MXPA97007977A - A method to prepare monome - Google Patents
A method to prepare monomeInfo
- Publication number
- MXPA97007977A MXPA97007977A MXPA/A/1997/007977A MX9707977A MXPA97007977A MX PA97007977 A MXPA97007977 A MX PA97007977A MX 9707977 A MX9707977 A MX 9707977A MX PA97007977 A MXPA97007977 A MX PA97007977A
- Authority
- MX
- Mexico
- Prior art keywords
- acrylate
- meth
- alcohol
- temperature
- vacuum
- Prior art date
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- -1 acrylate ester Chemical class 0.000 claims description 29
- YOBOXHGSEJBUPB-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 20
- 150000001298 alcohols Chemical class 0.000 claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 12
- 230000002401 inhibitory effect Effects 0.000 claims description 12
- 150000003755 zirconium compounds Chemical class 0.000 claims description 12
- 239000005749 Copper compound Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxybenzene-1,4-diol Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 claims description 3
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N Phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- 229950000688 Phenothiazine Drugs 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000001993 wax Substances 0.000 description 49
- 239000000047 product Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 28
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 17
- 238000007792 addition Methods 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 11
- 239000012456 homogeneous solution Substances 0.000 description 11
- 239000007921 spray Substances 0.000 description 11
- 238000005507 spraying Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-Hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000005809 transesterification reaction Methods 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N Copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene (PE) Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- SZRLKIKBPASKQH-UHFFFAOYSA-M CCCCN(C([S-])=S)CCCC Chemical compound CCCCN(C([S-])=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-M 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L Copper(II) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L Copper(II) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L Copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N Potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J Zirconium(IV) chloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- BGGIUGXMWNKMCP-UHFFFAOYSA-N 2-methylpropan-2-olate;zirconium(4+) Chemical compound CC(C)(C)O[Zr](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BGGIUGXMWNKMCP-UHFFFAOYSA-N 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L Copper(II) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N Titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J Zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical compound [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RJMWSMMKKAJPGD-UHFFFAOYSA-L azanium;2-hydroxypropane-1,2,3-tricarboxylate;zirconium(2+) Chemical compound [NH4+].[Zr+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O RJMWSMMKKAJPGD-UHFFFAOYSA-L 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- GYBISRSPJWPCSL-JJKGCWMISA-M copper(1+);(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Cu+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O GYBISRSPJWPCSL-JJKGCWMISA-M 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- SEKCXMNFUDONGJ-UHFFFAOYSA-L copper;2-ethylhexanoate Chemical compound [Cu+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O SEKCXMNFUDONGJ-UHFFFAOYSA-L 0.000 description 1
- 231100000078 corrosive Toxicity 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000011642 cupric gluconate Substances 0.000 description 1
- 235000019856 cupric gluconate Nutrition 0.000 description 1
- YIXQSYHBXUBLPM-UHFFFAOYSA-N dioxido(oxo)silane;zirconium(4+) Chemical compound [Zr+4].[O-][Si]([O-])=O.[O-][Si]([O-])=O YIXQSYHBXUBLPM-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- UDQGVYLBDJUFGB-UHFFFAOYSA-L magnesium;carbanide;carbonate Chemical compound [CH3-].[Mg+2].[O-]C([O-])=O UDQGVYLBDJUFGB-UHFFFAOYSA-L 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- XGZVLEAZGCUUPH-UHFFFAOYSA-N methylamino(methylimino)methanesulfonic acid Chemical compound CNC(=NC)S(O)(=O)=O XGZVLEAZGCUUPH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive Effects 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 1
- 229910000568 zirconium hydride Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- UXRMCZYAVOHQNB-UHFFFAOYSA-J zirconium(4+);disulfate;hydrate Chemical compound O.[Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O UXRMCZYAVOHQNB-UHFFFAOYSA-J 0.000 description 1
Abstract
A method for preparing monomers useful in a wide range of polymer is disclosed
Description
A METHOD FOR PREPARING MONOMERS
This invention relates to a method for preparing monomers, in particular to a suitable method for preparing monomers useful in a wide range of polymers. High molecular weight alcohols (C20 ~ 3QO) are known as synthetic wax alcohols and have been in commercial production for several years. While synthetic wax alcohols have limited use in candle waxes, synthetic wax monomers are very useful in a wide range of polymers. The use of synthetic wax alcohols would significantly increase if there were a process for converting them into synthetic wax monomers. There is a progressive need for a method of preparing synthetic wax monomers from synthetic wax alcohols. Japanese Patent Application J 6-329720 discloses polyethylene macromonomers with a terminal group of
(meth) acryloyl and a method for the preparation of these monomers. According to the method described, a polyethylene derivative is reacted with specific carbonyl compounds or oxidized with oxygen to produce the polyethylene alkoxide and then reacted with a halide of (meth) acrylic acid to supply the product wanted.
Another method known in the art is the use of transesterification to produce short chain acrylate esters. This method has been carried out routinely using catalysts selected from the elements of the IVA Group, such as, for example, Sn, Ge and Pb; Group IVB elements such as, for example, Ti and Hf; elements of the VA Group, such as, for example, the As and Sb; and the Fe as an element of Group VIII, see, for example, the patent of E. U. A., No. 5,037,948. These catalysts require relatively high levels of use to be effective and can be difficult to remove from the final product. Strong acids, such as, for example, methanesulphonic acid, and strong alkalis, such as, for example, lithium hydroxide, are also known to catalyze transesterifications. These catalysts are also inconvenient due to their corrosive nature. If not removed from the product, these catalysts can interfere with subsequent polymerizations and end uses. The removal of the catalyst from the product is also difficult. Despite the description of the prior art, there is a continuing need for a method of preparing synthetic wax monomers from synthetic wax alcohols.
We have found, surprisingly, that zirconium compounds are extremely effective in catalyzing the transesterification reactions that produce synthetic wax monomers from synthetic wax alcohols. Very low levels of zirconium compounds can be used effectively. An advantage of the present invention is that the zirconium compound does not need to be removed from the final product, due to its low use level and its benign character in downstream applications. The present invention provides a method for preparing synthetic wax monomers, this method comprises: mixing an alcohol of synthetic wax, an ester of
(meth) acrylate, a zirconium compound and an inhibitor, selected from the group consisting of the compounds containing nitroxyl, hydroquinone, methoxy-hydroquinone, phenothiazine and copper compounds; heat the mixture to 100-165 ° C, to supply the synthetic wax monomer, and remove the lower alcohol from the synthetic wax alcohol and the (meth) acrylate ester. The lower alcohol, formed from the reaction of the synthetic wax alcohol and the (meth) acrylate ester, can be removed by fractional distillation. The excess of (meth) acrylate ester can be separated from the product.
Synthetic wax alcohols are commercially available as the Unilin ™ or Unithox ™ products sold by Petrolite Inc. Suitable synthetic wax alcohols for use in this invention include the linear alcohols (C2? ~ C5?) And their ethoxylates. The (meth) acrylate esters are commercially available from Rohm and Haas Company. Suitable (meth) acrylate esters for use in this invention include, but are not limited to, methyl acrylate, ethyl acrylate, propyl acrylate, and n-butyl acrylate.; and methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate and t-butyl methacrylate. Typically, the (meth) acrylate ester and the synthetic wax alcohol are reacted on a molar basis of 2-ester of (meth) acrylate to 1 alcohol of synthetic wax to ester of (meth) acrylate to 1 alcohol of synthetic wax . More preferred is the ratio of 3-ester of (meth) acrylate to 1 alcohol of synthetic wax to 9-ester of (meth) acrylate to 1 alcohol of synthetic wax. Especially preferred is the ratio of 4-ester of (meth) acrylate to 1 alcohol of synthetic wax to 8 ester of (meth) acrylate to 1 alcohol of synthetic wax.
Zirconium compounds are commercially available from Aldrich Chemical Company. Zirconium compounds suitable for use in this invention include zirconium acetylacetonate, zirconium butoxide, zirconium tertiary butoxide, zirconium chloride, zirconium ammonium citrate complex, zirconium ethoxide, zirconium fluoride, zirconium hydride, complex of zirconium isopropoxide and isopropanol, zirconium oxide, zirconium propoxide, zirconium sulfate hydrate, zirconium tetrachloride and zirconium silicate. Zirconium acetylacetonate is preferred. The zirconium compound can be added from 0.1 to 10% based on the moles of the synthetic wax alcohol. More preferred is 0.5 to 7.5% of the zirconium compound based on the moles of the synthetic wax alcohol. Especially preferred is from 1 to 4% of the zirconium compound based on the moles of the synthetic wax alcohol. Suitable inhibitors for use in this invention include, but are not limited to, compounds containing nitroxyl, hydroquinone, methoxy-hydroquinone, phenothiazine and copper compounds. The inhibitors are commercially available from Aldrich Chemical Company. Suitable copper compounds include cupric acetate, cupric bromide, cupric chloride, cupric 2-ethylhexanoate, cupric fluoride, cupric gluconate, cupric nitrate, cupric methoxide, cupric sulfate, and cupric dibutyl-dithio-carbamate. The dibutyl-dithio-carbamate cupric is preferred. Compounds containing a suitable nitroxyl radical include 2, 2, 6, 6-tetramethyl-1-piperidinyloxy, ("4-hydroxy-TEMPO") free radical, 4-oxo-2, 2, 6, 6-tetramethyl -l-piperidinyloxy, ("4-oxo-TEMPO") free radical, and tertiary-dibutyl-nitroxyl (DtBN) (available from Nova Molecular Technologies, Lake Geneva, Wisconsin). The inhibitor can be added in 100 to 4,000 ppm based on the total weight of the synthetic wax alcohol and the (meth) acrylate ester to be reacted. More preferred is 500 to 3,000 ppm of the inhibitor, based on the total weight of the synthetic wax alcohol and the (meth) acrylate ester to be reacted. More preferred is 1,000 to 2,000 ppm of the inhibitor, based on the total weight of the synthetic wax alcohol and the (meth) acrylate ester to be reacted. The following examples attempt to illustrate the method of obtaining the synthetic wax monomers from the synthetic wax alcohols. All percentages are based on weight. The abbreviations used are: g = grams, mm = millimeters, 1 = liter,% = percent, N2 = nitrogen, O2 = oxygen, n = normal and ° C = degrees centigrade.
Example 1 - C40 Alcohol Acrylate A 5 liter flask, equipped with an overhead stirrer, a 5.08 cm Oldershaw column of 10 plates, a thermal and controller pair, a graduated receiver, a magnetically controlled reflux head and a spray of 8 % O2 / 92% of N2, at 19.5 cubic centimeters per minute, was charged with 2,000 g of Unilin® 550 (a synthetic, primary, linear wax alcohol). To this was added 1,164 g of n-butyl acrylate and 1.4 g of 4-hydroxy-TEMPO. While stirring and spraying, the batch was heated to 100 ° C. When the homogeneous solution was obtained, 20.0 g of zirconium acetylacetonate were added. The vacuum was increased to 200 mm and the temperature was increased to 120-125 ° C. The vacuum and temperature were kept constant until the steam temperature reached 97 ° C. At this point, the transesterification was complete. The total time from the addition of zirconium acetylacetonate to complete the reaction was 2.45 hours. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of the Unilin® 550 alcohol to the acrylate ester was quantitative, as measured by the Nuclear Magnetic Resonance ("NMR") spectrum. The product contained 0.12% residual butyl acrylate, as measured by gas chromatography ("GC").
Example 2 - Alcohol Acrylate C? N A 5 liter flask, equipped with an overhead stirrer, a 5.08 cm Oldersha column of 10 plates, a thermal and controller pair, a graduated receiver, a magnetically controlled reflux head and a spray from 8% O2 / 92% N2, to 19.5 cubic centimeters per minute, was loaded with 2,500 g Unilin® 700 (a synthetic, primary, linear wax alcohol). To this were added 1,250 g of n-butyl acrylate and 1.75 g of 4-hydroxy-TEMPO. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 25.0 g of zirconium acetylacetonate were added. The vacuum was increased to 200 mm and the temperature was increased to 120-125 ° C. The vacuum and temperature were kept constant until the steam temperature reached 97 ° C. At this point, the transesterification was complete. The total time from the addition of zirconium acetylacetonate to complete the reaction was 2.37 hours. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of the Unilin® 700 alcohol to the acrylate ester was 98.5%, as measured by the NMR spectrum. The product contained 0.1% residual butyl acrylate, as measured by gas chromatography ("GC").
Example 3 - C Alcohol Acrylate ?? A 5-liter flask, equipped with an overhead stirrer, a 5.0-inch Oldersha column of 10 plates, a thermal and controller pair, a graduated receiver, a magnetically controlled reflux head and a spray of 8% O2 / 92% N2, at 19.5 cubic centimeters per minute, was charged with 456.4 g of Alcohol Nafol® 1822 (a synthetic, primary, linear wax / 100% functionality alcohol). To this were added 581.5 g of n-butyl acrylate and 0.7 g of 4-hydroxy-TEMPO. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 9.9 g of zirconium acetylacetonate were added. The vacuum was increased to 200 mm and the temperature was increased to 120-125 ° C. The vacuum and temperature were kept constant until the steam temperature reached 97 ° C. At this point, the transesterification was complete. The total time from the addition of the zirconium acetylacetonate to complete the reaction was 0.90 hours. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of Nafol® 1822 alcohol to the acrylate ester was quantitative, as measured by the NMR spectrum. The product contained 0.24% residual butyl acrylate and residual butanol, as measured by gas chromatography ("GC").
Example 4 - Ethoxylated Alcohol Acrylate A 5 liter flask, equipped with an overhead stirrer, a 5.08 cm Oldershaw column of 10 plates, a thermal and controller pair, a graduated receiver, a magnetically controlled reflux head and a spray of 8 % O2 / 92% N2, at 19.5 cubic centimeters per minute, was charged with 2,373.5 g of Unithox® 450 Ethoxylate (a synthetic, primary, linear, ethoxylated wax alcohol / 82% alcohol functionality). To this were added 809.6 g of n-butyl acrylate and 1.2 g of 4-hydroxy-TEMPO. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 20.0 g of zirconium acetylacetonate were added. The vacuum was increased to 200 mm and the temperature was increased to 165 ° C. The vacuum and temperature were kept constant until the steam temperature reached 97 ° C. At this point, the transesterification was complete. The total time from the addition of the zirconium acetyl acetonate to complete the reaction was 3.60 hours. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of the ethoxylate alcohol Unithox® 450 to the acrylate ester was 92%, as measured by the NMR spectrum. The product contained 0.04% residual butyl acrylate, as measured by gas chromatography ("GC").
Example 5 - Cg Alcohol Methacrylate A 5 liter flask, equipped with an overhead stirrer, a 5.0 inch Oldersha column of 10 plates, a thermal and controller pair, a graduated receiver, a magnetically controlled reflux head and a spray of 8 % of O2 /
92% of N2, at 19.5 cubic centimeters per minute, was charged with 430 g of Unilin® 425 (a synthetic wax alcohol, primary, linear / 84.3% alcohol functionality). To this were added 240.3 g of methyl methacrylate and 0.5 g of 4-hydroxy-TEMPO. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 2.5 g of zirconium acetylacetonate were added. The vacuum was increased to 400 mm and the temperature was increased to 135 ° C. The vacuum and temperature were kept constant until the steam temperature reached 97 ° C. At this point, the transesterification was complete. The total time from the addition of zirconium acetylacetonate to complete the reaction was 1.0 hour. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of Unilin® 425 alcohol to the acrylate ester was quantitative, as measured by the NMR spectrum. No residual methyl methacrylate was detected by gas chromatography.
Example 6 - C Co Alcohol Acrylate and Comparison of Inhibitors Example 1 was repeated and the 4-hydroxy-TEMPO was replaced by 1,4-hydroquinone. A 5-liter flask, equipped with an overhead stirrer, a 5.08 cm Oldershaw column of 10 plates, a thermal and controller pair, a graduated receiver, a magnetically controlled reflux head and a spray of 8% O2 / 92% N2, at 19.5 cubic centimeters per minute, was charged with 2,000 g of Unilin® 550 (a synthetic, primary, linear wax alcohol). To this were added 1,164 g of n-butyl acrylate and 1.4 g of 1,4-hydroquinone. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 20.0 g of zirconium acetylacetonate were added. The vacuum was increased to 200 mm and the temperature was increased to 120-125 ° C. The vacuum and temperature were kept constant until the steam temperature reached 97 ° C. At this point, the transesterification was complete. The total time from the addition of zirconium acetylacetonate to complete the reaction was 2.45 hours. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of the Unilin® 550 alcohol to the acrylate ester was 98.%, as measured by the NMR spectrum. The product contained 0.28% residual butyl acrylate, as measured by gas chromatography.
Example 7 - Alcohol Methacrylate C n With Hydroquinone Inhibitor A 5-liter flask, equipped with an overhead stirrer, a 5.0-inch Oldershaw column of 10 plates, a thermal and controller pair, a graded receiver, a magnetically controlled reflux head and a spray of 8% O2 / 92% N2, at 19.5 cubic centimeters per minute, was charged with 500 g Unilin® 550 (a synthetic, primary, linear wax alcohol). To this were added 375 g of methyl methacrylate and 0.4 g of hydroquinone. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 0.8 g of zirconium acetylacetonate was added. The reaction was distilled at this temperature for 3 hours. Another 0.4 g of zirconium acetylacetonate was added, the temperature of the kettle was increased to 125 ° C and the reaction was distilled for one hour. The total time from the addition of the zirconium acetylacetonate to complete the reaction was 4.15 hours. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of Unilin® 550 alcohol to methacrylate ester was quantitative, as measured by the NMR spectrum. The product contained 0.45% residual butyl methacrylate, as measured by gas chromatography.
Example 8 - Methacrylate of Ethoxylated Alcohol With Hydroquinone Inhibitor A 5-liter flask, equipped with an overhead stirrer, a 5.0-inch Oldersha column of 10 plates, a thermal and controller pair, a graduated receiver, a magnetically controlled reflux head and a spray of 8% O2 / 92% N2, at 19.5 cubic centimeters per minute, was loaded with 451 g Unithox® 450 (a synthetic wax, primary, linear / 82% functionality alcohol). To this were added 719 g of methyl methacrylate and 1.0 g of hydroquinone. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 3.77 g of zirconium acetylacetonate were added. The vacuum was increased to 200 mm and the temperature was increased to 108 ° C. The reaction was distilled for 2.5 hours. The total time from the addition of the zirconium acetylacetonate to complete the reaction was 3.0 hours. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The residual methyl methacrylate was separated for another hour. The molten product was removed to
108 ° C. The conversion of Unithox® 450 alcohol to the methacrylate ester was 92%, as measured by the spectrum of
NMR. The product contained 0.44% residual methyl methacrylate, as measured by gas chromatography.
Example 9 - Comparative Example - Alcohol Acrylate With Potassium Tertiary Butoxide A 5-liter flask, equipped with an overhead stirrer, a 5.0-inch Oldersha column of 10 plates, a thermal and controller pair, a graduated receiver, a magnetically controlled reflux head and a spray of 8% O2 / 92% N2, at 19.5 cubic centimeters per minute, was charged with 2,000 g Unilin® 550 (a synthetic, primary, linear wax alcohol). To this was added 1,164 g of n-butyl acrylate and 1.4 g of 4-hydroxy-TEMPO. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 20.0 g of potassium tertiary butoxide were added. The vacuum was increased to 200 mm and the temperature was increased to 120-125 ° C. The vacuum and temperature were kept constant until the steam temperature reached 97 ° C. The total time from the addition of zirconium acetylacetonate to complete the reaction was 2.45 hours. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of the Unilin® 550 alcohol to the acrylate ester was 10.7%, as measured by the NMR spectrum. The product contained 0.63% residual butyl acrylate, as measured by gas chromatography.
Example 10 - Comparative Example Alcohol Acrylate With Dibutyl Tin Methoxide A 5 liter flask, equipped with an overhead stirrer, a 5.08 cm Oldershaw column of 10 plates, a thermal and controller pair, a graduated receiver, a magnetically controlled reflux head and a spray of 8% O2 / 92% N2, at 19.5 cubic centimeters per minute, was charged with 2,000 g Unilin® 550 (a synthetic, primary, linear wax alcohol). To this was added 1,164 g of n-butyl acrylate and 1.4 g of 4-hydroxy-TEMPO. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 20.0 g of dibutyltin dimethoxide was added. The vacuum was increased to 200 mm and the temperature was increased to 120-125 ° C. The vacuum and temperature were kept constant until the steam temperature reached 97 ° C. At this point, the transesterification was complete. The total time from the addition of zirconium acetylacetonate to complete the reaction was 2.45 hours. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of Unilin® 550 alcohol to the acrylate ester was quantitative, as measured by the NMR spectrum. The product contained 0.64% residual butyl acrylate, as measured by gas chromatography. Although the conversion was good, tin is quite toxic and has to be removed from the product. The removal of tin from the product was very difficult.
EXAMPLE 11 - COMPARATIVE EXAMPLE - C Cn Alcohol Acrylate with Magnesium Methoxide A 5 liter flask, equipped with an overhead stirrer, a 5.08 cm Oldershaw column of 10 plates, a thermal and controller pair, a graduated receiver, a head of magnetically controlled reflow and a spray of 8% O2 / 92% N2, at 19.5 cubic centimeters per minute, was charged with 2,000 g of Unilin® 550 (a synthetic, primary, linear wax alcohol). To this was added 1,164 g of n-butyl acrylate and 1.4 g of 4-hydroxy-TEMPO. While stirring and spraying, the batch was heated to 100 ° C. When a homogeneous solution was obtained, 20.0 g of methyl magnesium carbonate (8% in methanol) were added. The vacuum was increased to 200 mm and the temperature was increased to 120-125 ° C. The vacuum and temperature were kept constant until the steam temperature reached 97 ° C. The total time from the addition of zirconium acetylacetonate to complete the reaction was 2.45 hours. The vacuum and temperature were reduced. The column was removed and a deflection head of the straight direction was installed. The vacuum was then increased to 25 mm and the temperature was increased to 125 ° C. The temperature and vacuum were maintained until the distillation was stopped. The molten product was removed at 125 ° C. The conversion of Unilin® 550 alcohol to the acrylate ester was 1.5%, as measured by the NMR spectrum. The product contained 0.8% residual butyl acrylate, as measured by gas chromatography. The above examples demonstrate that the method of this invention is very effective in converting the synthetic wax alcohols into the synthetic wax monomers, without the need to remove the catalyst from the product. The other catalysts tested gave a poor conversion of the synthetic wax alcohol into the synthetic wax monomer, or required the removal of the catalyst from the product.
Claims (6)
- CLAIMS 1. A method for preparing synthetic wax monomers, this method comprises: mixing a synthetic wax alcohol, a (meth) acrylate ester, a zirconium compound and an inhibitor, selected from the group consisting of compounds containing radicals of nitroxyl, hydroquinone, methoxy-hydroquinone, phenothiazine and copper compounds; heat the mixture to 100-165 ° C, to supply the synthetic wax monomer; and removing the lower alcohol from the synthetic wax alcohol and the (meth) acrylate ester.
- 2. The method, according to claim 1, wherein the (meth) acrylate ester is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (met) acrylate of n. -butyl, isopropyl methacrylate, isobutyl methacrylate and t-butyl methacrylate.
- 3. The method, according to claim 2, in which the (meth) acrylate ester is methyl (meth) acrylate, the zirconium compound is zirconium acetylacetonate, and the inhibitor is the free radical of 2.2, 6,6-tetramethyl-1-piperidinyloxy.
- 4. The method, according to claim 2, in which the (meth) acrylate ester is n-butyl (meth) acrylate, the zirconium compound is zirconium acetylacetonate and the inhibitor is the free radical of 2.2 , 6,6-tetramethyl-1-piperidinyloxy.
- 5. The method, according to claim 1, wherein the synthetic wax alcohol is selected from the group consisting of linear alcohols (20-C50), and their ethoxylates.
- 6. The method, according to claim 1, further comprising the additional step of separating the excess of the (meth) acrylate ester.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US60/028,885 | 1996-10-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
MXPA97007977A true MXPA97007977A (en) | 1998-11-16 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5856611A (en) | Zirconium catalyzed transesterification process for preparing synthetic wax monomers | |
TWI335909B (en) | Transesterification process for production of (meth)acrylate ester monomers | |
CN100420675C (en) | Transesterification process for production of (meth)acrylate ester monomers | |
CN1140493C (en) | Process for preparing polyol di(methy) acrylate | |
AU643339B2 (en) | Preparation of alkoxyalkanoic acids | |
KR100468270B1 (en) | Process for the preparation of polyglycol(meth)acrylates | |
CN102686552A (en) | Method for producing (1-alkoxy-2-methyl-1-oxopropan-2-yl)-(meth)acrylate | |
JP2010511681A (en) | Process for the synthesis of (meth) acrylic esters catalyzed by polyol titanates | |
EP2113499B1 (en) | Use of metal salts of trifuoromethane sulphonic acid as esterification catalyst and/or transesterification catalyst | |
EP0160427B1 (en) | Alcoholysis of esters and metal alcoholates used in this process | |
CN1105992A (en) | Process for preparing alkylimidazolidone (meth) acrylates | |
JP2992965B2 (en) | Transesterification method | |
MXPA97007977A (en) | A method to prepare monome | |
US20020123643A1 (en) | Process for producing methylcyclohexyl (METH) acrylates | |
EP0185553B1 (en) | Process for preparation of poly(tetramethylene ether) glycol | |
AU2128002A (en) | Transesterification process | |
JPH0466555A (en) | Production of (meth)acrylic acid ester | |
CA2265501A1 (en) | Method for preparing perfluorocarbon-substituted methanols | |
JP3450470B2 (en) | Method for producing di (meth) acrylate | |
JP4656351B2 (en) | Process for producing ester by transesterification | |
JP2002241341A (en) | Method for producing high purity (meth)acrylic ester | |
JPH05286896A (en) | Production of allyl ester | |
WO1989009762A1 (en) | Transesterification of alkoxyesters | |
JPS5998118A (en) | Composition containing reactive monomer derived from lactone | |
JP3312806B2 (en) | Method for producing tetrahydrobenzyl (meth) acrylate |