CN106893007A - A kind of preparation method of the spherical PB Polybutene-1 of high isotactic - Google Patents
A kind of preparation method of the spherical PB Polybutene-1 of high isotactic Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
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Abstract
The invention discloses a kind of preparation method of the spherical PB Polybutene-1 of high isotactic, the method adjusts the isotacticity of PB Polybutene-1 using four sections of polymerisations and alkoxy silane and the compound external electron donor of ethers, specially：(1) to alkoxy silane and ethers compound external electron donor, co-catalyst, major catalyst, hydrogen and liquid propylene is added in tank reactor, one-step polymerization is carried out at being 10~25 DEG C in temperature；(2) being warming up to 30~70 DEG C carries out two sections of polymerizations, 3~60min of polymerization time；(3) hydrogen and butene-1 monomer are filled with, three stage polymerization is carried out at 10~25 DEG C；And (4) be warming up to 35~70 DEG C again at carry out four sections of polymerizations, 60~180min of time flashes unreacted monomer, obtains the spherical PB Polybutene-1 of high isotactic.Spherical PB Polybutene-1 isotacticity and catalyst efficiency prepared by the inventive method is higher, and substantially reduces the crystal transfer cycle.
Description
Technical field
The present invention relates to high molecular polymer field, more particularly to a kind of preparation method of the spherical PB Polybutene-1 of fabricated in situ high isotactic.
Background technology
Highly isotactic polybutene-1 has a light weight, creep resistance, resistance to hot pressing, wear-resistant, and shock resistance is excellent, nontoxic, the characteristics of environmental protection.Compared with PPR and PERT, PB Polybutene-1 resin material performance is more excellent, and service life is longer, and can at 80-90 DEG C long-term use, use temperature upper limit, up to 110 DEG C, is excellent hot water tube material.
The preparation method of traditional highly isotactic polybutene-1 includes vapor phase method and liquid phase method PB Polybutene-1.Gas phase polymerization technique is generally carried out using gas-phase fluidized-bed process, United States Patent (USP) 3922322,4503203,5241024,3580898,3168484 and Chinese patent CN 102040693A are directly reacted in gas fluidized bed using butene-1 monomer, obtain granular PB Polybutene-1.But requirement of this polymerization to catalyst is higher, conventionally employed is that the catalyst of liquid is loaded by carrier of Bio-sil, and the catalytic efficiency of this kind of catalyst is than relatively low, and ash content in polymer is higher.Meanwhile, requirement of the vapor phase method PB Polybutene-1 production technology to equipment is very high, and general medium-sized and small enterprises are difficult to industrialized production.
Liquid phase method PB Polybutene-1 production technology is included using hydro carbons as solvent or using excessive butene-1 monomer as the polymerization of solvent.Butene-1 polymerization is carried out as solvent using iso-butane in United States Patent (USP) 5037908 and 3944529, and United States Patent (USP) 5237013 carries out butene-1 polymerization using n-hexane as diluent, the PB Polybutene-1 of generation is precipitated or is dissolved in a solvent.Although polymerization operation is relatively simple, reaction heat also easily derives system, and polymerization needs to increase desolvation operation, solvent recovery and refining step after terminating, and makes complex manufacturing, increased production cost.Although the problems such as reacting later stage solvent removal as the polymerization of solvent is solved, reclaim and its separated with butene-1 with excessive butene-1 monomer, but the polymerization technique need control monomer conversion carried out less than less than 30%, otherwise polymer can it is swelling in butene-1 monomer/dissolving, cause system viscosity excessive, influence the carrying out of mass-and heat-transfer, so that the adhesion of PB Polybutene-1 product is in the block complexity for increasing production technology, wherein United States Patent (USP) 394429,6306996 open have used the method.
The C of Chinese patent CN 100488994 with butene-1 as reaction monomers and medium, under 0-70 DEG C of reaction temperature, PB Polybutene-1 powder are prepared using supported titanium catalyst by body precipitation polymerisation method；The novel load titanium catalyst that the A of Chinese patent CN 102040692 are prepared using the organic epoxide of addition and organic phosphorus compound, at a temperature of 0-100 DEG C, starching polymerization by liquid-phase bulk what carries out the copolyreaction of homopolymerization or butene-1 and other alpha-olefins to butene-1, obtains the PB Polybutene-1 product of spherical shape；Qingdao University of Science and Technology patent CN103951898A uses substance law, the two sections of in-situ polymerizations of mixing qi leel for being passed through propylene or butene-1 and propylene again by butene-1 pre-polymerization first to prepare the powdered alloy material including a small amount of butene-1/propylene copolymer based on PB Polybutene-1.What above-mentioned polymerization was used is isothermal reaction, is particularly easy to be sticked together between polymer, and when polymerization temperature is higher than 30 DEG C, PB Polybutene-1 will produce swelling in butene-1, cause system tacky, bring the difficulty of mass-and heat-transfer, the production efficiency of reduction.
Qingdao University of Science and Technology's patent (A of CN 103288993) has obtained the preferable spherical and spheric granules PB Polybutene-1 of form by the method that temperature-gradient method is polymerized, and solves PB Polybutene-1 Morphology Control Technology problem.But first paragraph reaction temperature is less than 0-20 DEG C, is unfavorable for the control of industrial installation, and the method also fails to solve the problems, such as the crystal transfer of PB Polybutene-1, and polymer morphology is poor, and there is the viscous connection of partial polymer.PB Polybutene-1 is heteromorphic polymer, that with practical value is crystal formation I, polymer can be automatically changeb to stable crystal formation I by after melting by the crystal formation II of thermodynamic instability, fringe time is generally 7 days to 10 days or so, so the PB Polybutene-1 pipe just produced needs to place several days curing moldings at room temperature, then coil pipe packaging is carried out again to sell, this just constrains the production efficiency of factory, therefore the crystal transfer for how accelerating PB Polybutene-1 product is manufacturing enterprise's technical barrier in the urgent need to address.
Hebei University of Technology's patent (A of CN 104193870) has been obtained powdered PB Polybutene-1 product by prepolymerization technology, and addition carboxylic acid or metal carboxylate auxiliary compound improve the problem of PB Polybutene-1 crystal transfer girth during by prepolymer and polymerization.But the method polymerization activity is too low, only up to 6500g/ (gCat8h), as 812.5g/ (gCath), the performance and purposes of the too high influence PB Polybutene-1 product of polymer ash content.Additionally, the product form of resulting polymers is poor, polymer bulk density is relatively low.
Therefore, there is following both sides in current batch process PB Polybutene-1 production technology, first, catalytic efficiency is relatively low, the product form of polymer is poor, and polymer bulk density is relatively low, content of ashes is high, influence product performance；Secondly, PB Polybutene-1 is heteromorphic polymer, that with practical value is crystal formation I, polymer can be automatically changeb to stable crystal formation I by after melting by the crystal formation II of thermodynamic instability, fringe time is generally 7 days to 10 days or so, so the PB Polybutene-1 pipe just produced needs to place several days curing moldings at room temperature, then coil pipe packaging is carried out again to sell, this just constrains the production efficiency of factory, therefore the crystal transfer for how accelerating PB Polybutene-1 product is manufacturing enterprise's technical barrier in the urgent need to address.
The content of the invention
Preparation method it is a primary object of the present invention to provide a kind of spherical PB Polybutene-1 of high isotactic, catalytic efficiency is low during solving to prepare the spherical PB Polybutene-1 of high isotactic in the prior art, the defect that spherical PB Polybutene-1 isotacticity is low, the crystal transfer cycle is long.
The object of the present invention is achieved like this, a kind of preparation method of the spherical PB Polybutene-1 of high isotactic, and the method adjusts the isotacticity of PB Polybutene-1 using four sections of polymerisations and alkoxy silane and the compound external electron donor of ethers, specifically includes following steps：
(1) to alkoxy silane and ethers compound external electron donor, co-catalyst, major catalyst, hydrogen and liquid propylene is added in tank reactor, one-step polymerization, 5~30min of polymerization time are carried out at being 10~25 DEG C in temperature；
(2) being warming up to 30~70 DEG C carries out two sections of polymerizations, and 3~60min of polymerization time obtains the polyalcohol catalyst with catalysis activity, then flash remaining propylene in removing reactor；
(3) to hydrogen and butene-1 monomer is filled with tank reactor, three stage polymerization is carried out at 10~25 DEG C, the time is 10~120min；And
(4) four sections of polymerizations are carried out at being warming up to 35~70 DEG C again, 60~180min of time flashes unreacted monomer, obtains the spherical PB Polybutene-1 of high isotactic.
The preparation method of the spherical PB Polybutene-1 of high isotactic of the present invention, wherein, the major catalyst is preferably supported Ziegler-Natta catalyst, carrier is spherical magnesium chloride or spherical magnesium ethylate, carried metal is titanium, and mass content of the Titanium in supported Ziegler-Natta sphere catalyst is preferably 0.5~4%.
The preparation method of the spherical PB Polybutene-1 of high isotactic of the present invention, wherein, the compound external electron donor is alkoxy silane and the compound external electron donor of ethers, and the mol ratio of wherein alkoxy silane and ethers is preferably 1:0.1~15, preferably 1:0.5~10, more preferably 1:2~8；
Wherein, the formula of alkoxy silane is preferably RnSi(OCH3)4-n, R is 1~18 alkyl of carbon, cycloalkyl or aryl in formula, and n is 1~3 positive integer；
Wherein, the formula of ethers is preferably R'OR ", R' is 1~18 alkyl of carbon, cycloalkyl or aryl, R in formula " be 1~5 carbon alkyl or cycloalkyl.
The preparation method of the spherical PB Polybutene-1 of high isotactic of the present invention, wherein, the major catalyst, co-catalyst and compound external electron donor mol ratio are with titanium：Aluminium：Silicon meter, preferably 1:100~600:10~60.
The preparation method of the spherical PB Polybutene-1 of high isotactic of the present invention, wherein, the co-catalyst is preferably one or two that triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chlorine diisopropyl aluminium, a chloro-di-isobutyl aluminum and a chlorine di-n-butyl aluminium constitutes in group.
The preparation method of the spherical PB Polybutene-1 of high isotactic of the present invention, wherein, the alkoxy silane is preferably Cyclohexylmethyldimethoxysilane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane or dimethoxydiphenylsilane；The ethers is preferably methyl n-butyl ether, methyl-isobutyl ether, methyl tertiary butyl ether(MTBE), methyl isopropyl ether, ethyl n-butyl ether, ethyl isobutyl ether, ethyl tert-butyl ether (ETBE) or ethyl isopropyl ether.
The preparation method of the spherical PB Polybutene-1 of high isotactic of the present invention, wherein, the step (1) and step (3) middle-molecular-weihydroxyethyl conditioning agent hydrogen partial pressure are both preferably 0.001~1MPa.
The preparation method of the spherical PB Polybutene-1 of high isotactic of the present invention, wherein, the liquid propylene addition is preferably 5000~30000g/g major catalysts.
The preparation method of the spherical PB Polybutene-1 of high isotactic of the present invention, wherein, the butene-1 monomer addition is preferably 5000~40000g/g major catalysts, more preferably 10000~30000g/g major catalysts.
The preparation method of the spherical PB Polybutene-1 of high isotactic of the present invention, wherein, preferably, also include internal electron donor in the major catalyst, the internal electron donor is phthalic anhydride, dibutyl phthalate, diisobutyl phthalate, 2, 3- diisopropyl ethyl succinates, 4- methylphthalic acid dibutyl esters, 4- methylphthalic acid diisobutyl esters, cyclohexene dioctyl phthalate diisobutyl ester, cis -1, 2- cyclohexyl dicarboxylic acid diisobutyl esters, anti-form-1, 2- cyclohexyl dicarboxylic acid diisobutyl esters, cis -4- methyl isophthalic acids, 2- cyclohexyl dicarboxylic acids diisobutyl ester and trans -4- methyl isophthalic acids, 2- cyclohexyl dicarboxylic acid diisobutyl esters constitute one or two in group, mass content of the internal electron donor in major catalyst is preferably 0.15~20%.
Beneficial effects of the present invention：
The present invention is used as stereo-tacticity regulator by the method for stage feeding polymerization in situ and using the compound external electron donor that alkoxy silane is constituted with ethers, the isotacticity of polymer is controlled more than 96.8%, and heap density is more than 0.35g/cm3, polymerization completes flash distillation and removes unreacted monomer and directly obtain the spheric granules PB Polybutene-1 product that particle diameter is 0.1~1mm, but also effectively shortens the PB Polybutene-1 crystal formation II transformation crystal formation I cycles, shortens the time of making the product of product；
After Propylene Pre-polymerization, 1- butene polymerizations are carried out again, the expression activitiy of catalyst is low, how key problem that catalytic efficiency be industrial raising yield is improved, the present invention is by the way that using compound external electron donor, the coordination ability of diether compounds is strong, and it is easier to be adsorbed onto on catalyst and replaces unstable electron donor compound, increase the cloud density around activated centre, promote 1- butene monomers to be easier to insert and be polymerized and form high polymer.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram piece of spheric catalyst used in embodiment 1；
Wherein, accelerating potential is 15kV, and multiplication factor is × 80；
Fig. 2 is the scanning electron microscope diagram piece of the spherical PB Polybutene-1 product of gained of embodiment 1；
Wherein, accelerating potential is 15kV, and multiplication factor is × 50.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is implemented under premised on technical solution of the present invention; give detailed implementation method and process; but protection scope of the present invention is not limited to following embodiments, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Method of testing：
(1) polymer isotacticity is determined：0.2~0.3g polymer samples are extracted 12 hours through boiling diethyl ether, ether insoluble matter is extracted 8 hours through the heptane that seethes with excitement again, wherein, heptane soluble fraction is isotactic PB Polybutene-1, and PB Polybutene-1 isotacticity accounts for the percentage of heptane soluble species and ether soluble substance summation for heptane soluble species.
(2) polymer stacks density measurement：Determined according to ASTM D1895, unit is g/cm3。
(3) flexible chain t1/2：Crystal formation II is to the time required for crystal formation I transformation half.
Compound external electron donor：
In the present invention, compound external electron donor is typically defined to alkoxy silane and ethers, and the mol ratio of alkoxy silane and ethers is typically defined to 1:0.1~15, the wherein formula of alkoxy silane is RnSi(CH3)4-n, R is 1~18 alkyl of carbon, cycloalkyl or aryl in formula, and n is 1~3 positive integer, and the formula of ethers is R'OR ", R' is 1~18 alkyl of carbon, cycloalkyl or aryl, R in formula " be 1~5 carbon alkyl or cycloalkyl.External electron donor of the invention has important effect to the form of regulation gained PB Polybutene-1.
The consumption of major catalyst, co-catalyst and compound external electron donor：
In the present invention, to the ratio between major catalyst, co-catalyst and compound external electron donor, with molar ratio computing as titanium：Aluminium：Silicon=1：100~600：10~60, if the ratio of major catalyst and co-catalyst is more than less than 1：100, then activated centre titanium is reduced in major catalyst amount not enough, catalyst it is active relatively low, if the ratio of major catalyst and co-catalyst is less than 1：600, then activated centre, by over reduction, causes number of active center to reduce in major catalyst, then activity is also reduced；If the ratio of major catalyst and external electron donor is less than 1：60, then the isotacticity of polymerizate can be improved, but be lost activity because excessive external electron donor causes part activated centre in catalyst to be poisoned, then catalyst activity reduction, if the ratio of major catalyst and external electron donor is more than 1：10, then because external electron donor addition not enough causes the low degree that the isotacticity of polymerizate improves, polymer isotacticity is relatively low.So three needs just play the effect for improving activity and polymer isotacticity in certain proportion.
The present invention accelerates PB Polybutene-1 crystal transfer speed by in-situ polymerization technology, shortens solidified forming time.Using spherical Ziegler-Natta catalyst, using hydrogen as molecular weight regulator, using the compound external electron donor of organo-silicon compound and ethers composition as the polymerisation of steric regularity adjusting control agent catalyzing butene -1, the composition and performance of polymer are adjusted by changing polymerization technique parameter, product form is controlled using four sections of polymerizations.Catalyst activity of the present invention >=8kg PB Polybutene-1s/g main Cat, polymer bulk density 0.35g/cm3~0.40g/cm3, isotacticity ＞ 96.8%.
Embodiment 1
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 2mmol methyl n-butyl ether, 1mmol dicyclopentyl dimethoxyl silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical MgCl2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.5%, internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), the electromicroscopic photograph of catalyst is shown in Fig. 1, hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 35 DEG C of constant temperature polymerization 20min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 1.5kg, hydrogen 0.03MPa, 18 DEG C of polymerization 10min, then 40 DEG C of constant temperature polymerization 2h, directly obtain the PB Polybutene-1 1.2kg (see Fig. 2) of spherical morphology, catalyst activity is 8kg PB Polybutene-1s/main Cat of g (main Cat refers to major catalyst), polymer bulk density 0.38g/cm3, melt index is 0.6g/10min, and isotacticity (heptane soluble species account for the percentage of heptane soluble species and ether soluble substance summation) is 97.1%, and polypropylene content is 5.1%, the flexible chain t of polymerizate crystallizing at room temperature1/2=4h (the flexible chain t of the PB Polybutene-1 homopolymers of measure1/2=26h).
Can be seen that product is spherical PB Polybutene-1 from Fig. 2 ESEMs.
Embodiment 2
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 0.5mmol methyl n-butyl ether, 2.5mmol dicyclopentyl dimethoxyl silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical Mg (EtO)2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.4%, internal electron donor is cis -1, 2- cyclohexyl dicarboxylic acids diisobutyl ester (mass content in the catalyst is 5.8%)), hydrogen partial pressure 0.08MPa, 25 DEG C of polymerization 10min, then 35 DEG C of constant temperature polymerization 20min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 1.5kg, hydrogen 0.03MPa, 18 DEG C of polymerization 10min, then 40 DEG C of constant temperature polymerization 120min, directly obtain the PB Polybutene-1 2.0kg of spherical morphology, catalyst activity is 13.3kg PB Polybutene-1s/main Cat of g, polymer bulk density 0.40g/cm3, melt index is 0.75g/10min, and isotacticity is 98%, and polypropylene content is 3.1%, the flexible chain t of polymerizate crystallizing at room temperature1/2=4.2h.
Embodiment 3
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 1mmol methyl n-butyl ether, 2mmol diisopropyl dimethoxy silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical Mg (EtO)2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.4%, internal electron donor is 2, 3- diisopropyls ethyl succinate (mass content in the catalyst is 4.9%)), hydrogen partial pressure 0.1MPa, 15 DEG C of polyase 13 0min, then 35 DEG C of constant temperature polymerization 20min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 1.5kg, hydrogen 0.01MPa, 18 DEG C of polymerization 10min, then 40 DEG C of constant temperature polymerization 120min, directly obtain the PB Polybutene-1 1.5kg of spherical morphology, catalyst activity is 10.0kg PB Polybutene-1s/main Cat of g, polymer bulk density 0.36g/cm3, melt index is 1.0g/10min, and isotacticity is 97%, and polypropylene content is 5.9%, the flexible chain t of polymerizate crystallizing at room temperature1/2=6.0h.
Embodiment 4
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 2.5mmol methyl n-butyl ether, 0.5mmol dicyclopentyl dimethoxyl silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical MgCl2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.5%, internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), the electromicroscopic photograph of catalyst is shown in Fig. 1, hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polymerization 20min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 1.5kg, hydrogen 0.03MPa, 18 DEG C of polymerization 10min, then 40 DEG C of constant temperature polymerization 120min, directly obtain the PB Polybutene-1 2.4kg of spherical morphology, catalyst activity is 16.0kg PB Polybutene-1s/main Cat of g, polymer bulk density 0.38g/cm3, melt index is 0.67g/10min, and isotacticity is 97%, and polypropylene content is 4.2%, the flexible chain t of polymerizate crystallizing at room temperature1/2=5.1h.
Embodiment 5
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 2.8mmol methyl n-butyl ether, 0.2mmol dicyclopentyl dimethoxyl silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical MgCl2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.5%, internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polyase 13 min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 1.5kg, hydrogen 0.03MPa, 18 DEG C of polymerization 60min, then 40 DEG C of constant temperature polymerization 120min, directly obtain the PB Polybutene-1 1.2kg of spherical morphology, catalyst activity is 8.0kg PB Polybutene-1s/main Cat of g, polymer bulk density 0.36g/cm3, melt index is 0.45g/10min, and isotacticity is 96.8%, and polypropylene content is 2.4%, the flexible chain t of polymerizate crystallizing at room temperature1/2=3.0h.
Embodiment 6
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 0.4mmol methyl n-butyl ether, 2.6mmol second, isobutyl dimethoxy silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical MgCl2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.5%, internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), hydrogen partial pressure 0.02MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polyase 13 min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 1.5kg, hydrogen 0.06MPa, 10 DEG C of polymerization 10min, then 40 DEG C of constant temperature polymerization 120min, directly obtain the PB Polybutene-1 1.43kg of spherical morphology, catalyst activity is 9.5kg PB Polybutene-1s/main Cat of g, polymer bulk density 0.38g/cm3, melt index is 0.58g/10min, and isotacticity is 98%, and polypropylene content is 6.4%, the flexible chain t of polymerizate crystallizing at room temperature1/2=5.6h.
Embodiment 7
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 0.1mmol methyl n-butyl ether, 2.9mmol second, isobutyl dimethoxy silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical MgCl2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.5%, internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), hydrogen partial pressure 0.15MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polymerization 20min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 1.5kg, hydrogen 0.02MPa, 25 DEG C of polymerization 90min, then 40 DEG C of constant temperature polymerization 120min, directly obtain the PB Polybutene-1 2.67kg of spherical morphology, catalyst activity is 17.8kg PB Polybutene-1s/main Cat of g, polymer bulk density 0.40g/cm3, melt index is 0.35g/10min, and isotacticity is 99%, and polypropylene content is 4.5%, the flexible chain t of polymerizate crystallizing at room temperature1/2=4.8h.
Embodiment 8
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 0.4mmol methylcyclohexyls ether, 2.6mmol second, isobutyl dimethoxy silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical MgCl2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.5%, internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polymerization 10min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 1.5kg, hydrogen 0.08MPa, 25 DEG C of polyase 13 0min, then 50 DEG C of constant temperature polymerization 120min, directly obtain the PB Polybutene-1 2.76kg of spherical morphology, catalyst activity is 18.4kg PB Polybutene-1s/main Cat of g, polymer bulk density 0.39g/cm3, melt index is 0.48g/10min, and isotacticity is 98%, and polypropylene content is 4.7%, the flexible chain t of polymerizate crystallizing at room temperature1/2=5.0h.
Embodiment 9
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 0.4mmol methyl benzethoniums ether, 2.6mmol second, isobutyl dimethoxy silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical MgCl2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.5%, internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polymerization 10min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 4.5kg, hydrogen 0.08MPa, 25 DEG C of polymerization 10min, then 50 DEG C of constant temperature polymerization 180min, directly obtain the PB Polybutene-1 3.1kg of spherical morphology, catalyst activity is 20.7kg PB Polybutene-1s/main Cat of g, polymer bulk density 0.38g/cm3, melt index is 0.54g/10min, and isotacticity is 98%, and polypropylene content is 4.8%, the flexible chain t of polymerizate crystallizing at room temperature1/2=5.2h.
Embodiment 10
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to sequentially added in reactor 1kg propylene monomers, 30mmol triethyl aluminums, 0.2mmol methyl benzethoniums ether, 2.8mmol second, isobutyl dimethoxy silanes and 0.15g heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical MgCl2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.5%, internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 40 DEG C of constant temperature polymerization 10min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 3.0kg, hydrogen 0.08MPa, 10 DEG C of polymerization 120min, then 50 DEG C of constant temperature polymerization 120min, directly obtain the PB Polybutene-1 3.15kg of spherical morphology, catalyst activity is 21.0kg PB Polybutene-1s/main Cat of g, polymer bulk density 0.39g/cm3, melt index is 0.48g/10min, and isotacticity is 98.5%, and polypropylene content is 4.7%, the flexible chain t of polymerizate crystallizing at room temperature1/2=5.0h.
Comparative example 1
10L stainless steel polymerization autoclave pump drainages and with high pure nitrogen replace for several times after, to the heterogeneous Ziegler-Natta catalyst of addition 1kg propylene monomers, 30mmol triethyl aluminums, 3.0mmol second, isobutyl dimethoxy silanes and 0.15g in reactor, (wherein, carrier is spherical MgCl2, titanium compound is TiCl4；Titanium mass content in the catalyst is 2.5%, internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 40 DEG C of constant temperature polymerization 10min, then unreacted monomer is flashed, and use nitrogen displacement, add butene-1 monomer 3.0kg, hydrogen 0.08MPa, 10 DEG C of polymerization 120min, then 50 DEG C of constant temperature polymerization 120min, directly obtain the PB Polybutene-1 0.92kg of spherical morphology, catalyst activity is 6.1kg polymer/gCat, polymer bulk density 0.33g/cm3, melt index is 0.48g/10min, and isotacticity is 96%, and polypropylene content is 7.8%, the flexible chain t of polymerizate crystallizing at room temperature1/2=9.4h.
Summarize：Compared with comparative example 1 by embodiment, compared with the PB Polybutene-1 prepared using single external electron donor second, isobutyl dimethoxy silane, the PB Polybutene-1 isotacticity for using compound external electron donor to be prepared for isotacticity conditioning agent is higher, compound external electron donor is used simultaneously also so that 1- butene polymerizations efficiency (catalyst activity) are improved, this is because the coordination ability of diether compounds is strong, it is easier to be adsorbed onto on catalyst and replaces unstable electron donor compound, increase the cloud density around activated centre, 1- butene monomers are promoted to be easier to insert and be polymerized and form high polymer；And by the change of polymerization technique parameter, catalyst activity, the particle shape of polymer, bulk density, isotacticity, melt index, flexible chain can significantly be improved, and using the available more regular spherical PB Polybutene-1 particle of four sections of polymerizations.
Beneficial effects of the present invention：
The PB Polybutene-1 that the present invention is provided aggregates into method process is simple, easy to operate, not only solves general catalytic polymerization and is difficult to the morphology issues of PB Polybutene-1, and improves PB Polybutene-1 crystal transfer cycle problem long.Stereo-tacticity regulator is used as with the compound of ethers composition using alkoxy silane by catalyst system external electron donor, the isotacticity of polymer is controlled more than 96.8%；
After Propylene Pre-polymerization, 1- butene polymerizations are carried out again, the expression activitiy of catalyst is low, how key problem that catalytic efficiency be industrial raising yield is improved, the present invention is by the way that using compound external electron donor, the coordination ability of diether compounds is strong, and it is easier to be adsorbed onto on catalyst and replaces unstable electron donor compound, increase the cloud density around activated centre, promote 1- butene monomers to be easier to insert and be polymerized and form high polymer.
Certainly; the present invention can also have other various embodiments; in the case of without departing substantially from spirit of the invention and its essence, those of ordinary skill in the art can make various corresponding changes and deformation according to the present invention, but these corresponding changes and deformation should all belong to the protection domain of the claims in the present invention.
Claims (10)
1. the preparation method of the spherical PB Polybutene-1 of a kind of high isotactic, it is characterised in that the method is used
Four sections of polymerisations and alkoxy silane and the compound external electron donor of ethers adjust the isotactic of PB Polybutene-1
Degree, specifically includes following steps：
(1) to addition alkoxy silane in tank reactor and ethers compound external electron donor, co-catalysis
Agent, major catalyst, hydrogen and liquid propylene, one-step polymerization is carried out at being 10~25 DEG C in temperature, is gathered
5~30min of conjunction time；
(2) being warming up to 30~70 DEG C carries out two sections of polymerizations, and 3~60min of polymerization time is had
The polyalcohol catalyst of catalysis activity, then flash remaining propylene in removing reactor；
(3) to hydrogen and butene-1 monomer is filled with tank reactor, three sections are carried out at 10~25 DEG C
Polymerization, the time is 10~120min；And
(4) four sections of polymerizations are carried out at being warming up to 35~70 DEG C again, 60~180min of time is flashed not
The monomer of reaction, obtains the spherical PB Polybutene-1 of high isotactic.
2. the preparation method of the spherical PB Polybutene-1 of high isotactic according to claim 1, its feature
It is that the major catalyst is supported Ziegler-Natta catalyst, carrier is spherical magnesium chloride or ball
Shape magnesium ethylate, carried metal is titanium, matter of the Titanium in supported Ziegler-Natta sphere catalyst
Amount content is 0.5~4%.
3. the preparation method of the spherical PB Polybutene-1 of high isotactic according to claim 1, its feature
It is that the compound external electron donor is alkoxy silane and the compound external electron donor of ethers, wherein alcoxyl
The mol ratio of base silane and ethers is 1:0.1~15；
Wherein, the formula of alkoxy silane is RnSi(OCH3)4-n, R is 1~18 alkane of carbon in formula
Base, cycloalkyl or aryl, n are 1~3 positive integer；
Wherein, the formula of ethers be R'OR ", in formula R' be 1~18 alkyl of carbon, cycloalkyl or
Aryl, R " is the alkyl or cycloalkyl of 1~5 carbon.
4. the preparation method of the spherical PB Polybutene-1 of high isotactic according to claim 1, its feature
It is that the major catalyst, co-catalyst and compound external electron donor mol ratio are with titanium：Aluminium：Silicon meter,
It is 1:100~600:10~60.
5. the preparation method of the spherical PB Polybutene-1 of high isotactic according to claim 1, its feature
Be, the co-catalyst be triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium,
Aluminium diethyl monochloride, a chlorine diisopropyl aluminium, a chloro-di-isobutyl aluminum and a chlorine di-n-butyl aluminium are constituted
One or two in group.
6. the preparation method of the spherical PB Polybutene-1 of high isotactic according to claim 1 or 3, its
It is characterised by, the alkoxy silane is Cyclohexylmethyldimethoxysilane, diisobutyl dimethoxy
Silane, dicyclopentyl dimethoxyl silane or dimethoxydiphenylsilane；The ethers is the positive fourth of methyl
Base ether, methyl-isobutyl ether, methyl tertiary butyl ether(MTBE), methyl isopropyl ether, ethyl n-butyl ether, ethyl
Isobutyl ether, ethyl tert-butyl ether (ETBE) or ethyl isopropyl ether.
7. the preparation method of the spherical PB Polybutene-1 of high isotactic according to claim 1, its feature
It is that the step (1) and step (3) middle-molecular-weihydroxyethyl conditioning agent hydrogen partial pressure be 0.001~
1MPa。
8. the preparation method of the spherical PB Polybutene-1 of high isotactic according to claim 1, its feature
It is that the liquid propylene addition is 5000~30000g/g major catalysts.
9. the preparation method of the spherical PB Polybutene-1 of high isotactic according to claim 1, its feature
It is that the butene-1 monomer addition is 5000~40000g/g major catalysts.
10. the preparation method of the spherical PB Polybutene-1 of high isotactic according to claim 2, its feature
It is also to include internal electron donor in the major catalyst, the internal electron donor is phthalic acid
Acid anhydride, dibutyl phthalate, diisobutyl phthalate, 2,3- diisopropyls ethyl succinate,
4- methylphthalic acids dibutyl ester, 4- methylphthalic acids diisobutyl ester, cyclohexene dioctyl phthalate two are different
Butyl ester, cis -1,2- cyclohexyl dicarboxylic acids diisobutyl ester, anti-form-1,2- cyclohexyl dicarboxylic acids diisobutyl ester,
Cis -4- methyl isophthalic acids, 2- cyclohexyl dicarboxylic acids diisobutyl ester and trans -4- methyl isophthalic acids, 2- cyclohexyl dicarboxylic acids two are different
Butyl ester constitutes one or two in group, mass content of the internal electron donor in major catalyst
It is 0.15~20%.
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