CN102010587A - Method for preparing novel flame-retardant flexible polyurethane foam and product thereof - Google Patents
Method for preparing novel flame-retardant flexible polyurethane foam and product thereof Download PDFInfo
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- CN102010587A CN102010587A CN2010105347091A CN201010534709A CN102010587A CN 102010587 A CN102010587 A CN 102010587A CN 2010105347091 A CN2010105347091 A CN 2010105347091A CN 201010534709 A CN201010534709 A CN 201010534709A CN 102010587 A CN102010587 A CN 102010587A
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Abstract
The invention relates to a method for preparing novel flame-retardant flexible polyurethane foam and a product thereof. In the preparation method, attapulgite serving as natural mineral soil and melamine serving as the conventional cheap organic flame retardant are compounded. The preparation process comprises the following steps of: uniformly mixing polyether glycol, a foam stabilizer, a foaming agent, a tin catalyst, a gel catalyst, the melamine, the attapulgite and the like to obtain a viscous mixture; quickly adding isocyanate into the viscous mixture under stirring; and slaking for a certain period of time at a certain temperature after complete foaming and curing are performed to obtain a flexible polyurethane foam product with flame retardant function. The invention has the characteristics that: the method for preparing the flame-retardant flexible polyurethane foam has a simple process and low production cost, does not need special equipment, is easy to industrialize and implement, and the like. The flame-retardant polyurethane foam product is flexible foam with high flame retardant property.
Description
Technical field
The present invention relates to the flame-retardant polyurethane foam plastic field, be specially preparation method of the good and flexible urethane foam that production cost is low of a kind of flame retardant resistance and products thereof.These flame-retardant flexible polyurethane foam plastics can be applicable to fields such as building, furniture.
Background technology
Urethane foam is one of principal item of polyurethane synthetic material, and ultimate production accounts for about 60% of polyurethane material.Because of it has excellent physical and mechanical properties, electric property, acoustical behavior and resistance to chemical corrosion, and have very strong cohesive force, be widely used in every field with multiple material.
According to soft or hard degree difference, urethane foam is broadly divided into following several: flexible PU foam, hard polyurethane foam and polyurethane semihard foam, wherein flexible PU foam is the flexible urethane foam goods owing to have good springiness, the little unrivaled advantage of other material that waits of specific tenacity height and density is widely used in furniture, communications and transportation, carpet underlay and other field and makes the pad material.
Though urethane foam has purposes widely in a lot of fields, it but has a very fatal weakness is inflammable and difficult from putting out.Contain combustible hydrocarbon segment in the urethane foam molecular structure, density is little, specific surface area is big, thermal conductivity is low, urethane foam without fire-retardant finish is inflammable substance, its limiting oxygen index(LOI) generally is lower than 19, meets fire burns and produces a large amount of toxic smogs, brings difficulty to fire extinguishing.Flexible urethane foam particularly, its percentage of open area is higher, and combustiblecomponents is many, in case catch fire, owing to have higher air circulation, have endlessly oxygen supply with, so inflammable and difficult from putting out, seriously limited it and has been extensive use of during burning.But many Application Areass of flexible urethane foam (as material of construction, mattress, furniture, lagging material, seat cushions and interior material etc.) all have the flame retardant properties requirement, especially in recent years, China to be used to build, the polyurethane foamed material of furniture, aircraft, steamer, train, automobile, other important place and facility, fire-retardant requirement has successively all been proposed.Therefore, the research of flame retardant polyurethane material is the focus of current polyurethane material research always.
At present, improve the flexible urethane foam flame retardant resistance and mainly contain two approach: the one, add additive flame retardant (compounds of elements such as chloride, bromine, phosphorus); Another is exactly to introduce reactive flame retardant, keys in atoms such as chlorine, bromine, phosphorus, antimony in polyurethane structural by it, obtains the structure-type fire retardant material.
The used reactive flame retardant of urethane mostly be various liquid state and solid-state phosphorous, nitrogen or (with) flame-proof polyol of halogen and phosphorous isocyanic ester etc.Reactive flame retardant participates in reaction as a kind of reacted constituent, keys in atoms such as chlorine, bromine, phosphorus, antimony in polyurethane structural, makes urethane itself contain flame-retardant composition, has little, the stable characteristics such as good of material property influence.But it is loaded down with trivial details that the introducing reactive flame retardant has operation, shortcomings such as production cost height, and industrial applications is less at present.
Adding additive flame retardant is the more convenient and economic effective ways that improve the urethane foam flame retardant resistance, is meant when making urethane foam, adds some and the nullvalent fire retardant of reactant, and this method also is the emphasis of present industrial application.Additive flame retardant mainly is divided into inorganic combustion inhibitor and organic fire-retardant: inorganic combustion inhibitor mainly is antimony, aluminium, boron, phosphorus compound; Organic fire-retardant mainly is phosphorus-halogen organic ester (halogenated phosphate), halogenated aliphatic hydrocarbon, organo phosphorous compounds etc.
At present, the fire retardant that can be used for flexible PU foam is usually based on organic fire-retardant, mainly is the organic compound of phosphorous, chlorine, bromo element.But such organic fire-retardant flame retardant effect remains further to be improved, and price is relatively expensive, has limited the application of flexible PU foam to a certain extent.Therefore, the good and lower new type soft polyurethane foam of production cost of exploitation flame retardant properties is a brand-new problem.
Summary of the invention
Remain further to be improved at existing organic fire-retardant flame retardant effect, and the relatively expensive deficiency of price, the technical problem that quasi-solution of the present invention is determined is: design preparation method of a kind of novel flame-retardant flexible urethane foam and products thereof.It is composite that this product adopts the native attapulgite of organic fire-retardant and mineral substance to carry out, characteristics such as have good flame retardation effect, production technique is simple, production cost is low, do not need specific installation, industrializing implementation is easy.
The technical scheme that the present invention solves described flame-retardant flexible polyurethane foam plastics preparation method technical problem is to select for use organic fire-retardant and attapulgite to carry out composite.Described attapulgite is a kind of natural mineral matter soil, for a kind of have a chain laminate structure contain Shuifu County's magnesium silicate clay mineral, typical chemical formula is Si
8Mg
6O
20(OH)
2(OH
2)
44H
2O, its structure belongs to 2: 1 type clay minerals.In each 2: 1 unit structure layer, tetrahedron wafer angle is pushed up at a certain distance direction and is put upside down, and the form layers chain forms the passage parallel with chain, filling zeolite water and crystal water in the passage at tetrahedron bar interband.
Flame-retardant flexible polyurethane foam plastics preparation method of the present invention comprises the steps:
(1) take by weighing polyether glycol 100g, isocyanic ester 100～110g, suds-stabilizing agent (silicone oil) 1～2g, whipping agent (water) 3～4g, tin catalyst 0.5～1g, gel catalyst triethylenediamine 0.5～1g, and fire retardant trimeric cyanamide 5～10g, attapulgite 5～10g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 40 ℃～60 ℃ following slakings 2～4 hours.
Beneficial effect of the present invention:
It is to utilize conventional organic fire-retardant trimeric cyanamide and attapulgite to act synergistically that the present invention solves described flame-retardant flexible polyurethane foam plastics.Contain zeolite water and crystal water in the attapulgite, the water that discharges when porous plastics burns can reduce the temperature of porous plastics, thereby plays certain fire retardation; In addition, contain Mg, Si element in the attapulgite, the oxide compound that generates during burning covers the Foam Plastic Surface starvation, thereby reaches fire-retardant purpose.
Compare with existing flexible urethane foam flame-retarded technology, the present invention adopts conventional inexpensive organic fire-retardant trimeric cyanamide and attapulgite to carry out composite, because attapulgite is cheap, composite back is under the situation that obtains same pole limited oxygen index value, the consumption of organic fire-retardant can be significantly reduced, thereby fire-retardant cost can be significantly reduced.
At present, utilize attapulgite to carry out that plastics are fire-retardant appear in the newspapers (CN101735516A), but the relevant attapulgite that utilizes come the research of cooperative flame retardant flexible urethane foam not appear in the newspapers as yet.The present invention adopts attapulgite cooperative flame retardant flexible urethane foam, and the foaming of flexible urethane foam, structure and performance Deng of porous plastics are influenced not quite, is suitable for industrial applications.
Flame-retardant flexible polyurethane foam plastics preparation method of the present invention is simple, production cost is low, do not need specific installation, industrializing implementation is easy, and adopts and use water as whipping agent, can not produce pollution.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1:
(1) take by weighing polyether glycol 100g, isocyanic ester 100g, suds-stabilizing agent 1g, whipping agent 3g, tin catalyst 0.5g, gel catalyst triethylenediamine 0.5g, and fire retardant trimeric cyanamide 5g, attapulgite 5g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 40 ℃ of following slakings 2 hours.
Embodiment 2:
(1) take by weighing polyether glycol 100g, isocyanic ester 100g, suds-stabilizing agent 1g, whipping agent 4g, tin catalyst 0.5g, gel catalyst triethylenediamine 0.5g, and fire retardant trimeric cyanamide 10g, attapulgite 5g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 60 ℃ of following slakings 2 hours.
Embodiment 3:
(1) take by weighing polyether glycol 100g, isocyanic ester 100g, suds-stabilizing agent 2g, whipping agent 4g, tin catalyst 0.5g, gel catalyst triethylenediamine 0.5g, and fire retardant trimeric cyanamide 10g, attapulgite 10g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 50 ℃ of following slakings 3 hours.
Embodiment 4:
(1) take by weighing polyether glycol 100g, isocyanic ester 110g, suds-stabilizing agent 2g, whipping agent 4g, tin catalyst 1g, gel catalyst triethylenediamine 1g, and fire retardant trimeric cyanamide 10g, attapulgite 5g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 40 ℃ of following slakings 4 hours.
Embodiment 5:
(1) take by weighing polyether glycol 100g, isocyanic ester 110g, suds-stabilizing agent 2g, whipping agent 3.5g, tin catalyst 1g, gel catalyst triethylenediamine 1g, and fire retardant trimeric cyanamide 8g, attapulgite 10g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 50 ℃ of following slakings 3 hours.
Embodiment 6:
(1) take by weighing polyether glycol 100g, isocyanic ester 110g, suds-stabilizing agent 2g, whipping agent 4g, tin catalyst 0.5g, gel catalyst triethylenediamine 1g, and fire retardant trimeric cyanamide 8g, attapulgite 10g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 60 ℃ of following slakings 2 hours.
Embodiment 7:
(1) take by weighing polyether glycol 100g, isocyanic ester 105g, suds-stabilizing agent 1.5g, whipping agent 3.5g, tin catalyst 1g, gel catalyst triethylenediamine 0.5g, and fire retardant trimeric cyanamide 5g, attapulgite 8g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 45 ℃ of following slakings 3.5 hours.
Embodiment 8:
(1) take by weighing polyether glycol 100g, isocyanic ester 102g, suds-stabilizing agent 1.8g, whipping agent 4g, tin catalyst 0.75g, gel catalyst triethylenediamine 0.8g, and fire retardant trimeric cyanamide 10g, attapulgite 5g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 60 ℃ of following slakings 4 hours.
Embodiment 9:
(1) take by weighing polyether glycol 100g, isocyanic ester 100g, suds-stabilizing agent 2g, whipping agent 3.8g, tin catalyst 0.8g, gel catalyst triethylenediamine 0.8g, and fire retardant trimeric cyanamide 10g, attapulgite 10g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 60 ℃ of following slakings 4 hours.
Embodiment 10:
(1) take by weighing polyether glycol 100g, isocyanic ester 110g, suds-stabilizing agent 2g, whipping agent 4g, tin catalyst 0.9g, gel catalyst triethylenediamine 0.6g, and fire retardant trimeric cyanamide 9g, attapulgite 9g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture.
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 50 ℃ of following slakings 3.5 hours.
Claims (4)
1. preparation method of the flexible urethane foam that flame retardant resistance is good and production cost is low and products thereof, it is characterized in that described flame-retardant flexible polyurethane foam plastics are that to utilize a kind of natural mineral matter soil attapulgite and conventional inexpensive organic fire-retardant trimeric cyanamide to carry out composite, its preparation process comprises:
(1) take by weighing polyether glycol 100g, isocyanic ester 100～110g, suds-stabilizing agent (silicone oil) 1～2g, whipping agent (water) 3～4g, tin catalyst 0.5～1g, gel catalyst triethylenediamine 0.5～1g, and fire retardant trimeric cyanamide 5～10g, attapulgite 5～10g.Adopt a step foam process, successively polyether glycol, suds-stabilizing agent, catalyzer, water and fire retardant are added in the beaker successively, under high speed electric stirs it is stirred and obtain viscous mixture;
(2) under whipped state, isocyanic ester is added in the heavy-gravity polyether glycol mixture fast, stir fast simultaneously.Before the reactant color begins to present oyster white, be poured in the preprepared mould.Wait to foam after complete and the curing, the mould that is filled with porous plastics is put into baking oven,, take out mold releasability at last and obtain the flame-retardant flexible polyurethane foam plastics in 40 ℃～60 ℃ following slakings 2～4 hours.
2. the preparation method of flame-retardant flexible polyurethane foam plastics according to claim 1, and it is characterized in that utilizing the mineral substance soil attapulgite and the inexpensive organic fire-retardant trimeric cyanamide of routine to carry out composite as fire retardant, fire retardant trimeric cyanamide 5～10g, protruding rod soil 5～10g.
3. flame-retardant flexible polyurethane foam plastics preparation method according to claim 1 is characterized in that described flame-retardant flexible polyurethane foam plastics flame retardant properties is good, cost is lower.
4. flame-retardant flexible polyurethane foam plastics preparation method according to claim 1, it is characterized in that described flame-retardant flexible polyurethane foam plastics flame-retardant flexible polyurethane foam plastics according to claim 1 preparation method, it is characterized in that described flame-retardant flexible polyurethane foam plastics can be applicable to fields such as building, furniture.
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|---|---|---|---|
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| CN102643403A (en) * | 2012-04-27 | 2012-08-22 | 中国林业科学研究院亚热带林业研究所 | Self-cleaning polyurethane soft foam and preparation method thereof |
| CN103483542A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Environment-friendly and flame-retardant polyurethane foam material |
| CN103483538A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Modified polyurethane rigid foam |
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| CN103483804A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Sound-proof and thermal-insulating polyurethane foaming plastic |
| CN103483543A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | High inflaming retarding polyurethane foaming plastic |
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| CN103483545A (en) * | 2013-09-26 | 2014-01-01 | 南京年吉冷冻食品有限公司 | Preparation method for environment-friendly, flame-retardant and soft polyurethane foaming plastic |
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| CN102643403A (en) * | 2012-04-27 | 2012-08-22 | 中国林业科学研究院亚热带林业研究所 | Self-cleaning polyurethane soft foam and preparation method thereof |
| CN103483523A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Polyurethane foam added with modified attapulgite |
| CN103483532A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Modified polyurethane foaming plastic |
| CN103483531A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Polyurethane foam material prepared from bean pulp |
| CN103483804A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Sound-proof and thermal-insulating polyurethane foaming plastic |
| CN103483543A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | High inflaming retarding polyurethane foaming plastic |
| CN103483806A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Grape vine-polyurethane composite foam materiel |
| CN103483538A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Modified polyurethane rigid foam |
| CN103483542A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Environment-friendly and flame-retardant polyurethane foam material |
| CN103483544A (en) * | 2013-09-23 | 2014-01-01 | 安徽济峰节能材料有限公司 | Polyurethane foam filled with glass beads |
| CN103497298B (en) * | 2013-09-23 | 2016-04-13 | 安徽济峰节能材料有限公司 | A kind of Heat insulation fluoride-free polyurethane foam material |
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Application publication date: 20110413 |