CN104194319B - A kind of halogen-free high flame-retardant polyisocyanurate foam and preparation method thereof - Google Patents
A kind of halogen-free high flame-retardant polyisocyanurate foam and preparation method thereof Download PDFInfo
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- CN104194319B CN104194319B CN201410493990.7A CN201410493990A CN104194319B CN 104194319 B CN104194319 B CN 104194319B CN 201410493990 A CN201410493990 A CN 201410493990A CN 104194319 B CN104194319 B CN 104194319B
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Abstract
The invention discloses a kind of halogen-free high flame-retardant polyisocyanurate foam and preparation method thereof, it is characterized in that: in foams, the part by weight of each raw material is: polyisocyanurate foam raw material 65～95%；Hypophosphite fire retardant 5～15%；Ammonium polyphosphate flame retardant 0～10%；Organic phosphonium flame retardant 0～10%；Polyisocyanurate foam raw material is made up of PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physical blowing agent and polyisocyanates.Halogen-free high flame-retardant polyisocyanurate foam obtained by the present invention, integrates that condensed phase is fire-retardant, gas phase is fire-retardant, has the highest fire resistance, good mechanical property and insulation heat-insulating property.
Description
Technical field
The invention belongs to technical field of flame retardant, be specifically related to a kind of halogen-free high flame-retardant polyisocyanurate foam and preparation side thereof
Method.
Background technology
Fire of high-rise building frequently occurs, and brings serious loss to the country and people, mainly due to inflammable exterior-wall heat insulation
Material causes.The anti-flammability how improving external-wall heat-insulation material becomes people's problem demanding prompt solution.Hard polyurethane foams,
There is the good characteristics such as insulation effect is good, lightweight, specific strength big, easy construction, be widely used in building, storage tank and pipeline
Insulation material.Polyurethane foam board is broadly divided into hard polyurethane foam board (RPUF) and polyisocyanurate foam plate (PIR).
Polyisocyanurate foam, owing to having stable isocyanuric acid ester hexatomic ring, has more compared with common hard polyurethane foams
High anti-flammability.
GB GB8624-2012 (construction material and product burns grading performance) specifying, metope insulation foamed plastic to be made reaches
B1 level (nonflammable material) requirement, needs foam plastics limited oxygen index LOI >=30.B2 level (combustible material) limited oxygen index
LOI≥26。
Polyisocyanurate foam is owing to containing substantial amounts of isocyanuric acid ester hexatomic ring in its structure, relative to general hard polyaminoester
Foam is easier to fire-retardant, particularly the poly-chlorinated isocyanurates foam containing aromatic ring polyester construction, only need to add a small amount of fire retardant the most permissible
Reach B2 level.But the report reaching B1 level flame-retardancy requirements is less.
Chinese patent CN103665305A discloses a kind of high-fire-resistance polysiocyanurate rigid foams and preparation method thereof, its
In mainly employ phosphorous chloride liquid combustion inhibitor (such as three (2-chloroethyl) ester (TCEP), tricresyl phosphate (2-chloropropyl) ester (TCPP)
Deng), phosphorous aromatic liquid race fire retardant and solid-state microencapsulated powder oil fire retardant, oxygen index (OI) is the highest can reach more than 30；In
State's patent CN102391465A discloses a kind of flame-retardant plate poly-chlorinated isocyanurates premixed systems and preparation method thereof, mainly
Using aromatic polyester polyol and phosphorous chloride liquid combustion inhibitor such as TCPP, TCEP etc., oxygen index (OI) can reach 34
Above.But described patent all employ halogen containing flame-retardant.Although these fire retardants have the highest flame retarding efficiency, but in combustion
The flue gas with corrosivity and toxicity can be discharged during burning, the Architectural Equipment of surrounding is had serious destructiveness, it is possible to also
Can cause secondary disaster, and very harmful to people of toxicity flue gas.Simple use halogen-free phosphorus-containing fire retardant agent to reach B1 level is fire-retardant wants
The polyisocyanurate foam asked rarely has report.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of halogen-free high flame-retardant polyisocyanurate foam and system thereof
Preparation Method, the polyisocyanurate foam oxygen index (OI) being prepared can reach 30, thus avoid the use of halogen containing flame-retardant,
There is good insulation thermal insulation and mechanical property simultaneously.
For solving the problems referred to above, the present invention adopts the technical scheme that:
Halogen-free high flame-retardant polyisocyanurate foam of the present invention, its feature is: the part by weight of each raw material in described foams
For: polyisocyanurate foam raw material 65～95%；Hypophosphite fire retardant 5～15%；Ammonium polyphosphate flame retardant 0～10%；
Organic phosphonium flame retardant 0～10%.
Halogen-free high flame-retardant polyisocyanurate foam of the present invention, its feature is: described polyisocyanurate foam raw material is by gathering
Ester polyol, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physical blowing agent and many isocyanides
Acid esters is constituted；
PEPA, amines catalyst, metal-based catalysts, water, poly-silica in described polyisocyanurate foam raw material
The mass ratio of alkanes foam stabiliser, physical blowing agent and polyisocyanates is 100:1-5:0.1-1:0.5-1.5:1-3:10-50:
250-350。
The preparation method of halogen-free high flame-retardant polyisocyanurate foam of the present invention, its feature is:
A, weigh PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physics
Foaming agent, polyisocyanates, hypophosphites, APP and organic phosphonium flame retardant constitute raw material group；
B, PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physics are sent out
Infusion and the mixing of organic phosphonium flame retardant, and stir, it is thus achieved that mixture A；
C, hypophosphites, APP and polyisocyanates being mixed, and mechanical agitation is uniform, it is thus achieved that mixture B；
D, the mixture A obtained in addition step b in the mixture B that step c is obtained, inject mould after stirring
Foams, after foam is initiated, are taken out and are placed on ripening 24 hours in 70 degree of baking ovens, obtain halogen-free high flame-retardant by middle foaming
Polyisocyanurate foam.
PEPA in raw material group described in step a, amines catalyst, metal-based catalysts, water, polysiloxanes class A foam A are steady
Determine agent, physical blowing agent, the mass ratio of polyisocyanates are: PEPA: amines catalyst: metal-based catalysts: water:
Polysiloxane-based foam stabiliser: physical blowing agent: polyisocyanates=100:1-5:0.1-1:0.5-1.5:1-3:10-50:
250-350；The quality of hypophosphites is the 5～15% of raw material group gross mass；The quality of APP be raw material group gross mass 0～
10%；The quality of organic phosphonium flame retardant is the 0～10% of raw material group gross mass.
Preferably, described PEPA is the benzoic anhydride polyester polyol of hydroxyl value 250～350mgKOH/g；
Described amines catalyst be air chemical industry Polycat 8 and in air chemical industry Polycat 46 one or both combination.
Described metal-based catalysts is one or both combinations in air chemical industry Dabco K-15 and air chemical industry Polycat 46；
Described polysiloxane-based foam stabiliser is polyether modified silicon oil；
Described physical blowing agent preferably one fluorine dichloroethanes (HCFC141b).
Described polyisocyanates is the polymethylene polyphenyl polyisocyanic acid that mass percent is 30～32wt% of NCO group
Ester；
Described hypophosphites is melamine hypophosphite, hypo-aluminum orthophosphate, calcium hypophosphite, cerous hypophosphate, zinc hypophosphite or secondary phosphorus
Acid lanthanum.
Described APP is polymerization degree n > the crystallization II-type high molecular APP of 1000 or microcapsule APP be (such as honey
Polyimide resin microcapsule APP, phenolic resin microcapsule APP and Silica hydrogel microcapsule APP).
Described organic phosphonium flame retardant is resorcinol double (diphenyl phosphoester) (RDP), bisphenol-A pair (diphenyl phosphoester)
(BDP), dimethyl methyl phosphonate (DMMP), diethyl ethylphosphate (DEEP), trimethyl phosphate (TMP), phosphoric acid
The mixing of one or more in triethyl (TEP).
Compared with the prior art, beneficial effects of the present invention is embodied in:
Principle And Method of Flame Retardation Design of the present invention integrates that condensed phase is fire-retardant, gas phase is fire-retardant, and raw material is easy to get, and preparation is simple, and flame retarding efficiency is high,
Low cost；Prepared polyisocyanurate foam self-extinguishment is very strong, can reach UL-94V-0 rank, and insulation insulation effect is good,
Good mechanical properties.
Specific embodiment
The preparation method of the present embodiment halogen-free high flame-retardant polyisocyanurate foam, is carried out as follows:
A, weigh PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physics
Foaming agent, polyisocyanates, hypophosphites, APP and organic phosphonium flame retardant constitute raw material group；
B, PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physics are sent out
Infusion and the mixing of organic phosphonium flame retardant, and stir, it is thus achieved that mixture A；
C, hypophosphites, APP and polyisocyanates being mixed, and mechanical agitation is uniform, it is thus achieved that mixture B；
D, the mixture A obtained in addition step b in the mixture B that step c is obtained, inject mould after stirring
Foams, after foam is initiated, are taken out and are placed on ripening 24 hours in 70 degree of baking ovens, obtain halogen-free high flame-retardant by middle foaming
Polyisocyanurate foam.
In raw material group, the quality of each raw material is as shown in table 1:
The formula of each raw material used by table 1 comparative example and embodiment 1-5
Note: the benzoic anhydride polyester polyol that PEPA is hydroxyl value 300mgKOH/g used in comparative example；Amines catalyst
For air chemical industry Polycat 8 and the mixture of air chemical industry Dabco TMR-2 1:1.5 in mass ratio；Metal-based catalysts is empty
Gasification work Dabco K-15；Water is deionized water；Foam stabiliser is polyether modified silicon oil；Physical blowing agent is fluorine two chloroethene
Alkane (HCFC141b)；Polyisocyanates is the poly methylene poly phenyl poly isocyanate of (NCO%=32%).
The benzoic anhydride polyester polyol that PEPA is hydroxyl value 330mgKOH/g used in embodiment 1；Amines catalyst is
Air chemical industry Polycat 8 and the mixture of air chemical industry Dabco TMR-2 1:2 in mass ratio；Metal-based catalysts is air
Work Dabco K-15；Water is deionized water；Foam stabiliser is polyether modified silicon oil；Physical blowing agent is a fluorine dichloroethanes
(HCFC141b)；Polyisocyanates is the poly methylene poly phenyl poly isocyanate of (NCO%=32%)；Hypophosphites is fire-retardant
Agent is melamine hypophosphite；Ammonium polyphosphate flame retardant is polymerization degree n > the crystallization II-type high molecular APP of 1000；Have
Machine phosphonium flame retardant is trimethyl phosphate (TMP).
The benzoic anhydride polyester polyol that PEPA is hydroxyl value 280mgKOH/g used in embodiment 2；Amines catalyst is
Air chemical industry Polycat 8 and the mixture of air chemical industry Dabco TMR-2 1:3 in mass ratio；Metal-based catalysts is air
Work Polycat 46；Water is deionized water；Foam stabiliser is polyether modified silicon oil；Physical blowing agent is a fluorine dichloroethanes
(HCFC141b)；Polyisocyanates is the poly methylene poly phenyl poly isocyanate of (NCO%=32%)；Hypophosphites is fire-retardant
Agent is calcium hypophosphite；Ammonium polyphosphate flame retardant is melamine resin microcapsule APP；Organic phosphonium flame retardant is ethylphosphonic acid two
Ethyl ester (DEEP).
The benzoic anhydride polyester polyol that PEPA is hydroxyl value 315mgKOH/g used in embodiment 3；Amines catalyst is
Air chemical industry Polycat 8 and the mixture of air chemical industry Dabco TMR-2 1:2.5 in mass ratio；Metal-based catalysts is air
Chemical industry Dabco K-15；Water is deionized water；Foam stabiliser is polyether modified silicon oil；Physical blowing agent is a fluorine dichloroethanes
(HCFC141b)；Polyisocyanates is the poly methylene poly phenyl poly isocyanate of (NCO%=32%)；Hypophosphites is fire-retardant
Agent is hypo-aluminum orthophosphate；Ammonium polyphosphate flame retardant is polymerization degree n > the crystallization II-type high molecular APP of 1000；Organic phosphorous resistance
Combustion agent is dimethyl methyl phosphonate (DMMP).
The benzoic anhydride polyester polyol that PEPA is hydroxyl value 300mgKOH/g used in embodiment 4；Amines catalyst is
Air chemical industry Polycat 8 and the mixture of air chemical industry Dabco TMR-2 1:2 in mass ratio；Metal-based catalysts is air
Work Dabco K-15；Water is deionized water；Foam stabiliser is polyether modified silicon oil；Physical blowing agent is a fluorine dichloroethanes
(HCFC141b)；Polyisocyanates is the poly methylene poly phenyl poly isocyanate of (NCO%=32%)；Hypophosphites is fire-retardant
Agent is hypophosphorous acid lanthanum；Ammonium polyphosphate flame retardant is phenolic resin microcapsule APP；Organic phosphonium flame retardant is that resorcinol is double
(diphenyl phosphoester) (RDP).
The benzoic anhydride polyester polyol that PEPA is hydroxyl value 330mgKOH/g used in embodiment 5；Amines catalyst is
Air chemical industry Polycat 8 and the mixture of air chemical industry Dabco TMR-2 1:3 in mass ratio；Metal-based catalysts is air
Work Dabco K-15 and the mixture of air chemical industry Polycat 46 1:1 in mass ratio；Water is deionized water；Foam stabiliser is
Polyether modified silicon oil；Physical blowing agent is a fluorine dichloroethanes (HCFC141b)；Polyisocyanates is (NCO%=32%'s)
Poly methylene poly phenyl poly isocyanate；Hypophosphite fire retardant is cerous hypophosphate；Ammonium polyphosphate flame retardant is Silica hydrogel microcapsule
APP；Organic phosphonium flame retardant is dimethyl methyl phosphonate (DMMP) and bisphenol-A pair (diphenyl phosphoester) (BDP)
The mixture of 2:1 in mass ratio.
The table 2 density of polyisocyanurate foam obtained by comparative example and embodiment 1-5, mechanical property, heat conductivity
And fire resistance.The halogen-free flameproof isocyanurate foam body that as can be seen from the table prepared by the present invention has good flame retardant effect
With good mechanical property and heat-insulating property.
The density of the polyisocyanurate foam obtained by table 2 comparative example and embodiment 1-5, mechanical property, heat conductivity and
Fire resistance
Above the present invention is done detailed description, its object is to allow the those of ordinary skill being familiar with this art will appreciate that
Present disclosure is also carried out, and can not limit the scope of the invention with this, all spirit institutes according to the present invention
The equivalent transformation made, all should contain within the scope of the present invention.
Claims (5)
1. a halogen-free high flame-retardant polyisocyanurate foam, it is characterised in that: in described foams, the part by weight of each raw material is: polyisocyanurate foam raw material 65～95%；Hypophosphite fire retardant 5～15%；Ammonium polyphosphate flame retardant 0～10%；Organic phosphonium flame retardant 0～10%；And the quality of APP and organic phosphonium flame retardant is not 0；
Described polyisocyanurate foam raw material is made up of PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physical blowing agent and polyisocyanates；
In described polyisocyanurate foam raw material, the mass ratio of PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physical blowing agent and polyisocyanates is 100:1-5:0.1-1:0.5-1.5:1-3:10-50:250-350.
Halogen-free high flame-retardant polyisocyanurate foam the most according to claim 1, it is characterised in that: described PEPA is the benzoic anhydride polyester polyol of hydroxyl value 250～350mgKOH/g；
Described amines catalyst be air chemical industry Polycat 8 and in air chemical industry Polycat 46 one or both combination；
Described metal-based catalysts is one or both combinations in air chemical industry Dabco K-15 and air chemical industry Polycat 46；
Described polysiloxane-based foam stabiliser is polyether modified silicon oil；
Described physical blowing agent is a fluorine dichloroethanes HCFC141b；
Described polyisocyanates is the poly methylene poly phenyl poly isocyanate that mass percent is 30～32wt% of NCO group.
Halogen-free high flame-retardant polyisocyanurate foam the most according to claim 1, it is characterised in that:
Described hypophosphite fire retardant is selected from melamine hypophosphite, hypo-aluminum orthophosphate, calcium hypophosphite, cerous hypophosphate, zinc hypophosphite or hypophosphorous acid lanthanum；
Described ammonium polyphosphate flame retardant is polymerization degree n > the crystallization II-type high molecular APP of 1000 or microcapsule APP；
Described organic phosphonium flame retardant is the mixing of one or more in resorcinol double (diphenyl phosphoester), bisphenol-A double (diphenyl phosphoester), dimethyl methyl phosphonate, diethyl ethylphosphate, trimethyl phosphate, triethyl phosphate.
4. the preparation method of a halogen-free high flame-retardant polyisocyanurate foam, it is characterised in that:
A, weigh PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physical blowing agent, polyisocyanates, hypophosphites, APP and organic phosphonium flame retardant constitute raw material group；
Wherein: PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physical blowing agent, the mass ratio of polyisocyanates are 100:1-5:0.1-1:0.5-1.5:1-3:10-50:250-350；
The quality of hypophosphites is the 5～15% of raw material group gross mass；The quality of APP is the 0～10% of raw material group gross mass；The quality of organic phosphonium flame retardant is the 0～10% of raw material group gross mass, and the quality of APP and organic phosphonium flame retardant is not 0；
B, PEPA, amines catalyst, metal-based catalysts, water, polysiloxane-based foam stabiliser, physical blowing agent and organic phosphonium flame retardant are mixed, and stir, it is thus achieved that mixture A；
C, hypophosphites, APP and polyisocyanates being mixed, and mechanical agitation is uniform, it is thus achieved that mixture B；
D, the mixture A obtained in addition step b in the mixture B that step c is obtained, inject in mould after stirring and foam, after foam is initiated, foams take out and are placed on ripening 24 hours in 70 degree of baking ovens, obtains halogen-free high flame-retardant polyisocyanurate foam.
Preparation method the most according to claim 4, it is characterised in that:
Described PEPA is the benzoic anhydride polyester polyol of hydroxyl value 250～350mgKOH/g；
Described amines catalyst be air chemical industry Polycat 8 and in air chemical industry Polycat 46 one or both combination；
Described metal-based catalysts is one or both combinations in air chemical industry Dabco K-15 and air chemical industry Polycat 46；
Described polysiloxane-based foam stabiliser is polyether modified silicon oil；
Described physical blowing agent is a fluorine dichloroethanes HCFC141b；
Described polyisocyanates is the poly methylene poly phenyl poly isocyanate that mass percent is 30～32wt% of NCO group；
Described hypophosphites is selected from melamine hypophosphite, hypo-aluminum orthophosphate, calcium hypophosphite, cerous hypophosphate, zinc hypophosphite or hypophosphorous acid lanthanum；
Described APP is polymerization degree n > the crystallization II-type high molecular APP of 1000 or microcapsule APP；
Described organic phosphonium flame retardant is the mixing of one or more in resorcinol double (diphenyl phosphoester), bisphenol-A double (diphenyl phosphoester), dimethyl methyl phosphonate, diethyl ethylphosphate, trimethyl phosphate, triethyl phosphate.
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| CN108467468B (en) * | 2018-04-03 | 2021-02-26 | 江苏中昌绝热技术工程有限公司 | Polyisocyanurate material catalyzed by ionic liquid and preparation method thereof |
| EP3549966A1 (en) * | 2018-04-03 | 2019-10-09 | Covestro Deutschland AG | Production of non-flammable pur/ pir hard foam |
| JP2021533234A (en) | 2018-08-08 | 2021-12-02 | コベストロ・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・アンド・コー・カーゲー | Phosphinate as a flameproof additive for PUR / PIR rigid foam materials |
| CN110591053A (en) * | 2019-10-09 | 2019-12-20 | 厦门珉瑶贸易有限公司 | Heat insulation material of hard polyurethane foam |
| CN112143209A (en) * | 2020-01-14 | 2020-12-29 | 济南奥美联亚工矿设备有限公司 | Flame-retardant high-resilience polyurethane foam plastic and preparation method thereof |
| CN114211587A (en) * | 2021-12-17 | 2022-03-22 | 河南佳诺威木业有限公司 | High-toughness flame-retardant foaming type PB plate and preparation process thereof |
| CN114989105B (en) * | 2022-07-15 | 2024-01-12 | 什邡市太丰新型阻燃剂有限责任公司 | Pollution-free method for synthesizing superfine melamine hypophosphite and flame-retardant method thereof |
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| CN103436001A (en) * | 2013-08-13 | 2013-12-11 | 东莞市安拓普塑胶聚合物科技有限公司 | Low-smoke halogen-free flame retardant thermoplastic polyurethane elastomer for cable and preparation method thereof |
| CN103804626A (en) * | 2014-01-27 | 2014-05-21 | 中国科学技术大学 | Halogen-free flame-retardant hard polyurethane foam and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436001A (en) * | 2013-08-13 | 2013-12-11 | 东莞市安拓普塑胶聚合物科技有限公司 | Low-smoke halogen-free flame retardant thermoplastic polyurethane elastomer for cable and preparation method thereof |
| CN103804626A (en) * | 2014-01-27 | 2014-05-21 | 中国科学技术大学 | Halogen-free flame-retardant hard polyurethane foam and preparation method thereof |
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