CN103788265A - Preparation method of polypropylene with high melt strength - Google Patents
Preparation method of polypropylene with high melt strength Download PDFInfo
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Abstract
The invention discloses a preparation method of polypropylene with high melt strength. The method includes i) a step of, under the action of a Ziegler-Natta catalyst containing a silane type external electron donor, subjecting propylene or propylene with other alpha-olefin to polymerization to obtain a polymer A having a melt mass flow rate of 0.01-0.4 g/min, with a hydrogen concentration being not more than 400 ppmV; ii) a step of adding a 1,3-diether type external electron donor and premixing the 1,3-diether type external electron donor and the polymer A; iii) a step of, under the existence of hydrogen and the premixed materials in the step ii), subjecting the propylene or the propylene with other alpha-olefin to polymerization to obtain a polymer B having a melt mass flow rate of 1.0-60 g/10min; and a step of preparing polypropylene C with high melt strength comprising the polymer A and the polymer B. The melt mass flow rate of the polypropylene C is 0.8-15 g/10min. The preparation method is simple and feasible and is convenient to operate and prone to industrial production. High-performance products with high melt strength and wide molecular weight distribution can be prepared by the method. The method has wide application prospect.
Description
Technical field
The present invention relates to a kind of polyacrylic preparation method, be specifically related to a kind of preparation method with wide molecular weight distribution, high melt strength, propylene.
Background technology
High melt strength, propylene relies on its higher melt strength, yield strength, modulus in flexure, heat-drawn wire, fusing point, Tc and shorter crystallization time, is widely used in thermoforming, foaming, the field such as extrusion coated.In these application, high melt strength, propylene can make product in higher temperature bottom knockout for thermoforming processing, shortens shaping cycle, improves output; In foaming process, can resist breaking of micro-pore wall, improve expansion ratio, reduce density, improve rate of closed hole; In extrusion coated process, show surface covered and very little constriction faster.Thereby high melt strength, propylene is the research emphasis of polypropylene production technology innovation.When so-called high melt strength, propylene (HMSPP) refers to melt tension fracture, need higher drawing force, usually, compared with the plain polypropylene of same melt mass flow rate, it is high more than 5 times that HMSPP melt strength is wanted.
Improve melt strength of polypropylene generally by improving polyacrylic molecular weight and distribution or introducing branched structure, particularly long branched chain structure is realized.Conventional method mainly contains: the methods such as blending modification method, reaction extrusion molding, x ray irradiation x method, polymeric modification.Blending modification method is to reach the object of improving melt strength of polypropylene by the resin of noncrystalline or low crystallization, elastomerics and mineral filler etc.Reaction extrusion method is by add superoxide and other polyfunctional reactant monomers in polypropylene powder, realizes polyacrylic crosslinked or branching, thereby improve polyacrylic melt strength in extrusion.X ray irradiation x method is the ionization of polypropylene molecule structure excited atom structure under the irradiation of radioactive source, forms branching by the mode of polypropylene linear chain chain rupture-transfer-restructuring, thereby improves polyacrylic melt strength.Polymeric modification method is in polypropylene polymerization process, in the time that catalyzer still has activity, adds second or the 3rd active ingredient, or in the time of polymerization, makes polypropylene produce side chain or ultra-high molecular weight component, thereby melt strength of polypropylene is improved greatly.
Wherein polymeric modification method is thought industrialized preparing process most economical, that product performance are the most stable by industry.The method is to prepare broad molecular weight distribution polypropylene by the reactor of multiple series connection, and realizes the high fondant-strength of final polymkeric substance.It normally optionally adds the different external electron donor of hydrogen response at different polymerization stages, by regulating the density of hydrogen in different reactor, carry out the size of regulatory molecule amount, thereby realize the polypropylene preparation that had not only comprised high molecular weight block but also comprised low molecular weight fraction, wherein, high molecular weight block has guaranteed the melt strength of final polymkeric substance, and the molecular weight distribution of widening has guaranteed the processing characteristics that it is good.
US7365136 and US6875826 have reported a kind of method of preparing wide molecular weight distribution, high melt strength, propylene, it selects the siloxanes of epoxy group(ing) is external electron donor (as dicyclopentyl dimethoxyl silane), in the reactor of multiple series connection, by regulating density of hydrogen, carry out regulatory molecule amount size.For example: do not add hydrogen or add less the polypropylene of hydrogen gas production high molecular weight block (MFR < 0.1g/10min) in the first stage, subordinate phase is added the polypropylene of hydrogen gas production low molecular weight fraction (MFR > 0.5g/10min), finally obtains wide molecular weight (M
w/ M
n> 6), the polypropylene of high fondant-strength.The method is only by regulating the density of hydrogen of different polymerization stages to realize the regulation and control of molecular weight distribution, because density of hydrogen all can have a upper limit in general reactor, in addition the hydrogen in the reactor of series connection is also easily played a reversed role, therefore the degree that, the method is widened molecular weight is greatly limited.The reactor that WO9426794 discloses multiple series connection is prepared the method for high melt strength, propylene, it is by regulating in different reactor concentration of hydrogen to prepare wide molecular weight distribution or bimodal distribution, high melt strength, propylene, the character of catalyzer does not adjust in each reactor, thereby having made of a large amount of hydrogen of product needed, and reactor operation is also very difficult.
CN102134290 and CN102134291 disclose the preparation method of a kind of wide molecular weight, high melt strength, propylene, it adopts multiple tandem reactors by controlling kind and the ratio of external electron donor component in the differential responses stage, the control of binding molecule amount conditioning agent hydrogen usage, has prepared wide molecular weight, high melt strength, propylene again.Specifically, it selects high, the poor silane of hydrogen response of degree of isotacticity if dicyclopentyl dimethoxyl silane is the first external electron donor at the first reactor, is not adding hydrogen or is adding less under the condition of hydrogen, preparation high molecular weight block polypropylene.The second reactor add siloxanes that hydrogen response is good as tetraethoxysilane be the second external electron donor, under higher density of hydrogen, prepare the polypropylene of low molecular weight fraction, finally obtained wide molecular weight distribution, linear high melt strength, propylene.This molecular weight distribution M
w/ M
n=6 ~ 20, molecular weight is greater than the content>=0.8wt% of 5,000,000 fractions, M
z+1/ M
n>=70.Although molecular weight distribution and the melt strength of the method preparation are all enhanced, but, in whole polymerization process, the total amount of the first external electron donor and the second external electron donor sum is next fixed according to the amount of aluminum alkyls, under given catalyst concn, the amount of aluminum alkyls is generally changeless, and therefore, the total amount of the first external electron donor and the second external electron donor remains unchanged substantially.And there are stronger complex ability in the first external electron donor dicyclopentyl dimethoxyl silane first adding and catalyst active center, the first external electron donor accounts for leading role, and the add-on of the second external electron donor tetraethoxysilane will be much larger than the amount of the first external electron donor, the second external electron donor competence exertion effect, this causes the rising of cost on the one hand, and adding of simultaneously a large amount of external electron donors also makes the ash content of product increase.In addition, within the first external electron donor can be controlled at an extremely low scope in polymerization process (< 10mol%), in addition, high molecular weight block and degree of isotacticity are mainly by the first external electron donor control, so, polypropylene high molecular weight block content prepared by the method and the degree of isotacticity of the finished product have been subject to restriction largely, and in whole process, will certainly waste some second external electron donors.Chinese patent application 201010524685.1,201110334872.8 and 201010530284.7 has also been reported the preparation method of a kind of wide molecular weight distribution, high fondant-strength random copolymer of propylene, they are in multiple tandem reactors, carry out multistage copolymerization of propylene reaction, by controlling kind and the ratio of external electron donor component in the differential responses stage, the preferably control of binding molecule amount conditioning agent hydrogen usage, again in conjunction with the adjusting of comonomer ethene add-on, prepare the random copolymer of propylene of wide molecular weight distribution, high fondant-strength.Specifically, it selects high, the poor siloxanes of hydrogen response of degree of isotacticity if dicyclopentyl dimethoxyl silane is the first external electron donor at the first reactor, is not adding hydrogen or is adding less under the condition of hydrogen, preparation high molecular weight block propylene copolymer.The second reactor add siloxanes that hydrogen response is good as tetraethoxysilane be the second external electron donor, under higher density of hydrogen, prepare the propylene copolymer of low molecular weight fraction, finally obtained wide molecular weight distribution, linear high fondant-strength random copolymer of propylene.This molecular weight distribution M
w/ M
n=6 ~ 20, molecular weight is greater than the content>=1.0wt% of 5,000,000 fractions, and the content of ethene in final product is at 0.5 ~ 10wt%, M
z+1/ M
n>=80.The method same existence the first external electron donor and catalyst active center's complex ability are strong, and the second external electron donor needs a large amount of defects that use competence exertion effects.
Summary of the invention
For deficiency of the prior art, the inventor, through further investigation, provides the preparation method of a kind of wide molecular weight distribution, high melt strength, propylene.The method adopts the method for Ziegler-Natta catalyst and direct polymerization, realize the regulation and control of the isotactic index between different reactor and hydrogen response to catalyzer by silicane and two kinds of dissimilar external electron donors of two ethers reasonably combined, obtain the polypropylene that there is wide molecular weight distribution and contain a large amount of ultra high molecular weight fractions, this polymkeric substance has good processing characteristics and mechanical property, particularly has very high melt strength.
More particularly, the present invention is hydrogen response, polymerization taxis and the different characteristic of complex ability with catalyst active center of utilizing external electron donor type difference to have, by changing that kind, the addition sequence of external electron donor in catalyst system comes and dissimilar external electron donor composite realized hydrogen response in different reactor and the regulation and control of taxis, the regulation and control of binding molecule amount conditioning agent consumption, realize the preparation of high-performance polypropylene again.
The preparation method who the invention provides a kind of high melt strength, propylene, it comprises:
I density of hydrogen is less than or equal to 400ppmV, and containing under the Ziegler-Natta catalyst effect of silicane external electron donor, propylene carries out equal polymerization or propylene and other alpha-olefin copolymers and closes and react that to obtain melt mass flow rate be 0.01 ~ 0.4g/min polymer A;
II adds 1,3-, bis-ethers external electron donors and polymer A pre-mixing;
Under the material of III after pre-mixing described in hydrogen and step II exists, the equal polymerization or the propylene that carry out propylene close and react with other alpha-olefin copolymers, and having prepared melt mass flow rate (230 ℃/2.16Kg) is 1.0 ~ 60g/10min polymer B;
The high melt strength, propylene C that comprises polymer A and B finally obtaining, its melt mass flow rate is 0.8 ~ 15g/10min.
In aforesaid method, 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 the catalyzer that can be greater than for the preparation of isotactic index 95% alfon.Described catalyzer contains the solid catalyst active ingredient of (1) titaniferous conventionally, and its main component is magnesium, titanium, halogen and internal electron donor; (2) organo-aluminium compound cocatalyst component; (3) external electron donor component.
Active solid catalyst component (can claim again Primary Catalysts) used in described catalyzer is well-known in patent documentation, and the specific examples that operational this class contains active solid catalyst component (1) is disclosed in Chinese patent literature CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4 and CN02100900.7.
Organo-aluminium compound preferred alkyl aluminum compound in described catalyzer, more preferably trialkylaluminium, as: triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, three hexyl aluminium etc.
In aforesaid method, in described catalyzer, the active solid catalyst component of titaniferous and the mol ratio of organo-aluminium compound are counted 1:10 ~ 1:500 with titanium/aluminium, preferably 1:25 ~ 1:100.
Described alpha-olefin can comprise at least one in ethene, 1-butylene, 1-hexene and 1-octene, and it is adjusted according to the different of target from the ratio of propylene.
In aforesaid method, it is R that described silicane external electron donor is selected from general formula
1r
2 msi (OR
3)
3-m, R
4 nsi (OR
5)
4-nand R
6r
7si (OR
8)
2compound at least one, or any mixture of two or more arbitrary proportion wherein, wherein: the integer that m, n are 0 ~ 2; R
1and R
2for identical or different C
1-C
10the aliphatic group of straight chain or branching or ring-type; R
3, R
4, R
5, R
6and R
8for identical or different C
1-C
3linear aliphatic group; R
7for C
3-C
6aliphatic group branching or ring-type.Specific examples includes but are not limited to tetramethoxy-silicane, n-propyl triethoxyl silane, isobutyl triethoxy silane, isobutyl-Trimethoxy silane, vinyltrimethoxy silane, n-propyl Trimethoxy silane, tetraethoxysilane, trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, methylcyclohexyl dimethoxy silane, methyl-isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane, phenyltrimethoxysila,e, dicyclopentyl dimethoxyl silane etc.
In a specific embodiment of aforesaid method, the weight ratio of the organo-aluminium compound in described Ziegler-Natta catalyst and silicane external electron donor is counted 1: 1 ~ 100:1 with aluminium/silicon, is preferably 10:1 ~ 60:1.
In aforesaid method, the described catalyzer that comprises silicane external electron donor can directly join in the first reactor, after the pre-contact and/or prepolymerization that also can know altogether through industry, then joins in the first reactor.Described prepolymerization refers to that catalyzer carries out the prepolymerization of certain multiplying power at a lower temperature, to obtain desirable particle shape and dynamic behavior control.Described prepolymerization can be the continuous prepolymerization of liquid phase body, can also be the batch pre-polymerization under inert solvent exists.Prepolymerization temperature is generally-10 ~ 50 ℃, is preferably 5 ~ 30 ℃.Pre-contact procedure was optionally set before prepolymerization technology.Described pre-contact procedure refers to that promotor in catalyst system, external electron donor and Primary Catalysts (solid active center component) carry out the complex reaction of catalyst system, to obtain the catalyst system with polymerization activity.The temperature of pre-contact procedure is controlled conventionally as-10 ~ 50 ℃, is preferably 5 ~ 30 ℃.
In aforesaid method, described 1, the general structure of 3-diether compound is:
In formula, R
1and R
2be selected from C
1-C
20the aliphatic group of straight chain, branching and ring-type, R
3, R
4, R
5, R
6, R
7and R
8be selected from the C of hydrogen, halogen atom and straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl, R
3~ R
8group between can be linked to be ring by key.Specific examples includes but are not limited to 2, 2-diisobutyl-1, 3-Propanal dimethyl acetal, 2, 2-phenyl-1, 3-Propanal dimethyl acetal, 2, 2-phenmethyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-3, 7-dimethyl octyl-Propanal dimethyl acetal, 2, 2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclohexyl methyl-1, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-di ethyl propyl ether, 2, 2-diisobutyl-1, 3-dipropoxy propane, 2-sec.-propyl-2-isopentyl-1, 3-di ethyl propyl ether, 2-sec.-propyl-2-isopentyl-1, 3-dipropoxy propane, 2, two (cyclohexyl methyl)-1 of 2-, 3-di ethyl propyl ether etc.
In a specific examples of aforesaid method, the mol ratio of the organo-aluminium compound in described Ziegler-Natta catalyst and 1,3-diether compound external electron donor is counted 1:1 ~ 30:1 with aluminium/oxygen, is preferably 2:1 ~ 15:1.
In aforesaid method, in described polymkeric substance C, the mass ratio of polymer A and polymer B is 20:80 ~ 80:20.
In aforesaid method, described high melt strength, propylene C comprises polymer A and polymer B, and the melt mass flow rate of described polypropylene C is 0.8 ~ 15g/10min, molecular weight distribution M
w/ M
nbe 6 ~ 25.
In aforesaid method, described polymerization procedure I can be in liquid phase-liquid phase, or carries out in gas phase-gas phase, or adopts liquid-gas combination technique to carry out.In a specific embodiment, the polymerization methods of described step I is liquid-phase bulk polymerization.In the time carrying out liquid polymerization, polymerization temperature is 50～100 ℃, with 60～85 ℃ for well; Polymerization pressure should be higher than propylene the saturated vapour pressure under corresponding polymerization temperature.In the time of vapour phase polymerization, polymerization temperature is 50～100 ℃, with 60～85 ℃ for well; Polymerization pressure can be normal pressure or higher, and preferred pressure is 1.0 ~ 3.0MPa(gauge pressure, lower same).
In aforesaid method, the copolymerization of described step III carries out conventionally in gas phase, and polymerization temperature is 50～100 ℃, with 60～85 ℃ for well; Polymerization pressure can be normal pressure or higher, and preferred pressure is 1.0 ~ 3.0MPa(gauge pressure, lower same).
In aforesaid method, described step I, step II and step III can be carried out continuously, also may be carried out batchwise.Successive polymerization can be Liquid-phase reactor and/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 or vertical mixing bed bioreactor or fluidized-bed reactor etc., also matched combined at random of above Liquid-phase reactor and Gas-phase reactor.In a specific embodiment, in described step I, polymerization reactor used is annular-pipe reactor.In another specific embodiment, in described step III, polymerization reactor used is fluidized-bed reactor.
In polymerization process of the present invention, the two ethers external electron donors that add are compared than the daughter of silicane dispatch from foreign news agency, there is stronger and ability catalyst active center's complexing, can with polymer A particle in catalytic active center react, generate new catalytic active center, continue to cause propylene or propylene and other alpha-olefin polymerizations.In addition, two ethers external electron donors have higher hydrogen response than the daughter of silicane dispatch from foreign news agency, can, under a small amount of hydrogen exists, prepare high melt mass flow rate polymkeric substance.Therefore, according to method provided by the invention, the add-on of external electron donor consumption, kind and the hydrogen in the differential responses stage that can add by adjustment, do not need with special catalyst, just can obtain containing ultra-high molecular weight fraction, the polymkeric substance (comprising polymer A and polymer B) of wide molecular weight distribution.Ultra-high molecular weight fraction has guaranteed the melt strength that it is higher, and wider molecular weight distribution has guaranteed the good processing characteristics of polymkeric substance; This polymkeric substance also has higher resistance to impact shock simultaneously.Therefore, method provided by the invention, simple, convenient operation, and be easy to suitability for industrialized production, and can prepare premium quality product, there is broad application prospect.
Accompanying drawing explanation
Fig. 1 is schema according to an embodiment of the invention.
Embodiment
Below will by specific embodiment, the present invention is described further, but do not form any limitation of the invention.
In embodiment, polymkeric substance relevant data obtains by following testing method:
1. polymkeric substance isotactic index.The method of describing by GB GB 2412 is measured.
2. melt strength: the Rheoten melt strength instrument that adopts German Geottfert Werkstoff Pruefmaschinen company to produce.This instrument comprises the roller that a pair of sense of rotation is contrary, and polymer melt is extruded from kapillary, is vertically stretched through roller.Draw speed has 3 kinds of experiment models: constant speed, etc. acceleration and index accelerate.Polymer melt is therefore by uniaxial extension, and drawing force can be measured by measuring sensor, i.e. so-called melt strength.Melt strength can be respectively to stretch ratio, rate of extension and tensile viscosity mapping.
3. melt mass flow rate (MFR) is pressed the method that ISO1133 describes, and adopts CEAST company 7026 type melt mass flow rate instrument, at 230 ℃, under 2.16kg load, measures.
4. molecular weight distribution (M
w/ M
n): adopt Polymer Laboratories company of Britain to produce molecular weight and the molecular weight distribution of the IR4 detector coupling working sample of PL-GPC 220 gel permeation chromatographs and Polymer Char company of Spain product, chromatographic column is 3 series connection Plgel 10 μ m MIXED-B posts, solvent and moving phase are 1,2,4-trichlorobenzene (containing 0.3g/1000ml oxidation inhibitor 2,6-dibutyl paracresol), 150 ℃ of column temperatures, flow velocity 0.95ml/min.
5. resin stretched intensity is pressed ASTM D638-00 measurement.
6. resin modulus in flexure is pressed ASTM D790-97 measurement.
7. Izod shock strength is measured according to method described in ASTM D256.
8. fusing point: measure by DSC method, polyacrylic dsc analysis carries out on Perkin-Elmer DSC-7, first the polypropylene specimen of about 5mg is raised to 200 ℃ with the speed of 10 ℃/min, maintain 5min, eliminate thermal history, then drop to 50 ℃ with identical speed, record Tc T
c, then be warmed up to 200 ℃ with 10 ℃/min speed, record fusing point T
m.
Embodiment 1:
Polyreaction is carried out on a set of 25Kg/hr polypropylene pilot plant.Its major equipment comprises prepolymerization reactor, first ring pipe reactor and the second annular-pipe reactor.Polymerization process and step are as follows:
Step I
Prepolymerization:
Primary Catalysts (DQ-III catalyzer, China Petrochemical Industry's catalyst Co. Beijing Ao Da branch office provides), promotor (triethyl aluminum), the first external electron donor (dicyclopentyl dimethoxyl silane) is through 6 ℃, after the pre-contact of 20min, add continuously continuously stirring autoclave prepolymerization reactor to carry out pre-polymerization reactor, triethyl aluminum (TEA) flow that enters prepolymerization reactor is 6.33g/hr, dicyclopentyl dimethoxyl silane (DCPMS) flow is 0.63g/hr, Primary Catalysts flow is 0.01g/hr, TEA/DCPMS is than being 20(mol ratio), wherein DCPMS is the first external electron donor.Prepolymerization is carried out under propylene liquid phase bulk environment, and temperature is 15 ℃, and the residence time is about 4min, and under this condition, the pre-polymerization multiple of catalyzer is approximately 120 ~ 150 times.
The equal polyreaction of propylene:
Pre-polymerization rear catalyst enters continuously and in first ring pipe reactor, completes the equal polyreaction of first stage propylene, 70 ℃ of endless tube polymeric reaction temperatures, reaction pressure 4.0MPa, does not add hydrogen in the charging of annular-pipe reactor, the density of hydrogen ﹤ 10ppmV that on-line chromatograph detects, obtains homo-polypropylene A.
Step II
Polymer slurries exit at the first reactor adds 2 of 0.63g/hr, 2-diisobutyl-1, and 3-Propanal dimethyl acetal (DIBMP), makes itself and polypropylene A pre-mixing.Wherein TEA/DIBMP is than being 20(mol ratio).
Step III
Material after pre-mixing in step II is entered to the second reactor.In the second reactor, add a certain amount of hydrogen, the density of hydrogen that on-line chromatograph detects is 4000ppmV, continues to cause the equal polyreaction of propylene at the second reactor, obtains homo-polypropylene B.
The final product (polymer A and B) obtaining after step III is removed the active and heat drying of the catalyzer of unreacted device through wet nitrogen, obtain polymer powders.In the powder that polymerization is obtained, add IRGAFOS 168 additives of 0.1wt%, IRGANOX 1010 additives of 0.2wt% and the calcium stearate of 0.05wt%, use twin screw extruder granulation.Polymerization process condition, resulting polymers analytical results and polymer physics performance are listed in table 1 ~ 3.
Embodiment 2:
Step is with embodiment 1, and difference is: in the first ring pipe reactor of step I, add a small amount of hydrogen, the density of hydrogen that on-line chromatograph detects is 300ppmV, and the density of hydrogen in the second annular-pipe reactor of step III changes 1000ppmV into.Polymerization process condition, resulting polymers analytical results and polymer physics performance are listed in table 1 ~ 3.
Embodiment 3:
Step is with embodiment 2, difference is: the ratio that has regulated aluminum alkyls and external electron donor in reactor in two steps, in the first reactor of step I, TEA/DCPMS is adjusted into 60(mol ratio), TEA/DIBMP in the second reactor is adjusted into 10(mol ratio), the density of hydrogen in the second annular-pipe reactor of step III changes 5000ppmV into.Polymerization process condition, resulting polymers analytical results and polymer physics performance are listed in table 1 ~ 3.
Embodiment 4:
Step is with embodiment 2, difference is: the ratio that has regulated aluminum alkyls and external electron donor in reactor in two steps, in the first reactor of step I, TEA/DCPMS is adjusted into 10(mol ratio), TEA/DIBMP in the second reactor is adjusted into 60(mol ratio), the density of hydrogen in the second annular-pipe reactor of step III changes 5000ppmV into.Polymerization process condition, resulting polymers analytical results and polymer physics performance are listed in table 1 ~ 3.
Embodiment 5:
Step is with embodiment 1, and difference is: in the first ring pipe reactor of step I, add a small amount of hydrogen, the density of hydrogen that on-line chromatograph detects is 400ppmV, and external electron donor changes Cyclohexylmethyldimethoxysilane (CHMMS) into; Change 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal (IPBMP) at the external electron donor of step III.Polymerization process condition, resulting polymers analytical results and polymer physics performance are listed in table 1 ~ 3.
Embodiment 6:
Step is with embodiment 1, and difference is: change the mixture of CHMMS/DCPMS at the external electron donor of step I, CHMMS/DCPMS is than being 50/50(mol ratio), TEA/ (CHMMS+DCPMS) is 20(mol ratio); In the second reactor of step III, density of hydrogen changes 8000ppmV into.Polymerization process condition, resulting polymers analytical results and polymer physics performance are listed in table 1 ~ 3.
Embodiment 7:
Step is with embodiment 1, and difference is: all add 1-butylene monomer at the first endless tube of step I and the second endless tube of step III, wherein in step I 1-butylene add-on be 6mol%, the butylene add-on in step III is 5mol%.Polymerization process condition, resulting polymers analytical results and polymer physics performance are listed in table 1 ~ 3.
Comparative example 1:
Step is with embodiment 1, and difference is: in step III, the second endless tube uses tetraethoxysilane (TEOS) to substitute 2,2-diisobutyl-1, and 3-Propanal dimethyl acetal is as external electron donor.Concrete technology parameter, resulting polymers analytical results and polymer physics performance are listed in table 1 ~ 3.
According to the result shown in table 2 and table 3, under identical reaction conditions, while adopting containing two ethers external electron donors in step III, catalyzer presents more significant hydrogen response, has effectively widened the molecular weight distribution of final product, is conducive to the forming process of product.In addition, adopt the prepared polypropylene B of two ethers external electron donors to there is better rigidity-toughness balanced over-all properties.The polymkeric substance (comprising polymer A and polymer B) finally obtaining, its melt strength is high, and molecular weight distribution is wide, has good shock resistance.
It should be noted in the discussion above that above-described embodiment, only for explaining the present invention, does not form any limitation of the invention.By with reference to exemplary embodiments, invention has been described, be descriptive and explanatory vocabulary but should be understood to word wherein used, rather than limited vocabulary.Can in the scope of the claims in the present invention, modify the present invention in accordance with regulations, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention who wherein describes relates to specific method, material and embodiment, and does not mean that the present invention is limited to wherein disclosed particular case, on the contrary, the present invention can extend to other all methods and applications with identical function.
Table 1
Table 2
Table 3
Claims (15)
1. a preparation method for high melt strength, propylene, it comprises:
I density of hydrogen is less than or equal to 400ppmV, and containing under the Ziegler-Natta catalyst effect of silicane external electron donor, propylene carries out equal polymerization or propylene and other alpha-olefin copolymers and closes and react that to obtain melt mass flow rate be 0.01 ~ 0.4g/min polymer A;
II adds 1,3-, bis-ethers external electron donors and polymer A pre-mixing;
Under the material of III after pre-mixing described in hydrogen and step II exists, propylene carries out equal polymerization or propylene and other alpha-olefin copolymers and closes and react that to obtain melt mass flow rate be 1.0 ~ 60g/10min polymer B;
The high melt strength, propylene C that comprises polymer A and B finally obtaining, its melt mass flow rate is 0.8 ~ 15g/10min.
2. method according to claim 1, it is characterized in that, described Ziegler-Natta catalyst comprises solid catalyst active ingredient, organo-aluminium compound cocatalyst component and the external electron donor component of titaniferous, the active solid catalyst component of described titaniferous and the mol ratio of organo-aluminium compound are counted 1:10 ~ 1:500 with titanium/aluminium, preferably 1:25 ~ 1:100.
3. method according to claim 1 and 2, is characterized in that, it is R that described silicane external electron donor is selected from general formula
1r
2 msi (OR
3)
3-m, R
4 nsi (OR
5)
4-nand R
6r
7si (OR
8)
2compound, wherein: the integer that m, n are 0 ~ 2; R
1and R
2for identical or different C
1-C
10the aliphatic group of straight chain or branching or ring-type; R
3, R
4, R
5, R
6and R
8for identical or different C
1-C
3linear aliphatic group; R
7for C
3-C
6the aliphatic group of branching or ring-type.
4. method according to claim 3, it is characterized in that, described silicane external electron donor is selected from tetramethoxy-silicane, n-propyl triethoxyl silane, isobutyl triethoxy silane, isobutyl-Trimethoxy silane, vinyltrimethoxy silane, n-propyl Trimethoxy silane, tetraethoxysilane, trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, methylcyclohexyl dimethoxy silane, methyl-isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane, phenyltrimethoxysila,e and dicyclopentyl dimethoxyl silane.
5. according to the method described in any one in claim 1 ~ 4, it is characterized in that, the weight ratio of the organo-aluminium compound in described Ziegler-Natta catalyst and silicane external electron donor is counted 1:1 ~ 100:1 with aluminium/silicon, is preferably 10:1 ~ 60:1.
6. according to the method described in any one in claim 1 ~ 5, it is characterized in that, described 1, the general structure of 3-diether compound is:
In formula, R
1and R
2be selected from C
1-C
20the aliphatic group of straight chain, branching and ring-type, R
3, R
4, R
5, R
6, R
7and R
8be selected from the C of hydrogen, halogen atom and straight or branched
1-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20alkaryl and C
7-C
20aralkyl, R
3~ R
8group between can be linked to be ring by key.
7. method according to claim 6, it is characterized in that, described 1, 3-diether compound is selected from 2, 2-diisobutyl-1, 3-Propanal dimethyl acetal, 2, 2-phenyl-1, 3-Propanal dimethyl acetal, 2, 2-phenmethyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, 3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-3, 7-dimethyl octyl-Propanal dimethyl acetal, 2, 2-sec.-propyl-1, 3-Propanal dimethyl acetal, 2-sec.-propyl-2-cyclohexyl methyl-1, 3-Propanal dimethyl acetal, 2, 2-diisobutyl-1, 3-di ethyl propyl ether, 2, 2-diisobutyl-1, 3-dipropoxy propane, 2-sec.-propyl-2-isopentyl-1, 3-di ethyl propyl ether, 2-sec.-propyl-2-isopentyl-1, 3-dipropoxy propane and 2, two (cyclohexyl methyl)-1 of 2-, 3-di ethyl propyl ether.
8. according to the method described in any one in claim 1 ~ 7, it is characterized in that, the mol ratio of the organo-aluminium compound in described Ziegler-Natta catalyst and 1,3-diether compound external electron donor is counted 1:1 ~ 30:1 with aluminium/oxygen, is preferably 2:1 ~ 15:1.
9. according to the method described in any one in claim 1 ~ 8, it is characterized in that, in described polymkeric substance C, the mass ratio of polymer A and polymer B is 20:80 ~ 80:20.
10. according to the method described in any one in claim 1 ~ 9, it is characterized in that, the polymerization temperature in described step I is 50 ~ 100 ℃, preferably 60 ~ 85 ℃.
11. according to the method described in any one in claim 1 ~ 10, it is characterized in that, the polymerization temperature in described step III is 55 ~ 100 ℃, preferably 60 ~ 85 ℃.
12. according to the method described in any one in claim 1 ~ 11, it is characterized in that, in described step I, polymerization reactor used is annular-pipe reactor.
13. according to the method described in any one in claim 1 ~ 12, it is characterized in that, the polymerization methods of described step I is liquid-phase bulk polymerization.
14. according to the method described in any one in claim 1 ~ 13, it is characterized in that, in described step III, polymerization reactor used is fluidized-bed reactor.
15. according to the method described in any one in claim 1 ~ 14, it is characterized in that, the polymerization methods of described step III is vapour phase polymerization.
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