CN110128628A - A kind of preparation method of novel fire resistant epoxy mold resin - Google Patents
A kind of preparation method of novel fire resistant epoxy mold resin Download PDFInfo
- Publication number
- CN110128628A CN110128628A CN201810129065.4A CN201810129065A CN110128628A CN 110128628 A CN110128628 A CN 110128628A CN 201810129065 A CN201810129065 A CN 201810129065A CN 110128628 A CN110128628 A CN 110128628A
- Authority
- CN
- China
- Prior art keywords
- resin
- component
- bisphenol
- fire resistant
- preparation
- 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
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 239000004593 Epoxy Substances 0.000 title claims abstract description 17
- 230000009970 fire resistant effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 claims abstract description 94
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229940106691 bisphenol a Drugs 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 17
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- FVCWZBVQRLEGDH-UHFFFAOYSA-N 1,2,2-trimethylcyclohexan-1-amine Chemical compound CC1(C)CCCCC1(C)N FVCWZBVQRLEGDH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims abstract description 8
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003822 epoxy resin Substances 0.000 claims description 44
- 229920000647 polyepoxide Polymers 0.000 claims description 44
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 12
- 239000012044 organic layer Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- -1 washing Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 150000002118 epoxides Chemical class 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000004848 polyfunctional curative Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 11
- 238000007259 addition reaction Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005452 bending Methods 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012258 stirred mixture Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- ZCFREEKATLZMOJ-UHFFFAOYSA-N 2,2,2-triphenylethylphosphane Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(CP)C1=CC=CC=C1 ZCFREEKATLZMOJ-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000012372 quality testing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- 150000003544 thiamines Chemical class 0.000 description 1
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
- C08G59/18—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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3227—Compounds containing acyclic nitrogen atoms
-
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
-
- 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
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- 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
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of preparation methods of novel fire resistant epoxy mold resin, including component A resin and B component curing agent: the component A resin: aminophenol triglycidyl ether (AFG-90) 20-30%, trihydroxymethylpropanyltri diglycidyl ether 25-40%, butanediol diglycidyl ether 10-25%, DGEBA30-40%；The B component curing agent: aminomethyl -3,5,5, trimethylcyclohexyl amine (trade name: isophorone diamine) content: 50-70%, diethyl toluenediamine (DETDA) content: 15-30%；Its advantage is that: by the way that a kind of auxiliary agent is added, effectively bisphenol-A, trihydroxymethylpropanyltri diglycidyl ether and hydroxide ion are flocked together, increase the chance mutually collided between anakmetomeres, improve reactivity, greatly reduce the generation of side reaction, by heating the mixture to 95~100 DEG C, catalyst is added, carry out addition reaction, the wherein viscosity of high temperature resistant lower shrinkage resin mould: 250-300mPa.s, mixing viscosity is low, high-temperature resistant tg high, the 500g reaction time: 180-220 minutes, the reaction time was long.
Description
Technical field
The present invention relates to a kind of epoxy resin applied technical fields, more particularly, to a kind of novel fire resistant epoxy mold tree
The preparation method of rouge.
Background technique
Epoxy resin refers in those molecules at least containing there are two the resin compound of reactive epoxy groups, epoxy resin
There are many excellent properties outstanding after cured, such as to a variety of materials be especially to the adhesion of metal very by force, have it is very strong resistance to
Chemical corrosivity, mechanical strength are very high, electrical insulating property is good, corrosion-resistant etc., in addition, epoxy resin can be in comparatively wide temperature model
Volume contraction is small when enclosing interior solidification, and solidifying, bisphenol A type epoxy resin be by bisphenol-A, epoxychloropropane under alkaline condition
Condensation, through washing, the refined high-molecular compound of desolventizing, because the manufactured goods of epoxy resin have good physical mechanical
Performance, chemical resistance, electrical insulation properties, therefore be widely used in coating, adhesive, glass reinforced plastic, laminate, electronics and pour
The fields such as casting, encapsulating, encapsulating, epoxy resin it is many kinds of, for the sake of difference, often before epoxy resin add different monomers
Title, such as diphenol propane (abbreviation bisphenol-A) epoxy resin (being made by bisphenol-A and epoxychloropropane)；Glycerol epoxy resin
(being made by glycerol and epoxychloropropane)；Butylene epoxy resin (is obtained) by polybutylene oxide；Cyclopentadiene epoxy resin is (by two
Cyclopentadiene epoxidation is made), in addition, for same type of epoxy resin, also not according to their viscosity and epoxide number
With and be divided into the different trades mark, therefore their performance and purposes also difference, most widely used at present is bisphenol-A type ring
Some trades mark of oxygen resin, usually said epoxy resin just refer to bisphenol A type epoxy resin.
With the presence of hydroxyl (> CH-OH), ether (- O -) and extremely active epoxy group in the structure of epoxy resin,
Hydroxyl and ether have the polarity of height, make epoxy molecule and adjacent interfaces produce stronger intermolecular force, and epoxy group
Free key of the group then with dielectric surface (especially metal surface) reacts, and forms chemical bond, thus, epoxy resin has very high
Cohesive force, have many uses, commercially be referred to as " all-purpose adhesive ", in addition, epoxy resin can also do coating, casting, dipping and mould
The purposes such as tool, still, epoxy resin are in thermoplastic linear structure before uncured, and when use must be added to curing agent, Gu
Agent and epoxy group of epoxy resin etc. are reacted, and are become the macromolecular of reticular structure, are become insoluble and insoluble thermosetting property finished product,
Relative molecular mass is not high before curing for epoxy resin, only could form bodily form macromolecule by solidification, epoxy resin
Solidification will be by curing agent, and there are many type of curing agent, mainly there is polyamine and polyacid, all containing active in their molecule
Hydrogen atom, wherein with the most use is the polynary amine of liquid, such as diethylenetriamines and triethylamine, epoxy resin is at room temperature
When solidification, also usually need to add a little promotors (such as multi-thiol), to reach quick-setting effect, the selection of curing agent and ring
The solidification temperature of oxygen resin is related, solidifies under typical temperature and generally uses polyamine and polynary thiamines etc., and at relatively high temperatures
Solidification is general to select acid anhydrides and polyacid for curing agent, different curing agent, and cross-linking reaction is also different.
Currently, being generally modified in the prior art using dimer (fatty acid) yl to bisphenol A type epoxy resin, United States Patent (USP)
US5391652 is reported with bisphenol A type epoxy resin and aliphatic unsaturation C36 dimeric dibasic acid, stearic acid in triphenyl ethyl phosphine
The lower reaction of hydrochlorate catalysis obtains the modified bisphenol A type epoxy resin of high molecular weight, although being modified using common C36 dimeric dibasic acid
Bisphenol A type epoxy resin improves the flexibility and processability of epoxy resin to a certain extent, but prepares modified bisphenol A type
The poor strength of yield and quality of epoxy resin, viscosity height lead to the poor fluidity of resin, are not easy uniformly to mix with curing agent, have
When must not be added without diluent, possibly even crystallized under low temperature, seriously constrain the use scope of bisphenol A type epoxy resin.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the existing defects, provides a kind of novel fire resistant epoxy mold resin
Preparation method, to solve the above problems.
To achieve the above object, the invention provides the following technical scheme: a kind of system of novel fire resistant epoxy mold resin
Preparation Method, including component A resin and B component curing agent:
The component A resin: aminophenol triglycidyl ether (AFG-90) 20-30%, trimethylolpropane tris shrink
Glycerin ether 25-40%, butanediol diglycidyl ether 10-25%, DGEBA30-40%；
The B component curing agent: aminomethyl -3,5,5, trimethylcyclohexyl amine (trade name: isophorone diamine) content:
50-70%, diethyl toluenediamine (DETDA) content: 15-30%；
The component A resin and B component hardener formula mixed proportion, and component A resin: B component curing agent=100:
26；
The mixture is dissolved in solvent, washing, liquid separation take organic layer, at 50 DEG C -100 DEG C, in the organic layer
0.03-0.29 times of alkali of the amount of the bisphenol-A substance is added, reacts 0.5-5 hours, adds the bisphenol-A quality
0.03-0.29 times of alkali of the amount of the auxiliary agent of 0.5%-10% and the bisphenol-A substance reacts 0.5-5 hours, and it is mixed to obtain reaction
Close liquid.
Preferably, the raw material is made of bisphenol A type epoxy resin, aminophenol triglycidyl ether and catalyst,
Wherein the mass ratio of the bisphenol A type epoxy resin and the aminophenol triglycidyl ether is 1~2:1, the catalyst
Quality account for the 0.01~3% of bisphenol A type epoxy resin and aminophenol triglycidyl ether.
Preferably, the epoxide equivalent of the bisphenol A type epoxy resin be 185~500 grams/equivalent, softening point be 12~
70℃。
Preferably, the auxiliary agent is water, ethylene glycol, glycerine, butanone, hexamethylene, cyclohexanone, propylene glycol monomethyl ether, first
Base isobutyl ketone, polyethylene glycol, 18- crown- 6 or benzyltrimethylammonium chloride.
Preferably, the alkali is sodium hydroxide, potassium hydroxide, sodium bicarbonate or saleratus.
The beneficial effects of the present invention are: the preparation method of this kind of novel fire resistant epoxy mold resin, by the way that one kind is added
Auxiliary agent effectively flocks together bisphenol-A, trihydroxymethylpropanyltri diglycidyl ether and hydroxide ion, increases activation point
The chance mutually collided between son improves reactivity, greatly reduces the generation of side reaction, pass through to optimize reaction process
95~100 DEG C are heated the mixture to, catalyst is added, carries out addition reaction, wherein high temperature resistant lower shrinkage resin mould is viscous
Degree: 250-300mPa.s, mixing viscosity is low, and high-temperature resistant tg high, the 500g reaction time: 180-220 minutes, the reaction time was long, together
When obtained novel bisphenol A type epoxy resin have the advantages that high dielectric constant and high withstand voltage value, be a kind of ideal
Novel bisphenol A type epoxy resin.
Specific embodiment
The present invention is clearly and completely described below with reference to embodiment, it is clear that described embodiment is only this
Invention a part of the embodiment, instead of all the embodiments, based on the embodiments of the present invention, those of ordinary skill in the art exist
Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation methods of novel fire resistant epoxy mold resin, including component A resin and B component
Curing agent:
The component A resin: aminophenol triglycidyl ether (AFG-90) 20-30%, trimethylolpropane tris shrink
Glycerin ether 25-40%, butanediol diglycidyl ether 10-25%, DGEBA30-40%；
The B component curing agent: aminomethyl -3,5,5, trimethylcyclohexyl amine (trade name: isophorone diamine) content:
50-70%, diethyl toluenediamine (DETDA) content: 15-30%；
The component A resin and B component hardener formula mixed proportion, and component A resin: B component curing agent=100:
26；
The mixture is dissolved in solvent, washing, liquid separation take organic layer, at 50 DEG C -100 DEG C, in the organic layer
0.03-0.29 times of alkali of the amount of the bisphenol-A substance is added, reacts 0.5-5 hours, adds the bisphenol-A quality
0.03-0.29 times of alkali of the amount of the auxiliary agent of 0.5%-10% and the bisphenol-A substance reacts 0.5-5 hours, and it is mixed to obtain reaction
Close liquid.
Wherein raw material is made of bisphenol A type epoxy resin, aminophenol triglycidyl ether and catalyst, bisphenol-A type ring
The mass ratio of oxygen resin and aminophenol triglycidyl ether be 1~2:1, the quality of catalyst account for bisphenol A type epoxy resin and
The 0.01~3% of aminophenol triglycidyl ether.
And the epoxide equivalent of bisphenol A type epoxy resin is 185~500 grams/equivalent, and softening point is 12~70 DEG C.
It is water, ethylene glycol, glycerine, butanone, hexamethylene, cyclohexanone, propylene glycol monomethyl ether, methyl-isobutyl by auxiliary agent
Ketone, polyethylene glycol, 18- crown- 6 or benzyltrimethylammonium chloride.
It is sodium hydroxide, potassium hydroxide, sodium bicarbonate or saleratus by alkali.
Embodiment 1: in the reaction kettle equipped with thermometer, condenser pipe and blender, component A resin is added and B component is solid
Agent is formulated mixed proportion, wherein component A resin: aminophenol triglycidyl ether (AFG-90) 20-30%, trihydroxy methyl third
Alkane triglycidyl ether 25-40%, butanediol diglycidyl ether 10-25%, DGEBA30-40%；Wherein B component curing agent:
Aminomethyl -3,5,5, trimethylcyclohexyl amine (trade name: isophorone diamine) content: 50-70%, diethyl toluenediamine
(DETDA) content: then 15-30% is stirred mixture under the conditions of nitrogen protection, while heating the mixture to 95
~100 DEG C, catalyst is added, carries out addition reaction, 114g bisphenol-A and 3g glycerine are mixed, 50 DEG C are heated to, to bisphenol-A
After being completely dissolved, the sodium hydrate aqueous solution that 15g mass percentage is 20% is added, reacts 2 hours, obtains reaction solution, it will
Above-mentioned reaction mixture is washed to neutrality, and liquid separation takes organic layer, and at 200 DEG C, solvent is isolated in 10kPa vacuum distillation, measures resistance to
The viscosity of high temperature lower shrinkage resin mould: 250-300mPa.s, the 500g reaction time: 180-220 minutes, linear shrinkage:
Between 0.25-0.35%, heatproof Tg is between 160-180, bending strength ASTMD790 135-140MPa, tensile modulus of elasticity
ASTMD638 3.0-3.5GPa, tensile strength ASTMD638 70-80MPa, at 50 DEG C.
Embodiment 2: in the reaction kettle equipped with thermometer, condenser pipe and blender, component A resin is added and B component is solid
Agent is formulated mixed proportion, wherein component A resin: aminophenol triglycidyl ether (AFG-90) 20-30%, trihydroxy methyl third
Alkane triglycidyl ether 25-40%, butanediol diglycidyl ether 10-25%, DGEBA30-40%；Wherein B component curing agent:
Aminomethyl -3,5,5, trimethylcyclohexyl amine (trade name: isophorone diamine) content: 50-70%, diethyl toluenediamine
(DETDA) content: then 15-30% is stirred mixture under the conditions of nitrogen protection, while heating the mixture to 95
~100 DEG C, catalyst is added, carries out addition reaction, 114g bisphenol-A and 3g glycerine are mixed, 50 DEG C are heated to, to bisphenol-A
After being completely dissolved, the sodium hydrate aqueous solution that 15g mass percentage is 20% is added, reacts 2 hours, obtains reaction solution, it will
Above-mentioned reaction mixture is washed to neutrality, and liquid separation takes organic layer, and at 200 DEG C, solvent is isolated in 10kPa vacuum distillation, measures resistance to
The viscosity of high temperature lower shrinkage resin mould: 300-400mPa.s, the 500g reaction time: 90-120 minutes, linear shrinkage:
Between 0.45-0.65%, heatproof Tg is between 140-160,790 135-140MPa tensile modulus of elasticity of bending strength ASTM D
ASTMD638 3.0-3.5GPa tensile strength ASTMD638 70-80MPa.
Embodiment 3: in the reaction kettle equipped with thermometer, condenser pipe and blender, component A resin is added and B component is solid
Agent is formulated mixed proportion, wherein component A resin: aminophenol triglycidyl ether (AFG-90) 20-30%, trihydroxy methyl third
Alkane triglycidyl ether 25-40%, butanediol diglycidyl ether 10-25%, DGEBA30-40%；Wherein B component curing agent:
Aminomethyl -3,5,5, trimethylcyclohexyl amine (trade name: isophorone diamine) content: 50-70%, diethyl toluenediamine
(DETDA) content: then 15-30% is stirred mixture under the conditions of nitrogen protection, while heating the mixture to 95
~100 DEG C, catalyst is added, carries out addition reaction, 114g bisphenol-A and 3g glycerine are mixed, 50 DEG C are heated to, to bisphenol-A
After being completely dissolved, the sodium hydrate aqueous solution that 15g mass percentage is 20% is added, reacts 2 hours, obtains reaction solution, it will
Above-mentioned reaction mixture is washed to neutrality, and liquid separation takes organic layer, and at 200 DEG C, solvent is isolated in 10kPa vacuum distillation, measures resistance to
The viscosity of high temperature lower shrinkage resin mould: 250-300mPa.s, the 500g reaction time: 180-220 minutes, linear shrinkage:
Between 0.25-0.35%, heatproof Tg is between 160-180, bending strength ASTMD790135-140MPa, stretch bending springform
Measure 790 3.0-3.5GPa of ASTM D, tensile strength ASTMD638 70-80MPa.
Embodiment 4: in the reaction kettle equipped with thermometer, condenser pipe and blender, component A resin is added and B component is solid
Agent is formulated mixed proportion, wherein component A resin: aminophenol triglycidyl ether (AFG-90) 20-30%, trihydroxy methyl third
Alkane triglycidyl ether 25-40%, butanediol diglycidyl ether 10-25%, DGEBA30-40%；Wherein B component curing agent:
Aminomethyl -3,5,5, trimethylcyclohexyl amine (trade name: isophorone diamine) content: 50-70%, diethyl toluenediamine
(DETDA) content: then 15-30% is stirred mixture under the conditions of nitrogen protection, while heating the mixture to 95
~100 DEG C, catalyst is added, carries out addition reaction, 114g bisphenol-A and 3g glycerine are mixed, 50 DEG C are heated to, to bisphenol-A
After being completely dissolved, the sodium hydrate aqueous solution that 15g mass percentage is 20% is added, reacts 2 hours, obtains reaction solution, it will
Above-mentioned reaction mixture is washed to neutrality, and liquid separation takes organic layer, and at 200 DEG C, solvent is isolated in 10kPa vacuum distillation, measures resistance to
The viscosity of high temperature lower shrinkage resin mould: 250-300mPa.s, the 500g reaction time: 180-200 minutes, linear shrinkage:
Between 0.25-0.35%, heatproof Tg is between 110-140, bending strength ASTMD790 135-140MPa, tensile modulus of elasticity
ASTMD6383.0-3.5GPa, tensile strength ASTMD63870-80MPa.
Concrete principle: in use, B component is added after bisphenol A type epoxy resin and catalyst are mixed by 1: 2~8 ratio
Curing agent, 2~4 times of ground organic solvents are uniformly mixed, successively toward be added in reaction kettle DGEBA30-40%, aminomethyl -3,
5,5, trimethylcyclohexyl amine: 50-70%；Stirring is opened, while opening vacuum pump, and with middle high revolving speed 2000-3000r/min
It is stirred under vacuum 60 minutes (mixing time is adjusted according to equipment situation), after being uniformly mixed, rises agitating shaft, scrape clean blade
And casing wall, the variation that liquid level rises when product vacuumizes should be noticed when vacuumizing, it is as too fast in risen, it needs to suspend vacuum pump, protects
Pressure a period of time, vacuum pump is then turned on after waiting bubbles liquid level to decline and continues to pump full range vacuum, after scraping clean casing wall and blade, then
With slow-speed of revolution stirring 30 minutes, while vacuum pump is opened, pumps full range vacuum, until being evacuated to bubble-free, vacuum degree is negative
101KPa, stirring stop, and measure the viscosity of high temperature resistant lower shrinkage resin mould: 250-300mPa.s, 500g reaction time: 180-
200 minutes, linear shrinkage: between 0.25-0.35%, heatproof Tg was between 110-140, bending strength ASTMD790 135-
140MPa, tensile modulus of elasticity ASTMD6383.0-3.5GPa, tensile strength ASTMD63870-80MPa, sampling 1.5kg or so
It send quality testing department to examine, is filled into metal bucket or ton barrel cage with 180 mesh filter screens after the assay was approved and fills, product temperature when packaging is answered
Control is between 50 degree to 35 degree.
The beneficial effects of the present invention are: the preparation method of this kind of novel fire resistant epoxy mold resin, by the way that one kind is added
Auxiliary agent effectively flocks together bisphenol-A, trihydroxymethylpropanyltri diglycidyl ether and hydroxide ion, increases activation point
The chance mutually collided between son improves reactivity, greatly reduces the generation of side reaction, pass through to optimize reaction process
95~100 DEG C are heated the mixture to, catalyst is added, carries out addition reaction, wherein high temperature resistant lower shrinkage resin mould is viscous
Degree: 250-300mPa.s, mixing viscosity is low, and high-temperature resistant tg high, the 500g reaction time: 180-220 minutes, the reaction time was long, together
When obtained novel bisphenol A type epoxy resin have the advantages that high dielectric constant and high withstand voltage value, be a kind of ideal
Novel bisphenol A type epoxy resin.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and embodiment shown here.
Claims (5)
1. a kind of preparation method of novel fire resistant epoxy mold resin, which is characterized in that solid including component A resin and B component
Agent:
The component A resin: aminophenol triglycidyl ether (AFG-90) 20-30%, trimethylolpropane tris glycidol
Ether 25-40%, butanediol diglycidyl ether 10-25%, DGEBA30-40%；
The B component curing agent: aminomethyl -3,5,5, trimethylcyclohexyl amine (trade name: isophorone diamine) content: 50-
70%, diethyl toluenediamine (DETDA) content: 15-30%；
The component A resin and B component hardener formula mixed proportion, and component A resin: B component curing agent=100:26；
The mixture is dissolved in solvent, washing, liquid separation take organic layer, at 50 DEG C -100 DEG C, be added in the organic layer
0.03-0.29 times of alkali of the amount of the bisphenol-A substance reacts 0.5-5 hours, adds the 0.5%- of the bisphenol-A quality
0.03-0.29 times of alkali of the amount of 10% auxiliary agent and the bisphenol-A substance reacts 0.5-5 hours, obtains reaction mixture.
2. a kind of preparation method of novel fire resistant epoxy mold resin according to claim 1, which is characterized in that institute
It states raw material to be made of bisphenol A type epoxy resin, aminophenol triglycidyl ether and catalyst, wherein the bisphenol type epoxy
The mass ratio of resin and the aminophenol triglycidyl ether is 1~2:1, and the quality of the catalyst accounts for bisphenol type epoxy
The 0.01~3% of resin and aminophenol triglycidyl ether.
3. a kind of preparation method of novel fire resistant epoxy mold resin according to claim 2, which is characterized in that institute
The epoxide equivalent for stating bisphenol A type epoxy resin is 185~500 grams/equivalent, and softening point is 12~70 DEG C.
4. a kind of preparation method of novel fire resistant epoxy mold resin according to claim 1, which is characterized in that institute
State auxiliary agent be water, ethylene glycol, glycerine, butanone, hexamethylene, cyclohexanone, propylene glycol monomethyl ether, methyl iso-butyl ketone (MIBK), polyethylene glycol,
18- crown- 6 or benzyltrimethylammonium chloride.
5. a kind of preparation method of novel fire resistant epoxy mold resin according to claim 1, which is characterized in that institute
Stating alkali is sodium hydroxide, potassium hydroxide, sodium bicarbonate or saleratus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810129065.4A CN110128628A (en) | 2018-02-08 | 2018-02-08 | A kind of preparation method of novel fire resistant epoxy mold resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810129065.4A CN110128628A (en) | 2018-02-08 | 2018-02-08 | A kind of preparation method of novel fire resistant epoxy mold resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110128628A true CN110128628A (en) | 2019-08-16 |
Family
ID=67567455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810129065.4A Pending CN110128628A (en) | 2018-02-08 | 2018-02-08 | A kind of preparation method of novel fire resistant epoxy mold resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110128628A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578315A (en) * | 2006-11-20 | 2009-11-11 | 陶氏环球技术公司 | Epoxy resins comprising a cycloalphatic diamine curing agent |
| CN102286138A (en) * | 2011-07-01 | 2011-12-21 | 蓝星(北京)化工机械有限公司 | Heat-resistant epoxide resin composition for rapid pultrusion |
| CN102977557A (en) * | 2012-12-11 | 2013-03-20 | 蓝星(北京)化工机械有限公司 | Room temperature curing epoxy resin composition and preparation method thereof |
| CN103881301A (en) * | 2012-12-24 | 2014-06-25 | 江苏绿材谷新材料科技发展有限公司 | High temperature-resistant epoxy resin composition for pultrusion and preparation method |
| CN107083025A (en) * | 2017-06-09 | 2017-08-22 | 北京化工大学 | A kind of preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system |
-
2018
- 2018-02-08 CN CN201810129065.4A patent/CN110128628A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101578315A (en) * | 2006-11-20 | 2009-11-11 | 陶氏环球技术公司 | Epoxy resins comprising a cycloalphatic diamine curing agent |
| CN102286138A (en) * | 2011-07-01 | 2011-12-21 | 蓝星(北京)化工机械有限公司 | Heat-resistant epoxide resin composition for rapid pultrusion |
| CN102977557A (en) * | 2012-12-11 | 2013-03-20 | 蓝星(北京)化工机械有限公司 | Room temperature curing epoxy resin composition and preparation method thereof |
| CN103881301A (en) * | 2012-12-24 | 2014-06-25 | 江苏绿材谷新材料科技发展有限公司 | High temperature-resistant epoxy resin composition for pultrusion and preparation method |
| CN107083025A (en) * | 2017-06-09 | 2017-08-22 | 北京化工大学 | A kind of preparation method of carbon fiber Automobile Part rapid shaping fire resistant resin system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2574054C2 (en) | Epoxy resin-based curable compositions and composite materials obtained therefrom | |
| CN103124757B (en) | Advanced composition epoxy resin | |
| US2965610A (en) | Process for curing polyepoxides and resulting products | |
| CA1149816A (en) | Propenyl-substituted phenolglycidyl ethers, processes for producing them, and their use | |
| NO144004B (en) | YSTEANORDNING. | |
| KR102628808B1 (en) | Use of low viscosity bis-anhydrohexitol ether compositions as reactive diluents for crosslinkable resins, adhesives, coatings and matrix compositions for composites. | |
| US5872196A (en) | Liquid epoxy resin composition | |
| US3329737A (en) | Curable composition containing a polyepoxide and an allylic polyphenolic novolac, free of methylol groups | |
| US6391979B1 (en) | Epoxidized poly-p-hydroxystyrene | |
| EP0148117B1 (en) | Triglycidyl compounds from aminophenols | |
| US2934506A (en) | Modified epoxide resins | |
| CN110128628A (en) | A kind of preparation method of novel fire resistant epoxy mold resin | |
| JPH05271211A (en) | Polyglycidyl ether of aliphatic polyfunctional secondary alcohol, its production and curable composition containing the same | |
| US3314912A (en) | Epoxy resin compositions containing triorgano phosphate diluents | |
| JPH11116566A (en) | Cyclic carbonate resin composition and its cured product | |
| WO1998022527A1 (en) | Epoxy resin composition suitable for sheet moulding | |
| KR102099795B1 (en) | Compound having anhydrosugar alcohol core and method for preparing the same | |
| US3784525A (en) | Long-chain diglycidyl esters | |
| US3641064A (en) | Polyglycidyl esters | |
| JP3940945B2 (en) | Epoxy resin composition for sealing electronic parts | |
| TWI802196B (en) | Resin composition and resin film | |
| JPH05287052A (en) | Epoxy resin composition, preparation of epoxy resin, and semiconductor sealing material | |
| US3379654A (en) | Process for the preparation of epoxygroup containing prepolymers from polyepoxy compounds | |
| US3083186A (en) | Curing spirobi(meta-dioxane) epoxides with polycarboxylic acid anhydrides in combination modifiers containing active hydrogen atoms | |
| KR101552341B1 (en) | Liquid methylenedianiline compositions |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190816 |
|
| RJ01 | Rejection of invention patent application after publication |