CN102675762A - Halogen-free flame-retardant polystyrene foam material and preparation method thereof - Google Patents
Halogen-free flame-retardant polystyrene foam material and preparation method thereof Download PDFInfo
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- CN102675762A CN102675762A CN2012101691722A CN201210169172A CN102675762A CN 102675762 A CN102675762 A CN 102675762A CN 2012101691722 A CN2012101691722 A CN 2012101691722A CN 201210169172 A CN201210169172 A CN 201210169172A CN 102675762 A CN102675762 A CN 102675762A
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Abstract
The invention discloses a halogen-free flame-retardant polystyrene foam material. The material is obtained by performing molten-state foaming on the following components in part by weight: 100 parts of expandable polystyrene (EPS) beads, 20 to 100 parts of halogen-free flame-retardant adhesive, 5 to 30 parts of synergist and 1 to 10 parts of reinforcing agent; and the vertical burning class of the material is UL94-V0, the limit oxygen index is 31 to 39.2 percent, the smoke density rating is 13.1 to 15.2, the bending strength is 0.30 to 0.40MPa, the compressive strength is 0.1 to 0.22MPa, the water adsorption is 1 to 2 percent, and the coefficient of heat conductivity is 0.037 to 0.043w/m.k. The invention also discloses a preparation method for the halogen-free flame-retardant polystyrene foam material. Through the co-action of the halogen-free flame-retardant adhesive, the synergist and the reinforcing agent which are coated among EPS foam particles, a condensed-phase expansion carbon layer with high expansion multiplying power is formed, a flame retardant can be uniformly dispersed on the surfaces of the foam particles, the compatibility and bonding strength of interfaces are improved, and the polystyrene foam material achieves an uncommon excellent flame-retardant effect and is also endowed with excellent mechanical properties; and the process is simple and mature.
Description
Technical field
The invention belongs to flame-retardant high-molecular foam materials and preparing technical field thereof, be specifically related to a kind of halogen-free flameproof polystyrene foamed material and preparation method thereof.
Background technology
(Expadable polystyrene EPS) is a kind of porous plastics of being developed and taken the lead in realizing suitability for industrialized production by German BASF AG the 1950's to the eps foam.Since its good use properties, the production moulding processing unit of less cost, simple and feasible and the product that can be made into different shape, different densities, thereby obtained swift and violent development.Even if in the maximum three kinds of porous plastics PS (PS) of output, urethane (PU), SE (PVC), also rank first place.At present, China has become the maximum EPS producing country in the whole world, and its production and consumption total amount all ranks first in the world, and 2011, the production of domestic EPS was broken through 4,750,000 tons, account for the world market about 6,000,000 tons more than 75%.Because the superior heat preservation and insulation of EPS is widely used in external-wall heat-insulation material, its consumption has surpassed 1,500,000 m
3, account in the energy saving building material more than 70%, and the annual requirement of EPS will be with 20% speed increase, market potential is very huge.
Because EPS is to be master's polymer materials with C, H element, it is again a kind of rigid foam of unicellular structure in addition but regrettably; Present thin-walled porous state after the foaming, every cubic metre of volume contains 300 ~ 6,000,000 independent closed bubbles, and the volume that includes gas accounts for more than 98%; Wherein except air, also comprise some residual flammable petroleum gas, the PS material only account for 2% or below, thereby make one of its material that becomes limiting oxygen index(LOI) minimum (~ 17%) in all polymer materialss; Very easily burning not only can be lighted at a lower temperature, and in case catch fire and promptly can acutely burn; Flame spreads at a high speed and diffuses to whole surface; Make the fusion of base material high shrinkage, do not become charcoal, produce the molten drop of yellowish-orange flame and a large amount of black smog, toxic gas and band naked light simultaneously; Cause the fast development of burning, make common EPS have following burning feature:
1) is difficult to into charcoal.Because the eps foam material can take place all to separate when being heated or non-ly all separate reaction, makes it to depolymerize to fully multiple lower molecular weight polymer volatile matter, be difficult in that crosslinking reaction generates crosslinking structure in the combustion processes, so be difficult to into charcoal.
2) thermal value is high.The combustion heat of EPS is 40180 kJ/kg, greater than the thermal value of timber, makes it more easy firing.
3) flame temperature is high.The flame temperature of EPS is 2210 ℃.
3) combustionvelocity is fast.The combustionvelocity of polystyrene foamed is not 1217～6315 mm/min, though and the EPS combustionvelocity of different foam expansion is different, all far above the combustionvelocity of PS.
4) amount of being fuming and toxicity are big.EPS in most cases is an incomplete combustion, can produce a large amount of smog, CO
2(carbonic acid gas), CO obnoxious flavoures such as (carbon monoxide).
Particularly when EPS is used for exterior-wall heat insulation, in case inside and outside the presence of fire in house, flame can from window opening inwardly, outer burning, involve window EPS thermal insulation layer all around.And the polystyrene heat-preservation material will shrink when temperature reaches 60 ~ 100 ℃, fuse, burning under the naked light state, and the intensity of a fire can spread in external thermal insulation, forms chimneyeffect, and whole thermal insulation layer is burnt fully.In recent years; The fire that causes because of the maximum eps foam material of usage quantity in building exterior wall heat preserving and the public place finishing will cause personnel's heavy casualties and property massive losses easily; Cause 1 firemen's death like building, CCTV cultural center in 2009 " 2.9 " fire; The people is severely injured surplus in the of 30, loses tens yuan; 14 floors are burnt in Nantong " first high building " " 5.31 " big fire in the Soviet Union that builds in 2010; 2 building high-rise buildings more than 100 meters are burnt in New Year's Eve in 2011 Shenyang feudal dynasties ten thousand prosperous hotel big fire; The Shanghai that particularly shocks the world " 11.15 " big fire causes 58 people dead, and 17 people are severely injured.Therefore, reduce the combustibility of polystyrene foamed material, preparing fire-retardant especially halogen-free flameproof polystyrene foamed material is the field of materials problem demanding prompt solution, also is the important need of the national economic development.
But because EPS has the characteristics of specific molecule chain structure, degraded and combustioncharacteristics and foamy structure; The halogen-free flameproof polystyrene foamed material that its flame-retardant modified quite difficulty, especially preparation are had excellent flame retardancy ability and mechanical property still belongs to global problem.
At present, the research work of fire-retardant eps foam of having had only a small amount of document and patent report, the fire retardant that relates to has halogen system, phosphorus system, nitrogen-phosphorus is compound and inorganic combustion inhibitor etc.Like U.S. Albemarle Corporation (CN101087819A, 2007; CN101087818A, 2007) adopt bromine based compound body fire retardant polystyrene, obtained certain flame retardant effect; Oohara etc. (US Patent:6569912,2003) have proposed to use nitrogenous phosphorus flame retardant such as ammonium phosphate or ammonium polyphosphate, nitrogenous compound such as trimeric cyanamide etc. to be used the flame retardant properties that fire-retardant PS has obtained higher level with hexabromocyclododecane (HBCD).But along with the enhancing of global environment safety and consciousness safe in utilization, halogen is that a series of safety issues that flame-retardant system brings have caused people's extensive concern day by day.Exploitation Halogen, efficient, novel flame-retardant eps foam material are the flame-retardant modified Development Trend of EPS.Some patents (CN 101014650 A, 2007; WO Patent:2009037236 (A1), 2007; EP:834529 (A1); 1996) reported employing P contained compound flame retardant polystyrene foam material again; But because the most of fire retardant that adopts is a small molecules, thereby brought in the use shortcoming because of fire retardant runs off and migration causes product performance to worsen.Some patents (CN1335866A, 2002 are also arranged; CN1329634A, 2002; US Patent:6384094; 2002) though reported that with expanded graphite and red phosphorus or phosphorus compound be fire retardant; Vinylbenzene is carried out suspension polymerization prepare halogen-free flameproof EPS; But do not provide fire-retardant rank that fire-retardant EPS reaches and other performances of material, do not see the report of suitability for industrialized production yet.Also has patent (CN101796114A; 2010) reported the particle diameter that uses 10-60wt% fire retardant and caking agent as 1-50 μ m; Expandable polystyrene bead and one step foaming bubble grain are carried out surface-coated; The insulativity and the flame retardant resistance of expanded polystyrene foam have been improved; The fire retardant that is adopted is one or more in metal or nonmetal oxide, metal or nonmetal oxyhydroxide, silicate, borate and the carbonate, but poor because of employed fire retardant and PS bubble intergranular consistency, the mechanical property of the polystyrol foam material of preparation is difficult to reach request for utilization.
Summary of the invention
The objective of the invention is the deficiency to the prior art existence, a kind of halogen-free flameproof polystyrene foamed material is provided, this foam materials is good flame resistance not only, and mechanical property is also all good.
Another object of the present invention provides a kind of preparation method of above-mentioned halogen-free flameproof polystyrene foamed material.
Halogen-free flameproof polystyrene foamed material provided by the invention is characterized in that this foam materials is to be got through melt foaming by by weight following component:
And its vertical combustion grade is a UL94-V0 level, and limiting oxygen index(LOI) is 31～39.2%, smoke density grade 13.1～15.2, flexural strength 0.30～0.40MPa, compressive strength 0.1～0.22MPa, water-intake rate 1～2 %, thermal conductivity 0.037～0.043w/mk.
Contained expandable polystyrene bead is the mixture of business-like vinylbenzene and additives such as styrene based copolymer and pneumatogen in this foam materials.
Contained halogen-free flameproof glue is the mixture that the modification melamine aqueous solutions of polymers of the Phosphation aminoresin aqueous solution and the solid content 20 ~ 60% of solid content 30 ~ 70% is formed in this foam materials, and the weight ratio of the two is 1 ~ 3: 1 ~ 2.Wherein contained modification melamine aqueous solutions of polymers is any in the Virahol modified melamine resin aqueous solution, the ethanol modified melamine resin aqueous solution, the tetramethylolmethane modified melamine resin aqueous solution or the polyvinyl alcohol modification melmac aqueous solution.
Contained synergist is any in tetramethylolmethane, phosphoric acid and verivate thereof, sulfocompound or the expansible black lead in this foam materials.Wherein phosphoric acid derivatives can be polyphosphoric acid, ammonium phosphate etc., and sulfocompound can be thiocarbamide, mercaptan, thiosemicarbazide etc.
In this foam materials contained toughener be in talcum powder, aluminum oxide, Natural manganese dioxide, hydrotalcite or the polynite any.
The preparation method of above-mentioned halogen-free flameproof polystyrene foamed material provided by the invention is characterized in that the process step of this method and condition are following:
(1) with 100 parts of expandable polystyrene beads, the foam device of putting into temperature and be 100-120 ℃, pressure and be 0.01-0.5MPa carries out pre-frothing, and keeps 5-120s to obtain PS pre-frothing particle;
(2) with the pre-frothing particle room temperature, normal pressure held 3-48 hour, make it slaking;
(3) earlier 20 ~ 100 parts of halogen-free flameproof glue, 5 ~ 30 portions of synergist, 1 ~ 10 part of toughener and slaking PS pre-frothing particle are fully mixed; The foam device of putting into temperature then and be 110-130 ℃, pressure and be 0.01-0.5MPa carries out second time of foaming; And keep 10-600s to obtain the halogen-free flameproof polystyrene foam
The umber of above material is weight part.
Expandable polystyrene bead described in the above method is the mixture of business-like vinylbenzene and additives such as styrene based copolymer and pneumatogen.
Halogen-free flameproof glue described in the above method is the mixture that the modification melamine aqueous solutions of polymers of the Phosphation aminoresin aqueous solution and the solid content 20 ~ 60% of solid content 30 ~ 70% is formed, and the weight ratio of the two is 1 ~ 3: 1 ~ 2.Wherein contained modification melamine aqueous solutions of polymers is any in the Virahol modified melamine resin aqueous solution, the ethanol modified melamine resin aqueous solution, the tetramethylolmethane modified melamine resin aqueous solution or the polyvinyl alcohol modification melmac aqueous solution.
Synergist described in the above method is any in tetramethylolmethane, phosphoric acid and verivate thereof, sulfocompound or the expansible black lead.Wherein phosphoric acid derivatives can be polyphosphoric acid, ammonium phosphate etc., and sulfocompound can be thiocarbamide, mercaptan, thiosemicarbazide etc.
Toughener described in the above method is any in talcum powder, aluminum oxide, Natural manganese dioxide, hydrotalcite and the polynite.
The present invention compared with prior art has following positively effect:
1, because the present invention combines the EPS industrialized producing technology; Made up the novel flame-retardant system that is suitable for polystyrene foam; Through the multi-functional condensation polymer type macromole expansion-type N-P fire retardant glue crosslinked formed fire-retardant network in the foaming course of processing that is coated on EPS bubble intergranular, and the aid dispersion function of synchronous synergistic effect of synergist high-temperature fusion agglutinating and toughener, not only can form the condensed phase expansion charcoal layer of high expansion multiplying power; Highly effective flame-retardant EPS; And fire retardant can be improved the consistency and the bonding strength at interface, thereby both make polystyrene foamed material obtain very rare excellent flame retardant effect at the surperficial homodisperse of bubble grain; Also give the polystyrene foamed material excellent mechanical property, and kept advantages such as insulation, light weight, the water-intake rate of polystyrene foamed material be low simultaneously.
2, because the halogen-free flameproof glue among the present invention is the hybrid thing, thereby the fire-retardant mechanism of condensed phase be can strengthen, the difficult one-tenth of polystyrene foamed material charcoal, the fire-retardant difficult problem of difficulty solved.
3, owing to the synergist among the present invention also can take blocking effect, thereby also can significantly suppress the EPS molecular chain degradation, slow down its thermolysis speed, significantly improve the system charring rate, improve the quality of condensed phase expansion charcoal layer.
4,, thereby also can improve the processibility of fire-retardant EPS foam materials because the toughener among the present invention also has lubrication.
5, because the inventive method is after the slaking of polystyrene foam one step foaming; Add fire retardant glue, synergist and toughener before the secondary frothing forming; Thereby need not change existing polystyrene foamed material production equipment and technology; Only need before second time of foaming, through common mixed stirring device PS pre-frothing particle, fire retardant glue, synergist and toughener mixing to be got final product, technology is simple, maturation.
Embodiment
Through embodiment the present invention is specifically described below; Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the present invention.
What be worth explanation is 1) each material umber of following examples is weight part; 2) gained halogen-free flameproof polystyrene foamed material vertical combustion performance is by the UL94-2006 standard testing; Limiting oxygen index(LOI) is by ASTM D2863-2009 standard testing; The smoke density grade is by GB/T 8627-1999 standard testing; Flexural strength is by GB/T 8812.1-2007 standard testing; Compressive strength is by GB/T 8813-2008 standard testing; Water-intake rate is by GB/T 8810-2005 standard testing; Thermal conductivity is by ASTM E1461 standard testing.
Embodiment 1
With 100 parts of eps master batches, the EPS foam device of putting into temperature and be 100 ℃, pressure and be 0.5MPa carries out pre-frothing, and keeps 5s to obtain PS pre-frothing particle; With the pre-frothing particle room temperature, normal pressure held 3 hours, with the slaking of PS pre-frothing particle; Is that 30% Phosphation aminoresin and solid content are that mixture, 5 parts of expansible black leads, 1 part of polynite and the above-mentioned PS pre-frothing particle that 60% the Virahol modified melamine resin aqueous solution is formed by weight 1:1 fully stirs with 20 parts by solid content; Mix; The EPS foam device of putting into temperature and be 110 ℃, pressure and be 0.01MPa carries out second time of foaming, and keeps 10s to obtain the halogen-free flameproof polystyrene foamed material.
The vertical combustion grade of this foam materials is the UL94-V0 level, limiting oxygen index(LOI) 31, smoke density grade 15.2, flexural strength 0.40MPa, compressive strength 0.22MPa, water-intake rate 2 %, thermal conductivity 0.037w/mk.
Embodiment 2
With 100 parts of eps master batches, the EPS foam device of putting into temperature and be 120 ℃, pressure and be 0.01MPa carries out pre-frothing, and keeps 120s to obtain PS pre-frothing particle; With the pre-frothing particle room temperature, normal pressure held 48 hours, with the slaking of PS pre-frothing particle; Is that 70% Phosphation aminoresin and solid content are that mixture, 30 parts of tetramethylolmethanes, 10 parts of Natural manganese dioxide and the above-mentioned PS pre-frothing particle that the 20% ethanol modified melamine resin aqueous solution is formed by weight 2:1 fully stirs with 100 parts by solid content; Mix; The EPS foam device of putting into temperature and be 130 ℃, pressure and be 0.5MPa carries out second time of foaming, and keeps 600s to obtain the halogen-free flameproof polystyrene foamed material.
The vertical combustion grade of this foam materials is the UL94-V0 level, limiting oxygen index(LOI) 39, smoke density grade 13.4, flexural strength 0.35MPa, compressive strength 0.19MPa, water-intake rate 1 %, thermal conductivity 0.043w/mk.
Embodiment 3
With 100 parts of eps master batches, the EPS foam device of putting into temperature and be 105 ℃, pressure and be 0.15MPa carries out pre-frothing, and keeps 60s to obtain PS pre-frothing particle; With the pre-frothing particle room temperature, normal pressure held 24 hours, with the slaking of PS pre-frothing particle; Is that 50% Phosphation aminoresin and solid content are that mixture, 20 parts of thiocarbamides, 10 parts of talcum powder and the above-mentioned PS pre-frothing particle that 40% the tetramethylolmethane modified melamine resin aqueous solution is formed by weight 1:2 fully stirs with 60 parts by solid content; Mix; The EPS foam device of putting into temperature and be 120 ℃, pressure and be 0.015MPa carries out second time of foaming, and keeps 100s to obtain the halogen-free flameproof polystyrene foamed material.
The vertical combustion grade of this foam materials is the UL94-V0 level, limiting oxygen index(LOI) 38, smoke density grade 13.6, flexural strength 0.30MPa, compressive strength 0.20MPa, water-intake rate 2%, thermal conductivity 0.040w/mk.
Embodiment 4
With 100 parts of eps master batches, the EPS foam device of putting into temperature and be 112 ℃, pressure and be 0.3MPa carries out pre-frothing, and keeps 80s to obtain PS pre-frothing particle; With the pre-frothing particle room temperature, normal pressure held 36 hours, with the slaking of PS pre-frothing particle; Is that 40% Phosphation aminoresin and solid content are that mixture, 10 parts of ammonium phosphate, 5 parts of polynites and the above-mentioned PS pre-frothing particle that 40% the polyvinyl alcohol modification melmac aqueous solution is formed by weight 3:1 fully stirs with 30 parts by solid content; Mix; The EPS foam device of putting into temperature and be 115 ℃, pressure and be 0.25MPa carries out second time of foaming, and keeps 300s to obtain the halogen-free flameproof polystyrene foamed material.
The vertical combustion grade of this foam materials is the UL94-V0 level, limiting oxygen index(LOI) 39.2, smoke density grade 13.1, flexural strength 0.33MPa, compressive strength 0.10MPa, water-intake rate 2%, thermal conductivity 0.040w/mk.
Claims (10)
1. halogen-free flameproof polystyrene foamed material is characterized in that this foam materials is to be got through melt foaming by by weight following component:
And its vertical combustion grade is a UL94-V0 level, and limiting oxygen index(LOI) is 31～39.2%, smoke density grade 13.1～15.2, flexural strength 0.30～0.40MPa, compressive strength 0.1～0.22MPa, water-intake rate 1～2 %, thermal conductivity 0.037～0.043w/mk.
2. halogen-free flameproof polystyrene foamed material according to claim 1; It is characterized in that halogen-free flameproof glue contained in this foam materials is the mixture that the modification melamine aqueous solutions of polymers of the Phosphation aminoresin aqueous solution and the solid content 20 ~ 60% of solid content 30 ~ 70% is formed, the weight ratio of the two is 1 ~ 3: 1 ~ 2.
3. halogen-free flameproof polystyrene foamed material according to claim 2 is characterized in that modification melamine aqueous solutions of polymers contained in this foam materials is any in the Virahol modified melamine resin aqueous solution, the ethanol modified melamine resin aqueous solution, the tetramethylolmethane modified melamine resin aqueous solution or the polyvinyl alcohol modification melmac aqueous solution.
4. according to claim 1 or 2 or 3 described halogen-free flameproof polystyrene foamed materials, it is characterized in that synergist contained in this foam materials is any in tetramethylolmethane, phosphoric acid and verivate thereof, sulfocompound or the expansible black lead.
5. according to claim 1 or 2 or 3 described halogen-free flameproof polystyrene foamed materials, it is characterized in that toughener contained in this foam materials is any in talcum powder, aluminum oxide, Natural manganese dioxide, hydrotalcite or the polynite.
6. according to the preparation method of the said halogen-free flameproof polystyrene foamed material of claim 1, it is characterized in that the process step of this method and condition are following:
(1) with 100 parts of expandable polystyrene beads, the foam device of putting into temperature and be 100-120 ℃, pressure and be 0.01-0.5MPa carries out pre-frothing, and keeps 5-120s to obtain PS pre-frothing particle;
(2) with the pre-frothing particle room temperature, normal pressure held 3-48 hour, make it slaking;
(3) earlier 20 ~ 100 parts of halogen-free flameproof glue, 5 ~ 30 portions of synergist, 1 ~ 10 part of toughener and slaking PS pre-frothing particle are fully mixed; The foam device of putting into temperature then and be 110-130 ℃, pressure and be 0.01-0.5MPa carries out second time of foaming; And keep 10-600s to obtain the halogen-free flameproof polystyrene foam
The umber of above material is weight part.
7. the preparation method of halogen-free flameproof polystyrene foamed material according to claim 6; It is characterized in that the halogen-free flameproof glue described in this method is the mixture that the modification melamine aqueous solutions of polymers of the Phosphation aminoresin aqueous solution and the solid content 20 ~ 60% of solid content 30 ~ 70% is formed, the weight ratio of the two is 1 ~ 3: 1 ~ 2.
8. the preparation method of halogen-free flameproof polystyrene foamed material according to claim 7 is characterized in that the modification melamine aqueous solutions of polymers described in this method is any in the Virahol modified melamine resin aqueous solution, the ethanol modified melamine resin aqueous solution, the tetramethylolmethane modified melamine resin aqueous solution or the polyvinyl alcohol modification melmac aqueous solution.
9. according to the preparation method of claim 6 or 7 or 8 described halogen-free flameproof polystyrene foamed materials, it is characterized in that the synergist described in this method is any in tetramethylolmethane, phosphoric acid and verivate thereof, sulfocompound or the expansible black lead.
10. according to the preparation method of claim 6 or 7 or 8 described halogen-free flameproof polystyrene foamed materials, it is characterized in that the toughener described in this method is any in talcum powder, aluminum oxide, Natural manganese dioxide, hydrotalcite or the polynite.
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| CN102977402A (en) * | 2012-12-18 | 2013-03-20 | 辽宁工程技术大学 | Preparation method of coated halogen-free flame-retardant foamable polystyrene |
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| CN103711211A (en) * | 2013-12-02 | 2014-04-09 | 苏州市建筑科学研究院有限公司 | Modified melamine formaldehyde resin-based EPS flame retardant thermal insulating board and preparation method thereof |
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| CN102977402B (en) * | 2012-12-18 | 2014-01-08 | 辽宁工程技术大学 | Preparation method of coated halogen-free flame-retardant foamable polystyrene |
| CN102977402A (en) * | 2012-12-18 | 2013-03-20 | 辽宁工程技术大学 | Preparation method of coated halogen-free flame-retardant foamable polystyrene |
| CN103121553A (en) * | 2013-01-28 | 2013-05-29 | 熊建珍 | Refrigeration refreshment box and method of manufacturing box materials |
| CN103711211B (en) * | 2013-12-02 | 2016-03-23 | 苏州市建筑科学研究院集团股份有限公司 | Modified melamine-formaldehyde resin base EPS fire-retardant heat insulation plate and preparation method thereof |
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| CN103980624B (en) * | 2014-05-19 | 2016-05-25 | 四川大学 | Halogen-free flameproof polystyrene foam composite material and preparation method thereof |
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