CN106893007B - A kind of preparation method of high isotactic spherical shape PB Polybutene-1 - Google Patents
A kind of preparation method of high isotactic spherical shape PB Polybutene-1 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/24—Polymer with special particle form or size
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
Abstract
The invention discloses a kind of preparation methods of high isotactic spherical shape PB Polybutene-1, this method adjusts the isotacticity of PB Polybutene-1 using four sections of polymerization reactions and the compound external electron donor of alkoxy silane and ethers, specifically: (1) alkoxy silane and the compound external electron donor of ethers, co-catalyst, major catalyst, hydrogen and liquid propylene are added into tank reactor, carries out one-step polymerization at being 10~25 DEG C in temperature；(2) 30~70 DEG C are warming up to and carries out two sections of polymerizations, 3~60min of polymerization time；(3) it is filled with hydrogen and butene-1 monomer, three stage polymerization is carried out at 10~25 DEG C；And (4) are warming up at 35~70 DEG C again and carry out four Duan Juhe, 60~180min of time flashes unreacted monomer, obtains high isotactic spherical shape PB Polybutene-1.The spherical PB Polybutene-1 isotacticity and catalyst efficiency of the method for the present invention preparation are higher, and substantially reduce the crystal transfer period.
Description
Technical field
The present invention relates to high molecular polymer field, in particular to a kind of fabricated in situ high isotactic spherical shape PB Polybutene-1
Preparation method.
Background technique
Highly isotactic polybutene-1 has light, and creep resistance, resistance to hot pressing, wear-resistant, shock resistance is excellent, nontoxic, green
The characteristics of colour circle is protected.Compared with PPR and PERT, PB Polybutene-1 resin material performance is more excellent, and the service life is longer, and can be with
It is used for a long time at 80-90 DEG C, use temperature upper limit is excellent hot water tube material up to 110 DEG C.
The preparation method of traditional highly isotactic polybutene-1 includes vapor phase method and liquid phase method PB Polybutene-1.Gas phase polymerization
Technique generallys use gas-phase fluidized-bed process and carries out, United States Patent (USP) 3922322,4503203, and 5241024,3580898,
3168484 and Chinese patent CN 102040693A is directly reacted in gas fluidized bed using butene-1 monomer,
Obtain granular PB Polybutene-1.But requirement of this polymerization to catalyst is relatively high, conventionally employed is with porous
Silica gel is that carrier loads the catalyst of liquid, and the catalytic efficiency of this kind of catalyst is relatively low, and the ash in polymer
Divide higher.Meanwhile requirement of the vapor phase method PB Polybutene-1 production technology to equipment is very high, general medium-sized and small enterprises are difficult to industrial metaplasia
It produces.
It include using hydro carbons as solvent or using excessive butene-1 monomer as molten in liquid phase method PB Polybutene-1 production technology
The polymerization of agent.Butene-1 polymerization is carried out as solvent using iso-butane in United States Patent (USP) 5037908 and 3944529, and it is beautiful
State's patent 5237013 carries out butene-1 polymerization as diluent using n-hexane, makes the PB Polybutene-1 generated precipitating or is dissolved in
In solvent.Although polymerization operation is simpler, reaction heat is also easy export system, needs to increase removing after polymerization
Solvent process, solvent recovery and refining step, complicate production technology, increase production cost.Although with excessive butylene-
1 monomer is the problems such as polymerization of solvent solves reaction later period solvent removal, recycling and its separates with butene-1, but this is poly-
Process requirement control monomer conversion is closed to carry out lower than 30% or less, otherwise polymer can be swollen in butene-1 monomer/it is molten
Solution, causes system viscosity excessive, influences the progress of mass-and heat-transfer, so that PB Polybutene-1 product adhesion increases production technology in blocky
Complexity, wherein United States Patent (USP) 394429,6306996 open have used the method.
100488994 C of Chinese patent CN is by ontology precipitation polymerisation method, using butene-1 as reaction monomers and medium, in
Under 0-70 DEG C of reaction temperature, PB Polybutene-1 powder is prepared using supported titanium catalyst；102040692 A of Chinese patent CN
Using the novel load titanium catalyst for adding organic epoxide and organic phosphorus compound preparation, at a temperature of 0-100 DEG C, lead to
It crosses liquid-phase bulk and homopolymerization or the copolyreaction of butene-1 and other alpha-olefins is carried out to butene-1 in slurry polymerization, obtain spherical
The PB Polybutene-1 product of shape；Qingdao University of Science and Technology patent CN103951898A uses substance law, first again by butene-1 pre-polymerization
The gaseous mixture for being passed through propylene or butene-1 and propylene is divided to two sections of in-situ polymerizations to be prepared based on PB Polybutene-1 including a small amount of
The powdered alloy material of butene-1/propylene copolymer.What above-mentioned polymerization used is isothermal reaction, is especially held between polymer
It is easily sticked together, when polymerization temperature is higher than 30 DEG C, PB Polybutene-1 will generate swelling in butene-1, and system is caused to be sent out
It is viscous, bring the difficulty of mass-and heat-transfer, the production efficiency of reduction.
It is preferable that Qingdao University of Science and Technology's patent (103288993 A of CN) by the method that temperature-gradient method polymerize has obtained form
Spherical and spheric granules PB Polybutene-1, solve PB Polybutene-1 Morphology Control Technology problem.But first segment reaction temperature
Lower than 0-20 DEG C, it is unfavorable for the control of industrial production equipment, and the method also fails to solve the crystal transfer of PB Polybutene-1 and asks
Topic, polymer morphology is poor, and has the viscous connection of partial polymer.PB Polybutene-1 is heteromorphic polymer, and with practical value is brilliant
Type I, polymer can be automatically changeb to stable crystal form I, fringe time after melting by the crystal form II of thermodynamic instability
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, so
It carries out coil pipe packaging again afterwards to sell, this just constrains the production efficiency of factory, therefore how to accelerate the crystal form of PB Polybutene-1 product
Transformation is manufacturing enterprise's technical problem in the urgent need to address.
Hebei University of Technology's patent (104193870 A of CN) has been made powdered PB Polybutene-1 by prepolymerization technology and has produced
Product, and PB Polybutene-1 crystal transfer week is improved by addition carboxylic acid when prepolymer and polymerization or metal carboxylate auxiliary compound
Long problem.But this method polymerization activity is too low, only up to 6500g/ (gCat8h), as 812.5g/ (gCat
H), the excessively high performance and purposes for influencing PB Polybutene-1 product of polymer ash content.In addition, the product form of resulting polymers is poor,
Polymer bulk density is lower.
Therefore, at present there is following both sides in batch process PB Polybutene-1 production technology, first, catalytic efficiency compared with
Low, the product form of polymer is poor, and polymer bulk density is lower, content of ashes is high, influences product service performance；Second,
PB Polybutene-1 is heteromorphic polymer, and that with practical value is crystal form I, and polymer can be by thermodynamic instability after melting
Crystal form II be automatically changeb to stable crystal form I, fringe time is generally 7 days to 10 days or so, so that just produces is poly-
Butene-1 pipe needs to place several days curing moldings at room temperature, then carries out coil pipe packaging again and sells, this just constrains factory
Production efficiency, therefore the crystal transfer for how accelerating PB Polybutene-1 product is manufacturing enterprise's technical problem in the urgent need to address.
Summary of the invention
It is existing to solve the main purpose of the present invention is to provide a kind of preparation method of high isotactic spherical shape PB Polybutene-1
Catalytic efficiency is low when preparing high isotactic spherical shape PB Polybutene-1 in technology, and spherical PB Polybutene-1 isotacticity is low, the crystal transfer period
Long defect.
The object of the present invention is achieved like this, and a kind of preparation method of high isotactic spherical shape PB Polybutene-1, this method is adopted
The isotacticity that PB Polybutene-1 is adjusted with four sections of polymerization reactions and the compound external electron donor of alkoxy silane and ethers, specifically includes
Following steps:
(1) alkoxy silane and the compound external electron donor of ethers, co-catalyst, main catalytic are added into tank reactor
Agent, hydrogen and liquid propylene carry out one-step polymerization, 5~30min of polymerization time at being 10~25 DEG C in temperature；
(2) 30~70 DEG C are warming up to and carries out two sections of polymerizations, 3~60min of polymerization time obtains the polymerization with catalytic activity
Object catalyst, then flash and remove remaining propylene in reactor；
(3) it is filled with hydrogen and butene-1 monomer into tank reactor, three stage polymerization is carried out at 10~25 DEG C, the time is
10~120min；And
(4) it is warming up at 35~70 DEG C again and carries out four Duan Juhe, 60~180min of time flashes unreacted monomer, obtains
To high isotactic spherical shape PB Polybutene-1.
The preparation method of high isotactic spherical shape PB Polybutene-1 of the present invention, wherein the major catalyst is preferably negative
Load type Ziegler-Natta catalyst, carrier are spherical magnesium chloride or spherical magnesium ethylate, and carried metal is titanium, and Titanium is negative
Mass content in load type ziegler-nata sphere catalyst is preferably 0.5~4%.
The preparation method of high isotactic spherical shape PB Polybutene-1 of the present invention, wherein the compound external electron donor is
Alkoxy silane and the compound external electron donor of ethers, wherein the molar ratio of alkoxy silane and ethers is preferably 1:0.1~15, excellent
It is selected as 1:0.5~10, further preferably 1:2~8；
Wherein, the general formula of alkoxy silane is preferably RnSi(OCH3)4-n, R is the alkyl of 1~18 carbon, naphthenic base in formula
Or aryl, the positive integer that n is 1~3；
Wherein, the general formula of ethers is preferably R'OR ", and R' is alkyl, naphthenic base or the aryl of 1~18 carbon, R " in formula
For the alkyl or naphthenic base of 1~5 carbon.
The preparation method of high isotactic spherical shape PB Polybutene-1 of the present invention, wherein the major catalyst, co-catalyst
With compound external electron donor molar ratio by titanium: aluminium: in terms of silicon, preferably 1:100~600:10~60.
The preparation method of high isotactic spherical shape PB Polybutene-1 of the present invention, wherein the co-catalyst is preferably three
Aluminium ethide, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chlorine diisopropyl aluminium, a chlorine two are different
One or both of butyl aluminium and a formed group of chlorine di-n-butyl aluminium.
The preparation method of high isotactic spherical shape PB Polybutene-1 of the present invention, wherein the alkoxy silane is preferably
Cyclohexylmethyldimethoxysilane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane or diphenyl diformazan
Oxysilane；The ethers is preferably methyl n-butyl ether, methyl-isobutyl ether, methyl tertiary butyl ether(MTBE), methyl isopropyl ether, second
Base n-butyl ether, ethyl isobutyl ether, ethyl tert-butyl ether (ETBE) or ethyl isopropyl ether.
The preparation method of high isotactic spherical shape PB Polybutene-1 of the present invention, wherein the step (1) and step (3)
Middle-molecular-weihydroxyethyl regulator hydrogen partial pressure is both preferably 0.001~1MPa.
The preparation method of high isotactic spherical shape PB Polybutene-1 of the present invention, wherein the liquid propylene additional amount is excellent
It is selected as 5000~30000g/g major catalyst.
The preparation method of high isotactic spherical shape PB Polybutene-1 of the present invention, wherein the butene-1 monomer additional amount
Preferably 5000~40000g/g major catalyst, more preferably 10000~30000g/g major catalyst.
The preparation method of high isotactic spherical shape PB Polybutene-1 of the present invention, wherein preferably, the major catalyst
In further include internal electron donor, the internal electron donor be phthalic anhydride, dibutyl phthalate, phthalic acid two
Isobutyl ester, 2,3- diisopropyl ethyl succinate, 4- methylphthalic acid dibutyl ester, two isobutyl of 4- methylphthalic acid
Ester, cyclohexene dioctyl phthalate diisobutyl ester, cis- -1,2- cyclohexyl dicarboxylic acid diisobutyl ester, anti-form-1, two isobutyl of 2- cyclohexyl dicarboxylic acid
Ester, cis- -4- methyl-1,2- cyclohexyl dicarboxylic acid diisobutyl ester and trans- -4- methyl-1,2- cyclohexyl dicarboxylic acid diisobutyl ester institute group
At one or both of 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 passes through the method for stage feeding polymerization in situ and the compound outer electron using alkoxy silane and ethers composition
Body can control the isotacticity of polymer and be greater than 96.8%, heap density is greater than 0.35g/ as stereo-tacticity regulator
cm3, polymerization, which is completed to flash, to be removed unreacted monomer and directly obtains the spheric granules PB Polybutene-1 product that partial size is 0.1~1mm,
But also the PB Polybutene-1 crystal form II transformation crystal form I period is effectively shortened, shorten the time of making the product of product；
By Propylene Pre-polymerization and then 1- butene polymerization is carried out, the expression activitiy of catalyst is low, how to improve catalysis effect
Rate is the industrial key problem for improving yield, and the present invention matches by using compound external electron donor, diether compounds
Capability is strong, it is easier to be adsorbed on catalyst and replaces unstable electron donor compound, keeps activated centre all
The cloud density enclosed increases, and 1- butene monomers is promoted to be easier to be inserted into and polymerize and form high polymer.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram piece of spheric catalyst used in embodiment 1；
Wherein, acceleration voltage 15kV, amplification factor are × 80；
Fig. 2 is the scanning electron microscope diagram piece of the spherical PB Polybutene-1 product of 1 gained of embodiment；
Wherein, acceleration voltage 15kV, amplification factor are × 50.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Test method:
(1) polymer isotacticity measures: 0.2~0.3g polymer samples extract 12 hours through boiling diethyl ether, and ether is insoluble
Object extracts 8 hours through boiling heptane again, wherein heptane soluble fraction is isotactic PB Polybutene-1, and PB Polybutene-1 isotacticity is heptane
Soluble matter accounts for the percentage of heptane soluble species and ether soluble substance summation.
(2) it polymer stacks density measurement: is measured according to ASTM D1895, unit g/cm3。
(3) flexible chain t1/2: crystal form II changes the time required for half to crystal form I.
Compound external electron donor:
In the present invention, compound external electron donor is typically defined to alkoxy silane and ethers, alkoxy silane and ethers
Molar ratio is typically defined to 1:0.1~15, and wherein the general formula of alkoxy silane is RnSi(CH3)4-n, R is 1~18 carbon in formula
Alkyl, naphthenic base or aryl, the positive integer that n is 1~3, the general formula of ethers are R'OR ", and R' is the alkane of 1~18 carbon in formula
Base, naphthenic base perhaps aryl R " be 1~5 carbon alkyl or naphthenic base.External electron donor of the invention is poly- to gained is adjusted
The form of butene-1 plays an important role.
The dosage 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, it is with molar ratio computing
Titanium: aluminium: silicon=1:100~600:10~60, if the ratio of major catalyst and co-catalyst, which is greater than, is less than 1:100, main catalytic
The amount that activated centre titanium is reduced in agent is inadequate, and the activity of catalyst is lower, if the ratio of major catalyst and co-catalyst is less than
1:600, then activated centre causes number of active center to reduce by over reduction in major catalyst, then activity also reduces；If main catalytic
The ratio of agent and external electron donor is less than 1:60, then the isotacticity of polymerizate can be improved, but due to excessive outer to electricity
Daughter causes part activated centre in catalyst to be poisoned and lost activity, then catalyst activity reduces, if major catalyst and outer
The ratio of electron donor is greater than 1:10, then due to journey that external electron donor additional amount not enough causes the isotacticity of polymerizate to improve
Spend low, polymer isotacticity is lower.So three needs just play raising activity and polymer in a certain proportion
The effect of isotacticity.
The present invention accelerates PB Polybutene-1 crystal transfer rate by in-situ polymerization technology, shortens solidified forming time.Using
Spherical Ziegler-Natta catalyst is formed with organo-silicon compound with ethers compound using hydrogen as molecular weight regulator
Polymerization reaction of the external electron donor as steric regularity adjusting control agent catalyzing butene -1 is adjusted by changing polymerization technique parameter
The composition and performance of polymer controls product form using four sections of polymerizations.Catalyst activity of the present invention >=8kg PB Polybutene-1/g
Main Cat, polymer bulk density 0.35g/cm3~0.40g/cm3, isotacticity > 96.8%.
Embodiment 1
10L stainless steel polymerization autoclave pump drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 2mmol methyl n-butyl ether, 1mmol dicyclopentyl dimethoxyl silane and 0.15g it is non-
(wherein, carrier is spherical shape MgCl to homogeneous Ziegler-Natta catalyst2, titanium compound TiCl4；The matter of titanium in the catalyst
Measuring content is 2.5%, and internal electron donor is diisobutyl phthalate (mass content in the catalyst is 6.5%)), it urges
The electromicroscopic photograph of agent is shown in Fig. 1, hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, and then 35 DEG C of constant temperature polymerize 20min, then
Unreacted monomer is flashed, and is replaced with nitrogen, butene-1 monomer 1.5kg, hydrogen 0.03MPa, 18 DEG C of polymerizations are added
10min, then 40 DEG C of constant temperature polymerize 2h, directly obtain the PB Polybutene-1 1.2kg (see Fig. 2) of spherical morphology, catalyst activity is
8kg PB Polybutene-1/main the Cat of g (main Cat refers to major catalyst), polymer bulk density 0.38g/cm3, melt index is
0.6g/10min, isotacticity (percentage that heptane soluble species account for heptane soluble species and ether soluble substance summation) are 97.1%, are gathered
Propylene content is 5.1%, the flexible chain t of polymerizate crystallizing at room temperature1/2=4h (the half of the PB Polybutene-1 homopolymer of measurement
Crystallization time t1/2=26h).
It can be seen that product for spherical PB Polybutene-1 from Fig. 2 scanning electron microscope.
Embodiment 2
10L stainless steel polymerization autoclave pump drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 0.5mmol methyl n-butyl ether, 2.5mmol dicyclopentyl dimethoxyl silane and 0.15g
Heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical shape Mg (EtO)2, titanium compound TiCl4；Titanium is in catalyst
In mass content be 2.4%, internal electron donor be cis- -1,2- cyclohexyl dicarboxylic acid diisobutyl ester (quality in the catalyst
5.8%) content is), hydrogen partial pressure 0.08MPa, 25 DEG C of polymerization 10min, then 35 DEG C of constant temperature polymerize 20min, then flash not
The monomer of reaction, and replaced with nitrogen, butene-1 monomer 1.5kg, hydrogen 0.03MPa, 18 DEG C of polymerization 10min are added, then
40 DEG C of constant temperature polymerize 120min, directly obtain the PB Polybutene-1 2.0kg of spherical morphology, and catalyst activity is 13.3kg polybutene-
1/g main Cat, polymer bulk density 0.40g/cm3, melt index 0.75g/10min, isotacticity 98%, polypropylene contains
Amount is 3.1%, the flexible chain t of polymerizate crystallizing at room temperature1/2=4.2h.
Embodiment 3
10L stainless steel polymerization autoclave pump drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 1mmol methyl n-butyl ether, 2mmol diisopropyl dimethoxy silane and 0.15g it is non-
(wherein, carrier is spherical shape Mg (EtO) to homogeneous Ziegler-Natta catalyst2, titanium compound TiCl4；Titanium is in the catalyst
Mass content is 2.4%, internal electron donor 2, and (mass content in the catalyst is 3- diisopropyl ethyl succinate
4.9%)), hydrogen partial pressure 0.1MPa, 15 DEG C of polyase 13 0min, then 35 DEG C of constant temperature polymerize 20min, then flash unreacted list
Body, and replaced with nitrogen, butene-1 monomer 1.5kg, hydrogen 0.01MPa, 18 DEG C of polymerization 10min are added, then 40 DEG C of constant temperature
It polymerize 120min, directly obtains the PB Polybutene-1 1.5kg of spherical morphology, catalyst activity is 10.0kg PB Polybutene-1/main Cat of g,
Polymer bulk density 0.36g/cm3, melt index 1.0g/10min, isotacticity 97%, polypropylene content 5.9%,
The flexible chain t of polymerizate crystallizing at room temperature1/2=6.0h.
Embodiment 4
10L stainless steel polymerization autoclave pump drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 2.5mmol methyl n-butyl ether, 0.5mmol dicyclopentyl dimethoxyl silane and 0.15g
Heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical shape MgCl2, titanium compound TiCl4；Titanium is in the catalyst
Mass content be 2.5%, internal electron donor is that (mass content in the catalyst is diisobutyl phthalate
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 polymerizations
Then 20min flashes unreacted monomer, and is replaced with nitrogen, add butene-1 monomer 1.5kg, hydrogen 0.03MPa, and 18
DEG C polymerization 10min, then 40 DEG C of constant temperature polymerize 120min, directly obtain the PB Polybutene-1 2.4kg of spherical morphology, and catalyst is living
Property be 16.0kg PB Polybutene-1/main Cat of g, polymer bulk density 0.38g/cm3, melt index 0.67g/10min, isotactic
Degree is 97%, polypropylene content 4.2%, the flexible chain t of polymerizate crystallizing at room temperature1/2=5.1h.
Embodiment 5
10L stainless steel polymerization autoclave pump drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 2.8mmol methyl n-butyl ether, 0.2mmol dicyclopentyl dimethoxyl silane and 0.15g
Heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical shape MgCl2, titanium compound TiCl4；Titanium is in the catalyst
Mass content be 2.5%, internal electron donor is that (mass content in the catalyst is diisobutyl phthalate
6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polyase 13 min, then flash unreacted list
Body, and replaced with nitrogen, butene-1 monomer 1.5kg, hydrogen 0.03MPa, 18 DEG C of polymerization 60min are added, then 40 DEG C of constant temperature
It polymerize 120min, directly obtains the PB Polybutene-1 1.2kg of spherical morphology, catalyst activity is 8.0kg PB Polybutene-1/main Cat of g,
Polymer bulk density 0.36g/cm3, melt index 0.45g/10min, isotacticity 96.8%, 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 drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 0.4mmol methyl n-butyl ether, 2.6mmol second, isobutyl dimethoxy silane and 0.15g
Heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical shape MgCl2, titanium compound TiCl4；Titanium is in the catalyst
Mass content be 2.5%, internal electron donor is that (mass content in the catalyst is diisobutyl phthalate
6.5%)), hydrogen partial pressure 0.02MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polyase 13 min, then flash unreacted list
Body, and replaced with nitrogen, butene-1 monomer 1.5kg, hydrogen 0.06MPa, 10 DEG C of polymerization 10min are added, then 40 DEG C of constant temperature
It polymerize 120min, directly obtains the PB Polybutene-1 1.43kg of spherical morphology, catalyst activity is 9.5kg PB Polybutene-1/g master
Cat, polymer bulk density 0.38g/cm3, melt index 0.58g/10min, isotacticity 98%, 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 drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 0.1mmol methyl n-butyl ether, 2.9mmol second, isobutyl dimethoxy silane and 0.15g
Heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical shape MgCl2, titanium compound TiCl4；Titanium is in the catalyst
Mass content be 2.5%, internal electron donor is that (mass content in the catalyst is diisobutyl phthalate
6.5%)), hydrogen partial pressure 0.15MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polymerize 20min, then flash unreacted
Monomer, and replaced with nitrogen, butene-1 monomer 1.5kg, hydrogen 0.02MPa, 25 DEG C of polymerization 90min are added, then 40 DEG C of perseverances
Temperature polymerization 120min, directly obtains the PB Polybutene-1 2.67kg of spherical morphology, and catalyst activity is 17.8kg PB Polybutene-1/g master
Cat, polymer bulk density 0.40g/cm3, melt index 0.35g/10min, isotacticity 99%, 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 drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 0.4mmol methylcyclohexyl ether, 2.6mmol second, isobutyl dimethoxy silane and 0.15g
Heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical shape MgCl2, titanium compound TiCl4；Titanium is in the catalyst
Mass content be 2.5%, internal electron donor is that (mass content in the catalyst is diisobutyl phthalate
6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polymerize 10min, then flash unreacted
Monomer, and replaced with nitrogen, butene-1 monomer 1.5kg, hydrogen 0.08MPa, 25 DEG C of polyase 13 0min are added, then 50 DEG C of perseverances
Temperature polymerization 120min, directly obtains the PB Polybutene-1 2.76kg of spherical morphology, and catalyst activity is 18.4kg PB Polybutene-1/g master
Cat, polymer bulk density 0.39g/cm3, melt index 0.48g/10min, isotacticity 98%, 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 drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 0.4mmol methyl benzethonium ether, 2.6mmol second, isobutyl dimethoxy silane and 0.15g
Heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical shape MgCl2, titanium compound TiCl4；Titanium is in the catalyst
Mass content be 2.5%, internal electron donor is that (mass content in the catalyst is diisobutyl phthalate
6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 70 DEG C of constant temperature polymerize 10min, then flash unreacted
Monomer, and replaced with nitrogen, butene-1 monomer 4.5kg, hydrogen 0.08MPa, 25 DEG C of polymerization 10min are added, then 50 DEG C of perseverances
Temperature polymerization 180min, directly obtains the PB Polybutene-1 3.1kg of spherical morphology, and catalyst activity is 20.7kg PB Polybutene-1/g master
Cat, polymer bulk density 0.38g/cm3, melt index 0.54g/10min, isotacticity 98%, 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 drainage and with high pure nitrogen displacement for several times after, 1kg third is sequentially added into reaction kettle
Alkene monomer, 30mmol triethyl aluminum, 0.2mmol methyl benzethonium ether, 2.8mmol second, isobutyl dimethoxy silane and 0.15g
Heterogeneous Ziegler-Natta catalyst (wherein, carrier be spherical shape MgCl2, titanium compound TiCl4；Titanium is in the catalyst
Mass content be 2.5%, internal electron donor is that (mass content in the catalyst is diisobutyl phthalate
6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerization 10min, then 40 DEG C of constant temperature polymerize 10min, then flash unreacted
Monomer, and replaced with nitrogen, butene-1 monomer 3.0kg, hydrogen 0.08MPa, 10 DEG C of polymerization 120min are added, then 50 DEG C of perseverances
Temperature polymerization 120min, directly obtains the PB Polybutene-1 3.15kg of spherical morphology, and catalyst activity is 21.0kg PB Polybutene-1/g master
Cat, polymer bulk density 0.39g/cm3, melt index 0.48g/10min, isotacticity 98.5%, 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 drainage and with high pure nitrogen displacement for several times after, into reaction kettle be added 1kg propylene list
The heterogeneous Ziegler-Natta catalysis of body, 30mmol triethyl aluminum, 3.0mmol second, isobutyl dimethoxy silane and 0.15g
(wherein, carrier is spherical shape MgCl for agent2, titanium compound TiCl4；The mass content of titanium in the catalyst is 2.5%, interior electron
Body is diisobutyl phthalate (mass content in the catalyst is 6.5%)), hydrogen partial pressure 0.05MPa, 15 DEG C of polymerizations
10min, then 40 DEG C of constant temperature polymerize 10min, then flash unreacted monomer, and replaced with nitrogen, add butene-1 list
Body 3.0kg, hydrogen 0.08MPa, 10 DEG C of polymerization 120min, then 50 DEG C of constant temperature polymerize 120min, directly obtain spherical morphology
PB Polybutene-1 0.92kg, catalyst activity are 6.1kg polymer/gCat, polymer bulk density 0.33g/cm3, melt index
For 0.48g/10min, isotacticity 96%, polypropylene content 7.8%, the flexible chain t of polymerizate crystallizing at room temperature1/2
=9.4h.
It summarizes: through embodiment compared with comparative example 1, with the single external electron donor second, isobutyl dimethoxy silane of use
The PB Polybutene-1 being prepared is compared, the PB Polybutene-1 isotactic for using compound external electron donor to be prepared for isotacticity regulator
Degree is higher, while using compound external electron donor that 1- butene polymerization efficiency (catalyst activity) is also made to be improved, this is
Since the coordination ability of diether compounds is strong, it is easier to be adsorbed on catalyst and replace unstable electron donor
Object is closed, the cloud density around activated centre is increased, 1- butene monomers is promoted to be easier to be inserted into and polymerize and form high polymerization
Object；And the variation for passing through polymerization technique parameter can significantly improve catalyst activity, the particle shape of polymer, accumulation
Density, isotacticity, melt index, flexible chain, and using the available more regular poly- fourth of spherical shape of four sections of polymerizations
- 1 particle of alkene.
Beneficial effects of the present invention:
It is simple, easy to operate that PB Polybutene-1 provided by the invention aggregates into method and process, not only solves general catalytic polymerization
Method is difficult to the morphology issues of PB Polybutene-1, and improves the problem of PB Polybutene-1 crystal transfer period length.By urging
Agent system external electron donor is used as stereo-tacticity regulator using alkoxy silane and the compound of ethers composition, makes polymer
Isotacticity can control be greater than 96.8%；
By Propylene Pre-polymerization and then 1- butene polymerization is carried out, the expression activitiy of catalyst is low, how to improve catalysis effect
Rate is the industrial key problem for improving yield, and the present invention matches by using compound external electron donor, diether compounds
Capability is strong, it is easier to be adsorbed on catalyst and replaces unstable electron donor compound, keeps activated centre all
The cloud density enclosed increases, and 1- butene monomers is promoted to be easier to be inserted into and polymerize and form high polymer.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (9)
1. a kind of preparation method of high isotactic spherical shape PB Polybutene-1, which is characterized in that this method use four sections of polymerization reactions with
And alkoxy silane and the compound external electron donor of ethers adjust the isotacticity of PB Polybutene-1, specifically comprise the following steps:
(1) alkoxy silane and the compound external electron donor of ethers, co-catalyst, major catalyst, hydrogen are added into tank reactor
Gas and liquid propylene carry out one-step polymerization, 5~30min of polymerization time at being 10~25 DEG C in temperature；
(2) 30~70 DEG C are warming up to and carries out two sections of polymerizations, 3~60min of polymerization time obtains having the polymer of catalytic activity to urge
Agent, then flash and remove remaining propylene in reactor；
(3) it is filled with hydrogen and butene-1 monomer into tank reactor, carries out three stage polymerization at 10~25 DEG C, the time is 10~
120min；And
(4) it is warming up at 35~70 DEG C again and carries out four Duan Juhe, 60~180min of time flashes unreacted monomer, obtains height
Isotacticity spherical shape PB Polybutene-1；
Wherein, the major catalyst is spherical Ziegler-Natta catalyst；The molar ratio of alkoxy silane and ethers is 1:0.1
~15；Major catalyst, co-catalyst and compound external electron donor molar ratio are by titanium: aluminium: being 1:100~600:10~60 in terms of silicon.
2. the preparation method of high isotactic spherical shape PB Polybutene-1 according to claim 1, which is characterized in that the main catalytic
Agent is supported Ziegler-Natta catalyst, and carrier is spherical magnesium chloride or spherical magnesium ethylate, and carried metal is titanium, metal
Mass content of the titanium in supported Ziegler-Natta catalyst is 0.5~4%.
3. the preparation method of high isotactic spherical shape PB Polybutene-1 according to claim 1, which is characterized in that the alkoxy
The general formula of silane is RnSi(OCH3)4-n, R is alkyl, naphthenic base or the aryl of 1~18 carbon in formula, n be 1~3 it is just whole
Number；
The general formula of the ethers is R'OR ", and R' is alkyl, naphthenic base or the aryl of 1~18 carbon in formula, and R " is 1~5 carbon
Alkyl or naphthenic base.
4. the preparation method of high isotactic spherical shape PB Polybutene-1 according to claim 1, which is characterized in that the co-catalysis
Agent is triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, a chlorine diisopropyl aluminium, one
One or both of chloro-di-isobutyl aluminum and a formed group of chlorine di-n-butyl aluminium.
5. the preparation method of high isotactic spherical shape PB Polybutene-1 according to claim 1 or 3, which is characterized in that the alkane
Oxysilane be Cyclohexylmethyldimethoxysilane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane or
Dimethoxydiphenylsilane；The ethers is methyl n-butyl ether, methyl-isobutyl ether, methyl tertiary butyl ether(MTBE), methyl isopropyl
Base ether, ethyl n-butyl ether, ethyl isobutyl ether, ethyl tert-butyl ether (ETBE) or ethyl isopropyl ether.
6. the preparation method of high isotactic spherical shape PB Polybutene-1 according to claim 1, which is characterized in that the step
(1) and step (3) middle-molecular-weihydroxyethyl regulator hydrogen partial pressure is 0.001~1MPa.
7. the preparation method of high isotactic spherical shape PB Polybutene-1 according to claim 1, which is characterized in that the liquid phase third
Alkene additional amount is 5000~30000g/g major catalyst.
8. the preparation method of high isotactic spherical shape PB Polybutene-1 according to claim 1, which is characterized in that the butene-1
Monomer additional amount is 5000~40000g/g major catalyst.
9. the preparation method of high isotactic spherical shape PB Polybutene-1 according to claim 2, which is characterized in that the main catalytic
It further include internal electron donor in agent, the internal electron donor is phthalic anhydride, dibutyl phthalate, 2,3- diisopropyl
Base ethyl succinate, 4- methylphthalic acid dibutyl ester, cyclohexene dioctyl phthalate diisobutyl ester, cis- -1,2- cyclohexyl dicarboxylic acid
Diisobutyl ester, anti-form-1,2- cyclohexyl dicarboxylic acid diisobutyl ester, cis- -4- methyl-1,2- cyclohexyl dicarboxylic acid diisobutyl ester and anti-
Formula -4- methyl-1, one or both of formed group of 2- cyclohexyl dicarboxylic acid diisobutyl ester, the internal electron donor is in main reminder
Mass content in agent is 0.15~20%.
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| CN104193870A (en) * | 2014-08-26 | 2014-12-10 | 河北工业大学 | Preparation method of high-isotacticity polybutene-1 powder |
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| CN104193870A (en) * | 2014-08-26 | 2014-12-10 | 河北工业大学 | Preparation method of high-isotacticity polybutene-1 powder |
| CN104628914A (en) * | 2015-02-15 | 2015-05-20 | 青岛科技大学 | Industrial production method and device for highly isotactic polybutylene alloy |
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