CN100434451C - Glassfiber-reinforced polyurethane-polyisocyanurate foam - Google Patents
Glassfiber-reinforced polyurethane-polyisocyanurate foam Download PDFInfo
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- CN100434451C CN100434451C CNB200610058849XA CN200610058849A CN100434451C CN 100434451 C CN100434451 C CN 100434451C CN B200610058849X A CNB200610058849X A CN B200610058849XA CN 200610058849 A CN200610058849 A CN 200610058849A CN 100434451 C CN100434451 C CN 100434451C
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- porous plastics
- glass fibre
- polyvalent alcohol
- foam
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- 239000011495 polyisocyanurate Substances 0.000 title claims abstract description 13
- 229920000582 polyisocyanurate Polymers 0.000 title claims abstract description 8
- 239000006260 foam Substances 0.000 title abstract description 16
- 239000003365 glass fiber Substances 0.000 claims abstract description 95
- 229920005862 polyol Polymers 0.000 claims abstract description 35
- 150000003077 polyols Chemical class 0.000 claims abstract description 35
- 239000012948 isocyanate Substances 0.000 claims abstract description 31
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 30
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 239000004033 plastic Substances 0.000 claims description 124
- 229920003023 plastic Polymers 0.000 claims description 124
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 239000011152 fibreglass Substances 0.000 claims description 31
- 238000012360 testing method Methods 0.000 claims description 30
- 238000009413 insulation Methods 0.000 claims description 27
- 239000003063 flame retardant Substances 0.000 claims description 14
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000002708 enhancing effect Effects 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 36
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002666 chemical blowing agent Substances 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 239000003340 retarding agent Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 31
- 230000006835 compression Effects 0.000 description 17
- 238000007906 compression Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 239000006071 cream Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000012774 insulation material Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- -1 isocyanate compound Chemical class 0.000 description 3
- 238000002803 maceration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000007348 radical reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 230000003387 muscular Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical compound C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 description 1
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- PGYPOBZJRVSMDS-UHFFFAOYSA-N loperamide hydrochloride Chemical group Cl.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)N(C)C)CCN(CC1)CCC1(O)C1=CC=C(Cl)C=C1 PGYPOBZJRVSMDS-UHFFFAOYSA-N 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- HKKDKUMUWRTAIA-UHFFFAOYSA-N nitridooxidocarbon(.) Chemical compound [O]C#N HKKDKUMUWRTAIA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
Images
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
- C08G18/28—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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0085—Use of fibrous compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
-
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
-
- 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
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- 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
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Polyurethane polyisocyanurate foam reinforced by glass fibers, obtained by: reacting an isocyanate component and a polyol component comprising first, second and third polyols, in the presence of a catalyst, a physical and/or chemical blowing agent, an emulsifier and optionally a flame retarding agent to obtain a composition; impregnating, the composition in a glass fiber stacking; and expanding and solidifying the composition to form a reinforced foam block containing the glass fiber stacking. Said reinforced foam block has an average density of 115-135 kg/m3>, and an isocyanate index of 100-180.
Description
Technical field
The present invention relates to relate to its production technique, and relate to it as the purposes of liquefied gas transfer cask especially liquefied gas tank vessel with the thermal insulation material of jar with glass fibre enhanced hard polyaminoester/poly-isocyanurate (PUIR) porous plastics.
Background technology
European patent 248 721 and 573 327 discloses the thermal insulation element of liquefied gas transfer cask especially, and described liquefied gas transfer cask is used for the liquefied gas tank vessel, is formed by the veneer case sub-portfolio of having filled the urethane foam thermal insulation material.Described thermal insulation element is distributed in two kinds of adiabatic barriers that are called first thermal insulation layer and second thermal insulation layer.These thermal insulation elements can be given gratifying thermal isolation effect, but also cause the settling time that quite to grow, not only to be tethered on the jar because constitute the chest of each first thermal insulation layer and second thermal insulation layer, but also want together fastened to each other, to constitute different thermal insulation layers.
In addition, developed multiple hard polyaminoester (PU) porous plastics, as thermal insulation material.For this purposes, such material demonstrates gratifying heat insulation characteristics, keeps easy operation and installation simultaneously.But, unless the PU porous plastics is incorporated in the glued board chest, otherwise and be not suitable for the liquefied gas tank vessel with jar thermal isolation, because it lacks the mechanical strength property of ultimate compression strength and tensile strength type, described mechanical strength property is meant is enough to resist the pressure that is in the liquefied gas in the motion in the jar, perhaps the acute variation of temperature.
In addition, such material has mixed environmental facies deleterious gas usually as whipping agent, chlorofluorocarbon HCFC 141b particularly, the latter use that has been under an embargo from January 1st, 2004 in Europe.
Such gas can be easily preferably replaces with hydro carbons such as pentane or iso-pentane.But the latter remains highly flammable gas.And, use this hydro carbons can hinder any detection that the gas leakage situation of liquefied gas transfer cask is carried out.
Summary of the invention
Target of the present invention is to propose following porous plastics, it has avoided above-mentioned shortcoming, not only demonstrate good heat insulation characteristics and under heat condition under (20 ℃) and the cool condition Z of (170 ℃) to the mechanical characteristics of ultimate compression strength (being the ultimate compression strength of the thickness direction of porous plastics) form, and demonstrate satisfactorily under heat condition and cool condition under Y to the mechanical characteristics of tensile strength (being the tensile strength of the length direction of porous plastics) form, these characteristics make its can be especially as the liquefied gas tank vessel with jar thermal insulating material.
The present invention proposes glass fibre enhanced urethane/polyisocyanurate foamed plastics, and described porous plastics obtains by following steps:
1) exist:
Be selected from the catalyzer of pink salt, carboxylic acid potassium and optional tertiary amine,
Physics and/or chemical foaming agent,
Emulsifying agent, and
Optional fire retardant
Exist down, make following two kinds of components contact:
The isocyanate component of viscosity between 200-600mPa.s,
The polyol component that comprises first polyvalent alcohol, second polyvalent alcohol and the 3rd polyvalent alcohol, the viscosity of described each polyvalent alcohol between 200-6000mPa.s,
2) the prescription impregnated glass fiber heap (stack) that obtains with step 1, described glass fibre heap is optional be the form of felt (mat), and chooses wantonly and be bound up by tackiness agent, and
3) make described prescription foaming and curing, form the enhancing foam-plastic blocks that comprises described glass fibre heap;
The mean density of described enhancing foam-plastic blocks is at 115-135kg/m
3Between, preferably at 120-130kg/m
3Between, be more preferably 130kg/m
3, isocyanate index is between 100-180, preferably between 130-180.
According to a feature of the present invention, described isocyanate component is diphenylmethanediisocyanate (MDI), and its average functionality is between 2.5-3.5, preferably between 2.9-3.1.
According to another feature of the present invention, described first polyvalent alcohol is a sorbitol derivatives, described second polyvalent alcohol is a polyether polyol, described the 3rd polyvalent alcohol is a polyester polyol, preferably, described polyether polyol is glycerol derivative preferably, and described polyester polyol is aromatics preferably.
Preferentially be, described polyol component is made up of with the 3rd polyvalent alcohol described first, second, wherein said first polyvalent alcohol is that the ratio of 10%-80% exists with quality with respect to the quality of described polyol component, wherein said second polyvalent alcohol is that the ratio of 10%-80% exists with quality with respect to the quality of described polyol component, and wherein said the 3rd polyvalent alcohol is that the ratio of 10%-80% exists with quality with respect to the quality of described polyol component.
Preferably, first, second and the 3rd polyvalent alcohol are respectively 60%, 20% and 20% with respect to the mass ratio of described polyol component quality.
Because the cause of the present invention's prescription, described porous plastics not only demonstrates gratifying heat insulation characteristics, and demonstrate the mechanical characteristics of ultimate compression strength and tensile strength form astoundingly, this therefore make this porous plastics can be in appropriate circumstances as the liquefied gas tank vessel with jar thermal insulation material.In addition, prescription of the present invention has been considered flooding fully and uniformly of glass fibre heap.
According to second feature of the present invention, described catalyzer is selected from pink salt and carboxylic acid potassium, and does not select tertiary amine.Therefore might avoid using in porous plastics of the present invention catalyzer based on tertiary amine, this is an advantage, because tertiary amine has pungency, therefore be inconvenient to operate, and harmful to environment.
According to the 3rd feature of the present invention, described whipping agent is a water.Therefore, because this feature there is no need to re-use the gas as 141b type chlorofluorocarbon and so on, these gases are harmful to environment, and are under an embargo from January 1st, 2004 in Europe, and perhaps highly inflammable gas is pentane for example.The reason of this feature is, water is as whipping agent and existence can cause the release of CO2 on every side, and it impels porous plastics to expand.CO2 has the less and non-flammable advantage of environmental hazard.
According to a kind of form, described whipping agent is HCF-365mfc or HCF-245fa.In addition, when using HCF-365mfc and/or HCF-245fa, can be used in combination water as whipping agent.
According to another kind of form, the halogenated fire retardant of described fire retardant right and wrong.Therefore, forming correlated with halogenated fire retardant is that mixing such fire retardant in composition does not have deleterious activity to environment.
According to first embodiment, described glass fibre heap is the form of the heap of fiberglass batts.Preferably, described fiberglass batts belongs to continuous strand felt (CSM) type.
Preferably, in first embodiment, the linear density of described glass fibre is 20-40 tex (tex), preferred 30 tex.
According to second embodiment, described glass fibre heap comprises the continuous glass fibre of being made by rove.
Preferential is that in second embodiment, the linear density of glass fibre is 30-300tex.
Preferably, described continuous glass fibre is made by following technology, and described technology comprises by the Webforming technology of for example Plastech T.T.Ltd exploitation comes defiber density to be lower than the step of the continuous glass fibre rove of rove.Second embodiment is more favourable than first, because at first it brings the wettability of improvement aspect glass fibre.The result of this feature at first is that the dipping of glass fibre is more even.In addition, the foam-plastic blocks according to second embodiment also demonstrates gratifying along the stretching of all axis and the mechanical properties of compression aspect.At last, glass fibre is from rove spool or package, both easier acquisitions of back, and their purchase cost is lower than the fiberglass batts.
According to a kind of form of first or second embodiment, described glass fibre is connected with each other by tackiness agent.
Preferably, in the embodiment of this another kind of form, the amount of described tackiness agent accounts between the 0.6%-3% of described glass fibre quality, and more preferably about 2.5%.This binder content helps glass fiber impregnated all even complete.
Preferential is that in second embodiment, described glass fibre is not bound up by tackiness agent.Therefore, when tackiness agent is used seldom (＜0.6%) or time spent not, glass fibre more is evenly distributed in and strengthens in the middle of the foam-plastic blocks, and this strengthens the better mechanical characteristics of foam-plastic blocks.
Preferably, in all embodiments, glass fibre all belongs to E type glass fibre.
Preferential is that every Gram Mass of described glass fibre heap is at 300-900g/m
2Between, preferred 450g/m
2
In the advantageous forms of first or second embodiment, with respect to the total mass that strengthens foam-plastic blocks, the quality of glass fibre accounts for 9%-13%, preferably accounts for 10%-12%.
The whole aforementioned parameters that relate to fiberglass batts and glass fibre itself also help impregnated glass fiber satisfactorily, and have proved and can give the gratifying tensile strength of porous plastics (i.e. the intensity of elongation aspect) characteristic.
Preferably, the flammable test according to DIN 4102-1 (B2) detected.
According to an embodiment preferred, porous plastics is the form of the foam-plastic blocks of thickness between 20-35cm.Therefore, depend on required purposes,, must determine the sufficient amount of prescription, glass fibre (being the form of felt in appropriate circumstances) and whipping agent, to produce foam-plastic blocks with required thickness for example as thermal insulation material.Production thickness is that the advantage of the foam-plastic blocks of 20cm is, after the foam-plastic blocks finishing, can be directly as second thermal insulation layer (this layer thickness is generally 18cm) of liquefied gas tank vessel and/or can be from the middle part crosscut, with first thermal insulation layer (this layer thickness is generally 9cm) of direct formation liquefied gas tank vessel.Equally, the thickness of producing be the foam-plastic blocks of 30cm through finishing with after the cutting of 1/3rd places of its thickness, can form first thermal insulation layer of 9cm and second thermal insulation layer of 18cm simultaneously.
The present invention proposes to produce the method for glass fibre enhanced urethane/polyisocyanurate foamed plastics in addition, said method comprising the steps of:
1) exist:
Be selected from the catalyzer of pink salt, carboxylic acid potassium and optional tertiary amine,
Whipping agent,
Emulsifying agent,
Optional fire retardant
Exist down, make following two kinds of components contact:
The isocyanate component of viscosity between 200-600mPa.s,
The polyol component that comprises first polyvalent alcohol, second polyvalent alcohol and the 3rd polyvalent alcohol, the viscosity of described each polyvalent alcohol between 200-6000mPa.s,
2) the prescription impregnated glass fiber heap that obtains with step 1, described glass fibre heap is optional be the form of felt, and chooses wantonly and be bound up mutually by tackiness agent,
3) make described prescription at the foaming after fixing, comprise the foam-plastic blocks that glass fibre is piled with formation,
4) top, bottom and the optional side of the described foam-plastic blocks of finishing, and optional
5) the described foam-plastic blocks of crosscut produces first thermal insulation layer and second thermal insulation layer.
At last, the invention provides the purposes of porous plastics in the thermal isolation of liquefied gas transfer cask especially liquefied gas tank vessel usefulness jar.
In detailed description subsequently, term " PUIR " expression " urethane/poly-isocyanurate ".Term " low viscosity " is represented viscosity between 200-600mPa.s for isocyanic ester, represents viscosity between 200-6000mPa.s for polyvalent alcohol, and all viscosity numbers that provide all refer to the viscosity number under 25 ℃ the temperature.At last, term " PUIR index " expression mol ratio [(poly-isocyanurate-NCO group/urethane-the OH group) * 100].
At last, in the following description, the glass fibre (second embodiment) that term " glass fibre heap " expression a pile fiberglass batts (first embodiment) or a pile are made by rove.
Hereinafter in particular with reference to appended synoptic diagram, a plurality of embodiments of the present invention are carried out in the process of detailed explanatory description, the present invention can obtain understanding better, other targets of the present invention, detailed content, feature and advantage will become clearer, and described a plurality of embodiments are property and non-limitative example and provide as an illustration purely.
Description of drawings
In these synoptic diagram of the process that explanation is piled according to the glass fibre of second embodiment in order to production:
Fig. 1 is the skeleton view of rove spool, and described rove is as raw material;
Fig. 2 is the skeleton view of supply capstan winch, the intermediary element between the dispenser head that described supply capstan winch is rove spool and glass fibre; And
Fig. 3 is the skeleton view of glass fibre production line.
Embodiment
According to the present invention, the reaction between the polyol component that the PUIR porous plastics is formed by isocyanate component with by polyol blends forms.Reaction between these different compounds is carried out according to following four steps:
Reaction 1
It is such step that the first step promptly causes step, wherein water molecules and isocyanate component-the NCO radical reaction, form amine groups and CO2 molecule.The release of CO2 causes that porous plastics expands.
In second step, amine groups that obtains from the first step and-NCO radical reaction form urea groups.
Concurrently, in the middle of the 3rd step, the hydroxyl of polyol component and-NCO radical reaction form urethane group.
At last, be the trimerizing step in the 4th step, combine to excessive-NCO group triad, form isocyanurate group.
These steps are heat releases, can cause that the CO2 expansible increases, thereby cause that porous plastics expands.
Caught up with before above-mentioned reaction begins to carry out, will be poured on a pile glass fibre that comprises fiberglass batts definite thickness or that ascertain the number by the prescription that mixes isocyanate component, polyol component and the acquisition of various additive immediately.
When the reaction beginning, naked eyes can not be observed, and just can observe up to having spent for some time, are called cream time (cream time) during this period of time.
Kind and concentration by catalyzer are regulated cream time, only make at the glass fibre heap or fiberglass batts is filled a prescription fully and equably behind the dipping, reaction just begins.Cream time is usually at 90-120 between second.
Subsequently, because the inner CO2 that discharges causes comprehensive expansion of porous plastics, reaction is displayed.
According to the present invention, preferably use its viscosity as mentioned above preferentially between 200-600mPa., preferably be lower than the isocyanate component of 300mPa.s.The molecular formula of isocyanate compound is R (NCO) n, n＞2 wherein, and R represents aliphatic series or aromatic group.The preferred vulcabond that uses more preferably uses diphenylmethanediisocyanate (MDI).
The functionality of isocyanate component is preferably between 2.5-3.5, preferably between 2.7-3.1.Exist in functionality each molecule by isocyanate component-average number of NCO group defines.
By-NCO group/100 these mass ratioes definition of gram isocyanate component-percentage ratio of NCO is preferably between 28%-32%.
Usually can adopt unprocessed or without the distillatory diphenylmethanediisocyanate.This product can obtain usually from the market, and its trade mark is Suprasec, is sold by Huntsman.
In the context of the present invention, polyol component comprises the mixture of three kinds of polyvalent alcohols, and its viscosity is between 200-6000mPa.s.
The viscosity of polyol component is preferably between 1000-3000mPa.s.
The reactivity of polyvalent alcohol defines with different parameters, as functionality, OH exponential sum aromaticity.
Its functionality of preferred polyhydric alcohols is between 2-6.
The hydroxyl groups index that preferably is used (OH index) is by mass ratio (mg KOH/g polyvalent alcohol) definition, preferably between 200-500mg KOH/g polyvalent alcohol.
Determine the feasible cross-linking efficiency that might assess prescription of OH index.
The representative example from the polyvalent alcohol of Sorbitol Powder of spreading out is to be the polyvalent alcohol of Daltolac from the trade mark of Huntsman for example.For the polyvalent alcohol that spreads out from Sorbitol Powder, its OH index is preferably 500.
The representative example of polyether polyol is the product from glycerine (its side chain extends with 1,2 epoxy prapane) of for example spreading out, as those products of being sold with trade mark Caradol by Shell Chemicals.For this second kind of polyvalent alcohol, its OH index is preferably 250.
The representative example of polyester polyol is the aliphatic polyester type polyvalent alcohol, and perhaps preferred aromatic polyester type polyvalent alcohol is as the derivative of Tetra hydro Phthalic anhydride.In the context of the present invention, preferentially adopt the derivative of diethylene glycol phthalate ester, as by Stepan with trade mark StepanPol product sold.For this third polyvalent alcohol, its OH index is preferably 250.
Advantage aspect use polyester polyol (it is applied to the production of urethane foam usually) makes to obtain such PUIR porous plastics that it demonstrates the sufficient mechanical characteristics under heat condition, and anti-fully inflammable characteristic.
Be such fact in the advantage aspect the use polyether polyol (it is applied to the production of polyisocyanurate foamed plastics usually), be that such polyvalent alcohol can make the physical strength of PUIR porous plastics under cool condition be improved, prescription is improved to the maceration of glass fibre heap or fiberglass batts heap.
In addition, in the context of the present invention, more than Ding Yi isocyanate index depends on the isocyanate component that is incorporated in the prescription and the ratio of polyvalent alcohol.
When isocyanate index was between about 95-110, the porous plastics that obtains from this prescription was urethane (PU) porous plastics.When isocyanate index greater than 200 the time, promptly excessive-during the NCO group, the porous plastics that obtains from this prescription is poly-isocyanurate (PIR) porous plastics when existing.When isocyanate index was between 110-200, the porous plastics that obtains from this prescription had the characteristic of urethane foam and polyisocyanate ester foamed plastic simultaneously, therefore was called urethane/poly-isocyanurate (PUIR) porous plastics.
In the context of the present invention, prescription further comprises the additive of the preparation that is generally used for the PUIR porous plastics, as one or more catalyzer, whipping agent, emulsifying agent and fire retardant.
Catalyzer can be gelling catalyst, swelling catalyst, curing catalysts and the trimerization catalyst that is generally used for the preparation of PUIR porous plastics.Particularly advantageous in the context of the present invention catalyzer is an organo-metallic catalyst for example, as the tetravalent tin catalyzer, and carboxylic acid tin (IV), particularly stannous octoate for example, and carboxylic acid potassium, particularly potassium octanoate.Also can adopt tertiary amine.
Preferably, when not using the catalyzer of amine type, use tin-based catalyst and potassium octanoate catalyzer simultaneously.
Tin-based catalyst is those catalyzer of the DBTDL type of for example being sold with trade mark Dabco by Air Products, and it preferably uses with the ratio that quality accounts between the 0.01%-1% of total mass of each polyvalent alcohol (being polyol component).
The potassium octanoate catalyzer is those catalyzer of for example being sold with trade mark Dabco equally by Air Products, and it preferably uses with the ratio that quality accounts between the 0.1%-2% of total mass of each polyvalent alcohol.
The catalyzer of amine type is those catalyzer of for example being sold with trade mark Polycat by Air Products, and it preferably uses with the ratio that quality accounts between the 0.01%-1% of total mass of each polyvalent alcohol.
Catalyzer is used for accelerating one or more above-mentioned different reactions steps.For example, tetravalent tin catalyzer and tertiary amine catalyst preferably act on step 1-3, and the potassium octanoate catalyzer preferably acts on trimerizing reaction (step 4).
The value volume and range of product that is incorporated into the catalyzer in the prescription directly influences the speed of reaction, and therefore influences cream time.
But, can be to the ratio change of the catalyzer introduced.Its reason is, when every Gram Mass of the tackiness agent in glass fibre heap or the fiberglass batts heap or ratio increase, must reduce the ratio that is incorporated into the catalyzer in the described prescription, to postpone cream time, make that pile equably by impregnated glass fiber heap or fiberglass batts before the reaction beginning for described prescription.
Therefore, the reactivity of prescription and viscosity depend on the reactivity of polyvalent alcohol, but also depend on the value volume and range of product of catalyzer.
Prescription further comprises one or more whipping agents, and it can be pneumatogen or chemical foaming agent.
The preferred pneumatogen that adopts is non-chlorating 3-pentafluorobutane compound, particularly 1,1,1,3, the 3-3-pentafluorobutane, it is also referred to as HFC-365mfc, especially trade mark is Solkane 365 (Solvay sale), and HFC-245fc by name, especially trade mark are Enovate 3000 (Honeywell sale).
The preferred chemical foaming agent that adopts is a water.
Above-mentioned pneumatogen and chemical foaming agent can use separately, perhaps use simultaneously.
The preferred amount of pneumatogen calculates as the function of the desired density that strengthens the PUIR porous plastics.With respect to the total mass of polyol component, this quantity preferably between 0-10% (quality), preferably is about 5% (quality).
The preferred amount of the water that is adopted depends on total desired density of PUIR porous plastics.With respect to the total mass of polyol component, the ratio of water preferentially between 0-1% (quality), preferably reaches 1% (quality) in fact in the composition.
Whipping agent makes prescription to foam.The kind of whipping agent influences the thermal insulation properties of porous plastics.Water is preferentially as whipping agent, because it causes that the release of CO2 increases, compared with the whipping agent of routine, CO2 is the whipping agent less to environmental hazard.In addition, CO2 can not hinder to the liquefied gas tank vessel with jar tank skin on anyly may leak the detection of carrying out.
At last, preferably use emulsifying agent, it can be silicone emulsifiers or non-silicone emulsifying agent.The example of silicone emulsifiers is the emulsifying agent sold with trade mark Tegostab 8804 of Goldschmidt for example.Such emulsifying agent preferably is used in the prescription with the ratio of 1% (quality) that account for the polyvalent alcohol total mass greatly.The example of non-silicone emulsifying agent is the emulsifying agent sold with trade mark LK443 of Goldschmidt for example.Such emulsifying agent preferably is used in the prescription with the ratio between the 0.5%-3% (quality) that accounts for the polyvalent alcohol total mass.
Emulsifying agent is used for making the whipping agent dissolving and makes cell stabilization.
Except above-mentioned key ingredient, in prescription of the present invention, be worth adopting other components toward contact.
Also use the fire retardant that under background of the present invention, has advantage, with the combustibility of further limit foam plastics.Fire retardant can be a halogenated fire-retardants---TCPP for example, for example sell by Akzo Nobel, and---perhaps preferred non-halogenated flame retardent---be the fire retardant of the Levagard-TEP type of Lanxess for example.Fire retardant preferably uses with the ratio of about 5%-20% (quality) of accounting for the polyvalent alcohol total mass.
Other additives also can preferably join in the prescription as filler, linking agent and dyestuff.
In case prepare by mixing the prescription that isocyanic ester, polyvalent alcohol and various additive obtain, fast it be poured on the heap of glass fibre heap or fiberglass batts the full depth of feasible prescription impregnated glass fiber heap or fiberglass batts heap.The mean density of the enhancing porous plastics of Huo Deing is 115-135kg/m like this
3, be preferably 120-130kg/m
3, be more preferably 130kg/m
3
Be made up of continuous Glass Fiber Mat (continuous strand felt) according to the preferential fiberglass batts of using of first embodiment, it is selected from by Vetrotex especially with trade mark Unifilo sale or by the continuous Glass Fiber Mat of Owens Corning with trade mark Advantex sale.
These glass fibre are bound up mutually by tackiness agent, and the amount that described tackiness agent exists preferably accounts for the 0.6%-3% (quality) of the total mass of fiberglass batts, preferably is about 2.5% (quality) in fact.In order to the tackiness agent of gluing glass fibre Resins, epoxy preferably.
Constitute the glass fibre of the preferential felt that adopts, its linear density is 20-40tex, i.e. the 20-40g/km fiber.
Every Gram Mass of fiberglass batts is preferably at 300-900g/m
2Scope, more preferably at 300-600g/m
2Scope, more preferably at 450g/m
2About.With respect to the total mass that strengthens the PUIR porous plastics, glass fibre preferably accounts for 6%-12% (quality).
The every Gram Mass that depends on the quantity and the fiberglass batts of tackiness agent, and in order to obtain acceptable mechanical properties, the number of glass mat is for example changing between the 4-12.
Preferably make according to the preferential glass fibre that uses of second embodiment from rove, rove promptly by be not twisted together but the glass fibre that keeps together in parallel to each other flat band that form, more or less wide.Glass fibre is preferably produced according to the Webforming technology of Plastech T.T.Ltd.
The linear density of the glass fibre of producing by this technology is preferably 30-300tex.
The Webforming technology of Fig. 1 to 3 explanation Plastech T.T.Ltd.
Fig. 1 shows the spool 1 of rove 2.Spool 1 is installed around turning axle 3, and the latter extends along rotation A.Rove 2 is wound on the spool 1.The transverse plane that is positioned at perpendicular to the planar spool 1 of rotation A is called vertical end 11 and 13.A far-end 31 of turning axle 3 extends to the central authorities of spool 1 from vertical end 11 central positions, turning axle 3 succeedinglys cross bearing 4 and rotating machine 5.
Rotating machine 5 is the overall shape with disk, the form that comprises the chest of servosystem (not shown).Rotating machine 5 preferred fit have the non-muscular energy braking system (not shown) by the control of computer system (not shown).The transmission speed of motor 5 is preferably controlled by the computer system (not shown).
Spool 1 is applicable to launch rove 2 by the speed of non-muscular energy braking system control.
Fig. 2 shows supply of power capstan winch 9.Capstan winch 9 comprises the rotating machine 6 of the chest form of the overall shape with disk.Motor 6 drives the turning axle 7 that extends along rotation B.
The transverse plane that is positioned at perpendicular to the planar motor 6 of rotation B is called vertical end 61 and 63.A far-end 71 of turning axle 7 extends to the central authorities of motor 6 from the middle part of vertical end 61.By drive plate 72, far-end 71 succeedinglys cross the top 81 of bearing 8, and terminate in the opposite (on the meaning of figure) of center of top of the center part 101 of dance roller 10.
The transmission speed of motor 6 reaches so the speed of rotation of turning axle 7 is preferably controlled by the computer system (not shown).
(for figure) radially extends dispense arm 102 towards the front.Dispense arm 102 comprises dispensing orifice 102a at its radial outer end.
(for figure) radially extends distance arms 103 towards the back.
F strain is adjusted arm 104 upwards (for figure) extension of front from the crown center of center part 101.Backward pull is adjusted arm 105 upwards (for figure) extension of back from the crown center of center part 101.F strain adjusts arm 104 and backward pull adjustment arm 105 has right cylinder 104a and 105a at their radial outer end, and described two right cylinders extend along the axis (not shown) parallel with rotation B respectively.
Fig. 3 is a synoptic diagram of producing the production line of glass fibre 15 according to foregoing Webforming technology from rove 2.
With reference to Fig. 3, rove 2 sends to capstan winch 9 continuously from spool 1.With reference to Fig. 2, rove (in Fig. 2 show) passes between the top of the bottom of the top of right cylinder 105a, drive plate 72 and right cylinder 104a.Rove crosses dispensing orifice 102a then.The drive plate 72 that is frictionally engaged with rove launches rove, and makes its speed adjusted.Specified as preamble, the development rate of rove 2 is controlled by the computer system (not shown).
According to Fig. 3, the production line of glass fibre 15 comprises the spool 1 (illustrating with rectangle) of upstream, and it is assigned to capstan winch 9 (illustrating with rectangle) with the speed of setting with rove 2.The speed and the tension force of 9 pairs of rove 2 of capstan winch carry out meticulousr adjusting.At last, rove 2 is directed to dispenser head 11 inlet of (illustrating with rectangle).Dispenser head 11 is arranged in the opposite at the top of travelling belt 12.The linear density of rove 2 preferably is about 2400tex between 1000-3000tex.In dispenser head 11 inside, rove 2 is separated into the glass fibre 15 with preferred low linear density between 30-300tex.It is that difference by dispenser head 11 pressure inside and air-flow realizes that rove 2 is separated into low linear density glass fibre 15.Pressure and air-flow are controlled by the computer system (not shown).
In addition, bootable dispenser head 11 is along axis X (as shown in the figure) and Y (defining as preamble) translation, so that distribute glass fibre with irregular alignment or according to pattern and isostatic quantity along these directions and along the thickness of piling (axis Y defines as preamble).The motion of dispenser head 11 and the height on travelling belt thereof are controlled by the computer system (not shown) equally.Therefore, every Gram Mass of heap can be controlled.Also in this embodiment, every Gram Mass is preferably at 300-900g/m
2Between.And with respect to the total mass that strengthens the PUIR porous plastics, preferably, glass fibre 15 accounts for 6%-12% (quality).
In addition, dispenser head 11 dispense adhesive in addition when distributing glass fibre.The amount that tackiness agent exists preferably accounts for the 0-3% (quality) of the total mass of glass fibre heap.Tackiness agent preferred epoxy in order to gluing glass fibre.
At last, dispenser head 11 preferred rate-allocation glass fibre with 3kg/min.Can use a plurality of dispenser heads 11, preferred 3, to obtain such speed.
In a word, depend on the reactivity and the viscosity of prescription according to the impregnating effect of the glass fibre heap of first or second embodiment, but also depend on the amount of the tackiness agent that is adopted.
Be preferably as follows in order to the method for producing the PUIR porous plastics and carry out: the various components of prescription can be mixed in the mixing tank of low pressure rigid foam mixer types.
But, carry out for making course of processing facility, usually whipping agent and various additive are incorporated in the container that accommodates polyol component.The mixture that will contain polyol component and various additives subsequently is mixed in the isocyanate component, and will be poured on by the prescription that this married operation obtains on the heap of glass fibre heap or two or many fiberglass batts.Can after polyol component and isocyanate component mixing, whipping agent and some additive or catalyzer be joined in the composition.
Preferably when scale operation strengthens the PUIR porous plastics, glass fibre heap or fiberglass batts pile up on the travelling belt that sidewall is housed continuously that (along the length direction of porous plastics) moves.With prescription be poured on glass fibre heap or the fiberglass batts heap container laterally (along the width of porous plastics) be displaced into the whole width of travelling belt between the two side (indicating by the label among Fig. 3 12 and 16 respectively).Sidewall is received the prescription that is poured into glass fibre heap or fiberglass batts heap, thereby produces uniform maceration.
The various components of prescription are mixed under envrionment temperature and normal atmosphere.Equally, formula optimization is being poured under envrionment temperature and the normal atmosphere on glass fibre heap or the fiberglass batts heap.
Spent for some time (being called cream time) afterwards, the various components that are incorporated in order to the prescription of impregnated glass fiber heap or fiberglass batts heap just begin reaction.
Reaction is proceeded, and is displayed by the foaming of the prescription of impregnated glass fiber heap or fiberglass batts heap.
Can be according to technician's knowledge, the function of sedimentation rate as the height of the speed of transportation, foam-plastic blocks and required density calculated.
Then, will strengthen the PUIR foam-plastic blocks dry 5-10 minute.The thickness that strengthens the PUIR foam-plastic blocks is preferably 25 or 35cm.
Then, the summit portion of porous plastics (existing for strengthening the form of foam-plastic blocks) and bottom surface portions and lateral parts (in appropriate circumstances) are removed.This pre-shaping step makes to produce to have intended size---for example 9 and/or the foam-plastic blocks of 18cm.
When plan made the liquefied gas tank vessel with the jar thermal insulation with these PUIR foam-plastic blocks, this moment can be with described foam-plastic blocks crosscut to 1/3rd of its thickness, to make these two thermal insulation layers of first and second thermal insulation layers.In this case, finishing is the thick foam-plastic blocks of cutting 30cm also, forming the foam-plastic blocks that thickness is 9cm and 18cm simultaneously, thereby forms first and second thermal insulation layers respectively.This single cutting step that single foam-plastic blocks is carried out, make to obtain first thermal insulation layer and second thermal insulation layer simultaneously, this equals not only to have saved material, because finishing has been lost still less, and saved the time, because only need single step just to produce two thermal insulation layers.
The embodiment purpose that hereinafter provides is explanation the present invention, can not be interpreted as so that no matter any way limits the present invention.Unless otherwise, all percentage ratios that provide are mass percent.
Following embodiment illustrates the result of following test
Z compression testing under heat condition and the cool condition (promptly strengthening the compression testing of the thickness direction of porous plastics), this test simulation is by the pressure of the sidewall that acts on jar of the motion generation of liquefied gas in the jar;
Y tension test under heat condition and the cool condition (promptly strengthening the tension test of the length direction of foam composition), this test simulation puts on the deformation among the tank skin, especially since when the loading and unloading liquefied gas tank skin expand and shrink the deformation of the elongation type of generation; And
Inflammability test.
When Z compression testing and Y tension test when carrying out, are to carry out at ambient temperature at " under the heat condition ".When these tests when carrying out, are that temperature is to carry out in the cryostat of-170 ℃ (causing with liquid nitrogen) therein at " under the cool condition ".
On technical scale,, get 30-50 sample and carry out these tests for the every kind of foam-plastic blocks that is obtained.
The Z compression testing is carried out according to ASTM D 1621 standards (perhaps being equal to standard).
Compressive strength is assessed by the pressure that measuring vertical puts on the surface of each sample, and described pressure is the function of the surface of each sample on thickness direction with respect to the displacement of its starting position.These observed values are marked and drawed on compressive strength curve (not shown).The peak pressure (maximum value on the described curve) that was applied before the structure deteriorate that strengthens porous plastics is corresponding to greatest compressive strength, and it is expressed as " Z compression " hereinafter.
Described slope of a curve is expressed as " modulus of compression " hereinafter corresponding to Young's modulus.
Depend on applicable cases, probable value must use the porous plastics that demonstrates high Z compression and low Z modulus of compression.
The Y tension test is carried out according to ASTM D 1623 standards (perhaps being equal to standard).
Tensile strength is assessed the resistance of the pulling force at the two ends that put on sample on the length direction of sample by measuring, and described resistance is the functions of described two ends with respect to the displacement of their starting position.These observed values are marked and drawed on the tensile strength curve (not shown).The maximum Y pulling force (maximum value on the described curve) that was applied before the structure deteriorate that strengthens porous plastics is corresponding to ultimate tensile strength, and it is expressed as " Y compression " hereinafter.
Described slope of a curve is corresponding to the Y modulus in tension.
According to applicable cases, probable value must use the porous plastics that demonstrates high Y tensile strength and low Y modulus in tension.
It should be noted that and to carry out similar test, with measured X tensile strength (promptly strengthening the tensile strength of the width of PUIR porous plastics).But, hereinafter only introduce the Y tensile strength test, because the Y tension test comes compared with the X tension test, acquisition can be difficult more with the result of the standard of jar by putting teeth in the liquefied gas tank vessel.Difference on this result is because the natural characteristics of common fiberglass batts of selling causes.
Below the composition of research PUIR porous plastics is to the influence of Z compressive strength.
The prescription that strengthens the different compositions of PUIR porous plastics is showing in the Table I down.
The various compositions of the component 1 of Table I are mixed.Then component 2 and component 3 are joined in the component 1 in succession.The prescription of gained is poured on the heap of 8 fiberglass batts formations, makes that the fibre content that strengthens the PUIR porous plastics is 9%, density is 130kg/m
3In these trials, every Gram Mass of fiberglass batts and binder content are respectively 450g/m2 and 0.8%.
After stable,, the Z compressive strength that each above-mentioned composition carries out under the heat condition and under the cool condition is tested with laboratory scale.
The result of these tests is providing in the Table II down.All numerical value that provide all refer to its density value is extrapolated to 130kg/m
3Each foam composition so that can their mechanical properties be compared.Because in this density range, each density and relation between the mechanical properties that strengthens foam composition is linear, it is practicable therefore doing this extrapolation.
Also above-mentioned each prescription is carried out the measurement of the ratio of closed pore according to ASTM D 2856 standards (program B), carry out inflammability test according to DIN 4102-1 standard.
In all following forms, given result is the mean value that is subjected to the numerical value of this acquisition of sample from all.
Table II: the result of the Z compression testing of different PUIR foam compositions
B3: do not meet DIN 4102-1 standard
B2: meet DIN 4102-1 standard
In Table II and following form, do not meet put teeth in the liquefied gas tank vessel with jar the result of standard show with runic." technical specifications " row demonstration in the Table II is put teeth in liquefied gas tank vessel all standards with jar in laboratory scale by applicant company.
Under heat (20 ℃) condition, all Z compressive strength results that composition drew generally speaking are gratifying.But, concerning be applied to the liquefied gas tank vessel with jar, isocyanate index is that 130 composition 3 and composition 4 demonstrate best result.
Under cold (170 ℃) condition, except that composition 6 (its isocyanate index is much larger than the isocyanate index that proposes claim, and it contains two kinds of polyvalent alcohols), all composition exhibiting go out the Z compressive strength greater than 3Mpa.
It is worth noting that isocyanate index is that 110 prescription demonstrates excellent mechanical intensity, but its inflammableness resistance prescription higher than isocyanate index is low.
In a word, between hot and cold compressive strength characteristic and inflammableness resistance characteristic, obtaining optimal compromise,, as if need three kinds of polyvalent alcohols for composition according to the present invention.
In addition, mixed the composition 4 of the 3rd polyvalent alcohol of 60% first polyvalent alcohol, 20% second polyvalent alcohol and 20% with respect to the total mass of polyol component, be the composition that the fiberglass batts maceration of the best can be provided, make the homogeneity that strengthens the PUIR porous plastics improve.
Below the overall consistency of the characteristic of research fiberglass batts and enhancing PUIR porous plastics is to the influence of Z compressive strength and Y tensile strength.
Showing in the Table III down at the different enhancing PUIR foam composition of studying on the technical scale.
Table III: the different compositions that strengthen the PUIR porous plastics
| Composition | Mean density (kg/m 3) | The ratio of fiber * | The number of plies of fiberglass batts | Every Gram Mass (the g/m of fiberglass batts 2) | |
| 8 | 123 | 11.1 | 10 | 450 | 2.5 |
| 9 | 132.5 | 7.6 | 8 | 450 | 2.5 |
| 10 | 131.5 | 11.1 | 7 | 600 | 0.8 |
| 11 | 132.5 | 10.1 | 8 | 600 | 2.5 |
| 12 | 131 | 11.3 | 10 | 450 | 2.5 |
*% (quality) is with respect to the total mass that strengthens porous plastics
More than each composition 8-12 be based on aforementioned compositions 4, but mixed fiber mat with different characteristics, described characteristic relates to the ratio of every Gram Mass, binder content, fiber and the aspects such as the number of plies of glass fibre.
Mean density and subsequent all results calculate by going up the results averaged that obtains in each level (bottom, middle part and top) that strengthens PUIR porous plastics thickness direction.
Test of Z compressive strength and Y tensile strength test are providing in the Table IV down under the heat condition." technical specifications " row demonstration of following table is put teeth in liquefied gas tank vessel all standards with jar in technical scale by applicant company.
Table IV: the Z compressive strength of (20 ℃) and Y tensile strength test under the heat condition
| Composition | Technical specifications (MPa) | 8 | 9 | 10 | 11 | 12 |
| Z compresses (MPa) | Greater than 1.5 | 1.42 | 1.47 | 1.72 | 1.62 | 1.65 |
| Deviation (is unit with Mpa) * | As far as possible little | 0.17 | 0.12 | 0.11 | 0.23 | 0.2 |
| Z modulus of compression (MPa) * | Less than 80 | 60 | 65 | 70 | 75 | 70 |
| Deviation (is unit with Mpa) * | As far as possible little | 10.9 | 8.2 | 7.3 | 9.1 | 6.0 |
| Y stretch (MPa) | Greater than 2.4 | 2.95 | 2.2 | 2.55 | 3.1 | 3.2 |
| Deviation (is unit with Mpa) * | As far as possible little | 0.95 | 0.72 | 0.23 | 0.65 | 1.2 |
| Y tensile modulus (MPa) | Less than 150 | 122 | 92 | 112 | 125 | 133 |
| Deviation (is unit with Mpa) * | As far as possible little | 40.5 | 51 | 20 | 48 | 35 |
*Deviation: the deviation between the sample that demonstrates minimum result and maximum result of single composition
Z compressive strength under the cool condition and Y tensile strength test result are providing in the Table V down.
Table V: the Z compressive strength of (170 ℃) and Y tensile strength test under the cool condition
| Composition | Technical specifications (MPa) | 8 | 9 | 10 | 11 | 12 |
| Z compresses (MPa) | Greater than 2.7 | 2.65 | 2.71 | 2.87 | 3.12 | 2.95 |
| Deviation (is unit with Mpa) * | As far as possible little | 0.31 | 0.23 | 0.33 | 0.7 | 0.26 |
| Z modulus of compression (MPa) | Less than 130 | 116 | 111 | 120 | 125 | 113 |
| Deviation (is unit with Mpa) * | As far as possible little | 21 | 26 | 12 | 18 | 22 |
| Y stretch (MPa) | Greater than 2.7 | NM | 2.65 | 1.6 | 3.41 | 3.4 |
| Deviation (is unit with Mpa) * | As far as possible little | NM | 0.71 | 1.14 | 0.85 | 1.75 |
| Y tensile modulus (MPa) | Less than 190 | NM | 177 | 152 | 215 | 167 |
| Deviation (is unit with Mpa) * | As far as possible little | NM | 58 | 40 | 61 | 42 |
NM: do not measure
*Deviation: the deviation between the sample that demonstrates minimum result and maximum result of single composition
Though generally speaking all prescriptions are all obtaining gratifying result aspect Y tensile strength and the Z compressive strength two,, clearly, still filling a prescription 11 demonstrates best average behaviour under heat condition He under the cool condition.
Further, should be pointed out that under heat condition that the prescription 9 of fibre content minimum (7.6%) causes the performance under heat condition low slightly.
In addition, the prescription 10 of binder content minimum (0.8%) causes the performance under cool condition low slightly.
Similarly, the prescription 8 that density is minimum demonstrates low slightly performance under heat condition He under the cool condition.
Prescription of the present invention demonstrates preferred compressive strength/modular ratio, for about 35-45.This characteristic makes enhancing PUIR porous plastics that fabulous balance be arranged between intensity and snappiness.
At last,, measure the foamy quality, carry out inflammability test, and the result is being provided in the Table VI down according to DIN 4102-1 standard by the measurement of carrying out the ratio of closed pore according to ASTM D 2856 standards (program B) also to each above-mentioned prescription.
Table VI: the measurement of the ratio of closed pore and flammability test
| Composition | |
8 | 9 | 10 | 11 | 12 |
| Average foam plastic density is (with kg/m3 | - | 123 | 122 | 131. 5 | 132.5 | 131 |
| Be unit) * | ||||||
| Deviation | As far as possible little | 8.3 | 9.5 | 5.8 | 11.0 | 8.8 |
| Flammable | DIN 4102-1 (B2) | B2 | B2 | B2 | B2 | B2 |
| The ratio of closed pore | ＞92％ | 92 | 93 | 93 | 94 | 92 |
*Deviation: the deviation between the sample that demonstrates minimum result and maximum result of single composition
Prescription 8-12 is all obtaining very gratifying result aspect the ratio two of inflammableness resistance and closed pore.
In a word, all above-mentioned prescriptions all demonstrate very gratifying mechanical strength property, can be applied to technical fields such as building, automobile.In addition, meet the above-mentioned prescription of the standard that is put teeth in by applicant company, also can be applicable to liquefied gas tank vessel jar, this is the significant more technical field of deformation and expansion stress.
Though invention has been described in conjunction with specific embodiment, but obviously, the present invention never is confined to this embodiment, and the present invention includes all equivalent technical solutions of described method and their combination, and these equivalent technical solutions and their combination fall within the scope of the present invention.
Claims (23)
1. glass fibre enhanced urethane/polyisocyanurate foamed plastics, described porous plastics obtains by following steps:
1) exist:
Be selected from pink salt and carboxylic acid potassium, and do not select the catalyzer of tertiary amine,
Physics and/or chemical foaming agent,
Emulsifying agent, and
Optional fire retardant
Exist down, make following two kinds of components contact:
The isocyanate component of viscosity between 200-600mPa.s,
The polyol component of forming by first polyvalent alcohol, second polyvalent alcohol and the 3rd polyvalent alcohol, described first polyvalent alcohol is a sorbitol derivatives, described second polyvalent alcohol is a polyether polyol, described the third polyvalent alcohol is a polyester polyol, the viscosity of described each polyvalent alcohol is between 200-6000mPa.s
2) the prescription impregnated glass fiber heap that obtains with step 1, and
3) make described prescription foaming and curing, form the enhancing foam-plastic blocks that comprises the glass fibre heap;
The mean density of described enhancing foam-plastic blocks is at 115-135kg/m
3Between, isocyanate index is between 130-180.
2. porous plastics according to claim 1, the mean density of described enhancing foam-plastic blocks is at 120-130kg/m
3Between.
3. porous plastics according to claim 2, the mean density of described enhancing foam-plastic blocks are 130kg/m
3
4. porous plastics according to claim 1, wherein said isocyanate component are the diphenylmethanediisocyanate of average functionality between 2.5-3.5.
5. porous plastics according to claim 4, wherein said isocyanate component are the diphenylmethanediisocyanate of average functionality between 2.9-3.1.
6. according to any described porous plastics in the claim 1 to 5, wherein said polyol component is made up of with the 3rd polyvalent alcohol described first, second, wherein said first polyvalent alcohol is that the ratio of 10%-80% exists with quality with respect to the total mass of described polyol component, wherein said second polyvalent alcohol is that the ratio of 10%-80% exists with quality with respect to the total mass of described polyol component, and wherein said the 3rd polyvalent alcohol is that the ratio of 10%-80% exists with quality with respect to the total mass of described polyol component.
7. porous plastics according to claim 6, wherein said first, second and the 3rd polyvalent alcohol are respectively 60%, 20% and 20% with respect to the mass ratio of described polyol component quality.
8. according to any described porous plastics in the claim 1 to 5, wherein said whipping agent is a water.
9. according to any described porous plastics in the claim 1 to 5, wherein said whipping agent is HCF-365mfc or HCF-245fa.
10. according to any described porous plastics in the claim 1 to 5, wherein said fire retardant right and wrong are halogenated.
11. according to any described porous plastics in the claim 1 to 5, wherein said glass fibre heap is the form of a pile fiberglass batts.
12. porous plastics according to claim 11, the linear density of the glass fibre of described porous plastics are the 20-40 tex.
13. porous plastics according to claim 1, wherein said glass fibre heap comprises the continuous glass fibre of being made by rove.
14. porous plastics according to claim 13, the linear density of the glass fibre of described porous plastics are the 30-300 tex.
15. porous plastics according to claim 13, wherein said continuous glass fibre is made by following technology, and described technology comprises that defiber density is lower than the step of the continuous glass fibre rove of rove.
16. according to any described porous plastics in the claim 1 to 5, wherein said glass fibre is bound up by tackiness agent.
17: porous plastics according to claim 16, the amount of wherein said tackiness agent accounts for the 0.6%-3% of described glass fibre quality.
18. according to claim 13 or 15 described porous plastics, wherein said glass fibre is not bound up by tackiness agent.
19. according to any described porous plastics in the claim 1 to 5, every Gram Mass of wherein said glass fibre heap is at 300-900g/m
2Between.
20. according to any described porous plastics in the claim 1 to 18, the quality of wherein said glass fibre accounts for the 7%-13% of the total mass that strengthens foam-plastic blocks.
21. according to any described porous plastics in the claim 1 to 5, the combustibility of described porous plastics detects according to DIN 4102-1 test.
22. according to any described porous plastics in the claim 1 to 5, described porous plastics is the form of the foam-plastic blocks of thickness between 20-35cm.
23. the making method of any described glass fibre enhanced urethane/polyisocyanurate foamed plastics in the claim 1 to 5 said method comprising the steps of:
1) exist:
Be selected from pink salt and carboxylic acid potassium, and do not select the catalyzer of tertiary amine,
Whipping agent,
Emulsifying agent,
Optional fire retardant
Exist down, make following two kinds of components contact:
The isocyanate component of viscosity between 200-600mPa.s,
The polyol component of forming by first polyvalent alcohol, second polyvalent alcohol and the 3rd polyvalent alcohol, described first polyvalent alcohol is a sorbitol derivatives, described second polyvalent alcohol is a polyether polyol, described the third polyvalent alcohol is a polyester polyol, the viscosity of described each polyvalent alcohol is between 200-6000mPa.s
2) the prescription impregnated glass fiber heap that obtains with step 1,
3) make described prescription at the foaming after fixing, comprise the enhancing foam-plastic blocks that glass fibre is piled with formation,
4) top, bottom and the optional side of the described foam-plastic blocks of finishing, and optional
5) the described foam-plastic blocks of crosscut produces first thermal insulation layer and second thermal insulation layer.
24. according to the purposes of any described porous plastics in the thermal isolation of liquefied gas transfer cask in the claim 1 to 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0502227 | 2005-03-04 | ||
| FR0502227A FR2882756B1 (en) | 2005-03-04 | 2005-03-04 | FOAM OF POLYURETHAN-POLYISOCYANURATE REINFORCED WITH GLASS FIBERS |
| FR0511111 | 2005-10-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1834130A CN1834130A (en) | 2006-09-20 |
| CN100434451C true CN100434451C (en) | 2008-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610058849XA Expired - Fee Related CN100434451C (en) | 2005-03-04 | 2006-03-02 | Glassfiber-reinforced polyurethane-polyisocyanurate foam |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN100434451C (en) |
| FR (2) | FR2882756B1 (en) |
| RU (1) | RU2317307C2 (en) |
| TW (1) | TWI292408B (en) |
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| CN101191010B (en) * | 2006-11-20 | 2011-06-15 | 中国船舶重工集团公司第七二五研究所 | Fibre enhancement modifying method for polyurethane foam plastic |
| CN100485001C (en) * | 2007-02-12 | 2009-05-06 | 江苏双良复合材料有限公司 | Section material product of continuous glass-fiber reinforced hard polyurethane microfoam and coextrusion forming process |
| CN101029456B (en) * | 2007-03-06 | 2010-05-19 | 天津工业大学 | Non-woven elastic substrate and its production |
| CA2745920A1 (en) * | 2008-12-10 | 2010-06-17 | Basf Se | Water-blown rigid foams with improved mechanical properties at low temperatures |
| ITMI20100440A1 (en) * | 2010-03-18 | 2011-09-19 | Dow Global Technologies Inc | PROCESS FOR THE PREPARATION OF POLYURETHANE REINFORCED WITH LONG FIBERS CONTAINING PARTICULAR FILLERS |
| CN101781395B (en) * | 2010-03-30 | 2011-08-31 | 上海交通大学 | Hard polyurethane adiabatic heat-insulation foam material and preparation method thereof |
| RU2465141C2 (en) * | 2011-01-12 | 2012-10-27 | Государственное образовательное учреждение высшего профессионального образования Балтийский государственный технический университет "ВОЕНМЕХ" им. Д.Ф. Устинова (БГТУ "ВОЕНМЕХ") | Method of making gas-filled plastic reinforced by discrete elements |
| JP2013043374A (en) * | 2011-08-24 | 2013-03-04 | Nakagawa Sangyo Kk | Manufacturing method of interior substrate for automobile |
| CN102504164B (en) * | 2011-11-22 | 2013-10-16 | 中国农业大学 | Manufacture method of enhanced corncob base polyurethane foam materials |
| TWI477552B (en) * | 2012-06-28 | 2015-03-21 | Fire-resistant polyurethane material and fire-resistant structure | |
| FR2993270B1 (en) * | 2012-07-12 | 2015-08-07 | Rhodia Operations | CHEMICAL FOAMING PROCESS IN THE PRESENCE OF REINFORCING LOADS |
| CN104540865B (en) * | 2012-08-20 | 2017-03-01 | 科思创德国股份有限公司 | Cast polyurethane resin and the potting compound being made from |
| DK2885331T3 (en) * | 2012-08-20 | 2019-12-09 | Covestro Deutschland Ag | FIBER ENHANCED COMPOSITION COMPONENTS AND THEIR PREPARATION |
| CN103641984B (en) * | 2013-11-13 | 2016-06-08 | 安徽金马海绵有限公司 | A kind of enhancing sponge and preparation method thereof |
| CN107090074A (en) * | 2016-02-17 | 2017-08-25 | 江苏雅克科技股份有限公司 | A kind of high-fire-resistance fiberglass reinforced hard polyaminoester ultra-low temperature heat preservation material and its preparation method |
| CN107099018A (en) * | 2016-02-22 | 2017-08-29 | 江苏雅克科技股份有限公司 | A kind of halogen-free flame-retardant glass fiber of resistance to ultralow temperature enhancement type hard polyurethane insulation material of green-blowing agent production and preparation method thereof |
| JP7208013B2 (en) * | 2016-05-04 | 2023-01-18 | コベストロ、ドイチュラント、アクチエンゲゼルシャフト | Method for producing polyisocyanurate composite material |
| CN108148166A (en) * | 2016-12-05 | 2018-06-12 | 江苏雅克科技股份有限公司 | Polyurethane heat-insulation composite material |
| CN107459617A (en) * | 2017-07-11 | 2017-12-12 | 上海交通大学 | A kind of LNG ship grad enhancement heat-insulating material and its short process making method |
| CN108997550A (en) * | 2018-06-27 | 2018-12-14 | 扬中市天正合成材料研究中心 | Environmental protection flame retardant foamed material and preparation method for tractor fuel tank |
| CN109503792A (en) * | 2018-11-08 | 2019-03-22 | 青岛正能交通装备有限公司 | A kind of polyurethane foam standard EMU operation bench mask and preparation method thereof |
| FR3088571B1 (en) * | 2018-11-19 | 2021-12-17 | Gaztransport Et Technigaz | PROCESS AND SYSTEM FOR PREPARING A BLOCK OF POLYURETHANE / POLYISOCYANURATE FOAM FROM A THERMAL INSULATION MASS OF A TANK |
| FR3091705B1 (en) * | 2019-01-16 | 2022-08-26 | Gaztransport Et Technigaz | PROCESS FOR PREPARING A BLOCK OF POLYURETHANE/POLYISOCYANURATE FOAM FROM A THERMAL INSULATION BLOCK FOR A TANK |
| FR3092837B1 (en) * | 2019-02-18 | 2021-08-27 | Gaztransport Et Technigaz | METHACRYLATE COPOLYMERS, AND THEIR USES FOR THE PREPARATION OF POLYURETHANE FOAM |
| FR3094451B1 (en) * | 2019-03-26 | 2022-12-23 | Gaztransport Et Technigaz | Polyurethane/polyisocyanurate foam block for a thermal insulation block for a tank and process for its preparation |
| FR3094449B1 (en) * | 2019-03-26 | 2022-12-23 | Gaztransport Et Technigaz | Polyurethane/polyisocyanurate foam block for a thermal insulation block for a tank and process for its preparation |
| CN110699858A (en) * | 2019-11-14 | 2020-01-17 | 江苏九鼎新材料股份有限公司 | Method for producing a continuous glass fibre mat for polyurethane reinforcement and use thereof |
| WO2022268328A1 (en) | 2021-06-24 | 2022-12-29 | Gaztransport Et Technigaz | Compositions of methacrylate copolymers and blowing agent, and uses thereof for the preparation of polyurethane foam |
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| JP2001247647A (en) * | 2000-03-08 | 2001-09-11 | Nkk Corp | Raw liquid composition for rigid polyurethane foam, and process for preparation of thermal insulation panel for extremely low temperature |
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| US4680214A (en) * | 1986-03-12 | 1987-07-14 | Polymetrics Corporation | Reinforced foam composites |
| FR2599468B1 (en) * | 1986-06-03 | 1988-08-05 | Technigaz | THERMALLY INSULATING WALL STRUCTURE OF WATERPROOF TANK |
| KR100416834B1 (en) * | 2001-07-05 | 2004-02-05 | 주식회사 한국화이바 | A making method and apparatus for the glass fiber reinforced polyurethane foam included continuous strand mat |
-
2005
- 2005-03-04 FR FR0502227A patent/FR2882756B1/en not_active Expired - Fee Related
- 2005-10-28 FR FR0511111A patent/FR2882755A1/en active Granted
-
2006
- 2006-02-14 TW TW095104891A patent/TWI292408B/en not_active IP Right Cessation
- 2006-03-02 CN CNB200610058849XA patent/CN100434451C/en not_active Expired - Fee Related
- 2006-03-03 RU RU2006106649/04A patent/RU2317307C2/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001247647A (en) * | 2000-03-08 | 2001-09-11 | Nkk Corp | Raw liquid composition for rigid polyurethane foam, and process for preparation of thermal insulation panel for extremely low temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2882756B1 (en) | 2007-04-27 |
| FR2882755B1 (en) | 2007-04-27 |
| RU2317307C2 (en) | 2008-02-20 |
| FR2882755A1 (en) | 2006-09-08 |
| CN1834130A (en) | 2006-09-20 |
| TW200639202A (en) | 2006-11-16 |
| FR2882756A1 (en) | 2006-09-08 |
| TWI292408B (en) | 2008-01-11 |
| RU2006106649A (en) | 2007-09-10 |
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