阅读说明：本技术 一种无卤阻燃剂可发性聚苯乙烯颗粒及其制备方法 (Halogen-free flame retardant expandable polystyrene particles and preparation method thereof ) 是由 王长军 王昶 张彬 高明 黄卫东 刘森 于 2019-11-29 设计创作，主要内容包括：本发明公开了一种无卤阻燃剂可发性聚苯乙烯颗粒,按照重量份计算,由以下组分混合制备而成：苯乙烯100份,石墨2.0～5.5份,水200～400份,阻燃剂6～10份,引发剂0.50～0.70份,成核剂1.5～2.5份,增塑剂0.6～1.5份,发泡剂6～9份,分散剂0.2～1.0份,乳化剂0.05～0.10,阻燃协效剂0.2～0.8份；本发明生产的聚苯乙烯颗粒极限氧指数高,导热系数低,保温阻燃效果好,采用磷系阻燃剂替代传统卤素类阻燃剂,磷系阻燃剂在燃烧时产生磷酸液态膜覆盖聚合物表面,在燃烧时发烟量小,燃烧不产生有毒或腐蚀性气体,安全系数高,符合相关环保要求。(The invention discloses halogen-free flame retardant expandable polystyrene particles which are prepared by mixing the following components in parts by weight: 100 parts of styrene, 2.0-5.5 parts of graphite, 200-400 parts of water, 6-10 parts of a flame retardant, 0.50-0.70 part of an initiator, 1.5-2.5 parts of a nucleating agent, 0.6-1.5 parts of a plasticizer, 6-9 parts of a foaming agent, 0.2-1.0 part of a dispersing agent, 0.05-0.10 part of an emulsifier and 0.2-0.8 part of a flame retardant synergist; the polystyrene particles produced by the invention have high limited oxygen index, low heat conductivity coefficient and good heat-insulating and flame-retardant effects, the phosphorus flame retardant is adopted to replace the traditional halogen flame retardant, the phosphorus flame retardant generates a phosphoric acid liquid film to cover the surface of the polymer during combustion, the smoke quantity is small during combustion, no toxic or corrosive gas is generated during combustion, the safety coefficient is high, and the related environmental protection requirements are met.)

1. The halogen-free flame retardant expandable polystyrene particle is characterized by being prepared by mixing the following components in parts by weight: 100 parts of styrene, 2.0-5.5 parts of graphite, 200-400 parts of water, 6-10 parts of a flame retardant, 0.50-0.70 part of an initiator, 1.5-2.5 parts of a nucleating agent, 0.6-1.5 parts of a plasticizer, 6-9 parts of a foaming agent, 0.2-1.0 part of a dispersing agent, 0.05-0.10 part of an emulsifier and 0.2-0.8 part of a flame retardant synergist;

the flame retardant is one or a combination of phosphorus oxychloride, resorcinol (diphenyl) phosphate, hydroquinone bis (diphenyl) phosphate (HDP), resorcinol tetraphenyl diphosphate, triphenyl thiophosphate isocyanate or polyphosphate;

the initiator is benzoyl peroxide or dibenzoyl peroxide;

the nucleating agent is phenolic resin or polyethylene wax;

the plasticizer is rape oil fatty acid alkanolamide boric acid ester or castor oil polyoxyethylene ether or the mixture of the rape oil fatty acid alkanolamide boric acid ester and the castor oil polyoxyethylene ether according to the proportion;

the dispersing agent is at least one of active calcium carbonate, calcium phosphate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, hydroxyethyl cellulose, sodium polymethacrylate, hydroxypropyl methyl cellulose, sodium tripolyphosphate and anhydrous sodium sulfate;

the foaming agent is pentane, butane or heptane, the emulsifier is calcium dodecyl benzene sulfonate (SDBSO), and the flame-retardant synergist is silicon dioxide or polysiloxane resin.

2. The halogen-free flame retardant expandable polystyrene particles according to claim 1, characterized by comprising the following components in parts by weight:

100 parts of styrene, 4.5 parts of graphite, 320 parts of water, 8.5 parts of a flame retardant, 0.60 part of an initiator, 2.1 parts of a nucleating agent, 1.2 parts of a plasticizer, 8 parts of a foaming agent, 0.65 part of a dispersant, 0.08 part of an emulsifier and 0.6 part of a flame retardant synergist;

the flame retardant is hydroquinone bis (diphenyl) phosphate (HDP), the initiator is benzoyl peroxide, the nucleating agent is polyethylene wax, the plasticizer is castor oil polyoxyethylene ether, the dispersing agent is polyvinyl alcohol, the foaming agent is pentane, specifically at least one of n-pentane, isopentane and neopentane, and the flame retardant synergist is silicon dioxide.

3. The halogen-free flame retardant expandable polystyrene particles according to claim 2, characterized in that: the foaming agent is a combination of n-pentane and neopentane, and the combination ratio is 3: 2.

4. The method for preparing halogen-free flame retardant expandable polystyrene particles according to any one of claims 1 to 3, characterized by comprising the steps of:

A. adding 100 parts of styrene, 6-10 parts of flame retardant, 0.2-0.8 part of flame retardant synergist, 2.0-5.5 parts of graphite and 0.05-0.1 part of emulsifier into a reaction kettle in sequence, and stirring for 0.5-1 h to prepare flame retardant styrene slurry;

B. adding 200-400 parts of water and 0.2-1 part of dispersing agent into a reaction kettle, mixing and stirring for 15-30 min to obtain a water system matrix, adding the flame-retardant styrene slurry prepared in the step A, and mixing and stirring for 2.5-8.5 h;

C. introducing high-temperature steam into the reaction kettle, heating to 50-55 ℃ at the speed of 0.5-1.0 ℃/min, adding 1.5-2.5 parts of nucleating agent, 0.6-1.5 parts of plasticizer and 0.5-1.0 part of initiator, continuously stirring, continuously heating to 88.5-89.5 ℃, carrying out low-temperature granulation reaction, and keeping the temperature for low-temperature granulation for 5.5-6 hours;

D. after low-temperature granulation is finished, 6-9 parts of foaming agent are added, the temperature is raised to 120.5-122.5 ℃ at the speed of 0.5-0.7 ℃/min to carry out high-temperature reaction, the constant temperature time of the high-temperature reaction is 4.5-5.5 hours, and the pressure is kept between 0.45-0.65 MP;

E. after foaming, the polystyrene particles are prepared by washing, drying, screening, coating, vibrating and packaging.

Technical Field

The invention relates to the technical field of foamed plastics, in particular to modified foamed polystyrene particles and a preparation method thereof.

Background

Expandable Polystyrene (EPS) is an important building thermal insulation material, and along with the gradual enhancement of environmental protection and safety awareness of people, people have higher and higher requirements on the flame retardant property of the thermal insulation material. In the aspect of heat conductivity coefficient, the material with the lowest heat conductivity coefficient is researched to be a graphite material, and the lowest heat conductivity coefficient can reach 0.033W/(m.K). According to the national standard GB/T29906-2013 'molded polyphenyl plate thin plastered external thermal insulation system material', the 039-grade thermal conductivity coefficient is less than or equal to 0.039W/(m.K), and the 032-grade thermal conductivity coefficient is less than or equal to 0.032W/(m.K), and the graphite material with the lowest thermal conductivity coefficient can hardly reach 032 grade; in the aspect of flame retardant performance, the combustion grade of the building material is divided into seven grades of A1, A2 and B, C, D, E, F according to GB8624-2006 building material combustion performance grading, at present, EPS molding polystyrene board for building heat preservation can reach grade B, the ignition point of graphite is 2000 ℃, and thus the flame retardant effect can be achieved by adding graphite, but the grade B1 is difficult to achieve, so that a flame retardant and some auxiliary materials are needed to further improve the flame retardant and heat insulation effects when preparing the polystyrene material.

At present, EPS is used as a high polymer material, most of halogen is used as a flame retardant, a halogen compound releases a large amount of toxic harmful gas hydrogen halide when the material is combusted, hydrohalic acid formed by the gas absorbing moisture in air has a strong corrosion effect to cause secondary pollution, statistics shows that 90% of death reasons are that people lose escape opportunities due to asphyxia and coma caused by strong and even toxic smoke generated during combustion when fire occurs, and therefore, research on halogen-free flame retardant EPS which generates small smoke amount during combustion and does not generate toxic and corrosive gases is very necessary.

Disclosure of Invention

Aiming at the technical problems, the invention provides halogen-free flame retardant expandable polystyrene particles and a preparation method thereof.

In order to achieve the purpose, the invention adopts the technical scheme that:

the halogen-free flame retardant expandable polystyrene particles are prepared by mixing the following components in parts by weight: 100 parts of styrene, 2.0-5.5 parts of graphite, 200-400 parts of water, 6-10 parts of a flame retardant, 0.50-0.70 part of an initiator, 1.5-2.5 parts of a nucleating agent, 0.6-1.5 parts of a plasticizer, 6-9 parts of a foaming agent, 0.2-1.0 part of a dispersing agent, 0.05-0.10 part of an emulsifier and 0.2-0.8 part of a flame retardant synergist;

the flame retardant is one or a combination of phosphorus oxychloride, resorcinol (diphenyl) phosphate, hydroquinone bis (diphenyl) phosphate (HDP), resorcinol tetraphenyl diphosphate, triphenyl thiophosphate isocyanate or polyphosphate;

the initiator is benzoyl peroxide or dibenzoyl peroxide;

the nucleating agent is phenolic resin or polyethylene wax;

the plasticizer is rape oil fatty acid alkanolamide boric acid ester or castor oil polyoxyethylene ether or the mixture of the rape oil fatty acid alkanolamide boric acid ester and the castor oil polyoxyethylene ether according to the proportion;

the dispersing agent is at least one of active calcium carbonate, calcium phosphate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, hydroxyethyl cellulose, sodium polymethacrylate, hydroxypropyl methyl cellulose, sodium tripolyphosphate and anhydrous sodium sulfate;

the foaming agent is pentane, butane or heptane, the emulsifier is calcium dodecyl benzene sulfonate (SDBSO), and the flame-retardant synergist is silicon dioxide or polysiloxane resin.

Further, the halogen-free flame retardant expandable polystyrene particles comprise the following components in parts by weight:

100 parts of styrene, 4.5 parts of graphite, 320 parts of water, 8.5 parts of a flame retardant, 0.60 part of an initiator, 2.1 parts of a nucleating agent, 1.2 parts of a plasticizer, 8 parts of a foaming agent, 0.65 part of a dispersant, 0.08 part of an emulsifier and 0.6 part of a flame retardant synergist;

the flame retardant is hydroquinone bis (diphenyl) phosphate (HDP), the initiator is benzoyl peroxide, the nucleating agent is polyethylene wax, the plasticizer is castor oil polyoxyethylene ether, the dispersing agent is polyvinyl alcohol, the foaming agent is pentane, specifically at least one of n-pentane, isopentane and neopentane, and the flame retardant synergist is silicon dioxide.

Further, the foaming agent is the combination of n-pentane and neopentane in a ratio of 3: 2.

A preparation method of halogen-free flame retardant expandable polystyrene particles comprises the following steps:

A. sequentially adding 100 parts of styrene, 6-10 parts of flame retardant, 0.2-0.8 part of flame retardant synergist, 0.05-0.1 part of emulsifier and 2.0-5.5 parts of graphite into a reaction kettle, and stirring for 0.5-1 h to prepare flame retardant styrene slurry;

B. adding 200-400 parts of water and 0.2-1 part of dispersing agent into a reaction kettle, mixing and stirring for 15-30 min to obtain a water system matrix, adding the flame-retardant styrene slurry prepared in the step A, and mixing and stirring for 2.5-8.5 h;

C. introducing high-temperature steam into the reaction kettle, heating to 50-55 ℃ at the speed of 0.5-1.0 ℃/min, adding 1.5-2.5 parts of nucleating agent, 0.6-1.5 parts of plasticizer and 0.5-1.0 part of initiator, continuously stirring, continuously heating to 88.5-89.5 ℃, carrying out low-temperature granulation reaction, and keeping the temperature for low-temperature granulation for 5.5-6 hours;

D. after low-temperature granulation is finished, 6-9 parts of foaming agent are added, the temperature is raised to 120.5-122.5 ℃ according to the speed of 0.5-0.7 ℃/min, high-temperature reaction is carried out, the constant temperature time of the high-temperature reaction is 4.5-5.5 ℃/min, and the pressure is kept between 0.45-0.65 MP;

E. after foaming, the polystyrene particles are prepared by washing, drying, screening, coating, vibrating and packaging.

Compared with the prior art, the halogen-free flame retardant expandable polystyrene particles provided by the invention optimize the addition proportion of the raw materials of styrene, graphite, water and other auxiliary reagents in the polystyrene polymerization reaction, and simultaneously replace the existing halogen flame retardant by the flame retardant prepared by the mixing reaction of the organic phosphorus flame retardant and the silicon flame retardant synergist, so that the heat conductivity coefficient of the polystyrene obtained by the polymerization reaction can be further reduced, the heat preservation effect is improved, meanwhile, the organic phosphorus flame retardant and the silicon flame retardant generate volatile free radicals during combustion, thereby capturing hydrogen free radicals and carboxyl free radicals in a gas-phase flame zone, reducing the concentration of the hydrogen free radicals in the flame zone, in addition, the organic phosphorus compound is decomposed to generate a phosphoric acid liquid film to protect a polymer matrix during combustion, phosphoric acid is further dehydrated to generate metaphosphoric acid, the metaphosphoric acid is further polymerized to generate polyvinylidene phosphate, the polyvinylidene phosphate dehydrates and carbonizes the polymer matrix, forming a carbon layer covering the surface of the polymer matrix to inhibit chain reaction, thereby improving the flame retardant property which can reach B1 level flame retardant; because the phosphoric acid liquid film covers the surface of the polymer matrix, the smoke quantity is small during combustion, no toxic or corrosive gas is generated, the safety coefficient is high, and the relevant environmental protection requirements are met.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description of the embodiments of the present invention:

the halogen-free flame retardant expandable polystyrene particles are prepared by mixing the following components in parts by weight: 100 parts of styrene, 2.0-5.5 parts of graphite, 200-400 parts of water, 6-10 parts of a flame retardant, 0.50-0.70 part of an initiator, 1.5-2.5 parts of a nucleating agent, 0.6-1.5 parts of a plasticizer, 6-9 parts of a foaming agent, 0.2-1.0 part of a dispersing agent, 0.05-0.10 part of an emulsifier and 0.2-0.8 part of a flame retardant synergist;

the flame retardant is one or a combination of phosphorus oxychloride or resorcinol (diphenyl) phosphate or hydroquinone bis (diphenyl) phosphate (HDP) or resorcinol tetraphenyl diphosphate or triphenyl thiophosphate isocyanate or polyphosphate;

the initiator is benzoyl peroxide or dibenzoyl peroxide;

the nucleating agent is phenolic resin or polyethylene wax;

the plasticizer is rape oil fatty acid alkanolamide boric acid ester or castor oil polyoxyethylene ether or the mixture of the rape oil fatty acid alkanolamide boric acid ester and the castor oil polyoxyethylene ether according to the proportion;

the dispersant is at least one of active calcium carbonate, calcium phosphate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, hydroxyethyl cellulose, sodium polymethacrylate, hydroxypropyl methyl cellulose, sodium tripolyphosphate and anhydrous sodium sulfate;

the foaming agent is pentane, butane or heptane, the emulsifier is calcium dodecyl benzene sulfonate (SDBSO), and the flame-retardant synergist is silicon dioxide or polysiloxane resin.

Preferably, the halogen-free flame retardant expandable polystyrene particles comprise the following components in parts by weight:

100 parts of styrene, 4.5 parts of graphite, 320 parts of water, 8.5 parts of a flame retardant, 0.60 part of an initiator, 2.1 parts of a nucleating agent, 1.2 parts of a plasticizer, 8 parts of a foaming agent, 0.65 part of a dispersant, 0.08 part of an emulsifier and 0.6 part of a flame retardant synergist;

the flame retardant is hydroquinone bis (diphenyl) phosphate (HDP), the initiator is benzoyl peroxide, the nucleating agent is polyethylene wax, the plasticizer is castor oil polyoxyethylene ether, the dispersing agent is polyvinyl alcohol, the foaming agent is pentane, specifically at least one of n-pentane, isopentane and neopentane, and the flame retardant synergist is silicon dioxide.

Preferably, the blowing agent is a combination of n-pentane and neopentane in a 3:2 ratio.

A preparation method of halogen-free flame retardant expandable polystyrene particles comprises the following steps:

A. adding 100 parts of styrene, 6-10 parts of flame retardant, 0.2-0.8 part of flame retardant synergist, 2.0-5.5 parts of graphite and 0.05-0.1 part of emulsifier into a reaction kettle in sequence, and stirring for 0.5-1 h to prepare flame retardant styrene slurry;

B. adding 200-400 parts of water and 0.2-1 part of dispersing agent into a reaction kettle, mixing and stirring for 15-30 min to obtain a water system matrix, adding the flame-retardant styrene slurry prepared in the step A, and mixing and stirring for 2.5-8.5 h;

C. introducing high-temperature steam into the reaction kettle, heating to 50-55 ℃ at the speed of 0.5-1.0 ℃/min, adding 1.5-2.5 parts of nucleating agent, 0.6-1.5 parts of plasticizer and 0.5-1.0 part of initiator, continuously stirring, continuously heating to 88.5-89.5 ℃, carrying out low-temperature granulation reaction, and keeping the temperature for low-temperature granulation for 5.5-6 hours;

D. after low-temperature granulation is finished, 6-9 parts of foaming agent are added, the temperature is raised to 120.5-122.5 ℃ at the speed of 0.5-0.7 ℃/min to carry out high-temperature reaction, the constant temperature time of the high-temperature reaction is 4.5-5.5 hours, and the pressure is kept between 0.45-0.65 MP;

E. after foaming, the polystyrene particles are prepared by washing, drying, screening, coating, vibrating and packaging.