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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Abstract
The invention relates to methacrylate-based copolymers and the uses thereof for manufacturing a polyurethane foam. The invention also relates to polyurethane foams comprising said methacrylate copolymers, to a process for manufacturing same, and to the use thereof as insulation material for liquefied gas transport tanks and in particular tanks on methane carriers.
Description
COPOLYMERES METHACRYLATES, ET LEURS UTILISATIONS POUR LA PREPARATION DE MOUSSE POLYURETHANE METHACRYLATE COPOLYMERS, AND THEIR USES FOR THE PREPARATION OF POLYURETHANE FOAM
La présente invention concerne des copolymères base méthacrylates, leurs utilisations pour la préparation d’une mousse polyuréthane. La présente invention concerne également des mousses polyuréthane comprenant lesdits copolymères méthacrylates, leur procédé de fabrication et leur utilisation comme matériau d'isolation des cuves de transport de gaz liquéfié et particulièrement des cuves de méthaniers. 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.
On connaît, notamment par les brevets européens n° 248 721 et n° 573 327, des éléments d'isolation de cuves de transport de gaz liquéfié, utilisés dans des méthaniers, composés de caissons de bois contreplaqué remplis d'un matériau isolant type mousse de polyuréthane. Les éléments d'isolation sont répartis en deux barrières d'isolation dites couches primaire et secondaire d'isolation. Ces éléments d'isolation confèrent une isolation thermique satisfaisante mais nécessitent cependant un temps de pose conséquent car les caissons constituant chaque couche primaire et secondaire doivent être non seulement fixées à la cuve mais également solidarisés entre eux afin de constituer les différentes couches d'isolation thermique. We know, in particular from European patents No. 248,721 and No. 573,327, 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. .
Par ailleurs, de nombreuses mousses rigides de type polyuréthane (PUR) ont été développées pour des utilisations comme matériau d'isolation. Ce type de matériau présente des caractéristiques d'isolation thermique satisfaisantes pour une telle utilisation et demeure facile à manipuler et à installer. Cependant, les mousses PUR ne peuvent pas, sans être incorporées à des caissons de bois contreplaqué, convenir à l'isolation thermique des cuves de méthaniers, car elles ne présentent pas des caractéristiques de résistance mécanique suffisantes, notamment du type résistance à la compression, à la fois à température ambiante et à froid, pour résister à la pression du gaz liquéfié en mouvement dans la cuve et aux variations brutales de température. Le brevet FR 2 882 756 décrit une mousse polyuréthane-polyisocyanurate renforcée de fibres de verre. Cependant, la résistance à la compression, à la fois à température ambiante et à froid, d’une telle mousse reste insuffisante. Il est connu classiquement pour compenser des faiblesses de propriétés mécaniques comme la compression d’augmenter la densité pour obtenir un niveau de performance meilleur. Néanmoins, l’effet escompté n’est pas obtenu systématiquement à température ambiante et à froid. Furthermore, many rigid polyurethane (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. However, 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. However, 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.
L'invention a pour but de proposer une mousse qui évite les inconvénients précités et qui présente à la fois des bonnes caractéristiques d'isolation thermique et des caractéristiques mécaniques du type résistance à la compression en Z (c'est-à-dire dans le sens de l'épaisseur de la mousse) à chaud (environ 20°C) et à froid (environ -170°C) améliorées, ces caractéristiques
lui permettant notamment d'être utilisée comme matériau d'isolation thermique des cuves de méthaniers lorsque la mousse est fibrée, ou pour d’autres applications sans fibre avec des températures relativement froides (environ -30°C). 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).
La mousse présente ainsi, grâce à futilisation d’un copolymère méthacrylates de l'invention tel que défini ci-après, à la fois des caractéristiques d'isolation thermique satisfaisantes et, de manière surprenante, des caractéristiques mécaniques de résistance à la compression à chaud et à froid particulièrement avantageuses, lui permettant ainsi d'être éventuellement utilisée comme matériau d'isolation de cuve de méthanier. 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.
Ainsi, selon un premier aspect, l’invention concerne l’utilisation d’un copolymère préparé à partir d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c) pour la préparation d’une mousse polyuréthane. Sans vouloir se limiter à une quelconque théorie, le copolymère de l’invention est susceptible de favoriser la solubilisation d’un agent gonflant, de stabiliser les cellules formées lors de la préparation de la mousse polyuréthane et de favoriser la nucléation. Thus, according to a first aspect, 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. Without wishing to be limited to any one theory, 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.
Selon un mode de réalisation particulier, l’invention concerne l’utilisation du copolymère tel que défini précédemment ou plus bas, en présence d’un agent gonflant et éventuellement d’un catalyseur, pour la préparation d’une mousse polyuréthane, en particulier à partir d’un composé isocyanate et d’au moins un composé polyol, l’agent gonflant, le catalyseur, le composé isocyanate et le au moins un composé polyol étant notamment tels que définis plus loin. According to a particular embodiment, 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.
Selon un mode de réalisation particulier, le méthacrylate fluoré (a) comprend une chaîne carbonée constituée d’une chaîne alkyle prolongée d’une chaîne fluorée, notamment perfluorée, ou d’une chaîne polyoxyfluoroalkylène prolongée d’une chaîne fluorée, notamment perfluorée. Selon un mode de réalisation plus particulier, le méthacrylate fluoré (a) est de formule (la) suivante, ou est un mélange de méthacrylates de formule (la) suivante : According to a particular embodiment, 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. According to a more particular embodiment, the fluorinated methacrylate (a) is of the following formula (la), or is a mixture of methacrylates of the following formula (la):
dans laquelle : in which :
q est un nombre entre 1 et 3, q étant en particulier égal à 2 ; q is a number between 1 and 3, q being in particular equal to 2;
r est un nombre entre 1 et 7 ou entre 3 et 7, notamment entre 6 et 7, r étant en particulier égal àr is a number between 1 and 7 or between 3 and 7, in particular between 6 and 7, r being in particular equal to
6. 6.
r peut être un nombre entier, et/ou q peut être un nombre entier.
r et/ou q peuvent également être des nombres rationnels. Le méthacrylate (a) est alors un mélange de méthacrylates de formule (la), dans lesquels, pour chaque méthacrylate de formule (la) du mélange, q est indépendamment un nombre entier entre 1 et 3, q étant en particulier égal à 2, et r est indépendamment un nombre entier entre 3 et 7, r étant en particulier égal à 6. Ainsi, la valeur r du mélange correspond à la moyenne des valeurs r de chaque méthacrylate de formule (la) du mélange, pondérée par les proportions respectives de chacun, et de même pour q· 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. Thus, 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
Selon un mode de réalisation plus particulier, le méthacrylate fluoré (a) est de formule (la’) suivante, ou est un mélange de méthacrylates de formule (la’) suivante : According to a more particular embodiment, the fluorinated methacrylate (a) is of the following formula (la ’), or is a mixture of methacrylates of the following formula (la’):
dans laquelle : in which :
A est un fluoroalkylène en C1-C5, en particulier un perfluoroalkylène en C1-C3, ou un alkylène en C1-C5 ; A is C1-C5 fluoroalkylene, in particular C1-C3 perfluoroalkylene, or C1-C5 alkylene;
q’ est un nombre entre 1 et 100, q’ étant en particulier compris entre 1 et 3 ; q ’is a number between 1 and 100, q’ being in particular between 1 and 3;
r est un nombre entre 1 et 7 ou entre 3 et 7, r étant en particulier égal à 3, 4, 5 ou 6. 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 peut être un nombre entier, et/ou q’ peut être un nombre entier. r can be an integer, and / or q ’can be an integer.
r et/ou q’ peuvent également être des nombres rationnels. Le méthacrylate (a) est alors un mélange de méthacrylates de formule (la’), dans lesquels, pour chaque méthacrylate de formule (la’) du mélange, q’ est indépendamment un nombre entier entre 1 et 100, q’ étant en particulier compris entre 1 et 3 , et r est indépendamment un nombre entier entre 3 et 7, r étant en particulier égal à 3, 4, 5 ou 6. Ainsi, la valeur r du mélange correspond à la moyenne des valeurs r de chaque méthacrylate de formule (la’) du mélange, pondérée par les proportions respectives de chacun, et de même pour q’. Selon un mode de réalisation particulier, le méthacrylate (b) contenant au moins un groupe oxyalkylène contient au moins un groupe oxyéthylène et au moins un groupe oxypropylène. 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 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. Thus, 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'. According to a particular embodiment, the methacrylate (b) containing at least one oxyalkylene group contains at least one oxyethylene group and at least one oxypropylene group.
Selon une variante de réalisation, le méthacrylate (b) contenant au moins un groupe oxyalkylène est de formule (Ib) suivante, ou est un mélange de méthacrylates de formule (Ib) suivante : According to an alternative embodiment, 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):
dans laquelle : in which :
B est un atome d’hydrogène, ou un alkyle linéaire ou ramifié en Ci à C4, en particulier le méthyle, ou un groupe acétate d’alkyle de formule -C(=0)-D, où D est un alkyle linéaire ou ramifié en Ci à C4, en particulier le méthyle, B is a hydrogen atom, or a linear or branched C1 to C 4 alkyl, in particular methyl, or an alkyl acetate group of the formula -C (= 0) -D, where D is linear alkyl or branched in C 1 to C 4 , in particular methyl,
à l’échelle du mélange, v et w sont des proportions molaires comprises entre 0 et 1, telles que v+w=l, avec w ¹ 0, et éventuellement v ¹0, on the scale of the mixture, v and w are molar proportions between 0 and 1, such that v + w = l, with w ¹ 0, and optionally v ¹0,
p est un nombre entier tel que : p is an integer such that:
v*p, le nombre d’unités propylène glycol (-0-ϋ¾-ϋί(ϋ¾)-) dans le méthacrylate (b), est compris entre 0 et 7, en particulier entre 3 et 7, et de préférence entre 4 et 6, v * p, the number of propylene glycol units (-0-ϋ¾-ϋί (ϋ¾) -) in the methacrylate (b) is between 0 and 7, in particular between 3 and 7, and preferably between 4 and 6,
w*p, le nombre d’unités éthylène glycol (-O-CH2-CH2)-) dans le méthacrylate (b), est compris entre 38 et 54. w * p, the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54.
En particulier, v*p est un nombre rationnel. Le méthacrylate (b) est alors un mélange de méthacrylates de formule (Ib), dans lesquels, pour chaque méthacrylate de formule (Ib) du mélange, v*p est indépendamment un nombre entier entre 0 et 7, en particulier entre 3 et 7, et w*p est indépendamment un nombre entier entre 38 et 54. Ainsi, la valeur v*p du mélange correspond à la moyenne des valeurs v*p de chaque méthacrylate de formule (Ib) du mélange, pondérée par les proportions respectives de chacun, et de même pour w*p. Toujours dans ce cas, v*p est en particulier un nombre rationnel compris entre 5 et 5,3, et/ou w*p est en particulier un nombre rationnel compris entre 38 et 54. In particular, 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. Thus, 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. Still in this case, v * p is in particular a rational number between 5 and 5.3, and / or w * p is in particular a rational number between 38 and 54.
v*p peut éventuellement être un nombre entier, en particulier égal à 5, et/ou w*p peut être un nombre entier, en particulier compris entre 38 et 54, w*p étant plus particulièrement égal à 42. A l’échelle d’une molécule, les groupements propylène glycol et éthylène glycol ont une répartition de type bloc ou statistique. 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. On the scale of a molecule, the propylene glycol and ethylene glycol groups have a block or random type distribution.
Selon un mode de réalisation encore plus particulier, le méthacrylate (b) contenant au moins un groupe oxyalkylène est de formule (Ib) suivante, ou est un mélange de méthacrylates de formule (Ib) suivante : According to an even more particular embodiment, 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):
dans laquelle v, w, p et D sont tels que définis précédemment, D étant en particulier un méthyle. Selon un mode de réalisation particulier, le méthacrylate d’alkyle (c) est de formule (le) suivante, ou est un mélange de méthacrylates de formule (le) suivante :
in which v, w, p and D are as defined above, D being in particular methyl. According to a particular embodiment, the alkyl methacrylate (c) is of the following formula (le), or is a mixture of methacrylates of the following formula (le):
dans laquelle s est un nombre entier entre 0 et 12 ou entre 2 et 12, s étant en particulier égal à 3 ou 4. in which s is an integer between 0 and 12 or between 2 and 12, s being in particular equal to 3 or 4.
s peut être un nombre entier. s can be an integer.
s peut également être un nombre rationnel. Le méthacrylate (c) est alors un mélange de méthacrylates de formule (le), dans lesquels, pour chaque méthacrylate de formule (le) du mélange, s est indépendamment un nombre entier entre 2 et 12, q’ étant en particulier égal à 3 ou 4. Ainsi, la valeur s du mélange correspond à la moyenne des valeurs de chaque méthacrylate de formule (le) du mélange, pondérée par les proportions respectives de chacun. Selon un mode de réalisation particulier, l’invention concerne rutilisation d’un copolymère d’un méthacrylate fluoré (a) comprenant une chaîne carbonée constituée d’une chaîne alkyle prolongée d’une chaîne fluorée, notamment perfluorée, d’un méthacrylate (b) contenant au moins un groupe oxyéthylène et au moins un groupe oxypropylène, et d’un méthacrylate d’alkyle (c) pour la préparation d’une mousse polyuréthane. 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. Thus, 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. According to a particular embodiment, 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.
Selon un mode de réalisation plus particulier, l’invention concerne l’utilisation d’un copolymère d’un méthacrylate fluoré (a) de formule (la), d’un méthacrylate (b) de formule (Ib) et d’un méthacrylate d’alkyle (c) de formule (le) pour la préparation d’une mousse polyuréthane. Selon un mode de réalisation particulier, la teneur pondérale en monomère (a) est comprise de 12 à 40 % par rapport audit copolymère, et/ou la teneur pondérale en monomère (b) est comprise de 20 à 65 % par rapport audit copolymère, et/ou la teneur pondérale en monomère (c) est comprise de 10 à 65 % par rapport audit copolymère. According to a more particular embodiment, 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. According to a particular embodiment, 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.
Selon un mode de réalisation particulier, la masse molaire moyenne en nombre est comprise entre 6000 et 15000 g/mol. According to a particular embodiment, the number-average molar mass is between 6000 and 15000 g / mol.
Selon un mode de réalisation plus particulier, la teneur pondérale en monomère (a) est d’ environ 36 % par rapport audit copolymère, la teneur pondérale en monomère (b) est d’environ 52 % par rapport audit copolymère, et la teneur pondérale en monomère (c) est d’environ 12 % par rapport audit copolymère, la masse molaire moyenne en nombre du copolymère étant notamment d’environ 7400 g/mol. According to a more particular embodiment, 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, and 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.
Selon un autre mode de réalisation plus particulier, la teneur pondérale en monomère (a) est d’environ 15 % par rapport audit copolymère, la teneur pondérale en monomère (b) est d’environ 36 % par rapport audit copolymère, et la teneur pondérale en monomère (c) est
d’environ 50 % par rapport audit copolymère, la masse molaire moyenne en nombre du copolymère étant notamment d’environ 9500 g/mol. According to another more particular embodiment, 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, and 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.
Selon un autre mode de réalisation plus particulier, la teneur pondérale en monomère (a) est d’environ 27 % par rapport audit copolymère, la teneur pondérale en monomère (b) est d’environ 62 % par rapport audit copolymère, et la teneur pondérale en monomère (c) est d’environ 11 % par rapport audit copolymère, la masse molaire moyenne en nombre du copolymère étant notamment d’environ 12700 g/mol. According to another more particular embodiment, 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, and 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.
Selon un autre mode de réalisation plus particulier, la teneur pondérale en monomère (a) est d’environ 15 % par rapport audit copolymère, la teneur pondérale en monomère (b) est d’environ 22 % par rapport audit copolymère, et la teneur pondérale en monomère (c) est d’environ 63 % par rapport audit copolymère, la masse molaire moyenne en nombre du copolymère étant notamment d’environ 14500 g/mol. According to another more particular embodiment, 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, and 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.
Selon un autre mode de réalisation plus particulier, la teneur pondérale en monomère (a) est d’environ 15 % par rapport audit copolymère, la teneur pondérale en monomère (b) est d’environ 26 % par rapport audit copolymère, et la teneur pondérale en monomère (c) est d’environ 59 % par rapport audit copolymère, la masse molaire moyenne en nombre du copolymère étant notamment d’environ 10400 g/mol. According to another more particular embodiment, 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, and 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.
Selon un mode de réalisation particulier, le copolymère est de formule (II) suivante : According to a particular embodiment, the copolymer has the following formula (II):
dans laquelle, indépendamment du motif répété n fois : in which, independently of the pattern repeated n times:
x, y et z sont respectivement les proportions molaires en monomère (a), (b) et (c) dans le copolymère, comprises entre 0 et 1, avec x+y+z= 1, sous réserve que x ¹0, y ¹0 et z ¹0 ; n, le degré de polymérisation en nombre DPn du copolymère de formule (II), est un nombre entier entre 1 et 1000, DPn étant de préférence compris entre 10 et 100, et très préférentiellement entre 10 et 80 ;
et dans laquelle, indépendamment du motif répété n fois : x, y and z are respectively the molar proportions of monomer (a), (b) and (c) in the copolymer, between 0 and 1, with x + y + z = 1, provided that x ¹0, y ¹0 and z ¹0; 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:
à l’échelle du mélange, v et w sont des proportions molaires comprises entre 0 et 1, telles que v+w=l, avec w 7 0, et éventuellement v ¹0, on the scale of the mixture, v and w are molar proportions between 0 and 1, such that v + w = l, with w 7 0, and optionally v ¹0,
p est un nombre entier tel que : p is an integer such that:
v*p, le nombre d’unités propylène glycol (-0-CH2-CH(CH3)-) dans le méthacrylate (b), est compris entre 0 et 7, en particulier entre 3 et 7, et de préférence entre 4 et 6, v * p, 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, le nombre d’unités éthylène glycol (-O-CH2-CH2)-) dans le méthacrylate (b), est compris entre 38 et 54. w * p, the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54.
q est un nombre entier entre 1 et 3, q étant en particulier égal à 2 ; q is an integer between 1 and 3, q being in particular equal to 2;
r est un nombre entier entre 1 et 7 ou entre 3 et 7, notamment entre 6 et 7, r étant en particulier égal à 6 ; 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 est un nombre entier entre 0 et 6 ou entre 2 et 12, s étant en particulier égal à 3 ou 4. s is an integer between 0 and 6 or between 2 and 12, s being in particular equal to 3 or 4.
Les monomères (a), (b) et (c) correspondent respectivement aux motifs présents x, y, et z fois. Ainsi, les valeurs v, w, p, q, r et s sont choisies comme indiqué ci-dessus, indépendamment de l’unité répétitive répétée n fois. Elles peuvent ainsi varier dans les plages définies ci-dessus d’une répétition à une autre de ladite unité. The monomers (a), (b) and (c) correspond respectively to the units present x, y, and z times. Thus, 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.
A l’échelle du mélange, les valeurs x, y, z, q, r, s, v, w et p et n peuvent être des nombres rationnels. On the scale of the mixture, the values x, y, z, q, r, s, v, w and p and n can be rational numbers.
Selon un mode de réalisation plus particulier, le copolymère est de formule (Ha) suivante : According to a more particular embodiment, the copolymer has the following formula (Ha):
x, y, z, v, w, p, r et n étant tels que définis plus haut, q étant tel que défini plus haut, et étant en particulier égal à 2. 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.
Selon un mode de réalisation avantageux, v*p est compris de 4 à 6, w*p est un nombre entre 38 et 54, r égal 6 ou 7, r étant notamment égal à 7, et DPn est un nombre entier de préférence entre 10 et 100, et très préférentiellement de 10 à 80. According to an advantageous embodiment, v * p is from 4 to 6, w * p is a number between 38 and 54, r equal 6 or 7, r being in particular equal to 7, and DPn is an integer preferably between 10 and 100, and very preferably from 10 to 80.
Selon un mode de réalisation avantageux, x est égal à environ 0,4, et y est égal à environ 0,1.
Selon un autre mode de réalisation avantageux, x est égal à environ 0,08, et y est égal à environAccording to an advantageous embodiment, 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
0,02. 0.02.
Selon un autre mode de réalisation avantageux, x est égal à environ 0,37, et y est égal à environ 0,16. According to another advantageous embodiment, x is equal to approximately 0.37, and y is equal to approximately 0.16.
Selon un autre mode de réalisation avantageux, x est égal à environ 0,07, et y est égal à environ According to another advantageous embodiment, x is equal to approximately 0.07, and y is equal to approximately
0,02. 0.02.
Selon un autre mode de réalisation avantageux, x est égal à environ 0,077, et y est égal à environ 0,025. According to another advantageous embodiment, x is equal to approximately 0.077, and y is equal to approximately 0.025.
Selon un autre aspect, l’invention concerne un procédé de préparation de mousse polyuréthane comprenant les étapes consistant à: According to another aspect, the invention relates to a process for preparing polyurethane foam comprising the steps of:
(i) mettre en contact un composé isocyanate et au moins un composé polyol, en présence : (i) bringing an isocyanate compound into contact with at least one polyol compound, in the presence:
d’un catalyseur choisi parmi les sels d'étain, les carboxylates de potassium et éventuellement les amines tertiaires, of a catalyst chosen from tin salts, potassium carboxylates and optionally tertiary amines,
d’un agent gonflant physique et/ou chimique, a physical and / or chemical blowing agent,
d’un copolymère d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c), tel que décrit ci-dessus, et a copolymer of a fluorinated methacrylate (a), a methacrylate (b) containing at least one oxyalkylene group and an alkyl methacrylate (c), as described above, and
éventuellement d’un retardateur de flamme, et possibly a flame retardant, and
(ii) laisser solidifier, après expansion, le mélange obtenu lors de l’étape (i) de façon à former une mousse polyuréthane. (ii) allow the mixture obtained in step (i) to solidify, after expansion, so as to form a polyurethane foam.
Selon un mode de réalisation, le copolymère et l’agent gonflant tels que définis plus haut sont mélangés ensemble préalablement à l’étape (i), notamment pour former une émulsion. According to one embodiment, the copolymer and the blowing agent as defined above are mixed together prior to step (i), in particular to form an emulsion.
Selon la présente invention, la mousse de polyuréthane est formée par la réaction du composé isocyanate et du au moins un composé polyol. Sans vouloir se limiter à une quelconque théorie, la réaction entre ces différents composés est susceptible de se dérouler selon les quatre réactions suivantes:
According to the present invention, the polyurethane foam is formed by the reaction of the isocyanate compound and the at least one polyol compound. Without wishing to be limited to any theory, the reaction between these different compounds is likely to take place according to the following four reactions:
La première réaction est la réaction dans laquelle les molécules d'eau réagissent avec les groupements NCO du composé isocyanate pour former des groupements amines et des molécules de CO2. Le dégagement de CO2 implique le gonflement de la mousse. 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.
Dans la deuxième réaction, les groupements amine issus de la deuxième réaction réagissent avec les groupements NCO pour former des groupements urée. In the second reaction, the amine groups resulting from the second reaction react with the NCO groups to form urea groups.
Parallèlement, lors de la troisième réaction, les groupements hydroxyle du composé polyol réagissent avec les groupements NCO pour former des groupements uréthane. At the same time, during the third reaction, the hydroxyl groups of the polyol compound react with the NCO groups to form urethane groups.
Enfin, lors la quatrième réaction, dite de trimérisation, les groupements NCO en excès s'associent par trois pour former des groupements isocyanurate. Finally, during the fourth reaction, called trimerization, the excess NCO groups combine in threes to form isocyanurate groups.
Les première et deuxième réactions (la deuxième réaction étant liée à la première), sont en concurrence avec les troisième et quatrième réactions telles que décrites ci-dessus. The first and second reactions (the second reaction being linked to the first), compete with the third and fourth reactions as described above.
En particulier, la quatrième réaction est très minoritaire dans le cadre de la présente invention. L’occurrence, ou non, de cette réaction peut notamment être liée à la valeur de l'index isocyanate, en base 100, tel que défini plus loin.
Ces réactions se manifestent à l’échelle macroscopique par un gonflement général de la mousse induite par le dégagement interne de CO2 et/ou l’évaporation de l’agent gonflant physique, liée à l’exotherme des réactions 1 à 3 principalement. In particular, 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.
Selon un mode de réalisation particulier, la quantité en copolymère est comprise de 0,1 à 10 % en masse par rapport au au moins un composé polyol, en particulier de 0,5 à 2% en masse, plus particulièrement environ 1,5 % en masse. According to a particular embodiment, 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.
Selon un mode de réalisation particulier, le composé isocyanate est tel que sa teneur massique en fonction isocyanate est comprise de 100 à 130, et/ou sa viscosité à 25°C est comprise de 200 à 600 mPa.s, et/ou sa fonctionnalité moyenne est comprise de 2,5 à 3,5, de préférence entre 2,7 et 3,1. La fonctionnalité moyenne est définie par le nombre de groupements NCO moyens présents dans chaque molécule de composé isocyanate. According to a particular embodiment, 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.
Le pourcentage de groupements NCO, défini par le rapport en masse des groupements NCO/100 grammes de composant isocyanate, est avantageusement compris entre 28 et 32 %. Selon un mode de réalisation particulier, le composé isocyanate est choisi parmi les diisocyanates de diphénylméthylène (MDI), notamment le 2,2'-diisocyanate de diphénylméthylène (2,2'-MDI), le 4,4'-diisocyanate de diphénylméthylène (4,4'-MDI) et le 2,4'- diisocyanate de diphénylméthylène (2,4'-MDI); les diisocyanates de toluène (TDI), notamment le 2,6-diisocyanate de toluène (2,6-TDI) et le 2,4-diisocyanate de toluène (2,4-TDI); le 4,4’- dibenzyl diisocyanate (4,4’-DBDI); le m-xylylène diisocyanate (m-XDI); le 2,4’-dibenzyl diisocyanate (2,4’-DBDI), le méthylène bis(4-cyclohexylisocyanate) (H12MDI); le diisocyanate d'isophorone (IPDI) ; le diisocyanate d'hexaméthylène (HDI) ; le diisocyanate de 1,5-naphthalène, le diisocyanate bitolylène ; et les polyisocyanates, notamment le poly- diisocyanate de diphénylméthylène (PMDI) ; le composé isocyanate étant en particulier un diisocyanate de diphénylméthylène ou un poly-diisocyanate de diphénylméthylène. The percentage of NCO groups, defined by the mass ratio of the NCO groups / 100 grams of isocyanate component, is advantageously between 28 and 32%. According to a particular embodiment, 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 diisocyanate (2,4'-DBDI), methylene bis (4-cyclohexylisocyanate) (H12MDI); isophorone diisocyanate (IPDI); hexamethylene diisocyanate (HDI); 1,5-naphthalene diisocyanate, bitolylene diisocyanate; and polyisocyanates, especially poly-diphenylmethylene diisocyanate (PMDI); the isocyanate compound being in particular a diphenylmethylene diisocyanate or a poly-diphenylmethylene diisocyanate.
Le poly-diisocyanate de méthylène diphényle non distillé ou brut peut être couramment utilisé. Ce produit est couramment disponible sur le marché sous la marque Suprasec commercialisé par Hunstman. 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.
Selon un mode de réalisation particulier, le au moins un composé polyol est tel que sa valeur en groupe hydroxyle est comprise de 200 à 500 mg KOH/g, et/ou sa viscosité à 25°C est comprise de 200 à 6000 mPa.s, préférentiellement entre 1000 et 3000 mPa.s, et/ou sa fonctionnalité moyenne est comprise de 2 et 6. According to a particular embodiment, 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.
L'indice d'hydroxyle (indice OH) des polyols est défini par le rapport massique de dosage en mg KOH par g de composés polyols. The hydroxyl number (OH number) of polyols is defined by the weight ratio of dosage in mg KOH per g of polyol compounds.
La détermination de l'indice OH permet d'apprécier la capacité de réticulation du/des polyol(s).
Selon un mode de réalisation particulier, le au moins un composé polyol est choisi parmi les polyesters, le sorbitol et ses dérivés, les polyéthers, le glycérol et ses dérivés, le saccharose et ses isomères et/ou dérivés, et leurs mélanges, le composé polyol étant en particulier un polyester aromatique. The determination of the OH number makes it possible to assess the crosslinking capacity of the polyol (s). According to a particular embodiment, 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.
Par « dérivé » d’un polyol donné, on entend notamment ledit polyol, substitué par au moins une chaîne poly(oxyde d'alkylène), en particulier une chaîne poly(oxyde d’éthylène et/ou oxyde de propylène). The term "derivative" 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.
Ce polyol ou ce mélange de polyols peut également être un polyétherpolyol, obtenu par polyaddition d’oxyde de propylène (PO) et/ou d'oxyde d'éthylène (EO) à au moins l’un des polyols tels que définis ci-dessus, selon l’un des procédés bien connus de l’état de l’art. 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.
Des exemples représentatifs des polyols dérivés du sorbitol, sont par exemple les polyols de la marque Daltolac de Huntsman. L'indice OH est compris dans un intervalle de 150 à 600, de préférence entre 300 et 600, par exemple de 500 pour le polyol de type dérivé du sorbitol. Representative examples of 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.
Des exemples représentatifs de polyols de type polyéther sont par exemple les produits dérivés dérivés du glycérol dont les chaînes latérales sont étendues par de l'oxyde de propylène, tels que ceux par exemple commercialisés par Shell Chemicals sous la marque Caradol, par Dow sous la marque Voranol, par Carpenter sous la marque Carpol ou par Coim sous la marque Isoter. L'indice OH est compris dans un intervalle de 150 à 600, de préférence entre 300 et 600, par exemple de 250 pour le deuxième polyol. Representative examples of 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.
Des exemples représentatifs de polyols de type polyester sont les polyols polyester aliphatiques ou préférentiellement les polyols polyester aromatiques tels que les dérivés de l'anhydride phtalique. Dans le cadre de la présente invention, les dérivés d'ortho-phtalate de diéthylène glycol, par exemple les produits commercialisés par Stepan sous la marque StepanPol sont préférentiellement utilisés. L'indice OH est par exemple de 250 pour le troisième polyol. Representative examples of polyester-type polyols are aliphatic polyester polyols or preferably aromatic polyester polyols such as phthalic anhydride derivatives. In the context of the present invention, 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.
Selon un mode de réalisation particulier, l’index isocyanate, c’est-à-dire le rapport molaire fonctions NCO sur fonctions OH est supérieur ou égal à 1, en particulier supérieur à 1. According to a particular embodiment, 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.
Lorsque l'index isocyanate, en base 100, est compris environ entre 95 et 150, la mousse issue de cette formulation est de type polyuréthane (PUR) et idéalement entre 105 et 130. Lorsque l'index isocyanate est supérieur à 200-250, c'est-à-dire quand il y a un excès de groupements NCO, la mousse issue de cette formulation est de type polyisocyanurate (PIR). When the isocyanate index, based on 100, is approximately between 95 and 150, the foam resulting from this formulation is of the polyurethane (PUR) type and ideally between 105 and 130. When the isocyanate index is greater than 200-250, that is to say when there is an excess of NCO groups, the foam resulting from this formulation is of the polyisocyanurate (PIR) type.
Selon un mode de réalisation particulier, l’agent gonflant chimique est de l’eau. According to a particular embodiment, the chemical blowing agent is water.
Selon un mode de réalisation particulier, la quantité en agent gonflant chimique est comprise de 0,05 à 5 % en masse par rapport au au moins un composé polyol, en particulier de 0,05 à 1% en masse, plus particulièrement environ 0,2-0, 3% en masse.
Selon un mode de réalisation particulier l’agent gonflant physique est choisi parmi les hydrochlorofluorocarbones (HCFC), les hydrofluorocarbones (HFC), les hydrocarbones (HC) en particulier choisi parmi le cyclopentane, le n-pentane, l’iso-pentane et l’iso-butane, le 1,1,1,3,3-pentafluoropropane, le trans-l-chloro-3,3,3-trifluoropropène, le 1,1, 1,3, 3- pentafluorobutane, le 1,1,1,2,3,3,3-heptafluoropropane et leurs mélanges, notamment les mélanges 1,1,1 ,3 ,3-pentafluorobutane/l , 1 , 1 ,2,3 ,3 ,3-heptafluoropropane. According to a particular embodiment, 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. According to a particular embodiment, 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.
Les agents d'expansion physiques préférentiellement utilisés sont les composés pentafluorobutane non chlorés et en particulier le 1,1,1,3,3-pentafluorobutane également connu sous le nom de HFC-365mfc notamment de la marque Solkane 365 commercialisé par Solvay et le HFC-245fc de la marque Enovate 3000 commercialisé par Honeywell, ainsi que le trans- l-chloro-3,3,3-trifluoropropene également connu sous le nom de Solstice Liquid Blowing Agent commercialisé par Honeywell. 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.
La quantité préférentielle d'agent d'expansion physique est calculée en fonction de la masse volumique de la mousse PU souhaitée. The preferred amount of physical blowing agent is calculated based on the density of the desired PU foam.
Selon un mode de réalisation, la quantité en agent gonflant physique est comprise de 0,1 à 30 % en masse par rapport au au moins un composé polyol, en particulier de 5 à 10% en masse, ou est d’environ 15% en masse. Selon un mode de réalisation particulier, la quantité en agent gonflant physique préféré est comprise de 0,1 à 30% en masse par rapport au au moins un composé polyol, en particulier de 5 à 10% en masse, notamment pour des mousses de masse volumique comprise entre 150 et 110 kg/m3, ou d’environ 15%, notamment pour une mousse de 50 kg/m3 environ avec l’ajout d’environ 2% d’agent gonflant chimique. According to one embodiment, 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. According to a particular embodiment, 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.
Selon un autre mode de réalisation particulier, la quantité en agent gonflant physique, lorsqu’il s’agit d’un dérivé du pentane tel que notamment défini précédemment, est comprise de 0,1 à 20 % en masse par rapport au au moins un composé polyol, notamment pour des mousses de masse volumique comprise entre 50 à 150 kg/m3. According to another particular embodiment, 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 .
Selon un mode de réalisation avantageux, l’agent gonflant physique est combiné à un agent gonflant chimique, en particulier l’eau, en tant qu'agent gonflant. According to an advantageous embodiment, the physical blowing agent is combined with a chemical blowing agent, in particular water, as a blowing agent.
Le catalyseur peut être un catalyseur de gélification, d'expansion, de durcissement, voire de trimérisation, couramment utilisé dans la préparation des mousses polyuréthane. The catalyst can be a gelation, expansion, hardening, or even trimerization catalyst, commonly used in the preparation of polyurethane foams.
En ce qui concerne le catalyseur choisi parmi les sels d'étain et de bismuth, les carboxylates de potassium et éventuellement les amines tertiaires, des catalyseurs particulièrement intéressants dans le cadre de la présente invention sont par exemple les carboxylates d'étain IV, en particulier le dilaurate de dibutylétain (DBTL) ou l'octanoate d'étain; et les carboxylates de potassium comme l'octanoate de potassium.
Avantageusement, des catalyseurs à base d'étain et/ou de type octanoate de potassium sont utilisés simultanément en l'absence de catalyseurs de type amine. As regards the catalyst 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. Advantageously, catalysts based on tin and / or of potassium octanoate type are used simultaneously in the absence of catalysts of amine type.
Les catalyseurs à base d'étain sont par exemple ceux du type DBTL commercialisés par Evonik sous la marque KOSMOS (anciennement Air Products sous la marque Dabco) et sont avantageusement utilisés dans une proportion comprise entre 0,01 et 1 % en masse de la masse totale des polyols (c'est-à-dire du composé polyol). 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).
Les catalyseurs de type octanoate de potassium sont par exemple ceux commercialisés par Air Products également sous la marque Dabco et sont avantageusement utilisés dans une proportion comprise entre 0,01 et 2 % en masse de la masse totale des polyols et de préférence entre 0.02 et 0.2%. 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. %.
Les catalyseurs de type amine sont notamment de type alkyl amine, en particulier choisis parmi bis(2-diméthylaminoéthyl)éther, N,N-diméthylaminopropylamine, N,N- diméthylcyclohéxylamine, N, N, N’, N’, N”-pentaméthyldiéthylène-triamine, triéthylènediamine, ou de type éthanol amine, en particulier choisis parmi diéthanolamine, 2(2- diméthylamino-éthoxy)éthanol, N-[2-(diméthylamino)éthyl]-N-méthyléthanolamine, diméthyléthanolamine . 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.
Les catalyseurs de type amine sont par exemple ceux commercialisés par Evonik sous la marque Polycat ou par Huntsman sous la marque JELLCAT (par exemple DMCHA ou PMDETA) et sont avantageusement utilisés dans une proportion comprise entre 0,01 et 1 % en masse de la masse totale des polyols. 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.
Selon un mode de réalisation particulier, le catalyseur est choisi parmi la triethylènediamine, la pentaméthyldiethylènetriamine, la diméthylcyclohexylamine, le 1,4-diazabicyclo (2,2,2)- octane, et le dilaurate de dibutylétain, le catalyseur étant en particulier le dilaurate de dibutylétain. According to a particular embodiment, 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.
Les catalyseurs sont utilisés pour accélérer une ou plusieurs des différentes étapes réactionnelles susmentionnées. Par exemple, les catalyseurs stanniques et les amines tertiaires agissent préférentiellement sur les étapes 1 à 3, tandis que les catalyseurs à base d'octanoate de potassium agissent préférentiellement sur la réaction de trimérisation (étape 4). The catalysts are used to accelerate one or more of the various reaction steps mentioned above. For example, 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).
Selon un mode de réalisation particulier, un tensioactif peut être utilisé dans le cadre de la présente invention en sus du copolymère tel que défini précédemment. According to a particular embodiment, a surfactant can be used in the context of the present invention in addition to the copolymer as defined above.
Des exemples de tensioactif sont les copolymères siloxane-oxyalkylène et d'autres organopolysiloxanes. Les produits d'alcoxylation d'alcools gras, d'oxoalcools, d'amines lipophiles, d'alkylphénols, de dialkylphénols, d'alkylcrésols, d'alkylrésorcinol, de naphtol, d'alkylnaphtol, de naphthol, de naphthylamine, d'aniline, d'alkylaniline, de toluidine, de
bisphénol A, de bisphénol alkylé A, d'alcool polyvinylique, mais également les produits d'alcoxylation de produits de condensation de formaldéhyde et d'alkylphénols, de formaldéhyde et de dialkylphénols, de formaldéhyde et d’alkylcrésorcinol, de formaldéhyde et d’alkylrésorcinol, de formaldéhyde et d’aniline, de formaldéhyde et de toluidine, de formaldéhyde et de naphtol, de formaldéhyde et d’alkylnaphtol, mais aussi deformaldéhyde et de bisphénol A, peuvent également être utilisés. Des mélanges de deux ou plusieurs de ces surfactants peuvent également être utilisés. Le surfactant est par exemple le copolymère Tegostab B 8404 (Evonik), ou le DC 193 (Dabco). Examples of the surfactant are siloxane-oxyalkylene copolymers and other organopolysiloxanes. Alkoxylation products of fatty alcohols, oxoalcohols, lipophilic amines, alkylphenols, dialkylphenols, alkyl cresols, alkylresorcinol, naphthol, alkylnaphthol, naphthol, naphthylamine, aniline , alkylaniline, toluidine, bisphenol A, alkylated bisphenol A, polyvinyl alcohol, but also the alkoxylation products of condensation products of formaldehyde and alkylphenols, formaldehyde and dialkylphenols, formaldehyde and alkyl cresorcinol, formaldehyde and alkylresorcinol , formaldehyde and aniline, formaldehyde and toluidine, formaldehyde and naphthol, formaldehyde and alkylnaphthol, but also deformaldehyde and bisphenol A, can also be used. Mixtures of two or more of these surfactants can also be used. The surfactant is for example the copolymer Tegostab B 8404 (Evonik), or DC 193 (Dabco).
Un retardateur de flamme peut être utilisé dans le cadre de la présente invention pour limiter davantage l'inflammabilité de la mousse. A flame retardant can be used within the scope of the present invention to further limit the flammability of the foam.
Les retardateurs de flamme connus de l'art antérieur peuvent généralement être utilisés. Les retardateurs de flamme sont, par exemple, les éthers bromés (Ixol B 251), les alcools bromés tels que l'alcool dibromonéopentyle, l'alcool tribromonéopentyle et le PHT-4-diol, ainsi que les phosphates chlorés tels que le tris(2-chloroéthyle) phosphate, le tris(2-chloroisopropyle) phosphate (TCPP), le tris(l,3-dichloroisopropyle) phosphate, le tris(2,3-dibromopropyle) phosphate et le tétrakis(2-chloroéthyle) éthylènediphosphate, ou leurs mélanges. The flame retardants known from the prior art can generally be used. 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.
Outre les phosphates halogénés susmentionnés, il est également possible d'utiliser des retardateurs de flamme inorganiques tels que le phosphore rouge, des préparations comprenant du phosphore rouge, du graphite expansible, de l'hydrate d'oxyde d'aluminium, du trioxyde d'antimoine, de l'oxyde d'arsenic, du polyphosphate d'ammonium et du sulfate de calcium ou des dérivés de l'acide cyanurique tels que la mélamine ou des mélanges d'au moins deux retardateurs de flamme tels que les polyphosphates d'ammonium et la mélamine. In addition to the aforementioned halogenated phosphates, it is also possible to use 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.
Comme autres retardateurs de flamme liquides sans halogène, il est possible d'utiliser du diéthyl éthanephosphonate (DEEP), du triéthyle phosphate (TEP), du diméthyl propylphosphonate (DMPP), du diphényle crésyle phosphate (DPC). As other halogen-free liquid flame retardants, it is possible to use diethyl ethanephosphonate (DEEP), triethyl phosphate (TEP), dimethyl propylphosphonate (DMPP), diphenyl cresyl phosphate (DPC).
Selon un mode de réalisation particulier, le retardateur de flamme est de type non halogéné. Ainsi, contrairement à un retardateur de flamme de type halogéné, l'incorporation de ce type de retardateur de flamme dans une composition n'a aucune action néfaste pour l'environnement. Le retardateur de flamme est préférentiellement utilisé dans des proportions d'environ 5% à 20% en masse de la masse totale du au moins au composé polyol. According to a particular embodiment, the flame retardant is of the non-halogenated type. Thus, unlike a halogen-type flame retardant, 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.
D'autres additifs tels que des charges, des agents de réticulation, des colorants peuvent avantageusement être rajoutés à la formulation. Other additives such as fillers, crosslinking agents, colorants can advantageously be added to the formulation.
Selon un mode de réalisation particulier, la mousse obtenue à l’issue de l’étape (ii) a une densité comprise entre 20 et 250kg/m3.
Selon un mode de réalisation particulier, le mélange obtenu lors de l’étape (i) est, préalablement à l’étape (ii), mis en contact avec un empilement de mats de fibres de verre éventuellement associées entre elles par un liant, afin d’obtenir un empilement de mats de fibres de verre imprégné par ledit mélange obtenu lors de l’étape (i). L'expansion et la solidification dudit mélange conduit à la formation d’un bloc de mousse renforcée contenant l'empilement de mats de fibres de verre. According to a particular embodiment, the foam obtained at the end of step (ii) has a density of between 20 and 250 kg / m 3. According to a particular embodiment, 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.
Préférentiellement, lesdits mats de fibres de verre présentent une masse surfacique comprise entre 300 à 900 g/m2, plus avantageusement, entre 300 et 600 g/m2. Les fibres de verre constituent préférentiellement de 6 à 13%, de préférence de 8 à 12% en masse par rapport à la masse totale du bloc de mousse renforcée. Preferably, 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.
Avantageusement, les mats de fibres de verre sont constitués de fibres de verre de masse linéique de 10 à 60 Tex, de préférence 20 à 40 Tex. Advantageously, the glass fiber mats consist of glass fibers with a linear density of 10 to 60 Tex, preferably 20 to 40 Tex.
L'ensemble des paramètres susmentionnés concernant les mats de fibres de verre et les fibres de verre elles-mêmes est également favorable à une imprégnation satisfaisante des mats de verre et s'est avéré pouvoir conférer à la mousse des caractéristiques du type résistance à la traction (c'est-à-dire à l'allongement) satisfaisantes. All the aforementioned parameters relating to the glass fiber mats and the glass fibers themselves are also favorable for a satisfactory impregnation of the glass mats and have been found to be able to give the foam characteristics of the tensile strength type. (i.e. elongation) satisfactory.
Les mats de fibres de verre préférentiellement utilisés pour la présente invention sont constitués de mats de fibres de verre continus (« continuous strand mat ») notamment commercialisés par Owens Corning sous la marque Unifilo ou commercialisés par 3B sous la marque CFM. 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.
En fonction de la quantité de liant et de la masse surfacique des mats de fibres de verre, et afin d’éventuellement contribuer à l’obtention de propriétés mécaniques acceptables, le nombre de mats de fibres de verre varie par exemple de 3 à 20. Depending on the amount of binder and the weight per unit area of the glass fiber mats, and in order to possibly help obtain acceptable mechanical properties, the number of glass fiber mats varies, for example, from 3 to 20.
Selon un mode de réalisation particulier, la mousse obtenue à l’issue de l’étape (ii) se présente sous la forme d'un bloc de mousse d'une épaisseur comprise entre 10 et 40 cm. Ainsi, selon l'utilisation souhaitée, par exemple comme matériau d'isolation, une quantité suffisante de formulation, éventuellement de mats de fibres de verre, et d'agent d'expansion va être définie de façon à préparer un bloc de mousse avec une épaisseur souhaitée. L'avantage de préparer des blocs de mousse d'une épaisseur 20 cm est que, après ébavurage, les blocs de mousse peuvent directement être utilisés comme couche d'isolation secondaire de méthanier, qui présente habituellement une épaisseur de 18 cm, et/ou découpés transversalement au niveau de leur moitié pour former directement une couche d'isolation primaire de méthanier, qui présente habituellement une épaisseur de 9 cm. De même, un bloc de mousse préparé avec une épaisseur de 30 cm, pourra, après ébavurage et découpe au tiers de son épaisseur, former simultanément une couche d'isolation primaire de 9 cm et une couche d'isolation secondaire de 18 cm. D’autres
configurations pour former des blocs sont envisageables telles que l’association d’une couche d'isolation primaire de 10 cm avec une couche d'isolation secondaire de 30 cm, ou bien d’une couche d'isolation primaire de 10 cm avec une couche d'isolation secondaire de 38 cm, ou bien une couche d'isolation primaire de 15 cm avec une couche d'isolation secondaire de 25 cm. La largeur et la longueur des blocs est par exemple de 100 cm par 300 cm. According to a particular embodiment, 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. Thus, depending on the desired use, for example as an insulation material, 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. Likewise, 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.
Le procédé de préparation de mousse polyuréthane se déroule avantageusement comme suit. Les différents composants de la formulation peuvent être mélangés dans un mélangeur de type mélangeur pour mousse rigide à basse pression. 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.
Cependant, pour faciliter le traitement, l'agent gonflant et les divers additifs sont généralement introduits dans le récipient comportant le ou les composés polyol. Puis le mélange comportant le ou les composés polyol et les divers additifs sont ensuite mélangés au composé isocyanate et la formulation issue de ce mélange est versée sur une surface, dans un moule, ou sur un empilement de plusieurs mats de fibres de verre. L'agent d'expansion et certains additifs ou catalyseurs peuvent être ajoutés à la composition après mélange du ou des composés polyol et du composé isocyanate. However, to facilitate the processing, 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.
Le débit de dépôt est calculé selon les connaissances de l'homme du métier en fonction de la vitesse du convoyeur, de la hauteur de bloc et la masse volumique souhaitée. 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.
Ensuite les blocs de mousse peuvent réticuler pendant une durée comprise entre 5 et 30 min. Alternativement, les blocs de mousse peuvent réticuler, notamment de façon complète, et refroidir jusqu’à température ambiante, pendant environ 48 à 96 heures, avant découpe. Then the foam blocks can crosslink for a period of between 5 and 30 min. Alternatively, the foam blocks can crosslink, in particular completely, and cool to room temperature for approximately 48 to 96 hours, before cutting.
Puis les parties supérieure et inférieure et éventuellement latérales de la mousse désormais sous forme de bloc de mousse sont retirées. Cette étape d'ébavurage permet d'obtenir des blocs de mousse de dimensions données, par exemple de 9 à 10 cm et/ou de 18 à 20 cm, et/ou de 25 à 30 cm. Then the upper and lower and possibly side parts of the foam now in the form of a foam block are removed. This deburring step makes it possible to obtain foam blocks of given dimensions, for example from 9 to 10 cm and / or from 18 to 20 cm, and / or from 25 to 30 cm.
Cette unique étape de découpe à partir d'un seul bloc de mousse permet d'obtenir simultanément une couche primaire et une couche secondaire d'isolation, ce qui constitue non seulement une économie de matière, car moins de pertes d'ébavurage sont produites, mais également une économie de temps, car une seule étape est nécessaire pour la production des deux couches d'isolation thermique. 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.
Selon un autre aspect, l’invention concerne une mousse de polyuréthane comprenant un copolymère d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c), ledit copolymère étant tel que décrit plus haut. Selon un mode de réalisation, la mousse de polyuréthane comprend des mats de fibres de verre.
Selon un autre mode de réalisation, la mousse de polyuréthane est dépourvue de mats de fibres de verre. Selon un autre aspect, rinvention concerne une composition, en particulier une émulsion, comprenant un copolymère d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c), ledit copolymère étant tel que décrit plus haut, et un agent gonflant physique, tel que défini plus haut. According to another aspect, 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. According to one embodiment, the polyurethane foam comprises mats of glass fibers. According to another embodiment, the polyurethane foam is devoid of mats of glass fibers. According to another aspect, 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.
Selon un autre aspect, l’invention concerne une mousse de polyuréthane susceptible d’être obtenu par le procédé tel que défini plus haut. According to another aspect, the invention relates to a polyurethane foam capable of being obtained by the process as defined above.
Selon un autre aspect, l’invention concerne l’utilisation d’une mousse telle que définie plus haut dans l'isolation thermique de cuves de transport de gaz liquéfié, et notamment de cuves de méthanier. According to another aspect, 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.
Selon un autre aspect, l’invention concerne un copolymère d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c), ledit alkyle étant une chaîne alkyle linéaire ou ramifiée ou cyclique ayant de 1 à 12 atomes de carbone. According to another aspect, 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.
En particulier, l’invention concerne un copolymère tel que défini dans les modes de réalisation mentionnés plus haut. In particular, the invention relates to a copolymer as defined in the embodiments mentioned above.
Aussi, selon un mode de réalisation particulier, le méthacrylate fluoré (a) comprend une chaîne carbonée constituée d’une chaîne alkyle prolongée d’une chaîne fluorée, notamment perfluorée, le méthacrylate fluoré (a) étant notamment de formule (la) ou (la’) suivante, ou est un mélange de méthacrylates de formule (la) ou (la’) suivante : Also, according to a particular embodiment, 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'):
dans laquelle : in which :
A est un fluoroalkylène en C1-C5, en particulier un perfluoroalkylène en C1-C3, ou un alkylène en C1-C5 ; A is C1-C5 fluoroalkylene, in particular C1-C3 perfluoroalkylene, or C1-C5 alkylene ;
q est un nombre entre 1 et 3, q étant en particulier égal à 2 ; q is a number between 1 and 3, q being in particular equal to 2;
q’ est un nombre entre 1 et 100, q’ étant de préférence compris entre 1 et 3 ; q "is a number between 1 and 100, q" preferably being between 1 and 3;
r est un nombre entre 1 et 7 ou entre 3 et 7, notamment entre 6 et 7, r étant en particulier égal à 6.
Selon un mode de réalisation particulier, le méthacrylate (b) contenant au moins un groupe oxyalkylène contient au moins un groupe oxyéthylène et au moins un groupe oxypropylène, le méthacrylate (b) contenant au moins un groupe oxyalkylène étant notamment de formule (Ib) suivante, ou étant un mélange de méthacrylates de formule (Ib) suivante : 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 6. According to a particular embodiment, 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):
dans laquelle : in which :
B est un atome d’hydrogène, ou un alkyle linéaire ou ramifié en Ci à C4, en particulier le méthyle, ou un groupe -C(=0)-D, où D est un alkyle linéaire ou ramifié en Ci à C4, en particulier le méthyle, B is a hydrogen atom, or a linear or branched C1 to C 4 alkyl, in particular methyl, or a group -C (= 0) -D, where D is a linear or branched C1 to C 4 alkyl , in particular methyl,
à l’échelle du mélange, v et w sont des proportions molaires comprises entre 0 et 1, telles que v+w=l, avec w ¹ 0, et éventuellement v ¹0, on the scale of the mixture, v and w are molar proportions between 0 and 1, such that v + w = l, with w ¹ 0, and optionally v ¹0,
p est un nombre entier tel que : p is an integer such that:
v*p, le nombre d’unités propylène glycol (-0-ϋ¾-ϋί(ϋ¾)-) dans le méthacrylate (b), est compris entre 0 et 7, en particulier entre 3 et 7, et de préférence entre 4 et 6, v * p, the number of propylene glycol units (-0-ϋ¾-ϋί (ϋ¾) -) in the methacrylate (b) is between 0 and 7, in particular between 3 and 7, and preferably between 4 and 6,
w*p, le nombre d’unités éthylène glycol (-O-CH2-CH2)-) dans le méthacrylate (b), est compris entre 38 et 54. w * p, the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54.
En particulier, v*p est un nombre rationnel. Le méthacrylate (b) est alors un mélange de méthacrylates de formule (Ib), dans lesquels, pour chaque méthacrylate de formule (Ib) du mélange, v*p est indépendamment un nombre entier entre 0 et 7, en particulier entre 3 et 7, et w*p est indépendamment un nombre entier entre 38 et 54. Ainsi, la valeur v*p du mélange correspond à la moyenne des valeurs v*p de chaque méthacrylate de formule (Ib) du mélange, pondérée par les proportions respectives de chacun, et de même pour w*p. Toujours dans ce cas, v*p est en particulier un nombre rationnel compris entre 5 et 5,3, et/ou w*p est en particulier un nombre rationnel compris entre 38 et 54. In particular, 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. Thus, 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. Still in this case, v * p is in particular a rational number between 5 and 5.3, and / or w * p is in particular a rational number between 38 and 54.
v*p peut éventuellement être un nombre entier, en particulier égal à 5, et/ou w*p peut être un nombre entier, en particulier compris entre 38 et 54, w*p étant plus particulièrement égal à 42. Selon un mode de réalisation particulier, le méthacrylate d’ alkyle (c) est de formule (le) suivante :
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. According to one mode of particular embodiment, the alkyl methacrylate (c) has the following formula (le):
dans laquelle s est un nombre entier entre 0 et 12 ou entre 2 et 6, s étant en particulier égal à 3 ou 4. in which s is an integer between 0 and 12 or between 2 and 6, s being in particular equal to 3 or 4.
Selon un mode de réalisation particulier, la masse molaire moyenne en nombre est comprise entre 6000 et 15000 g/mol. According to a particular embodiment, the number-average molar mass is between 6000 and 15000 g / mol.
Selon un mode de réalisation particulier, le copolymère est de formule (II) suivante : According to a particular embodiment, the copolymer has the following formula (II):
dans laquelle, indépendamment du motif répété n fois : in which, independently of the pattern repeated n times:
x, y et z sont respectivement les proportions molaires en monomère (a), (b) et (c) dans le copolymère, comprises entre 0 et 1, avec x+y+z= 1, sous réserve que x ¹0, y ¹0 et z ¹0 ; n, le degré de polymérisation en nombre DPn du copolymère de formule (II), est un nombre entier entre 1 et 1000, DPn étant de préférence compris entre 10 et 100, et très préférentiellement entre 10 et 80 ; x, y and z are respectively the molar proportions of monomer (a), (b) and (c) in the copolymer, between 0 and 1, with x + y + z = 1, provided that x ¹0, y ¹0 and z ¹0; 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;
et dans laquelle, indépendamment du motif répété n fois : and in which, independently of the pattern repeated n times:
à l’échelle du mélange, v et w sont des proportions molaires comprises entre 0 et 1, telles que v+w=l, avec w ¹ 0, et éventuellement v ¹0, on the scale of the mixture, v and w are molar proportions between 0 and 1, such that v + w = l, with w ¹ 0, and optionally v ¹0,
p est un nombre entier tel que : p is an integer such that:
v*p, le nombre d’unités propylène glycol (-0-CH2-CH(CH3)-) dans le méthacrylate (b), est compris entre 0 et 7, en particulier entre 3 et 7, et de préférence entre 4 et 6, v * p, 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, le nombre d’unités éthylène glycol (-O-CH2-CH2)-) dans le méthacrylate (b), est compris entre 38 et 54 ; w * p, the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54;
q est un nombre entier entre 1 et 3, q étant en particulier égal à 2 ; q is an integer between 1 and 3, q being in particular equal to 2;
r est un nombre entier entre 1 et 7 ou entre 3 et 7, notamment entre 6 et 7, r étant en particulier égal à 6 ;
s est un nombre entier entre 0 et 6 ou entre 2 et 12, s étant en particulier égal à 3 ou 4; 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;
le copolymère étant notamment de formule (Ha) suivante : the copolymer being in particular of the following formula (Ha):
x, y, z, v, w, p, r et n étant tels que définis plus haut, q étant tel que défini plus haut, et étant en particulier égal à 2. 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.
Selon un mode de réalisation particulier : According to a particular embodiment:
v*p est égal à 5, w*p est égal à 42 et r est égal à 6 ou 7, DPn étant en particulier égal à environ 15 ou environ 45 ; et/ou 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; and or
x est égal à environ 0,4, et y est égal à environ 0,1, 1a masse molaire moyenne en nombre étant notamment d’environ 7400 ; ou x is about 0.4, and y is about 0.1, the number average molar mass in particular being about 7,400; or
x est égal à environ 0,08, et y est égal à environ 0,02, la masse molaire moyenne en nombre étant notamment d’environ 9500. x is about 0.08, and y is about 0.02, the number-average molar mass in particular being about 9,500.
Selon un autre mode de réalisation particulier : According to another particular embodiment:
v*p est égal à environ 5,1, w*p est égal à environ 46,2 et r est égal à 6, DPn étant en particulier égal à environ 20, la masse molaire moyenne en nombre étant notamment d’environ 12800 ; et/ou x est égal à environ 0,37, et y est égal à environ 0,16. 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.
Selon un autre mode de réalisation particulier : According to another particular embodiment:
v*p est égal à environ 5,2, w*p est égal à environ 50 et r est égal à 6, DPn étant en particulier égal à environ 69, la masse molaire moyenne en nombre étant notamment d’environ 14500 ; et/ou 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 est égal à environ 0,07, et y est égal à environ 0,02. x is about 0.07, and y is about 0.02.
Selon un autre mode de réalisation particulier : According to another particular embodiment:
v*p est égal à environ 5,2, w*p est égal à environ 50 et r est égal à 6, DPn étant en particulier égal à environ 46, la masse molaire moyenne en nombre étant notamment d’environ 10400 ; et/ou 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 est égal à environ 0,077, et y est égal à environ 0,025.
Définitions x is about 0.077, and y is about 0.025. Definitions
Tel qu’on Tutilise dans la présente description, le terme « environ » se réfère à un intervalle de valeurs de ± 10 % d’une valeur spécifique. A titre d’exemple, l’expression « environ 20 » comprend les valeurs de 20 ± 10 %, soit les valeurs de 18 à 22. As used in this specification, the term "about" refers to a range of values of ± 10% of a specific value. For example, the expression "about 20" includes values of 20 ± 10%, or values from 18 to 22.
Au sens de la présente description, les pourcentages se réfèrent à des pourcentages en masse par rapport à la masse totale de la formulation, sauf indication contraire. For the purposes of the present description, the percentages refer to percentages by weight relative to the total weight of the formulation, unless otherwise indicated.
Tel qu’on l’entend ici, les plages de valeur sous forme de « x-y » ou « de x à y » ou « entre x et y » incluent les bornes x et y ainsi que les entiers compris entre ces bornes. A titre d’exemple, « 1-5 », ou « de 1 à 5 » ou « entre 1 et 5 » désignent les entiers 1, 2, 3, 4 et 5. Les modes de réalisations préférés incluent chaque entier pris individuellement dans la plage de valeur, ainsi que toute sous-combinaison de ces entiers. A titre d’exemple, les valeurs préférées pour « 1-5 » peuvent comprendre les entiers 1, 2, 3, 4, 5, 1-2, 1-3, 1-4, 1-5, 2-3, 2-4, 2-5, etc. As understood here, 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. By way of example, "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. By way of example, 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.
Par « méthacrylate », on entend notamment un ester dérivé de l’ion méthacrylate de formule CH2=C(CH )COCr. The term “methacrylate” is intended to mean in particular an ester derived from the methacrylate ion of formula CH 2 = C (CH) COCr.
Par « copolymère d’un méthacrylate (a), d’un méthacrylate (b) et d’un méthacrylate (c) », on entend un polymère issu de la copolymérisation de trois types de monomère, à savoir les monomères (a), (b), et (c). Cette copolymérisation peut se faire à partir d’un mélange de monomères comprenant les monomères (a), (b), et (c), ou à partir d’un mélange de monomères constitué des monomères (a), (b), et (c). By “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).
Par « méthacrylate fluoré », on entend notamment un ester dérivé de l’ion méthacrylate de formule CH2=C(CH3)COO , dont le groupe ester est fluoré, c’est-à-dire substitué par au moins un fluor. By "fluorinated methacrylate" is meant in particular an ester derived from the methacrylate ion of formula CH2 = C (CH3) COO, the ester group of which is fluorinated, that is to say substituted by at least one fluorine.
Par « méthacrylate contenant au moins un groupe oxyalkylène », on entend notamment un ester dérivé de l’ion méthacrylate de formule CH2=C(CH3)COO , dont le groupe ester contient au moins un résidu -O-alkyl-. By "methacrylate containing at least one oxyalkylene group" is meant in particular an ester derived from the methacrylate ion of formula CH2 = C (CH3) COO, the ester group of which contains at least one -O-alkyl- residue.
Par « au moins un composé polyol », on entend un composé polyol ou un mélange de composés polyols. Ainsi lorsqu’on mentionne un pourcentage en masse par rapport au au moins un composé polyol, ce pourcentage est donné par rapport au composé polyol quand il n’y en a qu’un, ou par rapport au mélange de polyols quand il y en a deux ou plus. By “at least one polyol compound” is meant a polyol compound or a mixture of polyol compounds. Thus, when a percentage by mass relative to at least one polyol compound is mentioned, 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.
Par « indépendamment du motif répété n fois », on entend que les indices x, y, z, v, w, p, q, r et s peuvent être différents d’une occurrence à une autre du motif répété n fois. En particulier, les indices x, y, z, v, w, p, q, r et s ont la même valeur, pour toute occurrence du motif répété n fois.
Par « alkyle », on entend, pour chaque occurrence, une chaîne alkyle linéaire ou ramifiée ou cyclique ayant de 1 à 12 atomes de carbone. By “independently of the pattern repeated n times”, it is meant that the 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. In particular, 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. By "alkyl" is meant, for each occurrence, a linear or branched or cyclic alkyl chain having from 1 to 12 carbon atoms.
Par « chaîne fluorée », on entend une chaîne alkyle linéaire ou ramifiée ou cyclique ayant de 1 à 12 atomes de carbone dont au moins l’un des atomes d’hydrogène est substitué par un fluor. De même, par « fluoroalkylène », on entend un alkylène dont au moins l’un des atomes d’hydrogène est substitué par un fluor. By "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. Likewise, by "fluoroalkylene" is meant an alkylene of which at least one of the hydrogen atoms is substituted by a fluorine.
Par « chaîne perfluorée », on entend une chaîne alkyle linéaire ou ramifiée ou cyclique ayant de 1 à 12 atomes de carbone dont tous les atomes d’hydrogène sont substitués par un fluor. By "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.
Par « fractions molaires en monomère (a), (b) et (c) dans le copolymère », respectivement x, y et z, on entend le rapport entre le nombre de moles de monomère (a), (b) ou (c) respectivement, sur le nombre de moles total en monomère (c’est-à-dire le nombre de moles de monomère (a), (b) et (c). Ainsi, on a x + y + z =l. By “molar fractions of monomer (a), (b) and (c) in the copolymer”, respectively x, y and z, 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). Thus, we have ax + y + z = 1.
Par « degré de polymérisation DPn du copolymère de formule (II) », on entend le nombre total d’unités monomériques, c’est-à-dire la somme des unités monomériques correspondant aux monomères (a), (b), et (c). The term “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).
Par « à l’échelle du mélange, v et w sont des proportions molaires... », on entend que v et w sont relatifs au mélange du monomère correspondant à l’unité propylène glycol (-O-CH2- CH(CH3)-) et du monomère correspondant à l’unité éthylène glycol (-O-CH2-CH2)-) susceptible de permettre l’obtention du méthacrylate de formule (Ib) ou du mélange de méthacrylates de formule (Ib). By "on the scale of the mixture, v and w are molar proportions ...", it is meant that 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).
Préparation des copolymères de l’ invention Preparation of the copolymers of the invention
Les copolymères de la présente invention peuvent être synthétisés par un procédé de polymérisation en solution, ou en émulsion, ou en suspension. Ils peuvent être sous la forme de polymères statistiques, polymères à gradient, polymères à bloc. Ils peuvent être obtenus par polymérisation radicalaire conventionnelle, polymérisation radicalaire contrôlée (RAFT, ATRP, NMP, RITP, ... ), ou polymérisation par transfert de groupe . The 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.
FIGURES FIGURES
La figure 1 illustre la résistance en compression à 23°C, en fonction de la densité, des mousses telles que mentionnées dans les exemples. Figure 1 illustrates the compressive strength at 23 ° C, as a function of density, of foams as mentioned in the examples.
La figure 2 illustre la résistance en compression à -170°C, en fonction de la densité, des mousses telles que mentionnées dans les exemples.
La figure 3 est un cliché de la mousse polyuréthane El telle que définie à l’exemple 2, ayant permis les mesures relatives à la mousse El consignées dans le tableau 3 dudit exemple 2.Figure 2 illustrates the compressive strength at -170 ° 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.
La figure 4 est un cliché de la mousse polyuréthane E2 telle que définie à l’exemple 2, ayant permis les mesures relatives à la mousse E2 consignées dans le tableau 3 dudit exemple 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.
La figure 5 est un cliché de la mousse polyuréthane E3 telle que définie à l’exemple 2, ayant permis les mesures relatives à la mousse E3 consignées dans le tableau 3 dudit exemple 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.
Exemples Examples
Exemple 1 : synthèse des copolymères Example 1: synthesis of the copolymers
Le méthacrylate fluoré (a), en particulier de formule (la), le méthacrylate (b) contenant au moins un groupe oxyalkylène, en particulier de formule (Ib), et le méthacrylate d’alkyle (c), en particulier de formule (le), sont dilués dans de la 2-butanone comme solvant (extrait sec - 20%). L’amorceur radicalaire utilisé pour déclencher la polymérisation est GAIBN (Azobisisobutyronitrile - 2,5 à 3 % massique). Le milieu réactionnel est placé sous atmosphère inerte par bullage d’argon pendant 30 min. La réaction de polymérisation se déroule à 70°C jusqu’à conversion totale. Après polymérisation, le polymère méthacrylique est obtenu par précipation dans le pentane et évaporation des solvants sous vide industriel. 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. After polymerization, the methacrylic polymer is obtained by precipitation in pentane and evaporation of the solvents under industrial vacuum.
Le méthacrylate fluoré (a) est en particulier le tridécafluorooctyl méthacrylate ([2144-53-8]). Le méthacrylate d’alkyle (c) est en particulier le méthacrylate de butyle. The fluorinated methacrylate (a) is in particular tridecafluorooctyl methacrylate ([2144-53-8]). The alkyl methacrylate (c) is in particular butyl methacrylate.
Le méthacrylate (b), avant acylation, est en particulier un composé Polyglykol commercialisé par Clariant, notamment le Polyglycol MA 350, MA 750, MA 1000 M70, MA 2000 M55, MA 3000, ou MA 50000 M50 ; ou encore le composé Visiomer MPEG 2005 MA W (Evonik). Lorsque dans le méthacrylate de formule (Ib), B est de formule -C(=0)-D telle que définie précédemment, ce méthacrylate est obtenu à partir d’un méthacrylate de formule (Ib), avec B=- OH, par réaction avec un chlorure d’acyle, notamment le chlorure d’acétyle (1,1 éq. par fonction alcool) en présence de triéthylamine dans le dichlorométhane. 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). When in the methacrylate of formula (Ib), B is of formula -C (= 0) -D as defined above, this methacrylate is obtained from a methacrylate of formula (Ib), with B = - OH, by reaction with an acyl chloride, in particular acetyl chloride (1.1 eq. per alcohol function) in the presence of triethylamine in dichloromethane.
Des copolymères particuliers sont obtenus en utilisant les fractions molaires en monomère de formule (la), (Ib), avec B=-C(=0)-Me et (le), dans le copolymère, respectivement x, y et z (telles que définies précédemment), comme indiqué dans le tableau suivant : Particular copolymers are obtained by using the molar fractions of monomer of formula (la), (Ib), with B = -C (= 0) -Me and (le), in the copolymer, respectively x, y and z (such as as defined previously), as indicated in the following table:
Exemple 2 : synthèse des mousses polyuréthanes Example 2: synthesis of polyurethane foams
Les différents éléments du composant 1 du tableau 2 sont mélangés uniformément. Les composants 3 puis 2 sont ensuite ajoutés au composant 1. Les formulations ainsi obtenues sont coulées sur un mat de fibre de verre de façon à ce que la mousse polyuréthane renforcée présente une teneur en fibres de 9% et une masse volumique de 130kg/m3. Dans ces essais, la masse surfacique, le taux de liant et le nombre de mats de fibres de verre sont respectivement de 450g/m2, de 0,8% et de 8. 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 . In these tests, 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.
Trois mousses polyuréthane, nommées El, E2 et E3, sont obtenues en utilisant respectivement les copolymères de l’invention, S 1/S2 et S3, et un copolymère commercial non objet de l’invention. 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.
Après stabilisation, des essais de résistance à la compression en Z à chaud et à froid sont effectués, à l'échelle laboratoire, sur chacune des 3 mousses polyuréthane précédentes. After stabilization, hot and cold Z compressive strength tests are carried out on a laboratory scale on each of the 3 previous polyurethane foams.
Les mousses polyuréthane de l’invention peuvent être obtenues par tout procédé bien connu de l’homme du métier à partir des formulations indiquées dans le tableau 2. En particulier, elles peuvent être obtenues par un procédé continu. Dans ce cas, par exemple : The 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:
les matières premières sont stockées, liquides, dans de grands réservoirs en acier inoxydable. Ces réservoirs sont équipés d'agitateurs pour garder les matériaux fluides. Un dispositif de dosage est fixé aux réservoirs afin que la quantité appropriée de matériau réactif puisse être pompée. Le rapport entre les différents composants est strictement contrôlé ; 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;
les différents composés sont passés à travers un échangeur de chaleur lorsqu'ils sont pompés dans les tuyaux. L'échangeur ajuste la température à la température de réaction. A l’extrémité des tuyaux se trouve une tête de distribution du polymère où démarrent les réactions chimiques citées précédemment; 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. At the end of the pipes is a polymer distribution head where the chemical reactions mentioned above start;
la tête de distribution est accrochée au-dessus de la ligne de traitement. Pour la production d'isolant en mousse de polyuréthane rigide, un rouleau de papier kraft est enroulé au début de la ligne de traitement. Ce papier est déplacé le long d'un convoyeur et amené sous la tête de distribution ;
au fur et à mesure que le papier passe, du polyuréthane est déposé dessus. Le polyuréthane augmente en volume grâce aux agents gonflants ; the distribution head is hung above the treatment line. For the production of rigid polyurethane foam insulation, 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;
après le début de la réaction d’expansion, une deuxième couche de papier, supérieure, peut êtredéposée sur la mousse polyuréthane. De plus, des papiers latéraux peuvent également être roulés dans le processus. La mousse rigide est passée à travers une série de panneaux qui contrôlent la largeur et la hauteur de la mousse. Lorsqu'ils traversent cette section de la chaîne de production, ils sont généralement séchés ; After the expansion reaction begins, a second, upper layer of paper can be applied to the polyurethane foam. Additionally, 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;
à la fin de la ligne de production, l'isolant en mousse est coupé à l'aide d'une scie automatique à la longueur désirée. at the end of the production line, the foam insulation is cut with an automatic saw to the desired length.
La taille des cellules des mousses obtenues est consignée dans le tableau suivant. The cell size of the foams obtained is given in the following table.
Ainsi, il apparaît que la modification des paramètres x, y et z tels que défini plus haut permet de faire varier facilement la taille des cellules de la mousse polyuréthane obtenue. Thus, it appears that the modification of the parameters x, y and z as defined above makes it possible to easily vary the size of the cells of the polyurethane foam obtained.
Exemple 3 : Tests de résistance à la compression Example 3: Compressive strength tests
Le présent exemple illustre les résultats des essais en compression en Z (c'est-à-dire dans l'épaisseur de la mousse renforcée), à chaud et à froid, qui simulent la pression au niveau des parois latérales des cuves, générée par le mouvement du gaz liquéfié au sein de la cuve d’un méthanier par exemple. 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.
Lorsque les essais en compression en Z ont lieu à chaud, ils se déroulent à température ambiante. Lorsque ces essais ont lieu à froid, ils se déroulent dans un cryostat dans lequel la température est de -170°C (par utilisation d'azote liquide). When the Z compression tests are carried out hot, they take place at room temperature. When these tests take place cold, they take place in a cryostat in which the temperature is -170 ° C (by using liquid nitrogen).
Ces essais sont effectués sur le premier bloc de mousse obtenu lors de la coulée (L) ou sur le deuxième bloc de la coulée (L2). These tests are carried out on the first block of foam obtained during casting (L) or on the second block of casting (L2).
Les essais en compression en Z sont réalisés selon la norme M3007: ISO 844 (ou équivalent). La résistance en compression est évaluée en mesurant la pression appliquée verticalement sur la surface de chacun des échantillons, en fonction du déplacement de la surface par rapport à sa position initiale dans le sens de l'épaisseur de chaque échantillon. Ces mesures sont reportées sur une courbe dite de résistance à la compression (non représentée). Le maximum de pression appliquée avant rupture de la structure de la mousse renforcée (maximum de ladite courbe) correspond à la résistance à la compression maximale qui est désignée ici-même par compression en Z. 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 (maximum of said curve) corresponds to the maximum compressive strength which is referred to here as Z compression.
Les résultats obtenus sont illustrés dans les figures 1 et 2. The results obtained are illustrated in Figures 1 and 2.
Il apparaît que les mousses de l’invention résistent mieux à la compression, à la fois à température ambiante et à froid, que les mousses actuelles, notamment la mousse E3.
It appears that the foams of the invention are more resistant to compression, both at room temperature and in cold conditions, than current foams, in particular E3 foam.
Claims
1. Mousse de polyuréthane comprenant un copolymère d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c). 1. Polyurethane foam comprising a copolymer of a fluorinated methacrylate (a), a methacrylate (b) containing at least one oxyalkylene group and an alkyl methacrylate (c).
2. Mousse selon la revendication 1, dans laquelle le méthacrylate fluoré (a) comprend une chaîne carbonée constituée d’une chaîne alkyle prolongée d’une chaîne fluorée, notamment perfluorée, le méthacrylate fluoré (a) étant notamment de formule (la) ou (la’) suivante, ou un mélange de méthacrylates de formule (la) ou (la’) suivante : 2. Foam according to claim 1, in which 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 (la ') following, or a mixture of methacrylates of formula (la) or (la') below:
dans laquelle : in which :
A est un fluoroalkylène en C1-C5, en particulier un perfluoroalkylène en C1-C3, ou un alkylène en C1-C5; A is C1-C5 fluoroalkylene, in particular C1-C3 perfluoroalkylene, or C1-C5 alkylene;
q est un nombre entre 1 et 3, q étant en particulier égal à 2 ; q is a number between 1 and 3, q being in particular equal to 2;
q’ est un nombre entre 1 et 100, q’ étant en particulier compris entre 1 et 3 ; q ’is a number between 1 and 100, q’ being in particular between 1 and 3;
r est un nombre entre 1 et 7, r étant en particulier égal à 3, 4, 5 ou 6. r is a number between 1 and 7, r being in particular equal to 3, 4, 5 or 6.
3. Mousse selon l’une quelconque des revendications précédentes dans laquelle le méthacrylate (b) contenant au moins un groupe oxyalkylène contient au moins un groupe oxyéthylène et au moins un groupe oxypropylène, ou le méthacrylate (b) contenant au moins un groupe oxyalkylène est de formule (Ib) suivante, ou un mélange de méthacrylates de formule (Ib) suivante : 3. Foam according to any one of the preceding claims, in which the methacrylate (b) containing at least one oxyalkylene group contains at least one oxyethylene group and at least one oxypropylene group, or the methacrylate (b) containing at least one oxyalkylene group is of formula (Ib) below, or a mixture of methacrylates of formula (Ib) below:
dans laquelle :
B est un atome d’hydrogène, ou un alkyle linéaire ou ramifié en Ci à C4, en particulier le méthyle, ou un groupe -C(=0)-D, où D est un alkyle linéaire ou ramifié en Ci à C4, en particulier le méthyle, in which : B is a hydrogen atom, or a linear or branched C1 to C4 alkyl, in particular methyl, or a group -C (= 0) -D, where D is a linear or branched C1 to C4 alkyl, in especially methyl,
à l’échelle du mélange, v et w sont des proportions molaires comprises entre 0 et 1, telles que v+w=l, avec w 4 0, et éventuellement v ¹0, on the scale of the mixture, v and w are molar proportions between 0 and 1, such that v + w = l, with w 4 0, and optionally v ¹0,
p est un nombre entier tel que : p is an integer such that:
v*p, le nombre d’unités propylène glycol (-0-CH2-CH(CH3)-) dans le méthacrylate (b), est compris entre 0 et 7, en particulier entre 3 et 7, et de préférence entre 4 et 6, v * p, 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, le nombre d’unités éthylène glycol (-O-CH2-CH2)-) dans le méthacrylate (b), est compris entre 38 et 54. w * p, the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54.
4. Mousse selon l’une quelconque des revendications précédentes dans laquelle le méthacrylate d’ alkyle (c) est de formule (le) suivante, ou un mélange de méthacrylates de formule (le) suivante : 4. Foam according to any one of the preceding claims wherein the alkyl methacrylate (c) is of the following formula (le), or a mixture of methacrylates of the following formula (le):
dans laquelle s est un nombre entre 0 et 12, s étant en particulier égal à 3 ou 4. in which s is a number between 0 and 12, s being in particular equal to 3 or 4.
5. Mousse selon l’une quelconque des revendications précédentes dans laquelle la masse molaire moyenne en nombre est comprise entre 6000 et 15000 g/mol. 5. Foam according to any one of the preceding claims wherein the number-average molar mass is between 6000 and 15000 g / mol.
6. Mousse selon l’une quelconque des revendications précédentes dans laquelle le copolymère est de formule (II) suivante : 6. Foam according to any one of the preceding claims, in which the copolymer is of the following formula (II):
dans laquelle, indépendamment du motif répété n fois : in which, independently of the pattern repeated n times:
x, y et z sont respectivement les proportions molaires en monomère (a), (b) et (c) dans le copolymère, comprises entre 0 et 1, avec x+y+z= 1, sous réserve que x ¹0, y ¹0 et z ¹0 ; n, le degré de polymérisation en nombre DPn du copolymère de formule (II), est un nombre entier entre 1 et 1000, DPn étant de préférence compris entre 10 et 100, et très préférentiellement entre 10 et 80 ; x, y and z are respectively the molar proportions of monomer (a), (b) and (c) in the copolymer, between 0 and 1, with x + y + z = 1, provided that x ¹0, y ¹0 and z ¹0; 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;
et dans laquelle, indépendamment du motif répété n fois : and in which, independently of the pattern repeated n times:
à l’échelle du mélange, v et w sont des proportions molaires comprises entre 0 et 1, telles que v+w=l, avec w 4 0, et éventuellement v ¹0, on the scale of the mixture, v and w are molar proportions between 0 and 1, such that v + w = l, with w 4 0, and optionally v ¹0,
p est un nombre entier tel que : p is an integer such that:
v*p, le nombre d’unités propylène glycol (-0-CH2-CH(CH3)-) dans le méthacrylate (b), est compris entre 0 et 7, en particulier entre 3 et 7, et de préférence entre 4 et 6, v * p, 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, le nombre d’unités éthylène glycol (-O-CH2-CH2)-) dans le méthacrylate (b), est compris entre 38 et 54. w * p, the number of ethylene glycol (-O-CH2-CH2) -) units in the methacrylate (b), is between 38 and 54.
q est un nombre entier entre 1 et 3, q étant en particulier égal à 2 ; q is an integer between 1 and 3, q being in particular equal to 2;
r est un nombre entier entre 1 et 7, notamment entre 6 et 7, r étant en particulier égal à 6 ; s est un nombre entier entre 0 et 6, s étant en particulier égal à 3 ou 4; le copolymère étant notamment de formule (Ha) suivante : r is an integer between 1 and 7, in particular between 6 and 7, r being in particular equal to 6; s is an integer between 0 and 6, s being in particular equal to 3 or 4; the copolymer being in particular of the following formula (Ha):
x, y, z, v, w, p, r et n étant tels que définis plus haut, q étant tel que défini plus haut, et étant en particulier égal à 2. 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.
7. Mousse selon la revendication 6 dans laquelle : 7. Foam according to claim 6 in which:
v*p est égal à 5, environ 5,1 ou environ 5,2, w*p est égal à 42, environ 46 ou environ 50, et r est égal à 6 ou 7, DPn étant en particulier égal à environ 45 ; et/ou
x est égal à environ 0,4, et y est égal à environ 0,1 ; ou v * p is equal to 5, about 5.1 or about 5.2, w * p is equal to 42, about 46 or about 50, and r is equal to 6 or 7, DPn being in particular equal to about 45; and or x is about 0.4, and y is about 0.1; or
x est égal à environ 0,08, et y est égal à environ 0,02 ; ou x is about 0.08, and y is about 0.02; or
x est égal à environ 0,37, et y est égal à environ 0,16 ; ou x is about 0.37, and y is about 0.16; or
x est égal à environ 0,07, et y est égal à environ 0,02 ; ou x is about 0.07, and y is about 0.02; or
x est égal à environ 0,077, et y est égal à environ 0,025. x is about 0.077, and y is about 0.025.
8. Utilisation d’un copolymère d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c) tel que défini dans l’une quelconque des revendications 1 à 7 pour la préparation d’une mousse polyuréthane. 8. Use of a copolymer of a fluorinated methacrylate (a), of a methacrylate (b) containing at least one oxyalkylene group and of an alkyl methacrylate (c) as defined in any one of the claims. 1 to 7 for the preparation of a polyurethane foam.
9. Procédé de préparation de mousse polyuréthane comprenant les étapes consistant à: 9. A process for preparing polyurethane foam comprising the steps of:
(i) mettre en contact un composé isocyanate et au moins un composé polyol, en présence : (i) bringing an isocyanate compound into contact with at least one polyol compound, in the presence:
d’un catalyseur choisi parmi les sels d'étain, les carboxylates de potassium et éventuellement les amines tertiaires, of a catalyst chosen from tin salts, potassium carboxylates and optionally tertiary amines,
d’un agent gonflant physique et/ou chimique, a physical and / or chemical blowing agent,
d’un copolymère d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c), tel que décrit dans l’une quelconque des revendications 1 à 7, et of a copolymer of a fluorinated methacrylate (a), of a methacrylate (b) containing at least one oxyalkylene group and of an alkyl methacrylate (c), as described in any one of claims 1 to 7, and
éventuellement d’un retardateur de flamme, et possibly a flame retardant, and
(ii) laisser solidifier, après expansion, le mélange obtenu lors de l’étape (i) de façon à former une mousse polyuréthane. (ii) allow the mixture obtained in step (i) to solidify, after expansion, so as to form a polyurethane foam.
10. Procédé de préparation selon la revendication 9, dans lequel la quantité en copolymère est comprise de 0,1 à 10 % en masse par rapport au au moins un composé polyol, en particulier de 0,5 à 2% en masse, plus particulièrement environ 1,5 % en masse. 10. Preparation process according to claim 9, wherein the amount of copolymer is from 0.1 to 10% by mass relative to at least one polyol compound, in particular from 0.5 to 2% by mass, more particularly about 1.5% by mass.
11. Procédé de préparation selon l’une quelconque des revendications 9 à 10, dans lequel le composé isocyanate est tel que sa teneur massique en fonction isocyanate est comprise de 100 à 130, et/ou sa viscosité à 25°C est comprise de 200 à 600 mPa.s, et/ou sa fonctionnalité
moyenne est comprise de 2,5 à 3,5, de préférence entre 2,9 et 3,1, et/ou est choisi parmi les diisocyanates de diphénylméthylène (MDI), notamment le 2,2'-diisocyanate de diphénylméthylène (2,2'-MDI), le 4,4'-diisocyanate de diphénylméthylène (4,4'-MDI) et le 2,4'- diisocyanate de diphénylméthylène (2,4'-MDI); les diisocyanates de toluène (TDI), notamment le 2,6-diisocyanate de toluène (2,6-TDI) et le 2,4-diisocyanate de toluène (2,4-TDI); le 4,4’- dibenzyl diisocyanate (4,4’-DBDI); le m-xylylène diisocyanate (m-XDI); le 2,4’-dibenzyl diisocyanate (2,4’-DBDI), le méthylène bis(4-cyclohexylisocyanate) (H12MDI); le diisocyanate d'isophorone (IPDI) ; le diisocyanate d'hexaméthylène (HDI) ; le diisocyanate de 1,5-naphthalène, le diisocyanate bitolylène ; et les polyisocyanates, notamment le poly- diisocyanate de diphénylméthylène (PMDI) ; le composé isocyanate étant en particulier un diisocyanate de diphénylméthylène ou un poly-diisocyanate de diphénylméthylène. 11. Preparation process according to any one of claims 9 to 10, wherein the isocyanate compound is such that its content by weight of isocyanate function is between 100 and 130, and / or its viscosity at 25 ° C is between 200. at 600 mPa.s, and / or its functionality average is from 2.5 to 3.5, preferably between 2.9 and 3.1, and / or is chosen from diphenylmethylene diisocyanates (MDI), in particular diphenylmethylene 2,2'-diisocyanate (2, 2'-MDI), diphenylmethylene 4,4'-diisocyanate (4,4'-MDI) and diphenylmethylene 2,4'-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 diisocyanate (2,4'-DBDI), methylene bis (4-cyclohexylisocyanate) (H12MDI); isophorone diisocyanate (IPDI); hexamethylene diisocyanate (HDI); 1,5-naphthalene diisocyanate, bitolylene diisocyanate; and polyisocyanates, especially poly-diphenylmethylene diisocyanate (PMDI); the isocyanate compound being in particular a diphenylmethylene diisocyanate or a poly-diphenylmethylene diisocyanate.
12. Procédé de préparation selon l’une quelconque des revendications 9 à 11, dans lequel le au moins un composé polyol est tel que sa valeur en groupe hydroxyle est comprise de 200 à 500 mg KOH/g, et/ou sa viscosité à 25°C est comprise de 200 à 6000 mPa.s, et/ou sa fonctionnalité moyenne est comprise de 2 et 6, et/ou est choisi parmi les polyesters, le sorbitol, les polyéthers, le glycérol et leurs mélanges, le composé polyol étant en particulier un polyester aromatique. 12. Preparation process according to any one of claims 9 to 11, wherein 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 between 200 and 6000 mPa.s, and / or its average functionality is between 2 and 6, and / or is chosen from polyesters, sorbitol, polyethers, glycerol and their mixtures, the polyol compound being in particular an aromatic polyester.
13. Procédé de préparation selon l’une quelconque des revendications 9 à 12, dans lequel l’index isocyanate, c’est-à-dire le rapport molaire fonctions NCO sur fonctions OH est supérieur ou égal à 1, en particulier supérieur à 1. 13. Preparation process according to any one of claims 9 to 12, wherein 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. .
14. Procédé de préparation selon l’une quelconque des revendications 9 à 13, dans lequel14. Preparation process according to any one of claims 9 to 13, wherein
- l’agent gonflant chimique est de l’eau, et /ou - the chemical blowing agent is water, and / or
- la quantité en agent gonflant chimique est comprise de 0,05 à 5 % en masse par rapport au au moins un composé polyol, en particulier de 0,05 à 1% en masse, plus particulièrement environ 0,2-0, 3% en masse. - 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% en masse.
15. Procédé de préparation selon l’une quelconque des revendications 9 à 14, dans lequel : l’agent gonflant physique est choisi parmi les hydrochlorofluorocarbones (HCFC), les hydrofluorocarbones (HFC), les hydrocarbones (HC) en particulier choisi parmi le cyclopentane, le u-pentane, l’/.so-pentane et l’/.so-butane, l’agent gonflant physique étant notamment choisi parmi le 1,1,1,3,3,-pentafluoropropane , le trans-l-chloro-3,3,3-
trifluoropropène, le 1 ,1 , 1 ,3,3-pcntafluorobutanc, le 1,1,1,2,3,3,3-heptafluoropropane et leurs mélanges, et/ou 15. Preparation process according to any one of claims 9 to 14, in which: the physical swelling agent is chosen from hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), hydrocarbons (HC) in particular chosen from cyclopentane , u-pentane, /. so-pentane and /. so-butane, the physical swelling agent being chosen in particular from 1,1,1,3,3, -pentafluoropropane, trans-1- chloro-3,3,3- trifluoropropene, 1, 1, 1, 3,3-pcntafluorobutanc, 1,1,1,2,3,3,3-heptafluoropropane and mixtures thereof, and / or
la quantité en agent gonflant physique est comprise de 0,1 à 30 % en masse par rapport au au moins un composé polyol, en particulier de 5 à 10% en masse, ou est d’environ 15% en masse. 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 about 15% by mass.
16. Procédé de préparation selon l’une quelconque des revendications 9 à 15, dans lequel le catalyseur est choisi parmi la triethylènediamine, la pentaméthyldiethylènetriamine, la diméthylcyclohexylamine, le 1,4-diazabicyclo (2,2,2)-octane, et le dilaurate de dibutylétain, le catalyseur étant en particulier le dilaurate de dibutylétain. 16. Preparation process according to any one of claims 9 to 15, wherein the catalyst is chosen from triethylenediamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, 1,4-diazabicyclo (2,2,2) -octane, and dibutyltin dilaurate, the catalyst being in particular dibutyltin dilaurate.
17. Procédé de préparation selon l’une quelconque des revendications 9 à 16, dans lequel la mousse obtenue à l’issue de l’étape (ii) a une densité comprise entre 20 et 250kg/m3. 17. Preparation process according to any one of claims 9 to 16, in which the foam obtained at the end of step (ii) has a density of between 20 and 250 kg / m 3 .
18. Utilisation de la mousse selon l'une quelconque des revendications 1 à 7 dans l'isolation thermique de cuves de transport de gaz liquéfié, et notamment de cuves de méthanier. 18. Use of the foam according to any one of claims 1 to 7 in the thermal insulation of liquefied gas transport tanks, and in particular of LNG tankers.
19. Copolymère d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c), ledit alkyle étant une chaîne alkyle linéaire ou ramifiée ou cyclique ayant de 1 à 12 atomes de carbone. 19. 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 linear or branched or cyclic alkyl chain having 1 to 12 carbon atoms.
20. Composition comprenant un copolymère d’un méthacrylate fluoré (a), d’un méthacrylate (b) contenant au moins un groupe oxyalkylène et d’un méthacrylate d’alkyle (c), et un agent gonflant physique.
20. A composition comprising a copolymer of a fluorinated methacrylate (a), a methacrylate (b) containing at least one oxyalkylene group and an alkyl methacrylate (c), and a physical blowing agent.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
Publications (1)
Publication Number | Publication Date |
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EP4103641A1 true EP4103641A1 (en) | 2022-12-21 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP20704045.2A Pending EP4103641A1 (en) | 2019-02-18 | 2020-02-14 | Methacrylate copolymers, and uses thereof for manufacturing polyurethane foam |
Country Status (5)
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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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Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
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US248721A (en) | 1881-10-25 | William deiscoll | ||
US573327A (en) | 1896-12-15 | Needle-throat for sewing-machines | ||
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 |
TWI385189B (en) * | 2003-11-26 | 2013-02-11 | Asahi Glass Co Ltd | Flexible polyurethane foam, method for its production, and automobile sheet employing it |
FR2882756B1 (en) * | 2005-03-04 | 2007-04-27 | Gaz Transp Et Technigaz Soc Pa | FOAM OF POLYURETHAN-POLYISOCYANURATE REINFORCED WITH GLASS FIBERS |
MX2014004563A (en) * | 2011-10-14 | 2014-08-01 | Dow Global Technologies Llc | 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 |
JP7065767B2 (en) * | 2015-10-02 | 2022-05-12 | ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー | Hydrophobic extender for 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 |
-
2019
- 2019-02-18 FR FR1901617A patent/FR3092837B1/en active Active
-
2020
- 2020-02-14 CN CN202080013713.5A patent/CN113423773B/en active Active
- 2020-02-14 WO PCT/EP2020/053956 patent/WO2020169482A1/en unknown
- 2020-02-14 EP EP20704045.2A patent/EP4103641A1/en active Pending
- 2020-02-14 KR KR1020217025313A patent/KR20210132653A/en unknown
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Publication number | Publication date |
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CN113423773A (en) | 2021-09-21 |
CN113423773B (en) | 2022-10-14 |
FR3092837A1 (en) | 2020-08-21 |
FR3092837B1 (en) | 2021-08-27 |
KR20210132653A (en) | 2021-11-04 |
WO2020169482A1 (en) | 2020-08-27 |
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