WO2011051623A1 - Utilisation d'oligomeres d'acide hydroxycarboxylique comme adhesifs, procede de fabrication et oligomeres d'acide hydroxycarboxylique obtenus - Google Patents
Utilisation d'oligomeres d'acide hydroxycarboxylique comme adhesifs, procede de fabrication et oligomeres d'acide hydroxycarboxylique obtenus Download PDFInfo
- Publication number
- WO2011051623A1 WO2011051623A1 PCT/FR2010/052304 FR2010052304W WO2011051623A1 WO 2011051623 A1 WO2011051623 A1 WO 2011051623A1 FR 2010052304 W FR2010052304 W FR 2010052304W WO 2011051623 A1 WO2011051623 A1 WO 2011051623A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydroxycarboxylic acid
- functionalized
- acid oligomer
- oligomer according
- functional agent
- Prior art date
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000853 adhesive Substances 0.000 title claims abstract description 27
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012978 lignocellulosic material Substances 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 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 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
- 235000019197 fats Nutrition 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 229920003319 Araldite® Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 241001048891 Jatropha curcas Species 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 150000003626 triacylglycerols Chemical class 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 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 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241000221089 Jatropha Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 241000218657 Picea Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 241000219492 Quercus Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 239000004823 Reactive adhesive Substances 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 208000003796 chancre Diseases 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- -1 fatty acid esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 208000006379 syphilis Diseases 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4283—Hydroxycarboxylic acid or ester
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Definitions
- the present invention relates to the use of at least one particular biodegradable hydroxycarboxylic acid oligomer as an adhesive.
- the invention also relates to a process for the manufacture of oligomers of biodegradable hydroxycarboxylic acid and the particular products obtained by the implementation of this process and the adhesive compositions incorporating them.
- An adhesive is defined as a product capable of adhering materials. Virtually all materials can be bonded together in a 3-step process: applying the adhesive to the surface of at least one of the materials to be bonded, contacting the materials, and drying or curing the adhesive.
- thermosetting such as phenolic compounds, epoxides, polyurethanes, etc.
- physical adhesives whose hardening corresponds to a change in physical state (from the liquid state to the solid state) such as the solvent products or the hot-melt products such as polyesters or ethylene-vinyl acetate copolymers. These adhesives are widely used because they have excellent bonding properties, and can be produced in industrial quantities at low cost.
- the functionalized hydroxycarboxylic acid oligomer is obtained by at least one polycondensation step of a hydroxycarboxylic acid and a functional agent derived from an oil or a fat of natural origin.
- hydroxycarboxylic acid oligomer is meant a molecule consisting of a finite number of monomers (from 1 to 1000) of hydroxycarboxylic acid coupled or crosslinked together covalently.
- Functionalized oligomer for the purposes of the invention is understood to mean an oligomer obtained by condensation of several hydroxycarboxylic acid monomers on themselves and for which part or all of the hydroxyl groups has been replaced by other groups.
- esterified oligomer an oligomer obtained by condensation of several hydroxycarboxylic acid monomers on themselves and for which part or all of the hydroxyl groups has been replaced by ester groups.
- Another subject of the invention relates to a particular process for producing functionalized hydroxycarboxylic acid oligomers useful as adhesives, from hydrocarboxylic acids in the presence of a functional agent.
- the invention also relates to the functionalized oligomers of hydroxycarboxylic acid obtained.
- Such molecules have the following formula:
- R2 representing a reactive function, preferably OH or
- - x being an integer greater than or equal to 1, preferably between 1 and 10,
- M represents a hydroxycarboxylic acid
- n an integer between 1 and 1000.
- a final subject of the invention relates to adhesive products or adhesive compositions also comprising functionalized oligomers of hydroxycarboxylic acid.
- the present invention makes it possible to obtain molecules having a good effectiveness in terms of adhesiveness, while being degradable in a natural environment and not harmful to the environment.
- the present invention therefore aims at the use as adhesive of at least one functionalized oligomer of hydroxycarboxylic acid obtained by at least one polycondensation step of a hydroxycarboxylic acid and a functional agent derived from an oil or a grease of natural origin. It could be in particular a hydroxycarboxylic acid oligomer with at least one acid or hydroxyl function.
- the functionalized hydroxycarboxylic acid oligomer is a hydroxycarboxylic acid oligomer ester.
- it is a functionalized hydroxycarboxylic acid oligomer having a degree of polymerization of 1 to 1000 with one or more hydroxyl function (s) or one or more acid function (s). Even more preferentially, the degree of polymerization is between 1 and 100.
- the acidic functions are preferably chosen from:
- linear or branched unsaturated fatty acids containing from 6 to 32 carbon atoms, preferably from 12 to 20, and from 1 to 10 unsaturations, such as linoleic acid or oleic acid.
- the functionalized hydroxycarboxylic acid oligomer can be used as an adhesive to bond materials, particularly as an adhesive of lignocellulosic materials.
- the lignocellulosic materials may be chosen from:
- the functionalized oligomer according to the invention may be applied alone directly to a material to be bonded, or integrated into a composition.
- the coated material of the functionalized oligomer is then brought into contact with another material, possibly also previously coated. After drying between about 1 minute and 40 hours, the materials are glued.
- it may be associated with at least one polyisocyanate dispersed beforehand in the oligomer during the application.
- the molar ratio between the polyisocyanate (s) and the functionalized oligomer according to the invention is between 0.1 and 50%.
- the polyisocyanates may be chosen in particular from methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate.
- MDI methylene diphenyl diisocyanate
- TDI toluene diisocyanate
- HDI hexamethylene diisocyanate
- isophorone diisocyanate isophorone diisocyanate.
- the functionalized hydroxycarboxylic acid oligomers useful according to the invention can be obtained by a particular manufacturing method.
- This process comprises at least one polycondensation step of at least one hydroxycarboxylic acid and at least one functional agent.
- functional agent is meant a natural compound having at least one reactive function, preferably between 1 and 10 reactive functions.
- the functional agent is a derivative of an oil or a fat of natural origin (lipid-rich raw materials), that is to say a functional agent obtained from monoglycerides or diglycerides themselves obtained from triglycerides, the main constituents of vegetable oils and animal fats.
- Vegetable oils in particular are indeed oils with a high triglyceride content or essentially consisting of triglycerides of fatty acid esters and glycerol.
- Jatropha curcas extracted from mature seeds of Jatropha curcas, is a liquid oil at room temperature, of unsaturated type and with a predominance of oleic (43-53%), linoleic (20-32%) and palmitic ( 13-15%).
- Fatty alcohols can also be used as a functional agent.
- oils having fatty acids having between 12 and 20 carbon atoms and more ideally rich in C18 such as oleic, linoleic or linolenic acid will be chosen.
- it is an acid or hydroxyl functional agent, polyacid or polyol, that is to say a functional agent whose reactive function (s) (s) are acid or hydroxyl functions.
- the molar ratio functional agent on hydroxycarboxylic acid is preferably between 0.01 and 50%.
- the process according to the invention consists in polycondensing at least one hydroxycarboxylic acid by direct dehydration in the presence of a hydroxyl or acid compound to form a functionalized oligomer.
- reaction that occurs can be schematized as follows:
- n an integer between 1 and 1000.
- R representing a carbon chain
- - ⁇ representing a reactive function, preferably OH or COOH
- x an integer> 1, preferably between 1 and 10.
- the hydroxycarboxylic acid is lactic acid or glycolic acid.
- the polycondensation is carried out under vacuum at high temperature, that is to say:
- the polycondensation can be carried out in the presence of one or more catalysts, which in particular make it possible to increase the reaction rate.
- catalysts that may be used for the present invention, there may be mentioned in particular sulfuric acid or metals of groups I, II, III and IV of the periodic table, or salts based on these metals.
- sulfuric acid or metals of groups I, II, III and IV of the periodic table or salts based on these metals.
- tin octoate tin dichloride
- titanium butoxide titanium isopropoxide
- tin oxide antimony oxide
- dibutyltin dilaurate dibutyltin dilaurate
- zirconia acetylacetonate zirconia acetylacetonate.
- the functionalized oligomers obtained according to the invention are biodegradable and have a low average molecular weight of between 200 and 10,000 g / mol.
- They also have a low polydispersity index, that is to say between 1 and 2, and are amorphous (with a glass transition temperature of between 30 and 70 ° C.).
- the functionalized oligomers obtainable by the process according to the invention may be represented by the following formula:
- - x being an integer greater than or equal to 1, preferably between 1 and 10,
- M represents a hydroxycarboxylic acid
- n an integer between 1 and 1000.
- Example 1 Stearic Acid on which 10 Lactic Acid Molecules are Grafted
- Example 2 Oleic acid on which are grafted 10 lactic acid molecules
- the functionalized hydroxycarboxylic acid oligomers may be incorporated in compositions or products intended for bonding materials, in particular for bonding lignocellulosic materials.
- These adhesive compositions comprise between 10 and 100% functionalized hydroxycarboxylic acid oligomers, preferably between 20 and 90%. These compositions may also contain a polyisocyanate dispersed in the oligomer. The molar ratio between the polyisocyanate and the functionalized oligomer is preferably between 0.1 and 50%.
- the polyisocyanates may be chosen from methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate.
- MDI methylene diphenyl diisocyanate
- TDI toluene diisocyanate
- HDI hexamethylene diisocyanate
- isophorone diisocyanate isophorone diisocyanate.
- the adhesive compositions according to the invention may also comprise other adjuvants and other tackifiers.
- the functionalized hydroxycarboxylic acid oligomers have good adhesiveness qualities, comparable to those of existing synthetic adhesives.
- the tensile characteristics are determined according to the recommendations described in the international standard ISO / 527 (determination of tensile characteristics). The tests were therefore performed under conditions of temperature, humidity and speed of separation of well-defined jaws.
- the tensile test consists in imposing an elongation on a test specimen of initial section So and of useful length Lo. The specimen is encased at both ends in jaws. One of these movable jaws is connected to a linear displacement speed drive system. The force measurement is done using an electronic force sensor (10 kN).
- the operating protocol is as follows.
- a flask containing a mixture of L-lactic acid, ricinoleic acid (6.66 mol% vis-a-vis lactic acid) and tin octoate (at 1 ° C.) is heated between 160 and 190 ° C. mass% of the total mass), and is connected to a rotary evaporator.
- the assembly is placed under reduced pressure in order to eliminate the water produced by the condensation reactions.
- the mixture is placed at 800mbar. After one hour, the pressure is gradually decreased to 25mbar. The reaction is stopped after 9.5 hours, and the following are recovered:
- lactide in the form of white crystals distributed on the walls of the assembly (between 0.01 and 0.1% of the initial mixture by mass), and
- AIRicl5 an oligomer according to the invention denoted AIRicl5.
- a piece of parquet boards (6 by 6 by 0.9 cm 3 ) is coated on one of the thicknesses of a certain quantity of the oligomer obtained, then put in contact by the coated side with an identical piece of floorboards .
- the set is placed on a compression / traction device.
- the two pieces undergo compression (30 seconds, 1 MPa compression force and 1.8mm / min compression speed) followed by traction (with a tensile speed of 5mm / min).
- the tensile characteristics are thus determined and compared with those obtained with synthetic commercial glues (wood glue, Araldite® glue and neoprene glue).
- synthetic commercial glues wood glue, Araldite® glue and neoprene glue.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Biological Depolymerization Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/503,882 US9040638B2 (en) | 2009-10-30 | 2010-10-27 | Use of hydroxycarboxylic acid oligomers as adhesives, manufacturing method and hydroxycarboxylic acid oligomers obtained |
JP2012535904A JP2013509477A (ja) | 2009-10-30 | 2010-10-27 | ヒドロキシカルボン酸オリゴマーの接着剤としての使用、製造方法および得られるヒドロキシカルボン酸オリゴマー |
BR112012009238A BR112012009238A2 (pt) | 2009-10-30 | 2010-10-27 | uso de pelo menos um olgômero de ácido hodroxicarboxílico funcionalizado como adesivo, processo de fabricação de um oxigênio de ácido hidroxicarboxílico funcionalizado, oligômetro de ácido hidroxicarboxílico funcionalizado e composição adesiva destinada a colagem de materiais. |
EP10790461A EP2493954A1 (fr) | 2009-10-30 | 2010-10-27 | Utilisation d'oligomeres d'acide hydroxycarboxylique comme adhesifs, procede de fabrication et oligomeres d'acide hydroxycarboxylique obtenus |
CA2778994A CA2778994A1 (fr) | 2009-10-30 | 2010-10-27 | Utilisation d'oligomeres d'acide hydroxycarboxylique comme adhesifs, procede de fabrication et oligomeres d'acide hydroxycarboxylique obtenus |
CN201080049967.9A CN102666646B (zh) | 2009-10-30 | 2010-10-27 | 羟基羧酸低聚物作为粘结剂的应用、制备方法及其得到的羟基羧酸低聚物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0957647 | 2009-10-30 | ||
FR0957647A FR2952061B1 (fr) | 2009-10-30 | 2009-10-30 | Utilisation d'oligomeres d'acide hydroxycarboxylique comme adhesifs, procede de fabrication et oligomeres d'acide hydroxycarboxylique obtenus |
Publications (1)
Publication Number | Publication Date |
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WO2011051623A1 true WO2011051623A1 (fr) | 2011-05-05 |
Family
ID=42226480
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2010/052304 WO2011051623A1 (fr) | 2009-10-30 | 2010-10-27 | Utilisation d'oligomeres d'acide hydroxycarboxylique comme adhesifs, procede de fabrication et oligomeres d'acide hydroxycarboxylique obtenus |
Country Status (8)
Country | Link |
---|---|
US (1) | US9040638B2 (fr) |
EP (1) | EP2493954A1 (fr) |
JP (1) | JP2013509477A (fr) |
CN (1) | CN102666646B (fr) |
BR (1) | BR112012009238A2 (fr) |
CA (1) | CA2778994A1 (fr) |
FR (1) | FR2952061B1 (fr) |
WO (1) | WO2011051623A1 (fr) |
Families Citing this family (1)
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KR101861777B1 (ko) * | 2016-07-26 | 2018-06-29 | 주식회사 한국하우톤 | 리시놀렉-라틱산 유도체 및 그를 포함하는 수용성 금속가공유 조성물과 그의 제공 방법 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1995010577A1 (fr) * | 1993-10-15 | 1995-04-20 | H.B. Fuller Licensing & Financing Inc. | Adhesifs thermofusibles biodegradables/recyclables en compost constitues de polyester d'acide lactique |
WO1998035631A1 (fr) * | 1997-02-14 | 1998-08-20 | Pathak Chandrashekar | Polymeres biocompatibles et procedes d'utilisation de ceux-ci |
EP0899274A1 (fr) * | 1997-08-26 | 1999-03-03 | National Starch and Chemical Investment Holding Corporation | Copolymères de greffage de lactides et colles thermofusibles préparées à partir de ces copolymères |
WO2002034857A2 (fr) * | 2000-10-27 | 2002-05-02 | Metabolix, Inc. | Compositions contenant des polyhydroxyalcanoates de faible poids moleculaire et procedes d'utilisation de celles-ci |
Family Cites Families (14)
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US3284417A (en) * | 1963-11-13 | 1966-11-08 | Union Carbide Corp | Process for the preparation of lactone polyesters |
US3760034A (en) * | 1971-01-26 | 1973-09-18 | Union Carbide Corp | Graft copolymers of lactone polyesters |
FR2124853A5 (en) * | 1971-01-26 | 1972-09-22 | Union Carbide Corp | Lactone graft copolymers - by polymerising vinyl monomer with reactive side groups and graft polymerising vinyl polymer with |
US3764365A (en) * | 1972-01-21 | 1973-10-09 | Gen Tire & Rubber Co | Adhesion improving agent for urethane coatings on rubber |
US4156676A (en) * | 1978-03-27 | 1979-05-29 | Chevron Research Company | Hot melt adhesives having improved thermal stability |
US5502158A (en) * | 1988-08-08 | 1996-03-26 | Ecopol, Llc | Degradable polymer composition |
JP3330390B2 (ja) * | 1992-06-11 | 2002-09-30 | 三井化学株式会社 | ホットメルト接着剤組成物 |
JP3698533B2 (ja) | 1996-11-07 | 2005-09-21 | 三井化学株式会社 | 分解性共重合体を生分解性接着剤として使用する方法 |
DE19845152A1 (de) * | 1998-10-01 | 2000-04-20 | Merck Patent Gmbh | Bioabbaubare Polyester-Oligomere |
US7749539B2 (en) * | 2000-11-30 | 2010-07-06 | Efrat Biopolymers Ltd. | Polymeric formulations for drug delivery |
US6540987B2 (en) * | 2001-03-15 | 2003-04-01 | Ethox Chemicals Llc | Polyesters based on hydroxy fatty acids and lower hydroxy alkyl acids and uses thereof |
JP4745540B2 (ja) * | 2001-06-15 | 2011-08-10 | 昭和電工株式会社 | 生分解性水分散系接着剤組成物 |
JP2004131675A (ja) * | 2002-10-10 | 2004-04-30 | Diabond Industry Co Ltd | 生分解性ポリエステル樹脂系ホットメルト接着剤 |
US8394410B2 (en) * | 2005-01-20 | 2013-03-12 | Massachusetts Institute Of Technology | Soft polylactides |
-
2009
- 2009-10-30 FR FR0957647A patent/FR2952061B1/fr active Active
-
2010
- 2010-10-27 CN CN201080049967.9A patent/CN102666646B/zh not_active Expired - Fee Related
- 2010-10-27 EP EP10790461A patent/EP2493954A1/fr not_active Withdrawn
- 2010-10-27 JP JP2012535904A patent/JP2013509477A/ja active Pending
- 2010-10-27 CA CA2778994A patent/CA2778994A1/fr not_active Abandoned
- 2010-10-27 US US13/503,882 patent/US9040638B2/en not_active Expired - Fee Related
- 2010-10-27 BR BR112012009238A patent/BR112012009238A2/pt not_active IP Right Cessation
- 2010-10-27 WO PCT/FR2010/052304 patent/WO2011051623A1/fr active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995010577A1 (fr) * | 1993-10-15 | 1995-04-20 | H.B. Fuller Licensing & Financing Inc. | Adhesifs thermofusibles biodegradables/recyclables en compost constitues de polyester d'acide lactique |
WO1998035631A1 (fr) * | 1997-02-14 | 1998-08-20 | Pathak Chandrashekar | Polymeres biocompatibles et procedes d'utilisation de ceux-ci |
EP0899274A1 (fr) * | 1997-08-26 | 1999-03-03 | National Starch and Chemical Investment Holding Corporation | Copolymères de greffage de lactides et colles thermofusibles préparées à partir de ces copolymères |
WO2002034857A2 (fr) * | 2000-10-27 | 2002-05-02 | Metabolix, Inc. | Compositions contenant des polyhydroxyalcanoates de faible poids moleculaire et procedes d'utilisation de celles-ci |
Also Published As
Publication number | Publication date |
---|---|
JP2013509477A (ja) | 2013-03-14 |
CN102666646A (zh) | 2012-09-12 |
CA2778994A1 (fr) | 2011-05-05 |
FR2952061B1 (fr) | 2012-02-10 |
BR112012009238A2 (pt) | 2019-09-24 |
FR2952061A1 (fr) | 2011-05-06 |
CN102666646B (zh) | 2015-09-09 |
US9040638B2 (en) | 2015-05-26 |
EP2493954A1 (fr) | 2012-09-05 |
US20120219709A1 (en) | 2012-08-30 |
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