CN105040444A - Novel nano water-borne epoxy resin sizing agent for carbon fibers and preparation method thereof - Google Patents
Novel nano water-borne epoxy resin sizing agent for carbon fibers and preparation method thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 150
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 150
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 63
- 238000004513 sizing Methods 0.000 title claims abstract description 57
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 50
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229960000583 acetic acid Drugs 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 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 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 47
- 239000005543 nano-size silicon particle Substances 0.000 claims description 41
- 235000012239 silicon dioxide Nutrition 0.000 claims description 26
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 15
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 2
- 238000000034 method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 241001502050 Acis Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 239000000839 emulsion Substances 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
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- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- -1 titanate ester Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention provides a novel nano water-borne epoxy resin sizing agent for carbon fibers and a preparation method thereof. The particular preparation method comprises the steps that epoxy resin is dissolved in an ethanol solvent, heating and stirring are conducted till the epoxy resin is fully dissolved, a diglycolamine solution is slowly and dropwise added, and modified epoxy resin is obtained after fast stirring is conducted; ethanol in the modified epoxy resin is removed, glacial acetic acid is dropwise added, homothermal stirring is conducted, and water-borne epoxy resin is obtained; distilled water is slowly added in the water-borne epoxy resin for dilution, heating is conducted till the temperature ranges from 90 DEG C to 100 DEG C to activate the water-borne epoxy resin, nano silica sol is added, heating is conducted till the temperature ranges from 150 DEG C to 160 DEG C for stirring reaction, and the water-borne epoxy resin modified through the nano silica sol is obtained; finally, an aromatic amine curing agent, an aromatic amine antioxidant and organic solvent are added, and the nano water-borne epoxy resin sizing agent for the carbon fibers is obtained after even stirring is conducted. The preparation technology of the the nano water-borne epoxy resin sizing agent prepared through the preparation method is simple, the sizing agent is excellent in sizing performance and stable in performance, and the toughness is strengthened.
Description
Technical field:
The invention belongs to textile material technical field, be specifically related to a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber and preparation method thereof.
Background technology:
Containing two or more epoxide group in each molecule of epoxy resin, epoxide group is the cell rings formed by an oxygen atom and two carbon atoms, there is the activity of height, can with the material of various active hydrogen, as chemical crosslink reaction occurs for amine, acid amides, phenol etc.Epoxy resin is the important thermosetting resin of a class, there is excellent adhesive property and antiseptic property, again by the cooperation of promoter, modifier, additive etc., thus obtain epoxy curing systems and the solidfied material of various performance and characteristic, almost can adapt to and meet the requirement of various different field serviceability and processing performance, have wide range of applications.
At field of textiles, epoxy resin is widely used in preparing carbon fiber-reinforced resin composite materials.Carbon fibre composite has a series of good characteristics such as quality is light, intensity is high, modulus is high, but the little and aobvious fragility of the carbon fiber elongation strain ability after surface treatment, in process, easily cause the phenomenons such as carbon fiber fluffing, single wire fracture, cause the intensity of carbon fiber to reduce.Therefore starching process must be carried out to carbon fiber, the impact preventing the existence of lousiness and working environment is produced.
The preparation method of the disclosed a kind of water-base epoxy resin sizing agent for carbon fiber of Chinese patent CN101736593B (publication date 2010.6.16), the aqueous epoxy resin emulsion of dilution is mixed with water-soluble epoxy resin curing agent, add auxiliary agent again and obtain water-base epoxy resin sizing agent for carbon fiber, the performance of this sizing agent is good, good to the humidification of carbon fiber, there is good convergence, smoothness, pliability, and cost is low compared with external emulsion-type sizing agent, and better than domestic emulsion-type sizing agent performance.
But epoxy resin is as the higher thermosets of crosslink density, its Crack Extension belongs to the expansion of typical fragility, exist wilful not enough after solidification, the shortcomings such as the poor and easy cracking of resistance to impact, particularly the fragility of low-molecular-weight epoxy resin, impact resistance are very poor, limit the application of epoxy resin at some high-technology field.
Nano silicon is unformed white powder, it is a kind of nontoxic, tasteless, free of contamination nonmetal functional material, nano silicon has larger specific area, there are blemish, non-matching atom and hydroxyl etc., can with polymer generation physics or chemically combined possibility larger, so can be used for strengthening the interface cohesion of polymeric matrix, improve the bearing capacity of polymer, thus reach the object of activeness and quietness polymer.
The in-situ polymerization method for preparing of the disclosed nylon 6/ epoxy resin/silicon dioxide nano composite material of Chinese patent CN100348665C (publication date 2006.10.11), by epoxy resin and esters of silicon acis under titanate ester catalyst action, make the hydroxyl reaction of esters of silicon acis and epoxy resin, then add aqueous solvent solution and obtain nylon 6/ epoxy resin/silicon dioxide nano composite material, the surface grafting nano silicon dioxide sol of this epoxy resin, play the interface interaction of two-phase, thus improve the shock resistance of nylon composite materials.
Summary of the invention:
The technical problem to be solved in the present invention is to provide a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber and preparation method thereof, the epoxy resin of washing modification is combined with nano silicon dioxide sol, and add aromatic amine curing agent, antioxidant and organic solvent, obtain the nanometer waterborne epoxy resin sizing agent for carbon fiber.The preparation technology of rice aqueous epoxy resins sizing agent prepared by the method is simple, and the sizing performance of sizing agent is excellent, stable performance, and toughness strengthens, and is particularly suitable for the sizing technique of carbon fiber.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of novel nano aqueous epoxy resins sizing agent for carbon fiber, it is characterized in that, the component of the described nanometer waterborne epoxy resin sizing agent for carbon fiber by weight, comprising: aqueous epoxy resins 20-40 part, nano silicon dioxide sol 1-8 part, aromatic amine curing agent 3-8 part, aromatic amine antioxidant 0.5-3 part and organic solvent 0-30 part.
Preferably, the component of the described nanometer waterborne epoxy resin sizing agent for carbon fiber by weight, comprising: aqueous epoxy resins 25-35 part, nano silicon dioxide sol 3-7 part, aromatic amine curing agent 4-7 part, aromatic amine antioxidant 0.5-2 part and organic solvent 0-30 part.
The present invention also provides a kind of preparation method of the nanometer waterborne epoxy resin sizing agent for carbon fiber, it is characterized in that: comprise the following steps:
(1) by weight, the epoxy resin of 1 part is dissolved in the alcohol solvent of 5-8 part, heating is stirred to epoxy resin and dissolves completely, then with 3-5 drip/speed of min slowly drips the diglycolamine solution of 0.5-0.9 part, rapid stirring obtains the epoxy resin of modification;
(2) by weight, ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, with 10-15 drip/min drips the glacial acetic acid of 0.3-0.7 part, constant temperature stirs, and obtains aqueous epoxy resins;
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 10-13 part, regulates PH to alkalescent, add thermal agitation, the ethanol water of slow dropping 8-10 part, constant temperature stirring reaction, naturally cools to room temperature and obtains nano silicon dioxide sol;
(4) slowly distilled water diluting is added in aqueous epoxy resins step (2) prepared, being heated to 90-100 DEG C makes aqueous epoxy resins activate, then nano silicon dioxide sol prepared by step (3) is added, be heated to 150-160 DEG C of stirring reaction, obtain nano-silicon dioxide modified aqueous epoxy resins;
(5) add aromatic amine curing agent, aromatic amine antioxidant and organic solvent in nano-silicon dioxide modified aqueous epoxy resins step (4) prepared, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
Preferred as technique scheme, in described step (1), epoxy resin is bisphenol A type epoxy resin.
Preferred as technique scheme, in described step (1), the temperature adding thermal agitation is 60-70 DEG C.
Preferred as technique scheme, in described step (2), the temperature that constant temperature stirs is 25-30 DEG C, and the time is 2-3h.
Preferred as technique scheme, in described step (3), weakly alkaline pH value is 8-9.
Preferred as technique scheme, in described step (3), in nano silicon dioxide sol, the particle diameter of nano silicon is 50-100nm.
Preferred as technique scheme, in described step (4), the content being diluted to aqueous epoxy resins is 5-8%.
Preferred as technique scheme, in described step (5), organic solvent is one or more in deionized water, isopropyl alcohol, ethyl acetate.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention prepare in the nanometer waterborne epoxy resin sizing agent of carbon fiber containing the epoxy resin of watersoluble modified process, by in glacial acetic acid and modified epoxy and salify, preparation method is easy, obtained aqueous epoxy resins aqueous temperature, preparation technology after being conducive to, combines with nano silicon.
(2) the present invention prepare in the nanometer waterborne epoxy resin sizing agent of carbon fiber containing by nano silicon, nano silicon can with aqueous epoxy resins generation physics or chemical bond, strengthen the interface cohesion of aqueous epoxy resins matrix and carbon fiber, improve the bearing capacity of aqueous epoxy resins sizing agent, thus reach the object of activeness and quietness carbon fiber.
(3) preparation technology of the nanometer waterborne epoxy resin sizing agent for carbon fiber for preparing of the present invention is simple, stable system, and storage characteristics is good, the sizing performance of the sizing agent of preparation is excellent, stable performance, toughness strengthens, and is particularly suitable for the sizing technique of carbon fiber.
Detailed description of the invention:
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1:
(1) by weight, the bisphenol A type epoxy resin of 1 part is dissolved in the alcohol solvent of 5 parts, be stirred to epoxy resin 60 DEG C of heating to dissolve completely, then slowly drip the diglycolamine solution of 0.5 part with the speed of 3/min, rapid stirring obtains the epoxy resin of modification.
(2) by weight, the ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, and drips the glacial acetic acid of 0.3 part with 10/min, and at 25 DEG C, constant temperature stirs 2h, obtains aqueous epoxy resins.
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 10-part, regulates PH to 8 alkalescent, add thermal agitation, the ethanol water of slow dropping 8 parts, constant temperature stirring reaction, naturally cools to the nano silicon dioxide sol that room temperature obtains 50nm.
(4) by weight, the aqueous epoxy resins solution of distilled water diluting to 5% is slowly added in the aqueous epoxy resins that the steps of 20 parts (2) are prepared, being heated to 90 DEG C makes aqueous epoxy resins activate, then the nano silicon dioxide sol of prepared by step (3) 1 part is added, be heated to 150 DEG C of stirring reactions, obtain nano-silicon dioxide modified aqueous epoxy resins, finally add the aromatic amine curing agent of 3 parts, the aromatic amine antioxidant of 0.5 part, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
Embodiment 2:
(1) by weight, the bisphenol A type epoxy resin of 1 part is dissolved in the alcohol solvent of 8 parts, be stirred to epoxy resin 70 DEG C of heating to dissolve completely, then slowly drip the diglycolamine solution of 0.9 part with the speed of 5/min, rapid stirring obtains the epoxy resin of modification.
(2) by weight, the ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, and drips the glacial acetic acid of 0.7 part with 15/min, and at 30 DEG C, constant temperature stirs 3h, obtains aqueous epoxy resins.
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 13 parts, regulates PH to 9 alkalescent, add thermal agitation, the ethanol water of slow dropping 10 parts, constant temperature stirring reaction, naturally cools to the nano silicon dioxide sol that room temperature obtains 100nm.
(4) by weight, the aqueous epoxy resins solution of distilled water diluting to 8% is slowly added in the aqueous epoxy resins that the steps of 40 parts (2) are prepared, being heated to 100 DEG C makes aqueous epoxy resins activate, then the nano silicon dioxide sol of prepared by step (3) 8 parts is added, be heated to 160 DEG C of stirring reactions, obtain nano-silicon dioxide modified aqueous epoxy resins, finally add the aromatic amine curing agent of 8 parts, the isopropyl alcohol of the aromatic amine antioxidant of 3 parts and 30 parts, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
Embodiment 3:
(1) by weight, the bisphenol A type epoxy resin of 1 part is dissolved in the alcohol solvent of 7 parts, be stirred to epoxy resin 65 DEG C of heating to dissolve completely, then slowly drip the diglycolamine solution of 0.7 part with the speed of 4/min, rapid stirring obtains the epoxy resin of modification.
(2) by weight, the ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, and drips the glacial acetic acid of 0.5 part with 13/min, and at 27 DEG C, constant temperature stirs 2.5h, obtains aqueous epoxy resins.
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 12 parts, regulates PH to 8.5 alkalescent, add thermal agitation, the ethanol water of slow dropping 9 parts, constant temperature stirring reaction, naturally cools to the nano silicon dioxide sol that room temperature obtains 80nm.
(4) by weight, the aqueous epoxy resins solution of distilled water diluting to 6% is slowly added in the aqueous epoxy resins that the steps of 30 parts (2) are prepared, being heated to 95 DEG C makes aqueous epoxy resins activate, then the nano silicon dioxide sol of prepared by step (3) 5 parts is added, be heated to 155 DEG C of stirring reactions, obtain nano-silicon dioxide modified aqueous epoxy resins, finally add the aromatic amine curing agent of 5 parts, the deionized water of the aromatic amine antioxidant of 2 parts and 10 parts, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
Embodiment 4:
(1) by weight, the bisphenol A type epoxy resin of 1 part is dissolved in the alcohol solvent of 6 parts, be stirred to epoxy resin 60 DEG C of heating to dissolve completely, then slowly drip the diglycolamine solution of 0.9 part with the speed of 3/min, rapid stirring obtains the epoxy resin of modification.
(2) by weight, the ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, and drips the glacial acetic acid of 0.3 part with 14/min, and at 25 DEG C, constant temperature stirs 3h, obtains aqueous epoxy resins.
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 113 parts, regulates PH to 8.2 alkalescent, add thermal agitation, the ethanol water of slow dropping 8.5 parts, constant temperature stirring reaction, naturally cools to the nano silicon dioxide sol that room temperature obtains 65nm.
(4) by weight, the aqueous epoxy resins solution of distilled water diluting to 7% is slowly added in the aqueous epoxy resins that the steps of 35 parts (2) are prepared, being heated to 92 DEG C makes aqueous epoxy resins activate, then the nano silicon dioxide sol of prepared by step (3) 3 parts is added, be heated to 155 DEG C of stirring reactions, obtain nano-silicon dioxide modified aqueous epoxy resins, finally add the aromatic amine curing agent of 58 parts, the deionized water of the aromatic amine antioxidant of 2 parts and 15 parts and isopropyl alcohol, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
Embodiment 5:
(1) by weight, the bisphenol A type epoxy resin of 1 part is dissolved in the alcohol solvent of 7 parts, be stirred to epoxy resin 70 DEG C of heating to dissolve completely, then slowly drip the diglycolamine solution of 0.5 part with the speed of 5/min, rapid stirring obtains the epoxy resin of modification.
(2) by weight, the ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, and drips the glacial acetic acid of 0.7 part with 10/min, and at 30 DEG C, constant temperature stirs 2h, obtains aqueous epoxy resins.
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 13 parts, regulates PH to 9 alkalescent, add thermal agitation, the ethanol water of slow dropping 9 parts, constant temperature stirring reaction, naturally cools to the nano silicon dioxide sol that room temperature obtains 85nm.
(4) by weight, the aqueous epoxy resins solution of distilled water diluting to 6.2% is slowly added in the aqueous epoxy resins that the steps of 30 parts (2) are prepared, being heated to 90 DEG C makes aqueous epoxy resins activate, then the nano silicon dioxide sol of prepared by step (3) 2 parts is added, be heated to 160 DEG C of stirring reactions, obtain nano-silicon dioxide modified aqueous epoxy resins, finally add the aromatic amine curing agent of 6 parts, the ethyl acetate of the aromatic amine antioxidant of 3 parts and 12 parts, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
Embodiment 6:
(1) by weight, the bisphenol A type epoxy resin of 1 part is dissolved in the alcohol solvent of 8 parts, be stirred to epoxy resin 60 DEG C of heating to dissolve completely, then slowly drip the diglycolamine solution of 0.9 part with the speed of 4/min, rapid stirring obtains the epoxy resin of modification.
(2) by weight, the ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, and drips the glacial acetic acid of 0.7 part with 15/min, and at 25 DEG C, constant temperature stirs 2h, obtains aqueous epoxy resins.
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 10 parts, regulates PH to 8 alkalescent, add thermal agitation, the ethanol water of slow dropping 10 parts, constant temperature stirring reaction, naturally cools to the nano silicon dioxide sol that room temperature obtains 80nm.
(4) by weight, the aqueous epoxy resins solution of distilled water diluting to 6% is slowly added in the aqueous epoxy resins that the steps of 40 parts (2) are prepared, being heated to 95 DEG C makes aqueous epoxy resins activate, then the nano silicon dioxide sol of prepared by step (3) 6 parts is added, be heated to 150 DEG C of stirring reactions, obtain nano-silicon dioxide modified aqueous epoxy resins, finally add the aromatic amine curing agent of 8 parts, the ethyl acetate of the aromatic amine antioxidant of 2 parts and 20 parts, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
After testing, the rate of sizing result of the rate of sizing of the nanometer waterborne epoxy resin sizing agent for carbon fiber prepared of embodiment 1-6 and common epoxy resin is as follows:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example |
| The rate of sizing (%) | 5.4 | 7.1 | 6.5 | 7.0 | 5.9 | 6.7 | 3.1 |
After testing, the mechanical performance for carbon fiber after the nanometer waterborne epoxy resin sizing agent starching of carbon fiber prepared of embodiment 1-6 and unsized result as follows:
As seen from the above table, the rate of sizing of the nanometer waterborne epoxy resin sizing agent for carbon fiber prepared by the present invention is high, and can significantly improve the toughness of carbon fiber, improves mechanical strength.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. the novel nano aqueous epoxy resins sizing agent for carbon fiber, it is characterized in that, the component of the described nanometer waterborne epoxy resin sizing agent for carbon fiber by weight, comprising: aqueous epoxy resins 20-40 part, nano silicon dioxide sol 1-8 part, aromatic amine curing agent 3-8 part, aromatic amine antioxidant 0.5-3 part and organic solvent 0-30 part.
2. a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber according to claim 1, it is characterized in that, the component of the described nanometer waterborne epoxy resin sizing agent for carbon fiber by weight, comprising: aqueous epoxy resins 25-35 part, nano silicon dioxide sol 3-7 part, aromatic amine curing agent 4-7 part, aromatic amine antioxidant 0.5-2 part and organic solvent 0-30 part.
3., for a preparation method for the novel nano aqueous epoxy resins sizing agent of carbon fiber, it is characterized in that: comprise the following steps:
(1) by weight, the epoxy resin of 1 part is dissolved in the alcohol solvent of 5-8 part, heating is stirred to epoxy resin and dissolves completely, then with 3-5 drip/speed of min slowly drips the diglycolamine solution of 0.5-0.9 part, rapid stirring obtains the epoxy resin of modification;
(2) by weight, ethanol in the epoxy resin of the modification step of 1 part (1) prepared is removed, with 10-15 drip/min drips the glacial acetic acid of 0.3-0.7 part, constant temperature stirs, and obtains aqueous epoxy resins;
(3) by volume part meter, after being stirred by the ethanol of the ethyl orthosilicate of 1 part and 10-13 part, regulates PH to alkalescent, add thermal agitation, the ethanol water of slow dropping 8-10 part, constant temperature stirring reaction, naturally cools to room temperature and obtains nano silicon dioxide sol;
(4) slowly distilled water diluting is added in aqueous epoxy resins step (2) prepared, being heated to 90-100 DEG C makes aqueous epoxy resins activate, then nano silicon dioxide sol prepared by step (3) is added, be heated to 150-160 DEG C of stirring reaction, obtain nano-silicon dioxide modified aqueous epoxy resins;
(5) add aromatic amine curing agent, aromatic amine antioxidant and organic solvent in nano-silicon dioxide modified aqueous epoxy resins step (4) prepared, stir the nanometer waterborne epoxy resin sizing agent obtained for carbon fiber.
4. the preparation method of a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber according to claim 3, it is characterized in that: in described step (1), epoxy resin is bisphenol A type epoxy resin.
5. the preparation method of a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber according to claim 3, it is characterized in that: in described step (1), the temperature adding thermal agitation is 60-70 DEG C.
6. the preparation method of a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber according to claim 3, is characterized in that: in described step (2), and the temperature that constant temperature stirs is 25-30 DEG C, and the time is 2-3h.
7. the preparation method of a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber according to claim 3, it is characterized in that: in described step (3), weakly alkaline pH value is 8-9.
8. the preparation method of a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber according to claim 3, it is characterized in that: in described step (3), in nano silicon dioxide sol, the particle diameter of nano silicon is 50-100nm.
9. the preparation method of a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber according to claim 3, it is characterized in that: in described step (4), the content being diluted to aqueous epoxy resins is 5-8%.
10. the preparation method of a kind of novel nano aqueous epoxy resins sizing agent for carbon fiber according to claim 3, it is characterized in that: in described step (5), organic solvent is one or more in deionized water, isopropyl alcohol, ethyl acetate.
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