CN104761664A - Catalyst composition used in olefin polymerization and application thereof - Google Patents
Catalyst composition used in olefin polymerization and application thereof Download PDFInfo
- Publication number
- CN104761664A CN104761664A CN201510109939.6A CN201510109939A CN104761664A CN 104761664 A CN104761664 A CN 104761664A CN 201510109939 A CN201510109939 A CN 201510109939A CN 104761664 A CN104761664 A CN 104761664A
- Authority
- CN
- China
- Prior art keywords
- dimethyl acetal
- propanal dimethyl
- compound
- butyl
- acid 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
- 0 COCC(*)(COC)N Chemical compound COCC(*)(COC)N 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a catalyst composition used in olefin polymerization, which includes: a solid catalyst component (A), aluminum alkyl (B) and a composite external electron donor (C) composed of an organic silicone compound represented as the general formula (I) and an 1,3-diether compound represented as the general formula (II), wherein the solid catalyst component (A) comprises at least one from following group: magnesium, titanium, halogens, and an internal electron donor containing lone pair electrons, such as an ether, an ester and the like. The catalyst composition has an excellent effect of high temperature self-quenching and has a high orientation capability and normal-temperature activity.
Description
Technical field
The invention belongs to olefin polymerization catalysis technical field, relate to a kind of catalyst composition for olefinic polymerization and application thereof.
Background technology
As everyone knows, using magnesium, titanium, halogen and electron donor as the solid titanium catalyst component of basal component, can be used for olefinic polyreaction, particularly can obtain higher yields and the polymkeric substance compared with high isotactic in the alpha-olefine polymerizing with 3 carbon or more carbon atom, wherein electron donor compound is one of requisite composition in catalyst component, and the development along with internal electron donor compound result in polyolefin catalyst and constantly updates, external electron donor also needs the supporting development with internal electron donor.At present, disclosed multiple electron donor compound in a large number, such as internal electron donor monocarboxylic ester or multi-carboxylate, ketone, monoether or polyether, amine etc. and derivative thereof, external electron donor conventional for general formula be R
xsi (OR)
4-Xorganosilicone compounds.This external electron donor coordinates with existing solid catalyst, be applied to catalyzing propone polymerization, higher activity and orientation property can be had, but be applied in some occasion particularly gas phase process time, because gaseous media dispersion is so uneven, heat-transfer effect, also not as in liquid phase medium, causes the focus that there will be local in polymerization process, and catalyzer still has higher activity in high temperature, and then there will be implode phenomenon.
Patent of invention CN101835812A discloses a kind of external electron donor with high temperature self-gravitation, but its usage quantity is very large, and the ratio as the aluminum alkyls that requires and its consumption is less than 4, and orientation property is not high, and activity also has much room for improvement in addition.Patent of invention 201410008950.9 has applied for a kind of external electron donor acyloxy silane with high temperature self-gravitation, but the activity under the orientation property of its gained catalyzer and normal temperature all has much room for improvement, patent of invention 201410379646.5 has applied for the external electron donor with high temperature self-gravitation function, though have higher orientation property, the activity under its normal temperature still has much room for improvement.
Summary of the invention
Now being surprisingly found out that, is Rn Si (OR ') 4-n (I) by general formula, and wherein n is the organosilicone compounds of 0 or 1 and the diether compounds of general formula (II)
Composite as after external electron donor, when coordinating with existing solid catalyst, both had the effect of high temperature self-gravitation, the degree of the activity decrease under the specific activity normal temps namely under high temperature far above original organo-siloxane, will have and have very high activity and orientation property.
The present invention still further provides the application in olefin polymerization of a kind of catalyst composition of the present invention.
The present invention also provides a kind of pre-polymerized catalyst composition for olefinic polymerization in addition.
For achieving the above object, according to a first aspect of the invention, provide a kind of catalyst composition for the preparation of olefin polymer, it comprises following component:
A. ingredient of solid catalyst, it contains Mg, Ti, halogen and contains lone-pair electron as the internal electron donor compound containing O, N, P, S;
B. alkylaluminium cpd;
C. as A and the B component of external electron donor.
Wherein component A is for having general formula R
nsi (OR ')
4-n(I) silicoorganic compound, wherein n is 0 or 1; R, R ' be C
1~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cyclic hydrocarbon radical, C
6~ C
10aryl, C
7~ C
15alkaryl or aralkyl, and C wherein can by hybrid atom MCM-41;
B component is the diether compounds of general formula (II)
Wherein, R
1and R
2can be identical or not identical, be substituted or unsubstituted C
1~ C
10straight chained alkyl, C
3~ C
15branched-chain alkyl, C
3~ C
15cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or aralkyl, be preferably substituted or unsubstituted C
2~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
15aryl or C
7~ C
15alkaryl or aralkyl; R
1and R
2optionally can be keyed to ring or not Cheng Huan.
The mol ratio of the compound of general formula (I) and general formula (II) is 0.01 ~ 100: 1
For the organic silane compound of above-mentioned general formula (I), R ' wherein may be the same or different, be preferably methyl or ethyl or propyl group, more specifically, tetramethoxy-silicane can be selected from, tetraethoxysilane, tetrapropoxysilane, cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane, cyclopentyl-trimethoxy-silane, phenyltrimethoxysila,e, isopropyltri-methoxysilane, cyclohexyltriethyloxysilane, t-butyltriethoxysilane, cyclopentyl triethoxyl silane, phenyl triethoxysilane, isopro-pyltriethoxysilane, cyclohexyl dimethoxyethoxy silane, tertiary butyl methoxyl group diethoxy silane, cyclopentyl dimethoxyethoxy silane, one or more in phenyl dimethoxyethoxy silane.
Then optional from being selected from 2-propyl group-2-sec.-propyl-1,3-Propanal dimethyl acetal for described diether compounds, 2-propyl group-2-butyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-isobutyl--1,3-Propanal dimethyl acetal, 2-propyl group-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-butyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-butyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-amyl group-1,3-Propanal dimethyl acetal, 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2,2-bis-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, one or more in 2,2-bis-(2-ethylhexyl)-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes etc.
For in described ingredient of solid catalyst a, the compound of described internal electron donor compound preferably certainly containing O atom, as ethers, ester class, phenolic ether class, phenolic ester class and ketone.Wherein ether compound can be selected from 1,3-diether compound, preferred 2-propyl group-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-butyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-isobutyl--1,3-Propanal dimethyl acetal, 2-propyl group-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-butyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-butyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-amyl group-1,3-Propanal dimethyl acetal, 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2,2-bis-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, one or more in 2,2-bis-(2-ethylhexyl)-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes etc.
Ester compound can be selected from polybasic ester; Be preferably selected from malonate compound, succinate compound, glutarate compound, phthalate compound.More preferably diethyl phthalate is selected from, n-butyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate, four tetramethyl-n-butyl phthalates, tetramethyl-diisobutyl phthalate, tetrabromophthalate di-n-butyl, tetrabromophthalate diisobutyl ester, 2, 3-diη-propyl ethyl succinate, 2, 3-di-isopropyl ethyl succinate, 2, 3-di-n-butyl ethyl succinate, 2, 3-diisobutyl ethyl succinate, 2, 3-diη-propyl di-iso-octyl succinate, 2, 3-di-isopropyl di-iso-octyl succinate, 2, 3-di-n-butyl di-iso-octyl succinate and 2, one or more in 3-diisobutyl di-iso-octyl succinate etc.
Ester compound also can be selected from the ester of polyvalent alcohol or phenol formation, be preferably selected from 1,3-diol ester compound and 1,2-biphenol ester cpds, be more preferably selected from 2,4-glycol dibenzoate, 2,4-pentanediol two aligns propylbenzoic acid ester, 2,4-pentanediol two cuminic acid ester, 2,4-pentanediol, two pairs of isobutyl-benzene manthanoate, 2,4-pentanediol, two pairs of n-butylbenzoic acid esters, 2,4-pentanediol two p-tert-butyl benzoic acid ester, 3,5-heptanediol dibenzoate, 3,5-heptanediol two p-methylbenzoic acid ester, 3,5-heptanediol two p-ethylbenzoic acid ester, 3,5-heptanediol two aligns propylbenzoic acid ester, 3,5-heptanediol two cuminic acid ester, 3,5-heptanediol, two pairs of isobutyl-benzene manthanoate, 3,5-heptanediol, two pairs of n-butylbenzoic acid esters, 3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol two p-methylbenzoic acid ester, 4-ethyl-3,5-heptanediol two p-ethylbenzoic acid ester, 4-ethyl-3,5-heptanediol two n-propyl benzoate ester, 4-ethyl-3,5-heptanediol two pairs of butylbenzoic acid esters, 4-ethyl-3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-propyl group-1,2-biphenol dibenzoate, 1,2-biphenol two aligns propylbenzoic acid ester, 1,2-biphenol two cuminic acid ester, 1,2-biphenol, two pairs of isobutyl-benzene manthanoate, 1,2-biphenol, two pairs of n-butylbenzoic acid esters, 1,2-biphenol two p-tert-butyl benzoic acid ester, the 4-tertiary butyl-1,2-biphenol two aligns propylbenzoic acid ester, 4,5-dipropyl-1,2-biphenol two cuminic acid ester, 4-ethyl-1,2-biphenol two pairs of isobutyl-benzene manthanoate, 4-sec.-propyl-1,2-biphenol two pairs of n-butylbenzoic acid esters, 4-isopentyl-1,2-biphenol two p-tert-butyl benzoic acid ester, 2-ethyl-1,2-biphenol two aligns propylbenzoic acid ester, 4-isobutyl--5-ethyl-1,2-biphenol two cuminic acid ester, one or more in the 4-tertiary butyl-5-ethyl-1,2-biphenol two pairs of isobutyl-benzene manthanoate etc.
Therefore, for catalyst composition of the present invention, it preferably comprises following component:
A. ingredient of solid catalyst, it contains Mg, Ti, halogen and is selected from phthalate compound, 1,3-diether compounds, 1,3-malonate compound, succinate compound, 1, the internal electron donor compound of one or more in 3-diol ester compound, 1,2-diphenol ester cpds;
B. alkylaluminium cpd;
C. as A and the B component of external electron donor.
Wherein component A is for having general formula R
nsi (OR ')
4-n(I) silicoorganic compound, wherein n is 0 or 1; R, R ' be C
1~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cyclic hydrocarbon radical, C
6~ C
10aryl, C
7~ C
15alkaryl or aralkyl, and C wherein can by hybrid atom MCM-41;
B component is the diether compounds of general formula (II)
Wherein, R
1and R
2can be identical or not identical, be substituted or unsubstituted C
1~ C
10straight chained alkyl, C
3~ C
15branched-chain alkyl, C
3~ C
15cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or aralkyl, be preferably substituted or unsubstituted C
2~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
15aryl or C
7~ C
15alkaryl or aralkyl; R
1and R
2optionally can be keyed to ring or not Cheng Huan.
The ratio of the compound of general formula (I) and general formula (II) is 0.01 ~ 100 (mol/mol), is preferably 0.1 ~ 10 (mol/mol), is more preferably 0.3 ~ 3.0 (mol/mol).
In ingredient of solid catalyst a of the present invention, based on the gross weight of ingredient of solid catalyst a, the content of described titanium is 1wt% ~ 7wt%, and the content of magnesium is 8wt% ~ 20wt%; Preferably, the content of described titanium is 1.5wt% ~ 4.5wt%, and the content of magnesium is 15wt% ~ 20wt%.
Described magnesium compound comprise one of them halogen atom in magnesium dihalide, alkoxyl magnesium, alkyl magnesium, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula by-oxyl or halo-oxyl the derivative of replacing.Preferably magnesium compound is the alcohol adduct of magnesium dihalide or magnesium dihalide, such as magnesium dichloride, dibrominated magnesium, diiodinating magnesium and their alcohol adduct etc.
The general formula of described titanium compound is the compound of TiXm (ORa) 4-m, and in formula, Ra is the alkyl of C1 ~ C20, and X is halogen, 1≤m≤4.Such as titanium compound can be titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium etc., and preferred titanium compound is titanium tetrachloride.
Ingredient of solid catalyst a described in the present invention is by the following method preparation enumerated.
Method one: as the method Kaolinite Preparation of Catalyst component disclosed according to patent CN1506384.First, magnesium compound is mixed with organic alcohol compound and inert solvent, rising temperature for dissolving, then add phthalic anhydride mixing.Then contact with the titanium compound of precooling, after being warming up to certain temperature, adding internal electron donor compound and react for some time at a certain temperature, then with titanium compound process gained solid, repeatedly wash solid particulate with inert solvent again, after drying, obtain catalyst component.
Method two: be first dissolved in by magnesium compound in the solvent system comprising organic epoxy compounds, organo phosphorous compounds and inert diluent composition, mix after forming homogeneous solution with titanium compound, under precipitation additive exists, separates out solids; This solids contacts with internal electron donor compound, makes it be attached on solids, if desired, then processes solids with titanium tetrahalide and inert diluent.
Method three: by titanium compound of the present invention, concrete as TiCl4, the adducts being MgCl2pROH with general formula reacts prepares ingredient of solid catalyst.In MgCl2pROH, p is the number of 0.1 ~ 6, preferably 2 ~ 3.5, and R is the alkyl with 1 ~ 18 carbon atom.Adducts can be made spherical by the following method aptly: under not miscible with adducts unreactive hydrocarbons exist, and by alcohol (ROH) and MgCl2 mixing, makes the rapid chilling of this emulsion, thus adducts is solidified with the form of spheroidal particle.The adducts so obtained can directly and titanium compound react, or its before reacting with titanium compound can in advance through the dealcoholization (80 ~ 130 DEG C) of thermal control to obtain a kind of adducts, wherein the mole number of alcohol is generally lower than 3, preferably between 0.1 ~ 2.7.Can by adducts (dealcoholysis or itself) be suspended in cold TiCl4 (general 0 DEG C), and mixture temperature programming to 80 ~ 130 DEG C are kept 0.1 ~ 2 hour at this temperature, carry out the reaction with titanium compound.TiCl4 process can be carried out once or repeatedly.Can add internal electron donor compound during with TiCl4 process to process, this process also can repeat once or repeatedly.
Specifically can according to the method Kaolinite Preparation of Catalyst component disclosed in patent CN1091748.
Method four: also can add in arene compound with dialkoxy magnesium and stir, forms suspension; Suspension
With the process of tetravalence titanium chloride, and add internal electron donor and react, the solid arene compound obtained washs; And then with the process of tetravalence titanium chloride, finally with inert solvent washing, drain, obtain ingredient of solid catalyst.
Method five: according to the method Kaolinite Preparation of Catalyst component disclosed in patent US4540679.First, magnesium alkoxide and carbon dioxide reaction obtain alkyl magnesiumcarbonate carrier.Then transistion metal compound (be preferably tetravalent titanium compound) and alkyl magnesiumcarbonate carrier and internal electron donor react in certain proportion in inert solvent, and obtain solid catalyst.
Prepare the method for ingredient of solid catalyst a, as in addition magnesium compound, electron donor etc. formed emulsion in thinner, adding titanium compound and making it fixedly obtain spherical solid, more treatedly obtain ingredient of solid catalyst.In the above-mentioned preparation method of any one, required internal electron donor compound both can add with the form of compound; Also can add in other manners, as can be obtained by the precursor original position adopting internal electron donor compound to be applicable to, this precursor becomes required electron donor compound by example chemical reaction as is known such as esterification etc.
According to the present invention, state on the invention in catalyst composition, the general formula of described alkylaluminium cpd b is AlRbnX3-n, and in formula, Rb is the alkyl of hydrogen or C1 ~ C20, and X is halogen, 1 < n≤3.
In one particular embodiment of the present invention, described alkylaluminium cpd comprises triethyl aluminum, tri-propyl aluminum, three n-butylaluminum, triisobutyl aluminium, tri-n-octylaluminium, triisobutyl aluminium, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride, preferred triethyl aluminum, triisobutyl aluminium etc.
According to the present invention, in described catalyst composition, the mol ratio of described component a and components b is with titanium: aluminium counts 1: (5 ~ 1000).Be preferably 1: (20 ~ 250).The mol ratio of described component a and amount of component b is with titanium: c counts 1: (0.1 ~ 100).Be preferably 1: (1 ~ 50).
According to a second aspect of the invention, provide a kind of pre-polymerized catalyst composition for olefinic polymerization, it comprises the prepolymer that the above-mentioned catalyst composition of at least one and alkene carry out prepolymerization gained, the pre-polymerization multiple of described prepolymer is 0.1 ~ 1000g olefin polymer/g component a, and described alkene is preferably propylene.In the present invention, " pre-polymerized catalyst " refers to the catalyzer of lower transforming degree through polymerization procedure.Preferably, the transforming degree of pre-polymerized catalyst components is about 0.2 ~ 500 gram of polymkeric substance/gram ingredient of solid catalyst a.
Prepolymerization operation can at-20 ~ 80 DEG C, preferably at the temperature of 0 ~ 50 DEG C, carry out in a liquid or in gas phase.Prepolymerization step can carry out online as the part in continuous polymerization technique, or carries out independently in periodical operation.For the polymkeric substance that preparation amount is 0.5 ~ 20g/g catalyst component, particularly preferably the present invention urges
The batch pre-polymerization of agent and propylene.Polymerization pressure is 0.01 ~ 10MPa.
According to a third aspect of the present invention, provide a kind of olefine polymerizing process, described alkene is polymerized under the effect of above-mentioned catalyst composition or above-mentioned pre-polymerized catalyst composition.
In the present invention, the general formula of described alkene is CH2=CHR, and wherein R is alkyl or the aryl of hydrogen or C1 ~ C12.Such as, described alkene comprises ethene, propylene, 1-butylene, 4-methyl-1-pentene and 1-hexene, and preferred described alkene is propylene.
In a specific embodiment of the present invention, above-mentioned catalyst composition of the present invention or above-mentioned catalyst composition may be used for propylene all polymerization with or other alkene of propylene copolymerization reaction in.
Catalyzer of the present invention can directly add in polymerization process in reactor, or catalyzer and alkene pre-polymerization obtain pre-polymerized catalyst after add in reactor.
Olefinic polyreaction of the present invention carries out according to known polymerization process, can carry out in liquid phase or gas phase, or also can carry out under the operation of liquid and gas polymerization stage combination.Adopt conventional technology as slurry process, gas-phase fluidized-bed etc.Adopt following reaction conditions preferably: polymerization temperature 0 ~ 150 DEG C, preferably 60 ~ 90 DEG C.
The present inventor, through many experiments, have been surprisingly found that, the present invention by adopt general formula be (I) organic silane compound as external electron donor for alkene especially propylene polymerization time, there is the effect of high temperature self-gravitation.
Embodiment
For making the present invention easier to understand, describe the present invention in detail below in conjunction with embodiment, these embodiments only play illustrative effect, are not limited to range of application of the present invention, NM specific experiment method in the following example, conveniently experimental technique carries out usually.
Testing method:
Polymkeric substance isotactic index adopts heptane extraction process to measure (heptane boiling extracting 6 hours): the polymer samples of 2g drying, be placed in extractor and after 6 hours with the extracting of boiling heptane, residuum be dried to the polymer weight (g) of constant weight gained and be isotactic index with the ratio of 2.
Embodiment
Propylene polymerization is tested
The purified nitrogen of the reaction flask of one 250ml is fully replaced, then 150ml is added through fully dry decane, fully saturated with polymerization-grade propylene again and nitrogen completely in replacement(metathesis)reaction bottle, reaction system is carried out completely under the atmosphere of propylene, after system temperature is risen to temperature of reaction, (triethyl aluminum consumption is AlEt to add a certain amount of triethyl aluminum and external electron donor
3/ Ti=100mol/mol, Ti are the content in added ingredient of solid catalyst a, AlEt
3/ external electron donor=20mol/mol), add ingredient of solid catalyst a and be about 60mg, start to carry out propylene polymerization, in process, pass into propylene continuously, and keep reaction flask pressure to be 0.01MPa, the temperature of reaction of maintenance setting 1 hour, then add the ethanol termination reaction of 30ml, obtain solids after filtration, and fully dry, obtain polymkeric substance, the ratio that the activity of catalyzer is obtained polymkeric substance and added solid catalysis dosage.
Aforesaid propylene polymerization result is in table 1 and table 2.
Table 1 propylene polymerization result
* CS-1-G is that Yingkou faces south Ke Hua group product; NG is Sinopec catalyzer company limited product; Ac
100/ Ac
67it is the ratio of the catalyst activity at 100 DEG C and 67 DEG C; External electron donor 1 in embodiment 1,2,3 and comparative example 2,3,4 and the mol ratio of external electron donor 2 are 1: 1.
As can be seen from Table 1, although comparative example 1 and 2 high temperature deactivation effect is fine, but its orientation property and activity are all too low, be difficult to practical application, compared to prior art, use compound external electron donor of the present invention, catalyzer both has good high temperature deactivation performance, there is the activity had under very high orientation property and normal temperature, be conducive to the practical application of catalyzer.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (17)
1., for the preparation of a catalyst composition for olefin polymer, it comprises following component:
A. ingredient of solid catalyst, it contains Mg, Ti, halogen and contains lone-pair electron as the internal electron donor compound containing O, N, P, S;
B. alkylaluminium cpd;
C. as A and the B component of external electron donor.
Wherein component A is for having general formula R
nsi (OR ')
4-n(I) silicoorganic compound, wherein n is 0 or 1; R, R ' be C
1~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cyclic hydrocarbon radical, C
6~ C
10aryl, C
7~ C
15alkaryl or aralkyl, and C wherein can by hybrid atom MCM-41;
B component is the diether compounds of general formula (II)
Wherein, R
1and R
2can be identical or not identical, be substituted or unsubstituted C
1~ C
10straight chained alkyl, C
3~ C
15branched-chain alkyl, C
3~ C
15cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or aralkyl, be preferably substituted or unsubstituted C
2~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
15aryl or C
7~ C
15alkaryl or aralkyl; R
1and R
2optionally can be keyed to ring or not Cheng Huan.
The mol ratio of the compound of general formula (I) and general formula (II) is 0.01 ~ 100: 1.
2. catalyst composition according to claim 1, is characterized in that:
R ' may be the same or different, and is methyl or ethyl or propyl group.
3. according to the catalyst system in claim 1 ~ 2 described in any one, it is characterized in that, described silicoorganic compound are selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane, cyclopentyl-trimethoxy-silane, phenyltrimethoxysila,e, isopropyltri-methoxysilane, cyclohexyltriethyloxysilane, t-butyltriethoxysilane, cyclopentyl triethoxyl silane, phenyl triethoxysilane, isopro-pyltriethoxysilane, cyclohexyl dimethoxyethoxy silane, tertiary butyl methoxyl group diethoxy silane, cyclopentyl dimethoxyethoxy silane, one or more in phenyl dimethoxyethoxy silane.
4. according to the catalyst system in claim 1 ~ 2 described in any one, it is characterized in that, described diether compounds is selected from 2-propyl group-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-butyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-isobutyl--1,3-Propanal dimethyl acetal, 2-propyl group-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-butyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-butyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-amyl group-1,3-Propanal dimethyl acetal, 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2,2-bis-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, one or more in 2,2-bis-(2-ethylhexyl)-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes etc.
5. according to the catalyst composition in Claims 1 to 4 described in any one, it is characterized in that, in described ingredient of solid catalyst a, the compound of described internal electron donor compound preferably certainly containing O atom, as ethers, ester class phenolic ether class, phenolic ester class and ketone.
6. according to the catalyst composition described in claim 5, it is characterized in that, in described ingredient of solid catalyst a, described internal electron donor compound is selected from 1,3-diether compound, preferred 2-propyl group-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-butyl-1,3-Propanal dimethyl acetal, 2-propyl group-2-isobutyl--1,3-Propanal dimethyl acetal, 2-propyl group-2-isopentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-butyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-butyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-isobutyl--2-amyl group-1,3-Propanal dimethyl acetal, 2-isobutyl--2-isopentyl-1,3-Propanal dimethyl acetal, 2-isopentyl-2-(2-ethyl-butyl)-1,3-Propanal dimethyl acetal, 2,2-bis-(2-methyl butyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, one or more in 2,2-bis-(2-ethylhexyl)-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl) fluorenes etc.
7. according to the catalyst composition described in claim 5, it is characterized in that, in described ingredient of solid catalyst a, described internal electron donor compound is selected from polybasic ester; Be preferably selected from malonate compound, succinate compound, glutarate compound, phthalate compound.More preferably diethyl phthalate is selected from, n-butyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate, four tetramethyl-n-butyl phthalates, tetramethyl-diisobutyl phthalate, tetrabromophthalate di-n-butyl, tetrabromophthalate diisobutyl ester, 2, 3-diη-propyl ethyl succinate, 2, 3-di-isopropyl ethyl succinate, 2, 3-di-n-butyl ethyl succinate, 2, 3-diisobutyl ethyl succinate, 2, 3-diη-propyl di-iso-octyl succinate, 2, 3-di-isopropyl di-iso-octyl succinate, 2, 3-di-n-butyl di-iso-octyl succinate and 2, one or more in 3-diisobutyl di-iso-octyl succinate etc.
8. according to the catalyst composition described in claim 5, it is characterized in that, in described ingredient of solid catalyst a, described internal electron donor compound is selected from the ester of polyvalent alcohol or phenol formation, be preferably selected from 1,3-diol ester compound and 1,2-biphenol ester cpds, be more preferably selected from 2,4-glycol dibenzoate, 2,4-pentanediol two aligns propylbenzoic acid ester, 2,4-pentanediol two cuminic acid ester, 2,4-pentanediol, two pairs of isobutyl-benzene manthanoate, 2,4-pentanediol, two pairs of n-butylbenzoic acid esters, 2,4-pentanediol two p-tert-butyl benzoic acid ester, 3,5-heptanediol dibenzoate, 3,5-heptanediol two p-methylbenzoic acid ester, 3,5-heptanediol two p-ethylbenzoic acid ester, 3,5-heptanediol two aligns propylbenzoic acid ester, 3,5-heptanediol two cuminic acid ester, 3,5-heptanediol, two pairs of isobutyl-benzene manthanoate, 3,5-heptanediol, two pairs of n-butylbenzoic acid esters, 3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol two p-methylbenzoic acid ester, 4-ethyl-3,5-heptanediol two p-ethylbenzoic acid ester, 4-ethyl-3,5-heptanediol two n-propyl benzoate ester, 4-ethyl-3,5-heptanediol two pairs of butylbenzoic acid esters, 4-ethyl-3,5-heptanediol two p-tert-butyl benzoic acid ester, 4-propyl group-1,2-biphenol dibenzoate, 1,2-biphenol two aligns propylbenzoic acid ester, 1,2-biphenol two cuminic acid ester, 1,2-biphenol, two pairs of isobutyl-benzene manthanoate, 1,2-biphenol, two pairs of n-butylbenzoic acid esters, 1,2-biphenol two p-tert-butyl benzoic acid ester, the 4-tertiary butyl-1,2-biphenol two aligns propylbenzoic acid ester, 4,5-dipropyl-1,2-biphenol two cuminic acid ester, 4-ethyl-1,2-biphenol two pairs of isobutyl-benzene manthanoate, 4-sec.-propyl-1,2-biphenol two pairs of n-butylbenzoic acid esters, 4-isopentyl-1,2-biphenol two p-tert-butyl benzoic acid ester, 2-ethyl-1,2-biphenol two aligns propylbenzoic acid ester, 4-isobutyl--5-ethyl-1,2-biphenol two cuminic acid ester, one or more in the 4-tertiary butyl-5-ethyl-1,2-biphenol two pairs of isobutyl-benzene manthanoate etc.
9. catalyst composition according to claim 1, is characterized in that comprising following component:
A. ingredient of solid catalyst, it contains Mg, Ti, halogen and is selected from phthalate compound, 1,3-diether compounds, 1,3-malonate compound, succinate compound, 1, the internal electron donor compound of one or more in 3-diol ester compound, 1,2-diphenol ester cpds;
B. alkylaluminium cpd;
C. as A and the B component of external electron donor.
Wherein component A is for having general formula R
nsi (OR ')
4-n(I) silicoorganic compound, wherein n is 0 or 1; R, R ' be C
1~ C
10straight chained alkyl, C
3~ C
10the alkyl of side chain, C
3~ C
10cyclic hydrocarbon radical, C
6~ C
10aryl, C
7~ C
15alkaryl or aralkyl, and C wherein can by hybrid atom MCM-41;
B component is the diether compounds of general formula (II)
Wherein, R
1and R
2can be identical or not identical, be substituted or unsubstituted C
1~ C
10straight chained alkyl, C
3~ C
15branched-chain alkyl, C
3~ C
15cycloalkyl, C
6~ C
20aryl or C
7~ C
20alkaryl or aralkyl, be preferably substituted or unsubstituted C
2~ C
10straight chained alkyl, C
3~ C
10branched-chain alkyl, C
3~ C
10cycloalkyl, C
6~ C
15aryl or C
7~ C
15alkaryl or aralkyl; R
1and R
2optionally can be keyed to ring or not Cheng Huan.
The ratio of the compound of general formula (I) and general formula (II) is 0.01 ~ 100 (mol/mol), is preferably 0.1 ~ 10 (mol/mol), is more preferably 0.3 ~ 3.0 (mol/mol).
10. according to the catalyst composition in claim 1 ~ 9 described in any one, it is characterized in that, in described ingredient of solid catalyst a, based on the gross weight of ingredient of solid catalyst a, the content of described titanium is 1wt% ~ 7wt%, and the content of magnesium is 8wt% ~ 20wt%; Preferably, the content of described titanium is 1.5wt% ~ 4.5wt%, and the content of magnesium is 15wt% ~ 20wt%.
11., according to the catalyst system in claim 1 ~ 10 described in any one, is characterized in that, the general formula of described alkylaluminium cpd is AlRbnX3-n, and wherein Rb is hydrogen or C
1~ C
20alkyl, X is halogen, 1 < n≤3.
12., according to the catalyst system in claim 1 ~ 11 described in any one, is characterized in that, the mol ratio of described component a and components b is with titanium: aluminium counts 1: (5 ~ 1000), preferably 1: (20 ~ 250); The mol ratio of component a and amount of component b is with titanium: external donor compound counts 1: (0.1 ~ 100), and preferably 1: (1 ~ 50).
13. 1 kinds of olefine polymerizing process, the catalyst composition of described alkene according to any one of claim 1 ~ 12 or effect under be polymerized.
14. methods according to claim 12, is characterized in that, the general formula of described alkene is CH2=CHR, and wherein R is hydrogen or C
1~ C
12alkyl or aryl; Preferred described alkene is propylene.
15. methods according to claim 12, is characterized in that, described being aggregated in gas-phase polymerization process is carried out.
16. methods according to claim 12, is characterized in that, described gas-phase polymerization process is UNIPOL propylene polymerization process.
17. methods according to claim 12, is characterized in that, described gas-phase polymerization process is Novolen propylene polymerization process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510109939.6A CN104761664A (en) | 2015-03-13 | 2015-03-13 | Catalyst composition used in olefin polymerization and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510109939.6A CN104761664A (en) | 2015-03-13 | 2015-03-13 | Catalyst composition used in olefin polymerization and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104761664A true CN104761664A (en) | 2015-07-08 |
Family
ID=53643791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510109939.6A Pending CN104761664A (en) | 2015-03-13 | 2015-03-13 | Catalyst composition used in olefin polymerization and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104761664A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111536A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111535A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111537A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111539A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109666092A (en) * | 2018-11-21 | 2019-04-23 | 北方华锦化学工业股份有限公司 | A kind of production technology of polypropylene lithium battery film special material |
| CN115873155A (en) * | 2023-01-03 | 2023-03-31 | 湖北华邦化学有限公司 | External electron donor composition, propylene polymerization catalytic composition and propylene polymerization method |
| CN116003656A (en) * | 2022-12-29 | 2023-04-25 | 湖北华邦化学有限公司 | External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001036496A1 (en) * | 1999-11-15 | 2001-05-25 | Basell Technology Company B.V. | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer |
| CN1958621A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Solid catalyst components in use for polymerizing olefin, catalyst, and application of catalyst |
| CN101423571A (en) * | 2007-11-01 | 2009-05-06 | 中国石油天然气股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN103154050A (en) * | 2010-10-19 | 2013-06-12 | 巴塞尔聚烯烃意大利有限责任公司 | Process for the polymerization of olefins |
-
2015
- 2015-03-13 CN CN201510109939.6A patent/CN104761664A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001036496A1 (en) * | 1999-11-15 | 2001-05-25 | Basell Technology Company B.V. | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer |
| CN1958621A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Solid catalyst components in use for polymerizing olefin, catalyst, and application of catalyst |
| CN101423571A (en) * | 2007-11-01 | 2009-05-06 | 中国石油天然气股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN103154050A (en) * | 2010-10-19 | 2013-06-12 | 巴塞尔聚烯烃意大利有限责任公司 | Process for the polymerization of olefins |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111536B (en) * | 2017-06-23 | 2021-03-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN109111535A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111537A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111539A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111539B (en) * | 2017-06-23 | 2021-02-05 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN109111536A (en) * | 2017-06-23 | 2019-01-01 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for olefinic polymerization |
| CN109111535B (en) * | 2017-06-23 | 2021-03-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst thereof |
| CN109666092A (en) * | 2018-11-21 | 2019-04-23 | 北方华锦化学工业股份有限公司 | A kind of production technology of polypropylene lithium battery film special material |
| CN109666092B (en) * | 2018-11-21 | 2021-05-11 | 北方华锦化学工业股份有限公司 | Production process of special material for polypropylene lithium battery membrane |
| CN116003656A (en) * | 2022-12-29 | 2023-04-25 | 湖北华邦化学有限公司 | External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process |
| CN116003656B (en) * | 2022-12-29 | 2024-04-26 | 湖北华邦化学有限公司 | External electron donor composition, ziegler-Natta catalyst composition and propylene polymerization process |
| CN115873155A (en) * | 2023-01-03 | 2023-03-31 | 湖北华邦化学有限公司 | External electron donor composition, propylene polymerization catalytic composition and propylene polymerization method |
| CN115873155B (en) * | 2023-01-03 | 2024-04-02 | 湖北华邦化学有限公司 | External electron donor composition, propylene polymerization catalyst composition and propylene polymerization method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104761664A (en) | Catalyst composition used in olefin polymerization and application thereof | |
| JP6745366B2 (en) | Olefin polymerization catalyst composition and use thereof | |
| KR102174946B1 (en) | Catalyst component for use in olefin polymerization reaction, catalyst, and application | |
| CN101921351B (en) | Preparation method of propylene polymerization solid titanium catalyst component | |
| CN105315390A (en) | Catalyst composition for olefin polymerization and application thereof | |
| CN103130931B (en) | A kind of Ball shape ethylene polymerization solid titanium catalytic and Synthesis and applications thereof | |
| CN103073661A (en) | Magnesium dichloride-based adducts and catalyst components obtained therefrom | |
| CN104974282A (en) | Catalyst component used in ethylene polymerization reaction, preparation method and catalyst | |
| CN104513330A (en) | Catalyst system used in olefin polymerization and application thereof | |
| CN104513327A (en) | Olefin polymerization catalyst composition and applications thereof | |
| CN104177520B (en) | It is used to prepare the ingredient of solid catalyst of olefin polymer | |
| CN109096421A (en) | A kind of catalyst and olefine polymerizing process for olefinic polymerization | |
| CN108084305A (en) | Solid titanium catalyst component for vinyl polymerization and preparation method thereof and ethane polymerization solid titanium catalyst | |
| CN104774281A (en) | Catalyst composition used for olefin polymerization, and applications thereof | |
| CN109096420A (en) | A kind of catalyst and olefine polymerizing process for olefinic polymerization | |
| CN109096417A (en) | A kind of catalyst and olefine polymerizing process for olefinic polymerization | |
| CN104513331A (en) | Catalyst composition used in olefin polymerization and application thereof | |
| CN103665199A (en) | Solid catalyst component for olefine polymerization, catalyst and application | |
| CN109096419A (en) | A kind of catalyst and olefine polymerizing process for olefinic polymerization | |
| CN103665200B (en) | A kind of ingredient of solid catalyst for olefinic polymerization, catalyzer and application | |
| CN103626893B (en) | For catalyst component and the method for preparing catalyst thereof of olefinic polyreaction | |
| CN104513332A (en) | Catalyst system used in olefin polymerization and application thereof | |
| CN106496374B (en) | A kind of catalyst system being used to prepare olefin polymer and its application | |
| CN105622800B (en) | A kind of catalytic component and its catalyst system for olefinic polyreaction | |
| CN104513328A (en) | Catalyst composition used in olefin polymerization reaction and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150708 |
|
| RJ01 | Rejection of invention patent application after publication |