阅读说明：本技术 一种含氟聚苯基硅硼阻燃剂及其制备方法 (Fluorine-containing polyphenyl silicon boron flame retardant and preparation method thereof ) 是由 王启瑶 孙佳男 陈杰 马博 于 2020-12-29 设计创作，主要内容包括：本发明涉及高分子阻燃技术领域,具体涉及一种含氟聚苯基硅硼阻燃剂及其制备方法,该制备方法以苯基硅氧烷单体、含氟硅氧烷偶联剂、烷基硅氧烷偶联剂和硼酸三丙酯按特定比例混合,再在酸性条件下发生水解缩聚反应,形成的高分子聚合物具有更好的阻燃协效作用,提高阻燃效果,与聚碳酸酯的相容性、分散性更好且不易迁移,从而具有良好的长效阻燃性；该制备方法操作简单,控制方便,生产效率高,耗能更低,可用于大规模生产。(The invention relates to the technical field of high molecular flame retardance, in particular to a fluorine-containing polyphenyl silicon boron flame retardant and a preparation method thereof, wherein a phenyl siloxane monomer, a fluorine-containing siloxane coupling agent, an alkyl siloxane coupling agent and tripropyl borate are mixed according to a specific proportion in the preparation method, and then hydrolytic polycondensation reaction is carried out under an acidic condition, so that the formed high molecular polymer has better flame retardance synergistic effect, the flame retardance effect is improved, the polycarbonate has better compatibility and dispersibility and is difficult to migrate, and thus, the long-acting flame retardance is good; the preparation method has the advantages of simple operation, convenient control, high production efficiency and lower energy consumption, and can be used for large-scale production.)

1. The preparation method of the fluorine-containing polyphenyl silicon boron flame retardant is characterized by comprising the following steps:

(A1) and mixing phenyl siloxane monomer, fluorine-containing siloxane coupling agent, alkyl siloxane coupling agent and tripropyl borate according to the weight ratio of 10-60: 10-50: 10-50: 10-50, uniformly mixing to obtain a coupling agent mixed solution;

(A2) adding 20-50 parts by weight of acidic aqueous solution into 100 parts by weight of the coupling agent mixed solution while stirring, continuously stirring for 2-3h, heating to 80-90 ℃, and vacuumizing to remove impurities to obtain transparent solid resin;

(A3) and drying and crushing the transparent solid resin to obtain the fluorine-containing polyphenyl silicon boron flame retardant.

2. The preparation method of the fluorine-containing polyphenyl silicon boron flame retardant according to claim 1, characterized in that: the phenyl siloxane monomer is at least one of phenyl trimethoxy silane, methyl phenyl dimethoxy silane, vinyl phenyl dimethoxy silane and methyl diphenyl methoxy silane.

3. The preparation method of the fluorine-containing polyphenyl silicon boron flame retardant according to claim 1, characterized in that: the fluorine-containing siloxane coupling agent is at least one of tridecafluorooctyl triethoxysilane, pentadecafluorooctyl triethoxysilane and heptafluoropentyl trimethoxysilane.

4. The preparation method of the fluorine-containing polyphenyl silicon boron flame retardant according to claim 1, characterized in that: the structural formula of the alkylsiloxane coupling agent is R-Si (OR')₃Wherein R is saturated long-chain alkyl with carbon number less than 12, and R' is methylOr an ethyl group.

5. The preparation method of the fluorine-containing polyphenyl silicon boron flame retardant according to claim 1, characterized in that: the acidic aqueous solution is a sulfuric acid solution, a hydrochloric acid solution or an acetic acid solution, and the concentration of the acidic aqueous solution is 0.2-3 wt%.

6. The preparation method of the fluorine-containing polyphenyl silicon boron flame retardant according to claim 1, characterized in that: in the step (A2), the acidic aqueous solution is added in a manner of dropwise addition in an amount of 20 to 50 parts by weight for 3 hours.

7. The preparation method of the fluorine-containing polyphenyl silicon boron flame retardant according to claim 1, characterized in that: in the step (A2), the temperature is raised to 30-60 ℃ before 20-50 parts by weight of the acidic aqueous solution is added.

8. The preparation method of the fluorine-containing polyphenyl silicon boron flame retardant according to claim 1, characterized in that: in the step (A2), the stirring speed is 500-800 rpm.

9. A fluorine-containing polyphenyl silicon boron flame retardant is characterized in that: prepared by the method for preparing the fluorine-containing polyphenyl silicon boron flame retardant according to any one of claims 1 to 8.

10. The fluorine-containing polyphenyl silicon boron flame retardant according to claim 9, characterized in that: the fluorine-containing polyphenyl silicon boron flame retardant is used in a polycarbonate flame-retardant modified material.

Technical Field

The invention relates to the technical field of high polymer flame retardance, and particularly relates to a fluorine-containing polyphenyl silicon boron flame retardant and a preparation method thereof.

Background

The development of highly effective flame retardants for thermoplastics and thermosets is a great demand for many industrial applications, and silicone-based flame retardants are an important area of development. However, the addition amount is high, and the flame retardant efficiency is insufficient.

The potassium perfluorobutylsulfonate is a commonly used flame retardant for polycarbonate, is usually added into PC independently, is too low in addition amount, is not easy to disperse uniformly, is easy to migrate due to small molecular weight, and is poor in flame retardant long-acting property.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the preparation method of the fluorine-containing polyphenyl silicon boron flame retardant, wherein a phenyl siloxane monomer, a fluorine-containing siloxane coupling agent, an alkyl siloxane coupling agent and tripropyl borate are mixed according to a specific proportion, and then a hydrolytic polycondensation reaction is carried out under an acidic condition, so that the formed high molecular polymer has a better flame-retardant synergistic effect, the flame-retardant effect is improved, the polycarbonate has better compatibility and dispersibility and is difficult to migrate, and thus, the long-acting flame-retardant property is good; the preparation method has the advantages of simple operation, convenient control, high production efficiency and lower energy consumption, and can be used for large-scale production.

The invention also aims to provide a fluorine-containing polyphenyl silicon boron flame retardant, which has better synergistic effect through the synergistic flame retardant effect of fluorine, boron and silicon copolymer, and the PC adopting the fluorine-containing polyphenyl silicon boron flame retardant has the advantages of obviously improved flame retardant level, slowed combustion, obviously reduced total heat release amount and average effective combustion heat and obviously increased ignition time.

The purpose of the invention is realized by the following technical scheme: a preparation method of a fluorine-containing polyphenyl silicon boron flame retardant comprises the following steps:

(A1) and mixing phenyl siloxane monomer, fluorine-containing siloxane coupling agent, alkyl siloxane coupling agent and tripropyl borate according to the weight ratio of 10-60: 10-50: 10-50: 10-50, uniformly mixing to obtain a coupling agent mixed solution;

(A2) adding 20-50 parts by weight of acidic aqueous solution into 100 parts by weight of the coupling agent mixed solution while stirring, continuously stirring for 2-3h, heating to 80-90 ℃, and vacuumizing to remove impurities to obtain transparent solid resin;

(A3) and drying and crushing the transparent solid resin to obtain the fluorine-containing polyphenyl silicon boron flame retardant.

According to the preparation method of the fluorine-containing polyphenyl silicon boron flame retardant, a phenyl siloxane monomer, a fluorine-containing siloxane coupling agent, an alkyl siloxane coupling agent and tripropyl borate are mixed according to a specific proportion, and then hydrolytic polycondensation reaction is carried out under an acidic condition, so that the formed high polymer has a better flame retardant synergistic effect, the flame retardant effect is improved, the high polymer has better compatibility and dispersibility with polycarbonate and is not easy to migrate, and thus, the long-acting flame retardant is good; the addition amount of the fluorine-containing polyphenyl silicon boron flame retardant is only 0.1-3% of the total mass of the polycarbonate, and the flame retardant effect is excellent; the preparation method has the advantages of simple operation, convenient control, high production efficiency and lower energy consumption, and can be used for large-scale production. Wherein, in the step (A1), the phenyl siloxane monomer, the fluorine-containing siloxane coupling agent, the alkyl siloxane coupling agent and the tripropyl borate are mixed according to a specific weight ratio, so that the excellent synergistic effect is achieved; preferably, the phenyl siloxane monomer, the fluorine-containing siloxane coupling agent, the alkyl siloxane coupling agent and the tripropyl borate are mixed in a weight ratio of 30-60: 20-50: 20-50: 20-50, if not, tend to cause deterioration of the synergistic effect and adversely affect the mechanical properties of PC.

Preferably, the phenyl siloxane monomer is at least one of phenyl trimethoxysilane, methyl phenyl dimethoxysilane, vinyl phenyl dimethoxysilane and methyl diphenyl methoxysilane.

By adopting the technical scheme, the specific phenyl siloxane monomer is adopted to provide better compatibility with PC for the fluorine-containing polyphenyl silicon boron flame retardant, the phenomenon that the flame retardant effect is deteriorated due to migration in the use process of the fluorine-containing polyphenyl silicon boron flame retardant is further avoided, and carbon formation is easier during combustion due to the existence of phenyl, so that the flame retardant effect is improved.

Preferably, the fluorine-containing siloxane coupling agent is at least one of tridecafluorooctyltriethoxysilane, pentadecafluorooctyltriethoxysilane and heptafluoropentyltrimethoxysilane.

By adopting the technical scheme, the formed fluorine-containing polyphenyl silicon boron flame retardant has the characteristic of low surface energy, and when PC is combusted, the fluorine-containing polyphenyl silicon boron flame retardant tends to form a flame-retardant protective layer on the surface of the PC, so that the flame-retardant effect is improved.

Preferably, the alkylsiloxane coupling agent has the formula R-Si (OR')₃Wherein R is saturated long-chain alkyl with the carbon number less than 12, and R' is methyl or ethyl.

By adopting the technical scheme, the specific alkyl siloxane coupling agent is adopted to provide better compatibility with PC (polycarbonate) for the fluorine-containing polyphenyl silicon boron flame retardant, and more preferably, the alkyl siloxane coupling agent is at least one of methyl trimethoxy silane, methyl triethoxy silane, phenyl triethoxy silane and octyl trimethoxy silane.

Preferably, the acidic aqueous solution is a sulfuric acid solution, a hydrochloric acid solution or an acetic acid solution, and the concentration of the acidic aqueous solution is 0.2-3 wt%.

By adopting the technical scheme, the hydrolysis polycondensation reaction of the coupling agent mixed solution is promoted under the conditions, the formed high molecular polymer has better flame retardant synergistic effect, the flame retardant effect is improved, the compatibility and the dispersibility with polycarbonate are better, and the migration is not easy, so that the long-acting flame retardant property is good.

Preferably, in the step (a2), the acidic aqueous solution is added in a manner of dropping in an amount of 20 to 50 parts by weight for 3 hours.

By adopting the technical scheme, the mixed solution of the coupling agent and the acidic aqueous solution is promoted to be mixed and pre-polymerized, the yield of the fluorine-containing polyphenyl silicon boron flame retardant is improved, and the performance reduction of the product caused by too fast reaction is avoided.

Preferably, in the step (A2), the temperature is raised to 30-60 ℃ before 20-50 parts by weight of the acidic aqueous solution is added.

By adopting the technical scheme, the mixed solution of the coupling agent and the acidic aqueous solution is promoted to be mixed and pre-polymerized, the yield of the fluorine-containing polyphenyl silicon boron flame retardant is improved, and the performance reduction of the product caused by the over-fast reaction is avoided by combining a dripping mode.

Preferably, in the step (A2), the rotation speed of stirring is 500-800 rpm.

By adopting the technical scheme, the mixed solution of the coupling agent and the acidic aqueous solution is promoted to be mixed and prepolymerized, and the yield of the fluorine-containing polyphenyl silicon boron flame retardant is improved.

The other purpose of the invention is realized by the following technical scheme: a fluorine-containing polyphenyl silicon boron flame retardant is prepared by adopting the preparation method of the fluorine-containing polyphenyl silicon boron flame retardant.

Preferably, the fluorine-containing polyphenyl silicon boron flame retardant is used in the polycarbonate flame-retardant modified material.

The invention has the beneficial effects that: according to the preparation method of the fluorine-containing polyphenyl silicon boron flame retardant, the phenyl siloxane monomer, the fluorine-containing siloxane coupling agent, the alkyl siloxane coupling agent and the tripropyl borate are mixed according to a specific proportion, and then hydrolytic polycondensation reaction is carried out under an acidic condition, so that the formed high polymer has a better flame retardant synergistic effect, the flame retardant effect is improved, the high polymer has better compatibility and dispersibility with polycarbonate and is not easy to migrate, and therefore, the long-acting flame retardant is good; the preparation method has the advantages of simple operation, convenient control, high production efficiency and lower energy consumption, and can be used for large-scale production.

The fluorine-containing polyphenyl silicon boron flame retardant has better synergistic effect through the synergistic flame retardant effect of fluorine, boron and silicon copolymer, the flame retardant grade of PC adopting the fluorine-containing polyphenyl silicon boron flame retardant is obviously improved, the combustion is slowed, the total heat release amount and the average effective combustion heat are obviously reduced, and the ignition time is obviously increased.

Detailed Description

The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.

Example 1

A preparation method of a fluorine-containing polyphenyl silicon boron flame retardant comprises the following steps:

(A1) and mixing phenyl siloxane monomer, fluorine-containing siloxane coupling agent, alkyl siloxane coupling agent and tripropyl borate according to the weight ratio of 45: 35: 35: 35, uniformly mixing to obtain a coupling agent mixed solution;

(A2) heating the coupling agent mixed solution to 45 ℃, dropwise adding 35 parts by weight of acidic aqueous solution into 100 parts by weight of the coupling agent mixed solution while stirring, keeping the dropwise adding time for 3 hours, continuously stirring for 2.5 hours, heating to 85 ℃, and vacuumizing to remove impurities to obtain transparent solid resin;

(A3) and drying and crushing the transparent solid resin, and sieving with a 800-mesh sieve to obtain the fluorine-containing polyphenyl silicon boron flame retardant.

The phenyl siloxane monomer is formed by mixing phenyl trimethoxy silane and vinyl phenyl dimethoxy silane according to the weight ratio of 2: 1.

The fluorine-containing siloxane coupling agent is tridecafluorooctyltriethoxysilane.

The alkyl siloxane coupling agent is methyl trimethoxy silane.

The acidic aqueous solution is hydrochloric acid, and the concentration of the acidic aqueous solution is 2 wt%.

In the step (A2), the stirring speed is 600 rpm.

Example 2

A preparation method of a fluorine-containing polyphenyl silicon boron flame retardant comprises the following steps:

(A1) and mixing phenyl siloxane monomer, fluorine-containing siloxane coupling agent, alkyl siloxane coupling agent and tripropyl borate according to the weight ratio of 30: 20: 20: 20, uniformly mixing to obtain a coupling agent mixed solution;

(A2) heating the coupling agent mixed solution to 30 ℃, dropwise adding 20 parts by weight of acidic aqueous solution into 100 parts by weight of the coupling agent mixed solution while stirring, keeping the dropwise adding time for 3 hours, continuously stirring for 2 hours, heating to 80 ℃, and vacuumizing to remove impurities to obtain transparent solid resin;

(A3) and drying and crushing the transparent solid resin, and sieving with a 800-mesh sieve to obtain the fluorine-containing polyphenyl silicon boron flame retardant.

The phenyl siloxane monomer is methyl phenyl dimethoxy silane.

The fluorine-containing siloxane coupling agent is pentadecafluorooctyl triethoxysilane.

The alkyl siloxane coupling agent is methyl triethoxysilane.

The acidic aqueous solution is a sulfuric acid solution, and the concentration of the acidic aqueous solution is 0.2 wt%.

In the step (A2), the stirring speed is 500 rpm.

Example 3

A preparation method of a fluorine-containing polyphenyl silicon boron flame retardant comprises the following steps:

(A1) and mixing phenyl siloxane monomer, fluorine-containing siloxane coupling agent, alkyl siloxane coupling agent and tripropyl borate according to the weight ratio of 60: 50: 50: 50, uniformly mixing to obtain a coupling agent mixed solution;

(A2) heating the coupling agent mixed solution to 60 ℃, dropwise adding 50 parts by weight of acidic aqueous solution into 100 parts by weight of the coupling agent mixed solution while stirring, keeping the dropwise adding time for 3 hours, continuously stirring for 3 hours, heating to 90 ℃, and vacuumizing to remove impurities to obtain transparent solid resin;

(A3) and drying and crushing the transparent solid resin, and sieving with a 800-mesh sieve to obtain the fluorine-containing polyphenyl silicon boron flame retardant.

The phenyl siloxane monomer is methyl diphenyl methoxy silane.

The fluorine-containing siloxane coupling agent is heptafluoropentyltrimethoxysilane.

The alkyl siloxane coupling agent is octyl trimethoxy silane.

The acidic aqueous solution is an acetic acid solution, and the concentration of the acidic aqueous solution is 3 wt%.

In the step (A2), the stirring speed is 800 rpm.

Example 4

A preparation method of a fluorine-containing polyphenyl silicon boron flame retardant comprises the following steps:

(A1) and mixing phenyl siloxane monomer, fluorine-containing siloxane coupling agent, alkyl siloxane coupling agent and tripropyl borate according to the weight ratio of 50: 30: 40: 30, uniformly mixing to obtain a coupling agent mixed solution;

(A2) heating the coupling agent mixed solution to 50 ℃, dropwise adding 30 parts by weight of acidic aqueous solution into 100 parts by weight of the coupling agent mixed solution while stirring, keeping the dropwise adding time for 3 hours, continuously stirring for 2.8 hours, heating to 88 ℃, and vacuumizing to remove impurities to obtain transparent solid resin;

(A3) and drying and crushing the transparent solid resin, and sieving with a 800-mesh sieve to obtain the fluorine-containing polyphenyl silicon boron flame retardant.

The phenyl siloxane monomer is phenyl trimethoxy silane.

The fluorine-containing siloxane coupling agent is tridecafluorooctyltriethoxysilane.

The alkyl siloxane coupling agent is methyl trimethoxy silane.

The acidic aqueous solution is hydrochloric acid, and the concentration of the acidic aqueous solution is 1 wt%.

In the step (A2), the stirring speed is 600 rpm.

Comparative example 1

This comparative example differs from example 1 in that:

the phenyl siloxane monomer, the fluorine-containing siloxane coupling agent, the alkyl siloxane coupling agent and the tripropyl borate are mixed according to the weight ratio of 20: 60: 60: 10, and mixing.

Comparative example 2

This comparative example differs from example 1 in that:

the acidic aqueous solution was replaced with a sodium hydroxide solution having a concentration of 2 wt%.

Comparative example 3

This comparative example differs from example 1 in that:

the step (A2) is to add the acidic aqueous solution directly at normal temperature.

Comparative example 4

This comparative example differs from example 1 in that:

the fluorine-containing polyphenyl silicon boron flame retardant does not contain a fluorine-containing siloxane coupling agent.

Comparative example 5

A flame retardant is potassium perfluorobutylsulfonate.

Example 5

Taking the flame retardants of the examples 1-4 and the comparative examples 1-5, combining the following raw materials, and performing melt extrusion granulation at the temperature of 300 ℃ by a double-screw extruder to prepare the flame-retardant modified PC materials of each group:

the flame-retardant modified PC materials of the experimental groups 1-8 and the comparative groups 1-10 are adopted to carry out the tests of flame retardance, long-acting flame retardance, limiting oxygen index, tensile strength, bending modulus and impact strength, and the test method is as follows:

flame retardancy: testing the flame retardant rating of 1.6mm according to UL-94 standard;

long-acting flame retardance: after heat treatment for 30 days at 60 ℃, testing the flame retardant rating of 1.6mm according to UL-94 standard;

limiting oxygen index: testing was performed according to ASTM D2863 in%;

tensile strength: preparing a class I sample according to the specification of ASTM-D638, testing the tensile strength of the class I sample at a tensile speed of 20mm/min in MPa;

bending strength: testing was performed according to ASTM D790, with a bending speed of 1.25mm/min in MPa;

flexural modulus: testing was performed according to ASTM D790, with a bending speed of 1.25mm/min in MPa;

impact strength: according to the regulations of GB/T1843-2008, the notch impact strength of the A-type notch is respectively tested under the normal temperature condition, and the unit is KJ/m²；

The test results are shown in the following table:

as can be seen from the table above, the flame retardant level of the PC adopting the fluorine-containing polyphenyl silicon boron flame retardant is obviously improved, the combustion is slowed down, the total heat release amount and the average effective combustion heat are obviously reduced, the ignition time is obviously increased, and the mechanical property is not greatly influenced.

The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.