EP4103641A1 - Methacrylate copolymers, and uses thereof for manufacturing polyurethane foam - Google Patents
Methacrylate copolymers, and uses thereof for manufacturing polyurethane foamInfo
- Publication number
- EP4103641A1 EP4103641A1 EP20704045.2A EP20704045A EP4103641A1 EP 4103641 A1 EP4103641 A1 EP 4103641A1 EP 20704045 A EP20704045 A EP 20704045A EP 4103641 A1 EP4103641 A1 EP 4103641A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- methacrylate
- copolymer
- diisocyanate
- equal
- foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 75
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 36
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 61
- -1 alkyl methacrylate Chemical group 0.000 claims description 76
- 239000000203 mixture Substances 0.000 claims description 73
- 239000006260 foam Substances 0.000 claims description 58
- 229920005862 polyol Polymers 0.000 claims description 49
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 38
- 238000009413 insulation Methods 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 239000012948 isocyanate Substances 0.000 claims description 20
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000004604 Blowing Agent Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 11
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical class C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002666 chemical blowing agent Substances 0.000 claims description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 claims description 5
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 4
- 238000001601 dielectric barrier discharge ionisation Methods 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims description 3
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000012774 insulation material Substances 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000003365 glass fiber Substances 0.000 description 19
- 150000003077 polyols Chemical class 0.000 description 19
- 238000009472 formulation Methods 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920000582 polyisocyanurate Polymers 0.000 description 3
- 239000011495 polyisocyanurate Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 2
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 2
- YWDFOLFVOVCBIU-UHFFFAOYSA-N 1-dimethoxyphosphorylpropane Chemical compound CCCP(=O)(OC)OC YWDFOLFVOVCBIU-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 229930188104 Alkylresorcinol Natural products 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000012669 compression test Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000004992 toluidines Chemical class 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- NVSXSBBVEDNGPY-UHFFFAOYSA-N 1,1,1,2,2-pentafluorobutane Chemical class CCC(F)(F)C(F)(F)F NVSXSBBVEDNGPY-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
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- CJWBPEYRTPGWPF-UHFFFAOYSA-N 2-[bis(2-chloroethoxy)phosphoryloxy]ethyl bis(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCOP(=O)(OCCCl)OCCCl CJWBPEYRTPGWPF-UHFFFAOYSA-N 0.000 description 1
- QEJPOEGPNIVDMK-UHFFFAOYSA-N 3-bromo-2,2-bis(bromomethyl)propan-1-ol Chemical compound OCC(CBr)(CBr)CBr QEJPOEGPNIVDMK-UHFFFAOYSA-N 0.000 description 1
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- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/03—Mixtures
- F17C2221/032—Hydrocarbons
- F17C2221/033—Methane, e.g. natural gas, CNG, LNG, GNL, GNC, PLNG
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
- F17C2223/0146—Two-phase
- F17C2223/0153—Liquefied gas, e.g. LPG, GPL
- F17C2223/0161—Liquefied gas, e.g. LPG, GPL cryogenic, e.g. LNG, GNL, PLNG
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/01—Applications for fluid transport or storage
- F17C2270/0102—Applications for fluid transport or storage on or in the water
- F17C2270/0105—Ships
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2270/00—Applications
- F17C2270/01—Applications for fluid transport or storage
- F17C2270/0102—Applications for fluid transport or storage on or in the water
- F17C2270/0105—Ships
- F17C2270/0107—Wall panels
Definitions
- the present invention relates to methacrylate-based copolymers, their uses for the preparation of a polyurethane foam.
- the present invention also relates to polyurethane foams comprising said methacrylate copolymers, their manufacturing process and their use as insulating material for liquefied gas transport tanks and particularly LNG tankers.
- insulating elements for liquefied gas transport tanks used in LNG carriers, made up of plywood boxes filled with an insulating material such as foam polyurethane.
- the insulation elements are divided into two insulation barriers called primary and secondary insulation layers. These insulation elements provide satisfactory thermal insulation but however require a significant installation time because the boxes constituting each primary and secondary layer must not only be fixed to the tank but also joined together in order to constitute the various thermal insulation layers. .
- PUR foams have been developed for use as an insulation material. This type of material has satisfactory thermal insulation characteristics for such use and remains easy to handle and install.
- PUR foams cannot, without being incorporated into plywood boxes, be suitable for thermal insulation of LNG tankers, because they do not have sufficient mechanical strength characteristics, in particular of the compressive strength type, both at room temperature and cold, to withstand the pressure of the liquefied gas moving in the tank and sudden temperature variations.
- Patent FR 2 882 756 describes a polyurethane-polyisocyanurate foam reinforced with glass fibers.
- the compressive strength, both at room temperature and cold, of such a foam remains insufficient. It is conventionally known to compensate for weaknesses in mechanical properties such as compression to increase density to obtain a better level of performance. However, the expected effect is not always obtained at room temperature and cold.
- the object of the invention is to provide a foam which avoids the aforementioned drawbacks and which exhibits both good thermal insulation characteristics and mechanical characteristics of the Z type compressive strength (that is to say in the direction of foam thickness) hot (about 20 ° C) and cold (about -170 ° C) improved, these characteristics allowing it in particular to be used as a thermal insulation material for LNG tankers when the foam is fiber-reinforced, or for other applications without fiber with relatively cold temperatures (around -30 ° C).
- the foam thus exhibits, thanks to the use of a methacrylate copolymer of the invention as defined below, both satisfactory thermal insulation characteristics and, surprisingly, mechanical characteristics of resistance to hot compression. and cold particularly advantageous, thus allowing it to be optionally used as an insulating material for an LNG tanker.
- the invention relates to the use of a copolymer prepared from a fluorinated methacrylate (a), a methacrylate (b) containing at least one oxyalkylene group and a methacrylate of alkyl (c) for the preparation of a polyurethane foam.
- the copolymer of the invention is capable of promoting the solubilization of a swelling agent, of stabilizing the cells formed during the preparation of the polyurethane foam and of promoting nucleation.
- the invention relates to the use of the copolymer as defined above or below, in the presence of a blowing agent and optionally of a catalyst, for the preparation of a polyurethane foam, in particular at starting from an isocyanate compound and at least one polyol compound, the swelling agent, the catalyst, the isocyanate compound and the at least one polyol compound being in particular as defined below.
- the fluorinated methacrylate (a) comprises a carbon chain consisting of an alkyl chain extended by a fluorinated chain, in particular perfluorinated, or of a polyoxyfluoroalkylene chain extended by a fluorinated chain, in particular perfluorinated.
- the fluorinated methacrylate (a) is of the following formula (la), or is a mixture of methacrylates of the following formula (la):
- q is a number between 1 and 3, q being in particular equal to 2;
- r is a number between 1 and 7 or between 3 and 7, in particular between 6 and 7, r being in particular equal to
- r can be an integer, and / or q can be an integer. r and / or q can also be rational numbers.
- the methacrylate (a) is then a mixture of methacrylates of formula (la), in which, for each methacrylate of formula (la) of the mixture, q is independently an integer between 1 and 3, q being in particular equal to 2, and r is independently an integer between 3 and 7, r being in particular equal to 6.
- the r value of the mixture corresponds to the average of the r values of each methacrylate of formula (la) of the mixture, weighted by the respective proportions of each, and the same for q
- the fluorinated methacrylate (a) is of the following formula (la ’), or is a mixture of methacrylates of the following formula (la’):
- A is C1-C5 fluoroalkylene, in particular C1-C3 perfluoroalkylene, or C1-C5 alkylene;
- q ’ is a number between 1 and 100, q’ being in particular between 1 and 3;
- r is a number between 1 and 7 or between 3 and 7, r being in particular equal to 3, 4, 5 or 6.
- r can be an integer, and / or q ’can be an integer.
- the methacrylate (a) is then a mixture of methacrylates of formula (la '), in which, for each methacrylate of formula (la') of the mixture, q 'is independently an integer between 1 and 100, q' being in particular between 1 and 3, and r is independently an integer between 3 and 7, r being in particular equal to 3, 4, 5 or 6.
- the r value of the mixture corresponds to the average of the r values of each methacrylate of formula (la ') of the mixture, weighted by the respective proportions of each, and the same for q'.
- the methacrylate (b) containing at least one oxyalkylene group contains at least one oxyethylene group and at least one oxypropylene group.
- the methacrylate (b) containing at least one oxyalkylene group is of the following formula (Ib), or is a mixture of methacrylates of the following formula (Ib):
- p is an integer such that:
- the number of propylene glycol units (-0- ⁇ 3 ⁇ 4- ⁇ ( ⁇ 3 ⁇ 4) -) in the methacrylate (b) is between 0 and 7, in particular between 3 and 7, and preferably between 4 and 6,
- w * p the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54.
- v * p is a rational number.
- the methacrylate (b) is then a mixture of methacrylates of formula (Ib), in which, for each methacrylate of formula (Ib) of the mixture, v * p is independently an integer between 0 and 7, in particular between 3 and 7 , and w * p is independently an integer between 38 and 54.
- the v * p value of the mixture corresponds to the average of the v * p values of each methacrylate of formula (Ib) of the mixture, weighted by the respective proportions of each, and the same for w * p.
- v * p is in particular a rational number between 5 and 5.3
- / or w * p is in particular a rational number between 38 and 54.
- v * p can optionally be an integer, in particular equal to 5, and / or w * p can be an integer, in particular between 38 and 54, w * p being more particularly equal to 42.
- the propylene glycol and ethylene glycol groups have a block or random type distribution.
- the methacrylate (b) containing at least one oxyalkylene group is of the following formula (Ib), or is a mixture of methacrylates of the following formula (Ib):
- the alkyl methacrylate (c) is of the following formula (le), or is a mixture of methacrylates of the following formula (le):
- s is an integer between 0 and 12 or between 2 and 12, s being in particular equal to 3 or 4.
- s can be an integer.
- s can also be a rational number.
- the methacrylate (c) is then a mixture of methacrylates of formula (le), in which, for each methacrylate of formula (le) of the mixture, s is independently an integer between 2 and 12, q 'being in particular equal to 3 or 4.
- the value s of the mixture corresponds to the average of the values of each methacrylate of formula (le) of the mixture, weighted by the respective proportions of each.
- the invention relates to the use of a copolymer of a fluorinated methacrylate (a) comprising a carbon chain consisting of an alkyl chain extended by a fluorinated chain, in particular perfluorinated, of a methacrylate (b ) containing at least one oxyethylene group and at least one oxypropylene group, and an alkyl methacrylate (c) for the preparation of a polyurethane foam.
- a fluorinated methacrylate comprising a carbon chain consisting of an alkyl chain extended by a fluorinated chain, in particular perfluorinated, of a methacrylate (b ) containing at least one oxyethylene group and at least one oxypropylene group
- an alkyl methacrylate (c) for the preparation of a polyurethane foam.
- the invention relates to the use of a copolymer of a fluorinated methacrylate (a) of formula (la), of a methacrylate (b) of formula (Ib) and of a methacrylate of alkyl (c) of formula (Ie) for the preparation of a polyurethane foam.
- the content by weight of monomer (a) is from 12 to 40% relative to said copolymer, and / or the content by weight of monomer (b) is from 20 to 65% relative to said copolymer, and / or the weight content of monomer (c) is from 10 to 65% relative to said copolymer.
- the number-average molar mass is between 6000 and 15000 g / mol.
- the content by weight of monomer (a) is approximately 36% relative to said copolymer
- the content by weight of monomer (b) is approximately 52% relative to said copolymer
- the content by weight in monomer (c) is approximately 12% relative to said copolymer, the number-average molar mass of the copolymer being in particular approximately 7400 g / mol.
- the content by weight of monomer (a) is approximately 15% relative to said copolymer
- the content by weight of monomer (b) is approximately 36% relative to said copolymer
- the content weight of monomer (c) is of approximately 50% relative to said copolymer, the number-average molar mass of the copolymer being in particular approximately 9500 g / mol.
- the content by weight of monomer (a) is approximately 27% relative to said copolymer
- the content by weight of monomer (b) is approximately 62% relative to said copolymer
- the content weight of monomer (c) is approximately 11% relative to said copolymer, the number-average molar mass of the copolymer being in particular approximately 12,700 g / mol.
- the content by weight of monomer (a) is approximately 15% relative to said copolymer
- the content by weight of monomer (b) is approximately 22% relative to said copolymer
- the content weight of monomer (c) is approximately 63% relative to said copolymer, the number-average molar mass of the copolymer being in particular approximately 14,500 g / mol.
- the content by weight of monomer (a) is approximately 15% relative to said copolymer
- the content by weight of monomer (b) is approximately 26% relative to said copolymer
- the content weight of monomer (c) is approximately 59% relative to said copolymer, the number-average molar mass of the copolymer being in particular approximately 10,400 g / mol.
- the copolymer has the following formula (II):
- n the degree of polymerization in number DPn of the copolymer of formula (II), is an integer between 1 and 1000, DPn preferably being between 10 and 100, and very preferably between 10 and 80; and in which, independently of the pattern repeated n times:
- p is an integer such that:
- the number of propylene glycol units (-0-CH 2 -CH (CH 3 ) -) in the methacrylate (b) is between 0 and 7, in particular between 3 and 7, and preferably between 4 and 6,
- w * p the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54.
- q is an integer between 1 and 3, q being in particular equal to 2;
- r is an integer between 1 and 7 or between 3 and 7, in particular between 6 and 7, r being in particular equal to 6;
- s is an integer between 0 and 6 or between 2 and 12, s being in particular equal to 3 or 4.
- the monomers (a), (b) and (c) correspond respectively to the units present x, y, and z times.
- the values v, w, p, q, r and s are chosen as indicated above, regardless of the repeating unit repeated n times. They can thus vary within the ranges defined above from one repetition to another of said unit.
- the values x, y, z, q, r, s, v, w and p and n can be rational numbers.
- the copolymer has the following formula (Ha):
- x, y, z, v, w, p, r and n being as defined above, q being as defined above, and being in particular equal to 2.
- v * p is from 4 to 6
- w * p is a number between 38 and 54
- r being in particular equal to 7
- DPn is an integer preferably between 10 and 100, and very preferably from 10 to 80.
- x is equal to approximately 0.4, and y is equal to approximately 0.1. According to another advantageous embodiment, x is equal to approximately 0.08, and y is equal to approximately
- x is equal to approximately 0.37
- y is equal to approximately 0.16.
- x is equal to approximately 0.07
- y is equal to approximately
- x is equal to approximately 0.077, and y is equal to approximately 0.025.
- the invention relates to a process for preparing polyurethane foam comprising the steps of:
- a catalyst chosen from tin salts, potassium carboxylates and optionally tertiary amines,
- step (ii) allow the mixture obtained in step (i) to solidify, after expansion, so as to form a polyurethane foam.
- the copolymer and the blowing agent as defined above are mixed together prior to step (i), in particular to form an emulsion.
- the polyurethane foam is formed by the reaction of the isocyanate compound and the at least one polyol compound.
- the reaction between these different compounds is likely to take place according to the following four reactions:
- the first reaction is the reaction in which the water molecules react with the NCO groups of the isocyanate compound to form amine groups and CO2 molecules.
- the release of CO2 involves the swelling of the foam.
- the amine groups resulting from the second reaction react with the NCO groups to form urea groups.
- the hydroxyl groups of the polyol compound react with the NCO groups to form urethane groups.
- trimerization the excess NCO groups combine in threes to form isocyanurate groups.
- the first and second reactions compete with the third and fourth reactions as described above.
- the fourth reaction is very minor in the context of the present invention.
- the occurrence, or not, of this reaction can in particular be linked to the value of the isocyanate index, in base 100, as defined below.
- These reactions are manifested on a macroscopic scale by a general swelling of the foam induced by the internal release of CO2 and / or the evaporation of the physical swelling agent, mainly linked to the exotherm of reactions 1 to 3.
- the amount of copolymer is from 0.1 to 10% by mass relative to the at least one polyol compound, in particular from 0.5 to 2% by mass, more particularly around 1.5%. en masse.
- the isocyanate compound is such that its content by mass of isocyanate function is from 100 to 130, and / or its viscosity at 25 ° C is from 200 to 600 mPa.s, and / or its functionality average is 2.5 to 3.5, preferably 2.7 to 3.1.
- the average functionality is defined by the number of average NCO groups present in each molecule of isocyanate compound.
- the isocyanate compound is chosen from diphenylmethylene diisocyanates (MDI), in particular diphenylmethylene 2,2'-diisocyanate (2,2'-MDI), diphenylmethylene 4,4'-diisocyanate ( 4,4'-MDI) and 2,4'-diphenylmethylene diisocyanate (2,4'-MDI); toluene diisocyanates (TDI), in particular toluene 2,6-diisocyanate (2,6-TDI) and toluene 2,4-diisocyanate (2,4-TDI); 4,4'-dibenzyl diisocyanate (4,4'-DBDI); m-xylylene diisocyanate (m-XDI); 2,4'-dibenzyl diiso
- Undistilled or crude methylene diphenyl poly-diisocyanate can be commonly used. This product is commonly available in the market under the brand name Suprasec marketed by Hunstman.
- the at least one polyol compound is such that its hydroxyl group value is from 200 to 500 mg KOH / g, and / or its viscosity at 25 ° C is from 200 to 6000 mPa.s , preferably between 1000 and 3000 mPa.s, and / or its average functionality is between 2 and 6.
- the hydroxyl number (OH number) of polyols is defined by the weight ratio of dosage in mg KOH per g of polyol compounds.
- the at least one polyol compound is chosen from polyesters, sorbitol and its derivatives, polyethers, glycerol and its derivatives, sucrose and its isomers and / or derivatives, and their mixtures, the compound polyol being in particular an aromatic polyester.
- derivatives of a given polyol is understood to mean in particular said polyol, substituted by at least one poly (alkylene oxide) chain, in particular a poly (ethylene oxide and / or propylene oxide) chain.
- This polyol or this mixture of polyols can also be a polyetherpolyol, obtained by polyaddition of propylene oxide (PO) and / or ethylene oxide (EO) to at least one of the polyols as defined above. , according to one of the methods well known in the state of the art.
- PO propylene oxide
- EO ethylene oxide
- polyols derived from sorbitol are, for example, the polyols of the brand Daltolac from Huntsman.
- the OH number is within a range of 150 to 600, preferably between 300 and 600, for example 500 for the polyol of the type derived from sorbitol.
- polyether type polyols are, for example, products derived from glycerol whose side chains are extended by propylene oxide, such as for example those marketed by Shell Chemicals under the brand Caradol, by Dow under the brand name. Voranol, by Carpenter under the Carpol brand or by Coim under the Isoter brand.
- the OH number is within a range of 150 to 600, preferably between 300 and 600, for example 250 for the second polyol.
- polyester-type polyols are aliphatic polyester polyols or preferably aromatic polyester polyols such as phthalic anhydride derivatives.
- the derivatives of diethylene glycol ortho-phthalate for example the products marketed by Stepan under the brand StepanPol are preferably used.
- the OH index is for example 250 for the third polyol.
- the isocyanate index that is to say the molar ratio of NCO functions to OH functions is greater than or equal to 1, in particular greater than 1.
- the foam resulting from this formulation is of the polyurethane (PUR) type and ideally between 105 and 130.
- PUR polyurethane
- the foam resulting from this formulation is of the polyisocyanurate (PIR) type.
- the chemical blowing agent is water.
- the amount of chemical blowing agent is from 0.05 to 5% by mass relative to at least one polyol compound, in particular from 0.05 to 1% by mass, more particularly approximately 0, 2-0.3% by mass.
- the physical swelling agent is chosen from hydrochlorofluorocarbons (HCFC), hydrofluorocarbons (HFC), hydrocarbons (HC) in particular chosen from cyclopentane, n-pentane, iso-pentane and l 'iso-butane, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, 1,1,1,3,3-pentafluorobutane, 1,1 , 1,2,3,3,3-heptafluoropropane and their mixtures, in particular mixtures 1,1,1, 3, 3-pentafluorobutane / l, 1, 1, 2,3, 3, 3-heptafluoropropane.
- the physical blowing agents preferentially used are the non-chlorinated pentafluorobutane compounds and in particular 1,1,1,3,3-pentafluorobutane also known under the name of HFC-365mfc in particular of the Solkane 365 brand marketed by Solvay and HFC -245fc of the Enovate 3000 brand marketed by Honeywell, as well as trans-1-chloro-3,3,3-trifluoropropene also known under the name Solstice Liquid Blowing Agent marketed by Honeywell.
- the preferred amount of physical blowing agent is calculated based on the density of the desired PU foam.
- the amount of physical blowing agent is from 0.1 to 30% by mass relative to the at least one polyol compound, in particular from 5 to 10% by mass, or is approximately 15% by mass. mass.
- the amount of preferred physical blowing agent is from 0.1 to 30% by mass relative to at least one polyol compound, in particular from 5 to 10% by mass, in particular for bulk foams. volume between 150 and 110 kg / m 3 , or approximately 15%, in particular for a foam of approximately 50 kg / m 3 with the addition of approximately 2% of chemical blowing agent.
- the amount of physical swelling agent when it is a pentane derivative as defined in particular above, is from 0.1 to 20% by mass relative to at least one polyol compound, in particular for foams with a density of between 50 to 150 kg / m 3 .
- the physical blowing agent is combined with a chemical blowing agent, in particular water, as a blowing agent.
- the catalyst can be a gelation, expansion, hardening, or even trimerization catalyst, commonly used in the preparation of polyurethane foams.
- catalysts chosen from tin and bismuth salts, potassium carboxylates and optionally tertiary amines
- particularly advantageous catalysts in the context of the present invention are for example tin IV carboxylates, in particular. dibutyltin dilaurate (DBTL) or tin octanoate; and potassium carboxylates such as potassium octanoate.
- DBTL dibutyltin dilaurate
- potassium carboxylates such as potassium octanoate.
- catalysts based on tin and / or of potassium octanoate type are used simultaneously in the absence of catalysts of amine type.
- the tin-based catalysts are for example those of the DBTL type marketed by Evonik under the KOSMOS brand (formerly Air Products under the Dabco brand) and are advantageously used in a proportion of between 0.01 and 1% by mass of the mass. total of the polyols (i.e. of the polyol compound).
- the potassium octanoate type catalysts are for example those marketed by Air Products also under the Dabco brand and are advantageously used in a proportion of between 0.01 and 2% by weight of the total weight of the polyols and preferably between 0.02 and 0.2. %.
- the catalysts of amine type are in particular of alkyl amine type, in particular chosen from bis (2-dimethylaminoethyl) ether, N, N-dimethylaminopropylamine, N, N-dimethylcyclohexylamine, N, N, N ', N', N ”-pentamethyldiethylene -triamine, triethylenediamine, or of the ethanol amine type, in particular chosen from diethanolamine, 2 (2-dimethylamino-ethoxy) ethanol, N- [2- (dimethylamino) ethyl] -N-methylethanolamine, dimethylethanolamine.
- alkyl amine type in particular chosen from bis (2-dimethylaminoethyl) ether, N, N-dimethylaminopropylamine, N, N-dimethylcyclohexylamine, N, N, N ', N', N ”-pentamethyldiethylene -triamine, tri
- Amine-type catalysts are for example those marketed by Evonik under the trademark Polycat or by Huntsman under the trademark JELLCAT (for example DMCHA or PMDETA) and are advantageously used in a proportion of between 0.01 and 1% by mass of the mass. total polyols.
- the catalyst is chosen from triethylenediamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, 1,4-diazabicyclo (2,2,2) - octane, and dibutyltin dilaurate, the catalyst being in particular dilaurate of dibutyltin.
- the catalysts are used to accelerate one or more of the various reaction steps mentioned above.
- the tin catalysts and the tertiary amines act preferentially on stages 1 to 3, while the catalysts based on potassium octanoate preferentially act on the trimerization reaction (stage 4).
- a surfactant can be used in the context of the present invention in addition to the copolymer as defined above.
- surfactant examples include siloxane-oxyalkylene copolymers and other organopolysiloxanes.
- a flame retardant can be used within the scope of the present invention to further limit the flammability of the foam.
- Flame retardants are, for example, brominated ethers (Ixol B 251), brominated alcohols such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol, as well as chlorinated phosphates such as tris ( 2-chloroethyl) phosphate, tris (2-chloroisopropyl) phosphate (TCPP), tris (l, 3-dichloroisopropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetrakis (2-chloroethyl) ethylenediphosphate, or their mixtures.
- brominated ethers Ixol B 251
- brominated alcohols such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol
- chlorinated phosphates such as tris ( 2-chloroethyl) phosphate, tri
- inorganic flame retardants such as red phosphorus, preparations comprising red phosphorus, expandable graphite, aluminum oxide hydrate, aluminum trioxide, antimony, arsenic oxide, ammonium polyphosphate and calcium sulphate or cyanuric acid derivatives such as melamine or mixtures of two or more flame retardants such as ammonium polyphosphates and melamine.
- DEEP diethyl ethanephosphonate
- TEP triethyl phosphate
- DMPP dimethyl propylphosphonate
- DPC diphenyl cresyl phosphate
- the flame retardant is of the non-halogenated type.
- the incorporation of this type of flame retardant in a composition has no harmful action for the environment.
- the flame retardant is preferably used in proportions of approximately 5% to 20% by mass of the total mass of at least the polyol compound.
- additives such as fillers, crosslinking agents, colorants can advantageously be added to the formulation.
- the foam obtained at the end of step (ii) has a density of between 20 and 250 kg / m 3.
- the mixture obtained during step (i) is, prior to step (ii), brought into contact with a stack of mats of glass fibers optionally associated with one another by a binder, in order to obtain a stack of mats of glass fibers impregnated with said mixture obtained during step (i).
- the expansion and solidification of said mixture leads to the formation of a block of reinforced foam containing the stack of mats of glass fibers.
- said mats of glass fibers have a basis weight of between 300 to 900 g / m 2 , more advantageously, between 300 and 600 g / m 2 .
- the glass fibers preferably constitute from 6 to 13%, preferably from 8 to 12% by mass relative to the total mass of the block of reinforced foam.
- the glass fiber mats consist of glass fibers with a linear density of 10 to 60 Tex, preferably 20 to 40 Tex.
- the glass fiber mats preferably used for the present invention consist of continuous strand glass mats in particular sold by Owens Corning under the Unifilo brand or marketed by 3B under the CFM brand.
- the number of glass fiber mats varies, for example, from 3 to 20.
- the foam obtained at the end of step (ii) is in the form of a block of foam with a thickness of between 10 and 40 cm.
- a sufficient amount of formulation, optionally of glass fiber mats, and of blowing agent will be defined so as to prepare a block of foam with a desired thickness.
- the advantage of preparing foam blocks with a thickness of 20 cm is that, after deburring, the foam blocks can directly be used as a secondary insulating layer of an LNG carrier, which usually has a thickness of 18 cm, and / or cut transversely at the level of their half to directly form a layer of primary LNG carrier insulation, which usually has a thickness of 9 cm.
- a block of foam prepared with a thickness of 30 cm can, after deburring and cutting to a third of its thickness, simultaneously form a primary insulation layer of 9 cm and a secondary insulation layer of 18 cm.
- Others configurations to form blocks are possible such as the association of a primary insulation layer of 10 cm with a secondary insulation layer of 30 cm, or a primary insulation layer of 10 cm with a layer 38 cm secondary insulation layer, or a 15 cm primary insulation layer with a 25 cm secondary insulation layer.
- the width and length of the blocks is for example 100 cm by 300 cm.
- the process for preparing polyurethane foam advantageously takes place as follows.
- the different components of the formulation can be mixed in a low pressure rigid foam mixer type mixer.
- the blowing agent and the various additives are generally introduced into the container comprising the polyol compound (s). Then the mixture comprising the polyol compound (s) and the various additives are then mixed with the isocyanate compound and the formulation resulting from this mixture is poured onto a surface, into a mold, or onto a stack of several mats of glass fibers.
- the blowing agent and certain additives or catalysts can be added to the composition after mixing the polyol compound (s) and the isocyanate compound.
- the deposition rate is calculated according to the knowledge of those skilled in the art as a function of the speed of the conveyor, the height of the block and the desired density.
- the foam blocks can crosslink for a period of between 5 and 30 min.
- the foam blocks can crosslink, in particular completely, and cool to room temperature for approximately 48 to 96 hours, before cutting.
- This single cutting step from a single block of foam makes it possible to simultaneously obtain a primary layer and a secondary insulation layer, which not only saves material, because less deburring losses are produced, but also a saving of time, because only one step is necessary for the production of the two layers of thermal insulation.
- the invention relates to a polyurethane foam comprising a copolymer of a fluorinated methacrylate (a), of a methacrylate (b) containing at least one oxyalkylene group and of an alkyl methacrylate (c), said copolymer being as described above.
- the polyurethane foam comprises mats of glass fibers.
- the polyurethane foam is devoid of mats of glass fibers.
- the invention relates to a composition, in particular an emulsion, comprising a copolymer of a fluorinated methacrylate (a), of a methacrylate (b) containing at least one oxyalkylene group and of an alkyl methacrylate (c ), said copolymer being as described above, and a physical blowing agent, as defined above.
- the invention relates to a polyurethane foam capable of being obtained by the process as defined above.
- the invention relates to the use of a foam as defined above in the thermal insulation of liquefied gas transport tanks, and in particular of LNG tankers.
- the invention relates to a copolymer of a fluorinated methacrylate (a), of a methacrylate (b) containing at least one oxyalkylene group and of an alkyl methacrylate (c), said alkyl being a chain linear or branched or cyclic alkyl having 1 to 12 carbon atoms.
- the invention relates to a copolymer as defined in the embodiments mentioned above.
- the fluorinated methacrylate (a) comprises a carbon chain consisting of an alkyl chain extended by a fluorinated chain, in particular perfluorinated, the fluorinated methacrylate (a) being in particular of formula (Ia) or ( the following '), or is a mixture of methacrylates of the following formula (la) or (la'):
- A is C1-C5 fluoroalkylene, in particular C1-C3 perfluoroalkylene, or C1-C5 alkylene ;
- q is a number between 1 and 3, q being in particular equal to 2;
- q is a number between 1 and 100, q" preferably being between 1 and 3;
- the methacrylate (b) containing at least one oxyalkylene group contains at least one oxyethylene group and at least one oxypropylene group, the methacrylate (b) containing at least one oxyalkylene group being in particular of the following formula (Ib) , or being a mixture of methacrylates of the following formula (Ib):
- p is an integer such that:
- the number of propylene glycol units (-0- ⁇ 3 ⁇ 4- ⁇ ( ⁇ 3 ⁇ 4) -) in the methacrylate (b) is between 0 and 7, in particular between 3 and 7, and preferably between 4 and 6,
- w * p the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54.
- v * p is a rational number.
- the methacrylate (b) is then a mixture of methacrylates of formula (Ib), in which, for each methacrylate of formula (Ib) of the mixture, v * p is independently an integer between 0 and 7, in particular between 3 and 7 , and w * p is independently an integer between 38 and 54.
- the v * p value of the mixture corresponds to the average of the v * p values of each methacrylate of formula (Ib) of the mixture, weighted by the respective proportions of each, and the same for w * p.
- v * p is in particular a rational number between 5 and 5.3
- / or w * p is in particular a rational number between 38 and 54.
- v * p can optionally be an integer, in particular equal to 5, and / or w * p can be an integer, in particular between 38 and 54, w * p being more particularly equal to 42.
- the alkyl methacrylate (c) has the following formula (le):
- s is an integer between 0 and 12 or between 2 and 6, s being in particular equal to 3 or 4.
- the number-average molar mass is between 6000 and 15000 g / mol.
- the copolymer has the following formula (II):
- n the degree of polymerization in number DPn of the copolymer of formula (II), is an integer between 1 and 1000, DPn preferably being between 10 and 100, and very preferably between 10 and 80;
- p is an integer such that:
- the number of propylene glycol units (-0-CH 2 -CH (CH 3 ) -) in the methacrylate (b) is between 0 and 7, in particular between 3 and 7, and preferably between 4 and 6,
- w * p the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54;
- q is an integer between 1 and 3, q being in particular equal to 2;
- r is an integer between 1 and 7 or between 3 and 7, in particular between 6 and 7, r being in particular equal to 6;
- s is an integer between 0 and 6 or between 2 and 12, s being in particular equal to 3 or 4;
- x, y, z, v, w, p, r and n being as defined above, q being as defined above, and being in particular equal to 2.
- v * p is equal to 5
- w * p is equal to 42 and r is equal to 6 or 7
- DPn being in particular equal to about 15 or about 45;
- x is about 0.4, and y is about 0.1, the number average molar mass in particular being about 7,400; or
- x is about 0.08, and y is about 0.02, the number-average molar mass in particular being about 9,500.
- v * p is equal to approximately 5.1
- w * p is equal to approximately 46.2 and r is equal to 6
- DPn being in particular equal to approximately 20
- the number-average molar mass being in particular approximately 12,800; and / or x is about 0.37, and y is about 0.16.
- v * p is equal to approximately 5.2, w * p is equal to approximately 50 and r is equal to 6, DPn being in particular equal to approximately 69, the number-average molar mass being in particular approximately 14,500; and or
- x is about 0.07, and y is about 0.02.
- v * p is equal to approximately 5.2, w * p is equal to approximately 50 and r is equal to 6, DPn being in particular equal to approximately 46, the number-average molar mass being in particular approximately 10,400; and or
- x is about 0.077, and y is about 0.025.
- the term “about” refers to a range of values of ⁇ 10% of a specific value.
- the expression “about 20” includes values of 20 ⁇ 10%, or values from 18 to 22.
- the percentages refer to percentages by weight relative to the total weight of the formulation, unless otherwise indicated.
- ranges of values in the form of "x-y” or “from x to y” or “between x and y” include the x and y bounds as well as the integers between these bounds.
- “1-5”, or “from 1 to 5" or “between 1 and 5" denote the integers 1, 2, 3, 4 and 5.
- Preferred embodiments include each integer taken individually in the range of values, as well as any sub-combinations of these integers.
- preferred values for "1-5" may include the integers 1, 2, 3, 4, 5, 1-2, 1-3, 1-4, 1-5, 2-3, 2 -4, 2-5, etc.
- copolymer of a methacrylate (a), of a methacrylate (b) and of a methacrylate (c) is meant a polymer resulting from the copolymerization of three types of monomer, namely the monomers (a), (b), and (c). This copolymerization can be done from a mixture of monomers comprising the monomers (a), (b), and (c), or from a mixture of monomers consisting of the monomers (a), (b), and (vs).
- At least one polyol compound is meant a polyol compound or a mixture of polyol compounds.
- this percentage is given relative to the polyol compound when there is only one, or relative to the mixture of polyols when there is one. two or more.
- indices x, y, z, v, w, p, q, r and s may be different from one occurrence to another of the pattern repeated n times.
- the indices x, y, z, v, w, p, q, r and s have the same value, for any occurrence of the pattern repeated n times.
- alkyl is meant, for each occurrence, a linear or branched or cyclic alkyl chain having from 1 to 12 carbon atoms.
- fluorinated chain is meant a linear or branched or cyclic alkyl chain having from 1 to 12 carbon atoms of which at least one of the hydrogen atoms is substituted by a fluorine.
- fluoroalkylene is meant an alkylene of which at least one of the hydrogen atoms is substituted by a fluorine.
- perfluorinated chain is meant a linear or branched or cyclic alkyl chain having 1 to 12 carbon atoms, all of the hydrogen atoms of which are substituted by fluorine.
- molar fractions of monomer (a), (b) and (c) in the copolymer is meant the ratio between the number of moles of monomer (a), (b) or (c ) respectively, on the total number of moles of monomer (i.e. the number of moles of monomer (a), (b) and (c).
- x + y + z 1.
- degree of polymerization DPn of the copolymer of formula (II) means the total number of monomer units, that is to say the sum of the monomer units corresponding to the monomers (a), (b), and ( vs).
- v and w are molar proportions "
- v and w relate to the mixture of the monomer corresponding to the propylene glycol unit (-O-CH2- CH (CH3) -) and of the monomer corresponding to the ethylene glycol unit (-O-CH2-CH2) -) capable of making it possible to obtain the methacrylate of formula (Ib) or of the mixture of methacrylates of formula (Ib).
- copolymers of the present invention can be synthesized by a process of polymerization in solution, or in emulsion, or in suspension. They can be in the form of random polymers, gradient polymers, block polymers. They can be obtained by conventional radical polymerization, controlled radical polymerization (RAFT, ATRP, NMP, RITP, etc.), or group transfer polymerization.
- Figure 1 illustrates the compressive strength at 23 ° C, as a function of density, of foams as mentioned in the examples.
- FIG. 3 is a photograph of the polyurethane foam E1 as defined in Example 2, which enabled the measurements relating to the E1 foam recorded in Table 3 of said Example 2.
- Figure 4 is a photograph of the polyurethane foam E2 as defined in Example 2, which allowed the measurements relating to the E2 foam recorded in Table 3 of said Example 2.
- Figure 5 is a photograph of the E3 polyurethane foam as defined in Example 2, which allowed the measurements relating to the E3 foam recorded in Table 3 of said Example 2.
- Fluorinated methacrylate (a), in particular of formula (la), methacrylate (b) containing at least one oxyalkylene group, in particular of formula (Ib), and alkyl methacrylate (c), in particular of formula ( le), are diluted in 2-butanone as solvent (dry extract - 20%).
- the radical initiator used to initiate the polymerization is GAIBN (Azobisisobutyronitrile - 2.5 to 3% by mass).
- the reaction medium is placed under an inert atmosphere by bubbling argon for 30 min.
- the polymerization reaction takes place at 70 ° C until complete conversion.
- the methacrylic polymer is obtained by precipitation in pentane and evaporation of the solvents under industrial vacuum.
- the fluorinated methacrylate (a) is in particular tridecafluorooctyl methacrylate ([2144-53-8]).
- the alkyl methacrylate (c) is in particular butyl methacrylate.
- the methacrylate (b), before acylation, is in particular a Polyglykol compound sold by Clariant, in particular Polyglycol MA 350, MA 750, MA 1000 M70, MA 2000 M55, MA 3000, or MA 50000 M50; or the compound Visiomer MPEG 2005 MA W (Evonik).
- component 1 of Table 2 The different elements of component 1 of Table 2 are mixed uniformly. Components 3 and then 2 are then added to component 1.
- the formulations thus obtained are cast on a glass fiber mat so that the reinforced polyurethane foam has a fiber content of 9% and a density of 130 kg / m. 3 .
- the weight per unit area, the rate of binder and the number of mats of glass fibers are respectively 450 g / m 2 , 0.8% and 8.
- Three polyurethane foams named El, E2 and E3, are obtained using the copolymers of the invention, S 1 / S2 and S3, respectively, and a commercial copolymer not object of the invention.
- polyurethane foams of the invention can be obtained by any process well known to those skilled in the art from the formulations indicated in Table 2. In particular, they can be obtained by a continuous process. In this case, for example:
- the raw materials are stored, liquid, in large stainless steel tanks. These tanks are equipped with agitators to keep the materials fluid.
- a metering device is attached to the reservoirs so that the appropriate amount of reactive material can be pumped. The relationship between the different components is strictly controlled;
- the various compounds are passed through a heat exchanger as they are pumped through the pipes.
- the exchanger adjusts the temperature to the reaction temperature.
- a polymer distribution head At the end of the pipes is a polymer distribution head where the chemical reactions mentioned above start;
- the distribution head is hung above the treatment line.
- a roll of kraft paper is wound up at the start of the processing line. This paper is moved along a conveyor and brought under the distribution head; As the paper passes, polyurethane is deposited on it. Polyurethane increases in volume thanks to blowing agents;
- a second, upper layer of paper can be applied to the polyurethane foam.
- side papers can also be rolled in the process.
- the rigid foam is passed through a series of panels which control the width and height of the foam. When they pass through this section of the production line, they are usually dried;
- the foam insulation is cut with an automatic saw to the desired length.
- the cell size of the foams obtained is given in the following table.
- This example illustrates the results of tests in Z compression (that is to say in the thickness of the reinforced foam), hot and cold, which simulate the pressure at the side walls of the tanks, generated by the movement of liquefied gas within the tank of an LNG carrier, for example.
- Z-compression tests are carried out according to standard M3007: ISO 844 (or equivalent).
- the compressive strength is evaluated by measuring the pressure applied vertically to the surface of each of the samples, as a function of the displacement of the surface from its initial position in the direction of the thickness of each sample. These measurements are plotted on a so-called compressive strength curve (not shown).
- the maximum pressure applied before rupture of the structure of the reinforced foam corresponds to the maximum compressive strength which is referred to here as Z compression.
- foams of the invention are more resistant to compression, both at room temperature and in cold conditions, than current foams, in particular E3 foam.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
Claims
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Application Number | Priority Date | Filing Date | Title |
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FR1901617A FR3092837B1 (en) | 2019-02-18 | 2019-02-18 | METHACRYLATE COPOLYMERS, AND THEIR USES FOR THE PREPARATION OF POLYURETHANE FOAM |
PCT/EP2020/053956 WO2020169482A1 (en) | 2019-02-18 | 2020-02-14 | Methacrylate copolymers, and uses thereof for manufacturing polyurethane foam |
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EP4103641A1 true EP4103641A1 (en) | 2022-12-21 |
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EP (1) | EP4103641A1 (en) |
KR (1) | KR20210132653A (en) |
CN (1) | CN113423773B (en) |
FR (1) | FR3092837B1 (en) |
WO (1) | WO2020169482A1 (en) |
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WO2021233765A1 (en) * | 2020-05-18 | 2021-11-25 | Basf Se | A polyurethane-forming system, a composite comprising the polyurethane-forming system and a fiber-reinforced material, a process for the production of the composite, and the use of the composite |
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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US573327A (en) | 1896-12-15 | Needle-throat for sewing-machines | ||
US248721A (en) | 1881-10-25 | William deiscoll | ||
JPS5475614A (en) * | 1977-11-28 | 1979-06-16 | Kawasaki Heavy Ind Ltd | Method of working heat insulating polyurethane foam of low temperature liquefied gas reservoir |
FR2599468B1 (en) | 1986-06-03 | 1988-08-05 | Technigaz | THERMALLY INSULATING WALL STRUCTURE OF WATERPROOF TANK |
FR2691520B1 (en) | 1992-05-20 | 1994-09-02 | Technigaz Ste Nle | Prefabricated structure for forming watertight and thermally insulating walls for containment of a fluid at very low temperature. |
DE19639121A1 (en) * | 1996-09-24 | 1998-03-26 | Basf Ag | Process for the production of rigid polyurethane foams |
DE10022370A1 (en) * | 2000-05-08 | 2001-11-15 | Bayer Ag | Stabilizer for polyurethane foam, for use as e.g. padding material in cars and furniture, is obtained by copolymerizing a special double bond-containing polyether-polyol with a fluoro-acrylate compound |
KR101029225B1 (en) * | 2003-11-26 | 2011-04-14 | 닛폰 하츠죠 가부시키가이샤 | Flexible polyurethane foam, process for producing the same, and automotive sheet employing the same |
FR2882756B1 (en) | 2005-03-04 | 2007-04-27 | Gaz Transp Et Technigaz Soc Pa | FOAM OF POLYURETHAN-POLYISOCYANURATE REINFORCED WITH GLASS FIBERS |
RU2609019C2 (en) * | 2011-10-14 | 2017-01-30 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Hybrid polyester-polyether polyols for improved demold expansion in polyurethane rigid foams |
US9957339B2 (en) * | 2015-08-07 | 2018-05-01 | Rohm And Haas Electronic Materials Llc | Copolymer and associated layered article, and device-forming method |
KR102158070B1 (en) * | 2015-10-02 | 2020-09-21 | 더 케무어스 컴퍼니 에프씨, 엘엘씨 | Hydrophobic extenders in non-fluorinated surface effect coatings |
CN105647087B (en) * | 2016-01-13 | 2017-11-10 | 3M创新有限公司 | Curable compositions, contact adhesive, adhesive tape, adhesive article |
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2019
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CN113423773B (en) | 2022-10-14 |
FR3092837A1 (en) | 2020-08-21 |
KR20210132653A (en) | 2021-11-04 |
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