CN110423334B - Preparation method of total-organism-based vitrimer - Google Patents
Preparation method of total-organism-based vitrimer Download PDFInfo
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- CN110423334B CN110423334B CN201910727777.0A CN201910727777A CN110423334B CN 110423334 B CN110423334 B CN 110423334B CN 201910727777 A CN201910727777 A CN 201910727777A CN 110423334 B CN110423334 B CN 110423334B
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- vitrimer
- soybean oil
- rosin
- acid derivative
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
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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
- C08G2280/00—Compositions for creating shape memory
Abstract
The invention discloses a preparation method of a full-biology-based vitrimer, which is prepared from rosin resin acid derivatives and epoxidized soybean oil under the action of a catalyst. The invention relates to a preparation method of a full-biology-based vitrimer, which prepares a full-biology-based vitrimer material containing a hydrogenated phenanthrene ring structure, and by using high-biocompatibility biology-based raw materials of epoxidized soybean oil and rosin resin acid derivatives, the problems of high toxicity of the traditional bisphenol A-type vitrimer, poor mechanical property of the soybean oil-based vitrimer and low glass transition temperature are effectively solved, and the obtained vitrimer is a nontoxic material completely based on biomass and has good biocompatibility and can be subjected to self-healing, reprocessing and shape memory; the preparation method is simple, strong in operability and easy to implement.
Description
Technical Field
The invention relates to a preparation method of a total-biology-base vitrimer, belonging to the field of preparation of vitrimers.
Background
Conventional polymer materials are classified into thermosetting resins and thermoplastic resins. Thermosetting resins have excellent mechanical properties, thermal stability and chemical resistance, but are difficult to recycle due to the permanently crosslinked network structure after curing; thermoplastic resins can be recycled after heating, but have poor mechanical properties and solvent resistance, and are structurally unstable at high temperatures. Therefore, a polymer material between a thermosetting resin and a thermoplastic resin, which combines good mechanical properties and thermal stability of the thermosetting resin and reworkability of the thermoplastic resin, has been widely focused and studied. Leibler et al, 2011, first proposed the concept of vitrimers, which have dynamic covalent bonds in the molecular network structure and exhibit rheological behavior similar to glass at high temperatures, and are therefore also referred to as glass-like polymers. The Vitrimer has a dynamic covalent exchange network that allows healing and rework to be achieved while maintaining the structural integrity of the network, while the Vitrimer has shape memory behavior due to the dynamic covalent exchange reaction. Based on the special properties of the material, the material can be better applied to the fields of adhesives, coatings, electronic materials, soft robots and the like.
However, most of the raw materials for preparing the epoxy vitrier are petrochemical-based products, and in consideration of environmental protection, the use of natural renewable, nontoxic and biocompatible biomass raw materials for preparing the epoxy vitrier is of great significance, and the development of the bio-based vitrier material also conforms to the concept of sustainable development.
Disclosure of Invention
The invention provides a preparation method of a full-biology-based vitrimer, which takes renewable biomass resources as raw materials to prepare the full-biology-based vitrimer with healing, reprocessing and shape memory properties.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing a total biological-based vitrimer is prepared from rosin resin acid derivatives and epoxidized soybean oil under the action of a catalyst.
The rosin resin acid derivative and the epoxidized soybean oil are renewable biomass resources. The epoxidized soybean oil is a biomass resource which is industrially produced, has wide source and low price, and simultaneously contains rich epoxy functional groups, and the inventor finds that the mechanical property of the prepared material is relatively poor due to the strong flexible chain structure of the epoxidized soybean oil, and the glass transition temperature is lower than the room temperature, so that the triple shape memory behavior of the vitrimer material is difficult to show; the epoxy soybean oil is solidified by introducing the rosin resin acid derivative containing the hydrogenated phenanthrene ring structure, so that the mechanical property and the glass transition temperature of the epoxy soybean oil-based vitrimer are remarkably improved, and the obtained vitrimer is completely based on biomass, is non-toxic and has good biocompatibility.
In order to further ensure the mechanical property of the product, the preparation method of the all-biobased vitrimer comprises the steps of uniformly mixing the rosin resin acid derivative and the epoxidized soybean oil, pre-curing for 2 hours at 110-120 ℃ under the action of a catalyst, and then curing for 5-8 hours at 140-160 ℃ to obtain the all-biobased vitrimer.
The preparation of the vitrimer is realized by curing the epoxidized soybean oil by utilizing the biobased rosin resin acid, the dynamic covalent crosslinking network structure of the obtained total biobased vitrimer material can endow the material with the capability of ester exchange, so that the vitrimer shows the self-healing, reprocessing and shape memory capabilities, the research field of the vitrimer is widened, and the used raw material is a renewable, nontoxic and good biocompatible biomass raw material.
In order to take account of cost and reaction efficiency, the solvent is absolute ethyl alcohol.
In order to ensure the comprehensive performance of the obtained product, the curing is performed for 2 hours at 110-120 ℃ under the protection of nitrogen, and then the temperature is raised to 140-160 ℃ at 3-10 ℃/min for curing for 6-8 hours. The inventor researches and discovers that curing is also one of the very critical steps for preparing the product, different curing temperatures and different curing times can bring qualitative influence to the product, and the product is cured under the conditions and the performance is best through practice verification.
In order to further improve the mechanical property of the full-biology-based vitrimer, the rosin-based resin acid derivative is at least one of acrylpimaric acid, fumararic acid or maleopimaric acid.
In order to further improve the self-healing property and the shape memory capability of the total biobased vitrimer, the epoxy value of the epoxidized soybean oil is more than or equal to 6.
The catalyst is a dynamic covalent bond exchange catalyst. In order to take reaction efficiency and product performance into consideration, the dynamic covalent bond exchange catalyst is at least one of zinc acetylacetonate, zinc acetate, Triazabicyldecene (TBD), tetrabutylammonium bromide, tetrabutylammonium chloride or tetramethylammonium hydroxide.
In order to improve the comprehensive performance of the product, the mass ratio of the rosin acid derivative to the epoxidized soybean oil is (2-3.5): 5; the molar amount of the catalyst is 5-15 mol% of that of the rosin-based resin acid derivative.
As a preferred implementation scheme, the preparation method of the total biobased vitrimer comprises the following steps:
step 1: uniformly mixing the rosin acid derivative with absolute ethyl alcohol to obtain a transparent solution, wherein the mass consumption of the absolute ethyl alcohol is 4-8 times of that of the rosin acid derivative;
step 2: adding a catalyst into the solution obtained in the step 1, and uniformly mixing at 40-60 ℃;
and step 3: adding epoxidized soybean oil into the solution obtained in the step (2), uniformly mixing, and then removing absolute ethyl alcohol through rotary evaporation to obtain colorless or light yellow transparent liquid;
and 4, step 4: and (3) pouring the colorless or light yellow transparent liquid obtained in the step (3) into a mold, transferring into a vacuum drying oven, vacuumizing under reduced pressure, introducing nitrogen, curing for 2 hours at 110-120 ℃, heating to 140-160 ℃, and curing for 6-8 hours to obtain the yellow transparent all-bio-based vitrimer material.
The absolute ethanol used in the step 1 is only used as a solvent and does not participate in the reaction.
In the step 4, the material of the mold is polytetrafluoroethylene material or stainless steel.
The dynamic covalent cross-linking network structure of the fully-biobased vitrimer material prepared by the method can endow the material with the capability of ester exchange, so that the vitrimer can show the self-healing, reprocessing and shape memory capabilities.
The prior art is referred to in the art for techniques not mentioned in the present invention.
The invention relates to a preparation method of a full-biology-based vitrimer, which prepares a full-biology-based vitrimer material containing a hydrogenated phenanthrene ring structure, and by using high-biocompatibility biology-based raw materials of epoxidized soybean oil and rosin resin acid derivatives, the problems of high toxicity of the traditional bisphenol A-type vitrimer, poor mechanical property of the soybean oil-based vitrimer and low glass transition temperature are effectively solved, and the obtained vitrimer is a nontoxic material completely based on biomass and has good biocompatibility and can be subjected to self-healing, reprocessing and shape memory; the preparation method is simple, strong in operability and easy to implement.
Drawings
FIG. 1 is a schematic representation of the dynamic covalent bond exchange reaction of the whole bio-based vitrimer in example 1;
FIG. 2 is a pictorial representation of the whole bio-based vimer obtained in example 1;
FIG. 3 is a DMA test curve for the whole biobased vitrimer obtained in example 1;
FIG. 4 is a stress-strain plot of the total biobased vitrimer obtained in example 1;
FIG. 5 is a self-healing graph of the whole bio-based vitrimer obtained in example 1;
FIG. 6 is a diagram of the reprocessing process of the whole bio-based vitrimer obtained in example 1;
FIG. 7 is a diagram of the shape memory process of the whole biobased vitrimer obtained in example 1.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Dissolving 3g of rosin resin acid derivative fumaropimaric acid (FPA) in 12g of absolute ethyl alcohol, adding 0.1g of ester exchange catalyst zinc acetylacetonate into the transparent clear solution, uniformly mixing at 50 ℃ to obtain a uniform colorless solution, adding 5g of epoxidized soybean oil (Shanghai Wenhua chemical industry pigment Co., Ltd., epoxy value is more than or equal to 6), and uniformly mixing; adding the solution into an eggplant-shaped bottle, and removing the solvent ethanol by rotary evaporation; pouring the thick liquid after rotary evaporation into a tetrafluoroethylene mold, placing the mold in a vacuum drying oven, vacuumizing under reduced pressure, introducing nitrogen, curing at 120 ℃ for 2h, heating to 140 ℃ at 5 ℃/min, and then post-curing at 140 ℃ for 5h to obtain the transparent yellow film material.
The glass transition temperature of the material is 65 ℃, and the tensile strength is 16 MPa. Scratching the obtained vitrimer material by using a blade (the scratch width is about 100 mu m), putting the material into an oven at 180 ℃, and basically completely healing the scratch on the surface of the material after 30-60 minutes; after 1g of a vitrimer material and 4ml of absolute ethyl alcohol are placed in a high-pressure reaction kettle, the material can be well degraded at 140 ℃, and the material can be cured again at 180 ℃ without a catalyst, so that the reprocessing of the vitrimer material is realized; the material can be transformed into permanent deformation and temporary deformation in two temperature ranges of 80 ℃ and 160 ℃, as shown in figure 7.
Example 2
Dissolving 2.4g of abietic resin acid derivative fumaropimaric acid (FPA) in 10g of absolute ethyl alcohol, adding 0.15g of ester exchange catalyst zinc acetylacetonate into the transparent clear solution, uniformly mixing at 50 ℃ to obtain a uniform colorless solution, adding 5g of epoxidized soybean oil (Shanghai Allantin reagent Co., Ltd.), and uniformly mixing; adding the solution into an eggplant-shaped bottle, and removing the solvent ethanol by rotary evaporation; pouring the thick liquid after rotary evaporation into a tetrafluoroethylene mold, placing the mold in a vacuum drying oven, vacuumizing under reduced pressure, introducing nitrogen, curing at 110 ℃ for 2h, heating to 160 ℃ at 8 ℃/min, and then performing post-curing at 160 ℃ for 4h to obtain the transparent yellow film material.
The glass transition temperature of the material is 56 ℃, and the tensile strength is 14.6 MPa. Scratching the obtained vitrimer material by a blade (the scratch width is about 120 mu m), and putting the material into an oven at 165 ℃, wherein the scratch on the surface of the material is basically and completely healed after a period of time; after 1g of a vitrimer material and 2.5ml of absolute ethyl alcohol are placed in a high-pressure reaction kettle, the material can be well degraded at 130 ℃, and the material can be cured again at 200 ℃ without a catalyst, so that the reprocessing of the vitrimer material is realized; the material can be converted into permanent deformation and temporary deformation in two temperature ranges of 65 ℃ and 150 ℃.
Example 3
Dissolving 2.4g of abietic resin acid derivative maleopimaric acid (MPA) in 9g of absolute ethyl alcohol, adding 0.15g of ester exchange catalyst zinc acetylacetonate into the transparent clear solution, uniformly mixing at 50 ℃ to obtain a uniform colorless solution, adding 5g of epoxidized soybean oil, and uniformly mixing; adding the solution into an eggplant-shaped bottle, and removing the solvent ethanol by rotary evaporation; pouring the thick liquid after rotary evaporation into a tetrafluoroethylene mold, placing the mold in a vacuum drying oven, vacuumizing under reduced pressure, introducing nitrogen, curing at 120 ℃ for 2h, heating to 140 ℃ at 5 ℃/min, and then post-curing at 140 ℃ for 6h to obtain the transparent yellow film material.
The glass transition temperature of the material is 60 ℃, and the tensile strength is 13.2 MPa. After scratching the obtained vitrimer material by a blade (the scratch width is about 135 mu m), putting the material into an oven at 170 ℃, wherein the scratches on the surface of the material are basically completely healed after a period of time; after 1g of a vitrimer material and 4ml of absolute ethyl alcohol are placed in a high-pressure reaction kettle, the material can be well degraded at 120 ℃, and the material can be cured again at 180 ℃ without a catalyst, so that the reprocessing of the vitrimer material is realized; the material can be converted into permanent deformation and temporary deformation in two temperature ranges of 80 ℃ and 160 ℃.
Comparative example 1
Dissolving 3g of Citric Acid (CA) in 12g of absolute ethyl alcohol, adding 0.1g of ester exchange catalyst zinc acetylacetonate and 5g of epoxidized soybean oil into the solution, and uniformly mixing; and (3) performing rotary evaporation on the uniformly mixed solution to remove the solvent absolute ethyl alcohol, pouring the obtained transparent viscous liquid into a mold, placing the mold in a vacuum drying oven, vacuumizing under reduced pressure, introducing nitrogen, curing at 120 ℃ for 2 hours, heating to 140 ℃ at the speed of 5 ℃/min, and curing at 140 ℃ for 5 hours to obtain the transparent film material ESO-CA. The obtained ESO-CA material is subjected to mechanical property tests, the tensile strength of the material is only 0.6MPa, the glass transition temperature is about 20 ℃ (lower than room temperature), and the triple shape memory behavior is difficult to show.
Application example 1
Dissolving 3g of rosin resin acid derivative fumaropimaric acid (FPA) in 12g of absolute ethyl alcohol, adding 0.1g of ester exchange catalyst zinc acetylacetonate into the transparent clear solution, uniformly mixing at 50 ℃ to obtain a uniform colorless solution, adding 5g of epoxidized soybean oil (Shanghai Wenhua chemical industry pigment Co., Ltd., epoxy value is more than or equal to 6), and uniformly mixing; and (4) performing rotary evaporation on the solution to remove the solvent ethanol. Spreading the rotary evaporated viscous liquid between two aluminum plates (aluminum plate type 6010) at an amount of 0.12mg/mm2After curing for 2 hours at 120 ℃, the temperature is raised to 140 ℃ at the rate of 5 ℃/min for curing for 5 hours, the aluminum plates can be well bonded together, and the bonding tensile shear strength is 12 MPa. At the same time, the sheets which failed bonding after the test were placed in a 180 ℃ chamber for bonding for 2 hours, due to dynamic covalent bond exchangeIn the presence, the aluminum plates can be bonded together again with a tensile shear strength of 10.8 MPa.
Claims (6)
1. A preparation method of a total biology base vitrimer is characterized in that: the rosin acid derivative and epoxidized soybean oil are prepared under the action of a catalyst, and the method comprises the following steps:
step 1: uniformly mixing the rosin acid derivative with absolute ethyl alcohol to obtain a transparent solution, wherein the mass consumption of the absolute ethyl alcohol is 4-8 times of that of the rosin acid derivative;
step 2: adding a catalyst into the solution obtained in the step (1), and uniformly mixing at 40-60 ℃, wherein the catalyst is at least one of zinc acetylacetonate, zinc acetate, triazabicyldecene, tetrabutylammonium bromide, tetrabutylammonium chloride or tetramethylammonium hydroxide;
and step 3: adding epoxidized soybean oil into the solution obtained in the step (2), uniformly mixing, and then removing absolute ethyl alcohol through rotary evaporation to obtain colorless or light yellow transparent liquid;
and 4, step 4: and (3) pouring the colorless or light yellow transparent liquid obtained in the step (3) into a mold, transferring into a vacuum drying oven, vacuumizing under reduced pressure, introducing nitrogen, curing for 2 hours at 110-120 ℃, heating to 140-160 ℃, and curing for 6-8 hours to obtain the yellow transparent all-bio-based vitrimer material.
2. The method of claim 1, wherein: curing is carried out under the protection of nitrogen, and the heating rate is 3-10 ℃/min.
3. The method of claim 1, wherein: the rosin-based resin acid derivative is at least one of acrylpimaric acid, fumaraaric acid or maleopimaric acid.
4. The production method according to any one of claims 1 to 3, characterized in that: the epoxy value of the epoxidized soybean oil is more than or equal to 6.
5. The production method according to any one of claims 1 to 3, characterized in that: the mass ratio of the rosin resin acid derivative to the epoxidized soybean oil is (2-3.5): 5; the molar amount of the catalyst is 5-15 mol% of that of the rosin-based resin acid derivative.
6. The production method according to any one of claims 1 to 3, characterized in that: in step 4, the material used by the die is polytetrafluoroethylene material or stainless steel.
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| CN112225712B (en) * | 2020-09-24 | 2023-02-03 | 仲恺农业工程学院 | Epoxidized soybean oil propylene pimaric acid ester and preparation method and application thereof |
| CN113136105B (en) * | 2021-04-16 | 2022-05-10 | 陕西科技大学 | Recyclable castor oil-based unsaturated polyester Virimer material based on dynamic disulfide bonds and preparation method thereof |
| CN114835880B (en) * | 2022-05-06 | 2023-10-10 | 盐城工学院 | Rosin-based vitrimer, preparation method thereof and application thereof in preparation of carbon fiber composite material |
| CN115028842B (en) * | 2022-06-20 | 2023-08-22 | 桂林理工大学 | Full rosin-based epoxy glass polymer material and preparation method and application thereof |
| CN115197460B (en) * | 2022-08-12 | 2024-03-15 | 中国林业科学研究院林产化学工业研究所 | Preparation method of easily degradable epoxy foam with self-repairing and shape memory effects |
| CN115636988A (en) * | 2022-10-13 | 2023-01-24 | 大连理工大学 | Preparation method of full-bio-based Vitrimer material based on epoxidized vegetable oil and polysaccharide derivatives |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977265A (en) * | 2012-11-07 | 2013-03-20 | 中国科学院宁波材料技术与工程研究所 | Bio-based unsaturated polyester cured product and preparation method thereof |
| CN104031205A (en) * | 2014-04-30 | 2014-09-10 | 中国科学院宁波材料技术与工程研究所 | Bio-based unsaturated polyester condensate and preparation method thereof |
| CN105837796A (en) * | 2016-04-14 | 2016-08-10 | 华东理工大学 | Preparation of thermosetting polymer high in biological base content |
| CN107602868A (en) * | 2017-09-30 | 2018-01-19 | 中国林业科学研究院林产化学工业研究所 | A kind of abietyl epoxy foam insulation material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977265A (en) * | 2012-11-07 | 2013-03-20 | 中国科学院宁波材料技术与工程研究所 | Bio-based unsaturated polyester cured product and preparation method thereof |
| CN104031205A (en) * | 2014-04-30 | 2014-09-10 | 中国科学院宁波材料技术与工程研究所 | Bio-based unsaturated polyester condensate and preparation method thereof |
| CN105837796A (en) * | 2016-04-14 | 2016-08-10 | 华东理工大学 | Preparation of thermosetting polymer high in biological base content |
| CN107602868A (en) * | 2017-09-30 | 2018-01-19 | 中国林业科学研究院林产化学工业研究所 | A kind of abietyl epoxy foam insulation material and preparation method thereof |
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