CN104558298B - A kind of electrical membrane acrylic resin and preparation method thereof - Google Patents
A kind of electrical membrane acrylic resin and preparation method thereof Download PDFInfo
- Publication number
- CN104558298B CN104558298B CN201310488478.9A CN201310488478A CN104558298B CN 104558298 B CN104558298 B CN 104558298B CN 201310488478 A CN201310488478 A CN 201310488478A CN 104558298 B CN104558298 B CN 104558298B
- Authority
- CN
- China
- Prior art keywords
- acrylic resin
- formula
- alkyl
- electron donor
- hydrogen
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of electrical membrane acrylic resin, the ash content of the acrylic resin is less than 50ppm；Cl ash contents are less than 6ppm；Melt flow index MFR is 1 8g/10min；Isotactic index is 96 99%；Molecular weight distributing index MW/MnFor 4 12；The unit group [mmmm] of microstructure five of polymer>93%, three unit groups [mm]>96%；Melting point polymer is 164 168 DEG C, and crystallization temperature is 110 116 DEG C.Present invention also offers the preparation method of the acrylic resin, using the catalyst of high activity, high vertical structure directionality, catalyst components are subjected to pre-contact reaction, it is preferred that pre-contact reaction product and olefinic polymerization monomer are subjected to prepolymerization, then propylene polymerization is carried out, the acrylic resin that a kind of ash content is low, molecular weight distribution is wider, high mechanical strength and tensile property are good can be obtained.
Description
Technical field
The present invention relates to a kind of electrical membrane acrylic resin and preparation method thereof, more specifically to one kind in spy
Determine to use acrylic resin and preparation method thereof made from special catalyst under polymerizing condition, the acrylic resin can be used for electrician
The production of film.
Background technology
Polypropylene has low loss factor and high specific volume resistance, thus it is applied to capacitor film.
The electric capacity C of electroplax capacitor is defined as：
C=ε Ad-1
Wherein ε is the dielectric constant determined by material, and A is the area of conductive plate, and d is the distance between conductive plate.Principle
On, the distance between conductive plate corresponds to the thickness of dielectric material, and the dielectric material can be according to the application electricity of such as capacitor
Pressure and desired life-span are selected, in order to make up any shortcoming in dielectric material such as polypropylene screen, it is necessary to use basis
The thicker film of thickness necessary to equation must use multiple relatively thin films to overlie one another together.In order to reduce electric capacity
The cost and size of device, Capacitor manufactures have strong interest to reducing the distance between conductive plate d；I.e. for very thin
Polypropylene screen it is interested.In order that these are machinable while meeting the requirement applied in capacitor, it is such
Polypropylene screen is needed with improved engineering properties and processing characteristics and low total ash content, and point wide in needs
The distribution of son amount and relatively high crystallinity.
It is suitable for the polypropylene of electrical membrane to realize desired extremely low impurity level to manufacture, it is necessary to cumbersome washing
The polypropylene, such process high energy consumption, cost are high.In order to overcome the washing step, develop in support type list
Polypropylene prepared in the presence of the catalyst of center, that there is levels of impurities, such as described in WO02/16455A1.However, it is
Realize this target of low impurity level, it is necessary to very carefully control process conditions.Lacked in addition, such polypropylene has
Point, i.e., they can not be processed in a stable manner.Especially, it is poly- based on what is prepared in the presence of supported single site catalyst
The film of propylene locks into sagging during fabrication and is easily broken off.
The content of the invention
It is an object of the invention to provide a kind of electrical membrane acrylic resin and preparation method thereof, acrylic resin tool
There is the characteristics of ash content is low, molecular weight distribution is wider, high mechanical strength and tensile property are good.
The ash content of the acrylic resin is less than 50ppm；Cl ash contents are less than 6ppm；Melt flow index MFR is 1-8g/
10min；Isotactic index is 96-99%；Molecular weight distributing index MW/MnFor 4-12；The unit group of microstructure five of polymer
[mmmm]>93%, three unit groups [mm]>96%；Melting point polymer is 164-168 DEG C, and crystallization temperature is 110-116 DEG C.
Preferably, the ash content of the acrylic resin is less than 40ppm；Cl ash contents are less than 4ppm；Melt flow index MFR is
2.5-3.5g/10min；Isotactic index is 97-98.5%；Molecular weight distributing index MW/MnFor 5-8；Melting point polymer is 165-167
DEG C, crystallization temperature is 111-114 DEG C.
The acrylic resin by propylene polymerization by being obtained in the presence of a catalyst.The polymerisation includes equal
Poly- and copolymerization, obtain being adapted to the acrylic resin needed for electrical membrane production.The reaction that described catalyst includes following components is produced
Thing：
（One）Ingredient of solid catalyst A, the ingredient of solid catalyst A include magnesium, titanium, halogen and at least two to electricity
Daughter a and b；
（Two）Alkyl aluminum compound B, Al/Ti mol ratio are 1~200, preferably 20~150；
（Three）It is not added with external electron donor or adds a kind of optional external electron donor C（ED）.When addition external electron donor
When, its dosage is that Al/ED mol ratios are 5~200, preferably 30~150.
In one particular embodiment of the present invention, the acrylic resin is prepared by the following method to obtain：
Catalytic component A, B and/or C are subjected to pre-contact reaction, pre-contact reaction temperature is -15-40 DEG C, during pre-contact
Between be 0.5-60mins, preferably 1-10mins.The polymerization activity of catalyst can be significantly improved and gather by carrying out pre-contact reaction
The apparent density of compound, and the anti-impurity interference performance of enhancing catalyst active center, and then reduce the ash content in polymer
With crushing for polymer beads.
After pre-contact reaction, before polymerisation, catalyst and propylene monomer are preferably subjected to prepolymerization.Prepolymerization
When can add a small amount of hydrogen or non-hydrogenation, prepolymerization temperature is 10-70 DEG C, preferably 15-30 DEG C, and prepolymerization time is
0-60mins, preferably 10-40mins.
Propylene polymerization is carried out according to known methods, in liquid monomer or atent solvent containing polymerized monomer, or in gas phase
In, or operated by the polymerization mix technique in liquid phase.Polymerization temperature is generally 50 DEG C~150 DEG C, preferably 60 DEG C
~90 DEG C.Polymerization pressure is normal pressure or higher.In the course of the polymerization process, hydrogen can be used as the addition of polymer molecular weight conditioning agent
The molecular weight and melt index of polymer are adjusted into polymer reactor, suitable added hydrogen is 100-1500ppm, preferably
150-1000ppm.The residence time of propylene monomer and catalyst in polymer reactor is 0.5-6h, preferably 1~4h.
Without washing process after polymerisation terminates, polymerizate is directly converted into pellet.Terminate in polymerisation
Afterwards without washing process, pellet is converted into.The additives such as antioxidant, stabilizer are preferably added in granulation process, wherein
It is preferred that not phosphorous organic additive.
The ingredient of solid catalyst A after following three kinds of substance reactions by obtaining：
（1）By formula（Ⅰ）Shown magnesium compound or formula（Ⅰ）The adduct of shown magnesium compound：MgR13R14（Ⅰ）；
（2）At least one is by formula（Ⅱ）Shown titanium compound：Ti(OR)4-kXk（Ⅱ）；
（3）At least two electron donor compound as and b；
Its formula of（Ⅰ）In, R13And R14It is identical or different, it is each independently halogen, C1-C5Straight or branched alcoxyl
Base, and C1-C5Straight or branched alkyl in one kind.
The formula（Ⅰ）The adduct of shown magnesium compound is MgR13R14·fR0OH·gE·hH2O, wherein R0For C1-
C18Alkyl, preferably C1-C5Alkyl, more preferably methyl, ethyl, n-propyl or isopropyl；F is in 0.1-6 scope
Within, preferably 2-3.5；E is a kind of electron donor compound, can with various electron donor compounds well known in the art,
Preferably ethers or esters Donor compound；G is within the scope of 0-2；H is within the scope of 0-0.7.
Preferred formula（Ⅰ）In, R13And R14Halogen is each independently, such as can be one kind in chlorine, bromine and iodine.
The adduct of the magnesium compound and/or magnesium compound can specifically use：Dimethoxy magnesium, diethoxy magnesium, two
Propoxyl group magnesium, diisopropoxy magnesium, dibutoxy magnesium, two isobutoxy magnesium, two amoxy magnesium, methoxy magnesium chloride, methoxyl group
Magnesium bromide, methoxyl group magnesium iodide, ethyoxyl magnesium chloride, ethyoxyl magnesium bromide, ethyoxyl magnesium iodide, propoxyl group magnesium chloride, the third oxygen
Base magnesium bromide, propoxyl group magnesium iodide, butoxy magnesium chloride, butoxy magnesium bromide, butoxy magnesium iodide, magnesium dichloride, dibrominated
Magnesium, magnesium diiodide, the alcohol adducts of magnesium dichloride, the alcohol adducts of dibrominated magnesium and magnesium diiodide alcohol adducts at least
It is a kind of.The more preferably alcohol adducts of magnesium dichloride, the alcohol adducts of the magnesium dichloride are spheric granules.
In the present invention, the magnesium compound is prepared in method known in the art, such as is referred to
CN1091748A, CN101050245A, CN101486722A, CN102796132A, CN102796129A and CN102796128A
Disclosed in the preparation method of adduct of magnesium halides carrier prepare.
Usually, the preparation method of the alcohol adducts of the spherical magnesium dichloride can include：By magnesium dichloride and R0OH
Mixed, temperature reaction generation magnesium dichloride alcohol adduct melt, reaction temperature is 90-140 DEG C.Carried out in decentralized medium high
Shearing, then obtained reaction product is placed in the cooling medium that temperature is -20 DEG C to 0 DEG C, forms spheric granules, it is scrubbed
With the dry alcohol adducts that can obtain spherical magnesium dichloride.The method of the high shear for example can be public in CN1330086
Method, the method disclosed in CN1580136A and the side disclosed in CN1463990A disclosed in the method opened, US6020279
Method.The decentralized medium can be hydrocarbon system solvent, such as：Kerosene, white oil, silicone oil, paraffin oil and/or vaseline oil.It is described cold
But medium can be raffinating oil in pentane, hexane, heptane, petroleum ether and/or petroleum refining process.
After the spheric granules of the alcohol adducts of the magnesium dichloride is prepared, by by the alcohol adducts of magnesium dichloride with
The titanium compound, internal electron donor compound a, internal electron donor compound b and external donor compound C react what is obtained
Catalytic component is also spheric granules.
In formula（Ⅱ）：Ti(OR)4-kXkIn, R C1~C20Alkyl, X F, Cl or Br, k be 1~4 integer.
The titanium compound can specifically use：Titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, tetraethoxy
Titanium, the titanium butoxide of a chlorine three, dichloro dibutoxy titanium, the titanium butoxide of trichlorine one, a chlorine triethoxy titanium, dichlorodiethyl epoxide
Titanium, the ethanolato-titanium of trichlorine one, one kind in titanium trichloride or their mixture, preferably titanium tetrachloride.
Wherein electron donor compound a is selected from formula（Ⅳ）Shown diol-lipid compound：
Formula（Ⅳ）In, R1And R2For identical or different C1-C10Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Virtue
Base, C7-C20Alkaryl, C7-C20Aralkyl, benzene ring hydrogen is optionally by halogen atom in the aryl or alkaryl or aromatic hydrocarbons
Substitution；R3-R6、R1-R2nGroup is hydrogen, halogen, the C of substituted or unsubstituted straight or branched identical or differ1-C20Alkane
Base, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl, C7-C20Aralkyl, C2-C10Alkylene, C10-C20Fused ring aryl or
Ester group, R3-R6And R1-R2nArbitrarily comprising the substituent one or several hetero atoms as carbon or hydrogen atom or both, institute on group
The hetero atom stated is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R3-R6And R1-R2nOne or more of group optionally mutually into
Ring；N is 0-10 integer.
Wherein electron donor compound b is selected from formula（Ⅴ）Shown diether compound：
Formula（Ⅴ）In, RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RⅥIt is identical or differ, selected from hydrogen, halogen atom, straight or branched
C1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20One kind in aralkyl, RⅦAnd RⅧIt is identical or different, selected from straight chain
Or the C of side chain1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl, C7-C20One kind in aralkyl；RⅠ-RⅥ
Group between it is optionally mutually cyclic.
The electron donor compound a is preferably formula（Ⅵ）Shown diol-lipid compound：
Formula（Ⅵ）In, R1-R6Group is hydrogen, the C of straight or branched identical or differ1-C20Alkyl.
Described electron donor compound a diol-lipid compound can specifically use：1,3- propylene glycol dibenzoates, 2-
Methyl-1,3-propanediol dibenzoate, 2- ethyl -1,3- propylene glycol dibenzoates, 2- propyl group -1,3- propane diols hexichol first
Acid esters, 2- butyl -1,3-PD dibenzoate, NPG dibenzoate, 2- ethyl -2- fourths
Base -1,3- propylene glycol dibenzoates, 2,2- diethyl -1,3- propylene glycol dibenzoates, 2- methyl-2-propyls -1,3- third
Bisbenzoate, 2- isopropyl -2- isopentyl -1,3- propylene glycol dibenzoates, 2,4-PD dibenzoate, 3-
Methyl -2,4-PD dibenzoate, 3- ethyls -2,4-PD dibenzoate, 3- propyl group -2,4-PD hexichol first
Acid esters, 3- butyl -2,4- glycol dibenzoate, 3,3- dimethyl -2,4- glycol dibenzoate, 2- methyl isophthalic acids, 3-
Glycol dibenzoate, 2,2- dimethyl -1,3- glycol dibenzoate, 2- ethyls -1,3- glycol dibenzoate,
2- butyl -1,3- glycol dibenzoate, 2- methyl isophthalic acids, 3- glycol dibenzoates, 2- ethyl -1,3- pentanediol hexichol
Formic acid esters, 2- propyl group -1,3- glycol dibenzoate, 2- butyl -1,3- glycol dibenzoate, 2,2- dimethyl -1,
3- glycol dibenzoates, 2- methyl isophthalic acids, 3- glycol dibenzoates, 2,2- dimethyl -1,3- pentanediol dibenzoic acids
Ester, 2- ethyl -1,3- glycol dibenzoates, 2- butyl -1,3- glycol dibenzoates, 2,2,4- trimethyls -1,3-
Glycol dibenzoate, 3- methyl -3- butyl -2,4-PD dibenzoate, 2,2- dimethyl -1,5- pentanediol hexichol
Formic acid esters, 1,6- hexylene glycols dibenzoate, 6- heptene -2,4- heptandiols dibenzoate, 2- methyl -6- heptene -2,4- heptan
Bisbenzoate, 3- methyl -6- heptene -2,4- heptandiols dibenzoate, 4- methyl -6- heptene -2,4- heptandiol two
Benzoic ether, 5- methyl -6- heptene -2,4- heptandiols dibenzoate, 6- methyl -6- heptene -2,4- heptandiol dibenzoic acids
Ester, 3- ethyl -6- heptene -2,4- heptandiols dibenzoate, 4- ethyl -6- heptene -2,4- heptandiols dibenzoate, 5- second
Base -6- heptene -2,4- heptandiols dibenzoate, 6- ethyl -6- heptene -2,4- heptandiols dibenzoate, 3- propyl group -6- heptan
Alkene -2,4- heptandiol dibenzoate, 4- propyl group -6- heptene -2,4- heptandiols dibenzoate, 5- propyl group -6- heptene -2,4-
Heptandiol dibenzoate, 6- propyl group -6- heptene -2,4- heptandiols dibenzoate, 3- butyl -6- heptene -2,4- heptandiols
Dibenzoate, 4- butyl -6- heptene -2,4- heptandiols dibenzoate, 5- butyl -6- heptene -2,4- heptandiol hexichol first
Acid esters, 6- butyl -6- heptene -2,4- heptandiols dibenzoate, 3,5- dimethyl -6- heptene -2,4- heptandiol dibenzoic acids
Ester, 3,5- diethyl -6- heptene -2,4- heptandiols dibenzoate, 3,5- dipropyl -6- heptene -2,4- heptandiol hexichol first
Acid esters, 3,5- dibutyl -6- heptene -2,4- heptandiols dibenzoate, 3,3- dimethyl -6- heptene -2,4- heptandiol hexichol
Formic acid esters, 3,3- diethyl -6- heptene -2,4- heptandiols dibenzoate, 3,3- dipropyl -6- heptene -2,4- heptandiol two
Benzoic ether, 3,3- dibutyl -6- heptene -2,4- heptandiols dibenzoate, 3,5- heptandiols dibenzoate, 2- methyl -
3,5- heptandiols dibenzoate, 3- methyl -3,5- heptandiols dibenzoate, 4- methyl -3,5- heptandiols dibenzoate,
5- methyl -3,5- heptandiols dibenzoate, 6- methyl -3,5- heptandiols dibenzoate, 3- ethyl -3,5- heptandiol hexichol
Formic acid esters, 4- ethyl -3,5- heptandiols dibenzoate, 5- ethyl -3,5- heptandiols dibenzoate, 3- propyl group -3,5- heptan
Bisbenzoate, 4- propyl group -3,5- heptandiols dibenzoate, 3- butyl -3,5- heptandiols dibenzoate, 2,3- bis-
Methyl -3,5- heptandiols dibenzoate, 2,4- dimethyl -3,5- heptandiols dibenzoate, 2,5- dimethyl -3,5- heptan two
Alcohol dibenzoate, 2,6- dimethyl -3,5- heptandiols dibenzoate, 3,3- dimethyl -3,5- heptandiols dibenzoate,
4,4- dimethyl -3,5- heptandiol dibenzoates, 6,6- dimethyl -3,5- heptandiols dibenzoate, 2,6- dimethyl -3,
5- heptandiols dibenzoate, 3,4- dimethyl -3,5- heptandiols dibenzoate, 3,5- dimethyl -3,5- heptandiol hexichol
Formic acid esters, 3,6- dimethyl -3,5- heptandiols dibenzoate, 4,5- dimethyl -3,5- heptandiols dibenzoate, 4,6- bis-
Methyl -3,5- heptandiol dibenzoate, 4,4- dimethyl -3,5- heptandiols dibenzoate, 6,6- dimethyl -3,5- heptan two
Alcohol dibenzoate, 2- methyl -3- ethyl -3,5- heptandiols dibenzoate, 2- methyl -4- ethyl -3,5- heptandiol hexichol
Formic acid esters, 2- methyl -5- ethyl -3,5- heptandiols dibenzoate, 3- methyl -3- ethyl -3,5- heptandiols dibenzoate,
3- methyl -4- ethyl -3,5- heptandiols dibenzoate, 3- methyl -5- ethyl -3,5- heptandiols dibenzoate, 4- methyl -
3- ethyl -3,5- heptandiols dibenzoate, 4- methyl -4- ethyl -3,5- heptandiols dibenzoate, 4- methyl -5- ethyls -
3,5- heptandiols dibenzoate, 2- methyl -3- propyl group -3,5- heptandiols dibenzoate, 2- methyl -4- propyl group -3,5- heptan
Bisbenzoate, 2- methyl -5- propyl group -3,5- heptandiols dibenzoate, 3- methyl -3- propyl group -3,5- heptandiols two
Benzoic ether, 3- methyl -4- propyl group -3,5- heptandiols dibenzoate, 3- methyl -5- propyl group -3,5- heptandiol dibenzoic acids
Ester, 4- methyl -3- propyl group -3,5- heptandiols dibenzoate, 4- methyl -4- propyl group -3,5- heptandiols dibenzoate, 4- first
Base -5- propyl group -3,5- heptandiol dibenzoates etc..It is preferred that pentadiol ester and heptandiol ester.
Electron donor compound b preferred formulas（Ⅵ）Shown 1,3- diether compounds：
R1R2C（CH2OR3）（CH2OR4）
（Ⅵ）
Wherein, R1And R2Can be with identical or differ, selected from C1-C18Alkyl, C3-C18Cycloalkyl, C6-C18Aryl, C7-C18
One kind in aralkyl, optionally bonded cyclization between group；R3And R4Can be with identical or differ, selected from C1-C10Alkyl.
Described electron donor compound b diether compounds can specifically use：2- (2- ethylhexyls) -1,3- dimethoxies
Base propane, 2- isopropyls -1,3- dimethoxy propane, 2- butyl -1,3- dimethoxy propane, 2- sec-butyl -1,3- dimethoxies
Base propane, 2- cyclohexyl -1,3- dimethoxy propane, 2- phenyl -1,3- dimethoxy propane, 2-（2- phenylethyls）- 1,3-
Dimethoxy propane, 2-（2- cyclohexyl-ethyls）- 1,3- dimethoxy propane, 2-（P- chlorphenyl）- 1,3- dimethoxy third
Alkane, 2-（Diphenyl methyl）- 1,3- dimethoxy propane, 2,2- dicyclohexyls -1,3- dimethoxy propane, the rings penta of 2,2- bis-
Base -1,3- dimethoxy propane, 2,2- diethyl -1,3- dimethoxy propane, 2,2- dipropyl -1,3- dimethoxy propane,
2,2- diisopropyl -1,3- dimethoxy propanes, 2,2- dibutyl -1,3- dimethoxy propane, 2- methyl-2-propyls -1,3-
Dimethoxy propane, 2- methyl -2- benzyls -1,3- dimethoxy propane, 2- methyl -2- ethyls -1,3- dimethoxy propane, 2-
Methyl -2- isopropyls -1,3- dimethoxy propane, 2- methyl -2- phenyl -1,3- dimethoxy propane, 2- methyl -2- hexamethylenes
Base -1,3- dimethoxy propane, 2,2- are double（2- cyclohexyl-ethyls）- 1,3- dimethoxy propane, 2- methyl -2- isobutyl group -1,
3- dimethoxy propanes, 2- methyl -2-（2- ethylhexyls）- 1,3- dimethoxy propane, 2,2- diisobutyl -1,3- dimethoxies
Base propane, 2,2- diphenyl -1,3- dimethoxy propane, 2,2- dibenzyl -1,3- dimethoxy propane, 2,2- are double（Cyclohexyl
Methyl）- 1,3- dimethoxy propane, 2- isobutyl group -2- isopropyls -1,3- dimethoxy propane, 2-（1- methyl butyls）- 2- is different
Propyl group -1,3- dimethoxy propane, 2- isopropyl -2- isopentyl -1,3- dimethoxy propane, 2- phenyl -2- isopropyls -1,3-
Dimethoxy propane, 2- phenyl -2- sec-butyls -1,3- dimethoxy propane, 2- benzyl -2- isopropyls -1,3- dimethoxy third
Alkane, 2- cyclopenta -2- isopropyls -1,3- dimethoxy propane, 2- cyclopenta -2- sec-butyls -1,3- dimethoxy propane, 2-
Cyclohexyl -2- isopropyls -1,3- dimethoxy propane, 2- cyclohexyl -2- sec-butyls -1,3- dimethoxy propane, 2- isopropyls
Base -2- sec-butyls -1,3- dimethoxy propane, 2- cyclohexyl -2- cyclohexyl methyl -1,3- dimethoxy propanes, 9,9- diformazans
Epoxide methyl fluorenes etc..It is preferred that 2- isopropyls -2- isopentyl -1,3- dimethoxy propane or 9,9- dimethoxy-methyl fluorenes.
In the present invention above-mentioned 1,3- diether compounds be disclosed in Chinese patent CN1020448C, CN100348624C and
In CN1141285A.Its disclosed related content is all incorporated herein by reference.
The mol ratio of the electron donor compound a and b is 0.55:1~50:1, preferably 0.65:1~10:1.
Alkyl aluminum compound B in the catalytic component, its formula are AlR'''3, R''' is identical or differs
C1--C8Alkyl, wherein one or two alkyl optionally substitutes by chlorine, one or more kinds of alkyl aluminums can be selected to mix
Close and use.The alkyl aluminum compound B is preferably triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, chlorination
Alkyl aluminum, Al (n-C6H13)3、Al(n-C8H17)3Deng.
External donor compound C in the catalytic component, for a kind of optional external donor compound, example
Such as single or multiple functional group's carboxylic acid, carboxylic acid anhydrides and carboxylate, ketone, ether, alcohol, lactone, and organophosphor and organo-silicon compound.It is preferred that
Organo-silicon compound.
The external electron donor is preferably containing at least one Si-OR keys, formula R1 aR2 bSi（OR3）cSilicon compound,
Wherein a and b be 0 to 2 integer, c be 1-3 integer and（a+b+c）And for 4；R1、R2And R3It is C1-C18Alkyl, optionally
Contain hetero atom in ground.Particularly preferred silicon compound, wherein a are 1, b 1, c 2, R1And R2In at least one be selected from tool
There are branched-alkyl, alkenyl, alkylidene, cycloalkyl or the aromatic yl group of 3-10 carbon atom, optionally contain hetero atom, and R3
For C1-C10Alkyl group, particularly methyl.Preferable silicon compound has：Cyclohexyl Methyl Dimethoxysilane, diisopropyl
Dimethoxysilane, di-n-butyl dimethoxysilane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, first
Base t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidines base -2- t-butyldimethoxysilanes and
（1,1,1- tri- fluoro- 2- propyl group）- 2- ethyl piperidine base dimethoxysilanes and（1,1,1- tri- fluoro- 2- propyl group）- methyl dimethoxy oxygen
Base silane.Furthermore it is preferred that silicon compound also have, wherein a is 0, c 3, R2For branched-alkyl or group of naphthene base, optionally contain
There are hetero atom, and R3For methyl.So optional silicon compound has：Cyclohexyl trimethoxy silane, tert-butyl group trimethoxy silicon
Alkane and tertiary hexyl trimethoxy silane.
Propylene co-monomer can be that formula is CH2=CHR alkene, wherein R are hydrogen or the alkane containing 2~6 carbon atoms
Base or aryl, preferably ethene and butylene.
Beneficial effect
Acrylic resin provided by the invention has that ash content is low, molecular weight distribution is wider, high mechanical strength and tensile property
The characteristics of good.The acrylic resin can directly be made by pre-contact and preferable prepolymerization, and follow-up polymerisation
It is standby to obtain, it is not required to wash the last handling process of deliming, can processes in a stable manner.It is emphasized that prepared by this method
Acrylic resin in Cl contents of ashes it is very low, can so greatly reduce the usage amount of halogen-absorber, this for reduce into
Originally, Improving The Quality of Products is also very favorable.
Embodiment
Following examples are provided so as to which the present invention is better described, are not intended to limit the scope of the present invention.
Method of testing：
1st, melt index (M.I)：Determined according to ASTM D1238-99.
2nd, polymer isotacticity (II)：Determined using heptane extraction process（Heptane boiling extracting 6 hours）：It is dry by 2 grams
Polymer samples, it is placed in extractor after being extracted 6 hours with boiling heptane, by the polymer weight obtained by residue drying to constant weight
Amount（g）With 2（g）Ratio be isotacticity.
3rd, polymer molecular weight profile exponent（Mw/Mn）：Using Shimadzu LC-10AT type gel permeation chromatographs（GPC）Survey
It is fixed, determined with PL-GPC220 by solvent of trichloro-benzenes at 150 DEG C（Standard specimen：Polystyrene, flow velocity：1.0ml/min）.
4th, the measure of polymer ash content：Determined according to GB/T9345-1988.
5th, the test of micmstructure of polymer：Using the type nuclear magnetic resonance of AVANCE III 400 purchased from Bruker companies of Switzerland
The unit group [mmmm] of microstructure five of spectrometer measure polymer and the molar fraction of three unit groups [mm].Sampling time：5s；Prolong
The slow time：1s；Sampling number：6000；Probe temperature：125℃.
6th, melting point polymer, the measure of crystallization temperature：Using the DSC-Diamond differential scanning amounts of PE companies of the U.S.
Hot instrument measure.Temperature range：50-200℃；Heating rate：10℃/min.
Embodiment 1
The preparation of spherical catalyst components
In the 300ml being sufficiently displaced from by high pure nitrogen with the glass reaction bottle of stirring, 90ml titanium tetrachloride is added
With 10ml hexane, -20 DEG C are cooled to, adds spherical chlorination magnesium alcoholate carrier 8g（Preparation method is referring to Chinese patent
CN1330086A）, under agitation, 110 DEG C are to slowly warm up to stage by stage, 1.5ml 2,4- pentanediols are added in temperature-rise period
2- isopropyl -2- isopentyl -1,3- dimethoxy propanes of dibenzoate and 1.5ml, after 110 DEG C of constant temperature 0.5h, filter off
Liquid, add titanium tetrachloride processing twice, each titanium tetrachloride dosage is 80ml, is then washed five times, after vacuum drying with hexane
Obtain spheric catalyst.
Propylene polymerization
In 5L autoclave, purged using stream of nitrogen gas, it is then past successively in stream of nitrogen gas to add
The hexane solution containing 0.25mmol triethyl aluminums is added in expects pipe, contains 0.005mmol Cyclohexyl Methyl Dimethoxysilanes
（CHMMS）Hexane solution, 10ml anhydrous hexane and 4mg spherical catalyst components, pre-contact reaction 1min, temperature 20
DEG C, after starting stirring, pre-contact reaction product is added in kettle, hydrogen 180ppm and 2.3L liquid propene is added, is warming up to
70 DEG C, it polymerize 1.5 hours.Test result is shown in Table 1.
Embodiment 2
The preparation of spherical catalyst components is the same as embodiment 1.
Propylene polymerization：Except pre-contact reacts 5mins, 25 DEG C of temperature is outer, with embodiment 1.
Embodiment 3
The preparation of spherical catalyst components is the same as embodiment 1.
Propylene polymerization：Except pre-contact reacts 10mins, 15 DEG C of temperature is outer, with embodiment 1.
Embodiment 4
The preparation of spherical catalyst components is the same as embodiment 1.
Propylene polymerization：Except pre-contact reaction product is added in kettle, prepolymerization 15mins is outer with embodiment 1 at 20 DEG C.
Embodiment 5
The preparation of spherical catalyst components is the same as embodiment 1.
Propylene polymerization：With embodiment 1 in addition to prepolymerization 8mins at 15 DEG C.
Embodiment 6
The preparation of spherical catalyst components is the same as embodiment 1.
Propylene polymerization：Except not introducing Cyclohexyl Methyl Dimethoxysilane（CHMMS）Outside with embodiment 1.
Embodiment 7
The preparation of spherical catalyst components is the same as embodiment 1.
Propylene polymerization：Except not introducing Cyclohexyl Methyl Dimethoxysilane（CHMMS）Outside with embodiment 4.
Comparative example 1
Spherical catalyst components：The DQ catalyst produced purchased from Sinopec Ao Da catalyst branch company（Referred to as：DC4, it is interior
Electron donor is diisobutyl phthalate）.
Propylene polymerization is the same as embodiment 1.
Comparative example 2
The preparation of spherical catalyst components is the same as embodiment 1.
Propylene polymerization：In 5L autoclave, purged using stream of nitrogen gas, then in stream of nitrogen gas
Contain 0.005mmol Cyclohexyl Methyl Dimethoxysilanes toward addition in charge pipe successively（CHMMS）Hexane solution, 5ml
The spherical catalyst components of anhydrous hexane and 4mg, after starting stirring, above-mentioned reactant is added in kettle, adds hydrogen 180ppm
With 1.1L liquid propene, after 15mins, then the hexane solution of 0.25mmol triethyl aluminums is added by charge pipe, add 1.2L
Liquid propene, be warming up to 70 DEG C, polymerize 1.5 hours.Test result is shown in Table 1.
Comparative example 3
The preparation of spherical catalyst components is the same as embodiment 1.
Propylene polymerization：In 5L autoclave, purged using stream of nitrogen gas, then in stream of nitrogen gas
, will after starting stirring successively toward the anhydrous hexane of hexane solution of the addition containing 0.25mmol triethyl aluminums, 5ml in charge pipe
Above-mentioned reactant is added in kettle, addition hydrogen 180ppm and 1.1L liquid propene, after 15mins, then is added and contained by charge pipe
There are 0.005mmol Cyclohexyl Methyl Dimethoxysilanes（CHMMS）Hexane solution, 5ml anhydrous hexane and the spherical of 4mg urge
Agent component, 1.2L liquid propene is added, be warming up to 70 DEG C, polymerize 1.5 hours.Test result is shown in Table 1.
Table 1
Table 2
| Fusing point (DEG C) | Crystallization temperature (DEG C) | |
| Embodiment 1 | 166 | 113 |
| Embodiment 2 | 167 | 114 |
| Embodiment 3 | 166 | 113 |
| Embodiment 4 | 165 | 112 |
| Embodiment 5 | 165 | 112 |
| Embodiment 6 | 166 | 113 |
| Embodiment 7 | 165 | 113 |
It can be seen that from embodiment 1-7 and comparative example 1-3 correction data and gathered using what the preparation method of the present invention obtained
Allyl resin total ash content is lower, and Cl contents of ashes are lower, and molecular weight distribution is wider, and molecular chain structure is more regular, and isotactic refers to
Number and melt index are appropriate, are suitable for use as electrical membrane materials.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (8)
1. a kind of electrical membrane acrylic resin, the acrylic resin passes through in the presence of a catalyst by propylene homo or copolymerization
Reaction obtains, and described catalyst includes the reaction product of following components：
(1) ingredient of solid catalyst A, the ingredient of solid catalyst A include magnesium, titanium, halogen and at least two electron donor a
And b；
(2) alkyl aluminum compound B, Al/Ti mol ratio are 20~150；
(3) optional a kind of external electron donor C；External electron donor dosage be Al/ external electron donors C mol ratio be 30~
150；
The ingredient of solid catalyst A after following three kinds of substance reactions by obtaining：
(1) as the magnesium compound shown in formula (I) or the adduct of the magnesium compound shown in formula (I)：MgR13R14(Ⅰ)；
(2) at least one is as the titanium compound shown in formula (II)：Ti(OR)4-kXk(Ⅱ)；
(3) at least two electron donor compound as and b；
In its formula of (I), R13And R14It is identical or different, it is each independently halogen, C1-C5Straight or branched alkoxyl,
And C1-C5Straight or branched alkyl in one kind；The adduct of magnesium compound shown in formula (I) is MgR13R14·
fR0OH·gE·hH2O, wherein R0For C1-C18Alkyl；F is within the scope of 0.1-6；E is a kind of electron donor chemical combination
Thing；G is within the scope of 0-2；H is within the scope of 0-0.7；
In formula (II) Ti (OR)4-kXkIn, R C1~C20Alkyl, X F, Cl or Br, k be 1~4 integer；
Wherein electron donor compound a is selected from the diol-lipid compound shown in formula (IV)：
In formula (IV), R1And R2For identical or different C1-C10Straight or branched alkyl, C3-C20Cycloalkyl, C6-C20Aryl,
C7-C20Alkaryl, C7-C20Aralkyl, benzene ring hydrogen is optionally taken by halogen atom in the aryl or alkaryl or aromatic hydrocarbons
Generation；R3-R6、R1-R2nGroup is hydrogen, halogen, the C of substituted or unsubstituted straight or branched identical or differ1-C20Alkyl,
C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl, C7-C20Aralkyl, C2-C10Alkylene, C10-C20Fused ring aryl or ester
Base, R3-R6And R1-R2nIt is described arbitrarily comprising the substituent one or several hetero atoms as carbon or hydrogen atom or both on group
Hetero atom be selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen atom, R3-R6And R1-R2nOne or more of group is optionally mutually cyclic；
N is 0-10 integer；
Wherein electron donor compound b is selected from the diether compound shown in formula (V)：
In formula (V), RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RⅥIt is identical or differ, selected from hydrogen, halogen atom, straight or branched C1-C20
Alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20One kind in aralkyl, RⅦAnd RⅧIt is identical or different, selected from straight chain or branch
The C of chain1-C20Alkyl, C3-C20Cycloalkyl, C6-C20Aryl, C7-C20Alkaryl, C7-C20One kind in aralkyl；RⅠ-RⅥBase
It is optionally mutually cyclic between group；
The mol ratio of the electron donor compound a and b is 0.55:1~50:1；
The acrylic resin is prepared by following preparation method：
By catalytic component A, B, optional external electron donor C progress pre-contact reactions are added, then carry out propylene polymerization；
The pre-contact reaction temperature is -15-40 DEG C, pre-contact time 0.5-60mins；
The polymerization temperature of the propylene polymerization is 50 DEG C~150 DEG C；The stop of propylene monomer and catalyst in polymer reactor
Time is 0.5-6h；Polymerization pressure is normal pressure or higher；Hydrogen is added in propylene polymerization processes, the added hydrogen is
100-1500ppm；
After pre-contact reaction, before polymerisation, catalyst and propylene monomer are subjected to prepolymerization；
Prepolymerization temperature is 10-70 DEG C, prepolymerization time 10-40mins；
The ash content of the acrylic resin is less than 50ppm；Cl ash contents are less than 6ppm；Melt flow index MFR is 1-3.5g/
10min；Isotactic index is 96-99%；Molecular weight distributing index MW/MnFor 4-12；The unit group of microstructure five of polymer
[mmmm]>93%, three unit groups [mm]>96%；Melting point polymer is 164-168 DEG C, and crystallization temperature is 110-116 DEG C.
2. acrylic resin according to claim 1, it is characterised in that
The pre-contact time is 1-10mins；
The polymerization temperature of the propylene polymerization is 60 DEG C~90 DEG C；During the stop in polymer reactor of propylene monomer and catalyst
Between be 1~4h；The added hydrogen is 150-1000ppm；
The prepolymerization temperature is 15-30 DEG C.
3. acrylic resin according to claim 1, it is characterised in that the ash content of the acrylic resin is less than 40ppm；
Cl ash contents are less than 4ppm；Melt flow index MFR is 2.5-3.5g/10min；Isotactic index is 97-98.5%；Molecular weight distribution
Index MW/MnFor 5-8；Melting point polymer is 165-167 DEG C, and crystallization temperature is 111-114 DEG C.
4. acrylic resin according to claim 1, it is characterised in that be selected from the monomer that propylene is copolymerized logical
Formula is CH2=CHR alkene, wherein R are hydrogen or the alkyl or aryl containing 2~6 carbon atoms.
5. acrylic resin according to claim 4, it is characterised in that with the monomer that propylene is copolymerized be ethene
Or butylene.
6. acrylic resin according to claim 1, it is characterised in that in formula (I), R13And R14It is identical or different, respectively
From independently being halogen；The adduct of magnesium compound shown in formula (I) is MgR13R14·fR0OH·gE·hH2O, wherein R0For
C1-C5Alkyl；F is 2-3.5；E is ethers or esters Donor compound；The mol ratio of the electron donor compound a and b
For 0.65:1~10:1.
7. acrylic resin according to claim 1, it is characterised in that the adduct of the magnesium compound shown in formula (I) is
MgR13R14·fR0OH·gE·hH2O, wherein R0For methyl, ethyl, n-propyl or isopropyl.
8. acrylic resin according to claim 1, it is characterised in that the electron donor compound a is formula (VI)
Shown diol-lipid compound：
In formula (VI), R1-R6Group is hydrogen, the C of straight or branched identical or differ1-C20Alkyl；
The electron donor compound b is 1, the 3- diether compounds shown in formula (VI)：
R1R2C(CH2OR3)(CH2OR4) (Ⅵ)
Wherein, R1And R2Can be with identical or differ, selected from C1-C18Alkyl, C3-C18Cycloalkyl, C6-C18Aryl, C7-C18Aralkyl
One kind in base, optionally bonded cyclization between group；R3And R4Can be with identical or differ, selected from C1-C10Alkyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310488478.9A CN104558298B (en) | 2013-10-17 | 2013-10-17 | A kind of electrical membrane acrylic resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310488478.9A CN104558298B (en) | 2013-10-17 | 2013-10-17 | A kind of electrical membrane acrylic resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558298A CN104558298A (en) | 2015-04-29 |
| CN104558298B true CN104558298B (en) | 2018-04-10 |
Family
ID=53075444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310488478.9A Active CN104558298B (en) | 2013-10-17 | 2013-10-17 | A kind of electrical membrane acrylic resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558298B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694428A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of polypropylene and its preparation method and application |
| CN109694427B (en) * | 2017-10-20 | 2022-03-15 | 中国石油化工股份有限公司 | Polypropylene, preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040690A (en) * | 2009-10-20 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing polypropylene with low ash content |
| CN103814050B (en) * | 2011-09-23 | 2016-05-04 | 巴塞尔聚烯烃意大利有限责任公司 | Prepare the method for high-purity propylene polymer |
-
2013
- 2013-10-17 CN CN201310488478.9A patent/CN104558298B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558298A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI650336B (en) | Catalyst component for olefin polymerization, preparation method thereof and catalyst containing same | |
| CN104193857B (en) | Self-limiting catalyst composition with bidentate internal donor | |
| KR101419757B1 (en) | Catalyst component for olefin polymerization and preparation method thereof | |
| KR102019727B1 (en) | Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor | |
| KR101761843B1 (en) | Polypropylene with narrow molecular weight distribution and process for preparation thereof | |
| CN104918971B (en) | High-performance Natta catalyst system, the production method of this loaded catalyst and application thereof | |
| CN106170500A (en) | Catalytic component for olefinic polymerization | |
| EP2135884A1 (en) | Super high molecular weight ethylene-alpha-olefin copolymer powder | |
| CN104250321B (en) | Catalyst component for olefin polymerization and olefin polymerization catalysis and olefine polymerizing process | |
| CN104558284A (en) | Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application | |
| CN103476806A (en) | Catalyst components for the polymerization of olefins | |
| BRPI0610978A2 (en) | alpha-olefin homo- or copolymer compositions | |
| CN109111539B (en) | Catalyst component for olefin polymerization and catalyst thereof | |
| CN104981486B (en) | High-performance Natta catalyst system, this MgCl2Production method of base catalyst and application thereof | |
| CN101165073B (en) | Catalyst component used for olefin polymerization reaction and catalyst thereof | |
| Zhou et al. | Effects of some new alkoxysilane external donors on propylene polymerization in MgCl2-supported Ziegler–Natta catalysis | |
| CN104558298B (en) | A kind of electrical membrane acrylic resin and preparation method thereof | |
| CN101759816B (en) | Method for preparing a catalyst component for olefinic polymerization, and a catalyst component thereof | |
| CN101824112A (en) | Preparation method of propylene homopolymer for geogrid and polymer thereof | |
| CN104479055B (en) | A kind of dialkoxy-magnesium support type ingredient of solid catalyst and catalyst | |
| BR112020023858A2 (en) | CATALYST COMPONENT, METHOD FOR PREPARING A CATALYST COMPONENT FOR OLEPHINE POLYMERIZATION, CATALYST FOR OLEPHINE POLYMERIZATION, PRE-POLYMERIZED CATALYST AND PROCESS FOR POLYMERIZING AN OLEFINE | |
| CN104558297A (en) | Polypropylene resin for biaxially oriented film and preparation method of polypropylene resin | |
| CN110016097A (en) | A kind of low leachable, low melting point, Narrow Molecular Weight Distribution, ethylene-propylene random copolymer of thermal oxidation stability and its preparation method and application | |
| CN102453184B (en) | Preparation method of propylene random copolymer | |
| CN107840906A (en) | A kind of ingredient of solid catalyst, catalyst system and pre-polymerized catalyst for olefinic polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |