CN1298761C - Flame retardant polyurethane composition and preparation method thereof - Google Patents
Flame retardant polyurethane composition and preparation method thereof Download PDFInfo
- Publication number
- CN1298761C CN1298761C CNB028288270A CN02828827A CN1298761C CN 1298761 C CN1298761 C CN 1298761C CN B028288270 A CNB028288270 A CN B028288270A CN 02828827 A CN02828827 A CN 02828827A CN 1298761 C CN1298761 C CN 1298761C
- Authority
- CN
- China
- Prior art keywords
- foam
- composition
- active hydrogen
- fire
- antimony
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
- C08G18/08—Processes
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
- C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- 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
- C08G2290/00—Compositions for creating anti-fogging
Abstract
The present invention relates to a polyurethane foam or a soft body which comprises an organic polyisocyanate component, a component containing active hydrogen, a catalyst component, a surface active agent and a flame retardant composition, wherein the component can react with the polyisocyanate component, and the viscidity of the component can be less than about 500 centipoises at room temperature. All the components are low VOC, and the flame retardant composition preferably comprises a compound based on antimony, a halogenated component containing active hydrogen and a halogenated fire retarding agent, wherein the component can react with the polyisocyanate component. The polyurethane can be used as cushion rings, sealing strips, paddings, etc. in vehicles.
Description
Invention field
The present invention relates to the soft polyurethane ester.What more properly, the present invention described is highly-filled soft polyurethane ester foam.
Background of invention
High density polyurethane foam and solid polyurethane are the materials with multiple application, are particularly useful for the seal washer in the electronic installation.These foam preferred density scopes are every cubic chi (pcf) about 10～about 65 pounds.Also answer emphasis to be pointed out that this foam has suitable compressive set, force of compression deviation, tensile strength, extensibility, tear strength, low outgassing and non-corrosive effect.
The foam of many prior arts meets above-mentioned requirements, for example the PORON that is sold by Rogers Corp., Rogers, CT
Foam, however these foams are difficult to reach good or fabulous fire retardation.For example, many commodity must satisfy flame-retardant standard, and these standards are according to Underwriters Laboratories, Inc.
The UL-94 bulletin testing procedures formulated detect, the combustibility check of the plastic material part in equipment and the apparatus, on October 29th, 1996 the 5th edition is with reference to its full content.What pay special attention to is " 20mm vertical combustion check; V-0, V-1 or V-2 " and " horizontal firing foam material check HBF, HF-1 or HF-2 ".UL 94V-0 or HF-1 grade are through being usually used in checking the foam near in the composition of power supply.
The step of preparation low density, soft polyurethane ester flame-retardant foam composition has obtained good elaboration in prior art.United States Patent (USP) the 4th, 022 has been lectured the polyurethane foam of preparation snappiness low-temperature curing for No. 718, and has been added 2,3-two bromo-1, and the 4-butylene glycol is as the method for chain extension agent and flame-retardant composition.United States Patent (USP) the 4th, 147 has been lectured for No. 847 and have been prepared method soft, flame retarded polyurethane foams, utilizes special suds-stabilizing agent, and it can reduce the consumption of common flame retardant additives.United States Patent (USP) the 4th, 162 has been lectured preparation soft polyurethane ester foamy method No. 353, has added a ring monobasic the alkylphosphonic for example trialkylphosphate of three (2-chloroethyl)-phosphoric acid salt and a non-replacement, for example triethyl phosphate at this.United States Patent (USP) the 4th, 849 has been described a kind of fire retardant soft polyurethane ester foam No. 459, and it comprises the reaction product of a polyether polyol and a toluene di isocyanate and has added trimeric cyanamide and another kind of fire retardant.All above-mentioned adding compositions at this all as a reference.
For reaching set target, above-mentioned soft polyurethane ester foam is low density, have lower tensile strength, lower tear strength, lower force of compression deviation and lack the compressive set resistibility.Because these deficiencies, these low-density prior art foams are not suitable for use in packing ring.Therefore, need a kind of high density polyurethane foam composition, it has the high flame retardant effect, and still keeps compressive set, force of compression deviation, unit elongation, the tear strength of required degree, low outgassing and non-corrosive effect.
Summary of the invention:
Discussed above and other the shortcoming and defect of prior art can be overcome by the composition that is formed by a kind of flame retarded polyurethane foams or be reduced, and this flame retarded polyurethane foams comprises a kind of organic polyisocyanate salt (Polyisocyanate) composition; A kind of composition that contains active hydrogen, it can react with the polyisocyanate salt component, should be less than about 500 centipoises in these preferred whole viscosity that contain the active hydrogen composition; A kind of catalyst component; A kind of tensio-active agent; And a kind of fire-retardant combination, wherein contain a kind of compound, a kind of halogenated active hydrogen composition that contains based on antimony, it can react with the polyisocyanate salt component, and a kind of halogenated fire retardant, in the viscosity of this preferred composition when not containing the polyisocyanate salt component, before being covered with foam, should be less than about 8,000 centipoises.The first-selected compound based on antimony comprises ANTIMONY TRIOXIDE SB 203 99.8 PCT, first-selected halogenation, contains the active hydrogen composition and comprises the liquid bromine glycol, and the halogenated fire-retardants of first-selection is solid, brominated organic compound.
In order to have low atomizing and low outgassing, these compositions are low VOC (volatile organic compounds).Therefore, in another embodiment, form low outgassing, low sprayability the composition of polyurethane foam fire retardant comprise the organic polyisocyanate salt component of a kind of low VOC; A kind of low VOC contains the active hydrogen composition, and it can react with the polyisocyanate salt component, should be less than about 500 centipoises in these preferred whole viscosity that contain the active hydrogen composition; A kind of catalyst component; A kind of tensio-active agent; And a kind of fire-retardant combination, wherein contain a kind of halogenated, composition of containing active hydrogen, it can react with the polyisocyanate salt component, in the viscosity of this preferred synthetics when not containing the polyisocyanate salt component, before being covered with foam, should be less than about 8,000 centipoises.
This foamy UL-94 grade is V-1 and/or HBF.The thickness of preferred foams is about 31～about 250mils, density be about 15～during about 30pcf, have UL 94V-0 grade, and foamy thickness is about 28～about 40mils, density be about 15～during about 30pcf, have UL 94V-0 grade.This foam has fabulous physical property, low outgassing (preferred weight is less than 1%) and non-aggressive.
Use fire retardant buffered occasion because These characteristics and advantage, material described here are particularly useful for needs, for example be used for the packing ring on electronic machine and the vehicle.Discussed above and other characteristics and advantage will be estimated and understood by following detailed.
The detailed description of preferred version:
Composition is specially adapted to form polyurethane foam, and adds a kind of fire-retardant combination at this, and it comprises:
A kind of organic polyisocyanate salt component;
A kind of composition that contains active hydrogen, it can fully react with the isocyanate of low-function and form polyisocyanate salt, should be less than about 500 centipoises in this this viscosity that contains the active hydrogen composition;
A kind of tensio-active agent is in chemically stable period and is cured until above-mentioned foam (froth) in the liquid phase of above-mentioned foam (froth), and this tensio-active agent has structurally been stablized the foam (froth) that produces according to following steps;
A kind of catalyzer has sufficient catalytic activity when solidifying said mixture; And a kind of fire-retardant combination, comprise a kind of halogenated, contain the active hydrogen composition, it can react with the polyisocyanate salt component.
Especially, when not comprising the polyisocyanate salt component, before being covered with foam, the viscosity of total composition should be less than 8,000 centipoises.Form the foamy process and comprise the formation above-mentioned composition; Disperse rare gas element fully equably in whole mixtures, beat forming a kind of curable foam (froth) of heat by mixture being carried out machinery, it structurally and chemically all very stable is only just had an effect under ambient conditions; And solidify above-mentioned foam (froth) to form cured foam.
Preferred those of organic polyisocyanate salt component have the compound of conventional formulation:
Q(NCO)
I
Represent 2 or bigger integer at this i, the Q representative contains the valent organic radical of i (organic radical).In one embodiment, the mean value of i is low, promptly 2.0～about 2.6, preferable range is 2.0～about 2.2.The polyisocyanate salt of use low-function (collaborative with the polyol that describes below) has improved the toughness of solidified polyurethane foam unexpectedly.
Q can be replaced or not replace by hydro carbons group (being alkylene group or aromatic group).Q has Q
1-Z-Q
1The group of order is at this Q
1Be alkylene group or aromatic group, Z is-O-,-O-Q
1-,-CO-,-S-,-S-Q
1-S-,-SO-or-SO
2-.The example of this compound comprises and encircles diisocyanate (hexamethylene diisocyanate), 1,8-two isocyanic acids-p-methane (1,8-diisocyanato-p-methane), xylyl diisocyanate (xylyl diisocyanate), two cyclic isocyanate hexylamines (diisocyanatocyclohexane), phenylene diisocyanate (phenylenediisocyanates), tolylene diisocyanate (tolylene diisocyanates), comprising 2,4-tolylene diisocyanate (2,4-tolylene diisocyanate), 2,6-tolylene diisocyanate (2,6-tolylene diisocyanate) and natural tolylene diisocyanate (crude tolylene diisocyanate), two (4-phenyl isocyanic acid) methane (bis (4-isocyanatophenyl) methane), chlorine phenylene diisocyanate (chlorophenylene diisocyanates), ditan-4,4 '-diisocyanate (diphenylmethane-4,4 '-diisocyanate) (also have known 4,4 '-biphenyl methane diisocyanate (4,4 '-diphenyl methane diisocyanate), or MDI) and adducts wherein, naphthalene-1,5-diisocyanate (naphthalene-1,5-diisocyanate), triphenyl methane-4,4 ', 4 " tri isocyanate (triphenylmethane-4; 4 ', 4 " triisocyanate), and isopropyl benzene-α-4-diisocyanate (isopropylbenzene-alpha-4-diisocyanate).Q also represents Q (NCO)
iIn have the valent polyurethanyl group of i, Q (NCO)
iBe generally prepolymer.This prepolymer is by the excessive polyisocyanate salt of the stoichiometric composition of above and hereinafter setting forth and a kind of active hydrogen-contg compound of elaboration hereinafter, especially have describe below contain polyhydric material or polyol reacts to each other formed.Usually, for example, the about 30%～about 200% stoichiometric surplus of the ratio that polyisocyanate salt is used, stoichiometry are based on the Equivalent of the isocyanate group of each hydroxyl Equivalent in polyol.
Useful polyisocyanate salt also has the dipolymer of isocyanate and diisocyanate and trimer and polymeric diisocyanate, and for example those have the compound of conventional formulation:
[Q
2(NCO)
i]
j
Wherein i represents 1 or bigger integer, and j represents 2 or bigger integer, Q
2It is a polyfunctional organic radical.An example is the polymethylene polyphenyl isocyanate.Q
2Can also be compound with conventional formulation:
L(NCO)
I
Wherein i represents 1 or bigger numerical value, and L represents single function or multi-functional atom or group.Such example comprises ethynyl di(2-ethylhexyl)phosphate isocyanate, C
2H
5P (O) (NCO)
2Phosphenylic acid diisocyanate C
6H
5P (O) (NCO)
2The compound that contains trivalent silicon cyanate group; From sulfonamide (QSO
2NCO) derive and next isocyanate; Cyanic acid and thiocyanic acid.All aforesaid compounds may all be used.Usually, the polyisocyanate salt of preferred fragrance, this is because they have bigger reactivity.
Certainly, the mixture of above-mentioned any isocyanate all can be used, as long as total mole of mean value of isocyanic acid alkali keeps within the required range.The consumption of polyisocyanate salt will slightly change along with the character of the urethane for preparing.Usually, always-the NCO Equivalent is that 0.8～1.2-NCO Equivalent is with respect to an active hydrogen Equivalent for the ratio of gross activity hydrogen Equivalent, the for example hydroxyl hydrogen of active hydrogen reactants, and preferred ratio is the Equivalent of about 1.0～1.05-NCO Equivalent with respect to an active hydrogen.
The composition that contains active hydrogen generally includes the mixture with polyol, for example is terminal poly-hydrocarbon (United States Patent (USP) the 2nd, 877, No. 212) with the hydroxyl; With the hydroxyl is terminal polyacetals (United States Patent (USP) the 2nd, 870, No. 097); Fatty acid triglycercide (United States Patent (USP) the 2nd, 878, No. 601); With the hydroxyl is terminal polyester (United States Patent (USP) the 2nd, 698, No. 838, the 2nd, 921, No. 915, the 2nd, 866, No. 762, the 2nd, 602, No. 783, the 2nd, 811, No. 493 and the 2nd, 621, No. 166); With the methylol is terminal perfluor methylene radical (perfluoromethylenes) (United States Patent (USP) the 2nd, 911, No. 390 and the 2nd, 902, No. 473); Poly-alkenylene ether ethylene glycol (United States Patent (USP) the 2nd, 808, No. the 733rd, 624, No. 391, English Patent); Poly-alkenylene ether ethylene glycol (United States Patent (USP) the 2nd, 808, No. the 733rd, 624, No. 391, English Patent); Poly-alkenylene fragrance metal ether ethylene glycol (United States Patent (USP) the 2nd, 808, No. 391); And poly-alkenylene ether trivalent alcohol (United States Patent (USP) the 2nd, 866, No. 774).
Especially preferably containing polyhydric material is polyether polyhydroxy-compound, be by chemical adduction alkenylene oxide compound, ethylene oxide,1,2-epoxyethane for example, propylene oxide and composition thereof and obtain, and it is joined in water or the polyhydroxy organic compound, vinyl ethylene glycol for example, propyleneglycoles, trimethylene ethylene glycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1,2-hexene ethylene glycol, 1, the 10-decanediol, 1, the 2-cyclohexanediol, 2-butylene-1, the 4-glycol, 3-cyclohexenyl-1, the 1-dimethanol, 4-methyl-3-cyclohexene-1, the 1-dimethanol, 3-methylene radical-1, the 5-pentanediol, glycol ether, (2-hydroxyethyl)-1-propyl alcohol, 4-(2-hydroxyethyl)-1-butanols, 5-(2-propoxyl)-1-amylalcohol, 1-(2-methylol)-2-hexanol, 1-(2-propoxyl)-sec-n-octyl alcohol, 3-allyloxy-1, the 5-pentanediol, 2-allyloxy methyl-2-methyl isophthalic acid, ammediol, [4, the 4-pentyloxy]-methyl]-1, ammediol, 3-(o-third rare phenoxy group)-1, the 2-propylene glycol, 2,2 '-two (the p-phenylene oxygen) di-alcohol of diisopropylidene, glycerine, 1,2,6-hexane trivalent alcohol, 1,1, the 1-trimethylolethane, 1,1, the 1-TriMethylolPropane(TMP), 3-(2-hydroxy ethoxy)-1, the 2-propylene glycol, 3-(2-propoxyl)-1, the 2-propylene glycol, 2,4-dimethyl-2-(2-hydroxy ethoxy)-methyl pentanediol-1,5,1,1,1-three [2-hydroxy ethoxy] methyl]-ethane, 1,1,1-three [2-propoxyl]-methyl] propane, glycol ether, dipropyl (support) glycol, tetramethylolmethane, sorbyl alcohol, sucrose, lactose, the methyl glucose glucoside, the alpha-hydroxyalkyl glycoside, resol, or the like.The alkylene oxide compound that uses when making the polyoxyalkylene polyol has 2～4 carbon atoms usually.Propylene oxide and mixture or the propylene oxide that contains ethylene oxide,1,2-epoxyethane are as preferred.Above-listed polyol itself can be used as active dydrogen compounds and uses.
The preferred kind of polyester polyol is usually by following formulate:
R[(OC
nH
2n)
zOH]
a
Wherein R is hydrogen or multivalence alkyl; A is the valency that an integer (promptly 1 or 2 to 6 to 8) equals R, and n is 2～4 integer in each embodiment, 2 and 4 be also included within (preferred 3), and z is that numerical value is 2～about 200 integer in each embodiment, preferred 15～about 100.
In addition contain the polymer that compound bearing active hydrogen is a cyclic ester.Prepare the cyclic ester polymer from least one cyclic ester monomer and for example be recorded in the patent documentation United States Patent (USP) the 3rd, 021, No. 309 to the 3rd, 021, No. 317, the 3rd, 169, No. 945 and the 2nd, 962, No. 524.Suitable cyclic ester monomer includes but are not limited to δ-Wu Neizhi, 6-caprolactone, ζ-oenantholacton, monoalkyl-valerolactone, for example monomethyl-, single ethyl group-and single hexyl-valerolactone.
Cyclic ester/alkylene oxide block copolymer also can be by the preparation that reacts to each other of mixture, this mixture comprises cyclic ester and alkylene oxide monomer, a kind of interface reagent is a solid for example, relatively high-molecular weight many (vinyl stearate salt) or lauryl alcohol methacrylate/vinyl chloride multipolymer (30 ℃ time reduced viscosity be about 0.3～about 1.0), the saturated aliphatic hydrocarbon solvent that this needs a kind of inertia, be generally liquid for example heptane and phosphorus pentafluoride as catalyzer, and under the temperature of a rising, for example about 80 ℃.
The material that contains active hydrogen of another type comprises the polymeric polyhydroxy compound composition, this is by at United States Patent (USP) the 3rd, (ethylenically) unsaturation monomer that polymerization contains ethylenic linkage in the polyol of describing in 383, No. 351 obtains, at this as a reference.The suitable monomer of producing this composition comprises the unsaturation monomer that contains ethylenic linkage of identifying and describing in third rare nitrile, vinyl chloride, vinylbenzene, divinyl, inferior ethene chlorine and other United States Patent (USP) that relates in the above.Suitable polyol comprise above with United States Patent (USP) in the compound listing and describe.The polymeric polyhydroxy compound composition contains 1～about 70 weight percents (wt%), more preferably from about 5～about 50wt%, the most preferably from about polyol of 10～about 40wt% monomer polymerization.In the time of 40 ℃～150 ℃, at catalysts for radical polymerization when for example superoxide, mistake (two) vitriol, percarbonate, perborate and nitrogenous compound exist, the monomer in the polyol that this composition is selected by polymerization is easily prepared.
The composition preferred, polyethers polyol that contains active hydrogen, the mixture of the mixture of polyether polyhydroxy-compound and polyethers and polyester polyol.Preferred polyether polyhydroxy-compound comprises polyoxyalkylene diols and trivalent alcohol, and contains the polystyrene that is connected on the polymer chain and/or the polyoxyalkylene diols and the trivalent alcohol of polyacrylonitrile, and their mixture.The preferred polyester polyol is based on caprolactone (caprolactone).Especially, the polyol composition is reformulated and has been produced a modulus (moduli) that scope is big.Also can add chain extension agent and linking agent, they have low VOC.The chain extension agent that can imitate and linking agent are to have a low-molecular-weight glycol, for example alkane diol and two allyl diglycols, and/or polyhydroxy-alcohol, and preferred trivalent alcohol and furans, its molecular weight is about 200～400.
In a preferred embodiment, the polyol composition comprises a polyether polyhydroxy-compound or its mixture, and molecular weight is about 500～about 1500; A polyethers oxide compound glycol (polyether oxide diol) or its mixture, molecular weight are about 1000～about 3000; And one contain polyether glycol or its mixture that polystyrene is connected with polyacrylonitrile, and molecular weight is about 1500～about 4000.This composition is used to produce the foam of low CFD (force of compression deviation).
In a further preferred embodiment, the polyol composition comprises a low-molecular-weight polyethers oxide compound glycol (polyether oxide diol) or its mixture, and molecular weight is about 250～about 750; A polyethers oxide compound glycol (polyether oxide diol) or its mixture, molecular weight are about 1000～about 3000; And one contain polypropylene oxide glycol (polypropylene oxide diol) or its mixture that polystyrene is connected with polyacrylonitrile, and molecular weight is about 2000～about 3000.This polyol composition is used to produce the foam of high CFD.
In order to merge required fire-retardant combination effectively according to the following method that will describe, keep the good performance characteristic of foam (froth) simultaneously, the viscosity of composition (not containing other composition) that contains active hydrogen is at room temperature preferably less than about 500 centipoises (cP), be more preferably less than about 300cP, most preferably less than about 250cP.Especially, the low viscosity polyol composition allows to use high-caliber flame retardant additives to reach desired characteristic and to keep the operability of final polyurethane foam and good physical property.
The hydroxyl value that polyol or polyol mixture have can in very large range change.Usually, the hydroxyl value in polyol or the mixture comprises other linking agent, if be used, can reach about 28～about 1000, perhaps higher, preferred about 100～about 800.Hydroxyl value is defined as the milligram number of the required potassium hydroxide of hydrolysate of the abundant acetylizad derivative that neutralizes fully, and wherein abundant acetylizad derivative derives from polyol or the polyol mixture that 1 gram contains or do not contain the linking agent of the present invention's use.Hydroxyl value also can be defined by following formula:
OH＝(56.1×1000×f)/M.W.
Wherein OH is the hydroxyl value of polyol, and f is functional group mean number (averagefunctionality), i.e. the hydroxyl value mean value of per molecule polyol, and M.W. is the molecular-weight average of polyol.
The application-dependent of accurate polyol or mixture is in the end-use of polyurethane foam.Especially, the variation of polyol composition can produce wide modulus of scope (moduli) and toughness.Suitably select molecular weight and hydroxyl value can produce soft foam.The polyol or the mixture that comprise crosslinking additives, when being used to soft foam formulation, the hydroxyl value that is had preferably about 45～about 700 or more.This is not to have a mind to restriction, only illustrates that the possible compound number of employed polyol is huge.
Interior variation can be used in stable foam to tensio-active agent on a large scale, preferably has organic silicon surface active agent.Preferred organic silicon surfactant is by SiO in essence
2(silicate) unit and (CH
3)
3SiO
0.5The multipolymer that (trimethylsiloxy group) unit is formed, wherein the unitary molar ratio of silicate and trimethylsiloxy group is about 0.8: 1～about 2.2: 1, preferred about 1: 1～about 2.0: 1.Another preferably has the organic silicon surface active stabilizer is a partial cross-linked siloxanes-polyoxyalkylene unit multipolymer and composition thereof, and wherein siloxane unit (blocks) is connected by silico-carbo with polyoxyalkylene unit (blocks), or is connected by silicon-oxygen-carbon.Siloxane unit (blocks) is made up of hydrocarbon-siloxane groups and is had on average at least two valent silicon in each unit of bonded with above-mentioned the connection.At least a portion polyoxyalkylene unit (blocks) is made up of oxyalkylene group and is polyvalent, just with above-mentioned connection the each unit of (linkage) bonded in the oxygen that connects of at least two valent carbon and/or carbon.Any remaining polyoxyalkylene unit (blocks) is made up of oxyalkylene group and is monovalent, just with the above-mentioned oxygen that has only valent carbon and/or carbon to connect in each unit of bonded that is connected.In addition, conventional organopolysiloxane-polyoxyalkylene unit (blocks) multipolymer for example those at United States Patent (USP) the 2nd, 834, No. 748, the 2nd, 846, No. 458, the 2nd, 868, No. 824, the 2nd, 917, No. 48 and the 3rd, 057, the composition of describing in No. 901 is used.The quantity that is used for the polymerizable organosilicon body of suds-stabilizing agent among the present invention can change in very wide limit, and for example containing in the active hydrogen composition of each hundred wt part has 0.5 wt part～10 wt parts or bigger approximately.The variation range of quantity on identical basis that preferably is present in the polymerizable organosilicon body in the foam formulation is about 1.0 wt parts～about 6.0 wt parts.
Catalyzer comprises multiple inorganic metal compound and the metallic compound that contains some organic group.More preferably metal acetylacetonates is for example aluminium, barium, cadmium, calcium, a cerium (III) of basis with following metal, chromium (III), cobalt (II), cobalt (III), copper (II), indium, iron (II), lanthanum, plumbous (II), manganese (II), manganese (III), neodymium, nickel (II), palladium (II), potassium, samarium, sodium, terbium, titanium, vanadium, yttrium, zinc and zirconium.A kind of catalyzer commonly used is two (2,4-acetylacetonate nickel (II)) (being called acetylacetonate nickel or bis-acetylacetonate nickel again) and for example two acetonitrile bis-acetylacetonate acid of derivative nickel thereof, two benzene nitrile bis-acetylacetonate acid nickel, two (triphenylphosphine) biacetyl acetylacetonate nickel or the like.Especially preferred ferric acetyl acetonade is because its relative stability, good catalytic activity and do not have toxicity.The The book of Changes of metal acetylacetonates dissolves in advance and for example joins in the suitable solvent dipropylene glycol or other contains hydroxy compound, and then participates in reaction and become the part of final product.
What be added into metal acetylacetonates is methyl ethyl diketone (2, the 4-diacetylmethane), as what disclose in No. the 5th, 733,945, the United States Patent (USP) of Simpson, at this as a reference.Found that methyl ethyl diketone can be used to delay or suppresses common reacting metal acetylacetonate, can make each composition reach correct mixing and casting under lower temperature.In other words, methyl ethyl diketone provides heating latent period, and mixing, casting and required time of other step are provided, and has avoided the deleterious course of processing too early in subzero treatment.Yet along with material in some heating region is cured and the temperature of polyurethane mixture rises, methyl ethyl diketone is eliminated (driven off).Along with methyl ethyl diketone and delay the elimination of function, metal acetylacetonates is continued its common hyperergy and the katalysis of high level is provided in final polyurethane reaction.This hyperergy is favourable in the fabrication cycles of back and physical property that improvement is provided compressive set for example.Usually, the ratio of metal acetylacetonates and methyl ethyl diketone is about 2: 1 on weight basis.The preferable range that is present in Liquid Phase by Catalytic agent consumption is to contain 0.03～3.0 wt part in the active dydrogen compounds of each hundred wt part.
Urethane in the prescription provides low atomizing and outgassing.Therefore, replaced normally used halogenation in the technology and/or based on the flame-retardant additive of phosphorus, they can cause atomizing and outgassing, fire-retardant combination comprises a kind of compound based on antimony; A kind of halogenated, composition of containing active hydrogen can react with the polyisocyanate salt component; And a kind of halogenated fire retardant, be about 2.0: 1～about 18.0: 1 at the molar ratio of this halogen and antimony.With reference to relevant technologies discussed above, can produce high-caliber fire retardation and should be and only use halogenation and/or phosphorus polyurethane foam as the fire retardant on basis.This reagent can cause atomizing and outgassing.The unexpected discovery of inventor can obtain tough and tensile, high flame-retardant polyurethane foam and not or have minimal atomizing or an outgassing by the fire-retardant synthetics that uses above-mentioned antimony with specific ratios and bromine.The advantage of a uniqueness is, the viscosity of selecting to contain the active hydrogen composition makes it possible to merge the fire-retardant combination of improvement, the favourable physical property of maintenance in the urethane that solidified simultaneously.Suitably the viscosity of selecting can also merge other weighting material and reaction or nonreactive additive.In addition, therefore the composition of selecteed fire-retardant combination or solid or can react be low VOC.
In another embodiment, by using the compound of a low VOC composition and a low VOC fire-retardant combination, cured compositions can obtain fire retardation and low atomizing and outgassing, and this low VOC fire-retardant combination comprises the composition that at least one low VOC is halogenated, contain active hydrogen.Therefore curable compositions comprises a low VOC isocyanate, and a low VOC contains the composition of active hydrogen, a low VOC tensio-active agent, a low VOC catalyzer and a low VOC fire-retardant combination.Low VOC fire-retardant combination comprises at least one low VOC, the halogenated composition that contains active hydrogen, and can select other low VOC composition.In addition, select the composition that contains active hydrogen of proper viscosity to make it possible to merge fire-retardant combination." low VOC " herein is meant the compound with low (2% or still less weight) volatile organic compounds level.Volatile organic compounds herein is meant in room temperature or when high-temperature for example reaches about 125 ℃ slightly, the compound that can be eliminated as steam.
Be used for the preferred ANTIMONY TRIOXIDE SB 203 99.8 PCT of the compound based on antimony of fire-retardant combination, be solid.
Preferred reactive, halogenated, as to contain active hydrogen composition is similar to the composition of above-mentioned composition urethane, removes a kind of halogen, beyond preferred bromine exists.Particularly preferred reacted constituent comprises the bromination glycol, under temperature of reaction as 25 ℃ be liquid, tetrabromophthalate salt for example.The solid brominated glycol that is dissolved in the response composite also is suitable for, for example, and dibromo neopentyl alcohol and/or tribromo neopentyl alcohol.Use liquid, a halogenation composition to make it possible to merge more other solid flame retardant and in acceptable limit, keep whole viscosity simultaneously, and provide and have good physical properties, for example the curing urethane of tensile strength, compressive set resistibility or the like.
Preferred nonreactive halogenated fire-retardants is solid, bromated organic compound normally, knownly uses in urethane.This reagent comprises, but be not limited to, ten hexabromocyclododecanes, the bromination indane, tetrabromo base phthalyl methylamine (ethylenebistetrabromophthalimide), two (tribromophenoxy) ethane (bis (tribromophenoxy) ethane), three (tribromo phenyl) cyanurate (tris (tribromophenyl) cyanurate), decabromodiphenyl oxide compound (decabromodiphenyl oxide), ten tetrabromos, third diphenol (tetradecabromodiphenoxybenzene), ethane-1, two (penta-bromophenyl) (ethane-1, the 2-bis (pentabromophenyl)) of 2-, and brominated Polystyrene (brominated polystyrene).
The fire-retardant weighting material that other is used, for example hibbsite (aluminumtrihydrate) and melamine cyanurate.Particularly advantageous fire-retardant weighting material is for example carbon black and nanometer potter's clay (nanoclays) of those materials with high surface area.Another advantage of nanometer potter's clay is high surface ratio, but may need the particular processing method with nanometer layer (nanolayers) separately thus reach required high surface area (stripping layer) (exfoliation).Spendable nanometer potter's clay is natural kaolinite, the product of SouthernClay for example, and it has used multiple organic modifier, and commodity are called CLOISITE 10A, 15A, 20A, 25A, 30B and 93A.For obtaining the stripping layer, preferred CLOISITE 30B.(100 ℃) use the stripping layer of CLOISITE 20A in PHT4-DIOL at elevated temperatures.
The effective content of fire-retardant combination is to determine that by a kind of technology commonly used in the technology its basis is the workability of the degree of fire retardation, prescription and required urethane characteristic.Significant quantity accounts for about 20～about 60 weight percents of the mixture that does not contain isocyanate usually.Adjust antimony (when existing) and always the relative content of bromine make the molar ratio of total bromine and antimony more than or equal to about 2.0: 1, be preferably greater than or equal about 2.5: 1, more preferably greater than or equal about 3.0: 1, most preferably more than or equal to about 4.0: 1.Especially the relative content of adjusting antimony (when existing) and total bromine makes the molar ratio of total bromine and antimony be less than or equal to about 24.0: 1, is less than or equal to about 18.0: 1, is less than or equal to about 16.0: 1, perhaps is less than or equal to about 14.0: 1.The molar ratio that find to use unexpectedly is about 10.0: 1 or when higher, can obtain fabulous fire retardation and have good characteristic.The molar ratio of total bromine and antimony is 2.0: 1 o'clock, and being about as much as weight ratio is 1.25: 1, and molar ratio is that to be about as much as weight ratio at 18.0: 1 o'clock be about 9.3: 1.
In addition, the weight percent (based on total composition) of selection bromine makes it possible to provide the fire retardation of a desired level, according to the preferred at least HBF of UL-94 standard, more preferably is at least V-1.Usually, the weight percent that bromine accounts for total composition is at least about 12, preferably is at least about 14.The bromine of low concentration can be used to contain the occasion of other flame-retardant additive, for example melamine cyanurate.Certainly, can also use the composition, other additive or the compound that contain higher levels of bromine and antimony, need only total viscosity and remain in machinable boundary to obtain the fire retardation of improvement.
In addition, in manufacturing processed, selectable additive can join in the polyurethane foam mixture.For example, the conventional additive of using such as other weighting material (tripoli, lime carbonate, potter's clay or the like), dyestuff, pigment (for example titanium dioxide and ferric oxide) or the like also can be used.
Another unexpected characteristics are, suitably select antioxidant also can produce the high temperature resistant function (high temperature resistance) of improvement and with low atomizing and outgassing.For example BHT is an antioxidant commonly used, at room temperature is solid, but can distillation under high slightly temperature.When being replaced based on the antioxidant of phenol and amine-can obtain the product of following trade(brand)name by Ciba Specialty Chemicals, IRGANOX1135, CAS No.125643-61-0 and IRGANOX 5057, CAS No.68411-46-1-high temperature resistant function improves and has reduced atomizing and outgassing.The significant quantity of IRGANOX 1135 antioxidants is about 0.05～about 0.25 weight percent, the significant quantity of IRGANOX 5057 is about 0.005～about 0.07 weight percent, IRGANOX 1135 preferred significant quantities are about 0.07～about 0.10 weight percent, and the preferred significant quantity of polyol composition is about 0.015～about 0.03 weight percent.Use the hindered amine light tranquilizer further to strengthen anti-UV effect.
A small amount of auxiliary blowing agent is employed.For example, use highly and seethe with excitement, such as at ebullient fluorocarbon more than 40 ℃.Special fluorocarbon for example comprises 1,1,2-three chloro-1,2, and the isomer of 2-Halothane and C2Cl4F2, tetrachloro one fluoroethane, or the like.Other auxiliary blowing agent, for example although less water necessary under the more expansible situations of those needs, also can be used so that more expansion is provided when being heating and curing.
The gas phase of novel (novel) foam (froth) is air most preferably, because air is cheap and be easy to obtain.Yet, if desired, can use other under external environment as gasiform gas and fully inertia or with the nonreactive gas of any liquid composition.This other gas comprises, for example, nitrogen, carbonic acid gas even fluorocarbon, they are generally gaseous state under external environment.Rare gas element is integrated with in the liquid phase, and this need be by, carrying out machinery to liquid phase and beat for example in Hobart mixing tank or the Oakes mixing tank at high speed shear device.The common working method of Oakes mixing tank is under pressure gas to be introduced, and perhaps sucks gas by beaing or lash (whipping) effect from atmosphere in the Hobart mixing tank.Machinery beats the operation preferred pressure should be not more than 100～200p.s.i.g.Meaningfully, only need to use mixing equipment conventional, that easily obtain, do not need specific installation.The time that machinery beats is several seconds to one minute in the Oakes mixing tank, is 3～30 minutes in the Hobart mixing tank, perhaps spends the time of long point to obtain required foam (froth) density in the mixing equipment that uses.
The foam (froth) that beats operation formation by machinery is very stable on chemistry and structure, and under outside temperature, for example about 10 ℃～about 40 ℃, is easy to use.The viscosity of foam (froth) depends on the initial viscosity of composition when not forming foam (froth).Easily the range of viscosities of processing compositions is hundreds of centipoise～8,000 centipoises.Low viscosity poly-hydroxy composition is used in conjunction with fire retardant or other weighting material or compositions of additives, and the viscosity of formation remains in machinable scope.
These foams (froth) can continue to be cast as thin slice or tubular, or are cast into complicated shape.The density of cured foam is generally about 10～about 65pcf, preferred about 15～about 40pcf, most preferably from about 15～about 30pcf.
One preferably characteristics be that the foam that above-mentioned composition forms is that the grade with UL-94 is V-2 and/or HBF, and/or passed through the fire retardant of MVSS No.302.Preferred thickness is about 10～about 500mils, 31～about 250mils more preferably from about, and density is the foam of about 15～about 30pcf, the grade of its UL-94 is V-1 and/or HF-2, most preferably V-0 and/or HF-1.Measure foam according to SAE J1756 and be low sprayability, measure foam according to ASTM E595 and be low outgassing.Placed 24 hours at 125 ℃, the weight of foam lost is less than 1%.
In the embodiment, foam has low modulus (modulus), promptly CFD be about 3～about 30, foam density be about 10～about 50, preferred about 15～about 30pcf, and tough and tensile reflects high-tear strength, high tensile and high elongation rate with respect to the modulus foam.The preferred compressive set of foam should be less than about 20%, is more preferably less than 10% (70 ℃ time 50% compression 22 hours).The preferred force of compression deviation of foam should be more preferably less than about 30psi less than about 85psi; Preferred elongation should be greater than about 100; Preferred tensile strength should be greater than about 50psi, more preferably greater than about 80psi; Preferred tear strength is greater than about 5, more preferably greater than about 8pli.
In another embodiment, foam has low modulus (modulus), and promptly CFD more than 30, preferably more than 50, more preferably more than 100, reaches about 200CFD about about about, the about 30～about 50pcf of density.The foamy tensile strength is about 200～and about 500, elongation should be greater than about 80, and tear strength is greater than about 30, and compressive set should be less than about 10% (70 ℃ time 25% compression 22 hours).
In order to improve the more fire retardation of composition, keep low atomizing and outgassing simultaneously, the solidified product can with the curable acrylic acid composition chromatography of UV-(overprinted).Material self adhered when this composition was used in particular for preventing to make.Suitable acrylic acid composition comprises for example RCE01496R, can obtain from Sun Chemical.
The foam that these compositions produce can be used for for example automotive industry, in automobile, aircraft and shipbuilding industry, can be used as the foam-filled of nest hole (cavities) and foam backing (backing) in refrigeration and building industry, for example plate (board) and control panel, as sandwiching part, the middle layer of perhaps foam-filled refrigerator and refrigeration package.Polyurethane foam also is applicable to packing ring and the strip of paper used for sealing in the vibration damping, and the insulating material for example packing ring and the strip of paper used for sealing of light-emitting diode display in the electronics, also have thing, device security lid and the central desk of wall lining, dwelling house construction part, cushion material, handrail, something or somebody to fall back on.
Polyurethane foam is further described by following nonrestrictive example: following table 1 has been enumerated chemical preparations, source and description thereof.Table 1.
| Trade(brand)name | The source | Describe |
| SAYTEX BT-93 | Albermarle Co. | Ethene two (tetrabromo phthalimide), 67% bromine weight |
| SAYTEX 102E | Albermarle Co. | Ten bromo-diphenyloxides, 83.3% bromine weight |
| Trade(brand)name | The source | Describe |
| SAYTEX 120 | Albermarle Co. | Ten tetrabromos-two phenoxy groups-benzene, 81.8% bromine weight |
| SAYTEX RB-79 | Albermarle Co. | 3,4,5,6-tetrabromo-1,2-benzenedicarboxylic acid; The mixed ester of glycol ether and propylene glycol |
| PHT4-DIOL | Great Lakes Chemical Co. | The tetrabromophthalate glycol, 46% bromine weight |
| Catalyzer | 0.25wt% ferric acetyl acetonade and 0.75 wt% methyl ethyl diketone in the polyol | |
| 3A SIEVE | UOP | The composite alkali aluminum silicate, K 12[(AlO 2) 12(SiO 2) 12]XH 2O |
| ANTIMONY TRIOXIDE SB 203 99.8 PCT | US Antimony company | Sb 2O 3, particle size is 0.4～0.8 micron .83.53 wt% antimony |
| L-5617 | Crompton/ OSi | Silicone resin is the tensio-active agent on basis |
| PPG-425 | Bayer | Polypropylene glycol, MW=425g/mol, viscosity 25 ℃=70 cP |
| Trade(brand)name | The source | Describe |
| PPG-1000 | Bayer | Polypropylene glycol, MW=1000g/mol, 25 ℃=164cP of viscosity |
| PPG-2000 | Bayer | Polypropylene glycol, MW=2000,25 ℃=347cP of viscosity |
| Niax 34-45 | Bayer | The polymer polyol-by the polyether-tribasic alcohol of vinylbenzene and the improvement of the third rare nitrile, 25 ℃=1260cP of viscosity |
| IRGANOX 1135 | Ciba | Interrupted phenol (antioxidant) |
| IRGANOX 5057 | Ciba | Aromatic amine (antioxidant) |
| PAPI 901 | Dow Chemical | Polymerization diphenylmethane diisocyanate salt, %NCO=31.6, average function=2.2 |
| Pigment | PAN Chemical | Tinting material in the polyol |
| Cloisite 30A | Southern Clay | The natural kaolinite that organic activator was handled |
| DPG | Lyondell Chemical | Dipropylene glycol |
| Trade(brand)name | The source | Describe |
| Chemical company |
Introduce the prescription of polyurethane foam below, table 2 and table 3 have been enumerated polyurethane foam combination.Non-isocyanate composition (be the poly-hydroxy mixture, wherein contain active hydrogen composition, catalyzer, fire-retardant combination and weighting material or additive) is mixed and be positioned in the storage tank and stir under drying nitrogen.This mixture is pumped in the high speed shear Oakes-type mixing head (high shear Oakes-type mixing head) with certain flow rate.Isocyanate is pumped into mixing head separately.The flow velocity that uses Matheson gas flow rate controller to regulate dry air makes it enter mixing head, makes solidify material reach required density.After mixing and the foaming, composition (coated release paper) on the coating separating shaped paper is cast, and allows be coated with the air dry oven drying of separating shaped paper through 275-300 before foam enters.The casting foam passes through knife over plate (KOP) coating machine again, and foam dispersion is become desired thickness.The casting foam passes through heating drum (upper limit 400 , lower limit 250～375 ) again and is solidified, with postcooling.On foam, be coated with the curable acrylic acid composition of one deck UV-again.The synthetic foam is checked by the following method.The results are shown in Table 2 and table 3.
The modulus of force of compression deviation (CFD) reflection is determined by Instron, use long 2 inches wide 2 inches cross cuttings packing sample (die-cut samples) and pile up (stackedto) to minimum 0.250 inch, be generally about 0.375 inch, every heap or every string use two to pile up (using two stacks per lot or run) and at the element of one 20,000 pounds of the bottom of Instron assemblings.The method of measuring CFD is to calculate sample is depressed into 25% o'clock of initial thickness, the poundage of (psi) required pressure per square inch.
Instron is used in the measurement of tensile strength and elongation, and is furnished with 50 pounds load cell (load cell), uses 10～20 pounds of pressure measurement scopes to decide according to thickness and density.The method of calculation of tensile strength are that the used strength of sample burst (psi) multiply by 2 again divided by thickness of sample.Elongation is extension per-cent.
Instron is used in the measurement of tear strength, and is furnished with 50 pounds load cell, uses 2,5 or 10 pounds of pressure ranges to decide according to sample thickness and density.The method of calculation of tear strength are that the tear edge that applies is divided by sample thickness.
The measurement of outgassing can be used ASTM E595 or sample is placed the weight percents of calculation sample loss in 24 hours under 125 ℃.For these and similar prescription, its outgassing is less than 1 weight percent usually.
Measure atomizing according to SAE J1756.These and similar prescription all can pass through this standard.
The measuring method of compressive set be calculate when the foamy standard test specimen 70 ℃ be subjected to 50% or 25% compression and reach 22 hours after, it can not return to the quantity per-cent of initial thickness.Table 2.
| Sample number into spectrum | ||||||
| 1 | 2 | 3a | 4a | 4b | 3b | |
| Thickness, mil | 125 | 125 | 31 | 31 | 62 | 31 |
| Density, pcf | 20 | 25 | 40 | 40 | 40 | 60 |
| SAYTEX BT93 | 13.63 | 16.77 | 12.96 | 14.00 | ||
| PHT4-DIOL | 13.63 | 12.58 | 12.96 | 14.00 | ||
| ANTIMONY TRIOXIDE SB 203 99.8 PCT | 3.79 | 5.59 | 3.60 | 7.54 | ||
| PPG-425 | 0.00 | 0.00 | 27.30 | 23.74 | ||
| PPG-1000 | 28.72 | 23.44 | 0.00 | 0.00 | ||
| PPG-2000 | 7.57 | 6.08 | 7.20 | 5.37 | ||
| DPG | 0.00 | 1.12 | 0.00 | 0.00 | ||
| Catalyzer | 3.03 | 4.19 | 2.88 | 2.70 | ||
| L-5617 | 3.79 | 3.49 | 3.60 | 1.88 | ||
| 3A SIEVE | 1.51 | 1.40 | 1.44 | 1.38 |
| IRGANOX 1135 | 0.09 | 0.08 | 0.09 | 0.08 | ||
| IRGANOX 5057 | 0.02 | 0.02 | 0.02 | 0.02 | ||
| Pigment | 5.17 | 4.77 | 4.92 | 4.29 | ||
| NIAX 34-45 | 2.21 | 2.04 | 0.00 | 1.83 | ||
| CLOISITE 30A | 0.00 | 1.40 | 0.00 | 0.00 | ||
| PAPI 901 | 16.84 | 17.03 | 23.03 | 23.17 | ||
| Amount to | 100.0 0 | 100.0 0 | 100.00 | 100.00 | ||
| Characteristic | ||||||
| CFD，psi | 5.3 | 12.2 | 31.3 | 108.3 | 146.3 | |
| Tensile strength, psi | 65.4 | 103.0 | 301.1 | 339.0 | 407.0 | |
| Elongation, % | 179 | 149 | 228 | 125 | 129 | |
| Tear strength, pli | 10.2 | 17.4 | 55.1 | 56.6 | 78.2 |
| Compressive set, % | 3.0 * | 4.9 * | 6.5 ** | 8.0 ** | 5.7 ** | |
| Br，moles | 0.201 4 | 0.2212 | 0.1915 | 0.2069 | ||
| Sb，moles | 0.026 0 | 0.0384 | 0.0247 | 0.0517 | ||
| Br/Sb，molar ratio | 7.75 | 5.77 | 7.75 | 4.0 | ||
| Br，wt％ *** | 15.40 | 17.02 | 14.64 | 15.82 | ||
| Sb，wt％ *** | 3.17 | 4.67 | 3.01 | 6.30 | ||
| Br/Sb, weight ratio | 4.87 | 3.65 | 4.87 | 2.51 | ||
| The check of UL94 vertical combustion | failed | V-1 | failed | failed | V-0 | |
| The horizontal firing check of UL94 side | - | - | HBF | HF-1 | HBF | HBF |
| The poly-hydroxy mixture viscosity, cP (approximately) | 2800 | 5500 | 1800 | 2300 | - | - |
*Measure 50% compression
*Measure 25% compression
* *Calculate the weight percent of total composition
Table 3
| Sample number into spectrum | |||||||
| 5 | 6 | 7 | 8 | 9 | 10 | 11 | |
| Thickness, mil | 125 | 62 | 62 | 62 | 62 | 31 | 31 |
| Density, pcf | 25 | 25 | 25 | 25 | 25 | 30 | 30 |
| Saytex 102E | 0.00 | 0.00 | 24.42 | 27.78 | 29.60 | 26.43 | 29.12 |
| Saytex 120 | 0.00 | 27.78 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| Saytex BT93 | 24.37 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| PHT4-DIOL | 12.90 | 12.63 | 12.63 | 12.63 | 12.68 | 12.01 | 13.24 |
| Antimony VF | 7.61 | 4.21 | 7.58 | 4.21 | 4.23 | 4.00 | 4.41 |
| PPG-425 | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 | 20.02 | 15.80 |
| PPG-1000 | 17.92 | 17.68 | 17.68 | 17.68 | 16.07 | 0.00 | 0.00 |
| PPG-2000 | 6.24 | 6.74 | 6.74 | 6.74 | 6.77 | 3.20 | 3.21 |
| DPG | 0.97 | 0.97 | 0.97 | 0.97 | 0.97 | 0.92 | 0.92 |
| CATMIXLOAA | 3.62 | 3.63 | 3.63 | 3.63 | 3.64 | 3.44 | 3.45 |
| L-5617 | 3.23 | 3.34 | 3.34 | 3.34 | 3.36 | 3.18 | 3.18 |
| 3A SIEVE | 1.20 | 1.20 | 1.20 | 1.20 | 1.20 | 1.15 | 1.15 |
| IRGANOX 1135 | 0.09 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| IRGANOX 5057 | 0.02 | 0.03 | 0.03 | 0.03 | 0.03 | 0.02 | 0.02 |
| JET BLACK | 4.12 | 4.13 | 4.13 | 4.13 | 4.14 | 3.92 | 3.93 |
| NIAX 34-45 | 1.76 | 1.77 | 1.75 | 1.76 | 1.78 | 1.70 | 1.69 |
| PAPI 901 | 15.94 | 15.80 | 15.80 | 15.80 | 15.43 | 19.91 | 19.78 |
| Amount to | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| Characteristic | |||||||
| CFD，psi | 20.2 | 15.6 | 9.8 | 12.9 | 12.8 | 33.6 | 153.0 |
| Tensile strength, psi | 150.1 | 145.9 | 128.1 | 144.8 | 135.4 | 230.3 | 369.6 |
| Extensibility, % | 137 | 140 | 143 | 155 | 133 | 135 | 80 |
| Tear strength, pli | 22.3 | 17.4 | 16.6 | 18.6 | 17 | 36.2 | 51.2 |
| Compressive set, % | 3.6 | 3.9 | 4.2 | 3.2 | 3.3 | 5.3 | 7.0 |
| Br，moles | 0.2792 | 0.3572 | 0.3273 | 0.3623 | 0.3816 | 0.3447 | 0.3798 |
| Sb，moles | 0.0522 | 0.0289 | 0.0520 | 0.0289 | 0.0290 | 0.0274 | 0.0303 |
| Br/Sb, molar ratio | 5.35 | 12.37 | 6.29 | 12.54 | 13.15 | 12.56 | 12.55 |
| Br，wt％ *** | 22.31 | 28.53 | 26.15 | 28.95 | 30.49 | 27.54 | 30.35 |
| Sb，wt％ *** | 6.36 | 3.52 | 6.33 | 3.52 | 3.53 | 3.34 | 3.68 |
| Br/Sb, the viscosity of weight ratio UL94 vertical combustion check poly-hydroxy mixture, cP (approximately) | 3.51 V-0 6960 | 8.11 V-0 4000 | 4.13 V-0 4600 | 8.23 V-0 5350 | 8.63 V-0 4600 | 8.24 V-0 5000 | 8.24 V-0 6590 |
*Measure 50% compression
*Measure 25% compression
* *Calculate the weight percent of total composition
Sample 1,2,5,6,7,8 and 9 is low modulus, and sample 3a, 4a, 4b, 10 and 11 are high-module.Above data show, polyurethane foam of the present invention meet UL 94 burning survey requirementes (V0, V1, HF1, HBF).This fire retardation is realized by a kind of liquid bromination reaction glycol, a kind of bromination SOLID ORGANIC weighting material and ANTIMONY TRIOXIDE SB 203 99.8 PCT are merged.The molar ratio of the two is about 2.0: 1～about 24.0: 1 when reaching synergistic enhancing effect between bromine and the antimony.Low viscous polyol feed intake (batch) regulated because the viscosity that additive causes increases.
Above-mentioned fire-retardant combination is more effective in making solid polyurethane, for example the flexible polyurethane gonosome.Prepare polymeric appropriate combination thing of soft urethane and method and done description,, No. 444, the 4th, 218, No. 543, the 4th, 444, No. 910, the 4th, 530, No. 941 and 4,269, describe in No. 945 for example at United States Patent (USP) the 4th, 297.Under room temperature or high slightly temperature, the close mixing of response composite being carried out the short period of time is to make this soft body, cast mixture or synthetic mixture is poured in the chunk then, or be injected in the closed molds, both of these case all needs heating.Reaction is when finishing, and mixture has formed the shape of mould, makes the flexible polyurethane gonosome that pre-determines structure, fully solidifies and with the minimum risk that causes distortion it is taken out from mould, and this distortion should be greater than the set final application that is allowed to.Promote soft body solidified felicity condition to comprise die temperature, be generally about 20～about 150 ℃, preferred about 35～about 75 ℃, more preferably from about 45～about 55 ℃.After the close mixing of reactant, such temperature can make the soft body of abundant solidified take out from mould in about 1～10 minute usually, about 1～5 minute commonly used.Optimal condition of cure depends on consumption that special composition comprises catalyzer and prepare soft body to be also had the size and dimension of goods and decides.
Showed and described embodiment preferred, but the multiple change that is provided and substitute and do not break away from marrow of the present invention and scope.Therefore, to can be understood as be a kind of mode of explaining and be not limited only to this to description of the invention.
Claims (11)
1. resistance combustion polyurethane foam comprises following component:
A kind of organic polyisocyanate salt component;
A kind of composition that contains active hydrogen, can be fully and the polyisocyanate reactant salt form urethane; The viscosity that wherein contains the active hydrogen composition at room temperature should be less than or equal to 500 centipoises;
A kind of tensio-active agent;
A kind of catalyzer has abundant catalytic activity in the curing of said mixture;
Selectable weighting material;
And a kind of fire-retardant combination, comprising:
A kind of compound based on antimony; With
A kind of halogenated, contain compound bearing active hydrogen, can react with the polyisocyanate salt component; With
A kind of halogenated fire retardant, the molar ratio of wherein total halogen and antimony is 2: 1～24: 1, wherein total composition contains the halogen of at least 12% weight.
2. foam according to claim 1, the viscosity of wherein said active hydrogen composition are at room temperature less than 300 centipoises.
3. foam according to claim 1 and 2, the mixture viscosity at room temperature that the composition of described active hydrogen, tensio-active agent, fire-retardant combination, selectable weighting material and catalyzer are formed should be less than 8,000 centipoises.
4. foam according to claim 3, described compound based on antimony is an ANTIMONY TRIOXIDE SB 203 99.8 PCT, composition halogenated, that contain active hydrogen is the bromination polyol.
5. foam according to claim 4, UL 94 grades that this foam has are V-0, V-1, HF1 or HBF.
6. foam according to claim 5, compressive set should be less than 10% during at 70 ℃ after 22 hours through 50% compression for this foam.The force of compression deviation is less than 30psi, and tear strength is greater than 5pli.
7. foam according to claim 5, compressive set should be less than 10% during at 70 ℃ after 22 hours through 25% compression for this foam, and the force of compression deviation is greater than 50psi, and tear strength is greater than 5pli.
8. one kind comprises the described foamy product of claim 1.
9. product according to claim 8, it is a packing ring.
10. a method for preparing resistance combustion polyurethane foam comprises the steps:
Disperse rare gas element fully equably in mixture, this mixture comprises:
A kind of organic polyisocyanate salt component;
A kind of composition that contains active hydrogen, can be fully and the isocyanate reaction form urethane; The viscosity that wherein contains the active hydrogen composition at room temperature should be less than or equal to 500 centipoises;
A kind of tensio-active agent;
A kind of catalyzer has sufficient catalytic activity in the curing of said mixture;
Selectable weighting material; And
A kind of fire-retardant combination comprises:
A kind of compound based on antimony; With
A kind of halogenated, contain compound bearing active hydrogen, can react with the polyisocyanate salt component; With
A kind of halogenated fire-retardant combination, the molar ratio of wherein total halogen and antimony is 2: 1～24: 1, and wherein total composition contains the halogen of at least 12% weight, forms a kind of heat-setting foam, this foam is in structure and chemically very stable, and just can use in external environment; And solidify above-mentioned foam to form cured foam.
11. method according to claim 10, UL 94 grades that described foam has are V-0, V-1, HF1 or HBF.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2002/013136 WO2003091308A1 (en) | 2002-04-25 | 2002-04-25 | Flame retardant polyurethane composition and method of manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1625576A CN1625576A (en) | 2005-06-08 |
| CN1298761C true CN1298761C (en) | 2007-02-07 |
Family
ID=29268421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028288270A Expired - Fee Related CN1298761C (en) | 2002-04-25 | 2002-04-25 | Flame retardant polyurethane composition and preparation method thereof |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP4627990B2 (en) |
| CN (1) | CN1298761C (en) |
| AU (1) | AU2002256360A1 (en) |
| DE (1) | DE10297709T5 (en) |
| GB (1) | GB2402395B (en) |
| WO (1) | WO2003091308A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7153901B2 (en) | 2003-11-21 | 2006-12-26 | Albemarle Corporation | Flame retardant, additive compositions, and flame retardant polyurethanes |
| WO2006060174A1 (en) * | 2004-11-15 | 2006-06-08 | Honeywell International Inc. | Isocyanate-based polymer foams with nano-scale materials |
| US20090239987A1 (en) * | 2008-03-19 | 2009-09-24 | Lubrizol Advanced Materials, Inc. | Halogen Flame Retardant Thermoplastic Polyurethane |
| JP5933114B2 (en) * | 2013-04-02 | 2016-06-08 | 株式会社イノアックコーポレーション | Polyurethane foam and method for producing the same |
| JP6298344B2 (en) * | 2013-04-03 | 2018-03-20 | 積水化学工業株式会社 | Flame retardant urethane resin composition |
| CN106220819A (en) * | 2016-08-16 | 2016-12-14 | 曹健 | A kind of preparation method of polyurethane high-strength compound thermal insulation board |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1020310A (en) * | 1963-12-23 | 1966-02-16 | Allied Chem | Process for preparing fire retardant polyurethane foams |
| US4022718A (en) * | 1974-03-06 | 1977-05-10 | Gaf Corporation | High resilience fire retardant urethane foam |
| US4147847A (en) * | 1973-11-14 | 1979-04-03 | Dow Corning Corporation | Method of preparing flexible flame retardant polyether based one-shot polyurethane foams and compositions therefore |
| US4162353A (en) * | 1975-12-29 | 1979-07-24 | Union Carbide Corporation | Method of producing flexible flame retarded polyurethane foam |
| US4511699A (en) * | 1982-06-21 | 1985-04-16 | The General Tire & Rubber Company | Flexible thermoplastic vinyl chloride polymers and acrylate terpolymers |
| US4849459A (en) * | 1985-06-27 | 1989-07-18 | Basf Corporation | Flame retardant polyurethane foams |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4511688A (en) * | 1984-02-29 | 1985-04-16 | The Dow Chemical Company | Flame retardant for use in rigid polyurethane foams |
| US4514524A (en) * | 1984-07-13 | 1985-04-30 | Stauffer Chemical Company | Intumescent flexible polyurethane foam |
| FR2705680B1 (en) * | 1993-05-24 | 1995-08-11 | Corning Inc | Thermosetting composition in a non-flammable elastomeric polyurethane, process for overmolding optical components using this composition, and optical components obtained. |
| JPH1025413A (en) * | 1996-05-10 | 1998-01-27 | Idemitsu Petrochem Co Ltd | Flame-retardant liquid polymer composition |
| DE19634886A1 (en) * | 1996-08-29 | 1998-03-05 | Basf Ag | Storage-stable, flame retardant-containing polyol component |
| JPH10204379A (en) * | 1997-01-22 | 1998-08-04 | Sanyo Chem Ind Ltd | Chipping-resistant coating composition |
| JPH10218956A (en) * | 1997-02-06 | 1998-08-18 | Inoac Corp | Flame-retardant polyurethane foam |
| WO1999031173A1 (en) * | 1997-12-13 | 1999-06-24 | Huntsmann Ici Chemicals Llc | Process for making rigid and flexible polyurethane foams |
| JP4421067B2 (en) * | 2000-04-07 | 2010-02-24 | 株式会社クラレ | Thermoplastic polyurethane resin composition |
-
2002
- 2002-04-25 CN CNB028288270A patent/CN1298761C/en not_active Expired - Fee Related
- 2002-04-25 AU AU2002256360A patent/AU2002256360A1/en not_active Abandoned
- 2002-04-25 WO PCT/US2002/013136 patent/WO2003091308A1/en active Application Filing
- 2002-04-25 GB GB0422767A patent/GB2402395B/en not_active Expired - Fee Related
- 2002-04-25 JP JP2003587862A patent/JP4627990B2/en not_active Expired - Fee Related
- 2002-04-25 DE DE10297709T patent/DE10297709T5/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1020310A (en) * | 1963-12-23 | 1966-02-16 | Allied Chem | Process for preparing fire retardant polyurethane foams |
| US4147847A (en) * | 1973-11-14 | 1979-04-03 | Dow Corning Corporation | Method of preparing flexible flame retardant polyether based one-shot polyurethane foams and compositions therefore |
| US4022718A (en) * | 1974-03-06 | 1977-05-10 | Gaf Corporation | High resilience fire retardant urethane foam |
| US4162353A (en) * | 1975-12-29 | 1979-07-24 | Union Carbide Corporation | Method of producing flexible flame retarded polyurethane foam |
| US4511699A (en) * | 1982-06-21 | 1985-04-16 | The General Tire & Rubber Company | Flexible thermoplastic vinyl chloride polymers and acrylate terpolymers |
| US4849459A (en) * | 1985-06-27 | 1989-07-18 | Basf Corporation | Flame retardant polyurethane foams |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1625576A (en) | 2005-06-08 |
| GB0422767D0 (en) | 2004-11-17 |
| AU2002256360A1 (en) | 2003-11-10 |
| DE10297709T5 (en) | 2005-05-25 |
| JP4627990B2 (en) | 2011-02-09 |
| WO2003091308A1 (en) | 2003-11-06 |
| JP2005523960A (en) | 2005-08-11 |
| GB2402395B (en) | 2005-12-07 |
| GB2402395A (en) | 2004-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6559196B2 (en) | Tough, fire resistant polyurethane foam and method of manufacture thereof | |
| US9908984B2 (en) | Flame retardant polyurethane foam and method for producing same | |
| US9725555B2 (en) | Sugar-based polyurethanes, methods for their preparation, and methods of use thereof | |
| CN105392814B (en) | Fire-retardant flexible polyurethane foam | |
| CN103221446A (en) | Flame resistant flexible polyurethane foam | |
| CN101031601A (en) | Molded flexible polyurethane foams with reduced flammability and superior durability | |
| RU2629020C2 (en) | Sugar-based polyurethanes, methods of their obtaining and application | |
| US20030050354A1 (en) | Flame retardant polyurethane composition and method of manufacture thereof | |
| US4526906A (en) | Non-burning, non-dripping instant set microcellular polyurethanes | |
| CN1298761C (en) | Flame retardant polyurethane composition and preparation method thereof | |
| US6653361B2 (en) | Flame retardant polyurethane composition and method of manufacture thereof | |
| WO2010024890A2 (en) | Decorative molded foams with good fire retardant properties | |
| CA1071350A (en) | Polyisocyanurate compositions and foams of improved friability and process of preparing same | |
| JP2020180169A (en) | Polyurethane foam-forming composition | |
| CN1229414C (en) | Isocyanic compositions and use thereof in the preparation of expanded polyurethanes with improved fire behaviour | |
| Frisch | Relationship of Chemical Structure and Properties of Rigid Urethane Foams | |
| JP2020180170A (en) | Halogen-containing polyether polyol composition | |
| JPH10218956A (en) | Flame-retardant polyurethane foam | |
| WO1990015833A1 (en) | Polyurethane compositions exhibiting reduced smoke density and method of preparing same | |
| AU2012386487B2 (en) | Sugar-based polyurethanes, methods for their preparation, and methods of use thereof | |
| CN1253483C (en) | Isocyanate compositions and their use in preparation of expanded polyurethane materials with endowed flame-resistance | |
| JPH10147707A (en) | Production of flame-retardant polyurethane elastomer | |
| JP2007297442A (en) | Polyurethane foam | |
| JPS6055019A (en) | Production of flame-retarding polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ROGERS INOAC (SUZHOU) CORPORATION Free format text: FORMER OWNER: WORLD PROPERTIES INC. Effective date: 20110808 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; TO: 215122 SUZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20110808 Address after: 215122 No. 368, Shen Xu Road, Suzhou Industrial Park, Jiangsu, China Patentee after: Rodgers Inoue high polymer material (Suzhou) Co., Ltd. Address before: Illinois Patentee before: World Properties Inc. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070207 Termination date: 20150425 |
|
| EXPY | Termination of patent right or utility model |