SG192737A1 - Polymers based on glycerol carbonate - Google Patents
Polymers based on glycerol carbonate Download PDFInfo
- Publication number
- SG192737A1 SG192737A1 SG2013061270A SG2013061270A SG192737A1 SG 192737 A1 SG192737 A1 SG 192737A1 SG 2013061270 A SG2013061270 A SG 2013061270A SG 2013061270 A SG2013061270 A SG 2013061270A SG 192737 A1 SG192737 A1 SG 192737A1
- Authority
- SG
- Singapore
- Prior art keywords
- oxide
- polymerization
- gly
- polymer
- carbonate
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 81
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 45
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 20
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 17
- 239000006260 foam Substances 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 239000012634 fragment Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002537 cosmetic Substances 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 229920005604 random copolymer Polymers 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- 229920000028 Gradient copolymer Polymers 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- WZYHGSHVTXRAFY-UHFFFAOYSA-N 2,2-dimethylimidazole Chemical compound CC1(C)N=CC=N1 WZYHGSHVTXRAFY-UHFFFAOYSA-N 0.000 claims description 2
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 claims description 2
- PTBPTNCGZUOCBK-UHFFFAOYSA-N 2,4,5-trimethyl-1h-imidazole Chemical compound CC1=NC(C)=C(C)N1 PTBPTNCGZUOCBK-UHFFFAOYSA-N 0.000 claims description 2
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 claims description 2
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-UHFFFAOYSA-N 0.000 claims description 2
- GXOYTMXAKFMIRK-UHFFFAOYSA-N 2-heptyloxirane Chemical compound CCCCCCCC1CO1 GXOYTMXAKFMIRK-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- LXVAZSIZYQIZCR-UHFFFAOYSA-N 2-nonyloxirane Chemical compound CCCCCCCCCC1CO1 LXVAZSIZYQIZCR-UHFFFAOYSA-N 0.000 claims description 2
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 claims description 2
- NMOFYYYCFRVWBK-UHFFFAOYSA-N 2-pentyloxirane Chemical compound CCCCCC1CO1 NMOFYYYCFRVWBK-UHFFFAOYSA-N 0.000 claims description 2
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 239000002826 coolant Substances 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000003651 drinking water Substances 0.000 claims description 2
- 235000020188 drinking water Nutrition 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 238000000855 fermentation Methods 0.000 claims description 2
- 230000004151 fermentation Effects 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- OTGHWLKHGCENJV-UHFFFAOYSA-N glycidic acid Chemical compound OC(=O)C1CO1 OTGHWLKHGCENJV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003906 humectant Substances 0.000 claims description 2
- 239000000976 ink Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000010985 leather Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229920006030 multiblock copolymer Polymers 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 239000000825 pharmaceutical preparation Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 claims 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 42
- -1 alkyl radicals Chemical class 0.000 description 24
- 239000002585 base Substances 0.000 description 20
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 16
- 150000003254 radicals Chemical class 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920000223 polyglycerol Polymers 0.000 description 5
- 125000001424 substituent group Chemical class 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000004007 reversed phase HPLC Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VUKCPUAOPNOVKC-UHFFFAOYSA-N OCC1OC(OC1)=O.OCC1OC(OC1)=O Chemical compound OCC1OC(OC1)=O.OCC1OC(OC1)=O VUKCPUAOPNOVKC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- IDWDPUULTDNNBY-UHFFFAOYSA-N ethyl n-(2-hydroxyethyl)carbamate Chemical class CCOC(=O)NCCO IDWDPUULTDNNBY-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
Abstract
16Polymers based on glycerol carbonate Abstract 5 The present invention relates to a polymer and the associated polymerization process,and to the use of the polymers according to the invention for example as foam suppressant, for the dispersion of solids or as surfactant for washing or cleaning purposes. The polymer is prepared by polymerization of 10 a) at least one alkylene oxide or a cyclic carbonate of the formula (I)0"00\(R1) (CH2) (I)„ mwhere 15 n is 1 to 10,m is 0 to 3 andR1 is CI-Cm-alkyl, C2-C10-alkenyl, aryl or aralkyl, b) glycerol carbonate,20where the polymerization is carried out in the presence of at least one base.No suitable figure
Description
Polymers based on glycerol carbonate
The present invention relates to a polymer and the associated polymerization process, and to the use of the polymers according to the invention for example as emulsifier, as foam regulator, as foam booster, as foam suppressant, for dispersing solids, as wetting agent for hard surfaces or as surfactant for washing or cleaning purposes. The polymers according to the invention are based on glycerol carbonate. The comonomer used is at least one alkylene oxide such as ethylene oxide or propylene oxide or a cyclic carbonate of the formula (I) defined below, such as ethylene carbonate or propylene carbonate. The polymerization is carried out in the presence of at least one base.
Glycerol carbonate is a basic chemical with a broad field of application. Thus, for example, it can react with anhydrides {o form ester bonds or with isocyanates to form urethane bonds. Furthermore, glycerol carbonate is used as a solvent in cosmetics or in medicine. On account of its low toxicity, its low evaporation rate, its low flammability and its moisturizing properties, glycerol carbonate is suitable as a wetting agent of cosmetic materials or as carrier solvent for medically effective substances.
Furthermore, glycerol carbonate can also be used as a starting material in polymer preparation. Alternatively to glycerol carbonate, epichlorohydrin, glycidol or glycerol can also be used during polymer preparation, it being possible for the oligomer or polymer structures prepared thereby to be varied depending on these glycerol derivatives used as starting material.
US-A 5,041,688 relates to a process for the preparation of polyglycerols which have a low fraction of cyclic products, where glycerol is reacted with epichlorohydrin in the presence of an acid such as phosphoric acid and a subsequent esterification with longer-chain carboxylic acids is carried out.
Problems with the polymerization process described above, however, are the low degree of condensation, the broad molecular weight distribution and the black, tar-like consistency of the product, which is caused by high thermal stresses during the condensation of the glycerol.
These problems were able to be overcome at least partially by using glycidol as in
DE-A 199 47 631 and EP-A 1785410 instead of glycerol or epichlorohydrin. On the other hand, on account of its carcinogenic properties and its high lability, the use of 40 glycidol is associated with additional problems.
DE-A 199 47 631 relates to a process for the preparation of polyols based on glycidol having a degree of polymerization of from 1 to 300, a polydispersity of < 1.7 and a content of branched units of up to ca. 30% (determined by C-NMR spectroscopy). In the associated process, a solution, comprising glycidol in dilute form, is reacted with a hydrogen-active starter compound with basic catalysis. A further process for the preparation of polymers based on glycidol is described in US-A 4,298,764, by means of which it is possible to prepare long-chain n-alkyl glyceryl ether alcohols with an n-alkyl chain length of from 10 to 20.
EP-A 1785 410 relates fo unbranched polyglycerol monoethers which are prepared by basic catalysis from an alcohol having up to 30 carbon atoms and glycidol. The polyglycerol monocethers prepared in the process have at least two fragments which are based on glycerol and/or glycidol building blocks. The polyglycerol monoether has a monoether fraction of at least 75% and a diether fraction of at most 5%, the particular fractions being determined by means of reverse-phase high-performance liquid chromatography (RP-HPLC).
As an alternative to the glycidol starting material, glycerol carbonate (4-(hydroxymethyl)-1,3-dioxolan-2-one), which is readily accessible from glycerol, has been proposed for the synthesis of oligoglycerols via a base-catalyzed polymerization.
For example, G. Rokicki et al., Green Chemistry, 2005, 7, pages 529 to 539 discloses a process for the preparation of hyperbranched aliphatic polyethers which are obtainable using glycerol carbonate as monomers. The hyperbranched aliphatic polyethers moreover have terminal units with two primary hydroxy groups. The ring-opening polymerization of glycerol carbonate is carried out with base catalysis using alkoxides.
Analogous processes for the preparation of amphiphilic glycerol or polyglycerol monoalkyl ethers using glycerol carbonate as starting material are described in
JP-A 2000 1119 205 or JP-A 11 335 313. In some cases, long-chain starter alcohols with alkyl radicals of up to 24 carbon atoms can also be used.
WO 2010/012562 relates to a catalytic process for the polymerization of cyclic carbonates which are obtained from renewable sources. The ring size of the cyclic carbonates is between 5 and 7 atoms, where a ring-opening polymerization is carried out in the presence of a system comprising a metal salt such as triflate and an alcohol.
Glycerol carbonate can also be used as cyclic carbonate. The polymers obtained in the process have carbonic acid ester building blocks, i.e. the polymerization takes place without the elimination of CO; since it is carried out in the presence of the metal salt, which acts as acidic catalyst.
DE-A 44 33 959 relates to a foaming detergent mixture with an improved foaming behavior which comprises alkyl and alkylene oligoglycoside glycerol ethers and also anionic, nonionic, cationic and/or amphoteric or zwitterionic surfactants. The alkyl and/or alkenyl oligoglycoside glycerol ethers present in the detergent mixtures are produced by etherifying alkyl and/or alkenyl oligoglycosides with glycerol glycine, glycerol carbonate or directly with glycerol and/or technical-grade oligoglycerol mixtures. Analogous alkyl and/or alkenyl oligoglycoside glycerol ethers are disclosed in
DE-A 43 35 947.
NN. Kihara et al. (Journal of Polymer Science: Part A: Polymer Chemistry, volume 31 (1993); pages 2765-2773) disclose a preparation process for polyhydroxyurethanes with a molecular weight M,, of from 20 000 to 30 000, where compounds which have two cyclic carbonate fragments are reacted with diamines such as hexamethylenediamine at 70 to 100°C over 24 h via a polyaddition. It is also described that cyclic carbonates with a ring size of 5 can be reacted easily at room temperature with primary aliphatic amines to give 2-hydroxyethylurethanes. The corresponding reactions of the cyclic carbonates with alcohols or carboxylic acids, and the aminolysis of the esters, however, do not take place under these reaction conditions.
The simultaneous use of glycerol carbonate and a comonomer, comprising alkylene oxide and/or a cyclic carbonate different from glycerol carbonate, such as ethylene carbonate, for the preparation of polymers has not yet been described.
The object underlying the present invention is therefore to provide further polymers based on glycerol carbonate, and also an associated polymerization process. The object is achieved by the polymers according to the invention prepared by polymerization of a) atleast one alkylene oxide or a cyclic carbonate of the formula (1) 1
RA
1 f,) (Rn (N where nis 11010, mis 0 to 3 and
R'is C-Cig-alkyl, C,-Cig-alkenyl, aryl or aralkyl,
b) glycerol carbonate, where the polymerization is carried out in the presence of at least one base.
The polymers according to the invention are characterized in that they can have both linear and branched structures. Depending on the polymerization conditions selected (e.g. temperature) and/or the monomers used (starting materials), polymers with different structures — for example different degrees of branching — and consequently variable application profiles can be prepared.
On account of using glycerol carbonate as monomer, the polymers according to the invention have an increased number of free OH functions. Each incorporated glycerol carbonate monomer brings about an additional potential linkage site in the polymer, by means of which the degree of branching can be controlled. As a result of the free OH functions, an increase in the water solubility, an improvement in salt compatibility (greater salt tolerance), and higher cloud points are achieved.
A further advantage is that, on account of the starting materials used and/or the polymerization conditions, polymers are prepared which have exclusively ether bonds and no ester bonds. The polymers according to the invention therefore have improved pH stability compared with conventional polymers in which the hydrophobic moiety and the hydrophilic moiety of the amphiphilic molecule or polymers are linked together via an ester bond. Depending on the choice of monomers, the polymers according to the invention can be amphiphilic, hydrophilic or hydrophobic.
The use of glycerol carbonate instead of glycidol as monomer during the polymerization is, moreover, associated with the advantage that glycerol carbonate is an easy-to-handle and nontoxic compound which can be readily polymerized with the elimination of CO,. In contrast to this, glycidol (as already described above) is a very hazardous substance which is toxic and expensive and for which, moreover, official operating approval is required in many countries. Furthermore, no protective groups are required when using glycerol carbonate. Moreover, the degree of branching of the polymers according to the invention can be controlled easily through the use of glycerol carbonate, as a result of which a multitude of polymers with different intended uses can be prepared.
Within the context of the present invention, definitions such as C;-Cp-alkyl, as for example defined above for the radical R' in formula (I), mean that this substituent 40 (radical} is an alkyl radical with a carbon atom number from 1 to 10. The alkyl radical may be linear or branched and also optionally cyclic. Alkyl radicals which have both a cyclic component and also a linear component likewise fall under this definition. The same is also true for other alkyl radicals, such as for example a C;-Cs-alkyl radical or a
C1-Cap-alkyl radical. The alkyl radicals can optionally also be mono- or polysubstituted 5 with functional groups such as amino, amido, ether, vinyl ether, isoprenyl, hydroxy, mercapto, carboxyl, halogen, aryl or heteroaryl. Unless stated otherwise, the alkyl radicals preferably have no functional groups as substituents. Examples of alky! radicals are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, isobuty!, 2-ethylhexyl, tertiary-butyl (tert-bu/t-Bu), pentyl, hexyl, heptyl, cyclohexyl, octyl, nonyl or decyl.
Within the context of the present invention, definitions such as C,-Cip-alkenyl, as for example defined above for the radical R' in formula (I), mean that this substituent (radical) is an alkenyl radical with a carbon atom number from 2 to 10. This carbon radical is preferably monounsaturated, but it can optionally also be di- or polyunsaturated. As regards linearity, branches, cyclic fractions and optionally present substituents, the analogous details as defined above with reference to the C;-Cyp-alkyl radicals are applicable. Preferably, within the context of the present invention, C,-Cqo- alkenyl is vinyl, 1-allyl, 3-allyl, 2-allyl, cis- or trans-2-butenyl, w-butenyl.
Within the context of the present invention, the term "aryl", as for example defined above for the radical R' in formula (I), means that the substituent (radical) is an aromatic. The aromatic may be a monocyclic, bicyclic or optionally polycyclic aromatic.
In the case of polycyclic aromatics, individual cycles can optionally be completely or partially saturated. Preferred examples of aryl are phenyl, naphthyl or anthracyl, in particular phenyl. The aryl radical can also optionally be mano- or polysubstituted with functional groups, as defined above for C;-C;g-alkyl.
Within the context of the present invention, the term aralkyl, as for example defined above for the radical R' in formula (I), means that an alkyl radical (alkylene) is in turn substituted with an aryl radical. The alkyl radical may be for example a C;-Cg-alkyl radical as per the above definitions.
In the above formula (1), the radical R' may be present once (m=1) or multiple times (m=2 or 3). The radical R' here can replace one or more hydrogen atoms on any desired carbon atoms of the cyclic carbonate — corresponding to its frequency. If two or more radicals R' are present, these can be attached to the same carbon atom or to different carbon atoms. For m=0, the corresponding cyclic carbonate is unsubstituted.
The present invention is presented in more detail below.
The present invention firstly provides a polymer prepared by polymerization of a) atleast one alkylene oxide or a cyclic carbonate of the formula (I) 1
RA
1
R (h (CH,), (Rm where nis 1to 10, mis 0 to 3 and
R'is C4-Cy-alkyl, C,-Cig-alkenyl, aryl or aralkyl, b) glycerol carbonate, where the polymerization is carried out in the presence of at least one base.
The polymers according to the invention are thus prepared by polymerization of the components a} and b) defined above in the presence of water and/or at least one base.
Polymerization processes per se are known to the person skilled in the art, they are defined in more detail in the fext below with regard to the polymerization process according to the invention.
As component a), at least one alkylene oxide or a cyclic carbonate of the formula (1) defined above is used. As component a), mixtures of 2 or more alkylene oxides and/or cyclic carbonates according to formula (1) can also be used. Preferably, the component a) comprises an alkylene oxide or a cyclic carbonate according to formula (1).
Alkylene oxides per se and also compounds which fall under the formula (1), are known in principle to the person skilled in the art. If present, the radical R' according to formula (1) is preferably unsubstituted, in particular unsubstituted C;-Cqg-alkyl. R? is particularly preferably methyl, ethyl or propyl. Preferably, m is 0 or 1, in particular m is 0. Preferably, nis 2 or 3.
Preferably, the component a) is an alkylene oxide which comprises a monomer which is selected from ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, 1-pentene oxide, styrene oxide, epichlorohydrin, glycidol, epoxypropionic acid and salts thereof, epoxypropionic acid alkyl esters, 1-hexene oxide, 1-heptene oxide, 1-ociene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide or 1-dodecene oxide.
Furthermore, it is preferred that the component a) is a cyclic carbonate of the formula (1) selected from ethylene carbonate or propylene carbonate. Examples of alkyl epoxypropionates are the corresponding methyl or ethyl esters and also higher esters.
The component a) is particularly preferably at least one alkylene oxide, in particular ethylene oxide and/or propylene oxide.
Glycerol carbonate is used as component b). Glycerol carbonate and processes for its preparation are known to the person skilled in the art. Preferably, glycerol carbonate is prepared from glycerol.
The components a) and b) may be used in any desired ratios relative to one another.
For example, the component b) is used to 0.5 to 99.5% by weight, preferably to 2 to 98% by weight (based on the total amount of component a) and b)).
The polymers according to the invention can be prepared by polymerization processes known to the person skilled in the art, where the polymerization is carried out in the presence of at least one base. Preferably, the polymerization takes place as base- initiated polyaddition. The base is therefore used as initiator. The polymerization process per se for the preparation of the polymers according to the invention is described in more detail in the text below.
Bases suitable for polymerization processes are known to the person skilled in the art, for example alkali metals, alkali metal hydrides, alkali metal hydroxides, alkali metal alcoholates or alkaline earth metals, alkaline earth metal hydrides, alkaline earth metal hydroxides or alkaline earth metal alcoholates and also tertiary and heteroaromatic amines can be used for this purpose.
All compounds known to the person skilled in the art can be used as alkali metal hydroxide or as alkaline earth metal hydroxide. Preferred alkali metal hydroxides are sodium hydroxide, potassium hydroxide or cesium hydroxide, preferred alkaline earth metal hydroxides are magnesium hydroxide or calcium hydroxide, preferred alkali metal alcoholates are sodium methanolate, sodium t-butylate and potassium methanolate, and also potassium t-butylate. Preferred amines are trimethylamine,
N,N-dimethylethanolamine and other N,N-dimethyl substituted tertiary amines, or imidazole and its derivatives.
Preferred bases are selected from KOH, KOCH; KO(t-Bu), KH, NaOH, NaO(t-Bu), 40 NaOCHj3;, NaH, Na, K, trimethylamine, N,N-dimethylethanclamine, N,N-dimethylcyclo-
hexylamine and higher N,N-dimethylalkylamines, N,N-dimethylaniline, N,N-dimethyl- benzylamine, N,N,N'N'-tetramethylethylenediamine, N,N,N',N",N"-pentamethyl- diethylenetriamine, imidazole, N-methylimidazole, 2-methylimidazole, 2,2-dimethyl- imidazole, 4-methylimidazole, 2,4,5-trimethylimidazole and 2-ethyl-4-methylimidazole.
Higher N,N-dimethylalkylamines are understood as meaning all amines whose alkyl substituent has more than 6 carbon atoms.
Particularly preferred bases are KO (t-Bu) (where t-Bu is the radical tertiary-butyl), KOH or NaOH.
The base is preferably used in amounts of from 0.05% by weight to 20% by weight, the base preferably being used in an amount of from 0.1 to 10% by weight, in particular from 0.1 to 1% by weight (in each case based on the amount of polymer (product)).
In a preferred embodiment of the present invention, the base is used in dissolved form.
Solvents which can be used are ali solvents known to the person skilled in the art in which the corresponding base dissolves. Preference is given to using water as solvent for the base, particularly in the case of alkali metal hydroxides. The base is preferably used in amounts of from 40 to 60% by weight (based on the solvent of the base).
The polymer according to the invention is preferably a random copolymer, a block copolymer, a comb polymer, a muitiblock copolymer or a gradient copolymer. This means that — depending on the polymerization conditions chosen — the monomers brought to polymerization (components a) and b) according to the definitions above) can be incorporated by polymerization in the polymer according to the invention in different ways.
Preferably, the polymer according to the invention comprises one or more fragments according to the following formulae (ll) to (IV). (Ahn - (Gly) «(Bp (In (An - (Gly)m -(B)p (C)q (1m
(An - (Gly)s - (Gly) - (Gly) - (B),
I
(Gly),
I
(Gly) — (Gly)u = (Ca
I
(Gly)
I
(C)y (Iv) where A, B and C, independently of one another, are formed from the component a) and
Gly is formed from the component b).
In the formula (il), n and m, independently of one another, have values between 1 and 1000 and p has values between 0 and 1000. If B is present, A and B are preferably formed from different monomers of the component a).
Inthe formula (lll), n, m, p and q, independently of one another, have values between 1 and 1000.
In the formula (IV), n, m, p, v and vy, independently of one another, have values between 1 and 1000 and q, s, t, u, w and x, independently of one another, have values between 0 and 1000.
For the sake of completeness, it is noted that the polymers according to the invention can also comprise two or more of the aforementioned fragments of the same formula.
Thus, it is conceivable that a polymer according to the invention comprises two fragments of the formula (II) and one fragment of for example the formula (lll). In the individual fragments, the variables such as A or B can have different meanings. The fragments of the formulae (II) to (IV) can be arranged for exampie as a random copolymer, block copolymer or other polymer arrangements as per the definition of the present invention. If, for example, ethylene oxide is used as component a) and glycerol carbonate is used as component b), the variables A and B in the formula (Il) have the same meaning (polymerization products of ethylene oxide). Thus, for example, if the polymerization is carried out with ethylene oxide and propylene carbonate as two different components a), the variables A and B in formula (ll), for example, have different meanings. One variable then stands for polymerized ethylene oxide, and the 40 other variable for polymerized propylene carbonate.
Specific examples of fragments in the polymers according to the invention are also as follows: (EO)(Gly)s-(EQ), (glycerol block) (EO) niz-(GIy)1-(EQ)nz~(Gly)1-(EO) nz (glycerol randomly distributed)
In these examples, EO means polymerized-in ethylene oxide and Gly means polymerized-in glycerol carbonate.
Preferred polymers, which comprise one or more fragments of the formula (11), are polymers based on ethylene oxide and propylene oxide or on ethylene carbonate and propylene carbonate as component a). Particular preference is given to polymers which comprise one or more fragments of the formula (ll), or polymers based on ethylene oxide or ethylene carbonate as component (a). Very particular preference is given to polymers based on ethylene carbonate as component (a). These (co)polymers may be present preferably as random copolymers, block polymers, multiblock copolymers or gradient copolymers. Preferably, all of the components of a fragment according to the formula (ll) are present in the same order of magnitude, i.e. the molar ratios of A, Gly and B are from ca. 1:0.5:0 via 1:1:1 to 0:0.5:1.
Preferred polymers, which comprise one or more fragments of the formula (lll), are copolymers based on ethylene oxide and/or propylene oxide or ethylene carbonate and/or propylene carbonate, particularly preferably of ethylene oxide or ethylene carbonate, very particularly preferably of ethylene oxide, which have a relatively low fraction of units originating from glycerol carbonate. Preference is given here to block polymers, comb polymers or random polymers. An increased degree of branching of polymers comprising fragments of the formula (lll) can be carried out via a further alkoxylation step.
Preferred polymers, which comprise one or more fragments according to the formula (IV), can be present as block-like or random polymers or comb or gradient polymers, preferably based on propylene oxide, ethylene oxide, propylene carbonate and/or ethylene carbonate. Polymers which comprise one or more fragments according to the formula (IV) can particularly preferably be present as block-like or random polymers or comb or gradient polymers, preferably based on ethylene oxide, and/or ethylene carbonate. Polymers which comprise one or more fragments according to the formula (IV) can very particularly preferably be present as block-like or random polymers or comb or gradient polymers, preferably based on ethylene oxide.
In one embodiment of the present invention, the polymer prepared according to the invention is obtainable by polymerization of a) at least one monomer selected from ethylene oxide, propylene oxide, ethylene carbonate and propylene carbonate, b) glycerol carbonate, where the polymerization is carried out in the presence of at least one base.
The base is preferably KO(t-Bu), KOH or NaOH.
The present invention further provides a process for the preparation of a polymer according to the definitions above. In the process according to the invention, the components a) and b) are subjected to a polymerization. The respective components a) and b) can be subjected to the polymerization individually or together and also in their entirety or stepwise.
The process according to the invention is carried out in temperature ranges for polymerization processes known to the person skilled in the art, preferably at elevated temperature, for example at 80 to 220°C.
The process according to the invention is carried out in the case of reacting cyclic carbonates (as component a)) preferably at elevated temperature, more preferably at 150 to 220°C, particularly preferably at 160 to 210°C.
The process according to the invention is carried out in the case of reacting alkylene oxides (as component a)) preferably at elevated temperature, more preferably at 80° to 220°C, particularly preferably at 120°C to 205°C.
The process according to the invention can also be carried out in the presence of a solvent. Solvents which can be used are all solvents for carrying out polymerization processes that are known to the person skilled in the art. Preferred solvents are toluene, xylene, tetrahydrofuran (THF) or dioxane. Preferably, the solvent is used in amounts of from 20 to 90% by weight, in particular from 30 to 70% by weight based on the total amount of components a) to b).
Preferably, in the process according to the invention, the polymerization is carried out as base-initiated polyaddition and/or with the release of CO,.
Furthermore, it is preferred in the process according to the invention to remove, in particular to completely remove, any water present in the system. The water can be removed for example by distillation. Preferably, the water is removed before the polymerization. The water to be removed is preferably water which is used as solvent for the base.
The present invention further provides the use of the polymers according to the invention as defined above as foam suppressant; as foam regulator; as foam booster; as dispersant; as emulsifier, in particular in emulsion polymerization; as wetting agent, in particular for hard surfaces; as lubricant; for dispersing solids, in particular for cement for thinning concrete; for thickening aqueous solutions; as carrier or filling material for pharmaceutical preparations; as surfactant for washing or cleaning purposes; as surfactant for the cleaning of hard surfaces; as humectant; in cosmetic, pharmaceutical or crop protection formulations; as adjuvant or solubilizer for active ingredients; in paints; in inks; in pigment preparations; in coating compositions; in adhesives; in leather degreasing compositions; in formulations for the textile industry, fiber processing, water treatment or the production of drinking water; in the food industry, the paper industry; as construction auxiliaries; as di- or polyol for the preparation of polyadducts or polymers such as polyesters; as coolant and lubricant; for fermentation; in mineral processing or metal processing, such as meta! refining or electroplating sector.
The present invention is illustrated below by reference to the examples.
Example: 1 g of 50% strength aqueous potassium hydroxide solution are introduced in a reactor as initial charge and rendered inert three times with nitrogen, then heated to 170°C under nitrogen {pre-pressure of 5 bar) and stirring. 66 g of ethylene oxide and 60.3 g of glycerol carbonate are then metered in simultaneously over the course of 120 minutes and the mixture is held at 170°C for a further 18 hours. The reaction solution is then flushed with nitrogen and degassed at 80°C and under a water-jet vacuum for 2 h.
This gives a clear, slightly viscous liquid which, in the infrared (IR), does not show any signals which suggest the presence of carbonyl groups. The weight-average molecular weight of the resulting polymer is 1400 g/mol (GPC, polystyrene standard).
Claims (10)
1. A polymer prepared by polymerization of a) atleast one alkylene oxide or a cyclic carbonate of the formula (1) 1 2 1 I fy R (1 where nis 1to0 10, mis 0 to 3 and R'is C4-Cyg-alkyl, C,-Cqo-alkenyl, aryl or aralkyl, b) glycerol carbonate, where the polymerization is carried out in the presence of at least one base.
2. The polymer according to claim 1, wherein the component a) comprises as alkylene oxide a monomer selected from ethylene oxide, propylene oxide, 1- butene oxide, 2-butene oxide, 1-pentene oxide, styrene oxide, epichlorohydrin, glycidol, epoxypropionic acid and salts thereof, epoxypropionic acid alkyl esters, 1-hexene oxide, 1-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide, 1-undecene oxide or 1-dodecene oxide and/or the cyclic carbonate of the formula (1) is selected from ethylene carbonate or propylene carbonate.
3. The polymer according to claim 2, wherein the component a) is at least one alkylene oxide, preferably ethylene oxide and/or propylene oxide.
4. The polymer according to any one of claims 1 to 3, wherein the polymerization is carried out as base-initiated polyaddition and/or a base selected from KOH, KOCH3;, KO(t-Bu), KH, NaOH, NaO(t-Bu), NaOCHj3, NaH, Na, K, trimethylamine, N,N-dimethylethanclamine, N,N-dimethylcyclohexylamine and higher N,N-dimethylalkylamines, N,N-dimethylaniline, N,N-dimethylbenzylamine, N,N,N'N'-tetramethylethylenediamine, N,N,N", N",N"-pentamethyldiethylene- friamine, imidazole, N-methylimidazole, 2-methylimidazole, 2,2-dimethyl- imidazole, 4-methylimidazole, 2,4,5-trimethylimidazole and 2-ethyl-4-methyl-
imidazole is used during the polymerization.
5. The polymer according to claim 4, wherein the base is used in amounts of from
0.05 to 20% by weight (based on the amount of polymer).
6. The polymer according to any one of claims 1 to 5, wherein the polymer is a random copolymer, a block copolymer, a comb polymer, a multiblock copolymer or a gradient copolymer.
7. The polymer according to any one of claims 1 to 6, wherein the polymer ’ comprises one or more fragments according to the formulae (11) to (IV) (An - (Gly)m -(B)o (11) (An - (Gly)m -(B)p (Ca (Ir) (A)a- (Gly)s - (Gly)m - (Gly - (B)g I (Gly). (Gly), — (Gly) — (C)q (Gly) 1 (Cy (IV) where A, B and C, independently of one another, are formed from the component a), Gly is formed from the component b), where, in the formula (I), n and m, independently of one another, have values between 1 and 1000 and p has values between 0 and 1000, where, in the formula (lll), n, m, p and q, independently of one ancther, have values between 1 and 1000, 40 where, in the formula (IV), n, m, p, v and y, independently of one another, have values between 1 and 1000 and q, s, {, u, w and x, independently of one another, have values between 0 and 1000.
8. A process for the preparation of a polymer according to any one of claims 1 to 7, wherein the components a) and b) are subjected to a polymerization in the presence of at least one base.
9. The process according to claim 8, wherein the polymerization is carried out as a base-initiated polyaddition and/or with the release of CO..
10. The use of the polymers according to any one of claims 1 to 7 as foam suppressant; as foam regulator; as foam booster; as dispersant; as emulsifier, in particular in emulsion polymerization; as wetting agent, in particular for hard surfaces; as lubricant; for dispersing solids, in particular for cement for thinning concrete; for thickening aqueous solutions; as carrier or filing material for pharmaceutical preparations; as surfactant for washing or cleaning purposes; as surfactant for the cleaning of hard surfaces; as humectant; in cosmetic, pharmaceutical or crop protection formulations; as adjuvant or solubilizer for active ingredients; in paints; in inks; in pigment preparations; in coating compositions; in adhesives; in leather degreasing compositions; in formulations for the textile industry, fiber processing, water treatment or the production of drinking water; in the food industry; the paper industry; as construction auxiliaries; as di- or polyol for the preparation of polyadducts or polymers such as polyesters; as coolant and lubricant; for fermentation; in mineral processing or metal processing, such as metal refining or electroplating sector.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11155403 | 2011-02-22 | ||
PCT/EP2012/051601 WO2012113616A1 (en) | 2011-02-22 | 2012-01-31 | Polymers based on glyceryl carbonate |
Publications (1)
Publication Number | Publication Date |
---|---|
SG192737A1 true SG192737A1 (en) | 2013-09-30 |
Family
ID=45833365
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
SG2013061270A SG192737A1 (en) | 2011-02-22 | 2012-01-31 | Polymers based on glycerol carbonate |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP2678375B1 (en) |
JP (1) | JP6245988B2 (en) |
KR (1) | KR101884163B1 (en) |
CN (1) | CN103380165B (en) |
AU (1) | AU2012219866B2 (en) |
BR (1) | BR112013021040A2 (en) |
ES (1) | ES2531397T3 (en) |
MX (1) | MX345671B (en) |
MY (1) | MY161362A (en) |
RU (1) | RU2600985C2 (en) |
SG (1) | SG192737A1 (en) |
WO (1) | WO2012113616A1 (en) |
ZA (1) | ZA201307056B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101884165B1 (en) * | 2011-02-22 | 2018-08-30 | 바스프 에스이 | Polymers on the basis of glycerin carbonate and an alcohol |
FR2997699B1 (en) * | 2012-11-05 | 2016-01-29 | Bostik Sa | LOW-MOLAR WEIGHT POLYMERS COMPRISING AT LEAST ONE 4-METHYLETHER-1,3-DIOXOLANE-2-ONE TERMINAL GROUP |
US10669380B2 (en) | 2014-07-30 | 2020-06-02 | Basf Se | Amphiphilic star-like polyether |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3351623B2 (en) * | 1994-05-27 | 2002-12-03 | 住友精化株式会社 | Coating composition |
JPH11335313A (en) * | 1998-05-18 | 1999-12-07 | Lion Corp | Production of glyceryl ether and cleanser composition containing the compound |
RU2151780C1 (en) * | 1999-02-02 | 2000-06-27 | Открытое акционерное общество "Нижнекамскнефтехим" | Method of preparing demulsifier |
EP1421073A2 (en) * | 2001-08-17 | 2004-05-26 | Ucb, S.A. | Process for making of a compound containing cyclic and linear carbonate groups |
FR2874217B1 (en) * | 2004-08-10 | 2006-10-27 | Agronomique Inst Nat Rech | GLYCEROL POLYCARBONATE - ORGANIC COMPOSITIONS CONTAINING THE SAME - PROCESS FOR OBTAINING THESE ORGANIC COMPOSITIONS AND METHOD FOR EXTRACTING GLYCEROL POLYCARBONATE AND THEIR APPLICATIONS |
GB0709460D0 (en) * | 2007-05-17 | 2007-06-27 | Croda Int Plc | Method of making polyglycerol esters |
JP2009155407A (en) * | 2007-12-26 | 2009-07-16 | Konishi Co Ltd | Curable resin composition and adhesive composition |
CN101392054B (en) * | 2008-10-31 | 2010-08-11 | 句容市宁武化工有限公司 | Method for preparing glyceryl polyether glycol |
MY157126A (en) * | 2009-07-30 | 2016-05-13 | Basf Se | Composition for metal plating comprising suppressing agent for void free submicron feature filling |
DE102009059104A1 (en) * | 2009-12-18 | 2011-06-22 | Johannes-Gutenberg-Universität Mainz, 55122 | Functional branched polyether copolymers and process for their preparation |
-
2012
- 2012-01-31 CN CN201280009450.6A patent/CN103380165B/en not_active Expired - Fee Related
- 2012-01-31 MY MYPI2013003086A patent/MY161362A/en unknown
- 2012-01-31 SG SG2013061270A patent/SG192737A1/en unknown
- 2012-01-31 JP JP2013553861A patent/JP6245988B2/en not_active Expired - Fee Related
- 2012-01-31 KR KR1020137022022A patent/KR101884163B1/en active IP Right Grant
- 2012-01-31 AU AU2012219866A patent/AU2012219866B2/en not_active Ceased
- 2012-01-31 MX MX2013009593A patent/MX345671B/en active IP Right Grant
- 2012-01-31 ES ES12708780T patent/ES2531397T3/en active Active
- 2012-01-31 BR BR112013021040A patent/BR112013021040A2/en not_active IP Right Cessation
- 2012-01-31 RU RU2013142809/04A patent/RU2600985C2/en not_active IP Right Cessation
- 2012-01-31 EP EP12708780.7A patent/EP2678375B1/en not_active Not-in-force
- 2012-01-31 WO PCT/EP2012/051601 patent/WO2012113616A1/en active Application Filing
-
2013
- 2013-09-19 ZA ZA2013/07056A patent/ZA201307056B/en unknown
Also Published As
Publication number | Publication date |
---|---|
CN103380165B (en) | 2016-10-12 |
EP2678375B1 (en) | 2014-12-10 |
RU2013142809A (en) | 2015-03-27 |
ES2531397T3 (en) | 2015-03-13 |
CN103380165A (en) | 2013-10-30 |
WO2012113616A1 (en) | 2012-08-30 |
EP2678375A1 (en) | 2014-01-01 |
JP6245988B2 (en) | 2017-12-13 |
MY161362A (en) | 2017-04-14 |
MX345671B (en) | 2017-02-10 |
KR20140005264A (en) | 2014-01-14 |
BR112013021040A2 (en) | 2016-10-11 |
AU2012219866B2 (en) | 2015-08-20 |
JP2014505775A (en) | 2014-03-06 |
ZA201307056B (en) | 2014-11-26 |
KR101884163B1 (en) | 2018-08-30 |
AU2012219866A1 (en) | 2013-09-12 |
RU2600985C2 (en) | 2016-10-27 |
MX2013009593A (en) | 2013-11-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6061494B2 (en) | Process for the preparation of alkoxylation products and DMC catalysts | |
US9296858B2 (en) | Polymers based on glycerol carbonate and an amine | |
KR101884165B1 (en) | Polymers on the basis of glycerin carbonate and an alcohol | |
KR101884164B1 (en) | Polymers on the basis of glycerin carbonate and an amine | |
US9994674B2 (en) | Polymers based on glycerol carbonate | |
EP2003110A9 (en) | Method for producing (poly)glyceryl ether | |
EP2308881A1 (en) | Isosorbide-derivatives | |
AU2012219866B2 (en) | Polymers based on glyceryl carbonate | |
US20120215032A1 (en) | Polymers based on glycerol carbonate and an alcohol | |
CN116323754A (en) | Novel defoaming agent | |
KR20150026269A (en) | Method for preparing amphiphilic block polymer |