准测得。
冲击强度：按照ASTM D256标准测得。
末端羧基含量：按照GB/T 14190-2008标准测得。
溶体恒温热失重：称取适量样品，在空气氛围加热炉内，初始温度为室温，升温速率为20℃/min，程序升温至260℃，保持120min。通过样品质量与温度关系的曲线变化，计算样品中挥发物的含量。
表面张力：按照GB/T 14216-2008标准测得。
实施例1:含有硅单元的PBT共聚酯的制备
浆料配制：1)将对苯二甲酸(PTA)和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U1，搅拌均匀，记为浆料S1，其中PTA为773G(G含义为质量单位克，下同)，BDO为520G。2)将α,ω-二羧基乙基聚二甲基硅氧烷和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U2，搅拌均匀，记为浆料S2，其中α,ω-二羧基乙基聚二甲基硅氧烷为210G，1,4丁二醇(BDO)为30G。
催化剂配制：将1,4丁二醇(BDO)100G和催化剂C(钛酸四丁酯)158.9G加入到配制罐U3中，真空状态下加热沸腾2-3小时，真空度为20-30KPa，温度为180℃，降温后将配置好的催化剂转入催化剂加料罐中。
酯化反应：将浆料罐U1中的浆料S1由浆料泵送入酯化釜E1中，将配置好的催化剂C通过齿轮泵送到酯化釜E1中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM1。所加催 化剂的量占浆料的质量比例C/S1为0.05％。酯化釜的反应条件为：温度为245℃，真空度为42KPa，反应时间为2小时，酯化率达99.2％。
酯化反应：将浆料罐U2中的浆料S2由浆料泵送入酯化釜E2中，将配置好的催化剂通过齿轮泵送到酯化釜E2中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM2。所加催化剂的量占浆料的质量比例C/S2为0.05％。酯化釜的反应条件为：温度为245℃，真空度为42KPa，反应时间为2小时，酯化率为99％。
预缩聚反应：将酯化釜E1和E2中的低聚物分别按比例送入预缩聚釜中，其中酯化釜E2中OM2加入的比例OM2/(OM1+OM2)为10％。酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应温度为245℃，真空度为-2KPa，反应时间为40min，生成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后进入缩聚反应器。
缩聚反应：预缩聚产物从预缩聚单元被送入缩聚反应器，预聚物继续反应，缩聚反应温度为248℃，真空度为120Pa，反应时间为200min，生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为0.61dL/g。
所得到的聚酯嵌段共聚物的结构如下式所示：
Figure PCTCN2018102638-appb-000005
固相增粘反应：将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜中，在10Pa的真空状态或者惰性气体保护的状态下，于设定的温度下进行固相反应，反应时间为20小时。
所得到的聚酯嵌段共聚物的特性粘度为0.92dL/g。温度的设定为 200℃。
实施例2：含有硅单元的PBT共聚酯的制备
浆料配制：1)将对苯二甲酸(PTA)和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U1，搅拌均匀，记为浆料S1，其中PTA为773G，BDO为520G。2)将α,ω-二羧基乙基聚二甲基硅氧烷和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U2，搅拌均匀，记为浆料S2，其中α,ω-二羧基乙基聚二甲基硅氧烷为300G，1,4丁二醇(BDO)为45G。
催化剂配制：将1,4丁二醇(BDO)100G和催化剂C(钛酸四丁酯)158.9G加入到配制罐U3中，真空状态下加热沸腾2-3小时，真空度为20-30KPa，温度为180℃，降温后将配置好的催化剂转入催化剂加料罐中。
酯化反应：将浆料罐U1中的浆料S1由浆料泵送入酯化釜E1中，将配置好的催化剂C通过齿轮泵送到酯化釜E1中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM1。所加催化剂的量占浆料的质量比例C/S1为0.05％。酯化釜的反应条件为：温度为245℃，真空度为42KPa，反应时间为2小时，酯化率达99.2％。
酯化反应：将浆料罐U2中的浆料S2由浆料泵送入酯化釜E2中，将配置好的催化剂通过齿轮泵送到酯化釜E2中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM2。所加催化剂的量占浆料的质量比例C/S2为0.05％。酯化釜的反应条件为：温度为245℃，真空度为42KPa，反应时间为2小时，酯化率为99％。
预缩聚反应：将酯化釜E1和E2中的低聚物分别按比例送入预缩聚釜中，其中酯化釜E2中OM2加入的比例OM2/(OM1+OM2)为20％。酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应温度为245℃，真空度为-2KPa，反应时间为50min，生成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后进入缩聚反应器。
缩聚反应：预缩聚产物从预缩聚单元被送入缩聚反应器，预聚物继续反应，缩聚反应温度为248℃，真空度为120Pa，反应时间为200min，生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为0.6dL/g。
所得到的聚酯嵌段共聚物的结构如下式所示：
Figure PCTCN2018102638-appb-000006
固相增粘反应：将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜中，在10Pa的真空状态或者惰性气体保护的状态下，于设定的温度下进行固相反应，反应时间为25小时。
所得到的聚酯嵌段共聚物的特性粘度为0.90dL/g。温度的设定为200℃。
实施例3：含有硅单元的PBT共聚酯的制备
浆料配制：1)将对苯二甲酸(PTA)和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U1，搅拌均匀，记为浆料S1，其中PTA为773G，BDO为520G。2)将α,ω-二羧基乙基聚二甲基硅氧烷和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U2，搅拌均匀，记为浆料S2，其中α,ω-二羧基乙基聚二甲基硅氧烷为420G，1,4丁二醇(BDO)为60G。
催化剂配制：将1,4丁二醇(BDO)100G和催化剂C(钛酸四丁酯)158.9G加入到配制罐U3中，真空状态下加热沸腾2-3小时，真空度为20-30KPa，温度为180℃，降温后将配置好的催化剂转入催化剂加料罐中。
酯化反应：将浆料罐U1中的浆料S1由浆料泵送入酯化釜E1中，将配置好的催化剂C通过齿轮泵送到酯化釜E1中，在催化剂的作用下发生 酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM1。所加催化剂的量占浆料的质量比例C/S1为0.05％。酯化釜的反应条件为：温度为245℃，真空度为42KPa，反应时间为2小时，酯化率达99.2％。
酯化反应：将浆料罐U2中的浆料S2由浆料泵送入酯化釜E2中，将配置好的催化剂通过齿轮泵送到酯化釜E2中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM2。所加催化剂的量占浆料的质量比例C/S2为0.05％。酯化釜的反应条件为：温度为245℃，真空度为42KPa，反应时间为2小时，酯化率为99％。
预缩聚反应：将酯化釜E1和E2中的低聚物分别按比例送入预缩聚釜中，其中酯化釜E2中OM2加入的比例OM2/(OM1+OM2)为30％。酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应温度为245℃，真空度为-2KPa，反应时间为50min，生成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后进入缩聚反应器。
缩聚反应：预缩聚产物从预缩聚单元被送入缩聚反应器，预聚物继续反应，缩聚反应温度为248℃，真空度为120Pa，反应时间为200min，生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为0.55dL/g。
所得到的聚酯嵌段共聚物的结构如下式所示：
Figure PCTCN2018102638-appb-000007
固相增粘反应：将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜中，在10Pa的真空状态或者惰性气体保护的状态下，于设定的温度下进行固相反应，反应时间为30小时。
所得到的聚酯嵌段共聚物的特性粘度为0.88dL/g。温度的设定为200℃。
实施例4：含有硅单元的PBT共聚酯的制备
浆料配制：1)将对苯二甲酸(PTA)和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U1，搅拌均匀，记为浆料S1，其中PTA为773G，BDO为520G。2)将α,ω-二羧基乙基聚二甲基硅氧烷和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U2，搅拌均匀，记为浆料S2，其中α,ω-二羧基乙基聚二甲基硅氧烷为100G，1,4丁二醇(BDO)为20G。
催化剂配制：将1,4丁二醇(BDO)100G和催化剂C(钛酸四丁酯)158.9G加入到配制罐U3中，真空状态下加热沸腾2-3小时，真空度为20-30KPa，温度为180℃，降温后将配置好的催化剂转入催化剂加料罐中。
酯化反应：将浆料罐U1中的浆料S1由浆料泵送入酯化釜E1中，将配置好的催化剂C通过齿轮泵送到酯化釜E1中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM1。所加催化剂的量占浆料的质量比例C/S1为0.05％。酯化釜的反应条件为：温度为245℃，真空度为42KPa，反应时间为2小时，酯化率达99.2％。
酯化反应：将浆料罐U2中的浆料S2由浆料泵送入酯化釜E2中，将配置好的催化剂通过齿轮泵送到酯化釜E2中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM2。所加催化剂的量占浆料的质量比例C/S2为0.05％。酯化釜的反应条件为：温度为245℃，真空度为42KPa，反应时间为2小时，酯化率为99％。
预缩聚反应：将酯化釜E1和E2中的低聚物分别按比例送入预缩聚釜中，其中酯化釜E2中OM2加入的比例OM2/(OM1+OM2)为5％。酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应温度为245℃，真空度为-2KPa，反应时间为40min，生成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后 进入缩聚反应器。
缩聚反应：预缩聚产物从预缩聚单元被送入缩聚反应器，预聚物继续反应，缩聚反应温度为248℃，真空度为120Pa，反应时间为200min，生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为0.65dL/g。
所得到的聚酯嵌段共聚物的结构如下式所示：
Figure PCTCN2018102638-appb-000008
固相增粘反应：将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜中，在10Pa的真空状态或者惰性气体保护的状态下，于设定的温度下进行固相反应，反应时间为20小时。
所得到的聚酯嵌段共聚物的特性粘度为0.93dL/g。温度的设定为200℃。
对比例1：不含有硅单元的PBT聚酯的制备
浆料配制：1)将对苯二甲酸(PTA)和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U1，搅拌均匀，记为浆料S1，其中PTA为773G，BDO为520G。
催化剂配制：将1,4丁二醇(BDO)100G和催化剂C(钛酸四丁酯)158.9G加入到配制罐U3中，真空状态下加热沸腾2-3小时，真空度为20-30KPa，温度为180℃，降温后将配置好的催化剂转入催化剂加料罐中。
酯化反应：将浆料罐U1中的浆料S1由浆料泵送入酯化釜E1中，将配置好的催化剂C通过齿轮泵送到酯化釜E1中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM1。所加催化剂的量占浆料的质量比例C/S1为0.05％。酯化釜的反应条件为：温度 为245℃，真空度为42KPa，反应时间为2小时，酯化率达99.2％。
预缩聚反应：将酯化釜E1中的低聚物送入预缩聚釜中，酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应温度为245℃，真空度为-2KPa，反应时间为40min，生成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后进入缩聚反应器。
缩聚反应：预缩聚产物从预缩聚单元被送入缩聚反应器，预聚物继续反应，缩聚反应温度为248℃，真空度为120Pa，反应时间为200min，生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为0.75dL/g。
固相增粘反应：将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜中，在10Pa的真空状态或者惰性气体保护的状态下，于设定的温度下进行固相反应，反应时间为20小时。
所得到的聚酯嵌段共聚物的特性粘度为0.95dL/g。温度的设定为200℃。
实施例5：含有硅单元的PCT共聚酯的制备
浆料配制：1)将对苯二甲酸(PTA)和1,4-环己烷二甲醇(CHDM)分别通过计量系统进入浆料配制罐U1，搅拌均匀，记为浆料S1，其中PTA为773G，CHDM为670G。2)将α,ω-二羧基乙基聚二甲基硅氧烷和浆料1)中所用的1,4-环己烷二甲醇(CHDM)分别通过计量系统进入浆料配制罐U2，搅拌均匀，记为浆料S2，其中α,ω-二羧基乙基聚二甲基硅氧烷为100G，1,4-环己烷二甲醇(CHDM)为30G。
催化剂配制：将1,4-环己烷二甲醇(CHDM)128.89G和催化剂C(钛酸四丁酯)158.9G加入到配制罐U3中，慢慢升温至200℃，真空状态下加热沸腾2-3小时，真空度为20-30KPa，降温后将配置好的催化剂转入 催化剂加料罐中。
酯化反应：将浆料罐U1中的浆料S1由浆料泵送入酯化釜E1中，将配置好的催化剂C通过齿轮泵送到酯化釜E1中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM1。所加催化剂的量占浆料的质量比例C/S1为0.05％。酯化釜的反应条件为：温度为280℃，真空度为42KPa，反应时间为2小时，酯化率达99.1％。
酯化反应：将浆料罐U2中的浆料S2由浆料泵送入酯化釜E2中，将配置好的催化剂通过齿轮泵送到酯化釜E2中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM2。所加催化剂的量占浆料的质量比例C/S2为0.05％。酯化釜的反应条件为：温度为245℃，真空度为42KPa，反应时间为2小时，酯化率为99％。
预缩聚反应：将酯化釜E1和E2中的低聚物分别按比例送入预缩聚釜中，其中酯化釜E2中OM2加入的比例OM2/(OM1+OM2)为5％。酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应温度为300℃，真空度为-2KPa，反应时间为40min，生成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后进入缩聚反应器。
缩聚反应：预缩聚产物从预缩聚单元被送入缩聚反应器，预聚物继续反应，缩聚反应温度为300℃，真空度为120Pa，反应时间为200min，生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为0.56dL/g。
所得到的聚酯嵌段共聚物的结构如下式所示：
Figure PCTCN2018102638-appb-000009
固相增粘反应：将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜 中，在10Pa的真空状态或者惰性气体保护的状态下，于设定的温度下进行固相反应，反应时间为20小时。
所得到的聚酯嵌段共聚物的特性粘度为0.82dL/g。温度的设定为260℃。
对比例2：不含有硅单元的PCT聚酯的制备
浆料配制：1)将对苯二甲酸(PTA)和1,4-环己烷二甲醇(CHDM)分别通过计量系统进入浆料配制罐U1，搅拌均匀，记为浆料S1，其中PTA为773G，CHDM为670G。
催化剂配制：将1,4-环己烷二甲醇(CHDM)128.89G和催化剂C(钛酸四丁酯)158.9G加入到配制罐U3中，慢慢升温至200℃，真空状态下加热沸腾2-3小时，真空度为20-30KPa，降温后将配置好的催化剂转入催化剂加料罐中。
酯化反应：将浆料罐U1中的浆料S1由浆料泵送入酯化釜E1中，将配置好的催化剂C通过齿轮泵送到酯化釜E1中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM1。所加催化剂的量占浆料的质量比例C/S1为0.05％。酯化釜的反应条件为：温度为280℃，真空度为42KPa，反应时间为2小时，酯化率达99.1％。
预缩聚反应：将酯化釜E1的低聚物送入预缩聚釜中，酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应温度为300℃，真空度为-2KPa，反应时间为40min，生成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后进入缩聚反应器。
缩聚反应：预缩聚产物从预缩聚单元被送入缩聚反应器，预聚物继续反应，缩聚反应温度为300℃，真空度为120Pa，反应时间为200min，生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为 0.61dL/g。
固相增粘反应：将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜中，在10Pa的真空状态或者惰性气体保护的状态下，于设定的温度下进行固相反应，反应时间为20小时。
所得到的聚酯嵌段共聚物的特性粘度为0.85dL/g。温度的设定为260℃。
实施例6：含有硅单元的PBN共聚酯的制备
浆料配制：1)将2,6-萘二甲酸(NDA)和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U1，搅拌均匀，记为浆料S1，其中NDA为997G，BDO为520G。2)将α,ω-二羧基乙基聚二甲基硅氧烷和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U2，搅拌均匀，记为浆料S2，其中α,ω-二羧基乙基聚二甲基硅氧烷为80G，1,4丁二醇(BDO)为20G。
催化剂配制：将1,4丁二醇(BDO)100G和催化剂C(钛酸四丁酯)158.9G加入到配制罐U3中，真空状态下加热沸腾2-3小时，真空度为20-30KPa，温度为180℃，降温后将配置好的催化剂转入催化剂加料罐中。
酯化反应：将浆料罐U1中的浆料S1由浆料泵送入酯化釜E1中，将配置好的催化剂C通过齿轮泵送到酯化釜E1中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM1。所加催化剂的量占浆料的质量比例C/S1为0.05％。酯化釜的反应条件为：温度为265℃，真空度为42KPa，反应时间为2小时，酯化率达99.2％。
酯化反应：将浆料罐U2中的浆料S2由浆料泵送入酯化釜E2中，将配置好的催化剂通过齿轮泵送到酯化釜E2中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM2。所加催化剂的量占浆料的质量比例C/S2为0.05％。酯化釜的反应条件为：温度为265℃，真空度为42KPa，反应时间为2小时，酯化率为98.6％。
预缩聚反应：将酯化釜E1和E2中的低聚物分别按比例送入预缩聚 釜中，其中酯化釜E2中OM2加入的比例OM2/(OM1+OM2)为5％。酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应温度为265℃，真空度为-2KPa，反应时间为40min，生成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后进入缩聚反应器。
缩聚反应：预缩聚产物从预缩聚单元被送入缩聚反应器，预聚物继续反应，缩聚反应温度为268℃，真空度为120Pa，反应时间为200min，生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为0.66dL/g。
所得到的聚酯嵌段共聚物的结构如下式所示：
Figure PCTCN2018102638-appb-000010
固相增粘反应：将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜中，在10Pa的真空状态或者惰性气体保护的状态下，于设定的温度下进行固相反应，反应时间为20小时。
所得到的聚酯嵌段共聚物的特性粘度为0.79dL/g。温度的设定为200℃。
对比例3：不含有硅单元的PBN聚酯的制备
浆料配制：1)将2,6-萘二甲酸(NDA)和1,4丁二醇(BDO)分别通过计量系统进入浆料配制罐U1，搅拌均匀，记为浆料S1，其中NDA为997G，BDO为520G。
催化剂配制：将1,4丁二醇(BDO)100G和催化剂C(钛酸四丁酯)158.9G加入到配制罐U3中，真空状态下加热沸腾2-3小时，真空度为20-30KPa，温度为180℃，降温后将配置好的催化剂转入催化剂加料罐中。
酯化反应：将浆料罐U1中的浆料S1由浆料泵送入酯化釜E1中，将配置好的催化剂C通过齿轮泵送到酯化釜E1中，在催化剂的作用下发生酯化反应，酯化反应至不再有水产生为止，生成的低聚物OM1。所加催化剂的量占浆料的质量比例C/S1为0.05％。酯化釜的反应条件为：温度为265℃，真空度为42KPa，反应时间为2小时，酯化率达99.2％。
预缩聚反应：将酯化釜E1中的低聚物送入预缩聚釜中，酯化反应中已开始的缩聚过程在预缩聚釜中继续进行，预缩聚反应温度为265℃，真空度为-2KPa，反应时间为40min，生成低分子量的聚酯共聚物，预缩聚产物通过预缩聚出料泵、预缩聚出料过滤器、预缩聚出料冷却器后进入缩聚反应器。
缩聚反应：预缩聚产物从预缩聚单元被送入缩聚反应器，预聚物继续反应，缩聚反应温度为268℃，真空度为120Pa，反应时间为200min，生成高分子量的聚酯嵌段共聚物。缩聚产物通过缩聚出料泵、聚合物粘度计、缩聚出料过滤器、缩聚出料分配阀后进入切粒机系统。经冷却切粒后得到了高分子量的聚酯嵌段共聚物产品。所得聚酯嵌段共聚物的特性粘度为0.75dL/g。
固相增粘反应：将缩聚反应得到的聚酯嵌段共聚物粒子送入增粘釜中，在10Pa的真空状态或者惰性气体保护的状态下，于设定的温度下进行固相反应，反应时间为20小时。
所得到的聚酯嵌段共聚物的特性粘度为0.85dL/g。温度的设定为200℃。
实验例
以上实施例1-6及对比例1-3制备的聚酯嵌段共聚物分析表征与评价结果见下表1-3。
表1
Figure PCTCN2018102638-appb-000011
Figure PCTCN2018102638-appb-000012
表2
性能 单位 对比例2# 实施例5#
特征粘度 dL/g 0.85 0.82
端羧基含量 Mmol/Kg 18 17
冲击强度(23℃) KJ/m 2 4 16
冲击强度(-40℃) KJ/m 2 2 12
热失重 ％ 1.6 1.5
表面张力 mN/m 39 27
表3
性能 单位 对比例3# 实施例6#
特征粘度 dL/g 0.85 0.79
端羧基含量 Mmol/Kg 17 16
冲击强度(23℃) KJ/m 2 4 18
冲击强度(-40℃) KJ/m 2 3 13
热失重 ％ 1.7 1.6
表面张力 mN/m 42 27
由表1-3可知，本发明所制备的聚酯嵌段共聚物具有较低的表面张力和较好的耐低温冲击性能，较低的热失重率，弥补了普通聚酯树脂的性能不足，拓展了其应用领域。
虽然，上文中已经用一般性说明、具体实施方式及试验，对本发明作 了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。
工业实用性
本发明提供一种聚酯嵌段共聚物及其制备方法。本发明通过共聚的方法，将含硅单元聚合至聚酯分子链中，所得到的共聚物具有优异的耐低温性能和较低的表面张力，改善了聚酯树脂不耐低温的特点，拓展了其在纤维、薄膜、吹塑和工程塑料领域的应用空间，具有较好的经济价值和应用前景。

Claims (11)

  1. 一种聚酯嵌段共聚物，其特征在于，其结构如下式(I)所示：
    A n-B t  (I)
    式(I)中：
    A嵌段是二元酸与二元醇反应得到的聚酯；其中，所述二元酸选自芳香族二元羧酸、脂肪族二元羧酸中的一种或者几种；所述二元醇选自脂肪族二元醇、脂环族二元醇中的一种或者几种；
    B嵌段结构如式(II)所示：
    Figure PCTCN2018102638-appb-100001
    式(II)中：R 4、R 5各自独立地选自甲基、乙基、丙基、苯基、α-甲基苯基或对甲基苯基；R 6表示(CH 2) 2、(CH 2) 3、(CH 2) 4、(CH 2) 6、
    Figure PCTCN2018102638-appb-100002
    中的一种或几种；s为大于1的整数；
    所述嵌段共聚物中，n为大于1的整数，t为大于1的整数；
    所述聚酯嵌段共聚物满足A嵌段占所述共聚物总质量的百分比与B嵌段占所述共聚物总质量的百分比之和为100％；
    优选地，所述B嵌段的质量占所述共聚物总质量的百分比为0.1％～50％，更优选为0.5％～30％，进一步优选为3％～20％，更进一步优选为10％～15％。
  2. 根据权利要求1所述的聚酯嵌段共聚物，其特征在于，A嵌段中，所述芳香族二元羧酸选自对苯二甲酸、间苯二甲酸、萘二酸中的一种或几种；所述脂肪族二元羧酸选自丁二酸、己二酸、辛二酸中的一种或几种；所述脂环族二元醇选自乙二醇、丙二醇、丁二醇、己二醇、1,4-环己烷二甲醇中的一种或几种；
    优选所述A嵌段中：所述的二元羧酸为对苯二甲酸、所述二元醇为 乙二醇；或者，所述的二元羧酸为对苯二甲酸、所述二元醇为1,3-丙二醇；或者，所述的二元羧酸为对苯二甲酸、所述二元醇为1,4-丁二醇；或者，所述的二元羧酸为对苯二甲酸、所述二元醇为1,4-环己烷二甲醇；或者，所述的二元羧酸为2,6-萘二甲酸、所述二元醇为乙二醇；或者，所述的二元羧酸为2,6-萘二甲酸、所述二元醇为1,4-丁二醇；或者，所述的二元羧酸为1,4-丁二酸、所述二元醇为1,4-丁二醇；或者，所述的二元羧酸为对苯二甲酸、所述二元醇为乙二醇和1,4-环己烷二甲醇。
  3. 根据权利要求1或2所述的聚酯嵌段共聚物，其特征在于，B嵌段中，1≤s≤100；优选地，1≤s≤50；更优选地，1≤s≤30；进一步优选地，1≤s≤20；
    和/或，R 4、R 5的结构相同，优选地，R 4与R 5均为甲基。
  4. 根据权利要求1～3任意一项所述的聚酯嵌段共聚物，其特征在于，所述聚酯嵌段共聚物的特性粘度为0.6～2.0dL/g，优选为0.79～1.33dL/g。
  5. 根据权利要求1～4任意一项所述的聚酯嵌段共聚物，其特征在于，选自如下结构的一种或多种：
    Figure PCTCN2018102638-appb-100003
  6. 一种聚酯嵌段共聚物的制备方法，其特征在于，包括以下步骤：
    (1)将二元羧酸与二元醇置于反应釜中，进行酯化反应；
    本步骤所述二元羧酸选自芳香族二元羧酸、脂肪族二元羧酸中的一种或者几种；本步骤所述二元醇选自脂肪族二元醇、脂环族二元醇中的一种或者几种；
    (2)将如式(III)所示的α,ω-二羧基聚硅烷与二元醇置于反应釜中，进行酯化反应；
    Figure PCTCN2018102638-appb-100004
    式(III)中，R 4、R 5各自独立地选自甲基、乙基、丙基、苯基、α-甲基苯基或对甲基苯基；s为大于1的整数；
    本步骤所述二元醇选自脂肪族二元醇、脂环族二元醇中的一种或者几种，优选为乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、1,4-环己烷二甲醇中的一种或几种；
    (3)将步骤(1)所得产物和步骤(2)所得产物置于反应釜中，进行预缩聚反应，生成预缩聚产物；
    (4)将步骤(3)所得预缩聚产物置于反应釜中，进行缩聚反应，得聚酯嵌段共聚物；
    优选地，所述方法还包括将步骤(4)制得的产物进行固相增粘反应，得到特性粘度为0.8～2.0dL/g、优选为0.79～1.33dL/g的聚酯嵌段共聚物。
  7. 根据权利要求6所述的制备方法，其特征在于，所述步骤(1)中，二元羧酸与二元醇的摩尔比为1:1～1:1.5；
    和/或，所述步骤(2)中，式(III)所示的化合物与二元醇的摩尔比为1:1.2～1:1.5；
    和/或，所述步骤(3)中，步骤(2)所得产物的用量占步骤(1)、(2)产物用量之和的比例为0.1％～50％，优选为0.5％～30％，更优选为3％～20％，进一步优选为10％～15％。
  8. 根据权利要求6或7所述的制备方法，其特征在于，步骤(3)所述预缩聚反应条件为：温度180～310℃，真空度1.5～2.5KPa；步骤(4)所述缩聚反应条件为：温度180～310℃，真空度100～200Pa；
    优选地，所述固相增粘反应的温度为100-260℃。
  9. 根据权利要求8所述的制备方法，其特征在于，当步骤(1)所述二元羧酸为2,6-萘二甲酸时，预缩聚反应温度范围为250～310℃，缩聚反应温度为250～310℃，优选固相增粘反应温度为200～240℃；
    当步骤(1)所述二元羧酸为对苯二甲酸、所述二元醇为1,4-环己烷二甲醇时，预缩聚反应温度范围为280～310℃，缩聚反应温度为280～310℃，优选固相增粘反应温度为240～260℃；
    当步骤(1)所述二元羧酸为对苯二甲酸、所述二元醇为除1,4-环己烷二甲醇之外的一种二元醇或为两种以上的二元醇的混合物时，预缩聚反应温度范围为200～250℃，缩聚反应温度为200～250℃，优选固相增粘反应温度为180～220℃；
    当步骤(1)所述二元羧酸为丁二酸时，预缩聚反应温度范围为100～200℃，缩聚反应温度为100～200℃，固相增粘反应温度为100～110℃。
  10. 权利要求6～9任一项所述制备方法制备得到的聚酯嵌段共聚物。
  11. 权利要求1～5任一项所述聚酯嵌段共聚物或权利要求10所述聚酯嵌段共聚物在制备纤维、薄膜、瓶罐、工程塑料方面的应用。
PCT/CN2018/102638 2017-09-27 2018-08-28 一种聚酯嵌段共聚物及其制备方法与应用 WO2019062428A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710889156.3A CN109553776B (zh) 2017-09-27 2017-09-27 一种聚酯嵌段共聚物及其制备方法与应用
CN201710889156.3 2017-09-27

Publications (1)

Publication Number Publication Date
WO2019062428A1 true WO2019062428A1 (zh) 2019-04-04

Family

ID=65863627

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/102638 WO2019062428A1 (zh) 2017-09-27 2018-08-28 一种聚酯嵌段共聚物及其制备方法与应用

Country Status (2)

Country Link
CN (1) CN109553776B (zh)
WO (1) WO2019062428A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115612080A (zh) * 2021-07-14 2023-01-17 华润化学材料科技股份有限公司 含硅聚酯及其制备方法
CN114933697A (zh) * 2022-02-28 2022-08-23 天津天达联合工程技术有限公司 一种生物可降解共聚酯及制备方法及应用
CN114605645A (zh) * 2022-03-24 2022-06-10 无锡宁融新材料有限公司 一种mlcc离型膜用聚酯母料及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4894427A (en) * 1987-09-30 1990-01-16 Mitsubishi Rayon Co., Ltd. Aromatic polyester-polyorganosiloxane block copolymer
CN102336898A (zh) * 2010-07-16 2012-02-01 东丽纤维研究所（中国）有限公司 一种共聚酯及其生产方法和用途
CN102485770A (zh) * 2010-12-06 2012-06-06 东丽纤维研究所（中国）有限公司 一种聚酯及其生产方法
CN103304795A (zh) * 2013-06-17 2013-09-18 中国纺织科学研究院 一种有机硅共聚酯
CN105504253A (zh) * 2016-01-22 2016-04-20 四川东材绝缘技术有限公司 一种硅氧烷-聚酯共聚物树脂、硅氧烷-聚酯共聚物复合基膜及其制备方法
US20170260337A1 (en) * 2016-03-14 2017-09-14 Xerox Corporation Cold pressure fix toners comprising crystalline co-polyester-co-poly(alkylsiloxane)
CN107325272A (zh) * 2017-07-11 2017-11-07 南通协鑫热熔胶有限公司 一种含有机硅大分子嵌段的半芳香型聚酯热熔胶及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3701815A (en) * 1971-01-20 1972-10-31 Union Carbide Corp Thermoplastic siloxane-polyester block copolymers
US4895965A (en) * 1989-04-28 1990-01-23 General Electric Company Method for making carboxy aryl terminated organosiloxanes
US7129310B2 (en) * 2003-12-23 2006-10-31 Wacker Chemical Corporation Solid siliconized polyester resins for powder coatings
CN102161860B (zh) * 2011-02-14 2012-07-11 广东恒宝昌电工科技股份有限公司 有机硅改性聚酯漆包线漆的制备方法
CN103193963B (zh) * 2013-04-09 2015-04-29 大连大学 超临界二氧化碳分散聚合稳定剂及其制备方法和使用方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4894427A (en) * 1987-09-30 1990-01-16 Mitsubishi Rayon Co., Ltd. Aromatic polyester-polyorganosiloxane block copolymer
CN102336898A (zh) * 2010-07-16 2012-02-01 东丽纤维研究所（中国）有限公司 一种共聚酯及其生产方法和用途
CN102485770A (zh) * 2010-12-06 2012-06-06 东丽纤维研究所（中国）有限公司 一种聚酯及其生产方法
CN103304795A (zh) * 2013-06-17 2013-09-18 中国纺织科学研究院 一种有机硅共聚酯
CN105504253A (zh) * 2016-01-22 2016-04-20 四川东材绝缘技术有限公司 一种硅氧烷-聚酯共聚物树脂、硅氧烷-聚酯共聚物复合基膜及其制备方法
US20170260337A1 (en) * 2016-03-14 2017-09-14 Xerox Corporation Cold pressure fix toners comprising crystalline co-polyester-co-poly(alkylsiloxane)
CN107325272A (zh) * 2017-07-11 2017-11-07 南通协鑫热熔胶有限公司 一种含有机硅大分子嵌段的半芳香型聚酯热熔胶及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
VESNA V ANTIC ET AL.: "The effect of segment length on some properties of thermoplastic poly(ester-siloxane)s", POLYMER INTERNATIONAL, 31 December 2003 (2003-12-31), XP055587836 *

Also Published As

Publication number Publication date
CN109553776B (zh) 2021-09-03
CN109553776A (zh) 2019-04-02

Similar Documents

Publication Publication Date Title
WO2019062428A1 (zh) 一种聚酯嵌段共聚物及其制备方法与应用
WO2022126812A1 (zh) 一种可生物降解的脂肪族-芳香族共聚酯及其合成方法
CN113929886B (zh) 一种长链支化petg共聚酯及其制备方法
WO2018045930A1 (zh) 聚酯树脂及其制备方法
TWI743592B (zh) 用於經黏合強度增強的黏合劑的聚酯樹脂和使用之的聚酯纖維
CN110713700B (zh) 一种聚酯复合材料及其制备方法和应用
TW200416238A (en) Crosslinked polyester copolymers
WO2024077921A1 (zh) 一种废弃pet的回收利用方法及采用该方法制备的生物可降解共聚酯
CN116554490A (zh) 一种纳米氮化硅颗粒接枝改性增强pbat的制备方法
CN115725060B (zh) 嵌段共聚酯及其制备方法和应用
KR101551633B1 (ko) 폴리에테르 에스테르 엘라스토머 및 제조 방법
CN114015403B (zh) 一种聚氨酯粘合剂及其制成的热压绝缘膜及应用
CN115612080A (zh) 含硅聚酯及其制备方法
KR20140002308A (ko) 수분산 조성물 및 이를 이용한 광학필름
KR20200127464A (ko) 열가소성 폴리에스테르 수지 조성물 및 이로부터 제조된 폴리에스테르 수지
CN102333810B (zh) 容器成形用对苯二甲酸乙二酯型聚酯树脂及其生产方法
US12037448B2 (en) Copolymer and method of manufacturing the same
CN115991863A (zh) 一种聚酯共聚物及其制备方法与应用
TW201811860A (zh) 提高黏結強度的黏結劑用聚酯纖維
CN115340670A (zh) 一种无纺专用聚酯切片生产工艺
KR101139130B1 (ko) 폴리에틸렌테레프탈레이트 수지와 투명 공중합폴리에스테르 수지의 블렌드, 그 제조방법 및 이를 이용한성형제품
CN117843937A (zh) 一种改性共聚酯材料及制备方法与应用
KR101873524B1 (ko) 공중합 폴리에스테르계 저융점 접착수지 조성물 및 이를 이용한 접착웹
WO2024036583A1 (zh) 热塑性聚酯及其制备方法与应用
CN114773583A (zh) 一种聚酯及制法和耐水解聚酯薄膜及其制法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18861336

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18861336

Country of ref document: EP

Kind code of ref document: A1