CN112920571A - Modified PLA (polylactic acid) and PHA (polyhydroxyalkanoate) blending material and preparation method thereof - Google Patents
Modified PLA (polylactic acid) and PHA (polyhydroxyalkanoate) blending material and preparation method thereof Download PDFInfo
- Publication number
- CN112920571A CN112920571A CN202110120372.8A CN202110120372A CN112920571A CN 112920571 A CN112920571 A CN 112920571A CN 202110120372 A CN202110120372 A CN 202110120372A CN 112920571 A CN112920571 A CN 112920571A
- Authority
- CN
- China
- Prior art keywords
- pla
- modified
- polylactic acid
- pha
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 74
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 66
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 title claims abstract description 43
- 229920000903 polyhydroxyalkanoate Polymers 0.000 title claims abstract description 43
- 238000002156 mixing Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 17
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 229920000728 polyester Polymers 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- 235000008170 thiamine pyrophosphate Nutrition 0.000 claims description 10
- 239000011678 thiamine pyrophosphate Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229960002363 thiamine pyrophosphate Drugs 0.000 claims description 5
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 5
- YXVCLPJQTZXJLH-UHFFFAOYSA-N thiamine(1+) diphosphate chloride Chemical compound [Cl-].CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N YXVCLPJQTZXJLH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 229920000642 polymer Polymers 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- 229920003023 plastic Polymers 0.000 abstract description 9
- 239000004033 plastic Substances 0.000 abstract description 9
- 229920000742 Cotton Polymers 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 235000009161 Espostoa lanata Nutrition 0.000 abstract description 5
- 240000001624 Espostoa lanata Species 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000004224 protection Effects 0.000 abstract description 3
- 230000036541 health Effects 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 244000005700 microbiome Species 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229920000704 biodegradable plastic Polymers 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides a modified PLA and PHA blending material, which comprises modified polylactic acid PLA, polyhydroxyalkanoate PHA and a blending aid, wherein the blending aid comprises an antioxidant, a crosslinking agent and a plasticizer; the components of the modified polylactic acid PLA comprise polylactic acid PLA, isophthalic acid-5-sodium sulfonate, polyethylene glycol, a catalyst and a stabilizer; the invention also comprises a preparation method of the modified PLA and PHA blending material, the modified PLA, PHA and the blending auxiliary agent are melted and blended in a reaction kettle for reaction, and then the mixture is discharged, cooled and made into a finished product of slices by a granulator; according to the invention, the hydrophilicity of the polyester is enhanced through sulfonic groups, the regularity of the polymer is destroyed through doping polyethylene glycol in a polymer chain, and the macroscopic softness and water absorption are improved, so that the plastic material disclosed by the invention can be better suitable for products such as cotton balls and cotton swabs in medical and health, the application range is enlarged, the degradation speed is accelerated, and the environmental protection performance is improved.
Description
Technical Field
The invention relates to the technical field of biodegradable plastics, in particular to a modified PLA and PHA blending material and a preparation method thereof.
Background
Since the polyester fiber was first developed and succeeded in laboratories using terephthalic acid and ethylene glycol as raw materials in j.r. winfield and j.t. dickson in the uk in 1941, the development of the polyester fiber industry has been rapidly advanced. The waste generated by the polyvinyl acetate fiber brings serious environmental protection problems while improving the living standard of people. With the improvement of environmental awareness of people, biodegradable high polymer material synthetic fibers draw more and more attention of people. Biodegradable high molecular material, also called "green ecological polymer", is a polymer whose physical and chemical properties are reduced and carbon dioxide, water, methane and other small molecular weight compounds are formed under the action of microorganisms, animals and plants under the aerobic and anaerobic conditions.
Biodegradable plastics refer to a class of plastics that are degraded by the action of microorganisms such as bacteria, molds (fungi), and algae that exist in nature. The ideal biodegradable plastic is a high molecular material which has excellent service performance, can be completely decomposed by environmental microorganisms after being discarded, and is finally inorganic to become a component of carbon circulation in nature. Biodegradable plastics are mainly used as soft and hard packaging materials for food due to good degradability, which is also the largest application field at present.
Biodegradable materials are considered as an effective approach to solve one of the problems of "white pollution" because they can be degraded by microorganisms into carbon dioxide and water in composting plants, with little environmental impact and reduced disposal costs. In addition, the matrix in these biodegradable materials, such as: the poly light fatty acid ester, the polylactic acid, the starch and the like come from renewable resources, and compensate the consumption of non-renewable energy sources and reduce the emission of greenhouse gases to a certain extent.
The polylactic acid is one of biodegradable materials, has good thermal stability, the processing temperature of 170-230 ℃, good solvent resistance, and can be processed in various modes, such as extrusion, spinning, biaxial stretching and injection blow molding. The product made of polylactic acid can be biodegraded, and has good biocompatibility, glossiness, transparency, hand feeling and heat resistance, and also has certain antibacterial property, flame retardance and ultraviolet resistance, so the polylactic acid has wide application, can be used as packaging materials, fibers, non-woven fabrics and the like, and is mainly used in the fields of clothing, buildings, agriculture, forestry, papermaking, medical sanitation and the like.
However, the existing polylactic acid plastic has certain problems, and the polymer thereof has the characteristics of poor air permeability, poor water absorption and smooth surface macroscopically due to the fact that the microstructure of the polymer is a regular linear structure, and particularly when the polylactic acid plastic is used in the medical field and used as materials such as environment-friendly cotton balls and cotton swabs, the problems of insufficient water absorption performance and insufficient fluffiness have great influence, so that a better polylactic acid polymer material is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a modified PLA and PHA blending material and a preparation method thereof, which solve the problems that polylactic acid plastic in the prior art is not enough in water absorption performance and not fluffy enough to be unfavorable for use when used as materials such as environment-friendly cotton balls and cotton swabs in the medical field.
According to an embodiment of the invention, the modified PLA and PHA blending material comprises the following components in parts by weight:
modified polylactic acid PLA: 74-95 parts;
polyhydroxyalkanoate PHA: 4-24 parts of a solvent;
blending auxiliary agent: 1-10 parts;
wherein the blending auxiliary agent comprises an antioxidant, a cross-linking agent and a plasticizer.
Further, the modified polylactic acid PLA comprises the following components in parts by weight:
polylactic acid PLA: 73-90 parts;
5-sodium isophthalic acid sulfonate: 3-11 parts;
polyethylene glycol: 5-15 parts of a solvent;
catalyst: 0.2-1.5 parts;
a stabilizer: 0.3 to 2.5 portions.
Preferably, the antioxidant comprises one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate or triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], wherein the antioxidant accounts for 10-40 wt% of the total weight of the modification aid.
Preferably, the cross-linking agent comprises one or more of dicumyl peroxide, benzoyl peroxide and di-tert-butyl peroxide, wherein the cross-linking agent accounts for 5-35 wt% of the total weight of the modification auxiliary agent.
Preferably, the plasticizer comprises one or more of glycerol, dimethyl amide, citric acid and glycol, wherein the plasticizer accounts for 28-70 wt% of the total weight of the modification auxiliary agent.
Preferably, the catalyst is antimony trioxide (CPC).
Preferably, the stabilizer comprises a mixture of thiamine pyrophosphate TPP and an antioxidant 1010.
The invention also comprises a preparation method of the modified PLA and PHA blended material, which comprises the following steps: and melting and blending the modified polylactic acid PLA, the polyhydroxyalkanoate PHA and the blending aid in a reaction kettle, reacting for 5-15 min at 75-180 ℃, discharging, cooling and preparing into a finished chip product by using a granulator.
Further, the preparation of the modified polylactic acid PLA is carried out firstly: adding sodium 5-sulfoisophthalate and polyethylene glycol into an esterification kettle, then adding a catalyst into a second esterification kettle, and reacting for 2 hours at the temperature of 240 ℃; and pressing the obtained product into a polycondensation kettle by using high-purity nitrogen, adding polylactic acid (PLA) and a stabilizer, uniformly mixing, and performing polycondensation reaction at the absolute pressure of 100Pa and the temperature of 280 ℃ to obtain a polyester product.
Further, the high purity nitrogen gas contains less than 10ppm of oxygen.
The technical principle of the invention is as follows: in the invention, sodium 5-sulfoisophthalate and polyethylene glycol are added into polylactic acid as raw materials as modification components, so that the hydrophilicity of polyester is enhanced through sulfonic groups, and in addition, the introduced polyethylene glycol is doped in a polymer chain, so that the regularity of the polymer is damaged to a certain extent, the molecular structure of the polymer is more disordered, and the macroscopic softness and water absorption are improved.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, sodium m-phthalate-5-sulfonate and polyethylene glycol are added into polylactic acid as modification components, so that the hydrophilicity of polyester is enhanced through sulfonic groups, and then the polyethylene glycol is doped in a polymer chain, so that the regularity of the polymer is damaged to a certain extent, and the molecular structure of the polymer is more disordered, thereby improving the macroscopic softness and water absorption, making the polymer more fluffy and soft, and having better water absorption performance; the plastic material can be better suitable for products such as cotton balls, cotton swabs and the like in medical and health, and the application range is enlarged;
2. in the invention, the phthalic acid-5-sodium sulfonate is used as a side chain modification component of the polylactic acid, so that the water absorption of the whole plastic material is enhanced, the plastic material is easier to damp and wet in natural environment, and is correspondingly easier to decompose by microorganisms such as bacteria, fungi and the like, the degradation speed is accelerated, and the environmental protection performance is improved.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
The chemical reagents used in the following examples of the present invention were purchased from the national pharmaceutical group and were all of analytical purity.
Example 1:
the raw materials in the embodiment comprise the following components in parts by weight: modified polylactic acid PLA: 74 parts of; polyhydroxyalkanoate PHA: 16 parts of a mixture; blending auxiliary agent: 10 parts of a blending auxiliary agent, wherein the blending auxiliary agent comprises an antioxidant, a cross-linking agent and a plasticizer.
Specifically, the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and accounts for 10 wt% of the total weight of the modification auxiliary agent; the cross-linking agent is dicumyl peroxide, and accounts for 20 wt% of the total weight of the modification auxiliary agent; the plasticizer comprises dimethyl amide, and accounts for 70 wt% of the total weight of the modifying auxiliary agent.
The modified polylactic acid PLA comprises the following components in parts by weight: polylactic acid PLA: 73 parts; 5-sodium isophthalic acid sulfonate: 10 parts of (A); polyethylene glycol: 13 parts; catalyst antimony trioxide: 1.5 parts; a stabilizer: 1:1 mixture of thiamine pyrophosphate TPP and antioxidant 1010: 2.5 parts.
The preparation process of this example includes the following steps:
(1) adding sodium 5-sulfoisophthalate and polyethylene glycol into an esterification kettle, then adding a catalyst into a second esterification kettle, and reacting for 2 hours at the temperature of 240 ℃; pressing the obtained product into a polycondensation kettle by using high-purity nitrogen with oxygen content less than 10ppm, adding polylactic acid (PLA) and a stabilizer, uniformly mixing, and performing polycondensation reaction at 100Pa absolute pressure and 280 ℃ to obtain modified polylactic acid (PLA);
(2) and melting and blending the modified polylactic acid PLA, the polyhydroxyalkanoate PHA and the blending aid in a reaction kettle, reacting for 15min at 75 ℃, discharging, cooling and preparing into a finished product of slices by using a granulator.
Example 2:
the raw materials in the embodiment comprise the following components in parts by weight: modified polylactic acid PLA: 75 parts of a mixture; polyhydroxyalkanoate PHA: 24 parts of (1); blending auxiliary agent: 1 part, wherein the blending auxiliary agent comprises an antioxidant, a cross-linking agent and a plasticizer.
Specifically, the antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate or diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] in an equal proportion, and the antioxidant accounts for 37 wt% of the total weight of the modification auxiliary agent; the cross-linking agent is a mixture of dicumyl peroxide, benzoyl peroxide and di-tert-butyl peroxide in equal proportion, and accounts for 35 wt% of the total weight of the modification auxiliary agent; the plasticizer is a mixture of glycerol, dimethyl amide, citric acid and glycol in equal proportion, and accounts for 28 wt% of the total weight of the modification auxiliary agent.
The modified polylactic acid PLA comprises the following components in parts by weight: polylactic acid PLA: 73.5 parts; 5-sodium isophthalic acid sulfonate: 11 parts of (1); polyethylene glycol: 15 parts of (1); catalyst antimony trioxide: 0.2 part; a stabilizer: 1:1 mixture of thiamine pyrophosphate TPP and antioxidant 1010: 0.3 part.
The preparation process of this example includes the following steps:
(1) adding sodium 5-sulfoisophthalate and polyethylene glycol into an esterification kettle, then adding a catalyst into a second esterification kettle, and reacting for 2 hours at the temperature of 240 ℃; pressing the obtained product into a polycondensation kettle by using high-purity nitrogen with oxygen content less than 10ppm, adding polylactic acid (PLA) and a stabilizer, uniformly mixing, and performing polycondensation reaction at 100Pa absolute pressure and 280 ℃ to obtain modified polylactic acid (PLA);
(2) and melting and blending the modified polylactic acid PLA, the polyhydroxyalkanoate PHA and the blending aid in a reaction kettle, reacting for 10min at 120 ℃, discharging, cooling and preparing into a finished product of slices by using a granulator.
Example 3:
the raw materials in the embodiment comprise the following components in parts by weight: modified polylactic acid PLA: 95 parts of (C); polyhydroxyalkanoate PHA: 4 parts of a mixture; blending auxiliary agent: 1 part, wherein the blending auxiliary agent comprises an antioxidant, a cross-linking agent and a plasticizer.
Specifically, the antioxidant comprises a 1:1 mixture of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate and diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], and the antioxidant accounts for 40 wt% of the total weight of the modification auxiliary agent; the cross-linking agent comprises a 1:1 mixture of dicumyl peroxide and benzoyl peroxide, and accounts for 5 wt% of the total weight of the modification auxiliary agent; the plasticizer comprises a 1:1 mixture of dimethyl amide and ethylene glycol, and accounts for 55 wt% of the total weight of the modification auxiliary agent.
The modified polylactic acid PLA comprises the following components in parts by weight: polylactic acid PLA: 90 parts of a mixture; 5-sodium isophthalic acid sulfonate: 3 parts of a mixture; polyethylene glycol: 5 parts of a mixture; catalyst antimony trioxide: 0.7 part; a stabilizer: 1:1 mixture of thiamine pyrophosphate TPP and antioxidant 1010: 1.3 parts.
The preparation process of this example includes the following steps:
(1) adding sodium 5-sulfoisophthalate and polyethylene glycol into an esterification kettle, then adding a catalyst into a second esterification kettle, and reacting for 2 hours at the temperature of 240 ℃; pressing the obtained product into a polycondensation kettle by using high-purity nitrogen with oxygen content less than 10ppm, adding polylactic acid (PLA) and a stabilizer, uniformly mixing, and performing polycondensation reaction at 100Pa absolute pressure and 280 ℃ to obtain modified polylactic acid (PLA);
(2) and melting and blending the modified polylactic acid PLA, the polyhydroxyalkanoate PHA and the blending aid in a reaction kettle, reacting for 5min at 180 ℃, discharging, cooling and preparing into a finished chip product by using a granulator.
The three examples of the present invention were compared for performance using a PLA polylactic acid degradation masterbatch from the company Ementada as a control, where the physical properties were measured using the American ASTM test standard, the water absorption was measured using the national Standard GB/T1034-2008, and the air permeability was measured using the national Standard GB/T5453-1997, with the following results:
| example 1 | Example 2 | Example 3 | Comparative example | |
| Tensile Strength (MPa) | 35.4 | 34.6 | 34.7 | 36.3 |
| Elongation (%) | 82.5 | 81.5 | 82.1 | 84.2 |
| Water absorption (%) | 0.39 | 0.42 | 0.44 | 0.22 |
| Air permeability (mm/s) | 215 | 213 | 220 | 161 |
TABLE 1
As can be seen from Table 1, the invention introduces sodium 5-sulfoisophthalate and polyethylene glycol, respectively increases branched chains and dopes main chain components, destroys the spatial structure of the polymer, thereby reducing the regularity of polyester molecules, slightly reducing the tensile strength and elongation index, but having insignificant reduction compared with other plastics and being in an acceptable range; meanwhile, the water absorption and air permeability are obviously improved, so that the cotton swab can be better matched with the medical field to be used as a raw material of cotton balls and cotton swabs.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. The modified PLA and PHA blending material is characterized by comprising the following components in parts by weight:
modified polylactic acid PLA: 74-95 parts;
polyhydroxyalkanoate PHA: 4-24 parts of a solvent;
blending auxiliary agent: 1-10 parts;
wherein the blending auxiliary agent comprises an antioxidant, a cross-linking agent and a plasticizer.
2. The modified PLA and PHA blend material of claim 1, wherein the components of the modified polylactic acid PLA comprise the following components in parts by weight:
polylactic acid PLA: 73-90 parts;
5-sodium isophthalic acid sulfonate: 3-11 parts;
polyethylene glycol: 5-15 parts of a solvent;
catalyst: 0.2-1.5 parts;
a stabilizer: 0.3 to 2.5 portions.
3. The modified PLA and PHA blend material of claim 1, wherein the antioxidant comprises one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate or triethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], wherein the antioxidant is present in an amount of 10 to 40 wt% based on the total weight of the modification aid.
4. The modified PLA and PHA blend material of claim 1, wherein: the cross-linking agent comprises one or more of dicumyl peroxide, benzoyl peroxide and di-tert-butyl peroxide, wherein the cross-linking agent accounts for 5-35 wt% of the total weight of the modification auxiliary agent.
5. The modified PLA and PHA blend material of claim 1, wherein: the plasticizer comprises one or more of glycerol, dimethyl amide, citric acid and glycol, wherein the plasticizer accounts for 28-70 wt% of the total weight of the modification auxiliary agent.
6. The modified PLA and PHA blend material of claim 2, wherein: the catalyst is antimony trioxide CPC.
7. The modified PLA and PHA blend material of claim 2, wherein: the stabilizer comprises a mixture of thiamine pyrophosphate TPP and an antioxidant 1010.
8. A method of preparing the modified PLA and PHA blend material of claim 1, wherein: and melting and blending the modified polylactic acid PLA, the polyhydroxyalkanoate PHA and the blending aid in a reaction kettle, reacting for 5-15 min at 75-180 ℃, discharging, cooling and preparing into a finished chip product by using a granulator.
9. The method of claim 8, wherein the modified PLA and PHA blend material is prepared by: firstly, preparing modified polylactic acid (PLA): adding sodium 5-sulfoisophthalate and polyethylene glycol into an esterification kettle, then adding a catalyst into a second esterification kettle, and reacting for 2 hours at the temperature of 240 ℃; and pressing the obtained product into a polycondensation kettle by using high-purity nitrogen, adding polylactic acid (PLA) and a stabilizer, uniformly mixing, and performing polycondensation reaction at the absolute pressure of 100Pa and the temperature of 280 ℃ to obtain a polyester product.
10. The method of claim 9, wherein the modified PLA and PHA blend material is prepared by: the high purity nitrogen gas contains less than 10ppm of oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110120372.8A CN112920571A (en) | 2021-01-28 | 2021-01-28 | Modified PLA (polylactic acid) and PHA (polyhydroxyalkanoate) blending material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110120372.8A CN112920571A (en) | 2021-01-28 | 2021-01-28 | Modified PLA (polylactic acid) and PHA (polyhydroxyalkanoate) blending material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112920571A true CN112920571A (en) | 2021-06-08 |
Family
ID=76168942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110120372.8A Pending CN112920571A (en) | 2021-01-28 | 2021-01-28 | Modified PLA (polylactic acid) and PHA (polyhydroxyalkanoate) blending material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112920571A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316542A (en) * | 2021-12-28 | 2022-04-12 | 青岛中宝塑业有限公司 | High-strength biodegradable plastic and preparation method thereof |
| CN116606536A (en) * | 2023-04-11 | 2023-08-18 | 富岭科技股份有限公司 | PHA modified full-biodegradable plastic for straw |
| CN116836531A (en) * | 2023-09-04 | 2023-10-03 | 北京蓝晶微生物科技有限公司 | Polyol-containing polyhydroxyalkanoate composition with high fluidity, molded body and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205356A (en) * | 2006-12-22 | 2008-06-25 | 深圳市奥贝尔科技有限公司 | Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid |
| CN101643541A (en) * | 2008-08-08 | 2010-02-10 | 中国科学院宁波材料技术与工程研究所 | Modified polylactic acid having good hydrophilicity and production method thereof |
| CA2798408A1 (en) * | 2010-05-17 | 2011-11-24 | Metabolix, Inc. | Toughening polylactic acid with polyhydroxyalkanoates |
| CN102892817A (en) * | 2010-06-21 | 2013-01-23 | 东丽株式会社 | Polylactic acid film |
| US20160185954A1 (en) * | 2014-12-30 | 2016-06-30 | Samsung Electronics Co., Ltd. | Thermoplastic resin composition, molded article made therefrom, and method of preparing the composition |
| CN111621127A (en) * | 2020-05-25 | 2020-09-04 | 南京金凯木纳米材料有限公司 | Polyethylene glycol modified PHA composite material and preparation method thereof |
| CN112812518A (en) * | 2020-12-31 | 2021-05-18 | 重庆和泰润佳股份有限公司 | Thermoplastic biodegradable plastic and preparation method thereof |
-
2021
- 2021-01-28 CN CN202110120372.8A patent/CN112920571A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205356A (en) * | 2006-12-22 | 2008-06-25 | 深圳市奥贝尔科技有限公司 | Polyhydroxylkanoates as well as blending modification for copolymer thereof and polylactic acid |
| CN101643541A (en) * | 2008-08-08 | 2010-02-10 | 中国科学院宁波材料技术与工程研究所 | Modified polylactic acid having good hydrophilicity and production method thereof |
| CA2798408A1 (en) * | 2010-05-17 | 2011-11-24 | Metabolix, Inc. | Toughening polylactic acid with polyhydroxyalkanoates |
| CN102892817A (en) * | 2010-06-21 | 2013-01-23 | 东丽株式会社 | Polylactic acid film |
| US20160185954A1 (en) * | 2014-12-30 | 2016-06-30 | Samsung Electronics Co., Ltd. | Thermoplastic resin composition, molded article made therefrom, and method of preparing the composition |
| CN111621127A (en) * | 2020-05-25 | 2020-09-04 | 南京金凯木纳米材料有限公司 | Polyethylene glycol modified PHA composite material and preparation method thereof |
| CN112812518A (en) * | 2020-12-31 | 2021-05-18 | 重庆和泰润佳股份有限公司 | Thermoplastic biodegradable plastic and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "合成树脂及塑料工业", 《中国石化文摘》 * |
| "聚酯纤维", 《化纤文摘》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316542A (en) * | 2021-12-28 | 2022-04-12 | 青岛中宝塑业有限公司 | High-strength biodegradable plastic and preparation method thereof |
| CN114316542B (en) * | 2021-12-28 | 2022-07-19 | 青岛中宝塑业有限公司 | High-strength biodegradable plastic and preparation method thereof |
| CN116606536A (en) * | 2023-04-11 | 2023-08-18 | 富岭科技股份有限公司 | PHA modified full-biodegradable plastic for straw |
| CN116606536B (en) * | 2023-04-11 | 2024-03-26 | 富岭科技股份有限公司 | PHA modified full-biodegradable plastic for straw |
| CN116836531A (en) * | 2023-09-04 | 2023-10-03 | 北京蓝晶微生物科技有限公司 | Polyol-containing polyhydroxyalkanoate composition with high fluidity, molded body and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112920571A (en) | Modified PLA (polylactic acid) and PHA (polyhydroxyalkanoate) blending material and preparation method thereof | |
| CN114539743B (en) | Degradable barrier composition and preparation method and application thereof | |
| CN106221165B (en) | A kind of whole life cycle design of high-barrier and preparation method thereof | |
| CN102875998B (en) | Biodegradable material containing aliphatic polycarbonate, and preparation method and application thereof | |
| CN104231582B (en) | A kind of polylactic acid-base composite material and its preparation method | |
| CN111286168A (en) | Biodegradable polyester/cellulose composite blown film material and preparation method thereof | |
| KR20140026634A (en) | Thermoplastic starch, biodegradable polyester/starch composite material and preparation method thereof | |
| CN111978691B (en) | Biodegradable mulching film and preparation method thereof | |
| CN102070880A (en) | Biodegradable resin composition and product thereof | |
| CN103013070A (en) | Polylactic acid composite material and preparation method thereof | |
| CN111621239B (en) | Full-biodegradable adhesive tape and preparation method thereof | |
| CN102295825A (en) | Biodegradable composition and preparation method thereof | |
| CN112812518A (en) | Thermoplastic biodegradable plastic and preparation method thereof | |
| KR20190067320A (en) | Eco-friendly biedegradable thermo plastic polymer resin composition and it's manufacturing film | |
| CN113956645A (en) | Environment-friendly virus sampling tube and preparation method thereof | |
| KR102466532B1 (en) | Water based biodegadable composition, products including the same and manufacturing method of water based biodegadable products | |
| WO2021080319A1 (en) | Renewable resin composition and product manufactured from same | |
| CN112778717A (en) | Biodegradable plastic particle, preparation method thereof and tableware | |
| JP4065006B2 (en) | Biodegradable resin composition | |
| CN110964298A (en) | Biodegradable modified material and preparation method thereof | |
| CN114232126B (en) | Full-biodegradation efficient dustproof net and preparation method thereof | |
| CN101914274B (en) | Completely biodegradable transparent high-toughness polylactic acid resin and preparation method thereof | |
| CN112625410A (en) | Environment-friendly degradable material based on modified polylactic acid and manufacturing process thereof | |
| CN111849177A (en) | Full-biodegradable material | |
| KR20120126936A (en) | Method of manufacturing biodegradable polyester resin |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210608 |