CN1161704A - rigid polyurethane foam - Google Patents

Abstract

Rigid polyurethane foams having a closed cell content higher than 85%, a core density of below 32 kg/m<3> and a dimensional stability, expressed as the sum of the absolute values of the relative linear changes in the three dimensions after exposure to -20 DEG C for 14 days, of below 15%.

Description

Rigid olyurethane foam

The present invention relates to rigid olyurethane foam or urethane-modified polyisocyanurate foamed plastics, relate to they the preparation method and this method in novel useful composition.

Rigid olyurethane foam and urethane-modified polyisocyanurate foamed plastics are on the whole by reacting suitable polymeric polyisocyanate and isocyanic ester-active compound (being generally polyvalent alcohol) to prepare in the presence of whipping agent.Purposes of these foamy is a kind of adiabatic medium as buildings, refrigerator and other family expenses device.

But industry member is seeking to have less dense does not show any harmful effect to other foam characteristics of for example dimensional stability rigid olyurethane foam always.

The porous plastics of low-density (ring) alkane foaming especially is difficult to obtain.

Provide a kind of stability low-density rigid olyurethane foam, and demonstrate gratifying dimensional stability, the porous plastics of especially a kind of (ring) alkane foaming is an one object of the present invention.

Can obtain a kind of rigid olyurethane foam or urethane-modified polyisocyanurate foamed plastics according to the present invention, this porous plastics has and is higher than 85% closed cell content, has the 32kg/m of being lower than ³Core density (core density) and be lower than 15% dimensional stability, this stable numerical value be expressed as adding of the absolute figure that is exposed to-20 ℃ of relative linear change on three directions after 14 days and.

Closed cell content is according to ISO DIS4590 canonical measure.Core density is according to DIN53420-78 or ISO845 canonical measure.Relative linear change on three directions is according to ISO2769 or ISO1923 canonical measure.

According to a preferred embodiment of the invention, this rigid olyurethane foam has the 28kg/m of being lower than ³, be preferably lower than 27kg/m ³, more preferably be lower than 26 or even 25kg/m ³, most preferably be lower than 22kg/m ³Core density.

According to another preferred embodiment of the present invention, this urethane foam has and is lower than 10%, is preferably lower than 7.5% dimensional stability.Generally, rigid olyurethane foam of the present invention has the 20kg/m of being lower than ³Core density and be lower than 15% dimensional stability; Has the 25kg/m of being lower than ³Core density and be lower than the rigid olyurethane foam of 10% dimensional stability and have the 28kg/m of being lower than ³Core density and be lower than the rigid olyurethane foam of 7.5% dimensional stability.

Rigid olyurethane foam of the present invention is particularly useful under lower temperature application (being lower than 5 ℃).

According to the present invention, the method of a kind of like this rigid olyurethane foam of a kind of preparation is provided simultaneously, this method is reacted under the foaming condition of the miscellany existence of a pneumatogen by making a kind of polyisocyanate composition and a kind of multi-functional based isocyanate activity composition, and each described pneumatogen has-40 ℃ to 80 ℃, preferably has 15 ℃ to 60 ℃ boiling point.

Preferably, used pneumatogen halogen atom not in the inventive method.

Have at least a kind of in used in the methods of the invention all pneumatogens, its heat conductivity of gas is preferably lower than the heat conductivity of gas of carbonic acid gas under the porous plastics use temperature, more preferably be lower than the heat conductivity of gas of Skellysolve A, most preferably be lower than the heat conductivity of gas of pentamethylene.

The porous plastics use temperature is defined as the minimum temperature that porous plastics in use is exposed to.For example, the use temperature that is used in the porous plastics in the refrigerator is-10 ℃, and in refrigerator is-25 ℃.

All whipping agent components (comprise pneumatogen and any CO that is produced by the chemical foaming agent resemble water ₂) the partial pressure sum preferably be at least 0.3bar, more preferably be at least 0.45bar, most preferably be at least 0.6bar.

Under the porous plastics use temperature, preferably have 40% at most in the pneumatogen miscellany, more preferably have 20% at most, more preferably have 10% at most, most preferably have 2% to be agglomerative at most.

The pneumatogen miscellany of Shi Yonging generally comprises at least 3 kinds of components in the methods of the invention, preferably includes at least 4 kinds of components, particularly when porous plastics is used for lower temperature application.Has preferably a kind of alkane of a kind of component or a kind of naphthenic hydrocarbon and/or acetone in the methods of the invention in the pneumatogen miscellany of Shi Yonging at least.

Used suitable component comprises in this pneumatogen miscellany: the 2-methylpentane, the 3-methylpentane, the 1-propionic aldehyde, instead-1, the 3-pentadiene, suitable-1, the 3-pentadiene, 1-amylene-4-alkynes, 4-methyl-cis-2-amylene, 4-methyl-1-pentene, 1-amylene-3-alkynes, trans-the 2-amylene, cis-2-amylene, methyl isocyanate, 1, the 5-hexadiene, 2, the 3-pentadiene, 1, the 2-pentadiene, 1, the 4-pentadiene, 2-methyl-1-butene alkene, 3,3-dimethyl-1-butylene, cyclopentadiene, 1, the 3-propylene oxide, 2-butyne, pentamethylene, cyclopentenes, the 1-propionic aldehyde, ethyl formate, oxalic dialdehyde, 2, the 3-dimethylbutane, methyl tert butyl ether, vinyl formate, the 1-pentyne, methyl-isobutyl ether, methyl isopropyl ether, the 3-methyl isophthalic acid, the 2-divinyl, 3-methyl isophthalic acid-butine, the methyl n-propyl ether, the 2-methyl-2-butene, azacyclopropane, furans, divinyl ether, diethylamine, formaldehyde, the 1-amylene, Skellysolve A, methyl-formiate, Tri N-Propyl Amine, propenal, iso-pentane, 2, the 2-dimethylbutane, isopropyl mercaptan, dimethyl thioether, the tetramethyl-silicomethane, 1, the 2-propylene oxide, methyl acetate, valylene, dithiocarbonic anhydride, acetaldehyde, the acetone sulfur alcohol, ether, hexanaphthene, methylcyclopentane, methylethylketone, sulfur dichloride, silicon tetrachloride, Trichloromonosilane, bromine, sulphur trioxide, 1,1-two chloro-1-fluoroethanes, the dimethyl chloride silicomethane, 1, the 1-C2H4F2 C2H4F2, the 2-propenyl chloride, normal propyl chloride, tert-butyl chloride, 1,2-two chloro-1,1, the 2-Halothane, 1,1-two chloro-2,2, the 2-Halothane, anti-form-1, the 2-Ethylene Dichloride, cis-1, the 2-Ethylene Dichloride, Hal, tetramethylene, normal hexane, Di Iso Propyl Ether, propargyl chloride, trimethylchlorosilane, the 2-N-PROPYLE BROMIDE, C2H4F2 C2H4F2, oxyethane, monochloroethane, perfluoropropane, methylvinylether, perfluorocyclobutane, perfluorobuttene, perfluorinated butane, chlorine pentafluoride, fluoroethane, dimethyl ether, cyclopropane, divinyl, maleic, anti-butylene, methacrylic, tetramethylene, butane, methylpropane, chlorine trifluoride, 1,1,1,2-Tetrafluoroethane 1, the 1-C2H4F2 C2H4F2,2 chlorobutadiene, 1, the 2-dibromotetrafluoroethane, chloromethyl ethyl ether, chlorallylene, 1,1, the 2-Refrigerant R 113, trichlorofluoromethane, dibromodifluoromethane, the methyl dichloro silicomethane, Acetyl Chloride 98Min., 1, the 1-Ethylene Dichloride, 1, the 1-ethylene dichloride, isopropyl chloride, methylene dichloride, monobromethane, methyl iodide, bromochlorodifluoromethane, Refrigerant 12, monochlorodifluoromethane, Dichloromonofluoromethane, bromotrifluoromethane, monochlorodifluoromethane, Dichloromonofluoromethane, one bromotrifluoethylene, one chlorotrifluoroethylene, one chloropentafluoroethane, dichloro tetrafluoro ethane, one chlorotrifluoroethylene, bromine ethene, chlorodifluoroethane, R 1216, Perfluoroacetone.

Preferably contain alkane in the used pneumatogen miscellany in the inventive method, randomly contain naphthenic hydrocarbon, and/or alkene, randomly contain cycloolefin, and/or in acetone and/or the following all hydrofluorocarbons one or more: 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,2-Tetrafluoroethane (HFC134a), 1,1,1,2,2-pentafluoride ethane (HFC125), 1,1-C2H4F2 C2H4F2 (HFC152a), 1,1,1,4,4,4-hexafluoro butane (HFC356mffm), 1,1,1,2,3-pentafluoropropane (HFC245eb), 1,1,2,2,3-pentafluoropropane (HFC245ca), 1,1,1,2,3,3-HFC-236fa (HFC236ea), 1,1,1,3,3,3-HFC-236fa (HFC236fa), 1,1,1,3, the isomer of 3-3-pentafluorobutane (HFC365mfc) and/or fluor alkaline and/or fluorinated ether, particularly E245 and E356.

The pneumatogen miscellany contains one or more (ring) alkane that contain 5 to 6 carbon atoms for most preferably, this type of alkane is for example: pentamethylene, Skellysolve A, iso-pentane, 2,2-dimethylbutane, 2-methylpentane, 3-methylpentane, randomly acetone, hydrofluorocarbons randomly.

The relative consumption of used component is definite like this in this pneumatogen miscellany, to press (preferably being higher than 0.3bar) in the gas that enables to obtain an optimal level and to condense (preferably under the porous plastics use temperature at the most 40%).

Remove above-mentioned pneumatogen miscellany, also may make a kind of chemical foaming agent that can produce CO2, for example water in the methods of the invention.

The whipping agent of Shi Yonging (physics and chemical foaming agent) total amount is definite so in the methods of the invention, (is lower than 32kg/m to obtain a suitable core density ³), and this amount is accounting for weight 2 to 25% based on the total reaction system in typical case.

The particularly preferred whipping agent miscellany of Shi Yonging comprises (pbw that quantity is expressed as isocyanic ester activity component) in the methods of the invention :-pentamethylene (3.9), acetone (2.3), 2,2-dimethylbutane (5.2), iso-pentane (10.5), Skellysolve A (7.1), 1,1,1,2-Tetrafluoroethane (3.3), water (3.9) (below be called MIX1);-pentamethylene (3.9), 2.2-dimethylbutane (5.3), 2-methylpentane (3.0), 3-methylpentane (2.6), Skellysolve A (7.2), iso-pentane (10.8), water (4.0) (below be called MIX2);-pentamethylene (3.3), acetone (2.0), 2,2-dimethylbutane (4.2), iso-pentane (7.0), water (1.5) (below be called MIX3);-pentamethylene (3.2), acetone (2.0), 2,2-dimethylbutane (4.2), iso-pentane (8.1), water (1.0), 3-methylpentane (1.0) (below be called MIX4);-pentamethylene (3.2), acetone (2.0), 2,2-dimethylbutane (4.2), iso-pentane (1.6), water (2.2), 3-methylpentane (3.0) (below be called MIX5);-pentamethylene (3.2), acetone (2.0), iso-pentane (7.7), water (2.2) (below be called MIX6);-pentamethylene (3.9), acetone (2.4), iso-pentane (9.9), Skellysolve A (12.0), water (2.0) (below be called MIX7);

MIX1 and MIX2 are used for being exposed to the 25kg/m of the building under-20 ℃ for preparation ³The rigid olyurethane foam of density is particularly useful.MIX3, MIX4, MIX5 and MIX6 are used for being exposed to the 27-29kg/m of the electrical equipment under-5 ℃ for preparation ³The rigid olyurethane foam of density is particularly useful.Used another the preferred whipping agent miscellany of the inventive method is one to comprise pentamethylene, iso-pentane, Skellysolve A, acetone and 2, the miscellany of 2-dimethylbutane, and the molar percentage of each material is as follows respectively: 13.8,36.6,24.7,9.8 and 15.2.

Used suitable organic polymeric polyisocyanate comprises any material for preparing poly-amino ester of rigidity and urethane-modified polyisocyanurate foamed plastics in known in the art being used in the inventive method, especially aromatic poly-isocyanate, for example 2 of the diphenylmethane diisocyanate ester, 4 '-, 2,2 '-, with 4,4 '-isomer and miscellany thereof, the miscellany of diphenylmethane diisocyanate ester (MDI) and its oligomer for example, this type of material are known as containing isocyanate functionality " life " greater than 2 or polymeric MDI (polymethylene polyphenylene polymeric polyisocyanate) in this area, and for example 2 of toluene-2,4-diisocyanate, 4-, 2,6-isomer and its miscellany, for example 1,5-naphthalene diisocyanate and 1, the 4-phenylene diisocyanate.Other organic polymeric polyisocyanate that can be mentioned comprises diisocyanate resin fat base ester, two isocyanic acid isophorone esters for example, 1, the diisocyanate based hexane of 6-and 4,4 '-diisocyanate based dicyclohexyl methyl hydride.

Polyisocyanate composition can react the polyfunctional isocyanate's activity composition that generates rigid olyurethane or urethane-modified polyisocyanurate foamed plastics with it and comprise any at the material that is used for this purpose known in the art.For preparing rigid foamed plastics particularly importantly polyvalent alcohol and polyvalent alcohol miscellany, they contain 300 to 1000, and particularly 300 to 700mgKOH/g average hydroxyl group number contains 2 to 8, particularly 3 to 8 hydroxy functionality.Fully described and comprise the reaction product of epoxy alkane in oneself the former field of suitable polyvalent alcohol, for example oxyethane and/or propylene oxide reach every mole of initiator that contains 2 to 8 active hydrogen atoms.Suitable initiator comprises: polyvalent alcohol, for example glycerine, TriMethylolPropane(TMP), trolamine, tetramethylolmethane, sorbyl alcohol and sucrose; And polyamines, for example quadrol, tolylene diamine, diaminodiphenyl-methane and polymethylene polyphenylene polyamine; And amino alcohol, for example thanomin and diethanolamine; And the miscellany of above-mentioned initiator.Other suitable polymerized polyalcohol comprise by the ethylene glycol of suitable proportion and high functionality polyvalent alcohol and binary or polycarboxylic acid polycondensation and must polyester (particularly Aromatic polyester).Polymerized polyalcohol preferably comprises terminal the be polythioether of hydroxyl, polymeric amide, polyesteramide, polycarboxylate, polyacetal, polyolefine and polysiloxane.

The consumption that desire participates in the polyisocyanate composition of reaction and poly-multifunctional isocyanic acid activity composition depends on the character of rigid olyurethane that desire is produced or urethane-modified polycyanurate porous plastics, and is easily those skilled in the art and determines.

Remove polymeric polyisocyanate and polyfunctionality isocyanic ester activity composition and blowing agent blends of the present invention, become the bubble reaction mixture will comprise one or more other auxiliary agent or additives usually, they are usual for the product preparation of rigid olyurethane and urethane-modified polyisocyanurate foamed plastics.These optional additives comprise linking agent, for example the low molecular weight polyols resemble the trolamine; Suds-stabilizing agent or tensio-active agent, for example siloxanes-oxyalkylene copolymers; Urethane catalyst, for example resemble tin compound or tertiary amine stannous octoate or the dibutyl tin two lauric acid salt, for example dimethylcyclohexylam,ne or triethylenediamine; And fire retardant, for example halogenated alkyl phosphate ester is as three (chloropropyl) phosphoric acid ester.

According to a special embodiment of the present invention, preparation is carried out producing in the presence of a kind of insoluble fluorochemical and is had the porous plastics that spilehole big or small and heat insulating ability has improved.A kind of urethane-modified polyisocyanurate foamed plastics (the NCO index is higher than 150) of preparation in the presence of a kind of like this fluorochemical also has the cracked performance that has improved.

Used soluble being defined as in isocyanic ester activity composition or polyisocyanate composition that it will mix with it of term when referring to soluble fluorochemical herein under 25 ℃ and atmospheric pressure, shows the solubleness that is less than the 500ppm weight ratio.

Used soluble fluorochemical comprises any material that is disclosed in the following patent in the inventive method: United States Patent (USP) 4,981,879; United States Patent (USP) 5,034,424; United States Patent (USP) 4,972,002; European patent application 0508649 and 0498628 and PCT patent application 95/18176.

Use a kind of insolublely, fluorizated or fluoridized compound are preferred basically, and this kind material has under atmospheric pressure and is at least 20 ℃, and preferably at least 40 ℃, more preferably the boiling point of at least 60 ℃ or 80 ℃ or 100 ℃.

Here about use in the methods of the invention insoluble, the term that uses " is fluoridized basically " and is understood to include in the fluorinated compound not the compound that at least 50% hydrogen atom has been replaced by fluorine atom during the fluorizated compound basically.

Suitable compounds comprises fluoridizes or fluoridized hydrocarbon polymer basically, fluoridizes basically or fluoridized ether, fluoridizes basically or fluoridized tertiary amine, fluoridizes basically or fluoridized amino ethers and fluoridizing basically or fluoridized sulfone.

Basically fluoridize or the suitable example of fluoridized hydrocarbon polymer is those hydrocarbon polymers that contain 1 to 15 carbon atom, they or for the ring or non-ring type, or aromatic series or be aliphatic, or be saturated or for undersaturated, for example fluoridize basically or fluoridized methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, tetramethylene, cyclooctane, hexanaphthene, pentamethylene, suberane, norbornadiene, decahydro closes naphthalene, the dimethyl tetramethylene, methylcyclohexane, 1-methyl decahydro closes naphthalene, luxuriant and rich with fragrance, the dimethyl tetramethylene, and their isomer.The spy should also be mentioned that the various isomer of perflenapent and perflexane, for example perfluor Skellysolve A and perfluoro-n-hexane, and the dimer and the trimerical various isomer of R 1216, for example perfluor (4-methyl-2-amylene).

Suitable in the methods of the invention some insoluble fluorochemical self that uses may be as whipping agent under about the condition that becomes the bubble reaction, particularly is lower than the occasion of the exothermic temperature that reaction mixture reaches at their boiling point.For avoiding query, these materials can be realized the function of whipping agent partially or completely outside the function of insolubility fluorochemical.

The consumption of used insolubility fluorochemical is from 0.05 to 10% by based on the weight percent meter of assembly foaming composition in the inventive method, preferably from 0.1 to 5%, most preferably from 0.6 to 2.3%.

The insolubility fluorochemical will be usually with the emulsion in one of principal reaction composition or preferably the form of microemulsion be mixed in among the bubble reaction mixture, that is to say it is mixed in isocyanic ester activity component and/or polyisocyanate component.Such emulsion or microemulsion can prepare with traditional technology and examples of suitable emulsifiers.

Be applicable to preparation liquid-fluorination thing in organic polymeric polyisocyanate and/or isocyanic acid activity compound stable emulsion or the emulsifying agent of microemulsion comprise the tensio-active agent of from nonionic, ionic (anionic or cationic) and amphoterics class, selecting.Preferred surfactants comprises silicone surfactant, fluorine surfactant and/or alkoxylate alkane.

The emulsifying agent consumption is that 0.02 to 5pbw every 100pbw becomes bubble reaction system and 0.05 to 10pbw every 100pbw polymeric polyisocyanate or polyhydric alcohol composition.

In the operating process of rigid foamed plastics constructed in accordance, can use known disposable, the traditional together mixed method of prepolymer or semi prepolymer technical battery, and rigid foamed plastics can be made the piece type, moulding compound, the die cavity stopping composition, eruption porous plastics, foaming porous plastics or with other material, for example hardboard, plasterboard, plastics, paper or metal etc. are laminated into various forms.

In many application, coming with the premix formulations based on initial polymeric polyisocyanate and isocyanic ester activity component is that the way of component is provided is easily to polyurethane preparation.Especially, many reaction systems are used a kind of polymeric polyisocyanate activity composition, and it is removed outside one or more polymeric polyisocyanate activity components, also comprise for example additive of whipping agent and catalyzer.

Therefore, the present invention also provides as above polyisocyanate composition that comprises a kind of pneumatogen miscellany that describes in detail or polymeric polyisocyanate activity composition.

All respects of the present invention are that following example is illustrated, but do not limit for it, have used following compositions in such example:

Polyvalent alcohol A is a kind of about 30% PET polyester polyol that reclaims the poly terephthalic acid di-alcohol that comprises, and it has about 2.3 functionality and the hydroxyl value of 350mg KOH/g.

Tegostab B 8408 is a kind of silicone surfactant available from Goldschmit.

Tegostab B 8406 is a kind of silicone surfactant available from Goldschmit.

TEP is a triethyl phosphate.

DMEA is N, the N-dimethylethanolamine.

NIAX A1 is a kind of amine catalyst available from Air Products.

Dacob T45 is a kind of catalyzer available from Air Products.

SUPRASEC2085 is a kind of polymeric polyisocyanate available from Imperial Chemical Industries PLC.

DALTOLAC XR 159 is a kind of polyether glycol available from Imperial Chemical IndustriesPLC.

DALTOLAC XR 144 is a kind of polyether glycol available from Imperial Chemical IndustriesPLC.

DALTOLACR130 is a kind of polyether glycol available from Imperial Chemical Industries PLC.

DALTOLACP744 is a kind of polyester polyol available from Imperial Chemical Industries PLC.

DALTOREZ XP805 is a kind of polyester polyol available from Imperial Chemical IndustriesPLC.

DALTOLACR105 is a kind of polyether glycol available from Imperial Chemical Industries PLC.

Tegostab B 8423 is a kind of silicone surfactant available from Goldschmit.

RS201 is a kind of available from the silicone surfactant of Union Carbide (Air Products).

RS210 is a kind of available from the silicone surfactant of Union Carbide (Air Products).

SR234 is a kind of available from the silicone surfactant of OSi.

PFO is perfluor (a 4-methyl-2-amylene).

Catalyst S FC is a kind of available from the amine catalyst of Imperial Chemical Industries PLC.

SUPRASEC DNR is a kind of polymeric polyisocyanate available from Imperial Chemical Industries PLC.

SUPRASEC DALTOLAC and DALTOREZ are the trade mark of Imperial ChemicalIndustries PLC.

Embodiment 1

Building class rigid olyurethane foam is from the initial preparation of prescription as shown in table 1 below.

The mixed also vigorous stirring of polyvalent alcohol miscellany quilt (mixing by hand or water screw) is until obtaining the uniform miscellany of a homophase or producing a uniform white emulsion.Adopt the standard foaming machine that this miscellany and polymeric polyisocyanate is mixed then.The initial temperature of these chemical substances is 23 ℃ ± 2 ℃.Before carrying out the physical properties measurement, allow porous plastics slaking at room temperature at least 16 hours.

Density to the gained porous plastics is measured, respectively-20 ℃ after following 1 day and-20 ℃ its dimensional stability is measured after following 14 days, its thermal conductivity (initial, reach 70 ℃ of following 3 weeks after 70 ℃ of next weeks after) is measured.The gained result is shown in following table 1.

These results show that porous plastics A and B for according to the present invention's preparation remove outside the improvement of dimensional stability aspect, and than the reference foam plastics, its thermal conductivity has improved basically.Table 1:

		The reference foam plastics	Porous plastics A	Porous plastics B
					Polyvalent alcohol A	???pbw	?????100	????100	????100
Tegostab?B8408	???pbw	?????2	????2	????2
					Triethyl phosphate	???pbw	?????15	????15	????15
DMEA	???pbw	?????3.6	????3.6	????3.6
					NIAX?A1	???pbw	?????0.16	????0.16	????0.16
Dabco?T45	???pbw	?????2.69	????2.69	????2.69
					Water	???pbw	?????4.1
Skellysolve A	???pbw	?????30
					MIX1	???pbw		????32.3
MIX2	???pbw			????32.8
					Suprasec2085	???pbw	?????385.87	????378.14	????385.87
Density	???kg/m 3	?????25.3	????25.5	????22.1
					Dimensional stability .1 days/-20 ℃
Length	????％	?????-13.3	???-0.3	???-1.2
					Width	????％	?????-8.9	???-0.5	???-1.8
Thickness	????％	?????0.7	???-0.3	????0.2
					Absolute value add and		?????22.9	????1.1	????3.2
14 days/-20 ℃ of dimensional stabilitys
					Length	????％	????-12.4	???-0.2	???-5.0
Width	????％	????-9.8	????0.5	???-5.8
					Highly	????％	?????2.4	????5.1	????0.7
Absolute value add and		?????24.6	????5.8	????11.5
					Thermal conductivity
Lambda is initial	???mW/mK	?????27.1	????23.7	????24.6
					Lambda 1 week/70 ℃	???mW/mK	?????29.4	????27.0	????27.9
Lambda 3 week/70 ℃	???mW/mK	?????29.7	????27.4	????29.1

Embodiment 2

Building type urethane be initial from the prescription shown in the table 2, according to embodiment 1 described path of preparing.Porous plastics for gained, measured close hole composition (CCC), measured respectively after-20 ℃ of next days and-20 ℃ of dimensional stabilitys after following 14 days, it is (initial to have measured thermal conductivity, after 70 ℃ of next weeks, under 70 ℃, reach after 70 ℃ of following 5 weeks after 3 weeks).The gained result is as shown in table 2 below.Table 2:

		The reference foam plastics	Porous plastics A	Porous plastics B	Porous plastics C	Porous plastics D
							Polyvalent alcohol A	??pbw	????50	????50	????50	????50	????50
Daltolac?XR159	??pbw	????50	????50	????50	????50	????50
							Tegostab?B8423	??pbw	????1.0	????1.0	????1.0	????1.0	????1.0
RS?210	??pbw	????1.0	????1.0	????1.0	????1.0	????1.0
							Niax?A1	??pbw	????0.1	????0.1	????0.1	????0.1	????0.1
Catalyst S FC	??pbw	????1.0	????1.0	????1.0	????1.0	????1.0
							Water	??pbw	????2.0
Pentamethylene	??pbw	????15
							MIX3	??pbw		????18.0
MIX4	??pbw			????19.5
							MIX5	??pbw				????16.2
MIX6	??pbw					????15.1
							Suprasec?DNR	??pbw	????140	????132	????124	????143	????143
Core density	??kg/m 3	????29.4	????27.7	????28.4	????28.1	????28.9
							Free initial density-emitting	??kg/m 3	????23.8	????23.3	????24.5	????24.6	????24.8
Overall consistency	??kg/m 3	????29.7	????29.4	????29.4	????29.4	????29.0
							Closed cell content	????％	????89	????92	????92	????92	????92
Dimensional stability 1d/-20 ℃
							Length	????％	???-0.32	???-0.08	???-0.11	????0.11	????0.17
Width	????％	????0.01	????0.05	????0.16	????0.01	????0.17

Thickness	??％	???0.32	???0.41	????0.86	????0.45	???1.19
							Absolute value add and		???0.65	???0.54	????1.13	????0.57	???1.53
Dimensional stability 14d/-20 ℃
							Length	??％	??-0.91	???0.05	???-0.77	????0.27	???0.20
Width	??％	???0.24	???3.7	????0.22	????0.13	???0.21
							Thickness	??％	???0.74	???1.28	????1.25	????1.69	???1.44
Absolute value add and		???1.89	???5.03	????2.24	????2.09	???1.85
							Lambda is initial	?mW/mK	???20.6	???22.2	????24.5	????22.7	???21.1
Lambda1 week/70 ℃	?mW/mK	???23.0	???24.3	????26.3	????25.2	???23.1
							Lambda3 week/70 ℃	?mW/mK	???24.5	???25.9	????27.9	????26.9	???24.4
Lambda5 week/70 ℃	?mW/mK	???25.8	???26.5	????28.4	????27.0	???25.4

Embodiment 3

Electrical equipment type rigid olyurethane foam is the initial preparation of listed prescription from table 3, according to embodiment 1 described route.For the porous plastics that obtains, measured close hole composition (CCC), measured at-20 ℃ after one day and-20 ℃ of dimensional stabilitys after 14 days, measured thermal conductivity (initial, after 70 ℃ of next weeks, 70 ℃ down three week the back and after 70 ℃ of 5 week).Measuring result is as shown in table 3: table 3:

		The reference foam plastics	Porous plastics E
				Daltolac?XR159	???pbw	????33	????33
Daltolac?XR144	???pbw	????30	????30
				Daltolac?R130	???pbw	????31	????31
Tegostab?B8423	???pbw	????1.15	????1.15
				?RS210	???pbw	????1.15	????1.15
?Niax?A1	???pbw	????0.1	????0.1
				Catalyst S FC	???pbw	????4.0	????5.0
Water	???pbw	????2.0

Pentamethylene	????pbw	?????24.0
				MIX7	????pbw		????30.1
Suprasec?DNR	????pbw	?????134.29	????134.29
				Core density	????kg/m 3	?????26.3	????26.0
Free initial density-emitting	????kg/m 3	?????17.5	????16.6
				Overall consistency	????kg/m 3	?????25.1	????25.1
Closed cell content	??????％	?????82	????90
				Dimensional stability 1d/-20 ℃
Length	??????％	????-0.47	???-0.04
				Width	??????％	????-0.22	???-0.2
Thickness	??????％	?????0.40	????0.00
				Absolute value add and		?????109	????0.06
Dimensional stability 14d/-20 ℃
				Length	??????％	????-0.31	????0.15
Width	??????％	????-0.11	????0.14
				Thickness	??????％	?????0.85	????0.36
Absolute value add and		?????1.27	????0.65
				Lambda is initial	????mW/mK	?????22.4	????25.8
Lambda1 week/70 ℃	????mW/mK	?????26.9	????28.9
				Lambda3 week/70 ℃	????mW/mK	?????28.4	????29.8
Lambda5 week/70 ℃	????mW/mk	?????29.0	????30.8

Embodiment 4

Electrical equipment type rigid olyurethane foam is initial from the prescription shown in the table 4, presses embodiment 1 described path of preparing.For the porous plastics that obtains, measured closed cell content (CCC), measured after-20 ℃ of next days and-20 ℃ of dimensional stabilitys after following 14 days, measured thermal conductivity (initial, after 70 ℃ of next days, 70 ℃ after following 3 days and 70 ℃ after following 5 days).Measuring result is as shown in table 4: table 4:

		Reference foam plastics A	Porous plastics F	Reference foam plastics B	Porous plastics G
						Daltolac?XR159	??pbw	????33	????33	????33	????33
Dalto1ac?XR144	??pbw	????30	????30	????30	????30
						Daltolac?R130	??pbw	????31	????31	????31	????31
Tegostab?B8423	??pbw	????1.15	????1.15	????1.15	????1.15
						RS210	??pbw	????1.15	????1.15	????1.15	????1.15
Niax?A1	??pbw	????0.1	????0.1	????0.1	????0.1
						Catalyst S FC	??pbw	????4.0	????5.0	????4.0	????5.0
Water	??pbw	????2.0		????2.0
						Pentamethylene	??pbw	????24.0		????24.0
MIX7	??pbw		????30.1		????30.1
						Suprasec?DNR	??pbw	????134.29	????134.29	????134.29	????134.29
Core density	??kg/m3	????25	????25	????20	????20
						Free initial density-emitting	??kg/m 3	????17.5	????16.6	????17.5	????16.6
Closed cell content	????％	????82	????90		????71
						Dimensional stability 1d/-20 ℃
Length	????％	???-0.47	???-0.04		???-1.68
						Width	????％	???-0.22	????0.02		???-0.5
Thickness	????％	????0.40	????0		???-0.95
						Absolute value add and		????1.09	????0.06		????3.13
Dimensional stability 14d/-20 ℃
						Length	????％	???-0.31	????0.15		???-5.23
Width	????％	???-0.11	????0.14		???-3.04
						Thickness	????％	????0.85	????0.36		???-7.36
Absolute value add and		????1.27	????0.65		????15.63
						Lambda is initial	??mW/mK	????22.4	????25.8		????25.5
Lambda1 week/70 ℃	??mW/mK	????26.9	????28.9		????29.2
						Lambda3 week/70 ℃	??mW/mK	????28.4	????29.8		????30.1
Lambda5 week/70 ℃	??mW/mK	????29.0	????30.8		????30.5

Reference foam plastics B acutely shrinks.

Embodiment 5

The building type rigid olyurethane foam is initial from the prescription shown in the following table 5, presses path of preparing that embodiment 1 describes.For the porous plastics that obtains, measured density, isotropy hole size, fragility (according to the BS4370 standard) and Lambda value (initial and 1 week, 2 weeks, 3 weeks, 4 weeks, 5 afterwards all).Measuring result is as shown in table 5.

Measuring result shows, compares with the porous plastics that does not contain insoluble fluorochemical, the porous plastics that is attended by insoluble fluorochemical among the present invention has more tiny hole, the thermal insulation properties that improved and the fragility of having improved.Table 5:

Porous plastics		????H	????I	????J	????K	????L	????M
								The polyvalent alcohol miscellany
Polyvalent alcohol A	??pbw	????100	????100	????100	????100	????100	????100
								TEP	??pbw	????15	????15	????15	????15	????15	????15
Tegostab?B8406	??pbw	????4	????4	????4	????4	????4	????4
								DMEA	??pbw	????3.6	????3.6	????3.6	????3.6	????3.6	????3.6
NIAX?A1	??pbw	????0.13	????0.13	????0.13	????0.13	????0.13	????0.13
								DABCO?T45	??pbw	????2.69	????2.69	????2.69	????2.69	????2.69	????2.69
MIX2	??pbw	????32.8	????32.8	????32.8	????32.8	????32.8	????32.8
								Emulsion
Suprasec?2085	??pbw	????100	????99	????98.5	????97.5	????96.5	????94.5
								SR234	??pbw		????0.5	????0.5	????0.5	????0.5	????0.5
PFO	??pbw		????0.5	????1	????2	????3	????5
								Polyol blends	??pbw	????29.25	????29	????28.85	????28.7	????28.5	????28.1
Emulsion	??pbw	????70.75	????71	????71.15	????71.3	????71.5	????71.9
								Index		????250	????250	????250	????250	????250	????250
Density	??kg/m 3	????23	????20.8	????20	????21.1	????21.1	????21.9
								Hole size	??μm	????350	????239	????211	????215	????190	????175
Fragility	???％	????15.8	????3.9	????0	????1	????1.6	????2.1
								Lambda is initial	???mW/mK	????25	????24	????24	????23.2	????23.2	????22.7

Lambda1 week	?mW/mK	??29	??28.1	??27.9	???27	??26.8	??26.2
								Lambda2 week	?mW/mK	??29.3	??28.3	??28.4	???27.3	??27.5	??27
Lambda3 week	?mW/mK	??29.6
								Lambda4 week	?mW/mK	??30	??28.5	??28.5	???27.9	??27.5	??27.1
Lambda5 week	?mW/mK	??29.2	??28.8	??28.8	???27.9	??27.6	??27.3

Embodiment 6

Building class rigid olyurethane foam is initial from prescription shown in the following table 6, press the path of preparing of embodiment 1 description.For the porous plastics that obtains, density and fragility have been measured.Measuring result is as shown in table 6 below: table 6:

		Porous plastics N	Porous plastics O	Porous plastics P	Porous plastics Q
						Polyol blends
Daltolac?XR144	??pbw	????4.79	????4.79	????4.79	????4.79
						Daltolac?P744	??pbw	????3.96	????3.96	????3.96	????3.96
Daltolac?XP805	??pbw	????3.42	????3.42	????3.42	????3.42
						Daltolac?R105	??pbw	????1.09	????1.09	????1.09	????1.09
SR234	??pbw	????1.4	????1.4	????1.4	????1.4
						TEP	??pbw	????3	????3	????3	????3
Catalyst S FC	??pbw	????0.35	????0.35	????0.35	????0.35
						DabcoT45	??pbw	????1.55	????1.55	????1.55	????1.55
MIX2	??pbw	????6	????6	????6	????6
						Emulsion
Suprasec2085	??pbw	????100	????98.95	????98.5	????97
						SR234	??pbw		????0.35	????0.5	????1
PFO	??pbw		????0.7	????1	????2
						The polyvalent alcohol miscellany	??pbw	????76	????75.4	????75.1	????74.3
Emulsion	??pbw	????224	????224.6	????224.9	????225.7
						Index		????400	????400	????400	????400
Density	??kg/m 3	????25.8	????24.8	????24.9	????25
						Fragility	???％	????47.2	????40.8	????37.4	????33.7

Claims (28)

1. Rigid polyurethane or urethane-modified polyisocyanurate foams having a closed cell content of more than about 85%, a core density of less than 32 kg/m ³ and a dimensional stability of less than 15% , the dimensional stability refers to the sum of the absolute values of the relative linear changes in the three directions after exposure at -20°C for 14 days. 2. Rigid polyurethane or urethane-modified polyisocyanurate foam as claimed in claim 1, having a core density of less than 28 kg/ ^m3 . 3. Rigid polyurethane or urethane-modified polyisocyanurate foam as claimed in claim 2, having a core density of less than 27 kg/ ^m3 . 4. Rigid polyurethane or urethane-modified polyisocyanurate foam as claimed in claim 2, having a core density of less than 25 kg/ ^m3 . 5. A rigid polyurethane or urethane-modified polyisocyanurate foam as claimed in any one of the preceding claims, having a dimensional stability of less than 10%, the so-called dimensional stability being exposure at -20°C The sum of the absolute values of the relative linear changes occurring in the three directions after 14 days. 6. The polyisocyanurate foamed plastic of rigid polyurethane or carbamate modification in claim 5, its dimensional stability is lower than 7.5%, so-called dimensional stability is meant to be exposed at-20 ℃ after 14 days three The sum of the absolute values of the relative linear changes occurring in each direction. 7. the preparation method of the polyisocyanurate foamed plastics of rigid polyurethane or carbamate modification in any one of claim 1 to 6, when i.e. there is the mixture of physical blowing agent under foaming condition, by a A polyisocyanurate composition is reacted with a multifunctional isocyanurate reactive composition, and each physical blowing agent has a boiling point between -20°C and 80°C. 8. The preparation method in claim 7, wherein each of said physical blowing agents has a boiling point in the range of 15°C to 60°C. 9. The production method according to claim 7 or 8, wherein each of said physical blowing agents does not contain chlorine atoms. 10. The preparation method of any one of claims 7 to 9, wherein at least one blowing agent is arranged in said physical blowing agent, and its gas phase thermal conductivity at the temperature of use of foamed plastics is higher than that of carbon dioxide at the same temperature. Low thermal conductivity. 11. the preparation method among the claim 10, wherein said physical blowing agent at least has a kind of blowing agent, and its vapor phase thermal conductivity ratio normal propane at the same temperature at the temperature of foamed plastics Low. 12. The preparation method in claim 11, wherein at least one foaming agent is arranged in said physical blowing agent, wherein the gas phase thermal conductivity at the same temperature is higher than the gas phase thermal conductivity of cyclopentane at the same temperature Low. 13. A process as claimed in any one of claims 7 to 12, wherein the sum of the gas partial pressures of all blowing agent components is at least 0.3 bar. 14. The preparation method of claim 13, wherein the sum of the gas partial pressures of all blowing agent components is at least 0.45 bar. 15. The preparation method as claimed in claim 14, wherein the sum of the gas partial pressures of all blowing agent components is at least 0.6 bar. 16. A process as claimed in any one of claims 7 to 15 wherein up to 40% of the mixture of physical blowing agent components coagulates at the temperature at which the foam is used. 17. A process as claimed in claim 16, wherein up to 20% of the physical blowing agent mixture coagulates at the temperature at which the foam is used. 18. The method of manufacture of claim 17, wherein at most 10% of the physical blowing agent mixture coagulates at the temperature at which the foam is used. 19. The method of manufacture of claim 18, wherein at most 2% of the physical blowing agent mixture coagulates at the temperature at which the foam is used. 20. The process of any one of claims 7 to 19, wherein said mixture of physical blowing agents comprises at least three components. 21. A process as claimed in any one of claims 7 to 20, wherein at least one component of said mixture of physical blowing agents is an alkane or naphthene. 22. A process as claimed in any one of claims 7 to 21 wherein at least one component of said mixture of physical blowing agents is acetone. 23. The preparation method in claim 21 or 22, wherein said physical blowing agent mixture comprises one or more (cyclo)alkanes containing 5 to 6 carbon atoms, optionally acetone and optionally hydrocarbon Fluorine compounds. 24. The production process according to any one of claims 7 to 23, wherein the reaction is carried out in the presence of water. 25. The production process according to any one of claims 7 to 24, wherein the reaction is carried out in the presence of an insoluble fluoride. 26. The production method in claim 25, wherein the insoluble fluorine compounds refer to substantially fluorinated or perfluorinated hydrocarbons. 27. The preparation method in claim 26, wherein the insoluble fluoride refers to perfluorinated pentane, or perfluorinated hexane, or perfluorinated 4-methylpent-2-ene. 28. A polyisocyanurate-reactive composition comprising a mixture of physical blowing agents as defined in any one of claims 7 to 23.