CN1154372A - Alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer - Google Patents
Alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer Download PDFInfo
- Publication number
- CN1154372A CN1154372A CN 96110738 CN96110738A CN1154372A CN 1154372 A CN1154372 A CN 1154372A CN 96110738 CN96110738 CN 96110738 CN 96110738 A CN96110738 A CN 96110738A CN 1154372 A CN1154372 A CN 1154372A
- Authority
- CN
- China
- Prior art keywords
- compound
- alpha
- ether
- alkyl
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
An alpha -olefin polymerization catalyst comprising (A) a solid catalyst component containing a tri-valent titanium compound whose preparation is as defined in the specification, (B) an organoaluminum compound and (C) an electron donative compound, and a process for producing an alpha -olefin polymer with said alpha -olefin polymerization catalyst.
Description
The method that the present invention relates to a kind of alpha-olefin polymerization catalyst and produce alpha-olefinic polymer.Especially, the present invention relates to obtain the alpha-olefin polymerization catalyst of the alpha-olefinic polymer of highly stereoregular, this polymkeric substance only contains a spot of especially residual catalyst and amorphous polymer, and have good mechanical property and a workability, in methods such as slurry polymerization, mass polymerization, vapour phase polymerization, each solid catalyst of described catalyzer and each titanium atom all have very high catalytic activity, relate to the method with described Catalyst Production highly stereoregular alpha-olefinic polymer in addition.
As the method for producing as the polymkeric substance of alpha-olefins such as propylene, 1-butylene, people have known can use the catalyzer that is referred to as Ziegler-Natta type, and this catalyzer contains the transistion metal compound and the 1st of 4-6 family in the periodic table of elements, the organometallic compound of the 2nd and the 13rd family.
In the production of alpha-olefinic polymer, remove highly stereoregular alpha-olefine polymerizing beyond the region of objective existence, also can generate amorphous polymer as by product, the highly stereoregular alpha-olefin has higher value in industrial application.The value of this amorphous polymer in industrial application is very low, and when the machine-shaping with alpha-olefinic polymer is moulded products, film, fiber and other formed article, mechanical property is had very big bad influence.The formation of amorphous polymer has caused the monomeric loss of starting material, also the equipment that is used for removing amorphous polymer must be arranged simultaneously, and from the viewpoint of industry, this is a king-sized shortcoming.Therefore need a kind of catalyzer of producing alpha-olefinic polymer, it does not form or seldom forms amorphous polymer.
In the alpha-olefinic polymer that is obtained, the catalyzer that contains transistion metal compound and organometallic compound can residually be arranged.Because these catalyst residues can produce variety of issue, as influence the stability of alpha-olefinic polymer and processing characteristics etc.Therefore must there be the equipment of removing catalyst residue to come stabilization of polymer.Because this defective can be improved by the catalytic activity that the weight that improves the alpha-olefinic polymer of being produced by the catalyzer of per unit weight is represented, so the above-mentioned equipment that is used for removing catalyst residue is just unnecessary, the production cost that reduces alpha-olefinic polymer also becomes possibility.
Know, by using the Ti-Mg compounding solid catalyst, the highly stereoregular of alpha-olefin and high reactivity polymerization can realize to a certain extent, this catalyzer is to reduce tetravalent titanium compound with organo-magnesium compound under the bar that has silicoorganic compound to exist, and formation magnesium-titanium eutectic mixture obtains, also be used in combination organo-aluminium compound as promotor in polymerization, silicoorganic compound are as the 3rd component.(Japanese Patent (careful) flat 3-43283 (1991), flat 1-319508 (1989)).
Under any circumstance, non-extraction and non-deliming process are on a possible level, yet it is desirable further improving.Specifically, in order to produce high-quality alpha-olefinic polymer, the Ziegler-Natta type polymerization that realization degree is higher is not sacrificed size distribution simultaneously, and this is desirable.Particularly in as forming field, wish to produce the polymkeric substance of high rigidity, and the highly stereoregular polymkeric substance can directly obtain high rigidity, so the more catalyzer of high stereospecific polymerization appears having in special hope.In actual applications, when using the such solid catalyst of Ziegler-Natta type, for loose density, particle diameter and the flowability of controlling polymers, coating of particles particularly important.About improving coating of particles, in order to overcome this problem, people attempt in vinyl polymerization, use the solid catalyst (Japanese Patent (not examining) clear and 54-148098 (1979) and clear and 56-47407 (1981)) that obtains on the silica gel by titanium-magnesium compound is deposited in.
Existing people draws, and in polyacrylic polymerization, can improve particle properties widely by using the solid catalyst (the clear and 62-256802 (1987) of Japanese Patent (not examining)) that titanium-magnesium compound is immersed on the silica gel.According to this method, can see the obvious improvement of particle shape really.Yet, stay in the product as the silica gel of carrier, can in the film forming application of system, form flake, this is undesirable.
Among the clear and 63-289004 alpha-olefin polymerization catalyst has been proposed at Japanese Patent (examine), it comprises: the solid catalytic ingredient that (A) contains titanous, it is by using earlier ester cpds, obtain with a kind of solid phase prod of the mixture process of ether compound and titanium tetrachloride then, this solid phase prod is under the condition that has silicoorganic compound and porous polymer particle to exist, and reduces Ti (OR with organo-magnesium compound
1)
aX
4-a(R
1Represent the alkyl that 1-20 carbon atom arranged, X represents halogen atom, and a represents it is a number that satisfies 0＜a≤4) obtain, described silicoorganic compound have the Si-O key, the aperture of described porous polymer particle is 100-5000A °, and micro pore volume is 0.1cc/g or bigger; (B) organo-aluminium compound; (C) electronic donor compound capable obviously improves the alpha-olefinic polymer coating of particles that obtains, and does not cause the inorganic oxide that forms flake and do not contain.
Yet in these methods, the stereospecific that further improves activity of such catalysts and the alpha-olefinic polymer of being produced is necessary.
An object of the present invention is to provide a kind of alpha-olefin polymerization catalyst that can obtain having the high stereospecific degree, described polymkeric substance have high bulk density, fine powder few, do not contain the mineral compound that can in the system film is used, produce flake as silica gel etc., described catalyzer should have sufficiently high catalytic activity so that needn't remove catalyst residue and amorphous polymer, and a kind of high-quality method with alpha-olefinic polymer of high stereospecific degree of producing also is provided.
According to the present invention, a kind of alpha-olefin polymerization catalyst is provided, it comprises: the solid catalytic ingredient that (A) contains titanous, it is by using earlier ester cpds, a kind of solid phase prod of the mixture process of the mixture of usefulness ether compound and titanium tetrachloride or ether compound, titanium tetrachloride and ester cpds obtains then, this solid phase prod is under the condition that has silicoorganic compound and porous polymer particle to exist, and reduces Ti (OR with organo-magnesium compound
1)
aX
4-a(R
1Represent the alkyl that 1-20 carbon atom arranged, X represents halogen atom, and a represents it is a number that satisfies 0＜a≤4) obtain, described silicoorganic compound have the Si-O key, the aperture of described porous polymer particle is 100-5000 , and micro pore volume is 0.1cc/g or bigger; (B) organo-aluminium compound; (C) electronic donor compound capable provides a kind of method of utilizing the multipolymer of described Catalyst Production alpha-olefin homo or a kind of alpha-olefin and another kind of alpha-olefin in addition.
By using this catalyzer, can reach above-mentioned purpose, particularly realize the highly stereoregular polymerization of alpha-olefin.
To describe the present invention in detail below.
Fig. 1 is convenient to understand schema of the present invention.This schema has been represented one embodiment of the invention.
(a) titanium compound
In the present invention, be used for the titanium compound of synthesis of solid catalyst component (A) with general formula Ti (OR1)
aX
4-a(R
1Represent the alkyl that 1-20 carbon atom arranged, the X table Show halogen atom, a represents it is a number that satisfies 0＜a≤4) representative. R1Comprise alkane Base is such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, penta Base, isopentyl, tertiary pentyl, hexyl, heptyl, octyl group, decyl, dodecyl etc.; Or aryl, such as phenyl, tolyl, xylyl, naphthyl etc.; Or alkenyl, such as third Thiazolinyl etc.; Aralkyl, such as benzyl etc., or its analog. Wherein, there is 2-18 carbon former The alkyl of son and the aryl of 6-18 carbon atom is arranged is preferably preferably has 2-especially The straight chained alkyl of 18 carbon atoms. Can use and have 2 or a plurality of different OR1Group Titanium compound.
Halogen atom with the X representative can comprise chlorine, bromine or iodine, and wherein chlorine can obtain preferably The result.
Using general formula Ti (OR1)
aX
4-nIn the titanium compound of representative, a is one to expire Foot 0＜a≤4, the number of preferred 2≤a≤4, especially preferred a=4.
As the synthetic general formula Ti (OR that uses
1)
aX
4-nThe method of the titanium compound of representative can be utilized a kind of known method.For example, can use Ti (OR
1)
4With TiX
4With the method for estimated rate reaction, or TiX
4Alcohol (R with predetermined amount
1OH) Fan Ying method.As titanium compound, can be with the diluting soln of its hydrocarbon compound or halogenated hydrocarbon compound.
With general formula Ti (OR
1)
aX
4-nThe example of the titanium compound of representative comprises: alkoxyl group three halogenated titanium compounds, and as the methoxyl group titanous chloride, oxyethyl group titanous chloride, butoxy titanous chloride, phenoxy group titanous chloride, oxyethyl group titanium tribromide etc.; Dialkoxy dihalide titanium compound, as the dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, two phenoxy group titanium dichloride, diethoxy dibrominated titanium etc.; Tri-alkoxy one halogenated titanium compound, as the trimethoxy titanium chloride, triethoxy titanium chloride, three butoxy titanium chlorides, triple phenoxyl titanium chloride, triethoxy titanium bromide etc.; Four alkoxy titanium compounds, as the tetramethoxy titanium, purity titanium tetraethoxide, four titanium butoxide, four phenoxide titaniums etc.(b) contain the silicoorganic compound of Si-O key
The example that contains the silicoorganic compound of Si-O key at its molecule that is used for synthetic solid catalytic ingredient of the present invention comprises the compound of representing with following general formula: Si (OR
2)
mR
3 4-mR
4(R
5 2SiO)
pSiR
6 3(R
7 2SiO)
qR wherein
2Be the alkyl that 1-20 carbon atom arranged, R
3, R
4, R
5, R
6, R
7Be alkyl or the hydrogen atom that 1-20 carbon atom arranged, m is a number that satisfies 0＜m≤4, and p is the integer of a 1-1000, and q is the integer of a 2-1000.The example of silicoorganic compound comprises tetramethoxy-silicane, dimethyldimethoxysil,ne, tetraethoxysilane, triethoxy ethyl silane, diethoxy diethylsilane, ethoxy triethyl silane, tetraisopropoxysilan, diisopropoxy di-isopropyl silane, tetrapropoxysilane, dipropoxy dipropyl silane, four butoxy silanes, dibutoxy dibutyl silane, two cyclopentyloxy diethylsilanes, diethoxy diphenyl silane, the cyclohexyloxy trimethyl silane, phenoxy trimethyl silicone alkane, tetraphenoxy-silicane alkane, triethoxyphenylsilan, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyl trisiloxanes, dimethyl polysiloxane, the phenylbenzene polysiloxane, methylhydrogenpolysi,oxane, phenyl hydrogen polysiloxanes etc.
In these silicoorganic compound, Si (OR
2)
mR
3 4-mThe organoalkoxysilane of representative is preferred, and preferred 1≤m≤4, and the tetraalkoxysilane of m=4 is particularly preferred.(C) porous polymer particle
The example that is used in the porous polymer particle in the component of the present invention (A) comprises polystyrene, polyacrylic ester, polymethacrylate, polyacrylonitrile, polyvinyl chloride, the porous polymer particle of polyolefine etc.Concrete example comprises polystyrene, the multipolymer of vinylbenzene-Vinylstyrene, vinylbenzene-N-N '-alkylidene group DMAA multipolymer, vinylbenzene-methyl di glycol ester multipolymer, polymethacrylate, poly-ethyl propylene acid esters, the multipolymer of methacrylic acid ester-Vinylstyrene, the multipolymer of ethyl propylene acid esters-Vinylstyrene, poly-methyl methacrylic acid ester, the multipolymer of methyl methacrylic acid ester-Vinylstyrene, polydimethyl methylacrylic acid glycol ester, polyacrylonitrile, the multipolymer of vinyl cyanide-Vinylstyrene, polyvinyl chloride, Polyvinylpyrolidone (PVP) (pyroridine), polyvinylpyridine, the multipolymer of vinyl xylene, ethyl vinyl benzene-Vinylstyrene, polyethylene, the multipolymer of ethylene-methyl acrylate, polypropylene etc.In these porous polymer particles, preferably use as polystyrene polyvinyl chloride, the porous polymer particle of polyolefine and polyacrylonitrile, further preferred polystyrene, the multipolymer of vinylbenzene-Vinylstyrene and the porous polymer particle of polyvinyl chloride of using.The median size of these polymer particles is preferably 5-1000 μ, and more preferably 10-600 μ most preferably is 15-500 μ.Micropore size is that the micro pore volume of 100-5000 is 0.1cc/g or higher, preferred 0.2cc/g or higher, preferred especially 0.25cc/g or higher.The porous polymer particle of planar water has been removed in further preferred use.Specifically, with its vacuum-drying under about 80 ℃ or higher temperature, or with the organometallic compound of aforementioned as organic magnesium compound etc., under about 60 ℃ or higher temperature, handle the exsiccant particulate.(d) ester cpds
Ester cpds as using in the present invention can use unit price or polyvalent carboxylicesters, and its example can comprise the representative examples of saturated aliphatic carboxylic ester, unsaturated aliphatic carboxylicesters, alicyclic carboxylic ether and aromatic carboxylic acid esters.Its concrete example comprises methyl acetate, ethyl acetate, phenylacetate, methyl propionate, ethyl propionate, ethyl butyrate, Valeric acid ethylester, methyl acrylate, ethyl propenoate, methyl methacrylate, ethyl benzoate, butyl benzoate, the toluic acid methyl esters, ethyl toluate, methoxybenzoic acid ethyl ester, ethyl succinate, dibutyl succinate, diethyl malonate, butyl ethyl malonate, dimethyl maleate, dibutyl maleinate, the methylene-succinic acid oxalic acid, dibutyl itaconate, phthalic acid mono ethyl ester, dimethyl phthalate, phthalic acid methyl ethyl ester, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, dinoctyl phthalate, diphenyl phthalate etc.
In these ester cpds, as methacrylic acid ester, unsaturated aliphatic carboxylic acid such as maleic acid ester and phthalic ester are preferred, and Bisphthalate is particularly preferred.(e) organo-magnesium compound
As organo-magnesium compound, can be used on any organo-magnesium compound that contains the Mg-carbon bond in the molecule in the present invention.
Especially, can preferably use by general formula R
8MgX (R
8Be the alkyl that 1-20 carbon atom arranged, X is a halogen atom) representative Grignard compound and by general formula R
9R
10Mg (R
9And R
10Be the alkyl that 1-20 carbon atom arranged) representative dialkyl magnesium compound or diaryl magnesium compound.
R
8, R
9And R
10Can be identical or different, its example includes the alkyl of 1-20 carbon atom, aryl, aralkyl and alkenyl, as methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, amyl group, isopentyl, hexyl, octyl group, 2-ethylhexyl, phenyl, benzyl etc.
The example of Grignard compound comprises methylmagnesium-chloride, ethylmagnesium chloride, ethylmagnesium bromide, the ethyl magnesium iodide, propyl group magnesium chloride, propyl group magnesium bromide, butylmagnesium chloride, butyl magnesium bromide, sec-butyl chlorination magnesium, sec-butyl bromination magnesium, tertiary butyl chlorination magnesium, tertiary butyl bromination magnesium, the amyl group magnesium chloride, isopentyl chlorination magnesium, hexyl magnesium chloride, phenyl-magnesium-chloride, phenyl-magnesium-bromide etc. are by general formula R
9R
10The compound of Mg representative comprises dimethyl magnesium, magnesium ethide, dipropyl magnesium, di-isopropyl magnesium, dibutylmagnesium, di-secondary dibutyl magnesium, di-t-butyl magnesium, butyl-sec-butyl magnesium, diamyl magnesium, dihexyl magnesium, diphenyl magnesium, butyl ethyl magnesium etc.
As the solvent of synthetic above-mentioned organo-magnesium compound, available ether solvents, as Anaesthetie Ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, hexyl ether, dicaprylyl ether, diphenyl ether, dibenzyl ether, phenyl ethyl ether, methyl-phenoxide, tetrahydrofuran (THF) etc.Available hydrocarbon solvent, as hexane, heptane, octane, hexanaphthene, methylcyclohexane, benzene, toluene, dimethylbenzene etc., the mixed solvent of also available ether and hydrocarbon.
Preferably under the condition of ethereal solution, use organo-magnesium compound,, use ether compound or cyclic ether compounds that 6 or more a plurality of carbon atoms are arranged in the molecule as ethereal solution.From the viewpoint of catalytic capability, preferably use by general formula R
8The Grignard compound of MgX representative is as ethereal solution.And can use above-mentioned organo-magnesium compound and the mixture that can be dissolved in the organometallic compound of hydrocarbon.As the example of these organometallic compounds, the organic compound of Li, Be, B, Al or Zn is arranged.(f) ether compound
As ether compound used in this invention, available dialkyl ether is as Anaesthetie Ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, di neo-pentyl ether, hexyl ether, dicaprylyl ether, methyl butyl ether, the methyl isoamyl ether, ethyl isobutyl ether etc.Wherein, dibutyl ether and diamyl ether are particularly preferred.(g) solid catalyst level part is synthetic
Solid catalytic ingredient of the present invention, be by using earlier ester cpds, come synthetic with the mixture of ether compound and titanium tetrachloride or a kind of solid phase prod of mixture process of ether compound, titanium tetrachloride and ester cpds then, this solid phase prod is that porous polymer particle is being arranged, under the condition that silicoorganic compound and ester cpds exist, obtain with organo-magnesium compound reduction titanium compound.All these building-up reactionss all are to carry out in the inert atmosphere as nitrogen, argon gas etc.
Solid phase prod is that porous polymer particle is being arranged, and under the condition that silicoorganic compound and ester cpds exist, with organo-magnesium compound reduction titanium compound synthetic, at this moment, because reduction reaction, deposition of solids is on porous polymer particle.Solid phase prod has kept poromeric shape, does not preferably form fine particle.
As method with organo-magnesium compound reduction titanium compound, or add organo-magnesium compound to titanium compound, silicoorganic compound, in the mixture of porous polymer particle and ester cpds, perhaps on the contrary with titanium compound, the mixture of silicoorganic compound and ester cpds adds in the mixture of organo-magnesium compound solution and porous polymer particle.From the viewpoint of activity of such catalysts, in these, add organo-magnesium compound to titanium compound, this method is preferred in the mixture of silicoorganic compound porous polymer particle and ester cpds.
Titanium compound, silicoorganic compound, porous polymer particle and ester cpds preferably use in the solution of appropriate solvent or diluent.These solvents comprise aliphatic hydrocarbon, as hexane, and heptane, octane, decane etc.; Aromatic hydrocarbons, as toluene, dimethylbenzene etc.; Alicyclic hydrocarbon, as hexanaphthene, methylcyclohexane, naphthalane etc.; Ether compound, as Anaesthetie Ether, dibutyl ether, diisoamyl ether, tetrahydrofuran (THF) etc.
Reduction temperature is-50 to 70 ℃, preferred-30 to 50 ℃, and preferred-25 to 35 ℃ especially.Reduction temperature is too high, and catalytic activity can reduce.
The dropping time is not particularly limited, and can be about 30 minutes to 12 hours.After reduction reaction is finished, can under 20-120 ℃, carry out postreaction (postreaction).
For the consumption of silicoorganic compound, be benchmark with the atom ratio (Si/Ti) of the titanium atom in Siliciumatom and the titanium compound, preferred 1-50, further preferred 3-30, preferred especially 5-25.For the consumption of ester cpds, (ester cpds/Ti) is a benchmark, preferred 0.05-10, further preferred 0.1-6, preferred especially 0.2-3 with the molar ratio of titanium atom in ester cpds and the titanium compound.Outside a little,, be benchmark with the total amount of Siliciumatom and titanium atom and the ratio of magnesium atom (Ti+Si/Mg) for the consumption of organo-magnesium compound, preferred 0.1-10, further preferred 0.2-5.0, preferred especially 0.2-2.0.Weight with solid phase prod is benchmark, the used preferred 20-95% of poromeric amount (weight), more preferably 30-85% (weight).
The solid phase prod that obtains by reduction reaction separates with solid-liquid isolation method, and with repeatedly washing as unreactive hydrocarbons solvents such as hexane, heptane.
Next, the solid phase prod that obtains by above mentioned method is handled with ester cpds.With respect to each mole titanium atom in the solid phase prod, preferably use 0.1-50mol, more preferably use 0.3-20mol, the ester cpds of preferred especially 0.5-10mol.With respect to the magnesium atom of each mole in the solid phase prod, the preferred 0.01-1.0mol of the amount of ester cpds, more preferably 0.03-0.5mol.
Handling solid phase prod with ester cpds can carry out with any known method that solid phase prod is contacted with ester cpds, as slurry method, or utilizes the method etc. of ball mill mechanical mill.Yet when utilizing mechanical mill, solid catalytic ingredient can form a large amount of particulates, and it is very wide that the distribution of particle diameter becomes, and from the viewpoint of industry, this is not preferred, but the contact to both is preferred under the condition that has thinner to exist.
As thinner, available aliphatic hydrocarbon, as pentane, hexane, heptane, octane etc., aromatic hydrocarbon, as benzene, toluene, dimethylbenzene etc., alicyclic hydrocarbon, as hexanaphthene, pentamethylene etc., halohydrocarbon, as 1,2-ethylene dichloride, mono chloro benzene etc.Wherein, aromatic hydrocarbon and halohydrocarbon are particularly preferred.
With respect to every gram solid phase prod, the preferred 0.1ml-1000ml of the consumption of thinner, more preferably 1ml-100ml.Preferred-50 to 150 ℃ of treatment temp, more preferably 0 to 120 ℃.Preferred 5 minutes of the treatment time or longer, further preferred 15 minutes to 3 hours.After finishing dealing with, the solid of handling is left standstill, from liquid phase, isolate solid, then, with the inert solvent washing several times, obtain the solid of handling with ester.Then, will use the mixture process of ether compound and titanium tetrachloride with the solid that ester was handled.This processing is preferably carried out under slurry condition, and the solvent that is used for slurries comprises aliphatic hydrocarbon, as pentane, and hexane, heptane, octane, decane etc., aromatic hydrocarbon, as toluene, dimethylbenzene etc., alicyclic hydrocarbon, as hexanaphthene, methylcyclohexane, naphthalane etc., halohydrocarbon, as ethylene dichloride, trieline, mono chloro benzene, dichlorobenzene, trichlorobenzene etc.Wherein, halohydrocarbon and aromatic hydrocarbon are particularly preferred.
The concentration of slurries is preferably 0.05-0.7g solid/ml-solvent, further preferred 0.1-0.5g solid/ml-solvent.The preferred 30-150 of temperature of reaction ℃, further preferred 40-135 ℃, preferred 60-120 ℃ especially.Reaction times is not particularly limited.Yet, preferred about 30 minutes to 6 hours usually.
As a kind of solid charging process of handling with ester, ether compound and titanium tetrachloride, or ether compound and titanium tetrachloride added on the solid that ester handled, or in contrast, the solid that ester was handled adds in the solution of ether compound and titanium tetrachloride, and these two kinds of methods can be used.In the method on ether compound and titanium tetrachloride being added to the solid that ester handled, after adding ether compound, add titanium tetrachloride again, perhaps add ether compound and titanium tetrachloride simultaneously, these two kinds of methods all are preferred, but this method of mixture of the previously prepared ether compound of interpolation and titanium tetrachloride is particularly preferred in the solid that ester was handled.
The solid of handling with ester and the reaction of ether compound and titanium tetrachloride can repeat twice or repeatedly.From the viewpoint of catalyst activity and stereospecific, preferably repeat at least twice with the reaction of the mixture of ether compound and titanium tetrachloride.
Contained each mole titanium atom in the relative solid phase prod, the preferred 0.1-100mol of the consumption of ether compound, further preferred 0.5-50mol, preferred especially 1-20mol.Contained each mole titanium atom in the relative solid phase prod, the preferred 1-1000mol of the consumption of titanium tetrachloride, further preferred 3-500mol, preferred especially 10-300mol.Relative each mole ether compound, the preferred 1-100mol of the consumption of titanium tetrachloride, further preferred 1.5-75mol, preferred especially 2-50mol.
Ester cpds can coexist in the solid process of handling with ester with the mixture process of ether compound and titanium tetrachloride.Relative contained each mole titanium atom in the solid phase prod, the preferred 30mol of the consumption of ester cpds or still less, further preferred 15mol or still less, preferred especially 5mol or still less.
The solid catalyst that contains trivalent titanium compound that utilizes the aforesaid method acquisition is through solid-liquid separation, again with as the washing of inert solvents such as hexane, heptane several times, to be used for carrying out polymerization.From catalytic activity and stereoregular viewpoint, after solid-liquid separation, solid catalyst is preferably under 50-120 ℃ temperature, with a large amount of as mono chloro benzene etc. halohydrocarbon or as the aromatic hydrocarbon solvent washing one or many of toluene etc., then, use aliphatic solvents, as hexane, washing such as heptane is used further to polymerization several times afterwards.(h) organo-aluminium compound (B)
The organo-aluminium compound that is used for the present invention has an Al-carbon bond at least in its molecule.Typical organo-aluminium compound is represented with following general formula: R
11 γAlY
3-γAnd R
12R
13Al-O-AlR
14R
15R wherein
11-R
15Representative has the alkyl of 1-20 carbon atom, and Y represents halogen, hydrogen or alkoxyl group, and γ is a number that satisfies 2≤γ≤3.
The example of organo-aluminium compound comprises trialkylaluminium, as triethyl aluminum, and triisobutyl aluminium, three hexyl aluminium etc.; The dialkyl group aluminum hydride, as ADEH, diisobutyl aluminium hydride etc.; Dialkylaluminum halides is as diethyl aluminum chloride etc.; The mixture of trialkylaluminium and dialkylaluminum halides is as the mixture of triethyl aluminum and diethyl aluminum chloride; Alkylaluminoxane (alkylalumoxanes), as tetraethyl-two aikyiaiurnirsoxan beta, the tetrabutyl two aikyiaiurnirsoxan beta etc.
In these organo-aluminium compounds, trialkylaluminium, the mixture of trialkylaluminium and dialkylaluminum halides and alkylaluminoxane are preferred, particularly preferably be triethyl aluminum, triisobutyl aluminium, the mixture of triethyl aluminum and diethyl aluminum chloride, tetraethyl-two aikyiaiurnirsoxan beta.
Each mole titanium atom that is contained in the relative solid catalyst, the optional 0.5-1000mol of the consumption of organo-aluminium compound, particularly preferred scope is 1-600mol.(c) electronic donor compound capable (C)
Be used for the polymeric electronic donor compound capable in the present invention, available oxygen containing electron donor(ED) is as the ester of alcohol, phenol, ketone, aldehyde, carboxylic acid, organic or inorganic acid, ether, acid amides (acid amides), acid anhydride etc.; Nitrogenous electron donor(ED) is as ammonia, amine, nitrile, isocyanide ester (isocyanates) etc.; With and analogue etc.Wherein, inorganic acid ester and ether are preferred.
Preferred inorganic acid ester is the silicoorganic compound with following general formula representative: R
16 nSi (OR
17)
4-n, wherein, R
16Be alkyl or the hydrogen that 1-20 carbon atom arranged, R
17Be the alkyl that 1-20 carbon atom arranged, R in a part
16, R
17Can be different, n is a number that satisfies 0≤n＜4.Its example comprises tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, tetraphenoxy-silicane alkane, methyltrimethoxy silane, ethyl trimethoxy silane, butyl trimethoxy silane, the isobutyl-Trimethoxy silane, tert-butyl trimethoxy silane, the sec.-propyl Trimethoxy silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, vinyltrimethoxy silane, dimethyldimethoxysil,ne, diethyl dimethoxy silane, dipropyl dimethoxy silane, the propyl group methyl dimethoxysilane, diisopropyl dimethoxy silane, dibutyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane, butyl methyl dimethoxy silane, butyl ethyl dimethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl ethyl dimethoxy silane, tertiary butyl n-propyl dimethoxy silane, isobutyl-sec.-propyl dimethoxy silane, tertiary butyl sec.-propyl dimethoxy silane, tertiary butyl normal-butyl dimethoxy silane, tertiary butyl isobutyl-dimethoxy silane, tertiary butyl sec-butyl dimethoxy silane, hexyl methyl dimethoxy silane, hexyl ethyl dimethoxy silane, dodecyl methyl dimethoxy silane, dicyclopentyl dimethoxyl silane, cyclopentyl-methyl dimethoxy silane, cyclopentyl ethyl dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silicon-alkane, cyclopentyl isobutyl-dimethoxy silane, cyclopentyl tertiary butyl dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclohexyl isobutyl-dimethoxy silane, cyclohexyl tertiary butyl dimethoxy silane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl phenyl dimethoxy silane, dimethoxydiphenylsilane, phenyl methyl dimethoxy silane, propyloxy phenyl base dimethoxy silane, phenyl isobutyl-dimethoxy silane, phenyl tertiary butyl dimethoxy silane, benzyl ring amyl group dimethoxy silane, the vinyl methyl dimethoxysilane, Union carbide A-162, ethyl triethoxysilane, the butyl triethoxyl silane, the isobutyl-triethoxyl silane, tertiary butyl triethoxyl silane, the sec.-propyl triethoxyl silane, the cyclohexyl triethoxyl silane, phenyl triethoxysilane, vinyltriethoxysilane, dimethyldiethoxysilane, the diethyl diethoxy silane, the dipropyl diethoxy silane, the propyl group methyldiethoxysilane, the di-isopropyl diethoxy silane, the dibutyl diethoxy silane, the diisobutyl diethoxy silane, the di-t-butyl diethoxy silane, the butyl methyl diethoxy silane, the butyl ethyl diethoxy silane, tertiary butyl methyldiethoxysilane, the hexyl methyl diethoxy silane, hexyl ethyl diethoxy silane, the dodecyl methyl diethoxy silane, two cyclopentyl diethoxy silanes, the dicyclohexyl diethoxy silane, the cyclohexyl methyl diethoxy silane, cyclohexyl ethyl diethoxy silane, the phenylbenzene diethoxy silane, the phenyl methyl diethoxy silane, the vinyl methyldiethoxysilane, ethyl three isopropoxy silane, vinyl three butoxy silanes, phenyl three tert.-butoxy silane, the basic Trimethoxy silane of 2-norbornane (norbornane), 2-norbornane (norbornane) ethyl triethoxy silicane alkane, 2-norbornane (norbornane) ylmethyl dimethoxy silane, trimethyl phenoxysilane, methyl three aryloxy silanes etc.
Preferably with the dialkyl ether and the diether compounds of following general formula representative:
Wherein, R
18-R
21Be respectively the alkyl that 1-20 carbon atom arranged, alicyclic radical, aryl, alkaryl or aralkyl straight chain or side chain, R
18Or R
19Can be hydrogen.The example comprises Anaesthetie Ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ether, diamyl ether, diisoamyl ether, di neo-pentyl ether, hexyl ether, dicaprylyl ether, methyl butyl ether, the methyl isoamyl ether, the ethyl isobutyl ether, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-3,7-dimethyl octyl group-1, the 3-Propanal dimethyl acetal, 2,2-di-isopropyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclohexyl methyl-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1, the 3-Propanal dimethyl acetal, 2,2-di-isopropyl-1, the 3-Propanal dimethyl acetal, 2,2-dipropyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclohexyl-1, the 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2-heptyl-2-amyl group-1,3-Propanal dimethyl acetal etc.
In these electronic donor compound capables, use general formula R
22R
23Si (OR
24)
2The silicoorganic compound of representative are preferred.(R wherein
22Be the alkyl that 3-20 carbon atom arranged, the carbon atom that links to each other with Si is the second month in a season or tertiary carbon atom, and its example comprises branched-chain alkyl, as sec.-propyl, sec-butyl, the tertiary butyl, tert-pentyl etc.; Cycloalkyl is as cyclopentyl, cyclohexyl etc.; Cycloalkenyl group (cycloalkenyl) is as cyclopentenyl etc.; Aryl is as phenyl, tolyl etc.R
23Be the alkyl that 1-20 carbon atom arranged, its example comprises straight chained alkyl, as methyl, ethyl, propyl group, butyl, amyl group etc.; Branched-chain alkyl, as sec.-propyl, sec-butyl, the tertiary butyl, tert-pentyl etc., cycloalkyl is as cyclopentyl, cyclohexyl etc.; Cycloalkenyl group is as cyclopentenyl etc.; Aryl is as phenyl, tolyl etc.R
24Be the alkyl that 1-20 carbon atom arranged, preferred alkyl has 1-5 carbon atom.)
The example that is used as the silicoorganic compound of electronic donor compound capable comprises diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl ethyl dimethoxy silane, tertiary butyl n-propyl dimethoxy silane, isobutyl-sec.-propyl dimethoxy silane, tertiary butyl sec.-propyl dimethoxy silane, tertiary butyl normal-butyl dimethoxy silane, tertiary butyl isobutyl-dimethoxy silane, tertiary butyl sec-butyl dimethoxy silane, dicyclopentyl dimethoxyl silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl isobutyl-dimethoxy silane, cyclopentyl tertiary butyl dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl ethyl dimethoxy silane, cyclohexyl sec.-propyl dimethoxy silane, cyclohexyl isobutyl-dimethoxy silane, cyclohexyl tertiary butyl dimethoxy silane, cyclohexyl ring amyl group dimethoxy silane, cyclohexyl phenyl dimethoxy silane, dimethoxydiphenylsilane, phenyl methyl dimethoxy silane, propyloxy phenyl base dimethoxy silane, phenyl isobutyl-dimethoxy silane, phenyl tertiary butyl dimethoxy silane, benzyl ring amyl group dimethoxy silane, the di-isopropyl diethoxy silane, the diisobutyl diethoxy silane, the di-t-butyl diethoxy silane, tertiary butyl methyldiethoxysilane, two cyclopentyl diethoxy silanes, the dicyclohexyl diethoxy silane, the cyclohexyl methyl diethoxy silane, cyclohexyl ethyl diethoxy silane, the phenylbenzene diethoxy silane, the phenyl methyl diethoxy silane, 2-norbornane ylmethyl dimethoxy silane etc.(j) polymerization process of alkene
Be used for alpha-olefin of the present invention and be having the alpha-olefin of 3 or more a plurality of carbon atoms, its example comprises straight chain mono-olefins, as propylene, butene-1, amylene-1, hexene-1, heptene-1, octene-1, decylene-1 etc.; The side chain monoolefine is as 3-methyl butene-1,3-methylpentene-1,4-methylpentene-1 etc.; Vinyl cyclohexane etc.These alpha-olefins can use separately, or two or more are used in combination.In these alpha-olefins, preferred propylene or butene-1 carry out homopolymerization, or carry out copolymerization in order to the mixed olefins of the main component of propylene conduct, especially preferably carry out homopolymerization with propylene, or carry out copolymerization in order to the mixed olefins of the main component of propylene conduct.In copolymerization of the present invention, can and be selected from the mixture of at least a alpha-olefin in the above-mentioned alpha-olefin with ethene.In this external copolymerization, can use the compound of 2 or a plurality of unsaturated link(age)s, as conjugated diene and non-conjugated diene hydrocarbon.Assorted-the block copolymerization (hetero-block copolymerization) that contains two or more polymerization procedures can be carried out at an easy rate.
Except that adding with drying regime under as inert atmospheres such as nitrogen, argon gas, the method that every kind of catalyst grade part joins in the aggregation container has no particular limits.
Solid catalytic ingredient (A), organo-aluminium compound (B) and electronic donor compound capable (C) can add separately, and perhaps any two kinds of contacts earlier in them add then.
In the present invention, can under the condition that has above-mentioned catalyzer to exist, make olefinic polymerization, but can before above-mentioned polymerization (main polymerization) carried out, carry out below with the prepolymerization of mentioning.
Prepolymerization is under the condition that has solid catalytic ingredient (A) and organo-aluminium compound (B) to exist, and a spot of alkene carries out by adding, and preferably carries out under slurry condition.As the solvent of pulping, available unreactive hydrocarbons are as propane, butane, Trimethylmethane, pentane, iso-pentane, hexane, heptane, octane, hexanaphthene, benzene or toluene.In the forming process of slurries, available liquid olefin replaces a part or all unreactive hydrocarbons.
In pre-polymerization, each mole titanium atom in the relative solid catalytic ingredient, the consumption of organo-aluminium compound can be selected in the wide scope of 0.5-700mol, preferred 0.8-500mol, further preferred 1-200mol.Every relatively 1g solid catalytic ingredient, the amount of the alkene of pre-polymerization are 0.01-1000g, preferred 0.05-500g, preferred especially 0.1-200g.
In pre-polymerization, the preferred 1-500g solid catalytic ingredient of the concentration of slurries/rise solvent, preferred especially 3-300g ingredient of solid catalyst/rise solvent.Preferred-20 to 100 ℃ of the temperature of pre-polymerization, further preferred 0-80 ℃.The preferred 0.01-20kg/cm of the dividing potential drop of alkene in the gas phase in pre-polymerization
2, preferred especially 0.1-10kg/cm
2, but this pre-polymerization pressure and temperature does not impose on liquefied olefines.In addition, the pre-polymerization time is not particularly limited, and often selects for use 2 minutes to 15 hours.
Carrying out in the process of pre-polymerization, solid catalytic ingredient (A), the adding of organo-aluminium compound (B) and alkene can be adopted following method: perhaps contact the back with organo-aluminium compound (B) at solid catalytic ingredient (A) and add alkene, perhaps contact the back with alkene at solid catalytic ingredient (A) and add organo-aluminium compound (B).
The adding of alkene can be adopted following method: perhaps add alkene to keep the intrinsic pressure in the aggregation container, perhaps add all the alkene with predetermined amount when beginning.For controlling the molecular weight of the polymkeric substance that is obtained, can add chain-transfer agent, as hydrogen.
In addition, in the pre-polymerization of the small amounts of olefins under the condition that has solid catalytic ingredient (A) and organo-aluminium compound (B) to exist, electronic donor compound capable (C) in case of necessity can coexist.Used electronic donor compound capable is part or all in the above mentioned electronic donor compound capable (C).Be contained in each mole titanium atom in the solid catalytic ingredient (A) relatively, the preferred 0.01-400mol of its consumption, further preferred 0.02-200mol, preferred especially 0.03-100mol; And each mole organo-aluminium compound (B) relatively, the preferred 0.003-5mol of its consumption, further preferred 0.005-3mol, preferred especially 0.01-2mol.
The adding method of electronic donor compound capable in pre-polymerization (C) is not particularly limited.Can be independent of organo-aluminium compound (B) and add, and contact the back adding with organo-aluminium compound (B).Alkene in the pre-polymerization can be with main poly-in used alkene identical or different.
Undertaken after the pre-polymerization by above-described, or do not carry out under the situation of pre-polymerization, can under the condition that has the above-mentioned alpha-olefin polymerization catalyst that contains solid catalytic ingredient (A), organo-aluminium compound (B) and electronic donor compound capable (C) to exist, carry out the main polymerization of alpha-olefin.
Be contained in each mole titanium atom in the solid catalytic ingredient (A) relatively, the consumption of organo-aluminium compound can be selected in the wide region of 1-1000mol in the main polymerization, be contained in each mole titanium atom in the solid catalytic ingredient (A) relatively, the scope of 5-600mol is particularly preferred.
In this polymerization, be contained in each mole titanium atom in the solid catalytic ingredient (A) relatively, the preferred 0.1-2000mol of consumption of electronic donor compound capable (C), further preferred 0.3-1000mol, preferred especially 0.5-800mol, each mole organo-aluminium compound (B) relatively, the preferred 0.001-5mol of its consumption, further preferred 0.005-3mol, preferred especially 0.01-1mol.
Main polymerization can preferably be carried out under 20-180 ℃ at-30 to 300 ℃.Polymerization pressure is had no particular limits.But from industry and economic viewpoint, pressure is preferably normal pressure to 100kg/cm
2, further preferred 2-50kg/cm
2As polymerized form, can batchwise polymerization or successive polymerization.Inert solvent is being arranged, and the slurry polymerization under the condition that exists as propane, butane, Trimethylmethane, pentane, hexane, heptane or octane or solution polymerization, the mass polymerization of using liquid hydrocarbon under polymerization temperature and media or vapour phase polymerization also can adopt.
In main polymerization, can add chain-transfer agent, the molecular weight of the polymkeric substance of being produced with control as hydrogen etc.
Embodiment
With reference to the following examples and comparing embodiment, will be described in detail the present invention, but the present invention is not confined to this especially.The appraisal procedure of the various material characters of polymkeric substance is as follows among the embodiment: (1) dissolves in the amount (being designated hereinafter simply as CXS) of dimethylbenzene under 20 ℃
After being dissolved in the 1g polymeric powder in the 200ml ebullient dimethylbenzene, resulting solution is cooled to 50 ℃ at leisure, under agitation is cooled to 20 ℃ again.After leaving standstill 3 hours under 20 ℃, by the sedimentary polymkeric substance of filtering separation.Remove removal xylene 60 ℃ of following vacuum-evaporation, therefore obtain drying, be recovered in the polymkeric substance that is dissolved in dimethylbenzene under 20 ℃.(2) limiting viscosity (hereinafter to be referred as [η])
It is measured down at 135 ℃ with 1,2,3,4-tetralin.(3) loose density
It is measured by JiS K-6721-1966.Synthesizing of embodiment 1 (a) solid catalytic ingredient
The flask of the 200ml of belt stirrer and funnel with the nitrogen replacement air after, multipolymer (result who measures with porosimeter is: micropore size is that the micro pore volume (dVp) of 100-5000 is 1.14cc/g) with 8.2g vinylbenzene-Vinylstyrene, 41ml toluene, 0.17ml diisobutyl phthalate, 0.45ml four titanium butoxide and 5.0ml tetraethoxysilane join in the flask, and at room temperature stir 2 hours.Then in flask, keep 5 ℃, in 1 hour, slowly drip the di-n-butyl ethereal solution (produced by YUKI GOSEI YAKUHIN company limited, the concentration of normal-butyl chlorination magnesium is 2.1mmol/ml) of the normal-butyl chlorination magnesium of 11.6ml from funnel.
After being added dropwise to complete, under 5 ℃ and room temperature, stirred 30 minutes, then stirred 3 hours down at 35 ℃ again.After gained mixture solid-liquid separation, 73ml toluene repeated washing three times of gained solid add 60ml toluene then.
Part solid phase prod slurries carry out proximate analysis as sample to it.Titanium atom is 0.41% (weight) in solid phase prod, and oxyethyl group is 9.3% (weight), and butoxy is 0.6% (weight).Concentration of slurry is 0.19g/ml.(b) solid of ester processing is synthetic
Take out 21ml toluene supernatant liquor from the slurries that contain the solid phase prod that is obtained by above-mentioned (a) after, the slurry temperature in the flask is brought up to 95 ℃, and stirs 1 hour.The diisobutyl phthalate that adds 3.7ml then, institute's mixture reacted 30 minutes down at 95 ℃.After the reaction, with gained reaction mixture solid-liquid separation.Twice of 73ml toluene wash of gained solid.(c) synthetic (activation treatment) of solid catalytic ingredient
After the washing of above-mentioned (b), in flask, add 39ml toluene, the 0.29ml diisobutyl phthalate, 0.33ml di-n-butyl ether and 39ml titanium tetrachloride reacted 3 hours down at 105 ℃.After reaction was finished, the gained mixture carried out solid-liquid separation under same temperature.And under same temperature with 73ml toluene with twice of gained solids wash.Next, in washed solid, add 39ml toluene, 0.29ml phthalic acid diisobutyl ester, 0.33ml di-n-butyl ether and 39ml titanium tetrachloride reacted 1 hour down at 105 ℃.After reaction was finished, the gained mixture was to carry out solid-liquid separation under same temperature, and the gained solid is after usefulness 73ml toluene wash under the same temperature three times, and the gained solid is used the 73ml hexane wash three times again, and vacuum-drying, obtains the 11.7g solid catalytic ingredient.
In above-mentioned solid catalytic ingredient, contain titanium atom 0.35% (weight), phthalic ester 2.1% (weight), oxyethyl group 0.1% (weight) does not detect butoxy.(d) polymerization of propylene
3 liters stirring-type stainless steel cauldron argon replaces air adds the 2.6mmol triethyl aluminum in reactor, 0.26mmol cyclohexyl ethyl dimethoxy silane and 43.3mg synthetic solid catalytic ingredient in (c), and add corresponding 0.33kg/cm
2The hydrogen of dividing potential drop.
Then add the propylene liquid of 780g in reactor, the temperature of reactor is brought up to 80 ℃, and polyreaction was carried out under 80 ℃ 1 hour.Polymerization is discharged unreacted monomer after finishing.The polymkeric substance of producing obtains the 282g polypropylene powder 60 ℃ of following vacuum-dryings 2 hours.
Therefore, the polypropylene production of every gram ingredient of solid catalyst (below be abbreviated as pp/Cat) is 6,510 (g/g).Under 20 ℃, that a part of ratio (CXS) that dissolves in dimethylbenzene in all products is 0.7 (wt%), and the limiting viscosity of polymkeric substance [η] is 1.82, and loose density is 0.47 (g/ml).Synthesizing of comparative example 1 (a) solid catalytic ingredient
The flask of the 200ml of belt stirrer and funnel with the nitrogen replacement air after, will be as the multipolymer of the 8.2g vinylbenzene-Vinylstyrene among the embodiment 1 (a), 41ml toluene, 0.45ml four titanium butoxide and 5.0ml tetraethoxysilane join in the flask, under one temperature with after the 73ml toluene wash three times, the gained solid is used the 73ml hexane wash three times again, and vacuum-drying, obtains the 11.7g solid catalytic ingredient.
In solid catalytic ingredient, contain titanium atom 0.51% (weight), phthalic ester 3.3% (weight), oxyethyl group 0.2% (weight), butoxy 0.01% (weight).(d) polymerization of propylene
The ingredient of solid catalyst that obtains in above-mentioned except that being used in (c), carry out the polymerization of propylene by the mode of embodiment 1 (d), pp/Cat is 4,830 (g/g).CXS is 0.9 (wt%), and [η] is 1.75, and loose density is 0.48 (g/ml).
According to the present invention, a kind of alpha-olefin polymerization catalyst is provided, it has so high stereospecific and catalytic activity, so that needn't remove catalyst residue and amorphous polymer, and have high loose density and a thin particle seldom, do not contain the inorganic oxide as silica gel etc. that can in film forming is used, form flake, a kind of method of producing the alpha-olefinic polymer of high quality and high stereospecific degree is provided in addition.And at room temperature stirred 2 hours.Then in flask, keep 5 ℃, in 1 hour, slowly drip the di-n-butyl ethereal solution (produced by YUKI GOSEI YAKUHIN company limited, the concentration of normal-butyl chlorination magnesium is 2.1mmol/ml) of the normal-butyl chlorination magnesium of 11.2ml from funnel.After being added dropwise to complete, the gained mixture stirred 30 minutes under 5 ℃ and room temperature, then stirred 3 hours down at 35 ℃ again.Obtain solid after gained mixture solid-liquid separation, 73ml toluene repeated washing three times of gained solid add 60ml toluene in washed solid.
Part solid phase prod slurries carry out proximate analysis as sample to slurries, and titanium atom is 0.44% (weight) in solid phase prod, and oxyethyl group is 9.6% (weight), and butoxy is 0.64% (weight), and concentration of slurry is 0.19g/ml.(b) ester processing solid is synthetic
Take out 21ml toluene supernatant liquor from the slurries that contain the solid phase prod that is obtained by above-mentioned (a) after, the slurry temperature in the flask is brought up to 95 ℃, and stirs 1 hour.The diisobutyl phthalate that adds 3.1ml then, and under 95 ℃, reacted 30 minutes.After the reaction, with gained reaction mixture solid-liquid separation.Twice of 73ml toluene wash of gained solid.(c) synthetic (activation treatment) of solid catalytic ingredient
After the washing of above-mentioned (b), in flask, add 39ml toluene, the 0.29ml diisobutyl phthalate, 0.33ml di-n-butyl ether and 39ml titanium tetrachloride reacted 3 hours down at 105 ℃.After reaction was finished, the gained mixture carried out solid-liquid separation under same temperature.And under same temperature with 73ml toluene with twice of gained solids wash.Next, add 39ml toluene, the 0.29ml diisobutyl phthalate, 0.33ml di-n-butyl ether and 39ml titanium tetrachloride reacted 1 hour down at 105 ℃.After reaction was finished, the gained mixture carried out solid-liquid separation under same temperature, and the solid after the separation is same
Claims (23)
1. alpha-olefin polymerization catalyst, it contains:
(A) contain the solid catalytic ingredient of trivalent titanium compound, it obtains by handle a kind of solid phase prod with ester cpds, this solid phase prod is under the condition that has silicoorganic compound, porous polymer particle and ester cpds to exist, and reduces Ti (OR with organo-magnesium compound
1)
aX
4-a(R
1Represent the alkyl that 1-20 carbon atom arranged, X represents halogen atom, a represents it is a number that satisfies 0＜a≤4) obtain, described silicoorganic compound have the Si-O key, the aperture of described porous polymer particle is 100-5000 , micro pore volume is 0.1cc/g or bigger, then the solid of handling with ester with the mixture process of the mixture of ether compound and titanium tetrachloride or ether compound, titanium tetrachloride and ester cpds;
(B) organo-aluminium compound; With
(C) electronic donor compound capable.
2. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: the silicoorganic compound that contain the Si-O key in the molecule are selected from the group of being made up of the silicoorganic compound of following general formula representative: Si (OR
2)
mR
3 4-mR
4(R
5 2SiO)
pSiR
6 3(R
7 2SiO)
qR wherein
2Be the alkyl that 1-20 carbon atom arranged, R
3, R
4, R
5, R
6, R
7Be alkyl or the hydrogen atom that 1-20 carbon atom arranged, m is a number that satisfies 0＜m≤4, and p is the integer of a 1-1000, and q is the integer of a 2-1000.
3. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: organo-magnesium compound is selected from the group of being made up of the organo-magnesium compound of following general formula representative: R
8MgX; And R
9R
10Mg is R wherein
8, R
9And R
10Be the alkyl that 1-20 carbon atom arranged, X is a halogen atom.
4. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: be used in the processing of reduction solid or and be selected from the group of forming by representative examples of saturated aliphatic carboxylic ester, unsaturated aliphatic carboxylicesters, alicyclic carboxylic ether and aromatic carboxylic acid esters as the ester cpds in ether compound, titanium tetrachloride and the ester cpds mixture.
5. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: ether compound is selected from the group of being made up of dialkyl ether, and wherein each alkyl has 2-10 carbon atom, and can be identical or different.
6. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: the diameter of polymer particles is 5-1000 μ.
7. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: in the processing of solid phase prod, each mole titanium atom in the relative solid phase prod, the consumption of ester cpds is 0.1-50mol, each mole magnesium atom in the relative solid phase prod, the consumption of ester cpds is 0.01-1.0mol.
8. according to the alpha-olefin polymerization catalyst of claim 1, it is characterized in that: electronic donor compound capable is selected from the group of being made up of alcohol, phenol, ketone, aldehyde, carboxylic acid, organic acid acetic, inorganic acid ester, ether, acid amides, acid anhydride, ammonia, amine, nitrile, isocyanic ester.
9. alpha-olefin polymerization catalyst according to Claim 8 is characterized in that: electronic donor compound capable is selected from by the inorganic acid ester with following general formula representative: R
16 nSi (OR
17)
4-nWherein, R
16Be alkyl or the hydrogen that 1-20 carbon atom arranged, R
17Be the alkyl that 1-20 carbon atom arranged, R in a part
16, R
17Can be different, n is a number that satisfies 0≤n＜4, and ether is shown from generation to generation by following general formula:
Wherein, R
18-R
21Be respectively the alkyl that 1-20 carbon atom arranged, alicyclic radical, aryl, alkaryl or aralkyl straight chain or side chain, R
18Or R
19Can be hydrogen.
10. method of producing alpha-olefinic polymer comprises with the alpha-olefin polymerization catalyst polymerization of Alpha-olefin that contains following component:
(A) contain the solid catalytic ingredient of trivalent titanium compound, it obtains by handle a kind of solid phase prod with ester cpds, this solid phase prod is under the condition that has silicoorganic compound, porous polymer particle and ester cpds to exist, and reduces Ti (OR with organo-magnesium compound
1)
aX
4-a(R
1Represent the alkyl that 1-20 carbon atom arranged, X represents halogen atom, a represents it is a number that satisfies 0＜a≤4) obtain, described silicoorganic compound have the Si-O key, the aperture of described porous polymer particle is 100-5000 , micro pore volume is 0.1cc/g or bigger, then the solid of handling with ester with the mixture process of the mixture of ether compound and titanium tetrachloride or ether compound, titanium tetrachloride and ester cpds;
(B) organo-aluminium compound; With
(C) electronic donor compound capable.
11. the method according to the production alpha-olefinic polymer of claim 10 is characterized in that: the silicoorganic compound that are used for reduction reaction are selected from the group of being made up of the silicoorganic compound of following general formula representative: Si (OR
2)
mR
3 4-mR
4(R
5 2SiO)
pSiR
6 3(R
7 2SiO)
qR wherein
2Be the alkyl that 1-20 carbon atom arranged, R
3, R
4, R
5, R
6, R
7Be alkyl or the hydrogen atom that 1-20 carbon atom arranged, m is a number that satisfies 0＜m≤4, and p is the integer of a 1-1000, and q is the integer of a 2-1000.
12. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: organo-magnesium compound is selected from the group of being made up of the organo-magnesium compound of following general formula representative: R
8MgX; And R
9R
10Mg is R wherein
8, R
9And R
10Be the alkyl that 1-20 carbon atom arranged, X is a halogen atom.
13. the method according to the production alpha-olefinic polymer of claim 10 is characterized in that: wherein be used in the reduction solid handle in or be selected from the group of forming by representative examples of saturated aliphatic carboxylic ester, unsaturated aliphatic carboxylicesters, alicyclic carboxylic ether and aromatic carboxylic acid esters as the ester cpds in ether compound, titanium tetrachloride and the ester cpds mixture.
14. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: ether compound is selected from the group of being made up of dialkyl ether, wherein each alkyl has 2-10 carbon atom, and can be identical or different.
15. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: wherein the diameter of polymer particles is 5-1000 μ.
16. method according to the production alpha-olefinic polymer of claim 10, it is characterized in that: in the processing of solid phase prod, each mole titanium atom in the relative solid phase prod, the consumption of ester cpds is 0.1-50mol, each mole magnesium atom in the relative solid phase prod, the consumption of ester cpds is 0.01-1.0mol.
17. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: organo-aluminium compound is selected from the group of being made up of the organo-aluminium compound of following general formula representative: R
11 γAlY
3-γAnd R
12R
13Al-O-AlR
14R
15R wherein
11-R
15Representative has the alkyl of 1-20 carbon atom, and Y represents halogen, hydrogen or alkoxyl group, and γ is a number that satisfies 2≤γ≤3.
18. the method according to the production alpha-olefinic polymer of claim 10 is characterized in that: each mole titanium atom that is contained in the solid catalyst relatively, the consumption of organo-aluminium compound is 0.5-1000mol.
19. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: electronic donor compound capable is selected from the group of being made up of alcohol, phenol, ketone, aldehyde, carboxylic acid, organic acid acetic, inorganic acid ester, ether, acid amides, acid anhydride, ammonia, amine, nitrile, isocyanic ester.
20. the method according to the production alpha-olefinic polymer of claim 19 is characterized in that: electronic donor compound capable is selected from by the inorganic acid ester with following general formula representative:
R
16 nSi (OR
17)
4-nWherein, R
16Be alkyl or the hydrogen that 1-20 carbon atom arranged, R
17Be the alkyl that 1-20 carbon atom arranged, R in a part
16, R
17Can be different, n is a number that satisfies 0≤n＜4, and the ether of following general formula representative:
Wherein, R
18-R
21Be respectively the alkyl that 1-20 carbon atom arranged, alicyclic radical, aryl, alkaryl or aralkyl straight chain or side chain, R
18Or R
19Can be hydrogen.
21. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: be contained in each mole titanium atom in the solid catalytic ingredient (A) relatively, the amount of electronic donor compound capable (C) is 0.1-1000mol.
22. the method according to the production alpha-olefinic polymer of claim 10 is characterized in that: carried out prepolymerization before alpha-olefine polymerizing.
23. according to the method for the production alpha-olefinic polymer of claim 10, it is characterized in that: polymerization is to carry out with the form of slurry polymerization, solution polymerization, mass polymerization or vapour phase polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96110738 CN1154372A (en) | 1995-06-07 | 1996-06-07 | Alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP140433/95 | 1995-06-07 | ||
| CN 96110738 CN1154372A (en) | 1995-06-07 | 1996-06-07 | Alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1154372A true CN1154372A (en) | 1997-07-16 |
Family
ID=5120907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96110738 Pending CN1154372A (en) | 1995-06-07 | 1996-06-07 | Alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1154372A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307219C (en) * | 1998-03-11 | 2007-03-28 | 住友化学工业株式会社 | Solid catalytic ingredient for polymerizing olefin, catalyst for polymerizing olefin, and production of polyolefin |
| WO2014044018A1 (en) * | 2012-09-18 | 2014-03-27 | 中国石油天然气股份有限公司 | Ethylene/α-olefin copolymerization catalyst and preparation and use thereof |
-
1996
- 1996-06-07 CN CN 96110738 patent/CN1154372A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307219C (en) * | 1998-03-11 | 2007-03-28 | 住友化学工业株式会社 | Solid catalytic ingredient for polymerizing olefin, catalyst for polymerizing olefin, and production of polyolefin |
| WO2014044018A1 (en) * | 2012-09-18 | 2014-03-27 | 中国石油天然气股份有限公司 | Ethylene/α-olefin copolymerization catalyst and preparation and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1117773C (en) | Solid catalyst component for alpha-olefin polymerization, catalyst for alpha-olefin polymerization, and process for producing alpha-olefin polymer | |
| CN1167715C (en) | An improved catalyst for homo-and Co-polymerization of olefin | |
| JP2557061B2 (en) | Alpha-olefin polymerization catalyst system containing suitable modifier components | |
| CN1043507A (en) | The polymerization that can prepare the gaseous ethene of the very narrow linear polyethylene of molecular weight distribution | |
| CN1189487C (en) | A method for producing ethylene homo-and co-polymer | |
| WO2011006278A1 (en) | Spherical magnesium halide adduct, catalyst component and catalyst for olefin polymerization prepared therefrom | |
| WO1997009355A1 (en) | Solid catalytic component and catalyst for polymerizing olefins | |
| JP3533202B2 (en) | Catalyst for ethylene polymerization and copolymerization | |
| CN1771268A (en) | Olefin polymerisation catalyst containing a cycloakane dicarboxylate as electron donor | |
| CN1152582A (en) | Method for preparing catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer with catalyst | |
| FI92835B (en) | Catalytic component for polymerization of olefin | |
| CN108148153A (en) | Solid catalyst and prepare the method for acrylic polymers or copolymer using it | |
| JP3306119B2 (en) | Method for producing olefin polymer | |
| CN1107682C (en) | alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer | |
| CN1141305A (en) | Alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer | |
| CN100339399C (en) | Method of polymerization and copolymerization of ethylene | |
| JPH06145269A (en) | Production of propylene block copolymer | |
| JPH0655787B2 (en) | Polyolefin manufacturing method | |
| CN1154372A (en) | Alpha-olefin polymerization catalyst and process for producing alpha-olefin polymer | |
| CN1218814A (en) | Catalyst for olefine polymerization and process for producing olefine polymers | |
| EP0187034A2 (en) | Process for producing poly-1-butene | |
| JP3468962B2 (en) | Crystalline polypropylene | |
| JP3415912B2 (en) | Crystalline polypropylene | |
| JPH01105A (en) | Method for producing stereoregular polyolefin | |
| JP3390231B2 (en) | Crystalline polypropylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |