CN114656619B - Vacuum-introduced epoxy resin composition and preparation method thereof - Google Patents
Vacuum-introduced epoxy resin composition and preparation method thereof Download PDFInfo
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- CN114656619B CN114656619B CN202210479870.6A CN202210479870A CN114656619B CN 114656619 B CN114656619 B CN 114656619B CN 202210479870 A CN202210479870 A CN 202210479870A CN 114656619 B CN114656619 B CN 114656619B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 55
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 80
- 239000005543 nano-size silicon particle Substances 0.000 claims description 40
- 235000012239 silicon dioxide Nutrition 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 27
- -1 alicyclic amine Chemical class 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 18
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 18
- 239000003085 diluting agent Substances 0.000 claims description 17
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 12
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000007822 coupling agent Substances 0.000 claims description 10
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 230000002195 synergetic effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- 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
- YGBFHAIFQIZTSB-UHFFFAOYSA-N 4,4-dimethylcyclohexane-1,1-diamine Chemical compound CC1(C)CCC(N)(N)CC1 YGBFHAIFQIZTSB-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 150000003141 primary amines Chemical group 0.000 abstract description 6
- 150000003512 tertiary amines Chemical class 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000000306 component Substances 0.000 description 146
- 238000007599 discharging Methods 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 11
- 229940125773 compound 10 Drugs 0.000 description 7
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 7
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 7
- 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 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 3
- 150000003335 secondary amines Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010125 resin casting Methods 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
- C08G59/40—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
- C08G59/5006—Amines aliphatic
-
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a vacuum-introduced epoxy resin composition capable of remarkably improving the strength and heat resistance of epoxy resin and a preparation method thereof. The epoxy resin composition curing agent component at least comprises a compound with a molecular formula of R 1R2NR3NH2. The R 1R2NR3NH2 curing agent contains both tertiary amine and primary amine functional groups, wherein the tertiary amine can catalyze the epoxy resin to form anionic polymerization reaction. The primary amine can carry out ring-opening polymerization reaction with epoxy groups in the epoxy resin; the invention adopts the same amine curing agent to realize two curing mechanisms of catalysis and curing, and the obtained epoxy resin composition has the advantages of long operability time, quick curing, high mechanical strength and high heat resistance; the epoxy resin composition can be used for preparing large composite material parts and products through a vacuum introduction process, and has wide application prospects in the industrial fields of ships, wind driven generator blades and the like.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to a vacuum-introduced epoxy resin composition and a preparation method thereof.
Background
Under the aim of double carbon, wind power is greatly valued as renewable clean energy. The wind power blade is a core component of a wind generating set, and matrix resin is a key material of the wind power blade. The development and progress of matrix resin materials for wind power blades are research hotspots in the wind power field.
As early as the 80 s of the last century, significant changes were made to the material system when the prototype of the first megawatt wind turbine was taken off line, and manufacturers began replacing the polyester resin system with an epoxy resin system. The epoxy resin has higher strength and better fatigue resistance, so that the epoxy resin becomes a standard resin system of the wind power blade. The epoxy resin has the advantages of moderate viscosity, long pot life, low VOC content, low requirements on moisture and humidity in the environment, good mechanical property, fatigue resistance and the like, and is the main stream resin of the wind power blade for decades. At present, the epoxy resin for wind power generally adopts cycloaliphatic amine and polyether amine as curing agents. However, typical wind power epoxy resins also have some significant drawbacks. Such as slow curing speed, low mechanical strength, etc.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a vacuum-introduced epoxy resin composition comprising:
And (3) a component A: a liquid epoxy resin and a reactive epoxy diluent;
and the component B comprises the following components: a curing agent comprising a compound having the formula R 1R2NR3NH2.
The invention introduces R 1R2NR3NH2 curing agent. The R 1R2NR3NH2 curing agent contains both tertiary amine and primary amine functional groups, wherein the tertiary amine can catalyze the epoxy resin to form anionic polymerization reaction. The primary amine can carry out ring-opening polymerization reaction with epoxy groups in the epoxy resin; the invention adopts the same amine curing agent to realize two curing mechanisms of catalysis and curing, and the obtained epoxy resin composition has the advantages of long operability time, quick curing, high mechanical strength and high heat resistance.
Preferably, the curing agent further comprises: polyetheramines and cycloaliphatic amines;
the polyetheramine is selected from one or more of difunctional polyetheramine D230 or polyetheramine D400 and trifunctional polyetheramine T403; the alicyclic amine is selected from one or more of isophorone diamine, 1, 2-cyclohexanediamine, dimethylcyclohexanediamine and 4, 4-dimethyldicyclohexylmethane.
Preferably, the curing agent comprises the following components in percentage by weight:
50-80% of polyether amine, 10-30% of alicyclic amine and 10-40% of R 1R2NR3NH2.
Preferably, R 1 in R 1R2NR3NH2 is selected from methyl, ethyl, propyl or phenyl, and R 2 is selected from methyl, ethyl or propyl; r 3 is selected from methyl, ethyl, propyl, dimethyl secondary amine group, diethyl secondary amine group or dipropyl secondary amine group.
Preferably, the component A comprises the following components in percentage by weight:
78% -90% of liquid epoxy resin and 10% -22% of reactive diluent;
The liquid epoxy resin is one or two of bisphenol A epoxy resin and bisphenol F epoxy resin; the reactive diluent is at least one of neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, C12-C14 alkyl glycidyl ether, butyl glycidyl ether and octyl glycidyl ether.
Preferably, the weight ratio of the component A to the component B is 100: 15-40.
Preferably, the component A further comprises, in weight percent:
3 to 5 percent of compatilizer, 1 to 3 percent of dispersant and 2.5 to 3.5 percent of modified nano silicon dioxide;
wherein the compatilizer is sodium petroleum sulfonate or calcium petroleum sulfonate; the dispersing agent is polyvinyl alcohol or polyvinylpyrrolidone;
Preferably, the preparation method of the modified nano silicon dioxide comprises the following steps: adding nano silicon dioxide into a high-pressure reaction kettle, adding ammonia water solution at the same time, soaking the nano silicon dioxide in the ammonia water solution, treating for 30-60 min under the supercritical condition of ammonia water, cooling to room temperature, taking out, drying for 12h at 60-80 ℃ to obtain pretreated nano silicon dioxide, adding the pretreated nano silicon dioxide into absolute ethyl alcohol, carrying out ultrasonic treatment to obtain dispersion liquid, adding titanate coupling agent into the dispersion liquid, adding the mixed material into a microwave-ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves, and carrying out synergistic treatment for 12h at the treatment temperature of 65-85 ℃; and (3) after cooling, centrifugally separating, washing with ethanol and deionized water to be neutral, and drying to obtain the modified nano silicon dioxide.
Preferably, the concentration of the ammonia water solution is 25-35 wt%, and the supercritical condition of the ammonia water is 300-320 ℃ and the pressure is 10-15 MPa; the mass volume ratio of the pretreated nano silicon dioxide to the absolute ethyl alcohol is 1 g:20-25 mL; the mass ratio of the pretreated nano silicon dioxide to the titanate coupling agent is 1:0.8-1.2; the frequency of ultrasonic treatment is 35-65 KHz; the microwave power of the cooperative treatment is 300-500W, the ultrasonic power is 300-500W, and the ultrasonic frequency is 35-65 KHz; the titanate coupling agent is any one of n-butyl titanate, n-ethyl titanate and isopropyl triisostearate titanate.
The invention also provides a preparation method of the vacuum-introduced epoxy resin composition, which comprises the steps of mixing the component A and the component B to obtain the vacuum-introduced epoxy resin composition;
The preparation method of the component A comprises the following steps: stirring and mixing the liquid epoxy resin and the reactive diluent uniformly at 45-55 ℃ to obtain a component A;
Or the preparation method of the component A comprises the following steps: uniformly stirring and mixing liquid epoxy resin, an active diluent, a compatilizer, a dispersing agent and modified nano silicon dioxide at 45-55 ℃ to obtain a component A;
The preparation method of the component B comprises the following steps: and uniformly stirring and mixing polyether amine, alicyclic amine and a compound with a molecular formula of R 1R2NR3NH2 at room temperature to obtain a component B.
The invention at least comprises the following beneficial effects: the R 1R2NR3NH2 curing agent contains both tertiary amine and primary amine functional groups, wherein the tertiary amine can catalyze the epoxy resin to form anionic polymerization reaction. The primary amine can carry out ring-opening polymerization reaction with epoxy groups in the epoxy resin; the invention adopts the same amine curing agent to realize two curing mechanisms of catalysis and curing, and the obtained epoxy resin composition has the advantages of long operability time, quick curing and high mechanical strength; the epoxy resin composition can be used for preparing large composite material parts and products through a vacuum introduction process, and has wide application prospects in the industrial fields of ships, wind driven generator blades and the like.
The specific embodiment is as follows:
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
And (3) a component A: 84% liquid epoxy resin, 16% diluent.
And the component B comprises the following components: 60% polyetheramine, 20% cycloaliphatic amine, 20% r 1R2NR3 NH compound;
When in use, the weight ratio of the component A to the component B is 100:30, mixing in proportion;
The preparation method of the component A comprises the following steps: adding liquid epoxy resin and a diluent into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60 minutes after the temperature of the materials reaches 50 ℃, and discharging to obtain a component A;
The preparation method of the component B comprises the following steps: adding polyether amine, alicyclic amine and R 1R2NR3NH2 compound into a reaction kettle according to the weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
Preparing a combined material: the weight ratio of the component A to the component B is 100:30, uniformly mixing the materials to obtain the composite material;
wherein the liquid epoxy resin is liquid bisphenol A type epoxy resin with the epoxy equivalent of 180-184g/mol, and is purchased from Jiangsu Yang nong jin lake chemical industry Co., ltd, and the model is YN1827; the diluent is 1, 4-butanediol diglycidyl ether, the polyether amine is polyether amine D230, the alicyclic amine is isophorone diamine, and the R 1R2NR3NH2 compound is N, N-dimethyl-1, 3-propylene diamine.
Example 2:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
and (3) a component A: 78% of bisphenol A epoxy resin, 10% of bisphenol F epoxy resin and 12% of C12-C14 alkyl glycidyl ether;
And the component B comprises the following components: polyetheramine D230%, 1, 2-cyclohexanediamine 30%, R 1R2NR3NH2 compound 10%; the R 1R2NR3NH2 compound is 3-diethylaminopropylamine;
when in use, the weight ratio of the component A to the component B is 100:25 by mixing in proportion;
The preparation method of the component A comprises the following steps: adding bisphenol A epoxy resin, bisphenol F epoxy resin and C12-C14 alkyl glycidyl ether into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60min after the material temperature reaches 50 ℃, and discharging to obtain a component A;
the preparation method of the component B comprises the following steps: adding polyether amine D230,1, 2-cyclohexanediamine and R 1R2NR3NH2 compound into a reaction kettle according to the weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
preparing a combined material: the weight ratio of the component A to the component B is 100:25, and uniformly mixing the components.
Example 3:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
And (3) a component A: 86% of bisphenol A epoxy resin and 14% of octyl glycidyl ether;
And the component B comprises the following components: polyetheramine D230%, methylcyclohexamethylenediamine 25%, R 1R2NR3NH2% compound 10%. The R 1R2NR3NH2 compound is 3-diethylaminopropylamine;
when in use, the weight ratio of the component A to the component B is 100:25 by mixing in proportion;
The preparation method of the component A comprises the following steps: putting bisphenol A epoxy resin and octyl glycidyl ether into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60min after the material temperature reaches 50 ℃, and discharging to obtain a component A;
The preparation method of the component B comprises the following steps: adding polyetheramine D230, methylcyclohexamethylenediamine and a compound R 1R2NR3NH2 into a reaction kettle according to a weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
preparing a combined material: the weight ratio of the component A to the component B is 100:25, and uniformly mixing the components.
Example 4:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
And (3) a component A: 84% liquid epoxy resin, 16% diluent.
And the component B comprises the following components: 60% polyetheramine, 20% cycloaliphatic amine, 20% r 1R2NR3 NH compound;
when in use, the weight ratio of the component A to the component B is 100:40 by weight;
The preparation method of the component A comprises the following steps: adding liquid epoxy resin and a diluent into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60 minutes after the temperature of the materials reaches 50 ℃, and discharging to obtain a component A;
The preparation method of the component B comprises the following steps: adding polyether amine, alicyclic amine and R 1R2NR3NH2 compound into a reaction kettle according to the weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
preparing a combined material: the weight ratio of the component A to the component B is 100:40, and uniformly mixing the materials to obtain the product;
Wherein the liquid epoxy resin is liquid bisphenol A type epoxy resin with the epoxy equivalent of 180-184g/mol, and is purchased from Jiangsu Yang nong jin lake chemical industry Co., ltd, and the model is YN1827; the diluent is 1, 4-butanediol diglycidyl ether, the polyether amine is polyether amine D230, the alicyclic amine is isophorone diamine, and the R 1R2NR3NH2 compound is dimethyl dipropyl triamine.
Example 5:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
And (3) a component A: 80% of bisphenol A epoxy resin, 8% of bisphenol F epoxy resin and 12% of butyl glycidyl ether;
and the component B comprises the following components: polyetheramine D230.55%, 4-diaminodicyclohexylmethane 35%, R 1R2NR3NH2 compound 10%; the R 1R2NR3NH2 compound is 3-diethylaminopropylamine;
when in use, the weight ratio of the component A to the component B is 100:25 by mixing in proportion;
The preparation method of the component A comprises the following steps: adding bisphenol A epoxy resin, bisphenol F epoxy resin and C12-C14 alkyl glycidyl ether into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60min after the material temperature reaches 50 ℃, and discharging to obtain a component A;
the preparation method of the component B comprises the following steps: adding polyether amine D230,1, 2-cyclohexanediamine and R 1R2NR3NH2 compound into a reaction kettle according to the weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
preparing a combined material: the weight ratio of the component A to the component B is 100:25, and uniformly mixing the components.
Example 6:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
And (3) a component A: 75% of bisphenol A epoxy resin, 8.5% of bisphenol F epoxy resin, 10% of C12-C14 alkyl glycidyl ether, 3% of compatilizer, 1% of dispersant and 2.5% of modified nano silicon dioxide;
And the component B comprises the following components: polyetheramine D230%, 1, 2-cyclohexanediamine 30%, R 1R2NR3NH2 compound 10%; the R 1R2NR3NH2 compound is 3-diethylaminopropylamine;
wherein the compatilizer is petroleum sodium sulfonate; the dispersing agent is polyvinyl alcohol;
The preparation method of the modified nano silicon dioxide comprises the following steps: adding nano silicon dioxide into a high-pressure reaction kettle, adding ammonia water solution at the same time, soaking all nano silicon dioxide into the ammonia water solution, treating for 45min under the supercritical condition of ammonia water, cooling to room temperature, taking out, drying at 80 ℃ for 12h to obtain pretreated nano silicon dioxide, adding 100g of pretreated nano silicon dioxide into 2L of absolute ethyl alcohol, carrying out ultrasonic treatment to obtain a dispersion liquid, adding 100g of titanate coupling agent into the dispersion liquid, adding the mixed material into a microwave and ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves, and carrying out synergistic treatment for 12h at the treatment temperature of 85 ℃; after cooling, centrifugally separating, washing with ethanol and deionized water to be neutral, and drying to obtain modified nano silicon dioxide; the concentration of the ammonia water solution is 30wt%, and the supercritical condition of the ammonia water is that the temperature is 300 ℃ and the pressure is 15MPa; the frequency of ultrasonic treatment is 45KHz; the microwave power of the cooperative treatment is 500W, the ultrasonic power is 500W, and the ultrasonic frequency is 45KHz; the titanate coupling agent is n-butyl titanate.
When in use, the weight ratio of the component A to the component B is 100:25 by mixing in proportion;
The preparation method of the component A comprises the following steps: adding bisphenol A epoxy resin, bisphenol F epoxy resin, C12-C14 alkyl glycidyl ether, compatilizer, dispersant and modified nano silicon dioxide into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60min after the material temperature reaches 50 ℃, and discharging to obtain a component A;
the preparation method of the component B comprises the following steps: adding polyether amine D230,1, 2-cyclohexanediamine and R 1R2NR3NH2 compound into a reaction kettle according to the weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
preparing a combined material: the component A and the component B are mixed according to the weight ratio of 100:25, and uniformly mixing the components.
Example 7:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
And (3) a component A: bisphenol a epoxy resin 81%, octyl glycidyl ether 11%; 4% of compatilizer, 1% of dispersant and 3% of modified nano silicon dioxide;
And the component B comprises the following components: polyetheramine D230%, methylcyclohexamethylenediamine 25%, R 1R2NR3NH2% compound 10%. The R 1R2NR3NH2 compound is 3-diethylaminopropylamine;
wherein the compatilizer is petroleum sodium sulfonate; the dispersing agent is polyvinylpyrrolidone;
The preparation method of the modified nano silicon dioxide comprises the following steps: adding nano silicon dioxide into a high-pressure reaction kettle, adding ammonia water solution at the same time, soaking all nano silicon dioxide into the ammonia water solution, treating for 45min under the supercritical condition of ammonia water, cooling to room temperature, taking out, drying at 80 ℃ for 12h to obtain pretreated nano silicon dioxide, adding 100g of pretreated nano silicon dioxide into 2L of absolute ethyl alcohol, carrying out ultrasonic treatment to obtain a dispersion liquid, adding 100g of titanate coupling agent into the dispersion liquid, adding the mixed material into a microwave and ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves, and carrying out synergistic treatment for 12h at the treatment temperature of 85 ℃; after cooling, centrifugally separating, washing with ethanol and deionized water to be neutral, and drying to obtain modified nano silicon dioxide; the concentration of the ammonia water solution is 30wt%, and the supercritical condition of the ammonia water is that the temperature is 300 ℃ and the pressure is 15MPa; the frequency of ultrasonic treatment is 45KHz; the microwave power of the cooperative treatment is 500W, the ultrasonic power is 500W, and the ultrasonic frequency is 45KHz; the titanate coupling agent is n-butyl titanate.
The component A and the component B are mixed according to the weight ratio of 100:25 by mixing in proportion;
The preparation method of the component A comprises the following steps: adding bisphenol A epoxy resin, octyl glycidyl ether, a compatilizer, a dispersing agent and modified nano silicon dioxide into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60 minutes after the material temperature reaches 50 ℃, and discharging to obtain a component A;
The preparation method of the component B comprises the following steps: adding polyetheramine D230, methylcyclohexamethylenediamine and a compound R 1R2NR3NH2 into a reaction kettle according to a weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
preparing a combined material: the component A and the component B are mixed according to the weight ratio of 100:25, and uniformly mixing the components.
Comparative example 1:
DQ200E/204H of Sichuan Dong New Material Co., ltd. Is vacuum-introduced into an epoxy resin system, and DQ200E/DQ204H of Dong New Material Co., ltd. Is vacuum-poured into the epoxy resin system, wherein DQ200E is epoxy resin, DQ204H is an amine curing agent, and the epoxy resin system can be commercially available.
Comparative example 2:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
And (3) a component A: 84% liquid epoxy resin, 16% diluent.
And the component B comprises the following components: 70% polyetheramine, 30% cycloaliphatic amine;
When in use, the weight ratio of the component A to the component B is 100:30, mixing in proportion;
The preparation method of the component A comprises the following steps: adding liquid epoxy resin and a diluent into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60 minutes after the temperature of the materials reaches 50 ℃, and discharging to obtain a component A;
The preparation method of the component B comprises the following steps: adding polyether amine and alicyclic amine into a reaction kettle according to the weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
Preparing a combined material: the weight ratio of the component A to the component B is 100:30, uniformly mixing the materials to obtain the composite material;
Wherein the liquid epoxy resin is liquid bisphenol A type epoxy resin with the epoxy equivalent of 180-184g/mol, and is purchased from Jiangsu Yang nong jin lake chemical industry Co., ltd, and the model is YN1827; the diluent is 1, 4-butanediol diglycidyl ether, the polyether amine is polyether amine D230, and the alicyclic amine is isophorone diamine.
Comparative example 3:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
and (3) a component A: 78% of bisphenol A epoxy resin, 10% of bisphenol F epoxy resin and 12% of C12-C14 alkyl glycidyl ether;
and the component B comprises the following components: polyetheramine D230%, 1, 2-cyclohexanediamine 35%;
when in use, the weight ratio of the component A to the component B is 100:25 by mixing in proportion;
The preparation method of the component A comprises the following steps: adding bisphenol A epoxy resin, bisphenol F epoxy resin and C12-C14 alkyl glycidyl ether into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60min after the material temperature reaches 50 ℃, and discharging to obtain a component A;
the preparation method of the component B comprises the following steps: adding polyether amine D230,1, 2-cyclohexanediamine and R 1R2NR3NH2 compound into a reaction kettle according to the weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
preparing a combined material: the weight ratio of the component A to the component B is 100:25, and uniformly mixing the components.
Comparative example 4:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
And (3) a component A: 75% of bisphenol A epoxy resin, 8.5% of bisphenol F epoxy resin, 10% of C12-C14 alkyl glycidyl ether, 3% of compatilizer, 1% of dispersant and 2.5% of nano silicon dioxide;
And the component B comprises the following components: polyetheramine D230%, 1, 2-cyclohexanediamine 30%, R 1R2NR3NH2 compound 10%; the R 1R2NR3NH2 compound is 3-diethylaminopropylamine;
wherein the compatilizer is petroleum sodium sulfonate; the dispersing agent is polyvinyl alcohol;
when in use, the weight ratio of the component A to the component B is 100:25 by mixing in proportion;
the preparation method of the component A comprises the following steps: adding bisphenol A epoxy resin, bisphenol F epoxy resin, C12-C14 alkyl glycidyl ether, a compatilizer, a dispersing agent and nano silicon dioxide into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60min after the material temperature reaches 50 ℃, and discharging to obtain a component A;
the preparation method of the component B comprises the following steps: adding polyether amine D230,1, 2-cyclohexanediamine and R 1R2NR3NH2 compound into a reaction kettle according to the weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
preparing a combined material: the component A and the component B are mixed according to the weight ratio of 100:25, and uniformly mixing the components.
Comparative example 5:
A vacuum-introduced epoxy resin composition comprising:
The weight percentages are as follows:
And (3) a component A: bisphenol a epoxy resin 81%, octyl glycidyl ether 11%; 4% of compatilizer, 1% of dispersant and 3% of nano silicon dioxide;
And the component B comprises the following components: polyetheramine D230%, methylcyclohexamethylenediamine 25%, R 1R2NR3NH2% compound 10%. The R 1R2NR3NH2 compound is 3-diethylaminopropylamine;
wherein the compatilizer is petroleum sodium sulfonate; the dispersing agent is polyvinylpyrrolidone;
the component A and the component B are mixed according to the weight ratio of 100:25 by mixing in proportion;
The preparation method of the component A comprises the following steps: adding bisphenol A epoxy resin, octyl glycidyl ether, a compatilizer, a dispersing agent and modified nano silicon dioxide into a reaction kettle according to the weight ratio, starting a heating device, continuously stirring for 60 minutes after the material temperature reaches 50 ℃, and discharging to obtain a component A;
The preparation method of the component B comprises the following steps: adding polyetheramine D230, methylcyclohexamethylenediamine and a compound R 1R2NR3NH2 into a reaction kettle according to a weight ratio, continuously stirring for 40min, and discharging to obtain a component B;
preparing a combined material: the component A and the component B are mixed according to the weight ratio of 100:25, and uniformly mixing the components.
The properties of the epoxy resin compositions prepared in the examples were measured, and the results are shown in Table 1. The testing method comprises the following steps:
the mixing viscosity was tested according to GB/T22314-2008 standard.
Gel time was measured according to ASTM D2471.
The glass transition temperature is measured according to GB/T19466.2-2004 standard.
The method for testing the curing time at 70 ℃ comprises the following steps: the epoxy resin composition was cured at 70 ℃ for a period of time to test the glass transition temperature of the epoxy resin casting, and when the glass transition temperature reached 65 ℃, the time required for the resin to cure was recorded.
The tensile properties of the body were tested according to GB/T2567-2008 standard. Curing conditions: the epoxy resin composition was kept at 25℃for 24 hours and at 70℃for 8 hours.
TABLE 1
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown, it is well suited to various fields of use for which the invention is suited, and further modifications may be readily made by one skilled in the art, and the invention is therefore not to be limited to the particular details and examples shown and described herein, without departing from the general concepts defined by the claims and the equivalents thereof.
Claims (5)
1. A vacuum-introduced epoxy resin composition, comprising the following components:
and (3) a component A: the weight percentage comprises: 78-90% of liquid epoxy resin, 10-22% of reactive diluent, 3-5% of compatilizer, 1-3% of dispersing agent and 2.5-3.5% of modified nano silicon dioxide; the sum of the components is 100 percent;
And the component B comprises the following components: the weight percentage comprises:
50% -80% of polyetheramine, 10% -30% of alicyclic amine and 10% -40% of compound with a molecular formula of R 1R2NR3NH2; the sum of the components is 100 percent;
The liquid epoxy resin is one or two of bisphenol A epoxy resin and bisphenol F epoxy resin; the reactive diluent is at least one of neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, C12-C14 alkyl glycidyl ether, butyl glycidyl ether and octyl glycidyl ether; the compatilizer is sodium petroleum sulfonate or calcium petroleum sulfonate; the dispersing agent is polyvinyl alcohol or polyvinylpyrrolidone;
R 1 in R 1R2NR3NH2 is selected from methyl, ethyl and propyl, and R 2 is selected from methyl, ethyl or propyl; r 3 is selected from methylene, ethylene, propylene, dimethyl secondary amine, diethyl secondary amine or dipropyl secondary amine;
The preparation method of the modified nano silicon dioxide comprises the following steps: adding nano silicon dioxide into a high-pressure reaction kettle, adding ammonia water solution at the same time, soaking the nano silicon dioxide in the ammonia water solution, treating for 30-60 min under the supercritical condition of ammonia water, cooling to room temperature, taking out, drying for 12h at 60-80 ℃ to obtain pretreated nano silicon dioxide, adding the pretreated nano silicon dioxide into absolute ethyl alcohol, carrying out ultrasonic treatment to obtain dispersion liquid, adding titanate coupling agent into the dispersion liquid, adding the mixed material into a microwave-ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves, and carrying out synergistic treatment for 12h at the treatment temperature of 65-85 ℃; and (3) after cooling, centrifugally separating, washing with ethanol and deionized water to be neutral, and drying to obtain the modified nano silicon dioxide.
2. The vacuum-introduced epoxy resin composition according to claim 1, wherein,
The polyetheramine is selected from one or more of difunctional polyetheramine D230 or polyetheramine D400 and trifunctional polyetheramine T403; the alicyclic amine is selected from one or more of isophorone diamine, 1, 2-cyclohexanediamine, dimethylcyclohexanediamine and 4, 4-dimethyldicyclohexylmethane.
3. The vacuum-introduced epoxy resin composition according to claim 1, wherein,
The weight ratio of the component A to the component B is 100: 15-40.
4. The vacuum-introduced epoxy resin composition according to claim 1, wherein the concentration of the aqueous ammonia solution is 25 to 35wt%, and the supercritical condition of aqueous ammonia is 300 to 320 ℃ and the pressure is 10 to 15mpa; the mass volume ratio of the pretreated nano silicon dioxide to the absolute ethyl alcohol is 1 g:20-25 mL; the mass ratio of the pretreated nano silicon dioxide to the titanate coupling agent is 1:0.8-1.2; the frequency of ultrasonic treatment is 35-65 KHz; the microwave power of the cooperative treatment is 300-500W, the ultrasonic power is 300-500W, and the ultrasonic frequency is 35-65 KHz; the titanate coupling agent is any one of n-butyl titanate, n-ethyl titanate and isopropyl triisostearate titanate.
5. A method of producing a vacuum-introduced epoxy resin composition according to any one of claims 1 to 4, wherein the vacuum-introduced epoxy resin composition is obtained by mixing the component a and the component B;
The preparation method of the component A comprises the following steps: uniformly stirring and mixing liquid epoxy resin, an active diluent, a compatilizer, a dispersing agent and modified nano silicon dioxide at 45-55 ℃ to obtain a component A;
The preparation method of the component B comprises the following steps: and uniformly stirring and mixing polyether amine, alicyclic amine and a compound with a molecular formula of R 1R2NR3NH2 at room temperature to obtain a component B.
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| CN101735564A (en) * | 2009-12-22 | 2010-06-16 | 上海康达化工有限公司 | Vacuum infusion resin for wind turbine blades and preparation method thereof |
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