CN1916000A - Compound of organic siloxane, and catalyst system including the compound - Google Patents
Compound of organic siloxane, and catalyst system including the compound Download PDFInfo
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Abstract
This invention provides an organosiloxane compound and catalyst system containing the organosiloxane compound for catalyzing olefin polymerization. The organosiloxane compound has a chemical formula of P(RI)Si(ORII)2, wherein P is cyclopentyl; RI is linear or branched C1-8 alkyl, or C6-10 cycloalkyl or aromatic group; RII is linear or branched C1-5 alkyl. The catalyst system comprises the organosiloxane compound, Ziegler-Natta catalyst and alkyl aluminum. The organosiloxane compound can coordinately donate electrons. The Ziegler-Natta catalyst system can reach the optimal catalytic efficiency, isotacticity and sensitivity to hydrogen simultaneously.
Description
Technical field
The invention provides a kind of electron donor that is used for the catalyst system of olefinic polymerization, and the catalyst system that comprises this electron donor.Particularly, the present invention relates to a kind of organosilicone compounds, it forms the catalyst system that is used for olefin catalytic as electron donor with Ziegler-natta (Ziegler-Natta) catalyzer and the aluminum alkyls of titanium system.
Background technology
The polyolefin catalyst that existing industrial production is used occupies the Qi Ge-Natta catalyst that is still of dominant position, through the development of decades, because updating and developing of catalyzer promoted the development of polymerization technique and the raising of polymer performance.
Be used for polyacrylic Qi Ge-natta catalyst systems composition and the preparation many disclosed documents all method report is arranged, usually be by MgCl
2The TiCl of load
4Be Primary Catalysts, promotor is that organo-aluminium compound and electron donor are formed.
Electron donor or title external electron donor are silicone compounds, and chemical general formula is SiR
m(OR`)
4-m, wherein R be alkyl, aryl, vinyl and other to contain the alkyl of N element and cycloalkyl and R ' be alkyl, usually select the less alkyl of molecular weight for use, as methyl, ethyl.
The effect of external electron donor is to improve polyacrylic degree of isotacticity or heptane extracting residuum, mmm or the unitary ratio of mmmmm in the polypropylene molecular chain that also useful NMR characterizes.Different silicone compounds has not same-action in polyacrylic degree of isotacticity, simultaneously owing to add external electron donor the polymerization efficiency of catalyzer and molecular weight and molecular weight distribution is had considerable influence.
Existing polypropylene mainly by on body endless tube technology, the caldron process or gas-phase polymerization process produce, in actual production, produce the polypropylene product of various grades, when producing the polypropylene of different grades, wish that catalyst system also can meet certain requirement, when hanging down the MFR polypropylene product as the production high molecular, need catalyst system insensitive to the hydrogen adjusting function, be easier to like this produce and contain the high-molecular weight polypropylene material, then need the good catalyst system of hydrogen adjusting function susceptibility for the polypropylene product that will produce higher MFR.Yet existing catalyst body ties up to catalyst efficiency, degree of isotacticity and hydrogen adjusting function susceptibility and is difficult to reach simultaneously best.Silane external electron donor commonly used at present has dimethoxydiphenylsilane (DDMS), dipropyl dimethoxy silane (DIP), second, isobutyl dimethoxy silane (DIB), cyclohexyl methyl dimethoxy silane (CMDM), dicyclopentyl dimethoxyl silane (D-DONOR), isobutyl-normal-butyl dimethoxy silane.Above-mentioned silane respectively has its characteristics, as described in Chinese patent CN87104647 and CN1176258, influence for catalyst activity is minimum with the dicyclopentyl dimethoxyl silane, and degree of isotacticity is the highest, but it is less that the catalyst system of its composition is regulated the influence of polypropylene molecule amount to hydrogen, is fit to the higher polymkeric substance of preparation molecular weight.The Z-N catalyst system that dipropyl dimethoxy silane, second, isobutyl dimethoxy silane are formed is regulated sensitivity of polypropylene molecule amount to hydrogen, it is less to be fit to the preparation molecular weight, the polymkeric substance that MFR is higher, catalyst activity is higher, but its degree of isotacticity is lower, the Z-N catalyst system that dimethoxydiphenylsilane, cyclohexyl methyl dimethoxy silane are formed, higher to hydrogen susceptibility and degree of isotacticity, the catalyst activity of composition is lower.
The inventor finds that the silane electron donor that connects two groups inequality on same Siliciumatom has synergistic effect, and adopts two kinds or the two above electron donor to mix when using, and does not then have the synergistic effect generation.
Summary of the invention
The purpose of this invention is to provide a kind of electron donor that is suitable for use in the catalyst system of olefinic polymerization.
A further object of the present invention provides a kind of catalyzer that is used for olefinic polymerization that comprises above-mentioned electron donor.
The invention provides a kind of organosilicone compounds: P (R with structure shown in the formula (I)
I) Si (OR
II)
2(I), wherein P is cyclopentyl, R
IBe selected from the C of straight or branched
1～C
8Alkyl, C
6～C
10Cycloalkyl or C
6～C
10Aromatic base, R
IIBe selected from C
1～C
5Alkyl.R
IAnd R
IICan be identical also can be inequality, in the described formula (I), R
IPreferred C
1～C
6Straight or branched alkyl, C
6～C
8Cycloalkyl or C
6～C
10Aromatic base, more preferred C
1～C
4Straight or branched alkyl or C
6Cycloalkyl or C
6Aromatic base is as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, cyclohexyl, phenyl; R
IIBe preferably C
1～C
3Alkyl, more preferably methyl, ethyl.R
IAnd R
IICan be methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-simultaneously.The electron donor of most preferred combinations is cyclopentyl isobutyl-dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl normal-butyl dimethoxy silane, cyclopentyl propyl group dimethoxy silane, cyclopentyl cyclohexyl dimethoxy silane, cyclopentyl phenyl dimethoxy silane among the present invention.
The present invention also provides a kind of catalyst system that is used for olefinic polymerization, this catalyst system comprises the organosilicone compounds of Ziegler-natta catalyst, aluminum alkyls and the claim 1 of titanium system, wherein, the proportioning of each catalyst component is: Al/Ti is 10～550, preferred 10～200, and Si/Ti is 2～100, preferred 2～30.Catalyst system in above-mentioned scope has the good active releasing rule, especially corresponding and three component polymerization systems.
Particularly, in catalyst system of the present invention, Ziegler-natta catalyst for titanium system, it generally is that Ti is carried in the magnesium chloride, it is for containing titanium, magnesium, halogen, its preparation process of the solid catalyst of composition such as multi-carboxylate and organo phosphorous compounds is seen Chinese patent CN1270185, quoted at this, also can being stated from the magnesium chloride with the preparation of other different methods, it is for containing titanium, magnesium, halogen, the solid catalyst of composition such as multi-carboxylate and organo phosphorous compounds, this component mainly comprises about 1.5～7.0 weight % titaniums, about 10～20 weight % magnesium, about 40～70 weight % are selected from chlorine, bromine, the halogenide of iodine; About 5～25 weight % are selected from aliphatics, aromatic series and alicyclic multi-carboxylate, about 0.1～2.5 weight % organo phosphorous compounds, and wherein each alkyl contains 1～6 carbon atom; Organo-aluminium compound can be triethyl aluminum, tri-butyl aluminum, triisobutyl aluminium, is the catalyzer initiation; Organosilane of the present invention is as electron donor, has the polyacrylic taxis of adjusting, control the effect of polyacrylic atactic form, it is a dimethoxy silicane structure, is cyclopentyl isobutyl-dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl normal-butyl dimethoxy silane, cyclopentyl propyl group dimethoxy silane in the present invention.
Organo-aluminium compound and electron donor mix and contacts afterwards, add reactor simultaneously with the Ziegler-natta catalyst of titanium system again and contact with propylene, and produce polyreaction at a certain temperature, can adopt different polymerization procedures, enter poly-unit and carry out polyreaction as adopting to contact with propylene again after the prepolymerization.
This catalyst body ties up in the propylene polymerization processes, can adopt various ways to realize, as liquid-phase bulk polymerization, vapour phase polymerization and the supercritical polymerization of continuous processing, interrupter method and the polymerization technique that adopts different array configurations.
Adopt the synthetic electron donor of the present invention of this area ordinary method.
The catalyst according to the invention system can be used for vapor phase process propylene polymerization and copolymerization, liquid phase method propylene polymerization and copolymerization and slurry method propylene polymerization and copolymerization, and the polypropylene production technique of above-mentioned different polymerization compositions, can prepare and produce alfon, multipolymer, comprise the atactic copolymerized polypropene of crushing-resistant copolymerization polypropylene and ethene and alhpa olefin.In the polymer product of the method for preparing of the application of the invention catalyst system, the heptane soluble part is 0.96～2.8% of a polymer product.
The present invention is in order to overcome the shortcoming that exists in the above-mentioned prior art, a kind of external electron donor that is used for olefinic polymerization or copolymerization is proposed, have synergistic effect owing to connect the silane electron donor of two groups inequality on same Siliciumatom, the Z-N catalyst system that uses this electron donor to form can make catalyst efficiency, degree of isotacticity and hydrogen response reach best simultaneously.Z-N catalyst system of the present invention has the polymerization efficiency that contains dicyclopentyl dimethoxyl silane (D-DONOR) catalyst system simultaneously, and better hydrogen regulation sensitivity is arranged than it, simultaneously degree of isotacticity is higher than adopting dipropyl dimethoxy silane (DIP), second, isobutyl dimethoxy silane (DIB), cyclohexyl methyl dimethoxy silane (CMDM), has higher using value.
Embodiment
Preparation embodiment 1: the preparation of cyclopentyl isobutyl-dimethoxy silane
Chloro-iso-butane at first, chlorocyclopentane is being that solvent and the effect of magnesium powder form Grignard reagent with anhydrous organic ether respectively, then in tetramethoxy-silicane/Grignard reagent ratio 1.1～1: 1 carries out the reaction of tetramethoxy-silicane and chlorocyclopentane Grignard reagent, and then in this reaction product, dripping the chloro-iso-butane Grignard reagent, reflux temperature is temperature of reaction.The organic ether solvent that adopts has methyl tertiary butyl ether, tetrahydrofuran (THF), ether, preferably adopts methyl tertiary butyl ether.
Preparation embodiment 2: the preparation of cyclopentyl sec.-propyl dimethoxy silane
Embodiment 1 is identical with preparation, and different is to replace chloro-iso-butane with chloroisopropane
Preparation embodiment 3: the preparation of cyclopentyl normal-butyl dimethoxy silane.
Embodiment 1 is identical with preparation, and different is to replace chloro-iso-butane with n-propylcarbinyl chloride
Preparation embodiment 4: the preparation of cyclopentyl cyclohexyl dimethoxy silane.
Embodiment 1 is identical with preparation, and different is to replace chloro-iso-butane with chlorocyclohexane
Preparation embodiment 5: the preparation of cyclopentyl phenyl dimethoxy silane.
Embodiment 1 is identical with preparation, and different is to replace chloro-iso-butane with chlorinated benzene
Preparation embodiment 6: the preparation of cyclopentyl-methyl dibutoxy silane.
Embodiment 1 is identical with preparation, and different is to replace chloro-iso-butane with methyl iodide,
Replace tetramethoxy-silicane with four butoxy silanes.
Preparation embodiment 7: the preparation of cyclopentyl iso-octyl dimethoxy silane.
Embodiment 1 is identical with preparation, and different is to replace chloro-iso-butane with chloro-iso-octane.
The trade names of the Ziegler-natta catalyst of the titanium system that uses are N and DQ type catalyzer, or Mitsui oiled TK260 polypropylene catalyst, and this catalyzer Ti content is 2.2%.
The alkylaluminium cpd that uses is triethyl aluminum AT, dilutes its concentration to 0.88mol/L with hexane before using.
The silane electron donor of preparation embodiment 1～5 preparation is diluted as 110mmol/L before use, and Dilution ratio is the hexane solution of 20: 1 (V/V).
Test event:
Degree of isotacticity: adopt the GB/T2412-80 standard testing;
Melt flow rate (MFR) MFR adopts ISO1133 C4 standard testing.
The data of each embodiment see Table 1.
Embodiment 1
Single still aggregation test carries out at the 5L polymermaking autoclave.Polymeric kettle is standby after with nitrogen purging, and each catalyst component is formulated in the hexane in proportion, adds a certain amount of catalyzer for preparing in the polymeric kettle under nitrogen protection; add a certain amount of liquid propylene; the hydrogen pressure pan with the pressure difference metering, enters reactor; after material adds; be rapidly heated, outlet temperature is controlled at 55 ℃～120 ℃ and carries out propylene polymerization, and stirring velocity is 240 rev/mins; emit material by baiting valve behind the polymerization certain hour, dry, weigh, analyze.
In embodiment 1-1 to 1-9, the Ziegler-natta catalyst of the titanium system that uses is N type catalyzer, and the electron donor kind is cyclopentyl isobutyl-dimethoxy silane (DE) solution, and the catalyzer of preparing with aluminum alkyls adds in the polymeric kettle.Add excessive propylene, feed hydrogen, be rapidly heated, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, and stirring velocity is 240 rev/mins, and the polymerization certain hour is emitted material by baiting valve, and is dry, weigh.
Embodiment 1-1, main catalyst component Ziegler-natta catalyst 20.0mg, catalyst proportion is Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), hydrogen add-on 5L, polymerization time 60min, melt flow rate (MFR) is 18.2g/10min, polymerization activity is 3.26 myriagrams polypropylene/gram catalyzer.
Embodiment 1-2, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=5/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 14.2g/10min, polymerization activity is 2.94 myriagrams polypropylene/gram catalyzer.
Embodiment 1-3, catalyst proportion are Al/Ti=50/1 (mol/mol), Si/Ti=2/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 14.3g/10min, polymerization efficiency is 2.92 myriagrams polypropylene/gram catalyzer.
Embodiment 1-4, catalyst proportion are Al/Ti=2/1 (mol/mol), Si/Ti=15/1 (mol/mol), hydrogen 5L, polymerization time 60min, product heavily are 1195g, melt flow rate (MFR) is 18.3g/10min, and polymerization efficiency is 3.29 myriagrams polypropylene/gram catalyzer.
Embodiment 1-5, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=20/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 19.9g/10min, polymerization efficiency is 3.06 myriagrams polypropylene/gram catalyzer.
Embodiment 1-6, catalyst proportion are Al/Ti=200/1 (mol/mol), Si/Ti=30/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 20.9g/10min, polymerization efficiency is 3.46 myriagrams polypropylene/gram catalyzer.
Embodiment 1-7, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 2.5L, polymerization time 60min, melt flow rate (MFR) is 9.9g/10min, polymerization efficiency is 3.36 myriagrams polypropylene/gram catalyzer.
Embodiment 1-8, catalyst proportion are Al/Ti=550/1 (mol/mol), Si/Ti=15/1 (mol/mol), and hydrogen 7.5L, polymerization time 60min, melt flow rate (MFR) is 29.9g/10min, polymerization efficiency is 3.56 myriagrams polypropylene/gram catalyzer.
Embodiment 1-9, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 10L, polymerization time 60min, melt flow rate (MFR) is 39.9g/10min, polymerization efficiency is 3.50 myriagrams polypropylene/gram catalyzer.
Embodiment 1-10, catalyst proportion are Al/Ti=200/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 12.5L, polymerization time 60min, melt flow rate (MFR) is 48.9g/10min, polymerization efficiency is 3.39 myriagrams polypropylene/gram catalyzer.
Embodiment 1-11, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 120min, melt flow rate (MFR) is 18.9g/10min, polymerization efficiency is 5.59 myriagrams polypropylene/gram catalyzer.
Embodiment 1-12, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 180min, melt flow rate (MFR) is 18.2g/10min, polymerization efficiency is 6.95 myriagrams polypropylene/gram catalyzer.
Embodiment 2
Ziegler-natta catalyst is a N type catalyzer, and DB is a cyclopentyl normal-butyl dimethoxy silane solution, and the catalyzer of aluminum alkyls preparation adds in the polymeric kettle.Add the excessive propylene of propylene, feed hydrogen, be rapidly heated, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, and stirring velocity is 240 rev/mins, and the polymerization certain hour is emitted material by baiting valve, and is dry, weigh.
Embodiment 2-1, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 2.5L, polymerization time 60min, melt flow rate (MFR) is 8.7g/10min, polymerization efficiency is 3.2 myriagrams polypropylene/gram catalyzer.
Embodiment 2-2, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 16.9g/10min, polymerization efficiency is 3.3 myriagrams polypropylene/gram catalyzer.
Embodiment 2-3, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=2.5/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 17.3g/10min, polymerization efficiency is 3.36 myriagrams polypropylene/gram catalyzer.
Embodiment 2-4, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=30/1 (mol/mol), and hydrogen 15L, polymerization time 60min, melt flow rate (MFR) is 50.3g/10min, polymerization efficiency is 3.1 myriagrams polypropylene/gram catalyzer.
Embodiment 3
Ziegler-natta catalyst is a N type catalyzer, and DP is a cyclopentyl sec.-propyl dimethoxy silane solution, and the catalyzer of aluminum alkyls preparation adds in the polymeric kettle.Add excessive propylene, feed hydrogen, be rapidly heated, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, and stirring velocity is 240 rev/mins, and the polymerization certain hour is emitted material by baiting valve, and is dry, weigh.
Embodiment 3-1, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 2.5L, polymerization time 60min, melt flow rate (MFR) is 9.6g/10min, polymerization efficiency is 3.4 myriagrams polypropylene/gram catalyzer.
Embodiment 3-2, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 15L, polymerization time 60min, melt flow rate (MFR) is 70.9g/10min, polymerization efficiency is 3.42 myriagrams polypropylene/gram catalyzer.
Embodiment 3-3, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=2.5/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 18.6g/10min, polymerization efficiency is 3.5 myriagrams polypropylene/gram catalyzer.
Embodiment 3-4, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=30/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 15.9g/10min, polymerization efficiency is 3.3 myriagrams polypropylene/gram catalyzer.
Embodiment 4
Ziegler-natta catalyst is a N type catalyzer, and DC is a cyclopentyl cyclohexyl dimethoxy silane solution, and the catalyzer of aluminum alkyls preparation adds in the polymeric kettle.Add excessive propylene, feed hydrogen, be rapidly heated, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, and stirring velocity is 240 rev/mins, and the polymerization certain hour is emitted material by baiting valve, and is dry, weigh.
Embodiment 4-1, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 2.5L, polymerization time 60min, melt flow rate (MFR) is 2.7g/10min, polymerization efficiency is 3.05 myriagrams polypropylene/gram catalyzer.
Embodiment 4-2, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 15L, polymerization time 60min, melt flow rate (MFR) is 30.9g/10min, polymerization efficiency is 3.14 myriagrams polypropylene/gram catalyzer.
Embodiment 4-3, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=2.5/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 10.9g/10min, polymerization efficiency is 3.16 myriagrams polypropylene/gram catalyzer.
Embodiment 4-4, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=30/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 10.1g/10min, polymerization efficiency is 2.89 myriagrams polypropylene/gram catalyzer.
Embodiment 5
Ziegler-natta catalyst is a N type catalyzer, and DC is a cyclopentyl cyclohexyl dimethoxy silane solution, and the catalyzer of aluminum alkyls preparation adds in the polymeric kettle.Add excessive propylene, heat up, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, and stirring velocity is 240 rev/mins, and the polymerization certain hour is emitted material by baiting valve, and is dry, weigh.
Embodiment 5-1, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 2.5L, polymerization time 60min, melt flow rate (MFR) is 3.7g/10min, polymerization efficiency is 2.96 myriagrams polypropylene/gram catalyzer.
Embodiment 5-2, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 15L, polymerization time 60min, melt flow rate (MFR) is 40.6g/10min, polymerization efficiency is 3.02 myriagrams polypropylene/gram catalyzer.
Embodiment 5-3, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=2.5/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 7.9g/10min, polymerization efficiency is 3.12 myriagrams polypropylene/gram catalyzer.
Embodiment 5-4, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=30/l (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 7.6g/10min, polymerization efficiency is 2.78 myriagrams polypropylene/gram catalyzer.
Ziegler-natta catalyst adopts the Ziegler-Natta catalyst of TK-260 or other titanium system can obtain similar result equally.
The comparative example 1:
Ziegler-natta catalyst is a N type catalyzer, and the electron donor kind is that the catalyzer of dicyclopentyl dimethoxyl silane (D-donor) solution and aluminum alkyls preparation adds in the polymeric kettle.Add excessive propylene, feed hydrogen, be rapidly heated, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, and stirring velocity is 240 rev/mins, and the polymerization certain hour is emitted material by baiting valve, and is dry, weigh.
Comparative example 1-1, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 5.9g/10min, polymerization efficiency is 3.26 myriagrams polypropylene/gram catalyzer.
Comparative example 1-2, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 7.5L, polymerization time 60min, melt flow rate (MFR) is 7.9g/10min, polymerization efficiency is 3.31 myriagrams polypropylene/gram catalyzer.
Comparative example 1-3, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 10L, polymerization time 60min, melt flow rate (MFR) is 16.9g/10min, polymerization efficiency is 3.35 myriagrams polypropylene/gram catalyzer.
Comparative example 1-4, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 2.5L, polymerization time 60min, melt flow rate (MFR) is 1.9g/10min, polymerization efficiency is 3.15 myriagrams polypropylene/gram catalyzer.
Comparative example 1-5, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 120min, melt flow rate (MFR) is 2.2g/10min, polymerization efficiency is 5.25 myriagrams polypropylene/gram catalyzer.
Comparative example 1-6, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 180min, melt flow rate (MFR) is 1.9g/10min, polymerization efficiency is 6.45 myriagrams polypropylene/gram catalyzer.
The comparative example 2
Ziegler-natta catalyst is a N type catalyzer, and the electron donor kind is second, isobutyl dimethoxy silane (DIB) solution, and the catalyzer of aluminum alkyls preparation adds in the polymeric kettle.Add excessive propylene, feed hydrogen, be rapidly heated, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, and stirring velocity is 240 rev/mins, and the polymerization certain hour is emitted material by baiting valve, and is dry, weigh.
Comparative example 2-1, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 2.5L, polymerization time 60min, melt flow rate (MFR) is 11.9g/10min, polymerization efficiency is 2.65 myriagrams polypropylene/gram catalyzer.
Comparative example 2-2, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 21.5g/10min, polymerization efficiency is 2.66 myriagrams polypropylene/gram catalyzer.
Comparative example 2-3, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 7.5L, polymerization time 60min, melt flow rate (MFR) is 32.5g/10min, polymerization efficiency is 2.72 myriagrams polypropylene/gram catalyzer.
Comparative example 2-4, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 10L, polymerization time 60min, melt flow rate (MFR) is 45.5g/10min, polymerization efficiency is 2.52 myriagrams polypropylene/gram catalyzer.
Comparative example 2-5, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 120min, melt flow rate (MFR) is 22.5g/10min, polymerization efficiency is 3.52 myriagrams polypropylene/gram catalyzer.
Comparative example 2-6, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 180min, melt flow rate (MFR) is 23.5g/10min, polymerization efficiency is 4.48 myriagrams polypropylene/gram catalyzer.
Comparative example 2-7, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=5/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 21.4g/10min, polymerization efficiency is 2.70 myriagrams polypropylene/gram catalyzer.
Comparative example 2-8, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=2/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 20.3g/10min, polymerization efficiency is 2.87 myriagrams polypropylene/gram catalyzer.
Comparative example 2-9, catalyst proportion is Al/Ti=100/1 (mol/mol), adopt and mix D electron donor and B electron donor (1: 1), Si/Ti=5/1 (mol/mol), hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 9.2g/10min, polymerization efficiency is 2.78 myriagrams polypropylene/gram catalyzer.
The comparative example 3
Ziegler-natta catalyst is a N type catalyzer, and the electron donor kind is dimethoxydiphenylsilane (DDMS) solution, and the catalyzer of aluminum alkyls preparation adds in the polymeric kettle.Add excessive propylene, feed hydrogen, be rapidly heated, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, and stirring velocity is 240 rev/mins, and the polymerization certain hour is emitted material by baiting valve, and is dry, weigh.
Comparative example 3-1, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 13.5g/10min, polymerization efficiency is 2.48 myriagrams polypropylene/gram catalyzer.
Comparative example 3-2, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 120min, melt flow rate (MFR) is 13.5g/10min, polymerization efficiency is 3.28 myriagrams polypropylene/gram catalyzer.
The comparative example 4:
Ziegler-natta catalyst is a N type catalyzer, and the electron donor kind is cyclohexyl methyl dimethoxy silane (C-DONOR) solution, and the catalyzer of aluminum alkyls preparation adds in the polymeric kettle.Add excessive propylene, feed hydrogen, be rapidly heated, temperature is controlled at 70 ± 1 ℃ and carries out mass polymerization, and stirring velocity is 240 rev/mins, and the polymerization certain hour is emitted material by baiting valve, and is dry, weigh.
Comparative example 4-1, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 60min, melt flow rate (MFR) is 10.5g/10min, polymerization efficiency is 2.52 myriagrams polypropylene/gram catalyzer.
Comparative example 4-2, catalyst proportion are Al/Ti=100/1 (mol/mol), Si/Ti=10/1 (mol/mol), and hydrogen 5L, polymerization time 120min, melt flow rate (MFR) is 10.1g/10min, polymerization efficiency is 3.42 myriagrams polypropylene/gram catalyzer.Comparative example's data see Table 2.
Table 1
| Embodiment | The electron donor kind | Al/Ti(mo l/mol) | Si/Ti (mol/m ol) | Time (min) | H 2(L) | Polymerization efficiency (ten thousand gP/gcat) | MFRg/10min | Heptane extract wt% |
| 1-1 | DE | 100/1 | 10 | 60 | 5 | 3.26 | 16.2 | 1.00 |
| 1-2 | DE | 100/1 | 5 | 60 | 5 | 2.94 | 14.2 | 1.26 |
| 1-3 | DE | 50/1 | 2 | 60 | 5 | 2.76 | 14.3 | 1.89 |
| 1-4 | DE | 100/1 | 15 | 60 | 5 | 3.29 | 16.3 | 0.96 |
| 1-5 | DE | 100/1 | 20 | 60 | 5 | 3.06 | 16.9 | 0.96 |
| 1-6 | DE | 200/1 | 10/1 | 60 | 5 | 3.46 | 17.1 | 1.10 |
| 1-7 | DE | 100/1 | 10/1 | 60 | 2.5 | 3.36 | 5.9 | 1.05 |
| 1-8 | DE | 100/1 | 10/1 | 60 | 7.5 | 3.56 | 22.6 | 1.06 |
| 1-9 | DE | 100/1 | 10/1 | 60 | 10 | 3.50 | 31.8 | 1.05 |
| 1-10 | DE | 100/1 | 10/1 | 60 | 12.5 | 3.39 | 44.9 | 1.18 |
| 1-11 | DE | 100/1 | 10/1 | 120 | 5 | 5.59 | 16.5 | 1.00 |
| 1-12 | DE | 100/1 | 10/1 | 180 | 5 | 6.95 | 15.5 | 1.02 |
| 2-1 | DB | 100/1 | 10//1 | 60 | 2.5 | 3.2 | 8.7 | 1.69 |
| 2-2 | DB | 100/1 | 10//1 | 60 | 5.0 | 3.3 | 16.9 | 1.62 |
| 2-3 | DB | 100/1 | 2.5/1 | 60 | 5.0 | 3.36 | 17.3 | 2.18 |
| 2-4 | DB | 100/1 | 30/1 | 60 | 15 | 3.1 | 50.3 | 1.36 |
| 3-1 | DP | 100/1 | 10/1 | 60 | 2.5 | 3.4 | 5.6 | 1.68 |
| 3-2 | DP | 100/1 | 10/1 | 60 | 15 | 3.42 | 70.9 | 1.98 |
| 3-3 | DP | 100/1 | 2.5/1 | 60 | 5 | 3.5 | 18.6 | 2.60 |
| 3-4 | DP | 100/1 | 30/1 | 60 | 5 | 3.30 | 15.9 | 1.53 |
| 4-1 | DC | 100/1 | 10/1 | 60 | 2.5 | 3.05 | 2.7 | 1.39 |
| 4-2 | DC | 100/1 | 10/1 | 60 | 15 | 3.14 | 30.9 | 1.49 |
| 4-3 | DC | 100/1 | 2.5/1 | 60 | 5 | 3.16 | 10.9 | 1.53 |
| 4-4 | DC | 100/1 | 30/1 | 60 | 5 | 2.89 | 10.1 | 1.30 |
| 5-1 | DD | 100/1 | 10/1 | 60 | 2.5 | 2.96 | 3.7 | 1.20 |
| 5-2 | DD | 100/1 | 10/1 | 60 | 15 | 3.02 | 40.6 | 1.19 |
| 5-3 | DD | 100/1 | 2.5/1 | 60 | 5 | 3.12 | 7.9 | 2.69 |
| 5-4 | DD | 100/1 | 30/1 | 60 | 5 | 2.78 | 7.6 | 1.02 |
Table 2
| The comparative example | The electron donor kind | Al/Ti(mo l/mol) | Si/Ti (mol/m ol) | Time (min) | H 2(L) | Polymerization efficiency (ten thousand gP/gcat) | MFRg/10min | Heptane extract wt% |
| 1-1 | D | 100/1 | 10/1 | 60 | 5 | 3.26 | 5.4 | 0.86 |
| 1-2 | D | 100/1 | 10/1 | 60 | 7.5 | 3.31 | 7.9 | 0.90 |
| 1-3 | D | 100/1 | 10/1 | 60 | 10 | 3.35 | 10.9 | 0.88 |
| 1-4 | D | 100/1 | 10/1 | 60 | 12.5 | 3.15 | 13.9 | 0.75 |
| 1-5 | D | 100/1 | 10/1 | 60 | 2.5 | 3.15 | 1.9 | 0.75 |
| 1-6 | D | 100/1 | 10/1 | 120 | 5 | 5.25 | 5.2 | 0.88 |
| 1-7 | D | 100/1 | 10/1 | 180 | 5 | 6.45 | 5.3 | 0.85 |
| 1-8 | D | 100/1 | 5/1 | 60 | 5 | 3.21 | 5.5 | 0.89 |
| 1-9 | D | 100/1 | 15/1 | 60 | 5 | 3.05 | 5.1 | 0.71 |
| 2-1 | B | 100/1 | 10/1 | 60 | 2.5 | 2.65 | 11.9 | 1.89 |
| 2-2 | B | 100/1 | 10/1 | 60 | 5 | 2.66 | 21.5 | 1.80 |
| 2-3 | B | 100/1 | 10/1 | 60 | 7.5 | 2.72 | 32.5 | 1.76 |
| 2-4 | B | 100/1 | 10/1 | 60 | 10 | 2.52 | 45.5 | 1.95 |
| 2-5 | B | 100/1 | 10/1 | 120 | 5 | 3.52 | 22.5 | |
| 2-6 | B | 100/1 | 10/1 | 180 | 5 | 4.48 | 23.2 | 1.9 |
| 2-7 | B | 100/1 | 5/1 | 60 | 5 | 2.70 | 21.4 | 2.05 |
| 2-8 | B | 100/1 | 2/1 | 60 | 5 | 2.87 | 20.3 | 5.80 |
| 2-9 | Mix D and B (1: 1) | 100/1 | 10/1 | 60 | 5 | 2.78 | 9.2 | 1.06 |
| 3-1 | DDMS | 100/1 | 10/1 | 60 | 5 | 2.48 | 13.5 | 1.67 |
| 3-2 | DDMS | 100/1 | 10/1 | 120 | 5 | 3.28 | 13.1 | |
| 4-1 | C-DON OR | 100/1 | 10/1 | 60 | 5 | 2.58 | 10.5 | 2.09 |
| 4-2 | C-DON OR | 100/1 | 10/1 | 120 | 5 | 3.42 | 10.1 |
DE is that cyclopentyl isobutyl-dimethoxy silane, DB are that cyclopentyl normal-butyl dimethoxy silane, DP are that cyclopentyl sec.-propyl dimethoxy silane, D are that two cyclopentyl dimethoxy silanes, B are that diisobutyl dimethoxy silane, C are that cyclohexyl methyl dimethoxy silane, DDS are that dimethoxydiphenylsilane, DC are that cyclopentyl cyclohexyl dimethoxy silane, DD are cyclopentyl phenyl dimethoxy silane.
Claims (10)
1, a kind of organosilicone compounds is characterized in that, has with the chemical formula shown in the following formula (I):
P(R
I)Si(OR
II)
2 (I)，
Wherein, P is a cyclopentyl, R
IC for straight or branched
1～C
8Alkyl, C
6～C
10Cycloalkyl or C
6～C
10Aromatic base, R
IIBe C
1～C
5The alkyl of straight or branched.
2, according to the organosilicone compounds of claim 1, it is characterized in that R
IAnd R
IIBe methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-simultaneously.
3, according to the organosilicone compounds of claim 1, it is characterized in that R
IBe C
1～C
6Straight or branched alkyl, C
6～C
8Cycloalkyl or C
6～C
10Aromatic base.
4, according to the organosilicone compounds of claim 1, it is characterized in that R
IBe C
1～C
4Straight or branched alkyl, C
6Cycloalkyl or C
6Aromatic base.
5, according to the organosilicone compounds of claim 1, it is characterized in that R
IIBe C
1～C
3Alkyl.
6, according to the organosilicone compounds of claim 1, it is characterized in that R
IIBe methyl or ethyl.
7, according to the organosilicone compounds of claim 1, it is characterized in that described organosilicone compounds is cyclopentyl isobutyl-dimethoxy silane, cyclopentyl sec.-propyl dimethoxy silane, cyclopentyl normal-butyl dimethoxy silane, cyclopentyl propyl group dimethoxy silane, cyclopentyl cyclohexyl dimethoxy silane or cyclopentyl phenyl dimethoxy silane.
8, a kind of catalyst system that is used for olefinic polymerization is characterized in that, comprises following component:
(1) Primary Catalysts: titanium is a Ziegler-natta catalyst;
(2) promotor: aluminum alkyls; And
(3) electron donor: the organosilicone compounds of claim 1,
Wherein, the proportioning of each catalyst component is: Al/Ti is 10～550, and Si/Ti is 2～100.
9, catalyst system according to Claim 8 is characterized in that, the proportioning of each catalyst component is: Al/Ti is 10～200, and Si/Ti is 2～30.
10, the described organosilicone compounds of claim 1 is as the application of electron donor.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665018A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Silane compound and preparation method thereof |
| CN103665201A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and preparation method and catalytic system thereof |
| CN103965234A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Bicyclic hydrocarbon substituted silane compound and application thereof |
| CN105461745A (en) * | 2015-08-17 | 2016-04-06 | 临邑县鲁晶化工有限公司 | Dialkyldialkoxysilane and synthetic method thereof |
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2005
- 2005-08-19 CN CN200510090899A patent/CN100586953C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665018A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Silane compound and preparation method thereof |
| CN103665201A (en) * | 2012-09-07 | 2014-03-26 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and preparation method and catalytic system thereof |
| CN103665018B (en) * | 2012-09-07 | 2017-02-15 | 中国石油化工股份有限公司 | Silane compound and preparation method thereof |
| CN103965234A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Bicyclic hydrocarbon substituted silane compound and application thereof |
| CN103965234B (en) * | 2013-01-30 | 2016-08-10 | 中国石油天然气股份有限公司 | Bicyclic hydrocarbon substituted silane compound and application thereof |
| CN105461745A (en) * | 2015-08-17 | 2016-04-06 | 临邑县鲁晶化工有限公司 | Dialkyldialkoxysilane and synthetic method thereof |
| CN105461745B (en) * | 2015-08-17 | 2019-04-02 | 临邑县鲁晶化工有限公司 | A kind of dialkyl dialkoxy silicane and its synthetic method |
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