阅读说明：本技术 一种含有环氧基团的磷硅协同阻燃剂及其制备方法 (A kind of phosphorus silicon synergistic fire retardant and preparation method thereof containing epoxy group ) 是由 袁福根 周国庆 杨雨蓉 于 2019-08-30 设计创作，主要内容包括：本发明提供一种含有环氧基团的磷硅协同阻燃剂,其具有如下分子结构：<Image he="455" wi="700" file="DSA0000189173480000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>含有环氧基团的磷硅协同阻燃剂的制备方法分两步：(1)以甲基三甲氧基硅烷和环氧丙醇为原料,钛酸四丁酯为催化剂,反应生成三(缩水甘油醚)甲基硅烷；(2)三(缩水甘油醚)甲基硅烷与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)以三苯磷为催化剂反应,生成含有环氧基团的磷硅协同阻燃剂。该制备工艺简单,反应条件温和,易于操作。本发明的阻燃剂含有硅、磷双重阻燃元素以及一个可反应的环氧基团。阻燃剂跟环氧树脂混和后再与固化剂混和反应,形成的阻燃环氧材料阻燃性能优异,成炭性好,且阻燃剂不会离析迁出,具有重要应用价值。(The present invention provides a kind of phosphorus silicon synergistic fire retardant containing epoxy group, with following molecular structure: The preparation method of phosphorus silicon synergistic fire retardant containing epoxy group is in two steps: (1) using methyltrimethoxysilane and epoxy prapanol as raw material, butyl titanate is catalyst, and reaction generates three (glycidol ether) methyl-monosilanes；(2) three (glycidol ether) methyl-monosilanes and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) generate the phosphorus silicon synergistic fire retardant containing epoxy group using triphen phosphorus as catalyst reaction.The preparation process is simple, and reaction condition is mild, easily operated.Fire retardant of the invention contains the dual ignition-proof element of silicon, phosphorus and a reactive epoxy group.Fire retardant is reacted with curing agent mixing again after mixing with epoxy resin, and the flame retardant epoxy Flame Retardancy of formation can be excellent, good at charcoal, and fire retardant will not be isolated and be moved out, and have significant application value.)

1. a kind of phosphorus silicon synergistic fire retardant containing epoxy group, it is characterised in that have following molecular structure:

2. a kind of phosphorus silicon synergistic fire retardant containing epoxy group according to claim 1, it is characterised in that the preparation method comprises the following steps:

The preparation of (1) three (glycidol ether) methyl-monosilane:

In the reaction flask equipped with blender, thermometer and distillation condenser pipe, methyltrimethoxysilane and ring is successively added Oxygen propyl alcohol, is then added tetrabutyl titanate catalyst, and heating and thermal insulation reaction constantly has methanol to distillate.Reaction terminates, and vacuumizes 5 Minute thorough methanol removal obtains white three (glycidol ether) methyl-monosilane solids, and molecular structure is shown below:

(2) preparation of the phosphorus silicon synergistic fire retardant containing epoxy group:

In the reaction flask equipped with blender, thermometer and reflux condensing tube, three (glycidol ether) methyl silicon are successively added Alkane and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), add triphen phosphorus catalyst, organic solvent, add Thermal response, final decompression pump solvent, obtain Chinese red solid, as the phosphorus silicon synergistic fire retardant containing epoxy group.

3. a kind of phosphorus silicon synergistic fire retardant preparation method containing epoxy group according to claim 2, it is characterised in that step Suddenly in (1), methyltrimethoxysilane and epoxy prapanol reaction mol ratio are 1: 3.

4. a kind of phosphorus silicon synergistic fire retardant preparation method containing epoxy group according to claim 2, it is characterised in that step Suddenly in (1), catalyst butyl titanate quality dosage is the 5-8% of methyltrimethoxysilane.

5. a kind of phosphorus silicon synergistic fire retardant preparation method containing epoxy group according to claim 2, it is characterised in that step Suddenly in (1), reaction temperature is at 90-105 DEG C, reaction time 2.5-3h.

6. a kind of phosphorus silicon synergistic fire retardant preparation method containing epoxy group according to claim 2, it is characterised in that step Suddenly in (2), three (glycidol ether) methyl-monosilanes and DOPO reaction mol ratio are 1: 2.

7. a kind of phosphorus silicon synergistic fire retardant preparation method containing epoxy group according to claim 2, it is characterised in that step Suddenly in (2), the quality dosage of catalyst triphen phosphorus is the 5-10% of DOPO.

8. a kind of phosphorus silicon synergistic fire retardant preparation method containing epoxy group according to claim 2, it is characterised in that step Suddenly in (2), it is one such that organic solvent can be dimethylbenzene, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, quality dosage Equal to 1.5-2 times of DOPO.

9. a kind of phosphorus silicon synergistic fire retardant preparation method containing epoxy group according to claim 2, it is characterised in that step Suddenly in (2), reaction temperature is at 120-140 DEG C, reaction time 4-6h.

Technical field

The present invention relates to flame retardant area, in particular to a kind of phosphorus silicon synergistic fire retardant containing epoxy group and its preparation Method.

Background technique

Epoxy resin has excellent mechanical performance, chemical corrosion resistance, electrical insulating property, adhesive property, processability, and And as cross-linking reaction type macromolecule, epoxy resin does not need solvent during curing molding, itself volatility is again low, uses In the process without pollution problem, therefore answered extensively in coating, adhesive, electronic package material, aerospace and automotive field With.But the limit oxygen index of epoxy resin (LOI) only has 19.8%, belongs to combustibles, there is great fire behavior in use Security risk.

In order to prepare fire-retardant epoxy resin, people in epoxy resin cure forming process first it is envisioned that be added resistance Agent is fired to improve the anti-flammability of epoxy material.Although the fire retardant kind reported at present is more, such as the resistance of phosphorus flame retardant, silicon systems Agent is fired, but these fire retardants tend to belong to addition type, that is, are blended into epoxy material by doping.Fire retardant and epoxy are high It is physical bond, inter-molecular binding force very little between molecule.During materials'use can slowly migration precipitation, this not only can be dirty It contaminates environment and uses object, and the flame retardant property of epoxy material can be made slowly to lose.

In order to prepare long-term effect fire-retardant epoxy resin, it may be considered that introduced in epoxy resin macromolecular or curing agent Ignition-proof element.For example, flood take on auspicious omen etc. report DOPO type epoxy resin preparation and flame retardant property (colloid and polymer, 2015, 33 (1): 17-19)；Patent CN109096471A reports a kind of novel P-N-Si cooperative resistance combustion epoxy curing agent.This A little methods solve the problems, such as the migration outflow of fire retardant, but are generally only applicable to the preparation of specific epoxy material, and when application has Biggish limitation.

The present invention provides a kind of phosphorus silicon synergistic fire retardant and preparation method thereof containing epoxy group, and this product not only has High efficiency flame retardance, and contain epoxy group after mixing with matrix epoxy resin, participates in carrying out crosslinking open loop with curing agent anti- It answers, is integrated in high molecular material by chemical bonding, the isolation for avoiding flame-retardant composition is moved out, upper with applicability in application Wide feature.

Summary of the invention

The purpose of the present invention is to provide a kind of the phosphorus silicon synergistic fire retardant and preparation method thereof containing epoxy group, preparation Simple process, reaction condition is mild, easily operated.

A kind of phosphorus silicon synergistic fire retardant containing epoxy group has following molecular structure:

Phosphorus silicon synergistic fire retardant containing epoxy group of the invention, preparation method are to carry out as steps described below:

The preparation of (1) three (glycidol ether) methyl-monosilane:

In the reaction flask equipped with blender, thermometer and distillation condenser pipe, methyltrimethoxysilane is successively added And epoxy prapanol, tetrabutyl titanate catalyst is then added, heating and thermal insulation reaction constantly has methanol to distillate.Reaction terminates, and takes out true Empty 5 minutes thorough methanol removals, obtain white three (glycidol ether) methyl-monosilane solids.Reaction equation is as follows:

In above-mentioned reaction, methyltrimethoxysilane and epoxy prapanol reaction mol ratio are 1: 3.

In above-mentioned reaction, catalyst butyl titanate quality dosage is the 5-8% of methyltrimethoxysilane.

In above-mentioned reaction, reaction temperature is at 90-105 DEG C, reaction time 2.5-3h.

(2) preparation of the phosphorus silicon synergistic fire retardant containing epoxy group:

In the reaction flask equipped with blender, thermometer and reflux condensing tube, three (glycidol ether) first are successively added Base silane and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), add triphen phosphorus catalyst, You Jirong Agent, heating and thermal insulation reaction, final decompression pump solvent, obtain Chinese red solid, and the phosphorus silicon as containing epoxy group cooperates with resistance Fire agent.Reaction equation is as follows:

In above-mentioned reaction, three (glycidol ether) methyl-monosilanes and DOPO reaction mol ratio are 1: 2.

In above-mentioned reaction, the quality dosage of catalyst triphen phosphorus is the 5-10% of DOPO.

In above-mentioned reaction, organic solvent can be dimethylbenzene, ethylene glycol diethyl ether, diethylene glycol dimethyl ether therein one Kind, quality dosage is equal to 1.5-2 times of DOPO.

In above-mentioned reaction, reaction temperature is at 120-140 DEG C, reaction time 4-6h.

Phosphorus silicon synergistic fire retardant containing epoxy group of the invention, can mix very well with epoxy resin, further with Epoxy hardener mixes manufactured epoxy material after reaction, and good flame resistance is good at charcoal, and fire retardant will not move in use It moves and is precipitated, therefore material has lasting flame retardant property.

Detailed description of the invention

Fig. 1 is the phosphorus silicon synergistic fire retardant molecular structure containing epoxy group

Fig. 2 is the infrared spectrogram of the phosphorus silicon synergistic fire retardant containing epoxy group

Fig. 3 is the phosphorus silicon synergistic fire retardant nuclear magnetic spectrum containing epoxy group

Specific embodiment

Illustrate the present invention below with reference to specific embodiment.It should be noted that the following examples are the present invention Example, be only used to illustrate the present invention, and be not limited to the present invention.