CN102532380A - Method for preparing high-fluidity anti-impact polypropylene - Google Patents
Method for preparing high-fluidity anti-impact polypropylene Download PDFInfo
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Abstract
The invention provides a method for preparing high-fluidity anti-impact polypropylene, which comprises two steps of polymerization in the presence of a Ziegler-Natta catalyst: in the first step, using an external ion donor with good sensitivity to hydrogen regulation as a catalyst in homopolymerization of polypropylene; in the second step, adding an external ion donor with weaker sensitivity to hydrogen regulation compared with sensitivity in the first step in copolymerization of polypropylene and alpha-olefin. By the method provided by the invention, the high-fluidity anti-impact polypropylene with the melt index of 25-100g/10min can be directly generated in a polymer reactor without using a melt flow enhancer subsequently.
Description
Technical field
The present invention relates to a kind of polyacrylic preparation method.Specifically, the present invention relates to a kind of preparation method of high fluidity punching proof acrylic.
Background technology
High fluidity punching proof acrylic has a wide range of applications in the injection moulding field, prepares the high method that flows impact polypropylene and mainly contains: methods such as the direct preparation of post-treatment modification and polymeric kettle.
The post-treatment method of modifying is a kind of common method of producing the high impact polypropylene that flows, and all prepares high fluidity punching proof acrylic resin for the post-treatment method of modifying like patent CN101338009, CN1034741 etc.The post-treatment modification prepares the method for the high impact polypropylene that flows, and will add superoxide usually, causes many defectives with organo-peroxide viscosity breaking meeting.All will discharge the by product of not expecting during the organo-peroxide degraded.The release of this by product (common by product is the trimethyl carbinol) has increased the danger of feed bin blast; And by product is deleterious; Also can make product that special odor and color are arranged, this has limited the application of product in fields such as food, medical treatment, health, and the post-treatment modification has increased this production stage of mixing; Increased production cost, the mobile impact polypropylene product performance fluctuation of the height that obtains is bigger.
It generally is through adopting the special catalyst system or adopting supercritical process in reactor drum, to add the purpose that a large amount of hydrogen reach the high melt flow polypropylene of reactor drum direct production that polymerization technique directly prepares the high method that flows impact polypropylene.
For example relate to the compsn of the propene polymer that comprises wide molecular weight distribution among the CN1832999A of BASELL house journal, the polymkeric substance of exploitation is mainly used in bumper and side band.At first with propylene homopolymerization in two reactor drums of polyphone; Through controlling the density of hydrogen of two reactor drums; Thereby obtain broad molecular weight distribution polypropylene, and then in placed in-line the 3rd reactor drum, carry out copolymerization, finally make the high impact Vestolen PP 7052 with other terminal olefins; But the product melting index of this patent is in the scope of 5～20g/10min, and the performance of catalyzer does not adjust in this process.
The CN1321178 of BASELL house journal prepares by A (wide molecular weight distribution HOPP or wide molecular weight distribution atactic copolymerized polypropene)+B (ethene and C through polymerization
4～C
10Alpha-olefin copolymer) impact-resistant polyolefin compositions of forming, but this method must be used the Ziegler-Natta catalyst of diether compounds as internal electron donor.
Patent CN101432321A mentions a kind of alfon of the high fluidity of molten with light smell and low volatile content or the working method of random copolymers; But must use the Ziegler-Natta catalyst of diether compounds, and this invention can't be used the high impact polypropylene that flows of this method direct production as internal electron donor.
Patent CN1156999A mentions a kind of special catalyst system, this catalyst system comprise with a kind of mixture blended that constitutes by tetraethoxysilane (TEOS) and dicyclopentyl dimethoxyl silane (DCPMS) by the titanium catalyst of carrier band.Find this catalyst system can make effectively have higher melt flow speed with in the Vestolen PP 7052 and the polypropylene copolymer of wide MWD.What this method was used is the silicane electron donor, and the electron donor kind of using with this patent is different.
Summary of the invention
To the difference of prior art, the purpose of this invention is to provide and a kind ofly directly in polymerization reactor, produce the impact polypropylene of high melt flow index and need not the method for follow-up use melt flow toughener.
The present invention relates to a kind of utilize general commercial Z-N (Ziegler-Natta) catalyzer directly in polymerization reactor the production melt flow index be 30～100g/10min (ASTM D1238; Condition L) impact polypropylene and need not the method for follow-up use melt flow toughener; In the presence of Z-N (Ziegler-Natta) catalyzer; Carry out the two-stage polymerization reaction; It is characterized in that the catalyzer of the homopolymerization of the first step propylene uses the good external electron donor of hydrogen regulation performance, add during the copolyreaction of the second step propylene and terminal olefin hydrogen regulation performance a little less than than the first step external electron donor.
More particularly, method provided by the invention is through changing external electron donor kind in the catalyst system, adjusting the hydrogen response of catalyzer in the differential responses device.Promptly in the differential responses device, add external electron donor with different hydrogen regulation performances.The first step is used the good external electron donor of hydrogen regulation performance; Can under less hydrogen usage, obtain the homopolymer of high fusion index, second step was used the relatively poor external electron donor of hydrogen regulation performance; Ensureing under the highly active density of hydrogen condition; Can in polymerization reactor, obtain propylene/alpha-olefins multipolymer (rubber phase) than good quality, i.e. the rubber of larger molecular weight and more rubber content, this is and other more different place of existing method.The melt flow index of final polymkeric substance is at 25～100g/10min (ASTMD1238, condition L), thereby realized with common commercial Ziegler-Natta catalyst preparation high fusion index impact polypropylene under the situation of less hydrogen usage.
According to preparation method provided by the invention, said catalyzer comprises but is not limited only to Ziegler-Natta catalyst, preferably has the catalyzer of high stereoselective.The Ziegler-Natta catalyst of high stereoselective described herein is meant and can be used to prepare the catalyzer of isotactic index greater than 95% alfon.Catalyzer described in Chinese patent CN85100997, CN93102795.0, CN98111780.5 and the CN02100900.7 is used for catalyzer of the present invention and has advantage especially.This type of Ziegler-Natta catalyst is open by lot of documents.
Said catalyzer contains (1) active solid catalyst component usually, is preferably titaniferous solid catalyst active ingredient; (2) organo-aluminium compound cocatalyst component; (3) external electron donor component.
Used active solid catalyst component is well-known in patent documentation in the above-mentioned catalyzer, and specific examples is disclosed in Chinese patent CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4, CN02100900.7.
The organo-aluminium compound preferred alkyl aluminum compound that above-mentioned catalyzer is used more preferably comprises trialkylaluminium, as: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum etc.
The active solid catalyst component is 1: 25～1: 100 with the ratio of organo-aluminium compound cocatalyst component with the Ti/Al molar ratio computing in the above-mentioned catalyzer.
According to method provided by the invention; The external electron donor of the raising catalyzer hydrogen response that in the first step reaction, adds is an ether compound, comprises ether (DEE), diisoamyl ether (EDIA), Ethyl Tertisry Butyl Ether (ETBE), MTBE (MTBE) and THF (THF).
According to method provided by the invention; The external electron donor of the reduction catalyzer hydrogen response that in the reaction of second step, adds is a silane compound, comprises dicyclopentyl dimethoxyl silane (DCPMS), cyclohexyl methyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane, the hydrogen isoquinoline dimethoxy silane of enjoying a double blessing.
Described catalyzer of the present invention can directly join in the homopolymerization device of the first step, also can pass through after the preparatory complexing and/or prepolymerization that industry knows altogether, joins in the homopolymerization device of the first step again.
Said preparatory complexing process can be carried out at the environment that has or do not have polymerization single polymerization monomer (in preparatory complexing or polymerization reactor).When carrying out preparatory complex reaction separately; The form of reactor drum can be a continuous stirred tank reactor; Also can be other means that can obtain the thorough mixing effect, like annular-pipe reactor, contain one section pipeline of static mixer, even also can be the pipeline that one section material is in turbulence state.The Controllable Temperature of complexing is between-10～60 ℃ in advance, and preferred temperature is 0～30 ℃.The time of complexing is controlled at 0.1～180min in advance, and the preferred time is 5～30min.
Through or can also carry out randomly prepolymerization without the catalyzer of preparatory complexing and handle.Prepolymerization can be carried out under the liquid phase bulk conditions continuously, also can carry out in the inert solvent discontinuous.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized Controllable Temperature is between-10～60 ℃, and preferred temperature is 0～40 ℃.Prepolymerized multiple is controlled at 0.5～1000 times, and preferred multiple is 1.0～500 times.
Described polyreaction can be in the propylene liquid phase, or in gas phase, carries out, or adopts liquid-gas combination technique to carry out.When carrying out liquid polymerization, polymerization temperature is 0～150 ℃, 40～100 ℃ of preferred polymerization temperatures; Polymerization pressure should be higher than the saturated vapour pressure of propylene under corresponding polymerization temperature.Polymerization temperature is 0～150 ℃ when vapour phase polymerization, and preferred polymerization temperature is 40～100 ℃; Polymerization pressure can be a normal pressure or higher, and preferred pressure is 1.0～3.0MPa (gauge pressure, down together).
According to method provided by the invention, said terminal olefin is preferably ethene, 1-butylene, one or more in the 4-methyl-1-pentene.Said propylene/alpha-olefins multipolymer can also comprise other components that can not make the performance of copolymer variation except comprising propylene and terminal olefin component, like diolefine etc.
Said polyreaction also comprises use molecular weight regulator hydrogen and regulates molecular weight.Said polyreaction can be carried out continuously, also may be carried out batchwise.The equipment of successive polymerization can be two or more placed in-line Liquid-phase reactor or Gas-phase reactor; Liquid-phase reactor can be annular-pipe reactor or stirred-tank reactor; Gas-phase reactor can be a horizontal type agitated bed reactor; Vertical agitated bed reactor or fluidized-bed reactor etc., above Liquid-phase reactor and Gas-phase reactor are matched combined at random also.
Polymkeric substance through preparing method's gained of the present invention can carry out extruding pelletization by use equipment, adds the additive that this technical field is used during granulation usually, like oxidation inhibitor, photostabilizer, thermo-stabilizer, tinting material and filler.
The present invention uses Ziegler-Natta catalyst to adopt the method for direct polymerization; Can through the hydrogen response of adjustment catalyzer in two above reactor drums of serial operation; The direct production melt flow index is the impact polypropylene of 25～100g/10min (ASTM D1238, condition L) and need not follow-up use melt flow toughener in polymerization reactor.The high fluidity punching proof acrylic of producing through the present invention not only can be used for the traditional field of washing machine inner tub material and mobile impact polypropylene such as height such as thin-walled injection grade, also can be used for food, health field, has expanded the use range of high fluidity punching proof acrylic.
Embodiment
To describe the present invention through concrete preferred embodiment below, preferred embodiment described herein only is used for explanation and explains the present invention, and is not used in qualification the present invention.
The polymkeric substance relevant data obtains by following testing method among the embodiment:
1. melt flow rate(MFR) (MFR): press ISO1133,230 ℃, measure under the 2.16kg load.
2. resin modulus in flexure: press ASTM D790-97 and measure.
3. Izod shock strength: press ASTM D256-00 and measure.
Embodiment 1
Primary Catalysts (titaniferous solid catalyst active ingredient) adopts the method that embodiment 1 describes among the Chinese patent CN93102795 to obtain its Ti content: 2.4wt%, Mg content: 18.0wt%, n-butyl phthalate content: 13wt%.Polymerization single polymerization monomer: propylene and ethene.
Polyreaction is carried out on a collar plumber plants the Vestolen PP 7052 pilot plant.Primary Catalysts, promotor (triethyl aluminum), external electron donor (diisoamyl ether EDIA, Ethyl Tertisry Butyl Ether ETBE, MTBE MTBE) are through 10 ℃, 20min in advance after the contact; Add prepolymerization reactor continuously and carry out the prepolymerization reaction; Prepolymerization is carried out under propylene liquid phase bulk environment; Temperature is 15 ℃, and the residence time is about 4min, and the pre-polymerization multiple of catalyzer is about 120-150 times under this condition.The pre-polymerization rear catalyst gets in the annular-pipe reactor.
Add an amount of hydrogen in the annular-pipe reactor charging, the density of hydrogen that on-line chromatograph detects is 3000ppmV.The triethyl aluminum flow that advances prepolymerization reactor is 5.5g/hr, and external electron donor (diisoamyl ether EDIA, Ethyl Tertisry Butyl Ether ETBE, MTBE MTBE) is 0.60g/hr, and the Primary Catalysts flow is 0.01g/hr.Because these catalyst components directly get into annular-pipe reactor after prepolymerization, annular-pipe reactor no longer includes any other charging except that propylene and hydrogen, and therefore, the Al/Si ratio is 9.2 (weight ratios) in the annular-pipe reactor.In annular-pipe reactor, accomplish the equal polymerization reaction of propylene.70 ℃ of endless tube polymeric reaction temperatures, reaction pressure 4.0MPa.Reaction mass gets into Gas-phase reactor afterwards.
Add external electron donor dicyclopentyl dimethoxyl silane (DCPMS) to Gas-phase reactor, flow is 1.2g/hr.80 ℃ of Gas-phase reactor interior reaction temperatures, reaction pressure 1.0Mpa.Concrete processing condition are seen table 1.
After the polymkeric substance that comes out from Gas-phase reactor goes out propylene through flash separation, remove unreacted activity of such catalysts and heat drying through wet nitrogen again, obtain polymer powders.
Add IRGAFOS 168 additives of 0.1wt%, IRGANOX 1010 additives and the calcium stearate of 0.05wt% and 0.3% the commercially available VP101B nanometer powder glue nucleator of 0.2wt% in the powder that polymerization is obtained, use the twin screw extruder granulation.The gained pellet is carried out performance test by existing relevant ASTM standard.Test result is seen table 3.
Embodiment 2
Embodiment 2 employed processing condition are all identical with embodiment 1 with testing method.Be to add the difference into the external electron donor kind with embodiment 1 difference, concrete processing condition are seen table 1, and test result is seen table 3.
Embodiment 3
Embodiment 3 employed processing condition are all identical with embodiment 1 with testing method.Be to add the difference into the external electron donor kind with embodiment 1 difference, concrete processing condition are seen table 1, and test result is seen table 3.
Comparative example
Polymer raw: catalyzer is identical with embodiment; Monomer: propylene and ethene; Poly-unit, polymerization temperature, pressure and testing method are identical with embodiment 1.Processing condition are seen table 2.Test result is seen table 3.
Table 1. embodiment 1,2,3 polymerization process conditions
Table 2. comparative example Vestolen PP 7052 polymerization process condition
Table 3. embodiment and comparative sample test data
Note: the V-360 melting index finger ring pipe reactor melt index of coming out in the table.
The result: through test, three impact polypropylene sample melted indexes that adopt method preparation of the present invention are all above 30g/min, and the highest embodiment 3 sample melted indexes reach 82.6g/10min, see table 3; And adopt the impact polypropylene sample of common silane electron donor preparation, melting index not to reach requirement (the high impact polypropylene general requirement melting index that flows >=30g/10min) of the high impact polypropylene that flows far away.
What should explain at last is: the above is merely the preferred embodiments of the present invention; Be not limited to the present invention; Although the present invention has been carried out detailed explanation with reference to previous embodiment; For a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (19)
- Directly in polymerization reactor the production melt flow index be the preparation method of the high fluidity punching proof acrylic of 25～100g/10min; In the presence of Ziegler-Natta catalyst; Carry out the two-stage polymerization reaction; It is characterized in that the catalyzer of the homopolymerization of the first step propylene uses the good external electron donor of hydrogen regulation performance, add the external electron donor of hydrogen regulation performance a little less than during the copolyreaction of the second step propylene and terminal olefin than the first step.
- 2. preparation method according to claim 1 is characterized in that, said Ziegler-Natta catalyst comprises active solid catalyst component, organo-aluminium compound cocatalyst component and external electron donor component.
- 3. preparation method according to claim 1 is characterized in that, the said external electron donor that uses in the first step is ether compound.
- 4. preparation method according to claim 3 is characterized in that, said ether compound is one or more in ether, diisoamyl ether, Ethyl Tertisry Butyl Ether, MTBE or the THF.
- 5. preparation method according to claim 1 is characterized in that, the said external electron donor that in second step, uses is silane compound.
- 6. preparation method according to claim 5; It is characterized in that said silane compound is one or more in dicyclopentyl dimethoxyl silane, cyclohexyl methyl dimethoxy silane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane or the hydrogen isoquinoline dimethoxy silane of enjoying a double blessing.
- 7. preparation method according to claim 1 is characterized in that, said terminal olefin is one or more in ethene, 1-butylene and the 4-methyl-1-pentene.
- 8. preparation method according to claim 2, said active solid catalyst component are titaniferous solid catalyst active ingredient.
- 9. preparation method according to claim 2, said organo-aluminium compound is an alkylaluminium cpd.
- 10. preparation method according to claim 2, the active solid catalyst component is 1: 25～1: 100 with the ratio of organo-aluminium compound cocatalyst component with the Ti/Al molar ratio computing in the said catalyzer.
- 11. preparation method according to claim 1 is characterized in that, described catalyzer is directly or after preparatory complexing or after prepolymerization, join in the homopolymerization device of the first step.
- 12. preparation method according to claim 11 is characterized in that, the temperature of said preparatory complexing is between-10～60 ℃, and the time of complexing is 0.1～180 minute in advance.
- 13. preparation method according to claim 11 is characterized in that, said prepolymerized temperature is between-10～60 ℃, and prepolymerized multiple is between 0.5～1000.
- 14. preparation method according to claim 1 is characterized in that, said polyreaction is carried out under propylene liquid phase, gas phase or liquid-gas combination condition.
- 15. preparation method according to claim 14 is characterized in that, said liquid polymerization temperature is 0～150 ℃, and polymerization pressure is normal pressure or is higher than the saturated vapour pressure of Vestolen PP 7052 under corresponding polymerization temperature.
- 16. preparation method according to claim 15 is characterized in that, said liquid polymerization temperature is 40～100 ℃.
- 17. preparation method according to claim 14 is characterized in that, said vapour phase polymerization temperature is 0～150 ℃, and polymerization pressure is normal pressure or is higher than normal pressure.
- 18. preparation method according to claim 17 is characterized in that, polymerization temperature is with 40～100 ℃ during said vapour phase polymerization, and pressure is 1.0～3.0MPa.
- 19. preparation method according to claim 1 is characterized in that, said polyreaction is carried out continuously or is intermittently carried out.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103571045A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | Preparation method of anti-impact polypropylene in-reactor alloy |
| CN104558336A (en) * | 2013-10-14 | 2015-04-29 | 中国石油化工股份有限公司 | Propylene copolymer and preparation method thereof |
| CN104974368A (en) * | 2014-04-04 | 2015-10-14 | 中国石油化工股份有限公司 | Preparation method of antistatic polypropylene foamed beads |
| CN104974367A (en) * | 2014-04-04 | 2015-10-14 | 中国石油化工股份有限公司 | Preparation method of antistatic polypropylene foamed boards or sheets |
| CN104974369A (en) * | 2014-04-04 | 2015-10-14 | 中国石油化工股份有限公司 | Preparation method of polypropylene foamed beads |
| CN105566533A (en) * | 2014-10-31 | 2016-05-11 | 中国石油化工股份有限公司 | Method for preparing anti-shocking polypropylene with low odor and low VOC content |
| CN106749788A (en) * | 2016-11-25 | 2017-05-31 | 联泓新材料有限公司 | A kind of production method of molten thin-walled injection moulding material high |
| CN108192005A (en) * | 2017-12-29 | 2018-06-22 | 黄河三角洲京博化工研究院有限公司 | A kind of polyolefin and preparation method thereof |
| CN109776955A (en) * | 2018-12-18 | 2019-05-21 | 东华能源(宁波)新材料有限公司 | A method of polypropylene material is prepared using hydrogen-regulating method |
| CN110551242A (en) * | 2018-05-31 | 2019-12-10 | 中国石油天然气股份有限公司 | Impact-resistant co-polypropylene and preparation method thereof |
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| CN103571045B (en) * | 2012-08-03 | 2016-04-20 | 中国石油化工股份有限公司 | The preparation method of anti-impact polypropylene in-reactor alloy |
| CN103571045A (en) * | 2012-08-03 | 2014-02-12 | 中国石油化工股份有限公司 | Preparation method of anti-impact polypropylene in-reactor alloy |
| CN104558336A (en) * | 2013-10-14 | 2015-04-29 | 中国石油化工股份有限公司 | Propylene copolymer and preparation method thereof |
| CN104974369B (en) * | 2014-04-04 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of preparation method of polypropylene foaming beads |
| CN104974367A (en) * | 2014-04-04 | 2015-10-14 | 中国石油化工股份有限公司 | Preparation method of antistatic polypropylene foamed boards or sheets |
| CN104974369A (en) * | 2014-04-04 | 2015-10-14 | 中国石油化工股份有限公司 | Preparation method of polypropylene foamed beads |
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| CN104974367B (en) * | 2014-04-04 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of preparation method of antistatic polypropylene foaming plate or sheet material |
| CN105566533B (en) * | 2014-10-31 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of low smell, low VOC content impact polypropylene preparation method |
| CN105566533A (en) * | 2014-10-31 | 2016-05-11 | 中国石油化工股份有限公司 | Method for preparing anti-shocking polypropylene with low odor and low VOC content |
| CN106749788A (en) * | 2016-11-25 | 2017-05-31 | 联泓新材料有限公司 | A kind of production method of molten thin-walled injection moulding material high |
| CN106749788B (en) * | 2016-11-25 | 2019-04-16 | 联泓新材料有限公司 | A kind of production method of high molten thin-walled injection moulding material |
| CN108192005A (en) * | 2017-12-29 | 2018-06-22 | 黄河三角洲京博化工研究院有限公司 | A kind of polyolefin and preparation method thereof |
| CN108192005B (en) * | 2017-12-29 | 2021-03-26 | 黄河三角洲京博化工研究院有限公司 | Polyolefin and preparation method thereof |
| CN110551242A (en) * | 2018-05-31 | 2019-12-10 | 中国石油天然气股份有限公司 | Impact-resistant co-polypropylene and preparation method thereof |
| CN110551242B (en) * | 2018-05-31 | 2022-03-29 | 中国石油天然气股份有限公司 | Impact-resistant co-polypropylene and preparation method thereof |
| CN109776955A (en) * | 2018-12-18 | 2019-05-21 | 东华能源(宁波)新材料有限公司 | A method of polypropylene material is prepared using hydrogen-regulating method |
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