CN114437501A - 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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- CN114437501A CN114437501A CN202011195938.5A CN202011195938A CN114437501A CN 114437501 A CN114437501 A CN 114437501A CN 202011195938 A CN202011195938 A CN 202011195938A CN 114437501 A CN114437501 A CN 114437501A
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- rubber
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- fully vulcanized
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 106
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 106
- 239000000843 powder Substances 0.000 title claims abstract description 81
- 239000003607 modifier Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229920001971 elastomer Polymers 0.000 claims abstract description 61
- 239000005060 rubber Substances 0.000 claims abstract description 61
- 239000003085 diluting agent Substances 0.000 claims abstract description 22
- 238000001723 curing Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229920000459 Nitrile rubber Polymers 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 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
- 229920002857 polybutadiene Polymers 0.000 claims description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 7
- 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
- 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 4
- -1 organic ester compounds Chemical class 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 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 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229920003049 isoprene rubber Polymers 0.000 claims description 3
- 229920000126 latex Polymers 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
- 239000005077 polysulfide Substances 0.000 claims description 3
- 229920001021 polysulfide Polymers 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
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 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 2
- 150000002170 ethers Chemical class 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
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 238000013007 heat curing Methods 0.000 claims 1
- 238000003701 mechanical milling Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000006185 dispersion Substances 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
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 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
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 239000011157 advanced composite material Substances 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010410 dusting 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
- 239000011521 glass Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Classifications
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- 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
Abstract
The invention provides a powder modifier for epoxy resin, a preparation method thereof and modified epoxy resin thereof, wherein the powder modifier comprises fully vulcanized powder rubber and a diluent, and the powder modifier is added into the epoxy resin to prepare an epoxy resin composition and finally prepare an epoxy resin cured product. Experimental results show that the powder rubber prepared by the invention has the using effect of being more easily dispersed on the premise of not reducing the performance of an epoxy resin cured product, and the viscosity of a premixing 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 of the powder modifier and the modified epoxy resin.
Background
Epoxy resins are an important class of thermosetting resins and are the most widely used matrix resins in polymer-based composites. The epoxy resin has the advantages of excellent bonding performance, wear resistance, mechanical performance, electrical insulation performance, chemical stability, high and low temperature resistance, low shrinkage, easy processing and forming, low cost and the like, and is widely applied to the fields of adhesives, electronic instruments, light industry, construction, machinery, aerospace, coatings, electronic and electrical insulation materials, advanced composite materials and the like.
The pure epoxy resin is a thermosetting material with high crosslinking degree after being cured, and the crack propagation belongs to typical brittle propagation, so the brittleness is high, and the application of the pure epoxy resin is limited. When the non-toughened epoxy resin is used as an adhesive, the bonding strength is relatively low; when the coating is used as a coating, the film forming property is poor, and a film layer is brittle; when used as insulating potting material, cracks tend to develop. These disadvantageous aspects limit to a large extent its application in certain high-tech areas. Therefore, it has been one of the most important issues in the field of epoxy resin research to improve the toughness of epoxy resins. Another disadvantage of epoxy resin is heat resistance, which cannot meet the requirement in aerospace and some adhesives requiring high temperature resistance, and although thermosetting resins such as bismaleimide resin resistant to higher temperature are developed, the thermosetting resins still have short processing properties, so how to improve the heat resistance of epoxy resin becomes another hot topic in the field of epoxy resin research.
Chinese patent CN1402752A and CN1330097A disclose a fully vulcanized powdered rubber and a preparation method thereof, and Chinese patent CN1412244A discloses a thermosetting resin toughened by the fully vulcanized powdered rubber and a preparation method thereof.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a powder modifier for epoxy resin and an epoxy resin composition added with the powder modifier, wherein a diluent is added into fully vulcanized rubber powder, so that the dispersibility of powder rubber in 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.
One of the objects of the present invention is to provide a powder modifier for epoxy resin, comprising a fully vulcanized powder rubber and a diluent blended together, said 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 powdered rubber;
the modifier is added with a diluent to help the dispersion of the powdered rubber and simultaneously reduce the viscosity of an epoxy resin system, wherein the diluent is selected from organic ether compounds or organic ester compounds containing epoxy groups, preferably C12-14At 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, and neopentyl glycol diglycidyl ether;
the powder modifier also contains a separant, and the separant can be common superfine inorganic powder, specifically, the separant is selected from inorganic compounds, preferably at least one of nano calcium carbonate, talcum powder and white carbon black; the amount of the release agent is 1 to 5 parts, preferably 1 to 3 parts, based on 100 parts by weight of the fully vulcanized powdered rubber.
In the modifier, the gel content in the fully vulcanized powdered rubber is 60 percent by weight or more, preferably 75 percent by weight or more, and the rubber fine powder can freely flow without adding a separant after being dried; the average particle size of the fully vulcanized powdered rubber is 20-200 nm, preferably 50-150 nm;
the fully vulcanized powdered rubber is obtained by vulcanizing rubber latex by an irradiation method, and is selected from fully vulcanized powdered natural rubber, fully vulcanized powdered styrene-butadiene rubber, fully vulcanized powdered carboxylated styrene-butadiene rubber, fully vulcanized powdered nitrile-butadiene rubber, fully vulcanized powdered carboxylated nitrile-butadiene rubber, fully vulcanized powdered polybutadiene rubber, fully vulcanized powdered chloroprene rubber, fully vulcanized powdered silicone rubber and fully vulcanized powdered acrylate rubber, at least one of fully vulcanized powdered butadiene-styrene-pyridine rubber, fully vulcanized powdered isoprene rubber, fully vulcanized powdered butyl rubber, fully vulcanized powdered ethylene-propylene rubber, fully vulcanized powdered polysulfide rubber, fully vulcanized powdered acrylate butadiene rubber, fully vulcanized powdered polyurethane rubber and fully vulcanized powdered fluorine rubber, preferably at least one of fully vulcanized powdered carboxyl nitrile rubber and fully vulcanized powdered nitrile rubber.
Each particle of the fully vulcanized powdered rubber used in the invention is homogeneous, i.e. the single particle is homogeneous in composition, and the phenomena of layering, phase separation and other heterogeneous phases are not found in the particles under the observation of the prior art.
The above-mentioned all-vulcanized powdery rubbers are preferably all-vulcanized powdery rubbers produced in accordance with the international patent application WO01/40356 filed by the applicant on 9/18/2000 (priority date 1999, 12/3/10) and the international patent application WO 01/98395 filed by the applicant on 6/15/2001 (priority date, 2000, 6/15). More preferably at least one of the following fully vulcanized powdered rubbers: fully vulcanized powder natural rubber, fully vulcanized powder styrene-butadiene rubber, fully vulcanized powder carboxylated styrene-butadiene rubber, fully vulcanized powder nitrile rubber, fully vulcanized powder carboxylated nitrile rubber, fully vulcanized powder polybutadiene rubber, fully vulcanized powder chloroprene rubber, fully vulcanized powder silicone rubber, fully vulcanized powder acrylate rubber, fully vulcanized powder styrene-butadiene-pyridine rubber, fully vulcanized powder isoprene rubber, fully vulcanized powder butyl rubber, fully vulcanized powder polysulfide rubber, fully vulcanized powder acrylate-butadiene rubber, fully vulcanized powder polyurethane rubber, fully vulcanized powder fluorine rubber and the like. The fully vulcanized powdery rubber is a rubber fine powder having a gel content of 60% by weight or more, preferably 75% by weight or more, and free-flowing without adding a release agent after drying. The powdered rubber of the above patent application has an average particle diameter of 0.02 to 1 μm, preferably 0.05 to 0.5 μm, and more preferably 0.05 to 0.2. mu.m. Each particle in the fully vulcanized powder rubber is homogeneous, namely, the single particle is homogeneous in composition, and the phenomena of layering, phase separation and other heterogeneous phenomena are not found in the particle under the observation of the prior art. The powder rubber is prepared by irradiating and crosslinking corresponding rubber latex to fix the particle size of rubber particles.
The rubber particles described above may also be cross-linked powder rubber prepared according to the applicant's chinese patent CN1353131A (application date is 2000, 11, 3, and No. ZL00130386.4), which includes at least one of the following cross-linked powder rubbers: crosslinked powdered styrene-butadiene rubber, crosslinked powdered polybutadiene rubber, or the like. The cross-linked powdered rubber is prepared from cross-linked synthetic rubber emulsion through drying. The cross-linked powdered rubber is free-flowing without the addition of a release agent. In this patent, the average particle diameter of the powdered rubber is 0.05 to 0.3. mu.m. The gel content is 80% by weight or more, preferably 85% by weight or more, in conformity with the gel content of the cross-linking type synthetic rubber emulsion as the raw material. Each particle in the cross-linked powder rubber is homogeneous, namely, the single particle is homogeneous in composition, and the phenomena of layering, phase separation and other heterogeneous phenomena are not found in the particles under the observation of the prior microscopic technology.
The other purpose of the invention is to provide a preparation method of the powder modifier for epoxy resin, which comprises the steps of mixing the fully vulcanized powder rubber with the components including the diluent, and optionally adding the release agent. Wherein the mixing comprises mechanical stirring and grinding, preferably three-roll grinding.
The invention also aims to provide a modified epoxy resin, which comprises the powder modifier for the epoxy resin or the powder modifier for the epoxy resin obtained by the preparation method and an epoxy resin prepolymer which are blended. The amount of the powder modifier for epoxy resin is 1-30 parts, preferably 5-20 parts, based on 100 parts by weight of the epoxy resin prepolymer.
The fourth purpose of the present invention is to provide a preparation method of the modified epoxy resin, which comprises the steps of mixing and curing the components including the powder modifier for epoxy resin and the epoxy resin prepolymer to obtain the modified epoxy resin, and specifically comprises the following steps:
step 1, premixing epoxy resin with a powder modifier and an epoxy resin prepolymer to obtain a modified epoxy resin premix;
and 2, adding an epoxy resin curing agent and optionally an epoxy resin curing accelerator into the premix, mixing the components, and heating for curing reaction to obtain the modified epoxy resin.
Preferably, the premixing temperature in the step 1 is 20-40 ℃, and preferably, the premixing is uniformly mixed under the conditions of room temperature and normal pressure;
the mixing temperature of each component in the step 2 is 90-100 ℃; mixing uniformly, wherein the general mixing time can be preferably 15-60 min, and more preferably 20-40 min;
the temperature for heating and curing in the step 2 is higher than 100 ℃, and preferably 110-180 ℃; the time for heating and curing can be preferably 1-10 h, more preferably 3-8 h and the like.
In the invention, fully vulcanized powdered rubber and a diluent are mixed, dispersed by a three-roll grinder or a kneader, added with a separant and stirred by a high-speed stirrer to prepare the powder modifier for epoxy resin. The powder modifier is added into epoxy resin, and simultaneously added with an auxiliary agent or other common auxiliary agents with curing effect, and then cured to obtain the cured epoxy resin. In the preparation method of the invention, the auxiliary agent with curing function 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 the conventional dosage in the prior art. In the above-mentioned 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 which is generally used for the processing of thermosetting resins. Specifically, a mixture obtained by the epoxy resin, the modifier, the curing agent and other conventional additives is vacuumized, and then the mixture is injected into a preheated mold and cured at a certain curing temperature to finally prepare an epoxy resin cured product. The curing auxiliaries and their amounts used here are also those customary for epoxy resins. In addition, other conventional additives in the epoxy resin processing technology can be added in a proper amount according to the processing requirements.
The powder modifier prepared by the invention has the using effect of easier dispersion on the premise of not reducing the performance of an epoxy resin cured product, and the viscosity of a premixing system is reduced. The more dispersible use effect is specifically represented by the reduction of the grinding times of a three-roll grinder, the dispersion of the product in the epoxy resin in the prior art needs to be ground at least three times, and the powder modifier provided by the invention can obtain the same dispersion 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 a system can be reduced, and the processability and mechanical property are 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 is simple and feasible in process.
Drawings
FIG. 1 is a TEM photograph of a 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 it can be seen from FIG. 2 that the modified epoxy resin prepared in comparative example 1 has a poor dispersibility of the modifier.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The test methods used in the examples are as follows:
the gel content determination method comprises the following steps: : testing the gel content in the powder rubber by adopting GB/T37498 and 2019 test standards;
the particle size measuring method comprises the following steps: philips PHILIPS CM12(S) TEM;
viscosity test method: the viscosity of the epoxy resin product was tested according to the epoxy viscosity determination method of GB 12007.4-89.
Example 1
Preparation of powder modifier for epoxy resin:
500g of commercially available powdered rubber VP-501 (fully vulcanized powdered carboxylated nitrile rubber, Yanghuagaku Co., Ltd., gel content 92%, average particle diameter 90nm) and 250g of commercially available diluent C12-14Fatty glycidyl ether (trade name AGE) was mixed, the mixture was manually preliminarily stirred with a glass rod and allowed to stand for 2 hours, and then the mixed powder was passed through a three-roll machine. Then adding the separant nano calcium carbonate with the weight of 3 percent of the weight of the powdered 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 commercially available CYD-128 resin, adding 90g of the powder modifier, standing for 1 day after three rollers for one time, and then grinding by three rollers again to obtain a modified epoxy resin premix, wherein the viscosity value is shown in Table 1;
step 2) weighing 100g of the epoxy resin premix dispersed with the powder modifier, putting the epoxy resin premix into a three-neck flask, and then adding 73g of a curing agent: methyl tetrahydrophthalic anhydride (commercially available) is heated to 90-100 ℃, stirred and vacuumized for 30min, and then 1.0g of curing accelerator is added: aluminum acetylacetonate (commercially available), stirring, evacuating for 5min, casting, heating and curing at 130 deg.C for 5h, and heating and curing at 150 deg.C for 1 h. To obtain an epoxy resin cured product.
Example 2
Changing the addition amount of diluent AGE from 250g to 500 g; the rest is the same as in example 1.
Example 3
VP-501 was changed to VP-401 (fully vulcanized powdery nitrile rubber, Yanghua Kokai Co., Ltd., gel content 91%, average particle diameter 100nm), and the rest was the same as in example 1.
Example 4
The amount of AGE as a diluent in the preparation of the powder modifier for epoxy resin was changed from 250g to 150g, the amount of talc as a dusting agent was changed to 1 wt% based on the weight of the powdered rubber, and the amount of the AGE as a powder modifier in the preparation of modified epoxy resin was changed to 25g, the remainder being the same as in example 1.
Example 5
The addition amount of a diluent AGE in the preparation of the powder modifier for epoxy resin is changed from 250g to 600g, and a separant is changed to nano calcium carbonate accounting for 5 wt% 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 for three times by using a three-roll grinder to obtain an epoxy resin premix, and testing the viscosity value of the epoxy resin premix to be shown in Table 1;
step 2) weighing 112g of the epoxy resin premix dispersed with the powdered rubber, putting the epoxy resin premix into a three-neck flask, adding 85g of methyl tetrahydrophthalic anhydride, heating to 90-100 ℃, stirring while vacuumizing for 30min, adding 1.0g of aluminum acetylacetonate, stirring and exhausting 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 viscosity test results of epoxy resin prepolymers 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 are compared with comparative examples 1 to 3, it can be seen that the viscosity of the epoxy resin prepolymer is significantly reduced and the processability is better after the diluent is added in examples 1 to 3.
Claims (12)
1. A powder modifier for epoxy resins comprising a blended fully vulcanized powder rubber and a diluent, said diluent containing epoxy groups.
2. The powder modifier according to claim 1,
the using amount of the diluent is 30-130 parts by weight based on 100 parts by weight of the fully vulcanized powdered rubber; and/or the presence of a gas in the gas,
the diluent is selected from organic ether compounds or organic ester compounds containing epoxy groups; and/or the presence of a gas in the gas,
the powder modifier also contains a release agent.
3. The powder modifier according to claim 2,
the using amount of the diluent is 50-100 parts by weight based on 100 parts by weight of the fully vulcanized powdered rubber; and/or the presence of a gas in the gas,
the diluent is selected from C12-14At 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, and neopentyl glycol diglycidyl ether; and/or the presence of a gas in the atmosphere,
the separant is selected from inorganic compounds, preferably at least one of nano calcium carbonate, talcum powder and white carbon black; and/or the presence of a gas in the gas,
the amount of the release agent is 1 to 5 parts, preferably 1 to 3 parts, based on 100 parts by weight of the fully vulcanized powdered rubber.
4. The powder modifier according to claim 1,
the gel content in the fully vulcanized powdery rubber is 60% by weight or more, preferably 75% by weight or more; and/or the presence of a gas in the gas,
the average particle size of the fully vulcanized powdered rubber is 20-200 nm, preferably 50-150 nm; and/or the presence of a gas in the gas,
the fully vulcanized powdered rubber is obtained by vulcanizing rubber latex by an irradiation method.
5. The powder modifier according to claim 1,
the fully vulcanized powdered rubber is selected from at least one of fully vulcanized powdered natural rubber, fully vulcanized powdered styrene-butadiene rubber, fully vulcanized powdered carboxylated styrene-butadiene rubber, fully vulcanized powdered nitrile rubber, fully vulcanized powdered carboxylated nitrile rubber, fully vulcanized powdered polybutadiene rubber, fully vulcanized powdered chloroprene rubber, fully vulcanized powdered silicone rubber, fully vulcanized powdered acrylate rubber, fully vulcanized powdered butadiene-styrene-pyridine rubber, fully vulcanized powdered isoprene rubber, fully vulcanized powdered butyl rubber, fully vulcanized powdered ethylene-propylene rubber, fully vulcanized powdered polysulfide rubber, fully vulcanized powdered acrylate butadiene rubber, fully vulcanized powdered polyurethane rubber and fully vulcanized powdered fluorine rubber, and preferably at least one of fully vulcanized powdered carboxylated nitrile rubber and fully vulcanized powdered nitrile rubber.
6. A process for preparing the powder modifier for epoxy resin as claimed in any one of claims 1 to 5, which comprises mixing the fully vulcanized powder rubber with the components including the diluent, and optionally adding the release agent.
7. The production method according to claim 6,
the mixing includes mechanical stirring and milling, preferably three-roll milling.
8. A modified epoxy resin comprising the powder modifier for epoxy resin according to any one of claims 1 to 5 or the powder modifier for epoxy resin obtained by the production method according to claim 6 or 7 and an epoxy resin prepolymer blended together.
9. The modified epoxy resin according to claim 8,
the amount of the powder modifier for epoxy resin is 1-30 parts, preferably 5-20 parts, based on 100 parts by weight of the epoxy resin prepolymer.
10. A method for preparing the modified epoxy resin of claim 8 or 9, comprising mixing and curing the components including the powder modifier for epoxy resin and the epoxy resin prepolymer to obtain the modified epoxy resin.
11. The method according to claim 10, wherein the method specifically comprises:
step 1, premixing epoxy resin with a powder modifier and an epoxy resin prepolymer to obtain a modified epoxy resin premix;
and 2, adding an epoxy resin curing agent and optionally an epoxy resin curing accelerator into the premix, mixing the components, and heating for curing reaction to obtain the modified epoxy resin.
12. The production method according to claim 11,
the premixing temperature in the step 1 is 20-40 ℃; and/or the presence of a gas in the gas,
the mixing temperature of each component in the step 2 is 90-100 ℃; and/or the presence of a gas in the gas,
the temperature for heat curing in step 2 is above 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 |
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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 |
| US20030088036A1 (en) * | 2001-10-12 | 2003-05-08 | China Petroleum And Chemical Corporation | Toughened thermosetting resins and preparation of the same |
| 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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