CN104479318A - Biodegradable aliphatic-aromatic copolyester composition and application thereof - Google Patents
Biodegradable aliphatic-aromatic copolyester composition and application thereof Download PDFInfo
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- CN104479318A CN104479318A CN201410711829.2A CN201410711829A CN104479318A CN 104479318 A CN104479318 A CN 104479318A CN 201410711829 A CN201410711829 A CN 201410711829A CN 104479318 A CN104479318 A CN 104479318A
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Abstract
The invention discloses a biodegradable aliphatic-aromatic copolyester composition. The biodegradable aliphatic-aromatic copolyester composition contains the following ingredients in percentage by mass: A: 69.95-89.95% of alkyl/alkoxy side chain-containing aliphatic-aromatic copolyester, B: 10-30% of polylactic acid and C: 0.05-3% of compatibilizer, wherein the A contains the following ingredients in percentage by mass: A1: 44-60% of aromatic polyester unit, A2: 39-55% of straight-chain aliphatic polyester unit and A3: 0.3-3% of alkyl/alkoxy side chain-containing aliphatic dibasic acid ester unit. According to the biodegradable aliphatic-aromatic copolyester composition disclosed by the invention, the alkyl/alkoxy side chain-containing aliphatic dibasic acid ester unit of a specific proportioning ratio is added, so that the yield strength of manufactured films is improved, the improvement of crop and weed puncture resistance of agricultural mulching films is facilitated, and the probability of occurrence of a hole breaking phenomenon is reduced; the oxygen gas permeability is improved, and the water vapor permeability is lowered, so that the manufactured films have better heat preserving and moisture preserving effects as the agricultural mulching films.
Description
Technical field
The invention belongs to polymer blend technical field, particularly a kind of containing the Biodegradable aliphatic-aromatic copolyester composition of alkyl/alkyloxy side chain and the application in agricultural film industry thereof.
Background technology
At present, the mulch film great majority used in agriculture production are synthetic polymers, as polyethylene (PE), polyvinyl chloride (PVC) etc.While using these film material to bring certain economic benefit to agricultural, also cause serious white pollution to environment.These materials are the long-term stable existence of meeting in physical environment, remains in the mulch film debris damage Soil structure in soil in a large number, makes soil hardening, and hinder crop from soil, absorb water and fertilizer, life-time service causes crop production reduction.Reclaim from Tanaka that mulch film workload is large, cost is high, and be difficult to mulch film to reclaim completely.Through long-time accumulation, mulch film relic can reduce the quality of soil greatly.
Biodegradable fatty race-aromatic polyester has high-flexibility, good shock strength, and good moulding processability.But its stiffness of thin film made is lower.By by itself and polylactic acid blend, the film product that deflection is excellent can be improved.And can in the physical environment in field, under the effect of water and microorganism, degradable in the time about some months to several years, final product is water and carbonic acid gas, is the ideal material making mulch film.
But, easily there is holes as during mulch film in common linear aliphatic race-aromatic copolyester (as PBAT etc.) and the tear-resistant scarce capacity of PLA blend, cause insulation, humidity-holding effect reduction under the effects such as weeds.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of Biodegradable aliphatic-aromatic copolyester composition containing alkyl/alkyloxy side chain.
Another object of the present invention is to provide the above-mentioned application of Biodegradable aliphatic-aromatic copolyester composition in agricultural mulching industry containing alkyl/alkyloxy side chain.
Object of the present invention realizes by following technical solution:
A kind of Biodegradable aliphatic-aromatic copolyester composition, by mass percentage, comprises following component:
A: containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester 69.95% ~ 89.95%;
B: poly(lactic acid) 10% ~ 30%;
C: compatilizer 0.05% ~ 3%;
Described A by mass percentage, comprises following component:
A1: aromatic polyester unit 44% ~ 60%;
A2: straight-chain aliphatic polyester unit 39% ~ 55%;
A3: containing alkyl/alkyloxy side chain fatty group dibasic acid unit 0.3% ~ 3%.
Described A3 reacts obtained for containing alkyl/alkyloxy side chain aliphatic dibasic acid or ester and dihydroxy compound; Described have following structure containing alkyl/alkyloxy side chain aliphatic dibasic acid:
Wherein R
1for alkyl or alkoxyl group;
R
1during for alkyl, R
1be the alkyl of 4 ~ 12, the side chain of 2 can be no more than in R1 containing carbonatoms, R
1in containing 0 ~ 1 carbon-carbon double bond, carbon-carbon double bond can at R
1any position; N1 is the integer of 0 ~ 9, and n2 is the integer of 0 ~ 9, and 0≤n1+n2≤9;
R
1during for alkoxyl group, there is following structure:
Wherein R
3for the one in hydrogen atom, methyl or ethyl, a is the integer of 2 ~ 4, and b is the integer of 1 ~ 6, and 4≤a × b≤12.
Described A1 is that aromatic acid or ester and dihydroxy compound react obtained; Described aromatic acid is selected from the one or more kinds of mixtures in terephthalic acid, m-phthalic acid, phthalic acid or its carboxylate.
Described A2 is that straight-chain aliphatic diprotic acid or ester and dihydroxy compound react obtained; Described straight-chain aliphatic diprotic acid is selected from the Straight chain diatomic acid residue containing 3 ~ 10 carbon atoms, is preferably the one or more kinds of mixtures in propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid.
Described dihydroxy compound is selected from the alkyl diol of C2 ~ C6, is preferably the one or more kinds of mixtures in ethylene glycol, 1,3-PD, BDO, 1,5-PD, 1,6-hexylene glycol.
The described degree of randomness containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 0.8 ~ 1.2, and described degree of randomness is obtained by 1H NMR test result calculations, testing method reference method of calculation reference " New Chemical Materials " 2012,40 volume, 12 phases, p85 ~ 93.
The described limiting viscosity containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 1.2 ~ 1.4dL/g, and described limiting viscosity records with reference to GB/T1632.5-2008, and probe temperature is 25
oc, solvent is phenol/orthodichlorobenzene (60/40, wt/wt), and the concentration of copolyesters is 0.5g/100mL, records with Ubbelohde viscometer.
The described melt mass flow rate containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 2 ~ 5g/10min, and described melt mass flow rate records with reference to GB/T 3682-2000, and temperature is 190
oc, load is 2.16Kg.
The described fusing point containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 115
oc ~ 150
oc; Described fusing point records with reference to GB/T 19466.3-2004.
The above-mentioned preparation method containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester:
1) can by conventional vacuum fusion polymerization directly obtained Biodegradable aliphatic-aromatic copolyester;
2) also first can obtain the prepolymer P0 that limiting viscosity is 0.9 ~ 1.1dL/g, then obtain Biodegradable aliphatic-aromatic copolyester by chain extension legal system.Wherein, chainextender can use bifunctional isocyanic ester; Described bifunctional isocyanic ester is selected from the mixture of one or more in 2,6-tolylene diisocyanate, 2,4 toluene diisocyanate, '-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isoflurane chalcone diisocyanate.
The preparation method of described Biodegradable aliphatic-aromatic copolyester composition:
By above-mentioned containing after alkyl/alkyloxy side chain aliphatic-aromatic copolyester, poly(lactic acid) and compatilizer mix in high mixer, add in twin screw extruder, in 170 ~ 220 with weighing balance
oc extruding pelletization can obtain Biodegradable aliphatic-aromatic copolyester composition.
Can containing the stablizer of no more than 1% in Biodegradable aliphatic-aromatic copolyester composition, stablizer is selected from the one or more kinds of mixtures in Hinered phenols stablizer, phosphite-type stabilisers, amines stabilizer, thioether class stablizer.
Above-mentioned Biodegradable aliphatic-aromatic copolyester composition can make film, sack etc. by processing modes such as blowings.The film made by Biodegradable aliphatic-aromatic copolyester composition can be used as agricultural mulching.
The present invention compared with prior art, has following beneficial effect:
1) in Biodegradable aliphatic-aromatic copolyester composition of the present invention due to add specific proportioning containing alkyl/alkyloxy side chain fatty group dibasic acid unit, the yield strength of the film made is improved, be conducive to the puncture resistance improving agricultural mulching tolerant crops and weeds, reduce the probability that holes phenomenon occurs;
2) the tear-resistant intensity of film made of Biodegradable aliphatic-aromatic copolyester composition of the present invention and the mark that falls impact damaged quality and are improved, and are conducive to preventing film from occurring holes in use procedure;
3) OTR oxygen transmission rate of Biodegradable aliphatic-aromatic copolyester composition of the present invention improves, and water vapor transmission rate (WVTR) reduces, and has better insulation, moisture-keeping function when the film made is used as agricultural mulching.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Now following explanation is done to embodiment and comparative example starting material used, but is not limited to these materials:
Pure terephthalic acid (PTA): premium grads, raises sub-petrochemical industry and produces;
Dimethyl terephthalate (DMT) (DMT): premium grads, Japanese Supreme Being people produces;
BDO (BDO): top grade product, Shanxi three-dimensional is produced;
Hexanodioic acid (AA): top grade product, Daqing petrochemical is produced;
Poly(lactic acid) (PLA): purchased from Natureworks;
Compatilizer is purchased to BASF, and the trade mark is ADR-4370, ADR-4300, ADR-4380, ADR-4368, ADR-4385 etc.;
Other raw material, if titanic acid ester, dodecenylsuccinic acid (T746), octenyl Succinic anhydried (ASA) are commercially available technical grade product;
Other synthesizes with reference to the method for " petrochemical complex " 1993,10, p675 ~ 678 containing alkyl/alkyloxy side chain aliphatic diacid.
preparation containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester A:
embodiment A 1
By dimethyl terephthalate (DMT) 8.73 Kg, BDO 9 Kg, drop in reactor, after the air in nitrogen replacement reactor, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 10 g, be warming up to 180 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches theoretical amount, add hexanodioic acid 7.96 Kg, dodecenylsuccinic acid 142 g, continue reaction to slipping out after water reaches theoretical amount, add isopropyl titanate 10g, be warming up to 230 ~ 250 DEG C gradually, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding.In reactor, be filled with high pure nitrogen, obtain containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester through tie rod, pelletizing after the mold pressing of melt per os is gone out.
embodiment A 2
Dimethyl terephthalate (DMT) 11.64Kg, BDO 9Kg, hexanodioic acid 5.40Kg, octenyl Succinic anhydried 630g are dropped in reactor, is warming up to 170 gradually
oc, adds tetrabutyl titanate 20g, after slipping out first alcohol and water and reaching theoretical amount, is warming up to 230 ~ 250 gradually
oc, about reacting kettle inner pressure is reduced to below 60Pa by 30min, and continuation reaction reaches set(ting)value to agitator motor power with this understanding; In reactor, be filled with high pure nitrogen, after the mold pressing of melt per os being gone out, obtain copolyesters base material A 20 through tie rod, pelletizing; After A20 is dried, react in twin screw extruder after mixing with 0.6% hexamethylene diisocyanate, obtain containing alkyl group side chain aliphatic-aromatic copolyester through pelletizing.
The middle aromatic acid that feeds intake, aliphatic dibasic acid and the ratio containing alkyl/alkyloxy side chain aliphatic diacid is changed in the proportioning of table 1, according to the preparation method of above-described embodiment A1 or embodiment A 2, can prepare different from alkyl/alkyloxy side chain aliphatic-aromatic copolyester A.
Table 1 contains proportioning and the performance test results of alkyl/alkyloxy side chain aliphatic-aromatic copolyester A
Wherein, the preparation method of B4 is: prepare polybutylene terephthalate prepolymer first respectively, the prepolymer of poly adipate succinic acid ester prepolymer, poly-dodecenylsuccinic acid butyleneglycol, then adds hexamethylene diisocyanate and in twin screw extruder, carries out chain extending reaction obtain.
embodiment 1 ~ 9 and comparative example 1 ~ 4:
By the proportioning of table 2 using containing after alkyl/alkyloxy side chain aliphatic-aromatic copolyester A, poly(lactic acid) and the compatilizer as compatilizer mix in high mixer, add in twin screw extruder, in 170 ~ 220 with weighing balance
oc extruding pelletization obtains Biodegradable aliphatic-aromatic copolyester composition.
The proportioning of table 2 Biodegradable aliphatic-aromatic copolyester composition P
The performance test results of table 3 Biodegradable aliphatic-aromatic copolyester composition P
As can be seen from table 2 and table 3, due to add specific proportioning containing alkyl/alkyloxy side chain fatty group dibasic acid unit, the film yield strength that Biodegradable aliphatic-aromatic copolyester composition obtains is improved, be conducive to the puncture resistance improving agricultural mulching tolerant crops and weeds, reduce the probability that holes phenomenon occurs; And the tear-resistant intensity of film that obtains of said composition and the mark that falls impact damaged quality is improved, be conducive in use procedure, preventing film from occurring holes;
In addition, the OTR oxygen transmission rate of Biodegradable aliphatic-aromatic copolyester composition improves, and water vapor transmission rate (WVTR) reduces, and has better insulation, moisture-keeping function when the film made is used as agricultural mulching.
each performance test standard or method:
Limiting viscosity records with reference to GB/T1632.5-2008, and probe temperature is 25
oc, solvent is phenol/orthodichlorobenzene (60/40, wt/wt), copolyesters A concentration is 0.5g/100mL, records with Ubbelohde viscometer;
Copolyesters
1h NMR VARIAN company Mercury300 nuclear magnetic resonance spectrometer records, and solvent is CDCl
3/ CD
3cOOD(9/1);
The degree of randomness of copolyesters A by
1h NMR test result calculations obtains, testing method reference method of calculation reference " New Chemical Materials " 2012,40 volume, 12 phases, p85 ~ 93;
Melt mass flow rate records with reference to GB/T 3682-2000, and temperature is 190
oc, load is 2.16Kg;
Fusing point records with reference to GB/T 19466.3-2004;
Film stretching performance records with reference to GB/T 1040.3-2006;
The tear-resistant intensity of film records with reference to GB/T 16578.2-2009;
Film shock resistance records with reference to GB/T 9639.1-2008;
Pellicular water vapor transmission rates records with reference to ASTM F 1249;
Thin-films Oxygen vapor permeability records with reference to ASTM D 3985.
Film thickness records with reference to GB/T 20220-2006.
Claims (10)
1. a Biodegradable aliphatic-aromatic copolyester composition, is characterized in that, by mass percentage, comprises following component:
A: containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester 69.95% ~ 89.95%;
B: poly(lactic acid) 10% ~ 30%;
C: compatilizer 0.05% ~ 3%;
Described A by mass percentage, comprises following component:
A1: aromatic polyester unit 44% ~ 60%;
A2: straight-chain aliphatic polyester unit 39% ~ 55%;
A3: containing alkyl/alkyloxy side chain fatty group dibasic acid unit 0.3% ~ 3%.
2. Biodegradable aliphatic-aromatic copolyester composition according to claim 1, is characterized in that, described A3 reacts obtained for containing alkyl/alkyloxy side chain aliphatic dibasic acid or ester and dihydroxy compound; Described have following structure containing alkyl/alkyloxy side chain aliphatic dibasic acid:
Wherein R
1for alkyl or alkoxyl group;
R
1during for alkyl, R
1for the alkyl of C4 ~ C12, the side chain of 2 can be no more than in R1 containing carbonatoms, R
1in containing 0 ~ 1 carbon-carbon double bond, carbon-carbon double bond can at R
1any position; N1 is the integer of 0 ~ 9, and n2 is the integer of 0 ~ 9, and 0≤n1+n2≤9;
R
1during for alkoxyl group, there is following structure:
Wherein R
3for the one in hydrogen atom, methyl or ethyl, a is the integer of 2 ~ 4, and b is the integer of 1 ~ 6, and 4≤a × b≤12.
3. Biodegradable aliphatic-aromatic copolyester composition according to claim 1, is characterized in that, described A1 is that aromatic acid or ester and dihydroxy compound react obtained; Described aromatic acid is selected from the one or more kinds of mixtures in terephthalic acid, m-phthalic acid, phthalic acid or its carboxylate.
4. Biodegradable aliphatic-aromatic copolyester composition according to claim 1, is characterized in that, described A2 is that straight-chain aliphatic diprotic acid or ester and dihydroxy compound react obtained; Described straight-chain aliphatic diprotic acid is selected from the Straight chain diatomic acid containing 3 ~ 10 carbon atoms, is preferably the one or more kinds of mixtures in propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid.
5. the Biodegradable aliphatic-aromatic copolyester composition according to any one of claim 2 ~ 4, it is characterized in that, described dihydroxy compound is selected from the alkyl diol of C2 ~ C6, be preferably ethylene glycol, 1, ammediol, 1, one or more kinds of mixtures in 4-butyleneglycol, 1,5-PD, 1,6-hexylene glycol.
6. Biodegradable aliphatic-aromatic copolyester composition according to claim 1, it is characterized in that, the described degree of randomness containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 0.8 ~ 1.2, described degree of randomness is obtained by 1H NMR test result calculations, testing method is with reference to method of calculation reference " New Chemical Materials " 2012,40 volumes, 12 phases, p85 ~ 93.
7. Biodegradable aliphatic-aromatic copolyester composition according to claim 1, it is characterized in that, the described limiting viscosity containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 1.2 ~ 1.4dL/g, and described limiting viscosity records with reference to GB/T1632.5-2008, and probe temperature is 25
oc, solvent is phenol/orthodichlorobenzene (60/40, wt/wt), and the concentration of copolyesters is 0.5g/100mL, records with Ubbelohde viscometer.
8. Biodegradable aliphatic-aromatic copolyester composition according to claim 1, it is characterized in that, the described melt mass flow rate containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 2 ~ 5g/10min, described melt mass flow rate records with reference to GB/T 3682-2000, and temperature is 190
oc, load is 2.16Kg.
9. Biodegradable aliphatic-aromatic copolyester composition according to claim 1, is characterized in that, the described fusing point containing alkyl/alkyloxy side chain aliphatic-aromatic copolyester is 115
oc ~ 150
oc; Described fusing point records with reference to GB/T 19466.3-2004.
10. the application of Biodegradable aliphatic-aromatic copolyester composition in agricultural mulching industry as described in any one of claim 1 ~ 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108260451A (en) * | 2018-01-18 | 2018-07-10 | 浙江大学 | It is a kind of can weeding Biodegradable mulch |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000056807A1 (en) * | 1999-03-23 | 2000-09-28 | Wolff Walsrode Ag | Biodegradable agricultural films |
| CN102344556A (en) * | 2011-08-08 | 2012-02-08 | 北京旭阳化工技术研究院有限公司 | Biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer |
| CN102492271A (en) * | 2011-12-02 | 2012-06-13 | 金发科技股份有限公司 | Full biodegradation plastic material and preparation method thereof |
| CN102516517A (en) * | 2011-12-13 | 2012-06-27 | 金发科技股份有限公司 | Method for preparing polyester-polyester blocked copolyester |
| CN102942770A (en) * | 2012-12-10 | 2013-02-27 | 中国热带农业科学院湛江实验站 | Completely-biodegradable agricultural mulching film |
| KR20140071747A (en) * | 2012-12-04 | 2014-06-12 | 주식회사 엘지화학 | Biodegradble resin composition |
-
2014
- 2014-12-01 CN CN201410711829.2A patent/CN104479318B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000056807A1 (en) * | 1999-03-23 | 2000-09-28 | Wolff Walsrode Ag | Biodegradable agricultural films |
| CN102344556A (en) * | 2011-08-08 | 2012-02-08 | 北京旭阳化工技术研究院有限公司 | Biodegradable branched aromatic polyester-aliphatic polyester multi-block polymer |
| CN102492271A (en) * | 2011-12-02 | 2012-06-13 | 金发科技股份有限公司 | Full biodegradation plastic material and preparation method thereof |
| CN102516517A (en) * | 2011-12-13 | 2012-06-27 | 金发科技股份有限公司 | Method for preparing polyester-polyester blocked copolyester |
| KR20140071747A (en) * | 2012-12-04 | 2014-06-12 | 주식회사 엘지화학 | Biodegradble resin composition |
| CN102942770A (en) * | 2012-12-10 | 2013-02-27 | 中国热带农业科学院湛江实验站 | Completely-biodegradable agricultural mulching film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108260451A (en) * | 2018-01-18 | 2018-07-10 | 浙江大学 | It is a kind of can weeding Biodegradable mulch |
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