CN102532380B - Method for preparing high-fluidity anti-impact polypropylene - Google Patents
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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 injection moulding field, prepares the high method that flows impact polypropylene and mainly contains: the methods such as the direct preparation of post-treatment modification and polymeric kettle.
Post-treatment method of modifying is a kind of common method of producing the high impact polypropylene that flows, if patent CN101338009, CN1034741 etc. are that post-treatment method of modifying is prepared high fluidity punching proof acrylic resin.The method of the high impact polypropylene that flows is prepared in post-treatment modification, conventionally will add superoxide, with organo-peroxide viscosity breaking meeting, causes many defects.During organo-peroxide degraded, all will discharge less desirable by product.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 poisonous, also can make product have special odor and color, this has limited the application of product in fields such as food, medical treatment, health, and post-treatment modification has increased this production stage of mixing, increased production cost, the mobile impact polypropylene product performance fluctuation of height obtaining is larger.
It is generally by adopting special catalyst system or adopting supercritical process to add a large amount of hydrogen to reach the object of the high melt flow polypropylene of reactor direct production in reactor that polymerization technique is directly prepared the high method that flows impact polypropylene.
For example in the CN1832999A of BASELL house journal, relate to the composition of the propene polymer that comprises wide molecular weight distribution, the polymkeric substance of exploitation is mainly used in bumper and side band.First by propylene homopolymerization in two reactors of series winding, by controlling the density of hydrogen of two reactors, thereby obtain broad molecular weight distribution polypropylene, and then carry out copolymerization with other alpha-olefins in the 3rd reactor of series connection, finally make high impact polypropylene, but the product melting index of this patent is in the scope of 5～20g/10min, and in this process, the performance of catalyzer does not adjust.
The CN1321178 of BASELL house journal prepares+B (ethene and C by A (wide molecular weight distribution homo-polypropylene or wide molecular weight distribution atactic copolymerized polypropene) by polymerization
4～C
10alpha-olefin copolymer) impact-resistant polyolefin compositions forming, but the Ziegler-Natta catalyst that the method must be internal electron donor with diether compounds.
Patent CN101432321A mentions a kind of alfon of high fluidity of molten or production method of random copolymers with light smell and low volatile content, but the Ziegler-Natta catalyst that must be internal electron donor with diether compounds, and this invention cannot be with the high impact polypropylene that flows of this method direct production.
Patent CN1156999A mentions a kind of special catalyst system, this catalyst system comprise mix with a kind of mixture being formed by tetraethoxysilane (TEOS) and dicyclopentyl dimethoxyl silane (DCPMS) by the titanium catalyst of carrier band.Find this catalyst system can effectively manufacture have higher melt flow speed and in polypropylene and the polypropylene copolymer of wide molecular weight distribution.What the method was used is silicane electron donor, and the electron donor kind of using from this patent is different.
Summary of the invention
For the difference of prior art, the object of this invention is to provide a kind of impact polypropylene of directly producing high melt flow index in polymerization reactor and without 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 production melt flow index be 30～100g/10min (ASTM D1238, condition L) impact polypropylene and without the method for follow-up use melt flow toughener, under Z-N (Ziegler-Natta) catalyzer exists, carry out two-stage polymerization reaction, it is characterized in that, the catalyzer of the homopolymerization of the first step propylene is used the good external electron donor of hydrogen regulation performance, a little less than adding hydrogen regulation performance than the first step during copolyreaction of second step propylene and alpha-olefin external electron donor.
More particularly, method provided by the invention is by changing external electron donor kind in catalyst system, adjusting the hydrogen response of catalyzer in different reactor.In different reactor, add the external electron donor with different hydrogen regulation performances.The first step is used the good external electron donor of hydrogen regulation performance, can be under less hydrogen usage, obtain the homopolymer of high fusion index, second step is used the poor external electron donor of hydrogen regulation performance, ensureing under highly active density of hydrogen condition, can in polymerization reactor, obtain the propylene/alpha-olefins multipolymer (rubber phase) compared with good quality, i.e. the rubber of larger molecular weight and more rubber content, this is and other existing method relatively big difference place.The melt flow index of final polymkeric substance is at 25～100g/10min (ASTMD1238, condition L), thereby realized with common commercial Ziegler-Natta catalyst, prepares high fusion index impact polypropylene in the situation that of less hydrogen usage.
According to preparation method provided by the invention, described catalyzer includes but are not limited to Ziegler-Natta catalyst, preferably has the catalyzer of high stereoselective.The Ziegler-Natta catalyst of high stereoselective described herein refers to and can be greater than for the preparation of isotactic index the catalyzer of 95% alfon.Catalyzer described in Chinese patent CN85100997, CN93102795.0, CN98111780.5 and CN02100900.7, has advantage especially for catalyzer of the present invention.This type of Ziegler-Natta catalyst is open by lot of documents.
Described catalyzer contains (1) active solid catalyst component conventionally, is preferably the solid catalyst active ingredient of titaniferous; (2) organo-aluminium compound cocatalyst component; (3) external electron donor component.
In above-mentioned catalyzer, active solid catalyst component used is well-known in patent documentation, 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.
In above-mentioned catalyzer, active solid catalyst component be take Ti/Al molar ratio computing as 1: 25～1: 100 with the ratio of organo-aluminium compound cocatalyst component.
According to method provided by the invention, the external electron donor of the raising catalyzer hydrogen response adding in the first step reaction is ether compound, comprises ether (DEE), diisoamyl ether (EDIA), Ethyl Tertisry Butyl Ether (ETBE), methyl tertiary butyl ether (MTBE) and tetrahydrofuran (THF) (THF).
According to method provided by the invention, the external electron donor of the reduction catalyzer hydrogen response adding in second step reaction is silane compound, comprises dicyclopentyl dimethoxyl silane (DCPMS), Cyclohexyl Methyl Dimethoxysilane, 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, after the pre-complexing and/or prepolymerization that also can know altogether through industry, then joins in the homopolymerization device of the first step.
Described pre-complexation process can have or carry out without the environment of polymerization single polymerization monomer (in pre-complexing or polymerization reactor).When carrying out pre-complex reaction separately, the form of reactor can be continuous stirred tank reactor, also can be other means that can obtain abundant mixed effect, as annular-pipe reactor, containing one section of pipeline of static mixer, can be even also the pipeline of one section of material in turbulence state.The temperature control of pre-complexing is between-10～60 ℃, and preferred temperature is 0～30 ℃.The time of pre-complexing is controlled at 0.1～180min, and the preferred time is 5～30min.
Through or without the catalyzer of pre-complexing, can also carry out optionally prepolymerization and process.Prepolymerization can be carried out continuously under liquid phase bulk conditions, also can carry out in inert solvent discontinuous.Pre-polymerization reactor can be continuous stirred tank, annular-pipe reactor etc.Prepolymerized temperature control 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 propylene liquid phase, or carries out in gas phase, 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 propylene the saturated vapour pressure under corresponding polymerization temperature.When vapour phase polymerization, polymerization temperature is 0～150 ℃, and preferred polymerization temperature is 40～100 ℃; Polymerization pressure can be normal pressure or higher, and preferred pressure is 1.0～3.0MPa (gauge pressure, lower same).
According to method provided by the invention, described alpha-olefin is preferably ethene, 1-butylene, one or more in 4-methyl-1-pentene.Described propylene/alpha-olefins multipolymer, except comprising propylene and alpha-olefin component, can also comprise other components that can not make performance of copolymer variation, as diolefine etc.
Described polyreaction also comprises with molecular weight regulator hydrogen carrys out Molecular regulator amount.Described polyreaction can be carried out continuously, also may be carried out batchwise.The equipment of successive polymerization can be Liquid-phase reactor or the Gas-phase reactor of two or more series connection, Liquid-phase reactor can be annular-pipe reactor or stirred-tank reactor, Gas-phase reactor can be horizontal type agitated bed reactor, vertical mixing bed bioreactor or fluidized-bed reactor etc., above Liquid-phase reactor and Gas-phase reactor be matched combined at random also.
Polymkeric substance by preparation method's gained of the present invention can carry out extruding pelletization by use equipment, conventionally adds the additive that this technical field is used, as oxidation inhibitor, photostabilizer, thermo-stabilizer, tinting material and filler during granulation.
The present invention uses Ziegler-Natta catalyst to adopt the method for direct polymerization, by adjusting catalyzer at more than two hydrogen response energy in reactor of serial operation, in polymerization reactor direct production melt flow index be 25～100g/10min (ASTM D1238, condition L) impact polypropylene and without follow-up use melt flow toughener.The high fluidity punching proof acrylic of producing by the present invention not only can be used for the traditional field of making internal drum of washer and the contour mobile impact polypropylene of thin-walled injection, also can be used for food, health field, has expanded the use range of high fluidity punching proof acrylic.
Embodiment
Below the preferred embodiment by concrete is described the present invention, preferred embodiment described herein only, for description and interpretation the present invention, is not intended to limit the present invention.
In embodiment, polymkeric substance relevant data obtains by following testing method:
1. melt flow rate (MFR) (MFR): press ISO1133,230 ℃, measure under 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 (the solid catalyst active ingredient of titaniferous) adopts the method that in Chinese patent CN93102795, embodiment 1 describes 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 set of endless tube technique polypropylene pilot plant.Primary Catalysts, promotor (triethyl aluminum), external electron donor (diisoamyl ether EDIA, Ethyl Tertisry Butyl Ether ETBE, methyl tertiary butyl ether MTBE) are after 10 ℃, the pre-contact of 20min, add continuously prepolymerization reactor to carry out prepolymerization, prepolymerization is carried out under propylene liquid phase bulk environment, temperature is 15 ℃, the residence time is about 4min, and under this condition, the pre-polymerization multiple of catalyzer is about 120-150 times.Pre-polymerization rear catalyst enters in annular-pipe reactor.
In annular-pipe reactor charging, add appropriate hydrogen, the density of hydrogen that on-line chromatograph detects is 3000ppmV.The triethyl aluminum flow that enters prepolymerization reactor is 5.5g/hr, and external electron donor (diisoamyl ether EDIA, Ethyl Tertisry Butyl Ether ETBE, methyl tertiary butyl ether MTBE) is 0.60g/hr, and Primary Catalysts flow is 0.01g/hr.Because these catalyst components directly enter annular-pipe reactor after prepolymerization, annular-pipe reactor no longer includes any other charging except propylene and hydrogen, and therefore, in annular-pipe reactor, Al/Si ratio is 9.2 (weight ratios).In annular-pipe reactor, complete the equal polyreaction of propylene.70 ℃ of endless tube polymeric reaction temperatures, reaction pressure 4.0MPa.Reaction mass enters Gas-phase reactor afterwards.
To Gas-phase reactor, add external electron donor dicyclopentyl dimethoxyl silane (DCPMS), flow is 1.2g/hr.80 ℃ of Gas-phase reactor interior reaction temperatures, reaction pressure 1.0Mpa.Concrete technology condition is in Table 1.
From Gas-phase reactor polymkeric substance out, after flash separation goes out propylene, then through wet nitrogen, remove the active and heat drying of unreacted catalyzer, obtain polymer powders.
In the powder that polymerization is obtained, add the calcium stearate of IRGAFOS 168 additives of 0.1wt%, IRGANOX 1010 additives of 0.2wt% and 0.05wt% and 0.3% commercially available VP101B nanometer powder glue nucleator, use twin screw extruder granulation.Gained pellet is carried out to performance test by existing relevant ASTM standard.Test result is in Table 3.
Embodiment 2
The processing condition that embodiment 2 is used and testing method are all identical with embodiment 1.Difference from Example 1 is to add the difference into external electron donor kind, and concrete technology condition is in Table 1, and test result is in Table 3.
Embodiment 3
The processing condition that embodiment 3 is used and testing method are all identical with embodiment 1.Difference from Example 1 is to add the difference into external electron donor kind, and concrete technology condition is in Table 1, and test result is in 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 in Table 2.Test result is in Table 3.
Table 1. embodiment 1,2,3 polymerization process conditions
Table 2. comparative example polypropylene polymerization process condition
Table 3. embodiment and comparative sample test data
Annotation: V-360 melting index finger ring pipe reactor melt index out in table.
Result: after tested, adopt three impact polypropylene sample melted indexes prepared by method of the present invention all over 30g/min, the highest embodiment 3 sample melted indexes reach 82.6g/10min, in Table 3; And the impact polypropylene sample that adopts common silane electron donor to prepare, melting index does not reach the requirement (the high impact polypropylene general requirement melting index >=30g/10min of flowing) of the high impact polypropylene that flows far away.
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (17)
1. the direct method of the high fluidity punching proof acrylic that production melt flow index is 25～100g/10min in polymerization reactor, under Ziegler-Natta catalyst exists, carry out two-stage polymerization reaction, it is characterized in that, the catalyzer of the homopolymerization of the first step propylene is used the good external electron donor of hydrogen regulation performance, external electron donor a little less than adding hydrogen regulation performance than the first step during copolyreaction of second step propylene and alpha-olefin, the external electron donor that described hydrogen regulation performance is good is ether compound, the external electron donor of described hydrogen regulation performance a little less than than the first step is silane compound.
2. method according to claim 1, is characterized in that, described Ziegler-Natta catalyst comprises active solid catalyst component, organo-aluminium compound cocatalyst component and external electron donor component.
3. method according to claim 1, is characterized in that, described ether compound is one or more in ether, diisoamyl ether, Ethyl Tertisry Butyl Ether, methyl tertiary butyl ether or tetrahydrofuran (THF).
4. method according to claim 1, it is characterized in that, described silane compound is dicyclopentyl dimethoxyl silane, Cyclohexyl Methyl Dimethoxysilane, second, isobutyl dimethoxy silane, di-t-butyl dimethoxy silane or one or more in hydrogen isoquinoline dimethoxy silane of enjoying a double blessing.
5. method according to claim 1, is characterized in that, described alpha-olefin is one or more in ethene, 1-butylene and 4-methyl-1-pentene.
6. method according to claim 2, the solid catalyst active ingredient that described active solid catalyst component is titaniferous.
7. method according to claim 2, described organo-aluminium compound is alkylaluminium cpd.
8. method according to claim 2, in described catalyzer, active solid catalyst component be take Ti/Al molar ratio computing as 1: 25～1: 100 with the ratio of organo-aluminium compound cocatalyst component.
9. method according to claim 1, is characterized in that, described catalyzer is directly or after complexing in advance or after prepolymerization, join in the homopolymerization device of the first step.
10. method according to claim 9, is characterized in that, the temperature of described pre-complexing is between-10～60 ℃, and the time of pre-complexing is 0.1～180 minute.
11. methods according to claim 9, is characterized in that, described prepolymerized temperature is between-10～60 ℃, and prepolymerized multiple is between 0.5～1000.
12. methods according to claim 1, is characterized in that, described polyreaction is carried out under propylene liquid phase, gas phase or liquid-gas combination condition.
13. methods according to claim 12, is characterized in that, described polyreaction is carried out under propylene liquid-phase condition, and polymerization temperature is 0～150 ℃, polymerization pressure be normal pressure or higher than polypropylene the saturated vapour pressure under corresponding polymerization temperature.
14. methods according to claim 13, is characterized in that, described polymerization temperature is 40～100 ℃.
15. methods according to claim 12, is characterized in that, described polyreaction is carried out under propylene gas phase condition, and polymerization temperature is 0～150 ℃, and polymerization pressure is normal pressure or higher than normal pressure.
16. methods according to claim 15, is characterized in that, described polymerization temperature is with 40～100 ℃, and pressure is 1.0～3.0MPa.
17. methods according to claim 1, is characterized in that, described polyreaction is carried out continuously or intermittently carried out.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN104558336B (en) * | 2013-10-14 | 2018-03-02 | 中国石油化工股份有限公司 | A kind of 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 |
| CN104974368B (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 expanded bead |
| 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 |
| 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 |
| 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 |
| 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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| CN101225130A (en) * | 2007-12-05 | 2008-07-23 | 浙江大学 | Stereo-tacticity regulator used for propylene polymerization and uses thereof |
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| CN101225130A (en) * | 2007-12-05 | 2008-07-23 | 浙江大学 | Stereo-tacticity regulator used for propylene polymerization and uses thereof |
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