CN103012636B - Halogen-free black material flame retardant polystyrene composite material and preparation method thereof - Google Patents

Halogen-free black material flame retardant polystyrene composite material and preparation method thereof Download PDF

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CN103012636B
CN103012636B CN201210528156.8A CN201210528156A CN103012636B CN 103012636 B CN103012636 B CN 103012636B CN 201210528156 A CN201210528156 A CN 201210528156A CN 103012636 B CN103012636 B CN 103012636B
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polymerization
parts
halogen
vinylbenzene
flame retardant
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CN201210528156.8A
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CN103012636A (en
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王标兵
李志超
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常州大学
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Abstract

The invention relates to a halogen-free black material flame retardant polystyrene composite material and a preparation method of the polystyrene composite material, and belongs to the field of organic/inorganic composite materials. As graphite has a very strong steric hindrance effect, suspension polymerization of styrene is badly affected with the increase of the use amount of graphite. The commonly adopted one-step method can enable the additive amount of expanded graphite to be increased by 5-10 percent to the highest degree, while through adopting the method, the additive amount of expanded graphite can be increased by 10-20 percent. The preparation method comprises the following steps: firstly dividing a reacted styrene monomer into two systems for polymerization; adding polystyrene to the pre-polymerized system at the same time, so as to improve the viscosity of styrene in the pre-polymerized system and enable the expanded graphite to be dispersed well in styrene; adding different amounts of initiator aiming at different systems at the same time, so as to enable the respective systems to be well polymerized at the earlier stage; and finally combining the two systems into a whole to perform suspension polymerization, so that the polystyrene particles with centralized particle size distribution and excellent flame retardant performance are prepared.

Description

A kind of Halogen-free black material flame retardant polystyrene composite material and preparation method thereof
Technical field
The invention belongs to organic/inorganic composite material field, relate to a kind of preparation method of Halogen-free black material Flameproof styrenic matrix material.
Background technology
In recent years, in building material field, energy-saving and environmental protection problem causes people to pay close attention to more and more.Polystyrene (PS) porous plastics, as the one of heat-insulating material, can pass through the hot-fluid between the cold and hot region of minimizing thus prevent energy loss, showing the advantage of its energy-conservation aspect fully.From environmental angle, it be in numerous porous plastics uniquely a kind of can without freonll-11 foaming porous plastics, and the saturated hydrocarbon of available relative environmental protection (as pentane), carbonic acid gas or water are as foaming agent foam, thus can not environmental pollution problem.In addition, PS porous plastics is easy to dissolve, and pulverizes, can reclaim and reproduce, also further reduce waste.Therefore, the use of PS porous plastics in building field has presented the trend grown with each passing day, and is obtained for and applies widely in the building slabs such as room item, wall, cellar, pipeline.Discharge a large amount of smog when the inflammableness of polystyrene (PS) porous plastics and burning, limit its range of application as lagging material.Giving the flame retardant resistance that PS porous plastics is certain, is the key of head it off.
Due to environmental grounds, in polystyrene plastic, the use of halogen should reduce.Halogen-free flameproof is a kind of development trend of flame retardant area,
Summary of the invention
For domestic the deficiencies in the prior art, the object of this invention is to provide the preparation method of the black material of a kind of halogen-free flameproof vinylbenzene.This matrix material can be processed into the halogen-free high flame-retardant type foaming plate that fire-protection rating is B and C.
The present invention specifically can be realized by following technical solution:
The present invention a kind of Halogen-free black material flame retardant polystyrene composite material, be made up of the raw material of following massfraction:
Vinylbenzene 100 parts,
Expansible black lead 10-20 part,
Benzoyl peroxide 0.8-1.2 part,
Initiator 0.3-0.5 part,
Calcium phosphate powder 1.2-2.0 part,
Gelatin 1.5-2.5 part,
Sodium dodecylbenzene sulfonate 0.004-0.012 part,
Polystyrene 5-20 part,
Polyethylene wax 0.2-0.4 part.
In the present invention, natural flaky graphite is made up of a lot of stratiform nanometer sheet, there is typical laminate structure, due to the specific physical character of graphite, easy reunion is difficult in polymeric matrix dispersed, not only have impact on the mechanical property of polymkeric substance, make the high-performance of graphite be difficult to play simultaneously, thus, greatly limit its range of application.Meanwhile, graphite surface has certain benzoquinones and quinoid inhibition group, has certain inhibition effect to polyreaction. and this just requires, before reactions, surface treatment is carried out to graphite, makes graphite in styrene monomer, have good dispersiveness, finally obtain graphite/granules of polystyrene.Expansible black lead size 50-500 order, preferred 200-400 order.Expansible black lead addition is the 5-50% of styrene monomer quality, preferred 5-20%.
Wherein the treatment process of expansible black lead is carried out according to following step:
(1) 100 part of expansible black lead, adds 10 parts of NaOH, and 90 parts of deionized waters, after boiling 30min, are washed till neutrality with deionized water.
(2) in above-mentioned expansible black lead, 10 parts of HNO are added 3, 90 parts of deionized waters, after boiling 30min, are washed till neutrality with deionized water.
(3) in above-mentioned expansible black lead, add 10 parts of dehydrated alcohols, 1 part of deionized water, 0.5 part of Silane coupling agent KH550, boils 30min at 90 DEG C.
(4) baking oven is put into, dry for standby.
Initiator used is superoxide, has dicumyl peroxide, peroxybenzoate, the one or more combination in dibenzoyl peroxide, and initiator amount is the 0.9-1.5% of styrene monomer weight.
The conventional dispersion agent of suspension polymerization has, the Polyvinylpyrolidone (PVP) of organic, hydroxypropylcellulose, polyacrylic acid, polyoxyethylene glycol, gelatin, the Sodium dodecylbenzene sulfonate of mineral-type, calcium phosphate powder, tricalcium phosphate, magnesium sulfate and sodium phosphate.
Prepare the method for above-mentioned Halogen-free black material Flameproof styrenic particle, carry out according to following steps:
(1) prepare suspension polymerization system: in reactor, add 100 parts of deionized waters, add 1.2-2.0 part calcium phosphate powder, 1.5-2.5 part gelatin, 0.004-0.012 part Sodium dodecylbenzene sulfonate successively, stir.Get 40-60 part vinylbenzene again, add 0.4-0.6 part benzoyl peroxide, 0.1-0.3 part dicumyl peroxide, after stirring, pour in above-mentioned suspension, be warming up to 90 DEG C, stir under 300 revs/min of rotating speeds, carry out suspension polymerization.
(2) prepolymerization system is prepared: get residue part vinylbenzene, add 5-20 part polystyrene, 0.2-0.4 part polyethylene wax, 10-20 part 200-500 order process expansible black lead stirs, then add 0.4-0.6 part benzoyl peroxide, 0.2-0.4 part dicumyl peroxide, after stirring, be warming up to 85 DEG C and carry out pre-polymerization, after pre-polymerization for some time, obtain vinylbenzene/expansible black lead performed polymer.
(3), after suspension polymerization system polymerization 100min, in suspension, the above-mentioned vinylbenzene/expansible black lead performed polymer prepared is poured into; Homogeneous phase mixing, after constant temperature suspension polymerization in 4 hours, obtains the granules of polystyrene with a certain size distribution.
(4) last, elimination moisture, clean by washed with de-ionized water, obtain Halogen-free black material Flameproof styrenic particle.
The method, start styrene monomer and be divided into two, wherein in suspension polymerization system, styrene content accounts for vinylbenzene gross weight and accounts for 40-60%.
The method, start styrene monomer and be divided into two, wherein in prepolymerization system, styrene content accounts for vinylbenzene gross weight and accounts for 40-60%.Pre-polymerization temperature 80-90 DEG C, the pre-polymerization time is 40min-70min.
The method, suspension system and after prepolymerization system each auto-polymerization for some time, the time adding another part vinylbenzene/expansible black lead performed polymer in styrene suspension polymerization system is after suspension system polymerization 90min-150min.
The suspension polymerization in aqueous phase of this composite particles obtains, and in system, the weight of aqueous phase accounts for 50-70%.
The suspension agent that present method adopts is inorganic/organic composite system, and raw materials used is the combination of one or more of above-mentioned suspension agent, and consumption is the 0.01-2.5% of styrene monomer quality.
Adopt aforesaid method, have the following advantages:
Because graphite has very strong steric hindrance, along with the increase of graphite levels, styrene suspension polymerization is had a negative impact.The single stage method of usual employing, the highest addition of expanded graphite that makes can accomplish 5-10%.And by adopting present method, the addition of expanded graphite can be made to be increased to 10-20%.Present method is first divided into two to the styrene monomer of reaction, is divided into two individual system and is polymerized, and adds polystyrene simultaneously, to improve cinnamic viscosity in prepolymerization system, make expansible black lead can obtain fabulous dispersion in vinylbenzene in prepolymerization system.Simultaneously for different system, add the initiator of different amount, respective system can be well polymerized in early stage.Finally again two individual system are united two into one, carry out suspension polymerization, obtained, centralized particle diameter, the styrene pellets of excellent fireproof performance.
Accompanying drawing explanation
Fig. 1 is the granules of polystyrene of 10% expansible black lead;
Fig. 2 is the granules of polystyrene of 15% expansible black lead;
Fig. 3 is the granules of polystyrene of 20% expansible black lead.
Embodiment
Below in conjunction with embodiment, (wherein all numbers, as without special mark, are all mass fraction) is further elaborated to the present invention.
The wherein treatment process of expansible black lead in embodiment, carry out according to following step:
(1) 100 part of expansible black lead, adds 10 parts of NaOH, and 90 parts of deionized waters, after boiling 30min, are washed till neutrality with deionized water.
(2) in above-mentioned expansible black lead, 10 parts of HNO are added 3, 90 parts of deionized waters, after boiling 30min, are washed till neutrality with deionized water.
(3) in above-mentioned expansible black lead, add 10 parts of dehydrated alcohols, 1 part of deionized water, 0.5 part of Silane coupling agent KH550, boils 30min at 90 DEG C.
(4) baking oven is put into, dry for standby.
Embodiment 1
Vinylbenzene 100 parts, 200 order process expansible black leads 10 parts, benzoyl peroxide 0.8 part, dicumyl peroxide 0.3 part, calcium phosphate powder 1.2 parts, 1.5 parts, gelatin, Sodium dodecylbenzene sulfonate 0.004 part, polystyrene 5 parts, polyethylene wax 0.3 part
Prepare the method for above-mentioned Halogen-free black material Flameproof styrenic particle, comprise the following steps:
(1) suspension polymerization system is prepared.Add 100 parts of deionized waters in reactor, add 1.2 parts of calcium phosphate powders, 1.5 parts of gelatin, 0.004 part of Sodium dodecylbenzene sulfonate successively, stir.Get 50 parts of vinylbenzene again, add 0.4 part of benzoyl peroxide, 0.2 part of dicumyl peroxide, after stirring, pour in above-mentioned suspension, be warming up to 90 DEG C, stir under 300 revs/min of rotating speeds, carry out suspension polymerization.
(2) prepolymerization system is prepared.Get 50 parts of vinylbenzene, add 5 parts of polystyrene, 0.3 part of polyethylene wax, 5 part of 200 order process expansible black lead stirs, then add 0.4 part of benzoyl peroxide, 0.1 part of dicumyl peroxide, after stirring, be warming up to 85 DEG C and carry out pre-polymerization, after pre-polymerization for some time, obtain vinylbenzene/expansible black lead performed polymer.
(3), after suspension polymerization system polymerization 100min, in suspension, the above-mentioned vinylbenzene/expansible black lead performed polymer prepared is poured into.Homogeneous phase mixing, after constant temperature suspension polymerization in 4 hours, obtains the granules of polystyrene with a certain size distribution.
(4) last, elimination moisture, clean by washed with de-ionized water, obtain Halogen-free black material Flameproof styrenic particle.
Embodiment 2
Vinylbenzene 100 parts, 400 order process expansible black leads 20 parts, benzoyl peroxide 1.2 parts, dicumyl peroxide 0.5 part, calcium phosphate powder 2.0 parts, 2.5 parts, gelatin, Sodium dodecylbenzene sulfonate 0.012 part, polystyrene 10 parts, polyethylene wax 0.4 part
Prepare the method for above-mentioned Halogen-free black material Flameproof styrenic particle, comprise the following steps:
(1) suspension polymerization system is prepared.Add 100 parts of deionized waters in reactor, add 2.0 parts of calcium phosphate powders, 2.5 parts of gelatin, 0.012 part of Sodium dodecylbenzene sulfonate successively, stir.Get 50 parts of vinylbenzene again, add 0.4 part of benzoyl peroxide, 0.4 part of dicumyl peroxide, after stirring, pour in above-mentioned suspension, be warming up to 90 DEG C, stir under 500 revs/min of rotating speeds, carry out suspension polymerization.
(2) prepolymerization system is prepared.Get 50 parts of vinylbenzene, add 10 parts of polystyrene, 0.4 part of polyethylene wax, 20 part of 400 order process expansible black lead stirs, then add 0.8 part of benzoyl peroxide, 0.1 part of dicumyl peroxide, after stirring, be warming up to 85 DEG C and carry out pre-polymerization, after pre-polymerization for some time, obtain vinylbenzene/expansible black lead performed polymer.
(3), after suspension polymerization system polymerization 100min, in suspension, the above-mentioned vinylbenzene/expansible black lead performed polymer prepared is poured into.Homogeneous phase mixing, after constant temperature suspension polymerization in 6 hours, obtains the granules of polystyrene with a certain size distribution.
(4) last, elimination moisture, clean by washed with de-ionized water, obtain Halogen-free black material Flameproof styrenic particle.
Embodiment 3
Vinylbenzene 100 parts, 300 order process expansible black leads 15 parts, benzoyl peroxide 1 part, dicumyl peroxide 0.4 part, calcium phosphate powder 1.5 parts, 1.8 parts, gelatin, Sodium dodecylbenzene sulfonate 0.008 part, polystyrene 8 parts, polyethylene wax 0.3 part
Prepare the method for above-mentioned Halogen-free black material Flameproof styrenic particle, comprise the following steps:
(1) suspension polymerization system is prepared.Add 100 parts of deionized waters in reactor, add 1.5 parts of calcium phosphate powders, 1.8 parts of gelatin, 0.008 part of Sodium dodecylbenzene sulfonate successively, stir.Get 50 parts of vinylbenzene again, add 0.2 part of benzoyl peroxide, 0.1 part of dicumyl peroxide, after stirring, pour in above-mentioned suspension, be warming up to 90 DEG C, stir under 400 revs/min of rotating speeds, carry out suspension polymerization.
(2) prepolymerization system is prepared.Get 50 parts of vinylbenzene, add 8 parts of polystyrene, 0.3 part of polyethylene wax, 15 part of 300 order process expansible black lead stirs, then add 0.8 part of benzoyl peroxide, 0.3 part of dicumyl peroxide, after stirring, be warming up to 85 DEG C and carry out pre-polymerization, after pre-polymerization for some time, obtain vinylbenzene/expansible black lead performed polymer.
(3), after suspension polymerization system polymerization 100min, in suspension, the above-mentioned vinylbenzene/expansible black lead performed polymer prepared is poured into.Homogeneous phase mixing, after constant temperature suspension polymerization in 5 hours, obtains the granules of polystyrene with a certain size distribution.
(4) last, elimination moisture, clean by washed with de-ionized water, obtain Halogen-free black material Flameproof styrenic particle.
Fig. 1 is the granules of polystyrene of 10% expansible black lead; Fig. 2 is the granules of polystyrene of 15% expansible black lead;
Fig. 3 is the granules of polystyrene of 20% expansible black lead.As can be seen from Fig. 1-3, along with the increase of content of graphite in polystyrene, graphite dispersion more even, the blackness of the granules of polystyrene of synthesis increases gradually.
The polystyrene performance test adopting aforesaid method obtained is as follows:
As can be seen from the above table, along with the increase of expansible black lead addition, the flame retardant properties of polystyrene improves gradually, and when addition reaches 20%, oxygen index is increased to 30.2. from 18.5.Fire-protection rating, brings up to B level from inflammable.

Claims (6)

1. a Halogen-free black material flame retardant polystyrene composite material, is characterized in that being made up of the raw material of following massfraction:
Vinylbenzene 100 parts,
Expansible black lead 10-20 part,
Benzoyl peroxide 0.8-1.2 part,
Initiator 0.3-0.5 part,
Calcium phosphate powder 1.2-2.0 part,
Gelatin 1.5-2.5 part,
Sodium dodecylbenzene sulfonate 0.004-0.012 part,
Polystyrene 5-20 part,
Polyethylene wax 0.2-0.4 part;
Wherein said expansible black lead, processes according to following step:
(1) 100 part of expansible black lead, adds 10 parts of NaOH, and 90 parts of deionized waters, after boiling 30min, are washed till neutrality with deionized water;
(2) in above-mentioned expansible black lead, 10 parts of HNO are added 3, 90 parts of deionized waters, after boiling 30min, are washed till neutrality with deionized water;
(3) in above-mentioned expansible black lead, add 10 parts of dehydrated alcohols, 1 part of deionized water, 0.5 part of Silane coupling agent KH550, boils 30min at 90 DEG C;
(4) baking oven is put into, dry for standby.
2. a kind of Halogen-free black material flame retardant polystyrene composite material according to claim 1, it is characterized in that initiator used is dicumyl peroxide, peroxybenzoate, one or more combination in dibenzoyl peroxide, initiator amount is the 0.9-1.5% of styrene monomer weight.
3. the preparation method of a kind of Halogen-free black material flame retardant polystyrene composite material according to claim 1, is characterized in that carrying out according to following steps:
(1) prepare suspension polymerization system: in reactor, add 100 parts of deionized waters, add 1.2-2.0 part calcium phosphate powder, 1.5-2.5 part gelatin, 0.004-0.012 part Sodium dodecylbenzene sulfonate successively, stir;
Get 40-60 part vinylbenzene again, add 0.4-0.6 part benzoyl peroxide, 0.1-0.3 part dicumyl peroxide, after stirring, pour in above-mentioned suspension, be warming up to 90 DEG C, stir under 300 revs/min of rotating speeds, carry out suspension polymerization;
(2) prepolymerization system is prepared: get residue part vinylbenzene, add 5-20 part polystyrene, 0.2-0.4 part polyethylene wax, 10-20 part 200-500 order process expansible black lead stirs, then add 0.4-0.6 part benzoyl peroxide, 0.2-0.4 part dicumyl peroxide, after stirring, be warming up to 85 DEG C and carry out pre-polymerization, after pre-polymerization for some time, obtain vinylbenzene/expansible black lead performed polymer;
(3), after suspension polymerization system polymerization 100min, in suspension, the above-mentioned vinylbenzene/expansible black lead performed polymer prepared is poured into; Homogeneous phase mixing, after constant temperature suspension polymerization in 4 hours, obtains the granules of polystyrene with a certain size distribution;
(4) last, elimination moisture, clean by washed with de-ionized water, obtain Halogen-free black material Flameproof styrenic particle.
4. the preparation method of a kind of Halogen-free black material flame retardant polystyrene composite material according to claim 3, is characterized in that the method, and start styrene monomer and be divided into two, wherein in suspension polymerization system, styrene content accounts for vinylbenzene gross weight and accounts for 40-60%.
5. the preparation method of a kind of Halogen-free black material flame retardant polystyrene composite material according to claim 3, is characterized in that the method, and start styrene monomer and be divided into two, wherein in prepolymerization system, styrene content accounts for vinylbenzene gross weight and accounts for 40-60%; Pre-polymerization temperature 80-90 DEG C, the pre-polymerization time is 40min-70min.
6. the preparation method of a kind of Halogen-free black material flame retardant polystyrene composite material according to claim 3, it is characterized in that the method, suspension system and after prepolymerization system each auto-polymerization for some time, the time adding another part vinylbenzene/expansible black lead performed polymer in styrene suspension polymerization system is after suspension system polymerization 90min-150min.
CN201210528156.8A 2012-12-10 2012-12-10 Halogen-free black material flame retardant polystyrene composite material and preparation method thereof CN103012636B (en)

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CN105295215A (en) * 2014-07-16 2016-02-03 江苏业达鑫化工有限公司 Preparation method for bead-shaped black polystyrene particles
CN105295085A (en) * 2015-11-26 2016-02-03 苗鹏 Preparation method of flame-resistant expandable polystyrene bead with low thermal conductivity
CN111635471A (en) * 2020-06-18 2020-09-08 北京理工大学 Flame-retardant polystyrene resin and preparation method and application thereof

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CN102587607A (en) * 2012-01-09 2012-07-18 武汉理工大学 Fireproof and flame-retarding type composite heat-insulation decorating plate for outer wall and preparation method of fireproof and flame-retarding type composite heat-insulation decorating plate

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CN102587607A (en) * 2012-01-09 2012-07-18 武汉理工大学 Fireproof and flame-retarding type composite heat-insulation decorating plate for outer wall and preparation method of fireproof and flame-retarding type composite heat-insulation decorating plate

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