阅读说明：本技术 一种四溴双酚a双烯丙基醚-苯乙烯共聚阻燃剂及其制备方法 (Tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant and preparation method thereof ) 是由 郭建树 赵震 王盛海 于 2020-07-02 设计创作，主要内容包括：本发明公开了一种四溴双酚A双烯丙基醚-苯乙烯共聚阻燃剂及其制备方法,其制备方法是：一种四溴双酚A双烯丙基醚-苯乙烯共聚阻燃剂的制备方法,其特征在于：在反应器中,加入二甲苯、四溴双酚A双烯丙基醚和引发剂,加热至反应温度,滴加苯乙烯,滴加完毕后,在反应温度下反应,反应结束后冷却,并将产物进行醇析,真空过滤,滤饼洗剂、干燥至恒重,得产品。本发明的四溴双酚A双烯丙基醚-苯乙烯共聚阻燃剂:分子量适中、流动性好、在PS中不易析出。(The invention discloses a tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant and a preparation method thereof, wherein the preparation method comprises the following steps: a preparation method of tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant is characterized by comprising the following steps: adding dimethylbenzene, tetrabromobisphenol A diallyl ether and an initiator into a reactor, heating to a reaction temperature, dropwise adding styrene, reacting at the reaction temperature after dropwise adding, cooling after the reaction is finished, performing alcohol precipitation on a product, performing vacuum filtration, and drying a filter cake lotion to constant weight to obtain the product. The tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant has moderate molecular weight and good fluidity and is not easy to precipitate in PS.)

1. A preparation method of tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant is characterized by comprising the following steps: adding dimethylbenzene, tetrabromobisphenol A diallyl ether and an initiator into a reactor, heating to a reaction temperature, dropwise adding styrene, reacting at the reaction temperature after dropwise adding, cooling after the reaction is finished, performing alcohol precipitation on a product, performing vacuum filtration, and drying a filter cake lotion to constant weight to obtain the product.

2. The method for preparing tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant according to claim 1, wherein the method comprises the following steps: the initiator is a peroxide initiator and an azo initiator; the mass ratio of tetrabromobisphenol A diallyl ether to the initiator is 1: 0.03-0.3.

3. The method for preparing tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant according to claim 1, wherein the method comprises the following steps: the mol ratio of the tetrabromobisphenol A diallyl ether to the styrene is 1: 6-125.

4. The method for preparing tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant according to claim 1, wherein the method comprises the following steps: the mass ratio of the tetrabromobisphenol A diallyl ether to the dimethylbenzene is 1: 2-10.

5. The method for preparing tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant according to claim 2, wherein the method comprises the following steps: the peroxide initiator is cumene hydroperoxide or dibenzoyl peroxide; the azo initiator is one of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, azodiisopropyl imidazoline hydrochloride and azodiisobutyl amidine dihydrochloride.

6. The method for preparing tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant according to claim 1, wherein the method comprises the following steps: the reaction temperature is 60-130 ℃; the reaction time is 4-8 h.

7. The method for preparing tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant according to claim 1, wherein the method comprises the following steps: and (3) cooling: cooling to 50-60 deg.C; and (3) drying: the drying temperature is 105-110 ℃.

8. The method for preparing tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant according to claim 1, wherein the method comprises the following steps: the alcohol precipitation: the reaction product was added dropwise to ethanol.

9. The method for preparing tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant according to claim 1, wherein the method comprises the following steps: the filter cake lotion comprises: the filter cake is washed 1-2 times with ethanol.

10. The method for preparing tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant according to claim 1, wherein the method comprises the following steps:

molecular weight M of tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant_W2388-5332, bromine content of 19-30%, and carbon-carbon unsaturated bond content of 0.05-0.08%.

Technical Field

The invention relates to the technical field of foam material flame retardance, in particular to a tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant and a preparation method thereof.

Background

Polystyrene (PS) foam is widely used in the fields of buildings, instruments, home appliances, automobiles, furniture, etc. because of its excellent heat insulation and earthquake resistance, but its flammability limits its application with the national improvement of fire safety requirements, and thus, it is required to perform flame retardant treatment. The addition of flame retardants is the most effective flame retardant treatment method for PS foams.

Hexabromocyclododecane (HBCD) has been widely used for PS foam flame retardancy, but due to its high toxicity, durability, bioaccumulation and easy precipitation, it is required to be banned globally in the united nations stockholm convention on persistent organic pollutants in 5 months in 2013, and china also decides to completely stop using HBCD 31 days 12 and 31 months in 2021. Flame retardants such as tetrabromobisphenol A-bis (2, 3-dibromo-2-methylpropyl) ether, tetrabromobisphenol A-bis (2, 3-dibromopropyl) ether, tris (2, 3-dibromopropyl) isocyanurate and the like also belong to small molecule compound flame retardants, and the small molecule flame retardants are easy to migrate and precipitate between PS molecular chain segments.

Patent CN201210265495.1 provides a microencapsulated tetrabromobisphenol A bis (allyl) ether flame retardant and application thereof, belonging to the field of high polymer materials. The microencapsulated flame retardant takes tetrabromobisphenol A bis (allyl) ether as a capsule core and thermosetting amino resin with flame retardant synergistic effect as a capsule wall material. After microencapsulation, the melting temperature of tetrabromobisphenol A bis (allyl) ether is increased from 115-120 ℃ to above 175 ℃, and the initial acid release temperature is increased from 120 ℃ to above 170 ℃. The invention is economical and simple, and under the condition of little flame retardant increment, the flame retardant material passes the B-level test standard of building materials, the oxygen index reaches more than 26.0 percent, and the hexabromocyclododecane can be completely or partially substituted for flame retardant modification of polystyrene extrusion molding foaming plates.

Although the brominated styrene-butadiene-styrene block polymer produced by Langsheng company is a high molecular polymer type flame retardant, the weight average molecular weight is up to 16 ten thousand, and the excessively high molecular weight affects the fluidity thereof, so that the problems of high viscosity and difficult dispersion are caused, and when the flame retardant XPS extruded sheet of the brominated styrene-butadiene-styrene block polymer is used, the phenomenon that the surface collapse affects the foaming is easily caused when the extrusion thickness exceeds 5 cm.

Disclosure of Invention

Aiming at the technical problems, the invention provides a tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant and a preparation method thereof, and the following aims are achieved: when the flame retardant is applied to PS foaming, the flame retardant has good dispersibility, is not easy to precipitate, has good fluidity and does not influence the PS foaming.

The preparation method of the tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant comprises the following steps:

a preparation method of tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant is characterized by comprising the following steps: adding dimethylbenzene, tetrabromobisphenol A diallyl ether and an initiator into a reactor, heating to a reaction temperature, dropwise adding styrene, reacting at the reaction temperature after dropwise adding, cooling after the reaction is finished, performing alcohol precipitation on a product, performing vacuum filtration, and drying a filter cake lotion to constant weight to obtain the product.

The initiator is a peroxide initiator and an azo initiator; the mass ratio of tetrabromobisphenol A diallyl ether to the initiator is 1: 0.03-0.3.

The mol ratio of the tetrabromobisphenol A diallyl ether to the styrene is 1: 6-125.

The mass ratio of the tetrabromobisphenol A diallyl ether to the dimethylbenzene is 1: 2-10.

The peroxide initiator is cumene hydroperoxide or dibenzoyl peroxide; the azo initiator is one of azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, azodiisopropyl imidazoline hydrochloride and azodiisobutyl amidine dihydrochloride.

The reaction temperature is 60-130 ℃; the reaction time is 4-8 h.

And (3) cooling: cooling to 50-60 deg.C.

The alcohol precipitation: the reaction product was added dropwise to ethanol.

The filter cake lotion comprises: the filter cake is washed 1-2 times with ethanol.

And (3) drying: the drying temperature is 105-110 ℃.

The invention leads tetrabromobisphenol A diallyl ether monomer to react with an initiator to generate free radicals, then styrene is dripped into the free radicals, and the styrene monomer is polymerized and grown along two ends of tetrabromobisphenol A diallyl ether molecules by utilizing the difference of reactivity ratios. The synthesis principle is as follows:

by adopting the technical scheme, the invention achieves the following beneficial effects:

the tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant is added into GPPS-535, so that the flame retardant property and the fluidity are good, and the flame retardant property reaches B1 level; and is resistant to precipitation. The preparation method has the product yield of 98-99.5 percent and the molecular weight M of the tetrabromobisphenol A diallyl ether-styrene copolymerization flame retardant_W2388-5332, bromine content of 19-30%, and carbon-carbon unsaturated bond content of 0.05-0.08%.

Drawings

FIG. 1 is a Gel Permeation (GPC) spectrum of tetrabromobisphenol A diallyl ether-styrene copolymerized flame retardant obtained in example 1 of the present invention;

FIG. 2 is a Gel Permeation (GPC) spectrum of tetrabromobisphenol A diallyl ether-styrene copolymerized flame retardant obtained in example 2 of the present invention;

FIG. 3 is a Gel Permeation (GPC) spectrum of tetrabromobisphenol A diallyl ether-styrene copolymerized flame retardant obtained in example 3 of the present invention.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.