CN103788256A - Preparation method of high-melt fluidity high-rigidity antishock polypropylene - Google Patents
Preparation method of high-melt fluidity high-rigidity antishock polypropylene Download PDFInfo
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Abstract
The invention discloses a method of high-melt fluidity high-rigidity antishock polypropylene. The method is characterized by comprising the following steps: 1) under the effect of hydrogen and a Ziegler-Natta catalyst of a trialkoxyl silicane-containing compounds external electron donor, propylene or propylene and alpha-alkene are polymerized to obtain a polymer A; 2) a dialkoxysilanes compound external electron donor is added for premixing with the polymer A; 3)under the premixed material in the step 2) and hydrogen, propylene and alpha-alkene are polymerized to obtain a polymer B with melt mass flux rate of 0.01-30g/min; the antishock polypropylene comprising the polymer A and the polymer B can be finally obtained, the melt mass flux rate is 20-1000g/10min, and preferably is 20-100g/10min. The provided method has the advantages of easy operation, convenient operation and easy industrial production, so that high performance polypropylene with high melt mass flux rate, high rigidity and high antishock strength is prepared, and the high-melt fluidity high-rigidity antishock polypropylene has wide application and 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 high fluidity of molten impact polypropylene.
Background technology
High melt flow polypropylenes easy-formation processing can reduce processing temperature, injection pressure, mold clamping pressure etc. in goods processing process, thereby reduces energy consumption, shortens the shaping cycle of goods, improves goods output.Especially aspect injection molding large thin-wall goods and the part with complicated structure, there is unique advantage.Along with the development of domestic large thin-wall injected articles, the demand of high melt flow polypropylenes raw material is grown with each passing day.The exploitation of high melt flow polypropylenes production technology becomes Ge great polypropylene manufacturing enterprise and the new challenge that will face that dominates the market of application enterprise, is also the research emphasis of polypropylene production technology innovation.High melt flow polypropylenes described herein refers to the propene polymer of melt mass flow rate (melt mass flow rate) >=20g/10min.
The conventional preparation method of high melt flow polypropylenes material mainly contains three kinds.1. adopt plain polypropylene and the high molten high melt flow polypropylenes of the polypropene blended production of mobility that refers to; 2. the polypropylene of producing with peroxide degradation reactor, obtains high melt flow polypropylenes.Peroxide degradation method is also accustomed to being referred to as controllable flow political reform; 3. select suitable catalyst system to adopt suitable technique from the high melt flow polypropylenes of reactor direct production.
Patent documentation CN1451689A has reported the preparation method who passes through the superelevation melt mass flow rate blend of conventional polypropylene powder and organo-peroxide degraded preparation; Patent documentation CN101338009A, WO2004113438 and WO02096986 have reported and have adopted the way of polymkeric substance and superoxide melt blending, and polymkeric substance is degraded, and have prepared the molten polypropylene way that refers to of height of melt mass flow rate >=30g/10min.The method is the method extensively adopting industry present stage, but adding of superoxide increased production cost on the one hand, simultaneously also can be because add-on is unstable and disperse the reason such as inhomogeneous to cause the fluctuation of quality product, in addition, superoxide exists for a long time in polymkeric substance, can bring the progressively variation of product yellowness index, physicals, and the unfriendly problem of environment such as peculiar smell, poisonous volatile matter effusion.
The polyacrylic method of the high melt mass flow rate of direct production in reactor, generation is originally lower, constant product quality, homogeneous, but need to select suitable catalyst system, and the technical requirements of polymerization technique is higher.Chinese patent application 201010604411, US7772338, US20030149196, US6900281, US6111039 and WO9521203 propose a kind of asymmetric external electron donor technology and produce the high molten polyacrylic method that refers to, in the first stage with the good external electron donor of a kind of hydrogen regulation performance (TEOS), produce the polypropylene of high fluidity of molten.Prepare with another kind of external electron donor dicyclopentyl dimethoxyl silane (DCPMS) homo-polypropylene or the propylene copolymer that eutectic refers in subordinate phase, and then obtain high melt flow polypropylenes material.The method is to adopt the good TEOS of hydrogen response as polyacrylic the first external electron donor of the high melt mass flow rate of preparation equally, and therefore, same the finished product exist the shortcoming that rigidity, modulus and intensity are lower.US7465776 has reported that with the Ziegler-Natta catalyst of phthalic ester+ethers or two kinds of internal electron donors of succinate compound adopting silane is that external electron donor can be prepared high melt mass flow rate polypropylene under higher hydrogen gas concentration.The method adopts the Ziegler-Natta catalyst of two kinds of internal electron donors, and higher density of hydrogen can cause production run not steady, and fluctuation is larger, therefore, has strengthened operation easier.US6087459, US5100981 and EP385765 have reported employing phenyl triethoxysilane (PTES) and DCPMS or Cyclohexylmethyldimethoxysilane (CHMMS) Mixed electron donor, under hydrogen exists, in polymerization reactor, direct polymerization is prepared the polyacrylic method of high melt mass flow rate.It is external electron donor that the method adopts PTES, and PTES contains phenyl ring, has toxicity or potential toxicity, unfavorable to human health.It is external electron donor that CN101270172 and CN101155838 disclose employing alkyltrialkoxysilaneand, then coordinates molecular weight regulator hydrogen, has prepared high melt flow polypropylenes.The method adopts single external electron donor, meet the requirement of hydrogen response, but do not realize the production of high impact resistance polypropylene, because the copolymerized ability of the alkyltrialkoxysilaneand that hydrogen response is good is poor, the molecular weight of the multipolymer of preparation is on the low side, and the amplitude of the raising to polymkeric substance erosion-resisting characteristics is very limited.CN101993509 has reported employing Two Liquid Phases+bis-gas phase process, by two kinds of external electron donors of isobutyl triethoxy silane (DIBTES) and second, isobutyl dimethoxy silane (DIBDMS) were separated and are joined in two Liquid-phase reactor in the homopolymerization stage, obtain the homopolymer of wide molecular weight distribution, pass into comonomer ethene in the second Gas-phase reactor, prepare high melt mass flow rate high impact resistance polypropylene, because homopolymer in this application technique is at first three reactor and mainly produce in the 3rd reactor, thereby the character of catalyzer is essentially identical in homopolymerization stage and copolymerization stage.
Summary of the invention
For deficiency of the prior art, the inventor, through further investigation, provides the preparation method of the high rigidity impact polypropylene of a kind of high fluidity of molten.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 dissimilar external electron donor reasonably combined, obtain having the alfon of high taxis, high melt mass flow rate, further obtain the impact polypropylene of high fluidity of molten, high strong and unyielding overall equilbrium.
More particularly, the present invention utilizes preferred dissimilar external electron donor, by change external electron donor in catalyst system kind, addition sequence, add implantation site and realize the regulation and control of different polymerization stage different catalysts performances, the regulation and control of binding molecule amount conditioning agent consumption again, comonomer consumption etc. is realized the preparation of high-performance impact polypropylene.
According to the present invention, a kind of method of preparing the high rigidity impact polypropylene of high fluidity of molten is provided, comprise
I is at hydrogen with containing under the Ziegler-Natta catalyst effect of trialkoxysilanes compound external electron donor, and propylene or propylene and alpha-olefin carry out polymerization and obtain polymer A;
II adds dialkoxy silicane compounds external electron donor and polymer A pre-mixing;
Under the material and hydrogen existence of III after pre-mixing described in step II, propylene and alpha-olefin carry out copolymerization and obtain the polymer B that melt mass flow rate is 0.01 ~ 30g/10min;
Finally obtain impact polypropylene C and comprise polymer A and polymer B, its melt mass flow rate is 20 ~ 1000g/10min, preferably 20 ~ 100g/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.
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 a specific embodiment of 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.
In aforesaid method, the general formula of described trialkoxysilanes compound is R
1si(OR
2)
3, in formula, R
2for C
1-C
3straight chain aliphatic group, R
1for C
3-C
20aliphatic group, or C
3-C
20carbon atom in aliphatic group is replaced the group obtaining by heteroatoms.Described heteroatoms comprises N, P, S etc.Specific examples includes but are not limited to isobutyl triethoxy silane, isobutyl-Trimethoxy silane, isobutyl-tripropoxy silane, isobutyl-three butoxy silanes, tertiary butyl triethoxyl silane, tertiary butyl tripropoxy silane, the tertiary butyl three butoxy silanes, cyclohexyltriethyloxysilane, cyclohexyl tripropoxy silane, diethylamino triethoxyl silane, diethylamino tripropoxy silane, dimethylamino triethoxyl silane etc.
In a specific examples of aforesaid method, the mol ratio of the organo-aluminium compound in described Ziegler-Natta catalyst and trialkoxysilanes compound 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 trialkoxysilanes compound 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, the form of the reactor of pre-contact can be various, its objective is catalyst components is mixed, there is the catalyst system of polymerization activity to obtain, can be continuous stirred tank reactor, annular-pipe reactor, even can be one section of pipeline.The temperature of pre-contact procedure is controlled conventionally as-10 ~ 50 ℃, is preferably 5 ~ 30 ℃.
In aforesaid method, the general formula of described dialkoxy silicane compounds is R
3r
4si(OR
5)
2, wherein in, R
3and R
4for identical or different C
1-C
12aliphatic group straight chain or branching or ring-type; R
5for C
1-C
4the aliphatic group of straight chain or branching.Specific examples includes but are not limited to cyclopentyl-methyl-dimethoxy silane, cyclopentyl-ethyl-dimethoxy silane, cyclopentyl-propyl group-dimethoxy silane, two 2-methyl butyl-dimethoxy silane, two 3-methyl butyl-dimethoxy silane, 2-methyl butyl-3-methyl butyl-dimethoxy silane, 22, 2-dimethyl-propyl group-dimethoxy silane, 2-methyl butyl-2, 2-dimethyl-propyl group-dimethoxy silane, 3-methyl butyl-2, 2-dimethyl-propyl group-dimethoxy silane dimethyldimethoxysil,ne, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, methylcyclohexyl dimethoxy silane, methyl-isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane, dicyclopentyl dimethoxyl silane etc.
In a specific examples of aforesaid method, the weight ratio of the organo-aluminium compound in described Ziegler-Natta catalyst and dialkoxy silicane compounds external electron donor is counted 1:1 ~ 60:1 with aluminium/silicon, is preferably 3:1 ~ 20:1.
In aforesaid method, described high fluidity of molten impact polypropylene comprises polymer A and polymer B, described polyacrylic molecular weight distribution M
w/ M
nbe 4 ~ 25.
High rigidity impact polypropylene described in the present invention refers to that modulus in flexure is greater than the impact polypropylene of 1.0Gpa.
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, first use catalyzer catalyzing propone or propylene and polymerization of alpha-olefin on a small quantity under certain density of hydrogen of the trisiloxanes class external electron donor that hydrogen response is good, isotactic index is higher, obtain the polymer A as the high melt mass flow rate of external phase; Then add the sily oxide class external electron donor that complex ability is stronger to contact in advance with polymer A, generate new catalytic active center, continue to cause propylene and close and react with other alpha-olefin copolymers, obtain the polymer B as rubber phase.The polypropylene of the product finally making for comprising external phase (polymer A) and rubber phase (polymer B).Present method only adds the add-on of external electron donor consumption, kind and the hydrogen in differential responses stage by adjustment, do not need with special catalyst, existing process unit is not needed to large change, can produce there is higher melt mass flow rate, the sample of high rigidity (high modulus in flexure) and high shock strength.Therefore, according to 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.
Embodiment
Below in conjunction with specific embodiments the present invention is explained in further detail, but these embodiment are only used to explanation rather than limit the scope of the invention.
In embodiment, polymkeric substance relevant data obtains by following testing method:
1. polymkeric substance cold xylene solubles content: measure according to method described in ASTM D5492;
2. limiting viscosity: measure according to method described in ASTM D5225;
3. melt mass flow rate (MFR): according to method described in ASTM D1238, with CEAST company 7026 type melt mass flow rate instrument, at 230 ℃, measure under 2.16kg load;
4. modulus in flexure: measure according to method described in ASTM D790;
5. Izod shock strength: measure according to method described in ASTM D256;
6. ethylene content: utilize infrared spectra (IR) method to measure.
7. isotactic index: measure according to method described in GB2412.
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, the second annular-pipe reactor and the 3rd Gas-phase reactor.Polymerization process and step are as follows:
Step I
Prepolymerization:
Primary Catalysts (DQ-VI catalyzer, China Petrochemical Industry's catalyst Co. Beijing Ao Da branch office provides), promotor (triethyl aluminum), the first external electron donor (isobutyl triethoxy silane) be after 6 ℃, 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, isobutyl triethoxy silane (DIBTES) flow is 0.63g/hr, Primary Catalysts flow is 0.01g/hr, and TEA/DIBTES is than being 10(mol/mol).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 60 ~ 120 times.
The equal polyreaction of propylene:
Pre-polymerization rear catalyst enters continuously in the second annular-pipe reactor of first ring pipe reactor and series connection and completes the equal polyreaction of first stage propylene, 70 ℃ of endless tube polymeric reaction temperatures, reaction pressure 4.0MPa, the about 1200ppm of density of hydrogen that adds hydrogen on-line chromatograph to detect in the charging of annular-pipe reactor, obtains homo-polypropylene A.
Step II
Add the dicyclopentyl dimethoxyl silane (DCPMS) of 0.63g/hr in the exit of the second annular-pipe reactor, make itself and polymer A carry out pre-mixing, TEA/DCPMS is than being 5(mol ratio), wherein DCPMS is the second external electron donor, DCPMS is before entering the 3rd Gas-phase reactor
Step III
Material after pre-mixing in step II is entered to the 3rd reactor, in the 3rd reactor, add a certain amount of hydrogen, H
2/ C
2=0.07(mol/mol), C
2/ C
2+ C
3=0.4(mol/mol) on-line chromatograph detect density of hydrogen be 4000ppm, the 3rd reactor continue cause ethylene/propylene copolymer close reaction, obtain ethylene-propylene copolymer 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.Resulting polymers analytical results and polymer physics performance are listed in table 1.
Embodiment 2 ~ 4:
Step is with embodiment 1, and difference is: the density of hydrogen that adds hydrogen on-line chromatograph to detect in the charging of the annular-pipe reactor in step I changes respectively 2000ppm, 3500ppm and 5000ppm into.Resulting polymers analytical results and polymer physics performance are listed in table 1.
Comparative example 1 ~ 3:
Step is with embodiment 1, difference is: in step I, use tetraethoxysilane to substitute isobutyl triethoxy silane as external electron donor, and change respectively the density of hydrogen in the annular-pipe reactor charging in step I into 2000ppm, 3500ppm and 5000ppm.Resulting polymers analytical results and polymer physics performance are listed in table 1.
Comparative example 4:
Step is with comparative example 1, and difference is: TEOS adds implantation site difference, carries out pre-mixing with polymer A, and DCPMS is directly added in the circulation gas pipeline of Gas-phase reactor, is equivalent to not have step I i.
Embodiment 5 ~ 7:
Step is with embodiment 1, and difference is: the H of the reactor in step III
2concentration changes respectively 6000ppm, 8000ppm and 10000ppm into.Resulting polymers analytical results and polymer physics performance are listed in table 1.
Can learn from table 1, the polypropylene of preparing according to method provided by the invention, its isotactic index has had and has significantly improved, and has improved the modulus in flexure of the finished product.By method provided by the invention, different step of reaction adds different silane compound external electron donors, engages the regulation and control of hydrogen add-on, can prepare the polypropylene material of Gao Gang, high-ductility, high melt flow rate (MFR).
Embodiment 8 ~ 20:
Step is with embodiment 1, and difference is: the add-on of the external electron donor in step I is constant, but external electron donor kind changes into respectively:
Sec.-propyl triethoxyl silane (IPTES),
N-propyl triethoxyl silane (NPTES),
N-propyl tripropoxy silane (NPTPS),
Ne-butyltriethoxysilaneand (NBTES),
Tertiary butyl triethoxyl silane (TBTES),
Isobutyl-tripropoxy silane (IBTPS),
Tertiary butyl tripropoxy silane (TBTPS),
The tertiary butyl three butoxy silanes (TBTBS),
Isobutyl-three butoxy silanes (IBTPS),
Cyclopentyl triethoxyl silane (CPTES),
Cyclopentyl tripropoxy silane (CPTPS)
Cyclohexyltriethyloxysilane (CHTES),
Cyclohexyl tripropoxy silane (CHTPS),
Resulting polymers analytical results and polymer physics performance are listed in table 2.
Embodiment 21 ~ 24:
Step is with embodiment 12, and the external electron donor in step I adopts TBTES, TEA/TBTES=10 (mol/mol).Be with embodiment 12 differences: under the prerequisite that the external electron donor in step III remains unchanged in add-on, its kind changes into:
Cyclopentyl-methyl-dimethoxy silane (CPMDMS),
Cyclopentyl-ethyl-dimethoxy silane (CPEDMS),
Cyclopentyl-propyl group-dimethoxy silane (CPPDMS), and
Second, isobutyl dimethoxy silane (DIBDMS)
Resulting polymers analytical results and polymer physics performance are listed in table 2.
According to the result shown in table 2, according to method provided by the invention, in the final product of preparation, rubber phase content is high, and shock resistance is good.In addition, trialkoxysilanes has all shown higher isotactic index, good hydrogen response to electronics outward, can be used in the high rigidity of preparation, high melt flow polypropylenes.
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 polymkeric substance test data
Table 2 polymkeric substance test data
Claims (15)
1. a method of preparing the high rigidity impact polypropylene of high fluidity of molten, comprises
I is at hydrogen with containing under the Ziegler-Natta catalyst effect of trialkoxysilanes compound external electron donor, and propylene or propylene and alpha-olefin carry out polymerization and obtain polymer A;
II adds dialkoxy silicane compounds external electron donor and polymer A pre-mixing;
Under the material and hydrogen existence of III after pre-mixing described in step II, propylene and alpha-olefin carry out copolymerization and obtain the polymer B that melt mass flow rate is 0.01 ~ 30g/10min;
Finally obtain impact polypropylene C and comprise polymer A and polymer B, its melt mass flow rate is 20 ~ 1000g/10min, preferably 20 ~ 100g/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, the general formula of described trialkoxysilanes compound is R
1si(OR
2)
3, wherein, R
2for C
1-C
3straight chain aliphatic group; R
1for C
3-C
20aliphatic group, or C
3-C
20the group that carbon atom in aliphatic group is replaced by heteroatoms.
4. method according to claim 3, it is characterized in that, described trialkoxysilanes compound is selected from isobutyl triethoxy silane, isobutyl-Trimethoxy silane, isobutyl-tripropoxy silane, isobutyl-three butoxy silanes, tertiary butyl triethoxyl silane, tertiary butyl tripropoxy silane, the tertiary butyl three butoxy silanes, cyclohexyltriethyloxysilane, cyclohexyl tripropoxy silane, diethylamino triethoxyl silane, diethylamino tripropoxy silane and dimethylamino triethoxyl silane.
5. according to the method described in any one in claim 1 ~ 4, it is characterized in that, the mol ratio of the organo-aluminium compound in described Ziegler-Natta catalyst and trialkoxysilanes compound 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, the general formula of described dialkoxy silicane compounds is R
3r
4si(OR
5)
2, wherein, R
3and R
4for identical or different C
1-C
12aliphatic group straight chain or branching or ring-type; R
5for C
1-C
4the aliphatic group of straight chain or branching.
7. method according to claim 6, it is characterized in that, described dialkoxy silicane compounds is selected from cyclopentyl-methyl-dimethoxy silane, cyclopentyl-ethyl-dimethoxy silane, cyclopentyl-propyl group-dimethoxy silane, two 2-methyl butyl-dimethoxy silane, two 3-methyl butyl-dimethoxy silane, 2-methyl butyl-3-methyl butyl-dimethoxy silane, 22, 2-dimethyl-propyl group-dimethoxy silane, 2-methyl butyl-2, 2-dimethyl-propyl group-dimethoxy silane, 3-methyl butyl-2, 2-dimethyl-propyl group-dimethoxy silane dimethyldimethoxysil,ne, dimethyldiethoxysilane, second, isobutyl dimethoxy silane, methylcyclohexyl dimethoxy silane, methyl-isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane and dicyclopentyl dimethoxyl silane.
8. according to the method described in any one in claim 1 ~ 7, it is characterized in that, the weight ratio of the organo-aluminium compound in described Ziegler-Natta catalyst and dialkoxy silicane compounds external electron donor is counted 1:1 ~ 60:1 with aluminium/silicon, is preferably 3:1 ~ 20:1.
9. according to the method described in any one in claim 1 ~ 8, it is characterized in that, the polymer A that described impact polypropylene C comprises and the mass ratio of polymer B are 20:80 ~ 80:20.
10. according to the method described in any one in claim 1 ~ 9, it is characterized in that, the polymeric reaction 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 copolyreaction temperature in described step III is 55 ~ 100 ℃, preferably 60 ~ 85 ℃; Polymerization pressure is 1.0 ~ 3.0MPa preferably.
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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622799A (en) * | 2014-11-06 | 2016-06-01 | 中国石油天然气股份有限公司 | Heterocycle-compound-containing olefin polymerization reaction catalyst system for producing high melt flow rate polyolefin |
| CN105622809A (en) * | 2014-10-31 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing impact-resistant polypropylene with low VOC (Volatile Organic Compounds) content |
| CN106749819A (en) * | 2016-11-25 | 2017-05-31 | 联泓新材料有限公司 | A kind of production method of impact copolymer polypropylene |
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| CN115232236A (en) * | 2021-04-25 | 2022-10-25 | 中国石油化工股份有限公司 | Propylene-based copolymer, preparation method and application thereof, and polypropylene composition |
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| CN115246906A (en) * | 2021-04-28 | 2022-10-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, olefin polymerization catalyst, olefin polymerization method and application |
| CN115558195A (en) * | 2021-07-01 | 2023-01-03 | 中国石油天然气股份有限公司 | High-impact co-polypropylene with high fluidity and rigidity and preparation method thereof |
| CN115558195B (en) * | 2021-07-01 | 2024-04-30 | 中国石油天然气股份有限公司 | High-impact-resistance copolymerized polypropylene with high fluidity and rigidity and preparation method thereof |
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| CN105622809A (en) * | 2014-10-31 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing impact-resistant polypropylene with low VOC (Volatile Organic Compounds) content |
| CN105622809B (en) * | 2014-10-31 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of preparation method of the impact polypropylene of low VOC content |
| CN105622799B (en) * | 2014-11-06 | 2018-03-13 | 中国石油天然气股份有限公司 | A kind of olefin polymerization catalyst system containing heterocycle compound for being used to produce high melt flow rate (MFR) polyolefin |
| CN105622799A (en) * | 2014-11-06 | 2016-06-01 | 中国石油天然气股份有限公司 | Heterocycle-compound-containing olefin polymerization reaction catalyst system for producing high melt flow rate polyolefin |
| CN106749819A (en) * | 2016-11-25 | 2017-05-31 | 联泓新材料有限公司 | A kind of production method of impact copolymer polypropylene |
| CN109111643A (en) * | 2018-06-15 | 2019-01-01 | 中国石油化工股份有限公司 | A kind of high flowing High-impact 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 |
| CN111635470B (en) * | 2019-03-01 | 2022-08-05 | 叶平山 | High-melt-index polypropylene resin and preparation method thereof |
| CN111635470A (en) * | 2019-03-01 | 2020-09-08 | 叶平山 | High-melt-index polypropylene resin and preparation method thereof |
| CN110577612A (en) * | 2019-09-05 | 2019-12-17 | 北方华锦化学工业股份有限公司 | production method of high-melt-index, high-impact-resistance and high-rigidity polypropylene resin |
| CN110885492A (en) * | 2019-11-18 | 2020-03-17 | 徐州聚西廷新型材料科技有限公司 | Preparation process of polypropylene with high ethylene propylene rubber phase content |
| CN115232236A (en) * | 2021-04-25 | 2022-10-25 | 中国石油化工股份有限公司 | Propylene-based copolymer, preparation method and application thereof, and polypropylene composition |
| CN115232235A (en) * | 2021-04-25 | 2022-10-25 | 中国石油化工股份有限公司 | Method for producing olefin polymer and olefin polymer |
| CN115232235B (en) * | 2021-04-25 | 2024-02-13 | 中国石油化工股份有限公司 | Method for producing olefin polymer and olefin polymer |
| CN115246906A (en) * | 2021-04-28 | 2022-10-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, olefin polymerization catalyst, olefin polymerization method and application |
| CN115246906B (en) * | 2021-04-28 | 2023-09-15 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component, olefin polymerization catalyst, olefin polymerization method and application |
| CN115558195A (en) * | 2021-07-01 | 2023-01-03 | 中国石油天然气股份有限公司 | High-impact co-polypropylene with high fluidity and rigidity and preparation method thereof |
| CN115558195B (en) * | 2021-07-01 | 2024-04-30 | 中国石油天然气股份有限公司 | High-impact-resistance copolymerized polypropylene with high fluidity and rigidity and preparation method thereof |
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