CN117603642A - Preparation method of modified epoxy electronic adhesive - Google Patents
Preparation method of modified epoxy electronic adhesive Download PDFInfo
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- CN117603642A CN117603642A CN202410095239.5A CN202410095239A CN117603642A CN 117603642 A CN117603642 A CN 117603642A CN 202410095239 A CN202410095239 A CN 202410095239A CN 117603642 A CN117603642 A CN 117603642A
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- dopo
- modified epoxy
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- epoxy
- stirring
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 75
- 239000000853 adhesive Substances 0.000 title claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000004814 polyurethane Substances 0.000 claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 claims abstract description 44
- 239000003822 epoxy resin Substances 0.000 claims abstract description 39
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 12
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003292 glue Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 19
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- -1 dimethoxy methyl vinyl siloxane Chemical class 0.000 claims description 13
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 11
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 11
- AXTADRUCVAUCRS-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrole-2,5-dione Chemical compound OCCN1C(=O)C=CC1=O AXTADRUCVAUCRS-UHFFFAOYSA-N 0.000 claims description 10
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000013530 defoamer Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 9
- 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 abstract description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003063 flame retardant Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 6
- 229960001669 kinetin Drugs 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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 relates to the technical field of electronic glue, and discloses a preparation method of modified epoxy electronic glue. And then polypropylene glycol, epoxy silane containing DOPO terminal hydroxyl and toluene diisocyanate are used as raw materials, and the reaction is carried out under the catalysis of stannous octoate to obtain the organic silicon polyurethane containing DOPO epoxy. Bisphenol A type epoxy resin, DOPO-containing epoxy organic silicon polyurethane, 2-furanmethylamine and trimaleimide cyanuric chloride-containing intermediate are used as raw materials to react to obtain the organic silicon polyurethane modified epoxy resin. And finally, uniformly mixing the organosilicon polyurethane modified epoxy resin, the defoaming agent, the curing agent and the like, and carrying out vacuum defoaming and vulcanization to obtain the modified epoxy electronic adhesive. The modified electronic adhesive prepared by the invention has excellent self-repairing performance and flame retardant property.
Description
Technical Field
The invention relates to the technical field of electronic glue, in particular to a preparation method of modified epoxy electronic glue.
Background
The electronic adhesive is mainly applied to bonding, sealing, coating protection and the like of electronic components, can play roles of moisture prevention, dust prevention, corrosion prevention and the like, is beneficial to miniaturization and light weight of the components, and along with development of high-tech fields such as large-scale integrated circuit boards, electronic display screens and the like, more severe requirements are put forward on the performance of the electronic adhesive, in practical application, the service effect of the electronic adhesive is seriously influenced by unavoidable damage or breakage, the service life is shortened, and therefore, the electronic adhesive has important practical significance for improving the self-repairing performance of the electronic adhesive.
The epoxy resin has the characteristics of good adhesion and strong electrical insulation, the epoxy resin electronic adhesive is one of common electronic adhesives, but the epoxy resin electronic adhesive has higher crosslinking degree and larger brittleness after being cured, so the epoxy resin electronic adhesive is one of hot spots of current researches. The organic silicon has excellent performances such as high temperature resistance, thermal aging resistance and the like, and can improve the performances such as heat resistance, toughness and the like of the epoxy electronic adhesive when applied to the epoxy electronic adhesive.
The invention discloses a halogen-free flame-retardant high-temperature-resistant epoxy resin sealant, which is prepared by modifying epoxy resin with melamine flame retardant to form flame-retardant epoxy resin, and improves the flame retardant property, mechanical property and high-temperature resistance of the sealant, but does not improve the self-repairing property of the sealant.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of modified epoxy electronic adhesive, and the prepared modified epoxy electronic adhesive has excellent flame retardant property and self-repairing property.
The preparation method of the modified epoxy electronic adhesive comprises the following steps:
(1) Adding polypropylene glycol, epoxy silane containing DOPO end hydroxyl and toluene diisocyanate into cyclohexanone solvent, stirring uniformly, heating to 80-90 ℃, adding stannous octoate catalyst into the mixture, carrying out reflux reaction for 4-8h, adding glycidol into the mixture, and carrying out reflux reaction for 5-10h to obtain the epoxy organosilicon polyurethane containing DOPO;
(2) Adding bisphenol A epoxy resin, DOPO-containing epoxy organic silicon polyurethane and 2-furanmethylamine into an acetone solvent, heating to 55-65 ℃, reacting for 5-12h, distilling under reduced pressure, adding a trimaleimide-containing cyanuric chloride intermediate and N, N-dimethylformamide into the mixture, heating to 55-70 ℃, reacting for 1-4h, distilling under reduced pressure, and drying to obtain the organic silicon polyurethane modified epoxy resin;
(3) And uniformly stirring the organosilicon polyurethane modified epoxy resin, the diluent, the dispersing agent and the defoaming agent, adding the curing agent and the accelerator into the mixture, uniformly mixing the mixture, performing vacuum defoaming, pouring the mixture into a mold, and vulcanizing the mixture to obtain the modified epoxy electronic adhesive.
Preferably, in the step (1), the dosage ratio of polypropylene glycol, epoxy silane containing DOPO end hydroxyl, toluene diisocyanate, stannous octoate catalyst and glycidol is 100g: (50-100) g: (75-150) g: (0.05-0.1) mL: (40-80) g.
Preferably, in the step (2), the dosage ratio of the bisphenol A type epoxy resin to the DOPO-containing epoxy organosilicon polyurethane to the 2-furanmethylamine to the trimaleimide cyanuric chloride-containing intermediate is 100g: (50-100) g: (30-50) g: (40-60) g.
Preferably, in the step (3), the usage ratio of the organosilicon polyurethane modified epoxy resin, the diluent, the dispersant, the defoamer, the curing agent and the accelerator is 100g: (5-25) g: (5-10) g: (2-5) g: (10-20) g: (0.006-0.02) g.
Preferably, in the step (1), the preparation method of the epoxy silane containing the DOPO terminal hydroxyl group comprises the following steps:
s1, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into tetrahydrofuran solvent under the condition of nitrogen, stirring and dissolving, adding dimethoxy methyl vinyl siloxane and azo diisobutyronitrile into the mixture, heating the mixture to 60-70 ℃, stirring and reacting for 20-36h, and carrying out reduced pressure distillation and drying after the reaction is finished to obtain DOPO-containing siloxane;
s2, adding diethoxy (3-glycidoxypropyl) methylsilane and DOPO-containing siloxane into deionized water, adding magnesium oxide into the deionized water, stirring for 3-8h, drying, and distilling under reduced pressure to obtain DOPO-containing hydroxyl-terminated epoxysilane.
Preferably, in the step S1, the dosage ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dimethoxymethylvinylsiloxane, and azobisisobutyronitrile is (1.5-2) g:1g: (0.01-0.06) g.
Preferably, in the step S2, the dosage ratio of diethoxy (3-glycidoxypropyl) methylsilane, DOPO-containing siloxane, and magnesium oxide is 1g: (1-1.5) g: (0.005-0.01) g.
Preferably, in the step (2), the preparation method of the cyanuric chloride intermediate containing the trimaleimide comprises the following steps:
adding cyanuric chloride and N- (hydroxyethyl) maleimide into a dichloromethane solvent at the temperature of 0-5 ℃, stirring and dispersing, adding triethylamine into the solvent, stirring and reacting for 5-10h, adding deionized water into the solvent after the reaction is finished, extracting with dichloromethane, drying, distilling under reduced pressure, washing with acetone, and drying to obtain the cyanuric chloride intermediate containing the trimaleimide.
Preferably, in the step, the dosage ratio of cyanuric chloride, N- (hydroxyethyl) maleimide and triethylamine is 1g: (2-3) g (1.5-2) g.
The beneficial effects are that: the invention takes 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dimethoxy methyl vinyl siloxane as raw materials to react under the initiation of azo diisobutyronitrile to obtain DOPO-containing siloxane. And then carrying out condensation reaction on the epoxy silane and diethoxy (3-glycidoxypropyl) methylsilane to obtain the epoxy silane containing DOPO terminal hydroxyl. And then polypropylene glycol, epoxy silane containing DOPO terminal hydroxyl and toluene diisocyanate are used as raw materials, and the reaction is carried out under the catalysis of stannous octoate to obtain the organic silicon polyurethane containing DOPO epoxy. Bisphenol A type epoxy resin, DOPO-containing epoxy organic silicon polyurethane, 2-furanmethylamine and trimaleimide cyanuric chloride-containing intermediate are used as raw materials to react to obtain the organic silicon polyurethane modified epoxy resin. And finally, uniformly mixing the organosilicon polyurethane modified epoxy resin, the diluent, the defoamer, the curing agent and the like, and carrying out vacuum defoaming and vulcanization to obtain the modified epoxy electronic adhesive.
The modified epoxy electronic adhesive prepared by the invention contains phosphorus element, nitrogen element and silicon element, wherein the nitrogen element can be heated to generate nonflammable gas, so that the concentration of flammable gas is diluted, and the purpose of flame retardance is achieved. The silicon element contained in the material has larger silicon-oxygen bond energy, can absorb more heat, and can absorb heat to generate a glass-shaped substance, so that the glass-shaped substance is covered on the surface of the material to isolate substance transportation and energy transfer. The phosphorus element contained in the flame retardant material can be heated to generate a strong dehydration substance of phosphoric acid and metaphosphoric acid, the dehydration of the material to carbon can be promoted, a polyphosphoric acid substance can be further formed on the surface of the base material, the transportation and energy transfer of the substance are isolated, and the three are synergistic, so that the flame retardant material has excellent flame retardant property.
The modified epoxy electronic adhesive prepared by the invention contains a D-A bond, belongs to a dynamic covalent bond, has the functions of dynamic covalent bond, reversible cracking and synthesis, and can play a self-repairing role when the material is subjected to external force. The modified electronic adhesive prepared by the invention has excellent self-repairing performance and flame retardant property.
Drawings
FIG. 1 is a schematic representation of the preparation route for DOPO-containing siloxanes according to the present invention;
FIG. 2 is a scheme for the preparation of a trimaleimide cyanuric chloride containing intermediate according to the present invention.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration only, but are not to be construed as limiting the scope of the invention, as many insubstantial modifications and adaptations of the invention as described above will be within the skill of the art.
Example 1: (1) Adding 4g of cyanuric chloride and 10g of N- (hydroxyethyl) maleimide into a dichloromethane solvent at the temperature of 0 ℃, stirring and dispersing, adding 8g of triethylamine into the solvent, stirring and reacting for 10 hours, adding deionized water into the solvent after the reaction is finished, extracting with dichloromethane, drying, distilling under reduced pressure, washing with acetone, and drying to obtain a cyanuric chloride intermediate containing the trimaleimide;
(2) Under the condition of nitrogen, adding 20g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into tetrahydrofuran solvent, stirring and dissolving, adding 10g of dimethoxy methyl vinyl siloxane and 0.5g of azo diisobutyronitrile, heating to 65 ℃, stirring and reacting for 24 hours, and after the reaction is finished, distilling under reduced pressure and drying to obtain DOPO-containing siloxane;
(3) Adding 10g of diethoxy (3-glycidoxypropyl) methylsilane and 12g of DOPO-containing siloxane into deionized water, adding 0.1g of magnesium oxide into the deionized water, stirring for 6 hours, drying, and distilling under reduced pressure to obtain DOPO-containing hydroxyl-terminated epoxysilane;
(4) Adding 100g of polypropylene glycol, 50g of DOPO-end hydroxyl-containing epoxy silane and 100g of toluene diisocyanate into a cyclohexanone solvent, uniformly stirring, heating to 85 ℃, adding 0.1mL of stannous octoate catalyst into the mixture, carrying out reflux reaction for 5 hours, adding 70g of glycidol into the mixture, and carrying out reflux reaction for 8 hours to obtain DOPO-end hydroxyl-containing organosilicon polyurethane;
(5) Adding 100g of bisphenol A type E-51 epoxy resin, 50g of DOPO epoxy-containing organosilicon polyurethane and 40g of 2-furanmethanamine into an acetone solvent, heating to 60 ℃, reacting for 10 hours, distilling under reduced pressure, adding 40g of trimaleimide cyanuric chloride-containing intermediate and N, N-dimethylformamide into the mixture, heating to 60 ℃, reacting for 2 hours, distilling under reduced pressure, and drying to obtain organosilicon polyurethane modified epoxy resin;
(6) 100g of organosilicon polyurethane modified epoxy resin, 10g of diluent CYH277, 9g of dispersant AA-75 and 4g of defoamer BYK A555 are uniformly stirred, and then 15g of tetraethylenepentamine curing agent and 0.02g of accelerator DMP-30 are added into the mixture, uniformly mixed, defoamed in vacuum, poured into a mold and vulcanized to obtain the modified epoxy electronic adhesive.
Example 2: (1) Adding 4g of cyanuric chloride and 9g of N- (hydroxyethyl) maleimide into a dichloromethane solvent at the temperature of 5 ℃, stirring and dispersing, adding 8g of triethylamine into the solvent, stirring and reacting for 6 hours, adding deionized water into the solvent after the reaction is finished, extracting with dichloromethane, drying, distilling under reduced pressure, washing with acetone, and drying to obtain a cyanuric chloride intermediate containing the trimaleimide;
(2) Under the condition of nitrogen, adding 20g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into tetrahydrofuran solvent, stirring and dissolving, adding 10g of dimethoxy methyl vinyl siloxane and 0.4g of azo diisobutyronitrile, heating to 65 ℃, stirring and reacting for 36h, and after the reaction is finished, distilling under reduced pressure and drying to obtain DOPO-containing siloxane;
(3) Adding 10g of diethoxy (3-glycidoxypropyl) methylsilane and 12g of DOPO-containing siloxane into deionized water, adding 0.1g of magnesium oxide into the deionized water, stirring for 8 hours, drying, and distilling under reduced pressure to obtain DOPO-containing hydroxyl-terminated epoxysilane;
(4) Adding 100g of polypropylene glycol, 60g of DOPO end hydroxyl epoxy silane and 100g of toluene diisocyanate into a cyclohexanone solvent, uniformly stirring, heating to 85 ℃, adding 0.06mL of stannous octoate catalyst into the mixture, carrying out reflux reaction for 8 hours, adding 60g of glycidol into the mixture, and carrying out reflux reaction for 8 hours to obtain DOPO epoxy organosilicon polyurethane;
(5) 100g of bisphenol A type E-51 epoxy resin, 60g of DOPO epoxy-containing organosilicon polyurethane and 50g of 2-furanmethanamine are added into an acetone solvent, the temperature is raised to 65 ℃, the reaction is carried out for 6 hours, reduced pressure distillation is carried out, 45g of trimaleimide cyanuric chloride intermediate and N, N-dimethylformamide are added into the mixture, the temperature is raised to 60 ℃, the reaction is carried out for 2 hours, the reduced pressure distillation is carried out, and the organosilicon polyurethane modified epoxy resin is obtained.
(6) 100g of organosilicon polyurethane modified epoxy resin, 5g of diluent CYH277, 7g of dispersant AA-75 and 4g of defoamer BYK A555 are uniformly stirred, and then 15g of tetraethylenepentamine curing agent and 0.01g of accelerator DMP-30 are added into the mixture, uniformly mixed, defoamed in vacuum, poured into a mold and vulcanized to obtain the modified epoxy electronic adhesive.
Example 3: (1) Adding 4g of cyanuric chloride and 10g of N- (hydroxyethyl) maleimide into a dichloromethane solvent at the temperature of 0 ℃, stirring and dispersing, adding 7g of triethylamine into the solvent, stirring and reacting for 7 hours, adding deionized water into the solvent after the reaction is finished, extracting with dichloromethane, drying, distilling under reduced pressure, washing with acetone, and drying to obtain a cyanuric chloride intermediate containing the trimaleimide;
(2) Under the condition of nitrogen, 18g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added into tetrahydrofuran solvent, stirred and dissolved, then 10g of dimethoxy methyl vinyl siloxane and 0.4g of azo diisobutyronitrile are added into the mixture, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 24 hours, and after the reaction is finished, the mixture is distilled under reduced pressure and dried to obtain DOPO-containing siloxane;
(3) Adding 10g of diethoxy (3-glycidoxypropyl) methylsilane and 12g of DOPO-containing siloxane into deionized water, adding 0.1g of magnesium oxide into the deionized water, stirring for 5 hours, drying, and distilling under reduced pressure to obtain DOPO-containing hydroxyl-terminated epoxysilane;
(4) Adding 100g of polypropylene glycol, 70g of DOPO end hydroxyl epoxy silane and 120g of toluene diisocyanate into a cyclohexanone solvent, uniformly stirring, heating to 85 ℃, adding 0.08mL of stannous octoate catalyst into the mixture, carrying out reflux reaction for 6 hours, adding 60g of glycidol into the mixture, and carrying out reflux reaction for 8 hours to obtain DOPO epoxy organosilicon polyurethane;
(5) Adding 100g of bisphenol A type E-51 epoxy resin, 70g of DOPO epoxy-containing organosilicon polyurethane and 35g of 2-furanmethanamine into an acetone solvent, heating to 60 ℃, reacting for 7 hours, distilling under reduced pressure, adding 50g of trimaleimide cyanuric chloride-containing intermediate and N, N-dimethylformamide into the mixture, heating to 60 ℃, reacting for 4 hours, distilling under reduced pressure, and drying to obtain organosilicon polyurethane modified epoxy resin;
(6) 100g of organosilicon polyurethane modified epoxy resin, 15g of diluent CYH277, 6g of dispersant AA-75 and 4g of defoamer BYK A555 are uniformly stirred, then 12g of tetraethylenepentamine curing agent and 0.02g of accelerator DMP-30 are added into the mixture, uniformly mixed, defoamed in vacuum, poured into a mold and vulcanized to obtain the modified epoxy electronic adhesive.
Example 4: (1) Adding 4g of cyanuric chloride and 8g of N- (hydroxyethyl) maleimide into a dichloromethane solvent at the temperature of 0 ℃, stirring and dispersing, adding 6g of triethylamine into the solvent, stirring and reacting for 7 hours, adding deionized water into the solvent after the reaction is finished, extracting with dichloromethane, drying, distilling under reduced pressure, washing with acetone, and drying to obtain a cyanuric chloride intermediate containing the trimaleimide;
(2) Under the condition of nitrogen, 18g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added into tetrahydrofuran solvent, stirred and dissolved, then 10g of dimethoxy methyl vinyl siloxane and 0.4g of azo diisobutyronitrile are added into the mixture, the temperature is raised to 65 ℃, the mixture is stirred and reacted for 28 hours, and after the reaction is finished, the mixture is distilled under reduced pressure and dried to obtain DOPO-containing siloxane;
(3) Adding 10g of diethoxy (3-glycidoxypropyl) methylsilane and 15g of DOPO-containing siloxane into deionized water, adding 0.1g of magnesium oxide into the deionized water, stirring for 6 hours, drying, and distilling under reduced pressure to obtain DOPO-containing hydroxyl-terminated epoxysilane;
(4) Adding 100g of polypropylene glycol, 80g of DOPO end hydroxyl epoxy silane and 80g of toluene diisocyanate into a cyclohexanone solvent, uniformly stirring, heating to 85 ℃, adding 0.08mL of stannous octoate catalyst into the mixture, carrying out reflux reaction for 5 hours, adding 60g of glycidol into the mixture, and carrying out reflux reaction for 6 hours to obtain DOPO epoxy organosilicon polyurethane;
(5) Adding 100g of bisphenol A type E-51 epoxy resin, 80g of DOPO epoxy-containing organosilicon polyurethane and 40g of 2-furanmethanamine into an acetone solvent, heating to 60 ℃, reacting for 10 hours, distilling under reduced pressure, adding 55g of trimaleimide cyanuric chloride-containing intermediate and N, N-dimethylformamide into the mixture, heating to 60 ℃, reacting for 2 hours, distilling under reduced pressure, and drying to obtain organosilicon polyurethane modified epoxy resin;
(6) 100g of organosilicon polyurethane modified epoxy resin, 15g of diluent CYH277, 8g of dispersant AA-75 and 4g of defoamer BYK A555 are uniformly stirred, 16g of tetraethylenepentamine curing agent and 0.02g of accelerator DMP-30 are added into the mixture, uniformly mixed, defoamed in vacuum, poured into a mold and vulcanized to obtain the modified epoxy electronic adhesive.
Example 5: (1) Adding 4g of cyanuric chloride and 12g of N- (hydroxyethyl) maleimide into a dichloromethane solvent at the temperature of 0 ℃, stirring and dispersing, adding 8g of triethylamine into the solvent, stirring and reacting for 6 hours, adding deionized water into the solvent after the reaction is finished, extracting with dichloromethane, drying, distilling under reduced pressure, washing with acetone, and drying to obtain a cyanuric chloride intermediate containing the trimaleimide;
(2) Under the condition of nitrogen, adding 16g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into tetrahydrofuran solvent, stirring and dissolving, adding 10g of dimethoxy methyl vinyl siloxane and 0.4g of azo diisobutyronitrile, heating to 65 ℃, stirring and reacting for 36h, and after the reaction is finished, distilling under reduced pressure and drying to obtain DOPO-containing siloxane;
(3) Adding 10g of diethoxy (3-glycidoxypropyl) methylsilane and 12g of DOPO-containing siloxane into deionized water, adding 0.1g of magnesium oxide into the deionized water, stirring for 6 hours, drying, and distilling under reduced pressure to obtain DOPO-containing hydroxyl-terminated epoxysilane;
(4) Adding 100g of polypropylene glycol, 90g of DOPO-end hydroxyl-containing epoxy silane and 100g of toluene diisocyanate into a cyclohexanone solvent, uniformly stirring, heating to 85 ℃, adding 0.1mL of stannous octoate catalyst into the mixture, carrying out reflux reaction for 8 hours, adding 60g of glycidol into the mixture, and carrying out reflux reaction for 10 hours to obtain DOPO-end hydroxyl-containing organosilicon polyurethane;
(5) Adding 100g of bisphenol A type E-51 epoxy resin, 90g of DOPO epoxy-containing organosilicon polyurethane and 40g of 2-furanmethanamine into an acetone solvent, heating to 60 ℃, reacting for 8 hours, distilling under reduced pressure, adding 60g of trimaleimide cyanuric chloride-containing intermediate and N, N-dimethylformamide into the mixture, heating to 60 ℃, reacting for 4 hours, distilling under reduced pressure, and drying to obtain organosilicon polyurethane modified epoxy resin;
(6) 100g of organosilicon polyurethane modified epoxy resin, 15g of diluent CYH277, 8g of dispersant AA-75 and 5g of defoamer BYK A555 are uniformly stirred, 18g of tetraethylenepentamine curing agent and 0.02g of accelerator DMP-30 are added into the mixture, uniformly mixed, defoamed in vacuum, poured into a mold and vulcanized to obtain the modified epoxy electronic adhesive.
Example 6: (1) Adding 4g of cyanuric chloride and 10g of N- (hydroxyethyl) maleimide into a dichloromethane solvent at the temperature of 5 ℃, stirring and dispersing, adding 8g of triethylamine into the solvent, stirring and reacting for 10 hours, adding deionized water into the solvent after the reaction is finished, extracting with dichloromethane, drying, distilling under reduced pressure, washing with acetone, and drying to obtain a cyanuric chloride intermediate containing the trimaleimide;
(2) Under the condition of nitrogen, 18g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added into tetrahydrofuran solvent, stirred and dissolved, then 10g of dimethoxy methyl vinyl siloxane and 0.5g of azo diisobutyronitrile are added into the mixture, the temperature is raised to 65 ℃, the mixture is stirred and reacted for 36 hours, and after the reaction is finished, the mixture is distilled under reduced pressure and dried to obtain DOPO-containing siloxane;
(3) Adding 10g of diethoxy (3-glycidoxypropyl) methylsilane and 14g of DOPO-containing siloxane into deionized water, adding 0.06g of magnesium oxide into the deionized water, stirring for 8 hours, drying, and distilling under reduced pressure to obtain DOPO-containing hydroxyl-terminated epoxysilane;
(4) Adding 100g of polypropylene glycol, 100g of DOPO end hydroxyl epoxy silane and 90g of toluene diisocyanate into a cyclohexanone solvent, uniformly stirring, heating to 85 ℃, adding 0.1mL of stannous octoate catalyst into the mixture, carrying out reflux reaction for 6 hours, adding 60g of glycidol into the mixture, and carrying out reflux reaction for 7 hours to obtain DOPO epoxy organosilicon polyurethane;
(5) Adding 100g of bisphenol A type E-51 epoxy resin, 100g of DOPO epoxy-containing organosilicon polyurethane and 50g of 2-furanmethanamine into an acetone solvent, heating to 60 ℃, reacting for 6 hours, distilling under reduced pressure, adding 60g of trimaleimide cyanuric chloride-containing intermediate and N, N-dimethylformamide into the mixture, heating to 60 ℃, reacting for 4 hours, distilling under reduced pressure, and drying to obtain organosilicon polyurethane modified epoxy resin;
(6) 100g of organosilicon polyurethane modified epoxy resin, 20g of diluent CYH277, 8g of dispersant AA-75 and 5g of defoamer BYK A555 are uniformly stirred, 18g of tetraethylenepentamine curing agent and 0.02g of accelerator DMP-30 are added into the mixture, uniformly mixed, defoamed in vacuum, poured into a mold and vulcanized to obtain the modified epoxy electronic adhesive.
The tensile properties of the materials were tested using an electronic universal tester.
And testing the impact property of the material by using a digital display pendulum impact property tester.
Table 1: mechanical property test data of epoxy electronic glue prepared in each embodiment
As can be seen from Table 1, the epoxy electronic adhesive prepared by the invention has excellent mechanical properties.
The oxygen index of the material was measured using an oxygen index meter.
The vertical burn rating of the material was tested using a horizontal vertical burn tester.
Table 2: flame retardant performance test data of epoxy electronic adhesives prepared in each example
As can be seen from Table 2, the epoxy electronic adhesive prepared by the invention has excellent flame retardant property.
Self-repairing performance test: the cured epoxy electronic adhesive is taken, the tensile strength before self-repairing is tested by using an electronic universal testing machine, the epoxy electronic adhesive is cut into two sections, the two sections are butted together to enable fracture parts to be in close contact, the epoxy electronic adhesive is preserved for 12 hours at the temperature of 80 ℃ in a vacuum drying oven, and is stretched after cooling, so that the tensile strength after self-repairing is measured, and the self-repairing efficiency = tensile strength after self-repairing/tensile strength before self-repairing.
Table 3: self-repairing performance test data of epoxy electronic adhesive prepared in each embodiment
As shown in Table 3, the epoxy electronic adhesive prepared by the invention has excellent self-repairing performance.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the modified epoxy electronic adhesive is characterized by comprising the following steps of:
(1) Adding polypropylene glycol, epoxy silane containing DOPO end hydroxyl and toluene diisocyanate into cyclohexanone solvent, stirring uniformly, heating to 80-90 ℃, adding stannous octoate catalyst into the mixture, carrying out reflux reaction for 4-8h, adding glycidol into the mixture, and carrying out reflux reaction for 5-10h to obtain the epoxy organosilicon polyurethane containing DOPO;
(2) Adding bisphenol A epoxy resin, DOPO-containing epoxy organic silicon polyurethane and 2-furanmethylamine into an acetone solvent, heating to 55-65 ℃, reacting for 5-12h, distilling under reduced pressure, adding a trimaleimide-containing cyanuric chloride intermediate and N, N-dimethylformamide into the mixture, heating to 55-70 ℃, reacting for 1-4h, distilling under reduced pressure, and drying to obtain the organic silicon polyurethane modified epoxy resin;
(3) And uniformly stirring the organosilicon polyurethane modified epoxy resin, the diluent, the dispersing agent and the defoaming agent, adding the curing agent and the accelerator into the mixture, uniformly mixing the mixture, performing vacuum defoaming, pouring the mixture into a mold, and vulcanizing the mixture to obtain the modified epoxy electronic adhesive.
2. The method for preparing modified epoxy electronic glue according to claim 1, wherein in the step (1), the dosage ratio of polypropylene glycol, epoxy silane containing DOPO end hydroxyl group, toluene diisocyanate, stannous octoate catalyst and glycidol is 100g: (50-100) g: (75-150) g: (0.05-0.1) mL: (40-80) g.
3. The method for preparing the modified epoxy electronic glue according to claim 1, wherein in the step (2), the dosage ratio of bisphenol a type epoxy resin, DOPO epoxy-containing organosilicon polyurethane, 2-furanmethylamine and trimaleimide cyanuric chloride-containing intermediate is 100g: (50-100) g: (30-50) g: (40-60) g.
4. The method for preparing modified epoxy electronic glue according to claim 1, wherein in the step (3), the usage ratio of the organosilicon polyurethane modified epoxy resin, the diluent, the dispersant, the defoamer, the curing agent and the accelerator is 100g: (5-25) g: (5-10) g: (2-5) g: (10-20) g: (0.006-0.02) g.
5. The method for preparing modified epoxy electronic glue according to claim 1, wherein in the step (1), the preparation method of epoxy silane containing DOPO terminal hydroxyl group comprises the following steps:
s1, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into tetrahydrofuran solvent under the condition of nitrogen, stirring and dissolving, adding dimethoxy methyl vinyl siloxane and azo diisobutyronitrile into the mixture, heating the mixture to 60-70 ℃, stirring and reacting for 20-36h, and carrying out reduced pressure distillation and drying after the reaction is finished to obtain DOPO-containing siloxane;
s2, adding diethoxy (3-glycidoxypropyl) methylsilane and DOPO-containing siloxane into deionized water, adding magnesium oxide into the deionized water, stirring for 3-8h, drying, and distilling under reduced pressure to obtain DOPO-containing hydroxyl-terminated epoxysilane.
6. The method for preparing modified epoxy electronic gum according to claim 5, wherein in the step S1, the amount ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dimethoxymethylvinylsiloxane, azobisisobutyronitrile is (1.5-2) g:1g: (0.01-0.06) g.
7. The method for preparing modified epoxy electronic glue according to claim 5, wherein in the step S2, the dosage ratio of diethoxy (3-glycidoxypropyl) methylsilane, DOPO-containing siloxane, magnesium oxide is 1g: (1-1.5) g: (0.005-0.01) g.
8. The method for preparing the modified epoxy electronic paste according to claim 1, wherein in the step (2), the method for preparing the melamine-containing three maleimide cyanuric chloride intermediate comprises the following steps:
adding cyanuric chloride and N- (hydroxyethyl) maleimide into a dichloromethane solvent at the temperature of 0-5 ℃, stirring and dispersing, adding triethylamine into the solvent, stirring and reacting for 5-10h, adding deionized water into the solvent after the reaction is finished, extracting with dichloromethane, drying, distilling under reduced pressure, washing with acetone, and drying to obtain the cyanuric chloride intermediate containing the trimaleimide.
9. The method for preparing the modified epoxy electronic glue according to claim 8, wherein in the step, the dosage ratio of cyanuric chloride, N- (hydroxyethyl) maleimide and triethylamine is 1g: (2-3) g (1.5-2) g.
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| CN117070180A (en) * | 2023-10-16 | 2023-11-17 | 山东凯恩新材料科技有限公司 | Reactive polyurethane hot melt adhesive and preparation method thereof |
| CN117417717A (en) * | 2023-12-18 | 2024-01-19 | 烟台隆达树脂有限公司 | Preparation method of modified polyurethane toughened epoxy resin electronic adhesive |
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| CN117070180A (en) * | 2023-10-16 | 2023-11-17 | 山东凯恩新材料科技有限公司 | Reactive polyurethane hot melt adhesive and preparation method thereof |
| CN117417717A (en) * | 2023-12-18 | 2024-01-19 | 烟台隆达树脂有限公司 | Preparation method of modified polyurethane toughened epoxy resin electronic adhesive |
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