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CN101636437A - Resistance combustion polyurethane foam preparation with few smoke performance - Google Patents

Resistance combustion polyurethane foam preparation with few smoke performance Download PDF

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Publication number
CN101636437A
CN101636437A CN200880008715A CN200880008715A CN101636437A CN 101636437 A CN101636437 A CN 101636437A CN 200880008715 A CN200880008715 A CN 200880008715A CN 200880008715 A CN200880008715 A CN 200880008715A CN 101636437 A CN101636437 A CN 101636437A
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CN
China
Prior art keywords
flame
retardant
additive
polyisocyanurate foam
retardant additive
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Pending
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CN200880008715A
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Chinese (zh)
Inventor
里纳斯·谢尔普斯
埃里克-杰克·赫拉德
扬·费韦曼
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Albemarle Europe SPRL
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Albemarle Europe SPRL
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Publication of CN101636437A publication Critical patent/CN101636437A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C08G18/3804—Polyhydroxy compounds
    • C08G18/3806—Polyhydroxy compounds having chlorine and/or bromine atoms
    • C08G18/381—Polyhydroxy compounds having chlorine and/or bromine atoms having bromine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present invention relates to have the resistance combustion polyurethane foam preparation of few smoke performance.

Description

Resistance combustion polyurethane foam preparation with few smoke performance
Invention field
The present invention relates to have the resistance combustion polyurethane foam preparation of few smoke performance.
Background of invention
In a lot of the application, use urethane or polyisocyanurate foam now.Because it uses widely, provides the research of flame retardant resistance to do much to urethane or polyisocyanurate foam.So far, provide these flame-retarding characteristics with halogenated fire-retardants and phosphorus fire retardant.Yet flame retardant resistance is a kind of desirable characteristic of urethane or polyisocyanurate foam.When urethane or polyisocyanurate foam burning, produce cigarette during the burning, therefore, also need to reduce the discharging of this cigarette.
Summary of the invention
The present invention relates to a kind of flame retardant polyurethane or polyisocyanurate foam, described foam comprises a) i) at least a (having only a kind of in certain embodiments) phosphonic acid ester is diethyl ethylphosphate in certain embodiments; Ii) at least a (having only a kind of in certain embodiments) p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a (having only a kind of in certain embodiments) triethyl phosphate and iv) i) to iv) combination; B) at least a (having only a kind of in certain embodiments) brominated flame-retardant is the reactive brominated diester/ether glycol of tetrabromophthalic anhydride in certain embodiments; C) at least a (having only a kind of in certain embodiments) metal hydroxides; At least d chooses any one kind of them) at least a dispersion agent/wetting agent, e) at least a thixotropic additive, and f) at least a (having only a kind of in certain embodiments) phosphoric acid ester is chlorinated phosphate in certain embodiments, is the monochloro phosphoric acid ester in certain embodiments.In certain embodiments, flame retardant polyurethane or polyisocyanurate foam comprise d) and e), component f) be optional.Also have among some embodiment, flame retardant polyurethane or polyisocyanurate foam comprise d), e) and f).
In another embodiment, the present invention relates to a kind of flame-retardant additive that is applicable to urethane or polyisocyanurate foam, described flame-retardant additive comprises a) i) at least a (having only a kind of in certain embodiments) phosphonic acid ester, also have to be diethyl ethylphosphate among some embodiment; Ii) at least a (having only a kind of in certain embodiments) p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a (having only a kind of in certain embodiments) triethyl phosphate, and iv) i) to iv) combination; B) at least a (having only a kind of in certain embodiments) brominated flame-retardant is the reactive brominated diester/ether glycol of tetrabromophthalic anhydride in some embodiment are arranged; C) at least a (having only a kind of in certain embodiments) metal hydroxides; At least d chooses any one kind of them) at least a dispersion agent/wetting agent, e) at least a thixotropic additive, and f) at least a (having only a kind of in certain embodiments) phosphoric acid ester is chlorinated phosphate in certain embodiments, is the monochloro phosphoric acid ester in certain embodiments.In certain embodiments, flame-retardant additive comprises d) and e), component f) be optional.Also have among some embodiment, flame-retardant additive comprises d), e) and f).
The invention still further relates to a kind of urethane or polyisocyanurate foam formulation, described preparation comprises a) i) at least a (having only a kind of in certain embodiments) phosphonic acid ester is diethyl ethylphosphate in certain embodiments; Ii) at least a (having only a kind of in certain embodiments) p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a (having only a kind of in certain embodiments) triethyl phosphate and iv) i) to iv) combination; B) at least a (having only a kind of in certain embodiments) brominated flame-retardant also has to be the reactive brominated diester/ether glycol of tetrabromophthalic anhydride among some embodiment; C) at least a (having only a kind of in certain embodiments) metal hydroxides; At least a kind of component e optional d)) and f), d wherein) be at least a dispersion agent/wetting agent, e) be at least a thixotropic additive, and f) is at least a (having only a kind of in certain embodiments) phosphoric acid ester, have to be chlorinated phosphate among some embodiment, also have to be the monochloro phosphoric acid ester among some embodiment; G) at least a (having only a kind of in certain embodiments) isocyanic ester, polyvalent alcohol or both have; And h) at least a (having only a kind of in certain embodiments) whipping agent.Be applicable to that whipping agent of the present invention can be easy to be selected by those skilled in the art, generally be selected from the mixture of water, volatilization hydrocarbon, halocarbon or halohydrocarbon or two or more these materials.In certain embodiments, urethane or polyisocyanurate foam formulation comprise d) and e), component f) be optional.In certain embodiments, urethane or polyisocyanurate foam formulation comprise d), e) and f).
The invention still further relates to a kind of urethane or polyisocyanurate foam formulation, described foam formulations obtains from following component: at least a (having only a kind of in certain embodiments) phosphonic acid ester a) i) is diethyl ethylphosphate among some embodiment; Ii) at least a (having only a kind of in certain embodiments) p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a (having only a kind of in certain embodiments) triethyl phosphate and iv) i) to iv) combination; B) at least a (having only a kind of in certain embodiments) brominated flame-retardant is the reactive brominated diester/ether glycol of tetrabromophthalic anhydride in certain embodiments; C) at least a (having only a kind of in certain embodiments) metal hydroxides; E) and at least a component f) optional d),, d wherein) be at least a dispersion agent/wetting agent, e) be at least a thixotropic additive, and f) is at least a (having only a kind of in certain embodiments) phosphoric acid ester, have to be chlorinated phosphate among some embodiment, also have to be the monochloro phosphoric acid ester among some embodiment; G) at least a (having only a kind of in certain embodiments) isocyanic ester, polyvalent alcohol or both have; And h) at least a (having only a kind of in certain embodiments) whipping agent.Use d in certain embodiments) and e), component f) be optional.Use d in certain embodiments), e) and f).
The invention still further relates to a kind of method that forms flame retardant polyurethane or polyisocyanurate foam, described method is included at least a (only a kind of in certain embodiments), and there is a) i of mixing down in catalyzer) at least a (having only a kind of in certain embodiments) phosphonic acid ester is diethyl ethylphosphate among some embodiment; Ii) at least a (having only a kind of in certain embodiments) p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a (having only a kind of in certain embodiments) triethyl phosphate and iv) i) to iv) combination; B) at least a (having only a kind of in certain embodiments) brominated flame-retardant is the reactive brominated diester/ether glycol of tetrabromophthalic anhydride among some embodiment; C) at least a (having only a kind of in certain embodiments) metal hydroxides; D) at least a dispersion agent/wetting agent, e) at least a thixotropic additive; With optional d), e) and at least a component f), d wherein) be at least a dispersion agent/wetting agent, e) be at least a thixotropic additive, and f) is at least a (having only a kind of in certain embodiments) phosphoric acid ester, be chlorinated phosphate among some embodiment, also have to be the monochloro phosphoric acid ester among some embodiment; G) at least a (having only a kind of in certain embodiments) isocyanic ester or polyvalent alcohol; And h) at least a (having only a kind of in certain embodiments) whipping agent.Use d in certain embodiments) and e), component f) choose wantonly.Also have among some embodiment and use d), e) and f).
Detailed Description Of The Invention
As mentioned above, the present invention relates to the method for urethane or polyisocyanurate foam, urethane or polyisocyanurate foam formulation and formation hard and soft flame retardant polyurethane foam formulations.The contriver finds, mixes a) i) at least a (having only a kind of in certain embodiments) phosphonic acid ester is diethyl ethylphosphate among some embodiment; Ii) at least a (having only a kind of in certain embodiments) p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a (having only a kind of in certain embodiments) triethyl phosphate; Iv) i) to iv) combination; B) at least a (having only a kind of in certain embodiments) brominated flame-retardant is the reactive brominated diester/ether glycol of tetrabromophthalic anhydride among some embodiment; C) at least a (having only a kind of in certain embodiments) metal hydroxides; With optional at least a: d) at least a dispersion agent/wetting agent, e) at least a thixotropic additive, and f) at least a (having only a kind of in certain embodiments) phosphoric acid ester, it among some embodiment chlorinated phosphate, also have among some embodiment to be the monochloro phosphoric acid ester, can provide and have few cigarette the flame retardant polyurethane or the polyisocyanurate foam of (good subtract smoke performance) and good flame-retardance.Know urethane and poly-isocyanurate, its foam and prepare the method for these polymkeric substance this area people, and it is recorded in the document.Consult for example Encyclopedia of Polymer Science and Technology (polymer science and technology encyclopedia), 11,506 563 pages of (1969 Wiley ﹠amp; Sons is outstanding) and 15,445 479 pages of (1971 Wiley ﹠amp; Sons) and U.S. Patent number 3,974,109,4,209,609,4,405,725,4,468,481,4,468,482,5,102,923,5,164,417,7,045,564 and 7,153,901 and Application No. 11/569,210, above-mentioned document this paper all is attached to herein by quoting in full.
As mentioned above, flame-retardant additive of the present invention comprises a) i) at least a (having only a kind of in certain embodiments) phosphonic acid ester is diethyl ethylphosphate among some embodiment; Ii) at least a (having only a kind of in certain embodiments) p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a (having only a kind of in certain embodiments) triethyl phosphate and iv) i) to iv) combination.In certain embodiments, flame-retardant additive comprises independent i)-iii) any component, in other embodiments, fire retardant is i) and ii); I) and iii); I), ii) and iii) or ii) and combination iii).In certain embodiments, a) for i) or have i) combination the time, i) be diethyl ethylphosphate.A) be sometimes referred to as component a) at this, as optional component f) when being present in flame-retardant additive, general amount a) that exists in flame-retardant additive is for arriving in the scope of about 9 weight percents based on about 2 of flame-retardant additive gross weight, be preferably about 3 to the scope of about 7 weight percents, more preferably about 4 to the scope of about 5 weight percents.As optional component f) when not existing, component amount a) greater than scope discussed above about 0 to about 75% scope, that is, the lower end of scope is about 2 to about 4.5 scope usually, the upper end of scope is about 9 to about 16 scope usually.It is any at the phosphonic acid ester that flame retardant resistances can effectively be provided hard or flexibel polyurethane or polyisocyanurate foam more known in the art to be applicable to that phosphonic acid ester of the present invention can be selected from.The unrestricted example that is fit to phosphonic acid ester comprises diethyl ethylphosphate, dimethyl methyl phosphonate, propyl phosphonic acid methyl ester etc.The unrestricted example diethyl ethylphosphate that is applicable to this can be at any diethyl ethylphosphate known in the art.In a preferred embodiment, diethyl ethylphosphate select for use by
Figure G2008800087154D00041
Company is with trade name
Figure G2008800087154D00042
Those compounds of selling, preferred
Figure G2008800087154D00043
V490.Be applicable to that p isopropylbenzoic acid base benzene diphenyl ester of the present invention can be at any p isopropylbenzoic acid base benzene diphenyl ester known in the art.In a preferred embodiment, p isopropylbenzoic acid base benzene diphenyl ester select for use by Company is with trade name
Figure G2008800087154D00051
Those compounds of selling are preferably
Figure G2008800087154D00052
500 series, preferred in certain embodiments 519.
The components b of flame-retardant additive) being at least a (having only a kind of in certain embodiments) brominated flame-retardant, is the reactive brominated diester/ether glycol of tetrabromophthalic anhydride among some embodiment.The unrestricted example that is applicable to brominated flame-retardant of the present invention can be at any brominated flame-retardant known in the art, for example
Figure G2008800087154D00054
Tribromoneoamyl alcohol (" TBNPA "), by
Figure G2008800087154D00055
Company is with trade name
Figure G2008800087154D00056
Those brominated flame-retardants of selling etc.The reactive brominated diester/ether glycol that is applicable to this tetrabromophthalic anhydride can be any known product in this area.In a preferred embodiment, the diester of tetrabromophthalic anhydride/ether glycol be by
Figure G2008800087154D00057
Company is with trade name
Figure G2008800087154D00058
Those diester/ether glycol of selling, preferred
Figure G2008800087154D00059
RB79, more preferably
Figure G2008800087154D000510
RB7970.The general components b that in flame-retardant additive, exists) amount for based on the additive gross weight about 16 to the scope of about 28 weight percents, preferred about 18 to the scope of about 26 weight percents, more preferably from about 20 to the scope of about 24 weight percents.
The amount of component b of flame-retardant additive) is at least a (having only a kind of in certain embodiments) metal hydroxides.Be applicable to that metal hydroxides of the present invention may be selected in and known in the artly has about 1 to about 15 scopes, preferred about 2 to about 12 scopes, more preferably from about the 3 any metal hydroxidess to about 9 scope d50.Metal hydroxides can be preferably aluminium hydroxide for magnesium hydroxide or aluminium hydroxide.In a preferred embodiment, metal hydroxides select for use by
Figure G2008800087154D000511
Company is with trade name
Figure G2008800087154D000512
Or
Figure G2008800087154D000513
Those metal hydroxidess of selling, preferred ON series, preferred in certain embodiments ON-906.The amount of the general metal hydroxides that in flame-retardant additive, exists for based on the additive gross weight about 45 to the scope of about 80 weight percents, in the scope of preferred about 50 to about 75 weight percent, more preferably from about 55 to the scope of about 70 weight percents.
The component d of flame-retardant additive) is at least a dispersion agent/wetting agent.The unrestricted example that is fit to dispersion agent/wetting agent comprises the solution of the multipolymer with acidic-group.In certain embodiments, dispersion agent select for use BYK Chemie with
Figure G2008800087154D000516
Those dispersion agents that product line is sold.Such as W-996.As fruit component d) in flame-retardant additive, exist, the then general component d that exists) amount be based on the metal hydroxides gross weight about 0.1 to about 3.5 weight percentage ranges, preferred about 0.25 to about 3 weight percentage ranges, and more preferably from about 0.5 to about 2.5 weight percentage ranges.
The optional components e of flame-retardant additive) is at least a thixotropic additive.The unrestricted example that is fit to thixotropic additive comprises N-Methyl pyrrolidone/Litiumchlorode solution.In certain embodiments, thixotropic additive be selected from BYK Chemie with
Figure G2008800087154D00061
Those thixotropic additive that product line is sold.The example that is applicable to thixotropic additive herein is
Figure G2008800087154D00062
W-410.The general component e that in the invention process, uses) amount for based on the metal hydroxides gross weight about 0.1 to about 3.5 weight percentage ranges, preferred about 0.25 to about 3 weight percentage ranges, more preferably from about 0.5 to about 2.5 weight percentage ranges.
The optional components f of flame-retardant additive) being at least a (having only a kind of in certain embodiments) phosphoric acid ester, is chlorinated phosphate among some embodiment, also has to be the monochloro phosphoric acid ester among some embodiment.In certain embodiments, flame-retardant additive comprises component f).Be applicable to that herein phosphoric acid ester can select for use any in phosphoric acid ester known in the art, that some flame retardant resistances can effectively be provided hard or flexibel polyurethane or polyisocyanurate foam.The unrestricted example of suitable phosphates comprises Firemaster 836, triphenylphosphate, Tritolyl Phosphate etc.Be applicable to that monochloro phosphoric acid ester herein can be in any monochloro phosphoric acid ester known in the art.In certain embodiments, the monochloro phosphoric acid ester select for use by
Figure G2008800087154D00063
Company is with name
Figure G2008800087154D00064
Those monochloro phosphoric acid ester of selling, preferred TMCP.As fruit component f) in flame-retardant additive, exist, the then general component f that exists) amount be based on the flame-retardant additive gross weight about 7 to the scope of about 12 weight percents, preferred about 8 to the scope of about 9 weight percents, and more preferably from about 9 to about 10 weight percentage ranges.
Flame-retardant additive of the present invention can be used to form any known procedure of urethane or polyisocyanurate foam with effective amount.Generally, flame-retardant additive is as one of in the various additives used in urethane or the polyisocyanurate foam forming process, and using under general urethane or polyisocyanurate foam formation condition.In addition, available urethane or polyisocyanurate foam are made article, as molded and/or crushed foam goods.
The significant quantity of flame-retardant additive is meant the amount that is enough to satisfy or surpass listed touchstone in the DIN 4102 B2 flammability tests.This generally based on flame retardant polyurethane or polyisocyanurate foam or flame retardant polyurethane or polyisocyanurate foam formulation gross weight about 130 to the scope of about 180phr flame-retardant additive.In a preferred embodiment, consider that significant quantity is in both about scopes of 140 to about 170phr based on same datum, more preferably in about scope of 150 to about 160phr.
Flame-retardant additive of the present invention also provides urethane or the polyisocyanurate foam with low smokiness.Low smokiness is meant that the urethane that comprises the significant quantity flame-retardant additive or polyisocyanurate foam have by ASTM E662 and measures about 70 to about 110 scopes in no flame mode, preferred about 70 to about 100 scopes, 70 correction smoke densities to about 90 scopes more preferably from about, and have by ASTM E662 and measure about 350 to about 600 scopes in the flame mode, preferred about 350 to about 500 scopes, more preferably from about 350 correction smoke densities to about 400 scopes are particularly useful for having about 35kg/m 3The foam of density and 75 * 75 * 30mm sample size.
Except these components, urethane or polyisocyanurate foam formulation can comprise known in the art and be used to form any other component soft and hard polyaminoester or polyisocyanurate foam, and these other components that are used to form urethane polymerization preparation or prescription are familiar with by those skilled in the art.For example, urethane or polyisocyanurate foam formulation can comprise the liquid C of tensio-active agent, antioxidant, thinner such as the low viscosity that also can comprise in composition of the present invention 1-4Halocarbon and/or wherein the halogen content be the halocarbon diluent of 1-4 bromine and/or chlorine atom.The unrestricted example of this type of thinner comprises bromochloromethane, methylene dichloride, 1,2-ethylene dichloride, glycol dibromide, isopropyl chloride, n-butyl bromide, sec-butyl bromide, n-butyl chloride, sec-butyl chloride, chloroform, tetrachloroethylene, trichloroethane and tetracol phenixin.
It should be noted that, these and other compositions that can in urethane of the present invention or polyisocyanurate foam formulation, use, and their usage ratio and method all are reported in the document.Referring to for example Herrington and Hock, Flexible Polyurethane Foams (flexible PU foam), The Dow ChemicalCompany, 1991,9.25 9.27 or Roegler, M. " Slabstock Foams " (foam blocks); Polyurethane Handbook (polyurethane handbook); Oertel, G., Ed.; Hanser Munich, 1985,176 177 or Woods, G.Flexible Polyurethane Foams (flexible PU foam), Chemistryand Technology (chemistry and technology); Applied Science Publishers, London, 1982,257 260, described document is attached to herein in full by reference; With No. the 11/569th, 210, U.S. Patent application, described patent is attached to herein by reference.
In enforcement of the present invention, can make urethane or polyisocyanurate foam formulation and catalyst mix, or in the presence of catalyzer, mix independent component, to form satisfied or to surpass the listed touchstone of DIN 4102 B2 flammability tests and have flame retardant polyurethane or the polyisocyanurate foam of proofreading and correct smoke density as discussed above.Preparation flexibel polyurethane or the used catalyzer of polyisocyanurate foam comprise amine catalyst, tin-based catalyst, bismuthino catalyzer or other organo-metallic catalysts etc.The used catalyzer of hard polyaminoester or polyisocyanurate foam comprises gel catalyst, blows and send out catalyzer, balanced gel/blow and send out catalyzer, catalyst for trimerization etc.
More than describe and relate to several embodiment of the present invention.Those skilled in the art will appreciate that in order to realize spirit of the present invention, can design the additive method of equivalence.It should be noted that also all scopes that the preferred embodiments of the present invention mean in this paper discussion comprise the scope of any low amount to any higher amount.
Following example explanation the present invention, but restriction invention never in any form.
Example
In order to determine the smoke suppression performance and the flame retardant properties of flame-retardant additive of the present invention, make four kinds of flame retarded rigid foams with following table 1 described prescription.Preparation 130106-1 is a preparation of the present invention, and 130106-2 is with making comparisons.Blow all foams as pneumatogen and water as chemical foaming agent with Skellysolve A, all foams satisfy DIN 4102 B2 touchstones.In forming, foam use dimethylcyclohexylam,ne (" DMCHA ") as catalyzer.According to making the polyurethane foam technology, we use tensio-active agent/stablizer, promptly polyether-modified polysiloxane.Used MDI is a polymeric MDI.
In addition, in following example, Martinal, Saytex and Antiblaze are the registered trademark of Albemarle company.
Table 1
Figure G2008800087154D00081
Smoke Detection obtains result shown in the following table 2.
Table 2
Figure G2008800087154D00091
Figure G2008800087154D00092
Figure G2008800087154D00093
Figure G2008800087154D00101
Result in the table 2 shows, in flame modes and nonflame pattern, under the situation of preparation 130106-1, proofreaies and correct smoke density (Cor.Ds maximum) better (lower) significantly.Other results show
Figure G2008800087154D00102
Comparison between ON-310 and the ON-906.We notice, two kinds of products are being proofreaied and correct aspect the smoke density performance classes seemingly.Because
Figure G2008800087154D00103
RB7970 and
Figure G2008800087154D00104
Dispersing property is better among the V490, and less at the placement postprecipitation, and ON-906 is preferred inorganic combustion inhibitor.

Claims (40)

1. flame-retardant additive that is applicable to urethane or polyisocyanurate foam, described flame-retardant additive comprises:
A) at least a phosphonic acid ester;
B) at least a brominated flame-retardant;
C) at least a metal hydroxides;
With optional
D) at least a wetting agent/dispersion agent;
E) at least a thixotropic additive; With
F) at least a phosphoric acid ester
In at least a component.
2. flame-retardant additive as claimed in claim 1, amount a) that wherein exists in the flame-retardant additive for based on the flame-retardant additive gross weight about 2 to the scope of about 9 weight percents; The b that exists in the flame-retardant additive) amount for based on the flame-retardant additive gross weight about 16 to the scope of about 28 weight percents; The c that exists in the flame-retardant additive) amount be the flame-retardant additive gross weight about 45 to the scope of about 80 weight percents.
3. flame-retardant additive as claimed in claim 1 a) is i wherein) at least a diethyl ethylphosphate; Ii) at least a p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a triethyl phosphate and iv) i)-iv) combination, and a) to be present in the flame-retardant additive to about 9 weight percentage ranges based on about 2 of flame-retardant additive gross weight.
4. flame-retardant additive as claimed in claim 3 a) is at least a diethyl ethylphosphate wherein.
5. flame-retardant additive as claimed in claim 1, wherein f) be at least a chlorinated phosphate, and b) be the reactive brominated diester/ether glycol of at least a tetrabromophthalic anhydride.
6. flame-retardant additive as claimed in claim 1 is wherein a) at about 2 diethyl ethylphosphates that exist to about 16 weight percentage ranges; B) be reactive brominated diester/ether glycol at about 16 tetrabromophthalic anhydrides that exist to about 28 weight percentage ranges; And c) exist to about 80 weight percentage ranges about 45, all components weight percent is all based on the gross weight of flame-retardant additive.
7. flame-retardant additive as claimed in claim 1 is wherein a) at about 2 diethyl ethylphosphates that exist to about 9 weight percentage ranges; B) be reactive brominated diester/ether glycol at about 16 tetrabromophthalic anhydrides that exist to about 28 weight percentage ranges; C) exist to about 80 weight percentage ranges about 45, and f) exist to about 12 weight percentage ranges about 7, all components weight percent is all based on the gross weight of flame-retardant additive.
8. flame-retardant additive as claimed in claim 1, wherein said flame-retardant additive comprises d) and e) or d), e) and f).
9. flame-retardant additive as claimed in claim 8, wherein f) be the monochloro phosphoric acid ester.
10. flame-retardant additive as claimed in claim 6, wherein d) and e) be present in the flame-retardant additive with about 0.5 amount to about 2.5 weight percentage ranges based on the metal hydroxides gross weight respectively.
11. as claim 3 or 6 each described flame-retardant additives, wherein said diethyl ethylphosphate is served as reasons
Figure A2008800087150003C1
Company is with title
Figure A2008800087150003C2
Those that sell; The diester of described tetrabromophthalic anhydride/ether glycol is served as reasons
Figure A2008800087150003C3
Company is with title
Figure A2008800087150003C4
Those that sell; Described monochloro phosphoric acid ester and brominated flame retardant are served as reasons
Figure A2008800087150003C5
Company is with title Those that sell; Described metal hydroxides is served as reasons
Figure A2008800087150003C7
Company is with title Or
Figure A2008800087150003C9
Those that sell and described wetting agent/dispersion agent and thixotropic additive are that BYK Chemie is with title
Figure A2008800087150003C10
The respective compound of selling.
12. flame-retardant additive as claimed in claim 11, wherein said diethyl ethylphosphate is V490; The diester of described tetrabromophthalic anhydride/ether glycol is
Figure A2008800087150003C12
RB79 or
Figure A2008800087150003C13
RB7970; Described monochloro phosphoric acid ester is TMCP; Described metal hydroxides is served as reasons
Figure A2008800087150003C15
Company is with title
Figure A2008800087150003C16
Those that ON series is sold, and wetting agent/dispersion agent and thixotropic additive are that BYK Chemie is with title
Figure A2008800087150003C17
Those that sell.
13. flame-retardant additive as claimed in claim 10, wherein f) be present in the flame-retardant additive with about 7 amounts to about 12 weight percentage ranges based on the flame-retardant additive gross weight.
14. flame retardant polyurethane or polyisocyanurate foam, described foam are included in about 130 flame-retardant additives to about 180phr scope, wherein said flame-retardant additive comprises:
A) at least a phosphonic acid ester;
B) at least a brominated flame-retardant;
C) at least a metal hydroxides;
With optional
D) at least a wetting agent/dispersion agent;
E) at least a thixotropic additive; With
F) at least a phosphoric acid ester
In at least a component.
15. flame retardant polyurethane as claimed in claim 14 or polyisocyanurate foam a) are i wherein) at least a diethyl ethylphosphate; Ii) at least a p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a triethyl phosphate and iv) i) to iv) combination, and a) be present in the flame-retardant additive to the scope of about 9 weight percents based on about 2 of flame-retardant additive gross weight.
16. flame retardant polyurethane as claimed in claim 14 or polyisocyanurate foam a) are at least a diethyl ethylphosphate wherein, and f) be at least a chlorinated phosphate.
17. flame retardant polyurethane as claimed in claim 14 or polyisocyanurate foam are wherein a) at about 2 diethyl ethylphosphates that exist to about 16 weight percentage ranges; B) be reactive brominated diester/ether glycol at about 16 tetrabromophthalic anhydrides that exist to about 28 weight percentage ranges; And c) exist to about 80 weight percentage ranges about 45, all components weight percent is all based on the gross weight of flame-retardant additive.
18. flame retardant polyurethane as claimed in claim 14 or polyisocyanurate foam, wherein said flame-retardant additive comprises d) and e) or d), e) and f).
19. flame retardant polyurethane as claimed in claim 18 or polyisocyanurate foam are wherein a) at about 2 diethyl ethylphosphates that exist to about 9 weight percentage ranges; B) be reactive brominated diester/ether glycol at about 16 tetrabromophthalic anhydrides that exist to about 28 weight percentage ranges; C) exist to about 80 weight percentage ranges about 45; F) exist in about 7 amounts to about 12 weight percentage ranges, all components weight percent is all based on the gross weight of flame-retardant additive; And d) and e) exist with about 0.5 amount to about 2.5 scopes respectively based on the metal hydroxides gross weight.
20. flame retardant polyurethane as claimed in claim 19 or polyisocyanurate foam, wherein f) be the monochloro phosphoric acid ester.
21. flame retardant polyurethane as claimed in claim 19 or polyisocyanurate foam, wherein said diethyl ethylphosphate is served as reasons
Figure A2008800087150004C1
Company is with title
Figure A2008800087150004C2
Those that sell; The diester of described tetrabromophthalic anhydride/ether glycol is served as reasons
Figure A2008800087150004C3
Company is with title
Figure A2008800087150004C4
Those that sell; Described monochloro phosphoric acid ester is served as reasons
Figure A2008800087150004C5
Company is with title
Figure A2008800087150004C6
Those that sell; Described metal hydroxides is served as reasons
Figure A2008800087150005C1
Company is with title
Figure A2008800087150005C2
Or
Figure A2008800087150005C3
Those that sell and described wetting agent/dispersion agent and thixotropic additive are that BYK Chemie is with title
Figure A2008800087150005C4
Those that sell.
22. flame retardant polyurethane as claimed in claim 21 or polyisocyanurate foam, wherein said diethyl ethylphosphate is
Figure A2008800087150005C5
V490; The diester of described tetrabromophthalic anhydride/ether glycol is
Figure A2008800087150005C6
RB79 or
Figure A2008800087150005C7
RB7970; Described monochloro phosphoric acid ester is TMCP; Described metal hydroxides is served as reasons Company is with title
Figure A2008800087150005C10
Those that ON series is sold and described wetting agent/dispersion agent and thixotropic additive are that BYK Chemie is with title Those that sell.
23. flame retardant polyurethane as claimed in claim 16 or polyisocyanurate foam, wherein said urethane or polyisocyanurate foam have by ASTM E662 with no flame mode measure, about 70 to about 110 scopes or at about 70 correction smoke densities to about 100 scopes.
24. flame retardant polyurethane as claimed in claim 22 or polyisocyanurate foam, wherein said urethane or polyisocyanurate foam have by ASTM E662 with no flame mode measure, about 70 to about 110 or about 70 to about 100 correction smoke density.
25. flame retardant polyurethane as claimed in claim 23 or polyisocyanurate foam, wherein said urethane or polyisocyanurate foam have 35kg/m for the sample of 75x75x30mm size 3Density.
26. as each described flame retardant polyurethane or polyisocyanurate foam in claim 16 or 24 to 26, wherein said urethane or polyisocyanurate foam satisfy or surpass listed touchstone in the DIN 4102B2 flammability test.
27. molded or extrude goods, described goods are made or are produced by described urethane of claim 14 or polyisocyanurate foam.
28. urethane or polyisocyanurate foam formulation, described foam formulations derives from maybe can derive from least a isocyanic ester or polyvalent alcohol; At least a whipping agent; With a kind of flame-retardant additive, wherein said flame-retardant additive comprises:
A) at least a diethyl ethylphosphate i); Ii) at least a p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a triethyl phosphate; Iv) i) to iv) combination;
B) at least a brominated flame-retardant;
C) at least a metal hydroxides;
With optional
D) at least a wetting agent/dispersion agent;
E) at least a thixotropic additive; With
F) at least a chlorinated phosphate
In at least a component.
29. flame retardant polyurethane as claimed in claim 28 or polyisocyanurate foam formulation are wherein a) at about 2 diethyl ethylphosphates that exist to about 16 weight percentage ranges; B) be reactive brominated diester/ether glycol at about 16 tetrabromophthalic anhydrides that exist to about 28 weight percentage ranges, and c) exist to the scope of about 80 weight percents about 45, all components weight percent is all based on the gross weight of flame-retardant additive.
30. flame retardant polyurethane as claimed in claim 28 or polyisocyanurate foam, wherein said flame-retardant additive comprises d) and e) or d), e) and f).
31. flame retardant polyurethane as claimed in claim 30 or polyisocyanurate foam formulation are wherein a) at about 2 diethyl ethylphosphates that exist to about 9 weight percentage ranges; B) be reactive brominated diester/ether glycol at about 16 tetrabromophthalic anhydrides that exist to about 28 weight percentage ranges; C) exist to about 80 weight percentage ranges about 45; D) and e) exist with about 0.5 amount to about 2.5 weight percentage ranges respectively, all components weight percent is all based on the gross weight of metal hydroxides.
32. flame retardant polyurethane as claimed in claim 31 or polyisocyanurate foam, wherein f) be the monochloro phosphoric acid ester.
33. urethane as claimed in claim 31 or polyisocyanurate foam formulation, wherein said diethyl ethylphosphate is served as reasons Company is with title
Figure A2008800087150006C2
Those that sell; The diester of described tetrabromophthalic anhydride/ether glycol is served as reasons
Figure A2008800087150006C3
Company is with title
Figure A2008800087150006C4
Those that sell; Described monochloro phosphoric acid ester is served as reasons
Figure A2008800087150006C5
Company is with title
Figure A2008800087150006C6
Those that sell; Described metal hydroxides is served as reasons
Figure A2008800087150006C7
Company is with title
Figure A2008800087150006C8
Or
Figure A2008800087150006C9
Those that sell and described wetting agent/dispersion agent and thixotropic additive are that BYK Chemie is with title
Figure A2008800087150006C10
Those that sell.
34. urethane as claimed in claim 31 or polyisocyanurate foam formulation, wherein said diethyl ethylphosphate is V490; The diester of described tetrabromophthalic anhydride/ether glycol is
Figure A2008800087150006C12
RB79 or
Figure A2008800087150006C13
RB7970; Described monochloro phosphoric acid ester is
Figure A2008800087150006C14
TMCP; Described metal hydroxides is served as reasons
Figure A2008800087150007C1
Company is with title
Figure A2008800087150007C2
Those that ON series is sold and described wetting agent/dispersion agent and thixotropic additive are that BYK Chemie is with title
Figure A2008800087150007C3
Those that sell.
35. being included under at least a catalyzer existence, a method that forms flame retardant polyurethane or polyisocyanurate foam, described method mix or gather at least a isocyanic ester or polyvalent alcohol; At least a whipping agent; And flame-retardant additive, wherein said flame-retardant additive comprises:
A) at least a phosphonic acid ester;
B) at least a brominated flame-retardant;
C) at least a metal hydroxides;
With optional
D) at least a wetting agent/dispersion agent;
E) at least a thixotropic additive; With
F) at least a phosphoric acid ester
In at least a component.
36. method as claimed in claim 35 a) is i wherein) at least a diethyl ethylphosphate; Ii) at least a p isopropylbenzoic acid base benzene diphenyl ester; Iii) at least a triethyl phosphate; Or iv) i), and a) to about 9 weight percentage ranges, is being present in the described flame-retardant additive based on about 2 of flame-retardant additive gross weight to iv) combination.
37. method as claimed in claim 35 a) is at least a diethyl ethylphosphate wherein, and f) be at least a chlorinated phosphate.
38. method as claimed in claim 37, wherein f) be the monochloro phosphoric acid ester.39. method as claimed in claim 37, wherein diethyl ethylphosphate is served as reasons
Figure A2008800087150007C4
Company is with title Those that sell; The diester of tetrabromophthalic anhydride/ether glycol is served as reasons Company is with title
Figure A2008800087150007C7
Those that sell; The monochloro phosphoric acid ester is served as reasons
Figure A2008800087150007C8
Company is with title
Figure A2008800087150007C9
Those that sell; Metal hydroxides is served as reasons
Figure A2008800087150007C10
Company is with title
Figure A2008800087150007C11
Or Those that sell; And wetting agent/dispersion agent and thixotropic additive are that BYKChemie is with title
Figure A2008800087150007C13
Those that sell.
40. method as claimed in claim 39, wherein said diethyl ethylphosphate is
Figure A2008800087150007C14
V490; The diester of described tetrabromophthalic anhydride/ether glycol is
Figure A2008800087150007C15
RB79 or
Figure A2008800087150007C16
RB7970; Described monochloro phosphoric acid ester is TMCP; Serve as reasons with described metal hydroxides
Figure A2008800087150008C2
Company is with title
Figure A2008800087150008C3
Those that ON series is sold and described wetting agent/dispersion agent and thixotropic additive are that BYK Chemie is with title Those that sell.
41. method as claimed in claim 35, wherein described flame retardant polyurethane that so produces or polyisocyanurate foam satisfy or surpass listed touchstone in DIN 4102B2 flammability test, and have by ASTM E662 with no flame mode measure, at about 70 correction smoke densities to about 110 scopes.
CN200880008715A 2007-03-26 2008-03-20 Resistance combustion polyurethane foam preparation with few smoke performance Pending CN101636437A (en)

Applications Claiming Priority (3)

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US89695607P 2007-03-26 2007-03-26
US60/896,956 2007-03-26
US60/943,934 2007-06-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585148A (en) * 2011-12-28 2012-07-18 烟台万华聚氨酯股份有限公司 Composition for preparing highly fire-resistant polyisocyanurate foam

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102585148A (en) * 2011-12-28 2012-07-18 烟台万华聚氨酯股份有限公司 Composition for preparing highly fire-resistant polyisocyanurate foam
CN102585148B (en) * 2011-12-28 2014-04-16 万华化学集团股份有限公司 Composition for preparing highly fire-resistant polyisocyanurate foam

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