CN105111357B - Acrylic polymers and preparation method thereof - Google Patents
Acrylic polymers and preparation method thereof Download PDFInfo
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- CN105111357B CN105111357B CN201510613519.1A CN201510613519A CN105111357B CN 105111357 B CN105111357 B CN 105111357B CN 201510613519 A CN201510613519 A CN 201510613519A CN 105111357 B CN105111357 B CN 105111357B
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 48
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000005977 Ethylene Substances 0.000 claims abstract description 37
- 239000003426 co-catalyst Substances 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 230000004044 response Effects 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000000386 donor Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 36
- -1 bicyclopentyl dioxane Chemical compound 0.000 claims description 32
- 238000006116 polymerization reaction Methods 0.000 claims description 32
- 239000000155 melt Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 229910000077 silane Inorganic materials 0.000 claims description 17
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 14
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 claims description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- ATGKAFZFOALBOF-UHFFFAOYSA-N cyclohexyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C1CCCCC1 ATGKAFZFOALBOF-UHFFFAOYSA-N 0.000 claims description 3
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 claims description 3
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- ASEHKQZNVUOPRW-UHFFFAOYSA-N tert-butyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)C ASEHKQZNVUOPRW-UHFFFAOYSA-N 0.000 claims description 3
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical group CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 229960002380 dibutyl phthalate Drugs 0.000 claims description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 2
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- YRMPTIHEUZLTDO-UHFFFAOYSA-N cyclopentyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C1CCCC1 YRMPTIHEUZLTDO-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000012545 processing Methods 0.000 description 9
- 238000012544 monitoring process Methods 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000012685 gas phase polymerization Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 1
- LNZBSVNIMBHSAG-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(methylamino)hexan-1-one Chemical compound CCCCC(NC)C(=O)c1ccc2OCOc2c1 LNZBSVNIMBHSAG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002370 organoaluminium group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a kind of acrylic polymers and preparation method thereof.The preparation method comprises the following steps：S1 after mixing ethylene, the first external electron donor, catalyst, co-catalyst and propylene, carries out the first polymerisation, the first product system is obtained, containing first polymer in first product system；S2 after mixing the second external electron donor, catalyst, co-catalyst and propylene, carries out the second polymerisation, obtains the second product system, second polymer is contained in second product system；S3 after the first product system is mixed with the second product system, obtains acrylic polymers；Wherein, catalyst includes at least one internal electron donor；Co-catalyst is organo-aluminum compound；The hydrogen response of second external electron donor is higher than the first external electron donor.Acrylic polymers prepared by the present invention has wider molecular weight distribution and higher isotacticity.
Description
Technical field
The present invention relates to organic synthesis field, in particular to a kind of acrylic polymers and preparation method thereof.
Background technology
Acrylic polymers be most widely used in the world at present, one of the synthetic resin that increase of production is most fast.
Current most of acrylic polymers be by propylene and choose any one kind of them or a variety of comonomers catalyst catalysis
It is prepared by the lower polymerization of effect.However, acrylic polymers poor toughness, the intensity of melt prepared by existing process is low, this is limited significantly
Its in Extrusion Coating, blow molding and the application in foaming field, therefore the acrylic polymers of high fondant-strength have it is good
Good application prospect.Theoretical research shows molecular weight height and the wide melt that can greatly enhance acrylic polymers of molecular weight distribution
Intensity, therefore how to prepare the wide acrylic polymers of molecular weight distribution and compare sense as theoretical circles and industrial quarters researcher
The research contents of interest.
In acrylic polymers field, from machining angle, the wide polymer of molecular weight distribution (MWD) polymer narrower than MWD
Melt strength bigger is suitable for the foam application of polymer.US2011034649A1、CN102159594A、CN101213249A
Disclose a kind of method for preparing acrylic polymers with CN1163621, but these patents be only based on catalyst composition or
The angle of technology controlling and process is studied, therefore the universality of preparation method is poor, propylene polymer molecule amount obtained distribution compared with
It is narrow, thus cause that there is poor melt strength by acrylic polymers made from existing preparation method, significantly limit third
The application range of alkene polymer.In addition, existing acrylic polymers catalyst also shows the problem of catalytic activity is not high.
Presence in view of the above problems, it is necessary to improve the catalytic activity of catalyst, and it is wider to prepare molecular weight distribution
Acrylic polymers.
The content of the invention
The present invention is intended to provide a kind of acrylic polymers and preparation method thereof, to solve the propylene prepared by existing method
Polymer there are molecular weight distribution it is relatively narrow the defects of.
To achieve these goals, according to an aspect of the invention, there is provided a kind of preparation method of acrylic polymers,
Comprise the following steps：After mixing ethylene, the first external electron donor, catalyst, co-catalyst and propylene, it is poly- to carry out first by S1
Reaction is closed, obtains the first product system, first polymer is contained in first product system；S2, by the second external electron donor, catalysis
After agent, co-catalyst and propylene mixing, the second polymerisation is carried out, the second product system is obtained, contains in second product system
Second polymer；And S3, after the first product system is mixed with the second product system, obtain acrylic polymers；Wherein, it is catalyzed
Agent includes at least one internal electron donor；Co-catalyst is organo-aluminum compound；The hydrogen response of second external electron donor is high
In the first external electron donor.
Further, when carrying out the first polymerisation in step S1, when the melt flow rate (MFR) of first polymer is less than
During 0.5g/10min, the first product system is obtained；When the second polymerisation is carried out in step S2, when the melt flow of second polymer
When dynamic rate is more than 50g/10min, the second product system is obtained.
Further, during the first product system is mixed with the second product system in step S3, the first product body
System and the weight ratio 3 of the second product system:7~7:3, it is preferably 4:6~6:4.
Further, for the mole of propylene, the additive amount of ethylene is 0.1~0.5% in step S1；It is preferred that
Ground, the additive amount of ethylene is 0.3~0.5%.
Further, the first external electron donor is bicyclopentyl dialkoxy silicane, is preferably dicyclopentyl dimethoxyl
One or more in the group of silane, bicyclopentyl diethoxy silane and diisopropyl dimethoxy silane compositions；And the
Two external electron donors are selected from alkylalkoxy silane, arylalkoxysilicane, cycloalkyl alkoxy silane or tetraalkoxysilane
One or more in the group of composition；
Preferably, alkylalkoxy silane is n-propyl trimethoxy silane, n-propyl triethoxysilane, isopropyl three
Methoxy silane, isopro-pyltriethoxysilane, tert-butyl trimethoxy silane or t-butyltriethoxysilane；Arylalkoxy
Base silane is phenyltrimethoxysila,e or phenyl triethoxysilane；Cycloalkyl alkoxy silane is cyclopenta trimethoxy silicon
Alkane, cyclopenta triethoxysilane, cyclohexyl trimethoxy silane or cyclohexyltriethyloxysilane；Tetraalkoxysilane is four
Methoxy silane or tetraethoxysilane.
Further, in step S1, with Al elements and the molar ratio computing of Si elements, co-catalyst and the first external electron donor
Amount ratio be 1~10；In step S2, with Al elements and the molar ratio computing of Si elements, co-catalyst and the second external electron donor
Amount ratio be 1~10.
Further, internal electron donor is selected from phthalic acid ester, phthalic acid di-n-butyl ester and phthalic acid
One or more in the group of diisobutyl ester composition.
Further, in step S1, the reaction temperature of the first polymerisation is 60~70 DEG C, is preferably 64~67 DEG C, instead
Pressure is answered as 2.0~2.5MPa, is preferably 2.2~2.3MPa；And/or in step S2, the reaction temperature of the second polymerisation is
60~70 DEG C, be preferably 64~67 DEG C, and reaction pressure is 2.0~2.5MPa, is preferably 2.2~2.3MPa.
Further, organo-aluminum compound be selected from triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum and
One or more in the group of tri-n-octylaluminium composition；Preferably, organo-aluminum compound is triethyl aluminum.
Further, catalyst further includes titanium compound and carrier, and at least containing there are one titanium-halogen keys in titanium compound；
Preferably, carrier is magnesium chloride.
Further, after step S3 is further included to the first product system is mixed with the second product system, inactivated, done
The step of dry processing.
According to another aspect of the present invention, a kind of acrylic polymers is provided, is made of the above method.
The present invention provides a kind of acrylic polymers and preparation method thereof.It applies the technical scheme of the present invention, the present invention should
With polymerisation twice.In the first polymerization process, except the first external electron donor, catalyst in propylene reaction system
Beyond co-catalyst, ethylene is also added into.It should be noted that in propylene polymerization system, the addition of ethylene is not to make
For comonomer, but in order to excite the catalytic activity of catalyst, and used as molecular weight regulator.This allows for first
It can generate that molecular weight is higher in polymerization process, and the first polymer that molecular weight distributing index itself is wider.And second
Ethylene is not added in polymerization process so that the molecular weight for the second polymer that the second polymerisation is formed is smaller.More
Particularly, the hydrogen response of above-mentioned the first external electron donor of first polymerization process is worse than in the second polymerization process
The hydrogen response of two external electron donors.The difference of hydrogen response can further improve the propylene that polymerisation is formed twice
The molecular weight difference of polymer.More than of both factor cause acrylic polymers prepared by the present invention that there is wider molecule
Amount distribution.In addition, twice in polymerization process, while internal electron donor is added in and external electron donor is conducive to enhancing and urges
The catalytic activity and stereoselectivity of agent, so that the acrylic polymers prepared by the present invention has higher isotacticity.
Specific embodiment
It should be noted that in the case where there is no conflict, the feature in embodiment and embodiment in the application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As background section is described, by acrylic polymers prepared by existing method there are molecular weight distribution compared with
The defects of narrow.To solve drawbacks described above, the present invention provides a kind of preparation methods of acrylic polymers, comprise the following steps：S1,
After ethylene, the first external electron donor, catalyst, co-catalyst and propylene are mixed, the first polymerisation is carried out, obtains the first production
Objects system, containing first polymer in first product system；S2, by the second external electron donor, catalyst, co-catalyst and third
After alkene mixing, the second polymerisation is carried out, obtains the second product system, second polymer is contained in second product system；S3, will
After first product system is mixed with the second product system, acrylic polymers is obtained；Wherein, catalyst is included at least one to electricity
Daughter；Co-catalyst is organo-aluminum compound；The hydrogen response of second external electron donor is higher than the first external electron donor.
In acrylic polymers preparation method provided by the invention, polymerisation twice is applied.In the first polymerisation mistake
Cheng Zhong in propylene reaction system in addition to the first external electron donor, catalyst and co-catalyst, is also added into ethylene.It needs
Illustrate, add in ethylene purpose not be as comonomer, inventor it was unexpectedly found that, in propylene polymerization system
Middle addition ethylene can excite the catalytic activity of catalyst, and can be used as molecular weight regulator.This allows for first
It can generate that molecular weight is higher in polymerization process, and the first polymer that molecular weight distributing index itself is wider.And second
Ethylene is not added in polymerization process so that the molecular weight for the second polymer that the second polymerisation is formed is smaller.More
Particularly, the hydrogen response of above-mentioned the first external electron donor of first polymerization process is worse than in the second polymerization process
The hydrogen response of two external electron donors.The difference of hydrogen response can further improve the propylene that polymerisation is formed twice
The molecular weight difference of polymer.More than of both factor cause acrylic polymers prepared by the present invention that there is wider molecule
Amount distribution.In addition, twice in polymerization process, while internal electron donor is added in and external electron donor is conducive to enhancing and urges
The catalytic activity and stereoselectivity of agent, so that the acrylic polymers prepared by the present invention has higher isotacticity.
External electron donor can be adsorbed onto in catalyst carrier and play catalytic action jointly.In the present invention " hydrogen response "
It is term well known in the art, is meant that finger uses certain polymerization system, melt flow rate (MFR) (MFR) becomes density of hydrogen
The sensibility of change.
The gas-phase polymerization process applied in the present invention refers to Innovene gas-phase polymerization process.
Ethylene is not used as what modification polypropylene segments used in the present invention, but is used as a kind of catalyst activity exciting agent
And molecular weight regulator.
Pass through above-mentioned preparation method, it is possible to prepare the acrylic polymers with wide molecular weight distribution.A kind of preferred
Embodiment in, further included in step S3 and the mixture of the first product system and the second product system inactivated and dried
The step of processing.This is conducive to the reactivity of residual catalyst in termination propylene polymerization objects system, makes the propylene polymerization of acquisition
Object is in more stable state.
In above-mentioned preparation process, as long as adding in ethylene during the first polymerisation in the reaction system excites catalyst
Catalytic activity, improve polyacrylic molecular weight, and widen the molecular weight distribution of acrylic polymers.In a kind of preferred embodiment party
In formula, for the mole of propylene, the additive amount of ethylene is 0.1~0.5% in step S1；Preferably 0.3~
0.5%.By the dosage control of ethylene within the above range, be conducive to farthest excite the activity of catalyst and further control
The molecular weight of first polymer processed, so as to promote acrylic polymers that there is broader molecular weight distribution.At the same time, additionally it is possible to subtract
The introduction volume of ethylene, even ethylene introduction volume are reduced to less than 0.5% in few acrylic polymers.
In preparation method provided by the invention, as long as the hydrogen response of the second external electron donor gives electricity higher than first outside
Daughter can be obtained by the acrylic polymers with wide molecular weight distribution.In a preferred embodiment, first outside to electricity
Daughter is cyclopenta dialkoxy silicane,；And second external electron donor be selected from alkylalkoxy silane, alkoxy aryl silicon
One or more in the group of alkane, cycloalkyl alkoxy silane or tetraalkoxysilane composition；In the addition of the first polymerisation
The isotacticity that the first external electron donor also advantageously improves first polymer is stated, and then improves the isotacticity of acrylic polymers, together
When reduce acrylic polymers low xylene soluble content；And it is preferable that above-mentioned hydrogen response is added in the second polymerisation
The second external electron donor, the molecular weight difference of the acrylic polymers that polymerisation twice is formed can be further improved, so as to
Further widen the molecular weight distribution of acrylic polymers.
Preferably, bicyclopentyl dialkoxy silicane includes but not limited to dicyclopentyl dimethoxyl silane, bicyclopentyl
One or more in the group of diethoxy silane or diisopropyl dimethoxy silane compositions；Alkylalkoxy silane includes
But n-propyl trimethoxy silane, n-propyl triethoxysilane, isopropyltri-methoxysilane are not limited to, three ethoxy of isopropyl
Base silane, tert-butyl trimethoxy silane or t-butyltriethoxysilane；Arylalkoxysilicane includes but not limited to phenyl
Trimethoxy silane or phenyl triethoxysilane；Cycloalkyl alkoxy silane includes but not limited to cyclopenta trimethoxy silicon
Alkane, cyclopenta triethoxysilane, cyclohexyl trimethoxy silane or cyclohexyltriethyloxysilane；Tetraalkoxysilane includes
But it is not limited to tetramethoxy-silicane or tetraethoxysilane.
In preparation method provided by the invention, those skilled in the art can select the first external electron donor, outside second
The amount ratio of electron donor and co-catalyst.In a preferred embodiment, in step S1, with Al elements and Si elements
The amount ratio of molar ratio computing, co-catalyst and the first external electron donor is 1~10；In step S2, with Al elements and Si elements
The amount ratio of molar ratio computing, co-catalyst and the second external electron donor is 1~10.External electron donor is added in, can correspondingly be carried
The stereoselectivity of high catalyst.And the amount ratio of the first external electron donor, the second external electron donor and co-catalyst is controlled
Within the above range, additionally it is possible to further improve the catalytic activity of catalyst, and prepare the propylene with various molecular weights and gather
Object is closed, so as to further widen the molecular weight distribution of acrylic polymers.
In above-mentioned preparation method, reactive polymeric reaction twice is carried out under the action of different external electron donors, reactant,
The acrylic polymers with wider molecular weight distribution can be prepared.In a preferred embodiment, above-mentioned steps S1
During the first polymerisation of middle progress, when the melt flow rate (MFR) of first polymer is less than 0.5g/10min, the first product is obtained
System；When the second polymerisation is carried out in step S2, when the melt flow rate (MFR) of second polymer is more than 50g/10min, obtain
To the second product system.The melt flow rate (MFR) of polymer is supervised using monitoring means commonly used in the art in the present invention
It surveys.According to the data of monitoring, the molecular weight of first polymer and the molecular weight of second polymer can be more accurately controlled,
So as to more effectively control the molecular weight distribution of final acrylic polymers.And by the molten of first polymer and second polymer
Body flow rate controls within the above range, and the molecular weight distribution that can make acrylic polymers is wider, while overall mechanical properties
More preferably.
By the control of the melt flow rate (MFR) of first polymer and second polymer within the above range, propylene polymerization can be made
The molecular weight distribution of object is wider, while overall mechanical properties are more preferably.In a preferred embodiment, by first in step S3
During product system is mixed with the second product system, the weight ratio 3 of the first product system and the second product system:7~7:
3, it is preferably 4:6~6:4.It by the control of the mixing ratio of first polymer and second polymer within the above range, can be further
Improve the overall mechanical properties of acrylic polymers.In actual mechanical process, can by be monitored online the first product system with
The reactor residence time of second product system, with the mixing ratio of both control.
In preparation method provided by the invention, internal electron donor can also be internal electron donor commonly used in the art.
In a kind of preferred embodiment, internal electron donor includes but not limited to phthalic acid ester, phthalic acid di-n-butyl ester
With the one or more in o-benzene butyl phthalate ester.Using the above-mentioned internal electron donor containing phenyl ring, it can also enhance and urge
The stereoselectivity of agent, when being used in conjunction with so as to it with external electron donor, the isotacticity that can make acrylic polymers is further
It improves.
In preparation method provided by the invention, those skilled in the art can select the technique of gas-phase polymerization processes twice
Parameter.In a preferred embodiment, in step S1, the reaction temperature of the first polymerisation is 60~70 DEG C, is preferably
64~67 DEG C, reaction pressure is 2.0~2.5MPa, is preferably 2.2~2.3MPa；And/or in step S2, the second polymerisation
Reaction temperature is 60~70 DEG C, is preferably 64~67 DEG C, and reaction pressure is 2.0~2.5MPa, is preferably 2.2~2.3MPa.
In preparation method provided by the invention, catalyst, which may be employed, commonly used in the art prepares urging for acrylic polymers
Agent, as long as it contains at least one internal electron donor.In a preferred embodiment, catalyst further includes titanizing
Object and carrier are closed, and at least containing there are one titanium-halogen keys in titanium compound.Preferably, carrier is magnesium chloride.
Above-mentioned introduction according to the present invention, those skilled in the art can be with the dosages of selecting catalyst.A kind of preferred
In embodiment, the weight percentage of internal electron donor is 5~15% in catalyst, and the weight percentage of titanium compound is
1~3%.Preferably CD catalyst or CDI catalyst.CD catalyst or CDI catalyst in the present invention are in use, and use ore deposit
Object oil is diluted to 30% concentration.
In preparation method provided by the invention, those skilled in the art can select common organo-aluminum compound as
Co-catalyst.In a preferred embodiment, organo-aluminum compound for triethyl aluminum, triisobutyl aluminium, three n-butylaluminums,
One or more in tri-n-hexyl aluminum and tri-n-octylaluminium.Above-mentioned co-catalyst can adsorb on a catalyst support, favorably
In more into the catalytic activity of level raising catalyst, and make the isotacticity higher of acrylic polymers.Preferably, organo-aluminium chemical combination
Object is triethyl aluminum.
Another aspect of the present invention additionally provides a kind of acrylic polymers, is made of above-mentioned preparation method.Propylene polymerization
The molecular weight distribution of object is more than 8, and weight ethylene percentage composition is less than 0.5% and isotacticity is more than 96.5%.Molecular weight distribution
Width can greatly improve the melt strength of acrylic polymers within the above range, be conducive to widen the application of acrylic polymers
Scope；In addition, higher isotacticity can reduce the low xylene soluble content of acrylic polymers.
The present invention is described in further detail below in conjunction with specific embodiment, these embodiments are it is not intended that limit this
Invent scope claimed.
Embodiment 1
First polymerisation and the second polymerisation carry out in two reactors respectively.By ethylene, bicyclopentyl diformazan
Oxysilane, CD catalyst, triisobutyl aluminium and propylene mix in the first reactor, are 60 DEG C in reaction temperature, 2.0MPa
Under conditions of, the first polymerisation is carried out, the first product system is formed, contains first polymer in first product system.Its
In, for the mole of propylene, the dosage of ethylene is 0.1%；With the molar ratio computing of Al elements and Si elements, outside first
The molar ratio of electron donor addition Al/Si is 5.When the first polymerisation is carried out in step S1, the molten of first polymer is monitored
After body flow rate reaches 0.25g/10min, the first product system is obtained.
After CD catalyst, triisobutyl aluminium, isopro-pyltriethoxysilane and propylene are mixed in the second reactor,
Reaction temperature is 70 DEG C, under conditions of 2.5MPa, carries out the second polymerisation, obtains the second product system, the second product body
Contain second polymer in system.Wherein, with Al elements and the molar ratio computing of Si elements, the second external electron donor addition Al/Si
Molar ratio be 5.When the second polymerisation is carried out in step S2, the melt flow rate (MFR) for monitoring second polymer is 81.2g/
After 10min, the second product system is obtained.
By weight, by the first product system and the second product system with weight ratio 7：After 3 mixing, inactivated and dried
Processing, obtains acrylic polymers.
Embodiment 2
First polymerisation and the second polymerisation carry out in two reactors respectively.By ethylene, bicyclopentyl diformazan
Oxysilane, BD catalyst, three n-butylaluminums and propylene mix in the first reactor, are 60 DEG C in reaction temperature, 2.5MPa
Under conditions of, the first polymerisation is carried out, the first product system is formed, contains first polymer in first product system.Its
In, for the mole of propylene, the dosage of ethylene is 0.3%；With the molar ratio computing of Al elements and Si elements, outside first
The molar ratio of electron donor addition Al/Si is 4.When the first polymerisation is carried out in step S1, the molten of first polymer is monitored
After body flow rate reaches 0.2g/10min, the first product system is obtained.
After CD catalyst, three n-butylaluminums, isopro-pyltriethoxysilane and propylene are mixed in the second reactor,
Reaction temperature is 70 DEG C, under conditions of 2.0MPa, carries out the second polymerisation, obtains the second product system, the second product body
Contain second polymer in system.Wherein, with Al elements and the molar ratio computing of Si elements, the second external electron donor addition Al/Si
Molar ratio be 4.When the second polymerisation is carried out in step S2, the melt flow rate (MFR) for monitoring second polymer is 80.2g/
After 10min, the second product system is obtained.
By weight, by the first product system and the second product system with weight ratio 5：After 5 mixing, inactivated and dried
Processing, obtains acrylic polymers.
Embodiment 3
First polymerisation and the second polymerisation carry out in two reactors respectively.By ethylene, bicyclopentyl diformazan
Oxysilane, CDI catalyst, triethyl aluminum and propylene mix in the first reactor, are 64 DEG C in reaction temperature, 2.2MPa's
Under the conditions of, the first polymerisation is carried out, the first product system is formed, contains first polymer in first product system.Wherein,
For the mole of propylene, the dosage of ethylene is 0.1%；With Al elements and the molar ratio computing of Si elements, given outside first
The molar ratio of electron addition Al/Si is 6.When the first polymerisation is carried out in step S1, the melt of first polymer is monitored
After flow rate reaches 0.25g/10min, the first product system is obtained.
After CD catalyst, triethyl aluminum, tetraethoxysilane and propylene are mixed in the second reactor, in reaction temperature
For 64 DEG C, under conditions of 2.3MPa, the second polymerisation is carried out, the second product system is obtained, contains in second product system
Second polymer.Wherein, with Al elements and the molar ratio computing of Si elements, the molar ratio of the second external electron donor addition Al/Si
For 6.When the second polymerisation is carried out in step S2, the melt flow rate (MFR) of second polymer is monitored after 140g/10min, to obtain
To the second product system.
By weight, by the first product system and the second product system with weight ratio 3：After 7 mixing, inactivated and dried
Processing, obtains acrylic polymers.
Embodiment 4
First polymerisation and the second polymerisation carry out in two reactors respectively.By ethylene, bicyclopentyl diformazan
Oxysilane, CDI catalyst, triethyl aluminum and propylene mix in the first reactor, are 67 DEG C in reaction temperature, 2.2MPa's
Under the conditions of, the first polymerisation is carried out, the first product system is formed, contains first polymer in first product system.Wherein,
For the mole of propylene, the dosage of ethylene is 0.3%；With Al elements and the molar ratio computing of Si elements, given outside first
The molar ratio of electron addition Al/Si is 5.When the first polymerisation is carried out in step S1, the melt of first polymer is monitored
After flow rate reaches 0.2g/10min, the first product system is obtained.
After CD catalyst, triethyl aluminum, tetraethoxysilane and propylene are mixed in the second reactor, in reaction temperature
For 67 DEG C, under conditions of 2.3MPa, the second polymerisation is carried out, the second product system is obtained, contains in second product system
Second polymer.Wherein, with Al elements and the molar ratio computing of Si elements, the molar ratio of the second external electron donor addition Al/Si
For 5.When the second polymerisation is carried out in step S2, the melt flow rate (MFR) of second polymer is monitored after 142g/10min, to obtain
To the second product system.
By weight, by the first product system and the second product system with weight ratio 6：After 4 mixing, inactivated and dried
Processing, obtains acrylic polymers.
Embodiment 5
First polymerisation and the second polymerisation carry out in two reactors respectively.By ethylene, bicyclopentyl diethyl
Oxysilane silane, CDI catalyst, triethyl aluminum and propylene mix in the first reactor, are 66 DEG C in reaction temperature,
Under conditions of 2.2MPa, the first polymerisation is carried out, the first product system is formed, contains the first polymerization in first product system
Object.Wherein, for the mole of propylene, the dosage of ethylene is 0.4%；With the molar ratio computing of Al elements and Si elements,
The molar ratio of first external electron donor addition Al/Si is 10.When the first polymerisation is carried out in step S1, the first polymerization of monitoring
After the melt flow rate (MFR) of object reaches 0.2g/10min, the first product system is obtained.
After CD catalyst, triethyl aluminum, tetraethoxysilane and propylene are mixed in the second reactor, in reaction temperature
For 64 DEG C, under conditions of 2.3MPa, the second polymerisation is carried out, the second product system is obtained, contains in second product system
Second polymer.Wherein, with Al elements and the molar ratio computing of Si elements, the molar ratio of the second external electron donor addition Al/Si
For 10.When the second polymerisation is carried out in step S2, the melt flow rate (MFR) of second polymer is monitored after 140g/10min, to obtain
To the second product system.
By weight, by the first product system and the second product system with weight ratio 6：After 4 mixing, inactivated and dried
Processing, obtains acrylic polymers.
Embodiment 6
First polymerisation and the second polymerisation carry out in two reactors respectively.By ethylene, diisopropyl diformazan
Oxysilane silane, CDI catalyst, triethyl aluminum and propylene mix in the first reactor, are 66 DEG C in reaction temperature,
Under conditions of 2.2MPa, the first polymerisation is carried out, the first product system is formed, contains the first polymerization in first product system
Object.Wherein, for the mole of propylene, the dosage of ethylene is 0.45%；With the molar ratio computing of Al elements and Si elements,
The molar ratio of first external electron donor addition Al/Si is 1.When the first polymerisation is carried out in step S1, the first polymerization of monitoring
After the melt flow rate (MFR) of object reaches 0.48g/10min, the first product system is obtained.
After CD catalyst, triethyl aluminum, tetraethoxysilane and propylene are mixed in the second reactor, in reaction temperature
For 64 DEG C, under conditions of 2.3MPa, the second polymerisation is carried out, the second product system is obtained, contains in second product system
Second polymer.Wherein, with Al elements and the molar ratio computing of Si elements, the molar ratio of the second external electron donor addition Al/Si
For 1.When the second polymerisation is carried out in step S2, the melt flow rate (MFR) of second polymer is monitored after 140g/10min, to obtain
To the second product system.
By weight, by the first product system and the second product system with weight ratio 6：After 4 mixing, inactivated and dried
Processing, obtains acrylic polymers.
Comparative example 1
First polymerisation and the second polymerisation carry out in two reactors respectively.By bicyclopentyl diethoxy silicon
Alkane, CD catalyst, tri-n-hexyl aluminum and propylene mix in the first reactor, are 58 DEG C in reaction temperature, the condition of 1.9MPa
Under, the first polymerisation is carried out, the first product system is formed, contains first polymer in first product system.Wherein, with Al members
The molar ratio computing of element and Si elements, the molar ratio of the first external electron donor addition Al/Si is 0.5.First is carried out in step S1
During polymerisation, monitor first polymer melt flow rate (MFR) reach 0.3g/10min after, obtain the first product system.
After CD catalyst, tri-n-hexyl aluminum, isopro-pyltriethoxysilane and propylene are mixed in the second reactor,
Reaction temperature is 58 DEG C, under conditions of 1.9MPa, carries out the second polymerisation, obtains the second product system, the second product body
Contain second polymer in system.Wherein, with Al elements and the molar ratio computing of Si elements, the second external electron donor addition Al/Si
Molar ratio be 0.5.When the second polymerisation is carried out in step S2, the melt flow rate (MFR) for monitoring second polymer is 82.2g/
After 10min, the second product system is obtained.
By weight, by the first product system and the second product system with weight ratio 6：After 4 mixing, propylene polymerization is obtained
Object.
Comparative example 2
First polymerisation and the second polymerisation carry out in two reactors respectively.By ethylene, bicyclopentyl diethyl
Oxysilane, BD. catalyst, tri-n-hexyl aluminum and propylene mix in the first reactor, are 60 DEG C in reaction temperature, 2.0MPa
Under conditions of, the first polymerisation is carried out, the first product system is formed, contains first polymer in first product system.Its
In, for the mole of propylene, the dosage of ethylene is 0.49%；With the molar ratio computing of Al elements and Si elements, first
The molar ratio of external electron donor addition Al/Si is 15.When the first polymerisation is carried out in step S1, first polymer is monitored
After melt flow rate (MFR) reaches 0.5g/10min, the first product system is obtained.
After BD catalyst, tri-n-hexyl aluminum, bicyclopentyl diethoxy silane and propylene are mixed in the second reactor,
It is 70 DEG C in reaction temperature, under conditions of 2.5MPa, carries out the second polymerisation, obtain the second product system, second product
Contain second polymer in system.Wherein, with Al elements and the molar ratio computing of Si elements, the second external electron donor addition Al/
The molar ratio of Si is 15.When the second polymerisation is carried out in step S2, the melt flow rate (MFR) for monitoring second polymer is 75g/
After 10min, the second product system is obtained.
By weight, by the first product system and the second product system with weight ratio 2：After 8 mixing, inactivated and dried
Processing, obtains acrylic polymers.
The molecular weight distribution of acrylic polymers obtained in embodiment 1 to 6 and comparative example 1 and 2
The test method of polymer obtained in embodiment 1 to 6 and comparative example 1 and 2：1st, according to GBT 3684-2000
The assay method of thermoplastic melt flow rate (MFR) and melt volume-flow rate is tested, and obtains polymer melt flow
Rate.2nd, acrylic polymers relative molecular mass and its distribution is tested by GPCV2000 gel permeation chrommatographs：Using polystyrene as
Demarcate object, solvent 1,2,4- trichloro-benzenes, 150 DEG C of operating temperature.
From above data, it can be seen that the above embodiments of the present invention realize following technique effect：Using this hair
The preparation method of bright offer, higher using isotacticity in the first polymerisation, the poor external electron donor of hydrogen response, and
Using the external electron donor that hydrogen response is higher in the second polymerisation, and it polymerize by adjusting first polymer and second
The melt flow rate (MFR) and external electron donor of object and the additive amount of co-catalyst so that the molecular weight distribution of acrylic polymers by
7.4 originally increase to 9.8, even broader 10；Isotacticity is also down to 96.5 from 97.5.
Invention applies polymerisations twice.In the first polymerization process, except first in propylene reaction system
Beyond external electron donor, catalyst and co-catalyst, ethylene is also added into.The addition of ethylene not be as comonomer, and
It is to excite the catalytic activity of catalyst, and is used as molecular weight regulator.This allows for the first polymerization process
In can generate that molecular weight is higher, and the first polymer that molecular weight distributing index itself is wider.And the second polymerization process
In do not add in ethylene so that the second polymerisation formed second polymer molecular weight it is smaller.More specifically, above-mentioned
The hydrogen response of one the first external electron donor of polymerization process is worse than the second external electron donor in the second polymerization process
Hydrogen response.The difference of hydrogen response can further improve the molecule of the acrylic polymers that polymerisation is formed twice
Measure difference.More than of both factor cause acrylic polymers prepared by the present invention that there is wider molecular weight distribution.Except this
Outside, twice in polymerization process, while add in internal electron donor and external electron donor is conducive to enhance the catalysis of catalyst
Activity and stereoselectivity, so that the acrylic polymers prepared by the present invention has higher isotacticity.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (14)
1. a kind of preparation method of acrylic polymers, which is characterized in that comprise the following steps：
S1 after mixing ethylene, the first external electron donor, catalyst, co-catalyst and propylene, carries out the first polymerisation, obtains
To the first product system, first polymer is contained in first product system；It is described for the mole of the propylene
The additive amount of ethylene described in step S1 is 0.3~0.5%；
S2 after mixing the second external electron donor, the catalyst, the co-catalyst and the propylene, carries out the second polymerization
Reaction obtains the second product system, contains second polymer in second product system；And
S3 after first product system is mixed with second product system, obtains the acrylic polymers；
Wherein, the catalyst includes at least one internal electron donor；The co-catalyst is organo-aluminum compound；Described second
The hydrogen response of external electron donor is higher than first external electron donor；
When carrying out first polymerisation in the step S1, when the melt flow rate (MFR) of the first polymer is less than
During 0.5g/10min, first product system is obtained；
When carrying out second polymerisation in the step S2, when the melt flow rate (MFR) of the second polymer is more than 50g/
During 10min, second product system is obtained.
2. preparation method according to claim 1, which is characterized in that in the step S3 by first product system with
During the second product system mixing, the weight ratio 3 of first product system and second product system:7~
7:3。
3. preparation method according to claim 2, which is characterized in that in the step S3 by first product system with
During the second product system mixing, the weight ratio of first product system and second product system is 4:6
~6:4.
4. preparation method according to claim 1, which is characterized in that first external electron donor is bicyclopentyl dioxane
Oxysilane；And
Second external electron donor is selected from alkylalkoxy silane, arylalkoxysilicane, cycloalkyl alkoxy silane or four
One or more in the group of alkoxy silane composition.
5. preparation method according to claim 4, which is characterized in that first external electron donor is bicyclopentyl diformazan
One or more in the group of oxysilane, bicyclopentyl diethoxy silane and diisopropyl dimethoxy silane composition；Institute
Alkylalkoxy silane is stated as n-propyl trimethoxy silane, n-propyl triethoxysilane, isopropyltri-methoxysilane, it is different
Propyl-triethoxysilicane, tert-butyl trimethoxy silane or t-butyltriethoxysilane；The arylalkoxysilicane is
Phenyltrimethoxysila,e or phenyl triethoxysilane；The cycloalkyl alkoxy silane is cyclopentyl-trimethoxy-silane,
Cyclopenta triethoxysilane, cyclohexyl trimethoxy silane or cyclohexyltriethyloxysilane；The tetraalkoxysilane is
Tetramethoxy-silicane or tetraethoxysilane.
6. preparation method according to claim 4, which is characterized in that
In the step S1, with Al elements and the molar ratio computing of Si elements, the co-catalyst and first external electron donor
Amount ratio be 1~10；
In the step S2, with Al elements and the molar ratio computing of Si elements, the co-catalyst and second external electron donor
Amount ratio be 1~10.
7. preparation method according to claim 1, which is characterized in that the internal electron donor is selected from phthalic acid ester,
The phthalic acid ester is selected from phthalic acid di-n-butyl ester and/or o-benzene butyl phthalate ester.
8. preparation method according to any one of claim 1 to 7, which is characterized in that
In the step S1, the reaction temperature of first polymerisation is 60~70 DEG C, and reaction pressure is 2.0~2.5MPa；
And/or
In the step S2, the reaction temperature of second polymerisation is 60~70 DEG C, and reaction pressure is 2.0~2.5MPa.
9. preparation method according to claim 8, which is characterized in that
In the step S1, the reaction temperature of first polymerisation is 64~67 DEG C, and reaction pressure is 2.2~2.3MPa；
And/or
In the step S2, the reaction temperature of second polymerisation is 64~67 DEG C, and reaction pressure is 2.2~2.3MPa.
10. preparation method according to claim 8, which is characterized in that the organo-aluminum compound is selected from triethyl aluminum, three
One or more in the group that aluminium isobutyl, three n-butylaluminums, tri-n-hexyl aluminum and tri-n-octylaluminium form.
11. preparation method according to claim 10, which is characterized in that the organo-aluminum compound is triethyl aluminum.
12. preparation method according to claim 10, which is characterized in that the catalyst further includes titanium compound and load
Body, and at least containing there are one titanium-halogen keys in the titanium compound.
13. preparation method according to claim 12, which is characterized in that the carrier is magnesium chloride.
14. preparation method according to claim 12, which is characterized in that the step S3 is further included to described first is produced
After objects system is mixed with second product system, inactivated, drying process the step of.
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| CN1163621A (en) * | 1994-10-11 | 1997-10-29 | 博雷尔斯股份公司 | Novel polypropylene compositions with broad molecular weight distribution |
| KR20060038102A (en) * | 2004-10-29 | 2006-05-03 | 삼성토탈 주식회사 | Catalyst for propylene polymerization and the method of propylene polymerization using the catalyst |
| CN102134291A (en) * | 2010-01-22 | 2011-07-27 | 中国石油化工股份有限公司 | Method for preparing polypropylene with high melt strength |
| CN102453163A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing propylene polymer and propylene polymer produced by the method |
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| CN1163621A (en) * | 1994-10-11 | 1997-10-29 | 博雷尔斯股份公司 | Novel polypropylene compositions with broad molecular weight distribution |
| KR20060038102A (en) * | 2004-10-29 | 2006-05-03 | 삼성토탈 주식회사 | Catalyst for propylene polymerization and the method of propylene polymerization using the catalyst |
| CN102134291A (en) * | 2010-01-22 | 2011-07-27 | 中国石油化工股份有限公司 | Method for preparing polypropylene with high melt strength |
| CN102453163A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing propylene polymer and propylene polymer produced by the method |
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