CN101993510A - Method for preparing ethylene-propylene copolymer - Google Patents
Method for preparing ethylene-propylene copolymer Download PDFInfo
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- CN101993510A CN101993510A CN2009101844321A CN200910184432A CN101993510A CN 101993510 A CN101993510 A CN 101993510A CN 2009101844321 A CN2009101844321 A CN 2009101844321A CN 200910184432 A CN200910184432 A CN 200910184432A CN 101993510 A CN101993510 A CN 101993510A
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Abstract
The invention discloses a method for preparing an ethylene-propylene copolymer, which concretely comprises the following step of: carrying out copolymerization reaction on ethylene and propylene under the existence of a catalyst system to obtain an ethylene-propylene copolymer, wherein the catalyst system comprises a loading type titanium system solid catalyst component with the structural formula of TiCl4/MgCl2 ID or TiCl4/MgCl2 ID/SiO2, an organoaluminium compound, an organosilicon compound with the structural formula of RR'Si(OCH3)2 and a monoether compound with the structural formula of R''OCH3, wherein ID is an electron donor. The crystalline fraction of the ethylene-propylene copolymer prepared according to the method of the invention has a longer propylene sequence. A modified polypropylene material with excellent rigidity and toughness balance performance can be obtained by carrying out toughness improvement modification on iPP (Isopentenylpyrophosphate) through the ethylene-propylene copolymer with the special structure.
Description
Technical field
The present invention relates to a kind of preparation method of ethylene propylene copolymer, more particularly, relate to a kind of selection and using method thereof for preparing the catalyst system component of ethylene propylene copolymer.
Background technology
Ethylene propylene copolymer is broad-spectrum synthesized polymer material.The ethylene propylene copolymer that ethylene content is lower than 5% (weight) is the modification kind of isotatic polypropylene (iPP), and commodity are called PPR, has the toughness and the transparency that are better than iPP, can be used for making a series of Application Areass that iPP such as tubing are difficult to be competent at.The ethylene propylene copolymer (EPR) of ethylene content between 20～50% then has elastomeric character, obtained to use widely as a kind of plastic toughening properties-correcting agent.The EPR of appropriate amount is blended into obtains the modified polypropylene material of a kind of erosion-resisting characteristics among the iPP, be applied to various fields such as bumper, anti-impact injection-molded item far above common iPP.The main at present two class catalyst systems that adopt of the industrial production of EPR, the homogeneous catalyst system that one class is made up of vanadium owner catalyzer and organoaluminum promotor, its synthetic ethylene propylene copolymer has highly random and characteristics low-crystalline, and its Application Areas mainly is a rubber type of material; Another kind ofly be carried on the heterogeneous catalyst systems that particulate state Primary Catalysts that magnesium chloride constitutes and organoaluminum promotor are formed, contain more crystallinity fraction (being generally about 20%) among its synthetic EPR by titanium chloride.EPR and iPP that random sequence distributes are incompatible, and EPR phase region size is bigger in the iPP/EPR intermingling material that itself and iPP blend obtain, and can not give full play of the toughening effect of EPR.Studies show that before, crystallinity fraction among the EPR of Titanium series catalyst system preparation is formed different ethylene, propylene segmented copolymers and is formed by a series of, wherein the segmented copolymer chain that propylene sequences is relatively long was both compatible with iPP, also good consistency is arranged with ethylene-propylene random copolymer, thereby can in the intermingling material of iPP and EPR, play compatibilization, the size of its EPR phase region is reduced, improve the efficient of random copolymers toughening effect.Structure properties to Titanium series catalyst synthetic EPR concerns that result of study shows, the propylene sequences length that improves crystallinity fraction among the EPR can be improved the consistency of EPR and iPP effectively, thereby improves the mechanical property of iPP/EPR intermingling material.Can prepare the high-performance poly olefin material that rigidity and toughness are held concurrently excellent with EPR that contains longer propylene sequences and iPP blend.
At the catalyst system that is used for preparing isotatic polypropylene, usually be carried on outside the particulate state Primary Catalysts (load-type Titanium series catalyst) and aluminum alkyl catalyst of magnesium chloride formation at titanium chloride, add the organic compound (be called and add electron donor) that brings electron group on a small quantity in addition, its effect is the stereospecificity that improves catalyzer, to prepare high normal polypropylene.General formula is RR ' Si (OCH
3)
2Silicoorganic compound are the most frequently used electron donors that add, wherein R and R ' are for to contain alkyl, the cycloalkyl of 4～20 carbon or to be with substituent phenyl.Chinese patent 98126383.6 adds the organosilicon external electron donor of different structure and regulates polyacrylic degree of isotacticity in the load-type Titanium series catalyst system.U.S. Pat 6,066,702, US6,111,039, US6,133,385, US6,147,024 all report form compound external electron donor with two or more silicoorganic compound and be used for the propylene polymerization system, to prepare the isotatic polypropylene of molecular weight distribution broad.In disclosed document, do not see as yet and form the report that compound external electron donor comes the ethylene propylene copolymerization characteristic of regulating load type Titanium series catalyst with silicoorganic compound and ether compound.
Summary of the invention
We are at research TiCl
4/ MgCl
2Being surprised to find during the reaction of ID class loaded catalyst catalyzed ethylene copolymerization of propylene, is RR ' Si (OCH with structural formula
3)
2Silicoorganic compound and structural formula be R " OCH
3Monoether compound when mixing the back as the compound external electron donor of this class catalyst system with suitable proportion, the propylene sequences length of the crystallinity fraction of gained ethylene propylene copolymer is greater than the system of using the organosilicon external electron donor separately.This variation helps improving the toughening efficiency of EPR to iPP.Ethylene propylene copolymer preparation method of the present invention has been proposed thus.In the present invention, the catalyst system that employing is made up of load-type Titanium series catalyst, aluminum alkyl catalyst, silicoorganic compound and the compound external electron donor of ether compound two-pack carries out the copolyreaction of ethene and propylene, has prepared more how long to contain the copolymerization product of propylene sequences crystallinity fraction.
The purpose of this invention is to provide a kind of method for preparing ethylene propylene copolymer, by the ethylene propylene copolymer of polyreaction with the ethylene, propylene segmented copolymer fraction that obtains containing longer propylene sequences.The approach that realizes this purpose is to improve ethylene propylene copolymerization catalyst for reaction system.More particularly, be the electron donor that adds that improves in the catalyst system.
The preparation method of ethylene propylene copolymer of the present invention, wherein catalyst system comprises following four components:
(A) structural formula is TiCl
4/ MgCl
2ID or TiCl
4/ MgCl
2ID/SiO
2The load-type Titanium series ingredient of solid catalyst, wherein ID is a kind of electron donor;
(B) organo-aluminium compound;
(C) structural formula is RR ' Si (OCH
3)
2Silicoorganic compound, wherein R, R ' are for containing alkyl, cycloalkyl or the phenyl of 1～6 carbon;
(D) structural formula is R " OCH
3The monoether compound, R wherein " for containing the alkyl or the benzyl of 4～8 carbon.
The silicoorganic compound that are suitable for ethylene propylene copolymer preparation method of the present invention comprise: Ph
2Si (OCH
3)
2, (cy-C
5H
9)
2Si (OCH
3)
2(cy-C
6H
11) (CH
3) Si (OCH
3)
2Be suitable for ethylene propylene copolymer preparation method of the present invention the monoether compound comprise: n-C
4H
9OCH
3, i-C
4H
9OCH
3, i-C
8H
15OCH
3, PhCH
2OCH
3
The copolymerization system of ethene and propylene by ethene and propylene two kinds of monomers, catalyst systems, the hydrogen and the varsol that are used to regulate molecular weight of copolymer form, polyreaction adopts the technology of slurry polymerization.Also can not use varsol, finish polyreaction by the gas-phase copolymerization technology of ethene and propylene.Primary Catalysts in the catalyst system is that a kind of general formula is TiCl
4/ MgCl
2ID or TiCl
4/ MgCl
2ID/SiO
2The loading type Ziegler-Natta catalyst, wherein ID is carboxylicesters or ether.Organo-aluminium compound is triethyl aluminum or triisobutyl aluminium, plays the effect of promotor.Aluminium is 100～500 to the molar ratio of titanium in the catalyst system, and aluminium is 10～50 to the molar ratio of silicon, and the monoether compound is 0.5～5 to the molar ratio of silicon.
Advantage of the present invention is: the conventional catalyst, promotor and the organosilicon external electron donor that adopt the preparation isotatic polypropylene, only, can obtain the long copolymerization product of propylene sequences of its crystallinity fraction by the copolymerization of ethylene, propylene by add second kind of external electron donor of the present invention (monoether compound) to polymerization system.With the ethylene propylene copolymer of this special construction iPP being carried out toughening modifying can obtain just-modified polypropylene material of tough balance quality excellence.
Ethylene propylene copolymer preparation method of the present invention can adopt following two kinds of embodiments: (1) ethene and propylene carry out the slurries copolymerization in the varsol that contains catalyst system and small quantity of hydrogen, obtain the viscous soln of copolymerization product behind the reaction certain hour.Obtain solid-state ethylene propylene copolymer after varsol in this solution removed; (2) gasiform ethene and propylene carry out the gas phase copolymerization reaction in the presence of catalyst system and small quantity of hydrogen, directly synthetic granular ethylene propylene copolymer.Used catalyst system is added these four components of electron donor and is constituted by the system supported Primary Catalysts of titanium, organoaluminum promotor, silicone based electron donor and the monoether class of adding.
Primary Catalysts in the catalyst system is that a kind of general formula is TiCl
4/ MgCl
2ID or TiCl
4/ MgCl
2ID/SiO
2The loading type Ziegler-Natta catalyst, wherein ID is carboxylicesters or ether.Organo-aluminium compound is triethyl aluminum or triisobutyl aluminium.Be suitable for comprising: Ph as the silicoorganic compound of external electron donor component
2Si (OCH
3)
2, (cy-C
5H
9)
2Si (OCH
3)
2, (cy-C
6H
11) (CH
3) Si (OCH
3)
2Be suitable for comprising: n-C as the monoether compound of external electron donor component
4H
9OCH
3, i-C
4H
9OCH
3, i-C
8H
15OCH
3, PhCH
2OCH
3Deng.
The concrete steps of implementing ethylene propylene copolymer preparation method of the present invention are as follows:
1) selects a kind of TiCl
4/ MgCl
2ID or TiCl
4/ MgCl
2ID/SiO
2The class loaded catalyst is as Primary Catalysts.Wherein ID is an internal electron donor, comprises phthalate (as: diisobutyl phthalate), succinate class, 1,3-diether compound, 1,2-diether compound etc.
2) selecting triethyl aluminum or triisobutyl aluminium is the promotor of polyreaction.
3) selected slurry method or gas phase polymerization reaction process carry out the copolymerization of ethylene, propylene in the mode of rhythmic reaction or successive reaction.
4) in polymerization reactor, add ethene and propylene, varsol (only slurry method technology is used), hydrogen (molecular weight regulator), promotor, silicoorganic compound, monoether compound and Primary Catalysts, after the polyreaction of certain hour, obtain the ethylene propylene copolymer product.
In above-mentioned ethylene propylene copolymerization system, aluminium is 100～500 to the molar ratio of titanium in the catalyst system, and aluminium is 10～50 to the molar ratio of silicon, and the monoether compound is 0.5～5 to the molar ratio of silicon.Suitable polymeric reaction temperature is 60～90 ℃.Ethene is 0.1～2 to the molar ratio of propylene in the monomer.Polymerization reaction time (or mean residence time of continuous process) is 0.5～4 hour.
By the embodiment of this specification sheets as seen, after in the ethylene propylene copolymerization system, adding the specific compound external electron donor of organosilicon/monoether, compare with the polymerization system that only adds the organosilicon external electron donor, the propylene sequences mean length of crystallinity fraction increases more than 20% in second third copolymerization product.Contain in the product of copolymerization system of the compound external electron donor of organosilicon/monoether at some, though the propylene sequences mean length of crystallinity fraction does not have raising, the content of crystallinity fraction has improved more than 30%.
Silicoorganic compound in the used external electron donor of catalyst system of the present invention and ether all can directly be bought or obtain by known method is synthetic easily.Primary Catalysts can use the propylene polymerization load-type Titanium series catalyst of buying from the market.Promotor such as triethyl aluminum and triisobutyl aluminium can use the commercially available reagent of buying.
When carrying out ethylene propylene copolymerization, can in a tank reactor, add the dry hydrocarbon kind solvent that a certain amount of purifying is crossed, after reactor rises to preset temperature, promotor and two kinds be added electron donor add reactor successively with the intermittent type slurry polymerization processes.The ethylene/propene gas mixture that under agitation is pressed into setting pressure in still begins polyreaction Primary Catalysts powder or its slurries adding reactor to vapor liquid equilibrium at last.The reaction certain hour after, remove monomer pressure, and the decompression remove residual monomer and solvent, can collect and obtain copolymer pellet.The multipolymer gram number that the catalytic efficiency of reaction is per hour produced with every gram catalyzer (g EPR/g catalyzer hour) expression.The crystallinity fraction content of ethylene propylene copolymer adopts the separated and dissolved method to measure, that is: multipolymer is dissolved in the boiling octane earlier, makes solution be cooled to room temperature to separate out solid-state crystallinity fraction then, filters to isolate crystallinity fraction after drying, weighs.The propylene units content of crystallinity fraction and propylene sequences mean length (n in the multipolymer
P) use the carbon-13 nmr spectra assay.
Embodiment
The following example is that example illustrates actual effect of the present invention with the slurries copolymerization result of ethylene, propylene, but range of application of the present invention is not exceeded with the polymerization system among these embodiment.As previously mentioned, the ethylene propylene copolymer preparation method of the present invention's proposition also can implement by gas-phase polymerization process.
Embodiment 1
Under high pure nitrogen protection, in 1 a liter reactor that has a mechanical stirring device, add 500 milliliters of normal heptanes, promotor Al (C successively
2H
5)
3And external electron donor Ph
2Si (OCH
3)
2And n-C
4H
9OCH
3, under agitation with still temperature rise to 70 ℃.Vacuumize the nitrogen in the still removed, in still, be pressed into 1: 1.5 ethylene/propene gas mixture of mol ratio to gauge pressure 0.2MPa, treat the solvent absorbing monomer reach saturated after, add the 0.050g Primary Catalysts, the beginning polyreaction.By the continuous supplementation intrinsic standoff ratio is that 1: 1.5 ethylene/propene gas mixture makes that the gas pressure intensity in the still remains on gauge pressure 0.2MPa between polymerization period.The main component of Primary Catalysts is TiCl
4, MgCl
2And diisobutyl phthalate, its titanium content is 2.7% (wt).In the promotor in aluminium and the Primary Catalysts mol ratio of titanium be 200, the silicon in the external electron donor and the mol ratio of titanium are 5, the n-C in the external electron donor
4H
9OCH
3With the mol ratio of titanium be 10.Be that reaction stopped after 30 minutes under 400 rev/mins the stirring in speed, reclaim and obtain ethylene-propylene copolymer.The catalyst efficiency that calculates according to product weight is a 1100g EPR/g catalyzer hour.The crystallization fraction content of multipolymer is 19%.The propylene content of crystallization fraction is 17% (mol), and the propylene sequences mean length is 6.1.
Comparative examples 2
Compare with embodiment 1, except that not adding second kind of external electron donor n-C
4H
9OCH
3Outward, all the other operations are all identical with condition.The catalyst efficiency of copolyreaction is a 1400g EPR/g catalyzer hour.The crystallization fraction content of multipolymer is 23%.The propylene content of crystallization fraction is 18% (mol), and the propylene sequences mean length is 3.4.
Embodiment 3
Compare with embodiment 1, remove and change the ether in the external electron donor into C
6H
5CH
2OCH
3In addition, all the other operations are all identical with condition.The catalyst efficiency of copolyreaction is a 1160g EPR/g catalyzer hour.The crystallization fraction content of multipolymer is 21%.The propylene content of crystallization fraction is 19% (mol), and the propylene sequences mean length is 4.1.
Embodiment 4
Compare with embodiment 3, remove C
6H
5CH
2OCH
3Bring up to beyond 20 with the mol ratio of titanium, all the other operations are all identical with condition.The catalyst efficiency of copolyreaction is a 1170g EPR/g catalyzer hour.The crystallization fraction content of multipolymer is 30%.The propylene content of crystallization fraction is 23% (mol), and the propylene sequences mean length is 3.1.
Embodiment 5
Compare with embodiment 1, remove and change the ether in the external electron donor into i-C
8H
17OCH
3, and with i-C
8H
17OCH
3Bring up to beyond 20 with the mol ratio of titanium, all the other operations are all identical with condition.The catalyst efficiency of copolyreaction is a 1250g EPR/g catalyzer hour.The crystallization fraction content of multipolymer is 23%.The propylene content of crystallization fraction is 19% (mol), and the propylene sequences mean length is 4.8.
Embodiment 6
Compare with embodiment 1, remove and change the silicoorganic compound in the external electron donor into (cyclo-C
5H
9)
2Si (OCH
3)
2And with n-C
4H
9OCH
3Bring up to beyond 20 with the mol ratio of titanium, all the other operations are all identical with condition.The catalyst efficiency of copolyreaction is a 1630g EPR/g catalyzer hour.The crystallization fraction content of multipolymer is 19%.The propylene content of crystallization fraction is 17% (mol), and the propylene sequences mean length is 5.3.
Comparative examples 7
Compare with embodiment 6, except that not adding second kind of external electron donor n-C
4H
9OCH
3Outward, all the other operations are all identical with condition.The catalyst efficiency of copolyreaction is a 1540g EPR/g catalyzer hour.The crystallization fraction content of multipolymer is 26%.The propylene content of crystallization fraction is 18% (mol), and the propylene sequences mean length is 2.8.
Embodiment 8
Compare with embodiment 1, remove and change the silicoorganic compound in the external electron donor into (cyclo-C
6H
11) (CH
3) Si (OCH
3)
2In addition, all the other operations are all identical with condition.The catalyst efficiency of copolyreaction is a 1170g EPR/g catalyzer hour.The crystallization fraction content of multipolymer is 21%.The propylene content of crystallization fraction is 19% (mol), and the propylene sequences mean length is 6.0.
Comparative examples 9
Compare with embodiment 8, except that not adding second kind of external electron donor n-C
4H
9OCH
3Outward, all the other operations are all identical with condition.The catalyst efficiency of copolyreaction is a 1410g EPR/g catalyzer hour.The crystallization fraction content of multipolymer is 18%.The propylene content of crystallization fraction is 20% (mol), and the propylene sequences mean length is 3.2.
Claims (10)
1. the preparation method of ethylene propylene copolymer in the presence of catalyst system, makes ethene and propylene obtain ethylene propylene copolymer through copolymerization, it is characterized in that wherein catalyst system comprises following four components:
(A) structural formula is TiCl
4/ MgCl
2ID or TiCl
4/ MgCl
2ID/SiO
2Ingredient of solid catalyst, wherein ID is interior electron donor(ED);
(B) organo-aluminium compound;
(C) structural formula is RR ' Si (OCH
3)
2Silicoorganic compound, wherein R, R ' are for containing alkyl, cycloalkyl or the phenyl of 1～6 carbon;
(D) structural formula is R " OCH
3The monoether compound, R wherein " for containing the alkyl or the benzyl of 4～8 carbon.
2. the preparation method of ethylene propylene copolymer according to claim 1, it is characterized in that: described ID is carboxylicesters or ether.
3. the preparation method of ethylene propylene copolymer according to claim 2, it is characterized in that: described ID is phthalate, succinate class, 1,3-diether compound, 1,2-diether compound.
4. the preparation method of ethylene propylene copolymer according to claim 1, it is characterized in that: described silicoorganic compound comprise Ph
2Si (OCH
3)
2, (cy-C
5H
9)
2Si (OCH
3)
2Or (cy-C
6H
11) (CH
3) Si (OCH
3)
2
5. the preparation method of ethylene propylene copolymer according to claim 1, it is characterized in that: described monoether compound comprises n-C
4H
9OCH
3, i-C
4H
9OCH
3,, i-C
8H
15OCH
3Or PhCH
2OCH
3
6. the preparation method of ethylene propylene copolymer according to claim 1, it is characterized in that: described organo-aluminium compound is triethyl aluminum or triisobutyl aluminium.
7. the preparation method of ethylene propylene copolymer according to claim 1 is characterized in that, in the said catalyst system, aluminium is 100～500 to the molar ratio of titanium.
8. the preparation method of ethylene propylene copolymer according to claim 1 is characterized in that, in the said catalyst system, aluminium is 10～50 to the molar ratio of silicon.
9. the preparation method of ethylene propylene copolymer according to claim 1 is characterized in that, in the said catalyst system, the monoether compound is 0.5～5 to the molar ratio of silicon.
10. the preparation method of ethylene propylene copolymer according to claim 1 is characterized in that, in the said copolymerization, ethene is 0.1～2 to the molar ratio of propylene.
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|---|---|---|---|
| CN2009101844321A CN101993510A (en) | 2009-08-14 | 2009-08-14 | Method for preparing ethylene-propylene copolymer |
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|---|---|---|---|
| CN2009101844321A CN101993510A (en) | 2009-08-14 | 2009-08-14 | Method for preparing ethylene-propylene copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571044A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | Preparation method of high-impact-strength polypropylene kettle internal alloy |
| CN104513332B (en) * | 2013-09-30 | 2017-06-06 | 中国石油化工股份有限公司 | Catalyst system and its application for olefinic polymerization |
| CN107522801A (en) * | 2016-06-22 | 2017-12-29 | 中国石化扬子石油化工有限公司 | A kind of propylene butene copolymerization catalyst system and its preparing the application of propylene butene copolymer |
| CN107540768A (en) * | 2016-06-23 | 2018-01-05 | 中国石化扬子石油化工有限公司 | A kind of preparation method of controllable high isotactic polybutene |
-
2009
- 2009-08-14 CN CN2009101844321A patent/CN101993510A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571044A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | Preparation method of high-impact-strength polypropylene kettle internal alloy |
| CN103571044B (en) * | 2012-08-03 | 2016-06-15 | 中国石油化工股份有限公司 | The preparation method of a kind of high-impact-strengthpolypropylene polypropylene kettle internal alloy |
| CN104513332B (en) * | 2013-09-30 | 2017-06-06 | 中国石油化工股份有限公司 | Catalyst system and its application for olefinic polymerization |
| CN107522801A (en) * | 2016-06-22 | 2017-12-29 | 中国石化扬子石油化工有限公司 | A kind of propylene butene copolymerization catalyst system and its preparing the application of propylene butene copolymer |
| CN107522801B (en) * | 2016-06-22 | 2020-07-31 | 中国石化扬子石油化工有限公司 | Propylene-butene copolymerization catalyst system and application thereof in preparation of propylene-butene copolymer |
| CN107540768A (en) * | 2016-06-23 | 2018-01-05 | 中国石化扬子石油化工有限公司 | A kind of preparation method of controllable high isotactic polybutene |
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Application publication date: 20110330 |