AU2019100561A4 - Biodegradable polymer composition and application thereof - Google Patents
Biodegradable polymer composition and application thereof Download PDFInfo
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- AU2019100561A4 AU2019100561A4 AU2019100561A AU2019100561A AU2019100561A4 AU 2019100561 A4 AU2019100561 A4 AU 2019100561A4 AU 2019100561 A AU2019100561 A AU 2019100561A AU 2019100561 A AU2019100561 A AU 2019100561A AU 2019100561 A4 AU2019100561 A4 AU 2019100561A4
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 229920002988 biodegradable polymer Polymers 0.000 title description 5
- 239000004621 biodegradable polymer Substances 0.000 title description 5
- 229920002472 Starch Polymers 0.000 claims abstract description 41
- 239000008107 starch Substances 0.000 claims abstract description 41
- 235000019698 starch Nutrition 0.000 claims abstract description 41
- 229920000728 polyester Polymers 0.000 claims abstract description 31
- 229920001634 Copolyester Polymers 0.000 claims abstract description 28
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 21
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 14
- 238000006065 biodegradation reaction Methods 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- -1 butylene glycol ester Chemical class 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000002361 compost Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012766 organic filler Substances 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 239000004597 plastic additive Substances 0.000 claims description 3
- 229920000223 polyglycerol Polymers 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- WWXUGNUFCNYMFK-UHFFFAOYSA-N Acetyl citrate Chemical compound CC(=O)OC(=O)CC(O)(C(O)=O)CC(O)=O WWXUGNUFCNYMFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000010459 dolomite Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000002557 mineral fiber Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000002362 mulch Substances 0.000 claims description 2
- 239000010813 municipal solid waste Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229920001896 polybutyrate Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims 1
- 239000003365 glass fiber Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 238000009264 composting Methods 0.000 abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- COHYTHOBJLSHDF-UHFFFAOYSA-N Indigo Chemical compound N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000013871 bee wax Nutrition 0.000 description 2
- 239000012166 beeswax Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000010806 kitchen waste Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 101100243951 Caenorhabditis elegans pie-1 gene Proteins 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a biodegradable polyester composition characterized by comprising, by weight: i) 58 to 80 parts by weight of an aliphatic-aromatic copolyester; ii) 20 to 32 parts by weight of starch; iii) 0 to 10 parts by weight of processing aid. The present invention has discovered by accident that an aliphatic-aromatic copolyester having an aromatic carboxylic acid as a total amount of dicarboxylic acid of 44% to 48% by mole is used as a matrix resin. The aliphatic-aromatic copolyester crystal has a peak width D of 5 ° C to 16 ° C, and a starch having a particle diameter D (50) of 2 im to 12 im as another phase, and a specific amount of processing aid is added, and the prepared polyester composition has excellent properties. The polyester composition has excellent transverse and longitudinal tearing strength, and the polyester composition meets industrial composting, the biodegradation rate is over 90% during the 12-week degradation test.
Description
Biodegradable polymer composition and application thereof
Technical Field
The invention belongs to the technical field of polymer material modification, and in particular relates to a biodegradable polymer composition and application thereof.
Background Technique
Biodegradable polyester is a kind of polymer material based on biological resources. Compared with petroleum-based polymers based on petrochemical resources, biodegradable polyesters can occur in biological or biochemical processes or in biological environments. Degradation is one of the most active and market-based degradation materials in biodegradable plastics research.
At present, a polyester composition based on an aliphatic polyester or an aliphatic-aromatic copolyester is widely used in the fields of shopping bags, kitchen waste bags, and the like. The longitudinal and transverse tear properties of the film are important indicators for evaluating the performance of the prepared shopping bags, kitchen waste bags and other products. One drawback of the currently available starch-based biodegradable bags on the market, as described in Chinese patent CN 101522797 B, is the lack of uniformity of mechanical properties, particularly in the transverse and longitudinal directions. In the case of a film prepared from a starch-based biodegradable polyester composition having a thickness of from 18 pm to 20 pm, the film is still too compliant or too brittle to withstand a certain ultimate weight. These performance limitations are particularly pronounced under low humidity conditions due to the absence of moisture in the composition.
Chinese patent CN 101522797 B uses a starch having an average size of less than 0.3 pm as a dispersed phase, and a rigid and brittle polymer having a modulus of more than 1000 MPa as an additional dispersed phase; at the same time, by reducing the composition in this manner Processing in an extruder or other machine of temperature and shear conditions yields a dispersed phase of a small particle size starch dispersed phase and a typical layered structure of a rigid and brittle polymer. Although the above method improves the uniformity of the longitudinal and transverse tearing properties of the material well, the following problems exist: the nano starch is used as the dispersed phase, and on the one hand, the agglomeration is easy due to the small starch particles, and in order to solve the dimensional stability problem, it is necessary to specify The processing equipment and processing technology are not universal; on the other hand, nano starch is more expensive than ordinary size starch, resulting in low cost performance.
Chinese patent CN 102639594 B uses an aliphatic-aromatic copolyester based on an aromatic acid content of 48 to 70 mol% of the total molar content of the dicarboxylic acid, and a starch having an average size of 1 pm as a dispersed phase. The mechanical properties of the polyester composition are somewhat improved.
Chinese patent CN 102597105 B reports that currently commercially available polyesters generally have an amount of aromatic carboxylic acid of less than 48 mole %, because above this threshold, the percentage of biodegradation of such polyesters is significantly reduced in industrial composting or Under the conditions of family composting, it is difficult to effectively degrade.
Muller et al. (Angew. Chem., Int. Ed (1999), 38, 1438-1441) reported polybutylene succinate-co-benzoic acid with a mole fraction of terephthalic acid of 42%. The formate type
2019100561 27 May 2019 copolymer was fully biodegraded in the compost for 12 weeks, while the product with a 51% terephthalate mole fraction had a percent biodegradation of less than 40%.
Chinese patent CN02804139.9 reports that in order to comply with the biodegradable nature of the CEN 13432 method, for biodegradable aliphatic-aromatic polymers, the amount of terephthalic acid contained (based on the moles of total acid) must not exceed 55%, preferably no more than 50%.
The present invention has discovered by accident that an aliphatic-aromatic copolyester having an aromatic carboxylic acid as a total amount of dicarboxylic acid of 44% by mole to 48% by mole is used as a matrix resin, and the aliphatic-aromatic copolymerization is carried out. The ester crystal has a peak width D of 5 ° C to 16 ° C, and a starch having a particle diameter D (50) of 2 pm to 12 pm as another phase, and a specific content of the processing aid is added, and the prepared polyester composition has excellent properties. The transverse longitudinal tear strength, and the polyester composition meets industrial composting, the biodegradation rate is over 90% during the 12-week degradation test.
Summary of The Invention
In order to overcome the deficiencies or deficiencies of the prior art, it is a primary object of the present invention to provide a biodegradable polyester composition having excellent transverse and longitudinal tear strength, and the polyester composition To meet industrial compost, the biodegradation rate reached over 90% during the 12-week degradation test.
The invention is achieved by the following technical solutions:
A biodegradable polyester composition, by weight, comprising the following components:
i) 58 to 80 parts by weight of an aliphatic-aromatic copolyester;
Ii) 20 to 32 parts by weight of starch;
lii) 0 to 10 parts by weight of processing aid.
Preferably, the biodegradable polyester composition, by weight, comprises the following components:
i) 62 to 80 parts by weight of an aliphatic-aromatic copolyester;
Ii) 20 to 30 parts by weight of starch;
lii) 0 to 8 parts by weight of processing aid.
Wherein, in the component i), in the aliphatic-aromatic copolyester, the total amount of the aromatic carboxylic acid in the diacid is from 44% by mole to 48% by mole, and the aliphatic-aromatic copolyester The crystallization peak width D is 5 ° C to 16 ° C, preferably 8 ° C to 12 ° C.
The invention selects an aliphatic-aromatic copolyester having an aromatic carboxylic acid content of 44 to 48 mol% of the total molar content of the diacid as a matrix resin, and the polyester is not caused by the low content of terephthalic acid. The mechanical properties of the composition are deteriorated, and the biodegradability of the polyester composition is not greatly affected by the high content of terephthalic acid. In addition, by selecting the alicyclic peak width D of the aliphatic-aromatic copolyester from 5 ° C to 16 ° C, the prepared polyester composition has better crystallization properties, and at the same time, the present invention requires mechanical properties of materials according to different application fields. The amount of aliphatic-aromatic copolyester added was screened.
In component i) according to the invention, the aliphatic-aromatic copolyester is selected from
2019100561 27 May 2019 the group consisting of polybutylene terephthalate PBAT, polybutylene terephthalate, butylene terephthalate PBSeT One of them or a mixture thereof.
The invention adopts starch as component ii) of the polyester composition, and considers starch as a natural source polymer, which has the advantages of low cost and low toxicity, and is blended with starch and aliphatic-aromatic copolyester, which can not only The mechanical properties of the polyester composition are enhanced and the cost of the composition can be greatly reduced; at the same time, the starch as a natural source polymer helps to improve the biodegradability of the polyester composition.
In the component ii) according to the present invention, the starch has a particle diameter D (50) of 2 pm to 12 pm, preferably 3 pm to 11 pm, more preferably 5 pm to 10 pm; the larger the particle size of the starch, the less likely to agglomerate. Conducive to the dispersion in the polyester composition; but when the starch particle size D (50) exceeds 12 pm, since the starch granules are too large, affecting the surface characteristics (roughness) of the film product, the polyester composition needs to be more processed during processing. High processing temperatures to plasticize the material, while too high processing temperatures can lead to degradation of the aliphatic-aromatic copolyester, which affects the properties of the material; at the same time, too high processing temperatures can lead to excessive Energy consumption and processing costs.
The processing aid is selected from the group consisting of water, glycerin, polyglycerol, epoxidized soybean oil, citric acid ester, acetyl citrate, ethylene glycol, polyethylene glycol, or a mixture of several, preferably water, glycerin Or a mixture of one or more of polyglycerols.
The biodegradable polymer composition further comprises, by weight, the 0 to 20 parts by weight of the organic or inorganic filler.
The organic filler is selected from the group consisting of natural fiber, straw, wood powder, or a mixture thereof; the inorganic filler is selected from the group consisting of talc, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, conductive carbon black a mixture of one or more of calcium chloride, iron oxide, dolomite, silica, wollastonite, titanium dioxide, silicate, mica, fiberglass or mineral fibers.
According to actual performance requirements, a biodegradable polymer composition according to the present invention, in parts by weight, further comprises 0 to 4 parts by weight of other auxiliary agents: a release agent, a surfactant, and a wax. , antistatic agents, dyes, anti-UV additives or other plastic additives.
The release agent is: silicone masterbatch, montan wax, erucamide, oleic acid amide;
The surfactant is one or a mixture of two or more of polysorbate, palmitate or laurate;
The wax is one or a mixture of two or more of stearic acid amide, behenic acid amide, beeswax or beeswax ester;
The antistatic agent is a permanent antistatic agent, and specifically one of PELESTAT-230, PELESTAT-6500, SUNNICO ASA-2500 or a mixture of two or more;
The dye is one of carbon black, black species, titanium white powder, zinc sulfide, indigo blue, fluorescent orange or a mixture of two or more.
Anti-UV additives include UV absorbers and UV stabilizers;
The UV absorber is one or more of UV-944, UV-234, UV531, UV326;
The UV stabilizer is one or more of UV-123, UV-3896, UV-328;
The other plastic additive may be a nucleating agent, an antifogging agent, a lubricant (e.g.,
2019100561 27 May 2019 calcium stearate), a primary antioxidant, a secondary antioxidant, a plasticizer, or the like.
The 12 am + 1 μ m film prepared by the polyester composition of the present invention has an excellent transverse and longitudinal tear strength, longitudinal tear strength 1000 mN, preferably 1100 mN, more preferably tested according to the standard ASTM D-882/88. 1200 mN; transverse tear strength 2400 mN; preferably 2600 mN, more preferably 2800 mN;
The 12 pm ± 1 pm film prepared by the polyester composition of the present invention was tested according to the standard ISO 16929 (2013), and the biodegradation rate after 12 weeks was more than 90%.
The polyester compositions of the present invention are biodegradable in industrial compost according to standard EN 13432.
The invention also discloses the above biodegradable polyester composition in preparing a shopping bag, a compost bag, a mulch film, a protective cover film, a silo film, a film tape, a fabric, a non-woven fabric, a textile, a fishing net, a load-bearing bag or a garbage bag. Application in . Compared with the prior art, the invention has the following beneficial effects:
The present invention has discovered by accident that an aliphatic-aromatic copolyester having an aromatic carboxylic acid as a total amount of dicarboxylic acid of 44% by mole to 48% by mole is used as a matrix resin, and the aliphatic-aromatic copolymerization is carried out. The ester crystal has a peak width D of 5 ° C to 16 ° C, and a starch having a particle diameter D (50) of 2 pm to 12 pm as another phase, and a specific amount of processing aid is added, and the prepared polyester composition has excellent properties. The transverse longitudinal tear strength, and the polyester composition meets industrial composting, the biodegradation rate is over 90% during the 12-week degradation test.
Detailed Description of preferred Embodiment
The invention is further illustrated by the following detailed description of the preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.
The materials used in the examples and comparative examples of the present invention are as follows:
The component i) is selected from PBAT-1: the aromatic carboxylic acid accounts for 46 mol% of the total amount of the diacid, and the crystallization peak width D is 11 ° C;
PBAT-2: aromatic carboxylic acid accounts for 44 mol% of the total amount of diacid, and the crystallization peak width D is 8 ° C;
PBAT-3: aromatic carboxylic acid accounts for 48 mol% of the total amount of diacid, and the crystallization peak width D is 15 ° C;
PBAT-4: aromatic carboxylic acid accounts for 38 mol% of the total amount of diacid, and the crystallization peak width D is 11 ° C;
PBAT-5: aromatic carboxylic acid accounts for 58 mol% of the total amount of diacid, and the crystallization peak width D is 11 ° C;
PBAT-6: aromatic carboxylic acid accounts for 46 mol% of the total amount of diacid, and the crystallization peak width D is 4 ° C;
PBAT-7: aromatic carboxylic acid accounts for 46 mol% of the total amount of diacid, and the crystallization peak width D is 25 ° C;
2019100561 27 May 2019
PBAT-8: aromatic carboxylic acid accounts for 58 mol% of the total amount of diacid, and the crystallization peak width D is 25 ° C;
PBSeT: aromatic carboxylic acid accounts for 46 mol% of the total amount of diacid, and the crystallization peak width D is 11 ° C;
Component ii) selected starch-1, particle size D (50) 4 pm;
Starch-2, particle size D (50) 8 pm;
Starch-3, particle size D (50) 12 pm;
Starch-4, particle size D (50) 16 pm;
Starch-5, particle size D (50) 1 pm;
Component iii) processing aid: water, glycerin;
Filler selection: talcum powder, calcium carbonate;
Other additives: citric acid ester for plasticizer; palmitate for surfactant;
All other components are derived from commercially available products.
Evaluation methods for each performance indicator:
Test method for crystallization peak width D of aliphatic-aromatic copolyesters:
The specific test method is as follows by differential scanning calorimeter (DSC): a high-purity standard (indium) calibration differential scanning calorimeter is used to place 5-10 mg of aliphatic-aromatic copolyester into aluminum crucible. Medium, heated to 220 ° C at a rate of 10 ° C / min (first scan), constant temperature 5 min, then cooled to -30 ° C at 10 ° C / min, from the first scan of the differential thermal analysis graph cooling curve A crystallization peak of an aliphatic-aromatic copolyester is obtained. The starting end and the ending end of the crystallization peak are taken as a tangential line, and the temperature difference between the ends of the two tangential lines is the crystallization peak width.
Test method for starch particle size D (50):
The particle size D (50) test method for the starch of the present invention is determined by the method of GB/T 19077.1 Particle Size Analysis Laser Diffraction Method.
Longitudinal and transverse tear strength of the polyester composition: The polyester composition was prepared into a 12 pm ± 1 pm film, which was tested according to standard ASTM D-882/88;
Biodegradation rate after 12 weeks of the polyester composition: The polyester composition was prepared into a film of 12 pm ± 1 pm and tested according to the standard ISO 16929 (2013).
Examples 1-11 and Comparative Examples 1-4:
According to the weight ratio of Table 1, the aliphatic-aromatic copolyester, starch, processing aid, filler, other additives are mixed and put into a single screw extruder, and extruded at 140 ° C 240 ° C The granules are obtained to obtain a biodegradable polyester composition. The performance test data of the obtained polyester composition are shown in Table 1.
Table 1 Distribution ratio and performance test results (parts by weight) of each group in the examples and comparative examples
| Components | Exam pie 1 | Examp le 2 | Exam pie 3 | Exam pie 4 | Exam pie 5 | Exam pie 6 | Exam pie 7 | Exam pie 8 | Exam pie 9 | Exam pie 10 | Exam pie 11 | |
| aliphati | PBAT-1 | 70 | ||||||||||
| PBAT-2 | 70 | 70 |
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| c-arom atic copoly ester | PBAT-3 | |||||||||||
| PBAT-4 | 70 | |||||||||||
| PBAT-5 | 70 | |||||||||||
| PBAT-6 | 70 | |||||||||||
| PBAT-7 | 70 | |||||||||||
| PBAT-8 | 70 | 70 | 70 | |||||||||
| PBSeT | 70 | |||||||||||
| Starch | Starch -1 | 25 | ||||||||||
| Starch -2 | 25 | |||||||||||
| Starch -3 | 25 | 25 | 25 | 25 | 25 | 25 | 25 | |||||
| Starch -4 | 25 | |||||||||||
| Starch -5 | 25 | |||||||||||
| proces sing aid | water | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| glycerin | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | |
| Filler | talcum powder | 2 | 2 | 2 | 2 | 2 | 2 | 2 | ||||
| calcium carbonate | 2 | 2 | 2 | 2 | ||||||||
| Other additiv es | citric acid ester for plasticizer | 0.1 | 0.1 | 0.1 | 0.1 | |||||||
| palmitate for surfactant | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |||||
| Longitudinal tear strength | 1098 | 1273 | 1156 | 1063 | 989 | 963 | 952 | 921 | 889 | 867 | 844 | |
| Transverse tear strength | 2793 | 3123 | 2901 | 2682 | 2374 | 2263 | 2193 | 2223 | 2102 | 2011 | 2000 | |
| Biodegradation rate after 12 weeks (%) | 96.7 | 98.3 | 97.1 | 96.2 | 95.3 | 94.2 | 93.6 | 93.1 | 92.4 | 91.2 | 91.1 |
Continued Table 1
| Components | Comparative Examplel | Comparative Example 2 | Comparativ e Example 3 | Comparative Example 4 | |
| aliphatic-aro matic copolyester | PBAT-1 | 50 | 90 | 70 | 70 |
| PBAT-2 | |||||
| PBAT-3 | |||||
| PBAT-4 | |||||
| PBAT-5 | |||||
| PBAT-6 | |||||
| PBAT-7 | |||||
| PBAT-8 | |||||
| PBSeT |
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| Starch | Starch -1 | 25 | 25 | 10 | 40 |
| Starch -2 | |||||
| Starch -3 | |||||
| Starch -4 | |||||
| Starch -5 | |||||
| processing aid | water | 3 | 3 | 3 | 3 |
| glycerin | 3 | 3 | 3 | 3 | |
| Filler | talcum powder | 2 | 2 | ||
| calcium carbonate | 2 | 2 | |||
| Other additives | citric acid ester for plasticizer | 0.1 | 0.1 | ||
| palmitate for surfactant | 0.1 | 0.1 | |||
| Longitudinal tear strength | 782 | 801 | 712 | 698 | |
| Transverse tear strength | 1912 | 1908 | 1954 | 1783 | |
| Biodegradation rate after 12 weeks (%) | 90.7 | 90.4 | 90.1 | 90.3 |
2019100561 27 May 2019
Claims (11)
1. A biodegradable polyester composition characterized by comprising the following components by weight:
i) 58 to 80 parts by weight of an aliphatic-aromatic copolyester;
li) 20 to 32 parts by weight of starch;
lii) 0 to 10 parts by weight of processing aid.
2. The biodegradable polyester composition according to claim 1, characterized in that, by weight, the following components are included:
i) 62 to 80 parts by weight of an aliphatic-aromatic copolyester;
li) 20 to 30 parts by weight of starch;
lii) 0 to 8 parts by weight of processing aid.
3. The biodegradable polyester composition according to claim 1 or 2, wherein in the component i), among the aliphatic-aromatic copolyesters, the total amount of the aromatic carboxylic acid accounting for diacids is from 44% by mole to 48% by mole, and the aliphatic-aromatic copolyester has a crystallization peak width D of from 5 °C to 16 °C, preferably from 8 ° C to 12 ° C.
4. The biodegradable polyester composition according to claim 1 or 2, wherein in the component ii), the starch has a particle diameter D (50) of from 2 pm to 12 pm, preferably from 3 pm to 11 pm, more preferably, it is 5 pm -10 pm.
5. The biodegradable polyester composition according to claim 1 or 2, wherein the polyester composition has a longitudinal tear strength of 12 pm ± 1 pm film tested according to standard ASTM D-882/88, 2s 1000 mN; preferably 2s 1100 mN, more preferably =2=1200 mN; the 12 p m ± 1 p m film prepared from the polyester composition has a transverse tear strength 2=2400 mN according to the standard ASTM D-882/88; preferably 2=2600 mN, More preferably 2=2800 mN; the 12 ±1 pm film prepared from the polyester composition has a biodegradation rate of greater than 90% after 12 weeks according to the standard ISO 16929 (2013).
6. The biodegradable polyester composition according to claim 1 or 2, wherein, in component i), the aliphatic-aromatic copolyester is selected from the group consisting of polyadipate terephthalic acid, butylene glycol ester PBAT, polybutylene terephthalate terephthalate PBSeT or a mixture thereof.
7. The biodegradable polyester composition according to any one of claims 1 to 2, wherein the processing aid is selected from the group consisting of water, glycerin, polyglycerin, epoxidized soybean oil, citric acid ester, acetyl citrate, ethylene glycol, polyethylene glycol, preferably a mixture of one or more of water, glycerin or polyglycerol.
8. The biodegradable polyester composition according to any one of claims 1 to 2, wherein the biodegradable polyester composition further comprises 0 to 20 parts of organic or inorganic filler by weight.
9. The biodegradable polyester composition according to claim 8, wherein the organic filler is selected from the group consisting of one or a combination of natural fibers, straw, and wood flour; the filler is selected from the group consisting of talc, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, conductive carbon black, calcium chloride, iron oxide, dolomite, silica, wollastonite, titanium dioxide, silicate, mica , a mixture of one or more of glass fibers or mineral fibers.
2019100561 27 May 2019
10. The biodegradable polyester composition according to any one of claims 1 to 2, wherein the polymer composition further comprises 0 to 4 parts by weight of the following other parts by weight Additives: release agents, surfactants, waxes, antistatic agents, dyes, anti-UV additives or other plastic additives.
11. The biodegradable polyester composition according to any one of claims 1 to 10 in the preparation of shopping bags, compost bags, mulch films, protective cover films, silo films, film strips, fabrics, non-woven fabrics, textiles , fishing nets, load-bearing bags or garbage bags.
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