CN102838702A - Catalyst for ethylene and alpha-olefin copolymerization and preparation method thereof - Google Patents
Catalyst for ethylene and alpha-olefin copolymerization and preparation method thereof Download PDFInfo
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- CN102838702A CN102838702A CN2012103088049A CN201210308804A CN102838702A CN 102838702 A CN102838702 A CN 102838702A CN 2012103088049 A CN2012103088049 A CN 2012103088049A CN 201210308804 A CN201210308804 A CN 201210308804A CN 102838702 A CN102838702 A CN 102838702A
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Abstract
The invention relates to a catalyst for ethylene and alpha-olefin copolymerization and a preparation method thereof. The catalyst comprises a magnesium compound, a titanium compound, an electron donor I and an electron donor II. The electron donor I is an ester compound. The electron donor II is a siloxane compound. The preparation method of the catalyst includes that the magnesium compound is dissolved in a hydrocarbon solvent and an alcohol solvent, and reacts for 2-4 hours under the temperature of 70-90 DEG C; the electron donor I is added and reacts for 0.5-2 hours, and then the electron donor II is added and reacts for 0.5-2 hours; the titanium compound is added dropwisely under the room temperature, and reactions undergo 1-3 hours under the temperature of 70-90 DEG C; the solvents are eliminated; the hydrocarbon solvent is added; after the electron donor II reacts for 1-2 hours, the electron donor I is added and reacts for 1-2 hours; the titanium compound is added and reacts for 1-3 hours; and filtering, washing and drying are carried out to produce the catalyst. According to the catalyst, the catalyst activity for the ethylene and the long-chain alpha-olefin copolymerization is high, so the inserting rate of the long-chain alpha-olefin of produced copolymer is high.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for ethene and alpha-olefin copolymer; Relate in particular to Ziegler-Natta catalyst that is used for ethene and long-chain alpha-olefin copolymerization of a kind of electron donor modification and preparation method thereof, belong to the olefin polymerization catalysis field.
Background technology
Linear low density polyethylene (LLDPE) is the ethene succeeded in developing the seventies in 20th century and the multipolymer of terminal olefin (ethene and 1-butylene, ethene and 4-methyl-1-pentene), and molecule is linear structure, and density is 0.91-0.94g/cm
3, similar with the LDPE that high-pressure process is produced, be called as Vilaterm third generation product.Make the macromole that makes contain a considerable amount of side chains after introducing 'alpha '-olefin monomers in the polymkeric substance, these short-chain branchs and long-chain branch can exert an influence to its rerum natura, can wait through regulation and control side chain length, the degree of branching and co-monomer content to prepare desired product.LLDPE combines many advantages of new LDPE (film grade) and high density polyethylene(HDPE), therefore has low-temperature flexibility, high-modulus, resistance to bend(ing), puncture resistance, tear strength, is widely used in fields such as film, tubing.
Ziegler-Natta catalyst is because its catalytic efficiency (is high, the polymkeric substance good combination property of production, and cost is low, therefore in poly production, occupies an important position.Ziegler-Natta catalyst can not only catalyzed ethylene, the propylene homopolymerization, can also catalyzed ethylene and terminal olefin (like 1-butylene, propylene) copolymerizing linear low-density polyethylene (LLDPE).
The PDT R&D Representative of LLDPE the major transformation of polyethylene catalysts and Technology, the scope of polyethylene product significantly enlarges.But the production requirement catalyst system of long-chain branch LLDPE possesses high reactivity and good copolymerization performance; And traditional Ziegler-Natta catalyst is when catalyzed ethylene and long-chain alpha-olefin (like 1-hexene, 1-octene, 1-decene base) polymerization; Long-chain alpha-olefin insertion rate is low, and the synthetic ethylene copolymer has very wide composition distribution; This chain structure characteristic has a negative impact to many performances of LLDPE, causes transparency, intensity, surface tackiness, heat sealability and the thermal viscosity of film to descend.CN1953809A discloses a kind of Catalysts and its preparation method that is used for ethylene copolymer; Its catalyzer is through chlorobenzene solution that is dissolved with metal magnesium powder and dibutyl ether and acvator---the Butyryl Chloride solution reaction that contains iodine prepares organo-magnesium compound, and then with contain PhCCl
3Chlorobenzene solution prepared in reaction magnesium-containing carrier, in carrier, add titanium tetrachloride reaction again and make catalyzer.This catalyzer is used for ethene and the 1-hervene copolymer has very high activity, and the resulting polymers particle form is better, but 1-hexene content is lower in the multipolymer, has only 1.2wt%.In order to solve the problem that 1-hexene insertion rate is low in the ethylene copolymer and to obtain forming narrowly distributing and the ethene hexene copolymer of MWD broad; Many patents add electron donor Ziegler-Natta catalyst are carried out modification, possess the catalyst system of high reactivity and good copolymerization performance in the hope of preparation.The method of the disclosed ethylene copolymerization of CN1229092A is to be dissolved in organic epoxy compounds, organo phosphorous compounds through magnesium chloride to add electron donor again and form homogeneous solution, obtains with the halogenide of at least a precipitation additive and transition metals Ti and verivate effect thereof again; This catalyst ethene and 1-hervene copolymer are active high, and 1-hexene insertion rate is higher in the multipolymer, but this catalystsystem mother liquor in the preparation process is more sticking, and catalyst solid separates difficult with mother liquor, and 1-hexene skewness in the multipolymer.CN1194993A discloses a kind of catalyzer that is used for the ethene slurry polymerization; It is dissolved in the homogeneous solution of organic epoxy compounds, organo phosphorous compounds and inert solvent through magnesium chloride; Add electron donor again, a kind of muriate of thinner and transition metals Ti that helps prepares; This catalyzer also can be used for ethene and alpha-olefin copolymer closes, but does not realize that ethene and 1-hervene copolymer form the instance of LLDPE.
Therefore, still have and to develop a kind of catalyzer that is used for ethene and alpha-olefin copolymer, so that the LLDPE for preparing has higher terminal olefin insertion rate and good performance with higher catalytic activity.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of catalyzer that is used for ethene and alpha-olefin copolymer.The catalytic activity of this catalyst ethene and long-chain alpha-olefin copolymerization is high, make the long-chain alpha-olefin insertion rate of the multipolymer for preparing high, and particle form is good.
The present invention also aims to provide a kind of above-mentioned Preparation of catalysts method that is used for ethene and alpha-olefin copolymer.
Another purpose of the present invention is to provide a kind of catalyst composition that is used for ethene and alpha-olefin copolymer, and it comprises above-mentioned catalyzer.
For reaching above-mentioned purpose, the present invention provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its raw material comprises magnesium compound, titanium compound, electron donor I and electron donor II;
Wherein, said magnesium compound is formula M gR
1 nX
1 2-nShown in one or more combination in the compound, in the formula, X
1Be halogen, n is the integer of 0-2, R
1Be C
1-C
15Alkyl or aryl;
Said titanium compound is general formula Ti (OR
2)
mX
2 4-mShown in one or more combination in the compound, in the formula, X
2Be halogen, m is the integer of 0-4, R
2Be C
1-C
6Alkyl or aryl;
Said electron donor I is an ester compound;
Said electron donor II is a siloxane compound, and it is a general formula R
3 xR
4 ySi (OR
5)
zShown in one or more combination in the compound, in the formula, R
3Be alkyl, hydrochloric ether or halogen, R
4Be alkyl, hydrochloric ether or halogen, R
5Be alkyl, 0≤x＜2,0≤y＜2,0＜z≤4 and x, y and z are integer;
The ratio of said magnesium compound, titanium compound, electron donor I and electron donor II is 1 gram magnesium compound: 15.75-62.5 milliliter titanium compound: 0.075-0.375 milliliter electron donor I:0.10-0.39 milliliter electron donor II.
In above-mentioned catalyzer, said magnesium compound can be one or more the combination in magnesium chloride, magnesium bromide, magnesium iodide and the diethoxy magnesium etc.Preferably, said magnesium compound is a magnesium chloride.
In above-mentioned catalyzer, said titanium compound can be one or more the combination in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, purity titanium tetraethoxide and the chlorine triethoxy titanium etc.Preferably, said titanium compound is a titanium tetrachloride.
In above-mentioned catalyzer, said electron donor I (ester compound) can be one or more the combination in methyl-formiate, methyl acetate, ETHYLE ACETATE, oil of Niobe, ethyl benzoate, propyl benzoate, diethyl succinate, n-butyl phthalate, diisobutyl phthalate, trimethyl phosphite 99, triethyl phosphate, tributyl phosphate and the triphenylphosphate etc.Preferably, said electron donor I is one or more the combination in diethyl succinate, ethyl benzoate, diisobutyl phthalate and the tributyl phosphate etc.
In above-mentioned catalyzer, said electron donor II (siloxane compound) can be one or more the combination in tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, Union carbide A-162, ethyl triethoxysilane, n-propyl triethoxyl silane, a chlorine triethoxyl silane, 3-chloropropyl triethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane, isobutyl-Trimethoxy silane, hexyl trimethoxy silane, dimethyldimethoxysil,ne, diisopropyl dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane and the phenyl methyl dimethoxy silane etc.Preferably, said electron donor II is one or more the combination in tetraethoxysilane, 3-chloropropyl triethoxysilane, hexyl Trimethoxy silane, isobutyl-Trimethoxy silane and the dimethoxydiphenylsilane etc.
The present invention also provides the above-mentioned Preparation of catalysts method that is used for ethene and alpha-olefin copolymer, and it may further comprise the steps:
Magnesium compound is dissolved in an amount of hydrocarbon solvent, adds alcoholic solvent, reaction is 2-4 hour under 70-90 ℃ of agitation condition;
Add electron donor I then, agitation condition reacted 0.5-2 hour down, added electron donor II again, and agitation condition reacted 0.5-2 hour down;
Be cooled to room temperature, drip titanium compound, in 1-2 hour, drip and finish, be warming up to 70-90 ℃ then, agitation condition reacted 1-3 hour down;
Above-mentioned reactant press filtration is desolvated to remove, add an amount of hydrocarbon solvent stirring, be warming up to 70-90 ℃, add electron donor II, agitation condition reacted 1-2 hour down, added electron donor I then, and agitation condition reacted 1-2 hour down;
Add titanium compound, agitation condition reacted 1-3 hour down;
Filter, washing, drying obtains the described catalyzer that is used for ethene and alpha-olefin copolymer;
Wherein, the ratio of said magnesium compound, alcoholic solvent, titanium compound, electron donor I and electron donor II is 1 gram magnesium compound: 1.5-6.0 milliliter alcoholic solvent: 15.75-62.5 milliliter titanium compound: 0.075-0.375 milliliter electron donor I:0.10-0.39 milliliter electron donor II; Titanium compound adds at twice, and the first time, the volume ratio with the add-on second time was 1: 2-4: 1; Electron donor I adds at twice, and the first time, the volume ratio with the add-on second time was 2: 1-1: 6; Electron donor II adds at twice, and the first time, the volume ratio with the add-on second time was 3: 1-7: 1.
In above-mentioned preparation method, said hydrocarbon solvent can be one or more the combination in aliphatic hydrocarbon, cycloaliphates, aromatic hydrocarbon and the halohydrocarbon, and the addition of hydrocarbon solvent is as the criterion reacting smoothly.Wherein, said aliphatic hydrocarbon can be one or more the combination in pentane, hexane, heptane, octane and the decane etc.; Said cycloaliphates can be one or more the combination in pentamethylene, methylcyclopentane, hexanaphthene and the methylcyclohexane etc.; Said aromatic hydrocarbon can be one or more the combination in benzene,toluene,xylene, ethylbenzene and the isopropyl benzene etc.; Said halohydrocarbon can be one or more the combination in tetracol phenixin, ethylene dichloride, propylene dichloride and the chlorobenzene etc.Preferably, described hydrocarbon solvent is hexane and/or heptane.
In above-mentioned preparation method, said alcoholic solvent can be fatty alcohol and/or alicyclic alcohol.Wherein, said fatty alcohol can be one or more the combination in methyl alcohol, ethanol, Virahol, isopropylcarbinol, amylalcohol, hexanol, 2-ethyl butanol, 2-second hexanol, octanol, dodecanol, VLTN 6 and the terepthaloyl moietie etc.; Said alicyclic alcohol can be one or more the combination in hexalin and the methyl-cyclohexanol etc.Preferably, said alcoholic solvent is isopropylcarbinol and/or hexanol.
The present invention also provides a kind of catalyst composition that is used for ethene and alpha-olefin copolymer, and it comprises following component:
The above-mentioned catalyzer that is used for ethene and alpha-olefin copolymer;
A kind of promotor, it is a general formula R
6 fMX
3 3-fShown in one or more combination in the compound, in the formula, R
6Be C
1-C
15Alkyl, X
3Be halogen, M is a metallic element, and f is the integer of 1-3;
Wherein, the mol ratio of said catalyzer and said promotor is 1: 30-1: 150, and respectively in the molar weight of M metallic element in the molar weight of titanium elements in the catalyzer and the promotor.
In above-mentioned catalyst composition, the R in the promotor general formula
6Can be methyl, ethyl, n-propyl, isobutyl-, cyclopentyl, cyclohexyl and phenyl etc.; Said M can be aluminium element etc.According to the preferred embodiments of the invention, said promotor is one or more the combination in trimethylaluminium, triethyl aluminum, triisobutyl aluminium, chlorodimethylalumiu, diethylaluminum chloride, di-isobutyl aluminum chloride, sesquialter methyl chloride aluminium, sesquialter ethylaluminium chloride, methylaluminium dichloride and the ethylaluminium dichloride etc.More preferably, said promotor is triethyl aluminum and/or triisobutyl aluminium.
The Catalysts and its preparation method that is used for ethene and alpha-olefin copolymer provided by the invention has the following advantages:
(1) in the preparation process, the gradation through electron donor I, II adds the purpose that realizes the Ziegler-Natta catalyst modification, and catalyst preparation process is simple, and technical process is short, and easy to operate, cost is low.
(2) catalyzer provided by the invention can be applicable to ethene and alpha-olefin copolymer closes reaction; Especially ethene and long-chain alpha-olefin copolymerization; Copolymerization like ethene and 1-hexene, ethene and 1-octene, ethene and 1-decene can make higher ethene of terminal olefin content and alpha-olefin copolymer.The catalytic activity of ethene and terminal olefin polymerization under atmospheric pressure can reach 550gPE (hgcat)
-1More than, the content of terminal olefin can reach more than the 6wt% in the multipolymer that makes; And polymer beads is even, and form is good.
Embodiment
Below in conjunction with embodiment the present invention is described further, but protection scope of the present invention is not limited only to following embodiment.
Embodiment 1
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and it prepares through following steps:
(1) through adding 2 gram Magnesium Chloride Anhydrous, 60 milliliters of hexanes and 6.5 milliliters of isopropylcarbinols in the there-necked flask of argon replaces, stirs and be heated to 70 ℃, reacted then 3 hours, obtain suspension-s;
(2) in this suspension-s, add 0.18 milliliter tributyl phosphate,, add 0.6 milliliter tetraethoxysilane then, 70 ℃ of following stirring reactions 1 hour 70 ℃ of following stirring reactions 1 hour;
(3) be cooled to room temperature, slowly drip 47 milliliters titanium tetrachloride, the dropping time is 90 minutes, progressively is warming up to 70 ℃, and the TRT is 2 hours, restir reaction afterwards 2 hours;
(4) press filtration supernatant liquid then adds 50 ml n-hexanes, is warmed up to 70 ℃, adds 0.10 milliliter tetraethoxysilane, and stirring reaction 1 hour adds 0.12 milliliter tributyl phosphate, stirring reaction 1 hour then;
(5) add 23 milliliters titanium tetrachloride again, reacted 2 hours;
(6) after reaction finishes, repeatedly wash with normal hexane, up to eliminating the intact titanium tetrachloride of unreacted, vacuum drying obtains solid catalyst 1 then.
The mensuration of titanium content adopts spectrophotometry in the catalyzer, and its body experimental procedure comprises: make catalyzer through concentrated sulfuric acid dissolution, add H then
2O
2Reaction with it, itself and Ti
4+Form yellow complex, maximum absorption wavelength carries out the quantitatively determined of titanium at the 420nm place with spectrophotometry.The titanium content of this catalyzer 1 is 6.11wt%.
Embodiment 2
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its preparation method is with embodiment 1, and difference is:
The isopropylcarbinol consumption is 12 milliliters in the step (1).
Replace tributyl phosphate, 0.06 milliliter of its consumption with diisobutyl phthalate in the step (2); Substitute tetraethoxysilane, 0.17 milliliter of its consumption with the isobutyl-Trimethoxy silane.
The titanium tetrachloride consumption is 83 milliliters in the step (3), and the dropping time is 2 hours, and the reaction times is 1 hour.
Substitute tetraethoxysilane with the isobutyl-Trimethoxy silane in the step (4), 0.03 milliliter of its consumption, the reaction times is 2 hours; Replace tributyl phosphate with diisobutyl phthalate, 0.22 milliliter of its consumption, the reaction times is 2 hours.
The titanium tetrachloride consumption is 42 milliliters in the step (5), and the reaction times is 3 hours.
The titanium content of the solid catalyst 2 for preparing is 3.54wt%.
Embodiment 3
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its preparation method is with embodiment 1, and difference is:
The isopropylcarbinol consumption is 4.30 milliliters in the step (1).
Substitute tributyl phosphate, 0.30 milliliter of its consumption with diethyl succinate in the step (2); Substitute tetraethoxysilane, 0.21 milliliter of its consumption with the 3-chloropropyl triethoxysilane.
The titanium tetrachloride consumption is 31 milliliters in the step (3), and the dropping time is 2 hours, and the reaction times is 1 hour.
Substitute tetraethoxysilane with the 3-chloropropyl triethoxysilane in the step (4), 0.04 milliliter of its consumption, the reaction times is 2 hours; Substitute tributyl phosphate, 0.15 milliliter of its consumption with diethyl succinate.
The titanium tetrachloride consumption is 15.50 milliliters in the step (5).
The titanium content of the solid catalyst 3 for preparing is 5.20wt%.
Embodiment 4
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its preparation method is with embodiment 1, and difference is:
The isopropylcarbinol consumption is 3.0 milliliters in the step (1).
The tributyl phosphate consumption is 0.05 milliliter in the step (2); Substitute tetraethoxysilane, 0.40 milliliter of its consumption with the hexyl Trimethoxy silane.
The titanium tetrachloride consumption is 21 milliliters in the step (3), and the dropping time is 1 hour, and the reaction times is 3 hours.
Substitute tetraethoxysilane, 0.07 milliliter of its consumption with the hexyl Trimethoxy silane in the step (4); 0.29 milliliter of tributyl phosphate consumption.
The titanium tetrachloride consumption is 10.5 milliliters in the step (5), 1 hour reaction times.
The titanium content of the solid catalyst 4 for preparing is 6.60wt%.
Embodiment 5
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its preparation method is with embodiment 1, and difference is:
The isopropylcarbinol consumption is 9.20 milliliters in the step (1).
Replace tributyl phosphate, 0.30 milliliter of its consumption with ethyl benzoate in the step (2); Substitute tetraethoxysilane, 0.41 milliliter of its consumption with the phenylbenzene Trimethoxy silane.
The titanium tetrachloride consumption is 66 milliliters in the step (3), and the dropping time is 2 hours.
Substitute tetraethoxysilane with the phenylbenzene Trimethoxy silane in the step (4), 0.07 milliliter of its consumption, the reaction times is 2 hours; Replace tributyl phosphate with ethyl benzoate, 0.45 milliliter of its consumption, the reaction times is 2 hours.
The titanium tetrachloride consumption is 33 milliliters in the step (5).
The titanium content of the solid catalyst 5 for preparing is 6.63wt%.
Embodiment 6
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its preparation method is with embodiment 1, and difference is:
The isopropylcarbinol consumption is 5.40 milliliters in the step (1).
Replace tributyl phosphate, 0.18 milliliter of its consumption with diethyl succinate in the step (2); Substitute tetraethoxysilane, 0.65 milliliter of its consumption with the 3-chloropropyl triethoxysilane.
The titanium tetrachloride consumption is 38 milliliters in the step (3).
Substitute tetraethoxysilane, 0.11 milliliter of its consumption with the 3-chloropropyl triethoxysilane in the step (4); Replace tributyl phosphate, 0.10 milliliter of its consumption with diethyl succinate.
The titanium tetrachloride consumption is 19 milliliters in the step (5), and the reaction times is 3 hours.
The titanium content of the solid catalyst 6 for preparing is 3.42wt%.
Embodiment 7
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its preparation method is with embodiment 1, and difference is:
Replace hexane with octane in the step (1), 90 ℃ were reacted 2 hours.
Temperature of reaction is 90 ℃ in the step (2), and the reaction times is 0.5 hour; Substitute tetraethoxysilane with the isobutyl-Trimethoxy silane, the reaction times is 2 hours.
The titanium tetrachloride reaction temperature is 90 ℃ in the step (3), and the reaction times is 1 hour.
Temperature of reaction is 90 ℃ in the step (4), substitutes tetraethoxysilane with the isobutyl-Trimethoxy silane.
The titanium content of the solid catalyst 7 for preparing is 5.01wt%.
Embodiment 8
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its preparation method is with embodiment 1, and difference is:
Replace hexane with octane in the step (1), replace isopropylcarbinol with hexanol, 90 ℃ were reacted 4 hours.
Temperature of reaction is 90 ℃ in the step (2), replaces tributyl phosphate with diethyl succinate.
The titanium tetrachloride consumption is 19 milliliters in the step (3), and temperature of reaction is 90 ℃.
Temperature of reaction is 90 ℃ in the step (4), replaces tributyl phosphate with diethyl succinate.
The titanium content of the solid catalyst 8 for preparing is 5.12wt%.
Embodiment 9
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its preparation method is with embodiment 1, and difference is:
The isopropylcarbinol consumption is 5.4 milliliters in the step (1).
The tributyl phosphate consumption is 0.25 milliliter in the step (2), and the reaction times is 2 hours; 0.35 milliliter of tetraethoxysilane, the reaction times is 0.5 hour.
The titanium tetrachloride consumption is 44 milliliters in the step (3).
0.05 milliliter of step (4) tetraethoxysilane consumption, 0.25 milliliter of tributyl phosphate consumption.
The titanium tetrachloride consumption is 22 milliliters in the step (5).
The titanium content of the solid catalyst 9 for preparing is 4.18wt%.
Embodiment 10
Present embodiment provides a kind of catalyzer that is used for ethene and alpha-olefin copolymer, and its preparation method is with embodiment 1, and difference is:
The tributyl phosphate consumption is 0.30 milliliter in the step (2), 0.20 milliliter of tetraethoxysilane consumption.
0.066 milliliter of step (4) tetraethoxysilane consumption, 0.40 milliliter of tributyl phosphate consumption.
The titanium tetrachloride consumption is 33 milliliters in the step (5).
The titanium content of the solid catalyst 10 for preparing is 5.03wt%.
Application examples 1-12
Application examples 1-12 provides catalyzer 1-10 that the foregoing description makes polymerisation process and result that catalyzed ethylene and alpha-olefin copolymer under different condition close.This polyreaction makes ethene and terminal olefin in 250 milliliters there-necked flask, carry out copolymerization, ethylene pressure 0.1MPa.Its polymerization method may further comprise the steps: after fully replacing there-necked flask with argon gas; 100 milliliters of the normal hexanes that adding is handled through anhydrous and oxygen-free; Add the triethyl aluminium solution (promotor) of a certain amount of 2.0 mol (mol/L), add a certain amount of catalyzer while stirring, be warming up to 45 ℃; The comonomer that adds 1.86-3.8mL, logical vinyl polymerization 0.5 hour.After reaction finishes, add 10% acidifying ethanol termination reaction, and use the washing with alcohol polymkeric substance; After the vacuum-drying polymkeric substance is weighed; Calculate catalytic activity, catalytic activity is calculated unit: gPE (hgcat) with the polymer weight (gram) that every gram catalyzer is per hour produced
-1
Polymerizing condition and the polymerization result of application examples 1-12 are as shown in table 1, and wherein, the terminal olefin assay adopts
13The C-NMR method records, and the following fine polymer powder content of 150 μ m adopts the screen cloth method to record.
As shown in table 1, the catalytic activity of ethene and 1-hexene polymerization under atmospheric pressure reaches 570-872gPE (hgcat)
-1, the content of 1-hexene is 6.54-10.6% (mass percent) in the multipolymer that makes; Ethene and 1-octene, 1-decene polymerization under atmospheric pressure activity are greater than 705gPE (hgcat)
-1, the content of 1-octene, 1-decene is greater than 7% (mass percent) in the multipolymer that makes; The following fine powder content of copolymer 1 50 μ m that makes is less than 5 (wt%).Can draw through table 1 experimental result: catalyzer provided by the invention can be applicable to ethene and long-chain alpha-olefin copolymerization; Copolymerization like ethene and 1-hexene, ethene and 1-octene, ethene and 1-decene; Can make higher ethene of terminal olefin content and alpha-olefin copolymer; And the uniform particles of the polymkeric substance that makes, form is good.
Table 1
Claims (10)
1. catalyzer that is used for ethene and alpha-olefin copolymer, its raw material comprises magnesium compound, titanium compound, electron donor I and electron donor II;
Wherein, said magnesium compound is formula M gR
1 nX
1 2-nShown in one or more combination in the compound, in the formula, X
1Be halogen, n is the integer of 0-2, R
1Be C
1-C
15Alkyl or aryl;
Said titanium compound is general formula Ti (OR
2)
mX
2 4-mShown in one or more combination in the compound, in the formula, X
2Be halogen, m is the integer of 0-4, R
2Be C
1-C
6Alkyl or aryl;
Said electron donor I is an ester compound;
Said electron donor II is a siloxane compound, and it is a general formula R
3 xR
4 ySi (OR
5)
zShown in one or more combination in the compound, in the formula, R
3Be alkyl, hydrochloric ether or halogen, R
4Be alkyl, hydrochloric ether or halogen, R
5Be alkyl, 0≤x＜2,0≤y＜2,0＜z≤4 and x, y and z are integer;
The ratio of said magnesium compound, titanium compound, electron donor I and electron donor II is 1 gram magnesium compound: 15.75-62.5 milliliter titanium compound: 0.075-0.375 milliliter electron donor I:0.10-0.39 milliliter electron donor II.
2. catalyzer according to claim 1, wherein, said magnesium compound is one or more the combination in magnesium chloride, magnesium bromide, magnesium iodide and the diethoxy magnesium.
3. catalyzer according to claim 1, wherein, said titanium compound is one or more the combination in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, purity titanium tetraethoxide and the chlorine triethoxy titanium.
4. catalyzer according to claim 1; Wherein, said electron donor I is one or more the combination in methyl-formiate, methyl acetate, ETHYLE ACETATE, oil of Niobe, ethyl benzoate, propyl benzoate, diethyl succinate, n-butyl phthalate, diisobutyl phthalate, trimethyl phosphite 99, triethyl phosphate, tributyl phosphate and the triphenylphosphate.
5. catalyzer according to claim 1; Wherein, said electron donor II is one or more the combination in tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, Union carbide A-162, ethyl triethoxysilane, n-propyl triethoxyl silane, a chlorine triethoxyl silane, 3-chloropropyl triethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane, isobutyl-Trimethoxy silane, hexyl trimethoxy silane, dimethyldimethoxysil,ne, diisopropyl dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane and the phenyl methyl dimethoxy silane.
6. each described Preparation of catalysts method that is used for ethene and alpha-olefin copolymer of claim 1-5, it may further comprise the steps:
Magnesium compound is dissolved in the hydrocarbon solvent, adds alcoholic solvent, reaction is 2-4 hour under 70-90 ℃ of agitation condition;
Add electron donor I then, agitation condition reacted 0.5-2 hour down, added electron donor II again, and agitation condition reacted 0.5-2 hour down;
Be cooled to room temperature, drip titanium compound, in 1-2 hour, drip and finish, be warming up to 70-90 ℃ then, agitation condition reacted 1-3 hour down;
Above-mentioned reaction product press filtration is desolvated to remove, add the hydrocarbon solvent stirring, be warming up to 70-90 ℃, add electron donor II, reaction is 1-2 hour under the agitation condition, adds electron donor I then, and agitation condition reacted 1-2 hour down;
Add titanium compound, agitation condition reacted 1-3 hour down;
Filter, washing, drying obtains the described catalyzer that is used for ethene and alpha-olefin copolymer;
Wherein, the ratio of said magnesium compound, alcoholic solvent, titanium compound, electron donor I and electron donor II is 1 gram magnesium compound: 1.5-6.0 milliliter alcoholic solvent: 15.75-62.5 milliliter titanium compound: 0.075-0.375 milliliter electron donor I:0.10-0.39 milliliter electron donor II; Titanium compound adds at twice, and the first time, the volume ratio with the add-on second time was 1: 2-4: 1; Electron donor I adds at twice, and the first time, the volume ratio with the add-on second time was 2: 1-1: 6; Electron donor II adds at twice, and the first time, the volume ratio with the add-on second time was 3: 1-7: 1.
7. preparation method according to claim 6, wherein, said hydrocarbon solvent is one or more the combination in aliphatic hydrocarbon, cycloaliphates, aromatic hydrocarbon and the halohydrocarbon.
8. preparation method according to claim 6, wherein, said alcoholic solvent is fatty alcohol and/or alicyclic alcohol.
9. catalyst composition that is used for ethene and alpha-olefin copolymer, it comprises following component:
Each described catalyzer that is used for ethene and alpha-olefin copolymer of claim 1-5;
A kind of promotor, it is a general formula R
6 fMX
3 3-fShown in one or more combination in the compound, in the formula, R
6Be C
1-C
15Alkyl, X
3Be halogen, M is a metallic element, and f is the integer of 1-3.
10. catalyst composition according to claim 9; Wherein, said promotor is one or more the combination in trimethylaluminium, triethyl aluminum, triisobutyl aluminium, chlorodimethylalumiu, diethylaluminum chloride, di-isobutyl aluminum chloride, sesquialter methyl chloride aluminium, sesquialter ethylaluminium chloride, methylaluminium dichloride and the ethylaluminium dichloride.
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| CN105985464A (en) * | 2015-03-05 | 2016-10-05 | 中国石油天然气股份有限公司 | Olefin polymerization solid catalyst component and catalyst thereof |
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