CN116355189A - Carbon dioxide-based multi-component copolymer modified by naphthalene anhydride and preparation method thereof - Google Patents
Carbon dioxide-based multi-component copolymer modified by naphthalene anhydride and preparation method thereof Download PDFInfo
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- CN116355189A CN116355189A CN202310310518.4A CN202310310518A CN116355189A CN 116355189 A CN116355189 A CN 116355189A CN 202310310518 A CN202310310518 A CN 202310310518A CN 116355189 A CN116355189 A CN 116355189A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 60
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 60
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- -1 naphthalene anhydride Chemical class 0.000 title claims abstract description 56
- 229920001577 copolymer Polymers 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 30
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 30
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 31
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 9
- IZJDCINIYIMFGX-UHFFFAOYSA-N benzo[f][2]benzofuran-1,3-dione Chemical compound C1=CC=C2C=C3C(=O)OC(=O)C3=CC2=C1 IZJDCINIYIMFGX-UHFFFAOYSA-N 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 4
- 229920005604 random copolymer Polymers 0.000 claims description 4
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 230000004888 barrier function Effects 0.000 abstract description 18
- 229920000642 polymer Polymers 0.000 abstract description 4
- 229920006238 degradable plastic Polymers 0.000 abstract description 3
- 229920006029 tetra-polymer Polymers 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000007334 copolymerization reaction Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000005033 polyvinylidene chloride Substances 0.000 description 5
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 5
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 3
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BGULNPVMQAPGLT-UHFFFAOYSA-N [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Cl-].[NH4+].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 BGULNPVMQAPGLT-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- DWGRAWXTWKMPOT-UHFFFAOYSA-N fluoro-bis(2,3,4-trimethylphenyl)borane Chemical compound CC1=C(C(=C(C=C1)B(C1=C(C(=C(C=C1)C)C)C)F)C)C DWGRAWXTWKMPOT-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical group [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- 238000002834 transmittance Methods 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
- 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
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- 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
- C08G63/78—Preparation processes
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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
A carbon dioxide-based multi-component copolymer modified by naphthalene anhydride and a preparation method thereof belong to the technical field of degradable plastics. The method is characterized in that: is random or block tetrapolymer of propylene oxide, phthalic anhydride, naphthalene anhydride and carbon dioxide, and is prepared by the following steps: mixing the materials, adding the mixture into a reaction kettle, and adding a catalyst; filling carbon dioxide to carry out quaternary ring-opening copolymerization reaction; and after the reaction is finished, washing, devolatilizing, granulating and drying to obtain the purified tetrapolymer. According to the invention, the naphthalene ring structure is introduced into the carbon dioxide-based multi-component copolymer, so that the barrier property of the polymer is further improved by a proper amount of naphthalene ring structure, and meanwhile, the temperature resistance of the carbon dioxide-based multi-component copolymer is also improved by introducing the naphthalene ring structure.
Description
Technical Field
A carbon dioxide-based multi-component copolymer modified by naphthalene anhydride and a preparation method thereof belong to the technical field of degradable plastics.
Background
The high barrier plastics commonly used today are mainly polyvinylidene chloride (PVDC), ethylene vinyl alcohol copolymer (EVOH). Wherein PVDC has high water resistance, and water vapor permeability is 0.1 g/(m) 2 ﹒24h）~1g/（m 2 24 h), but has a problem of poor processability; while EVOH has high oxygen barrier property, and oxygen permeability of 0.1cm 3 /（m 2 ﹒24h﹒0.1MPa）~1cm 3 /（m 2 24h 0.1 MPa), but poor water resistance; and PVDC and EVOH are not degradable, and a large amount of PVDC and EVOH can cause environmental pollution.
Polymerization of propylene oxide and carbon dioxidePropylene Carbonate (PPC) is a transparent, fully degradable binary copolymer with high barrier property and water vapor permeability at 23 ℃ lower than 36 g/(m) 2 24 h), oxygen transmission rate at 23 ℃ is lower than 108cm 3 /（m 2 24h 0.1 MPa). The third monomer phthalic anhydride is introduced on the basis of PPC, and propylene oxide, phthalic anhydride and carbon dioxide are subjected to ternary polymerization to form the propylene phthalate-propylene carbonate copolymer (PPCP) which can ensure that the transparency and biodegradability of the material are not reduced, the barrier property is further improved, and the water vapor permeability at 23 ℃ is 1.2 g/(m) 2 24 h) or less, and an oxygen transmission rate of 2.5cm at 23 DEG C 3 /（m 2 24h 0.1 MPa) or less. PPCP is the degradable plastic with the best barrier property at present, the water resistance is close to PVDC, the oxygen resistance is close to EVOH, and the PPCP can be biodegraded without causing environmental pollution. However, in some areas where barrier properties are required to be higher, the barrier properties of PPCP remain somewhat inadequate.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art and provides a carbon dioxide-based multipolymer modified by naphthalene anhydride and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows: the carbon dioxide-based multi-component copolymer modified by naphthalene anhydride is characterized by being a quaternary or penta-component random or block copolymer of alkylene oxide, phthalic anhydride, naphthalene anhydride and carbon dioxide.
According to the invention, the naphthalene ring structure is introduced into the carbon dioxide-based multi-component copolymer, so that the barrier property and the temperature resistance of the polymer can be further improved.
The random or block copolymer of the carbon dioxide based multipolymer modified by the naphthalene anhydride has the structural general formula:
wherein Ar is 1 、Ar 2 Phenyl or naphthyl, ar 1 、Ar 2 Different; r is R 1 、R 2 、R 3 respectively-H or alkyl with carbon number less than 6, R 1 And R is 3 Can form a four-membered ring, a five-membered ring or a six-membered ring with the main chain; a is more than or equal to 1 and less than or equal to 10000, b is more than or equal to 1 and less than or equal to 10000, c is more than or equal to 0 and less than or equal to 20000, d is more than or equal to 0 and less than or equal to 20000, c+d is more than or equal to 1 and less than or equal to 20000, e is more than or equal to 0 and less than or equal to 1000, f is more than or equal to 0 and less than or equal to 1000, e is more than or equal to 0 and less than or equal to 1000, c+e is more than or equal to 1 and less than or equal to a, b, c, d, e, f, g are integers.
According to the invention, a naphthalene ring structure is introduced into the carbon dioxide-based multi-component copolymer, a proper amount of naphthalene ring structure can promote molecular chains to be in a plane, and the plane-type molecular chains can form a tiling effect, so that the barrier property of the polymer is further improved, and the water vapor transmittance at 23 ℃ is 0.7 g/(m) 2 24 h) or less, and an oxygen transmission rate of 1.3cm at 23 DEG C 3 /（m 2 24h 0.1 MPa) or less. And meanwhile, the introduction of the naphthalene ring structure can also improve the temperature resistance of the carbon dioxide-based multi-component copolymer.
Preferably, in the above structural formula:
3000≤a≤10000,300≤b+c≤1200,1500≤d≤5000,0≤e≤300。
the preferable ratio between the chain segments is that the barrier property and heat resistance of the material are better.
The preparation method of the carbon dioxide-based multi-component copolymer modified by the naphthalene anhydride comprises the following preparation steps:
1) Mixing alkylene oxide, phthalic anhydride and naphthalene anhydride, adding the mixture into a reaction kettle, and adding a catalyst; the molar ratio of the alkylene oxide to the phthalic anhydride is 4-10:1; the molar ratio of the epoxypropane to the naphthalene anhydride is 70-350:1; the molar ratio of the alkylene oxide to the catalyst is 600-1400:1;
2) The filling pressure of the carbon dioxide is 0.1-4 MPa, the carbon dioxide is heated to the reaction temperature of 30-100 ℃ for ring-opening copolymerization, and the reaction time is controlled to be 3-20 h; and after the reaction is finished, washing, devolatilizing, granulating and drying to obtain the purified copolymer.
The introduction of naphthalene anhydride can naturally improve the barrier properties and temperature resistance of carbon dioxide-based multi-component copolymers, but naphthalene anhydride also has greater steric hindrance during polymerization. Thus, it is more difficult to obtain a copolymer having a large molecular weight. According to the invention, the naphthalene anhydride is promoted to participate in polymerization mainly through material matching, the mixture ratio of the materials is based on alkylene oxide, phthalic anhydride and naphthalene anhydride which are properly mixed are matched, and the naphthalene anhydride is promoted to participate in copolymerization by utilizing the structural similarity of the phthalic anhydride and the naphthalene anhydride, so that the carbon dioxide-based multi-component copolymer with high naphthalene anhydride copolymerization content and high polymerization degree is obtained. The polymerization process is favorable for the participation of naphthalene anhydride in copolymerization, and the mass percentage of the copolymer which accords with the structural formula in the product after the polymerization is completed reaches more than 93 percent.
Conventional metal catalyst and nonmetal catalyst polymerization meet the basic catalytic requirements of the invention, and the catalyst is preferably selected from the group consisting of nonmetal catalysts in the step 1): a composite catalyst formed by the coordination of Lewis acid/alkali pairs. The nonmetallic catalyst is preferably used in the invention: the lewis acid/base pair does not introduce metallic impurities.
The Lewis acid/alkali pair in the step 1) is formed by compounding a composite catalyst, wherein the Lewis acid is triethylboron, tributylboron or/and di (trimethylphenyl) boron fluoride, and the Lewis base is one or more of tetra-n-butyl ammonium fluoride, tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium iodide or di (triphenylphosphine) ammonium chloride. The specific Lewis acid/alkali pair compatibility can meet the catalytic requirement of the invention and promote the copolymerization of naphthalene anhydride.
Preferably, the method for preparing the carbon dioxide-based copolymer modified by naphthalene anhydride is characterized in that: the catalyst in the step 1) is a composite catalyst of tetra-n-butyl ammonium halide or/and tetra-n-propyl ammonium halide and triethylboron or/and tributylboron. The preferable composite catalyst has more ideal catalytic effect on the invention, and the obtained copolymer has higher naphthalene anhydride content and better material barrier property. More preferably, the catalyst in the step 1) is a composite catalyst of triethylboron and tetra-n-butyl ammonium halide according to the mass ratio of (2-2.5): 1.
Preferably, the method for preparing the carbon dioxide-based copolymer modified by naphthalene anhydride is characterized in that: the naphthalene anhydride in the step 1) is 1, 8-naphthalene dicarboxylic anhydride or/and 2, 3-naphthalene dicarboxylic anhydride. The two kinds of naphthalene anhydride can obviously improve the barrier property of the copolymer after participating in copolymerization. Preference is given to 1, 8-naphthalenedicarboxylic acid anhydride. Firstly, 1, 8-naphthalene dicarboxylic anhydride is easier to participate in copolymerization in the invention, and carbon dioxide-based copolymer with higher naphthalene anhydride content and better barrier property is easy to obtain; secondly, the 1, 8-naphthalene dicarboxylic anhydride participates in the copolymerization to form a tiling effect on the molecular chain, and better barrier performance is shown under the condition that the naphthalene anhydride with similar content is copolymerized.
Preferably, the method for preparing the carbon dioxide-based copolymer modified by naphthalene anhydride is characterized in that: the molar ratio of the alkylene oxide to the phthalic anhydride in the step 1) is 6-8:1.
Preferably, the above-mentioned method for preparing a carbon dioxide-based copolymer modified with naphthalene anhydride is characterized in that: the molar feed ratio of the alkylene oxide to the naphthalene anhydride in the step 1) is 120-260:1.
Under the preferable material proportion, the material proportion is adapted to the copolymerization participation rate of the phthalic anhydride and the phthalic anhydride, so that the material utilization rate can be improved, and the workload of later washing and devolatilization can be reduced.
Preferably, the above-mentioned method for preparing a carbon dioxide-based copolymer modified with naphthalene anhydride is characterized in that: the molar ratio of the alkylene oxide to the catalyst in the step 1) is 800-1000:1.
Preferably, the above-mentioned method for preparing a carbon dioxide-based copolymer modified with naphthalene anhydride is characterized in that: the carbon dioxide filling pressure in the step 2) is 2.9-3.8 MPa, the reaction temperature is 30-45 ℃, and the reaction time is 4-9 h.
Under the preferable catalyst dosage and process conditions, the controlled reaction rate can better ensure that the naphthalene anhydride participates in the copolymerization, and the naphthalene anhydride content of copolymer species is improved. The process conditions adopt a low-temperature high-pressure mode as much as possible, so that more space is formed for the naphthalene anhydride while the carbon dioxide is promoted to participate in the copolymerization, and the naphthalene anhydride is facilitated to participate in the copolymerization.
Compared with the prior art, the carbon dioxide-based multi-component copolymer modified by the naphthalene anhydride and the preparation method thereof have the following beneficial effects: according to the invention, the naphthalene anhydride is promoted to participate in polymerization mainly through material matching, the mixture ratio of the materials is based on alkylene oxide, phthalic anhydride and naphthalene anhydride which are properly mixed are matched, and the naphthalene anhydride is promoted to participate in copolymerization by utilizing the structural similarity of the phthalic anhydride and the naphthalene anhydride, so that the carbon dioxide-based multi-component copolymer with high naphthalene anhydride copolymerization content and high polymerization degree is obtained. According to the invention, a naphthalene ring structure is introduced into the carbon dioxide-based multi-component copolymer, a proper amount of naphthalene ring structure can promote molecular chains to be in a plane, and the plane-type molecular chains can form a tiling effect, so that the barrier property of the polymer is further improved, and meanwhile, the temperature resistance of the carbon dioxide-based multi-component copolymer can be improved due to the introduction of the naphthalene ring structure.
Detailed Description
The present invention will be specifically described below by way of examples. All materials are commercially available, unless otherwise indicated.
Example 1
1) In a dried kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, propylene oxide, phthalic anhydride and 1, 8-naphthalene dicarboxylic anhydride are mixed and then added into a reaction kettle, a catalyst and a tetrahydrofuran solvent are added, and the catalyst is tetra-n-butyl ammonium chloride and triethylboron according to a molar ratio of 2: 1; the molar ratio of the epoxypropane to the phthalic anhydride is 7:1; the molar ratio of the epoxypropane to the 1, 8-naphthalene dicarboxylic anhydride is 190:1; the molar ratio of the propylene oxide to the catalyst is 900:1;
2) The filling pressure of the carbon dioxide is 3.4MPa, the mixture is heated to the reaction temperature of 35 ℃ to carry out quaternary ring-opening copolymerization reaction, and the reaction time is controlled to be 7h; dissolving with dichloromethane after reaction, adding small amount of acid to terminate reaction, precipitating with ethanol, devolatilizing the precipitate solid phase, granulating, drying, and analyzing and testing, M n =1.49×10 5 g/mol, PDI=2.26, and the mass percentage of the copolymer conforming to the structural formula in the detected product reaches more than 96%. .
Example 2
1) In a dried kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, alkylene oxide, phthalic anhydride and 2, 3-naphthalene dicarboxylic anhydride are mixed and then added into a reaction kettle, and a catalyst and a tetrahydrofuran solvent are added, wherein the catalyst is a composite catalyst of tetra-n-butyl ammonium chloride and triethylboron according to a molar ratio of 2:1; the molar ratio of alkylene oxide to phthalic anhydride is 7:1; the molar ratio of the alkylene oxide to the 2, 3-naphthalene dicarboxylic anhydride is 190:1; the molar ratio of alkylene oxide to catalyst is 900:1; alkylene oxide is ethylene oxide and propylene oxide in a molar ratio of 2:1, a mixture of two or more of the above-mentioned materials;
2) The filling pressure of the carbon dioxide is 3.4MPa, the mixture is heated to the reaction temperature of 35 ℃ to carry out quaternary ring-opening copolymerization reaction, and the reaction time is controlled to be 7h; dissolving with dichloromethane after reaction, adding small amount of acid to terminate reaction, precipitating with ethanol, devolatilizing the precipitate solid phase, granulating, drying, and analyzing and testing, M n =1.46×10 5 g/mol, PDI=2.64, and the mass percentage of the copolymer conforming to the structural formula in the detected product reaches more than 95.6 percent. .
Example 3
1) In a dried kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, alkylene oxide, phthalic anhydride and 1, 8-naphthalene dicarboxylic anhydride are mixed and then added into a reaction kettle, and a catalyst and a tetrahydrofuran solvent are added, wherein the catalyst is a composite catalyst of tetra-n-butyl ammonium bromide and triethylboron according to a mass ratio of 2.5:1; the molar ratio of alkylene oxide to phthalic anhydride is 8:1; the molar ratio of the alkylene oxide to the 1, 8-naphthalene dicarboxylic anhydride is 260:1; the molar ratio of alkylene oxide to catalyst is 1000:1; the alkylene oxide is propylene oxide and cyclohexane oxide according to the mol ratio of 4:1, a mixture of two or more of the above-mentioned materials;
2) The filling pressure of the carbon dioxide is 3.8MPa, the mixture is heated to the reaction temperature of 45 ℃ to carry out quaternary ring-opening copolymerization reaction, and the reaction time is controlled to be 4 hours; dissolving with dichloromethane after reaction, adding small amount of acid to terminate reaction, precipitating with ethanol, devolatilizing the precipitate solid phase, granulating, drying, and analyzing and testing, M n =1.48×10 5 g/mol, PDI=2.63, and the mass percentage of the copolymer conforming to the structural formula in the detected product reaches more than 95.4 percent. .
Example 4
1) In a dried kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, propylene oxide, phthalic anhydride and 1, 8-naphthalene dicarboxylic anhydride are mixed and then added into a reaction kettle, and a catalyst and a tetrahydrofuran solvent are added, wherein the catalyst is a composite catalyst of tetra-n-butyl ammonium fluoride and triethylboron according to a molar ratio of 2.3:1; the molar ratio of the epoxypropane to the phthalic anhydride is 6:1; the molar ratio of the epoxypropane to the 1, 8-naphthalene dicarboxylic anhydride is 120:1; the molar ratio of the propylene oxide to the catalyst is 800:1;
2) The filling pressure of the carbon dioxide is 2.9MPa, the mixture is heated to the reaction temperature of 30 ℃ to carry out quaternary ring-opening copolymerization reaction, and the reaction time is controlled to be 9h; dissolving with dichloromethane after reaction, adding small amount of acid to terminate reaction, precipitating with ethanol, devolatilizing the precipitate solid phase, granulating, drying, and analyzing and testing, M n =1.48×10 5 g/mol, PDI=2.41, and the mass percentage of the copolymer conforming to the structural formula in the detected product reaches more than 93.8 percent.
Example 5
1) In a dried kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, propylene oxide, phthalic anhydride and 1, 8-naphthalene dicarboxylic anhydride are mixed and then added into a reaction kettle, a catalyst and a tetrahydrofuran solvent are added, and the catalyst is tetra-n-propyl ammonium chloride and tributylboron according to a mole ratio of 3: 1; the molar ratio of the epoxypropane to the phthalic anhydride is 4:1; the molar ratio of the epoxypropane to the 1, 8-naphthalene dicarboxylic anhydride is 70:1; the molar ratio of the propylene oxide to the catalyst is 1400:1;
2) The filling pressure of the carbon dioxide is 0.1MPa, the mixture is heated to the reaction temperature of 30 ℃ to carry out quaternary ring-opening copolymerization reaction, and the reaction time is controlled to be 20h; dissolving with dichloromethane after reaction, adding small amount of acid to terminate reaction, precipitating with ethanol, devolatilizing the precipitate solid phase, granulating, drying, and analyzing and testing, M n =1.44×10 5 g/mol, PDI=2.33, and the mass percentage of the copolymer conforming to the structural formula in the detected product reaches more than 93.7 percent.
Example 6
1) In a dried kettle, high-purity carbon dioxide is adopted to replace air in the kettle, then feeding is started, alkylene oxide, phthalic anhydride and 1, 8-naphthalene dicarboxylic anhydride are mixed and then added into a reaction kettle, a catalyst and a tetrahydrofuran solvent are added, and the catalyst is tetra-n-propyl ammonium fluoride and triethylboron according to the mole ratio of 1.5: 1; the molar ratio of alkylene oxide to phthalic anhydride is 10:1; the molar ratio of the alkylene oxide to the 1, 8-naphthalene dicarboxylic anhydride is 350:1; the molar ratio of alkylene oxide to catalyst was 600:1; alkylene oxide is ethylene oxide and cyclohexane oxide according to the mol ratio of 10:1, a mixture of two or more of the above-mentioned materials;
2) The filling pressure of the carbon dioxide is 4Mpa, the reaction temperature is heated to 100 ℃ to carry out quaternary ring-opening copolymerization reaction, and the reaction time is controlled to be 3h; dissolving with dichloromethane after reaction, adding small amount of acid to terminate reaction, precipitating with ethanol, devolatilizing the precipitate solid phase, granulating, drying, and analyzing and testing, M n =1.42×10 5 g/mol, PDI=2.66, and the mass percentage of the copolymer conforming to the structural formula in the detected product reaches more than 93.2 percent.
Comparative example 1
The material proportioning and preparation process of example 1 were carried out, except that the 1, 8-naphthalene dicarboxylic anhydride in the material was replaced with the same molar amount of phthalic anhydride; m of the resulting copolymer n =1.40×10 5 g/mol，PDI=2.27。
The copolymers obtained in examples and comparative examples were made into samples for performance testing:
1. the water vapor transmission was measured in accordance with GB/T1037, and the film thickness was 80. Mu.m.
2. The oxygen permeation amount was measured in accordance with GB/T1038, and the film thickness was 80. Mu.m.
The water vapor and oxygen transmission rates of the copolymers prepared in examples 1 to 3 and comparative example 1 of the present invention are compared with the following table:
| examples | Glass transition temperature (DEG C) | Pyrolysis temperature (DEG C) | Oxygen transmission capacity cm 3 /（m 2 ﹒24h﹒0.1MPa） | Water vapor transmission rate g/(m) 2 ﹒24h |
| Example 1 | 83.4 | 318 | 1.1 | 0.4 |
| Example 2 | 81.2 | 311 | 1.2 | 0.5 |
| Example 3 | 82.4 | 316 | 1.1 | 0.4 |
| Example 4 | 82.2 | 316 | 1.1 | 0.5 |
| Example 5 | 80.6 | 310 | 1.2 | 0.6 |
| Example 6 | 80.1 | 305 | 1.3 | 0.7 |
| Comparative example 1 | 68.4 | 263 | 2.0 | 1.1 |
Therefore, compared with the propylene oxide-phthalic anhydride-carbon dioxide, the biodegradable propylene oxide-phthalic anhydride-naphthalene anhydride-carbon dioxide tetrapolymer prepared by the invention can ensure the degradability and simultaneously obviously improve the barrier property. The invention can be applied to the modification of PPCP materials and can lead the application of the PPCP materials to be wider.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (9)
1. A carbon dioxide-based multi-component copolymer modified by naphthalene anhydride is characterized by being a quaternary or penta-component random or block copolymer of alkylene oxide, phthalic anhydride, naphthalene anhydride and carbon dioxide.
2. The carbon dioxide-based copolymer modified with naphthalene anhydride according to claim 1, wherein the random or block copolymer has the general structural formula:
wherein Ar is 1 、Ar 2 Phenyl or naphthyl, ar 1 、Ar 2 Different; r is R 1 、R 2 、R 3 respectively-H or alkyl with carbon number less than 6, R 1 And R is 3 Can form a four-membered ring, a five-membered ring or a six-membered ring with the main chain; a is more than or equal to 1 and less than or equal to 10000, b is more than or equal to 1 and less than or equal to 10000, c is more than or equal to 0 and less than or equal to 20000, d is more than or equal to 0 and less than or equal to 20000, c+d is more than or equal to 1 and less than or equal to 20000, e is more than or equal to 0 and less than or equal to 1000, f is more than or equal to 0 and less than or equal to 1000, e is more than or equal to 0 and less than or equal to 1000, c+e is more than or equal to 1 and less than or equal to a, b, c, d, e, f, g are integers.
3. A process for the preparation of a carbon dioxide based copolymer modified with naphthalene anhydride according to claim 1 or 2, characterized by the steps of:
1) Mixing alkylene oxide, phthalic anhydride and naphthalene anhydride, adding the mixture into a reaction kettle, and adding a catalyst; the molar ratio of the alkylene oxide to the phthalic anhydride is 4-10:1; the molar ratio of the epoxypropane to the naphthalene anhydride is 70-350:1; the molar ratio of the alkylene oxide to the catalyst is 600-1400:1;
2) The filling pressure of the carbon dioxide is 0.1-4 MPa, the carbon dioxide is heated to the reaction temperature of 30-100 ℃ for ring-opening copolymerization, and the reaction time is controlled to be 3-20 h; and after the reaction is finished, washing, devolatilizing, granulating and drying to obtain the purified copolymer.
4. A process for the preparation of a carbon dioxide based copolymer modified with naphthalene as claimed in claim 3, wherein: the catalyst in the step 1) is a composite catalyst of tetra-n-butyl ammonium halide or/and tetra-n-propyl ammonium halide and triethylboron or/and tributylboron.
5. A process for the preparation of a carbon dioxide based copolymer modified with naphthalene as claimed in claim 3, wherein: the naphthalene anhydride in the step 1) is 1, 8-naphthalene dicarboxylic anhydride or/and 2, 3-naphthalene dicarboxylic anhydride.
6. A process for the preparation of a carbon dioxide based copolymer modified with naphthalene as claimed in claim 3, wherein: the molar ratio of the alkylene oxide to the phthalic anhydride in the step 1) is 6-8:1.
7. A process for the preparation of a carbon dioxide based copolymer modified with naphthalene as claimed in claim 3, wherein: the molar feed ratio of the alkylene oxide to the naphthalene anhydride in the step 1) is 120-260:1.
8. A process for the preparation of a carbon dioxide based copolymer modified with naphthalene as claimed in claim 3, wherein: the molar ratio of the alkylene oxide to the catalyst in the step 1) is 800-1000:1.
9. A process for the preparation of a carbon dioxide based copolymer modified with naphthalene as claimed in claim 3, wherein: the carbon dioxide filling pressure in the step 2) is 2.9-3.8 MPa, the reaction temperature is 30-45 ℃, and the reaction time is 4-9 h.
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