CN114591709B - High-toughness epoxy resin adhesive and preparation method thereof - Google Patents
High-toughness epoxy resin adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN114591709B CN114591709B CN202210250492.4A CN202210250492A CN114591709B CN 114591709 B CN114591709 B CN 114591709B CN 202210250492 A CN202210250492 A CN 202210250492A CN 114591709 B CN114591709 B CN 114591709B
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- CN
- China
- Prior art keywords
- cardanol
- tetrahydrophthalic anhydride
- adhesive
- methyl tetrahydrophthalic
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000853 adhesive Substances 0.000 title claims abstract description 40
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 40
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 40
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 40
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 40
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 23
- -1 cardanol modified methyl tetrahydrophthalic anhydride compound Chemical class 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 239000003292 glue Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 229920006335 epoxy glue Polymers 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 3
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 238000011056 performance test Methods 0.000 description 4
- 239000012745 toughening agent Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241000863480 Vinca Species 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses high-toughness epoxy resin adhesive and a preparation method thereof, relates to the field of epoxy resin adhesive, and solves the problem that the toughness requirement of special parts cannot be met at present. The adhesive comprises adhesive A and adhesive B, wherein the adhesive B comprises methyl tetrahydrophthalic anhydride, cardanol and a catalyst, part of the methyl tetrahydrophthalic anhydride, the cardanol and the catalyst are mixed for polymerization reaction to obtain cardanol modified methyl tetrahydrophthalic anhydride compound, the cardanol modified methyl tetrahydrophthalic anhydride is used as a reaction product of the methyl tetrahydrophthalic anhydride and the cardanol, the cardanol modified methyl tetrahydrophthalic anhydride can be used as a curing agent of epoxy resin adhesive, the benzene ring structure of the cardanol has the characteristics of aromatic compounds, the high temperature resistance is improved, and the adhesive B has the characteristics of long straight-chain hydrocarbon group structure, namely good flexibility, self-drying property and the like, so that the adhesive B has a softening structure, overcomes the cracking caused by curing shrinkage and temperature rise change and plays a role in toughening.
Description
Technical Field
The invention relates to the field of epoxy resin adhesives, in particular to a high-toughness epoxy resin adhesive and a preparation method thereof.
Background
The epoxy resin glue is generally an adhesive prepared by taking epoxy resin as a main body, the characteristics of the epoxy resin glue are reprocessed or modified on the basis of the epoxy resin, so that the performance parameters and the like of the epoxy resin glue meet specific requirements, the epoxy resin glue can be used by being matched with a curing agent generally and can be completely cured after being uniformly mixed, the epoxy resin glue is generally called glue A or a main agent, the curing agent is generally called glue B or an auxiliary agent, and the epoxy resin glue has the characteristics of high heat resistance, high strength, flame retardance, voltage resistance and the like and is widely applied to the fields of electronics and electrics. However, epoxy resin adhesives are applied to special parts of electrical appliances, particularly parts with more bending, are very easy to crack in the curing shrinkage and temperature rise change process, and a toughening agent or a curing agent needs to be added into the adhesive A and the adhesive B, but the existing toughening agent or curing agent can improve the cracking condition although having a certain effect, but still cannot meet the requirement and cause insufficient toughness to a certain extent.
Disclosure of Invention
The purpose of the invention is that: in order to overcome the defects of the prior art, the invention provides high-toughness epoxy resin adhesive and a preparation method thereof, and solves the problem that a special piece cannot be easily cracked in the curing process at the present stage.
The technical scheme of the invention is as follows: the high-toughness epoxy resin adhesive comprises an adhesive A and an adhesive B, wherein the adhesive B comprises methyl tetrahydrophthalic anhydride, cardanol and a catalyst, and part of the methyl tetrahydrophthalic anhydride, the cardanol and the catalyst are mixed for polymerization reaction to obtain cardanol modified methyl tetrahydrophthalic anhydride compounds, and the cardanol modified methyl tetrahydrophthalic anhydride compounds are represented by the following chemical formulas:
1.
2. in the above chemical formula, n may be an integer of 0 to 3.
The invention is further provided with: the mass ratio of the methyl tetrahydrophthalic anhydride to the cardanol to the catalyst is as follows: 1:0.6-0.8:8 per mill-1%.
Still further, the present invention provides: the catalyst is a sulfonic acid compound.
Still further, the present invention is provided with: the catalyst is p-toluenesulfonic acid.
The other technical scheme of the invention is as follows: the preparation method of the high-toughness epoxy resin adhesive comprises the following steps of: 1. uniformly mixing methyl tetrahydrophthalic anhydride, cardanol and a catalyst in a reaction kettle; 2. heating to 120-160 deg.c, maintaining the pressure at 0.1-0.15MPa and reaction for 12-14 hr.
The beneficial effects of the invention are as follows: the invention takes the biological base material as the main raw material to prepare the epoxy resin adhesive, adopts natural and renewable cardanol as a substituent, eliminates the method of adopting chemical products as the substituent in the prior art, adopts plant groups, and has the advantages of environmental protection, degradability, low cost and wide raw material sources; the cardanol modified methyl tetrahydrophthalic anhydride is used as a reaction product of methyl tetrahydrophthalic anhydride and cardanol, can be used as a toughening agent of epoxy resin glue, has the characteristics of aromatic compounds in the benzene ring structure of cardanol, improves the high temperature resistance, has the characteristics of a long straight-chain hydrocarbon group structure, namely good flexibility, self-drying property and the like, ensures that the glue B has a flexible structure, overcomes cracking caused by solidification shrinkage and temperature rise change, and plays a role in toughening.
Detailed Description
The high-toughness epoxy resin adhesive comprises an adhesive A and an adhesive B, wherein the main component raw materials of the adhesive A are bisphenol A type epoxy resin, the component raw materials of the adhesive B comprise methyltetrahydrophthalic anhydride, cardanol and a catalyst, part of the methyltetrahydrophthalic anhydride, the cardanol and the catalyst are mixed for polymerization reaction to obtain a cardanol modified methyltetrahydrophthalic anhydride compound, and the cardanol modified methyltetrahydrophthalic anhydride compound is represented by the following chemical formula:
3. in the above chemical formula, n may be an integer of 0 to 3.
The chemical reaction equation of methyl tetrahydrophthalic anhydride and cardanol is as follows:
+/>
the mass ratio of the methyl tetrahydrophthalic anhydride to the cardanol to the catalyst is as follows: 1:0.6-0.8:8 per mill-1%.
The catalyst is a sulfonic acid compound, which can be p-toluenesulfonic acid.
The preparation method of the high-toughness epoxy resin adhesive comprises the following steps of: 1. uniformly mixing methyl tetrahydrophthalic anhydride, cardanol and a catalyst in a reaction kettle; 2. heating to 120-160 deg.c, maintaining the pressure at 0.1-0.15MPa and reaction for 12-14 hr.
Example 1: the mass ratio of methyl tetrahydrophthalic anhydride, cardanol and catalyst of the adhesive B is 1:0.6: 8%o of the components are uniformly mixed in a reaction kettle, heated and heated, the temperature is controlled at 150 ℃, the reaction is carried out for 12 hours, the catalyst is a sulfonic acid compound, particularly p-toluenesulfonic acid, the cardanol modified methyl tetrahydrophthalic anhydride compound and the methyl tetrahydrophthalic anhydride are obtained, and the performance test is carried out after the cardanol modified methyl tetrahydrophthalic anhydride compound and the methyl tetrahydrophthalic anhydride are mixed with the adhesive A.
Example 2: the mass ratio of methyl tetrahydrophthalic anhydride to cardanol to catalyst is 1:0.8:1% of the components are uniformly mixed in a reaction kettle, heated and heated, the temperature is controlled at 150 ℃, the reaction time is 12 hours, the catalyst is a sulfonic acid compound, particularly p-toluenesulfonic acid, the cardanol modified methyl tetrahydrophthalic anhydride compound and the methyl tetrahydrophthalic anhydride are obtained, and the performance test is carried out on the cardanol modified methyl tetrahydrophthalic anhydride compound and the methyl tetrahydrophthalic anhydride after the cardanol modified methyl tetrahydrophthalic anhydride compound and the methyl tetrahydrophthalic anhydride are mixed with the adhesive A.
Example 3: the mass ratio of methyl tetrahydrophthalic anhydride to cardanol to catalyst is 1:0.7: 8%o of the components are uniformly mixed in a reaction kettle, heated and heated, the temperature is controlled at 150 ℃, the reaction is carried out for 12 hours, the catalyst is a sulfonic acid compound, particularly p-toluenesulfonic acid, the cardanol modified methyl tetrahydrophthalic anhydride compound and the methyl tetrahydrophthalic anhydride are obtained, and the performance test is carried out after the cardanol modified methyl tetrahydrophthalic anhydride compound and the methyl tetrahydrophthalic anhydride are mixed with the adhesive A.
Comparative example: the component of the adhesive B is methyl tetrahydrophthalic anhydride and a toughening agent, and the mass ratio of the components is 1:0.1765, namely the mixture ratio commonly used in the prior art, is uniformly mixed in a reaction kettle, and the generated reactant is mixed with the adhesive A to perform performance test.
The performance index of each example obtained by the experiment is shown in table 1.
Remarks: the tensile shear strength detection equipment is a DL-1000B electronic tensile testing machine manufactured by vinca nonmetallic material testing machine; the impact strength detection device is XJU-5.5 pendulum impact strength tester manufactured by Maillard vernal detection instruments.
Compared with the prior art, the impact strength of the epoxy resin adhesive prepared by the invention is an important index for verifying the toughness of thermosetting materials, and the tensile shear strength is an index for verifying the bonding performance and toughness.
Claims (5)
1. The utility model provides a high toughness epoxy glues, is including A glues and B glues, its characterized in that: the component raw materials of the adhesive B comprise methyl tetrahydrophthalic anhydride, cardanol and a catalyst, wherein a part of the methyl tetrahydrophthalic anhydride, the cardanol and the catalyst are mixed for polymerization reaction to obtain a cardanol modified methyl tetrahydrophthalic anhydride compound, and the cardanol modified methyl tetrahydrophthalic anhydride compound is represented by the following chemical formula:
in the above chemical formula, n may be an integer of 0 to 3.
2. The high toughness epoxy resin glue according to claim 1, wherein: the mass ratio of the methyl tetrahydrophthalic anhydride to the cardanol to the catalyst is as follows: 1:0.6-0.8:0.008-0.01.
3. The high toughness epoxy resin glue according to claim 1, wherein: the catalyst is a sulfonic acid compound.
4. A high toughness epoxy resin glue according to claim 3, wherein: the catalyst is p-toluenesulfonic acid.
5. The method for preparing the high-toughness epoxy resin adhesive according to any one of claims 1 to 4, wherein: the preparation method of the adhesive B comprises the following steps:
1. uniformly mixing methyl tetrahydrophthalic anhydride, cardanol and a catalyst in a reaction kettle;
2. heating to 120-160 deg.c, maintaining the pressure at 0.1-0.15MPa and reaction for 12-14 hr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210250492.4A CN114591709B (en) | 2022-03-15 | 2022-03-15 | High-toughness epoxy resin adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210250492.4A CN114591709B (en) | 2022-03-15 | 2022-03-15 | High-toughness epoxy resin adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114591709A CN114591709A (en) | 2022-06-07 |
| CN114591709B true CN114591709B (en) | 2023-11-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210250492.4A Active CN114591709B (en) | 2022-03-15 | 2022-03-15 | High-toughness epoxy resin adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
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| CN (1) | CN114591709B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012841A (en) * | 2012-12-18 | 2013-04-03 | 四川大学 | Cardanol-aromatic diamine type benzoxazine flexibilizer as well as preparation method and purposes thereof |
| CN104271691A (en) * | 2012-04-24 | 2015-01-07 | 陶氏环球技术有限公司 | Epoxy resin composition for marine maintenance and repair coatings with improved overcoat ability |
| CN104744725A (en) * | 2014-12-23 | 2015-07-01 | 安徽美东生物材料有限公司 | Cardanol modified plasticizer and preparation method thereof |
| CN105860903A (en) * | 2016-06-08 | 2016-08-17 | 蚌埠市正园电子科技有限公司 | Composite epoxy pouring sealant high in surface lubrication degree and prone to demolding for LED display screen |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | Cardanol modified waterborne epoxy curing agent and preparation method thereof |
| CN111793195A (en) * | 2020-06-19 | 2020-10-20 | 华南农业大学 | Cardanol modified amine epoxy resin curing agent and preparation method and application thereof |
| CN113881376A (en) * | 2021-11-01 | 2022-01-04 | 江南大学 | Bio-based epoxy resin pouring sealant and preparation method thereof |
-
2022
- 2022-03-15 CN CN202210250492.4A patent/CN114591709B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104271691A (en) * | 2012-04-24 | 2015-01-07 | 陶氏环球技术有限公司 | Epoxy resin composition for marine maintenance and repair coatings with improved overcoat ability |
| CN103012841A (en) * | 2012-12-18 | 2013-04-03 | 四川大学 | Cardanol-aromatic diamine type benzoxazine flexibilizer as well as preparation method and purposes thereof |
| CN104744725A (en) * | 2014-12-23 | 2015-07-01 | 安徽美东生物材料有限公司 | Cardanol modified plasticizer and preparation method thereof |
| CN105860903A (en) * | 2016-06-08 | 2016-08-17 | 蚌埠市正园电子科技有限公司 | Composite epoxy pouring sealant high in surface lubrication degree and prone to demolding for LED display screen |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | Cardanol modified waterborne epoxy curing agent and preparation method thereof |
| CN111793195A (en) * | 2020-06-19 | 2020-10-20 | 华南农业大学 | Cardanol modified amine epoxy resin curing agent and preparation method and application thereof |
| CN113881376A (en) * | 2021-11-01 | 2022-01-04 | 江南大学 | Bio-based epoxy resin pouring sealant and preparation method thereof |
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| CN114591709A (en) | 2022-06-07 |
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