CN116904004B - Degradable starch crosslinked particle modified PBAT polyester master batch and preparation process thereof - Google Patents
Degradable starch crosslinked particle modified PBAT polyester master batch and preparation process thereof Download PDFInfo
- Publication number
- CN116904004B CN116904004B CN202311177696.0A CN202311177696A CN116904004B CN 116904004 B CN116904004 B CN 116904004B CN 202311177696 A CN202311177696 A CN 202311177696A CN 116904004 B CN116904004 B CN 116904004B
- Authority
- CN
- China
- Prior art keywords
- starch
- master batch
- weight
- parts
- polylactic acid
- 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.)
- Active
Links
- 239000002245 particle Substances 0.000 title claims abstract description 77
- 229920002472 Starch Polymers 0.000 title claims abstract description 57
- 239000008107 starch Substances 0.000 title claims abstract description 57
- 235000019698 starch Nutrition 0.000 title claims abstract description 57
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 49
- 229920000728 polyester Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229920001896 polybutyrate Polymers 0.000 title claims abstract 14
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 50
- 239000004626 polylactic acid Substances 0.000 claims abstract description 50
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 69
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 31
- 150000003949 imides Chemical class 0.000 claims description 27
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims description 23
- 229940049953 phenylacetate Drugs 0.000 claims description 23
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- JQYSLXZRCMVWSR-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1CCCCC(=O)OCCCCO1 JQYSLXZRCMVWSR-UHFFFAOYSA-N 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 10
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 9
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 9
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- JAUFWTSSYRTLLB-UHFFFAOYSA-N (2-phenylacetyl) 2-phenylacetate Chemical compound C=1C=CC=CC=1CC(=O)OC(=O)CC1=CC=CC=C1 JAUFWTSSYRTLLB-UHFFFAOYSA-N 0.000 claims description 8
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 claims description 8
- JDTUPLBMGDDPJS-UHFFFAOYSA-N 2-methoxy-2-phenylethanol Chemical compound COC(CO)C1=CC=CC=C1 JDTUPLBMGDDPJS-UHFFFAOYSA-N 0.000 claims description 8
- PXHIYFMTRHEUHZ-UHFFFAOYSA-N 5-hydroxy-2-benzofuran-1,3-dione Chemical compound OC1=CC=C2C(=O)OC(=O)C2=C1 PXHIYFMTRHEUHZ-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- -1 phthalic anhydride phenyl acetate Chemical compound 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- MZQZXSHFWDHNOW-UHFFFAOYSA-N 1-phenylpropane-1,2-diol Chemical compound CC(O)C(O)C1=CC=CC=C1 MZQZXSHFWDHNOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000004642 Polyimide Substances 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 229920001721 polyimide Polymers 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 229960004063 propylene glycol Drugs 0.000 description 21
- 235000013772 propylene glycol Nutrition 0.000 description 21
- 239000000243 solution Substances 0.000 description 16
- 239000000155 melt Substances 0.000 description 6
- 238000006065 biodegradation reaction Methods 0.000 description 4
- 229920000881 Modified starch Polymers 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000005690 diesters Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006150 hyperbranched polyester Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- VCBXDDWTBDJIQH-UHFFFAOYSA-N n-(4,5-dihydro-1,3-thiazol-2-yl)-3-(1,3-dioxoisoindol-2-yl)benzamide Chemical compound C=1C=CC(N2C(C3=CC=CC=C3C2=O)=O)=CC=1C(=O)NC1=NCCS1 VCBXDDWTBDJIQH-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
- C08J2403/08—Ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention relates to the technical field of degradable materials, and discloses a degradable starch crosslinked particle modified PBAT polyester master batch and a preparation process thereof, wherein the prepared starch-polyimide-polylactic acid crosslinked particle can be melt-blended with PBAT, has good compatibility and dispersibility in PBAT, overcomes the problem that starch is difficult to melt and process, has a stable three-dimensional crosslinked network and a polyimide structure with high temperature resistance, is favorable for improving the thermal decomposition stability of the PBAT master batch, and shows better heat resistance. The starch-polyimide-polylactic acid cross-linked particles contain biodegradable starch and polylactic acid structures, and the polyimide structures also contain hydrolysable and degradable double ester bonds, so that the cross-linked particles have strong biological degradation activity, and the biological degradation performance of the PBAT master batch is improved.
Description
Technical Field
The invention relates to the technical field of degradable materials, in particular to a degradable starch crosslinked particle modified PBAT polyester master batch and a preparation process thereof.
Background
Plastic is one of three macromolecular materials, and has important application in various fields of national economy, but with the excessive use of traditional plastics, the environmental problems such as white pollution are increasingly serious. In order to cope with the environmental pollution problem in recent years, environment-friendly degradable materials such as polylactic acid, poly (butylene adipate-terephthalate), starch, cellulose and the like are greatly developed in various countries of the world, wherein the poly (butylene adipate-terephthalate) (PBAT) has good ductility, tensile property and impact property, is widely applied biodegradable plastic, improves the heat resistance and the biodegradability of the PBAT polyester, and has important significance in expanding the practical application of the PBAT.
Starch is a cheap, readily available, nontoxic, pollution-free and biodegradable green resource, and the combination of the starch and the PBAT can improve the mechanical property, the biodegradability and the like of the PBAT, but the starch and the intermolecular hydrogen bond of the starch have stronger acting force and poorer fluidity, are difficult to process and shape, and can be blended with a high polymer material only by modifying the starch or adding other compatilizers; the modified starch/PBAT composite material compatibility and performance research respectively takes hydroxyl-terminated hyperbranched polyester and trifluoroacetic anhydride as modifiers to modify corn starch, and then the modified starch and PBAT are melt blended to prepare the composite material, so that the dispersibility and compatibility of the starch in PBAT are improved, the tensile strength and tensile modulus of the PBAT are improved, but the PBAT material has the problems of lower thermal decomposition temperature and low heat resistance. The invention prepares starch-polyimide-polylactic acid cross-linked particles, and the cross-linked particles are melt-blended with PBAT, so as to improve the heat resistance and the biodegradability of the PBAT.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a starch-polyimide-polylactic acid cross-linked particle, which solves the problem of low heat resistance and biodegradability of PBAT polyester master batch.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: 70-95 parts by weight of poly (butylene adipate-terephthalate) and 5-30 parts by weight of starch-polyimide-polylactic acid cross-linked particles are added into a torque rheometer, and the mixture is subjected to melt blending and discharging to prepare the degradable starch cross-linked particle modified PBAT polyester master batch.
Further, the melting temperature in the torque rheometer is 130-150 ℃, the blending time is 10-15 min, and the rotating speed is 50-80 r/min.
Further, the preparation process of the starch-polyimide-polylactic acid cross-linked particles comprises the following steps: adding 100 parts by weight of carboxymethyl starch, 15-80 parts by weight of bis (propylene glycol imide phenyl acetate), 50-200 parts by weight of polylactic acid, 25-100 parts by weight of 1-hydroxybenzotriazole and 32-150 parts by weight of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into dimethyl sulfoxide, carrying out suction filtration after esterification crosslinking reaction, and washing sequentially with deionized water, ethanol and methylene dichloride to obtain the starch-polyimide-polylactic acid crosslinked particles.
Further, the temperature of the esterification and crosslinking reaction is between 35 and 60 ℃, and the reaction time is between 12 and 36 and h.
Further, the preparation process of the bis (propylene glycol imide phenyl acetate) comprises the following steps:
s1, adding 210-280 parts by weight of 4-hydroxyphthalic anhydride, 100 parts by weight of succinyl chloride and 120-160 parts by weight of pyridine into a solvent under ice water bath, reacting, removing the solvent by rotary evaporation, and washing with diethyl ether to obtain a bis (phthalic anhydride phenyl acetate) intermediate.
S2, adding 100 parts by weight of bis (phenyl acetic anhydride) intermediate and 45-65 parts by weight of 2-amino-1, 3-propanediol into glacial acetic acid solution, reacting, cooling, precipitating, filtering, washing with saturated sodium carbonate solution, separating and purifying the crude product by silica gel column chromatography, wherein the eluent is ethyl acetate and petroleum ether, and the volume ratio is 1:9, thus obtaining the bis (phenyl propylene glycol imide acetate).
Further, the solvent in S1 is selected from one of ethyl acetate, acetonitrile, dichloromethane or chloroform.
Further, the reaction temperature in S1 is between 20 and 35 ℃ and the reaction time is between 3 and 10 h.
Further, the reaction temperature in S2 is between 110 and 125 ℃ and the reaction time is between 10 and 20 and h.
Compared with the prior art, the invention has the technical effects that:
the invention utilizes 4-hydroxy phthalic anhydride and succinyl chloride to carry out esterification reaction, then carries out imide cyclization reaction with 2-amino-1, 3-propanediol to prepare bis (propylene glycol imide phenyl acetate) with diester groups, and then carries out esterification crosslinking reaction on the hydroxy groups of the bis (propylene glycol imide phenyl acetate), carboxyl groups of carboxymethyl starch and hydroxyl end groups and carboxyl groups of polylactic acid in a reaction system of 1-hydroxybenzotriazole and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to form starch-polyimide-polylactic acid crosslinked particles. The crosslinked and modified starch particles can be melt-blended with PBAT, have good compatibility and dispersibility in PBAT, overcome the problem that starch is difficult to melt and process, have stable three-dimensional crosslinked network and contain polyimide structure of high temperature resistance in the starch-polyimide-polylactic acid crosslinked particles, are favorable for improving the thermal decomposition stability of PBAT master batch, and show better heat resistance. The starch-polyimide-polylactic acid cross-linked particles contain biodegradable starch and polylactic acid structures, and the polyimide structures also contain hydrolysable and degradable double ester bonds, so that the cross-linked particles have strong biological degradation activity, and the biological degradation performance of the PBAT master batch is improved.
Drawings
FIG. 1 is a scheme for the preparation of bis (phenylpropylene glycol imide acetate).
FIG. 2 is a graph of bis (propyleneglycol imide phenyl acetate) in CDCl 3 Nuclear magnetic hydrogen spectrogram of (a).
FIG. 3 is a graph of bis (propyleneglycol imide phenyl acetate) in CDCl 3 Nuclear magnetic carbon spectrogram of (a).
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
PBAT poly (butylene adipate-terephthalate): brand C1200; injection molding grade.
Polylactic acid: brand PLA-122139; injection molding grade.
Carboxymethyl starch: cargo number 20200510. The content of the effective substances is 99 percent.
Example 1
The preparation process of the bis (propylene glycol imide phenyl acetate) comprises the following steps:
adding 42 g of 4-hydroxyphthalic anhydride, 15 g of succinyl chloride and 24 g of pyridine into 500 mL ethyl acetate solvent under ice water bath, removing the ice water bath, controlling the reaction temperature to 20 ℃, controlling the reaction time to h, removing the solvent by rotary evaporation, and washing with diethyl ether to obtain the bis (phenyl acetic anhydride acetate) intermediate.
Adding 40g bis (phenyl acetic anhydride) acetate intermediate and 21 g 2-amino-1, 3-propanediol into 600 mL glacial acetic acid solution, reacting at 120 ℃ for 20 h, cooling, precipitating, filtering, washing with saturated sodium carbonate solution, separating and purifying the crude product by silica gel column chromatography, eluting with ethyl acetate and petroleum ether at a volume ratio of 1:9, and obtaining the bis (propylene glycol imide phenyl acetate).
The preparation process of the starch-polyimide-polylactic acid cross-linked particles comprises the following steps: adding 60g carboxymethyl starch, 9 g bis (propylene glycol imide phenyl acetate), 30 g polylactic acid, 15 g 1-hydroxybenzotriazole and 19.2 g 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into 1L dimethyl sulfoxide, carrying out esterification crosslinking reaction at 60 ℃ for 12 h, carrying out suction filtration, and washing sequentially with deionized water, ethanol and dichloromethane to obtain the starch-polyimide-polylactic acid crosslinked particles.
The preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: the preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: adding 950g of poly (butylene adipate-terephthalate) and 50g of starch-polyimide-polylactic acid cross-linked particles into a torque rheometer, carrying out melt blending, wherein the melt temperature is 140 ℃, the blending time is 10 min, the rotating speed is 60 r/min, and discharging to obtain the degradable starch cross-linked particle modified PBAT polyester master batch.
Example 2
The preparation process of the bis (propylene glycol imide phenyl acetate) comprises the following steps:
63 g of 4-hydroxyphthalic anhydride, 30 g of succinyl chloride and 36 g of pyridine are added into 500 mL acetonitrile solvent under ice water bath, then the ice water bath is removed, the reaction temperature is controlled to be 35 ℃, the reaction time is controlled to be 5 h, the solvent is removed by rotary evaporation, and diethyl ether is used for washing, so as to obtain the bis (phenyl acetic anhydride acetate) intermediate.
Adding 20g bis (phenyl acetic anhydride) acetate intermediate and 11 g 2-amino-1, 3-propanediol into 200 mL glacial acetic acid solution, reacting at 125 ℃ for 10 h, cooling, precipitating, filtering, washing with saturated sodium carbonate solution, separating and purifying the crude product by silica gel column chromatography, eluting with ethyl acetate and petroleum ether at a volume ratio of 1:9, and obtaining the bis (propylene glycol imide phenyl acetate).
The preparation process of the starch-polyimide-polylactic acid cross-linked particles comprises the following steps: adding 30 g carboxymethyl starch, 24 g bis (propylene glycol imide phenyl acetate), 55 g polylactic acid, 30 g 1-hydroxybenzotriazole and 82 g 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into 1L dimethyl sulfoxide, carrying out esterification crosslinking reaction at 45 ℃ for 36 h, carrying out suction filtration, and washing sequentially with deionized water, ethanol and dichloromethane to obtain the starch-polyimide-polylactic acid crosslinked particles.
The preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: the preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: adding 900g of poly (butylene adipate-terephthalate) and 100g of starch-polyimide-polylactic acid cross-linked particles into a torque rheometer, carrying out melt blending, wherein the melt temperature is 150 ℃, the blending time is 10 min, the rotating speed is 50 r/min, and discharging to obtain the degradable starch cross-linked particle modified PBAT polyester master batch.
Example 3
The preparation process of the bis (propylene glycol imide phenyl acetate) comprises the following steps:
adding 72 g of 4-hydroxyphthalic anhydride, 30 g of succinyl chloride and 41 g of pyridine into 800 mL of chloroform solvent under ice water bath, removing the ice water bath, controlling the reaction temperature to 35 ℃, controlling the reaction time to 5 h, removing the solvent by rotary evaporation, and washing with diethyl ether to obtain the bis (phenyl acetic anhydride acetate) intermediate.
Adding 40g bis (phenyl acetic anhydride) acetate intermediate and 18 g 2-amino-1, 3-propanediol into 500 mL glacial acetic acid solution, reacting at 110 ℃ for 20 h, cooling, precipitating, filtering, washing with saturated sodium carbonate solution, separating and purifying the crude product by silica gel column chromatography, eluting with ethyl acetate and petroleum ether, and obtaining bis (propylene glycol imide phenyl acetate) with a volume ratio of 1:9.
The preparation process of the starch-polyimide-polylactic acid cross-linked particles comprises the following steps: adding 60g carboxymethyl starch, 48 g bis (propylene glycol imide phenyl acetate), 100g polylactic acid, 54 g 1-hydroxybenzotriazole and 72 g 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into 2L dimethyl sulfoxide, carrying out esterification crosslinking reaction at 60 ℃ for 12 h, carrying out suction filtration, and washing sequentially with deionized water, ethanol and dichloromethane to obtain the starch-polyimide-polylactic acid crosslinked particles.
The preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: the preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: adding 820g of poly (butylene adipate-terephthalate) and 180g of starch-polyimide-polylactic acid cross-linked particles in parts by weight into a torque rheometer, carrying out melt blending, wherein the melt temperature is 140 ℃, the blending time is 15 min, the rotating speed is 80 r/min, and discharging to obtain the degradable starch cross-linked particle modified PBAT polyester master batch.
Example 4
The preparation process of the bis (propylene glycol imide phenyl acetate) comprises the following steps:
adding 21 g of 4-hydroxyphthalic anhydride, 10 g of succinyl chloride and 12 g of pyridine into 400 mL of dichloromethane solvent under ice water bath, removing the ice water bath, controlling the reaction temperature to 20 ℃, controlling the reaction time to h, removing the solvent by rotary evaporation, and washing with diethyl ether to obtain the bis (phenyl acetic anhydride acetate) intermediate.
Adding 20g bis (phenyl acetic anhydride) acetate intermediate and 13 g 2-amino-1, 3-propanediol into 300 mL glacial acetic acid solution, reacting at 125 ℃ for 12 h, cooling, precipitating, filtering, washing with saturated sodium carbonate solution, separating and purifying the crude product by silica gel column chromatography, eluting with ethyl acetate and petroleum ether at a volume ratio of 1:9, and obtaining the bis (propylene glycol imide phenyl acetate).
The preparation process of the starch-polyimide-polylactic acid cross-linked particles comprises the following steps: adding 30 g carboxymethyl starch, 24 g bis (propylene glycol imide phenyl acetate), 60g polylactic acid, 30 g 1-hydroxybenzotriazole and 45 g 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into 1200 mL dimethyl sulfoxide, carrying out esterification crosslinking reaction at 45 ℃ for 24 h, carrying out suction filtration, and washing sequentially with deionized water, ethanol and dichloromethane to obtain the starch-polyimide-polylactic acid crosslinked particles.
The preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: the preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: and (3) adding 760g of poly (butylene adipate-terephthalate) and 240g of starch-polyimide-polylactic acid cross-linked particles in parts by weight into a torque rheometer, carrying out melt blending, wherein the melt temperature is 130 ℃, the blending time is 12 min, the rotating speed is 50 r/min, and discharging to obtain the degradable starch cross-linked particle modified PBAT polyester master batch.
Example 5
The preparation process of the bis (propylene glycol imide phenyl acetate) comprises the following steps:
63 g of 4-hydroxyphthalic anhydride, 30 g of succinyl chloride and 40g of pyridine are added into 800 mL ethyl acetate solvent under ice water bath, then the ice water bath is removed, the reaction temperature is controlled to be 25 ℃, the reaction time is 3 h, the solvent is removed by rotary evaporation, and diethyl ether is used for washing, so that the bis (phenyl acetic anhydride) intermediate is obtained.
Adding 40g bis (phenyl acetic anhydride) acetate intermediate and 24 g 2-amino-1, 3-propanediol into 800 mL glacial acetic acid solution, reacting at 125 ℃ for 10 h, cooling, precipitating, filtering, washing with saturated sodium carbonate solution, separating and purifying the crude product by silica gel column chromatography, eluting with ethyl acetate and petroleum ether at a volume ratio of 1:9, and obtaining the bis (propylene glycol imide phenyl acetate).
The preparation process of the starch-polyimide-polylactic acid cross-linked particles comprises the following steps: adding 60g carboxymethyl starch, 25 g bis (propylene glycol imide phenyl acetate), 65 g polylactic acid, 32 g 1-hydroxybenzotriazole and 42 g 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into 2L dimethyl sulfoxide, carrying out esterification crosslinking reaction at 35 ℃ for 36 h, carrying out suction filtration, and washing sequentially with deionized water, ethanol and dichloromethane to obtain the starch-polyimide-polylactic acid crosslinked particles.
The preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: the preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: adding 700g of poly (butylene adipate-terephthalate) and 300g of starch-polyimide-polylactic acid cross-linked particles into a torque rheometer, carrying out melt blending, wherein the melt temperature is 150 ℃, the blending time is 12 min, the rotating speed is 60 r/min, and discharging to obtain the degradable starch cross-linked particle modified PBAT polyester master batch.
Comparative example 1
The preparation process of the starch-polylactic acid cross-linked particles comprises the following steps: adding 60g carboxymethyl starch, 30 g polylactic acid, 15 g 1-hydroxybenzotriazole and 19.2 g 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into 1L dimethyl sulfoxide, carrying out esterification crosslinking reaction at 60 ℃ for 12 h, carrying out suction filtration, and washing sequentially with deionized water, ethanol and dichloromethane to obtain starch-polylactic acid crosslinked particles.
The preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: the preparation process of the degradable starch crosslinked particle modified PBAT polyester master batch comprises the following steps: adding 950g of poly (butylene adipate-terephthalate) and 50g of starch-polylactic acid cross-linked particles into a torque rheometer, carrying out melt blending, wherein the melt temperature is 140 ℃, the blending time is 10 min, the rotating speed is 60 r/min, and discharging to obtain the degradable starch cross-linked particle modified PBAT polyester master batch.
Thermal performance analysis: the degradable starch crosslinked particle modified PBAT polyester master batch with the specification of 2cm multiplied by 2cm is tested in a thermogravimetric analyzer, the flow is 50 mL/min, the heating rate is 20 ℃/min, and the testing temperature is 30-800 ℃.
TABLE 1 Heat resistance test of PBAT polyester masterbatch
After TG thermal performance testing: in each example, as the content of the starch-polyimide-polylactic acid cross-linked particles in the degradable starch cross-linked particle modified PBAT polyester master batch increases, the initial decomposition temperature and the temperature at 50% mass loss show a tendency of decreasing after increasing gradually, and in example 3, when the ratio of the poly (butylene adipate-terephthalate) to the starch-polyimide-polylactic acid cross-linked particles is 82:18, the initial decomposition temperature and the temperature at 50% mass loss of the PBAT polyester master batch reach 396.2 ℃ and 446.2 ℃ at the maximum, and the mass residual rate is 27.6%; the mass residual ratio tended to increase gradually with increasing amounts of the starch-polyimide-polylactic acid crosslinked particles, and the mass residual ratio of the polybutylene adipate-terephthalate and g starch-polyimide-polylactic acid crosslinked particles of example 5 was at most 39.2% when the ratio was 70:30. And the comparative example 1 is added with starch-polylactic acid crosslinking particles, does not contain a polyimide structure with high temperature resistance, and the obtained PBAT polyester master batch has the worst heat stability.
Degradation performance test of degradable starch crosslinked particle modified PBAT polyester master batch: with reference to GB/T19277-2003, the final aerobic biodegradation performance of PBAT polyester master batch under controlled industrial composting conditions was determined, and at 55℃for industrial aerobic composting, a 500 g mass of culture soil and a 80g mass of PBAT polyester master batch were placed in a degradation reaction vessel as experimental groups to determine the final aerobic biodegradation capacity of the material without adding PBATThe polyester master batch is used as a blank control group, and CO generated in a reaction container 2 The amount of production was measured by an infrared on-line gas analysis system.
TABLE 2 biodegradability test of PBAT polyester master batch
The biodegradable starch crosslinked particle modified PBAT polyester master batch of examples 1-5 reached a percent biodegradation of 88.6-92.3% at 120 days. When the ratio of poly (butylene adipate-terephthalate) to starch-polyimide-polylactic acid cross-linked particles is 76:24, the percent biodegradation of the PBAT polyester master batch is up to 92.3%.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A preparation process of a degradable starch crosslinked particle modified PBAT polyester master batch is characterized by comprising the following steps of: the preparation process comprises the following steps: adding 70-95 parts by weight of poly (butylene adipate-terephthalate) and 5-30 parts by weight of starch-polyimide-polylactic acid cross-linked particles into a torque rheometer, and carrying out melt blending and discharging to obtain degradable starch cross-linked particle modified PBAT polyester master batch;
the preparation process of the starch-polyimide-polylactic acid cross-linked particles comprises the following steps: adding 100 parts by weight of carboxymethyl starch, 15-80 parts by weight of bis (propylene glycol imide phenyl acetate), 50-200 parts by weight of polylactic acid, 25-100 parts by weight of 1-hydroxybenzotriazole and 32-150 parts by weight of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride into dimethyl sulfoxide, carrying out suction filtration after esterification crosslinking reaction, and washing sequentially with deionized water, ethanol and methylene dichloride to obtain the starch-polyimide-polylactic acid crosslinked particles.
2. The process for preparing the degradable starch crosslinked particle modified PBAT polyester master batch according to claim 1, which is characterized in that: the melting temperature in the torque rheometer is 130-150 ℃, the blending time is 10-15 min, and the rotating speed is 50-80 r/min.
3. The process for preparing the degradable starch crosslinked particle modified PBAT polyester master batch according to claim 1, which is characterized in that: the temperature of the esterification and crosslinking reaction is between 35 and 60 ℃, and the reaction time is between 12 and 36 and h.
4. The process for preparing the degradable starch crosslinked particle modified PBAT polyester master batch according to claim 1, which is characterized in that: the preparation process of the bis (propylene glycol imide phenyl acetate) comprises the following steps:
s1, adding 210-280 parts by weight of 4-hydroxyphthalic anhydride, 100 parts by weight of succinyl chloride and 120-160 parts by weight of pyridine into a solvent under ice water bath, reacting, removing the solvent by rotary evaporation, and washing with diethyl ether to obtain a bis (phthalic anhydride phenyl acetate) intermediate;
s2, adding 100 parts by weight of bis (phenyl acetic anhydride) intermediate and 45-65 parts by weight of 2-amino-1, 3-propanediol into glacial acetic acid solution, reacting, cooling, precipitating, filtering, washing with saturated sodium carbonate solution, separating and purifying the crude product by silica gel column chromatography, wherein the eluent is ethyl acetate and petroleum ether, and the volume ratio is 1:9, thus obtaining the bis (phenyl propylene glycol imide acetate).
5. The process for preparing the degradable starch crosslinked particle modified PBAT polyester master batch according to claim 4, which is characterized in that: the solvent in S1 is selected from one of ethyl acetate, acetonitrile, dichloromethane or chloroform.
6. The process for preparing the degradable starch crosslinked particle modified PBAT polyester master batch according to claim 4, which is characterized in that: the reaction temperature in S1 is between 20 and 35 ℃ and the reaction time is between 3 and 10 and h.
7. The process for preparing the degradable starch crosslinked particle modified PBAT polyester master batch according to claim 4, which is characterized in that: the reaction temperature in S2 is between 110 and 125 ℃ and the reaction time is between 10 and 20 and h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311177696.0A CN116904004B (en) | 2023-09-13 | 2023-09-13 | Degradable starch crosslinked particle modified PBAT polyester master batch and preparation process thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311177696.0A CN116904004B (en) | 2023-09-13 | 2023-09-13 | Degradable starch crosslinked particle modified PBAT polyester master batch and preparation process thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116904004A CN116904004A (en) | 2023-10-20 |
CN116904004B true CN116904004B (en) | 2023-11-14 |
Family
ID=88367245
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311177696.0A Active CN116904004B (en) | 2023-09-13 | 2023-09-13 | Degradable starch crosslinked particle modified PBAT polyester master batch and preparation process thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN116904004B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1134433A (en) * | 1996-04-17 | 1996-10-30 | 北京市海淀区太生新工程材料研究所 | Reversible cross-linked starch resin compound and its preparation method |
CN1451027A (en) * | 2000-01-11 | 2003-10-22 | E·喀硕吉工业有限公司 | Thermoplastic starch compositions in corporating a particulate filler component |
CN1564848A (en) * | 2001-08-03 | 2005-01-12 | 东丽株式会社 | Resin composition and molding, film and fiber each comprising the same |
FI20185730A1 (en) * | 2018-09-01 | 2020-03-02 | Sulapac Oy | Compostable wood composite material |
CN115073894A (en) * | 2022-07-05 | 2022-09-20 | 威海市铎豪碳纳米科技有限公司 | Filling master batch for high-compatibility degradable material and preparation method thereof |
-
2023
- 2023-09-13 CN CN202311177696.0A patent/CN116904004B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1134433A (en) * | 1996-04-17 | 1996-10-30 | 北京市海淀区太生新工程材料研究所 | Reversible cross-linked starch resin compound and its preparation method |
CN1451027A (en) * | 2000-01-11 | 2003-10-22 | E·喀硕吉工业有限公司 | Thermoplastic starch compositions in corporating a particulate filler component |
CN1564848A (en) * | 2001-08-03 | 2005-01-12 | 东丽株式会社 | Resin composition and molding, film and fiber each comprising the same |
FI20185730A1 (en) * | 2018-09-01 | 2020-03-02 | Sulapac Oy | Compostable wood composite material |
CN115073894A (en) * | 2022-07-05 | 2022-09-20 | 威海市铎豪碳纳米科技有限公司 | Filling master batch for high-compatibility degradable material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN116904004A (en) | 2023-10-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100278237B1 (en) | Thermoplastic Compositions Containing Microfiber Reinforced Biodegradable Starch Ester | |
WO2014032393A1 (en) | Fully biodegradable material and preparation method thereof | |
US5852078A (en) | Biodegradable polyester compositions with natural polymers and articles thereof | |
CN111205604A (en) | Ultrathin high-strength high-toughness biodegradable mulching film material and film, and preparation method and application thereof | |
JP2014098095A (en) | β-1,3-GLUCAN DERIVATIVE AND MANUFACTURING METHOD OF β-1,3-GLUCAN DERIVATIVE | |
CN111349253B (en) | Modified lignin/PBS (Poly Butylene succinate) bioplastic film and preparation method thereof | |
CN110358273B (en) | Biomass antibacterial film with high puncture resistance | |
CN116904004B (en) | Degradable starch crosslinked particle modified PBAT polyester master batch and preparation process thereof | |
TWI770680B (en) | Biodegradable polyester | |
CN106751568B (en) | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof | |
CN111234484B (en) | Full-bio-based degradable polylactic acid/starch composite material and preparation method thereof | |
CN110903606B (en) | Plant oil-based composite material and preparation method thereof | |
CN110863261B (en) | Phase-change temperature-regulating composite fiber with chitosan as matrix and preparation method thereof | |
CN113308100B (en) | Biodegradable polylactic acid/lignin composite material, preparation method and application | |
CN112321999B (en) | Preparation method of hyperbranched polybutylene adipate terephthalate material | |
CN114106538A (en) | Fully-degradable plastic processing technology | |
CN114479440A (en) | Low-water-absorption PA56T/PET composite material and preparation method thereof | |
CN111057350B (en) | Full-biodegradable composite material with excellent mechanical property and preparation method thereof | |
CN116903961B (en) | Straw micro-nanofiber modified plastic master batch and preparation method thereof | |
CN115558264B (en) | Non-reactive compatibilized PLA/PBAT composite material and preparation method thereof | |
CN113088096B (en) | Rice hull powder/polyethylene composite material and preparation method thereof | |
CN114957941B (en) | Functional material of modified carboxyl nitrile rubber toughened polylactic acid and preparation method thereof | |
CN113025012B (en) | PBAT (poly (butylene adipate-co-terephthalate)) bio-based polyester composite material filled with modified fibers and preparation method thereof | |
CN111423704B (en) | Polylactic acid stereo complex and preparation method thereof | |
CN112300595B (en) | Environment-friendly full-biodegradable mulching film and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |