CN112375209B - Curing agent in epoxy resin adhesive with controllable gel time and preparation method thereof - Google Patents
Curing agent in epoxy resin adhesive with controllable gel time and preparation method thereof Download PDFInfo
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- CN112375209B CN112375209B CN202011199718.XA CN202011199718A CN112375209B CN 112375209 B CN112375209 B CN 112375209B CN 202011199718 A CN202011199718 A CN 202011199718A CN 112375209 B CN112375209 B CN 112375209B
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- curing agent
- epoxy resin
- gel time
- resin adhesive
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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
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/28—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
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- 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
Abstract
The invention belongs to the technical field of epoxy resin curing agents, and particularly relates to a curing agent in an epoxy resin adhesive with controllable gel time and a preparation method thereof, wherein the preparation method specifically comprises the following steps: according to the mass parts, 60-90 parts of tribromobenzene is added into a four-neck flask, 600-1400 parts of polythiol is added, 20-30 parts of sodium methoxide is added, stirring is carried out, the temperature is increased to 60-75 ℃, heat preservation reaction is carried out for 6-10 hours, water washing and rotary evaporation are carried out to remove water to obtain a curing agent, the gel time of the epoxy resin adhesive prepared by using the curing agent can be regulated and controlled within 1 min-16 hours, and very many use scenes can be met.
Description
Technical Field
The invention belongs to the technical field of epoxy resin curing agents, and particularly relates to a curing agent in an epoxy resin adhesive with controllable gel time and a preparation method thereof.
Background
The basic components of the epoxy resin adhesive are epoxy resin and a curing agent, and according to the requirements of different performances, the epoxy resin adhesive can also comprise a toughening agent, a plasticizer, a diluent, an accelerator, an antioxidant, a filler, a coupling agent and the like. The epoxy resin used as the adhesive has a relative molecular weight of 300 to 7000 and a viscosity of 15 to 55 pas. The main species are glycidyl type epoxy resins and epoxidized olefins. Because the epoxy resin is a thermoplastic linear compound and can not be directly used as an adhesive, a curing agent must be added and the curing and crosslinking reaction is carried out under certain conditions to generate a non-fusible and insoluble body type network structure. The gel time of the epoxy resin adhesive prepared by the curing agent on the market at present is fixed, the gel time can not be changed at will according to the actual use condition, and the use requirement can not be met.
Disclosure of Invention
Aiming at the technical problems at present, the invention provides a curing agent in an epoxy resin adhesive with controllable gel time and a preparation method thereof, and the gel time of the epoxy resin adhesive prepared by using the curing agent can be regulated and controlled within 1 min-16 h, so that a great number of use scenes are met.
The technical scheme of the invention is as follows:
a curing agent in an epoxy resin adhesive with controllable gel time has a molecular structural formula as follows:
wherein m is 1-20 and is an integer.
Preferably, m is 5-10.
A preparation method of a curing agent in an epoxy resin adhesive with controllable gel time comprises the following specific steps: adding 60-90 parts of tribromobenzene into a four-neck flask, adding 600-1400 parts of polythiol, adding 20-30 parts of sodium methoxide, stirring, heating to 60-75 ℃, performing heat preservation reaction for 6-10 hours, washing with water, and removing water by rotary evaporation to obtain an epoxy resin curing agent, wherein the molecular structural formula of polythiol is as follows:
m is 1 to 20 and is an integer.
The structure of the tribromobenzene is shown as follows:
preferably, 70-80 parts of tribromobenzene, 688-1343 parts of polythiol and 24-28 parts of sodium methoxide are added into the four-neck flask according to parts by mass.
Preferably, the temperature is increased to 65-70 ℃.
Preferably, the reaction is carried out for 8-9 h under the condition of heat preservation.
According to the invention, the size of m in the curing agent is changed, the proportion of sulfydryl and epoxy groups is changed, when the epoxy resin adhesive is prepared, the dosage of epoxy resin and DMP-30(2, 4, 6-tris (dimethylaminomethyl) phenol) is further adjusted by changing the size of m in the curing agent and the addition amount of the curing agent, the gel time for preparing the epoxy resin adhesive can be regulated and controlled within 1 min-16 h, and the requirement of various scenes on the gel time can be met.
The curing agent in the epoxy resin adhesive with controllable gel time is simple in preparation method and capable of being industrially produced, the gel time of the epoxy resin adhesive prepared by the curing agent can be regulated and controlled within 1 min-16 h, so that the curing agent meets a great number of use scenes, and has a good development prospect.
Detailed Description
The present invention is further described below in conjunction with the specific embodiments, which enable one skilled in the art to further understand the present invention, but not to limit the content of the present invention, and the technology based on the principle described in the present invention is within the scope of the present invention.
Example 1
A preparation method of a curing agent in an epoxy resin adhesive with controllable gel time comprises the following steps:
adding 70g of tribromobenzene into a four-neck flask, adding 688g of polythiol (m is 5), adding 26g of sodium methoxide, stirring, heating to 65 ℃, carrying out heat preservation reaction for 8 hours, washing with water, and carrying out rotary evaporation to remove water to obtain the epoxy resin curing agent, wherein the yield is 91.7%.
Example 2
A preparation method of a curing agent in an epoxy resin adhesive with controllable gel time comprises the following steps:
adding 70g of tribromobenzene into a four-neck flask, adding 819g of polythiol (m is 6), adding 26g of sodium methoxide, stirring, heating to 65 ℃, carrying out heat preservation reaction for 8 hours, washing with water, and carrying out rotary evaporation to remove water to obtain the epoxy resin curing agent, wherein the yield is 91.5%.
Example 3
A preparation method of a curing agent in an epoxy resin adhesive with controllable gel time comprises the following steps:
adding 70g of tribromobenzene into a four-neck flask, adding 950g of polythiol (m is 7), adding 26g of sodium methoxide, stirring, heating to 65 ℃, carrying out heat preservation reaction for 8 hours, washing with water, and removing water by rotary evaporation to obtain the epoxy resin curing agent with the yield of 91.4%.
Example 4
A preparation method of a curing agent in an epoxy resin adhesive with controllable gel time comprises the following steps:
adding 70g of tribromobenzene into a four-neck flask, adding 1081g of polythiol (m is 8), adding 26g of sodium methoxide, stirring, heating to 65 ℃, keeping the temperature for reaction for 8 hours, washing with water, and carrying out rotary evaporation to remove water to obtain the epoxy resin curing agent, wherein the yield is 91.2%.
Example 5
A preparation method of a curing agent in an epoxy resin adhesive with controllable gel time comprises the following steps:
adding 70g of tribromobenzene into a four-neck flask, adding 1212g of polythiol (m is 9), adding 26g of sodium methoxide, stirring, heating to 65 ℃, carrying out heat preservation reaction for 8 hours, washing with water, and carrying out rotary evaporation to remove water to obtain the epoxy resin curing agent, wherein the yield is 90.9%.
Example 6
A preparation method of a curing agent in an epoxy resin adhesive with controllable gel time comprises the following steps:
adding 70g of tribromobenzene into a four-neck flask, adding 1342g of polythiol (m is 10), adding 26g of sodium methoxide, stirring, heating to 65 ℃, carrying out heat preservation reaction for 8 hours, washing with water, and carrying out rotary evaporation to remove water to obtain the epoxy resin curing agent, wherein the yield is 90.7%.
Example 7
A preparation method of a curing agent in an epoxy resin adhesive with controllable gel time comprises the following steps:
adding 70g of tribromobenzene into a four-neck flask, adding 688g of polythiol (m is 5), adding 26g of sodium methoxide, stirring, heating to 75 ℃, carrying out heat preservation reaction for 9 hours, washing with water, and carrying out rotary evaporation to remove water to obtain the epoxy resin curing agent, wherein the yield is 92.4%.
Example 8
A preparation method of a curing agent in an epoxy resin adhesive with controllable gel time comprises the following steps:
adding 70g of tribromobenzene into a four-neck flask, adding 688g of polythiol (m is 5), adding 26g of sodium methoxide, stirring, heating to 65 ℃, carrying out heat preservation reaction for 9 hours, washing with water, and carrying out rotary evaporation to remove water to obtain the epoxy resin curing agent, wherein the yield is 92.0%.
Test examples
Firstly adding the epoxy resin curing agent prepared in the embodiment, then adding DMP-30, finally adding epoxy resin and uniformly stirring to prepare an epoxy resin adhesive, curing at the normal temperature of 25 ℃, and testing the gel time and the shear strength, wherein the results are shown in Table 1;
the epoxy resin adhesive comprises the following components in parts by mass: curing agent: x, E51 epoxy resin: y, DMP-30(2, 4, 6-tris (dimethylaminomethyl) phenol): z;
TABLE 1 epoxy adhesive curing Strength gel time test
The table shows that the gel time of the epoxy resin adhesive prepared by the curing agent can be regulated and controlled within 1 min-16 h, and the epoxy resin adhesive prepared by the curing agent can control the gel time by changing the numerical value of m in the curing agent and the addition of the curing agent, meets a great number of use scenes, and has better development prospect.
Claims (6)
1. The curing agent in the epoxy resin adhesive with controllable gel time is characterized in that the molecular structural formula of the curing agent is as follows:
wherein m is 1-20 and is an integer.
2. The curing agent for epoxy resin adhesives according to claim 1, wherein m is 5-10.
3. The preparation method of the curing agent in the epoxy resin adhesive with controllable gel time as claimed in claim 1, is characterized in that the preparation method specifically comprises the following steps: adding 60-90 parts of tribromobenzene into a four-neck flask, adding 600-1400 parts of polythiol, adding 20-30 parts of sodium methoxide, stirring, heating to 60-75 ℃, reacting for 6-10 h under heat preservation, washing with water, and removing water by rotary evaporation to obtain an epoxy resin curing agent,
wherein the polythiol has the molecular structural formula:
m is 1 to 20 and is an integer.
4. The preparation method of the curing agent in the epoxy resin adhesive with the controllable gel time according to claim 3, characterized by adding 70-80 parts of tribromobenzene, 688-1343 parts of polythiol and 24-28 parts of sodium methoxide into a four-neck flask by mass.
5. The preparation method of the curing agent in the epoxy resin adhesive with the controllable gel time according to claim 3, wherein the curing agent is heated to 65-70 ℃.
6. The preparation method of the curing agent in the epoxy resin adhesive with the controllable gel time as claimed in claim 3, wherein the heat preservation reaction is carried out for 8-9 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011199718.XA CN112375209B (en) | 2020-10-30 | 2020-10-30 | Curing agent in epoxy resin adhesive with controllable gel time and preparation method thereof |
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| CN202011199718.XA CN112375209B (en) | 2020-10-30 | 2020-10-30 | Curing agent in epoxy resin adhesive with controllable gel time and preparation method thereof |
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| CN112375209A CN112375209A (en) | 2021-02-19 |
| CN112375209B true CN112375209B (en) | 2022-07-22 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343495A (en) * | 2019-08-13 | 2019-10-18 | 山东益丰生化环保股份有限公司 | A kind of epoxy resin adhesive and preparation method thereof |
| CN111040133A (en) * | 2019-12-17 | 2020-04-21 | 山东益丰生化环保股份有限公司 | High-temperature-resistant epoxy resin curing agent, and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013053100A1 (en) * | 2011-10-11 | 2013-04-18 | Henkel China Co. Ltd. | Gel time controllable two part epoxy adhesive |
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- 2020-10-30 CN CN202011199718.XA patent/CN112375209B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343495A (en) * | 2019-08-13 | 2019-10-18 | 山东益丰生化环保股份有限公司 | A kind of epoxy resin adhesive and preparation method thereof |
| CN111040133A (en) * | 2019-12-17 | 2020-04-21 | 山东益丰生化环保股份有限公司 | High-temperature-resistant epoxy resin curing agent, and preparation method and application thereof |
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| CN112375209A (en) | 2021-02-19 |
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Address after: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee after: Yifeng New Material Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee before: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. |