CN102604000B - Synthetic method and application of epoxy vinyl ester resin with high bromine content - Google Patents
Synthetic method and application of epoxy vinyl ester resin with high bromine content Download PDFInfo
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- CN102604000B CN102604000B CN201210082026.6A CN201210082026A CN102604000B CN 102604000 B CN102604000 B CN 102604000B CN 201210082026 A CN201210082026 A CN 201210082026A CN 102604000 B CN102604000 B CN 102604000B
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Abstract
The invention belongs to the technical field of synthesizing resin flame retardant additives, and relates to a synthetic method and application of epoxy vinyl ester resin with high bromine content. The synthetic method is characterized by comprising the following steps: calculating components in a container by weight parts, firstly, adding 50-75 parts of bisphenol A epoxy resin with high bromine content and 8-20 parts of unsaturated carboxylic acid, raising the temperature to 80-140 DEG C for reacting in the presence of a catalyst and a polymerization inhibitor until the acid value is less than 30mgKOH/g, and then adding 10-40 parts of a diluent for stirring, diluting and cooling to obtain the final reaction product of epoxy vinyl ester resin with high bromine content. The product is used as a reactive-type flame retardant additive to mix with the non-flame retardant epoxy vinyl ester resin or unsaturated polyester resin by any proportion to obtain flame-retardant resin with different flame-retardant levels and prepare resin-based composite materials meeting the flame-retardant requirements. The preparation method in the invention has the characteristics of simple process, convenient operation and the like.
Description
Technical field
The invention belongs to synthetic resins flame-retardant additive technical field, relate to a kind of preparation method and use of high bromine content epoxy vinyl ester resin, product can be used as reactive flame-retardant additive, is widely used in the polymer matrix composites that preparation has flame-retardancy requirements.
Background technology
Most of synthetic resins has a common shortcoming, easily decomposes in air at high temperature, burns.Their limiting oxygen index(LOI) is all less than 21% mostly, and the oxygen level in air is 21%, and therefore, as long as run into burning things which may cause a fire disaster or temperature reaches point of ignition, most of synthetic resins all can be lighted.And synthetic resins may produce multiple poisonous or acrid volatile products and smog when thermo-cracking and burning, not only easily cause key part in electronics, electrical equipment impaired and cause the malfunctioning of whole plant, and more seriously have serious harm to the respiratory tract of human body and other organs, affect escape chance and lifesaving opportunity of people adversely.The secondary pollution caused in a fire and harm, or even more than the several times of loss that cause of fire itself.China specifies that many fields macromolecular material used must be fire-retardant, to reduce fire hazard.In resin, whether participate in chemical reaction according to fire retardant to distinguish, can be divided into addition type and response type two class, what generally use at present is additive flame retardant mostly.
Although additive flame retardant is easy to use, price is lower, but due to adding of this based flame retardant, reduce the mechanical property (as tensile strength, tensile modulus, flexural strength, modulus in flexure etc.) of product, improve the viscosity of resin simultaneously, formed product in producing to glass reinforced plastic brings difficulty, and the time has grown the flame retardant effect instability of additive flame retardant.Therefore synthesize the reaction-type flame-retarding additive that a kind of high flame-retardant is broad-spectrum, good with other resin compatible, good market outlook will be had.
Summary of the invention
The object of this invention is to provide a kind of high bromine content epoxy vinyl ester resin synthetic method being used as reaction-type flame-retarding additive.
For achieving the above object, the technical scheme adopted is: select a kind of epoxy resin of high bromine content as raw material, react with unsaturated carboxylic acid, then with thinner dilution, obtains final reacting product: high bromine content epoxy vinyl ester resin.
A synthetic method for high bromine content epoxy vinyl ester resin, is characterized in that comprising the following steps:
(1) prepare burden: each component with parts by weight, high bromine content bisphenol A epoxide resin 50 ~ 75 parts, unsaturated carboxylic acid 8 ~ 20 parts, catalyzer 0.1 ~ 1 part, stopper 0.01 ~ 0.1 part;
(2) synthesize: load weighted high bromine content bisphenol A epoxide resin, unsaturated carboxylic acid, catalyzer, stopper are dropped in there-necked flask, be warming up to 80 ~ 140 DEG C, stir, survey acid number at set intervals, until termination reaction when acid number is less than 30mgKOH/g, obtain high bromine content epoxy vinyl ester;
(3) dilute: thinner 10 ~ 40 parts is added in flask while stirring, and is cooled to room temperature, obtain high bromine content epoxy vinyl ester resin.
In step (1):
Described high bromine content bisphenol A epoxide resin oxirane value is 0.23 ~ 0.26, and brominated amount is 46% ~ 50%;
Described unsaturated carboxylic acid is one or both in methacrylic acid, vinylformic acid, fumaric acid;
Described catalyzer is benzyldimethylamine, N, the one in N '-dimethyl aniline, tetramethyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride;
Described stopper is one or both in Resorcinol, tert-butyl catechol, methyl hydroquinone, para benzoquinone;
Described in step (3), thinner refers to one or both in vinylbenzene, Vinyl toluene, methyl methacrylate, Phthalic acid, diallyl ester, dicyclopentadiene acrylate.
The purposes of the high bromine content epoxy vinyl ester resin produced by described batching-synthesis-dilution step, be to be used as reaction-type flame-retarding additive, mix mutually with arbitrary proportion and non-flame resistant epoxy vinyl ester resin or unsaturated polyester resin, preparation has the polymer matrix composites of flame-retardancy requirements.
The present invention compared with the existing technology, has following major advantage:
Synthetic product bromine content of the present invention can reach more than 35%, product is originally as low molecular weight epoxy vinyl ester resin, therefore can be used as reaction-type flame-retarding additive, mix mutually with arbitrary proportion with other non-flame resistant epoxy vinyl ester resin (VER) or unsaturated polyester resin (UPR), obtain the flame-retarded resin with different bromine content (i.e. different fire-retardant rank).Except giving the latter with except the flame retardant resistance expected, and the mechanical property of the latter and erosion resistance are not affected.Pour mass after solidification has good mechanical property, and some performance to unmodified resin, and such as heat-drawn wire also increases.
Synthetic method provided by the invention has the advantages such as technique is simple, easy to operate.
Specific embodiments
Below by way of specific embodiment, the invention will be further described.
In combustion, halide-containing decomposes generation hydrogen halide, and the hydrogen halide of generation then as the trapping agent of living radical HO and H, thus suppresses the carrying out of combustion processes.Therefore content of halogen is higher, and suppress the effect of burning more obvious, namely flame retardant effect is better.In order to synthesize high bromine content epoxy vinyl ester resin, we select high bromine content epoxy resin that domestic production, brominated amount is the highest as raw material, as the high bromine content EX-48 bisphenol A epoxide resin that Wuxi resin processing plant produces, its oxirane value 0.23 ~ 0.26, bromine content is 46% ~ 50%; The high bromine content CYDB-400 bisphenol A epoxide resin that epoxy resin factory of Yueyang petro-chemical corporation produces, its oxirane value is 0.23 ~ 0.26, and bromine content is 46% ~ 50%.
Respectively prepare burden with parts by weight in embodiment.
Embodiment 1
High bromine content EX-48 bisphenol A epoxide resin 600g is dropped in the there-necked flask of 1000ml with thermometer, agitator, prolong, methacrylic acid 105g, fumaric acid 11.6g, Resorcinol 0.35g, N, N '-dimethyl aniline 3.5g, be warming up to 80 DEG C ~ 90 DEG C, stir simultaneously, survey acid number at set intervals, until it is reaction end that acid number is less than 30mgKOH/g, stopped reaction.Reaction product is cooled to less than 100 DEG C, adds vinylbenzene 320g, stir and be cooled to room temperature, obtain high bromine content epoxy vinyl ester resin.
Embodiment 2
High bromine content EX-48 bisphenol A epoxide resin 600g is dropped in the there-necked flask of 1000ml with thermometer, agitator, prolong, methacrylic acid 120g, Resorcinol 0.35g, tetramethyl ammonium chloride 3.5g, be warming up to 90 DEG C ~ 100 DEG C, stir simultaneously, survey acid number at set intervals, until it is reaction end that acid number is less than 30mgKOH/g, stopped reaction.Reaction product is cooled to less than 100 DEG C, adds vinylbenzene 160g, Vinyl toluene 160g, stir and be cooled to room temperature, obtain high bromine content epoxy vinyl ester resin.
Embodiment 3
High bromine content CYDB-400 bisphenol A epoxide resin 500g is dropped in the there-necked flask of 1000ml with thermometer, agitator, prolong, methacrylic acid 101g, fumaric acid 11.6g, methyl Pyrogentisinic Acid 0.35g, benzyltriethylammoinium chloride 3.0g, be warming up to 90 DEG C ~ 100 DEG C, stir simultaneously, survey acid number at set intervals, until it is reaction end that acid number is less than 30mgKOH/g, stopped reaction.Reaction product is cooled to less than 100 DEG C, adds vinylbenzene 350g, stir and be cooled to room temperature, obtain high bromine content epoxy vinyl ester resin.
Embodiment 4
High bromine content CYDB-400 bisphenol A epoxide resin 500g is dropped in the there-necked flask of 1000ml with thermometer, agitator, prolong, vinylformic acid 100g, Resorcinol 0.2g, tert-butyl catechol 0.15g, tetramethyl ammonium chloride 3.0g, be warming up to 105 DEG C ~ 120 DEG C, stir simultaneously, survey acid number at set intervals, until it is reaction end that acid number is less than 30mgKOH/g, stopped reaction.Reaction product is cooled to less than 100 DEG C, adds vinylbenzene 200g, Phthalic acid, diallyl ester 100g, stir and be cooled to room temperature, obtain high bromine content epoxy vinyl ester resin.
Embodiment 5
High bromine content EX-48 bisphenol A epoxide resin 600g is dropped in the there-necked flask of 1000ml with thermometer, agitator, prolong, methacrylic acid 105g, fumaric acid 11.6g, para benzoquinone 0.35g, benzyl dimethylammonium 3.5g, be warming up to 120 DEG C ~ 130 DEG C, stir simultaneously, survey acid number at set intervals, until it is reaction end that acid number is less than 30mgKOH/g, stopped reaction.Reaction product is cooled to less than 100 DEG C, adds vinylbenzene 280g, stir and be cooled to room temperature, obtain high bromine content epoxy vinyl ester resin.
Embodiment 6
High bromine content EX-48 bisphenol A epoxide resin 600g is dropped in the there-necked flask of 1000ml with thermometer, agitator, prolong, methacrylic acid 120g, Resorcinol 0.35g, tetramethyl ammonium chloride 3.5g, be warming up to 130 DEG C ~ 140 DEG C, stir simultaneously, survey acid number at set intervals, until it is reaction end that acid number is less than 30mgKOH/g, stopped reaction.Reaction product is cooled to less than 100 DEG C, adds vinylbenzene 80g, stir and be cooled to room temperature, obtain high bromine content epoxy vinyl ester resin.
(oxygen index is 20% to MFE-2 vinyl ester resin high bromine content epoxy vinyl ester resin (bromine content >=35%) of the present invention and East China University Of Science And Technology Huachang Polymer Co., Ltd produced, heat-drawn wire 105 DEG C) mixed (by weight 3: 7 mixing) obtain mutually the oxygen index of casting resin is 32%, heat-drawn wire 110 DEG C.
It is the typical performance test data of gained resin in each embodiment in table.
High bromine content epoxy vinyl ester resin of the present invention, after appropriate vinylbenzene dilution, adds Al (OH) according to weight ratio 1: 1
3, obtain viscosities il
25the flame-retarded resin of < 500 mPas, after solidification, the oxygen index of its casting matrix can reach 44%.
Claims (7)
1. a synthetic method for high bromine content epoxy vinyl ester resin, is characterized in that comprising the following steps:
(1) prepare burden: each component with parts by weight, high bromine content bisphenol A epoxide resin 50 ~ 75 parts, unsaturated carboxylic acid 8 ~ 20 parts, catalyzer 0.1 ~ 1 part, stopper 0.01 ~ 0.1 part;
(2) synthesize: load weighted high bromine content bisphenol A epoxide resin, unsaturated carboxylic acid, catalyzer, stopper are dropped in there-necked flask, be warming up to 80 ~ 140 DEG C, stir, survey acid number at set intervals, until acid number is less than 30mgKOH/g termination reaction, obtain high bromine content epoxy vinyl ester;
(3) dilute: thinner 10 ~ 40 parts is added in flask while stirring, and is cooled to room temperature, obtain high bromine content epoxy vinyl ester resin.
2., by the synthetic method of a kind of high bromine content epoxy vinyl ester resin described in claim 1, it is characterized in that the described high bromine content bisphenol A epoxide resin of step (1), oxirane value is 0.23 ~ 0.26, and brominated amount is 46% ~ 50%.
3., by the synthetic method of a kind of high bromine content epoxy vinyl ester resin described in claim 1, it is characterized in that step (1) described unsaturated carboxylic acid is one or both in methacrylic acid, vinylformic acid, fumaric acid.
4. by the synthetic method of a kind of high bromine content epoxy vinyl ester resin described in claim 1, it is characterized in that step (1) described catalyzer is benzyldimethylamine, N, the one in N '-dimethyl aniline, tetramethyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride.
5., by the synthetic method of a kind of high bromine content epoxy vinyl ester resin described in claim 1, it is characterized in that step (1) described stopper is one or both in Resorcinol, tert-butyl catechol, methyl hydroquinone, para benzoquinone.
6. by the synthetic method of a kind of high bromine content epoxy vinyl ester resin described in claim 1, it is characterized in that thinner described in step (3) refers in vinylbenzene, Vinyl toluene, methyl methacrylate, Phthalic acid, diallyl ester, dicyclopentadiene acrylate one or both.
7. the purposes of the high bromine content epoxy vinyl ester resin prepared by synthetic method described in claim 1, it is characterized in that being used as reaction-type flame-retarding additive, mix mutually with arbitrary proportion and non-flame resistant epoxy vinyl ester resin or unsaturated polyester resin, preparation has the polymer matrix composites of flame-retardancy requirements.
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| CN104479106B (en) * | 2014-12-05 | 2017-02-08 | 上海昭和高分子有限公司 | Vinyl ester resin and preparation method thereof |
| CN105017729A (en) * | 2015-08-21 | 2015-11-04 | 永悦科技股份有限公司 | Synthetic method of efficient flame-retardant epoxy vinyl ester resin |
| CN106589313B (en) * | 2015-10-14 | 2020-09-04 | 中国石油化工股份有限公司 | Unsaturated acid modified epoxy resin universal carbon fiber sizing agent, preparation method and application thereof |
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| CN106832797A (en) * | 2016-12-29 | 2017-06-13 | 浙江诺比高分子材料有限公司 | A kind of flame-proof ethylene base resin and its preparation technology |
| CN106833063A (en) * | 2016-12-29 | 2017-06-13 | 浙江诺比高分子材料有限公司 | A kind of wet type electrostatic precipitator vinylite |
| CN109627423B (en) * | 2018-12-07 | 2021-08-06 | 湖南普瑞迪新材料有限公司 | Flexible chain modified epoxy acrylate resin and preparation method thereof |
| CN111072872B (en) * | 2019-12-31 | 2023-07-04 | 华东理工大学华昌聚合物有限公司 | Temperature-resistant flame-retardant epoxy vinyl ester resin and high-toughness temperature-resistant flame-retardant glass flake clay containing same |
| CN111995755A (en) * | 2020-08-24 | 2020-11-27 | 浙江晨诺高分子材料有限公司 | Vinyl ester flame-retardant resin containing polyester structure and preparation method thereof |
| CN114213628A (en) * | 2021-11-29 | 2022-03-22 | 济南绿洲复合材料有限公司 | Vinyl type unsaturated polyester resin and preparation method thereof |
| CN114249879A (en) * | 2022-01-12 | 2022-03-29 | 广东美亨新材料科技有限公司 | Environment-friendly vinyl ester resin |
| CN115677948B (en) * | 2022-11-18 | 2023-09-22 | 广东热浪新材料科技有限公司 | High specific gravity transparent resin composition and method for preparing particles thereof |
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| CN1935870A (en) * | 2006-08-08 | 2007-03-28 | 华东理工大学华昌聚合物有限公司 | Process for synthesizing low-styrene-content high-temperature-resistance epoxy vinyl ester resin |
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| CN1237133C (en) * | 2003-10-22 | 2006-01-18 | 深圳丹邦科技有限公司 | Siliconless fire-retardant type quick solidifying covering film for flexible circuit and its preparation method |
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Address after: 201507 Shanghai city Fengxian District Muhua Road No. 130 Patentee after: Huachang Polymer Co., Ltd., Huadong Tech Univ. Address before: 200237 Meilong Road, Shanghai, No. 352 mailbox, No. 130 Patentee before: Huachang Polymer Co., Ltd., Huadong Tech Univ. |