CN116285284B - CO (carbon monoxide)2Composition of base biodegradable copolymer, preparation method and application thereof - Google Patents
CO (carbon monoxide)2Composition of base biodegradable copolymer, preparation method and application thereof Download PDFInfo
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- CN116285284B CN116285284B CN202211719147.7A CN202211719147A CN116285284B CN 116285284 B CN116285284 B CN 116285284B CN 202211719147 A CN202211719147 A CN 202211719147A CN 116285284 B CN116285284 B CN 116285284B
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- carbon dioxide
- propylene oxide
- phthalic anhydride
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title 1
- 229910002091 carbon monoxide Inorganic materials 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 47
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 47
- 229920006029 tetra-polymer Polymers 0.000 claims abstract description 27
- 229920001897 terpolymer Polymers 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 70
- -1 propylene oxide-phthalic anhydride-carbon dioxide Chemical compound 0.000 claims description 67
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 42
- 238000007334 copolymerization reaction Methods 0.000 claims description 35
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 28
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 24
- QEYNXBRMPSQXIG-UHFFFAOYSA-N carbon dioxide;2-methyloxirane Chemical compound O=C=O.CC1CO1 QEYNXBRMPSQXIG-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 14
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000004970 Chain extender Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229920006027 ternary co-polymer Polymers 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 239000002671 adjuvant Substances 0.000 claims description 5
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000006082 mold release agent Substances 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 230000004888 barrier function Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- 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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a composition of a CO 2 -based biodegradable copolymer, a preparation method and application thereof, and belongs to the technical field of plastic materials. The composition provided by the invention comprises an epoxypropane-phthalic anhydride-carbon dioxide terpolymer, an epoxypropane-epoxycyclohexane-phthalic anhydride-carbon dioxide tetrapolymer, an epoxypropane-carbon dioxide bipolymer and an epoxypropane-epoxyethane-phthalic anhydride-carbon dioxide tetrapolymer which are excellent in high temperature resistance, elongation at break and toughness, and the composition obtained by controlling the dosage of each component has good high temperature resistance, elongation at break and toughness.
Description
Technical Field
The invention belongs to the technical field of plastic materials, and particularly relates to a composition of a CO 2 -based biodegradable copolymer, a preparation method and application thereof.
Background
The carbon dioxide-based degradable resin refers to a biodegradable binary or multi-component copolymer formed by copolymerizing carbon dioxide and other monomers. However, carbon dioxide-based degradable resins generally have the defect of poor high temperature resistance.
Aiming at the defect of poor temperature resistance of the carbon dioxide-based degradable resin, a rigid monomer can be added for copolymerization in the synthesis process, so that the glass transition temperature is improved. Common such rigid monomers include phthalic anhydride, epoxycyclohexane. For example, the heat resistance of the propylene oxide-phthalic anhydride-carbon dioxide terpolymer and the propylene oxide-epoxycyclohexane-phthalic anhydride-carbon dioxide tetrapolymer are greatly improved. However, the copolymer has a problem of insufficient tensile strain at break and toughness after improving heat resistance.
Disclosure of Invention
The invention aims to provide a composition of a CO 2 -based biodegradable copolymer, a preparation method and application thereof, and the composition has good high temperature resistance, elongation strain at break and toughness.
The invention provides a composition of a CO 2 -based biodegradable copolymer, which comprises the following components: copolymers and adjuvants; the copolymer comprises 0.1-99% of propylene oxide-carbon dioxide binary copolymer, 0.1-99% of propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer, 0-99% of propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide quaternary copolymer and 0-99% of propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide quaternary copolymer by mass percent.
Preferably, the auxiliary agent comprises one or more of a lubricant, a chain extender, a filler, an opening agent and a mold release agent.
Preferably, the preparation method of the propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer comprises the following steps:
carrying out copolymerization reaction on propylene oxide, ethylene oxide, phthalic anhydride, a nonmetal catalyst and carbon dioxide to obtain the propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer; the pressure of the carbon dioxide is 0.1-4.0 MPa;
the molar ratio of the epoxypropane to the phthalic anhydride is 4-10: 1, a step of;
The molar ratio of the epoxypropane to the epoxyethane is 0.5-5:1.
Preferably, the preparation method of the propylene oxide-phthalic anhydride-carbon dioxide terpolymer comprises the following steps:
Carrying out copolymerization reaction on propylene oxide, phthalic anhydride, a nonmetallic catalyst and carbon dioxide to obtain the propylene oxide-phthalic anhydride-carbon dioxide terpolymer; the molar ratio of the epoxypropane to the phthalic anhydride is 4-10: 1, a step of; the pressure of the carbon dioxide is 0.1-4.0 MPa.
Preferably, the preparation method of the propylene oxide-carbon dioxide binary copolymer comprises the following steps:
carrying out copolymerization reaction on propylene oxide, a nonmetallic catalyst and carbon dioxide to obtain the propylene oxide-carbon dioxide binary copolymer; the pressure of the carbon dioxide is 0.1-4.0 MPa.
Preferably, the propylene oxide-cyclohexane oxide-phthalic anhydride-carbon dioxide tetrapolymer comprises the following steps:
Carrying out copolymerization reaction on propylene oxide, cyclohexene oxide, phthalic anhydride and carbon dioxide to obtain the propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide tetrapolymer;
the molar ratio of the epoxypropane to the phthalic anhydride is 4-10: 1, a step of;
the ratio of the mass of the propylene oxide to the total mass of the cyclohexene oxide and the phthalic anhydride is 2-10: 1, a step of;
The pressure of the carbon dioxide is 0.1-4.0 MPa.
Preferably, the temperature of the copolymerization reaction is 40-100 ℃ and the time is 4-10 h.
Preferably, the nonmetallic catalyst includes one or more of tetra-n-butyl ammonium halide, tetra-n-propyl ammonium halide, triethylboron, and tributylboron.
The invention also provides a preparation method of the CO 2 -based biodegradable copolymer composition, which comprises the following steps:
and mixing the copolymer and the auxiliary agent, and extruding to obtain the composition.
The invention also provides application of the composition according to the scheme or the composition obtained by the preparation method according to the scheme in film bag products, sheet products, injection molding products or hollow bottle products.
The invention provides a composition of a CO 2 -based biodegradable copolymer, which comprises the following components: copolymers and adjuvants; the copolymer comprises 0.1-99% of propylene oxide-carbon dioxide binary copolymer, 0.1-99% of propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer, 0-99% of propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide quaternary copolymer and 0-99% of propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide quaternary copolymer by mass percent. The composition provided by the invention comprises PPCP and PPCCP with excellent high temperature resistance, PPC and PPCEP with excellent elongation strain at break and toughness, and the content of each component is controlled, so that the obtained composition has good high temperature resistance, elongation strain at break and toughness.
Detailed Description
The invention provides a composition of a CO 2 -based biodegradable copolymer, which comprises the following components: copolymers and adjuvants; the copolymer comprises 0.1-99% of propylene oxide-carbon dioxide binary copolymer, 0.1-99% of propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer, 0-99% of propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide quaternary copolymer and 0-99% of propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide quaternary copolymer by mass percent.
The copolymer of the present invention comprises 0.1 to 99% by mass, preferably 10 to 80% by mass, more preferably 40 to 60% by mass of propylene oxide-carbon dioxide binary copolymer (PPC).
The copolymer of the present invention comprises, in mass%, 0.1 to 99%, preferably 10 to 80%, more preferably 40 to 60% of a propylene oxide-phthalic anhydride-carbon dioxide terpolymer (PPCP).
The copolymer of the present invention comprises propylene oxide-epoxycyclohexane-phthalic anhydride-carbon dioxide tetrapolymer (PPCCP) in an amount of 0 to 99% by mass, preferably 10 to 80% by mass, more preferably 40 to 60% by mass.
The copolymer of the present invention comprises propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer (PPCEP) in an amount of 0 to 99% by mass, preferably 10 to 80% by mass, more preferably 40 to 60% by mass.
When the copolymer is PPC, PPCP, PPCEP and PPCCP, the mass of PPCEP is preferably 1 to 99%, more preferably 20 to 80%, still more preferably 40 to 60% of the total mass of the copolymer; the mass of the PPC is preferably 0.1-99% of the total mass of the PPC, the PPCP and PPCCP.
In the present invention, when the copolymer is PPCP and PPCCP, the mass of PPCP is preferably 0.1 to 99% of the total mass of the copolymer.
In the present invention, the auxiliary agent preferably includes one or more of a lubricant, a chain extender, a filler, an opening agent, and a mold release agent, and more preferably includes a filler and/or a chain extender. In the present invention, the filler preferably includes one or more of silica, heavy calcium carbonate, nano calcium carbonate, light calcium carbonate, titanium dioxide and zinc oxide. In the present invention, the chain extender preferably includes one or more of JoncrylADR 4468, toluene diisocyanate, and 4, 4' -diphenylmethane diisocyanate. In the invention, the auxiliary agent can further improve the high temperature resistance, elongation strain at break and toughness of the composition. In the present invention, when the auxiliary agent is a filler and a chain extender, the mass ratio of the filler to the copolymer is preferably 1 to 100:100, more preferably 10 to 80:100, and still more preferably 20 to 30:100. The mass ratio of the chain extender to the copolymer is preferably 0.01-1: 100, more preferably 0.05 to 0.8:100, still more preferably 0.1 to 0.5:100.
In the present invention, the preparation of the propylene oxide-phthalic anhydride-carbon dioxide terpolymer preferably comprises the steps of:
Carrying out copolymerization reaction on propylene oxide, phthalic anhydride, a nonmetallic catalyst and carbon dioxide to obtain the propylene oxide-phthalic anhydride-carbon dioxide terpolymer; the molar ratio of the epoxypropane to the phthalic anhydride is 4-10: 1, a step of; the pressure of the carbon dioxide is 0.1-4.0 MPa.
In the present invention, the molar ratio of propylene oxide to phthalic anhydride is preferably 4 to 10:1, more preferably 5 to 9:1, more preferably 6 to 8:1.
In the present invention, the molar ratio of the propylene oxide to the nonmetallic catalyst is preferably 570 to 1700:1, more preferably 800 to 1500:1, and still more preferably 1000 to 1350:1. In the present invention, the nonmetallic catalyst preferably includes one or more of tetra-n-butyl ammonium halide, tetra-n-propyl ammonium halide, triethylboron and tributylboron, more preferably tetra-n-butyl ammonium halide and triethylboron. In the present invention, the molar ratio of tetra-n-butyl ammonium halide to triethylboron is preferably 1:1 to 5, more preferably 1:2 to 4, more preferably 1:2.1 to 2.8. In the present invention, the tetra-n-butylammonium halide is preferably tetra-n-butylammonium chloride and/or tetra-n-butylammonium bromide. In the present invention, the triethylboron and tributylboron are preferably involved in the reaction in the form of triethylboron solution, and the concentrations of the triethylboron solution and the tributylboron solution are preferably 1mol/L. In the invention, the solvent in the triethylboron solution is tetrahydrofuran or diethyl ether or n-butyl ether.
In the present invention, the copolymerizing propylene oxide, phthalic anhydride, a nonmetallic catalyst with carbon dioxide preferably comprises: mixing propylene oxide, phthalic anhydride and a nonmetallic catalyst in a closed container, filling CO 2 into the closed container until the pressure of the carbon dioxide is reached, and then raising the temperature to the temperature of copolymerization. The present invention is not particularly limited to the above-described closed container, and may be a closed container known to those skilled in the art. Specifically, in the examples of the present invention, a 50L autoclave was used. The present invention is not particularly limited to the mixing, and the mixing may be performed uniformly by using a scheme well known to those skilled in the art. Specifically, in the practice of the present invention, the mixing is carried out under stirring conditions at a stirring speed of 100r/min.
In the present invention, the temperature of the copolymerization reaction is preferably 40 to 100 ℃, more preferably 60 to 80 ℃, and the time is preferably 4 to 10 hours, more preferably 6 to 8 hours. In the present invention, the copolymerization is preferably carried out under stirring.
In the present invention, the pressure of the carbon dioxide is preferably 0.1 to 4.0MPa, more preferably 1 to 2MPa. In the present invention, the copolymerization is preferably carried out under anaerobic conditions.
After the copolymerization reaction is finished, the obtained copolymerization reaction product is preferably decompressed, decompressed and dissolved in dichloroethane, and then ethanol is added to obtain a precipitate; and devolatilizing, granulating and drying the precipitate to obtain the epoxypropane-phthalic anhydride-carbon dioxide terpolymer. The amount of the dichloroethane used in the present invention is not particularly limited, and the copolymerization reaction product obtained may be completely dissolved. The amount of ethanol used in the present invention is not particularly limited, and the ethanol may be completely precipitated. The devolatilization, granulation and drying are not particularly limited, and the technical scheme well known to the person skilled in the art can be adopted. In the present invention, the propylene oxide-phthalic anhydride-carbon dioxide terpolymer preferably has a number average molecular weight of 1.7X10 5 g/mol.
In the present invention, the preparation method of the propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer preferably comprises the following steps:
carrying out copolymerization reaction on propylene oxide, ethylene oxide, phthalic anhydride, a nonmetal catalyst and carbon dioxide to obtain the propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer; the pressure of the carbon dioxide is 0.1-4.0 MPa;
the molar ratio of the epoxypropane to the phthalic anhydride is 4-10: 1, a step of;
The molar ratio of the epoxypropane to the epoxyethane is 0.5-5:1.
In the present invention, the molar ratio of propylene oxide to ethylene oxide is 0.5 to 5:1, more preferably 1 to 5:1, still more preferably 1 to 2:1.
In the present invention, the types of the non-noble metal catalyst, the molar ratio of propylene oxide to the non-noble metal catalyst, and the conditions of the copolymerization reaction are the same as those in the preparation of the propylene oxide-phthalic anhydride-carbon dioxide terpolymer by the above scheme, and the molar ratio of propylene oxide to the non-noble metal catalyst, and the conditions of the copolymerization reaction are not described in detail herein. In the present invention, the propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer preferably has a number average molecular weight of 2.01X10 5 g/mol.
In the present invention, the preparation method of the propylene oxide-carbon dioxide binary copolymer preferably comprises the following steps:
carrying out copolymerization reaction on propylene oxide, a nonmetallic catalyst and carbon dioxide to obtain the propylene oxide-carbon dioxide binary copolymer; the pressure of the carbon dioxide is 0.1-4.0 MPa.
In the present invention, the types of the non-noble metal catalyst, the molar ratio of propylene oxide to the non-noble metal catalyst, and the conditions of the copolymerization reaction are the same as those in the preparation of the propylene oxide-phthalic anhydride-carbon dioxide terpolymer by the above scheme, and the molar ratio of propylene oxide to the non-noble metal catalyst, and the conditions of the copolymerization reaction are not described in detail herein.
After the copolymerization reaction is finished, the method preferably reduces the pressure of the second copolymerization reaction product, releases the pressure, dissolves the second copolymerization reaction product in dichloroethane, and adds ethanol to obtain precipitate; and devolatilizing, granulating and drying the precipitate to obtain the propylene oxide-carbon dioxide binary copolymer. The amount of the dichloroethane used in the present invention is not particularly limited, and the second copolymerization reaction product obtained may be completely dissolved. The amount of ethanol used in the present invention is not particularly limited, and the ethanol may be completely precipitated. The devolatilization, granulation and drying are not particularly limited, and the technical scheme well known to the person skilled in the art can be adopted. In the present invention, the propylene oxide-carbon dioxide binary copolymer preferably has a number average molecular weight of 1.2X10 5 g/mol.
In the present invention, the preparation method of the propylene oxide-epoxycyclohexane-phthalic anhydride-carbon dioxide tetrapolymer preferably comprises the following steps:
Carrying out copolymerization reaction on propylene oxide, cyclohexene oxide, phthalic anhydride and carbon dioxide to obtain the propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide tetrapolymer;
the molar ratio of the epoxypropane to the phthalic anhydride is 4-10: 1, a step of;
The pressure of the carbon dioxide is 0.1-4.0 MPa.
In the present invention, the ratio of the amount of the substance of propylene oxide to the total amount of the substances of cyclohexene oxide and phthalic anhydride is preferably 2 to 10:1, more preferably 2.5 to 8:1, more preferably 3 to 6:1.
In the present invention, the types of the non-noble metal catalyst, the molar ratio of propylene oxide to the non-noble metal catalyst, and the conditions of the copolymerization reaction are the same as those in the preparation of the propylene oxide-phthalic anhydride-carbon dioxide terpolymer by the above scheme, and the molar ratio of propylene oxide to the non-noble metal catalyst, and the conditions of the copolymerization reaction are not described in detail herein.
After the copolymerization reaction is finished, the obtained copolymerization reaction product is preferably decompressed, decompressed and dissolved in dichloroethane, and then ethanol is added to obtain a precipitate; and devolatilizing, granulating and drying the precipitate to obtain the epoxypropane-epoxycyclohexane-phthalic anhydride-carbon dioxide tetrapolymer. The amount of the dichloroethane used in the present invention is not particularly limited, and the second copolymerization reaction product obtained may be completely dissolved. The amount of ethanol used in the present invention is not particularly limited, and the ethanol may be completely precipitated. The devolatilization, granulation and drying are not particularly limited, and the technical scheme well known to the person skilled in the art can be adopted. In the present invention, the propylene oxide-epoxycyclohexane-phthalic anhydride-carbon dioxide tetrapolymer preferably has a number average molecular weight of 5.8X10 4 g/mol.
The invention takes the epoxypropane-phthalic anhydride-carbon dioxide terpolymer and epoxypropane-epoxycyclohexane-phthalic anhydride-carbon dioxide tetrapolymer which have excellent high temperature resistance and epoxypropane-carbon dioxide bipolymer which has excellent elongation strain at break and toughness as main components, and controls the dosage of each component to obtain the composition with good high temperature resistance, elongation strain at break and toughness.
The invention provides a preparation method of the composition according to the scheme, which comprises the following steps: the composition is obtained by mixing and extruding the copolymer and the auxiliary agent according to the composition.
The mixing is not particularly limited, and may be uniformly mixed by means well known to those skilled in the art. Specifically, in the embodiment of the present invention, mixing is performed in a mixer. In the present invention, the extrusion is preferably performed in a twin screw extruder. The extrusion temperature is preferably 150℃to 180 ℃. When the auxiliary agent contains a chain extender, the copolymer can undergo a crosslinking reaction under the action of the chain extender during extrusion, so that the high temperature resistance, elongation at break strain and toughness are improved.
In the present invention, each preparation raw material is preferably dried before the mixing, and the drying temperature is not particularly limited, and the drying temperature is used to dry the mixture to a constant weight, which is well known to those skilled in the art. Specifically, in the examples of the present invention, vacuum drying was performed at 40 ℃.
The invention also provides application of the composition according to the scheme or the composition obtained by the preparation method according to the scheme in film bag products, sheet products, injection molding products or hollow bottle products.
In the present invention, the applied processing process preferably includes one of film blowing, casting, calendaring, injection molding, blow molding, plastic sucking and biaxial stretching.
For further explanation of the present invention, the composition of the CO 2 -based biodegradable copolymer provided by the present invention, and the preparation method and application thereof are described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
30 Parts of propylene oxide-carbon dioxide binary copolymer, 10 parts of propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer, 40 parts of propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer, 20 parts of propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide tetrapolymer, 10 parts of nano calcium carbonate and 0.2 part of chain extender (JoncrylADR 4468).
Propylene oxide-carbon dioxide binary copolymer:
20kg of propylene oxide, 300g of triethylboron in tetrahydrofuran (concentration: 1 mol/L) and 39g of tetra-n-butylammonium chloride were charged into a 50L high-pressure stirred reactor, and carbon dioxide was charged to 1.5MPa and stirred at 65℃for 10 hours. Dissolving the prepared glue solution with dichloroethane, precipitating with ethanol, devolatilizing, granulating and drying to obtain the finished propylene oxide-carbon dioxide binary copolymer. The analytical test number average molecular weight was 1.2X10 5 g/mol.
Propylene oxide-phthalic anhydride-carbon dioxide terpolymer:
20kg of propylene oxide, 6.6kg of phthalic anhydride, 200g of triethylboron in tetrahydrofuran (concentration: 1 mol/L) and 24g of tetra-n-butylammonium chloride were charged into a 50L high-pressure stirred reactor, and carbon dioxide was charged to 1MPa and stirred at 70℃for reaction for 6 hours. Dissolving the prepared glue solution with dichloroethane, precipitating with ethanol, devolatilizing, granulating, and drying to obtain the finished product propylene oxide-phthalic anhydride-carbon dioxide terpolymer. The analytical test number average molecular weight was 1.7X10 5 g/mol.
Preparation of propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer:
20kg of propylene oxide, 5kg of ethylene oxide, 7.72kg of phthalic anhydride, 210g of a solution of triethylboron in tetrahydrofuran (concentration 1 mol/L) and 38.5g of tetra-n-butylammonium bromide were added to a 50L high-pressure stirred reactor, carbon dioxide was charged to 1.2MPa, and the reaction was stirred at 70℃for 6.5 hours. Dissolving the prepared glue solution with dichloroethane, precipitating with ethanol, devolatilizing, granulating, and drying to obtain the finished product propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer. The analytical test number average molecular weight was 2.01X10 5 g/mol.
Propylene oxide-cyclohexane oxide-phthalic anhydride-carbon dioxide tetrapolymer:
20kg of propylene oxide, 4.2kg of cyclohexene oxide, 7.5kg of phthalic anhydride, 240g of triethylboron in tetrahydrofuran (1 mol/L) and 38.5g of tetra-n-butyl ammonium chloride are put into a 50L high-pressure reaction kettle, stirring is carried out quickly to 100r/min, carbon dioxide is filled to the pressure of 1.2MPa, and stirring reaction is carried out for 6 hours at 70 ℃. Cooling, decompressing, dissolving the glue solution in dichloroethane, precipitating with ethanol, devolatilizing, granulating and drying to obtain the finished product propylene oxide-epoxycyclohexane-phthalic anhydride-carbon dioxide tetrapolymer. The analytical test number average molecular weight was 5.8X10 4 g/mol.
Vacuum drying the formula at 40 ℃, putting the mixture into a mixer, uniformly mixing, adding the mixture into a double-screw extruder, and extruding at 160 ℃ to obtain the composition of the CO 2 -based biodegradable copolymer.
Example 2
60 Parts of propylene oxide-carbon dioxide binary copolymer, 30 parts of propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer, 10 parts of propylene oxide-epoxycyclohexane-phthalic anhydride-carbon dioxide quaternary copolymer, 20 parts of nano calcium carbonate and 0.3 part of MDI.
Propylene oxide-carbon dioxide binary copolymer, propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer, and propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide quaternary copolymer were the same as in example 1.
Vacuum drying the formula at 40 ℃, putting the mixture into a mixer, uniformly mixing, adding the mixture into a double-screw extruder, and extruding at 160 ℃ to obtain the composition of the CO 2 -based biodegradable copolymer.
Example 3
70 Parts of propylene oxide-carbon dioxide binary copolymer, 10 parts of propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer, 20 parts of propylene oxide-epoxycyclohexane-phthalic anhydride-carbon dioxide quaternary copolymer, 20 parts of nano calcium carbonate and 0.5 part of TDI.
Propylene oxide-carbon dioxide binary copolymer, propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer, and propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide quaternary copolymer were the same as in example 1.
Vacuum drying the formula at 40 ℃, putting the mixture into a mixer, uniformly mixing, adding the mixture into a double-screw extruder, and extruding at 160 ℃ to obtain the composition of the CO 2 -based biodegradable copolymer.
Comparative example 1
70 Parts of polybutylene terephthalate-adipate, 30 parts of propylene oxide-phthalic anhydride-carbon dioxide terpolymer, 20 parts of nano calcium carbonate and 0.2 part of chain extender (JoncrylADR 4468).
Propylene oxide-phthalic anhydride-carbon dioxide terpolymer was prepared as in example 1.
Vacuum drying the formula at 40 ℃, putting the mixture into a mixer, uniformly mixing, adding the mixture into a double-screw extruder, and extruding at 170 ℃ to obtain the composition of the CO 2 -based biodegradable copolymer.
Performance test: the thermal properties and mechanical properties of the compositions prepared in examples 1 to 3 and comparative example 1 were measured, and the results are shown in Table 1. The analytical test method is as follows:
1. the water vapor permeability was measured in accordance with GB/T1037, and the film thickness was 80. Mu.m.
2. Oxygen permeability was measured in accordance with GB/T1038, film thickness 80 μm.
3. Transmittance: according to GB/T2410 test standard, spectrophotometry is adopted to test the light transmittance of the prepared composite copolymer.
4. Tensile strength and tensile strain at break were measured according to GB/T1040.1 and GB/T1040.2.
5. Vicat softening temperature was measured according to GB/T1633.
Table 1 table of analytical test results
As can be seen from Table 1, the composition of the CO 2 -based biodegradable copolymer of the invention has better barrier property and transparency and has larger application value, and the barrier property is obviously reduced after the composition is blended with other kinds of degradable plastics.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. A composition of CO 2 -based biodegradable copolymers, comprising the following components: copolymers and adjuvants; the copolymer comprises 0.1-99% of propylene oxide-carbon dioxide binary copolymer, 0.1-99% of propylene oxide-phthalic anhydride-carbon dioxide ternary copolymer, 0-99% of propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide quaternary copolymer and 0-99% of propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide quaternary copolymer by mass percent.
2. The composition of claim 1, wherein the adjuvant comprises one or more of a lubricant, a chain extender, a filler, an opening agent, and a mold release agent.
3. The composition of claim 1, wherein the propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer is prepared by a process comprising the steps of:
carrying out copolymerization reaction on propylene oxide, ethylene oxide, phthalic anhydride, a nonmetal catalyst and carbon dioxide to obtain the propylene oxide-ethylene oxide-phthalic anhydride-carbon dioxide tetrapolymer; the pressure of the carbon dioxide is 0.1-4.0 MPa;
the molar ratio of the epoxypropane to the phthalic anhydride is 4-10: 1, a step of;
The molar ratio of the epoxypropane to the epoxyethane is 0.5-5:1.
4. The composition of claim 1, wherein the propylene oxide-phthalic anhydride-carbon dioxide terpolymer is prepared by a process comprising the steps of:
Carrying out copolymerization reaction on propylene oxide, phthalic anhydride, a nonmetallic catalyst and carbon dioxide to obtain the propylene oxide-phthalic anhydride-carbon dioxide terpolymer; the molar ratio of the epoxypropane to the phthalic anhydride is 4-10: 1, a step of; the pressure of the carbon dioxide is 0.1-4.0 MPa.
5. The composition of claim 1, wherein the propylene oxide-carbon dioxide binary copolymer is prepared by a process comprising the steps of:
carrying out copolymerization reaction on propylene oxide, a nonmetallic catalyst and carbon dioxide to obtain the propylene oxide-carbon dioxide binary copolymer; the pressure of the carbon dioxide is 0.1-4.0 MPa.
6. The composition of claim 1, wherein the propylene oxide-cyclohexane oxide-phthalic anhydride-carbon dioxide tetrapolymer is prepared by a process comprising the steps of:
Carrying out copolymerization reaction on propylene oxide, cyclohexene oxide, phthalic anhydride and carbon dioxide to obtain the propylene oxide-cyclohexene oxide-phthalic anhydride-carbon dioxide tetrapolymer;
the molar ratio of the epoxypropane to the phthalic anhydride is 4-10: 1, a step of;
the ratio of the amount of the substance of the propylene oxide to the total amount of the substances of the cyclohexene oxide and the phthalic anhydride is 2 to 10:1, a step of;
The pressure of the carbon dioxide is 0.1-4.0 MPa.
7. The composition according to claim 3 or 4 or 5 or 6, wherein the temperature of the copolymerization reaction is 40 to 100 ℃ for 4 to 10 hours.
8. The composition of claim 3 or 4 or 5 or 6, wherein the nonmetallic catalyst comprises one or more of tetra-n-butyl ammonium halide, tetra-n-propyl ammonium halide, triethylboron, and tributylboron.
9. A process for the preparation of a composition of CO 2 -based biodegradable copolymers according to any one of claims 1 to 8, characterized in that it comprises the following steps:
the composition is obtained by mixing and extruding the copolymer and the auxiliary agent according to the composition.
10. Use of a composition according to any one of claims 1 to 8 or a composition obtainable by a process according to claim 9 in a film bag product, sheet product, injection molded product or hollow bottle product.
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