CN101684173A - Biodegradable copolyester and method for preparing same - Google Patents
Biodegradable copolyester and method for preparing same Download PDFInfo
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- CN101684173A CN101684173A CN200810120877A CN200810120877A CN101684173A CN 101684173 A CN101684173 A CN 101684173A CN 200810120877 A CN200810120877 A CN 200810120877A CN 200810120877 A CN200810120877 A CN 200810120877A CN 101684173 A CN101684173 A CN 101684173A
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Abstract
The invention provides a biodegradable copolyester and a method for preparing same, which comprises an aromatic polyester structural unit, a poly(oxy-acid) polyester structural unit, and is prepared by non-regular co-polymerization of dihydric alcohol or oxy-acid with dibasic acid; the method condenses the esterification product of aromatic polyester and the poly(oxy-acid) pre-polymer in a certainproportioning and pressure reducing condition when melting, wherein the temperature is controlled at 160-300 DEG C, the reaction time is 20-600min. Compared with prior art, the advantages of the method of the invention are that: the copolymer disclosed in the invention is made biodegradable by introducing rapid degradation components, and combining the thermotolerance of aromatic compoumds, the copolymer can be widely used for fibre material and thin film products.
Description
Technical field
The present invention relates to the copolyesters of a kind of biodegradable poly(lactic acid) or polyglycolic acid and aromatic polyester, the invention still further relates to the preparation method of this copolyesters.
Background technology
Aromatic polyester, as polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT), have good thermotolerance, HDT temperature height, resistance to chemical attack, be the macromolecular material of high comprehensive performance, be widely used in fields such as fiber and film at present.Yet, the waste product huge amount after it uses and very strong to the resistivity of microorganism, having the cycle is 30-50, and environment is caused very big pollution.
In order to improve the degradation property of aromatic polyester, the investigator is carrying out a large amount of work aspect blend and the modification by copolymerization both at home and abroad.Aspect blend, blend result synthetic or natural polymer such as PET and PLA, PEG, starch, PCL shows that easily the degraded of degradable component can cause the part biological of material to destroy.(Polym.Int. 199639:83) adopts direct polycondensation method to prepare a series of PET-PEG multipolymers to Nagata etc., and experimental result shows that the introducing of PEG has reduced PET segmental regularity, has increased the wetting ability of polymkeric substance.In addition, there is the scholar to adopt ester-interchange method to prepare a series of multipolymers, as PET-PGA (Polish patent such as Niekraszewicz, 171 062 B1; Polym.Prepr., 198930:197), PET-PHB (Japanese patent such as Imu, 08 217 865 A2), PET-PBS (Pollimo. such as Kim, 1996 20:431), PET-PCL (Polym.Degrad.Stabil. such as Tokiwa, 199445:205), PET-PEA (J.Environ.Polym.Degrad. such as Heidary, 19942:19), yet this series reaction needs very high temperature of reaction, this can cause the degraded of aliphatic polyester, and transesterify efficient is lower.
On the main chain of aromatic polyester, introduce the structural unit of aliphatic polyester or the degradation property that segment can improve multipolymer, through the synthetic aliphatic-aromatic copolyester PBAT (Ecoflex of BASF and the Biomax of Dupont) that obtains of polycondensation, is a kind of polyester material of Wholly-degradable as butyleneglycol, hexanodioic acid and terephthalic acid.Poly(lactic acid) (PLA) and polyglycolic acid main chains such as (PGA) are made of ester bond, easily a large amount of microorganisms or the intravital enzyme liberating of animals and plants that is existed by nature becomes oligopolymer or monomer, become carbonic acid gas and water through microbial transformation again, be a kind of Biodegradable material of complete natural circulation type, can be used for the biomedical material of human body by U.S. food medicine office (FDA) approval.Therefore, can develop a kind of copolyester material of biodegradable performance with poly(lactic acid) or polyglycolic acid and aromatic polyester copolymerization.
(European Polymer Journal such as Olewnik, 2007 43:1009-1019) reported a kind of multi-block copolyesters of polyethylene terephthalate-poly (l-lactic acid), yet because tin protochloride and the Catalyzed by p-Toluenesulfonic Acid agent adopted have certain katalysis to the polycondensation of L-lactic acid at a lower temperature, easily catalysis lactic acid polymer easily generates rac-Lactide under comparatively high temps, and the polymeric fusing point of diglycol terephthalate is about 211 ℃, therefore the polycondensation of this system can not thoroughly be carried out, therefore its molecular weight of products therefrom only has several thousand, can not use as material.
(Polym-Plast Tech Eng such as Acar, 2006,45:351-359) having reported that employing poly(lactic acid) and recovery PET polyester are raw material, is that catalyzer carries out the multi-block copolyesters that copolymerization obtains polyethylene terephthalate-poly (l-lactic acid) with the Dibutyltin oxide in o-nitrophenol solution.Because system is used noxious solvent, and described copolyesters is not seen the report of the structure and the performance of its material.
In sum, the method that needs a kind of degradable copolyester of development and fusion copolymerization thereof.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of biodegradable copolyesters at the above-mentioned state of the art, and it is synthetic easily, the molecular weight height.
Second technical problem that the present invention solves provides the preparation method of a kind of technology biodegradable copolyesters simple, with low cost.
The present invention solves the technical scheme that above-mentioned first technical problem adopts: a kind of biodegradable copolyesters, form by aromatic polyester structural unit and polyhydroxy acid polyester structural units such as poly(lactic acid), polyglycolic acid.Further, described copolyesters is formed by dibasic alcohol, alcohol acid and terephthalic acid or other diprotic acid random copolymerization.
As preferably, described alcohol acid is the compound that contains hydroxyl and carboxyl, as L-lactic acid, D-lactic acid, D, and L-lactic acid or oxyacetic acid etc. a kind of or more than one.
Described dibasic alcohol is that structural formula is HO (CH
2)
nOH, 1＜n＜7, compound, as ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, or structural formula is HO (CH
2CH
2O)
nOne or more of H (1＜n＜5).
Described diprotic acid is terephthalic acid, m-phthalic acid, 1, and 4-naphthalic acid, 2,6-naphthalic acid or structural formula are HOOC (CH
2)
nThe compound of COOH (1＜n＜7) one or more, structural formula is HOOC (CH
2)
nThe compound of COOH (1＜n＜7) is as propanedioic acid, Succinic Acid, hexanodioic acid.
It is the fusion direct condensation that the present invention solves above-mentioned second technical scheme that technical problem adopted, specific as follows:
Get terephthalic acid ethylene glycol copolyesters and aliphatic polyester prepolymer by certain proportioning, under catalyst action, under 160～300 ℃ of temperature, reacted 20～600 minutes, slough small molecules, polycondensation makes product.
Further, be added with catalyzer during melt blending, this catalyzer is for containing zinc, antimony, manganese, the compound of metallic elements such as cobalt is as tetrabutyl titanate, metatitanic acid four isobutyl esters, titanium dioxide, zinc acetate, zinc oxide, antimony acetate, three oxidations two are shaved, Cobaltous diacetate, tin protochloride, one or more of stannous octoate.
Described reduced pressure is to be decompressed to 80～10Pa gradually.
Compared with prior art, the invention has the advantages that: copolyesters of the present invention is synthetic easily, the molecular weight height, can become a kind of can biodegradable material, in conjunction with aromatic resistance toheat, this multipolymer can be widely used in filamentary material and plastics, and that the preparation method is a technology is simple, with low cost.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1: the preparation of polyethylene terephthalate-poly(lactic acid) copolyesters
1) preparation of lactic acid prepolymer.
In the 1L polymeric kettle, the L-lactic acid and the 6g butyleneglycol that add 474g 88%, logical nitrogen decompression displacement three times is warming up to 140 ℃, steams free water, preliminary polycondensation is after 30 minutes, add the 0.04g stannous octoate catalyst, stir and be warming up to 180 ℃, be depressurized to 80Pa gradually, reaction 2h obtains the white powder Hydroxyl Terminated Lactic Acid Prepolymer.Gel permeation chromatography (GPC) is measured weight-average molecular weight 5600, and it is 128 ℃ that difference formula scanning calorimetry (DSC) records fusing point.
2) preparation of diglycol terephthalate.
With 166g terephthalic acid (TPA), 124g ethylene glycol (EG), catalyzer 0.1g antimonous oxide, 0.1g Cobaltous diacetate, add in the 1L polymeric kettle, logical nitrogen decompression displacement three times, the esterification 2.5h that dewaters under 235～245 ℃, 4 normal atmosphere obtains the diglycol terephthalate esterification products.It is 218 ℃ that DSC records fusing point
3) preparation of polyethylene terephthalate-poly(lactic acid) copolyesters
With 180g diglycol terephthalate prepolymer, the 60g lactic acid prepolymer, catalyzer 0.1g tetrabutyl titanate, 0.1g antimonous oxide, an amount of stablizer triphenylphosphate adds in the 1L polymeric kettle, logical nitrogen decompression displacement three times, in 225～235 ℃ gradually the decompression carry out polycondensation, be evacuated to 10Pa, the reaction 2h, obtain ethylene glycol terephthalate-polylactic acid polymer.It is 39400 that GPC measures weight-average molecular weight, and it is 197 ℃ that DSC records fusing point.
Embodiment 2. poly terephthalic acid ethylene glycol glycol ether ester--the preparations of poly(lactic acid) copolyesters
1) preparation of terephthalic acid ethylene glycol-glycol ether esterification products.
With 249g terephthalic acid (TPA), 111.6g ethylene glycol (EG), 47.7g glycol ether, catalyzer 0.1g manganese acetate, 0.2g zinc acetate, add in the 1L polymeric kettle, logical nitrogen decompression displacement three times, the esterification of dewatering under 235～245 ℃, 4 normal atmosphere obtains esterification products terephthalic acid ethylene glycol glycol ether ester.It is 201 ℃ that DSC records fusing point.
2) preparation of poly terephthalic acid ethylene glycol glycol ether ester-poly(lactic acid) copolyesters
With 180g terephthalic acid ethylene glycol glycol ether esterification products, the 60g lactic acid prepolymer, catalyzer 0.1g tetrabutyl titanate, 0.1g antimonous oxide, an amount of stablizer triphenylphosphate adds in the 1L polymeric kettle, logical nitrogen decompression displacement three times, in 225～235 ℃ gradually the decompression carry out polycondensation, be evacuated to 10Pa, the reaction 2h, obtain terephthalic acid ethylene glycol glycol ether ester-polylactic acid polymer.It is 56200 that GPC measures weight-average molecular weight, and it is 182 ℃ that DSC records fusing point.
Embodiment 3. polybutylene terephthalate glycol ether ester--the preparations of polyglycolic acid copolyesters
1) preparation of polyglycolic acid prepolymer.
In the 1L polymeric kettle, the oxyacetic acid and the 6g butyleneglycol that add 450 grams 70%, logical nitrogen decompression displacement three times is warming up to 120 ℃, steams free water, preliminary polycondensation is after 30 minutes, add the 0.04g stannous octoate catalyst, stir and be warming up to 210 ℃, be depressurized to 80Pa gradually, reaction 2h obtains the white powder Hydroxyl Terminated Lactic Acid Prepolymer.It is 7400 that gel permeation chromatography (GPC) is measured weight-average molecular weight, and it is 184 ℃ that difference formula scanning calorimetry (DSC) records fusing point.
2) preparation of terephthalic acid butyleneglycol-glycol ether ester.
With 249g terephthalic acid (TPA), 162gl, 4-fourth ethylene glycol (BDO), 47.7g glycol ether, catalyzer 0.1g zinc acetate adds in the 1L polymeric kettle, logical nitrogen decompression displacement three times, the esterification 2.5h that dewaters under 235～245 ℃, 4 normal atmosphere obtains terephthalic acid dibutylene glycol ester esterification products.It is 209 ℃ that DSC records fusing point.
3) preparation of polybutylene terephthalate-glycol ether ester-polyglycolic acid copolyesters
With 180g terephthalic acid butyleneglycol-glycol ether esterification products, 60g polyglycolic acid prepolymer, catalyzer 0.1g tetrabutyl titanate, 0.1g antimonous oxide, an amount of stablizer triphenylphosphate adds in the 1L polymeric kettle, logical nitrogen decompression displacement three times, in 225～235 ℃ gradually the decompression carry out polycondensation, be evacuated to 10Pa, the reaction 2h, obtain terephthalic acid ethylene glycol glycol ether ester-polylactic acid polymer.It is 56200 that GPC measures weight-average molecular weight, and it is 204 ℃ that DSC records fusing point.
Claims (8)
1, a kind of biodegradable copolyesters is characterized in that aromatic polyester structural unit and polyhydroxy acid polyester structural units form, and is to be formed by dibasic alcohol or alcohol acid and diprotic acid random copolymerization.
2, biodegradable copolyesters according to claim 1 is characterized in that described dibasic alcohol is that structural formula is HO (CH
2)
nThe compound of OH, 1＜n＜7, or structural formula is HO (CH
2CH
2O)
nOne or more of the compound of H, 1＜n＜5.
3, biodegradable copolyesters according to claim 1 is characterized in that described alcohol acid for comprising L-lactic acid, D-lactic acid, D, and L-lactic acid or oxyacetic acid etc. contain one or more of hydroxyl and carboxylic compound.
4. biodegradable copolyesters according to claim 1 is characterized in that described diprotic acid is terephthalic acid, m-phthalic acid, 1,4-naphthalic acid, 2, and 6-naphthalic acid, structural formula are HOOC (CH
2)
nThe compound of COOH, 1＜n＜7 one or more.
5, a kind of preparation method of biodegradable copolyesters, it is characterized in that getting the esterification products of aromatic polyester and polyhydroxy acid prepolymer by certain proportioning, melt phase polycondensation under reduced pressure, controlled temperature are 160～300 ℃, and the reaction times is 20-600 minute.
6, preparation method according to claim 5 is added with catalyzer when it is characterized in that described melt phase polycondensation, this catalyzer be contain zinc, calcium halophosphate activated by antimony andmanganese, cobalt, tin metal element compound one or more.
7, preparation method according to claim 6, it is characterized in that described catalyzer is tetrabutyl titanate, metatitanic acid four isobutyl esters, titanium dioxide, zinc acetate, zinc oxide, antimony acetate, three oxidations two are shaved, Cobaltous diacetate, tin protochloride, one or more of stannous octoate.
8, preparation method according to claim 5 is characterized in that described reduced pressure is to be decompressed to 80～10Pa gradually.
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| WO2013071802A1 (en) * | 2011-10-12 | 2013-05-23 | 苏州莫立克新型材料有限公司 | Fast degradable polyester polymer and preparation method and use thereof |
| CN105504254A (en) * | 2016-01-11 | 2016-04-20 | 常州大学 | Low-price and easy-to-get catalyst for producing polyglycolic acid |
| CN107584841A (en) * | 2017-08-22 | 2018-01-16 | 芜湖蓝天工程塑胶有限公司 | Degradable paper-plastic stick paper and preparation method thereof |
| CN109438682A (en) * | 2018-11-16 | 2019-03-08 | 中国科学院宁波材料技术与工程研究所 | Copolyesters and preparation method thereof, product |
| CN111393620A (en) * | 2020-04-22 | 2020-07-10 | 浙江恒澜科技有限公司 | Preparation method of degradable polytrimethylene terephthalate copolyester |
| CN111423569A (en) * | 2020-04-22 | 2020-07-17 | 浙江恒澜科技有限公司 | Antibacterial degradable polyethylene glycol terephthalate copolyester and preparation method thereof |
| CN112029122A (en) * | 2019-06-04 | 2020-12-04 | 同济大学 | Biodegradable film and preparation method thereof |
| CN112194781A (en) * | 2020-09-28 | 2021-01-08 | 长春工业大学 | Method for preparing polyester polyol from glycolic acid |
| CN113234214A (en) * | 2021-06-23 | 2021-08-10 | 中国科学院大连化学物理研究所 | Copolyester and preparation method thereof |
| CN113493939A (en) * | 2020-04-08 | 2021-10-12 | 中国石油化工股份有限公司 | Degradable hydrophilic polyester fiber and preparation method thereof |
| CN113683744A (en) * | 2021-08-23 | 2021-11-23 | 扬州惠通科技股份有限公司 | Production method and application of hydrophilic copolymer containing polylactic acid chain segment |
| CN115124702A (en) * | 2021-03-26 | 2022-09-30 | 华润化学材料科技股份有限公司 | Degradable aromatic-aliphatic copolyester material and preparation method and application thereof |
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2008
- 2008-09-22 CN CN200810120877A patent/CN101684173A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013071802A1 (en) * | 2011-10-12 | 2013-05-23 | 苏州莫立克新型材料有限公司 | Fast degradable polyester polymer and preparation method and use thereof |
| EP2767554A1 (en) * | 2011-10-12 | 2014-08-20 | Bin Huang | Fast degradable polyester polymer and preparation method and use thereof |
| JP2014528502A (en) * | 2011-10-12 | 2014-10-27 | ファン，ビン | Rapidly degradable polyester polymer and process for its production and use thereof |
| EP2767554A4 (en) * | 2011-10-12 | 2015-09-23 | Bin Huang | Fast degradable polyester polymer and preparation method and use thereof |
| CN105504254A (en) * | 2016-01-11 | 2016-04-20 | 常州大学 | Low-price and easy-to-get catalyst for producing polyglycolic acid |
| CN107584841A (en) * | 2017-08-22 | 2018-01-16 | 芜湖蓝天工程塑胶有限公司 | Degradable paper-plastic stick paper and preparation method thereof |
| CN109438682A (en) * | 2018-11-16 | 2019-03-08 | 中国科学院宁波材料技术与工程研究所 | Copolyesters and preparation method thereof, product |
| CN109438682B (en) * | 2018-11-16 | 2022-04-26 | 中国科学院宁波材料技术与工程研究所 | Copolyester, preparation method and product thereof |
| CN112029122B (en) * | 2019-06-04 | 2022-02-22 | 同济大学 | Biodegradable film and preparation method thereof |
| CN112029122A (en) * | 2019-06-04 | 2020-12-04 | 同济大学 | Biodegradable film and preparation method thereof |
| CN113493939A (en) * | 2020-04-08 | 2021-10-12 | 中国石油化工股份有限公司 | Degradable hydrophilic polyester fiber and preparation method thereof |
| CN113493939B (en) * | 2020-04-08 | 2023-07-28 | 中国石油化工股份有限公司 | Degradable hydrophilic polyester fiber and preparation method thereof |
| CN111423569B (en) * | 2020-04-22 | 2022-11-15 | 浙江恒逸石化研究院有限公司 | Antibacterial degradable polyethylene glycol terephthalate copolyester and preparation method thereof |
| CN111423569A (en) * | 2020-04-22 | 2020-07-17 | 浙江恒澜科技有限公司 | Antibacterial degradable polyethylene glycol terephthalate copolyester and preparation method thereof |
| CN111393620A (en) * | 2020-04-22 | 2020-07-10 | 浙江恒澜科技有限公司 | Preparation method of degradable polytrimethylene terephthalate copolyester |
| CN111393620B (en) * | 2020-04-22 | 2022-07-05 | 浙江恒逸石化研究院有限公司 | Preparation method of degradable polytrimethylene terephthalate copolyester |
| CN112194781A (en) * | 2020-09-28 | 2021-01-08 | 长春工业大学 | Method for preparing polyester polyol from glycolic acid |
| CN115124702A (en) * | 2021-03-26 | 2022-09-30 | 华润化学材料科技股份有限公司 | Degradable aromatic-aliphatic copolyester material and preparation method and application thereof |
| CN115124699A (en) * | 2021-03-26 | 2022-09-30 | 华润化学材料科技股份有限公司 | Degradable aromatic-aliphatic copolyester material and preparation method and application thereof |
| CN113234214B (en) * | 2021-06-23 | 2022-02-15 | 中国科学院大连化学物理研究所 | Copolyester and preparation method thereof |
| CN113234214A (en) * | 2021-06-23 | 2021-08-10 | 中国科学院大连化学物理研究所 | Copolyester and preparation method thereof |
| CN113683744A (en) * | 2021-08-23 | 2021-11-23 | 扬州惠通科技股份有限公司 | Production method and application of hydrophilic copolymer containing polylactic acid chain segment |
| CN115948817A (en) * | 2022-09-09 | 2023-04-11 | 江苏国泰博创实业有限公司 | Degradable fiber, preparation method thereof and plush toy |
| CN115948817B (en) * | 2022-09-09 | 2023-11-17 | 江苏国泰博创实业有限公司 | Degradable fiber, preparation method thereof and plush toy |
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Application publication date: 20100331 |