CN101942088B - Method for synthesizing acetoacetate ester compound - Google Patents
Method for synthesizing acetoacetate ester compound Download PDFInfo
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- CN101942088B CN101942088B CN2010102629255A CN201010262925A CN101942088B CN 101942088 B CN101942088 B CN 101942088B CN 2010102629255 A CN2010102629255 A CN 2010102629255A CN 201010262925 A CN201010262925 A CN 201010262925A CN 101942088 B CN101942088 B CN 101942088B
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- China
- Prior art keywords
- ester
- alcohol
- diacetyl
- acid
- acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 acetoacetate ester compound Chemical class 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 47
- 150000002148 esters Chemical class 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 235000019439 ethyl acetate Nutrition 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 claims description 11
- PVGHQBCTMALNFO-UHFFFAOYSA-N 2-acetyl-3-oxobutanoic acid Chemical compound CC(=O)C(C(C)=O)C(O)=O PVGHQBCTMALNFO-UHFFFAOYSA-N 0.000 claims description 10
- 239000004135 Bone phosphate Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- 239000004632 polycaprolactone Substances 0.000 claims description 9
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 8
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical group CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 8
- 150000003077 polyols Chemical class 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 7
- 229920005906 polyester polyol Polymers 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Substances CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229940059574 pentaerithrityl Drugs 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- IHPDTPWNFBQHEB-UHFFFAOYSA-N hydrobenzoin Chemical compound C=1C=CC=CC=1C(O)C(O)C1=CC=CC=C1 IHPDTPWNFBQHEB-UHFFFAOYSA-N 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 3
- CXURGFRDGROIKG-UHFFFAOYSA-N 3,3-bis(chloromethyl)oxetane Chemical compound ClCC1(CCl)COC1 CXURGFRDGROIKG-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- CASPZMCSNJZQMV-UHFFFAOYSA-N ethane;2-methyloxirane Chemical compound CC.CC1CO1 CASPZMCSNJZQMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229940059936 lithium bromide Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 2
- 125000004185 ester group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 16
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 235000010980 cellulose Nutrition 0.000 description 5
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 4
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
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- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
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- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
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- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
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- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the field of polymer materials, relating to a method for synthesizing acetoacetate ester modified polymer. The method comprises the following steps: taking polymer containing hydroxyl and micromolecule acetoacetate ester as raw materials, and performing reaction under the condition of microwave irradiation; and the equation is shown in the specification, wherein R2(OH)n is polymer containing multi-hydroxy. The invention synthesizes the polymer of which side chains or chain ends have a plurality of acetoacetate ester groups by the process of catalytic ester exchange. The synthetic method has the advantages of high efficiency, mild synthetic method and high safety. In addition, in the method, the catalyst can be added, thereby improving synthetic efficiency; the synthetic rate of the method is greatly improved compared with the prior art; and the reaction time is shortened to 2-30min.
Description
Technical field
The invention belongs to the macromolecule chemical industry field of materials, be specifically related to the method for a kind of fast and convenient synthetic many acetylacetic esters based polyalcohol/acetoacetate groups macromolecular cpd.
Background technology
Industrial circles such as coating, printing ink, tackiness agent, polymer composites relate generally to the crosslinking polymerization problem of polymer materials, to improve the mechanical property and the environmental resistance of material, make material have certain protection effect and work-ing life.Tradition crosslinking polymerization mode comprises mainly that radical polymerization is crosslinked, isocyanic ester/polyol crosslink etc.Based on the compound of beta-dicarbonyl structure because folded methylene radical (CO-CH between two carbonyls
2-CO-) have a suitable chemical reactivity; Can be down and alpha such as propenoate at suitable catalytic condition; The carbon-to-carbon double bond of beta ring filling structure carries out Michael addition, if this reaction occurs between multifunctional beta-dicarbonyl compound and the polyfunctional acrylic ester material, chemically crosslinked takes place then; Be a kind ofly to have the more novel crosslinking curing mode of potential using value, be suitable for heat cross-linking and solidify or novel photo-crosslinking solidify material in material processing field.In addition, in multifunctional beta-dicarbapentaborane polymkeric substance, add some metal-salt, also can realize another comparatively novel crosslinking curing through the sequestering action of metals ion and a plurality of beta-dicarbonyl structures.More particularly, the linking agent that the beta-dicarbonyl compound can be used as a base polymer uses, and also can use as one type of polymer materials that can be crosslinked.Remove in addition, aspects such as the compound that contains a plurality of beta-dicarbapentaborane is functionalized at metal ion-chelant, chemical enrichment separation, environment protection, material modification, sensitive materials preparation also have potential comparatively widely using value.
Above-mentioned beta-dicarbonyl compound can beta-diketone carbonyl or the form of acyl methyl ester exist, the former is meant in the molecular structure between two ketone carbonyls methylene radical at interval, is also referred to as beta-diketone carbonyl compound, can use general structure R-CO-CH
2-CO-R ' representes that its typical case's representative comprises methyl ethyl diketone, trifluoroacetylacetone, hexafluoroacetylacetone etc.The beta-dicarbonyl compound of acyl methyl ester form can be used general structure R-CO-CH
2-CO-O-R ' representes that its typical case's representative comprises methyl aceto acetate, methyl acetoacetate, tert-butyl acetoacetate etc., is the acetylacetic ester compounds, the common micromolecular compound that is monofunctional.The beta-dicarbonyl compound of acetoacetic ester can obtain the etheric acid ester products of multifunctional group easily owing to the reactivity of ester bond structure makes the deriving of product, modification design more flexible.
At present, the method for existing multiple synthesis of acetyl acetate compound, but aspect synthetic many acetylacetic esters based polyalcohol or acetoacetate groups macromolecular cpd, still exist more deficiency.The most traditional acetylacetic ester compound is synthetic to be under alkaline condition, to react realization through similar ester classes such as ETHYLE ACETATE, and according to said method, products therefrom only limits to the etheric acid ester cpds of simple function, and synthesis yield is not high.Adopting ketene dimer technology synthesis of acetyl acetic ester is the mainstream technology method of current scale operation etheric acid ester cpds; Alcohols reaction with ketene dimer and various different structures; Can obtain the acetylacetic ester of various structures; Comprise multifunctional etheric acid ester cpds, and productive rate is higher, no coupling product.But ketene dimer belongs to inflammable and explosive dangerous goods, can not transport, and in-field use is met the water combustion explosion only, and danger is very high.Therefore, the technological line through ketene dimer synthesis of acetyl acetate compound has significant limitation.Adopting the more complicated etheric acid ester cpds of tert-butyl acetoacetate pyrolysis synthetic molecules structure is the more new technique method of current report, and the tert-butyl acetoacetate thermostability is relatively poor relatively, through the heat of tert-butyl acetoacetate; Decompose and slough the trimethyl carbinol; Form the ketene midbody, instant and other raw polyols reactions of difficult relatively evaporable obtain acetylacetic ester; This method needs the continuous high temperature condition, and the reaction times reaches several hours.Because these deficiencies, these methods all have bigger limitation on polyfunctional group acetylacetic ester application of compound.
Microwave irradiation technology obtains more application in organic synthesis, macromolecular material, field of inorganic nonmetallic material at present, and development has formed many synthetic and materials processing technologies with actual application value.Like the epoxy resin microwave radiation fast setting technology of field of polymer technology, Michael addition crosslinking curing technology etc.But it then is a newer direction that microwave irradiation technology is used for the synthetic of many acetylacetic esters based polyalcohol.
Summary of the invention
The objective of the invention is to deficiency, a kind of method that can synthesize many acetylacetic esters based polyalcohol efficiently and safely is provided to prior art.
The present invention mixes poly-hydroxy macromolecular cpd (polyhydroxylated polymer) with single acetyl acetic ester or diacetyl acetate ester cpds, add catalyzer again, as reaction mass, carries out the polymkeric substance that building-up reactions obtains to contain acetoacetate groups through microwave exposure.Specifically, technology involved in the present invention is to adopt microwave promotion method, through synthetic many acetylacetic esters based polyalcohol of the process of similar transesterify or acetoacetate groups macromolecular cpd.Microwave promotes synthetic reaction process to represent with following equation in the technology of the present invention:
Two types of starting material of Technology Need of the present invention; One type is the less etheric acid ester cpds of molecular weight; On chemical property, require such raw material to have the certain reaction activity, easy reaction of taking off-oxyl forms very unsettled ketene dimer under heating or other shooting conditionss; Can react with more difficult evaporable hydroxy component in the system, form comparatively stable etheric acid ester products.Here the indication-oxyl group that is prone to leave away is combining hydrogen promptly to change corresponding alcohol or phenol later on into, and corresponding-oxyl is alkoxyl group or phenol oxygen base.Based on some special acetylacetic ester-oxyl structure; As replace the diacetyl acetate ester cpds of 1 or together with carbon alkylidene group diacetyl acetic acid ester cpds, also can be when taking off-oxyl; The more complicated rearrangement of-oxyl experience waits reaction, generates ketone or aldehyde.Acetylacetic ester decomposes the alcohols that produces should have higher relatively volatile, promptly under reaction conditions, removes from system through the distillatory method easily.The present invention excites the acetylacetic ester raw material to decompose through the microwave exposure method; Form highly active ketene dimer; And timely and high-molecular weight polyol reaction, form title product many acetoacetate groups macromolecular cpd (many acetylacetic esters based polyalcohol).
The acetylacetic ester raw material is to contain
The compound of substruction comprises single acetyl acetic ester or diacetyl acetate ester cpds, i.e. R
1Group can connect one or two acetoacetate groups.Its atmospheric boiling point is higher than 120 degrees centigrade, R
1Group is a carbonatoms 4～16, and relatively is prone to the alkyl of leaving away.Can as the acetylacetic ester of synthesis material of the present invention preferably the tertiary alcohol, together with carbon glycol (isomerized ketone or aldehyde), that pure etheric acid ester cpds of sheet; Comprise etheric acid-2-propyloxy phenyl ester, tert-butyl acetoacetate, etheric acid tert-pentyl ester, the own ester of etheric acid uncle, the inferior isopropyl ester of diacetyl acetic acid, the inferior isobutylate of diacetyl acetic acid, the inferior cyclohexyl of diacetyl acetic acid, etheric acid phenyl ester, 2 specifically; 3-dimethyl--2; 3-butyleneglycol diacetyl acetic ester, 2; 3-phenylbenzene-2,3-butyleneglycol diacetyl acetic ester, 1,2-diphenylethyleneglycol diacetyl acetic ester.
Specifically, the acetylacetic ester raw material be meant those be heated or other shooting conditionss under relatively easy cracking deviate from-oxyl group, and produce the etheric acid ester cpds of ketene dimer.In general, compound thermostabilitys such as methyl acetoacetate, methyl aceto acetate are higher, though split product methyl alcohol, ethanol are more volatile, cracking temperature own is too high, and are suitable to acetylacetic ester raw material of the present invention.The etheric acid ester cpds of other simple monobasic primary alconols, monobasic secondary alcohol is also similar.Can as the acetylacetic ester of synthesis material of the present invention preferably the tertiary alcohol, together with carbon glycol (isomerized ketone or aldehyde), that pure etheric acid ester cpds of sheet; Comparatively responsive to heat or microwave radiation, cracking forms the ketene dimer and products such as corresponding alcohol, ketone, aldehyde of high reaction activity easily.These acetylacetic ester raw materials comprise etheric acid-2-propyloxy phenyl ester, etheric acid-2-cyclohexyl isopropyl ester, tert-butyl acetoacetate, etheric acid tert-pentyl ester, the own ester of etheric acid uncle, the inferior isopropyl ester of diacetyl acetic acid, the inferior isobutylate of diacetyl acetic acid, diacetyl acetic acid-1; The inferior cyclohexyl of 1-, etheric acid phenyl ester, NSC 6366 diacetyl acetic ester, 2; 3-dimethyl--2; 3-butyleneglycol diacetyl acetic ester, 2; 3-phenylbenzene-2,3-butyleneglycol diacetyl acetic ester, 1,2-diphenylethyleneglycol diacetyl acetic ester etc.
The required another kind of starting material of the present invention's technology are the macromolecular cpd that contains a plurality of hydroxyls, comprise Mierocrystalline cellulose, polysaccharide, polyether glycol, polyester polyol, polyacrylate polyol, oleyl alcohol mixture, other polymer polyatomic alcohols etc.
Here the Mierocrystalline cellulose of indication comprises various types of Mierocrystalline celluloses and modified-cellulose, like Microcrystalline Cellulose, noncrystalline cellulose, FM, cellulose propionate, cellulose acetate butyrate (CAB); Polysaccharide comprises sucrose, VISOSE etc.; Polyether glycol comprise polyoxyethylene glycol, W 166, epoxy ethane-epoxy propane copolymerization divalent alcohol, glycerine cause oxyethane gained polyether-tribasic alcohol, glycerine cause propylene oxide gained polyether-tribasic alcohol, TriMethylolPropane(TMP) cause oxyethane gained polyether-tribasic alcohol, TriMethylolPropane(TMP) cause propylene oxide gained polyether-tribasic alcohol, tetramethylolmethane cause oxyethane gained polyethers tetravalent alcohol, tetramethylolmethane cause propylene oxide gained polyethers tetravalent alcohol, penton polyvalent alcohol, based on 1, the polyether glycol of 4-butyleneglycol etc.; Polyester polyol comprise the Synolac polyvalent alcohol, based on the polyester diol of di-carboxylic acid and diol monomer, based on diacid and the monomeric polyester polyol of trivalent alcohol, based on tribasic carboxylic acid and diol monomer polyester polyol, polycaprolactone divalent alcohol, polycaprolactone trivalent alcohol, polycaprolactone tetravalent alcohol, aliphatic acid ester carbonate divalent alcohol, based on 2, the monomeric dendritic polyester polyvalent alcohol of 2-dimethylol propionic acid; Polyacrylate polyol comprise Hydroxyethyl acrylate (or methacrylic ester hydroxyl ethyl ester, propenoate hydroxypropyl acrylate, Rocryl 410) with (propenoate, vinylbenzene, the functionalized allyl monomer etc.) copolymerization of other vinyl monomers and poly-hydroxy side chain multipolymer; Other polymer polyatomic alcohols or macromolecular polyol comprise the melamine polyvalent alcohol; Vegetables oil and polyvalent alcohol (glycerine; TriMethylolPropane(TMP) etc.) transesterify and the oleyl alcohol mixture; Modified polyhydroxy epoxy resin (hydroxy fatty acid and bisphenol A epoxide resin esterification by ring opening and polyhydroxy resin; Diethylolamine is to epoxy resin modification gained polyhydroxy resin etc.); The ZGK 5 of carbon containing alcoholic extract hydroxyl group (end hydroxypropyl YSR 3286; End hydroxypropyl polyphenyl methyl siloxane; Side chain hydroxyalkylation ZGK 5) etc.Polymer polyatomic alcohol that the present invention is fit to or macromolecular polyol are not limited to above-mentioned giving an example, and in principle, molecular weight is rich in primary hydroxyl greater than 300, and has the polymkeric substance of certain thermostability all can adopt in the present invention.Adopting the acetylacetic ester of special construction is one of important innovations of the present invention as etheric acid esterification raw material.
Reaction system to solid material alcohol; At the raw material acetylacetic ester effectively under the dissolved situation; Can make organic solvent help dissolving; Promote reaction to carry out, selected solvent also should have relative higher and characteristic such as hydroxyl not except that the requirement of solvability aspect; The solvent that can select for use comprises toluene, YLENE, pimelinketone, N-BUTYL ACETATE, methylethylketone, orthodichlorobenzene, ethyl cellosolve, ethylene glycol butyl ether, dimethyl phthalate, N, N-methylacetamide, DMSO etc.The reaction system of liquid towards raw material also can be used solvent.
Technology of the present invention comprises the use of certain catalyzer; Promote raw alcohol and the reaction of acetylacetic ester raw material under microwave exposure; Catalyzer is the inorganic or organic metal salt of tin, zinc, titanium, zirconium, lithium, comprises in Mono-n-butyltin, Dibutyltin oxide, zinc acetate, isocaprylic acid zinc, dibutyl tin dilaurate, tetrabutyl zirconate, tetrabutyl titanate, titanium isopropylate, Lithium Sulphate, lithiumbromide, lithium chloride, the Lithium Acetate one or more.Catalyst levels is 0.05～8% of a reaction mass gross weight.In the transesterification reaction of acetylacetic ester, use catalyzer, significantly improve transesterify efficient, this is two of innovation of the present invention.
The microwave condition of indication of the present invention is the microwave exposure reaction system of 2450 ± 50MHz frequency of emission when utilizing microwave oven work, promotes building-up reactions.Adopt microwave technology to promote that the acetylacetic ester and the reaction of alcohol are three of important innovations points of the present invention.Preferred following material proportion and reaction conditions during reaction: 200～10000 watts of the required microwave exposure power of per 1 liter of material; Single acetyl acetic ester or diacetyl acetate ester cpds in the material, with the ratio of poly-hydroxy macromolecular cpd be 1: 1～1: 100 (mol ratio according to acetoacetate groups and hydroxyl is calculated); Catalyzer shared weight percent in the material gross weight is 0.05%～8%.
The microwave oven that is adopted can be a household microwave oven, also can be industrial microwave oven, in the present invention; The microwave oven that can adopt from 200 watts to 3600 watts; During concrete the utilization, can select the different operating gear, make microwave oven launched microwave under the state that is lower than its full load power; Promote reaction, and don't as for making temperature of reaction system too high., microwave oven real work power can be in 10～100% scopes of its full output rating flexible.Synthesising reacting time under microwave promotes is 2～30 minutes.For in above-mentioned power range, the lower microwave oven of power can be taked the gear of operating at full capacity at full capacity, adds fast response and carries out.
The microwave reaction device that is adopted is at the last through hole that is stamped, and in order to reflux condensing tube or still tube to be installed, reflux condensing tube or still tube are connected with the intravital reaction vessel in microwave exposure chamber.Reaction can be an interval type, also can adopt the flowing reactive pattern.No matter to which kind of reaction pattern, every liter of required microwave power of reaction mass is controlled between 200～10000 watts, but accepts the time free adjustment of microwave exposure.
The comparatively typical synthetic operation process of the present invention is:
Alcohols feedstock is mixed with the acetylacetic ester raw material by a certain percentage, transfers in the microwave oven in the homogeneous phase admixture, under certain power condition, through the microwave exposure certain hour.Reaction mixture is taken out, carry out suitable post-processing operation, comprise distillation, obtain the etheric acid ester cpds (acetylacetic ester based polyalcohol) of macromolecule or/and deposition (layering) etc. are removed byproduct of reaction (being mainly micromolecular alcohols, ketone etc.).Concrete aftertreatment technology will be looked the character of product, raw alcohol and decide.
Compared with prior art, the present invention has following beneficial effect:
(1) method provided by the present invention can be synthesized multiple macromole etheric acid ester cpds/acetylacetic ester based polyalcohol efficiently.
(2) compound method provided by the present invention is gentle, and is safe, and improved synthesis rate greatly, and the reaction times foreshortens to 2～30 minutes.
(3) compound method productive rate provided by the present invention is high, and the waste of raw material reduces, and has practiced thrift cost.
(4) adopt present method, obtain very high reaction conversion ratio in a short period of time, practiced thrift the energy.
Embodiment
Below further specify technical scheme of the present invention through concrete embodiment.
Embodiment 1
In an amount of Polyethylene Glycol-600 (PEG600), add small amount of toluene, handle the evaporated under reduced pressure solvent through azeotropic dehydration; Take by weighing 120g (0.20mol) PEG600 that anhydrates after the sealing cooling, join in 67g (0.42mol) tert-butyl acetoacetate, add the 0.3g zinc acetate; Thorough mixing is even, and placing output rating at full capacity is in 700 watts the perforate microwave oven, to load onto still tube, TM, prolong and receiving tube; Microwave oven work gear is adjusted to 50% of its full load power, and the working hour is set at 15min, opens microwave oven; Overhead product appears behind about 1min, distillate basicly stable between 80～85 ℃, behind about 12min; Overhead product is near complete, and the TM indication descends.Stop microwave reaction, after the cooling of question response bottle, take out reaction flask, carry out underpressure distillation again, remove volatile constituent (the residual tert-butyl acetoacetate and the trimethyl carbinol), get product polyoxyethylene glycol diacetyl acetic ester, by PEG600, yield 102%.Product is through 300MHz
1The HNMR test, chemical shift is δ (CDCl
3, ppm): 2.25 (s, 2 * 3H), 3.51 (s, 2 * 2H), 4.15 (m, 2 * 2H), 3.61 (m ,-OCH
2CH
2O-, 50.3H).
Embodiment 2
Get the Microcrystalline Cellulose 16.0g of vacuum-drying, join in the 200ml DMAC N,N; Add the 0.05g Lithium Acetate as catalyzer, add the inferior isopropyl ester of 20.0g diacetyl acetic acid, placing output rating at full capacity is in 700 watts the perforate microwave oven; Load onto still tube, TM, prolong and receiving tube, microwave oven work gear is adjusted to 50% of its full load power, the working hour is set at 20min; Open microwave oven, distillate basicly stable between 30～45 ℃, behind about 15min; Overhead product is near complete, and the TM indication descends.Stop microwave reaction, take out reaction flask, pour in the 800ml methyl alcohol, separate out solid polymer, filter, washing, drying.Get product etheric acid esterified cellulose 23.1g.Product is tested through proton nmr spectra, and its acetoacetate groups percentage of grafting is 57%.
Embodiment 3
Get molecular weight and be 1000 polycaprolactone divalent alcohol 200g, join in 67g (0.42mol) tert-butyl acetoacetate, add the 0.8g zinc acetate; Thorough mixing is even, and placing output rating at full capacity is in 700 watts the perforate microwave oven, to load onto still tube, TM, prolong and receiving tube; Microwave oven work gear is adjusted to 80% of its full load power, and the working hour is set at 20min, opens microwave oven; Overhead product appears behind about 1min, distillate basicly stable between 80～85 ℃, behind about 14min; Overhead product is near complete, and the TM indication descends.Stop microwave reaction; After the cooling of question response bottle, take out reaction flask, carry out underpressure distillation again; Remove volatile constituent (the residual tert-butyl acetoacetate and the trimethyl carbinol); Getting the product end group is the polycaprolactone 232.8g of etheric acid esterification, and through the NMR test, polycaprolactone divalent alcohol etheric acid esterification reaction conversion ratio reaches 95%.
Claims (8)
1. the method for a synthesis of acetyl acetate compound is characterized in that the poly-hydroxy macromolecular cpd, mixes with single acetyl acetic ester or diacetyl acetate ester cpds, adds catalyzer again, as reaction mass, carries out building-up reactions through microwave exposure and obtains; Described single acetyl acetic ester or diacetyl acetate ester cpds are to contain
The compound of substruction, R
1Group is a carbonatoms 4～16; Described single acetyl acetic ester or diacetyl acetate ester cpds be the tertiary alcohol, together with carbon glycol or that pure etheric acid ester cpds of sheet.
2. the method for claim 1 it is characterized in that described poly-hydroxy macromolecular cpd is that molecular weight is the macromolecular cpd of 300 to 1000000 units, and the average hydroxy functionality is more than or equal to 2.
3. method as claimed in claim 2 is characterized in that described poly-hydroxy macromolecular cpd is polysaccharide, polyether glycol, polyester polyol or polyacrylate polyol.
4. method as claimed in claim 3; It is characterized in that described poly-hydroxy macromolecular cpd be Mierocrystalline cellulose, FM, sucrose, VISOSE, polyoxyethylene glycol, W 166, epoxy ethane-epoxy propane copolymerization divalent alcohol, glycerine cause oxyethane gained polyether-tribasic alcohol, glycerine cause propylene oxide gained polyether-tribasic alcohol, TriMethylolPropane(TMP) cause oxyethane gained polyether-tribasic alcohol, TriMethylolPropane(TMP) cause propylene oxide gained polyether-tribasic alcohol, tetramethylolmethane cause oxyethane gained polyethers tetravalent alcohol, tetramethylolmethane cause propylene oxide gained polyethers tetravalent alcohol, penton polyvalent alcohol, based on the polyester diol of di-carboxylic acid and diol monomer, based on diacid and the monomeric polyester polyol of trivalent alcohol, based on tribasic carboxylic acid and diol monomer polyester polyol, polycaprolactone divalent alcohol, polycaprolactone trivalent alcohol, polycaprolactone tetravalent alcohol, aliphatic acid ester carbonate divalent alcohol or based on 2, the monomeric dendritic polyester polyvalent alcohol of 2-dimethylol propionic acid.
5. the method for claim 1; It is characterized in that described single acetyl acetic ester or diacetyl acetate ester cpds are etheric acid-2-propyloxy phenyl ester, tert-butyl acetoacetate, etheric acid tert-pentyl ester, the own ester of etheric acid uncle, the inferior isopropyl ester of diacetyl acetic acid, the inferior isobutylate of diacetyl acetic acid, the inferior cyclohexyl of diacetyl acetic acid, etheric acid phenyl ester, 2; 3-dimethyl--2; 3-butyleneglycol diacetyl acetic ester, 2; 3-phenylbenzene-2,3-butyleneglycol diacetyl acetic ester or 1,2-diphenylethyleneglycol diacetyl acetic ester.
6. the method for claim 1; It is characterized in that described synthetic reaction process is under the condition that catalyzer exists, to carry out; Described catalyzer is the inorganic or organic metal salt of tin, zinc, titanium, zirconium, lithium, comprises in Mono-n-butyltin, Dibutyltin oxide, zinc acetate, isocaprylic acid zinc, dibutyl tin dilaurate, tetrabutyl zirconate, tetrabutyl titanate, titanium isopropylate, Lithium Sulphate, lithiumbromide, lithium chloride, the Lithium Acetate one or more.
7. the method for claim 1, the relation that it is characterized in that said reaction mass and microwave exposure is 200～10000 watts of the required microwave exposure power of per 1 liter of material; Single acetyl acetic ester or diacetyl acetate ester cpds, and the proportionlity between the poly-hydroxy macromolecular cpd is 1: 1～1: 100, this ratio is to calculate according to the mol ratio of acetoacetate groups and hydroxyl; Catalyzer shared weight percent in the material gross weight is 0.05%～8%.
8. the method for claim 1 is characterized in that launching the microwave exposure of 2450 ± 50 MHz frequencies when described microwave exposure is microwave oven work, and stove power is 200 watts to 3600 watts; Reaction times is 2～30 minutes.
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| CN104812800A (en) * | 2012-09-28 | 2015-07-29 | 陶氏环球技术有限责任公司 | Functionalized oligomers |
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| CN108641003A (en) * | 2018-04-13 | 2018-10-12 | 东华大学 | A kind of heterogeneous method for preparing acetoacetate cellulose material |
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