CN103483522A - High molecular weight aliphatic-aromatic copolyester and preparation method thereof - Google Patents
High molecular weight aliphatic-aromatic copolyester and preparation method thereof Download PDFInfo
- Publication number
- CN103483522A CN103483522A CN201210190249.4A CN201210190249A CN103483522A CN 103483522 A CN103483522 A CN 103483522A CN 201210190249 A CN201210190249 A CN 201210190249A CN 103483522 A CN103483522 A CN 103483522A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- chainextender
- molecular
- pbat
- aromatic copolyester
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of polymer materials, and especially relates to high molecular weight aliphatic-aromatic copolyester and a preparation method thereof. The preparation method of high molecular weight aliphatic-aromatic copolyester comprises following steps: (1) adding aromatic monomers, 1,4-butanediol, hexanedioic acid, and a catalyst into an intermittent reactor, carrying out esterification reactions under the protection of inert gas, and carrying out condensation polymerization reactions after the esterification reactions are over so as to obtain a PBAT prepolymer; (2) subjecting the obtained PBAT prepolymer to a chain propagation treatment with a double screw extruder when adopting a chain extender so as to obtain a PBAT copolyester with a number-average molecular weight Mn of 10000 to 100000. Compared to the prior art, the preparation method of PBAT copolyester is capable of simplifying the production technology, and has the advantages of controllable operation, realization of continuous production, and reduction on production cost.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly high-molecular-weight aliphatic-aromatic copolyester and preparation method thereof.
Background technology
Be accompanied by economic rapid growth, the use of macromolecular material has been penetrated into the every field of people's life.Yet, because macromolecular material commonly used is difficult to biological degradation mostly, be discarded into after use in the Nature and caused serious impact to ecotope.Therefore, develop environment amenable biodegradable polymer and become domestic and international study hotspot.
Poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester (PBAT) is a kind of aliphatic-aromatic copolyester.Both there is good ductility and toughness, there is again good thermotolerance and impact property; Simultaneously, this copolyesters also has good biodegradability, is a kind of environmentally friendly macromolecular material, can be widely used in the wrapping material fields such as film, substitute traditional non-degradable plastics film, the problem of environmental pollution that the use of minimizing conventional films brings.
PBAT is with terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT), 1,4-butyleneglycol (BG) and hexanodioic acid (AA) are raw material, under catalyst action, by direct esterification or ester-interchange method, be polymerized, whole building-up process can be divided into Esterification Stage and polycondensation phase.For obtaining the copolyesters of high molecular, Esterification Stage is to carry out under normal pressure rare gas element (as nitrogen); Polycondensation phase is to carry out under high temperature, low pressure condition of high vacuum degree.Although, and PBAT has good snappiness and shock resistance, its tensile strength is low, especially when molecular weight is not high.In order to make the final product molecular weight high, to improve the tensile strength of PBAT, method commonly used is improve the vacuum tightness of polycondensation or extend the time of polycondensation.But at high temperature long meeting of reaction times makes polyester generation oxidation, side reaction increases, and product is easily painted.Higher vacuum tightness is had relatively high expectations to equipment etc., and cost is higher.And the method that adopts the chainextender chain extension can effectively improve the molecular weight of polymkeric substance.Patent CN101173037 has introduced the method for the standby waterborne polyester of a kind of chain extension legal system.Be first synthesizing polyester prepolymer in reactor, then temperature of reaction reduced, add chainextender to carry out chain extending reaction.The flat 6-256461 of Japanese Patent, by after diprotic acid and dibasic alcohol melt phase polycondensation, adds the isocyanic ester chainextender to carry out the polyester that chain extension prepares high molecular in the later stage in reaction system.The polyester prepolyer of patent CN1247654 first anamorphic zone hydroxyl in reactor then adds the organic silazane hydride compounds to prepare high molecular weight polyesters as chainextender in system.These methods are all in process of polyester synthesizing, in the polycondensation later stage, in system, add chainextender to carry out chain extension.Because the chainextender reactive behavior is high, so this method generally all will reduce system temperature when adding chainextender, simultaneously add to improve the dispersiveness of chainextender in batches, prevent the local gelatin phenomenon that occurs.But there is complicated operation in this kind of chain extension mode, uppity defect.
Summary of the invention
The object of the invention is to provide a kind of preparation method of high-molecular-weight aliphatic-aromatic copolyester, the chain extension mode complicated operation existed with the preparation method who solves PBAT of the prior art, uppity technical matters.
Another object of the present invention is to provide a kind of high-molecular-weight aliphatic-aromatic copolyester.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of high-molecular-weight aliphatic-aromatic copolyester comprises the following steps:
(1) by fragrant same clan monomer, 1,4-butyleneglycol, hexanodioic acid and catalyzer add in batch reactor, carry out esterification under protection of inert gas, and esterification finishes, carry out polycondensation, the PBAT prepolymer that to obtain number-average molecular weight Mn be 2000-40000;
(2) on twin screw extruder, adopt chainextender to carry out chain extension the PBAT prepolymer of above-mentioned gained, the PBAT copolyesters that to obtain number-average molecular weight Mn be 10000-100000.
Preferably, described fragrant same clan monomer is 0.1 ~ 2:1 with the ratio of the amount of substance of hexanodioic acid; Described fragrant same clan monomer is 1 ~ 2:1 with hexanodioic acid amount of substance sum with the ratio of the amount of BDO monomeric substance; Described catalyst levels is to account for 0.01% ~ 1.5% of total mass sour in monomer; Described chainextender add-on is 0.05% ~ 1.9% of PBAT prepolymer quality.
Preferably, described step (2) further comprises: if described chainextender is solid, first by chainextender and dry PBAT prepolymer pre-mixing, join again in twin screw extruder afterwards, be 90 ~ 180 ℃ at the twin screw extruder barrel zone temperature, under the condition that screw speed is 5 ~ 200rpm, extruded chain extension.
Preferably, described step (2) further comprises: if described chainextender is liquid, dry PBAT prepolymer and described chainextender directly can be added in twin screw extruder, be 90 ~ 180 ℃ at the twin screw extruder barrel zone temperature, under the condition that screw speed is 5 ~ 200rpm, extruded chain extension.
Preferably, the length-to-diameter ratio of described twin screw extruder is 30 ~ 70.
Preferably, the material adition process in described step (1) further comprises: by described fragrant same clan monomer, BDO (BG) with hexanodioic acid (AA) is disposable all adds in reactor, or add in batches; Described catalyzer all adds when feeding intake for the first time.
Preferably, refer to first fragrant same clan monomer and part BDO are carried out to esterification described in batches adding, when the cut water of esterification or methyl alcohol go out to the greatest extent, then hexanodioic acid and part BDO are added and proceed esterification.
Preferably, the rare gas element in described esterification is nitrogen; Described esterification reaction temperature is 160 ~ 190 ℃; Described polycondensation temperature is 240 ~ 280 ℃; Described polycondensation pressure is less than 1000Pa; Described polycondensation reaction time is 4 ~ 10h.
A kind of high-molecular-weight aliphatic-aromatic copolyester, made by the raw material that comprises following component: PBAT prepolymer and chainextender; Described PBAT prepolymer is made by the raw material that comprises following component: fragrant same clan monomer, BDO, hexanodioic acid and catalyzer; Wherein, described fragrant same clan monomer is 0.1 ~ 2:1 with the ratio of the amount of substance of hexanodioic acid; Described fragrant same clan monomer is 1 ~ 2:1 with hexanodioic acid amount of substance sum with the ratio of the amount of BDO monomeric substance; Described catalyst levels is to account for 0.01% ~ 1.5% of total mass sour in monomer; Described chainextender add-on is 0.05% ~ 1.9% of PBAT prepolymer quality.
Preferably, described fragrant same clan monomer is selected from terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT).
Preferably, described catalyzer is selected from a kind of in tetrabutyl titanate, antimonous oxide, antimony acetate, germanium dioxide, sodium germanate or trimethyl phosphite 99.
Preferably, described chainextender is selected from one or more in isocyanates, epoxy resin, anhydrides, bisoxazoline class, polyalcohols or the polynary acids of functionality >=2.
Preferably, described isocyanates chainextender is selected from one or more in hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, an xylylene diisocyanate, PPDI, dimethyl diphenyl vulcabond, isophorone diisocyanate, lysinediisocyanate or polymethylene multi-phenenyl isocyanate.
Preferably, described epoxy resin chainextender is selected from epoxy resin E-51, epoxy resin E-55, epoxy resin E-44, epoxy resin E-42, epoxy resin E-35, epoxy resin E-31, epoxy resin E-20, epoxy resin E-14, epoxy resin E-12, epoxy resin E-06, epoxy resin E-03, epoxy resin E-01, 4, 4 '-dihydroxyl hexichol bisglycidyl ether epoxy resin, Resorcinol bisglycidyl ether type epoxy resin, Phloroglucinol monomethyl ether triglycidyl ether epoxy resin, epoxy resin 711, epoxy resin TDE-85, one or more in epoxy resin CYD-011 or epoxy resin CYD-128.
Preferably, described anhydrides chainextender is selected from one or more in Succinic anhydried, maleic anhydride, Tetra hydro Phthalic anhydride or pyromellitic acid dianhydride.
Preferably, described bisoxazoline class chainextender is selected from 2,2 ＇-bis-(2-oxazolines) or 1,3-penylene-bis-(2-oxazolines).
Preferably, described polyalcohols chainextender is selected from one or more in sorbyl alcohol, hexylene glycol or tetramethylolmethane.
Preferably, described polynary acids chainextender is selected from one or more in propanedioic acid, hexanodioic acid, succinic acid, terephthalic acid or m-phthalic acid.
Compared with prior art, the preparation method of PBAT of the present invention can simplify production technique, operates controlledly, can realize serialization production, reduces production costs.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but be to be understood that lifted embodiment is just in order to explain the present invention, and be not intended to limit protection scope of the present invention.Adopt the molecular weight of gel permeation chromatography (GPC) test polymer, moving phase is chloroform, and flow rate 1mL/min be take polystyrene as standard test specimen.
Embodiment 1
PTA, AA, BG and antimonous oxide are added in the 10L intermittence type polymerization still with agitator, the ratio n (PTA) of amount of substance wherein: n (AA)=1:1, n (PTA+AA): n (BG)=1.2:1, antimonous oxide accounts for the 0.5wt% of sour total mass.By the logical nitrogen of system, be warming up to 180 ℃ under normal pressure and carry out esterification.When going out to the greatest extent, the cut water of esterification starts to vacuumize, and the rising temperature of reaction, carrying out polycondensation under 240 ℃, after polycondensation 5h, reaction finishes, and obtains the PBAT prepolymer, and recording number-average molecular weight is 2320.
PBAT prepolymer and chainextender tolylene diisocyanate are added to twin screw extruder by the homogenizer stirring at normal temperature after evenly.Chainextender accounts for the 0.3wt% of PBAT prepolymer, and the forcing machine length-to-diameter ratio is 44, screw diameter 35mm.Each district's temperature of screw machine is that Yi, 2nd district are 120 ℃, three, Si, 5th district are 130 ℃, six, Qi, 8th district are that 140 ℃, Jiu, tenth district are 150 ℃, 155 ℃ of heads.Screw speed is 10rpm, and rate of feeding is 1.5kg/h.PBAT number-average molecular weight after chain extension is 10750.
Embodiment 2
PTA, BG and tetrabutyl titanate are added in the 10L intermittence type polymerization still with agitator, the molar percentage that the add-on of BG accounts for total BG is the molar percentage that PTA accounts for total acid, by the logical nitrogen of system, be warming up to 190 ℃ under normal pressure and carry out esterification, when aquifer yield reaches theoretical value, then AA, BG are added in reactor.The ratio n (PTA) of total amount of substance wherein: n (AA)=1.2:1, n (PTA+AA): n (BG)=1.3:1, tetrabutyl titanate accounts for the 0.3wt% of sour total mass.Esterification is carried out in continuation under 190 ℃.When going out to the greatest extent, the cut water of esterification starts to vacuumize, and the rising temperature of reaction, carrying out polycondensation under 270 ℃, after polycondensation 6h, reaction finishes, and obtains the PBAT prepolymer, and recording number-average molecular weight is 18740.
The PBAT prepolymer is added to twin screw extruder from main spout, and the chainextender diphenylmethanediisocyanate adds twin screw extruder with peristaltic pump from auxiliary spout.Chainextender accounts for the 0.7wt% of PBAT prepolymer, and the forcing machine length-to-diameter ratio is 44, screw diameter 35mm.Each district's temperature of screw machine is that Yi, 2nd district are 120 ℃, three, Si, 5th district are 140 ℃, six, Qi, 8th district are that 150 ℃, Jiu, tenth district are 160 ℃, 165 ℃ of heads.Screw speed is 20rpm, and rate of feeding is 2kg/h.PBAT number-average molecular weight after chain extension is 45370.
Embodiment 3
DMT, BG and antimony acetate are added in the 10L intermittence type polymerization still with agitator, the molar percentage that the add-on of BG accounts for total BG is the molar percentage that PTA accounts for total acid, by the logical nitrogen of system, be warming up to 170 ℃ under normal pressure and carry out esterification, when the cut methyl alcohol of esterification goes out to the greatest extent, then AA, BG are added in reactor.The ratio n (DMT) of total amount of substance wherein: n (AA)=1.3:1, n (DMT+AA): n (BG)=1.5:1, antimony acetate accounts for the 0.3wt% of sour total mass.Esterification is carried out in continuation under 170 ℃, when going out to the greatest extent, the cut water of esterification and methyl alcohol starts to vacuumize, and the rising temperature of reaction, carry out polycondensation under 280 ℃, after polycondensation 8h, reaction finishes, and obtains the PBAT prepolymer, and recording number-average molecular weight is 32180.
PBAT prepolymer and chainextender epoxy resin CYD-011 are added to twin screw extruder by the homogenizer stirring at normal temperature after evenly.Chainextender accounts for the 0.8wt% of PBAT prepolymer, and the forcing machine length-to-diameter ratio is 44, screw diameter 35mm.Each district's temperature of screw machine is that Yi, 2nd district are 125 ℃, three, Si, 5th district are 135 ℃, six, Qi, 8th district are that 145 ℃, Jiu, tenth district are 155 ℃, 160 ℃ of heads.Screw speed is 25rpm, and rate of feeding is 2kg/h.PBAT number-average molecular weight after chain extension is 78960.
Embodiment 4
PTA, AA, BG and trimethyl phosphite 99 are added in the 10L intermittence type polymerization still with agitator, the ratio n (PTA) of amount of substance wherein: n (AA)=1.1:1, n (PTA+AA): n (BG)=1.6:1, trimethyl phosphite 99 accounts for the 0.7wt% of sour total mass.By the logical nitrogen of system, be warming up to 160 ℃ under normal pressure and carry out esterification.When going out to the greatest extent, the cut water of esterification starts to vacuumize, and the rising temperature of reaction, carrying out polycondensation under 250 ℃, after polycondensation 10h, reaction finishes, and obtains the PBAT prepolymer, and recording number-average molecular weight is 38640.
PBAT prepolymer and chainextender pyromellitic acid dianhydride are added to twin screw extruder by the homogenizer stirring at normal temperature after evenly.Chainextender accounts for the 0.8wt% of PBAT prepolymer, and the forcing machine length-to-diameter ratio is 44, screw diameter 35mm.Each district's temperature of screw machine is that Yi, 2nd district are 110 ℃, three, Si, 5th district are 130 ℃, six, Qi, 8th district are that 150 ℃, Jiu, tenth district are 170 ℃, 175 ℃ of heads.Screw speed is 10rpm, and rate of feeding is 1.5kg/h.PBAT number-average molecular weight after chain extension is 86310.
Embodiment 5
PTA, AA, BG and tetrabutyl titanate are added in the 10L intermittence type polymerization still with agitator, the ratio n (PTA) of amount of substance wherein: n (AA)=0.9:1, n (PTA+AA): n (BG)=1.4:1, tetrabutyl titanate accounts for the 0.5wt% of sour total mass.By the logical nitrogen of system, be warming up to 170 ℃ under normal pressure and carry out esterification.When going out to the greatest extent, the cut water of esterification starts to vacuumize, and the rising temperature of reaction, carrying out polycondensation under 260 ℃, after polycondensation 9h, reaction finishes, and obtains the PBAT prepolymer, and recording number-average molecular weight is 30230.
PBAT prepolymer and chainextender 2,2 ＇-bis-(2-oxazolines) are added to twin screw extruder by the homogenizer stirring at normal temperature after evenly.Chainextender accounts for the 1wt% of PBAT prepolymer, and the forcing machine length-to-diameter ratio is 44, screw diameter 35mm.Each district's temperature of screw machine is that Yi, 2nd district are 110 ℃, three, Si, 5th district are 130 ℃, six, Qi, 8th district are that 150 ℃, Jiu, tenth district are 170 ℃, 175 ℃ of heads.Screw speed is 60rpm, and rate of feeding is 2kg/h.PBAT number-average molecular weight after chain extension is 69080.
Embodiment 6
DMT, AA, BG and germanium dioxide are added in the 10L intermittence type polymerization still with agitator, the ratio n (DMT) of amount of substance wherein: n (AA)=0.1:1, n (DMT+AA): n (BG)=1:1, germanium dioxide accounts for the 0.01wt% of sour total mass.By the logical nitrogen of system, be warming up to 160 ℃ under normal pressure and carry out esterification.When going out to the greatest extent, the cut first alcohol and water of esterification starts to vacuumize, and the rising temperature of reaction, carrying out polycondensation under 240 ℃, after polycondensation 9h, reaction finishes, and obtains the PBAT prepolymer, and recording number-average molecular weight is 37560.
PBAT prepolymer and hexylene glycol are added to twin screw extruder by the homogenizer stirring at normal temperature after evenly.Chainextender accounts for the 1.9wt% of PBAT prepolymer, and the forcing machine length-to-diameter ratio is 44, screw diameter 35mm.Each district's temperature of screw machine is that Yi, 2nd district are 120 ℃, three, Si, 5th district are 140 ℃, six, Qi, 8th district are that 160 ℃, Jiu, tenth district are 180 ℃, 185 ℃ of heads.Screw speed is 60rpm, and rate of feeding is 2kg/h.PBAT number-average molecular weight after chain extension is 74610.
Embodiment 7
PTA, AA, BG and sodium germanate are added in the 10L intermittence type polymerization still with agitator, wherein the ratio n (PTA) of amount of substance: n (AA)=2:1, n (PTA+AA): n (BG)=2:1, sodium germanate accounts for the 1.5wt% of sour total mass.By the logical nitrogen of system, be warming up to 160 ℃ under normal pressure and carry out esterification.When going out to the greatest extent, the cut water of esterification starts to vacuumize, and the rising temperature of reaction, carrying out polycondensation under 280 ℃, after polycondensation 10h, reaction finishes, and obtains the PBAT prepolymer, and recording number-average molecular weight is 39640.
PBAT prepolymer and chainextender hexanodioic acid are added to twin screw extruder by the homogenizer stirring at normal temperature after evenly.Chainextender accounts for the 0.05wt% of PBAT prepolymer, and the forcing machine length-to-diameter ratio is 44, screw diameter 35mm.Each district's temperature of screw machine is that Yi, 2nd district are 110 ℃, three, Si, 5th district are 130 ℃, six, Qi, 8th district are that 150 ℃, Jiu, tenth district are 170 ℃, 175 ℃ of heads.Screw speed is 10rpm, and rate of feeding is 1.5kg/h.PBAT number-average molecular weight after chain extension is 96310.
Compared with prior art, preparation method's operating procedure of PBAT copolyesters of the present invention is simple, and easy control of process conditions is convenient to industrialization and is produced continuously, enhances productivity.
Above disclosed be only several specific embodiments of the application, but the application is not limited thereto, the changes that any person skilled in the art can think of, all should drop in the application's protection domain.
Claims (18)
1. the preparation method of a high-molecular-weight aliphatic-aromatic copolyester, is characterized in that, comprises the following steps:
(1) by fragrant same clan monomer, 1,4-butyleneglycol, hexanodioic acid and catalyzer add in batch reactor, carry out esterification under protection of inert gas, and esterification finishes, carry out polycondensation, the PBAT prepolymer that to obtain number-average molecular weight Mn be 2000-40000;
(2) on twin screw extruder, adopt chainextender to carry out chain extension the PBAT prepolymer of above-mentioned gained, the PBAT copolyesters that to obtain number-average molecular weight Mn be 10000-100000.
2. the preparation method of a kind of high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 1, is characterized in that, described fragrant same clan monomer is 0.1 ~ 2:1 with the ratio of the amount of substance of hexanodioic acid; Described fragrant same clan monomer is 1 ~ 2:1 with hexanodioic acid amount of substance sum with the ratio of the amount of BDO monomeric substance; Described catalyst levels is to account for 0.01% ~ 1.5% of total mass sour in monomer; Described chainextender add-on is 0.05% ~ 1.9% of PBAT prepolymer quality.
3. the preparation method of a kind of high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 1, it is characterized in that, described step (2) further comprises: if described chainextender is solid, first by chainextender and dry PBAT prepolymer pre-mixing, join again in twin screw extruder afterwards, be 90 ~ 180 ℃ at the twin screw extruder barrel zone temperature, under the condition that screw speed is 5 ~ 200rpm, extruded chain extension.
4. the preparation method of a kind of high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 1, it is characterized in that, described step (2) further comprises: if described chainextender is liquid, can directly add in twin screw extruder by dry PBAT prepolymer and described chainextender, be 90 ~ 180 ℃ at the twin screw extruder barrel zone temperature, under the condition that screw speed is 5 ~ 200rpm, extruded chain extension.
5. the preparation method of a kind of high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 1, is characterized in that, the length-to-diameter ratio of described twin screw extruder is 30 ~ 70.
6. the preparation method of a kind of high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 1, it is characterized in that, material adition process in described step (1) further comprises: by described fragrant same clan monomer, 1,4-butyleneglycol and hexanodioic acid are disposable all to add in reactor, or adds in batches; Described catalyzer all adds when feeding intake for the first time.
7. the preparation method of a kind of high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 6, it is characterized in that, refer to first by fragrant same clan monomer and part 1 described in batches adding, the 4-butyleneglycol carries out esterification, when the cut water of esterification or methyl alcohol go out to the greatest extent, again hexanodioic acid and part BDO are added and proceed esterification.
8. the preparation method of a kind of high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 1, is characterized in that, the rare gas element in described esterification is nitrogen; Described esterification reaction temperature is 160 ~ 190 ℃; Described polycondensation temperature is 240 ~ 280 ℃; Described polycondensation pressure is less than 1000Pa; Described polycondensation reaction time is 4 ~ 10h.
9. a high-molecular-weight aliphatic-aromatic copolyester, is characterized in that, by the raw material that comprises following component, made: PBAT prepolymer and chainextender; Described PBAT prepolymer is made by the raw material that comprises following component: fragrant same clan monomer, BDO, hexanodioic acid and catalyzer; Wherein, described fragrant same clan monomer is 0.1 ~ 2:1 with the ratio of the amount of substance of hexanodioic acid; Described fragrant same clan monomer is 1 ~ 2:1 with hexanodioic acid amount of substance sum with the ratio of the amount of BDO monomeric substance; Described catalyst levels is to account for 0.01% ~ 1.5% of total mass sour in monomer; Described chainextender add-on is 0.05% ~ 1.9% of PBAT prepolymer quality.
10. high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 9, is characterized in that, described fragrant same clan monomer is selected from terephthalic acid or dimethyl terephthalate (DMT).
11. high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 9, is characterized in that, described catalyzer is selected from a kind of in tetrabutyl titanate, antimonous oxide, antimony acetate, germanium dioxide, sodium germanate or trimethyl phosphite 99.
12. high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 9, it is characterized in that, described chainextender is selected from one or more in isocyanates, epoxy resin, anhydrides, bisoxazoline class, polyalcohols or the polynary acids of functionality >=2.
13. high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 12, it is characterized in that, described isocyanates chainextender is selected from one or more in hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, an xylylene diisocyanate, PPDI, dimethyl diphenyl vulcabond, isophorone diisocyanate, lysinediisocyanate or polymethylene multi-phenenyl isocyanate.
14. high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 12, it is characterized in that, described epoxy resin chainextender is selected from epoxy resin E-51, epoxy resin E-55, epoxy resin E-44, epoxy resin E-42, epoxy resin E-35, epoxy resin E-31, epoxy resin E-20, epoxy resin E-14, epoxy resin E-12, epoxy resin E-06, epoxy resin E-03, epoxy resin E-01, 4, 4 '-dihydroxyl hexichol bisglycidyl ether epoxy resin, Resorcinol bisglycidyl ether type epoxy resin, Phloroglucinol monomethyl ether triglycidyl ether epoxy resin, epoxy resin 711, epoxy resin TDE-85, one or more in epoxy resin CYD-011 or epoxy resin CYD-128.
15. high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 12, is characterized in that, described anhydrides chainextender is selected from one or more in Succinic anhydried, maleic anhydride, Tetra hydro Phthalic anhydride or pyromellitic acid dianhydride.
16. high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 12, is characterized in that, described bisoxazoline class chainextender is selected from 2,2 ＇-bis-(2-oxazolines) or 1,3-penylene-bis-(2-oxazolines).
17. high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 12, is characterized in that, described polyalcohols chainextender is selected from one or more in sorbyl alcohol, hexylene glycol or tetramethylolmethane.
18. high-molecular-weight aliphatic-aromatic copolyester as claimed in claim 12, is characterized in that, described polynary acids chainextender is selected from one or more in propanedioic acid, hexanodioic acid, succinic acid, terephthalic acid or m-phthalic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210190249.4A CN103483522A (en) | 2012-06-11 | 2012-06-11 | High molecular weight aliphatic-aromatic copolyester and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210190249.4A CN103483522A (en) | 2012-06-11 | 2012-06-11 | High molecular weight aliphatic-aromatic copolyester and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103483522A true CN103483522A (en) | 2014-01-01 |
Family
ID=49824152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210190249.4A Pending CN103483522A (en) | 2012-06-11 | 2012-06-11 | High molecular weight aliphatic-aromatic copolyester and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103483522A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474230A (en) * | 2017-07-03 | 2017-12-15 | 涂志秀 | A kind of PBAT resins and preparation method thereof |
| CN107474227A (en) * | 2017-07-03 | 2017-12-15 | 涂志秀 | A kind of PBST resins and preparation method thereof |
| CN110573548A (en) * | 2017-04-26 | 2019-12-13 | 巴斯夫欧洲公司 | Process for preparing polyurethanes using polyester polyols comprising polycyclic aromatic moieties |
| CN112724384A (en) * | 2020-12-26 | 2021-04-30 | 杭州鑫富科技有限公司 | Method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene glycol succinate by chain extension method |
| CN112920391A (en) * | 2021-01-29 | 2021-06-08 | 临朐齐力催化剂有限公司 | Preparation method of fully-degradable PBAT for soft product |
| CN113354928A (en) * | 2021-06-29 | 2021-09-07 | 浙江中邦塑胶股份有限公司 | Biological plastic for manufacturing degradable film and preparation method thereof |
| CN113416281A (en) * | 2021-07-05 | 2021-09-21 | 常州天马集团有限公司（原建材二五三厂） | Unsaturated polyester resin for sheet molding compound and preparation method thereof |
| CN113861394A (en) * | 2021-10-13 | 2021-12-31 | 万华化学集团股份有限公司 | Preparation method of poly (terephthalic acid) -adipic acid-butanediol copolyester |
| CN114920914A (en) * | 2022-05-28 | 2022-08-19 | 东北师范大学 | Preparation and application of bio-based polyester based on 1, 3-butanediol |
| CN115197403A (en) * | 2022-09-01 | 2022-10-18 | 东北师范大学 | Crystalline degradable polyester based on 1, 3-butanediol and preparation method thereof |
| CN115386072A (en) * | 2021-05-25 | 2022-11-25 | 宜科万斯有限公司 | Biodegradable polyester resin, method for producing same, and biodegradable polyester film comprising same |
| EP4095179A1 (en) * | 2021-05-25 | 2022-11-30 | Ecovance Co. Ltd | Biodegradable polyester resin, preparation method thereof, and biodegradable polyester molded article comprising the same |
| CN115746275A (en) * | 2022-12-16 | 2023-03-07 | 青岛科技大学 | Poly (butylene succinate)/terephthalate copolymer and preparation method thereof |
| WO2023071796A1 (en) * | 2021-10-26 | 2023-05-04 | 江苏金发科技新材料有限公司 | Semi-aromatic polyester, and preparation method therefor and application thereof |
-
2012
- 2012-06-11 CN CN201210190249.4A patent/CN103483522A/en active Pending
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110573548A (en) * | 2017-04-26 | 2019-12-13 | 巴斯夫欧洲公司 | Process for preparing polyurethanes using polyester polyols comprising polycyclic aromatic moieties |
| CN110573548B (en) * | 2017-04-26 | 2022-10-18 | 巴斯夫欧洲公司 | Process for preparing polyurethanes using polyester polyols comprising polycyclic aromatic moieties |
| CN107474230A (en) * | 2017-07-03 | 2017-12-15 | 涂志秀 | A kind of PBAT resins and preparation method thereof |
| CN107474227A (en) * | 2017-07-03 | 2017-12-15 | 涂志秀 | A kind of PBST resins and preparation method thereof |
| CN112724384A (en) * | 2020-12-26 | 2021-04-30 | 杭州鑫富科技有限公司 | Method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene glycol succinate by chain extension method |
| CN112724384B (en) * | 2020-12-26 | 2022-06-10 | 杭州鑫富科技有限公司 | Method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene glycol succinate by chain extension method |
| CN112920391A (en) * | 2021-01-29 | 2021-06-08 | 临朐齐力催化剂有限公司 | Preparation method of fully-degradable PBAT for soft product |
| CN115386072B (en) * | 2021-05-25 | 2024-04-02 | 宜科万斯有限公司 | Biodegradable polyester resin, method for producing same, and biodegradable polyester film comprising same |
| TWI831219B (en) * | 2021-05-25 | 2024-02-01 | 南韓商宜科萬斯有限公司 | Biodegradable polyester resin, preperation method thereof, and biodegradable polyester molded article comprising the same |
| JP7291268B2 (en) | 2021-05-25 | 2023-06-14 | エコバンス カンパニー・リミテッド | Biodegradable polyester resin, method for producing the same, and biodegradable polyester film containing the same |
| US11667751B2 (en) | 2021-05-25 | 2023-06-06 | Ecovance Co. Ltd. | Biodegradable polyester resin, preperation method thereof, and biodegradable polyester film comprising the same |
| CN115386072A (en) * | 2021-05-25 | 2022-11-25 | 宜科万斯有限公司 | Biodegradable polyester resin, method for producing same, and biodegradable polyester film comprising same |
| EP4095179A1 (en) * | 2021-05-25 | 2022-11-30 | Ecovance Co. Ltd | Biodegradable polyester resin, preparation method thereof, and biodegradable polyester molded article comprising the same |
| EP4095180A1 (en) * | 2021-05-25 | 2022-11-30 | Ecovance Co. Ltd | Biodegradable polyester resin, preparation method thereof, and biodegradable polyester film comprising the same |
| JP2022181205A (en) * | 2021-05-25 | 2022-12-07 | エコバンス カンパニー・リミテッド | Biodegradable polyester resin, method for producing the same, and biodegradable polyester film containing the same |
| JP2022181209A (en) * | 2021-05-25 | 2022-12-07 | エコバンス カンパニー・リミテッド | Biodegradable polyester resin, preparation method thereof, and biodegradable polyester molded article comprising the same |
| CN113354928A (en) * | 2021-06-29 | 2021-09-07 | 浙江中邦塑胶股份有限公司 | Biological plastic for manufacturing degradable film and preparation method thereof |
| CN113416281A (en) * | 2021-07-05 | 2021-09-21 | 常州天马集团有限公司（原建材二五三厂） | Unsaturated polyester resin for sheet molding compound and preparation method thereof |
| CN113861394A (en) * | 2021-10-13 | 2021-12-31 | 万华化学集团股份有限公司 | Preparation method of poly (terephthalic acid) -adipic acid-butanediol copolyester |
| WO2023071796A1 (en) * | 2021-10-26 | 2023-05-04 | 江苏金发科技新材料有限公司 | Semi-aromatic polyester, and preparation method therefor and application thereof |
| CN114920914A (en) * | 2022-05-28 | 2022-08-19 | 东北师范大学 | Preparation and application of bio-based polyester based on 1, 3-butanediol |
| CN115197403B (en) * | 2022-09-01 | 2023-05-26 | 东北师范大学 | Crystalline degradable polyester based on 1, 3-butanediol and preparation method thereof |
| CN115197403A (en) * | 2022-09-01 | 2022-10-18 | 东北师范大学 | Crystalline degradable polyester based on 1, 3-butanediol and preparation method thereof |
| CN115746275A (en) * | 2022-12-16 | 2023-03-07 | 青岛科技大学 | Poly (butylene succinate)/terephthalate copolymer and preparation method thereof |
| CN115746275B (en) * | 2022-12-16 | 2024-05-17 | 青岛科技大学 | Poly (butylene succinate)/terephthalic acid butanediol copolymer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103483522A (en) | High molecular weight aliphatic-aromatic copolyester and preparation method thereof | |
| CN103030766B (en) | Carbon dioxide-based poly (carbonic ester-ether) polyurethane and preparation method thereof | |
| US9187595B2 (en) | Method for manufacturing biodegradable copolymer by split-injecting aromatic dicarboxylic acid compound | |
| CN106957514B (en) | PBAT base biodegradation composite material with high water vapor barrier property | |
| WO2022142512A1 (en) | Semi-aromatic polyester, and preparation method therefor and application thereof | |
| EP1148074A2 (en) | Process for producing aliphatic polyester | |
| CN101684173A (en) | Biodegradable copolyester and method for preparing same | |
| AU2013303463B2 (en) | Method for preparing biodegradable aliphatic-aromatic polyester copolymer resin with improved hydrolysis resistance | |
| CN103571158A (en) | High interfacial compatibility PLA/PBAT blend and preparation method | |
| CN102229702A (en) | Production method of complete biodegradable aliphatic polyester | |
| CN106146855B (en) | A kind of graft copolymer and its synthetic method of cellulose and its derivates | |
| AU2012302534A1 (en) | Production method for a biodegradable polyester copolymer resin | |
| US9102782B2 (en) | Transparent copolyester, preparing method thereof and articles made from the same | |
| CN115746275B (en) | Poly (butylene succinate)/terephthalic acid butanediol copolymer and preparation method thereof | |
| WO2024077921A1 (en) | Recycling method for waste pet and biodegradable copolyester prepared by using same | |
| CN115322350B (en) | Degradable bio-based polyester and preparation method and application thereof | |
| TWI606091B (en) | Method of preparation for biodegradable co-polyester resin | |
| CN107057017A (en) | PCL multi-block copolyesters containing sugared twin nuclei and its preparation method and application | |
| CN109467666B (en) | Preparation method of polyurethane with smooth surface | |
| JP2968466B2 (en) | Method for producing aliphatic polyester | |
| CN111116883A (en) | Biodegradable copolyester and preparation method thereof | |
| CN113493598B (en) | Biodegradable polyester and preparation method thereof | |
| CN114044886B (en) | Production method of polycaprolactone | |
| CN114790273B (en) | Polyurethane, high-solid-content aqueous polyurethane emulsion and preparation method thereof | |
| WO2023280478A1 (en) | Polyester polyol and the preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140101 |