CN104402777A - Diol sulfonate compound and preparation method and application thereof - Google Patents
Diol sulfonate compound and preparation method and application thereof Download PDFInfo
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- CN104402777A CN104402777A CN201410736720.4A CN201410736720A CN104402777A CN 104402777 A CN104402777 A CN 104402777A CN 201410736720 A CN201410736720 A CN 201410736720A CN 104402777 A CN104402777 A CN 104402777A
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- phenyl
- group
- hydrogen
- dibasic alcohol
- alkyl
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- -1 Diol sulfonate compound Chemical class 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 44
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 claims abstract description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- 125000005843 halogen group Chemical group 0.000 claims abstract description 20
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 76
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 238000006555 catalytic reaction Methods 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 18
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 abstract 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 abstract 1
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 235000011147 magnesium chloride Nutrition 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000008247 solid mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 3
- UIMJANTUJQGSEX-UHFFFAOYSA-N 2,2'-biphenyldimethanol Chemical compound OCC1=CC=CC=C1C1=CC=CC=C1CO UIMJANTUJQGSEX-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- UIOXNNAWANDJCZ-UHFFFAOYSA-N 1,1-dimethoxypropane Chemical compound CCC(OC)OC UIOXNNAWANDJCZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- ZWINORFLMHROGF-UHFFFAOYSA-N 9,9-bis(methoxymethyl)fluorene Chemical class C1=CC=C2C(COC)(COC)C3=CC=CC=C3C2=C1 ZWINORFLMHROGF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical class OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a diol sulfonate compound and a preparation method and application thereof. The diol sulfonate compound has the following general formula I,wherein n is not less than 3, R1And R2Selected from the group consisting of linear and branched C1-C20 alkyl groups, C3-C20 cycloalkyl groups, C6-C20 aryl groups, C7-C20 aralkyl and alkaryl groups, C2-C20 alkenyl groups, and C6-C20 fused ring aryl groups; r3-R8Selected from hydrogen, halogen atoms, straight-chain and branched-chain C1-C20 alkyl groups, C3-C20 cycloalkyl groups, C6-C20 aryl groups, C7-C20 aralkyl and alkaryl groups, C2-C20 alkylene groups and C6-C20 condensed ring aryl groups; r3-R8Not all hydrogen and/or halogen atoms. The diol sulfonate is prepared by esterifying a diol. The invention also provides the application of the dihydric alcohol sulfonate in preparing an olefin polymerization catalyst.
Description
Technical field
The present invention relates to a kind of dibasic alcohol sulfonate compound and preparation method thereof, and this dibasic alcohol sulfonate compound is preparing the application in olefin polymerization catalysis, belongs to olefin polymerization catalysis technical field.
Background technology
CH is can be used for using titanium, magnesium, halogen and electron donor as the solid titanium catalyst of basic raw material
2=CHR olefinic polyreaction (mainly as Primary Catalysts), the polymkeric substance of higher yields and higher tacticity particularly can be obtained in the alpha-olefine polymerizing with 3 carbon or more carbon atom, wherein electron donor compound is one of requisite composition in catalyzer, and constantly updates along with the development of electron donor compound result in olefin polymerization catalysis.Disclosed electron donor compound mainly comprises polycarboxylic acid, monocarboxylic ester or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and their derivative in a large number at present, wherein comparatively conventional is aromatic carboxylates's class of binary, such as n-butyl phthalate and diisobutyl phthalate etc., can see US4784983 and CN85100997A.
In recent years, people start to adopt other compounds to use as the electron donor in olefin polymerization catalysis, such as at US4971937, disclosed in US2004014597 and EP0728769 in the catalyzer of olefinic polyreaction, it is special in 1 of two ether groups to have employed, 3-diether compound is as electron donor, such as 2-sec.-propyl-2-isopentyl-1, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-Propanal dimethyl acetal and 9, 9-bis-(methoxymethyl) fluorenes etc., also can see CN1042547A about this kind of electron donor invention, CN1143651A and US2003027715 and WO03076480.Disclosed in CN1054139A in the solid catalyst of olefinic polyreaction, have employed 1,3-cyclohexadione compounds as electron donor, such as 2,2,4,6,6-pentamethyl--3,5-heptadione and 2,2,6,6-tetramethyl--4-ethyl-3,5-heptadione etc.
Again disclose the dibasic aliphatic carboxylic acid ester compound that a class is special recently, as (see WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215) such as succinate, malonic ester, glutarates, the use of this kind of electron donor compound not only can improve the activity of catalyzer, and the molecular weight distribution of the propene polymer of gained is obviously widened.
But, adopt above-mentioned disclosed binary aromatic carboxylic acid's ester compound, containing 1 of two ether groups, catalyzer for olefinic polymerization prepared by 3-diether compound and dibasic aliphatic carboxylic acid ester compound all also exists certain defect in actual applications, such as adopt the catalyst activity of binary aromatic carboxylic acid's ester compound lower, and the molecular weight distribution of resulting polymers is also narrower; Adopt 1, although the catalyzer activity of 3-diether compound is higher, and the hydrogen response of catalyzer, the narrow molecular weight distribution of resulting polymers, is unfavorable for the exploitation of the different trade mark of polymkeric substance; And adopt the activity of the catalyzer of disclosed dibasic aliphatic carboxylicesters in the recent period still on the low side, and when not adopting external electron donor, the degree of isotacticity of resulting polymers is lower.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of dibasic alcohol sulfonate compound.This dibasic alcohol sulfonate compound can be used as electron donor for the preparation of olefin polymerization catalysis, and can prepare the olefin polymerization catalysis of high comprehensive performance.
The present invention also aims to the preparation method that this dibasic alcohol sulfonate compound is provided.
Another object of the present invention is to provide this dibasic alcohol sulfonate compound preparing the application in olefin polymerization catalysis.
For achieving the above object, the invention provides a kind of dibasic alcohol sulfonate compound with following formula I,
Wherein, n >=3;
R
1and R
2identical or not identical, and be selected from the group be made up of the fused ring aryl of the aralkyl of the aryl of the cycloalkyl of the alkyl of the C1-C20 of straight chain and side chain, C3-C20, C6-C20, C7-C20, the alkaryl of C7-C20, the alkylene of C2-C20 and C6-C20 respectively;
R
3, R
4, R
5, R
6, R
7and R
8identical or not identical, and be selected from the group be made up of the fused ring aryl of the alkaryl of the aralkyl of the aryl of the cycloalkyl of the alkyl of the C1-C20 of hydrogen, halogen atom, straight chain and side chain, C3-C20, C6-C20, C7-C20, C7-C20, the alkylene of C2-C20 and C6-C20 respectively;
R
3, R
4, R
5, R
6, R
7and R
8be not hydrogen and/or halogen entirely.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
3, R
4, R
5, R
6, R
7and R
8one or several carbon atom arbitrary in described alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkylene and fused ring aryl in the group be selected from and/or hydrogen atom are replaced by halogen atom.
In above-mentioned dibasic alcohol sulfonate compound, preferably, n=3 or 4 or 5.
In above-mentioned dibasic alcohol sulfonate compound, preferably, n=3, and R
3, R
4, R
5, R
6, R
7and R
8in have two at least for hydrogen, and R
3, R
4, R
5, R
6, R
7and R
8in the several groups be connected on different carbon atom form condensed ring; More preferably, and R
1and R
2in have at least one to be selected from the group be made up of aryl and alkaryl.Particularly preferably, R
1and R
2all be selected from the group be made up of aryl and alkaryl.
In above-mentioned dibasic alcohol sulfonate compound, preferably, n=4, and R
3, R
4, R
5, R
6, R
7and R
8between not Cheng Huan, and R
1and R
2in have a group selecting the substituted or unsubstituted aryl of free halogen and alkaryl to form at least.More preferably, R
1and R
2all select the group that the substituted or unsubstituted aryl of free halogen and alkaryl form.
In above-mentioned dibasic alcohol sulfonate compound, preferably, when n>=5, R
3, R
4, R
5, R
6, R
7and R
8between not Cheng Huan.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
1and R
2in have at least one to be group containing phenyl ring.More preferably, the described group containing the phenyl ring phenyl that is phenyl, replaced by the alkyl of C1-C20 and/or halogen atom.Particularly preferably, R
1and R
2the phenyl all select free phenyl, being replaced by the alkyl of C1-C20 and/or halogen atom the group that forms.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
3and R
4in have at least a phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl to form group, and R
3and R
4be not phenyl entirely; R
5and R
6in have at least a phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl to form group, and R
5and R
6be not phenyl entirely; R
7and R
8(identical or not identical) is selected from the group that the phenyl that replaced by the alkyl of hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 and halogenophenyl form respectively, and R
7and R
8be not phenyl entirely.
More preferably, R
3and R
4in one be hydrogen, the group that another phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl form; R
5and R
6in one be hydrogen, the group that another phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl form; And R
3and R
4in be not group and the R of hydrogen
5and R
6in be not that the group of hydrogen is entirely for phenyl; R
7and R
8(identical or not identical) is selected from the group that the phenyl that replaced by the alkyl of hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 and halogenophenyl form respectively, and R
7and R
8be not phenyl entirely.
In above-mentioned dibasic alcohol sulfonate compound, preferably, work as R
3and R
4in one be hydrogen, another is methyl, and R
5and R
6in one be hydrogen, another is methyl, and R
7and R
8complete for hydrogen or when being respectively hydrogen and methyl, R
1and R
2in have a phenyl replaced by halogen atom and/or alkyl at least.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
7and R
8in have at least one to be group containing phenyl ring.More preferably, the described group containing the phenyl ring phenyl that is phenyl, replaced by the alkyl of C1-C20 and/or halogen atom.Particularly preferably, R
7and R
8the phenyl all select free phenyl, being replaced by the alkyl of C1-C20 and/or halogen atom the group that forms.
In above-mentioned dibasic alcohol sulfonate compound, more preferably, R
1and R
2the phenyl all select free phenyl, being replaced by the alkyl of C1-C20 and/or halogen atom the group that forms; And R
3and R
4in one be hydrogen, the group that another phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl form; R
5and R
6in one be hydrogen, the group that another phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl form; And R
3and R
4in be not group and the R of hydrogen
5and R
6in be not that the group of hydrogen is entirely for phenyl; R
7and R
8(identical or not identical) is selected from the group that the phenyl that replaced by the alkyl of hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 and halogenophenyl form respectively, and R
7and R
8be not phenyl entirely.Preferably, and n=3 or 4 particularly.
The present invention also provides the preparation method of above-mentioned dibasic alcohol sulfonate compound, it comprises the following steps: make dibasic alcohol (comprise diphenol, and the hydroxyl carrying out esterification is connected with aryl, the compound that another hydroxyl is connected with alkyl) carry out esterification with sulfonic acid or SULPHURYL CHLORIDE, obtain described dibasic alcohol sulfonate compound.
Dibasic alcohol sulfonate compound of the present invention prepares by multiple method.According to the specific embodiment of the present invention, the preparation method of above-mentioned dibasic alcohol sulfonate compound comprises the following steps: make alkylsulphonic acid (RSO
3h, wherein, R is above-mentioned R
1or R
2) or alkyl sulfonyl chloride (RSO
3cl, wherein, R is above-mentioned R
1or R
2) carry out esterification with the dibasic alcohol with general formula I I, obtain described dibasic alcohol sulfonate compound,
Wherein, R
3, R
4, R
5, R
6, R
7and R
8identical or not identical, and be selected from the group be made up of the fused ring aryl of the alkaryl of the aralkyl of the aryl of the cycloalkyl of the alkyl of the C1-C20 of hydrogen, halogen atom, straight chain and side chain, C3-C20, C6-C20, C7-C20, C7-C20, the alkylene of C2-C20 and C6-C20 respectively;
R
3, R
4, R
5, R
6, R
7and R
8be not hydrogen and/or halogen entirely.
R
3, R
4, R
5, R
6, R
7and R
8preferable range as described above, repeat no more herein.
In above-mentioned preparation method, have general formula II dibasic alcohol can conventionally in preparation method obtained by, as the preparation method etc. of dibasic alcohol disclosed in 5-6 page in CN1041752A and CN1141285A.Quoting in full in this as a reference herein by above-mentioned two sections of documents.
In above-mentioned preparation method, the parameters such as the concrete steps of esterification and temperature and time mainly change along with different reactants, and those skilled in the art can carry out conventional regulation and control to the concrete steps of esterification and temperature and time etc.
The present invention also provides above-mentioned dibasic sulfoacid ester cpds preparing the application in olefin polymerization catalysis.
The preparation that dibasic sulfoacid ester cpds of the present invention is applied to olefin polymerization catalysis can obtain the catalyzer of high comprehensive performance.This catalyzer not only catalytic activity is high, and also fine to the susceptibility of hydrogen tune, and the polymkeric substance stereospecificity of gained is high and molecular weight distribution is wider.
Olefin polymerization catalysis of the present invention can conventionally in method prepare, than several method described as follows.
Wherein a kind of method is: by the magnesium dichloride of anhydrous state and dibasic alcohol sulfonate compound of the present invention together with magnesium dichloride grinding; By grinding after mixture at 80-135 DEG C with excessive TiCl
4once or several times, each reaction times is 0.5-4h in reaction; Then use the solid mixture after varsol washing reaction (all need after every secondary response washing) until its not chloride ion-containing, obtain olefin polymerization catalysis.
Another kind method is: the magnesium dichloride of anhydrous state, titanium compound and dibasic alcohol sulfonate compound of the present invention are ground, and obtains the mixture after grinding; Then adopt the halohydrocarbon of such as 1,2-ethylene dichloride, chlorobenzene, methylene dichloride and so at 40 DEG C of temperature to halohydrocarbon boiling point with this grinding after mixture reaction 1-4 hour; Then use the solid mixture after the inert hydrocarbon solvent washing reaction of hexane and so on, obtain olefin polymerization catalysis.
A kind of method is in addition: magnesium dichloride is carried out pre-activate by known method, then adopts the excessive TiCl containing dibasic alcohol sulfonate compound of the present invention
4solution at 80-135 DEG C with pre-activate after magnesium dichloride react once or several times, then with the solid mixture after the inert hydrocarbon solvent cleaning reactions such as hexane to remove unreacted TiCl
4, obtain olefin polymerization catalysis.
A kind of method is had to be again: to make the alcoholate of magnesium or chlorohydrin and the excessive TiCl containing dibasic alcohol sulfonate compound of the present invention
4solution reacts to prepare olefin polymerization catalysis at 80-135 DEG C.The optimal technical scheme of the method is: make general formula be TiZ
m(OQ)
4-mtitanium compound (alkyl of Q to be carbonatoms be 1-20 in formula, Z is halogen atom, m=1-4, is preferably TiCl
4) with general formula be MgCl
2the adducts of pTOH (in formula, p is the integer of 0.1-6, is preferably 2-4, and T is carbonatoms be the alkyl of 1-20) reacts 0.5-2 hour to prepare olefin polymerization catalysis at 80-130 DEG C.Wherein, general formula is MgCl
2the adducts of pTOH can be made spherical by the following method aptly: under not miscible with this adducts inert hydrocarbon solvent exists, and by alcohol and magnesium chloride mixing, makes the rapid chilling of this emulsion, thus this adducts is solidified with the form of spheroidal particle.According to spherical MgCl prepared by the method
2visible USP4399054 and USP4469648 of example of pTOH adducts.Adopt the MgCl that this method obtains
2pTOH adducts can directly and titanium compound react, or its can in advance through the dealcoholization (carrying out at 80-130 DEG C) of thermal control to obtain a kind of new adducts, wherein the mole number of alcohol is generally lower than 4, is preferably 2-3.5.Can pass through MgCl
2pTOH adducts (dealcoholysis or non-dealcoholysis) is suspended in cold TiCl
4in (being generally less than 0 DEG C), carry out the reaction with titanium compound.Wherein TiCl
4be as titanium compound, other titanium compounds also can be adopted to substitute TiCl
4, with TiCl
4reaction can carry out once or several times.Can at TiCl
4in add dibasic alcohol sulfonate compound of the present invention and react, can react once or several times.After reaction, solid mixture is cleaned, can olefin polymerization catalysis be obtained.
Another method is: with the TiCl containing dibasic alcohol sulfonate compound of the present invention
4aromatic hydrocarbons (such as toluene, dimethylbenzene etc.) solution, react with two magnesium hydrocarbyloxy compound of such as dialkoxy magnesium or two aryloxy magnesium and so at 80-130 DEG C, reaction times is 0.5-4h, can react once or several times, afterwards reacted solid mixture is cleaned, obtain olefin polymerization catalysis.。
The diatomic alcohol acid ester cpds with special construction of the present invention, is applied to the preparation of olefin polymerization catalysis, can obtains the catalyzer of high comprehensive performance as electron donor.When this catalyzer is used for propylene polymerization, gratifying polymerization yield rate can be obtained; And the stereospecificity of the polymkeric substance of gained is high, even if when not using external electron donor, the polymkeric substance compared with high isotactic still can be obtained; Simultaneously the susceptibility adjusted hydrogen of catalyzer is also fine; And the molecular weight distribution of resulting polymers is wider, be conducive to the exploitation of the different trade mark of polymkeric substance.In addition, this catalyzer, when particularly Propylene polymerization reacts the copolymerization for alkene, can obtain less gel content, therefore have better copolymerization performance.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Testing method
1, melting index: use
mI-4 fusion index instrument measures, and testing method is according to GB/T3682-2000.
2, the mensuration of nucleus magnetic resonance: use Bruker-400 nuclear magnetic resonance analyser
1h-NMR (400MHz, solvent C DCl
3, TMS is interior mark, and mensuration temperature is 300K) measure.
3, molecular weight distribution MWD (MWD=Mw/Mn): be that solvent carries out measuring (standard specimen: PS, flow velocity: 1.0ml/min) at 150 DEG C with trichlorobenzene.
4, polymkeric substance degree of isotacticity adopts heptane extraction process to carry out measuring (boiling heptane extracting 6 hours): 2 grams of dry polymer samples, be placed in extractor and after 6 hours with the extracting of boiling heptane, remaining polymer samples be dried to the polymer weight (g) of constant weight gained and be degree of isotacticity with the ratio of 2.
Embodiment 1
The present embodiment provides 1,5-phenylbenzene-1,5-PD two p-methyl benzenesulfonic acid ester, and it is prepared by following methods:
1,5-phenylbenzene-1,5-diacetylmethane lithium aluminium hydride reduction is become 1,5-phenylbenzene-1,5-PD; 0.03mol1,5-phenylbenzene-1,5-PD is joined in 30mL tetrahydrofuran (THF), and adds 0.09mol pyridine, under agitation add 0.075mol p-methyl benzene sulfonic chloride in batches, be then heated to backflow, insulation reaction 4h; With the water washing of 20mL saturated common salt after cooling, then be extracted with ethyl acetate, then use anhydrous Na
2sO
4drying, except desolventizing; Column chromatography for separation afterwards, obtains product.The nuclear magnetic resonance measuring result of this product is: δ 1.3-1.5 (2H), 1.9-2.1 (4H), 2.3-2.6 (6H), 5.9-6.0 (2H), 7.2-8.0 (8H).Can determine that the present embodiment has prepared 1,5-phenylbenzene-1,5-PD two p-methyl benzenesulfonic acid ester.
Embodiment 2
The present embodiment provides 1,4-hexylene glycol two tolysulfonyl ester, its preparation method is identical with the preparation method in embodiment 1, unique difference is raw material 1, the 5-phenylbenzene-1,5-PD in embodiment 1 to replace with 1,4-hexylene glycol, its added in molar amounts is in the same manner as in Example 1, and saves the step that ketone body powder becomes alcohol, obtains product.The nuclear magnetic resonance measuring result of this product is: δ 1.1-1.2 (8H), 1.8-1.9 (2H), 2.3-2.6 (6H), 4.2-4.3 (4H), 7.2-7.8 (8H).Can determine that the present embodiment has prepared Isosorbide-5-Nitrae-hexylene glycol two tolysulfonyl ester.
Embodiment 3
The present embodiment provides 1,5-hexylene glycol two p-toluenesulfonic esters, its preparation method is identical with the preparation method in embodiment 1, unique difference is raw material 1, the 5-phenylbenzene-1,5-PD in embodiment 1 to replace with 1,5-hexylene glycol, its added in molar amounts is in the same manner as in Example 1, and saves the step that ketone body powder becomes alcohol, obtains product.The nuclear magnetic resonance measuring result of this product is: δ 1.3-1.4 (3H), 1.5-1.6 (2H), 1.6-1.7 (2H), 1.7-1.8 (2H), 2.3-2.6 (6H), 4.3-4.4 (2H), 5.2-5.3 (1H), 7.2-7.8 (8H).Can determine that the present embodiment has prepared 1,5-hexylene glycol two p-toluenesulfonic esters.
Embodiment 4
The present embodiment provides 2,2 '-biphenyl dimethanol two p-toluenesulfonic esters, its preparation method is identical with the preparation method in embodiment 1, unique difference is raw material 1, the 5-phenylbenzene-1,5-PD in embodiment 1 to replace with 2,2 '-biphenyl dimethanol, its added in molar amounts is in the same manner as in Example 1, and saves the step that ketone body powder becomes alcohol, obtains product.The nuclear magnetic resonance measuring result of this product is: δ 1.0-1.1 (6H), 2.2-2.3 (4H), 2.3-2.6 (6H), 4.8-4.9 (4H), 5.2-5.3 (1H), 7.2-7.8 (16H).Can determine that the present embodiment has prepared 2,2 '-biphenyl dimethanol two p-toluenesulfonic esters.
Embodiment 5-8
Embodiment 5-8 provides a kind of olefin polymerization catalysis respectively, and it prepares according to preparation method as described below:
In the reactor of replacing through high pure nitrogen, add magnesium chloride 4.80g successively, toluene 95mL, epoxy chloropropane 4mL, tributyl phosphate 12.5mL; Under agitation be warming up to 50 DEG C, and insulation reaction 2.5 hours, treat that solid dissolves completely; Add Tetra hydro Phthalic anhydride 1.40g, continue insulation reaction 1 hour; Solution is cooled to less than-25 DEG C, in 1 hour, drips TiCl
456mL; Then be slowly warming up to 80 DEG C, in temperature-rise period, separate out solids gradually; Then the dibasic alcohol sulfonate compound 6mmol prepared in embodiment 1-4 is added respectively, insulation reaction 1 hour; After filtration, add toluene 70mL, wash twice, obtain solid sediment; Then toluene 60mL is added, TiCl
440mL, is warmed up to 100 DEG C of reactions 2 hours, after venting filtrate, then adds toluene 60mL, TiCl
440mL, 100 DEG C of reactions 2 hours, venting filtrate; Add toluene 60mL, boiling state washs three times, then adds hexane 60mL, and boiling state washs three times, then adds hexane 60mL, after normal temperature washes twice, obtains the olefin polymerization catalysis of embodiment 5-8.
Comparative example 1
This comparative example provides a kind of olefin polymerization catalysis, and its preparation method is substantially identical with the preparation method in embodiment 5-8, and unique difference is dibasic alcohol sulfonate compound (electron donor) to replace with ethylene glycol bisthioglycolate p-toluenesulfonic esters.
Comparative example 2
This comparative example provides a kind of olefin polymerization catalysis, and its preparation method is substantially identical with the preparation method in embodiment 5-8, and unique difference is dibasic alcohol sulfonate compound (electron donor) to replace with ethyl benzoate.
Comparative example 3
This comparative example provides a kind of olefin polymerization catalysis, and its preparation method is substantially identical with the preparation method in embodiment 5-8, and unique difference is dibasic alcohol sulfonate compound (electron donor) to replace with n-butyl phthalate.
Propylene polymerization is tested
The solid catalyst of above-described embodiment 5-8 and comparative example 1-3 is adopted to carry out catalyzing propone polymerization respectively.This propylene polymerization carries out in accordance with the following methods: make volume be that the stainless steel cauldron of 5L is fully replaced through gaseous propylene, then add AlEt wherein
32.5mmol, Cyclohexylmethyldimethoxysilane (CHMMS) 0.1mmol, add the solid catalyst 8-10mg and 1.2L hydrogen that prepare in above-described embodiment 5-8 and comparative example 1-3 more respectively, pass into liquid propene 2.3L afterwards, then 70 DEG C are warming up to, insulation reaction is after 1 hour, and cooling, pressure release, obtain polypropylene (PP) powder.Wherein, the solid catalyst, the AlEt that prepare in embodiment 5-8 and comparative example 1-3
3combination catalyst is formed, co-catalysis propylene polymerization with CHMMS.
Calculate catalyst activity, catalyst activity is calculated by the gauge of the polyacrylic amount that obtains/add catalyzer and is obtained, and the polypropylene powder obtained is carried out the test of degree of isotacticity, melting index and molecular weight distribution, testing method is described above, and result is as shown in table 1.
Table 1
As can be seen from Table 1, the catalytic activity of the olefin polymerization catalysis of the embodiment of the present invention is high, and the polymkeric substance stereospecificity utilizing this catalyst preparing to obtain is high and molecular weight distribution is wider.
Claims (20)
1. there is a dibasic alcohol sulfonate compound for following formula I,
Wherein, n >=3;
R
1and R
2identical or not identical, and be selected from the group be made up of the fused ring aryl of the aralkyl of the aryl of the cycloalkyl of the alkyl of the C1-C20 of straight chain and side chain, C3-C20, C6-C20, C7-C20, the alkaryl of C7-C20, the alkylene of C2-C20 and C6-C20 respectively;
R
3, R
4, R
5, R
6, R
7and R
8identical or not identical, and be selected from the group be made up of the fused ring aryl of the alkaryl of the aralkyl of the aryl of the cycloalkyl of the alkyl of the C1-C20 of hydrogen, halogen atom, straight chain and side chain, C3-C20, C6-C20, C7-C20, C7-C20, the alkylene of C2-C20 and C6-C20 respectively;
R
3, R
4, R
5, R
6, R
7and R
8be not hydrogen and/or halogen entirely.
2. dibasic alcohol sulfonate compound according to claim 1, wherein, R
3, R
4, R
5, R
6, R
7and R
8one or several carbon atom arbitrary in described alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkylene and fused ring aryl in the group be selected from and/or hydrogen atom are replaced by halogen atom.
3. dibasic alcohol sulfonate compound according to claim 1, wherein, n=3 or 4 or 5.
4. dibasic alcohol sulfonate compound according to claim 1, wherein, n=3, and R
3, R
4, R
5, R
6, R
7and R
8in have two at least for hydrogen, and R
3, R
4, R
5, R
6, R
7and R
8in the several groups be connected on different carbon atom form condensed ring, and R
1and R
2in have at least one to be selected from the group be made up of aryl and alkaryl.
5. dibasic alcohol sulfonate compound according to claim 4, wherein, R
1and R
2all be selected from the group be made up of aryl and alkaryl.
6. dibasic alcohol sulfonate compound according to claim 1, wherein, n=4, and R
3, R
4, R
5, R
6, R
7and R
8between not Cheng Huan, and R
1and R
2in have a group selecting the substituted or unsubstituted aryl of free halogen and alkaryl to form at least.
7. dibasic alcohol sulfonate compound according to claim 6, wherein, R
1and R
2all select the group that the substituted or unsubstituted aryl of free halogen and alkaryl form.
8. dibasic alcohol sulfonate compound according to claim 1, wherein, when n>=5, R
3, R
4, R
5, R
6, R
7and R
8between not Cheng Huan.
9. dibasic alcohol sulfonate compound according to claim 1, wherein, R
1and R
2in have at least one to be group containing phenyl ring.
10. dibasic alcohol sulfonate compound according to claim 9, wherein, the phenyl that the described group containing phenyl ring is phenyl, is replaced by the alkyl of C1-C20 and/or halogen atom.
11. dibasic alcohol sulfonate compounds according to claim 1, wherein, R
1and R
2the phenyl all select free phenyl, being replaced by the alkyl of C1-C20 and/or halogen atom the group that forms.
12. dibasic alcohol sulfonate compounds according to claim 1, wherein, R
3and R
4in have at least a phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl to form group, and R
3and R
4be not phenyl entirely; R
5and R
6in have at least a phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl to form group, and R
5and R
6be not phenyl entirely; R
7and R
8be selected from the group that the phenyl that replaced by the alkyl of hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 and halogenophenyl form respectively, and R
7and R
8be not phenyl entirely.
13. dibasic alcohol sulfonate compounds according to claim 1, wherein, R
3and R
4in one be hydrogen, the group that another phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl form; R
5and R
6in one be hydrogen, the group that another phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl form; And R
3and R
4in be not group and the R of hydrogen
5and R
6in be not that the group of hydrogen is entirely for phenyl; R
7and R
8be selected from the group that the phenyl that replaced by the alkyl of hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 and halogenophenyl form respectively, and R
7and R
8be not phenyl entirely.
14. dibasic alcohol sulfonate compounds according to claim 1, wherein, work as R
3and R
4in one be hydrogen, another is methyl, and R
5and R
6in one be hydrogen, another is methyl, and R
7and R
8complete for hydrogen or when being respectively hydrogen and methyl, R
1and R
2in have a phenyl replaced by halogen atom and/or alkyl at least.
15. dibasic alcohol sulfonate compounds according to claim 1, wherein, R
7and R
8in have at least one to be group containing phenyl ring.
16. dibasic alcohol sulfonate compounds according to claim 15, wherein, the phenyl that the described group containing phenyl ring is phenyl, is replaced by the alkyl of C1-C20 and/or halogen atom.
17. dibasic alcohol sulfonate compounds according to claim 1, wherein, R
7and R
8the phenyl all select free phenyl, being replaced by the alkyl of C1-C20 and/or halogen atom the group that forms.
18. dibasic alcohol sulfonate compounds according to any one of claim 1-17, wherein, R
3and R
4in one be hydrogen, the group that another phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl form; R
5and R
6in one be hydrogen, the group that another phenyl selecting the alkyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 to replace and halogenophenyl form; And R
3and R
4in be not group and the R of hydrogen
5and R
6in be not that the group of hydrogen is entirely for phenyl; R
7and R
8be selected from the group that the phenyl that replaced by the alkyl of hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, C1-C20 and halogenophenyl form respectively, and R
7and R
8be not phenyl entirely; And R
1and R
2the phenyl all select free phenyl, being replaced by the alkyl of C1-C20 and/or halogen atom the group that forms; And n=3 or 4.
The preparation method of the dibasic alcohol sulfonate compound according to any one of 19. 1 kinds of claim 1-18, it comprises the following steps: make dibasic alcohol and sulfonic acid or SULPHURYL CHLORIDE carry out esterification, obtain described dibasic alcohol sulphonate.
Dibasic alcohol sulfonate compound according to any one of 20. claim 1-18 is preparing the application in olefin polymerization catalysis.
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| WO2016086836A1 (en) * | 2014-12-05 | 2016-06-09 | 中国石油天然气股份有限公司 | Disulfonic acid ester compound, olefin polymerization catalyst component and olefin polymerization catalyst |
| WO2016086837A1 (en) * | 2014-12-05 | 2016-06-09 | 中国石油天然气股份有限公司 | Disulfonic acid ester compound and application thereof, olefin polymerization catalyst component and olefin polymerization catalyst |
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