CN104610056A - Compound, catalyst solid composition containing compound, and catalyst - Google Patents
Compound, catalyst solid composition containing compound, and catalyst Download PDFInfo
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- CN104610056A CN104610056A CN201310535348.6A CN201310535348A CN104610056A CN 104610056 A CN104610056 A CN 104610056A CN 201310535348 A CN201310535348 A CN 201310535348A CN 104610056 A CN104610056 A CN 104610056A
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- propanal dimethyl
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Abstract
The invention discloses a compound with a novel structure. Structural formula of the compound is represented by formula (1), wherein R1, R2, R3, and R4 may be used for representing the same groups or different groups, and are independently selected from substituted or unsubstituted C1-C20 alkyl groups, and are optimally selected from substituted or unsubstituted C1-C10 aliphatic hydrocarbon groups, C3-C10 naphthene grous, C6-C20 aryl groups, and C7-C20 alkaryl groups, and R3 and R4 can be randomly connected to obtain a ring or no rings. The compound represented by formula (1) can be taken as an internal electron donor compound; a catalyst with excellent comprehensive properties can be obtained; when the compound is used for olefin polymerization, polymerization activity is high, stereotactic performance is excellent, and obtained polymers are high in isotacticity and melt index.
Description
Technical field
The present invention is specifically related to a kind of compound of novel texture, the catalyst component obtained for internal electron donor with described compound and the catalyzer containing this catalyst component.The invention still further relates to the application in olefin polymerization of described catalyzer.
Background technology
Using magnesium, titanium, halogen and internal electron donor as the catalyzer that the solid titanium catalyst component of basal component is formed, namely Ziegler-Natta catalyst known in the field, can be used for CH
2the polyreaction of=CHR alkene, particularly can obtain the polymkeric substance of higher yields and higher tacticity in the alpha-olefine polymerizing with 3 carbon or more carbon atom.As everyone knows, Donor compound is one of requisite composition in Ziegler-Natta catalyst component.From early stage disclosed monocarboxylic acid ester compound, such as ethyl benzoate, the binary aromatic carboxylic acid's ester compound widely used up till now, such as n-butyl phthalate or o-benzoic acid diisobutyl ester, arrive recent disclosed 1 again, 3-bis-ethers (CN1020448C), succinate compound (CN1313869) and 1,3-diol-lipid (CN1213080C) compound, the development of internal electron donor compound result in polyolefin catalyst and constantly updates just.
Along with the continuous progress of catalyst research, people wish to find new internal electron donor, thus obtain the catalyzer with better over-all properties, to meet the needs of olefinic polymerization development.
Summary of the invention
For deficiency of the prior art, the present inventor passes into deep experimental study, provide a kind of compound of novel texture, it can be used as the internal electron donor compound of catalyst solid constituent (or claiming catalyst component), and comprises catalyst component and the catalyzer of described compound.Olefinic polymerization is used for, the advantage such as have that catalytic activity is good, stereospecificity is good, degree of isotacticity is high, melting index is high and hydrogen regulation performance is good according to catalyst solid constituent provided by the invention and catalyzer.
According to an aspect of the present invention, the invention provides a kind of compound of novel texture, its structural formula is as shown in the formula shown in (I):
In formula, R
1, R
2, R
3and R
4can be identical or not identical, be selected from substituted or unsubstituted C independently of one another
1-C
20alkyl, be preferably selected from substituted or unsubstituted C
1-C
10aliphatic group, C
3-C
10cycloalkyl, C
6-C
20aryl and C
7-C
20alkaryl; R
3and R
4ring or not Cheng Huan can be connected into arbitrarily.
According to the present invention, the C of described replacement
1-C
10alkyl, C
6-C
20aryl and C
7-C
20the group that replaces of alkaryl etc., refer to as described in hydrogen atom in alkyl, aryl or alkaryl on phenyl ring optionally by the replacement of halogen (mix) atom, alkyl or alkoxyl group, the carbon atom on described main chain is optionally by hybrid atom MCM-41.In the present invention, described aliphatic group can be straight or branched structure, includes saturated alkyl and undersaturated group as thiazolinyl etc.Described heteroatoms is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom etc.
According to a specific embodiment of the present invention, described R
1and R
2group is selected from substituted or unsubstituted C
1-C
10aliphatic group, C
3-C
10cycloalkyl and C
6-C
20aryl; Preferred R
1and R
2group is substituted or unsubstituted C
1-C
6alkyl, as methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, allyl group etc. can be comprised.
According to another specific embodiment of the present invention, described R
3and R
4group is selected from substituted or unsubstituted C
1-C
10aliphatic group, C
3-C
10cycloalkyl and C
6-C
20aryl; Preferred R
3and R
4group is selected from substituted or unsubstituted C
1-C
6alkyl and C
6-C
12aryl, as methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, allyl group, phenyl, phenmethyl etc. can be comprised.
According to the catalyst component in the present invention, for the compound shown in described formula (I), suitable examples of compounds is selected from but is not limited to: two (acetoxyl group methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (propionyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (isobutyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (valeryl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1-methyl) butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (isoamyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((pivaloyl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (hexylyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1-methyl) valeryl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((2-methyl) valeryl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (dissident's acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1,1-dimethyl) butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (special hexylyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1,2-dimethyl) butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (allyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (benzoxy methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, be preferably selected from two (acetoxyl group methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (propionyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (isobutyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (valeryl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (isoamyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((pivaloyl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (hexylyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (dissident's acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (special hexylyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1,2-dimethyl) butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (allyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-and two (benzoxy methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, more preferably 2 are selected from, two (the acetoxyl group methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the propionyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the butyryl acyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the isobutyl acyl-oxygen methylene)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the valeryl oxygen methylene)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the isoamyl acyl-oxygen methylene)-1 of 2-, 3-Propanal dimethyl acetal, 2, two ((the pivaloyl oxygen methylene)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the hexylyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the dissident's acyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the special hexylyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the benzoxy methylene)-1 of 2-, 3-Propanal dimethyl acetal.
According to compound provided by the invention; it is prepared by following steps: first synthesize 2; two (methoxymethylene)-1 of 2-; ammediol; then reacted by itself and corresponding acylating reagent, obtain compound shown in the formula I described in the present invention (as can with the reaction such as alkyl acyl chloride).Wherein, described 2, two (methoxymethylene)-1 of 2-, ammediol obtains Reactive Synthesis by following step: tetramethylolmethane and phenyl aldehyde react under the effect of catalyzer (as concentrated hydrochloric acid), carry out solid-liquid separation after obtaining solid, solid processed, purifying, obtain 2-((2-phenyl)-1,3-dioxocyclohex base)-1,3-PD; Then 2-((2-phenyl)-1,3-dioxocyclohex base)-1, ammediol and excessive sodium hydride react, add excessive methyl-sulfate again, after reaction terminates, through purifying, (as adding water washing, separatory, drying, underpressure distillation etc.) obtains 2-((2-phenyl)-1,3-dioxocyclohex base)-1,3-Propanal dimethyl acetal; Then its hydrogenation under lower Pd-C katalysis obtains two (the methoxymethylene)-1,3-PD of 2,2-.The reaction of above-mentioned steps can be carried out in suitable solvent according to selecting.
According to the compound of novel texture provided by the invention, can be used for olefinic polymerization, as the internal electron donor as catalyst solid constituent, the catalyzer obtained has good over-all properties, has broad application prospect.
According to another aspect of the present invention, additionally provide a kind of catalyst solid constituent for olefinic polymerization (or claiming catalyst component, ingredient of solid catalyst), comprise titanium, magnesium, the compound shown in halogen and above-mentioned formula (I).
Catalyst according to the invention solid ingredient, the content of described titanium (element) is 1.0-8.0wt%, is preferably 1.6-6.0wt%; The content of magnesium (element) is preferably 10-70wt%, is preferably 15-40wt%; The content of halogen (element) is 20-85wt%, is preferably 30-80%; Compound (internal electron donor compound) content 2-30wt% shown in described formula (I), preferred 3-20wt%.
According to catalyst solid constituent of the present invention, it is magnesium compound, the compound reaction product in a solvent shown in titanium compound and formula (I).Consumption for the preparation of the titanium compound of described catalyst solid constituent, magnesium compound and internal electron donor compound is not particularly limited, and can be respectively conventional substances and the consumption of this area.
In a preferred embodiment, described magnesium compound is selected from formula M gR
4r
5shown magnesium compound, formula M gR
4r
5pH
2the hydrate of the magnesium compound shown in O and formula M gR
4r
5qR
6the alcohol adducts of the magnesium compound shown in OH, in general formula, R
4and R
5be selected from halogen, C independently of one another
1-C
8the alkoxyl group of straight or branched and C
1-C
8straight or branched alkyl; P and q is separately selected from 0.1-6, preferred 2-3.5; R
6for C
1-C
18alkyl, be preferably C
1-C
8alkyl, be more preferably selected from methyl, ethyl, n-propyl and sec.-propyl.Such as, described magnesium compound can be dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two pentyloxy magnesium, two oxygen base magnesium, two (2-ethyl) oxygen base magnesium, methoxyl group magnesium chloride, methoxyl group magnesium bromide, methoxyl group magnesium iodide, oxyethyl group magnesium chloride, oxyethyl group magnesium bromide, oxyethyl group magnesium iodide, propoxy-magnesium chloride, propoxy-magnesium bromide, propoxy-magnesium iodide, butoxy magnesium chloride, butoxy magnesium bromide, butoxy magnesium iodide, methylmagnesium-chloride, ethylmagnesium chloride, propyl group magnesium chloride, butylmagnesium chloride, amyl group magnesium chloride, phenyl-magnesium-chloride, magnesium dichloride, dibrominated magnesium, diiodinating magnesium, the alcohol adducts of magnesium dichloride, at least one in the alcohol adducts of dibrominated magnesium and the alcohol adducts of diiodinating magnesium.Most preferably, described magnesium compound contains at least one in diethoxy magnesium, butylmagnesium chloride, oxyethyl group magnesium chloride, magnesium dichloride.
Preferred at another, the general formula of described titanium compound is TiX
m(OR
7)
4-m, in formula, X is halogen, R
7for C
1-C
20alkyl, preferred C
1-C
5alkyl, m is the integer of 0-4.Such as: at least one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium and trichlorine one ethanolato-titanium.Most preferably, described titanium compound is titanium tetrachloride.
In the specific embodiment of the inventive method, catalyst component is such as prepared by following method.
Method one, is suspended in alkoxyl magnesium or Alkoxymagnesium halides in inert diluent and forms suspension, then is mixed with above-mentioned titanium compound, internal electron donor by this suspension and contact to obtain solids dispersion system, is commonly referred to mother liquor.Filtered by mother liquor, gained solid matter is suspended in the solution containing titanium tetrachloride and carries out contact pairs, is commonly referred to titanium process; Then after filtration, washing can obtain catalyst solid constituent of the present invention.
As the object lesson of above-mentioned alkoxyl magnesium, dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two pentyloxy magnesium, two hexyloxy magnesium, two (2-ethyl) hexyloxy magnesium etc. or its mixture can be enumerated, be preferably the mixture of diethoxy magnesium or diethoxy magnesium and other alkoxyl magnesium.The preparation method of this alkoxyl magnesium compound, can be prepared by method well known in the art, MAGNESIUM METAL and fatty alcohol is prepared under a small amount of iodine exists disclosed in patent CN101906017A.
As the object lesson of above-mentioned Alkoxymagnesium halides, methoxyl group magnesium chloride, oxyethyl group magnesium chloride, propoxy-magnesium chloride, butoxy magnesium chloride etc. can be enumerated, preferred oxyethyl group magnesium chloride.The preparation method of this alkoxy magnesium compound, can be prepared by method well known in the art, prepares oxyethyl group magnesium chloride as Grignard reagent butylmagnesium chloride mixed with purity titanium tetraethoxide and tetraethoxy-silicane.
The inert diluent that the formation of the mother liquor in aforesaid method one uses can adopt at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.The consumption of each composition that the formation of mother liquor uses, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0.5-100 mole, is preferably 1-50 mole; The total amount of electronic donor compound capable is generally 0.005-10 mole, is preferably 0.01-1 mole.During the formation of mother liquor, the Contact Temperature of described each component is generally-40 ~ 200 DEG C, is preferably-20 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-8 hours.
In described method one, in described titanium treating processes, use alternative in the solution containing titanium tetrachloride to add inert diluent, as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene; In described titanium treating processes, use consumption containing each composition in titanium tetrachloride solution, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0-100 mole, is preferably 0-50 mole; Titanium number of processes is 0-10 time, preferred 1-5 time.In described titanium treating processes, alternative adds above-mentioned electronic donor compound capable, and wherein internal electron donor consumption is generally 0.005-10 mole, is preferably 0.01-1 mole.Described titanium treatment temp is generally 0 ~ 200 DEG C, is preferably 30 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-6 hours.
Method two, magnesium dihalide is dissolved in the solvent system that organic epoxy compound thing, organo phosphorous compounds, aliphatic alcohols compound and inert diluent form, with above-mentioned titanium compound, electron donor compound contact reacts after formation homogeneous solution, under precipitation additive exists, separate out solids, form mother liquor; Filtered by mother liquor, gained solid matter is suspended in the solution containing titanium tetrachloride and carries out contact pairs, is below commonly referred to as titanium process; Then after filtration, washing can obtain catalyst solid constituent of the present invention.
The precipitation additive used in method two is not particularly limited, as long as it is shaping that solid particulate can be made to separate out.Adducible example has: at least one in organic acid anhydride, organic acid, ester, ether and ketone.The object lesson of described organic acid anhydride can be diacetyl oxide, Tetra hydro Phthalic anhydride, at least one in Succinic anhydried and MALEIC ANHYDRIDE etc., described organic acid object lesson can be acetic acid, propionic acid, butyric acid, at least one in vinylformic acid and methacrylic acid etc., the object lesson of described ester can be dibutyl phthalate, 2, 4-glycol dibenzoate, 3-ethyl-2, 4-glycol dibenzoate, 2, 3-di-isopropyl-1, 4-butyleneglycol dibenzoate, 3, 5-heptanediol dibenzoate and 4-ethyl-3, at least one in 5-heptanediol dibenzoate, the object lesson of described ether can be methyl ether, ether, propyl ether, butyl ether, amyl ether, 2-sec.-propyl-2-isopentyl Propanal dimethyl acetal and 9, 9-(dimethoxy methyl) at least one in fluorenes, described ketone can be acetone, at least one in methylethylketone and benzophenone.
In method two, the organic epoxy compound thing of described use can for being selected from least one in oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether and diglycidylether etc., preferred epoxy chloropropane.The organo phosphorous compounds of described use can be hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, the object lesson of this organo phosphorous compounds can be enumerated: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or phosphorous acid benzene methyl etc., preferred ortho-phosphoric acid tri-n-butyl.The aliphatic alcohols compound of described use can be straight or branched alkane unitary or the multi-alcohol of carbonatoms 1-20, the straight or branched unitary fatty alcohol of preferred carbonatoms 1-10, object lesson can be enumerated: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, enanthol, (2-ethyl) hexyl alcohol, octanol, nonyl alcohol, decyl alcohol etc., preferably (2-ethyl) hexyl alcohol.
In method two, the inert diluent that mother liquor forms middle use can adopt at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.Mother liquor forms the consumption of each composition of middle use, and in every mole of magnesium halide, organic epoxy compound thing can be 0.2-10 mole, is preferably 0.5-4 mole; Organo phosphorous compounds can be 0.1-3 mole, is preferably 0.3-1.5 mole; Fat alcohol compound can be 0.2-10 mole, is preferably 0.5-3 mole; Titanium compound can be 0.5-20 mole, is preferably 5-15 mole; Helping and separating out component to be 0.01-0.3 mole, is preferably 0.02-0.2 mole; Electronic donor compound capable total amount can be 0-10 mole, is preferably 0.02-0.3 mole.During the formation of mother liquor, the Contact Temperature of described each component is generally-40 ~ 200 DEG C, is preferably-20 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-8 hours.
In method two, in described titanium treating processes, use alternative in the solution containing titanium tetrachloride to add inert diluent, as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.In described titanium treating processes, use consumption containing each composition in titanium tetrachloride solution, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0-100 mole, is preferably 0-50 mole.Described titanium number of processes is 0-10 time, preferred 1-5 time.In described titanium treating processes, alternative adds above-mentioned electronic donor compound capable, and wherein internal electron donor consumption is generally 0.005-10 mole, is preferably 0.01-1 mole.Described titanium treatment temp is generally 0 ~ 200 DEG C, is preferably 30 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-6 hours.
Method three, is suspended in the alcohol adducts of magnesium dihalide in inert diluent and forms suspension, then is mixed with above-mentioned titanium compound, internal electron donor by this suspension and contact to obtain solids dispersion system, is below commonly referred to as mother liquor.Filtered by mother liquor, gained solid matter is suspended in the solution containing titanium tetrachloride and carries out contact pairs, is below commonly referred to as titanium process; Then after filtration, washing can obtain catalyst solid constituent of the present invention.
In method three, the alcohol adducts of described magnesium dihalide can obtain by the following method: under not miscible with adducts inert solvent (as hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene etc.) exists, alcohol (as methyl alcohol, ethanol, propyl alcohol or Virahol etc.) and magnesium halide are mixed to form emulsion, make the rapid chilling dispersion of this emulsion, gained spheroidal particle is the alcohol adducts of magnesium dihalide.
In aforesaid method three, the inert diluent that the formation of mother liquor uses can adopt at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.The consumption of each composition that the formation of mother liquor uses, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0.5-100 mole, is preferably 1-50 mole; The total amount of electronic donor compound capable is generally 0.005-10 mole, is preferably 0.01-1 mole.During the formation of mother liquor, the Contact Temperature of described each component is generally-40 ~ 200 DEG C, is preferably-20 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-8 hours.
In method three, in described titanium treating processes, use alternative in the solution containing titanium tetrachloride to add inert diluent, as at least one in hexane, heptane, octane, decane, benzene, toluene and dimethylbenzene.In titanium treating processes, use consumption containing each composition in titanium tetrachloride solution, in every mole of magnesium, the usage quantity 0.5-100 mole of titanium compound, is preferably 1-50 mole; The usage quantity of inert diluent is generally 0-100 mole, is preferably 0-50 mole.Titanium number of processes is 0-10 time, preferred 1-5 time.In titanium treating processes, alternative adds above-mentioned electronic donor compound capable, and wherein internal electron donor consumption is generally 0.005-10 mole, is preferably 0.01-1 mole.Titanium treatment temp is generally 0 ~ 200 DEG C, is preferably 30 ~ 150 DEG C; Be generally 1 minute-20 hours duration of contact, be preferably 5 minutes-6 hours.
According to another aspect of the present invention, provide a kind of catalyst for olefines polymerizing, it comprises the reaction product of following component:
A. above-mentioned catalyst solid constituent;
B. organo-aluminium compound;
C. optionally, external donor compound.
According to olefin polymerization catalysis of the present invention, the various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst that the organo-aluminium compound as promotor can be commonly used for field of olefin polymerisation.Preferred described organo-aluminium compound is for being general formula AlR'
n'x'
3-n'shown organo-aluminium compound, wherein, R' is selected from hydrogen, C
1-C
20alkyl and C
6-C
20aryl; X' is halogen, and n' is the integer of 1-3.
In above-mentioned catalyzer, at least one of described organo-aluminium compound preferably in following compound: at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.More preferably triethyl aluminum and/or triisobutyl aluminium.
In above-mentioned catalyzer, the consumption of described organo-aluminium compound can be the conventional amount used of this area.Usually, the mol ratio of the aluminium in described organo-aluminium compound and the titanium in described catalyzer is 5-5000:1; Be preferably 20-1000:1; Be more preferably 50-500:1.
In above-mentioned catalyzer, describedly optionally mean the reaction product that described catalyzer can comprise component a and b, also can comprise the reaction product of component a, b and c.According to olefin polymerization catalysis of the present invention, described external electron donor component can be various external electron donors known in the industry, is not particularly limited.
In above-mentioned catalyzer, described external electron donor is preferably general formula R
1"
m "r
2"
n "si (OR
3")
4-m "-n "shown silicoorganic compound, in formula, R
1" and R
2" identical or different, be selected from independently of one another: halogen, hydrogen atom, C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; R
3" be selected from C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; M " and n " is respectively the integer of 0-3, and m "+n " <4.Preferably, described silicoorganic compound are selected from least one in following compound: trimethylmethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, di-t-butyl dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tertiary butyl propyldimethoxy-silane, ter /-butylisopropyl dimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, Dicyclohexyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl dimethoxysilane, two (2-methylcyclopentyl) dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, butyl trimethoxy silane, butyl triethoxyl silane, trimethoxysilane, isobutyl triethoxy silane, amyltrimethoxysilane, isopentyl Trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tetramethoxy-silicane, tetraethoxysilane or four butoxy silanes, these silicoorganic compound can individually use, and also two or more can be combinationally used.
According to olefin polymerization catalysis of the present invention, the consumption of external electron donor is not particularly limited.In the preferred case, the mol ratio of the aluminium in described organo-aluminium compound and described external donor compound is 0.1-500:1, preferred 1-300:1, more preferably 3-100:1.Namely, when described external donor compound selects silicoorganic compound, the mol ratio of described organo-aluminium compound and silicoorganic compound counts 0.1:1-500:1 with aluminium/silicon, preferred 1:1-300:1, more preferably 3:1-100:1.
According to another aspect of the present invention, provide a kind of olefine polymerizing process, described alkene is polymerized under the effect of above-mentioned catalyst component or above-mentioned catalyzer.
According to olefine polymerizing process of the present invention, it both can be used for the homopolymerization of alkene, also can be used for the copolymerization of alkene.
According to the present invention, described alkene general formula be CH
2=CHR, R are hydrogen or C
1-C
12alkyl, be preferably hydrogen or C
1-C
6alkyl.As described in alkene be preferably selected from least one in following compound: ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene; More preferably at least one in ethene, propylene and 1-butylene is selected from.
According to olefine polymerizing process of the present invention, described olefin polymerization conditions is the temperature of olefinic polymerization is 0-150 DEG C, preferred 60-130 DEG C; Time is 0.1-5 hour, preferred 0.5-4 hour, and pressure is 0.01-10MPa, is preferably 0.5-5MPa.The consumption of catalyzer can be the consumption of the various catalyzer of prior art.
Catalyst according to the invention component and catalyzer, when it is for olefinic polymerization, have the high and melting index advantages of higher of the degree of isotacticity of the polymkeric substance that polymerization activity is high, stereotaxis ability is good, obtain.
According to the present invention, adopt the catalyzer that the compound shown in formula (I) of novel texture obtains as internal electron donor compound, be comparing of internal electron donor (it being proved the Fertility being unfavorable for people) with employing phthalate the most frequently used in prior art, there is higher security, and significantly improve the melting index (meaning the hydrogen regulation performance that improve catalyzer) of polymkeric substance.When catalyst according to the invention is used for olefinic polymerization, there is polymerization activity and be suitable for the advantage good with stereotaxis ability, and the polymkeric substance obtained has high, the higher melting index of good degree of isotacticity and tap density, be conducive to the exploitation of different trade mark polymkeric substance.Especially there is high melting index, mean that catalyzer has good hydrogen regulation performance, be suitable for the exploitation of specific acrylic resin.According to novel catalyzer provided by the invention, there is excellent over-all properties, there is broad application prospect.
Embodiment
Embodiment given below is used for further illustrating the present invention, but does not form any limitation of the invention.
Testing method:
1, the titanium content in catalyzer: according to 721 spectrophotometer tests.
2, catalyst grain size distribution: measure according to Malvern 2000 normal hexane dispersion agent laser diffractometry.
3, the mensuration of melt index: measure according to GB/T3682-2000.
4, polymkeric substance degree of isotacticity adopts heptane extraction process to measure: 2 grams of dry polymer samples, are placed in extractor and after 6 hours, residuum are dried to polymer weight (g) and the 2(g of constant weight gained with the extracting of boiling heptane) ratio be degree of isotacticity.
5,
1h NMR measures: use Bruker dmx nmr determination (300MHz, solvent C DCl
3, interior mark TMS, measures temperature 300K).
6, internal electron donor content uses Agilent7890Series gas Chromatographic Determination.
One, synthesis example:
The synthesis of two (the methoxymethylene)-1,3-PD of 2,2-:
1) synthesis of 2-((2-phenyl)-1,3-dioxocyclohex base)-1,3-PD:
54.4g tetramethylolmethane (Mw=136.15,0.4mol) is dissolved in 500mL water.Be warming up to 40 DEG C, add 42.4g phenyl aldehyde (Mw=106,0.4mol) and 2mL concentrated hydrochloric acid, stirring reaction 6 hours.Reaction system hold over night.Suction filtration, filter cake adds 800mL water and 0.5g salt of wormwood, stirs rising temperature for dissolving, crystallisation by cooling.Filter, obtain the 75 DEG C of dryings of crude product vacuum.Crude product re crystallization from toluene, final product 72.6g, productive rate 81%.
1H NMR(CDCl
3/TMS,300MHz)δ(ppm):3.56(s,4H,-C(CH
2OH)
2),3.76,3.79(s,4H,-C(CH
2O)
2CH-),5.44(s,1H,phCH-),7.37-7.39(m,5H,C
6H
5CH-)。
2) synthesis of 2-((2-phenyl)-1,3-dioxocyclohex base)-1,3-Propanal dimethyl acetal:
20g60wt%NaH(Mw=24.0,0.5mol) be scattered in 200mL dry tetrahydrofuran.Get 44.8g2-((2-phenyl)-1,3-dioxocyclohex base)-1,3-PD (Mw=224.25,0.2mol) is dissolved in 400mL dry tetrahydrofuran, instill under normal temperature in the suspension of NaH, dropwise rear 25-30 DEG C and continue reaction 2 hours.Be cooled to 10 DEG C, drip 42.6mol methyl-sulfate (0.45mol), add rear room temperature and continue reaction 4 hours, back flow reaction 4 hours.Stopped reaction, drips 100mL water.Organic phase washes 2 times, dry, filters.Steaming desolventizes, underpressure distillation, collects product and is about 46.3g, productive rate 92%.
1H NMR(CDCl
3/TMS,300MHz)δ(ppm):3.30(s,6H,-C(CH
2OCH
3)
2),3.70(s,4H,-C(CH
2O-)
2),3.86,3.88(s,4H,-C(CH
2OCH
3)
2),7.37-7.47(m,5H,C
6H
5CH-)。
3) synthesis of 2,2-two (methoxymethylene)-1,3-PDs:
300mL acetic acid is added, 5g10wt%Pd-C in high-pressure reactor (nitrogen replacement).50g2-((2-phenyl)-1,3-dioxocyclohex base)-1,3-Propanal dimethyl acetal is dissolved in 100mL acetic acid, adds in high-pressure reactor.Be filled with hydrogen (5atm), be warming up to 40 DEG C of reactions 24 hours.Terminate reaction, filtrate revolving desolventizes, and adds 120mL20%NaOH solution, temperature rising reflux 2 hours.Dichloromethane extraction.Merge organic phase, dry, filter, be spin-dried for solvent, obtain product 26.4g, productive rate 81%.
1H NMR(CDCl
3/TMS,300MHz)δ(ppm):3.34(s,6H,-C(CH
2OCH
3)
2),3.44(s,4H,-C(CH
2OH)
2),3.64,3.66(s,4H,-C(CH
2OCH
3)
2)。
The synthesis of two (acetoxyl group methylene radical)-1, the 3-Propanal dimethyl acetal of compound 1:2,2-:
Two (the methoxymethylene)-1,3-PD of 24g (145mmol) 2,2-, 38g, 52.2mL (376mmol) triethylamine mixes, and adds in the trichloromethane of 150mL drying.29.52g, 26.73mL (376mmol) Acetyl Chloride 98Min. is dissolved in the trichloromethane of 90mL drying, and instillation wherein, keeps temperature-stable below 5 DEG C in dropping process, dropwises and rises to 30 DEG C of reactions 2 hours, is warming up to 50 DEG C of reactions 4 hours.Reaction terminates, and is spin-dried for solvent, adds 250mL ethyl acetate, solids removed by filtration.Add 300mL water, separatory, aqueous phase makes to be extracted with ethyl acetate twice, merges organic phase, anhydrous magnesium sulfate drying, and filter, be spin-dried for solvent, underpressure distillation obtains final product 30.1g, productive rate 83%.
1H NMR(CDCl
3/TMS,300MHz)δ(ppm):2.12(s,6H,-OCOCH
3),3.27(s,6H,-OCH
3),3.82(s,4H,-CH
2OCH
3),4.03(s,4H,-CH
2OCOCH
3)。
The synthesis of two (isobutyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of compound 2:2,2-:
Two (the methoxymethylene)-1,3-PD of 20g (122mmol) 2,2-, 30.36g (300mmol) triethylamine mixes, and adds the methylene dichloride of 150mL drying.31.2g (292.7mmol) isobutyryl chloride is dissolved in the methylene dichloride of 100mL drying, and instillation wherein, keeps temperature-stable below 5 DEG C, dropwises nature and rise to stirred overnight at room temperature in dropping process.Reaction terminates, and adds 300mL water, separatory, and aqueous phase uses dichloromethane extraction three times, merges organic phase, anhydrous magnesium sulfate drying, and filter, be spin-dried for solvent, underpressure distillation obtains final product 29.2g, productive rate 79%.
1H NMR(CDCl
3/TMS,300MHz)δ(ppm):1.16-1.25(d,12H,(-COCH(CH
3)
2)),2.51-2.60(m,2H,(-COCH(CH
3)
2)),3.30(s,6H,-OCH
3),3.36(s,4H,-CH
2OCH
3),4.09(s,4H,-CH
2OCOCH
2(CH
3)
2)。
The synthesis of two (benzoxy methylene)-1, the 3-Propanal dimethyl acetal of compound 3:2,2-:
Two (the methoxymethylene)-1,3-PD of 20g (122mmol) 2,2-, 30.36g (300mmol) triethylamine mixes, and adds the methylene dichloride of 120mL drying.41.1g (292.7mmol) Benzoyl chloride is dissolved in the methylene dichloride of 150mL drying, and instillation wherein, keeps temperature-stable below 5 DEG C, dropwises nature and rise to stirred overnight at room temperature in dropping process.Reaction terminates, and adds 300mL water, separatory, and aqueous phase uses dichloromethane extraction three times, merges organic phase, anhydrous magnesium sulfate drying, and filter, be spin-dried for solvent, underpressure distillation obtains final product 33.1g, productive rate 73%.
1H NMR(CDCl
3/TMS,300MHz)δ(ppm):3.31(s,6H,-OCH
3),3.54(s,4H,-CH
2OCH
3),4.49(s,4H,-CH
2OCOC
6H
5),7.34-7.42(m,4H,-C
6H
5),7.52-7.61(m,2H,-C
6H
5),7.7.96-8.08(m,4H,-C
6H
5)。
Two: application examples
Embodiment 1:
The preparation of alkoxyl magnesium
Prepared by alkoxyl magnesium: with in the 1L reactor of agitator, reflux condensing tube, thermometer and drop-burette, after fully replacing, add ethanol 550mL in reactor, Virahol 10mL with nitrogen, iodine 0.68g dissolves.Heat up after opening stirring, until reach the reflux temperature of reaction system.Then magnesium powder 32g is successively added; React to no longer including hydrogen discharge.Then carry out washing, filtering and drying, obtain tap density 0.25g/cm
3, the alkoxyl magnesium 147g of median size (D50) 47.0 μm.
The preparation of ingredient of solid catalyst:
Get above-mentioned obtained alkoxyl magnesium carrier 10g, toluene 50mL and 2.5g internal electron donor (compound 1 of above-mentioned preparation), be mixed with suspension; In the reactor repeating the 300mL replaced through high pure nitrogen, add toluene 40mL and titanium tetrachloride 60mL, then the suspension prepared is added in still, be warming up to 80 DEG C, constant temperature 1 hour is follow-up is continuously warming up to 115 DEG C, constant temperature after 2 hours by clean for liquid (mother liquor) press filtration.The mixed solution adding toluene 90mL and titanium tetrachloride 60mL is warming up to 110 DEG C of stir process 1 hour (titanium process), by clean for liquid (mother liquor) press filtration, the mixed solution adding toluene 120mL and titanium tetrachloride 30mL is again warming up to 110 DEG C of stir process 2 hours (titanium process), elimination liquid, the solid of gained washs 3 times at 55 DEG C with normal hexane 150mL, room temperature with n-hexane once, elimination liquid is also dry, obtains catalyst component 1-3 of the present invention.
Propylene polymerization
In 5 liters of autoclaves, after gas-phase propene is fully replaced, at room temperature add the hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of 5 milliliters of triethyl aluminums, the hexane solution (concentration of CHMMS is 0.10mmol/mL) of l milliliter Cyclohexyl Methyl Dimethoxysilane (CHMMS), 10mL anhydrous hexane and the above-mentioned ingredient of solid catalyst prepared of 10mg.Close autoclave, introduce the liquid propene that 4.5 standards rise hydrogen and 2L; In under agitation 10 minutes, temperature is risen to 70 DEG C.At 70 DEG C, polyreaction is after 1 hour, stops stirring, and removes unpolymerized propylene monomer, collected polymer.Catalyst activity is calculated with the ratio of the catalyst quality (g) used by the polymer quality (Kg) obtained.
Embodiment 2-3:
Internal electron donor, with embodiment 1, is changed to the compound 2 and 3, consumption 2.5g of above-mentioned preparation by step respectively in the process just prepared at ingredient of solid catalyst.
Comparative example 1:
Internal electron donor, with embodiment 1, is changed to n-butyl phthalate (DNBP), consumption 2.5g in the process just prepared at ingredient of solid catalyst by step.
The performance of table 1 catalyzer
In table, content
arefer to the mass percent of internal electron donor in catalyzer.
As can be seen from Table 1, catalyzer prepared by the catalyst component that use comprises ad hoc structure internal electron donor of the present invention (compound shown in the formula I of novel texture), with comparing containing n-butyl phthalate the most frequently used in prior art, not only increase the security of catalyzer, and significantly improve the melting index (meaning the hydrogen regulation performance that improve catalyzer) of polymkeric substance.When catalyst according to the invention is used for olefinic polymerization, there is suitable polymerization activity and the good advantage of stereotaxis ability, and the polymkeric substance obtained have high, the higher melting index of good degree of isotacticity and tap density.Especially there is high melting index, mean that catalyzer has good hydrogen regulation performance, be suitable for the exploitation of specific acrylic resin.According to novel catalyzer provided by the invention, there is excellent over-all properties, there is broad application prospect.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (13)
1. a compound, its structure such as formula shown in I,
In formula, R
1, R
2, R
3and R
4can be identical or not identical, be selected from substituted or unsubstituted C independently of one another
1-C
20alkyl, be preferably selected from substituted or unsubstituted C
1-C
10aliphatic group, C
3-C
10cycloalkyl, C
6-C
20aryl and C
7-C
20alkaryl; R
3and R
4connect into arbitrarily ring or not Cheng Huan.
2. compound according to claim 1, is characterized in that, described R
1and R
2for substituted or unsubstituted C
1-C
6alkyl.
3. compound according to claim 1 and 2, is characterized in that, described R
3and R
4be selected from substituted or unsubstituted C
1-C
6alkyl and C
6-C
12aryl.
4. according to the compound in claim 1-3 described in any one, it is characterized in that, the compound shown in described formula I is selected from two (acetoxyl group methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (propionyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (isobutyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (valeryl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1-methyl) butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (isoamyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((pivaloyl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (hexylyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1-methyl) valeryl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((2-methyl) valeryl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (dissident's acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1,1-dimethyl) butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (special hexylyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1,2-dimethyl) butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (allyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (benzoxy methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, be preferably selected from two (acetoxyl group methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (propionyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (isobutyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (valeryl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (isoamyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((pivaloyl oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, two (hexylyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (dissident's acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (special hexylyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two ((1,2-dimethyl) butyryl acyloxy methylene radical)-1, the 3-Propanal dimethyl acetal of 2,2-, two (allyl acyl-oxygen methylene)-1, the 3-Propanal dimethyl acetal of 2,2-and two (benzoxy methylene)-1, the 3-Propanal dimethyl acetal of 2,2-, more preferably 2 are selected from, two (the acetoxyl group methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the propionyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the butyryl acyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the isobutyl acyl-oxygen methylene)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the valeryl oxygen methylene)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the isoamyl acyl-oxygen methylene)-1 of 2-, 3-Propanal dimethyl acetal, 2, two ((the pivaloyl oxygen methylene)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the hexylyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the dissident's acyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the special hexylyloxy methylene radical)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the benzoxy methylene)-1 of 2-, 3-Propanal dimethyl acetal.
5., for a catalyst solid constituent for olefinic polymerization, comprise the compound shown in the formula I in titanium, magnesium, halogen and claim 1-4 described in any one.
6. catalyst solid constituent according to claim 5, is characterized in that, the content of described titanium is 1.0-8.0wt%, is preferably 1.6-6.0wt%; The content of described magnesium is preferably 10-70wt%, is preferably 15-40wt%; The content of described halogen is 20-85wt%, is preferably 30-80%; The content 2-30wt% of the compound shown in described formula I, preferred 3-20wt%.
7. the catalyst component according to claim 5 or 6, is characterized in that, described catalyst component comprises the reaction product in a solvent of the compound shown in magnesium compound, titanium compound and formula I.
8. catalyst solid constituent according to claim 7, is characterized in that, described magnesium compound is selected from formula M gR
4r
5shown magnesium compound, formula M gR
4r
5pH
2the hydrate of the magnesium compound shown in O and formula M gR
4r
5qR
6the alcohol adducts of the magnesium compound shown in OH, in general formula, R
4and R
5be selected from halogen, C independently of one another
1-C
8the alkoxyl group of straight or branched and C
1-C
8straight or branched alkyl; P and q is separately selected from 0.1-6, preferred 2-3.5; R
6for C
1-C
18alkyl, be preferably C
1-C
8alkyl, be more preferably selected from methyl, ethyl, n-propyl and sec.-propyl.
9. the catalyst solid constituent according to claim 7 or 8, is characterized in that, the general formula of described titanium compound is TiX
m(OR
7)
4-m, in formula, X is halogen, R
7for C
1-C
20alkyl, preferred C
1-C
5alkyl, m is the integer of 0-4, most preferably is titanium tetrachloride.
10., for a catalyzer for olefinic polymerization, it comprises the reaction product of following component:
A. the catalyst solid constituent in claim 5-9 described in any one;
B. organo-aluminium compound, is preferably general formula AlR'
n'x'
3-n'shown organo-aluminium compound, wherein, R' is selected from hydrogen, C
1-C
20alkyl and C
6-C
20aryl; X' is halogen, and n' is the integer of 1-3;
C. optionally, external donor compound, is preferably general formula R
1"
m "r
2"
n "si (OR
3")
4-m "-n "shown silicoorganic compound, in formula, R
1" and R
2" identical or different, be selected from independently of one another: halogen, hydrogen atom, C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; R
3" be selected from C
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl and C
1-C
20haloalkyl; M " and n " is respectively the integer of 0-3, and m "+n " <4.
11. catalyzer according to claim 10, it is characterized in that, the mol ratio of described organo-aluminium compound and catalyst solid constituent counts 5:1-5000:1 with aluminium/titanium, is preferably 20:1-1000:1, is more preferably 50:1-500:1; Aluminium in described organo-aluminium compound and the mol ratio of external donor compound are 0.1:1-500:1, preferred 1:1-300:1, more preferably 3:1-100:1.
12. 1 kinds of olefine polymerizing process, are polymerized under the effect of described alkene catalyzer described in catalyst solid constituent described in any one or claim 10 or 11 in claim 5-9.
13. methods according to claim 12, is characterized in that, described alkene general formula be CH
2=CHR, R are hydrogen or C
1-C
12alkyl, be preferably hydrogen or C
1-C
6alkyl, be preferably selected from ethene, propylene, 1-n-butene, the positive amylene of 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene, be more preferably selected from ethene, propylene and 1-butylene.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6118019A (en) * | 1994-09-28 | 2000-09-12 | Showa Denko K.K. | 3-alkoxypropionic ester derivative |
| CN1292800A (en) * | 1998-11-04 | 2001-04-25 | 蒙特尔技术有限公司 | Components and catalysts for polymerization of olefins |
-
2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6118019A (en) * | 1994-09-28 | 2000-09-12 | Showa Denko K.K. | 3-alkoxypropionic ester derivative |
| CN1292800A (en) * | 1998-11-04 | 2001-04-25 | 蒙特尔技术有限公司 | Components and catalysts for polymerization of olefins |
Non-Patent Citations (4)
| Title |
|---|
| ABDUL-RAHMAN ET AL.: "Pentaerythritol derivatives. V. Preparation of diethers of pentaerythritol by reduction of acetals and ketals", 《JOURNAL OF ORGANIC CHEMISTRY》, vol. 27, 31 January 1962 (1962-01-31), pages 67 - 70 * |
| STANLEY WAWZONEK ET AL.: "Formation of ethers in the preparation of pentaerythritol", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, vol. 70, 31 July 1948 (1948-07-31), pages 2433 - 2435 * |
| 王华等: "新型醚醋类内给电子体的合成与性能研究", 《石油化工》, vol. 37, 31 December 2008 (2008-12-31), pages 430 - 432 * |
| 美国化学会: "856344-18-8", 《REGISTRY 数据库》, 21 July 2005 (2005-07-21), pages 1 - 2 * |
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