CN101525408A - Epoxy vinyl ester resin and preparing method thereof - Google Patents
Epoxy vinyl ester resin and preparing method thereof Download PDFInfo
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- CN101525408A CN101525408A CN200910045988A CN200910045988A CN101525408A CN 101525408 A CN101525408 A CN 101525408A CN 200910045988 A CN200910045988 A CN 200910045988A CN 200910045988 A CN200910045988 A CN 200910045988A CN 101525408 A CN101525408 A CN 101525408A
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Abstract
The invention relates to epoxy vinyl ester resin which is prepared from the following components by the weight percent: 30 to 50 of bisphenol A-type epoxy resin, 5 to 20 of unsaturated monoaicd, 0 to 30 of HET acid, 0.05 to 0.5 of catalyst, 0.01 to 0.1 of polymerizing inhibitor and 30 to 45 of cross-linkable monomer. The preparing method of the epoxy vinyl ester resin is as follows: the bisphenol A-type epoxy resin is put into a reaction kettle, the temperature is risen to 60 DEG C, and the unsaturated monoacid, the HET acid, the catalyst and part of polymerizing inhibitor are sequentially added to the reaction kettle; the temperature is risen to 110 to 130 DEG C to be kept for 1 to 4 hours until the acid value is decreased to be lower than 15 kg KOH/g; the mixture is cooled to be lower than 100 DEG C, the cross-linkable monomer and the residual polymerizing inhibitor are added to the mixture to be sufficiently stirred, and the epoxy vinyl ester resin is obtained. The preparing method is simple and causes no waste water, waste gas or waste slag. The epoxy vinyl ester modified by the HET acid has the media of high-temperature resistance, flame resistance and strong-oxidizing resistance and good stability, and can be used for producing the FRP equipment of chloride-alkali paper-pulp industrial chlorine dioxide and chlorine-bleaching systems, and in particular can satisfy the special requirements of the production of corrosion resistant composite materials under the condition of high-temperature resistant oxidizing media.
Description
Technical field
The present invention relates to a kind of epoxy vinyl ester resin that is applicable to chlor-alkali Pulp industry bleaching system and preparation method thereof.
Background technology
Epoxy vinyl ester resin is the product by Resins, epoxy and double bond containing unsaturated monocarboxylic acid addition, has the characteristics of epoxy and two kinds of thermosetting resins of unsaturated polyester concurrently.Epoxy vinyl ester resin can be by the radical polymerization self-vulcanizing, and processing performance is similar to unsaturated polyester resin, and resin contains epoxy resin structural, has favorable mechanical performance, thermotolerance and chemical resistant properties.Epoxy vinyl ester resin is used widely in chemical anticorrosion equipment and engineering mainly as a kind of corrosion resistant material of excellent property at present, in order to make various composite products such as corrosion protection equipment lining, pipeline, basin, washer and pipe fitting.
China's paper pulp industry is in succession from the external dioxide peroxide pulping bleaching technology of having introduced since the nineties, but dioxide peroxide is a kind of SYNTHETIC OPTICAL WHITNER of explosive, poisonous and high corrosion, must adopt the height noncorrosive materials in dioxide peroxide generation, storage and the bleaching system.Chlor-alkali industry is the important Elementary Chemical Industry industry of China, at present China chlor-alkali enterprise in process of production, what contact in the device almost is the strong corrosive medias such as water vapor of high warm and humid chlorine, chloride alkali lye, hypochlorous acid and the saturated chlorine of high temperature.The chemical property of these media is very active, and except that the metal titanium material, most of metallic substance and non-metallic material are not corrosion-resistant under this environment.Some producers adopt steel-lined rubbers etc. to solve, and as the chlorine house steward etc., but general work-ing life is all about 2～3 years.
Hydrolytic action and oxygenizement can take place in universal epoxy vinyl ester resin easily in high temperature strong oxidizing property medium, fracture takes place and destroys in macromolecular chain, matrix resin produces corrosion largely at short notice, has influence on the work-ing life of glass reinforced plastic equipment and the normal operation of production.
Summary of the invention
The object of the invention provides a kind of epoxy vinyl ester resin that is applicable to chlor-alkali Pulp industry bleaching system and preparation method thereof.
Purpose of the present invention realizes like this, by the general epoxy vinyl ester resin of hexachloro endoethylene tetrahydrophthalic acid modification, obtains having concurrently excellent thermotolerance, flame retardant resistance and erosion resistance epoxy vinyl ester resin.The component of hexachloro endoethylene tetrahydrophthalic acid modified epoxy vinyl esters resin is proportioning by mass percentage, comprising:
Bisphenol A type epoxy resin 30～50%
Unsaturated monoprotic acid 5～20%
Hexachloro endoethylene tetrahydrophthalic acid 0～30%
Catalyzer 0.05%～0.5%
Stopper 0.01%～0.1%
Crosslinkable monomers 30%～45%
The preparation method of the epoxy vinyl ester resin of hexachloro endoethylene tetrahydrophthalic acid modification is: reacted under the condition that catalyzer, stopper exist by bisphenol A type epoxy resin, unsaturated monoprotic acid, hexachloro endoethylene tetrahydrophthalic acid, can obtain product with the crosslinkable monomers dilution then.Concrete steps comprise:
(1) drop into bisphenol A epoxide resin in the reactor that has thermometer, agitator, nitrogen ingress pipe and condenser, stirring also progressively is warming up to and adds unsaturated monoprotic acid, hexachloro endoethylene tetrahydrophthalic acid, catalyzer and part stopper about 60 ℃ successively;
(2) stir and heat up gradually, control reactant insulation reaction 1～4 hour between 110～130 ℃ drops to below the 15mgKOH/g until acid number;
(3) reaction product is cooled to adding crosslinkable monomers below 100 ℃ and residue stopper, promptly obtains the epoxy vinyl ester resin of hexachloro endoethylene tetrahydrophthalic acid modification after fully stirring.
Unsaturated monoprotic acid provides the epoxy vinyl ester resin unsaturated double-bond, makes the molecule two ends have active site, and unsaturated monoprotic acid of the present invention is meant methacrylic acid, vinylformic acid, butenoic acid or 2-phenylacrylic acid.
Catalyzer is meant benzyldimethylamine, benzyl trimethyl ammonium chloride or benzyltriethylammoinium chloride.
Stopper is meant and is selected from Resorcinol, methyl hydroquinone, 2, a kind of in 6-tert-butyl catechol, 2,5 di tert butyl hydroquinone, para benzoquinone or the copper naphthenate solution or two kinds.
Crosslinkable monomers is meant a kind of in vinylbenzene, Vinylstyrene, chloro-styrene, methyl methacrylate, butyl acrylate, dicyclopentadiene acrylate, the Phthalic acid, diallyl ester.
Hexachloro endoethylene tetrahydrophthalic acid claims chlordene bridge subunit phthalic acid again, is called for short HET acid, and chlorinity is up to 54.7% in its molecule.Introduce the flame retardant resistance that the hexachloro endoethylene tetrahydrophthalic acid structure has improved resin in the epoxy vinyl ester resin molecule, two continuous five-rings give resin good thermotolerance again in the molecule of HET acid, and the protection that ester group is subjected to HET acid skeleton has improved the erosion resistance of resin.Therefore the epoxy vinyl ester resin of hexachloro endoethylene tetrahydrophthalic acid modification has improved the over-all properties of resin, has multiple excellent properties such as heat-resisting, fire-retardant and corrosion-resistant concurrently.
HET acid modified resins has the unique molecular structure: the scale resistance ability improves behind the halogen that induces one in the molecule; The strong ester bond of polarity is more stable and be subjected to steric protection than ehter bond.Under the effect of the strong especially high warm and humid chlorine of oxidizing medium, the epoxy vinyl ester resin corrosion resistance nature advantage of HET acid modification is obvious.The corrosion-resistant mechanism of action more complicated of hexachloro endoethylene tetrahydrophthalic acid resin; it has been generally acknowledged that HET acid resin and wet chlorine reaction generate one deck " chlorine cream " (chlorination process); this layer structure plays a protective role, and delays or stop the further corrosion of resin, thereby reaches the protection against corrosion purpose.
Compared with prior art, the present invention has the following advantages: synthesis technique is simple, environmental protection does not have " three wastes " and produces, epoxy vinyl ester resin has been introduced HET acid distinctive molecular structure, resin after the HET acid modification has high temperature resistant simultaneously, many premium propertiess such as flame retardant resistance and powerful oxidation corrosion resistance medium, product stability is good, can replace making such as metal titanium material to be applied to chlor-alkali Pulp industry dioxide peroxide, the FRP equipment of chlorine bleaching system, brick board liner, storage tank in clay etc. and the chlorine industry, washer, water cooler, equipment such as electro bath-lid and pipeline particularly can satisfy the special requirement that the protection against corrosion matrix material is made under the high temperature oxidation resisting ambient condition.
Embodiment
Followingly the present invention is described in more detail by embodiment.
Embodiment 1:
Drop into bisphenol A-type E51 Resins, epoxy 200g in having thermometer, agitator, nitrogen ingress pipe and condenser reactor, stirring also progressively is warming up to and adds methacrylic acid 84g, HET acid 20g, benzyldimethylamine 0.6g, Resorcinol 0.05g about 60 ℃ successively.Stir and intensification gradually, keep 120 ℃ of reactions 2 hours, drop to below the 15mgKOH/g up to acid number.Reaction product is cooled to the vinylbenzene of adding below 100 ℃ 150g, 2, and 6-tert-butyl catechol 0.05g fully stirs after-filtration and obtains lurid viscous liquid.
Embodiment 2:
Drop into bisphenol A-type E51 Resins, epoxy 200g in reactor shown in the embodiment 1, stirring also progressively is warming up to and adds methacrylic acid 66g, HET acid 60g, benzyl trimethyl ammonium chloride 0.7g, methyl hydroquinone 0.05g about 60 ℃ successively.Stir and intensification gradually, keep 110 ℃ of reactions 4 hours, drop to below the 15mgKOH/g up to acid number.Reaction product is cooled to the methyl methacrylate of adding below 100 ℃ 150g, 2,5 di tert butyl hydroquinone 0.05g, fully stirs after-filtration and obtain lurid viscous liquid.
Embodiment 3:
Drop into bisphenol A-type E51 Resins, epoxy 200g in reactor shown in the embodiment 1, stirring also progressively is warming up to and adds butenoic acid 48g, HET acid 100g, benzyltriethylammoinium chloride 0.5g, Resorcinol 0.05g about 60 ℃ successively.Stir and intensification gradually, keep 130 ℃ of reactions 1 hour, drop to below the 15mgKOH/g up to acid number.Reaction product is cooled to the chloro-styrene of adding below 100 ℃ 150g, copper naphthenate liquid 0.05g, fully stirs after-filtration and obtain lurid viscous liquid.
Embodiment 4:
Drop into bisphenol A-type E51 Resins, epoxy 200g in reactor shown in the embodiment 1, stirring also progressively is warming up to and adds vinylformic acid 63g, HET acid 40g, benzyldimethylamine 1.0g, Resorcinol 0.05g about 60 ℃ successively.Stir and intensification gradually, keep 120 ℃ of reactions 2 hours, drop to below the 15mgKOH/g up to acid number.Reaction product is cooled to the Phthalic acid, diallyl ester of adding below 100 ℃ 150g, copper naphthenate liquid 0.03g, fully stirs after-filtration and obtain lurid viscous liquid.
Embodiment 5:
Drop into bisphenol A-type E51 Resins, epoxy 200g in reactor shown in the embodiment 1, stirring also progressively is warming up to and adds vinylformic acid 48g, HET acid 80g, benzyltriethylammoinium chloride 0.8g, para benzoquinone 0.05g about 60 ℃ successively.Stir and intensification gradually, keep 130 ℃ of reactions 1 hour, drop to below the 15mgKOH/g up to acid number.Reaction product is cooled to the vinylbenzene of adding below 100 ℃ 150g, 2, and 6-tert-butyl catechol 0.05g fully stirs after-filtration and obtains lurid viscous liquid.
Embodiment 6:
Drop into bisphenol A-type E51 Resins, epoxy 200g in reactor shown in the embodiment 1, stirring also progressively is warming up to and adds 2-phenylacrylic acid 82g, HET acid 100g, benzyl trimethyl ammonium chloride 0.6g, 2,6-tert-butyl catechol 0.05g about 60 ℃ successively.Stir and intensification gradually, keep 110 ℃ of reactions 4 hours, drop to below the 15mgKOH/g up to acid number.Reaction product is cooled to the Vinylstyrene of adding below 100 ℃ 150g, 2, and 6-tert-butyl catechol 0.05g fully stirs after-filtration and obtains lurid viscous liquid.
Embodiment 7:
Drop into bisphenol A-type E44 Resins, epoxy 232g in reactor shown in the embodiment 1, stirring also progressively is warming up to and adds vinylformic acid 70g, HET acid 20g, benzyl trimethyl ammonium chloride 0.8g, Resorcinol 0.05g about 60 ℃ successively.Stir and intensification gradually, keep 120 ℃ of reactions 2 hours, drop to below the 15mgKOH/g up to acid number.Reaction product is cooled to the butyl acrylate of adding below 100 ℃ 150g, 2, and 6-tert-butyl catechol 0.05g fully stirs after-filtration and obtains lurid viscous liquid.
Embodiment 8:
Drop into bisphenol A-type E44 Resins, epoxy 232g in reactor shown in the embodiment 1, stirring also progressively is warming up to and adds methacrylic acid 57g, HET acid 80g, benzyl trimethyl ammonium chloride 0.8g, 2,6-tert-butyl catechol 0.05g about 60 ℃ successively.Stir and intensification gradually, keep 120 ℃ of reactions 2 hours, drop to below the 15mgKOH/g up to acid number.Reaction product is cooled to the dicyclopentadiene acrylate of adding below 100 ℃ 150g, 2, and 6-tert-butyl catechol 0.05g fully stirs after-filtration and obtains lurid viscous liquid.More than among each embodiment the typical quality index of gained resin as follows:
| Project | Unit | Technical indicator | Testing method |
| Outward appearance | The transparent thick liquid of light color | Range estimation | |
| Acid number | mgKOH/g | 14～22 | GB/T2895-1987 |
| Viscosity (25 ℃) | Pa·s | 0.35～0.55 | GB/T7193.1-1987 |
| Solids content | ％ | 60～66 | GB/T7193.3-1987 |
| Gel time (25 ℃) | min | 15～25 | GB/T7193.6-1987 |
The typical mechanical property of casting resin is as follows:
| Project | Unit | Technical indicator | Testing method |
| Ba Keer hardness | / | 45 | GB/T 3854-1983 |
| Tensile strength | MPa | 40 | GB/T 2568-1995 |
| Tensile modulus | MPa | 3600 | GB/T 2568-1995 |
| Elongation at break | ％ | 2 | GB/T 2568-1995 |
| Flexural strength | MPa | 88 | GB/T 2570-1995 |
| Modulus in flexure | MPa | 3200 | GB/T 2570-1995 |
| Heat-drawn wire (1.8MPa) | ℃ | 95 | GB/T 1634-1989 |
The typical corrosion resistance nature of casting resin is as follows:
| Medium | Concentration % | Temperature | Medium | Concentration % | Temperature |
| Sulfuric acid | 75 | 80 | Dioxide peroxide | Saturated | 60 |
| Nitric acid | 40 | 50 | Hypochlorous acid | 20 | 30 |
| Acetic acid | 25 | 80 | Clorox | 15 | 40 |
| Hydrochloric acid | 35 | 70 | Clorox | 10 | 60 |
| Hydrofluoric acid | 40 | 30 | Perchloric acid | 70 | 30 |
| Chromic acid | 20 | 60 | Wet chlorine | Saturated | 90 |
| Potassium bichromate | Saturated | 90 | Chlorine water | Saturated | 90 |
| Copper sulfate | Electrolytic solution | 90 | Hydrogen peroxide | 30 | 60 |
Claims (6)
1. epoxy vinyl ester resin is characterized in that: component proportioning by mass percentage comprises:
Bisphenol A type epoxy resin 30～50%
Unsaturated monoprotic acid 5～20%
Hexachloro endoethylene tetrahydrophthalic acid 0～30%
Catalyzer 0.05%～0.5%
Stopper 0.01%～0.1%
Crosslinkable monomers 30%～45%.
2. the preparation method of the described epoxy vinyl ester resin of claim 1 is characterized in that: comprise the following steps:
(1) drop into bisphenol A epoxide resin in the reactor that has thermometer, agitator, nitrogen ingress pipe and condenser, stirring also progressively is warming up to and adds unsaturated monoprotic acid, hexachloro endoethylene tetrahydrophthalic acid, catalyzer and part stopper about 60 ℃ successively;
(2) stir and heat up gradually, control reactant insulation reaction 1～4 hour between 110～130 ℃ drops to below the 15mgKOH/g until acid number;
(3) reaction product is cooled to adding crosslinkable monomers below 100 ℃ and residue stopper, promptly obtains the epoxy vinyl ester resin of hexachloro endoethylene tetrahydrophthalic acid modification after fully stirring.
3. according to claim 1 or 2 described epoxy vinyl ester resins and preparation method thereof, it is characterized in that: described unsaturated monoprotic acid is meant methacrylic acid, vinylformic acid, butenoic acid or 2-phenylacrylic acid.
4. according to claim 1 or 2 described epoxy vinyl ester resins and preparation method thereof, it is characterized in that: described catalyzer is meant benzyldimethylamine, benzyl trimethyl ammonium chloride or benzyltriethylammoinium chloride.
5. according to claim 1 or 2 described epoxy vinyl ester resins and preparation method thereof, it is characterized in that: described stopper is meant and is selected from Resorcinol, methyl hydroquinone, 2, a kind of in 6-tert-butyl catechol, 2,5 di tert butyl hydroquinone, para benzoquinone or the copper naphthenate solution or two kinds.
6. according to claim 1 or 2 described epoxy vinyl ester resins and preparation method thereof, it is characterized in that: described crosslinkable monomers is meant a kind of in vinylbenzene, Vinylstyrene, chloro-styrene, methyl methacrylate, butyl acrylate, dicyclopentadiene acrylate, the Phthalic acid, diallyl ester.
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| CN200910045988A CN101525408A (en) | 2009-01-23 | 2009-01-23 | Epoxy vinyl ester resin and preparing method thereof |
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| CN200910045988A CN101525408A (en) | 2009-01-23 | 2009-01-23 | Epoxy vinyl ester resin and preparing method thereof |
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| CN101787179A (en) * | 2010-03-19 | 2010-07-28 | 新时代(济南)民爆科技产业有限公司 | Air-drying epoxy vinylit resin and processing technic thereof |
| CN102153726A (en) * | 2010-12-16 | 2011-08-17 | 华东理工大学华昌聚合物有限公司 | Synthesis method of modified epoxy vinyl ester resin |
| CN103342798A (en) * | 2013-07-16 | 2013-10-09 | 华东理工大学 | Synthesis method for low-viscosity high-temperature-resistant modified epoxy resin |
| CN103396517A (en) * | 2013-07-22 | 2013-11-20 | 南通天和树脂有限公司 | High temperature resistant vinyl ester resin |
| CN104558523A (en) * | 2015-01-28 | 2015-04-29 | 华东理工大学华昌聚合物有限公司 | Synthesis method of modified epoxy resin composition |
| CN105885011A (en) * | 2014-09-05 | 2016-08-24 | 薛俊峰 | High temperature oxidation resistant modified epoxy resin and preparation method thereof |
| CN109467651A (en) * | 2018-11-07 | 2019-03-15 | 华东理工大学华昌聚合物有限公司 | Light-cured epoxy vinyl ester resin and its synthetic method |
| CN109806821A (en) * | 2018-12-27 | 2019-05-28 | 昆山市淀山湖宝波树脂涂料厂 | A kind of production equipment of epoxy resin |
| CN110054757A (en) * | 2019-04-26 | 2019-07-26 | 永悦科技股份有限公司 | A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin |
| WO2023134036A1 (en) * | 2022-01-12 | 2023-07-20 | 广东美亨新材料科技有限公司 | Environment-friendly vinyl ester resin |
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| CN101787179B (en) * | 2010-03-19 | 2011-08-31 | 新时代(济南)民爆科技产业有限公司 | Air-drying epoxy vinylit resin and processing technic thereof |
| CN101787179A (en) * | 2010-03-19 | 2010-07-28 | 新时代(济南)民爆科技产业有限公司 | Air-drying epoxy vinylit resin and processing technic thereof |
| CN102153726B (en) * | 2010-12-16 | 2015-07-01 | 华东理工大学华昌聚合物有限公司 | Synthesis method of modified epoxy vinyl ester resin |
| CN102153726A (en) * | 2010-12-16 | 2011-08-17 | 华东理工大学华昌聚合物有限公司 | Synthesis method of modified epoxy vinyl ester resin |
| CN103342798A (en) * | 2013-07-16 | 2013-10-09 | 华东理工大学 | Synthesis method for low-viscosity high-temperature-resistant modified epoxy resin |
| CN103342798B (en) * | 2013-07-16 | 2015-08-19 | 华东理工大学 | A kind of synthetic method of low viscosity, fire resistant modified epoxy |
| CN103396517A (en) * | 2013-07-22 | 2013-11-20 | 南通天和树脂有限公司 | High temperature resistant vinyl ester resin |
| CN105885011A (en) * | 2014-09-05 | 2016-08-24 | 薛俊峰 | High temperature oxidation resistant modified epoxy resin and preparation method thereof |
| CN104558523A (en) * | 2015-01-28 | 2015-04-29 | 华东理工大学华昌聚合物有限公司 | Synthesis method of modified epoxy resin composition |
| CN109467651A (en) * | 2018-11-07 | 2019-03-15 | 华东理工大学华昌聚合物有限公司 | Light-cured epoxy vinyl ester resin and its synthetic method |
| CN109467651B (en) * | 2018-11-07 | 2021-01-15 | 华东理工大学华昌聚合物有限公司 | Light-cured epoxy vinyl ester resin and synthetic method thereof |
| CN109806821A (en) * | 2018-12-27 | 2019-05-28 | 昆山市淀山湖宝波树脂涂料厂 | A kind of production equipment of epoxy resin |
| CN110054757A (en) * | 2019-04-26 | 2019-07-26 | 永悦科技股份有限公司 | A kind of synthetic method of improved high-efficiency flame retardant type epoxy vinyl ester resin |
| WO2023134036A1 (en) * | 2022-01-12 | 2023-07-20 | 广东美亨新材料科技有限公司 | Environment-friendly vinyl ester resin |
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Application publication date: 20090909 |