SE514075C2 - Process for manufacturing an acrylate composition comprising at least one dendritic polyester acrylate oligomer and at least one acrylate monomer - Google Patents
Process for manufacturing an acrylate composition comprising at least one dendritic polyester acrylate oligomer and at least one acrylate monomerInfo
- Publication number
- SE514075C2 SE514075C2 SE9901517A SE9901517A SE514075C2 SE 514075 C2 SE514075 C2 SE 514075C2 SE 9901517 A SE9901517 A SE 9901517A SE 9901517 A SE9901517 A SE 9901517A SE 514075 C2 SE514075 C2 SE 514075C2
- Authority
- SE
- Sweden
- Prior art keywords
- propanediol
- acid
- process according
- hydroxyalkyl
- alcohol
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229920000728 polyester Polymers 0.000 title claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 32
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 28
- 229940035437 1,3-propanediol Drugs 0.000 claims description 27
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- -1 ditrimethylolethane Chemical compound 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 150000002924 oxiranes Chemical group 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000539 dimer Substances 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 150000002596 lactones Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 4
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 4
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000412 dendrimer Substances 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 claims description 4
- 229960000380 propiolactone Drugs 0.000 claims description 4
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 125000005113 hydroxyalkoxy group Chemical group 0.000 claims description 3
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 claims description 2
- VCKSNYNNVSOWEE-UHFFFAOYSA-N 1,3-dioxan-5-ol Chemical compound OC1COCOC1 VCKSNYNNVSOWEE-UHFFFAOYSA-N 0.000 claims description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- KWMLJOLKUYYJFJ-UHFFFAOYSA-N 2,3,4,5,6,7-Hexahydroxyheptanoic acid Chemical compound OCC(O)C(O)C(O)C(O)C(O)C(O)=O KWMLJOLKUYYJFJ-UHFFFAOYSA-N 0.000 claims description 2
- HPVOTSMEHLZBJY-UHFFFAOYSA-N 2-(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)C(O)=O HPVOTSMEHLZBJY-UHFFFAOYSA-N 0.000 claims description 2
- ZMZQVAUJTDKQGE-UHFFFAOYSA-N 2-ethylhydracrylic acid Chemical compound CCC(CO)C(O)=O ZMZQVAUJTDKQGE-UHFFFAOYSA-N 0.000 claims description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 claims description 2
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims 2
- JWQKMEKSFPNAIB-UHFFFAOYSA-N 1-methyl-5-prop-1-en-2-ylcyclohexene Chemical compound CC(=C)C1CCC=C(C)C1 JWQKMEKSFPNAIB-UHFFFAOYSA-N 0.000 claims 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical group CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims 1
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 239000000047 product Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 210000000056 organ Anatomy 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- TWGSXTJXQLNWNP-UHFFFAOYSA-N 1,3-dioxolan-4-ol Chemical compound OC1COCO1 TWGSXTJXQLNWNP-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- WACQLQIAUWURGA-UHFFFAOYSA-N 3-hydroxy-2,2-bis(hydroxymethyl)propanoic acid Chemical compound OCC(CO)(CO)C(O)=O WACQLQIAUWURGA-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZTISUHQLYYPYFA-UHFFFAOYSA-N [5-(hydroxymethyl)-1,3-dioxan-5-yl]methanol Chemical compound OCC1(CO)COCOC1 ZTISUHQLYYPYFA-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- UCDHYFZYUGDETN-UHFFFAOYSA-N cyanophosphonic acid Chemical compound OP(O)(=O)C#N UCDHYFZYUGDETN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
-
- 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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- 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
- C08G63/91—Polymers modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyethers (AREA)
Abstract
Description
514 075 2 t.ex. akrylatoligomerer där hög molekylvikt och hög akrylatfiinktíonalitet kombineras med en för molekylvikten låg viskositet, vilket är ett ofia eftersträvat förhållande vid tillverkning och användning av t.ex. akrylatoligomerer och -monomerer. Vidare ger dendritiska strukturer, inkluderande hyperförgrenade molekyler och dendrimerer, en unik balans mellan till exempel filrnhårdhet, ythårdhet, vidhäfiriing och flexibilitet. Vid akrylering av dendritiska polyestrar har emellertid problem visat sig kunna uppstå under upparbetning och rening. Ett vanligt förfarande vid nämnda upparbetning och rening är bland armat urlakning av oreagerad akrylsyra med vatten. Denclritiska polyestrars höga molekylvikt och höga polaritet tenderar i dessa sammanhang att ge upphov till stabila eller tämligen stabila emulsioner, vilka markant försvårar nämnda upparbetning och rening. Det har emellertid helt överraskande visat sig att detta problem kan överkommas eller markant reduceras genom att före akrylering späda eller blanda en, eventuellt partiellt kedjeterminerad eller funktionaliserad, dendritisk polyester vilken har minst en terminal hydroxylgrupp med minst en alkohol, vilken har minst en hydroxylgrupp, en molvikt som företrädesvis är högst 2000, såsom 60-1500 eller 100-1000, och vilken företrädesvis är flytande vid en temperatur av 20-50°C eller genererar flytande blandningar med nänmda dendritiska polyester vid denna temperatur. Erhållen blandning alayleras därefter med sedvanliga och välkända förfaranden, såsom genom reaktion med minst en förening innefattande minst en akrylomättriad. En reaktionsblandning innefattande en akrylatkomposition, vilken i sig innefattar minst en dendritisk polyesteralcrylatoligomer och minst en akrylatmonomer, erhålles vid akryleringen. Akrylatkompositionen kan därefter utvinnas och renas med kända förfaranden, såsom urlakning med vatten, utan att störande stabila emulsioner bildas. Utöver detta underlättas i de flesta fall såväl akrylering som upparbetning och rening genom att polyester/alkoholblandningen normalt har lägre viskositet än däri ingående polyester. 514 075 2 e.g. acrylate oligomers where high molecular weight and high acrylate al inctionality are combined with a low molecular weight viscosity, which is an otherwise desired ratio in the manufacture and use of e.g. acrylate oligomers and monomers. Furthermore, dendritic structures, including hyperbranched molecules and dendrimers, provide a unique balance between, for example, film hardness, surface hardness, adhesion and flexibility. However, in the acrylic of dendritic polyesters, problems have been found to arise during reprocessing and purification. A common procedure in said work-up and purification is, among other things, leaching of unreacted acrylic acid with water. The high molecular weight and high polarity of the critical polyesters in these contexts tend to give rise to stable or rather stable emulsions, which markedly complicate said work-up and purification. However, it has quite surprisingly been found that this problem can be overcome or markedly reduced by diluting or blending, optionally partially chain-terminated or functionalized, dendritic polyester having at least one terminal hydroxyl group with at least one alcohol having at least one hydroxyl group, e.g. molecular weight which is preferably not more than 2000, such as 60-1500 or 100-1000, and which is preferably liquid at a temperature of 20-50 ° C or generates surface mixtures with said dendritic polyester at this temperature. The resulting mixture is then alaylated by conventional and well known methods, such as by reaction with at least one compound comprising at least one acrylomethyl triad. A reaction mixture comprising an acrylate composition, which itself comprises at least one dendritic polyester acrylate oligomer and at least one acrylate monomer, is obtained in the acrylation. The acrylate composition can then be recovered and purified by known methods, such as leaching with water, without the formation of disturbingly stable emulsions. In addition to this, in most cases both acrylation as well as reprocessing and purification are facilitated by the fact that the polyester / alcohol mixture normally has a lower viscosity than the polyester contained therein.
Olika utföringsformer av förfarandet enligt föreliggande uppfinning innefattar blandningar där alkoholen är en diol, såsom en etylenglykol, en 1,2- eller 1,3-propylenglykol, en butandiol eller en di-, tri- eller polyglykol, till exempel en dietylenglykol, en trietylenglykol, en polyetylenglykol, en dipropylenglykol, en tripropylenglykol, en polypropylenglykol eller en glykolpolymerer såsom en polymer innefattande en eller flera etylenglykoler och en eller flera propylenglykoler. Ytterligare föredragna utföringsfonner innefattar alkoholer vilka är reaktionsprodukter mellan en 2-hydroxialkyl-lß-propandiol, en 2-alkyl-2-hydroxialkyl- -1,3-propandiol eller en 2,2-di(liydroxialkyl)-1,3-propandiol och minst en alkylenoxid vid ett molförhållande nämnd l,3-propandiol till alkylenoxid av l:0,2 till 1:50, såsom 1:1 till 1:20 eller är reaktionsprodukter mellan en dimer, trimer eller polyrner av nämnda 1,3-propandioler och minst en alkylenoxid vid ett molförhållande nämnd dimer, trimer eller polymer till alkylenoxid av l:0,2 till 1:50, såsom 1:1 till 1:20. Dessa reaktionsprodukter kan lämpligen exempliñeras med alkoxylerad, såsom etoxylerad och/eller propoxylerad, trimetyloletan, trimetylolpropan, pentaerytritol, ditrimetyloletan, ditrimetylolpropan och dipentaerytritol. 514 075 Vidare kan alkoholen med fördel vara en rak eller grenad alkanol, till exempel en Cl-Czr; alkanol eller företrädesvis en C4-C12 alkanol, såsom en butanol, en heptanol, en hexanol, en oktanol, en nonanol, en dekanol och/eller en dodecanol, och/eller vara en 1,3-dioxanalkohol eller 1,3-dioxolanalkohol, såsom en 5-hydroxi-1,3-dioxolan, en 5-hydroxi- -1,3-dioxan, en 5 -hydroxialkyl-lß-dioxan, en S-alkyl-S-hydroxialkyl-l ,3-dioxan och/eller en 5,5-dí(hydroxialkyl)-1,3-dioxan. Ytterligare lärnpliga alkoholer finns bland reaktionsprodukter mellan lß-dioxanalkoholer eller lß-dioxolanalkoholer enligt ovan och minst en alkylenoxid vid molförhållanden enligt ovan. Alkoxylerade lß-dioxanalkoholer kan exempliñeras med bland annat etoxylerad och/eller propoxylerad S-hydroxirnetyl-lß-dioxan och 5,5-di(hydroximetyl)-l,3-dioxan. Alkyl är i alla ovan beslcivna föredragna utföringsformer företrädesvis och inbördes oberoende Cl-Clz-akanyl eller Cz-Clz-alkenyl. Alkylenoxiden är likaledes företrädesvis etylenoxid, propylenoxid, butylenoxid, fenyletylenoxid (styrenoxid) eller en blandning av två eller flera alkylenoxider.Various embodiments of the process of the present invention include mixtures wherein the alcohol is a diol, such as an ethylene glycol, a 1,2- or 1,3-propylene glycol, a butanediol or a di-, tri- or polyglycol, for example a diethylene glycol, a triethylene glycol , a polyethylene glycol, a dipropylene glycol, a tripropylene glycol, a polypropylene glycol or a glycol polymers such as a polymer comprising one or fl your ethylene glycols and one or fl your propylene glycols. Further preferred embodiments include alcohols which are reaction products between a 2-hydroxyalkyl-1β-propanediol, a 2-alkyl-2-hydroxyalkyl--1,3-propanediol or a 2,2-di (hydroxyalkyl) -1,3-propanediol and at least one alkylene oxide at a molar ratio of said 1,3-propanediol to alkylene oxide of 1: 0.2 to 1:50, such as 1: 1 to 1:20 or are reaction products between a dimer, trimer or polyrene of said 1,3-propanediols and at least one alkylene oxide at a molar ratio of said dimer, trimer or polymer to alkylene oxide of 1: 0.2 to 1:50, such as 1: 1 to 1:20. These reaction products may conveniently be exemplified by alkoxylated, such as ethoxylated and / or propoxylated, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolethane, ditrimethylolpropane and dipentaerythritol. 514 075 Furthermore, the alcohol may advantageously be a straight or branched alkanol, for example a C1-C2r; alkanol or preferably a C4-C12 alkanol, such as a butanol, a heptanol, a hexanol, an octanol, a nonanol, a decanol and / or a dodecanol, and / or be a 1,3-dioxane alcohol or 1,3-dioxolane alcohol, such as a 5-hydroxy-1,3-dioxolane, a 5-hydroxy--1,3-dioxane, a 5-hydroxyalkyl-1β-dioxane, an S-alkyl-S-hydroxyalkyl-1,3-dioxane and / or and 5,5-di (hydroxyalkyl) -1,3-dioxane. Additional essential alcohols are present among reaction products between β-dioxane alcohols or β-dioxolane alcohols as above and at least one alkylene oxide at molar ratios as above. Alkoxylated β-dioxane alcohols can be exemplified by, inter alia, ethoxylated and / or propoxylated S-hydroxymethyl-β-dioxane and 5,5-di (hydroxymethyl) -1,3-dioxane. Alkyl in all of the above preferred embodiments is preferably and independently C 1 -C 12 acanyl or C 2 -C 12 alkenyl. The alkylene oxide is also preferably ethylene oxide, propylene oxide, butylene oxide, phenylethylene oxide (styrene oxide) or a mixture of two or more alkylene oxides.
Den dendritiska polyestem ingående i blandningen enligt föreliggande förfarande är i föredragna utföringsfonner uppbyggd av en kärnmolekyl, vilken har en eller flera hydroxyl- eller epoxidgrupper, och en eller flera dendroner bundna till nämnda grupper. En dendron innefattar därvid företrädesvis två eller flera förgrenande generationer uppbyggda av minst en hydroxi- och/eller epoxifiutlctionell karboxylsyra, vilken syra har minst en karboxylgrupp och minst två hydroxyl- och/eller epoxidgrupper, samt eventuellt en eller flera utsträckande generationer uppbyggda av minst en monohydroxi- eller monoepoxifinildionell monokarboxylsyra och/eller minst en lakton. Alternativt kan den dendritiska polyestem utgöras av nämnda dendron. Vidare kan den dendritiska polyestem vara partiellt kedjetenninerad eller funktionaliserad, varvid minst en terminal hydroxylgrupp finnes, eventuellt i kombination med en eller flera epoxid-, alkenyl-, amino-, amid-, an1inoan1id-, tiol-, anhydrid-, karboxyl-, cyano-, fosfat-, fosfit-, fosfin-, sufat- och/eller sulfitgrupper etc.The dendritic polyester included in the mixture according to the present process is in preferred embodiments composed of a core molecule, which has one or fl your hydroxyl or epoxide groups, and one or fl your dendrons attached to said groups. A dendron preferably comprises two or fl your branching generations made up of at least one hydroxy and / or epoxy fi functional carboxylic acid, which acid has at least one carboxyl group and at least two hydroxyl and / or epoxide groups, and optionally one or fl your extending generations made up of at least one monohydroxy or monoepoxy nildional monocarboxylic acid and / or at least one lactone. Alternatively, the dendritic polyester may be said dendron. Furthermore, the dendritic polyester may be partially chain-terminated or functionalized, with at least one terminal hydroxyl group present, optionally in combination with one or more epoxide, alkenyl, amino, amide, aminoanide, thiol, anhydride, carboxyl, cyano , phosphate, phosphate, phosphorus, sulphate and / or salt groups, etc.
Utföiingsformer av förfarandet enligt föreliggande uppfinning innefattar minst en dendritisk polyester i vilken en kärnmolekyl ingår. Denna kämmolekyl är i dessa utföringsformer företrädesvis en lß-propandíol, såsom en 2-alkyl-1,3-propandiol, en 2,2-dia1kyl- -1,3-propandiol, en 2-hydroxi-2-alkyl-1,3-propandiol, en 2-hydroxialkyl-2-alkyl-L3- -propandiol, en 2,2-di(hydroxialkyl)-1,3-propandiol, en 2-hydroxialkoxi-2-alkyl-1,3- -propandiol eller en 2,2-di(hydroxia1koxi)-1,3-propandiol eller en dimer, trimer eller polymer av en nämnd lß-propandiol. Alkyl är företrädesvis och inbördes oberoende Cl-Clz-alkanyl eller Cz-Clg-alkenyl och alkoxi är, likaledes företrädesvis och inbördes oberoende, etoxi, propoxi eller butoxi innefattande 1 till 50, såsom l till 20, enheter av respektive alkoxi. Dessa kärnmolekyler kan lämpligen exemplifieras med 2-butyl-2-etyl-1ß-propandiol, neopentylglykol, tiimetyloletan, trimetylolpropan, pentaerytritol, ditrimetyloletan, ditiimetylolpropan, anhydroennea-heptitol och dipentaerytritol samt reaktionsprodukter mellan U'l __; -N CD \'l O? nämnda di-, tri och polyalkoholer och minst en alkylenoxid, såsom etylenoxid, propylenoxid eller butylenoxid, vid ett molförhållande alkohol till alkylenoxid av l:0,2 till 1:50, såsom 1:1 till 1:20.Embodiments of the process of the present invention comprise at least one dendritic polyester in which a core molecule is included. This core molecule in these embodiments is preferably an β-propanediol, such as a 2-alkyl-1,3-propanediol, a 2,2-dialkyl--1,3-propanediol, a 2-hydroxy-2-alkyl-1,3 -propanediol, a 2-hydroxyalkyl-2-alkyl-L3- -propanediol, a 2,2-di (hydroxyalkyl) -1,3-propanediol, a 2-hydroxyalkoxy-2-alkyl-1,3--propanediol or a 2,2-di (hydroxyalkoxy) -1,3-propanediol or a dimer, trimer or polymer of said β-propanediol. Alkyl is preferably and independently C 1 -C 12 alkanyl or C 2 -C 18 alkenyl and alkoxy is, also preferably and independently, ethoxy, propoxy or butoxy comprising 1 to 50, such as 1 to 20, units of respective alkoxy. These core molecules may conveniently be exemplified by 2-butyl-2-ethyl-1β-propanediol, neopentyl glycol, dimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolethane, dithimethylolpropane, anhydroenea-heptitol and dipentry; -N CD \ 'l O? said di-, tri and polyalcohols and at least one alkylene oxide, such as ethylene oxide, propylene oxide or butylene oxide, at a molar ratio of alcohol to alkylene oxide of 1: 0.2 to 1:50, such as 1: 1 to 1:20.
Föredragna utföringsfonner av förfarande enligt föreliggande uppfinning innefattar en dendritisk polyester vari en eller flera dendroner innefattar minst en generation uppbyggd av minst en di-, tri- eller polyhydroxifiniktionell monokarboxylsyra. Nämnda karboxylsyror kan lärnpligen exemplifieras med dimetylolpropionsyra, ot,ot-bis(hydroximetyl)smörsyra, ot,ot-bis(liydroximetyl)valeriansyra, ot,oz-bis(hydroxi)propionsyra, 3,5-dihydroxibensoesyra, ot,ot,ot-tris(hydroximetyl)ättiksyra, citronsyra och heptonsyra. Vidare kan en dendron eventuellt innefatta minst en generation uppbyggd av minst en monohydroxifurilctionell monokarboxylsyra eller lakton, vilken syra eller lakton lärnpligen kan exemplifieras med hydroxivaleriarisyra, hydroxipropionsyra, hydroxipivalinsyra, glykolid, ö-valerolaldon, ß-propiolakton och s-kaprolakton.Preferred embodiments of the process of the present invention comprise a dendritic polyester in which one or more of the dendrons comprises at least one generation composed of at least one di-, tri- or polyhydroxy-functional monocarboxylic acid. Said carboxylic acids may be exemplified by dimethylolpropionic acid, ot, ot-bis (hydroxymethyl) butyric acid, ot, ot-bis (hydroxymethyl) valeric acid, ot, oz-bis (hydroxy) propionic acid, 3,5-dihydroxybenzoic acid, ot, tris (hydroxymethyl) acetic acid, citric acid and heptonic acid. Furthermore, a dendron may optionally comprise at least one generation composed of at least one monohydroxifurilctional monocarboxylic acid or lactone, which acid or lactone may be exemplified by hydroxyvaleric acid, hydroxypropionic acid, hydroxypivalic acid, glycolide, δ-valerolaldone, β-propiolactone and β-propiolactone.
Den dendritiska polyestem ingående i förfarandet enligt föreliggande uppfinning kan vidare i olika utföringsforrner därav vara partiellt kedjeterminerad genom Lex. reaktion med minst en alkanyl-, cykloalkanyl-, alkenyl-, cykloalkenyl-, alkynyl-, eller arylförening, såsom en mono- di-, tri eller polyfunktionell karboxylsyra, vilken karboxylsyra lärnpligen kan exemplifieras med mättade eller omättade monokarboxylsyror och dikarboxylsyror med upp till 24, såsom 6-18, kolatomer.Furthermore, in various embodiments thereof, the dendritic polyester included in the process of the present invention may be partially chain terminated by Lex in various embodiments thereof. reaction with at least one alkanyl, cycloalkanyl, alkenyl, cycloalkenyl, alkynyl, or aryl compound, such as a mono-di-, tri- or polyfunctional carboxylic acid, which carboxylic acid may be exemplified by saturated or unsaturated monocarboxylic acids and dicarboxylic acids , such as 6-18, carbon atoms.
Förfarandet enligt föreliggande uppfinning innefattar i sina mest föredragna utföringsforrner att den dendritiska polyestem och alkoholen före akrylering blandas i ett viktsförhållande polyester till alkohol av 90:10 till 10:90, såsom 25:75 till 75:25 eller 40:60 till 60:40.The process of the present invention comprises in its most preferred embodiments that the dendritic polyester and the alcohol before acrylation are mixed in a weight ratio of polyester to alcohol of 90:10 to 10:90, such as 25:75 to 75:25 or 40:60 to 60:40 .
Akrylering av polyester/alkoholblandningen sarnt utvinning och rening av därvid erhållen akrylatkomposition utförs lämpligen med i litteraturen kända förfaranden, vilka beskrivs i bland annat Kirk-Othmer Encyclopedia of Chemical Technology - 1980 vol. 1 sid. 386-413 "Acrylic Ester Polymers", Ullmanns Encyklopädie der technischen Chemie - 3:e uppl. 1953, Band 3, sid. 78-81 "Acrylsäureester" och i Technical Inforrnation Leaflets 0900-0912 utgivna av Perstorp Polyols, Sverige. Akryleringen är företrädesvis en direkt omsättning, såsom forestring, med akrylsyra, metakrylsyra, krotonsyra (ß-metakrylsyra) och/eller en direkt omsättning med till nämnda alcrylsyror korresponderande anhydrider och/eller halider, varvid molfórhållandet hydroxylgrupper till närrmd syra, anhydrid och/eller halid företrädesvis är 120,1 till 1:5, såsom 1:0,5 till 1:l,5. Ytterligare akrylatföreningar lämpliga för akrylering av polyester/alkoholblandningen enligt föreliggande förfarande innefattar Lex. epoxid- eller anhydridfiuilctionella akrylater och metalcrylater såsom glycidylmetaluylat.Acrylation of the polyester / alcohol mixture, as well as recovery and purification of the acrylate composition thus obtained, is conveniently carried out by methods known in the literature, which are described in, inter alia, the Kirk-Othmer Encyclopedia of Chemical Technology - 1980 vol. 1 p. 386-413 "Acrylic Ester Polymers", Ullmann's Encyclopedia of Technical Chemistry - 3rd ed. 1953, Volume 3, p. 78-81 "Acrylic acid ester" and in the Technical Information Lea 099-0912 published by Perstorp Polyols, Sweden. The acrylation is preferably a direct reaction, such as esterification, with acrylic acid, methacrylic acid, crotonic acid (β-methacrylic acid) and / or a direct reaction with anhydrides and / or halides corresponding to said acrylic acids, the molar ratio of hydroxyl groups to proximal acid, anhydride and / or hydride and / or preferably 120.1 to 1: 5, such as 1: 0.5 to 1: 1.5. Additional acrylate compounds suitable for acrylating the polyester / alcohol blend of the present process include Lex. epoxide or anhydride functional acrylates and metal acrylates such as glycidyl methaluylate.
U"1 .__\ -l> (D \-] O' l Föreliggande uppfinning kommer i det följande att ytterligare illustreras genom utföringsexempel 1-6, varvid - Exempel 1 visar tillverkning av en akrylatkomposition enligt uppfinningen samt uppmätning av fasseparation.The present invention will be further illustrated in the following by working examples 1-6, wherein - Example 1 shows the manufacture of an acrylate composition according to the invention and the measurement of phase separation.
- Exempel 2 och 3 visar en jämförande akrylering utanför uppfmningens ram samt test resultat i jämförelse med exempel 1.Examples 2 and 3 show a comparative acrylation outside the scope of the invention and test results in comparison with Example 1.
- Exempel 4-6 visar utvärdering av produkter erhållna i exempel 1 och 3.Examples 4-6 show evaluation of products obtained in examples 1 and 3.
Exempel 1 40,0 g av en dendritisk polyester med teoretiskt 16 terminala hydroxylgrupper (Boltorn® H20, Perstorp Specialty Chemicals, Sverige), 160,0 g av en trifiuilctionell polyalkohol (Polyol TP30“', Perstorp Specialty Chemicals, Sverige) blandades och satsades tillsammans med 163,8 g akxylsyra, 10 droppar nitrobensen, 0,5 g metoxifenol samt 425 ml toluen i en trehalsad mndkolv försedd med magnetomrörare, gasinledning, vattenseparator (Dean-Stark), kylare samt oljebad. Ornrörning samt genombubbling av luft startades och lösningen värmdes till 55°C, varvid 3,27 g metansulfonsyra satsades. Reaktionsblandningen värmdes sedan ytterligare till 90°C, vid vilken temperatur reaktionsvatten började avgå. Temperaturen höjdes sedan under 180 min successivt från 90°C till ll0°C. Reaktionen fick fortgå vid denna temperatur under ytterligare 210 min, tills vatten slutade avgå. Reaktionsblandningen kyldes nu till rumstemperatur.Example 1 40.0 g of a dendritic polyester with theoretically 16 terminal hydroxyl groups (Boltorn® H 2 O, Perstorp Specialty Chemicals, Sweden), 160.0 g of a tri-functional polyalcohol (Polyol TP30®, Perstorp Specialty Chemicals, Sweden) were mixed and charged together with 163.8 g of axylic acid, 10 drops of nitrobenzene, 0.5 g of methoxyphenol and 425 ml of toluene in a three-necked flask equipped with a magnetic stirrer, gas inlet, water separator (Dean-Stark), cooler and oil bath. Stirring and bubbling of air were started and the solution was heated to 55 ° C, with 3.27 g of methanesulfonic acid being charged. The reaction mixture was then further heated to 90 ° C, at which temperature reaction water began to evaporate. The temperature was then raised for 180 minutes successively from 90 ° C to 110 ° C. The reaction is continued at this temperature for a further 210 minutes, until water ceases to evaporate. The reaction mixture was now cooled to room temperature.
Den rumstempererade reaktionsblandningen hälldes sedan över i en 2 l bägare försedd med magnetomrörare och pH-elektrod. Lösningen neutraliserades under omröming med 425 ml 1% NaOH (aq) tills ett pH av 7,0 uppnåtts. Blandningen hälldes över i en 2 l separertratt och tiden till fasseparation uppmättes. Fullständig separation av organfas och vattenfas erhölls inom 30 min. Vattenfasen avskiljdes och organfasen tvättades sedan med 2 x 500 ml vatten, med avskiljning av vattenfas emellan tvättningarna. Fasseparation studerades i båda tvättningarna och fullständig separation av fasema erhölls i båda fallen inom 30 min.The room temperature reaction mixture was then poured into a 2 L beaker equipped with a magnetic stirrer and pH electrode. The solution was neutralized with stirring with 425 ml of 1% NaOH (aq) until a pH of 7.0 was reached. The mixture was poured into a 2 l separatory funnel and the time to phase separation was measured. Complete separation of organ phase and aqueous phase was obtained within 30 minutes. The aqueous phase was separated and the organ phase was then washed with 2 x 500 ml of water, separating the aqueous phase between washes. Phase separation was studied in both washes and complete separation of the phases was obtained in both cases within 30 minutes.
Den tvättade organfasen rullindunstades sedan under vakuum och genombubbling av lufi, varvid al-:rylerad slutprodukt erhölls som en lågviskös, klar och färglös vätska.The washed organ phase was then roller evaporated under vacuum and bubbling through lu fi to give the alkylated final product as a low viscosity, clear and colorless liquid.
Erhållen slutprodukt hade följande produktdata: Omsättning av OH-grupper till akrylat, mol% 94.5 Slutsyratal, mg KOH/g 0.75 Viskositet, Brookfield, 23 °C, mPas 180 Torrhalt, % 98.9 514 075 Exempel 2 (Jämlörande) 250,0 g av en dendritisk polyester med teoretiskt 16 terrninala hydroxylgrupper (Boltom® H20, Perstorp Specialty Chemicals, Sverige) satsades till en trehalsad rundkolv försedd med magnetomrörare, gasinledning, vattenseparator (Dean-Stark), kylare samt oljebad. Produkten värmdes tills en homogen smälta erhölls. 178,6 g akrylsyra, 17 droppar nitrobensen, 0,9 g metoxifenol, 6,43 g metansulfonsyra samt 300 ml toluen satsades därpå till produkten.The final product obtained had the following product data: Conversion of OH groups to acrylate, mol% 94.5 Final acid number, mg KOH / g 0.75 Viscosity, Brook fire, 23 ° C, mPas 180 Dry content,% 98.9 514 075 Example 2 (Comparative) 250.0 g of a dendritic polyester with theoretically 16 terminal hydroxyl groups (Boltom® H20, Perstorp Specialty Chemicals, Sweden) was invested in a three-necked round-bottomed flask equipped with a magnetic stirrer, gas inlet, water separator (Dean-Stark), cooler and oil bath. The product was heated until a homogeneous melt was obtained. 178.6 g of acrylic acid, 17 drops of nitrobenzene, 0.9 g of methoxyphenol, 6.43 g of methanesulfonic acid and 300 ml of toluene were then added to the product.
Omrörning samt genombubbling av luft startades och lösningen värmdes till 105°C, varvid reaktionsvatten började avgå. Temperaturen höjdes sedan successivt till 113°C och reaktionen fick fortgå vid denna temperatur, tills vatten slutade avgå. Reaktionsblandningen kyldes nu till rumstemperatur.Stirring and bubbling of air was started and the solution was heated to 105 ° C, whereby reaction water began to evaporate. The temperature was then raised gradually to 113 ° C and the reaction was continued at this temperature until water stopped evaporating. The reaction mixture was now cooled to room temperature.
Den rumstempererade reaktionsblandningen hälldes sedan över till en 2 l bägare försedd med magnetornrörare och pH-elektrod. Lösningen neutraliserades under omrörning med 425 ml 1% NaOH (aq) tills ett pH på 7,0 uppnåtts. Blandningen hälldes över i en 2 l separertratt och tiden till fasseparation uppmättes. Fullständig separation av organfas och vattenfas erhölls efter separation över natt (> 12 h). Vattenfasen avskiljdes och organfasen tvättades sedan med 2 x 500 ml vatten, med avskiljning av vattenfas emellan tvättarna på samma sätt som ovan.The room temperature reaction mixture was then poured into a 2 L beaker equipped with a magnet stirrer and pH electrode. The solution was neutralized with stirring with 425 ml of 1% NaOH (aq) until a pH of 7.0 was reached. The mixture was poured into a 2 l separatory funnel and the time to phase separation was measured. Complete separation of organ phase and aqueous phase was obtained after separation overnight (> 12 hours). The aqueous phase was separated and the organ phase was then washed with 2 x 500 ml of water, separating the aqueous phase between the washes in the same manner as above.
Organfasen upparbetades på samma sätt som i exempel 1, varvid slutprodukten erhölls som en viskös, transparent, gulaktig produkt.The organ phase was worked up in the same manner as in Example 1, the final product being obtained as a viscous, transparent, yellowish product.
Erhållen slutprodukt hade följande produktdata: Omsättning av OH-grupper till akrylat, mol% 95.1 Slutsyratal, mg KOH/g 5.4 Viskositet, Brookfield, 23°C, mPas 53600 Torrhalt, % 98.2 Exempel 3 (jämförande) En blandning av akrylerad dendritisk polyester enligt exempel 2 sarnt en kommersiell polyolakrylat baserad på etoxylerad trimetylolpropan (Sartomer SR 454m) framställdes och utvärderades med avseende på viskositet och fárgtal. 20,0 g dendritisk alcrylat enligt exempel 2 vägdes in i en 100 ml glasburk. Till denna satsades 80,0 g av Sartomer SR454“'. Produkterna blandades under omrörning, varvid en klar svagt gulaktig vätska erhölls. Blandningen tempererades till 23°C, varvid viskositeten bestämdes i 514 075 en Brookfieldviskosimeter och jämfördes med viskositetsdata för produkt framställd enligt exempel 1. Vidare bestämdes respektive produkts färgtal. Följande produktdata erhölls: Produkt Viskositet, Brookñeld, 23°C, mPas Färgtal, APHA Exempel 1 180 127 Exempel 3 200 898 Produkt framtagen enligt föreliggande uppfinning, uppvisade signifikant lägre viskositet.The final product obtained had the following product data: Conversion of OH groups to acrylate, mol% 95.1 Final acid number, mg KOH / g 5.4 Viscosity, Brook fire, 23 ° C, mPase 53600 Dry content,% 98.2 Example 3 (comparative) A mixture of acrylated dendritic polyester according to Example 2 where a commercial polyol acrylate based on ethoxylated trimethylolpropane (Sartomer SR 454m) was prepared and evaluated for viscosity and color number. 20.0 g of dendritic acrylate according to Example 2 were weighed into a 100 ml glass jar. To this was charged 80.0 g of Sartomer SR454 The products were mixed with stirring to give a clear pale yellowish liquid. The mixture was tempered to 23 ° C, the viscosity being determined in 514,075 a Brook fire viscometer and compared with the viscosity data of product prepared according to Example 1. Further, the color number of each product was determined. The following product data were obtained: Product Viscosity, Brookñeld, 23 ° C, mPas Color ratio, APHA Example 1 180 127 Example 3 200 898 Product produced according to the present invention showed significantly lower viscosity.
Vidare erhölls signifikant lägre fárgtal för produkt framställd enligt exempel 1 järntört för produkt framställd enligt exempel 3.Furthermore, a significantly lower color number was obtained for product prepared according to Example 1, iron tar for product prepared according to Example 3.
Exempel 4 Tre klarlacksforrnuleringar framställdes genom att, till produkter framställda enligt exempel 1 respektive exempel 3 samt till en kommersiell akrylat baserad på etoxylerad trimetylolpropan (Sartomer SR454'"), tillsätta fotoinitiator (Darocurem 1173, Ciba Geigy, Switzerland).Example 4 Three clearcoat formulations were prepared by adding photoinitiator (Darocurem 1173, Ciba Geigy, Switzerland) to products prepared according to Example 1 and Example 3 and to a commercial acrylate based on ethoxylated trimethylolpropane (Sartomer SR454 ').
Följande lackforrnuleringar erhölls: Prod. enl ex. 1 Prod. enl. ex. 3 SR454 Produkt, vikts-% 96.0 96.0 96.0 Darocure 1173, vikts-% 4.0 4.0 4.0 Exempel 5 De tre klarlackema enligt exempel 4 applicerades på glasplattor i 30 um tjocka skikt och UV-härdades i en UV-ugn (Wallace Knight, 20 m/min, 240 mJ/mz) med 1, 2 och 4 passager genom ugnen. Erhållna härdade klarlacksfilmer var av mycket god kvalitet helt utan defekter och med hög ytglans. De härdade lackfilmerna konditionerades 24 timmar vid 23°C och 50% relativ lufifiiktighet, varefter respektive ñlmhårdhet uppmättes som König sekunder (Ks) med en Königpendel.The following paint formulations were obtained: Prod. according to ex. 1 Prod. according to. ex. SR454 Product, wt% 96.0 96.0 96.0 Darocure 1173, wt% 4.0 4.0 4.0 Example 5 The three clearcoats of Example 4 were applied to glass plates in 30 μm thick layers and UV cured in a UV oven (Wallace Knight, 20 m / min, 240 mJ / mz) with 1, 2 and 4 passages through the oven. The obtained cured clearcoat films were of very good quality, completely without defects and with a high surface gloss. The cured varnishes were conditioned for 24 hours at 23 ° C and 50% relative lightness, after which the respective hardness was measured as König seconds (Ks) with a König pendulum.
Följande filmhårdhet uppmättes för de tre lackema: Prod. enl ex. 1 Prod. enl. ex. 3 SR454 lpassage, Ks 109 105 40 2 passager, Ks 134 142 138 4 passager, Ks 151 152 145 514 075 8 Produkt enligt föreliggande uppfinning (exempel 1), uppvisade mycket bra reaktivitet och var helt likvärdig med lack exempel 3. Vidare kan påpekas att både lack enligt exempel 1 och 3 uppvisade betydligt högre initial reaktivitet jämfört med lack SP454.The following hardness was measured for the three paints: Prod. according to ex. 1 Prod. according to. ex. SR454 lpassage, Ks 109 105 40 2 passages, Ks 134 142 138 4 passages, Ks 151 152 145 514 075 8 Product according to the present invention (example 1), showed very good reactivity and was completely equivalent to lacquer example 3. Furthermore, it can be pointed out that both lacquers according to examples 1 and 3 showed significantly higher initial reactivity compared to lacquer SP454.
Exempel 6 En hydroxylfiinktionell dendritisk polyester (Boltorn® H20, Perstorp Specialty Chemicals, Sverige) blandades i 20 vikts-% med tripropylenglykol, varvid följande viskositet erhölls Boltom® H20, vikts-%: 20 Tripropylenglykol, vikts-%: 80 Viskositet, 23°C, mPas: 660 Ovanstående resultat är ett exempel på dendritiska polyestrars utmärkta löslighet i olika typer av alkoholer. Andra exempel på lämpliga alkoholer är glycerol, etoxylerad glycerol samt propoxylerad glycerol, och andra typer av såväl etoxylerade som propoxylerade alkoholer.Example 6 A hydroxyl-functional dendritic polyester (Boltorn® H 2 O, Perstorp Specialty Chemicals, Sweden) was blended in 20% by weight with tripropylene glycol to give the following viscosity Boltom® H 2 O, wt%: Tripropylene glycol, wt%: 80 Viscosity, 23 ° C, mPas: 660 The above results are an example of the excellent solubility of dendritic polyesters in different types of alcohols. Other examples of suitable alcohols are glycerol, ethoxylated glycerol and propoxylated glycerol, and other types of both ethoxylated and propoxylated alcohols.
Claims (9)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9901517A SE514075C2 (en) | 1999-04-27 | 1999-04-27 | Process for manufacturing an acrylate composition comprising at least one dendritic polyester acrylate oligomer and at least one acrylate monomer |
| AU46318/00A AU4631800A (en) | 1999-04-27 | 2000-04-12 | Process for production of an acrylate composition |
| PCT/SE2000/000696 WO2000064975A1 (en) | 1999-04-27 | 2000-04-12 | Process for production of an acrylate composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9901517A SE514075C2 (en) | 1999-04-27 | 1999-04-27 | Process for manufacturing an acrylate composition comprising at least one dendritic polyester acrylate oligomer and at least one acrylate monomer |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| SE9901517D0 SE9901517D0 (en) | 1999-04-27 |
| SE9901517L SE9901517L (en) | 2000-10-28 |
| SE514075C2 true SE514075C2 (en) | 2000-12-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| SE9901517A SE514075C2 (en) | 1999-04-27 | 1999-04-27 | Process for manufacturing an acrylate composition comprising at least one dendritic polyester acrylate oligomer and at least one acrylate monomer |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU4631800A (en) |
| SE (1) | SE514075C2 (en) |
| WO (1) | WO2000064975A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE525758C2 (en) * | 2002-08-16 | 2005-04-19 | Perstorp Specialty Chem Ab | Waterborne homo- or copolymer dispersion, process for its preparation and its use in adhesives for its preparation and its use in adhesives for surface coatings |
| SE524961C2 (en) * | 2002-08-16 | 2004-11-02 | Celanese Emulsions Norden Ab | Waterborne copolymer dispersion and its use in coatings |
| DE10348463A1 (en) | 2003-10-14 | 2005-05-25 | Basf Ag | Hyperbranched polyesters with ethylenically unsaturated groups |
| FR2862650B1 (en) * | 2003-11-24 | 2007-04-20 | Rhodia Cons Spec Ltd | NEW MONOPHOSPHONIC TERMINATED DENDRIMERS, PROCESS FOR PREPARING SAME AND USE THEREOF |
| FR2862651B1 (en) | 2003-11-24 | 2006-03-31 | Rhodia Cons Spec Ltd | NOVEL DENDRIMERS WITH BISPHOSPHONIC AND DERIVED TERMINATIONS, PROCESS FOR PREPARING SAME AND USE THEREOF |
| US7189456B2 (en) | 2004-03-04 | 2007-03-13 | Transitions Optical, Inc. | Photochromic optical article |
| US7666331B2 (en) * | 2005-08-31 | 2010-02-23 | Transitions Optical, Inc. | Photochromic article |
| US7258437B2 (en) | 2005-09-07 | 2007-08-21 | Transitions Optical, Inc. | Photochromic multifocal optical article |
| US7906214B2 (en) | 2007-01-26 | 2011-03-15 | Transitions Optical, Inc. | Optical elements comprising compatiblizing coatings and methods of making the same |
| TWI444445B (en) | 2008-06-23 | 2014-07-11 | Sicpa Holding Sa | Intaglio printing ink comprising dendrimers |
| US9056302B2 (en) | 2009-06-15 | 2015-06-16 | Basf Se | Highly branched polymers as cross-linking agents in microcapsule wall |
| GB2499944B (en) * | 2010-11-15 | 2018-05-02 | Shanghai Weikai Optoelectronics New Mat Co Ltd | Crosslinkable curing super-branched polyester and cured product and preparation method thereof |
| EP2735903B1 (en) | 2012-11-22 | 2019-02-27 | Eastman Kodak Company | Negative working lithographic printing plate precursors comprising a hyperbranched binder material |
| WO2015085141A1 (en) * | 2013-12-06 | 2015-06-11 | Microtek Laboratories, Inc. | Microcapsules having acrylic polymeric shells |
| CN116396474B (en) * | 2023-04-10 | 2024-06-18 | 宜兴市江山生物科技有限公司 | Hyperbranched polyether ester with multiple purposes and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SE468771B (en) * | 1992-02-26 | 1993-03-15 | Perstorp Ab | DENDRITIC MACROMOLECYLE OF POLYESTER TYPE, PROCEDURES FOR PRODUCING THEREOF AND USING THEREOF |
| SE502634C2 (en) * | 1994-10-27 | 1995-11-27 | Perstorp Ab | Binder composition containing a dendritic or hyper-branched polyester |
| SE503622C2 (en) * | 1994-12-21 | 1996-07-22 | Perstorp Ab | A thermosetting material made of a thermosetting composition comprising a chain terminated dendritic or hyper-branched polyester type macromolexyl |
-
1999
- 1999-04-27 SE SE9901517A patent/SE514075C2/en not_active IP Right Cessation
-
2000
- 2000-04-12 AU AU46318/00A patent/AU4631800A/en not_active Abandoned
- 2000-04-12 WO PCT/SE2000/000696 patent/WO2000064975A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| SE9901517L (en) | 2000-10-28 |
| AU4631800A (en) | 2000-11-10 |
| WO2000064975A1 (en) | 2000-11-02 |
| SE9901517D0 (en) | 1999-04-27 |
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