CN114437501B - Powder modifier for epoxy resin, preparation method thereof and modified epoxy resin thereof - Google Patents
Powder modifier for epoxy resin, preparation method thereof and modified epoxy resin thereof Download PDFInfo
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- CN114437501B CN114437501B CN202011195938.5A CN202011195938A CN114437501B CN 114437501 B CN114437501 B CN 114437501B CN 202011195938 A CN202011195938 A CN 202011195938A CN 114437501 B CN114437501 B CN 114437501B
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- 239000000843 powder Substances 0.000 title claims abstract description 134
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 111
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 111
- 239000003607 modifier Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920001971 elastomer Polymers 0.000 claims abstract description 60
- 239000005060 rubber Substances 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000001723 curing Methods 0.000 claims description 23
- 239000003085 diluting agent Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- 229920000459 Nitrile rubber Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- -1 ether compound Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- FDYSSWYQRTVFIS-UHFFFAOYSA-N buta-1,3-diene 3-phenylprop-2-enoic acid Chemical compound C=CC=C.C(=O)(O)C=CC1=CC=CC=C1 FDYSSWYQRTVFIS-UHFFFAOYSA-N 0.000 claims description 3
- 229920005549 butyl rubber Polymers 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 229920003049 isoprene rubber Polymers 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000800 acrylic rubber Polymers 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229920001973 fluoroelastomer Polymers 0.000 claims description 2
- 238000013007 heat curing Methods 0.000 claims description 2
- 150000002484 inorganic compounds Chemical group 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- YFRNYWVKHCQRPE-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid Chemical compound C=CC=C.OC(=O)C=C YFRNYWVKHCQRPE-UHFFFAOYSA-N 0.000 description 1
- JCOJVKFKIOBIRH-UHFFFAOYSA-N buta-1,3-diene;pyridine;styrene Chemical compound C=CC=C.C1=CC=NC=C1.C=CC1=CC=CC=C1 JCOJVKFKIOBIRH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a powder modifier for epoxy resin, a preparation method thereof and modified epoxy resin thereof. Experimental results show that the powder rubber prepared by the invention has the use effect of being easier to disperse on the premise of not reducing the performance of the epoxy resin condensate, and the viscosity of the pre-mixed system is reduced.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a powder modifier for epoxy resin, a preparation method thereof and modified epoxy resin.
Background
Epoxy resins are an important class of thermosetting resins, being the most widely used matrix resins in polymer matrix composites. The epoxy resin has the advantages of excellent adhesive property, wear resistance, mechanical property, electrical insulation property, chemical stability, high and low temperature resistance, low shrinkage, easy processing and forming, low cost and the like, and can be widely applied to the fields of adhesives, electronic instruments, light industry, buildings, machinery, aerospace, coatings, electronic and electrical insulation materials, advanced composite materials and the like.
The cured pure epoxy resin is a thermosetting material with high crosslinking degree, and crack propagation belongs to typical brittleness extension, so that the epoxy resin has high brittleness, and the application of the epoxy resin is limited. When the non-toughened epoxy resin is used as an adhesive, the adhesive strength is relatively low; when used as a coating, the coating has poor film forming property and a brittle film layer; when used as an insulating potting material, cracks tend to occur. These disadvantageous aspects limit to a large extent its application in certain high-tech fields. Therefore, improving toughness of epoxy resins has been one of the hot subjects in the field of epoxy resin research. Another disadvantage of epoxy resins is the heat resistance, which is not satisfactory in aerospace and certain adhesives where high temperature resistance is required, and although thermosetting resins such as bismaleic resins which are more resistant to higher temperatures are also developed at present, short boards still remain in terms of process performance, etc., so how to improve the heat resistance of epoxy resins is another hot subject in the field of epoxy resin research.
Chinese patent CN1402752A and CN1330097A disclose fully vulcanized powder rubber and a preparation method thereof, chinese patent CN1412244A discloses thermosetting resin toughened by the fully vulcanized powder rubber and a preparation method thereof, and in the technical scheme disclosed in the patent, the toughness of the epoxy resin modified by the fully vulcanized powder rubber is greatly improved, and the heat resistance is not reduced but is limited.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the powder modifier for the epoxy resin and the epoxy resin composition added with the powder modifier, and the diluent is added into the fully vulcanized rubber powder, so that the dispersibility of the powder rubber in the epoxy resin can be improved, the viscosity of an epoxy resin system can be reduced, and the processability of the epoxy resin can be improved.
It is an object of the present invention to provide a powder modifier for epoxy resins comprising a blended fully vulcanized powder rubber and a diluent containing an epoxy group.
In the modifier, the diluent is used in an amount of 30 to 130 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of the fully vulcanized powder rubber;
the addition of a diluent to the above-mentioned modifier, which is selected from the group consisting of epoxy group-containing organic ether compounds or organic ester compounds, preferably from the group consisting of C, aids in the dispersion of the powder rubber while reducing the viscosity of the epoxy resin system 12-14 At least one of aliphatic glycidyl ether, alkylene glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, benzyl glycidyl ether, 1, 6-hexanediol diglycidyl ether, o-tolyl glycidyl ether, neopentyl glycol diglycidyl ether;
the powder modifier also contains a release agent, wherein the release agent can be commonly used superfine inorganic powder, specifically, the release agent is selected from inorganic compounds, preferably at least one of nano calcium carbonate, talcum powder and white carbon black; the release agent is used in an amount of 1 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the fully vulcanized powder rubber.
In the modifier, the gel content of the fully vulcanized powder rubber is 60% by weight or more, preferably 75% by weight or more, and the fully vulcanized powder rubber can be free-flowing rubber micro powder without adding a release agent after drying; the average particle diameter of the fully vulcanized powder rubber is 20-200 nm, preferably 50-150 nm;
the fully vulcanized powder rubber is obtained by vulcanizing rubber latex through an irradiation method, and is at least one selected from fully vulcanized powder natural rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder carboxyl styrene-butadiene rubber, fully vulcanized powder nitrile rubber, fully vulcanized powder carboxyl nitrile rubber, fully vulcanized powder polybutadiene rubber, fully vulcanized powder chloroprene rubber, fully vulcanized powder silicone rubber, fully vulcanized powder acrylic rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder isoprene rubber, fully vulcanized powder butyl rubber, fully vulcanized powder ethylene propylene rubber, fully vulcanized powder polysulfide rubber, fully vulcanized powder acrylic butadiene rubber, fully vulcanized powder polyurethane rubber and fully vulcanized powder fluorine rubber, preferably at least one selected from fully vulcanized powder carboxyl nitrile rubber and fully vulcanized powder nitrile rubber.
Each particle in the fully vulcanized powder rubber used in the present invention is homogeneous, i.e., the individual particles are homogeneous in composition, and no inhomogeneities such as delamination, phase separation, etc. are found in the particles under observation of the prior art.
The above-mentioned fully vulcanized powder rubber is preferably a fully vulcanized powder rubber prepared according to International patent application WO01/40356 filed by the applicant at 18/9/2000 (12/3/1999/priority date) and International patent application WO 01/98395 filed by the applicant at 15/6/2001 (15/2000/priority date). More preferably at least one of the following fully vulcanized powdered rubbers is used: fully vulcanized powdered natural rubber, fully vulcanized powdered styrene-butadiene rubber, fully vulcanized powdered carboxyl styrene-butadiene rubber, fully vulcanized powdered nitrile rubber, fully vulcanized powdered carboxyl nitrile rubber, fully vulcanized powdered polybutadiene rubber, fully vulcanized powdered neoprene rubber, fully vulcanized powdered silicone rubber, fully vulcanized powdered acrylate rubber, fully vulcanized powdered styrene-butadiene-pyridine rubber, fully vulcanized powdered isoprene rubber, fully vulcanized powdered butyl rubber, fully vulcanized powdered polysulfide rubber, fully vulcanized powdered acrylate-butadiene rubber, fully vulcanized powdered polyurethane rubber or fully vulcanized powdered fluororubber, and the like. The fully vulcanized powder rubber is rubber micropowder with gel content of 60% by weight or more, more preferably 75% by weight or more, and can flow freely after drying without adding a release agent. The average particle diameter of the powder rubber in the above patent application is 0.02 to 1. Mu.m, preferably 0.05 to 0.5. Mu.m, more preferably 0.05 to 0.2. Mu.m. Each of the particles in the fully vulcanized powdered rubber described above is homogeneous in composition, i.e., the individual particles are homogeneous in composition, and no inhomogeneities such as delamination, phase separation, etc. are found in the particles under observation of prior art microscopy. The powder rubber is produced by irradiation crosslinking of the corresponding rubber latex to fix the particle size of the rubber particles.
The rubber particles described above may also be crosslinked powder rubber prepared according to chinese patent CN1353131a (filing date of 11/3/2000, patent No. ZL 00130386.4) of the present applicant, which includes at least one of the following crosslinked powder rubbers: crosslinked powdered styrene-butadiene rubber or crosslinked powdered polybutadiene rubber, and the like. The cross-linked powder rubber is prepared by taking cross-linked synthetic rubber emulsion as a raw material and drying. The crosslinked powder rubber can flow freely without adding a release agent. The average particle diameter of the powder rubber in this patent is 0.05 to 0.3. Mu.m. The gel content thereof is kept in conformity with the gel content of the cross-linked synthetic rubber emulsion as a raw material, and is 80% by weight or more, preferably 85% by weight or more. Each particle in the crosslinked powder rubber is homogeneous, i.e., the individual particles are homogeneous in composition, and no inhomogeneities such as delamination, phase separation, etc. are found in the particles under observation in the prior art.
The second object of the present invention is to provide a method for producing the powder modifier for epoxy resin described above, comprising mixing the fully vulcanized powder rubber with the components including the diluent, optionally adding the release agent. Wherein the mixing comprises mechanical stirring and milling, preferably three-roll milling.
The third object of the present invention is to provide a modified epoxy resin comprising the powder modifier for epoxy resin or the powder modifier for epoxy resin and the epoxy resin prepolymer obtained by the above-mentioned production method blended. The powder modifier for epoxy resin is used in an amount of 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the epoxy resin prepolymer.
The fourth object of the present invention is to provide a method for preparing the modified epoxy resin, comprising the steps of mixing and curing components including the powder modifier for epoxy resin and the epoxy resin prepolymer to obtain the modified epoxy resin, which comprises the following steps:
step 1, premixing an epoxy resin powder modifier and an epoxy resin prepolymer to obtain a modified epoxy resin premix;
and 2, adding an epoxy resin curing agent, optionally an epoxy resin curing accelerator, into the premix, mixing the components, and performing heating curing reaction to obtain the modified epoxy resin.
Preferably, the premixing temperature in the step 1 is 20-40 ℃, preferably, the premixing is carried out under the conditions of room temperature and normal pressure;
the temperature for mixing the components in the step 2 is 90-100 ℃; the mixing is carried out until the mixture is uniform, and the mixing time can be preferably 15 to 60 minutes, more preferably 20 to 40 minutes;
the heating and curing temperature in the step 2 is higher than 100 ℃, preferably 110-180 ℃; the time for the heat curing may be preferably 1 to 10 hours, more preferably 3 to 8 hours, and the like.
The powder modifier for epoxy resin is prepared by mixing fully vulcanized powder rubber and a diluent, dispersing the mixture by a three-roll grinder or a kneader, adding a release agent and stirring the mixture by a high-speed stirrer. The powder modifier is added into epoxy resin, and an auxiliary agent or other common auxiliary agents with a curing effect are added, and then the epoxy resin cured product is obtained after curing. In the preparation method of the invention, the auxiliary agent for curing comprises an epoxy resin curing agent and/or an epoxy resin curing accelerator (such as methyl tetrahydrophthalic anhydride and aluminum acetylacetonate), and the dosage of the auxiliary agent is conventional in the prior art. In the above-described process for preparing the epoxy resin composition of the present invention, the mixing temperature, curing (or crosslinking) conditions (including temperature, time) and equipment used for the epoxy resin prepolymer are all processing and curing (or crosslinking) equipment used in the usual processing of thermosetting resins. Specifically, the mixture obtained by the epoxy resin, the modifier, the curing agent and other conventional auxiliary agents is vacuumized, and then the mixture is injected into a preheated mold to be cured at a certain curing temperature, so that the epoxy resin cured product is finally prepared. The curing auxiliaries and their amounts used here are also those customary for epoxy resins. In addition, other conventional auxiliary agents in the epoxy resin processing technology can be added in proper amount according to the processing requirements.
The powder modifier prepared by the invention has the use effect of being easier to disperse on the premise of not reducing the performance of the epoxy resin condensate, and reduces the viscosity of the pre-mixed system. The use effect of easier dispersion is particularly shown by the reduction of the grinding times of a three-roller grinder, the dispersion of the product in the epoxy resin in the prior art needs to be ground for at least three times, and the powder modifier provided by the invention can obtain the same dispersing effect only by grinding twice.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
(1) According to the invention, the diluent is added into the powder modifier for the epoxy resin, so that the powder rubber is easier to disperse in the epoxy resin; the powder modifier is dispersed in the epoxy resin prepolymer, so that the viscosity of the system can be reduced, and the processability and mechanical properties can be improved;
(2) The powder modifier prepared by adopting a three-roller grinding mode can be better dispersed in the epoxy resin prepolymer;
(3) The preparation method provided by the invention has simple and feasible process.
Drawings
FIG. 1 is a TEM photograph of the modified epoxy resin prepared in example 1, and it can be seen from FIG. 1 that the modifier prepared in example 1 is uniformly dispersed in the epoxy resin system;
fig. 2 is a TEM photograph of the modified epoxy resin prepared in comparative example 1, and as can be seen from fig. 2, the modified epoxy resin prepared in comparative example 1 has poor dispersibility of the modifier.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test methods used in the examples are as follows:
gel content determination method: : testing the gel content in the powdered rubber by using a GB/T37498-2019 test standard;
the particle size measurement method comprises the following steps: philips PHILIPS CM (S) TEM;
the viscosity test method comprises the following steps: the viscosity of the epoxy resin product was tested according to the GB12007.4-89 epoxy resin viscosity measurement method.
Example 1
Preparation of powder modifier for epoxy resin:
will 500g of commercially available powder rubber VP-501 (fully vulcanized powder carboxylated nitrile rubber, available from Yan Gao Kogyo Co., ltd., gel content 92%, average particle size 90 nm) and 250g of commercially available diluent C 12-14 Fatty glycidyl ether (trade name AGE) was mixed, and a glass rod was manually stirred initially and allowed to stand for 2 hours, and then the mixed powder was passed through a three-roll mill. Then adding 3 wt% of release agent nano calcium carbonate based on the weight of the powder rubber, and stirring at high speed to prepare composite powder, wherein the epoxy value of the composite powder is 0.11.
Preparing modified epoxy resin:
step 1) weighing 500g of commercial CYD-128 resin, adding 90g of the powder modifier, standing for 1 day after three times, grinding again by three rollers to obtain a modified epoxy resin premix, and testing the viscosity number of the modified epoxy resin premix to be shown in Table 1;
step 2) weighing 100g of the epoxy resin premix with the powder modifier dispersed therein, putting the epoxy resin premix into a three-neck flask, and adding 73g of a curing agent: methyl tetrahydrophthalic anhydride (commercially available), heated to 90-100 ℃, stirred while being evacuated for 30min, and then added with 1.0g of curing accelerator: aluminum acetylacetonate (commercially available), stirred and pumped for 5min, cast, heat cured at 130℃for 5h, and heat cured at 150℃for 1h. An epoxy resin cured product was obtained.
Example 2
Changing the addition amount of the diluent AGE from 250g to 500g; the remainder was the same as in example 1.
Example 3
VP-501 was changed to VP-401 (fully vulcanized powder nitrile rubber, available from Yan Gao Ke Co., ltd., gel content 91%, average particle size 100 nm), and the remainder was the same as in example 1.
Example 4
The amount of the diluent AGE added in the preparation of the powder modifier for epoxy resin was changed from 250g to 150g, the release agent was changed to talc powder in an amount of 1% by weight based on the weight of the powdered rubber, and the powder modifier in the preparation of the modified epoxy resin was changed to 25g, and the rest was the same as in example 1.
Example 5
The addition amount of the diluent AGE in the preparation of the powder modifier for the epoxy resin is changed from 250g to 600g, and the release agent is changed into nano calcium carbonate accounting for 5 weight percent of the weight of the powder rubber; the powder modifier in the preparation of the modified epoxy resin was changed to 5g, and the rest was the same as in example 1.
Comparative example 1
Preparation of modified epoxy resin:
step 1) adding 59g of VP-501 powder rubber into 500g of CYD-128 type epoxy resin, grinding the mixture three times by a three-roller grinder to obtain an epoxy resin premix, and testing the viscosity number of the epoxy resin premix to obtain a viscosity number shown in table 1;
step 2) weighing 112g of the epoxy resin premix with the dispersed powder rubber, putting the epoxy resin premix into a three-neck flask, adding 85g of methyl tetrahydrophthalic anhydride, heating to 90-100 ℃, stirring, vacuumizing for 30min, adding 1.0g of aluminum acetylacetonate, stirring, vacuumizing for 5min, casting, heating and curing at 130 ℃ for 5h, and heating and curing at 150 ℃ for 1h to obtain an epoxy resin cured product.
Comparative example 2
The amount of VP-501 was changed from 56g to 44g, and the rest was the same as in comparative example 1.
Comparative example 3
VP-501 was changed to VP-401, and the rest was the same as in comparative example 1.
TABLE 1 epoxy resin prepolymer viscosity test results obtained in examples 1 to 3 and comparative examples 1 to 3
As can be seen from the test results in Table 1, when examples 1 to 3 and comparative examples 1 to 3 are compared, it can be seen that the viscosity of the epoxy resin prepolymer is significantly lowered after the diluent is added in examples 1 to 3, and the processability is improved.
Claims (14)
1. The powder modifier for the epoxy resin comprises blended fully-vulcanized powder rubber and a diluent, wherein the diluent contains epoxy groups, and the fully-vulcanized powder rubber is obtained by vulcanizing rubber latex by an irradiation method; the fully vulcanized powder rubber is at least one of fully vulcanized powder natural rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder carboxyl styrene-butadiene rubber, fully vulcanized powder nitrile rubber, fully vulcanized powder carboxyl nitrile rubber, fully vulcanized powder polybutadiene rubber, fully vulcanized powder chloroprene rubber, fully vulcanized powder silicone rubber, fully vulcanized powder acrylic rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder isoprene rubber, fully vulcanized powder butyl rubber, fully vulcanized powder ethylene propylene rubber, fully vulcanized powder polysulfide rubber, fully vulcanized powder acrylic butadiene rubber, fully vulcanized powder polyurethane rubber and fully vulcanized powder fluororubber, the gel content in the fully vulcanized powder rubber is 60% by weight or more, and the average particle size of the fully vulcanized powder rubber is 20-200 nm; the powder modifier also comprises a release agent, wherein the release agent is used in an amount of 1-5 parts by weight and the diluent is used in an amount of 30-130 parts by weight based on 100 parts by weight of the fully vulcanized powder rubber;
the preparation method of the powder modifier for the epoxy resin comprises the steps of mixing the fully vulcanized powder rubber with the components including the diluent and adding the isolating agent; the mixing includes three-roll milling.
2. A powder modifier as claimed in claim 1, wherein,
the diluent is selected from an organic ether compound or an organic ester compound containing an epoxy group.
3. A powder modifier as claimed in claim 2, wherein,
the usage amount of the diluent is 50-100 parts by weight based on 100 parts by weight of the fully vulcanized powder rubber; and/or the number of the groups of groups,
the diluent is selected from C 12-14 At least one of aliphatic glycidyl ether, alkylene glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, phenyl glycidyl ether, polypropylene glycol diglycidyl ether, benzyl glycidyl ether, 1, 6-hexanediol diglycidyl ether, o-tolyl glycidyl ether, neopentyl glycol diglycidyl ether; and/or the number of the groups of groups,
the isolating agent is selected from inorganic compounds; and/or the number of the groups of groups,
the release agent is used in an amount of 1-3 parts by weight based on 100 parts by weight of the fully vulcanized powder rubber.
4. A powder modifier according to claim 3,
the isolating agent is at least one selected from nano calcium carbonate, talcum powder and white carbon black.
5. A powder modifier as claimed in claim 1, wherein,
the gel content in the fully vulcanized powder rubber is 75% by weight or more; and/or the number of the groups of groups,
the average particle size of the fully vulcanized powder rubber is 50-150 nm.
6. A powder modifier as claimed in claim 1, wherein,
the fully vulcanized powder rubber is at least one selected from fully vulcanized powder carboxyl nitrile rubber and fully vulcanized powder nitrile rubber.
7. A method for producing the powder modifier for epoxy resins according to any one of claims 1 to 6, comprising mixing the fully vulcanized powder rubber with the components including the diluent and adding the release agent.
8. The method according to claim 7, wherein,
the mixing includes three-roll milling.
9. A modified epoxy resin comprising the powder modifier for epoxy resin according to any one of claims 1 to 6 or the powder modifier for epoxy resin obtained by the production method according to any one of claims 7 to 8 and an epoxy resin prepolymer.
10. The modified epoxy resin of claim 9, wherein,
the powder modifier for epoxy resin is used in an amount of 1-30 parts by weight based on 100 parts by weight of the epoxy resin prepolymer.
11. The modified epoxy resin of claim 10, wherein,
the powder modifier for the epoxy resin is used in an amount of 5-20 parts by weight based on 100 parts by weight of the epoxy resin prepolymer.
12. A method for preparing a modified epoxy resin according to any one of claims 9 to 11, comprising mixing and curing components including the powder modifier for epoxy resin and the epoxy resin prepolymer to obtain the modified epoxy resin.
13. The preparation method according to claim 12, wherein the preparation method specifically comprises:
step 1, premixing an epoxy resin powder modifier and an epoxy resin prepolymer to obtain a modified epoxy resin premix;
and 2, adding an epoxy resin curing agent, optionally an epoxy resin curing accelerator, into the premix, mixing the components, and performing heating curing reaction to obtain the modified epoxy resin.
14. The method of claim 13, wherein the process comprises,
the premixing temperature in the step 1 is 20-40 ℃; and/or the number of the groups of groups,
the temperature for mixing the components in the step 2 is 90-100 ℃; and/or the number of the groups of groups,
the temperature of the heat curing in step 2 is higher than 100 ℃.
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| CN1412244A (en) * | 2001-10-12 | 2003-04-23 | 中国石油化工股份有限公司 | Toughened thermosetting resin and its preparation method |
| CN101050344A (en) * | 2007-04-30 | 2007-10-10 | 湖南神力实业有限公司 | Epoxy binder modified by micropowder of crosslinked rubber, and preparation method |
| CN101935435A (en) * | 2009-07-03 | 2011-01-05 | 中国石油化工股份有限公司 | Toughened epoxy resin composition and preparation method thereof |
| CN102268174A (en) * | 2010-06-04 | 2011-12-07 | 中国石油化工股份有限公司 | Epoxy resin composition with high thermal resistance and high ductility, and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1412244A (en) * | 2001-10-12 | 2003-04-23 | 中国石油化工股份有限公司 | Toughened thermosetting resin and its preparation method |
| CN101050344A (en) * | 2007-04-30 | 2007-10-10 | 湖南神力实业有限公司 | Epoxy binder modified by micropowder of crosslinked rubber, and preparation method |
| CN101935435A (en) * | 2009-07-03 | 2011-01-05 | 中国石油化工股份有限公司 | Toughened epoxy resin composition and preparation method thereof |
| CN102268174A (en) * | 2010-06-04 | 2011-12-07 | 中国石油化工股份有限公司 | Epoxy resin composition with high thermal resistance and high ductility, and preparation method thereof |
| WO2011150864A1 (en) * | 2010-06-04 | 2011-12-08 | 中国石油化工股份有限公司 | Epoxy resin composition and its preparing method |
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