CN104558277B - A catalyst used for olefin polymerization, a preparing method thereof and an olefin polymerization method - Google Patents
A catalyst used for olefin polymerization, a preparing method thereof and an olefin polymerization method Download PDFInfo
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Abstract
A catalyst used for olefin polymerization is disclosed. The catalyst comprises reaction products of following components: (A) a magnesium compound, (B) an organic alcohol ether compound, (C) a monooleate compound, (D) an organic phosphorus compound, (E) an organic epoxy compound, (F) a precipitation assistant, (G) an internal electron donor and (H) a titanium compound. The catalyst is higher in activity in olefin polymerization reactions, good in hydrogen regulation sensitivity and improved in particle shape, and the obtained polymer has less fine powder.
Description
Technical field
The present invention relates to a kind of catalyst for olefines polymerizing and its preparation method and application, relates in particular to a kind of single oil
Modified catalyst for olefines polymerizing of acid esters compound and organic alcohol ethers compound and its preparation method and application.
Background technology
Prepare high activity carried catalyst conventional method and be generally co-mulled and made into method, grind infusion process, spray carrier forming process
And high-speed stirred carrier forming process etc..Using catalyst major defect obtained in polishing be gained catalyst particle shape not
Good and particle diameter distribution width, therefore resulting polymers particle shape is bad, fine powder is more, and apparent density is low, more difficult to process units, and
Catalysis activity and capacity of orientation are undesirable；The catalyst of the preparation such as spray carrier forming process and high-speed stirred carrier forming process,
The particle shape of catalyst has obtained larger improvement, but the equipment and technique of carrier shaping are complex.
It is to be eutectoid out method that another kind prepares high activity carried catalyst conventional method, and magnesium halide is dissolved in into a kind of solvent body
Homogeneous solution is formed in system, then is separated out magnesium halide in active with halogenated titanium, and while the load of titanium active component is got on.Patent
CN85100997A discloses a kind of for olefinic polymerization and the catalyst system of combined polymerization, and the catalyst system includes：(first) contains
The ingredient of solid catalyst of Ti, (second) alkyl aluminum compound, (third) organosilicon, wherein (first) component be dissolved in by magnesium halide it is organic
Epoxide and organic phosphorus compound form homogeneous solution, and the solution and titanium tetrahalide or derivatives thereof mix, and are helping precipitation
In the presence of agent such as organic acid anhydride, organic acid, ether, ketone compound, solids is separated out；This solids is processed with multi-carboxylate,
It is attached on solids, then processed with titanium tetrahalide and inert diluent and obtained.The catalyst system is poly- for propylene
The isotacticity of resulting polymers is higher during conjunction, and apparent density is big, but catalyst activity is not high, and grain type is not so good.
CN1453298A discloses glycol ester compounds that a class contains special construction as electron donor, this kind of electron
The use of body can not only improve the activity of catalyst, and the molecular weight distribution of gained acrylic polymers is substantially widened, but such
The synthesis of glycol ester compounds and purifying technique are complicated, make Catalyst Production relatively costly.
In recent years, Z-N catalyst prods both domestic and external emerge in an endless stream, and catalyst stability is also continuous with polymerization catalytic activity
Improve.But still there is deficiency in terms of catalyst granules regularity and particle diameter distribution, this will result directly in gained polyolefin products heap
Product density is low, fine powder content is high, or even the generation in production the problems such as viscous kettle, extension kettle, obstruction pipeline, greatly have impact on industry
Productivity effect.What is be badly in need of in production at present is to develop a kind of equal spheric catalyst of particle diameter distribution of preparation process is simple to produce
Product.Monoleate class compound belongs to a kind of nonionic surface active agent, improves olefinic polymerization with surfactant at present and urges
The report of the precipitation of agent is also rarely found.The change that the present invention passes through introducing monoleate type of structured compound and material of organic ethers structure
Compound is improving the grain type and hydrogen response of catalyst.Unexpectedly, the activity of catalyst there has also been very big raising.
The content of the invention
The invention provides the modified olefin polymerization of a kind of monoleate class compound and organic alcohol ethers compound is urged
Agent, due to the presence of monoleate class compound and organic alcohol ethers compound, the particle shape of the catalyst is improved, and is used for
Very high activity and good hydrogen response are embodied during olefinic polymerization, resulting fine polymer powder content is low.
Concrete technical scheme is as follows：
An object of the present invention is to provide a kind of catalyst for olefines polymerizing, and the catalyst includes the reaction of following components
Product：（A）Magnesium compound（B）Organic alcohol ethers compound（C）Monoleate class compound（D）Organic phosphorus compound（E）It is organic
Epoxide（F）Precipitation additive（G）Internal electron donor（H）Titanium compound.
Described organic monoleate class compound is single oleic acid and the compound obtained by various alcohol esterifications, and wherein alcohol can be with
Selected from C1～C20Aliphatic monool, C2～C20Aliphatic glycol, C3～C20Fatty triol, C4～C20Aliph polyols, C6
～C30Aromatic alcohol, C3～C30Heterocyclylalkyl alcohol.Particular compound selected from glyceryl monooleate, single oleic acid propylene glycol ester, two
One kind in ethylene glycol monoleate, polyvinyl alcohol monoleate, sorbester p17, sorbitol monooleate, xylitol monoleate
Or it is various.It is preferred that one or more in glyceryl monooleate, single oleic acid propylene glycol ester, sorbester p17, especially preferably single oleic acid
Glyceride.
The formula of described organic alcohol ethers compound is（I）HO R1（OR2）n R3, formula（I）Middle n is the whole of 1≤n≤10
Number, R1、R2For C1～C4Alkyl, R3Selected from hydroxyl, C1～C30Aliphatic group, C3～C30Cycloalkyl, C6～C30Fragrance
Alkyl, C2～C30Heterocyclylalkyl.Particular compound is selected from diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol list
Butyl ether, 3- ethyoxyl -1- propyl alcohol, 1- ethyoxyl -2- propyl alcohol, 1,3- diethoxy -2- propyl alcohol, dipropylene glycol, diethylene glycol (DEG)
One or more in phenetole, triethylene glycol monoisopropyl ether, DPE.It is preferred that diethylene glycol monoethyl ether, diethyl
In glycol monomethyl ether, diethylene glycol monobutyl ether, 3- ethyoxyl -1- propyl alcohol, diethylene glycol (DEG) phenetole, triethylene glycol monoisopropyl ether one
Kind or it is various, especially preferably diethylene glycol monoethyl ether, one or more of 3- ethyoxyl -1- propyl alcohol.
Described magnesium compound is formula（II）Shown magnesium compound, formula（II）The hydrate and formula of shown magnesium compound
（II）At least one in the alcohol adducts of shown magnesium compound,
MgR4R5（II）
Formula（II）Middle R4And R5Respectively halogen, C1～C5Straight or branched alkoxyl and C1～C5Straight or branched alkane
One kind in base；Preferably magnesium dichloride, dibrominated magnesium, magnesium diiodide, the alcohol adducts of magnesium dichloride, the alcohol of dibrominated magnesium add
At least one in the alcohol adducts of compound and magnesium diiodide, in particularly preferred magnesium dichloride, dibrominated magnesium, magnesium diiodide
Plant or various, particularly preferably magnesium dichloride.
The organic phosphorus compound can be various organic phosphorus compounds commonly used in the art, for example, can be phosphoric acid, Asia
The hydrocarbyl carbonate and/or phosphoric acid of phosphoric acid, the halogenated hydrocarbons base ester of phosphoric acid, specifically for example can for trimethyl phosphate, triethyl phosphate,
In tributyl phosphate, triphenyl phosphate, Trimethyl phosphite, triethyl phosphite, tributyl phosphite, phosphorous acid benzene methyl
One or more, wherein preferably tributyl phosphate and/or tributyl phosphite.
The organic epoxy compound thing can be various organic epoxides commonly used in the art, for example, can be carbon atom
One or more in aliphatic olefin, the oxidation product of halogenated aliphatic alkene of number 2～8, for example can be specifically ring
Oxidative ethane, expoxy propane, epoxy chloroethanes, epoxychloropropane, epoxy butane, butadiene oxide, butadiene double oxide, ring
One or more in oxygen chloropropane, methyl glycidyl ether, diglycidyl ether, particularly preferably epoxychloropropane.
The titanium compound is formula（III）Shown compound,
TiXm(OR6)4-mFormula（III）
Formula（III）In, X is halogen, R6For C1～C20Alkyl, m is the integer of 0≤m≤4；Preferably titanium tetrachloride, four
Titanium bromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium and the second of trichlorine one
At least one in epoxide titanium, wherein one or more preferably in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, especially excellent
Elect titanium tetrachloride as.
The precipitation additive can be various precipitation additives commonly used in the art, for example can for organic acid, organic acid anhydride,
In one or more in organic ether, organic ketone, the preferably organic acid anhydride of carbon number 2～20, organic acid, ether and ketone one
Plant or various；For example can be specifically acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, Pyromellitic Acid
Dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, MEK, benzophenone, methyl ether, ether, propyl ether, butyl ether,
One or more in amyl ether, particularly preferably phthalic anhydride.
The solvent can dissolve magnesium compound, organic alcohol ethers compound, organic epoxy compound thing, have for various
The solvent commonly used in the art of the mixture of machine phosphorus compound and internal electron donor compound, specifically for example can for toluene,
One or more in ethylbenzene, benzene, dimethylbenzene, chlorobenzene, hexane, heptane, octane, decane, wherein preferably toluene.
The internal electron donor can be various internal electron donors commonly used in the art, for example, can be selected from aliphatic series or virtue
One or more in Arrcostab, aliphatic ether, cyclic aliphatic ether, the aliphatic ketone of race's carboxylic acid.The aliphatic series or the alkyl of aromatic carboxylic acid
Ester, aliphatic ether, cyclic aliphatic ether, aliphatic ketone can be the various conventional use of compounds in this area, for example, can be selected from C1
～C4The C of aliphatic saturated monocarboxylic acid1～C4Arrcostab, C7～C8The C of aromatic carboxylic acids1～C4Arrcostab, C2～C6Aliphatic ether, C3～C4Ring
Ether, C3～C6Saturated fat ketone.Particular compound can be diisobutyl phthalate, n-butyl phthalate, adjacent benzene
Dioctyl phthalate di-isooctyl, the diamyl ester of phthalic acid 1,3, methyl formate, Ethyl formate, n-propyl formate, isopropyl formate, formic acid
Butyl ester, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, propionic acid
N-propyl, isopropyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyl butyrate,
Ether, propyl ether, butyl ether, amyl ether, hexyl ether, tetrahydrofuran（THF）, acetone, butanone, 2 pentanone, the one kind in methyl iso-butyl ketone (MIBK)
Or it is various；Wherein it is preferably diisobutyl phthalate, n-butyl phthalate, the diamyl ester of phthalic acid 1,3, formic acid
Ethyl ester, n-propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate,
Butyl acetate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, butyl propionate, methyl butyrate, ethyl butyrate,
One or more in propyl butyrate, isopropyl isobutyrate, butyl butyrate, particularly preferably n-butyl phthalate and/
Or diisobutyl phthalate.
Relative to every mole of magnesium elements, the consumption of monoleate class compound is 0.001～1 mole, organic alcohol ethers
The consumption of compound is 0.01～5 mole, and the consumption of organic epoxy compound thing is 0.2～10 mole, the consumption of organic phosphorus compound
For 0.1～3 mole, the consumption of titanium compound is 0.5～20 mole, and the consumption of precipitation additive is 0.03～1 mole, interior electron
The consumption of body is 0.01～1 mole；It is preferred that the consumption of monoleate class compound is 0.005～0.2 mole, organic alcohol ethers
The consumption of compound is 0.05～1 mole, and the consumption of organic epoxy compound thing is 0.5～4 mole, and the consumption of organic phosphorus compound is
0.3～1 mole, the consumption of titanium compound is 1～15 mole, and the consumption of precipitation additive is 0.05～0.4 mole, internal electron donor
Consumption be 0.04～0.2 mole.
Second object of the present invention is to provide a kind of preparation method of catalyst for olefines polymerizing.The preparation of the catalyst
Process is comprised the following steps：
（1）By magnesium compound, monoleate class compound, organic alcohol ethers compound, organic phosphorus compound and organic ring
Oxygen compound is contacted in a solvent, forms homogeneous solution；
（2）In the presence of precipitation additive, the homogeneous solution is contacted with titanium compound and obtains mixture；
（3）By step（2）Gained mixture is contacted with internal electron donor compound, is filtered, washing, is dried to obtain alkene and is gathered
Close catalyst；At least one of wherein described magnesium compound and titanium compound are halogen-containing compound.
Relative to every mole of magnesium elements, the consumption of monoleate class compound is 0.001～1 mole, organic alcohol ethers
The consumption of compound is 0.01～5 mole, and the consumption of organic epoxy compound thing is 0.2～10 mole, the consumption of organic phosphorus compound
For 0.1～3 mole, the consumption of titanium compound is 0.5～20 mole, and the consumption of precipitation additive is 0.03～1 mole, interior electron
The consumption of body is 0.01～1 mole；It is preferred that the consumption of monoleate class compound is 0.005～0.2 mole, organic alcohol ethers
The consumption of compound is 0.05～1 mole, and the consumption of organic epoxy compound thing is 0.5～4 mole, and the consumption of organic phosphorus compound is
0.3～1 mole, the consumption of titanium compound is 1～15 mole, and the consumption of precipitation additive is 0.05～0.4 mole, internal electron donor
Consumption be 0.04～0.2 mole.
Monoleate class compound is not limited in step（1）Middle introducing, can be in step（2）In, homogeneous solution with
After titanium compound contact, solid particle is introduced before separating out.
Organic alcohol ethers compound is also not limited in step（1）Middle introducing, can in preparation process any step
Introduce, can reach the purpose for improving hydrogen response.
The present invention is to step（1）、（2）With（3）The condition of contact is without particular/special requirement, and can refer to prior art is carried out, excellent
In the case of choosing, step（1）The condition of contact includes that the temperature of contact is 10～100 DEG C, and preferably 30～80 DEG C, the time is 0.5
～6 hours, preferably 1～4 hour；Step（2）The condition of contact include contact temperature be -30 to 60 DEG C, preferably -30 to
5 DEG C, the time is 0.1～5 hour, preferably 0.2～4 hour；Step（3）The condition of contact include contact temperature be 50～
200 DEG C, preferably 60～180 DEG C, the time is 0.5～8 hour, preferably 1～6 hour.
To the filtration, washing, dry method and condition are referred to prior art and enter the present invention without particular/special requirement
OK, will not be described here.
In the present invention, the titanium compound, magnesium compound, monoleate class compound, organic alcohol ethers compound, interior give
Electron compound, organic epoxy compound thing, precipitation additive, the species of solvent have been described in above, and here is no longer
Repeat.
Preferred embodiment of the invention, the method for preparing olefin polymerization catalysis of the present invention includes following step
Suddenly：
Under agitation by magnesium halide be dissolved in monoleate class compound, organic ether compound, organic epoxy compound thing,
In the solvent solution of organic phosphorus compound, contact 0.5～6 hour at a temperature of 10～100 DEG C, connect at a temperature of preferably 30～80 DEG C
Touch 1～4 hour, form homogeneous solution；In the presence of precipitation additive, -30 to 5 DEG C of temperature are preferably at a temperature of -30 to 60 DEG C
Under, titanium compound is instilled into above-mentioned homogeneous solution or homogeneous solution is instilled in titanium compound, contact 0.1～5 hour, preferably
Contact 0.2～4 hour；Again reactant mixture is warming up to into 50～200 DEG C, preferably 60～180 DEG C, adds internal electron donor
Compound, contacts 0.5～8 hour under stirring, preferably 1～6 hour, filters off mother liquor, detergent（Such as toluene）Washing, then
With the halide and detergent of transition metals Ti（Such as toluene）Mixture process 3～4 times, leach liquid, use detergent（Example
Such as hexane, toluene）Washing solids, is obtained olefin polymerization catalysis.
The catalyst of the present invention contains magnesium elements, titanium elements, P elements, internal electron donor compound and halogen.With weight
Meter, the content of the titanium is 1～10%, and the content of the magnesium is 10～20%, and the content of the phosphorus is 0.01～0.5%, described interior
The content of electron donor compound is 2～25%, and the content of the halogen is 40～70%；Further preferably, by weight, it is described
The content of titanium is 1～3%, and the content of the magnesium is 15～20%, and the content of the phosphorus is 0.1～0.2%, the internal electron donor
The content of compound is 4～12%, and the content of the halogen is 45～65%.
Present invention also offers a kind of olefine polymerizing process, the method is included under olefin polymerization conditions, according to following（A）
With（B）One of two ways is contacted：
（A）One or more alkene is contacted with above-mentioned olefin polymerization catalysis and alkyl aluminum compound, wherein, described one
Ethylene molar content is more than 80% in kind or various alkene；
（B）One or more alkene is connect with above-mentioned olefin polymerization catalysis, alkyl aluminum compound and organo-silicon compound
Touch.
Although（B）The alkene is not limited when mode is contacted, but for the polymerisation of ethene is mainly used in, such as
Fruit is only the other alkene in part, is at this time only taken（A）Mode is contacted and be capable of achieving the purpose of the present invention, therefore preferable case
Under, with（B）When mode is contacted, the molar content of ethene is below 80% in one or more alkene.
According to the present invention, the mol ratio one of the titanium in the aluminium in the alkyl aluminum compound and the olefin polymerization catalysis
As be 5-5000：1, preferably 20-500：1.The consumption of the organo-silicon compound can be adjusted according to real needs, this
Invention is without particular/special requirement.
According to the present invention, the alkyl aluminum compound is formula（Ⅳ）Shown compound,
AlR'n'X'3-n'（Ⅳ）
Formula（Ⅳ）In, R' for hydrogen, the alkyl of carbon number 1～20 or carbon number 6～20 aryl, X' is halogen, n'
For 1～3 integer.Wherein be preferably trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, one
In hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride at least one
Plant, preferably triethyl aluminum.
The formula of the organo-silicon compound is RnSi（OR1）4-n, n is the integer of 0≤n≤3 in formula, and R is alkyl, cycloalkanes
One or more in base, aryl, halogenated alkyl, halogen, hydrogen atom, R1For in alkyl, cycloalkyl, aryl, halogenated alkyl
One or more；Preferably trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyl two
Methoxy silane, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, dimethoxydiphenylsilane, hexichol
Base diethoxy silane, two cyclohexyl dimethoxysilanes, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyl
Trimethoxy silane, Cyclohexylmethyldimethoxysilane, dicyclopentyl dimethoxyl silane, the tertiary fourths of 2- ethyl piperidine base -2-
Base dimethoxysilane, (the fluoro- 2- propyl group of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilanes and (the fluoro- 2- third of 1,1,1- tri-
Base) at least one in-methyl dimethoxysilane, preferably Cyclohexylmethyldimethoxysilane.
According to the present invention, the alkene can be various conventional alkene, for example, can be the 1- alkene of carbon number 2-6
In at least one, preferably ethene, propylene, 1- n-butenes, 1- n-pentenes, 1- n-hexylenes, the positive octenes of 1- and 4- methyl-1-pentenes
At least one in alkene.The olefine polymerizing process of the present invention, is particularly well-suited to the random common of the homopolymerization of propylene, propylene and ethene
Polymerization and multiphase crushing-resistant copolymerization are closed.
According to the present invention, the olefin polymerization conditions can be olefin polymerization conditions commonly used in the art, generally temperature
For 0-150 DEG C, the time is 0.5-5 hours, and pressure is 0.1-10MPa.
Under preferable case, the olefine polymerizing process of the present invention is carried out in the presence of solvent, and the contact is in the presence of solvent
Carry out, the olefin polymerization conditions include：Temperature is 0～150 DEG C, and the time is 0.5～5 hour, and pressure is 0.1～10MPa, with
Titanium meter in olefin polymerization catalysis, olefin polymerization catalysis concentration in a solvent can be this area normal concentration,
It for example can be 0.0001～1 mol/L.Under preferable case, the contact is carried out in presence of hydrogen, and the partial pressure of hydrogen can be with
For partial pressure commonly used in the art, preferably 0.1～2MPa.
The catalyst activity obtained using the method for the present invention is high, for olefinic polymerization catalysis activity compared with prior art
Catalyst activity is high by 10%～30%.With very high catalysis activity when being particularly useful for propylene polymerization and combined polymerization, the present invention's urges
Agent is applicable to various polymerization techniques such as slurry method, substance law and vapor phase method.
The olefin polymerization catalysis of the present invention are more existing by introducing monoleate class compound and organic alcohol ethers compound
There is technology to compare, high for activity during olefinic polymerization, hydrogen response is good, and the fine powder content of resulting polymers is low, catalyst
Grain type is good.In addition the raw material of the preparation method of catalyst of the present invention is easy to get, low production cost.
Specific embodiment
Method of testing
Melt index (MI)：It is measured with 6932 type melt indexers of Italian CEAST companies, is joined
According to GB/T3682-2000 standards；
Polymer bulk density：With reference to ASTM D1895-96 standards；
It is explained further catalyst and preparation method thereof of the present invention by way of example below, but the present invention not office
It is limited to these embodiments.
Embodiment 1
In the normal-pressure reaction kettle that high pure nitrogen repeats displacement, 4.8 grams of anhydrous magnesium chlorides, 70 milliliters of first are sequentially added
Benzene, 4.0 milliliters of epoxychloropropane, 12.5 milliliters of tributyl phosphates and 0.3 milliliter of glyceryl monooleate, 0.5 milliliter of ethylene glycol list
Ether, under conditions of temperature is for 60 DEG C, reacts 0.5 hour, adds 1.4 grams of phthalic anhydrides and 40 milliliters of toluene, continues
Reaction one hour, is cooled to -28 DEG C, and 56 milliliters of titanium tetrachloride is added dropwise（1 milliliter/min of rate of addition）, it is gradually heating to 85 DEG C
（Heating rate is 5 DEG C/min）, 1.1 milliliters of n-butyl phthalates (DNBP), constant temperature one hour, mistake are added at 80 DEG C
Filter, solid washes twice with toluene, adds 48 milliliters of titanium tetrachloride, 72 milliliters of toluene, the mistake after 110 DEG C of constant temperature 0.5 hour
Filter, repeat the step 2 time, then by gained solid wash with hexane 5 times afterwards be vacuum dried obtain olefin polymerization catalysis.
Embodiment 2
In the normal-pressure reaction kettle that high pure nitrogen repeats displacement, 4.8 grams of anhydrous magnesium chlorides, 70 milliliters of first are sequentially added
Benzene, 4.0 milliliters of epoxychloropropane, 12.5 milliliters of tributyl phosphates and 0.3 milliliter of glyceryl monooleate, in the bar that temperature is 60 DEG C
Under part, react 0.5 hour, add 1.4 grams of phthalic anhydrides and 40 milliliters of toluene, continue to react one hour, be cooled to -28
DEG C, 56 milliliters of titanium tetrachloride is added dropwise（1 milliliter/min of rate of addition）, it is gradually heating to 85 DEG C（Heating rate is 5 DEG C/min）,
1.1 milliliters of n-butyl phthalates (DNBP) and 0.5 milliliter of ethylene glycol monoethyl ether are added when 80 DEG C, constant temperature one hour, mistake
Filter, solid washes twice with toluene, adds 48 milliliters of titanium tetrachloride, 72 milliliters of toluene, the mistake after 110 DEG C of constant temperature 0.5 hour
Filter, repeat the step 2 time, then by gained solid wash with hexane 5 times afterwards be vacuum dried obtain olefin polymerization catalysis.
Embodiment 3
Consistent with the preparation method of embodiment 1, except for the difference that the consumption of glyceryl monooleate is 0.5 milliliter.
Embodiment 4
Consistent with the preparation method of embodiment 1, except for the difference that the consumption of glyceryl monooleate is 0.2 milliliter.
Embodiment 5
Consistent with the preparation method of embodiment 1, except for the difference that the consumption of ethylene glycol monoethyl ether is 1.0mL.
Embodiment 6
Consistent with the preparation method of embodiment 1, except for the difference that the consumption of ethylene glycol monoethyl ether is 0.3mL.
Comparative example
In the normal-pressure reaction kettle that high pure nitrogen repeats displacement, 4.8 grams of anhydrous magnesium chlorides, 70 milliliters of first are sequentially added
Benzene, 4.0 milliliters of epoxychloropropane, 12.5 milliliters of tributyl phosphates, under conditions of temperature is for 60 DEG C, react 2 hours, add
1.4 grams of phthalic anhydrides and 40 milliliters of toluene, continue to react one hour, are cooled to -28 DEG C, and 56 milliliters of titanium tetrachloride is added dropwise
（1 milliliter/min of rate of addition）, it is gradually heating to 85 DEG C（Heating rate is 5 DEG C/min）, 1.1 milliliters of adjacent benzene are added at 80 DEG C
Dioctyl phthalate di-n-butyl (DNBP), constant temperature one hour is filtered, and solid is washed twice with toluene, adds 48 milliliters of titanium tetrachloride,
72 milliliters of toluene, filters after 0.5 hour in 110 DEG C of constant temperature, repeats the step 2 time, then gained solid is washed into 5 with hexane
Vacuum drying after secondary obtains olefin polymerization catalysis.
Application Example 1
This application embodiment provides the olefinic polymerization of embodiment 1～6 and comparative example gained catalyst olefinic polymerization
Method and result：The polymerisation is comprised the following steps：By 5 liters of stainless steel autoclaves Jing after nitrogen is sufficiently displaced from, 5 are added
Milliliter concentration is the hexane solution of the triethyl aluminum of 0.5 mol/L and methylcyclohexyl diformazan that 1 milliliter of concentration is 1 mol/L
10 milligrams of catalyst prepared by the hexane solution of TMOS (CMMS) and embodiment 1, is subsequently adding 10 milliliters of hexanes flushings and adds
Expects pipe line, adds 1 liter of (under standard state) hydrogen, and 2 liters of refined propylene, is warming up to 70 DEG C, makes hydrogen partial pressure be 0.2Mpa,
Polymerisation 1 hour at this temperature.After reaction terminates, reactor is lowered the temperature and stops stirring and discharges product, obtain alkene
Polymer, concrete outcome refers to table 1.
Application Example 2
With Application Example 1, this application embodiment provides embodiment 1～6 and comparative example gained catalyst alkene
The olefine polymerizing process and result of polymerization：Except for the difference that the amounts of hydrogen for adding is 4L, and hydrogen partial pressure is 0.9MPa, and concrete outcome is detailed
It is shown in Table 2.
The polymerization result of table 1
The polymerization result of table 2
From test result indicate that, after adding monoleate class compound and organic ether compound, substantially reduce halogenation
The dissolution time of magnesium, catalyst activity has significant raising, and hydrogen response is improved, and particle diameter distribution is good, gained polymerization
Thing fine powder is few.
Claims (12)
1. a kind of catalyst for olefines polymerizing, it is characterised in that the catalyst includes the product of following components：(A) magnesium chemical combination
Organic alcohol ethers compound (C) monoleate class compound (D) organic phosphorus compound (E) the organic epoxy compound thing (F) of thing (B) is helped
Precipitation agent (G) internal electron donor (H) titanium compound；At least one of described magnesium compound and titanium compound are halogen-containingization
Compound；The consumption of various components is in terms of every mole of magnesium elements, and the consumption of monoleate class compound is 0.001～1 mole, organic
The consumption of alcohol ethers compound is 0.01～5 mole, and the consumption of organic epoxy compound thing is 0.2～10 mole, organophosphor chemical combination
The consumption of thing is 0.1～3 mole, and the consumption of titanium compound is 0.5～20 mole, and the consumption of precipitation additive is 0.03～1 mole,
The consumption of internal electron donor is 0.01～1 mole；Described monoleate class compound is selected from glyceryl monooleate, single oleic acid third
In diol ester, diethylene glycol monoleate, polyvinyl alcohol monoleate, sorbitol monooleate, xylitol monoleate extremely
Few one kind.
2. a kind of catalyst for olefines polymerizing according to claim 1, it is characterised in that described organic alcohol ethers chemical combination
The formula of thing is (I) HO R1(OR2)nR3, n is the integer of 1≤n≤10 in formula (I), R1、R2For C1～C4Alkyl, R3Selected from hydroxyl
Base, C1～C30Aliphatic group, C3～C30Cycloalkyl, C6～C30Aryl radical, C2～C30Heterocyclylalkyl.
3. a kind of catalyst for olefines polymerizing according to claim 1, it is characterised in that described organic alcohol ethers chemical combination
Thing selected from diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, 3- ethyoxyl -1- propyl alcohol, 1- ethyoxyls -
2- propyl alcohol, 1,3- diethoxy -2- propyl alcohol, dipropylene glycol, diethylene glycol (DEG) phenetole, triethylene glycol monoisopropyl ether, dipropyl two
At least one in alcohol list ether.
4. a kind of catalyst for olefines polymerizing according to claim 1, it is characterised in that described magnesium compound is formula
(II) the alcohol adduction of the magnesium compound shown in the hydrate and formula (II) of the magnesium compound shown in magnesium compound, formula (II) shown in
At least one in thing,
MgR4R5 (II)
R in formula (II)4And R5Respectively halogen, C1～C5Straight or branched alkoxyl and C1～C5Straight or branched alkyl in
One kind.
5. a kind of catalyst for olefines polymerizing according to claim 4, it is characterised in that the magnesium compound is dichloride
Magnesium.
6. a kind of catalyst for olefines polymerizing according to claim 1, it is characterised in that the titanium compound is formula (III)
Shown compound,
TiXm(OR6)4-mFormula (III)
In formula (III), X is halogen, R6For C1～C20Alkyl, m is the integer of 0≤m≤4.
7. a kind of catalyst for olefines polymerizing according to claim 6, it is characterised in that the titanium compound is four chlorinations
Titanium.
8. a kind of catalyst for olefines polymerizing according to claim 1, it is characterised in that the consumption of various components is often rubbing
That magnesium elements meter, the consumption of monoleate class compound is 0.005～0.2 mole, and the consumption of organic alcohol ethers compound is
0.05～1 mole, the consumption of organic epoxy compound thing is 0.5～4 mole, and the consumption of organic phosphorus compound is 0.3～1 mole,
The consumption of titanium compound is 1～15 mole, and the consumption of precipitation additive is 0.05～0.4 mole, and the consumption of internal electron donor is
0.04～2 mole.
9. the preparation method of a kind of catalyst for olefines polymerizing described in one of claim 1-8, including：(1) by magnesium compound,
Monoleate class compound, organic alcohol ethers compound, organic phosphorus compound and organic epoxy compound thing contact in a solvent shape
Uniformly solution；(2) in the presence of precipitation additive, the homogeneous solution is contacted with titanium compound and obtains mixture；(3) will step
Suddenly (2) gained mixture is contacted with internal electron donor compound, is filtered, and washing is dried to obtain olefin polymerization catalysis；Wherein institute
At least one of magnesium compound and titanium compound are stated for halogen-containing compound.
10. the preparation method of a kind of catalyst for olefines polymerizing according to claim 9, including：Under agitation by halogenation
Magnesium be dissolved in monoleate class compound, organic alcohol ethers compound, organic epoxy compound thing, organic phosphorus compound solvent it is molten
In liquid, contact at a temperature of 10～100 DEG C 0.5～6 hour and form homogeneous solution；In the presence of precipitation additive, at -30～60 DEG C
At a temperature of, titanium compound is instilled into above-mentioned homogeneous solution or homogeneous solution is instilled in titanium compound, contact 0.1～5 hour；Again
Reactant mixture is warming up to into 50～200 DEG C of addition internal electron donor compounds, is contacted 0.5～8 hour under stirring, filtered off
Mother liquor, washing is obtained olefin polymerization catalysis.
A kind of 11. olefine polymerizing process, under being included in olefin polymerization conditions, are carried out according to one of following (A) and (B) two ways
Contact：
(A) one or more alkene is contacted with one of the claim 1-8 catalyst and alkyl aluminum compound, wherein described
Ethylene molar content is more than 80% in one or more alkene；
(B) by one of one or more alkene and claim the 1-8 catalyst, alkyl aluminum compound and organo-silicon compound
Contact.
A kind of 12. olefine polymerizing process according to claim 11, it is characterised in that the aluminium in the alkyl aluminum compound
It is 5-5000 with the mol ratio of the titanium in one of the claim 1-8 catalyst：1.
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| CN102453127A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Spherical carrier for olefin polymerization catalyst and preparation method thereof |
| CN102875704A (en) * | 2012-09-05 | 2013-01-16 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst as well as preparation method and application thereof |
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| CN102453127A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Spherical carrier for olefin polymerization catalyst and preparation method thereof |
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