CN105482008B - A kind of preparation method of polyolefin heterophasic copolymer - Google Patents
A kind of preparation method of polyolefin heterophasic copolymer Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of polyolefin heterophasic copolymer, comprise the following steps：(1) with propylene as monomer, MgCl2/ID/TiCl4Loaded catalyst is major catalyst, and trialkylaluminium is co-catalyst, R1R2Si(OCH3)2It is external electron donor, hydrogen carries out liquid-phase bulk polymerization for molecular weight regulator；(2) ethene or ethene/hydrogen mixed gas and then by monomer are switched to, gas-phase polymerization is carried out；(3) monomer is switched into ethylene/propene gaseous mixture or ethylene/propene/hydrogen mixed gas again, carries out gas phase copolymerization, you can obtain containing polyethylene and polyacrylic polyolefin heterophasic copolymer.It is the subsphaeroidal or regular spherical particle of 0.5~2mm of diameter, the good fluidity of particle through above-mentioned steps polymerization gained polyolefin heterophasic copolymer due to using the spherical high efficiency load type ziegler natta catalyst with magnesium chloride as carrier.There is no inter-adhesive, caking phenomenon between particle in polymerization process, the problem that particle adheres to kettle wall does not occur yet.
Description
Technical field
The present invention relates to a kind of preparation method of polyolefin heterophasic copolymer.
Background technology
Polyethylene and polypropylene are the material being of wide application in five big resins for universal use.Polyethylene has excellent resistance to
Cryogenic property, chemical stability is good, and toughness is preferable, but mechanical property is more general, and tensile strength is low, and heat-resistant aging is poor.And
Polyacrylic crystallinity is high, compound with regular structure, and with preferable tensile strength, compressive strength and rigidity, but toughness is poor, and low temperature is easy
Embrittlement.Both different properties, in order to obtain material of the combination property better than both of which polymers, can exist with mechanical blending or directly
Polyolefin heterophasic copolymer is prepared in reactor.Hdpe Blends prepared by mechanical blending method, due to both be total to
The mixed easy degree of scatter of thing is uneven, and the mixture of gained is not substantially better than both of which polymers, particularly shock strength index not
Can significantly improve.And it is the elder generation for directly passing through ethene and propylene in the reactor to prepare polyolefin heterophasic copolymer in the reactor
Stage feeding polymerization, directly generates the polyolefin heterophasic copolymer containing polypropylene-polyethylene afterwards.Because the copolymer is by chemistry
Method synthesizes, and can there is a small amount of ethylene, propylene segmented copolymer in building-up process, as compatilizer, so that poly- third
Combine more firm between alkene phase and polyethylene phase, obtain material of the combination property better than both homopolymers.With with chlorination
Magnesium is the extensive use of the spherical high efficiency load type Ziegler-Natta catalyst of carrier, and the polyolefin particles of its synthesis are also in rule
Spherical morphology then.On this basis, the excellent polyolefin heterophasic copolymer of multi-stage polymeric synthesis performance can be carried out.Based on ball
The representative art of the polyolefin heterophasic copolymer of shape catalyst has：Spheripol, Catalloy technology etc. (US 4,521,
566；DE 430,429).Such polyolefin heterophasic copolymer with ethene, propylene as parent is developed, its rigidity and toughness are difficult to
Take into account simultaneously.During with EP rubbers tenacity-increased profax, improving toughness can cause rigid decline.
The content of the invention
It is an object of the invention to provide a kind of preparation method of polyolefin heterophasic copolymer.Can obtain having higher curved
The polyolefin heterophasic copolymer of bent modulus and shock strength higher.Polymer particle sizes are regular, with preferable mobility,
Easy to knot groups, does not glue kettle, it is ensured that long period quantity-produced is steadily carried out.
A kind of preparation method step of polyolefin heterophasic copolymer is as follows：
(1) first with propylene as monomer, MgCl2/ID/TiCl4Loaded catalyst is major catalyst, and trialkylaluminium is to help
Catalyst, R1R2Si(OCH3)2It is external electron donor, hydrogen carries out liquid-phase bulk polymerization for molecular weight regulator, wherein ID is,
9,9- bis- (methyl methoxy base) fluorenes, 9,9- double (benzoyloxy methyl) fluorenes, the benzoyloxies of 2- isopropyl -2- isopentyl -1,3- two
One of propane, 2,2- diisobutyl -1, the benzoyloxy propane of 3- bis-, or both mixtures wherein any, R1、R2Respectively phase
The alkyl or aryl of same or different carbon number 1~12.
(2) ethene or ethene/hydrogen mixed gas and then by monomer are switched to, gas-phase polymerization is carried out.Reactor domestic demand is by third
The atmosphere of alkene polymerization procedure is discharged to being passed through ethene or ethene/hydrogen again close to after 0.1MPa (absolute pressure, pressures below is absolute pressure)
Gas gaseous mixture.
(3) monomer is switched into ethylene/propene gaseous mixture or ethylene/propene/hydrogen mixed gas again, carries out gas-phase copolymerization
Close, you can obtain containing polyethylene and polyacrylic polyolefin heterophasic copolymer.Reactor domestic demand is by vinyl polymerization step atmosphere
Release to being passed through ethylene/propene gaseous mixture or ethylene/propene/hydrogen mixed gas close to after 0.1MPa again.
Specifically, the present invention relates to the content of following aspect：
With propylene and ethene as principal monomer, with MgCl2/ID/TiCl4(ID is internal electron donor) loaded catalyst is
Major catalyst, trialkylaluminium are co-catalyst, R1R2Si(OCH3)2It is external electron donor, carries out liquid propylene homopolymerization；Treat propylene
After homopolymerization terminates, pressure switches to ethene atmosphere to 0.1MPa in release kettle, carries out ethene gas-phase homopolymerization；Treat ethylene homo knot
Shu Hou, release kettle in pressure to 0.1MPa, switching to ethylene/propene gaseous mixture carries out copolymerization, be obtained with polypropylene, polyethylene and
Random ethylene-propylene copolymer is the granular polyolefin heterophasic copolymer of main component.
It is to contain titanium, magnesium, chlorine and organic by one kind to prepare the major catalyst used by polyolefin heterophasic copolymer of the invention
The solia particle or powder of electron donor.The composition of catalyst is：Titanium 1.5~3.5%, chlorine 52~65%, magnesium 10~23% has
Machine electron donor (9,9- bis- (methyl methoxy base) fluorenes, 9,9- double (benzoyloxy methyl) fluorenes, 2- isopropyl -2- isopentyl -1,3-
One of two benzoyloxy propane, 2,2- diisobutyl -1, the benzoyloxy propane of 3- bis-, or both mixtures wherein any) 6.0
~20.0%, atent solvent 1~6% (is weight percentage).The specific surface area of catalyst is 250~500m2/ g, particle diameter
Distribution is 5~150 microns.The preparation method of this kind of major catalyst can be found in published patent document (such as：ZL
85100997, ZL 93102795.0, ZL 1258684, ZL 1298887, ZL 1298888, ZL 1436766, ZL1436796,
ZL 1436760, ZL 02100897.3, ZL 021000894.9, ZL 03109781.2).Co-catalyst is triethyl aluminum, three
Aluminium isobutyl, trimethyl aluminium or wherein both mixture.
The preparation method of polyolefin heterophasic copolymer includes that propylene homo, ethylene homo close three tandems of Propylene polymerization
Reactions steps.Concrete operation method and process conditions are as follows：
Step 1：With propylene as monomer, MgCl2/ID/TiCl4Loaded catalyst is major catalyst, and trialkylaluminium is urged to help
Agent, R1R2Si(OCH3)2It is external electron donor, hydrogen carries out liquid-phase bulk polymerization for molecular weight regulator, and wherein ID is 9,9-
Double (benzoyloxy methyl) fluorenes of two (methyl methoxy base) fluorenes, 9,9-, the benzoyloxy propane of 2- isopropyl -2- isopentyl -1,3- two,
One of 2,2- diisobutyl -1, the benzoyloxy propane of 3- bis-, or both mixtures wherein any, R1、R2It is respectively identical or not
The alkyl or aryl of same carbon number 1~12.The temperature of polymerisation is 60~90 DEG C, and appropriate hydrogen, hydrogen are contained in system
It is 0.001 with the mol ratio of propylene:1~0.2:1, the mol ratio of the titanium in aluminium in co-catalyst and major catalyst for 50~
300, the mol ratio of the silicon in aluminium in co-catalyst and external electron donor is 5~40, reacting kettle inner pressure is 2.0~
3.5MPa, reactant residence time is 0.5~2 hour.
Step 2：Monomer is switched into ethene or ethene/hydrogen mixed gas, gas-phase polymerization is carried out.Reactor domestic demand is by propylene
The atmosphere of polymerization procedure is discharged to ethylene gas are passed through again close to after 0.1MPa, and hydrogen is 0 with the mol ratio of ethene:1~0.2:
1.The temperature of polymerisation is 60~90 DEG C, and reacting kettle inner pressure is 0.5~2.0MPa, and reactant residence time is 0.2~1 small
When.
Step 3：Monomer is switched into ethylene/propene gaseous mixture or ethylene/propene/hydrogen mixed gas, ethene and propylene again
Mol ratio 1:0.5~1:2, hydrogen is 0 with the mol ratio of the co-monomer of second third:1~0.2:1, carry out gas phase copolymerization, you can obtain
Contain polyethylene and polyacrylic polyolefin heterophasic copolymer.Reactor domestic demand discharges to close the atmosphere of vinyl polymerization step
Ethylene/propene gaseous mixture or ethylene/propene/hydrogen mixed gas are passed through after 0.1MPa again.The temperature of polymerisation is 60~90 DEG C,
Reacting kettle inner pressure is 0.5~1.5MPa, and reactant residence time is 0.2~1 hour.Product is granular polyolefin
Heterophasic copolymer.
Whole course of reaction total reaction time is at least 80~120 minutes, and general control, can at 100 minutes or more
With terminating reaction.
Beneficial effect
(1) main advantages of the present invention are：Prepared polyolefin heterophasic copolymer have bending modulus higher and compared with
Shock strength high.Polymer particle sizes are regular, and with preferable mobility, easy to knot groups, does not glue kettle, it is ensured that long period connects
The steady of continuous production is carried out.It is then subsequently gas-phase polymerization, nothing using only medium and monomer that propylene liguid reacts as the first step
Saturated hydrocarbons medium need to be used, the operations such as corresponding hydrocarbon medium purifying, recovery are eliminated.Can be with letter using monomer switching atmosphere
Chemical industry skill, reduces cost simultaneously make corresponding regulation to performance of copolymer in certain limit.
(2) advantage using the method is the polyethylene and ethylene propylene copolymer that can cause step 2 and 3 generations
It is sufficient filling with polyacrylic precursor granule, exists while due to polyethylene and ethylene propylene copolymer so that the polyene
Hydrocarbon heterophasic copolymer toughness increases.
(3) due to using the spherical high efficiency load type Ziegler-Natta catalyst with magnesium chloride as carrier, through above-mentioned steps
Polymerization gained polyolefin heterophasic copolymer is the subsphaeroidal or regular spherical particle of 0.5~2mm of diameter, and the mobility of particle is good
It is good.There is no inter-adhesive, caking phenomenon between particle in polymerization process, the problem that particle adheres to kettle wall does not occur yet.Poly- second
Alkene and ethylene propylene copolymer more uniformly can be dispersed in polypropylene matrix so that the compatibility of three is good, made
Standby polyolefin heterophasic copolymer can simultaneously have bending modulus and shock strength higher higher.According to GB/T1843 and
The method of GB/T1943-1996 is determined, and the polyolefin heterophasic copolymer synthesized using the above method shows excellent mechanical property
Can, it is mainly characterized in that：With stronger rigidity (bending modulus is in more than 1000MPa), there is erosion-resisting characteristics (cantilever very high again
Beam notch impact strength is more than 50kJ/m2), shock strength under low temperature is also more prominent, and (- 20 DEG C of cantilever beam shock strengths are more than
10kJ/m2)。
Specific embodiment
Specific embodiment of the invention is described in detail below, it should be noted however that protection of the invention
Scope is not limited to these specific embodiments, but determined by claims.
Embodiment 1
The reactor for preparing polyolefin heterophasic copolymer is the pressure-resistant anti-steel with mechanical stirring device and temperature control chuck
Kettle is answered, the volume of kettle is 10L.Gaseous monomer feed mouthful and valve are respectively provided with the bottom of reactor and kettle cover, on kettle cover
Also catalyst feeds, pressure gauge and the exhaust line with pressure controller.Kettle temperature is first risen to 100 DEG C before reaction, is passed through
Catalyst feeds vacuumize 2 hours to kettle to remove moisture and air in kettle, and kettle temperature then is down into 20~25 DEG C, and stirring turns
Velocity modulation adds hydrogen to 0.1MPa to 250 revs/min, and polymer grade propylene liguid is added by the gaseous monomer feed mouthful of kettle cover
1kg, co-catalyst triethyl aluminum (2M n-heptane solutions), external electron donor methyl cyclohexane are sequentially added into from catalyst feeds
Base dimethoxysilane (0.5M n-heptane solutions) and 50.2mg MgCl2/ID/TiCl4Loaded catalyst and remainder 1.5kg gather
Close level propylene liguid.Aluminium and the mol ratio of titanium in major catalyst are 100 in co-catalyst:1, the aluminium in co-catalyst is with outer to electricity
The mol ratio of the silicon in daughter is 20.Kettle temperature is risen to 70 DEG C, pressure reaches 3.3MPa in kettle, react 1hr.In polymerization process kettle
Pressure remains at 3.2~3.3MPa.After 1hr, open kettle cover exhaust valve, from blast pipe discharge gas reactor to
0.1MPa, the intake valve for opening kettle cover is passed through ethene/hydrogen mixed gas, and hydrogen volume content 1% is maintained at kettle internal pressure power
1.0MPa, 70 DEG C of kettle temperature reacts 20min.After 20min, open kettle cover exhaust valve, from blast pipe discharge gas reactor to
0.1MPa, the intake valve for opening kettle cover is passed through ethylene/propene/hydrogen mixed gas, hydrogen volume content 1%, and ethene rubs with propylene
You compare 1:1.25, kettle internal pressure power is maintained at 1.0MPa, react 20min.Gas reactor, bottom are discharged after copolyreaction 20min
Open discharge valve and obtain polyolefin heterophasic copolymer.The catalytic efficiency of polymerisation is 20.2kg polymer/g catalyst.Polymerization
Product is free flowable fine-powdered particle, Ethylene mass content 9.8%.The mechanical experimental results of polymerizate are listed in
Table 1.
Embodiment 2
In embodiment 2, major catalyst consumption is 49.1mg, and the external electron donor for using is dicyclopentyl dimethoxyl silane
(0.5M n-heptane solutions), remaining operation sequence and polymeric reaction condition are same as Example 1.The catalytic efficiency of polymerisation
It is 22.9kg polymer/g catalyst.Polymerizate is free flowable fine-powdered particle, Ethylene mass content 11.2%.It is poly-
The mechanical experimental results for closing product are listed in table 1.
Embodiment 3
In embodiment 3, major catalyst consumption is 49.5mg, and the external electron donor for using is second, isobutyl dimethoxy silane
(0.5M n-heptane solutions), remaining operation sequence and polymeric reaction condition are same as Example 1.The catalytic efficiency of polymerisation
It is 23.1kg polymer/g catalyst.Polymerizate is free flowable fine-powdered particle, Ethylene mass content 11.5%.It is poly-
The mechanical experimental results for closing product are listed in table 1.
Embodiment 4
In embodiment 4, major catalyst consumption is 49.6mg, and the external electron donor for using is diisopropyl dimethoxy silane
(0.5M n-heptane solutions), remaining operation sequence and polymeric reaction condition are same as Example 1.The catalytic efficiency of polymerisation
It is 20.8kg polymer/g catalyst.Polymerizate is free flowable fine-powdered particle, Ethylene mass content 9.5%.It is poly-
The mechanical experimental results for closing product are listed in table 1.
Embodiment 5
In embodiment 5, major catalyst consumption is 50.5mg, and the co-catalyst for using is triethyl aluminum and triisobutyl aluminium
(mol ratio is 4 to mixture:1,2M n-heptane solution), remaining operation sequence and polymeric reaction condition are same as Example 1.It is poly-
The catalytic efficiency for closing reaction is 19.7kg polymer/g catalyst.Polymerizate is free flowable fine-powdered particle, ethene
Mass content 10.4%.The mechanical experimental results of polymerizate are listed in table 1.
Comparative examples 6
In comparative examples 6, major catalyst consumption is 50.1mg, after propylene liquid phase homopolymerization 1hr, opens the intake valve of kettle cover
Propylene/hydrogen mixed gas are passed through, hydrogen volume content 1% reacts 20min.After 20min, ethylene/propene/hydrogen mixing is passed through
Gas, reacts 20min.Remaining operation sequence and polymeric reaction condition are same as Example 1.The catalytic efficiency of polymerisation is
19.2kg polymer/g catalyst.Polymerizate is free flowable fine-powdered particle, Ethylene mass content 4.7%.Polymerization
The mechanical experimental results of product are listed in table 1.
Table 1
Although be described in detail to specific embodiment of the invention above in conjunction with the embodiments, however it is necessary that referring to
Go out, protection scope of the present invention is not limited to these specific embodiments, but determined by claims.This
Art personnel can are not departed from the range of technological thought of the invention and purport these implementation methods are carried out it is appropriate
Change, and the implementation method after these changes is obviously also included within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of polyolefin heterophasic copolymer, comprises the following steps：
（1）With propylene as monomer, MgCl2/ID/TiCl4Loaded catalyst is major catalyst, and trialkylaluminium is co-catalyst,
R1R2Si(OCH3)2It is external electron donor, ID is internal electron donor, and hydrogen carries out liquid-phase bulk polymerization for molecular weight regulator；
Ethylene mass percentage composition 9.5 ~ 11.5% in the chain structure unit of described polyolefin heterophasic copolymer；
In described external electron donor, R1、R2The respectively alkyl or aryl of carbon number 1 ~ 12；
The mol ratio of the titanium in aluminium in described co-catalyst and major catalyst is 50 ~ 300, the aluminium in co-catalyst with give outward
The mol ratio of the silicon in electron is 5 ~ 40；
（2）Then monomer is switched into ethene or ethene/hydrogen mixed gas, carries out gas-phase polymerization；
（3）Monomer is switched into ethylene/propene gaseous mixture or ethylene/propene/hydrogen mixed gas again, gas phase copolymerization is carried out, i.e.,
Can obtain containing polyethylene and polyacrylic polyolefin heterophasic copolymer.
2. according to the preparation method of the polyolefin heterophasic copolymer described in claim 1, it is characterised in that described co-catalyst
In aluminium and major catalyst in the mol ratio of titanium be 70 ~ 160, the silicon in the aluminium in co-catalyst and external electron donor mole
Than being 15 ~ 25.
3. according to the preparation method of the polyolefin heterophasic copolymer described in claim 1, it is characterised in that the polymerization procedure
（1）In, hydrogen is 0.001 with the mol ratio of propylene:1~0.2:1, the temperature of propylene homo reaction is 60 ~ 90 DEG C, in reactor
Pressure is 2.0 ~ 3.5MPa, and reactant residence time is 0.5 ~ 2 hour.
4. according to the preparation method of the polyolefin heterophasic copolymer described in claim 1, it is characterised in that the polymerization procedure
（2）In, hydrogen is 0 with the mol ratio of ethene:1~0.2:1, the temperature of polymerisation is 60 ~ 90 DEG C, and reacting kettle inner pressure is 0.5
~ 2.0MPa, reactant residence time is 0.2 ~ 1 hour.
5. according to the preparation method of the polyolefin heterophasic copolymer described in claim 1, it is characterised in that the polymerization procedure
（3）In, ethene and propylene molar ratio 1:0.5~1:2, hydrogen is 0 with the mol ratio of the co-monomer of second third:1~0.2:1, polymerisation
Temperature be 60 ~ 90 DEG C, reacting kettle inner pressure be 0.5 ~ 1.5MPa, reactant residence time be 0.2 ~ 1 hour.
6., according to the preparation method of the polyolefin heterophasic copolymer described in any claim in claim 1 to 5, its feature exists
In：Described internal electron donor ID is selected from diisobutyl phthalate, n-butyl phthalate, (the methyl first of 9,9- bis-
Epoxide) fluorenes, double (benzoyloxy methyl) fluorenes of 9,9-, the benzoyloxy propane of 2- isopropyl -2- isopentyl -1,3- two or 2,2- bis- it is different
One or two in the benzoyloxy propane of butyl -1,3- two.
7., according to the preparation method of the polyolefin heterophasic copolymer described in any one claim in claim 1 to 5, it is special
Levy and be, during switching monomer, the atmosphere of previous polymerization procedure is discharged to close to after 0.1MPa and is passed through other again by reactor domestic demand
Monomer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1344793A1 (en) * | 2002-03-15 | 2003-09-17 | Borealis Technology Oy | Polyolefin composition with improved properties |
| EP1477525A1 (en) * | 2003-05-15 | 2004-11-17 | Borealis Technology OY | Polyolefin composition |
| CN1796422A (en) * | 2004-12-22 | 2006-07-05 | 中国科学院化学研究所 | Method for preparing shock resistant material of polypropylene |
| CN103360522A (en) * | 2013-07-17 | 2013-10-23 | 中国石油化工股份有限公司 | Preparation method for multiphase polyolefin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1344793A1 (en) * | 2002-03-15 | 2003-09-17 | Borealis Technology Oy | Polyolefin composition with improved properties |
| EP1477525A1 (en) * | 2003-05-15 | 2004-11-17 | Borealis Technology OY | Polyolefin composition |
| CN1796422A (en) * | 2004-12-22 | 2006-07-05 | 中国科学院化学研究所 | Method for preparing shock resistant material of polypropylene |
| CN103360522A (en) * | 2013-07-17 | 2013-10-23 | 中国石油化工股份有限公司 | Preparation method for multiphase polyolefin |
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