CN102604291B - Halogen-free flame-retardant polyvinyl alcohol foam material and preparation method thereof - Google Patents
Halogen-free flame-retardant polyvinyl alcohol foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a halogen-free flame-retardant polyvinyl alcohol foam material and a preparation method of the halogen-free flame-retardant polyvinyl alcohol foam material. The preparation method comprises the steps of preparing composite powder by uniformly mixing 100 parts of polyvinyl alcohol, 20-35 parts of nitrogen-phosphorus halogen-free flame retardant, 0.1-10 parts of catalyst and 0.1-10 parts of nucleating agent, adding the composite powder into mixed solution formed by 0.1-10 parts of surface active agent, 0.1-10 parts of cross-linking agent and 30-40 parts of plasticizing foaming agent, and swelling sufficiently at the temperature of 60 DEG C-80 DEG C, and then continuously extruding and foaming to obtain the halogen-free flame-retardant polyvinyl alcohol foam material at the temperature of 140 DEG C-180 DEG C and with the pressure 8-10MPa. According to the halogen-free flame-retardant polyvinyl alcohol foam material provided by the invention, the limit oxygen index reaches 36%, the vertical burning reaches L94-V0 level and the material can extinguish automatically without fire, the halogen-free flame-retardant property is good, the hole density of the foaming material can be improved, and the halogen-free flame-retardant polyvinyl alcohol foam material can be widely applied to the fields of heat insulation, sound isolation, shock absorption, packaging, sport equipment, clothes and back cushions, soles, sofa, cushions and the like. In addition, the foam is extruded continuously by melting, so that the preparation process is simple, low in cost and environment-friendly, and the halogen-free flame-retardant polyvinyl alcohol foam material is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to polyvinyl alcohol foam material and preparing technical field thereof, be specifically related to a kind of Zero halogen flame resistance polyethylene alcohol foam materials and preparation method thereof.
Background technology
Foam materials is to take macromolecule resin matrix as main body, includes the composite porous of countless abscesses.Because foam materials has light weight, sound insulation, heat insulation, buffering, and the feature such as specific tenacity is high, physicals degree of amplitude modulation is large, contour machining procedure is simple, be widely used in the fields such as industry, agricultural, daily, medical, building, communications and transportation, military affairs, aerospace, and become a kind of irreplaceable structure or functional materials.
The macromolecule resin of nearly all kind all can be made foam materials through suitable foaming forming technique in theory, but the impact due to foaming technology, at present scale operation and application only have a few, and be only limited to nonpolar or low-pole resin, as polystyrene (PS), polyolefine (PP, PE), urethane (PU) etc., greatly limited the Application Areas of foam materials.In addition, because macromolecule resin majority is comprised of hydrocarbon polymer, there is combustibility, not only more inflammable as the polymeric foamed material with vesicular structure, and also can discharge a large amount of poisonous, obnoxious flavour, the grievous injury person and property safety in the process of burning.Therefore, especially research and development application is significant with the fire retardant foam in the person and the closely related field of property safety in mattress, sofa, furniture packaging buffering, lightweight concrete building block and building energy conservation heat insulation etc. for research and development flame-retardant high-molecular foam materials.
Polyvinyl alcohol (PVA) is as a kind of water-soluble high-molecular material, not only because poly-hydroxy, strong hydrogen bonding structure have been given the excellent specific properties such as its strong polarity, high-melting-point, thermotolerance, antistatic, physiologically acceptable, solvent resistance, but also be a kind of synthesized polymer material that can complete biodegradable, in addition, polyvinyl alcohol also can be prepared by Non oil-based route, thereby today day by day lacking at petroleum resources, greatly develop polyvinyl alcohol associated materials, comprise that high-performance, multi-functional polyvinyl alcohol polarity foam materials have even more important meaning.At present, polyvinyl alcohol foam material is mainly that the method by solution machinery or chemical foaming makes, but solution method complex process, the production cycle is longer, and production cost is higher.This seminar once take water and by melt molding complete processing, successfully prepared polyvinyl alcohol polarity foam materials (CN101153089B) as the softening agent pneumatogen of holding concurrently.Although this technology provides new approach for production high-performance, multi-functional, low-cost polyvinyl alcohol polarity foam materials, but, the limiting oxygen index(LOI) extremely low (LOI value is about 19) of prepared polyvinyl alcohol foam material, very easily burn, greatly limited the Application Areas of polyvinyl alcohol foam material.
As fire-retardant polymeric foamed material, can be divided into eigenmode or addition type two classes.Wherein eigenmode fire retardant foam is fire-retardant because of the matrix itself that requires to foam, and this family macromolecule material quantity is limited.Research and development success at present the melamine foam material that only has BASF Aktiengesellschaft being applied.But this class melamine foam material still exists such as the difficult coordination of formaldehyde release, modulus and flame retardant resistance, fragility is larger, on the high side and produce the problems such as quilt monopolization.And additive flame retardant foam materials, as the polyurethane foam of low-pole, no matter whether flame-retardant modified, in the process of burning, all can produce molten drop phenomenon, and discharge the hazardous and noxious substances such as a large amount of prussic acid, oxynitride, isocyanic acid compound, the serious threat person and property safety.
The existing Wang Yu of method ，Ru Sichuan University about polyvinyl alcohol halogen-free flameproof is loyal waits people by ammonium polyphosphate, layered double hydroxide and polyvinyl alcohol composite in solution being prepared to Zero halogen flame resistance polyethylene alcohol; In addition, they also prepare Zero halogen flame resistance polyethylene alcohol (CN101058730A by ammonium polyphosphate, metallo-chelate and polyvinyl alcohol composite in solution; Wang D.L.et al./Polymer Degradation and Stability92 (2007) 1555-1564; Zhao C.X. et al./Polymer Degradation and Stability93 (2008) 1323-1331); And for example the people such as Sichuan University's Xu Jianjun, by phosphoric acid ester fire retardant, various auxiliary agent and polyvinyl alcohol blend in solution being made to spinning solution, prepares halogen-free flameproof high strength poly vinyl alcohol fiber (CN102002770A) with wet-spinning; For another example University Of Qingdao prolongs and the people such as causes and adopt solution method to prepare polyvinyl alcohol/silicon-dioxide fire-retardant fibre (CN101343781A in the summer; CN101343782A).Yet; Zero halogen flame resistance polyethylene alcohol material prepared by these methods is neither Zero halogen flame resistance polyethylene alcohol foam materials; and the fire retardant using and polyvinyl alcohol matrix affinity be poor, it is serious to separate out phenomenon; in addition be all to realize by solution blending; thereby there is complicated process of preparation; cost is high, is difficult to realize the problems such as continuous large-scale production.
Summary of the invention
The object of the invention is the problem existing for prior art, first a kind of Zero halogen flame resistance polyethylene alcohol foam materials is provided, this Zero halogen flame resistance polyethylene alcohol foam materials is to adopt commercialization, raw material cheaply, by improved melting continuous extrusion complete processing foaming, obtains.
Another object of the present invention is to provide a kind of preparation method of above-mentioned Zero halogen flame resistance polyethylene alcohol foam materials.
The invention provides Zero halogen flame resistance polyethylene alcohol foam materials,, it is characterized in that this foam materials is to be obtained through melt foaming by following component by weight:
And the limiting oxygen index(LOI) of this foam materials is 28～36% by ASTM D2863 standard testing, vertical combustion is UL94V0 level by ASTMD3801 standard testing.
Described in above-mentioned Zero halogen flame resistance polyethylene alcohol foam materials, polyvinyl alcohol is the polymerization degree 500～2400, in alcoholysis degree 88～99% any, preferred degree of polymerization 1700, alcoholysis degree 99%.Nitrogen-phosphorus halogen-free flame retardants is the series derivates that trimeric cyanamide and phosphoric acid form, preferably in melamine phosphate, melamine polyphosphate or melamine pyrophosphate any.Plasticising whipping agent is any mixture forming by weight 1: 1～5: 1 in water and ethanol, ethylene glycol, glycerol, tetramethylolmethane or sorbyl alcohol.Catalyzer for can catalyzed polyethylene dehydration of alcohols become the compound of charcoal, in preferential oxidation aluminium, magnesium oxide, phosphomolybdate, aluminosilicate, silicomolybdate, 4A molecular sieve, hydrotalcite or polynite any.Nucleator is for promoting the compound of polyvinyl alcohol foam material heterogeneous nucleation, in preferably talc powder, calcium carbonate, silicon-dioxide or zinc oxide any; Tensio-active agent is for reducing the compound of gas-liquid-solid interfacial free energy, in preferred alkyl vitriol, alkylsulfonate, stearate, siloxanes or fluorine carbon tensio-active agent any; Linking agent can impel the compound of polyvinyl alcohol generation crosslinking reaction, preferred boric acid or borax.
The preparation method of above-mentioned Zero halogen flame resistance polyethylene alcohol foam materials provided by the invention, is characterized in that the processing step of the method and condition are as follows:
(1) first 100 parts of polyvinyl alcohol, 20～35 parts of nitrogen-phosphorus halogen-free flame retardantss, 0.1～10 part of catalyzer, 0.1～10 portion of nucleator are added in high-speed mixer and mix and make composite granule, then 0.1～10 part of tensio-active agent and 0.1～10 part of linking agent are added in 30～45 parts of plasticising whipping agents and be mixed with mixing solutions, then composite granule is added in mixing solutions in 60～80 ℃ of abundant swellings;
(2) the composite granule of abundant swelling continuous extrusion foaming under 140～180 ℃ of melt temperatures, pressure 8～10MPa is obtained to Zero halogen flame resistance polyethylene alcohol foam materials.
Wherein the method polyvinyl alcohol used is the polymerization degree 500～2400, in alcoholysis degree 88～99% any, preferred degree of polymerization 1700, alcoholysis degree 99%.Nitrogen-phosphorus halogen-free flame retardants is the series derivates that trimeric cyanamide and phosphoric acid form, preferably in melamine phosphate, melamine polyphosphate or melamine pyrophosphate any.Plasticising whipping agent is any mixture forming by weight 1: 1～5: 1 in water and ethanol, ethylene glycol, glycerol, tetramethylolmethane or sorbyl alcohol.Catalyzer for can catalyzed polyethylene dehydration of alcohols become the compound of charcoal, in preferential oxidation aluminium, magnesium oxide, phosphomolybdate, aluminosilicate, silicomolybdate, 4A molecular sieve, hydrotalcite or polynite any.Nucleator is for promoting the compound of polyvinyl alcohol foam material heterogeneous nucleation, in preferably talc powder, calcium carbonate, silicon-dioxide or zinc oxide any; Tensio-active agent is for reducing the compound of gas-liquid-solid interfacial free energy, in preferred alkyl vitriol, alkylsulfonate, stearate, siloxanes or fluorine carbon tensio-active agent any; Linking agent can impel the compound of polyvinyl alcohol generation crosslinking reaction, preferred boric acid or borax.
The present invention compared with prior art, has following positively effect:
1) because polyvinyl alcohol foam material provided by the invention contains halogen-free flame retardants, and be again through melting continuous extrusion foaming, thereby not only realized first the halogen-free flameproof of polyvinyl alcohol foam material, make this foam materials have advantage and the halogen-free flameproof characteristic of polyvinyl alcohol foam material concurrently, can greatly expand polyvinyl alcohol foam material Application Areas, and melting continuous extrusion foaming preparation technology is simple, with low cost, environmental friendliness, is suitable for large-scale commercial production.
2) due to the inventive method be using commercialization, low cost, eco-friendly containing melamine phosphate compound and derivative thereof the halogen-free flame retardants as polyvinyl alcohol foam material, in addition be wherein also added with char forming catalyst, thereby both greatly improved the flame retardant properties of polyvinyl alcohol foam material, and there is again the advantage of environmental protection, cheap, Sustainable development.
3) because the inventive method is set about from raw material composition and complete processing, by adding fire retardant and various solid phase processing aid, both increased the nucleation site in foaming process, improve the hole density of foam materials and (seen accompanying drawing 1, 2), again by adding tensio-active agent, improved the dispersiveness of various fillers in polyvinyl alcohol matrix, the affinity that comprises fire retardant and polyvinyl alcohol matrix, reduced each alternate interfacial energy in foaming process, improved heterogeneous nucleation efficiency in foaming process, thereby overcome and existingly by melt-processed, prepared as bigger than normal in foam aperture that polyvinyl alcohol foam material runs into, size distribution is inhomogeneous, foam easily subsides, form is difficult to be controlled, the shortcomings such as stably manufactured serialization level is low, be easy to continuously, efficiently, realize economically suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the polyvinyl alcohol foam material prepared of existing melt processing;
Fig. 2 is the stereoscan photograph of the polyvinyl alcohol foam material prepared of the inventive method.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make according to the present invention some nonessential improvement and adjustment.
What deserves to be explained is, the limiting oxygen index(LOI) of following examples is by ASTM D2863 standard testing, and vertical combustion is by ASTM D3801 standard testing.
Embodiment 1
0588,20 parts of melamine phosphates of 100 parts of polyvinyl alcohol, 0.1 part of hydrotalcite and 0.1 part of calcium carbonate are mixed and make composite granule in high-speed mixer; 0.1 part of borax and 0.1 part of sodium lauryl sulphate are dissolved in to 30 parts of plasticising whipping agents (water: ethanol=5: 1), be mixed with mixing solutions; Above-mentioned composite granule is added in mixing solutions, mix rear sealing and be stored in abundant swelling in 60 ℃ of constant temperature ovens; Mixture after abundant swelling is obtained to Zero halogen flame resistance polyethylene alcohol foam materials by screw extrusion press continuous extrusion foaming under 140 ℃ of melt temperatures, pressure 8MPa.The limiting oxygen index(LOI) of this foam materials is 28%, and vertical combustion is UL94-V0 level.
1799,30 parts of melamine polyphosphates of 100 parts of polyvinyl alcohol, 3 parts of sodium aluminium silicates and 3 parts of zinc oxide are mixed and make composite granule in high-speed mixer; 3 parts of boric acid and 3 parts of silicone oil are dissolved in to 40 parts of plasticising whipping agents (water: ethylene glycol=5: 1), be mixed with mixing solutions; Above-mentioned composite granule is added in mixing solutions, mix rear sealing and be stored in abundant swelling in 70 ℃ of constant temperature ovens; Mixture after abundant swelling is obtained to Zero halogen flame resistance polyethylene alcohol foam materials by screw extrusion press continuous extrusion foaming under 160 ℃ of melt temperatures, pressure 9MPa.The limiting oxygen index(LOI) of this foam materials is 32%, and vertical combustion is UL94-V0 level.
Embodiment 3
2499,35 parts of melamine pyrophosphates of 100 parts of polyvinyl alcohol, 10 parts of 4A molecular sieves and 10 parts of talcum powder are mixed and make composite granule in high-speed mixer; 10 parts of boric acid and 10 parts of sodium laurylsulfonates are dissolved in to 45 parts of plasticising whipping agents (water: glycerol=1: 1), be mixed with mixing solutions; Above-mentioned composite powder is added in mixing solutions, mix rear sealing and be stored in abundant swelling in 80 ℃ of constant temperature ovens; Mixture after abundant swelling is obtained to Zero halogen flame resistance polyethylene alcohol foam materials by screw extrusion press continuous extrusion foaming under 180 ℃ of melt temperatures, pressure 10MPa.The limiting oxygen index(LOI) of this foam materials is 36%, and vertical combustion is UL94-V0 level.
Embodiment 4
1799,25 parts of melamine phosphates of 100 parts of polyvinyl alcohol, 1 part of sodium phosphomolybdate and 1 part of calcium carbonate are mixed and make composite granule in high-speed mixer; 1 part of borax and 1 portion of FC-100 fluorocarbon surfactant are dissolved in to 35 parts of plasticising whipping agents (water: glycerol=2: 1), be mixed with mixing solutions; Above-mentioned composite granule is added in mixing solutions, mix rear sealing and be stored in abundant swelling in 65 ℃ of constant temperature ovens; Mixture after abundant swelling is obtained to Zero halogen flame resistance polyethylene alcohol foam materials by screw extrusion press continuous extrusion foaming under 150 ℃ of melt temperatures, pressure 8.5MPa.The limiting oxygen index(LOI) of this foam materials is 30%, and vertical combustion is UL94-V0 level.
Embodiment 5
1799,30 parts of melamine phosphates of 100 parts of polyvinyl alcohol, 5 parts of molybdenum silicic acid acid sodium and 5 parts of silicon-dioxide are mixed and make composite granule in high-speed mixer; 5 parts of boraxs and 5 parts of sodium lauryl sulphate are dissolved in to 40 parts of plasticising whipping agents (water: glycerol=3: 1), be mixed with mixing solutions; Above-mentioned composite granule is added in mixing solutions, mix rear sealing and be stored in abundant swelling in 70 ℃ of constant temperature ovens; Mixture after abundant swelling is obtained to Zero halogen flame resistance polyethylene alcohol foam materials by screw extrusion press continuous extrusion foaming under 160 ℃ of melt temperatures, pressure 9MPa.The limiting oxygen index(LOI) of this foam materials is 33%, and vertical combustion is UL94-V0 level.
Embodiment 6
1799,35 parts of melamine phosphates of 100 parts of polyvinyl alcohol, 6 parts of polynites and 6 parts of talcum powder are mixed and make composite granule in high-speed mixer; 6 parts of boric acid and 6 parts of calcium stearates are dissolved in to 40 parts of plasticising whipping agents (water: tetramethylolmethane=4: 1), be mixed with mixing solutions; Above-mentioned composite granule is added in mixing solutions, mix rear sealing and be stored in abundant swelling in 75 ℃ of constant temperature ovens; Mixture after abundant swelling is obtained to Zero halogen flame resistance polyethylene alcohol foam materials by screw extrusion press continuous extrusion foaming under 170 ℃ of melt temperatures, pressure 9.5MPa.The limiting oxygen index(LOI) of this foam materials is 34%, and vertical combustion is UL94-V0 level.
Embodiment 7
1799,35 parts of melamine phosphates of 100 parts of polyvinyl alcohol, 8 parts of aluminum oxide and 8 parts of zinc oxide are mixed and make composite granule in high-speed mixer; 8 parts of boric acid and 8 parts of sodium lauryl sulphate are dissolved in to 45 parts of plasticising whipping agents (water: sorbyl alcohol=4: 1), be mixed with mixing solutions; Above-mentioned composite granule is added in mixing solutions, mix rear sealing and be stored in abundant swelling in 80 ℃ of constant temperature ovens; Mixture after abundant swelling is obtained to Zero halogen flame resistance polyethylene alcohol foam materials by screw extrusion press continuous extrusion foaming under 175 ℃ of melt temperatures, pressure 10MPa.The limiting oxygen index(LOI) of this foam materials is 35%, and vertical combustion is UL94-V0 level.
Embodiment 8
1799,35 parts of melamine phosphates of 100 parts of polyvinyl alcohol, 10 parts of magnesium oxide and 10 parts of calcium carbonate are mixed and make composite granule in high-speed mixer; 10 parts of boric acid and 10 parts of sodium lauryl sulphate are dissolved in to 45 parts of plasticising whipping agents (water: glycerol=5: 1), be mixed with mixing solutions; Above-mentioned composite granule is added in mixing solutions, mix rear sealing and be stored in abundant swelling in 80 ℃ of constant temperature ovens; Mixture after abundant swelling is obtained to Zero halogen flame resistance polyethylene alcohol foam materials by screw extrusion press continuous extrusion foaming under 180 ℃ of melt temperatures, pressure 10MPa.The limiting oxygen index(LOI) of this foam materials is 36%, and vertical combustion is UL94-V0 level.
Claims (4)
1. a Zero halogen flame resistance polyethylene alcohol foam materials, is characterized in that this foam materials is to be obtained through melt foaming by following component by weight:
Wherein nitrogen-phosphorus halogen-free flame retardants be in melamine phosphate, melamine polyphosphate or melamine pyrophosphate any; Plasticising whipping agent is any mixture forming by weight 1:1～5:1 in water and ethanol, ethylene glycol, glycerol, tetramethylolmethane or sorbyl alcohol; Catalyzer be in aluminum oxide, magnesium oxide, phosphomolybdate, aluminosilicate, silicomolybdate, 4A molecular sieve, hydrotalcite or polynite any; Nucleator be in talcum powder, calcium carbonate, silicon-dioxide or zinc oxide any; Tensio-active agent be in alkyl-sulphate, alkylsulfonate, stearate, siloxanes or fluorine carbon tensio-active agent any; Linking agent is boric acid or borax, and the limiting oxygen index(LOI) of this foam materials is 28～36% by ASTM D2863 standard testing, and vertical combustion is UL94V0 level by ASTM D3801 standard testing.
2. Zero halogen flame resistance polyethylene alcohol foam materials as claimed in claim 1, is characterized in that described polyvinyl alcohol is the polymerization degree 500～2400, in alcoholysis degree 88～99% any.
3. the preparation method of Zero halogen flame resistance polyethylene alcohol foam materials as claimed in claim 1, is characterized in that the processing step of the method and condition are as follows:
(1) first 100 parts of polyvinyl alcohol, 20～35 parts of nitrogen-phosphorus halogen-free flame retardantss, 0.1～10 part of catalyzer, 0.1～10 portion of nucleator are added in high-speed mixer and mix and make composite granule, then 0.1～10 part of tensio-active agent and 0.1～10 part of linking agent are added in 30～45 parts of plasticising whipping agents and be mixed with mixing solutions, then composite granule is added in mixing solutions in 60～80 ℃ of abundant swellings;
(2) the composite granule of abundant swelling continuous extrusion foaming under 140～180 ℃ of melt temperatures, pressure 8～10MPa is obtained to Zero halogen flame resistance polyethylene alcohol foam materials.
4. the preparation method of Zero halogen flame resistance polyethylene alcohol foam materials as claimed in claim 3, is characterized in that the method polyvinyl alcohol used is the polymerization degree 500～2400, in alcoholysis degree 88～99% any.
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| CN103351561A (en) * | 2013-01-25 | 2013-10-16 | 北京工商大学 | Polyvinyl alcohol/montmorillonite nano-alloy foam material and preparation method thereof |
| CN104177115B (en) * | 2013-05-27 | 2018-03-27 | 乌鲁木齐益好天成新型节能材料有限公司 | A kind of method that solid phase Silica hydrogel prepares foamed material |
| CN104876532B (en) * | 2015-05-15 | 2017-06-16 | 山东聊建集团有限公司 | A kind of roofing extruded sheet applies material with envelope |
| CN105713328B (en) * | 2016-01-29 | 2018-08-28 | 四川大学 | Height fills high heat-proof polythene alcohol radical fretting map type fire retardant papers and its thermoplastic processing method |
| CN109562998A (en) | 2016-07-20 | 2019-04-02 | 西索斯公司 | Application of the geo-polymer additive together with non-brominated fire retardant in foam of polymers |
| CN106496896B (en) * | 2016-11-22 | 2019-05-31 | 四川大学 | A kind of polyvinyl alcohol cellular material and preparation method thereof |
| CN109467734A (en) * | 2018-10-01 | 2019-03-15 | 宁波大学 | A kind of polyvinyl alcohol/silicon dioxide composition microcellular foam material |
| CN113150475B (en) * | 2021-02-26 | 2023-05-02 | 四川大学 | Method for preparing large-size interface flame-retardant polyvinyl alcohol foam material |
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| CN101058730A (en) * | 2007-06-06 | 2007-10-24 | 四川大学 | Phosphorus-nitrogen type halogen-free ionic fire retardant, preparation method thereof and fire retarding polyvinyl alcohol material prepared from the same |
| CN101153089A (en) * | 2007-09-06 | 2008-04-02 | 四川大学 | Polyvinyl alcohol polarity sponge plastics and method of producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101058730A (en) * | 2007-06-06 | 2007-10-24 | 四川大学 | Phosphorus-nitrogen type halogen-free ionic fire retardant, preparation method thereof and fire retarding polyvinyl alcohol material prepared from the same |
| CN101153089A (en) * | 2007-09-06 | 2008-04-02 | 四川大学 | Polyvinyl alcohol polarity sponge plastics and method of producing the same |
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