CN101817970B - Hydroxychloroethylene-vinyl acetate modified epoxy resin compound and preparation method thereof - Google Patents
Hydroxychloroethylene-vinyl acetate modified epoxy resin compound and preparation method thereof Download PDFInfo
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- CN101817970B CN101817970B CN201010148688XA CN201010148688A CN101817970B CN 101817970 B CN101817970 B CN 101817970B CN 201010148688X A CN201010148688X A CN 201010148688XA CN 201010148688 A CN201010148688 A CN 201010148688A CN 101817970 B CN101817970 B CN 101817970B
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Abstract
The invention discloses a hydroxychloroethylene-vinyl acetate modified epoxy resin compound and a preparation method thereof. Hydroxychloroethylene-vinyl acetate, bisphenol A liquid epoxy resin, boron trifluoride ether complexing compound, acetone and the like are used as raw materials. In an acetone solvent, under the action of a boron trifluoride ether complexing compound catalyst, an epoxy group in the bisphenol A liquid epoxy resin and a hydroxyl group in the hydroxychloroethylene-vinyl acetate undergo a grafting reaction to form a hydroxychloroethylene-vinyl acetate modified bisphenol A epoxy resin compound. The compound has the characteristics of adhesion of adhesive using the epoxy resin, hardness, rigidity, chemical resistance, corrosion resistance, quick dryness and the like; andmeanwhile, the epoxy resin has the characteristics of high toughness, combustion-supporting resistance, improved impact resistance, improved crispness and reduced cracking phenomenon. The compound can be widely applied to protective coating and anticorrosive coating for paper, metal, building material and the like.
Description
Technical field
The present invention relates to a kind of Hydroxychloroethylen--vinyl acetate modified epoxy resin compound and preparation method thereof, this mixture consists of the mixture of a kind of hydroxy chloride ethylene-vinyl acetate grafting bisphenol A type epoxy resin graft copolymer and bisphenol A type epoxy resin homopolymer.
Background technology
Crisp at epoxy resin cured product matter, shock strength is low, is easy to generate stress cracking, thereby influence insulation pouring Products Quality shortcoming, people are devoted to increase the tough Journal of Sex Research of Resins, epoxy always.Initial people adopt and add methods such as some softening agent, flexibilizing agent in Resins, epoxy, but add thermotolerance, hardness, modulus and the electrical property that these low molecular weight substances can reduce material greatly.Also there is in Resins, epoxy the rubber of adding powder that Resins, epoxy is carried out modification, Huang Fan, Qiao Jinliang etc. disclose " a kind of epoxy resin toughened composition and method of making the same " (CN1536021) and " a kind of composition epoxy resin and preparation method thereof " (CN1536020), with inorganic particulate, rubber particles modified epoxy, make Resins, epoxy significantly improve toughness.It is filling-modified that this kind method of modifying belongs to physics, and no chemical bond exists between weighting material and Resins, epoxy macromole, and loading level hour modifying function is not obvious, and the epoxy resin cured product mechanical property is reduced.Carried out again subsequently with the epoxy resin toughened research work of reactive liquefied compound, in the hope of improving the toughness of Resins, epoxy under descending little situation at thermal characteristics, modulus and electrical property.Zhang Bin, Liu Weiqu disclose " a kind of method of modifying epoxy resin by organosilicon " (CN1328071), adopt the first dispersion and emulsion of organosilicon and Resins, epoxy to mix, and then the method for reacting under hot conditions, the modified epoxy material; Liu Xiaoya, Liu Jingcheng etc. disclose " a kind of preparation method of reactive fluid rubber-epoxide resin polymer " (CN101591422), in 100-200 part Resins, epoxy, the reactive fluid rubber that contains carboxyl or hydroxyl that adds 5-50 part is made properties-correcting agent, has prepared a kind of reactive fluid rubber-epoxide resin polymer of tenacity excellent; Clean China discloses " a kind of modified epoxide resin adhesive and preparation method thereof " (CN1670109), with polyurethane prepolymer Resins, epoxy is carried out modification and handles, and epoxy resin cured product shock strength after the modification and toughness have had and significantly improves.But the reactive liquefied compound that adds in Resins, epoxy is the elastomerics prepolymer, and it is good to increase the consumption toughening effect, but can reduce the rigidity and the hardness of epoxy resin cured product.
Hydroxy chloride ethylene-vinyl acetate polymkeric substance is a kind of industrialized commodity, because the self-plasticizing action of vinyl acetate, make the hydroxy chloride ethylene-vinyl acetate have good machining at low temperature performance and low temperature flexibility, solubility property improves, and have the strong viscosity and the plasticity-of erosion resistance, uninflammability and the vinyl acetate of polyvinyl chloride, be easy to characteristics such as processing.But the existence of hydroxyl makes the hydroxy chloride ethylene-vinyl acetate have response characteristic, is widely used as the binding material of timber, footwear, glass, soft, hard PVC film and plate, the sticking decoration paint of paper, can lacquer and tape adhesive coating, printing ink.The contriver applies for that a kind of " modified polyurethane composition and preparation method thereof " of authorizing (CN1746223), is with vinyl chloride-vinyl acetate polyether(poly)urethane to be carried out modification, to improve the electrical insulating property and the flame retardant resistance of polyurethane elastomer.Patent of the present invention is in the presence of the solvent and under the catalyst action, hydroxy chloride ethylene-vinyl acetate macromole is introduced in the Resins, epoxy macromolecular chain by chemical reaction, hydroxyl on the hydroxy chloride ethylene-vinyl acetate macromolecular chain and the epoxy group(ing) in the Resins, epoxy are reacted, in epoxy-resin systems, form hydroxy chloride ethylene-vinyl acetate grafting Resins, epoxy graft copolymer.The hydroxy chloride ethylene-vinyl acetate is introduced in the epoxy-resin systems, can obviously improve the snappiness and the resistance to impact shock of epoxy resin cured product, reduces the stress cracking phenomenon, can keep higher hardness of epoxy resin cured product and rigidity simultaneously.Also further improved consistency, sticking power and wear resistance, the flame retardant resistance of Resins, epoxy and other material, can use as tackiness agent and coating material in multiple field.
Summary of the invention
Based on above-mentioned prior art, crisp at the curing material after the curing of bisphenol A-type liquid-state epoxy resin, shock strength is low, be easy to generate stress cracking, thereby influence the shortcoming of quality of item, the invention provides a kind of Hydroxychloroethylen--vinyl acetate modified epoxy resin compound and preparation method thereof, with the hydroxy chloride ethylene-vinyl acetate is properties-correcting agent, the bisphenol A-type liquid-state epoxy resin is carried out chemical modification, in epoxy-resin systems, introduce and at room temperature have flexible hydroxy chloride ethylene-vinyl acetate macromole, make that hydroxyl reacts in part epoxy group(ing) in the epoxy-resin systems and the hydroxy chloride ethylene-vinyl acetate macromolecular chain, make the graft copolymer that contains hydroxy chloride ethylene-vinyl acetate grafting Resins, epoxy in the epoxy-resin systems, improve the toughness and the intensity of Resins, epoxy, and do not influence the primary characteristic of Resins, epoxy, enlarge its Application Areas.
To achieve these goals, a kind of Hydroxychloroethylen--vinyl acetate modified epoxy resin compound that the present invention calls oneself, its composition is the mixture of a kind of hydroxy chloride ethylene-vinyl acetate grafting bisphenol A type epoxy resin graft copolymer and bisphenol A type epoxy resin homopolymer, and the composition structural formula of its mixture is as follows:
It is 70～73% that the segment mole of above-mentioned graft copolymer consists of vinylchlorid segment molar content, and vinyl acetate segmental molar content is 11～13%, and vinyl alcohol grafting Resins, epoxy segmental molar content is 16～17%.
The preparation method of the aforesaid a kind of Hydroxychloroethylen--vinyl acetate modified epoxy resin compound of the present invention realizes by following steps, feeding quantity according to the mass fraction:
(1) hydroxy chloride ethylene-vinyl acetate solution preparation: take by weighing relative molecular mass and be 22000～24000 hydroxy chloride ethylene-vinyl acetate and be dissolved in 500 parts of acetone for 40～70 parts, it is standby that it is dissolved fully;
(2) graft modification reaction: take by weighing 120～150 parts of bisphenol A-type liquid-state epoxy resins, add and have in the container of reflux, put into water bath with thermostatic control, add again 54～57 parts above-mentioned steps (1) solution and account for 0.03～0.06% boron trifluoride ethyl ether complex of hydroxy chloride ethylene-vinyl acetate and liquid-state epoxy resin total mass, it is fully mixed; Stirring heats up in 82～88 ℃ of following isothermal reactions 5～6 hours, obtains containing the hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin of acetone solvent;
(3) with the reactant solution of above-mentioned steps (2) under 50～56 ℃, vacuumize part acetone or whole acetone solvents, make hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin product, reduce to room temperature, sealing is preserved.
The present invention is a raw material with hydroxylation vinyl chloride-vinyl acetate, bisphenol A-type liquid-state epoxy resin, boron trifluoride ethyl ether complex, acetone etc., preparation hydroxy chloride ethylene-vinyl acetate modification liquid-state epoxy resin, the mixture that consists of a kind of hydroxy chloride ethylene-vinyl acetate grafting bisphenol A type epoxy resin graft copolymer and bisphenol A type epoxy resin homopolymer of this modifier.Recording the epoxide group molar content by hydrochloric acid acetone method (mensuration of GB/T1677-2008 softening agent oxirane value) is 0.38～0.42mol/100g.At room temperature, this modified epoxy can form the curable epoxide thing with the multiple material generation chemical crosslink reaction that contains reactive hydrogen.The introducing of hydroxy chloride ethylene-vinyl acetate macromolecular chain; make behind the epoxy resin cure in formed cured article molecular structure; embedded and had flexible hydroxy chloride ethylene-vinyl acetate molecule segment under the room temperature; also maintain the original superperformance of Resins, epoxy simultaneously; this modified epoxy had both embodied the sticking power of Resins, epoxy as tackiness agent; hardness; rigidity; chemical resistant properties; anticorrosive; characteristics such as quick-drying; because the introducing of hydroxy chloride ethylene-vinyl acetate macromolecular chain; the cured article that gives Resins, epoxy simultaneously has high tenacity; nonflammable; not combustion-supporting characteristics; improved the shock-resistance of bisphenol A type epoxy resin cured article; improve bisphenol A type epoxy resin and solidified the crisp defective of rerum natura; reduced curable epoxide thing stress cracking phenomenon; enlarge the bonding scope and the Application Areas of Resins, epoxy, can be widely used as paper; metal; the protective coating of material of construction etc. and protective system.
This modified toughened Resins, epoxy preparation method technology is simple, the adaptation of product is strong, after this modified epoxy and the reaction of triethylene tetramine solidifying agent, (intensive to be improved as crackle less by unmodified crackle for 1kg * 50cm), and the shock strength testing method is to be undertaken by the regulation among " paint film shock-resistance assay method " GB/T1732-1993 for the shock strength of its paint film; The paint film flexibility radius-of-curvature is improved to 0.5mm by 1.5mm, and the snappiness testing method is to be undertaken by the regulation among " paint film flexibility assay method " GB/T1731-1993; Unmodified curable epoxide thing hardness of paint film is 0.42, hardness of paint film is 0.41 after the modification, hardness of paint film is to carry out with reference to " hardness of paint film assay method pendulum dampingtest " GB1730-82, illustrate that thus cured article snappiness and fragility that this hydroxy chloride ethylene-vinyl acetate modified epoxy resin multipolymer and solidifying agent reaction back forms have obtained obvious improvement, resistance to impact shock is significantly improved, and hardness and rigidity are not subjected to obviously to influence.
Embodiment
The present invention is a properties-correcting agent with the hydroxy chloride ethylene-vinyl acetate, the bisphenol A-type liquid-state epoxy resin is carried out chemical modification, in epoxy-resin systems, introduce and at room temperature have flexible hydroxy chloride ethylene-vinyl acetate macromole, make that hydroxyl reacts in part epoxy group(ing) in the epoxy-resin systems and the hydroxy chloride ethylene-vinyl acetate macromolecular chain, make the graft copolymer that contains hydroxy chloride ethylene-vinyl acetate grafting Resins, epoxy in the epoxy-resin systems.
The present invention mixes the bisphenol A type epoxy resin graft copolymer in proportion with the bisphenol A type epoxy resin homopolymer, promptly obtains a kind of mixture of hydroxy chloride ethylene-vinyl acetate graft modification bisphenol A type epoxy resin.
Further describe below by specific embodiment, the feeding quantity of present embodiment according to the mass fraction:
Embodiment 1
(1) hydroxy chloride ethylene-vinyl acetate solution preparation: take by weighing relative molecular mass and be 22000～24000 hydroxy chloride ethylene-vinyl acetate and be dissolved in 500 parts of acetone for 40 parts, it is standby that it is dissolved fully.
(2) graft modification reaction: the bisphenol A-type liquid-state epoxy resin (E-44) that takes by weighing 120 parts, add and have in the container of reflux, put into water bath with thermostatic control, add the solution of 54 parts of above-mentioned steps (1) and boron trifluoride ethyl ether complex (boron trifluoride ethyl ether complex account for hydroxy chloride ethylene-vinyl acetate and liquid-state epoxy resin total amount 0.03～0.06%) again, make fully to mix.Stirring heats up in 87 ℃ of following isothermal reactions 5 hours, must contain the hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin of acetone solvent.
(3) with the reactant solution of above-mentioned steps (2) under 53 ℃, vacuumize part acetone or whole acetone solvents, make hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin, reduce to room temperature, sealing is preserved.
The hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin mixture that makes, its composition structural formula is:
It is 70～73% that the segment mole of above-mentioned graft copolymer consists of vinylchlorid segment molar content, and vinyl acetate segmental molar content is 11～13%, and vinyl alcohol grafting Resins, epoxy segmental molar content is 16～17%.
Embodiment 2
Method as tool embodiment 1, with relative molecular mass is that 22000～24000 hydroxy chloride ethylene-vinyl acetate is dissolved in 500 parts of acetone for 50 parts, it is dissolved fully, get 55 parts of hydroxylation vinyl chloride-vinyl acetate acetone solns, join in the container, add 130 parts of bisphenol A-type liquid-state epoxy resins (E-51) and boron trifluoride ethyl ether complex (add-on is identical with embodiment 1) again, fully mix.In 85 ℃ of following isothermal reactions 5.5 hours, must contain the hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin of acetone solvent.Above-mentioned reactant solution under 55 ℃, is vacuumized part acetone and obtains hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin mixture, reduce to room temperature, sealing preservation.It forms structural formula:
It is 70～73% that the segment mole of above-mentioned graft copolymer consists of vinylchlorid segment molar content, and vinyl acetate segmental molar content is 11～13%, and vinyl alcohol grafting Resins, epoxy segmental molar content is 16～17%.
Embodiment 3
Method as embodiment 1, with relative molecular mass is that 22000～24000 hydroxy chloride ethylene-vinyl acetate is dissolved in 500 parts of acetone for 60 parts, it is dissolved fully, get 56 parts of hydroxylation vinyl chloride-vinyl acetate acetone solns, join in the container, add 140 parts of bisphenol A-type liquid-state epoxy resins (E-44) and boron trifluoride ethyl ether complex (add-on is identical with embodiment 1) again, fully mix.In 83 ℃ of following isothermal reactions 6 hours, must contain the hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin of acetone solvent.Above-mentioned reactant solution under 54 ℃, is vacuumized part acetone and gets hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin mixture, and its composition structural formula is:
It is 70～73% that the segment mole of above-mentioned graft copolymer consists of vinylchlorid segment molar content, and vinyl acetate segmental molar content is 11～13%, and vinyl alcohol grafting Resins, epoxy segmental molar content is 16～17%.
Embodiment 4
Method as embodiment 1, with relative molecular mass is that 22000～24000 hydroxy chloride ethylene-vinyl acetate is dissolved in 500 parts of acetone for 70 parts, it is dissolved fully, get 57 parts of above-mentioned hydroxylation vinyl chloride-vinyl acetate acetone solns, join in the container, add 150 parts of bisphenol A-type liquid-state epoxy resins (E-51) and boron trifluoride ethyl ether complex (add-on is identical with embodiment 1) again, fully mix.In 86 ℃ of following isothermal reactions 5.5 hours, must contain the hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin of acetone solvent.Above-mentioned reactant solution under 54 ℃, is vacuumized part acetone and gets hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin mixture, reduce to room temperature, sealing preservation.It forms structural formula:
It is 70～73% that the segment mole of above-mentioned graft copolymer consists of vinylchlorid segment molar content, and vinyl acetate segmental molar content is 11～13%, and vinyl alcohol grafting Resins, epoxy segmental molar content is 16～17%.
Embodiment 5
Method as embodiment 1, with relative molecular mass is that 22000～24000 hydroxy chloride ethylene-vinyl acetate is dissolved in 500 parts of acetone for 55 parts, it is dissolved fully, get 56 parts of hydroxylation vinyl chloride-vinyl acetate acetone solns, join in the container, add 135 parts of bisphenol A-type liquid-state epoxy resins (E-51) and boron trifluoride ethyl ether complex (add-on is identical with embodiment 1) again, fully mix.In 84 ℃ of following isothermal reactions 6 hours, must contain the hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin of acetone solvent.Above-mentioned reactant solution under 54 ℃, is vacuumized part acetone and gets hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin mixture, and its composition structural formula is:
It is 70～73% that the segment mole of above-mentioned graft copolymer consists of vinylchlorid segment molar content, and vinyl acetate segmental molar content is 11～13%, and vinyl alcohol grafting Resins, epoxy segmental molar content is 16～17%.
Claims (3)
1. Hydroxychloroethylen--vinyl acetate modified epoxy resin compound, it is the mixture of a kind of hydroxy chloride ethylene-vinyl acetate grafting bisphenol A type epoxy resin graft copolymer and bisphenol A type epoxy resin homopolymer that its described mixture is formed.
2. a kind of Hydroxychloroethylen--vinyl acetate modified epoxy resin compound as claimed in claim 1, the composition structural formula of its described epoxy resin composite is as follows:
It is 70～73% that the segment mole of above-mentioned graft copolymer consists of vinylchlorid segment molar content, and vinyl acetate segmental molar content is 11～13%, and vinyl alcohol grafting Resins, epoxy segmental molar content is 16～17%;
Its preparation method follows these steps to carry out, feeding quantity according to the mass fraction:
(1) hydroxy chloride ethylene-vinyl acetate solution preparation: take by weighing relative molecular mass and be 22000～24000 hydroxy chloride ethylene-vinyl acetate and be dissolved in 500 parts of acetone for 40～70 parts, it is standby that it is dissolved fully;
(2) graft modification reaction: take by weighing 120～150 parts of bisphenol A-type liquid-state epoxy resins, add have reflux container in, put into water bath with thermostatic control, add again 54～57 parts above-mentioned steps (1) solution and account for 0.03～0.06% boron trifluoride ethyl ether complex of hydroxy chloride ethylene-vinyl acetate and liquid-state epoxy resin total mass, it is fully mixed; Stirring heats up in 82～88 ℃ of following isothermal reactions 5～6 hours, obtains containing the hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin of acetone solvent;
(3) with the reactant solution of above-mentioned steps (2) under 50～56 ℃, vacuumize part acetone or whole acetone solvents, make hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin product, reduce to room temperature, sealing is preserved.
3. preparation method who is used for claim 1 or 2 described Hydroxychloroethylen--vinyl acetate modified epoxy resin compounds, its preparation method follows these steps to carry out, feeding quantity according to the mass fraction:
(1) hydroxy chloride ethylene-vinyl acetate solution preparation: take by weighing relative molecular mass and be 22000～24000 hydroxy chloride ethylene-vinyl acetate and be dissolved in 500 parts of acetone for 40～70 parts, it is standby that it is dissolved fully;
(2) graft modification reaction: take by weighing 120～150 parts of bisphenol A-type liquid-state epoxy resins, add have reflux container in, put into water bath with thermostatic control, add again 54～57 parts above-mentioned steps (1) solution and account for 0.03～0.06% boron trifluoride ethyl ether complex of hydroxy chloride ethylene-vinyl acetate and liquid-state epoxy resin total mass, it is fully mixed; Stirring heats up in 82～88 ℃ of following isothermal reactions 5～6 hours, obtains containing the hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin of acetone solvent;
(3) with the reactant solution of above-mentioned steps (2) under 50～56 ℃, vacuumize part acetone or whole acetone solvents, make hydroxy chloride ethylene-vinyl acetate modified bisphenol A type liquid-state epoxy resin product, reduce to room temperature, sealing is preserved.
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| CN102633986B (en) * | 2012-04-11 | 2015-07-29 | 上海雄润树脂有限公司 | A kind of extra-high voltage SF 6the constituent of electric insulation epoxy resin |
| CN104271691B (en) | 2012-04-24 | 2017-07-11 | 陶氏环球技术有限公司 | The composition epoxy resin with maintenance finish is safeguarded for the ship with the recoatability for improving |
| KR101991314B1 (en) * | 2012-04-24 | 2019-06-20 | 다우 글로벌 테크놀로지스 엘엘씨 | Epoxy resin composition for marine maintenace and repair coatings with improved overcoatability |
| CN103396722B (en) * | 2013-07-05 | 2015-12-23 | 广东工业大学 | Fluorine-alcohol modified epoxypaint of a kind of water-based UV-curable and preparation method thereof |
| CN108504042A (en) * | 2018-04-13 | 2018-09-07 | 安徽瑞瑶环保科技有限公司 | A kind of composite glass fiber reinforced septic tank of three formats |
| EP3693180B1 (en) * | 2019-02-05 | 2023-09-13 | Flooring Industries Limited, SARL | Method for manufacturing a decorative foil and a panel comprising such foil |
| CN116535110B (en) * | 2023-04-18 | 2024-02-23 | 石家庄市长安育才建材有限公司 | Basalt fiber alkali-resistant agent and preparation method thereof |
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