CN105777958A - Long-chain branched polyolefin and preparation method thereof - Google Patents
Long-chain branched polyolefin and preparation method thereof Download PDFInfo
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- CN105777958A CN105777958A CN201610348836.XA CN201610348836A CN105777958A CN 105777958 A CN105777958 A CN 105777958A CN 201610348836 A CN201610348836 A CN 201610348836A CN 105777958 A CN105777958 A CN 105777958A
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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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
Abstract
The invention provides long-chain branched polyolefin and a preparation method thereof. The preparation method comprises the following steps: in the presence of a titanium-containing Ziegler-Natta catalyst, a promoter alkyl aluminum compound and a branching agent, performing a polymerization reaction of olefin to obtain long-chain branched polyolefin, wherein the branching agent is unsaturated long-chain alkyl aluminum. Compared with prior art, in the invention, by adopting a phosphate compound as the titanium-containing Ziegler-Natta catalyst of an internal electron donor and unsaturated long-chain alkyl aluminum as the branching agent, the obtained long-chain branched polyolefin has the advantages of adjustable number of branching points and narrow distribution of branch-chain molecular weight; and meanwhile, the unsaturated long-chain alkyl aluminum has relatively good compatibility with the main-chain polyolefin, and the branch chain contains a certain number of double bonds so that the long-chain branched polyolefin can be moderately cross-linked in the processing process and the melt strength and polymer impact performance of the long-chain branched polyolefin can be further improved.
Description
Technical field
The invention belongs to Modification of Polyolefins With Grafting Techniques field, particularly relate to a kind of long-chain branched polyolefins and
Its preparation method.
Background technology
Polypropylene (PP) is widely used in vapour because of excellent performance, with low cost, cost performance high
The fields such as car, household electrical appliance, electronics, packaging and building materials.But owing to the molecular structure of PP is linear straight chain
Type, therefore softening point and fusing point very close to, after exceeding its fusing point, melt strength can be decreased obviously, and melts simultaneously
Body, in elongational flow, does not draw high hardening effect so that it is the application in fields such as foaming, thermoformings is subject to
To a definite limitation, it is therefore desirable to improve polyacrylic melt strength.
Melt strength of polypropylene by increasing polyacrylic molecular weight and can introduce the sides such as long chain branched
Method improves, and wherein the raising to melt strength that introduces of long branched chain structure becomes apparent from, and this is due to length
The structure of chain branching makes strand produce chain entanglement and then occur caused by strain hardening phenomenon.At present, industry
More ripe technology many employings x ray irradiation x and processing modified, reactive extrursion.Such as Patent No. 5541236
With 5047485 United States Patent (USP), the Chinese patent of Publication No. CN102329405A, Publication No. CN
The Chinese patent of 1986589B and the Chinese patent of Publication No. CN1986589B propose linearly to gather with commodity
Propylene is raw material, introduces branched knot by the method for modifying such as x ray irradiation x or reactive extrursion in polypropylene chains
Structure, the advantages such as it is simple that these methods have technique, small investment, but there is degradation of polypropylene and gel in it
Problem, affects polyacrylic processing characteristics.
Along with the development of metallocene catalyst, direct polymerization is prepared high melt strength, propylene and has been obtained very well
Development, the Chinese patent of Application No. CN200910085490.9 is reported and is closed by metallocene catalyst
Master chain is become to be the long-chain branching polypropylene of isotactic polypropylene；In Publication No. CN 102127176A
Metallocene catalyst is used in mixed way by state's patent especially with Ziegler-Natta catalyst, prepares in-situ blending
Long-chain branching polypropylene and the alloy of HOPP.Above method is obtained in that the long chain branching of better performances
Polypropylene, but due to the introducing of metallocene catalyst and need to use the MAO that price is higher be co-catalysis
Agent, makes the production cost of this technique improve, and there is the problems such as catalyst use complexity.
MgCl2/TiCl4/ electron donor catalyst technical maturity, it is strong due to the suitability, resin combination property
Superior and be in irreplaceable status.The Chinese patent of Publication No. CN103804795A discloses one
Plant and use magnesium oxide/titanium tetrachloride/9,9-double (methoxy) fluorenes (BMMF) class efficient Z-N catalysis
The method of HMSPP is prepared in agent.First the method carries out propylene homo conjunction, and preparation homopolymerization PP matrix skeleton-
Linear PP matrix, introduces α afterwards, and ω-diolefinic monomer carries out combined polymerization, generates long chain branching and part is handed over
Connection copolymerization PP and be dispersed in linear PP matrix, finally give and there is long chain branched
HMSPP.The Chinese patent of Publication No. CN101812165A disclose one prepare high fondant-strength gather
The method of propylene, first first synthesizes the side chain reactive PP intermediate containing styrene group with Z-N catalyst,
It is added into again in radical reaction system, utilizes the reactivity of styrene double bond, pass through reactive extrursion
Method prepare structure clearly, branched structure content is adjustable, have the HMSPP of long chain branched.With top
Method effectively utilizes Ziegler-Natta catalyst activation characteristics, but preparation process is complicated, need to carry out subsequent reactions.
The Chinese patent alkadienes of Publication No. CN101768242B prepares HMSPP as modified monomer,
Owing to alkadienes is good with the PP compatibility, the tensile property of HMSPP can be improved；Additionally, diolefinic monomer
Activity is relatively low, can promote graft reaction to a certain extent, and the melt of made HMSPP also has and draws more greatly
Stretch than with good malleability.But the polyacrylic branch lengths of graft copolymerization prepared by the method is relatively short,
And branched chain molecule amount skewness.
Summary of the invention
In view of this, the technical problem to be solved in the present invention be to provide a kind of long-chain branched polyolefins and
Preparation method, long-chain branched polyolefins branch lengths prepared by the method and the branched adjustable and side chain of counting divide
Son amount narrow distribution.
The invention provides the preparation method of a kind of long-chain branched polyolefins, including:
Under conditions of titanium system Ziegler-Natta catalyst, promoter exist with branching agent, alkene is entered
Row bulk polymerization, obtains long-chain branched polyolefins；Described titanium system Ziegler-Natta catalyst is with formula (I)
Shown phosphate compound is internal electron donor；Described branching agent is unsaturated chain alkyl aluminum；
Wherein, R1、R2With R3It is each independently alkyl or aromatic radical；Described alkyl is C1's～C10
Alkyl；Described aromatic radical is phenyl, the substituted phenyl of alkyl or the substituted phenyl of alkoxyl.
Preferably, described titanium system Ziegler-Natta catalyst is prepared in accordance with the following methods:
By the chloride of titanium, magnesium-containing compound with the phosphate compound shown in formula (I) in organic solvent
Mixing, reacting by heating, obtain titanium system Ziegler-Natta catalyst.
Preferably, the quality of described titanium system Ziegler-Natta catalyst is alkene quality
0.001%～0.1%.
Preferably, described promoter is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, two isobutyls
Base hydrogen aluminum, diethylhydroaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride and in sesquialter ethylmercury chloride aluminum
Plant or multiple.
Preferably, the quality of described promoter is the 0.01%～1% of alkene quality.
Preferably, the molecular weight of described branching agent is 200～3500, and molecular weight distributing index is less than 2.0.
Preferably, described branching agent is prepared in accordance with the following methods:
Rare earth compound, diolefin, alkyl aluminum and chloride are mixed, reacts, obtain unsaturation
Chain alkyl aluminum；Described rare earth compound includes that rare earth carboxylate, rare earth superphosphate, rare earth are acid
Phosphonate and alkoxy rare-earth；Described diolefin is (50～1000) with the mol ratio of rare earth compound: 1.
Preferably, described polyreaction is solution polymerization；The solvent of described polyreaction is C4～C10
Alkane and C6～C24 aromatic hydrocarbon in one or more.
Present invention also offers a kind of long-chain branched polyolefins, described long-chain branched polyolefins is spheroidal particle；
The particle diameter of described spheroidal particle is 20～5000 μm；The bulk density of described long-chain branched polyolefins granule is
0.35～0.46g/cm3；The isotacticity of the main chain of described long-chain branched polyolefins is more than 90%.
Preferably, the branched chain molecule amount of described long-chain branched polyolefins is 200～3500；Described long chain branching
Polyolefinic side chain degree is 0.5%～10%.
The invention provides a kind of long-chain branched polyolefins and preparation method thereof, including: in titanium system
Under conditions of Ziegler-Natta catalyst, promoter alkyl aluminum compound exist with branching agent, by alkene
Carry out bulk polymerization, obtain long-chain branched polyolefins；Described titanium system Ziegler-Natta catalyst is with formula
(I) phosphate compound shown in is internal electron donor；Described branching agent be end group be unsaturated long alkane
Base aluminum；Wherein, R1、R2With R3It is each independently alkyl or aromatic radical；Described alkyl is C1～C10
Alkyl；Described aromatic radical is phenyl, the substituted phenyl of alkyl or the substituted phenyl of alkoxyl.With existing
Technology is compared, the titanium system Ziegler-Natta catalysis that the present invention uses phosphate compound to be internal electron donor
Agent, with unsaturated chain alkyl aluminum as branching agent to long-chain branched polyolefins there is side chain
Length is adjustable with branch point number, the advantage of branched chain molecule amount narrowly distributing, meanwhile, and unsaturated chain alkyl
Aluminum and main chain polyolefin have the preferable compatibility, and containing a number of double bond in side chain, thus
Make long-chain branched polyolefins can carry out in the course of processing appropriately crosslinked, can further improve long chain branching and gather
The melt strength of alkene and polymer impact performance.
Accompanying drawing explanation
Fig. 1 is the rheological curve figure of the long-chain branching polypropylene obtained in the embodiment of the present invention 10～12；
Fig. 2 is the rheological curve figure of the long-chain branching polypropylene obtained in the embodiment of the present invention 10～12；
Fig. 3 is the rheological curve figure of the long-chain branching polypropylene obtained in the embodiment of the present invention 10～12；
Fig. 4 is the GPC curve obtaining branching agent in the embodiment of the present invention 7～9；
Fig. 5 is to obtain branching agent and embodiment 22,23 gained long chain branching poly-third in the embodiment of the present invention 9
The GPC curve of alkene；
Fig. 6 be the embodiment of the present invention 7 and embodiment 20,21 gained long-chain branching polypropylene obtain branched
The GPC curve of agent.
Detailed description of the invention
Below in conjunction with the accompanying drawing of the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clearly
Chu, it is fully described by, it is clear that described embodiment is only a part of embodiment of the present invention, and not
It it is whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under creative work premise, broadly falls into the scope of protection of the invention.
The invention provides a kind of long-chain branched polyolefins, described long-chain branched polyolefins is spheroidal particle；
The particle diameter of described spheroidal particle is 20～5000 μm, preferably 100～4000 μm, more preferably 500～3000
μm, is further preferably 1000～2000 μm；The packing density of particle of described long-chain branched polyolefins is
0.35～0.46g/cm3；The isotacticity of the main chain of described long-chain branched polyolefins is more than 90%.
In the present invention, described long-chain branched polyolefins is preferably long-chain branching polypropylene；Described long chain branching
Polyolefinic branched chain molecule amount is preferably 200～3500, and more preferably 500～3000 are further preferably
600～2500；The side chain degree of described long-chain branched polyolefins is preferably 0.5%～10%, more preferably
2%～8%.
Present invention also offers the preparation method of a kind of above-mentioned long-chain branched polyolefins, including:
Under conditions of titanium system Ziegler-Natta catalyst, promoter exist with branching agent, alkene is entered
The poly-body of row closes reaction, obtains long-chain branched polyolefins；Described titanium system Ziegler-Natta catalyst is with formula (I)
Shown phosphate compound is internal electron donor；Described branching agent is unsaturated chain alkyl aluminum；
Wherein, R1、R2With R3It is each independently alkyl or aromatic radical；Described alkyl is C1's～C10
Alkyl；Described aromatic radical is phenyl, the substituted phenyl of alkyl or the substituted phenyl of alkoxyl.
Wherein, described titanium system Ziegler-Natta catalyst is prepared the most in accordance with the following methods: by titanium
Chloride, magnesium-containing compound mix in organic solvent with the phosphate compound shown in formula (I), heating
Reaction, obtains titanium system Ziegler-Natta catalyst.
The chloride of the titanium that the chloride of described titanium is well known to those skilled in the art, it is special to there is no
Limit, the present invention is preferably TiCl3、TiCl4With TiOCl3In one or more.
The magnesium-containing compound that described magnesium-containing compound is well known to those skilled in the art, it is special to there is no
Limit, the present invention is preferably the aluminum chloride containing magnesium and/or the alkoxide compound containing magnesium, more preferably
MgCl2、Mg(OEt)2With Mg (OBu)2In one or more.
Shown in described phosphate compound such as formula (I), wherein, R1、R2With R3It is each independently alkyl
Or aromatic radical；Described alkyl is the alkyl of the alkyl of C1～C10, preferably C1～C6, more preferably C1～C4
Alkyl；Described aromatic radical is phenyl, the substituted phenyl of alkyl or the substituted phenyl of alkoxyl, is preferably
Phenyl, the substituted phenyl of alkyl of C1～C10 or the substituted phenyl of alkoxyl of C1～C10, more preferably
Phenyl, the substituted phenyl of alkyl of C1～C6 or the substituted phenyl of alkoxyl of C1～C6, be further preferably benzene
Base, the substituted phenyl of alkyl of C1～C4 or the substituted phenyl of alkoxyl of C1～C4.In the present invention, institute
State phosphate compound and be most preferably trimethyl phosphate, triethyl phosphate, tributyl phosphate, phosphoric acid triphen
Ester, tri-p-cresyl phosphate, tri-o-cresyl phcsphate, tri m tolyl phosphate, tricresyl phosphate p-isopropyl
Phenyl ester, tricresyl phosphate to tert-butyl group phenyl ester, tricresyl phosphate to methoxyl group phenyl ester, phosphoric acid pheiiyldimetliyl ester, phosphorus
Acid diethylamino phenyl base ester, phosphoric acid phenyl dibutyl ester, diphenyl phosphate methyl ester, diphenyl phosphate ethyl
Ester, diphenyl phosphate butyl ester, phosphoric acid p-methylphenyl dimethyl ester, phosphoric acid p-methylphenyl diethylester, phosphoric acid
P-methylphenyl dibutyl ester, phosphoric acid o-tolyl dimethyl ester, phosphoric acid o-tolyl diethylester, phosphoric acid neighbour's toluene
Tolyl two fourth between tolyl diethylester, phosphoric acid between tolyl dimethyl ester, phosphoric acid between base dibutyl ester, phosphoric acid
Ester, di(2-ethylhexyl)phosphate p-methylphenyl methyl ester, di(2-ethylhexyl)phosphate p-methylphenyl ethyl ester, di(2-ethylhexyl)phosphate p-methylphenyl butyl ester, phosphorus
Acid is between di-o-tolyl methyl ester, di(2-ethylhexyl)phosphate o-tolyl ethyl ester, di(2-ethylhexyl)phosphate o-tolyl butyl ester, di(2-ethylhexyl)phosphate
Between tolyl methyl ester, di(2-ethylhexyl)phosphate between tolyl ethyl ester, di(2-ethylhexyl)phosphate tolyl butyl ester, di(2-ethylhexyl)phosphate to isopropylbenzene
Base methyl ester, di(2-ethylhexyl)phosphate to cumenyl ethyl ester, di(2-ethylhexyl)phosphate to cumenyl butyl ester, phosphoric acid to cumenyl
Dimethyl ester, phosphoric acid to cumenyl diethylester, phosphoric acid to cumenyl dibutyl ester, phosphoric acid to tert-butyl benzene
Base dimethyl ester, phosphoric acid to tert-butyl-phenyl diethylester, phosphoric acid to tert-butyl-phenyl dibutyl ester, di(2-ethylhexyl)phosphate pair
Tert-butyl-phenyl methyl ester, di(2-ethylhexyl)phosphate to tert-butyl-phenyl ethyl ester, di(2-ethylhexyl)phosphate to tert-butyl-phenyl butyl ester, phosphorus
Acid phenyl two to toluene ester, phosphoric acid phenyl two to isopropyl phenyl ester, phosphoric acid phenyl two to 2-methyl-2-phenylpropane ester, phosphoric acid
P-methylphenyl diphenyl ester, phosphoric acid p-methylphenyl p-Diisopropylbenzene base ester, phosphoric acid p-methylphenyl are to two 2-methyl-2-phenylpropanes
Base ester, phosphoric acid o-tolyl p-Diisopropylbenzene base ester, phosphoric acid o-tolyl are to two 2-methyl-2-phenylpropane base esters, phosphoric acid
Between between tolyl p-Diisopropylbenzene base ester, phosphoric acid tolyl to two 2-methyl-2-phenylpropane base esters, phosphoric acid to isopropylbenzene two
P-methylphenyl ester, phosphoric acid to isopropylbenzene di-o-tolyl ester, phosphoric acid to isopropylbenzene two tolyl esters, phosphorus
Acid to isopropylbenzene two to phenylester and phosphoric acid to isopropylbenzene two to one or more in tert-butyl-phenyl ester.
The chloride of described titanium, magnesium-containing compound are excellent with the mass ratio of the phosphate compound shown in formula (I)
Elect as (200～800): (1～20): (1～5), more preferably (200～700): (5～20):
(1～5), are further preferably (300～500): (5～15): (2～5)；The present invention provide some
The chloride of titanium described in embodiment, magnesium-containing compound and the quality of the phosphate compound shown in formula (I)
Ratio preferably 415.2:10:2.726.
The chloride of partial-titanium is the most first cooled down by the present invention, is preferably cooled to 0 DEG C～-30 DEG C, adds
Magnesium-containing compound, preferably reaction 0.5～2h, slowly heats up, is preferably warming up to 50 DEG C～90 DEG C, more preferably
It is warming up to 70 DEG C～90 DEG C, adds the phosphate compound shown in formula (I) and organic solvent, preferably react
0.3～1h, then reacting by heating, it is preferably heated to 100 DEG C～150 DEG C, is more preferably heated to 100 DEG C～120 DEG C,
Reaction 1～3h, adds the chloride of remaining titanium, reacting by heating, is preferably heated to 100 DEG C after filtration
～150 DEG C, more preferably it is heated to 100 DEG C～120 DEG C, reacts 1～3h, obtain titanium system Ziegler-Natta and urge
Agent.
The Functionality, quality and appealing design of described titanium system Ziegler-Natta catalyst elects the 0.001%～0.1% of alkene quality as, more
It is preferably 0.005%～0.05%, is further preferably 0.005%～0.03%, most preferably 0.005%～0.01%；
In some embodiments that the present invention provides, the Functionality, quality and appealing design of described titanium system Ziegler-Natta catalyst elects alkene as
The 0.008% of hydrocarbonaceous amount；In some embodiments that the present invention provides, described titanium system Ziegler-Natta urges
The Functionality, quality and appealing design of agent elects the 0.006% of alkene quality as；In some embodiments that the present invention provides, described
The Functionality, quality and appealing design of titanium system Ziegler-Natta catalyst elects the 0.005% of alkene quality as；There is provided in the present invention
In some embodiments, the Functionality, quality and appealing design of described titanium system Ziegler-Natta catalyst elects alkene quality as
00047%；In some embodiments that the present invention provides, the matter of described titanium system Ziegler-Natta catalyst
Amount is preferably the 0.004% of alkene quality；In some embodiments that the present invention provides, described titanium system
The Functionality, quality and appealing design of Ziegler-Natta catalyst elects the 0.0066% of alkene quality as；The present invention provide some
In embodiment, the Functionality, quality and appealing design of described titanium system Ziegler-Natta catalyst elects the 0.008% of alkene quality as；
In other embodiments that the present invention provides, the Functionality, quality and appealing design of described titanium system Ziegler-Natta catalyst is elected as
The 0.0093% of alkene quality.
The promoter that described promoter is well known to those skilled in the art, there is no special restriction,
Preferred alkyl aluminum compound and/or alkyl-al hydride in the present invention, more preferably trimethyl aluminium, triethyl aluminum,
Triisobutyl aluminium, diisobutyl hydrogen aluminum, diethylhydroaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride with times
One or more in sesquialter ethylmercury chloride aluminum (sesquialter aluminum)；The Functionality, quality and appealing design of described promoter elects alkene as
The 0.01%～1% of hydrocarbonaceous amount, more preferably 0.01%～0.5%, be further preferably 0.05%～0.2%；At this
In some embodiments of bright offer, the Functionality, quality and appealing design of described promoter elects the 0.16% of alkene quality as；At this
In some embodiments that invention provides, the Functionality, quality and appealing design of described promoter elects the 0.1% of alkene quality as；?
In other embodiments that the present invention provides, the Functionality, quality and appealing design of described promoter elects alkene quality as
0.08%.
Described branching agent is unsaturated chain alkyl aluminum, and it is unsaturated long that it is well known to those skilled in the art
Alkyl group aluminum, there is no special restriction, the molecular weight of heretofore described unsaturated chain alkyl aluminum
Being preferably 200～3500, more preferably 500～3000, be further preferably 600～2500；Described unsaturated long-chain
The source of alkyl aluminum can be commercially available, it is possible to for self-control, there is no special restriction, in the present invention preferably according to
Following methods is prepared: rare earth compound, diolefin, metallic aluminium organic compound and chloride are mixed
Close, react, obtain unsaturated chain alkyl aluminum；Described rare earth compound include rare earth carboxylate,
Rare earth superphosphate, rare earth acidity phosphonate and alkoxy rare-earth.
Rare earth compound, diolefin and metallic aluminium organic compound are preferably mixed by the present invention, react,
Obtain midbody product；Described midbody product is mixed with chloride, reacts, obtain unsaturation
Chain alkyl aluminum.
In the present invention, described rare earth compound includes rare earth carboxylate, rare earth superphosphate, rare earth
Acid phosphonate and alkoxy rare-earth；Preferably include neodymium caprate Nd (vers)3, neodymium iso-octanate Nd (EHA)3,
Lanthanum naphthenate La (naph)3, (2-ethylhexyl) acid neodymium Nd (P204)3, (2-ethylhexyl) phosphonic acids neodymium list-2-second
Base ester Nd (P507)3, ethyoxyl neodymium, positive propoxy neodymium, isopropoxy lanthanum, isobutoxy shirt, tertiary fourth
One or more in epoxide neodymium and different octyloxy neodymium.
In the present invention, described diolefin includes conjugated diolefin, preferably includes butadiene and/or isoamyl two
Alkene；Described diolefin is preferably (10～200) with the mol ratio of rare earth compound: 1, more preferably
(50～200): 1；In some embodiments that the present invention provides, described diolefin rubs with rare earth compound
You are ratio preferably 50:1；In other embodiments that the present invention provides, described diolefin and rare earth chemical combination
The mol ratio of thing is preferably 200:1.
In the present invention, described metallic aluminium organic compound is preferably trialkylaluminium and/or alkyl aluminium hydride,
More preferably triisobutyl aluminium, trioctylaluminum, dimethyl hydrogenated aluminum, diisobutylaluminium hydride, diethyl
Aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, di-n-hexyl aluminum hydride, dicyclohexyl hydrogen
Change one or more in aluminum, di-n-octyl aluminum hydride and triethyl aluminum；Described metallic aluminium organic compound
It is preferably (10～60): 1 with the mol ratio of rare earth compound；In some embodiments that the present invention provides,
Described metallic aluminium organic compound is preferably 10:1 with the mol ratio of rare earth compound；There is provided in the present invention
In other embodiments, described metallic aluminium organic compound is preferably 60:1 with the mol ratio of rare earth compound.
In the present invention, described chloride preferably include a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, times
Half aluminium ethide, tertiary butyl chloride, benzyl chloride, allyl chloride, methyl trichlorosilane, dimethyldichlorosilane,
One or more in trim,ethylchlorosilane and Silicon chloride.；Described chloride and rare earth compound mole
Than being preferably (1～5): 1, more preferably (1～3): 1, it is further preferably (1～2): 1；At this
In some embodiments of bright offer, described chloride is preferably 2:1 with the mol ratio of rare earth compound；At this
In other embodiments that invention provides, described chloride is preferably 1:1 with the mol ratio of rare earth compound.
In the present invention, the total time preparing described unsaturated chain alkyl aluminum is preferably 2～12h, system
The response time of standby described midbody product is preferably 0～3h, more preferably 0.1～2h, most preferably
0.25～2h；The reaction temperature preparing described midbody product is preferably 0 DEG C～80 DEG C, more preferably 0 DEG C
～60 DEG C, most preferably 0 DEG C～50 DEG C；In some embodiments that the present invention provides, prepare and produce in the middle of described
The reaction temperature of thing is preferably 0 DEG C；By the reaction of the unsaturated chain alkyl aluminum of described midbody product preparation
Time is preferably 2～10h, more preferably 3～9h, most preferably 4～8h；The present invention provide some
In embodiment, the time of the reaction of the unsaturated chain alkyl aluminum of described midbody product preparation it is preferably 5h；
In other embodiments that the present invention provides, by the unsaturated chain alkyl aluminum of described midbody product preparation
Time of reaction be preferably 7h；By the reaction of the unsaturated chain alkyl aluminum of described midbody product preparation
Temperature is preferably 20 DEG C～80 DEG C, more preferably 30 DEG C～60 DEG C；In some embodiments that the present invention provides,
The reaction temperature of the unsaturated chain alkyl aluminum of preparation is preferably 80 DEG C.
The present invention preferably carries out the preparation of described unsaturated chain alkyl aluminum under protective gas atmosphere；Preferably
The reaction preparing long-chain unsaturated alkyl aluminum be solution polymerization；The solvent of described reaction is C4～C10
Alkane and C6～C24 aromatic hydrocarbon in one or more.
Described unsaturated chain alkyl aluminum is preferably 0.5%～10% with the mass ratio of alkene, is preferably
1%～8%, it is further preferably 2%～6%.
Under conditions of titanium system Ziegler-Natta catalyst, promoter exist with branching agent, alkene is entered
Row bulk polymerization；Wherein, the alkene that described alkene is well known to those skilled in the art, there is no
Special restriction, is preferably propylene in the present invention.The present invention is preferably additionally added dimethoxydiphenylsilane,
The polyolefinic isotacticity of long-chain can be improved.
Heretofore described polyreaction is bulk polymerization, and the temperature of described polyreaction is preferably 0 DEG C
～120 DEG C, more preferably 30 DEG C～120 DEG C, be further preferably 30 DEG C～80 DEG C；The present invention provide some
In embodiment, the temperature of described polyreaction is preferably 80 DEG C；The time of described polyreaction is preferably
0.5～2h；In some embodiments that the present invention provides, the time of described polyreaction is preferably 40min；
In some embodiments that the present invention provides, the time of described polyreaction is preferably 65min；At this
In some embodiments of bright offer, the time of described polyreaction is preferably 30min；There is provided in the present invention
Some embodiments in, the time of described polyreaction is preferably 60min；The present invention provide another
In a little embodiments, the time of described polyreaction is preferably 100min.The present invention uses polymerisation in bulk or silt
Slurry polymerisation step prepares long-chain branched polyolefins, has technique simple, excellent to polyplant strong adaptability etc.
Point.
Titanium system Ziegler-Natta catalyst that the present invention uses phosphate compound to be internal electron donor, with not
Saturated chain alkyl aluminum is branching agent to long-chain esterification polyolefin have branch lengths with
Change is counted out adjustable, the advantage of branched chain molecule amount narrowly distributing, meanwhile, and unsaturated chain alkyl aluminum and main chain
Polyolefin has the preferable compatibility, and containing a number of double bond in side chain, so that long-chain props up
Change polyolefin and can carry out humidity crosslinking in the course of processing, can further improve the molten of long-chain branched polyolefins
Body intensity and polymer impact performance.
In order to further illustrate the present invention, a kind of long chain branching present invention provided below in conjunction with embodiment
Polyolefin and preparation method thereof is described in detail.
Reagent used in following example is commercially available.
Embodiment 1
Under nitrogen protection, in churned mechanically there-necked flask, 120ml TiCl is added4, it is cooled to
-22 DEG C, add 10g ball type carrier MgCl2, react 1h, be to slowly warm up to 80 DEG C, add 2.726g
Tricresyl phosphate and 2.058g diisobutyl phthalate, react 0.5h, be to slowly warm up to 120 DEG C,
Filter after reaction 2h, add the TiCl of 100ml4, it is warming up to 120 DEG C, reacts 2h, filter, with boiling
Rise hexane washing in hexane without Cl-, obtain titanium system Ziegler-Natta catalyst.
Being analyzed obtaining titanium system Ziegler-Natta catalyst in embodiment 1, obtaining its component is:
Ti:2.54%, TMPP tricresyl phosphate: 5.9%, TIBP diisobutyl phthalate: 6.4%.
Embodiment 2
Under nitrogen protection, in churned mechanically there-necked flask, 120ml TiCl is added4, it is cooled to
-22 DEG C, add 10g ball type carrier MgCl2, react 1h, be to slowly warm up to 80 DEG C, add 2.726g
Tricresyl phosphate, reacts 0.5h, is to slowly warm up to 120 DEG C, filters, add 100ml after reaction 2h
TiCl4, it is warming up to 120 DEG C, reacts 2h, filter, wash to hexane without Cl with boiling hexane-For
Only, titanium system Ziegler-Natta catalyst is obtained.
Being analyzed obtaining titanium system Ziegler-Natta catalyst in embodiment 2, obtaining its component is:
Ti:2.54%, TMPP tricresyl phosphate: 11.2%.
Comparative example 1
Under nitrogen protection, in churned mechanically there-necked flask, 120ml TiCl is added4, it is cooled to
-22 DEG C, add 10g ball type carrier MgCl2, react 1h, be to slowly warm up to 80 DEG C, add 2.058g
Diisobutyl phthalate, reacts 0.5h, is to slowly warm up to 120 DEG C, filters, add after reaction 2h
The TiCl of 100ml4, it is warming up to 120 DEG C, reacts 2h, filter, wash to nothing in hexane with boiling hexane
Cl-Till, the titanium system Ziegler-Natta catalyst obtained.
Being analyzed the titanium system Ziegler-Natta catalyst obtained in comparative example 1, obtaining its component is:
Ti:2.54%, TIBP:10.8%.
Embodiment 3～6
Under nitrogen protection, in dry polymer reactor, it is sequentially added into neodymium according to the component of table 1
Compound (A), butadiene (B) and hydrogen aluminum (C), the mol ratio of B Yu A is 50:1, C and A
Mol ratio is 10:1, reacts 2h, add D at 0 DEG C, and wherein the mol ratio of D Yu A is 2:1,
React 5h at 50 DEG C, obtain branching agent.
The branching agent obtained in embodiment 3～6 is analyzed, obtains the results are shown in Table 1.
The microstructure of branching agent use Germany's Bruker company Vertex-70FTIR type infrared spectrometer and
Germany's Bruker company AVANCE400 type NMR spectrometer with superconducting magnet measures；Molecular weight and molecualr weight distribution
TDA302 type chromatograph of gel permeation (GPC) using Viscotek company of the U.S. measures, tetrahydrochysene furan
Mutter for flowing phase, Narrow distribution polystyrene is standard specimen, and flow velocity is 1.0ml/min, test temperature be 30 DEG C.
The kind of component and gained branching agent analysis result in table 1 embodiment 3～6
Embodiment 7～9
Under nitrogen protection, in dry polymer reactor, according to the component of table 2 be sequentially added into A, B,
C and D, wherein B component is isoprene, and the mol ratio of B Yu A is the mol ratio of 200:1, C and A
Mol ratio for 60:1, D and A is 1:1, reacts 7h, obtain branching agent at 80 DEG C.
The branching agent obtained in embodiment 7～9 is analyzed, obtains the results are shown in Table 2.
Each constituent species and the analysis result of gained branching agent in table 2 embodiment 7～9
Note: the polymer chain number that average each active center produces: Np=B/A × 68 × Yield/Mn。
Embodiment 10
500ml propylene, 1.5ml tri-it is sequentially added in the 2L bulk polymerizer being sufficiently displaced from through nitrogen
Aluminium ethide (TEA), 0.6ml dimethoxydiphenylsilane (DDS), obtain in embodiment 3 props up
The catalyst 63.2mg that agent 15ml, embodiment 1 obtain, finally with 1L propylene flushing line, opens
Dynamic stirring, speed setting is 200r/min, 80 DEG C of reaction 90min, obtains long-chain branching polypropylene 610g.
The performance of the long-chain branching polypropylene obtained in embodiment 10 is tested, obtains the results are shown in Table 3.
Polymer particle diameter 2100 μm, bulk density 0.43g/cm3, isotacticity 96.2%, the degree of branching 1.5%
Embodiment 11
Add branching agent 30ml, the catalyst 45mg obtained in embodiment 1 obtained in embodiment 3,
TEA 1ml, remaining is with embodiment 10.
The performance of the long-chain branching polypropylene obtained in embodiment 11 is tested, obtains the results are shown in Table 3.
Polymer particle diameter 2500 μm, bulk density 0.40g/cm3, isotacticity 93.2%, side chain degree 2.5%
Embodiment 12
Add the branching agent 45ml, the catalyst 39.8mg obtained in embodiment 1 obtained in embodiment 3
Remaining is with embodiment 10 outward.
The performance of the long-chain branching polypropylene obtained in embodiment 12 is tested, obtains the results are shown in Table 3.
Utilize the senior flow graph of rheologic, measure the method for method of polymer low frequency range storage modulus to enforcement
The rheological property of the long-chain branching polypropylene obtained in example 10～12 is tested, and obtains its rheological curve figure
As shown in FIG. 1 to 3, test condition: 200 DEG C, frequency scanning, scope is from 10-2-100r/s。
Polymer particle diameter 3000 μm, bulk density 0.40g/cm3, isotacticity 92.5%, side chain degree 5.0%
Comparative example 2
It is sequentially added into 1500ml propylene, 1.5ml in the 2L bulk polymerizer being sufficiently displaced from through nitrogen
TEA, 0.6ml DDS, embodiment 3 catalyst 73.9mg, finally with 1L propylene flushing line,
Starting stirring, speed setting is 200r/min, 80 DEG C of reaction 90min, obtains polypropylene 550g.
The performance of the long-chain branching polypropylene obtained in comparative example 2 is tested, obtains the results are shown in Table 3.
Utilize the rheological characteristic of the rheologic senior flow graph long-chain branching polypropylene to obtaining in comparative example 2
Can test, obtain its rheological curve figure as shown in FIG. 1 to 3.
Particle diameter 3200 μm, bulk density 0.46%, isotacticity 98.2%.
Embodiment 13
The 2L bulk polymerizer being sufficiently displaced from through nitrogen is sequentially added into 500ml propylene, 1ml TEA,
0.6ml DDS, the catalyst 40mg that the branching agent 50ml obtained in embodiment 5, embodiment 1 obtain,
Finally with 1L propylene flushing line, starting stirring, speed setting is 200r/min, 80 DEG C of reaction 40min,
Obtain long-chain branching polypropylene 390g.
The performance of the long-chain branching polypropylene obtained in embodiment 13 is tested, obtains the results are shown in Table 3.
Particle diameter 2000 μm, bulk density 0.40%, isotacticity 91.5%, side chain degree 5.4%
Embodiment 14
The 2L bulk polymerizer being sufficiently displaced from through nitrogen is sequentially added into 500ml propylene, 1ml TEA,
0.6ml DDS, the catalyst 35.6 obtained in the branching agent 100ml obtained in embodiment 5, embodiment 1
Mg, finally with 1L propylene flushing line, starts stirring, and speed setting is 200r/min, 80 DEG C of reactions
40min, obtains long-chain branching polypropylene 382g.
The performance of the long-chain branching polypropylene obtained in embodiment 14 is tested, obtains the results are shown in Table 3.
Embodiment 15
The 2L bulk polymerizer being sufficiently displaced from through nitrogen is sequentially added into 500ml propylene, 1ml TEA,
0.6ml DDS, the catalyst 30.2 obtained in the branching agent 100ml obtained in embodiment 6, embodiment 1
Mg, finally with 1L propylene flushing line, starts stirring, and speed setting is 200r/min, 80 DEG C of reactions
40min, obtains long-chain branching polypropylene 388g.
The performance of the long-chain branching polypropylene obtained in embodiment 15 is tested, obtains the results are shown in Table 3.
Embodiment 16
The 2L bulk polymerizer being sufficiently displaced from through nitrogen is sequentially added into 500ml propylene, 1ml TEA,
0.6ml DDS, the catalyst 40.5 obtained in the branching agent 50ml obtained in embodiment 6, embodiment 1
Mg, finally with 1L propylene flushing line, starts stirring, and speed setting is 200r/min, 80 DEG C of reactions
40min, obtains long-chain branching polypropylene 340g.
The performance of the long-chain branching polypropylene obtained in embodiment 16 is tested, obtains the results are shown in Table 3.
Embodiment 17
The 2L bulk polymerizer being sufficiently displaced from through nitrogen is sequentially added into 500ml propylene, 1ml TEA,
0.6mlDDS, the branching agent 150ml obtained in embodiment 7, embodiment 1 catalyst 40mg,
Finally with 1L propylene flushing line, hydrogenation 0.01Mpa.Starting stirring, speed setting is 200r/min,
80 DEG C of reaction 65min, obtain long-chain branching polypropylene 395g.
The performance of the long-chain branching polypropylene obtained in embodiment 17 is tested, obtains the results are shown in Table 3.
Embodiment 18
It is sequentially added into 500ml propylene, 0.8ml in the 2L bulk polymerizer being sufficiently displaced from through nitrogen
TEA, 0.6ml DDS, the catalysis obtained in the branching agent 40ml obtained in embodiment 7, embodiment 1
Agent 50mg, finally with 1L propylene flushing line, hydrogenation 0.01Mpa.Start stirring, speed setting
For 200r/min, 80 DEG C of reaction 90min, obtain long-chain branching polypropylene 95g.
The performance of the long-chain branching polypropylene obtained in embodiment 18 is tested, obtains the results are shown in Table 3.
Embodiment 19
Add in embodiment 7 the branching agent 100ml, the embodiment 1 that obtain catalyst 70mg, remaining
Condition is with embodiment 18.
The performance of the long-chain branching polypropylene obtained in embodiment 19 is tested, obtains the results are shown in Table 3.
Embodiment 20
It is sequentially added into 500ml propylene, 0.8ml in the 2L bulk polymerizer being sufficiently displaced from through nitrogen
TEA, 0.6ml DDS, the catalysis obtained in the branching agent 40ml obtained in embodiment 8, embodiment 1
Agent 70mg, finally with 1L propylene flushing line, hydrogenation 0.01Mpa.Start stirring, speed setting
For 200r/min, 80 DEG C of reaction 40min, obtain long-chain branching polypropylene 485g.
The performance of the long-chain branching polypropylene obtained in embodiment 20 is tested, obtains the results are shown in Table 3.
Embodiment 21
It is sequentially added into 500ml propylene, 0.8ml in the 2L bulk polymerizer being sufficiently displaced from through nitrogen
TEA, 0.6ml DDS, the catalysis obtained in the branching agent 100ml obtained in embodiment 8, embodiment 1
Agent 50mg, finally with 1L propylene flushing line, starts stirring, and speed setting is 200r/min, 80 DEG C
Reaction 100min, obtains long-chain branching polypropylene 577g.
The performance of the long-chain branching polypropylene obtained in embodiment 21 is tested, obtains the results are shown in Table 3.
Embodiment 22
It is sequentially added into 500ml propylene, 0.8ml in the 2L bulk polymerizer being sufficiently displaced from through nitrogen
TEA, 0.6ml DDS, the catalysis obtained in the branching agent 40ml obtained in embodiment 9, embodiment 1
Agent 60mg, finally with 1L propylene flushing line, starts stirring, and speed setting is 200r/min, 80 DEG C
Reaction 30min, obtains long-chain branching polypropylene 550g.
The performance of the long-chain branching polypropylene obtained in embodiment 22 is tested, obtains the results are shown in Table 3.
Embodiment 23
It is sequentially added into 500ml propylene, 0.8ml in the 2L bulk polymerizer being sufficiently displaced from through nitrogen
TEA, 0.6ml DDS, the catalysis obtained in the branching agent 60ml obtained in embodiment 9, embodiment 1
Agent 50mg, finally with 1L propylene flushing line, starts stirring, and speed setting is 200r/min, 80 DEG C
Reaction 60min, obtains long-chain branching polypropylene 220g.
The performance of the long-chain branching polypropylene obtained in embodiment 23 is tested, obtains the results are shown in Table 3.
Table 3 long-chain branching polypropylene mechanical experimental results
Claims (10)
1. the preparation method of a long-chain branched polyolefins, it is characterised in that including:
Under conditions of titanium system Ziegler-Natta catalyst, promoter exist with branching agent, alkene is entered
Row bulk polymerization, obtains long-chain branched polyolefins；Described titanium system Ziegler-Natta catalyst is with formula (I)
Shown phosphate compound is internal electron donor；Described branching agent is unsaturated chain alkyl aluminum；
Wherein, R1、R2With R3It is each independently alkyl or aromatic radical；Described alkyl is C1's～C10
Alkyl；Described aromatic radical is phenyl, the substituted phenyl of alkyl or the substituted phenyl of alkoxyl.
Preparation method the most according to claim 1, it is characterised in that described titanium system Ziegler-Natta
Catalyst is prepared in accordance with the following methods:
By the chloride of titanium, magnesium-containing compound with the phosphate compound shown in formula (I) in organic solvent
Mixing, reacting by heating, obtain titanium system Ziegler-Natta catalyst.
Preparation method the most according to claim 1, it is characterised in that described titanium system Ziegler-Natta
The quality of catalyst is the 0.001%～0.1% of alkene quality.
Preparation method the most according to claim 1, it is characterised in that described promoter is selected from three
Aluminium methyl, triethyl aluminum, triisobutyl aluminium, diisobutyl hydrogen aluminum, diethylhydroaluminum, a chlorine diethyl
Aluminum, ethyl aluminum dichloride and one or more in sesquialter ethylmercury chloride aluminum.
Preparation method the most according to claim 1, it is characterised in that the quality of described promoter
For alkene quality 0.01%～1%.
Preparation method the most according to claim 1, it is characterised in that the molecular weight of described branching agent
Being 200～3500, molecular weight distributing index is less than 2.0.
Preparation method the most according to claim 1, it is characterised in that described branching agent is according to following
Prepared by method:
Rare earth compound, diolefin, alkyl aluminum and chloride are mixed, reacts, obtain unsaturation
Chain alkyl aluminum；Described rare earth compound includes that rare earth carboxylate, rare earth superphosphate, rare earth are acid
Phosphonate and alkoxy rare-earth；Described diolefin is (50～1000) with the mol ratio of rare earth compound: 1.
Preparation method the most according to claim 7, it is characterised in that described reaction is polymerisation in solution
Reaction；The solvent of described reaction is the alkane of C4～C10 and one or more in the aromatic hydrocarbon of C6～C24.
9. the long-chain branched polyolefins prepared by claim 1～8 any one, it is characterised in that
Described long-chain branched polyolefins is spheroidal particle；The particle diameter of described spheroidal particle is 20～5000 μm；Described
The packing density of particle of long-chain branched polyolefins is 0.35～0.46g/cm3；The master of described long-chain branched polyolefins
The isotacticity of chain is more than 90%.
Long-chain branched polyolefins the most according to claim 9, it is characterised in that described long-chain props up
Changing polyolefinic branched chain molecule amount is 200～3500；The side chain degree of described long-chain branched polyolefins is
0.5%～10%.
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| CN113773423A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Solid catalyst component for preparing olefin polymer and application thereof |
| CN113773425A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and application thereof |
| CN116178596A (en) * | 2023-01-30 | 2023-05-30 | 国家石油天然气管网集团有限公司 | Preparation method of ultrahigh molecular weight multi-arm polyolefin |
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| CN1974612A (en) * | 2006-12-15 | 2007-06-06 | 中国科学院长春应用化学研究所 | Application of phosphate ester compound |
| CN101125898A (en) * | 2007-07-19 | 2008-02-20 | 中国科学院长春应用化学研究所 | Catalyst used for synthesizing polypropylene with wide molecular weight distribution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974612A (en) * | 2006-12-15 | 2007-06-06 | 中国科学院长春应用化学研究所 | Application of phosphate ester compound |
| CN101125898A (en) * | 2007-07-19 | 2008-02-20 | 中国科学院长春应用化学研究所 | Catalyst used for synthesizing polypropylene with wide molecular weight distribution |
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| CN113773423A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Solid catalyst component for preparing olefin polymer and application thereof |
| CN113773425A (en) * | 2020-06-09 | 2021-12-10 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and application thereof |
| CN116178596A (en) * | 2023-01-30 | 2023-05-30 | 国家石油天然气管网集团有限公司 | Preparation method of ultrahigh molecular weight multi-arm polyolefin |
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