CN113980243A - Polyfunctional epoxy resin and preparation method thereof - Google Patents

Polyfunctional epoxy resin and preparation method thereof Download PDF

Info

Publication number
CN113980243A
CN113980243A CN202111503928.8A CN202111503928A CN113980243A CN 113980243 A CN113980243 A CN 113980243A CN 202111503928 A CN202111503928 A CN 202111503928A CN 113980243 A CN113980243 A CN 113980243A
Authority
CN
China
Prior art keywords
epoxy resin
hours
alkane
washing
reaction
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.)
Pending
Application number
CN202111503928.8A
Other languages
Chinese (zh)
Inventor
娄星原
冯朝波
黎灿光
唐华
陈建军
刘光华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Baiyun Chemical Industry Co Ltd
Guangdong Baiyun Technology Co Ltd
Original Assignee
Guangzhou Baiyun Chemical Industry Co Ltd
Guangdong Baiyun Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guangzhou Baiyun Chemical Industry Co Ltd, Guangdong Baiyun Technology Co Ltd filed Critical Guangzhou Baiyun Chemical Industry Co Ltd
Priority to CN202111503928.8A priority Critical patent/CN113980243A/en
Publication of CN113980243A publication Critical patent/CN113980243A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
    • 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

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)

Abstract

The invention discloses a polyfunctional epoxy resin, which has the following structure:
Figure DDA0003401819290000011
wherein R is1Is C4～C12The alkyl group is one of linear alkane, linear cycloalkane, branched alkane and branched cycloalkane. The preparation method comprises the following steps: (1) and (3) performing addition reaction on the epoxy halogenated hydrocarbon and the tetracarboxylic alkane to obtain an intermediate. (2) The preparation condition of the intermediate is 120-160 ℃, and the reaction time is 2-8 hours. (3) The intermediate is subjected to intramolecular elimination reaction in an alkali and alcohol environment to obtain the polyfunctional epoxy resin. (4) The preparation condition of the polyfunctional epoxy resin is 100-180 ℃, the reaction time is 2-8 hours, and after the reaction is finished, deionized water is used for washing for 2-5 times, and the washing temperature is 30-60 ℃; and (3) after washing, vacuumizing for 1-3 hours at the temperature of 100 ℃. The invention can solve the problem of common epoxy glue adhesionThe agent does not provide good rework and insufficient electrical properties.

Description

Polyfunctional epoxy resin and preparation method thereof
Technical Field
The invention relates to the technical field of viscose, in particular to polyfunctional epoxy resin and a preparation method thereof.
Background
Epoxy adhesives are one of the general adhesives, and are often selected for engineering applications such as structural bonding, pouring sealing, repairing, reinforcing and the like. Due to the excellent bonding property of the epoxy adhesive, epoxy potting adhesive materials are often adopted for battery protection and circuit board security design in the fields of new energy and electronic and electrical appliances. The requirements for the epoxy pouring sealant mainly include adhesiveness and electrical properties, and secondly, the cured product of the epoxy pouring sealant needs to be ensured to keep non-cracking and non-debonding properties under high-temperature and low-temperature circulation.
With the continuous improvement of the precision of instruments, equipment and products of downstream customers and the rise of the cost, part of the current epoxy pouring sealant manufacturers have proposed the requirement on the repair performance of the adhesive so as to ensure that the surface colloid of the product can be removed when the product has problems, and the product is re-filled and sealed after being repaired. Most circuit boards are made of epoxy resin, so that the epoxy adhesive is convenient to adhere and brings great trouble to repair. On the other hand, in the field of new energy batteries, in addition to the conventional adhesiveness and the above-mentioned reworkability requirements, there is a great demand for the electrical properties of the epoxy adhesive.
Disclosure of Invention
The invention provides a polyfunctional epoxy resin, which aims to solve the problem that a common epoxy adhesive has high adhesion and cannot provide good repair performance, and overcome the defects of the common epoxy adhesive in electrical performance.
The multifunctional epoxy resin provided by the invention has the following molecular structure:
Figure BDA0003401819280000021
wherein R is1Is C4～C12The alkyl group is one of linear alkane, linear cycloalkane, branched alkane and branched cycloalkane.
The multifunctional epoxy resin provided by the invention is mainly prepared by the reaction of epoxy halogenated hydrocarbon and tetracarboxylic alkane, and the preparation method comprises the following steps:
(1) preparation of an intermediate: the addition reaction of an epoxy alkyl halide with a tetracarboxylic acid alkane has the following reaction formula:
Figure BDA0003401819280000022
(2) preparing polyfunctional epoxy resin: the intermediate is subjected to intramolecular elimination reaction in an alkali and alcohol environment to obtain the polyfunctional epoxy resin, and the reaction formula is as follows:
Figure BDA0003401819280000031
the preparation condition of the intermediate is 120-160 ℃, and the reaction time is 2-8 hours.
The preparation conditions of the polyfunctional epoxy resin are 100-180 ℃, the reaction time is 2-8 hours, and after the reaction is finished, deionized water is used for washing for 2-5 times, and the washing temperature is 30-60 ℃; and (3) after washing, vacuumizing for 1-3 hours at the temperature of 100 ℃.
Halogen in the epoxy halogenated hydrocarbon is one of Cl, Br and I.
The epoxy halogenated hydrocarbon is preferably epichlorohydrin.
The tetracarboxylic alkane is preferably selected from tetracarboxylic butane or tetracarboxylic cyclopentane.
The toughening agent, the acid anhydride curing agent, the quaternary ammonium salt accelerator and the like can be added as appropriate according to the prior art.
Detailed Description
Some examples and comparative examples are given below to facilitate a better understanding of the technical solutions and advantages of the present invention.
Example 1
Preparation of BTCA epoxy resin:
(1) weighing 23.4 parts of tetracarboxybutane and 37 parts of epichlorohydrin by weight, adding the tetracarboxybutane and the epichlorohydrin into a three-neck flask, heating to 100 ℃ for 1 hour under the conditions of stirring and condensation reflux, and heating to 150 ℃ again for 4 hours to obtain an intermediate of the polyfunctional epoxy resin.
(2) Adding 50ml of absolute ethyl alcohol solution and 0.01mol of KOH into a three-neck flask, adding the intermediate, heating to 150 ℃ under the conditions of stirring, condensation and reflux, keeping for 3 hours, washing the product with deionized water at 60 ℃ for 3 times, putting the product into a 100 ℃ oven, vacuumizing and keeping for 1 hour to obtain the multifunctional group BTCA epoxy resin with the yield of 96%.
Example 2
Preparation of BTCA epoxy resin:
(1) weighing 23.4 parts of tetracarboxybutane and 63.2 parts of epichlorohydrin by weight, adding the tetracarboxybutane and the epichlorohydrin into a three-neck flask, heating to 120 ℃ under the conditions of stirring, condensing and refluxing for 1 hour, and heating to 140 ℃ again for 4 hours to obtain an intermediate of the polyfunctional group epoxy resin.
(2) Adding 50ml of absolute ethyl alcohol solution and 0.01mol of KOH into a three-neck flask, adding the intermediate, heating to 160 ℃ under the conditions of stirring, condensation and reflux, keeping for 2 hours, washing the product with deionized water at 50 ℃ for 3 times, putting the product into a 100 ℃ oven, vacuumizing and keeping for 2 hours to obtain the multifunctional BTCA epoxy resin with the yield of 68%.
Example 3
Preparation of BTCA epoxy resin:
(1) weighing 23.4 parts of tetracarboxybutane and 81.9 parts of epichlorohydrin by weight, adding the tetracarboxybutane and the epichlorohydrin into a three-neck flask, heating to 120 ℃ under the conditions of stirring, condensing and refluxing for 1 hour, and heating to 160 ℃ again for 4 hours to obtain an intermediate of the polyfunctional epoxy resin.
(2) Adding 50ml of absolute ethyl alcohol solution and 0.01mol of KOH into a three-neck flask, adding the intermediate, heating to 170 ℃ under the conditions of stirring, condensation and reflux, keeping for 7 hours, washing the product with deionized water at 40 ℃ for 3 times, putting the product into a 100 ℃ oven, vacuumizing and keeping for 3 hours to obtain the multifunctional BTCA epoxy resin with the yield of 56%.
Example 4
Preparation of CPTCA epoxy resin:
(1) weighing 24.6 parts of tetracarboxylcyclopentane and 37 parts of epichlorohydrin by weight, adding the tetracarboxylcyclopentane and 37 parts of epichlorohydrin into a three-neck flask, heating to 120 ℃ under the conditions of stirring and condensation reflux, keeping the temperature for 1 hour, and heating to 150 ℃ again and keeping the temperature for 4 hours to obtain an intermediate of the polyfunctional epoxy resin.
(2) Adding 50ml of absolute ethyl alcohol solution and 0.01mol of KOH into a three-neck flask, adding the intermediate, heating to 150 ℃ under the conditions of stirring and condensation reflux, keeping for 3 hours, washing the product with deionized water at 60 ℃ for 3 times, putting the product into a 100 ℃ oven, vacuumizing and keeping for 1 hour to obtain the multifunctional CPTCA epoxy resin with the yield of 97%.
Example 5
Preparation of CPTCA epoxy resin:
(1) weighing 24.6 parts of tetracarboxylcyclopentane and 66.4 parts of epichlorohydrin by weight, adding the tetracarboxylcyclopentane and 66.4 parts of epichlorohydrin into a three-neck flask, heating to 120 ℃ under the conditions of stirring and condensation reflux, keeping the temperature for 1 hour, and heating to 140 ℃ again and keeping the temperature for 4 hours to obtain an intermediate of the polyfunctional epoxy resin.
(2) Adding 50ml of absolute ethyl alcohol solution and 0.01mol of KOH into a three-neck flask, adding the intermediate, heating to 160 ℃ under the conditions of stirring and condensation reflux, keeping for 2 hours, washing the product with deionized water at 50 ℃ for 3 times, putting the product into a 100 ℃ oven, vacuumizing and keeping for 2 hours to obtain the multifunctional CPTCA epoxy resin with the yield of 66%.
Example 6
Preparation of CPTCA epoxy resin:
(1) weighing 24.6 parts of tetracarboxylcyclopentane and 86.1 parts of epichlorohydrin by weight, adding the tetracarboxylcyclopentane and the epichlorohydrin into a three-neck flask, heating to 120 ℃ for 1 hour under the conditions of stirring and condensation reflux, and heating to 160 ℃ again for 4 hours to obtain an intermediate of the polyfunctional epoxy resin.
(2) Adding 50ml of absolute ethyl alcohol solution and 0.01mol of KOH into a three-neck flask, adding the intermediate, heating to 170 ℃ under the conditions of stirring, condensation and reflux, keeping for 7 hours, washing the product with deionized water at 40 ℃ for 3 times, putting the product into a 100 ℃ oven, vacuumizing and keeping for 3 hours to obtain the multifunctional CPTCA epoxy resin with the yield of 54%.
Example 7
Preparing and characterizing a polyfunctional BTCA epoxy resin adhesive and colloid:
(1) taking 45 parts of polyfunctional BTCA epoxy resin as a component A; taking 55.3 parts of methyl tetrahydrophthalic anhydride and 0.5 part of tetrabutylammonium bromide, uniformly mixing, and keeping at 70 ℃ for 90min to serve as a component B.
(2) And (3) uniformly mixing the component A and the component B, preparing a condensate of the component A and an Al-Al single lap joint tensile shear test piece, putting the condensate and the Al-Al single lap joint tensile shear test piece into a 70 ℃ oven to be kept for 1 hour, and heating to 100 ℃ to be kept for 2 hours to obtain a polyfunctional group BTCA epoxy resin condensate and an application sample.
(3) Test results of cured products and application samples:
(a) al — Al single lap tensile shear strength: the average value was 16.7MPa at 25 ℃, 14.9MPa at 90 ℃ and 7.3MPa at 120 ℃.
(b) Glass transition temperature: 107 deg.C.
(c) The tensile strength was 39 MPa.
(d) Volume resistivity of 6.1 x 1015Ω·mm。
(e) The breakdown voltage is 15 KV/mm.
(f) High temperature and high humidity aging test: the average value after 24 hours was 15.1MPa, the average value after 72 hours was 14.4MPa, and the average value after 168 hours was 12.7 MPa.
(g)120 ℃ damp heat pressure holding test: the average value after 24 hours was 14.4MPa, after 72 hours was 6.3MPa, and after 168 hours was 2.2MPa
Example 8
Preparing and characterizing a polyfunctional CPTCA epoxy resin adhesive and colloid:
(1) taking 47 parts of polyfunctional BTCA epoxy resin as a component A; taking 56.4 parts of methyl tetrahydrophthalic anhydride and 0.5 part of tetrabutylammonium bromide, uniformly mixing, and keeping at 70 ℃ for 90min to serve as a component B.
(2) And (3) uniformly mixing the component A and the component B, preparing a condensate of the component A and an Al-A1 single lap joint tensile shear test piece, putting the condensate and the Al-A1 single lap joint tensile shear test piece into a 70 ℃ oven, keeping the temperature for 1 hour, heating to 100 ℃ and keeping the temperature for 2 hours to obtain a polyfunctional group CPTCA epoxy resin condensate and an application sample piece.
(3) Test results of cured products and application samples:
(a) Al-A1 Single lap tensile shear Strength: the average value at 25 ℃ is 17.3MPa, and the average value at 90 DEG C
16.1MPa, and an average value of 7.1MPa at 120 ℃.
(b) Glass transition temperature: 113 ℃.
(c) The tensile strength was 43 MPa.
(d) Volume resistivity of 3.7 x 1015Ω·mm。
(e) The breakdown voltage is 15 KV/mm.
(f) High temperature and high humidity aging test: the average value after 24 hours was 15.4MPa, the average value after 72 hours was 14.2MPa, and the average value after 168 hours was 12.4 MPa.
(g)120 ℃ damp heat pressure holding test: the average value after 24 hours was 14.4MPa, the average value after 72 hours was 7.1MPa, and the average value after 168 hours was 2.1 MPa.
Summary of Property parameters of cured products and samples obtained in examples 7 and 8
Figure BDA0003401819280000061
Comparative example 1:
preparing an adhesive condensate and an Al-Al single lap tensile shear test piece by using E51 epoxy resin:
(1) taking 50 parts of E51 epoxy resin as the component A.
(2) Taking 37.5 parts of methyl tetrahydrophthalic anhydride and 0.4 part of tetrabutylammonium bromide, uniformly mixing, and keeping at 70 ℃ for 90min to obtain a component B.
(3) And (3) uniformly mixing the component A and the component B, preparing a cured product and an Al-Al single lap joint tensile shear test piece, putting the cured product and the Al-Al single lap joint tensile shear test piece into a 70 ℃ oven, keeping for 1 hour, heating to 100 ℃ and keeping for 2 hours to obtain a cured product of the E51 epoxy resin adhesive and an application sample.
Comparative table of Properties of cured products and applied samples obtained in examples 7 and 8 and comparative example 1
Figure BDA0003401819280000071
The invention has the advantages of
The invention is characterized in that the invention provides epoxy resin with four functional groups, the epoxy value is 0.85mol/eq, and the main chain structure of alkane and cyclane makes the epoxy resin provide lower glass transition temperature; the existence of the ester group enables the epoxy resin to meet the conditions of disassembly and repair under the condition of moist heat pressure maintaining, the conventional moist heat aging cannot be easily hydrolyzed and aged under the protection of high crosslinking density, and meanwhile, the ester group also has excellent color fixing performance, and the use of a coloring agent can be reduced/cancelled for a color matching system; the four epoxy groups bring high crosslinking density and high-strength adhesiveness to a cured product of the epoxy resin, and the resin and the cured product have a discontinuous conjugated structure and low polarity, so that the epoxy resin has excellent electrical properties including low electrostatic effect, high volume resistivity and high breakdown voltage. The epoxy adhesive can meet the requirement of high adhesiveness of epoxy adhesives in various fields, and can also meet the requirement of repair convenience trend required in the fields of new energy and electronic appliances, thereby playing an important role in recycling electronic products and simultaneously relieving the problem of environmental pollution caused by high waste rate.

Claims (4)

1. A multifunctional epoxy resin, wherein the multifunctional epoxy resin has the following structure:
Figure FDA0003401819270000011
wherein R is1Is C4～C12The alkyl group is one of linear alkane, linear cycloalkane, branched alkane and branched cycloalkane.
2. The multifunctional epoxy resin of claim 1, which is prepared by reacting an epoxy-based halogenated hydrocarbon and a tetracarboxylic acid alkane, and which is prepared by a method comprising:
(1) performing addition reaction on epoxy halogenated hydrocarbon and tetracarboxylic alkane to obtain an intermediate;
(2) the preparation condition of the intermediate is 120-160 ℃, and the reaction time is 2-8 hours;
(3) the intermediate is subjected to intramolecular elimination reaction in an alkali and alcohol environment to obtain polyfunctional epoxy resin;
(4) the preparation conditions of the polyfunctional epoxy resin are 100-180 ℃, the reaction time is 2-8 hours, and after the reaction is finished, deionized water is used for washing for 2-5 times, and the washing temperature is 30-60 ℃; and (3) after washing, vacuumizing for 1-3 hours at the temperature of 100 ℃.
3. The multifunctional epoxy resin of claim 2 wherein the epoxy-based halogenated hydrocarbon is epichlorohydrin.
4. The multifunctional epoxy resin according to claim 2 wherein the tetracarboxylic alkane is tetracarboxylic butane or tetracarboxylic cyclopentane.
CN202111503928.8A 2021-12-09 2021-12-09 Polyfunctional epoxy resin and preparation method thereof Pending CN113980243A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111503928.8A CN113980243A (en) 2021-12-09 2021-12-09 Polyfunctional epoxy resin and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111503928.8A CN113980243A (en) 2021-12-09 2021-12-09 Polyfunctional epoxy resin and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113980243A true CN113980243A (en) 2022-01-28

Family

ID=79733650

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111503928.8A Pending CN113980243A (en) 2021-12-09 2021-12-09 Polyfunctional epoxy resin and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113980243A (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5010893A (en) * 1973-06-04 1975-02-04

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5010893A (en) * 1973-06-04 1975-02-04

Similar Documents

Publication Publication Date Title
CN107779147B (en) High-strength epoxy honeycomb adhesive and preparation method thereof
CN110194942B (en) Low-temperature fast thermosetting one-component epoxy adhesive and preparation method thereof
CN101781536B (en) Thermosetting acrylic structural adhesive and preparation method
CN112646523A (en) High-performance medium-temperature curing single-component epoxy structural adhesive and preparation method thereof
CN104449508A (en) Flexible epoxy structural adhesive and preparation method thereof
CN109628038B (en) Novel modified epoxy resin adhesive for building and preparation method thereof
CN112646524A (en) Single-component epoxy adhesive for bonding self-lubricating steel plates and preparation method thereof
KR101693605B1 (en) A epoxy adhesive composition comprising poly-thiolhardner and manufacturetingmthetod of it
CN114702909A (en) UV-thermal dual-curing adhesive and preparation method thereof
Bolger Structural adhesives: today’s state of the art
CN113980243A (en) Polyfunctional epoxy resin and preparation method thereof
CN116463091B (en) Double-component weather-resistant epoxy adhesive and preparation method thereof
CN109400849B (en) Piperazine epoxy resin curing agent, epoxy resin composition prepared from same and application of curing agent
CN112680156A (en) High-toughness bi-component epoxy structural adhesive and preparation method thereof
WO2015044757A9 (en) A self-healing epoxy resin composition
CN111187294A (en) Epoxy group-containing unsaturated organosilicon compound, heat-resistant high-toughness peelable adhesive, and preparation method and application thereof
CN114752336B (en) Solvent-free epoxy adhesive with good flame retardance and application thereof
CN111040692A (en) High-elasticity high-elongation epoxy adhesive special for PVC bonding
CN115011296B (en) Epoxy adhesive for high-viscosity optical fiber and preparation method thereof
CN114989759B (en) Modified epoxy resin with low shrinkage, high toughness and low stress and preparation method thereof
CN117384467B (en) Heat-resistant epoxy resin composite material and preparation method thereof
CN116836666B (en) Preparation method of solvent-free bi-component epoxy adhesive
KR101738017B1 (en) Method for manufacturing resin layer for heavy using resin composition for heavy having mechanical and electrical function
CN116751533B (en) Non-post-curing epoxy adhesive tape and preparation method thereof
CN115340834B (en) Explosion-proof membrane and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination