CN102604000A - 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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- CN102604000A CN102604000A CN2012100820266A CN201210082026A CN102604000A CN 102604000 A CN102604000 A CN 102604000A CN 2012100820266 A CN2012100820266 A CN 2012100820266A CN 201210082026 A CN201210082026 A CN 201210082026A CN 102604000 A CN102604000 A CN 102604000A
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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 fire-retardant requirement.
Background technology
Most of synthetic resins all have a common shortcoming, in air, are prone under the high temperature decompose, burn.Their limiting oxygen index(LOI) is mostly all less than 21%, and airborne oxygen level 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 possibly produce multiple poisonous or acrid volatile products and smog when thermo-cracking and burning; Cause easily not only in electronics, the electrical equipment that key part is impaired and cause the malfunctioning of whole plant; And more serious be that respiratory tract to human body has serious harm with other organs, affect people's escape chance and lifesaving opportunity adversely.Secondary pollution that in fire, causes and harm, or even more than the several times of the loss that causes of fire itself.China stipulates that the used macromolecular material in many fields must be fire-retardant, to reduce fire hazard.In resin, whether participate in chemical reaction according to fire retardant and distinguish, can be divided into two types of addition type and response types, what generally use at present is additive flame retardant mostly.
Though additive flame retardant is easy to use, price is lower; But because the adding of this based flame retardant; Reduced the mechanical property (like tensile strength, tensile modulus, flexural strength, modulus in flexure etc.) of product; Improved the viscosity of resin simultaneously, brought difficulty, and the time has been grown the flame retardant effect instability of additive flame retardant to the formed product in the glass reinforced plastic production.Therefore synthetic a kind of height fire-retardant broad-spectrum, with the good reaction-type flame-retarding additive of other resin compatible, will have good market outlook.
Summary of the invention
The purpose of this invention is to provide a kind of high bromine content epoxy vinyl ester resin compound method as the reaction-type flame-retarding additive.
For achieving the above object, the technical scheme that is adopted is: the epoxy resin of selecting a kind of high bromine content for use reacts with unsaturated carboxylic acid as raw material, uses diluent again, obtains final reacting product: the high bromine content epoxy vinyl ester resin.
A kind of compound method of high bromine content epoxy vinyl ester resin is characterized in that may further comprise the steps:
(1) batching: each component is in weight part, 50～75 parts of high bromine content bisphenol A epoxide resins, 8～20 parts of unsaturated carboxylic acids, 0.1～1 part of catalyzer, 0.01～0.1 part of stopper;
(2) synthetic: that load weighted high bromine content bisphenol A epoxide resin, unsaturated carboxylic acid, catalyzer, stopper are dropped in the there-necked flask; Be warming up to 80～140 ℃; Stir; Survey acid number at set intervals,, obtain the high bromine content epoxy vinyl ester until acid number termination reaction during less than 30mgKOH/g;
(3) dilution: thinner is added in the flask for 10～40 parts while stirring, and be cooled to room temperature, obtain the high bromine content epoxy vinyl ester resin.
In the step (1):
Said high bromine content bisphenol A epoxide resin oxirane value is 0.23～0.26, and brominated amount is 46%～50%;
Said unsaturated carboxylic acid is one or both in methylacrylic acid, vinylformic acid, the fumaric acid;
Said catalyzer is benzyldimethylamine, N, a kind of in N '-xylidine, tetramethyl ammonium chloride, benzyl trimethyl ammonium chloride, the benzyltriethylammoinium chloride;
Said stopper is one or both in Resorcinol, tert-butyl catechol, methyl hydroquinone, the para benzoquinone;
Thinner is meant one or both in vinylbenzene, Vinyl toluene, TEB 3K, Phthalic acid, diallyl ester, the dicyclopentadiene acrylate described in the step (3).
Purposes by said batching-high bromine content epoxy vinyl ester resin that synthetic-dilution step is produced; Be as the reaction-type flame-retarding additive; Mix mutually with non-flame retardant epoxy vinyl ester resin or unsaturated polyester resin with arbitrary proportion, preparation has the polymer matrix composites of fire-retardant requirement.
The present invention compares with prior art, has following major advantage:
Synthetic product bromine content of the present invention can reach more than 35%; Product is originally as the low molecular weight epoxy vinyl ester resin; Therefore can be used as the reaction-type flame-retarding additive; Mix obtain the having different bromine contents flame-retarded resin of (being different fire-retardant ranks) mutually with arbitrary proportion with other non-flame retardant epoxy vinyl ester resin (VER) or unsaturated polyester resin (UPR).Except that giving the flame retardant resistance of the latter, and the latter's mechanical property and erosion resistance do not influenced with expectation.Pour mass after solidifying has the good mechanical performance, and to some performance of unmodified resin, for example heat-drawn wire also improves to some extent.
Compound method provided by the invention has advantages such as technology is simple, easy to operate.
Specific embodiments
Below through specific embodiment the present invention is further described.
In combustion processes, halide-containing decompose to generate hydrogen halide, and the hydrogen halide of generation is then as the trapping agent of living radical HO and H, thus the carrying out of inhibition combustion processes.Therefore content of halogen is high more, and it is obvious more to suppress effect of combustion, and promptly flame retardant effect is good more.For synthetic high bromine content epoxy vinyl ester resin; We select for use the highest high bromine content epoxy resin of amount domestic production, brominated as raw material; Like 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 are 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, bromine content is 46%～50%.
Each batching is in weight part among the embodiment.
Embodiment 1
Have at 1000ml and to drop into high bromine content EX-48 bisphenol A epoxide resin 600g, methylacrylic acid 105g, fumaric acid 11.6g in the there-necked flask of TM, whisking appliance, prolong; Resorcinol 0.35g, N, N '-xylidine 3.5g; Be warming up to 80 ℃～90 ℃, stir simultaneously, survey acid number at set intervals; Is reaction end until acid number less than 30mgKOH/g, stopped reaction.Reaction product is cooled to below 100 ℃, adds vinylbenzene 320g, stir and be cooled to room temperature, get the high bromine content epoxy vinyl ester resin.
Embodiment 2
Have at 1000ml and to drop into high bromine content EX-48 bisphenol A epoxide resin 600g, methylacrylic acid 120g, Resorcinol 0.35g in the there-necked flask of TM, whisking appliance, prolong; Tetramethyl ammonium chloride 3.5g; Be warming up to 90 ℃～100 ℃, stir simultaneously, survey acid number at set intervals; Is reaction end until acid number less than 30mgKOH/g, stopped reaction.Reaction product is cooled to below 100 ℃, adds vinylbenzene 160g, Vinyl toluene 160g stirs and is cooled to room temperature, gets the high bromine content epoxy vinyl ester resin.
Embodiment 3
Have at 1000ml and to drop into high bromine content CYDB-400 bisphenol A epoxide resin 500g, methylacrylic acid 101g, fumaric acid 11.6g in the there-necked flask of TM, whisking appliance, prolong; Methyl Pyrogentisinic Acid 0.35g, benzyltriethylammoinium chloride 3.0g is warming up to 90 ℃～100 ℃; Stir simultaneously; Surveying acid number at set intervals, is reaction end until acid number less than 30mgKOH/g, stopped reaction.Reaction product is cooled to below 100 ℃, adds vinylbenzene 350g, stir and be cooled to room temperature, get the high bromine content epoxy vinyl ester resin.
Embodiment 4
Have at 1000ml and to drop into high bromine content CYDB-400 bisphenol A epoxide resin 500g, vinylformic acid 100g, Resorcinol 0.2g in the there-necked flask of TM, whisking appliance, prolong; Tert-butyl catechol 0.15g, tetramethyl ammonium chloride 3.0g is warming up to 105 ℃～120 ℃; Stir simultaneously; Surveying acid number at set intervals, is reaction end until acid number less than 30mgKOH/g, stopped reaction.Reaction product is cooled to below 100 ℃, adds vinylbenzene 200g, Phthalic acid, diallyl ester 100g stirs and is cooled to room temperature, gets the high bromine content epoxy vinyl ester resin.
Embodiment 5
Have at 1000ml and to drop into high bromine content EX-48 bisphenol A epoxide resin 600g, methylacrylic acid 105g, fumaric acid 11.6g in the there-necked flask of TM, whisking appliance, prolong; Para benzoquinone 0.35g, benzyl dimethylammonium 3.5g is warming up to 120 ℃～130 ℃; Stir simultaneously; Surveying acid number at set intervals, is reaction end until acid number less than 30mgKOH/g, stopped reaction.Reaction product is cooled to below 100 ℃, adds vinylbenzene 280g, stir and be cooled to room temperature, get the high bromine content epoxy vinyl ester resin.
Embodiment 6
Have at 1000ml and to drop into high bromine content EX-48 bisphenol A epoxide resin 600g, methylacrylic acid 120g, Resorcinol 0.35g in the there-necked flask of TM, whisking appliance, prolong; Tetramethyl ammonium chloride 3.5g; Be warming up to 130 ℃～140 ℃, stir simultaneously, survey acid number at set intervals; Is reaction end until acid number less than 30mgKOH/g, stopped reaction.Reaction product is cooled to below 100 ℃, adds vinylbenzene 80g, stir and be cooled to room temperature, get the high bromine content epoxy vinyl ester resin.
(oxygen index is 20% to the MFE-2 vinyl ester resin that high bromine content epoxy vinyl ester resin of the present invention (bromine content >=35%) and East China University Of Science And Technology Huachang Polymer Co., Ltd are produced; 105 ℃ of heat-drawn wires) oxygen index that mixes the casting resin that (mixing by weight 3: 7) obtain mutually is 32%, 110 ℃ of heat-drawn wires.
It in the table the typical performance test data of gained resin among each embodiment.
High bromine content epoxy vinyl ester resin of the present invention adds Al (OH) according to weight ratio at 1: 1 after an amount of vinylbenzene dilution
3, obtain viscosities il
25The flame-retarded resin of＜500 mPas, the oxygen index of its casting matrix can reach 44% after solidifying.
Claims (7)
1. the compound method of a high bromine content epoxy vinyl ester resin is characterized in that may further comprise the steps:
(1) batching: each component is in weight part, 50～75 parts of high bromine content bisphenol A epoxide resins, 8～20 parts of unsaturated carboxylic acids, 0.1～1 part of catalyzer, 0.01～0.1 part of stopper;
(2) synthetic: that load weighted high bromine content bisphenol A epoxide resin, unsaturated carboxylic acid, catalyzer, stopper are dropped in the there-necked flask; Be warming up to 80～140 ℃; Stir; Survey acid number at set intervals, less than the 30mgKOH/g termination reaction, obtain the high bromine content epoxy vinyl ester until acid number;
(3) dilution: thinner is added in the flask for 10～40 parts while stirring, and be cooled to room temperature, obtain the high bromine content epoxy vinyl ester resin.
2. by the compound method of the said a kind of high bromine content epoxy vinyl ester resin of claim 1, it is characterized in that the said 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 compound method of the said a kind of high bromine content epoxy vinyl ester resin of claim 1, it is characterized in that the said unsaturated carboxylic acid of step (1) is one or both in methylacrylic acid, vinylformic acid, the fumaric acid.
4. press the compound method of the said a kind of high bromine content epoxy vinyl ester resin of claim 1; It is characterized in that the said catalyzer of step (1) is benzyldimethylamine, N, a kind of in N '-xylidine, tetramethyl ammonium chloride, benzyl trimethyl ammonium chloride, the benzyltriethylammoinium chloride.
5. by the compound method of the said a kind of high bromine content epoxy vinyl ester resin of claim 1, it is characterized in that the said stopper of step (1) is one or both in Resorcinol, tert-butyl catechol, methyl hydroquinone, the para benzoquinone.
6. by the compound method of the said a kind of high bromine content epoxy vinyl ester resin of claim 1, it is characterized in that thinner described in the step (3) is meant one or both in vinylbenzene, Vinyl toluene, TEB 3K, Phthalic acid, diallyl ester, the dicyclopentadiene acrylate.
7. by the purposes of the high bromine content epoxy vinyl ester resin of the said compound method of claim 1 preparation; It is characterized in that as the reaction-type flame-retarding additive; Mix mutually with non-flame retardant epoxy vinyl ester resin or unsaturated polyester resin with arbitrary proportion, preparation has the polymer matrix composites of fire-retardant requirement.
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| CN104479106A (en) * | 2014-12-05 | 2015-04-01 | 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 |
| CN106589313A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Unsaturated acid modified epoxy resin universal carbon fiber sizing agent, and preparation method and application thereof |
| CN106703056A (en) * | 2016-12-21 | 2017-05-24 | 中国市政工程中南设计研究总院有限公司 | Method for connecting pipelines in underwater dry environment through utilizing steel-concrete connection well |
| 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 |
| 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 |
| CN109627423A (en) * | 2018-12-07 | 2019-04-16 | 湖南普瑞迪新材料有限公司 | Flexible chain modified epoxy acrylic ester resin and preparation method thereof |
| CN111072872A (en) * | 2019-12-31 | 2020-04-28 | 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 daub 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 |
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| 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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Cited By (16)
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| CN104479106A (en) * | 2014-12-05 | 2015-04-01 | 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 |
| CN106589313A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Unsaturated acid modified epoxy resin universal carbon fiber sizing agent, and preparation method and application thereof |
| CN106703056A (en) * | 2016-12-21 | 2017-05-24 | 中国市政工程中南设计研究总院有限公司 | Method for connecting pipelines in underwater dry environment through utilizing steel-concrete connection well |
| CN106703056B (en) * | 2016-12-21 | 2019-04-19 | 中国市政工程中南设计研究总院有限公司 | It is a kind of to utilize the engineering method that pipeline connection is carried out in steel-concrete connection well under water dry environment |
| 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 |
| 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 |
| CN109627423A (en) * | 2018-12-07 | 2019-04-16 | 湖南普瑞迪新材料有限公司 | Flexible chain modified epoxy acrylic ester resin and preparation method thereof |
| CN111072872A (en) * | 2019-12-31 | 2020-04-28 | 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 daub containing same |
| 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 |
| 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 |
| CN115677948A (en) * | 2022-11-18 | 2023-02-03 | 广东热浪新材料科技有限公司 | High specific gravity transparent resin composition and method for producing particles thereof |
| 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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