CN104496865A - Diol sulfonate compound as well as preparation method and application thereof - Google Patents
Diol sulfonate compound as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a diol sulfonate compound as well as a preparation method and application thereof. The diol sulfonate compound has the following general formula I as shown in the description, wherein R1 and R2 are selected from the group consisting of linear and branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl and alkaryl, C2-C20 olefin and C6-C20 fused polycyclic aryl, R3 to R6 are selected from the group consisting of hydrogen, halogen atoms, linear and branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl and alkaryl, C2-C20 alkylene and C6-C20 fused polycyclic aryl, and R3 to R6 are not all hydrogen and/or halogen atoms. The diol sulfonate compound is prepared by esterifying diol. The invention also provides application of diol sulfonate in preparation of 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
As everyone knows, can be used for CH 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,
R
1and R
2identical or not identical, R
1and R
2be 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
5and R
6identical or not identical, R
3, R
4, R
5and R
6be 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
5and R
6be not hydrogen and/or halogen atom entirely.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
1, R
2, R
3, R
4, R
5and R
6in described alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkylene and fused ring aryl in the group be selected from, one or several carbon atom arbitrary and/or hydrogen atom are replaced by halogen atom.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
1and R
2one 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, R
1and R
2the group that (identical or not identical) selects the alkyl phenyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, cyclopentyl, cyclohexyl, phenyl, alkyl phenyl, halogenophenyl, halo, indenyl, benzyl, phenylethyl and fused ring aryl to form respectively.More preferably, R
1and R
2the group that (identical or not identical) selects free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, alkyl phenyl and halogenophenyl to form respectively.
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 phenyl that the group that should contain phenyl ring is preferably phenyl or is 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
3, R
4, R
5and R
6cheng Huan (the diversification of forms of Cheng Huan between (and the carbon be connected with these substituting groups), as triatomic ring, tetra-atomic ring, five-ring, six-ring), form the dibasic alcohol sulphonate of cycloalkyl substituted or two sulfocarbolate of aryl replacement, and an oxygen in ester group is connected with aryl (phenol), another oxygen is connected with alkyl the sulphonate of (alcohol).
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
3, R
4, R
5and R
6in described alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkylene and fused ring aryl in the group be selected from, one or several carbon atom arbitrary and/or hydrogen atom are replaced by halogen atom.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
3, R
4, R
5and R
6in have at least one to be selected from the group be made up of hydrogen, halogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, alkyl phenyl and halogenophenyl.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
3, R
4, R
5and R
6(identical or not identical) is selected from the group be made up of hydrogen, halogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, alkyl phenyl and halogenophenyl respectively.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
3, R
4, R
5and R
6in have at least one not to be hydrogen, this is not group that the group of hydrogen selects free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, phenyl and alkyl phenyl to form.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
3and R
4in one when being hydrogen, another is not group that the group of hydrogen selects free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, phenyl and alkyl phenyl to form.
In above-mentioned dibasic alcohol sulfonate compound, preferably, R
5and R
6in one when being hydrogen, another is not group that the group of hydrogen selects free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, phenyl and alkyl phenyl to form.
According to the specific embodiment of the present invention, preferably, described dibasic alcohol sulfonate compound has following general formula II:
Wherein,
X is C or N, and Y is C or N;
When X is N, then there is not substituent R
6'; When Y is N, then there is not substituent R
5'; When X and Y is N, then there is not substituent R
5' and R
6';
R
1and R
2identical or not identical, R
1and R
2be 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' and R
6' identical or not identical, R
3', R
4', R
5' and R
6' 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.
According to the specific embodiment of the present invention, preferably, described dibasic alcohol sulfonate compound has following general formula III:
Wherein,
A and B is selected from the group be made up of C, N, O and S respectively;
When A is N, then there is not substituent R
5"; When B is O or S, then there is not substituent R
3" and R
4"; When B is N, then there is not substituent R
3";
R
1and R
2identical or not identical, R
1and R
2be 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" and R
6" identical or not identical, R
3", R
4", R
5" and R
6" 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.
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 V, obtain described dibasic alcohol sulfonate compound,
Wherein, R
3, R
4, R
5and R
6identical or not identical, R
3, R
4, R
5and R
6be 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.Preferably, R
3, R
4, R
5and R
6cheng Huan (the diversification of forms of Cheng Huan between (and the carbon be connected with these substituting groups), as triatomic ring, tetra-atomic ring, five-ring, six-ring), form the dibasic alcohol of cycloalkyl substituted or the diphenol of aryl replacement, and a hydroxyl is connected with aryl, the compound that another hydroxyl is connected with alkyl.R
3, R
4, R
5and R
6other preferable range described above, repeat no more herein.
In above-mentioned preparation method, the synthetic method with the dibasic alcohol of general formula I V can with reference to 9,9-(two methylol) fluorenes (Acta Chemica Scandina-vica 21, pp.718-720) synthetic method, also can refer to the preparation method of dibasic alcohol disclosed in 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 alcohol sulfonate compound preparing the application in olefin polymerization catalysis.
The preparation that dibasic alcohol sulfonate compound 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
n(OQ)
4-ntitanium compound (alkyl of Q to be carbonatoms be 1-20 in formula, Z is halogen atom, n=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 dibasic alcohol sulfonate compound 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 1,2-butyleneglycol xylene sulfonate, and it is prepared by following methods:
1 is added in reactor, 2-butyleneglycol (2.50g), pyridine (8.80g) and tetrahydrofuran (THF) (70mL), after mixing, divide and add p-methyl benzene sulfonic chloride (10.60g) for four times, then 0 DEG C of reaction 4 hours, rise to room temperature afterwards and continue reaction 6 hours, then add water in reaction system until inorganic phase is transparent; Separate organic phase, after extracted with diethyl ether inorganic phase, the diethyl ether solution after extraction and organic phase are merged, wash the organic phase being associated with the rear diethyl ether solution of extraction with water, then use anhydrous sodium sulfate drying, after concentrated, isolate product, obtain 4.37g product.The nuclear magnetic resonance measuring result of this product is: δ 1.0-1.1 (3H), 1.7-1.9 (2H), 2.3-2.6 (6H), 4.4-4.6 (2H), 5.4-5.5 (1H), 7.2-8.0 (8H).Can determine that the present embodiment has prepared 1,2-butyleneglycol xylene sulfonate.
Embodiment 2
The present embodiment provides 2,3-butanediol xylene sulfonate, and its preparation method is identical with the preparation method in embodiment 1, unique difference is raw material 1, the 2-butyleneglycol in embodiment 1 to replace with 2,3-butanediol, its added in molar amounts is in the same manner as in Example 1, obtains product 4.69g.The nuclear magnetic resonance measuring result of this product is: δ 1.4-1.6 (6H), 2.3-2.6 (6H), 5.3-5.5 (2H), 7.2-8.0 (8H).Can determine that the present embodiment has prepared 2,3-butanediol xylene sulfonate.
Embodiment 3
The present embodiment provides pyrocatechol two p-toluenesulfonic esters, and it is prepared by following methods:
By joining in 50mL tetrahydrofuran (THF) in 2.75g pyrocatechol, under agitation adding 12.10mL pyridine, after stirring, slowly adding 11.66g p-methyl benzene sulfonic chloride, stirring at room temperature 1 hour, be then heated to backflow, insulation reaction 4 hours; Add the salt that 70mL deionized water dissolving generates, then with toluene extraction, separate organic phase, by organic phase saturated common salt water washing 3 times, then use anhydrous sodium sulfate drying, remove solvent, then wash and after recrystallization, obtain product 4.02g.The nuclear magnetic resonance measuring result of this product is: δ 1.0-1.1 (6H), 2.3-2.6 (6H), 4.4-4.6 (4H), 7.3-7.6 (8H).Can determine that the present embodiment has prepared pyrocatechol two p-toluenesulfonic esters.
Embodiment 4
The present embodiment provides 2,5-dicarboxylic acid dimethyl ester-3,4-dihydroxyl two p-toluenesulfonic esters, and it is prepared by following methods:
6.50g3,4-dihydroxyl thiophene-2,5-dicarboxylic acid dimethyl ester is joined in 80mL tetrahydrofuran (THF), under agitation add 12.10mL pyridine, after stirring, slowly add 11.66g p-methyl benzene sulfonic chloride, stirring at room temperature 1 hour, then backflow is heated to, insulation reaction 4 hours; Add the salt that 70mL deionized water dissolving generates, then with toluene extraction, separate organic phase, by organic phase saturated common salt water washing 3 times, then use anhydrous sodium sulfate drying, remove solvent, then wash and after recrystallization, obtain product 6.80g.The nuclear magnetic resonance measuring result of this product is: δ 2.3-2.6 (6H), 7.3-7.6 (8H), 7.9-8.2 (4H).Can determine that the present embodiment has prepared 2,5-dicarboxylic acid dimethyl ester-3,4-dihydroxyl 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 or diphenol 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, its preparation method is substantially identical with the preparation method in embodiment 5-8, and unique difference is dibasic alcohol sulfonate compound or diphenol 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, its preparation method is substantially identical with the preparation method in embodiment 5-8, and unique difference is dibasic alcohol sulfonate compound or diphenol sulfonate compound (electron donor) to replace with ethyl benzoate.
Comparative example 3
This comparative example provides a kind of olefin polymerization catalysis, its preparation method is substantially identical with the preparation method in embodiment 5-8, and unique difference is dibasic alcohol sulfonate compound or diphenol 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 (17)
1. there is a dibasic alcohol sulfonate compound for following formula I,
Wherein,
R
1and R
2identical or not identical, R
1and R
2be 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
5and R
6identical or not identical, R
3, R
4, R
5and R
6be 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
5and R
6be not hydrogen and/or halogen atom entirely.
2. dibasic alcohol sulfonate compound according to claim 1, wherein, R
1and R
2one 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, R
1and R
2select the group that the alkyl phenyl of free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, cyclopentyl, cyclohexyl, phenyl, alkyl phenyl, halogenophenyl, halo, indenyl, benzyl, phenylethyl and fused ring aryl form respectively.
4. the dibasic alcohol sulfonate compound according to claim 1 or 3, wherein, R
1and R
2select the group that free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, alkyl phenyl and halogenophenyl form respectively.
5. dibasic alcohol sulfonate compound according to claim 1, wherein, R
1and R
2in have at least one to be group containing phenyl ring.
6. dibasic alcohol sulfonate compound according to claim 5, wherein, the phenyl that the described group containing phenyl ring is phenyl or is replaced by the alkyl of C1-C20 and/or halogen atom.
7. dibasic alcohol sulfonate compound according to claim 1 or 5, 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.
8. dibasic alcohol sulfonate compound according to claim 1, wherein, R
3, R
4, R
5and R
6between Cheng Huan, form two sulfocarbolate that the dibasic alcohol sulphonate of cycloalkyl substituted or aryl replace.
9. dibasic alcohol sulfonate compound according to claim 1, wherein, R
3, R
4, R
5and R
6in described alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkylene and fused ring aryl in the group be selected from, one or several carbon atom arbitrary and/or hydrogen atom are replaced by halogen atom.
10. dibasic alcohol sulfonate compound according to claim 1, wherein, R
3, R
4, R
5and R
6in have at least one to be selected from the group be made up of hydrogen, halogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, alkyl phenyl and halogenophenyl.
11. dibasic alcohol sulfonate compounds according to claim 1 or 10, wherein, R
3, R
4, R
5and R
6be selected from the group be made up of hydrogen, halogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl, alkyl phenyl and halogenophenyl respectively.
12. dibasic alcohol sulfonate compounds according to claim 1, wherein, R
3, R
4, R
5and R
6in have at least one not to be hydrogen, this is not group that the group of hydrogen selects free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, phenyl and alkyl phenyl to form.
13. dibasic alcohol sulfonate compounds according to claim 1 or 12, wherein, R
3and R
4in one when being hydrogen, another is not group that the group of hydrogen selects free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, phenyl and alkyl phenyl to form; R
5and R
6in one when being hydrogen, another is not group that the group of hydrogen selects free methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, phenyl and alkyl phenyl to form.
14. dibasic alcohol sulfonate compounds according to claim 1, wherein, described dibasic alcohol sulfonate compound has following general formula II:
Wherein,
X is C or N, and Y is C or N;
When X is N, then there is not substituent R
6'; When Y is N, then there is not substituent R
5'; When X and Y is N, then there is not substituent R
5' and R
6';
R
1and R
2identical or not identical, R
1and R
2be 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' and R
6' identical or not identical, R
3', R
4', R
5' and R
6' 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.
15. dibasic alcohol sulfonate compounds according to claim 1, wherein, described dibasic alcohol sulfonate compound has following general formula III:
Wherein,
A and B is selected from the group be made up of C, N, O and S respectively;
When A is N, then there is not substituent R
5"; When B is O or S, then there is not substituent R
3" and R
4"; When B is N, then there is not substituent R
3";
R
1and R
2identical or not identical, R
1and R
2be 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" and R
6" identical or not identical, R
3", R
4", R
5" and R
6" 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.
The preparation method of the dibasic alcohol sulfonate compound according to any one of 16. 1 kinds of claim 1-15, 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 17. claim 1-15 is preparing the application in olefin polymerization catalysis.
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| PCT/CN2015/096118 WO2016086836A1 (en) | 2014-12-05 | 2015-12-01 | Disulfonic acid ester compound, olefin polymerization catalyst component and olefin polymerization catalyst |
| PCT/CN2015/096119 WO2016086837A1 (en) | 2014-12-05 | 2015-12-01 | Disulfonic acid ester compound and application thereof, olefin polymerization catalyst component and olefin polymerization catalyst |
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| 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 |
| 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 |
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