CN106632832A - Polymer catalyst used for synthesizing isophorone and preparation method of polymer catalyst - Google Patents
Polymer catalyst used for synthesizing isophorone and preparation method of polymer catalyst Download PDFInfo
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- CN106632832A CN106632832A CN201610757377.0A CN201610757377A CN106632832A CN 106632832 A CN106632832 A CN 106632832A CN 201610757377 A CN201610757377 A CN 201610757377A CN 106632832 A CN106632832 A CN 106632832A
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- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920000642 polymer Polymers 0.000 title claims description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 8
- 230000005494 condensation Effects 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 66
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- -1 DCP Chemical compound 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 230000002328 demineralizing effect Effects 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 229920000620 organic polymer Polymers 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- 235000002597 Solanum melongena Nutrition 0.000 description 5
- 244000061458 Solanum melongena Species 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- SHOJXDKTYKFBRD-UHFFFAOYSA-N 4-Methyl-3-penten-2-one, 9CI Chemical compound CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000005882 aldol condensation reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OPQYYINFGFKYSM-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(C(C)C)(=O)O Chemical compound N=NC=NN.N=NC=NN.C(C(C)C)(=O)O OPQYYINFGFKYSM-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 229930193351 phorone Natural products 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a crosslinking type organic polymer catalyst and a preparation method and application thereof, in particular to an organic polymer catalyst used for synthesizing isophorone and a preparation method and application of the organic polymer catalyst. When the catalyst is used for preparing the isophorone through a one-step method, the catalyst has the advantages that the catalyst is high in recycling rate; water generated after catalytic condensation is neutral or slightly alkaline and can be discharged after simple process, and safety and environment protection are achieved; the conversion rate and total selectivity of acetone are high.
Description
Technical field
The present invention relates to a kind of cross-linking type high temperature resistant organic polymer catalyst and preparation method and application；It is concrete and
Speech, is related to a kind of organic polymer catalyst for synthesis of isophorone and preparation method and application.
Background technology
Isophorone (3,5,5- trimethyl -2- cyclonenes, Isophorone, abbreviation IP) is a kind of colourless or water white
To yellow low volatilyty liquid, with minty note or camphor taste.It is mainly used as the aspects such as agricultural chemicals, coating and can coating；It is used as
Nitro spray painting, the high boiling solvent of synthetic resin coating；Dissolvable phenolic resin and ring are used in mixed way with methyl iso-butyl ketone (MIBK)
Oxygen tree fat；As paint, ink, coating, natural gum, resin, the solvent of nitrocellulose and chemical synthesis intermediate etc..
At present the preparation method of isophorone mainly has isopropylidene acetone method and acetone method.Isopropylidene acetone method：In alkalescence
Under the conditions of, Catalyzed By Phase-transfer Catalyst isopropylidene acetone and ethyl acetoacetate Jing cyclisation, hydrolysis isophorone can be obtained,
Yield is 78%.Reaction equation is：
Because ethyl acetoacetate price is higher, this kind of method is only applicable in laboratory prepare a small amount of isophorone,
It is difficult to industrialize.
Acetone method：Under the high temperature conditions, base catalyst is catalyzed two molecule acetone elder generation Jing aldol condensations, dehydration and generates isopropyl
Fork acetone, then again with a molecule acetone Michael's addition, cyclisation be obtained isophorone.Reaction equation is：
Acetone condensation method is divided into liquid phase condensations method and vapour phase condensation method.Liquid phase condensations method is more ripe industrialization road
Line, typically using the strong alkali as a catalyst such as potassium hydroxide, is reacted under high-temperature and high-pressure conditions, and acetone conversion is not generally high,
Side reaction is more, high energy consumption；And due to making catalyst using inorganic strong alkali, a large amount of alkali lye contained in reacted waste liquid are located afterwards
Reason is more difficult, while catalyst recovery yield is low, easily causes environmental pollution, and production cost is higher.For example, it is public in patent US344226
The method opened, adds acetone, the NaOH aqueous solution of 20wt%, 150 DEG C of reaction temperature, 3 hours reaction time, reaction in autoclave
Pressure 160psi, the conversion ratio of acetone is 17%, and the selectivity of isophorone is 39%.
Vapour phase condensation method, at relatively high temperatures acetone continue through solid base (Ca (OH) in vapour form2- CaO, calcium aluminium
Compound, magnalium complexes etc.) beds, and be sequentially completed aldol condensation, dehydration, addition, cyclisation, be dehydrated again etc. it is anti-
Should, finally give isophorone.Such catalyst life is short, regeneration is difficult, product isophorone is selectively relatively low.For example, specially
Sharp US4535187 discloses a kind of calcium oxide/alumina composite catalyst, 300 DEG C of reaction temperature, and acetone conversion is 15.9～
24.3%.US5055620 discloses a kind of magnalium solid base catalyst for aldol condensation, controlling reaction temperature 300-350
DEG C, acetone conversion is 42.9%, and isophorone is selectively 71.5%.
The content of the invention
It is an object of the invention to provide a kind of preparation method of cross-linking type high temperature resistant organic polymer catalyst and its urging
Change the application in synthesis of isophorone from acetone.The catalyst that the present invention is provided has when preparing isophorone for acetone through one-step method
Advantages below：(1) catalyst recovery yield is high；(2) after catalyzing and condensing, the water of generation is in neutral or alkalescent, simple process
Discharge, safety and environmental protection；(3) high (overall selectivity includes isopropylidene acetone, DAA, different for the conversion ratio of acetone and overall selectivity
Phorone).
The preparation method of described organic polymer catalyst：Monomer A, monomer B, monomer are sequentially added in pressure reaction bulb
C, cross-linking monomer D, initiator and solvent, stirring and dissolving, deoxygenation.React under certain polymerization temperature, react product after terminating
By precipitating, being centrifuged, being dried to obtain catalyst J-PNLD；
The structural formula of the catalyst J-PNLD is：
Described organic polymer catalyst is made up of following component, and the molar part of each component is：
A) 75～95 parts of monomer A, preferably 80～90 parts；
B) 3～20 parts of monomer B, preferably 5～15 parts；
C) 3～20 parts of monomer C, preferably 5～15 parts；
D) 0.005～3.5 part of cross-linking monomer D, preferably 0.5～2.5 part；
E) 0.1～1.5 part of initiator, preferably 0.5～1.2 part；
Described monomer A isR1For hydrogen, substituted or unsubstituted C1-C5 alkyl, preferred hydrogen, do not take
The C1-C3 alkyl in generation；R2For hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxyls, replacement
Or unsubstituted C6-C20 aryl, C6-C20 aryloxy group, aldehyde radical, the carbonyl for connecting substituted or unsubstituted C1-C10 alkyl, company
Connect the carbonyl of substituted or unsubstituted C6-C10 aryl, preferred hydrogen, substituted or unsubstituted C1-C10 alkyl, replacement or unsubstituted
C1-C10 alkoxyls；R2For hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxyls, take
Generation or unsubstituted C6-C20 aryl, C6-C20 aryloxy group, aldehyde radical, the carbonyl for connecting substituted or unsubstituted C1-C10 alkyl,
Connect the carbonyl of substituted or unsubstituted C6-C10 aryl, preferred hydrogen, substituted or unsubstituted C1-C10 alkyl, replace or do not take
The C1-C10 alkoxyls in generation；
The monomer B isR4It is preferred hydrogen, unsubstituted for hydrogen, substituted or unsubstituted C1-C5 alkyl
C1-C3 alkyl；N represents the number of carbon, and scope is 0～6, preferably 0～4；
The monomer C isR5For Deng five yuan or hexa-atomic nitrogen heterocyclic ring functional group, preferably
The cross-linking monomer D is vinyltoluene, divinylbenzene (DVB), cumyl peroxide (DCP), two isocyanides
One or more in acid esters, vinyl acetate, diethylene glycol acrylate, preferred DVB, DCP, vinyl acetate, diethyl two
Alcohol acrylate；
Described initiator is azodiisobutyronitrile (AIBN), ABVN (ABVN), the isobutyric acid diformazan of azo two
Ester, benzoyl peroxide (BPO) etc.；
Described monomer A is commercially available；
The preparation process of monomer B is：20～80mL of trifluoroacetic acid, preferably 30～60mL, ice are added in four-hole bottle (250mL)
Ethylene glycol bath is cooled to 0 DEG C, and stirring is sequentially added dry5～35g, preferably 10～25g；Trifluoro
0.5～3.5mL of methanesulfonic acid, preferably 1.0～2.5mL；Add after 5 minutes7.5～60g, preferably 20～40g, reactant
It is stirred at room temperature 3 hours, is then cooled down with ice ethylene glycol bath.50～500mL of ether is slowly added to, preferably 100～300mL is arrived
In reaction system.Resulting product, vacuum filter, and precipitation is washed with ether twice, and it is little to be dried 12 at room temperature, at a normal
When (yield 60～70%).Product uses again triethylamine demineralizing acid.
The preparation process of monomer C is：20～80mL of trifluoroacetic acid, preferably 30～60mL, ice are added in four-hole bottle (250mL)
Ethylene glycol bath is cooled to 0 DEG C, and stirring is sequentially added dry5～35g, preferably 10～25g；TFMS 0.5
～3.5mL, preferably 1.0～2.5mL, add 7.5～60mL of methacrylic chloride, preferably 20～40mL, reactant to exist after 5 minutes
Stir at 60 DEG C 6 hours, then cooled down with ice ethylene glycol bath.50～500mL of ether is slowly added to, preferably 100～300mL is to instead
In answering system.Resulting product, vacuum filter, and precipitation is washed with ether twice, and be dried 12 hours at room temperature, at a normal
(preparing yield 50～60%).Product uses again triethylamine demineralizing acid.
Described solvent is methyl alcohol (MA), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMA) or two
First sulfoxide (DMSO) etc., by monomer A, B, C, cross-linking monomer D, initiator the solution of 30～250g/L of total concentration is made into, and preferably 100
～200g/L；
Described precipitating reagent is ether or tetrahydrofuran, and consumption is 5～50 times of solvent load of volume, preferably 10～
30 times of volume；
Described reaction temperature is 50～110 DEG C, preferably 70～90 DEG C；
The described reaction time is 4～15 hours, preferably 6～10 hours.
Described polymer catalyst is applied to catalytic triad condensation of acetone and prepares isophorone, and course of reaction is as follows：
A certain amount of catalyst J-PNLD, acetone are weighed in 48mL pressure-resistant seal pipes, N2Displacement, when reacting one section at a certain temperature
Between；After completion of the reaction, system is cooled to into room temperature, catalyst is reclaimed in centrifugation；Wherein J-PNLD contains monomer A side chains and third
Ketone mol ratio is 0.001～0.15:1, preferably 0.01～0.10:1；120～200 DEG C of reaction temperature, preferably 140～180 DEG C；Instead
It is 8～48 hours, preferably 10～24 hours between seasonable；
Described post catalyst reaction reclaiming method：After centrifugation, vacuum drying removing moisture；
Play a part of catalyzing and condensing, dehydration, cyclisation containing monomer B in described macromolecular structure；Monomer C is played to help and urged
Change is acted on, and improves the conversion ratio of acetone；Monomer A plays a part of dispersed monomer B, C, both monomers is uniformly dispersed
Open, it is to avoid produce gel effect；Cross-linking monomer D plays the high molecular effect of crosslinking low-molecular-weight, improves organic polymer catalysis
The heat resistance of agent；
Described catalyst can efficiently accomplish acetone through one-step method and prepare isophorone.
Specific embodiment
Preparation and application of the following examples to this catalyst is specifically described.Embodiment is not intended to the present invention's
Usage range is limited in the condition described in embodiment.
Embodiment 1
Monomer A (R are sequentially added in 50mL with arm reaction eggplant bottles1For hydrogen, R2、R3It is methyl) 1.1300g, monomer B
(R4It is 1) 0.4000g, monomer C (R for methyl, n5For) 0.1150g, cross-linking monomer D DCP 0.0338g, initiator
AIBN 0.0205g and solvent MA10mL, stirring and dissolving, deoxygenation.8h is reacted in 110 DEG C of oil baths, anhydrous with 100mL after reaction terminates
Ether is precipitating reagent, and product is precipitated, centrifugation, and sediment 50 DEG C of vacuum drying oven of placement is dried into 12h, obtains catalyst J-
PNLD-I 1.2668g, prepare yield 75.45%, wherein the monomer mole ratio for containing is A:B:C=16:3:1.
Embodiment 2
Monomer A (R are sequentially added in 50mL with arm reaction eggplant bottles1、R2、R3It is methyl) 1.2700g, monomer B (R4
It is 2) 0.2633g, monomer C (R for hydrogen, n5For) 0.2300g, cross-linking monomer D DCP 0.0169g, initiator A BVN
0.0250g and solvent DMSO 15mL, stirring and dissolving, deoxygenation.12h is reacted in 90 DEG C of oil baths, after reaction terminates, with 100mL anhydrous four
Hydrogen furans is precipitating reagent, and product is precipitated, and is centrifuged, and sediment 50 DEG C of vacuum drying oven of placement is dried into 12h, obtains catalyst J-
PNLD-II 1.1685g, prepare yield 65.63%, wherein the monomer mole ratio for containing is A:B:C=16:2:2.
Embodiment 3
Monomer A (R are sequentially added in 50mL with arm reaction eggplant bottles1For hydrogen, R2、R3It is methyl) 2.5425g, monomer B
(R4It is 5) 0.1856g, monomer C (R for ethyl, n5For) 0.3713g, cross-linking monomer D vinyltoluene 0.0303g,
Initiator azo-bis-iso-dimethyl 0.0302g and solvent MA 15mL, stirring and dissolving, deoxygenation.20h is reacted in 90 DEG C of oil baths, instead
After should terminating, with 100mL absolute ethers as precipitating reagent, product is precipitated, be centrifuged, sediment is placed into 50 DEG C of dryings of vacuum drying oven
12h, obtains catalyst J-PNLD-III 1.8983g, prepares yield 61.24%, wherein the monomer mole ratio for containing is A:B:C
=36:1:3.
Embodiment 4
Monomer A (R are sequentially added in 50mL with arm reaction eggplant bottles1For ethyl, R2For methyl, R3For hydrogen) 1.2700g,
Monomer B (R4It is 1) 0.1673g, monomer C (R for hydrogen, n5For) 0.0505g, cross-linking monomer D DVB 0.0444g, initiator
AIBN 0.0273g and solvent DMF 10mL, stirring and dissolving, deoxygenation.14h are reacted in 70 DEG C of oil baths, after reaction terminates, with 100mL without
Water ether is precipitating reagent, and product is precipitated, and is centrifuged, and sediment is placed into the drying 12 hours of 50 DEG C of vacuum drying oven, obtains catalyst
J-PNLD-IV 1.1876g, prepare yield 77.29%, wherein the monomer mole ratio for containing is A:B:C=36:3:1.
Embodiment 5
Monomer A (R are sequentially added in 50mL with arm reaction eggplant bottles1For hydrogen, R2For methyl, R3For ethyl) 1.2700g,
Monomer B (R4It is 3) 0.1906g, monomer C (R for methyl, n5For) 0.0505g, cross-linking monomer D vinyl acetates
0.0338g, initiator azo-bis-iso-dimethyl 0.0288g and solvent DMF 20mL, stirring and dissolving, deoxygenation.60 DEG C of oil baths
Reaction 10h, after reaction terminates, with 100mL absolute ethers as precipitating reagent, product is precipitated, and is centrifuged, and sediment is placed into vacuum and is dried
50 DEG C of case is dried 12h, obtains catalyst J-PNLD-V 1.1831g, prepares yield 76.58%, wherein the monomer mole ratio for containing
For A:B:C=36:3:1.
Embodiment 6
Catalyst J-PNLD-I, 5.0g acetone prepared by 0.5000g, N are added in 100mL autoclaves2Displacement, 180
24h is reacted at DEG C (catalytic performance data are shown in Table 1).After completion of the reaction, system is cooled to into 30 DEG C, centrifugation is reclaimed and urged
Agent 0.4565g.
Embodiment 7
Catalyst J-PNLD-II, 5.0g acetone prepared by 0.7500g, N are added in 100mL pressure-resistant seal pipes2Displacement,
12h is reacted at 120 DEG C (catalytic performance data are shown in Table 1).After completion of the reaction, system is cooled to into 30 DEG C, centrifugation is reclaimed
Obtain catalyst 0.6548g.
Embodiment 8
Catalyst J-PNDL-III, 5.0g acetone prepared by 3.0000g, N are added in 100mL autoclaves2Displacement,
16h is reacted at 200 DEG C (catalytic performance data are shown in Table 1).After completion of the reaction, system is cooled to into 30 DEG C, centrifugation is reclaimed
To catalyst 2.2590g.
Embodiment 9
Catalyst J-PNLD-IV, 5.0g acetone prepared by 1.0000g, N are added in 100mL autoclaves2Displacement, 150
12h is reacted at DEG C (catalytic performance data are shown in Table 1).After completion of the reaction, system is cooled to into 30 DEG C, centrifugation is reclaimed and urged
Agent 0.9270g.
Embodiment 10
Catalyst J-PNLD-V, 5.0g acetone prepared by 1.0000g, N are added in 100mL autoclaves2Displacement, 180
48h is reacted at DEG C (catalytic performance data are shown in Table 1).After completion of the reaction, system is cooled to into 30 DEG C, centrifugation is reclaimed and urged
Agent 0.8900g.
Embodiment 11
Catalyst J-PNLD-IV, 5.0g acetone prepared by 1.0000g, N are added in 100mL autoclaves2Displacement, 150
12h is reacted at DEG C (catalytic performance data are shown in Table 1).After completion of the reaction, system is cooled to into 30 DEG C, centrifugation is reclaimed and urged
Agent 0.9260g.After catalyst is reclaimed, circular response five times (circular response performance data is shown in Table 2).
Table 1：Catalytic performance data
Table 2：The circular response performance data of embodiment 11
Claims (10)
1. a kind of polymer catalyst for synthesis of isophorone, it is characterised in that the structural formula of the catalyst J-PNLD
For：
。
2. a kind of polymer catalyst for synthesis of isophorone according to claim 1, it is characterised in that R1For hydrogen,
Substituted or unsubstituted C1-C5 alkyl, preferred hydrogen, unsubstituted C1-C3 alkyl；R2For hydrogen, substituted or unsubstituted C1-C10
Alkyl, substituted or unsubstituted C1-C10 alkoxyls, substituted or unsubstituted C6-C20 aryl, C6-C20 aryloxy group, aldehyde radical, company
The carbonyl of substituted or unsubstituted C1-C10 alkyl is connect, connecting the carbonyl of substituted or unsubstituted C6-C10 aryl, preferred hydrogen, is taken
Generation or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxyls；R3For hydrogen, substituted or unsubstituted C1-C10
Alkyl, substituted or unsubstituted C1-C10 alkoxyls, substituted or unsubstituted C6-C20 aryl, C6-C20 aryloxy group, aldehyde radical, company
The carbonyl of substituted or unsubstituted C1-C10 alkyl is connect, connecting the carbonyl of substituted or unsubstituted C6-C10 aryl, preferred hydrogen, is taken
Generation or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxyls；R4For hydrogen, substituted or unsubstituted C1-C5
Alkyl, preferred hydrogen, unsubstituted C1-C3 alkyl；N represents the number of carbon, and scope is 0～6, preferably 0～4；；R5For
It is preferred that
3. the preparation method of a kind of polymer catalyst for synthesis of isophorone according to claim 1：Its feature
It is that monomer A, monomer B, monomer C, cross-linking monomer D, initiator and solvent, stirring and dissolving are sequentially added in pressure reaction bulb, removes
Oxygen, reacts under certain polymerization temperature, and product is precipitated, be centrifuged, being dried to obtain catalysis by reaction after terminating by adding precipitating reagent
Agent J-PNLD.
4. the preparation method of a kind of polymer catalyst for synthesis of isophorone according to claim 3, its feature
It is that the molar part of each component is：
A) 75～95 parts of monomer A, preferably 80～90 parts；B) 3～20 parts of monomer B, preferably 5～15 parts；
C) 3～20 parts of monomer C, preferably 5～15 parts；D) 0.005～3.5 part of cross-linking monomer D, preferably 0.5～2.5 part；E) draw
Send out 0.1～1.5 part of agent, preferably 0.5～1.2 part.
5. the preparation method of a kind of polymer catalyst for synthesis of isophorone according to claim 3, its feature
It is that described monomer A isR1It is preferred hydrogen, unsubstituted for hydrogen, substituted or unsubstituted C1-C5 alkyl
C1-C3 alkyl；R2For hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxyls, replace or not
Substituted C6-C20 aryl, C6-C20 aryloxy group, aldehyde radical, the carbonyl for connecting substituted or unsubstituted C1-C10 alkyl, connection take
Generation or the carbonyl of unsubstituted C6-C10 aryl, it is preferred hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted
C1-C10 alkoxyls；R3For hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxyls, replacement
Or unsubstituted C6-C20 aryl, C6-C20 aryloxy group, aldehyde radical, the carbonyl for connecting substituted or unsubstituted C1-C10 alkyl, company
Connect the carbonyl of substituted or unsubstituted C6-C10 aryl, preferred hydrogen, substituted or unsubstituted C1-C10 alkyl, replacement or unsubstituted
C1-C10 alkoxyls；
The monomer B isR4For hydrogen, substituted or unsubstituted C1-C5 alkyl, preferred hydrogen, unsubstituted C1-
C3 alkyl；N represents the number of carbon, and scope is 0～6, preferably 0～4；The monomer C isR5For Deng five
First or hexa-atomic nitrogen heterocyclic ring functional group, preferablyThe cross-linking monomer D is vinyl first
Benzene, divinylbenzene (DVB), cumyl peroxide (DCP), diisocyanate, vinyl acetate, diethylene glycol acrylate
In one or more, preferred DVB, DCP, vinyl acetate, diethylene glycol acrylate.
6. the preparation method of a kind of polymer catalyst for synthesis of isophorone according to claim 3, its feature
Be, described initiator be azodiisobutyronitrile (AIBN), ABVN (ABVN), azo-bis-iso-dimethyl,
Benzoyl peroxide (BPO) etc.；The solvent is methyl alcohol (MA), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide
(DMA) or dimethyl sulfoxide (DMSO), monomer A, B, C, cross-linking monomer D, initiator are made into into the solution of 30～250g/L of total concentration,
It is preferred that 100～200g/L；Precipitating reagent is ether or tetrahydrofuran, and consumption is 5～50 times of solvent load of volume, preferably 10
～30 times of volume.
7. the preparation method of a kind of polymer catalyst for synthesis of isophorone according to claim 3, its feature
It is that described reaction temperature is 50～110 DEG C, preferably 70～90 DEG C；The described reaction time be 4～15 hours, preferably 6～
10 hours.
8. the preparation method of a kind of polymer catalyst for synthesis of isophorone according to claim 3, its feature
It is that the preparation process of monomer B is：20～80mL of trifluoroacetic acid, preferably 30～60mL, ice second are added in four-hole bottle (250mL)
Glycol bath is cooled to 0 DEG C, and stirring is sequentially added dry5～35g, preferably 10～25g；Fluoroform
0.5～3.5mL of sulfonic acid, preferably 1.0～2.5mL；Add after 5 minutes7.5～60g, preferably 20～40g, reactant
It is stirred at room temperature 3 hours, is then cooled down with ice ethylene glycol bath, be slowly added to 50～500mL of ether, preferably 100～300mL is arrived
In reaction system, resulting product, vacuum filter, and precipitation is washed with ether twice, and it is little to be dried 12 at room temperature, at a normal
When, product uses again triethylamine demineralizing acid.
9. the preparation method of a kind of polymer catalyst for synthesis of isophorone according to claim 3, its feature
It is that the preparation process of monomer C is：20～80mL of trifluoroacetic acid, preferably 30～60mL, ice second are added in four-hole bottle (250mL)
Glycol bath is cooled to 0 DEG C, and stirring is sequentially added dry5～35g, preferably 10～25g；TFMS 0.5～
3.5mL, preferably 1.0～2.5mL, add 7.5～60mL of methacrylic chloride, preferably 20～40mL after 5 minutes, reactant is 60
Stir at DEG C 6 hours, then cooled down with ice ethylene glycol bath, be slowly added to 50～500mL of ether, preferably 100～300mL is to reaction
In system, resulting product, vacuum filter, and precipitation is washed with ether twice, and be dried 12 hours at room temperature, at a normal, produce
Thing uses again triethylamine demineralizing acid.
10. a kind of polymer catalyst for synthesis of isophorone according to claim is applied to catalytic triad third
Ketone condensation prepares isophorone, it is characterised in that course of reaction is as follows：Weigh a certain amount of catalyst J-PNLD, acetone in
In 48mL pressure-resistant seal pipes, N2Displacement, reaction at a certain temperature is for a period of time；After completion of the reaction, system is cooled to into room temperature,
Catalyst is reclaimed in centrifugation；It is 0.001～0.15 that wherein J-PNLD contains monomer A side chains with acetone mol ratio:1, preferably
0.01～0.10:1；120～200 DEG C of reaction temperature, preferably 140～180 DEG C；Reaction time be 8～48 hours, preferably 10～
24 hours.
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| CN105348428A (en) * | 2015-10-20 | 2016-02-24 | 华东师范大学 | Preparation method and application of cross-linking type polymerization catalyst |
| CN105728040A (en) * | 2015-12-28 | 2016-07-06 | 南京大学 | Preparation method of polymer catalyst for acetone condensation |
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| CN105348428A (en) * | 2015-10-20 | 2016-02-24 | 华东师范大学 | Preparation method and application of cross-linking type polymerization catalyst |
| CN105728040A (en) * | 2015-12-28 | 2016-07-06 | 南京大学 | Preparation method of polymer catalyst for acetone condensation |
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