CN114539743B - Degradable barrier composition and preparation method and application thereof - Google Patents
Degradable barrier composition and preparation method and application thereof Download PDFInfo
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- CN114539743B CN114539743B CN202111110604.8A CN202111110604A CN114539743B CN 114539743 B CN114539743 B CN 114539743B CN 202111110604 A CN202111110604 A CN 202111110604A CN 114539743 B CN114539743 B CN 114539743B
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- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 230000004888 barrier function Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 239000004611 light stabiliser Substances 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009264 composting Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000004626 polylactic acid Substances 0.000 description 25
- 229920000747 poly(lactic acid) Polymers 0.000 description 24
- -1 polyethylene Polymers 0.000 description 13
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 6
- 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 description 5
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 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 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002362 mulch Substances 0.000 description 3
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
-
- 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
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a degradable barrier composition, which comprises the following preparation raw materials in parts by weight: 1-9 parts of PPCP, 1-9 parts of PLA, 0.01-2 parts of solubilizer and 0.1-1 part of auxiliary agent. According to the degradable barrier composition, the weight ratio of PPCP, PLA and compatibilizer is optimized, so that the barrier composition achieves better tensile strength, and the mechanical property of the composite material is greatly improved; the biodegradability of the barrier composition is improved through the preparation method, the preparation raw materials and the auxiliary agents of the PPCP, complete degradation can be realized after forced composting for 3 months, and the prepared barrier composition still keeps good transparency and water vapor and oxygen barrier property through the mixing of the preferable PLA and the PPCP, and the production cost is greatly reduced due to the introduction of the PPCP, so that large-scale industrial production can be realized.
Description
Technical Field
The invention relates to a degradable barrier composition, a preparation method and application thereof, and mainly relates to a composition of C08L and a high molecular compound.
Background
The polyethylene and polypropylene, which are traditional plastic materials, are not easy to degrade in natural environment, and the use of a large number of plastic products can cause environmental problems of white pollution, so that the development of degradable polymeric materials is of great importance. PPC is an environment-friendly plastic capable of realizing complete degradation, but the molecular weight distribution of PPC is wider, which is unfavorable for the realization of a film blowing processing technology and limits the application range of PPC materials. PLA is also an environment-friendly plastic with good biodegradability, but the plant raw material is used as the raw material, so that the finished product is high, and the large-scale production and use are not facilitated.
Patent CN201310192444.5 develops that the PPC/PLA composite material has good biodegradability, but has poor tensile property and poor thermal stability, and is easy to age in performance in the long-time use process, so that the service life is influenced; patent CN201610384458.0 develops a degradable agricultural mulch film with good heat preservation and degradability, but the introduction of light stabilizer such as carbon black, zinc oxide and titanium dioxide can affect the transparency of the mulch film to a certain extent, resulting in the decrease of the absorptivity of plants to light and the influence on the usability of the mulch film. The invention develops a propylene oxide-phthalic anhydride-carbon dioxide terpolymer (PPCP) and polylactic acid (PLA) copolymer, which realizes good degradability and has good mechanical property.
Disclosure of Invention
In order to improve the degradability of the barrier composition and at the same time to improve the mechanical properties of the barrier composition, a first aspect of the present invention provides a degradable barrier composition, which is prepared from the following raw materials in parts by weight: 1-9 parts of PPCP, 1-9 parts of PLA, 0.01-2 parts of solubilizer and 0.1-1 part of auxiliary agent.
As a preferred embodiment, the PPCP has a number average molecular weight of 10 ten thousand to 20 ten thousand g/mol.
As a preferred embodiment, the PPCP is purchased from shandong co-invasive polymer limited.
As a preferred embodiment, the PLA has a number average molecular weight of 5 to 25 tens of thousands of g/mol, a melt flow rate of 3 to 15g/10min at 190℃and a density of 1.24g/cm 3 。
The applicant finds that, in the experimental process, the barrier composition with better tensile strength and better transparency can be prepared by selecting PLA with a melt flow rate of 3-15g/10min and PPCP with a molecular weight of 10-20 ten thousand g/mol to combine, and the possible reasons are hypothesized to be: the physical blending reaction between the PPCP and the PLA occurs, and the hexamethylene diisocyanate can improve the interfacial compatibility between the PPCP and the PLA, improve the interfacial binding force, improve the stability of a disperse phase, reduce the generation of cracks in the stretching process and greatly improve the tensile strength of the PPCP and PLA composite material. And a density of 1.24g/cm 3 The introduction of PLA can not increase the absorption of the composite material to visible light, so that the PPCP/PLA composite material still has better transparency and better water vapor barrier property. Preferably compatibilizationThe agent is hexamethylene diisocyanate, so that the glass transition temperature of PLA can be reduced, PLA and PPCP can be mixed and melted in the same temperature interval, a good compatibilization effect is achieved, the condition of phase separation is avoided, and the tensile strength and the impact strength can be improved.
As a preferred embodiment, the weight ratio of PPCP to PLA is 1: (1-9).
As a preferred embodiment, the weight ratio of PPCP to PLA is 1: (1-6).
Further preferably, the weight ratio of PPCP to PLA is 1: (1-3).
As a preferred embodiment, the compatibilizer is 0.1% -20% of the total weight of PPCP and PLA.
As a preferred embodiment, the compatibilizer is selected from one or a combination of several of ethylene-butyl acrylate, maleic anhydride graft copolymer, polycaprolactone, tetrabutyl titanate, epoxy compatibilizer, isocyanate compatibilizer, oxazoline compatibilizer, and LOTADER AX 8900.
As a preferred embodiment, the compatibilizer is hexamethylene diisocyanate.
As a preferred embodiment, the auxiliary agent is selected from one or a combination of several of antioxidant, light stabilizer, plasticizer, lubricant, flame retardant, antistatic agent and mold release agent.
As a preferred embodiment, the auxiliary agent is an antioxidant, a lubricant or a light stabilizer.
As a preferred embodiment, the weight ratio of the antioxidant, the lubricant and the light stabilizer is 1: (1-2): (0.3-0.8).
As a preferred embodiment, the antioxidant is selected from one or a combination of several of zinc dialkyldithiophosphate, dialkyldithiocarbamic acid, N-phenyl-alpha-naphthylamine, alkylphenothiazine, tris [2, 4-di-tert-butylphenyl ] phosphite, dialkyldiphenylamine, tributyl phosphite, triphenyl phosphite, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
As a preferred embodiment, the antioxidant is a combination of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite.
As a preferred embodiment, the weight ratio of the pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] to the tris [2, 4-di-tert-butylphenyl ] phosphite is 1: (2-3).
Applicants have found that the use of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris [2, 4-di-tert-butylphenyl ] phosphite can improve the aging resistance of the barrier composition prepared, eliminate free radicals generated during the preparation of the barrier composition, and provide heat stability to the barrier composition.
As a preferred embodiment, the lubricant is selected from one or a combination of several of stearic acid, butyl stearate, oleamide, ethylene bis stearamide, liquid paraffin, polyethylene wax.
As a preferred embodiment, the lubricant is ethylene bis stearamide.
The applicant finds that the ethylene bis-stearamide is selected as a lubricant in the experimental process, and the ethylene bis-stearamide is compounded with a compatilizer, so that the compatibility of the ethylene bis-stearamide in the barrier composition can be increased, the intermolecular cohesion of the barrier composition is reduced, and the surface smoothness and gloss of the barrier composition are improved.
As a preferred embodiment, the light stabilizer is selected from one or a combination of several of o-hydroxybenzophenone, benzotriazole, salicylate, triazine and substituted acrylonitrile.
As a preferred embodiment, the light stabilizer is an o-hydroxybenzophenone.
The applicant finds that the o-hydroxybenzophenone can form a synergistic effect with pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] antioxidant by being used as a light stabilizer in the experimental process, so that the absorption of the barrier composition to visible light is reduced, the breakage among polymer molecular chains is reduced, and the service life of the barrier composition is prolonged.
In a second aspect, the invention provides a method of preparing a degradable barrier composition comprising the steps of:
(1) Drying PPCP, PLA and compatibilizer at 50-60deg.C for 3-5 hr;
(2) Adding PPCP, PLA, solubilizer and auxiliary agent into a mixer, mixing and stirring for 10-30min at normal temperature;
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, and extruding and granulating at 100-180 ℃ to obtain the degradable barrier composition.
In a third aspect, the invention provides the use of a degradable barrier composition in the preparation of sheets, pipes, films, injection molded parts, fibrous articles.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the degradable barrier composition, the weight ratio of PPCP, PLA and compatibilizer is optimized, so that the barrier composition achieves better tensile strength, and the mechanical property of the composite material is greatly improved.
(2) The degradable barrier composition improves the biodegradability of the barrier composition through the preparation method, the preparation raw materials and the auxiliary agent of the PPCP, and can realize complete degradation after forced composting for 3 months.
(3) According to the degradable barrier composition, the prepared barrier composition still maintains good transparency through the mixing of the optimized PLA and the PPCP, and the introduction of the PPCP greatly reduces the production cost, so that large-scale industrial production can be realized.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
In addition, the raw materials used are commercially available unless otherwise indicated.
Example 1
A degradable barrier composition is prepared from the following raw materials in parts by weight: 3 parts of PPCP, 7 parts of PLA, 0.05 part of solubilizer and 0.5 part of auxiliary agent.
The preparation method of the PPCP comprises the following steps:
(1) In the case of vacuum drying, the input molar ratio was 1:10:10:0.005:0.002 phthalic anhydride, propylene oxide, ethylene oxide, tetra-n-butyl ammonium bromide and triethylboron solution;
(2) Introducing carbon dioxide gas, boosting the pressure to 1.2MPa, heating to 65 ℃ and reacting for 10 hours;
(3) Cooling to 34 ℃, ending the reaction, and washing and drying to obtain the PPCP.
The number average molecular weight of the prepared PPCP is 100000g/mol.
The PLA has a number average molecular weight of 60000g/mol, a melt flow rate of 10g/10min at 190℃and a density of 1.24g/cm 3 Available from Nature Works, U.S. model XDBio-S013.
The compatilizer is hexamethylene diisocyanate.
The auxiliary agent is an antioxidant, a lubricant and a light stabilizer, and the weight ratio is 1:1.5:0.6.
the antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tri [2, 4-di-tert-butylphenyl ] phosphite, and the weight ratio is 1:2.5.
the lubricant is ethylene bis stearamide.
The light stabilizer is o-hydroxybenzophenone.
A method of making a degradable barrier composition comprising the steps of:
(1) Drying PPCP, PLA and compatibilizer at 60 ℃ for 4 hours;
(2) Adding PPCP, PLA, solubilizer and auxiliary agent into a mixer, mixing and stirring for 20min at normal temperature;
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, and extruding and granulating at 150 ℃ to obtain the degradable barrier composition.
Example 2
A degradable barrier composition is prepared from the following raw materials in parts by weight: 4 parts of PPCP, 6 parts of PLA, 0.02 part of solubilizer and 0.3 part of auxiliary agent.
The preparation method of the PPCP comprises the following steps:
(1) In the case of vacuum drying, the input molar ratio was 1:10:10:0.005:0.002 phthalic anhydride, propylene oxide, ethylene oxide, tetra-n-butyl ammonium bromide and triethylboron solution;
(2) Introducing carbon dioxide gas, boosting the pressure to 1.2MPa, heating to 65 ℃ and reacting for 10 hours;
(3) Cooling to 34 ℃, ending the reaction, and washing and drying to obtain the PPCP.
The number average molecular weight of the prepared PPCP was 92800g/mol.
The PLA has a number average molecular weight of 60000g/mol, a melt flow rate of 10g/10min at 190℃and a density of 1.24g/cm 3 Available from Nature Works, U.S. model XDBio-S013.
The compatibilizer is an epoxy compatibilizer, and is purchased from Pasteur, germany and has the model of ADR-4370F.
The auxiliary agent is an antioxidant, a lubricant and a light stabilizer, and the weight ratio is 1:1:0.4.
the antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tri [2, 4-di-tert-butylphenyl ] phosphite, and the weight ratio is 1:2.
the lubricant is butyl stearate.
The light stabilizer is benzotriazole.
A method of making a degradable barrier composition comprising the steps of:
(1) Drying PPCP, PLA and compatibilizer at 55deg.C for 5 hr;
(2) Adding PPCP, PLA, solubilizer and auxiliary agent into a mixer, mixing and stirring for 15min at normal temperature;
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, and extruding and granulating at 165 ℃ to obtain the degradable barrier composition.
Example 3
A degradable barrier composition, a preparation method and application thereof, and the specific steps are the same as in example 1, except that PPCP is 5 parts by weight and PLA is 4 parts by weight.
Example 4
A degradable barrier composition, a preparation method and application thereof, and specific steps are the same as those of the embodiment 1, except that the compatibilizer is 0.08% of the total weight of PPCP and PLA.
Example 5
A degradable barrier composition, a preparation method and application thereof, and specific steps are the same as in example 1, except that the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Performance test:
1. tensile strength: the tensile strength of the prepared barrier composition was tested according to GB/T1040 test standard.
2. Transmittance: according to GB/T2410 test standard, spectrophotometry is adopted to test the light transmittance of the prepared barrier composition.
3. Biodegradability: according to GB/T19277 test standard, the biodegradability of the prepared barrier composition is tested, the test environment temperature is 58+/-2 ℃, forced composting is carried out, and the time required by complete degradation is realized.
4. Water vapor transmission performance: according to GB/T21332-2008 test standard, the water vapor permeability of the prepared barrier composition is tested.
5. Oxygen transmission performance: the oxygen transmission properties of the resulting barrier compositions were tested according to ASTM F2622-2020 test standard.
The examples were tested according to the above criteria and the results are shown in table 1.
TABLE 1
Claims (9)
1. A degradable barrier composition characterized by the fact that the raw materials for the preparation comprise, in parts by weight: 1-9 parts of PPCP, 1-9 parts of PLA, 0.01-2 parts of compatibilizer and 0.1-1 part of auxiliary agent;
the compatibilizer is one or a combination of more of ethylene-butyl acrylate, maleic anhydride graft copolymer, polycaprolactone, tetrabutyl titanate, epoxy compatibilizer, isocyanate compatibilizer and oxazoline compatibilizer;
the preparation method of the PPCP comprises the following steps:
(1) In the case of vacuum drying, the input molar ratio was 1:10:10:0.005:0.002 phthalic anhydride, propylene oxide, ethylene oxide, tetra-n-butyl ammonium bromide and triethylboron solution;
(2) Introducing carbon dioxide gas, boosting the pressure to 1.2MPa, heating to 65 ℃ and reacting for 10 hours;
(3) Cooling to 34 ℃, ending the reaction, and washing and drying to obtain the PPCP.
2. The degradable barrier composition of claim 1, wherein the PPCP has a number average molecular weight of 10-20 ten thousand g/mol.
3. The degradable barrier composition of claim 1, wherein the PLA has a number average molecular weight of 5 to 25 thousand g/mol and a melt flow rate of 3 to 15g/10min at 190 ℃.
4. The degradable barrier composition of claim 1, wherein the weight ratio of PPCP to PLA is 1: (1-9).
5. The degradable barrier composition of claim 1, wherein the compatibilizer is 0.1% -20% of the total weight of PPCP and PLA.
6. The degradable barrier composition of claim 1, wherein the auxiliary agent is selected from one or a combination of several of antioxidants, light stabilizers, plasticizers, lubricants, flame retardants, antistatic agents, mold release agents.
7. The degradable barrier composition of claim 6, wherein the antioxidant is selected from one or a combination of several of zinc dialkyldithiophosphate, dialkyldithiocarbamic acid, N-phenyl-a-naphthylamine, alkylphenothiazine, dialkyldiphenylamine, tributyl phosphite, triphenyl phosphite.
8. A method of preparing a degradable barrier composition according to any one of claims 1 to 7, comprising the steps of:
(1) Drying PPCP, PLA and compatibilizer at 50-60deg.C for 3-5 hr;
(2) Adding PPCP, PLA, compatibilizer and auxiliary agent into a mixer, mixing and stirring for 10-30min at normal temperature;
(3) And (3) adding the mixture obtained in the step (2) into a double-screw extruder, and extruding and granulating at 100-180 ℃ to obtain the degradable barrier composition.
9. Use of a degradable barrier composition according to any one of claims 1-7 in the preparation of sheets, pipes, films, injection moulded parts, fibre products.
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| CN114539743B (en) * | 2021-09-23 | 2024-03-19 | 山东联欣环保科技有限公司 | Degradable barrier composition and preparation method and application thereof |
| CN114524930A (en) * | 2021-09-24 | 2022-05-24 | 山东联欣环保科技有限公司 | Quaternary copolymer containing phthalic anhydride and ethylene oxide |
| CN115584109A (en) * | 2022-11-08 | 2023-01-10 | 山东联欣环保科技有限公司 | Composite material, preparation method and application thereof, and degradable mulching film |
| CN115772321A (en) * | 2023-02-10 | 2023-03-10 | 山东联欣环保科技有限公司 | Biodegradable composite membrane and preparation method thereof |
| CN116021850B (en) * | 2023-03-30 | 2023-06-16 | 山东联欣环保科技有限公司 | Barrier biodegradable cigarette packaging film and preparation process thereof |
| CN116120730B (en) * | 2023-04-12 | 2023-06-23 | 山东联欣环保科技有限公司 | Carbon dioxide-based biodegradable bottle-shaped plastic container and composition thereof |
| CN116120132B (en) * | 2023-04-13 | 2023-06-23 | 山东联欣环保科技有限公司 | Full-biodegradation plastic controlled-release fertilizer coating material and fertilizer forming process |
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