CN114525017B - Semi-aromatic carbon dioxide based copolymer high-toughness composition and preparation method thereof - Google Patents
Semi-aromatic carbon dioxide based copolymer high-toughness composition and preparation method thereof Download PDFInfo
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention provides a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer and a preparation method thereof. The composition is prepared from the semi-aromatic carbon dioxide-based copolymer, the PBAT, the filler and the compatibilizer, and the glass transition temperature of the composition is improved and the biodegradability of the composition is improved by regulating and controlling the structure of a molecular chain segment in the semi-aromatic carbon dioxide-based copolymer, so that the biodegradable material with good transparency, strong light transmittance, mechanical property, processability and service performance meeting the requirements of practical application is obtained.
Description
Technical Field
The invention belongs to the technical field of C08G63/64, and particularly relates to a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer and a preparation method thereof.
Background
Propylene oxide and carbon dioxide copolymers have biodegradability and excellent gas barrier properties, but their low glass transition temperature limits their use. PBAT is a plastic with excellent biodegradability and higher heat resistance, but the PBAT has low tensile strength due to the molecular structure of the PBAT, so that the application of the PBAT in the field of high-strength films is limited.
Chinese patent CN101724251B discloses a blend of PPC (propylene oxide and carbon dioxide copolymer) and PBAT, but the resulting blend has little improvement in tensile strength and lower glass transition temperature. Still, the use in the special field is not satisfied. Based on the above, the applicant provides a high-toughness composition of semi-aromatic carbon dioxide-based copolymer and a preparation method thereof, and a degradable high-toughness composition with good tensile strength is obtained.
Disclosure of Invention
The invention provides a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer, which comprises 1-99 parts of the semi-aromatic carbon dioxide-based copolymer, 1-99 parts of PBAT and 0.1-20 parts of functional auxiliary agents.
In a preferred embodiment, the raw materials comprise, by weight, 20-50 parts of the semi-aromatic carbon dioxide-based copolymer, 50-80 parts of the PBAT, and 1-15 parts of the functional auxiliary agent.
In a preferred embodiment, the tensile strength of the PBAT is from 12 to 25MPa.
In a preferred embodiment, the tensile strength of the PBAT is in the range of 20-25MPa.
In a preferred embodiment, the PBAT is purchased from polyester limited, model TH801T, of mountain, singapore.
In a preferred embodiment, the semi-aromatic carbon dioxide based copolymer is prepared by the following method:
(1) Adding phthalic anhydride, partial epoxypropane and a catalyst into a reactor, introducing carbon dioxide, and reacting;
(2) And adding the rest propylene oxide, continuing the reaction, and drying in vacuum after the reaction is finished to obtain the semi-aromatic carbon dioxide-based copolymer.
In a preferred embodiment, part of the propylene oxide in step (1) comprises 30-80% of the total mass of propylene oxide.
In a preferred embodiment, the portion of propylene oxide in step (1) comprises 80% of the total mass of propylene oxide.
In a preferred embodiment, the molar ratio of phthalic anhydride to propylene oxide is (1-5): (5-12).
In a preferred embodiment, the molar ratio of phthalic anhydride to propylene oxide is 1.5:10.
In a preferred embodiment, the catalyst is a combination of tetrabutylammonium halide and triethylboron free.
In a preferred embodiment, the molar ratio of tetrabutylammonium halide to triethylboron is 1:8.
in a preferred embodiment, the molar ratio of propylene oxide to metal-free two-component catalyst is 440:1.
the applicant found in the experimental process that propylene oxide is added twice in the process of preparing the semi-aromatic carbon dioxide-based copolymer in the system, and especially when part of propylene oxide in the step (1) accounts for 80% of the total mass of propylene oxide, the glass transition temperature of propylene carbonate can be increased and the tensile strength of propylene carbonate can be improved under the condition of improving the random distribution of soft segments and hard segments in the prepared propylene carbonate molecular chain segments.
In a preferred embodiment, the functional auxiliary is at least one selected from the group consisting of a compatibilizer, a lubricant, a filler, an opening agent, and a mold release agent.
In a preferred embodiment, the compatibilizer is selected from at least one of ethylene-butyl acrylate, hexamethylene diisocyanate, polycaprolactone, tetrabutyl titanate, epoxy chain extender, oxazoline chain extender.
In a preferred embodiment, the mass ratio of the compatibilizer to the semi-aromatic carbon dioxide based copolymer is 1: (20-60).
In a preferred embodiment, the mass ratio of the compatibilizer to the semi-aromatic carbon dioxide based copolymer is 1:20.
In a preferred embodiment, the semi-aromatic carbon dioxide based copolymer and PBAT are present in a mass ratio of (3-5): (5-7).
In a preferred embodiment, the semi-aromatic carbon dioxide based copolymer and PBAT are present in a mass ratio of 3:7.
In the application, the specific semi-aromatic carbon dioxide-based copolymer and the specific PBAT are prepared into the high-toughness composition according to the specific raw material proportion, so that the melt viscosity of the semi-aromatic carbon dioxide-based copolymer is improved, the compatibility of the semi-aromatic carbon dioxide-based copolymer and the specific PBAT is improved, and the stability of the composition is improved by adding the compatibilizer. The composition obtained by the application shows good flexibility, mechanical processing performance and excellent biodegradability.
In a preferred embodiment, the filler is selected from at least one of silica, ground calcium carbonate, titanium dioxide, zinc oxide.
In a preferred embodiment, the filler is titanium dioxide.
In a preferred embodiment, the titanium dioxide is a silane coupling agent modified titanium dioxide.
In a preferred embodiment, the particle size of the titanium dioxide is 15nm.
In a preferred embodiment, the silane coupling agent is selected from at least one of an alkenyl silane coupling agent, an amino silane coupling agent, and an epoxy silane coupling agent.
In a preferred embodiment, the silane coupling agent modified titanium dioxide is a compound of an aminosilane coupling agent modified titanium dioxide and an alkenylsilane coupling agent modified titanium dioxide.
In a preferred embodiment, the mass ratio of the aminosilane coupling agent-modified titanium dioxide to the alkenylsilane coupling agent-modified titanium dioxide is (2.5-4.8): 1.
in a preferred embodiment, the mass ratio of the aminosilane coupling agent modified titanium dioxide to the alkenylsilane coupling agent modified titanium dioxide is 3.5:1.
in the present application, the kinds of the aminosilane coupling agent and the alkenylsilane coupling agent are not particularly limited, and 3-aminopropyl triethoxysilane and vinyltris (2-methoxyethoxy) silane are preferable.
In a preferred embodiment, the mass ratio of filler to PBAT is 1: (5-15).
In a preferred embodiment, the mass ratio of filler to PBAT is 1:7.
The applicant finds that the addition of modified titanium dioxide with specific particle size can improve the toughness of the composition and can also improve the compatibility degree and the temperature resistance of the composition in the experimental process. The applicant speculates that the possible reason is that the modified titanium dioxide may act as a junction point between the semi-aromatic carbon dioxide based copolymer and the PBAT in the system, promoting the compatibility of the composition while also promoting the formation of a three-dimensional structure of the composition, increasing the toughness and tensile strength of the composition.
The second aspect of the invention provides a method for preparing a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer, comprising the following steps: dehydrating and drying the semi-aromatic carbon dioxide-based copolymer, the PBAT and the functional auxiliary agent at 55-70 ℃, putting into a mixer, uniformly mixing, adding the mixture into a double-screw extruder, and extruding at 100-160 ℃ to obtain the high-toughness composition.
Compared with the prior art, the invention has the beneficial effects that:
according to the composition obtained by blending the carbonic acid copolymer, the PBAT, the compatibilizer and the modified titanium dioxide, the composition is promoted to form a three-dimensional structure by regulating and controlling the structure of a molecular chain segment in the semi-aromatic carbon dioxide-based copolymer, adding the modified titanium dioxide and other methods, the glass transition temperature of the composition is improved, the toughness of the composition is improved, the biodegradability of the composition is improved, and the biodegradable material which has good transparency, strong light transmittance, mechanical property, processability and service performance and meets the requirement of practical application is obtained.
Detailed Description
Example 1
The invention provides a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer, which is prepared from the following raw materials of 30 parts of the semi-aromatic carbon dioxide-based copolymer, 70 parts of PBAT, 1.5 parts of compatibilizer and 10 parts of filler.
The compatibilizer is an epoxy compound chain extender, and specifically is glycidyl methacrylate.
The filler is silane coupling agent modified titanium dioxide, the silane coupling agent modified titanium dioxide is a compound substance of 3-aminopropyl triethoxysilane modified titanium dioxide and vinyl tri (2-methoxyethoxy) silane modified titanium dioxide, and the mass ratio of the 3-aminopropyl triethoxysilane modified titanium dioxide to the vinyl tri (2-methoxyethoxy) silane modified titanium dioxide is 3.5:1.
The preparation method of the silane coupling agent modified titanium dioxide comprises the following steps: 5g of titanium dioxide is dispersed in 50ml of absolute ethyl alcohol, ultrasonic is carried out for 10min, 3g of silane coupling agent is added, the temperature is kept at 70 ℃, and ultrasonic is carried out for 1.5h, thus obtaining modified titanium dioxide.
The titanium dioxide is purchased from Beijing De island gold technology Co., ltd, and has a particle size of 15nm.
The semi-aromatic carbon dioxide-based copolymer is prepared according to the following steps:
(1) Adding phthalic anhydride, propylene oxide accounting for 80 percent of the total mass of the propylene oxide, tetrabutylammonium bromide and triethylboron into a reactor, introducing carbon dioxide to a pressure of 1.1MPa, and reacting for 6 hours at 70 ℃;
(2) And adding propylene oxide accounting for 20% of the total mass of the propylene oxide, continuously reacting for 2 hours at 70 ℃, and drying in vacuum after the reaction is finished to obtain the semi-aromatic carbon dioxide-based copolymer.
Wherein, the mole ratio of phthalic anhydride to epoxypropane is 1.5:10; the molar ratio of propylene oxide to the metal-free two-component catalyst was 440:1, a step of; the molar ratio of tetrabutylammonium bromide to triethylboron is 1:8.
the PBAT is purchased from polyester limited company of mountain Tuber He in Xinjiang, and the model is TH801T.
The second aspect of the invention provides a method for preparing a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer, comprising the following steps: and (3) dehydrating and drying the semi-aromatic carbon dioxide-based copolymer, the PBAT and the compatibilizer at the temperature of 60 ℃, putting the mixture into a mixer, uniformly mixing, adding the mixture into a double-screw extruder, and extruding at the temperature of 140 ℃ to obtain the high-toughness composition.
Example 2
The first aspect of the invention provides a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer, which is prepared from 40 parts of the semi-aromatic carbon dioxide-based copolymer, 60 parts of PBAT, 2 parts of a compatibilizer and 8.57 parts of a filler.
The compatibilizer is an oxazoline type chain extender, and is purchased from Shanghai Han Luo New Material Co., ltd, and the model is RAS-1005.
The filler is silane coupling agent modified titanium dioxide, the silane coupling agent modified titanium dioxide is a compound substance of 3-aminopropyl triethoxysilane modified titanium dioxide and vinyl tri (2-methoxyethoxy) silane modified titanium dioxide, and the mass ratio of the 3-aminopropyl triethoxysilane modified titanium dioxide to the vinyl tri (2-methoxyethoxy) silane modified titanium dioxide is 3.5:1.
The preparation method of the silane coupling agent modified titanium dioxide comprises the following steps: 5g of titanium dioxide is dispersed in 50ml of absolute ethyl alcohol, ultrasonic is carried out for 10min, 3g of silane coupling agent is added, the temperature is kept at 70 ℃, and ultrasonic is carried out for 1.5h, thus obtaining modified titanium dioxide.
The titanium dioxide is purchased from Beijing De island gold technology Co., ltd, and has a particle size of 15nm.
The semi-aromatic carbon dioxide-based copolymer is prepared according to the following steps:
(1) Adding phthalic anhydride, propylene oxide accounting for 80 percent of the total mass of the propylene oxide, tetrabutylammonium bromide and triethylboron into a reactor, introducing carbon dioxide to a pressure of 1.1MPa, and reacting for 6 hours at 70 ℃;
(2) And adding propylene oxide accounting for 20% of the total mass of the propylene oxide, continuously reacting for 2 hours at 70 ℃, and drying in vacuum after the reaction is finished to obtain the semi-aromatic carbon dioxide-based copolymer.
Wherein, the mole ratio of phthalic anhydride to epoxypropane is 1.5:10; the molar ratio of propylene oxide to the metal-free two-component catalyst was 440:1, a step of; the molar ratio of tetrabutylammonium bromide to triethylboron is 1:8.
the PBAT is purchased from polyester limited company of mountain Tuber He in Xinjiang, and the model is TH801T.
The second aspect of the invention provides a method for preparing a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer, comprising the following steps: and (3) dehydrating and drying the semi-aromatic carbon dioxide-based copolymer, the PBAT and the compatibilizer at the temperature of 60 ℃, putting the mixture into a mixer, uniformly mixing, adding the mixture into a double-screw extruder, and extruding at the temperature of 140 ℃ to obtain the high-toughness composition.
Example 3
The first aspect of the invention provides a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer, which is prepared from the following raw materials of 30 parts of the semi-aromatic carbon dioxide-based copolymer, 70 parts of PBAT and 1.5 parts of a compatibilizer.
The compatibilizer is an epoxy compound chain extender, and specifically is glycidyl methacrylate.
The semi-aromatic carbon dioxide-based copolymer is prepared according to the following steps:
(1) Adding phthalic anhydride, propylene oxide accounting for 80 percent of the total mass of the propylene oxide, tetrabutylammonium bromide and triethylboron into a reactor, introducing carbon dioxide to a pressure of 1.1MPa, and reacting for 6 hours at 70 ℃;
(2) And adding propylene oxide accounting for 20% of the total mass of the propylene oxide, continuously reacting for 2 hours at 70 ℃, and drying in vacuum after the reaction is finished to obtain the semi-aromatic carbon dioxide-based copolymer.
Wherein, the mole ratio of phthalic anhydride to epoxypropane is 1.5:10; the molar ratio of propylene oxide to the metal-free two-component catalyst was 440:1, a step of; the molar ratio of tetrabutylammonium bromide to triethylboron is 1:8.
the PBAT is purchased from polyester limited company of mountain Tuber He in Xinjiang, and the model is TH801T.
The second aspect of the invention provides a method for preparing a high-toughness composition of a semi-aromatic carbon dioxide-based copolymer, comprising the following steps: and (3) dehydrating and drying the semi-aromatic carbon dioxide-based copolymer, the PBAT and the compatibilizer at the temperature of 60 ℃, putting the mixture into a mixer, uniformly mixing, adding the mixture into a double-screw extruder, and extruding at the temperature of 140 ℃ to obtain the high-toughness composition.
Performance testing
The high-toughness composition prepared in the example is prepared according to a method commonly used by a person skilled in the art, the tensile property and the elongation at break of the sample are tested according to national standard GB/T1040, and the biodegradability is tested according to national standard GB/T19277. The data are recorded in table 1.
TABLE 1
Claims (6)
1. A high-toughness composition of semi-aromatic carbon dioxide-based copolymer is characterized in that the raw materials are prepared from the following raw materials in parts by weight,
comprises 20-50 parts of semi-aromatic carbon dioxide-based copolymer, 50-80 parts of PBAT and 1-15 parts of functional auxiliary agent;
the functional auxiliary agent is at least one selected from a compatibilizer, a lubricant, a filler, an opening agent and a release agent;
the filler is titanium dioxide;
the titanium dioxide is silane coupling agent modified titanium dioxide;
the molar ratio of phthalic anhydride to propylene oxide is 1.5:10;
the preparation method of the semi-aromatic carbon dioxide-based copolymer comprises the following steps:
(1) Adding phthalic anhydride, partial epoxypropane and a catalyst into a reactor, introducing carbon dioxide, and reacting; the part of propylene oxide accounts for 30-80% of the total mass of the propylene oxide;
(2) And adding the rest propylene oxide, continuing the reaction, and drying in vacuum after the reaction is finished to obtain the semi-aromatic carbon dioxide-based copolymer.
2. The high toughness composition according to claim 1, wherein the tensile strength of the PBAT is 12-25MPa.
3. The high toughness composition according to claim 1, wherein the tensile strength of the PBAT is 20-25MPa.
4. The high toughness composition according to claim 1, wherein the compatibilizer is selected from at least one of ethylene-butyl acrylate, hexamethylene diisocyanate, polycaprolactone, tetrabutyl titanate, epoxy chain extender, oxazoline type chain extender.
5. The high-toughness composition according to claim 1, wherein the silane coupling agent is at least one selected from the group consisting of an alkenyl silane coupling agent, an aminosilane coupling agent, and an epoxy silane coupling agent.
6. A method of preparing a high toughness composition according to any one of claims 1-5, comprising the steps of: dehydrating and drying the semi-aromatic carbon dioxide-based copolymer, the PBAT and the functional auxiliary agent at 55-70 ℃, putting into a mixer, mixing uniformly, adding the mixture into a double-screw extruder, and extruding at 100-160 ℃ to obtain the high-toughness composition.
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| CN202111118683.7A CN114525017B (en) | 2021-09-24 | 2021-09-24 | Semi-aromatic carbon dioxide based copolymer high-toughness composition and preparation method thereof |
| PCT/CN2022/119498 WO2023045850A1 (en) | 2021-09-24 | 2022-09-19 | High-toughness composition of semi-aromatic carbon dioxide-based copolymer and preparation method therefor |
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| CN114525017B (en) * | 2021-09-24 | 2023-04-28 | 山东联欣环保科技有限公司 | Semi-aromatic carbon dioxide based copolymer high-toughness composition and preparation method thereof |
| CN115521591B (en) * | 2022-11-07 | 2023-01-31 | 山东联欣环保科技有限公司 | High-toughness composition of carbon dioxide-based quadripolymer 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 |
| CN116355194A (en) * | 2023-05-25 | 2023-06-30 | 山东联欣环保科技有限公司 | Method for improving barrier property of polycarbonate |
| CN117024941A (en) * | 2023-10-08 | 2023-11-10 | 山东联欣环保科技有限公司 | Carbon dioxide-based biodegradable barrier composition |
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| US4855356A (en) * | 1987-12-30 | 1989-08-08 | General Electric Company | Ternary polymer blends containing a polyetherimide, a polyphthalate carbonate, and rubber modified vinyl aromatic polymer |
| JP2854139B2 (en) * | 1992-10-23 | 1999-02-03 | ゼネラル・エレクトリック・カンパニイ | Thermoformable flame retardant compounds of copolymer resins |
| CN101724242B (en) * | 2009-12-11 | 2012-02-29 | 内蒙古蒙西高新技术集团有限公司 | Blend of PPC, PBAT, PCL and PLA and preparation method thereof |
| CN101985430A (en) * | 2010-09-02 | 2011-03-16 | 福建师范大学 | Novel poly(propylene carbonate) as well as preparation method and application thereof as chain extender |
| US8586183B2 (en) * | 2011-01-13 | 2013-11-19 | Sabic Innovative Plastics Ip B.V. | Thermoplastic compositions, method of manufacture, and uses thereof |
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| CN103694464A (en) * | 2013-12-05 | 2014-04-02 | 青岛农业大学 | Environment-friendly plasticizer and preparation method thereof |
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| CN114525017B (en) * | 2021-09-24 | 2023-04-28 | 山东联欣环保科技有限公司 | Semi-aromatic carbon dioxide based copolymer high-toughness composition and preparation method thereof |
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