CN106589183A - Olefin polymer and preparation method thereof - Google Patents
Olefin polymer and preparation method thereof Download PDFInfo
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- CN106589183A CN106589183A CN201510661256.1A CN201510661256A CN106589183A CN 106589183 A CN106589183 A CN 106589183A CN 201510661256 A CN201510661256 A CN 201510661256A CN 106589183 A CN106589183 A CN 106589183A
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- DDQXBDLAGHZBMP-UHFFFAOYSA-N CCC(C)CC1CCCCC1 Chemical compound CCC(C)CC1CCCCC1 DDQXBDLAGHZBMP-UHFFFAOYSA-N 0.000 description 1
- 0 CCC=CC[S-][N+](C)(*)C* Chemical compound CCC=CC[S-][N+](C)(*)C* 0.000 description 1
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Abstract
The present invention discloses a syndiotactic polymer, which has a structure formula comprising a monomer unit represented by a formula I and an optional monomer unit represented by a formula II, wherein R is a hydrogen atom or C1-C30 alkyl. The present invention further relates to a preparation method of the syndiotactic polymer. According to the present invention, the polymer has the syndiotactic structure, such that the polymer has the high melting point of higher than 180 DEG C, and further has advantages of good heat resistance and high thermal decomposition temperature. The formulas I and II are defined in the specification.
Description
Technical field
The invention belongs to be catalyzed and field of olefin polymerisation, it is related to polymer and its preparation side of a kind of allyl cyclohexane
Method；Alternatively contain other olefin units in polymer, polymer is syndiotactic structure, and the polymer has very high fusing point.
Technical background
The single centre transition-metal catalyst of olefin polymerization recent decades be always Organometallic Chemistry, catalysis learn,
The study hotspot of polymer chemistry and materialogy.Using this kind of catalyst, molecular weight distribution and chemical composition distribution can be obtained
All well-proportioned olefin polymer, at the same the molecular structure and molecular weight of polymer can by adjustment catalyst structure height can
Control.By single-site catalysts, the not getable olefin polymer of traditional Ziegler-Natta catalyst can be obtained.
Between advise olefin polymer most disclosed in United States Patent (USP) US 3258455, this be Natta et al. pass through trichlorine
Change syndiotactic polypropylene prepared by titanium and diethyl aluminum chloride catalysis, later, Natta et al. uses vanadium series catalyst again, organic
Syndiotactic polypropylene (US 3305538) is prepared in the presence of aluminium compound.In patent document US 3364190, using titanium vanadium
Mixed system, in the presence of various aluminium compounds and some other lewis base, be prepared for syndiotactic polypropylene.
So-called syndiotactic polypropylene, with common isotactic polypropylene is visibly different in structure and performance.In structure
Main difference is that the position of methyl is different, such as assume the methylene (CH for constituting main chain2) and methine (CH) in same
Plane, then the branched chain methyl (CH of isotactic polypropylene3) all in the side of plane, that is, be in together above plane or following；
And branched chain methyl (the CH of syndiotactic polypropylene3) then successively staggeredly above plane and following.Using Fischer projection formula table
Reach, isotactic polypropylene is represented by：
Letter therein " m " represents that the relation of two neighboring propylene units is isotactic.
And syndiotactic polypropylene is then expressed as：
Letter therein " r " represents that the relation of two neighboring propylene units is advised between being.
This structure at present generally by nuclear magnetic resonance C13 spectrum (13C-NMR) determine, generally n propylene list in polypropylene
The sequence of unit's composition becomes n tuples, generally can represent polyacrylic stereoregularity, such as binary m and r with n tuples, and three
Tuple mm, mr and rr.
In polyacrylic strand, it will usually there is stereoregular defect, for example, insert the mistake and direction of insertion of conformation
Mistake.For example in isotaxy, the vertical structure defect that a kind of possible insertion conformation mistake can be caused is represented by：
Wherein, after a propylene units make a mistake insertion, next propylene molecules will be according to original correct side
Formula is continued into, that is, corrected the insertion of mistake, to be caused in propylene sequences and advise conformation between continuous two " rr ", it is this to insert
Enter and be polymerized for activated centre control.And another kind of conformation is erroneously inserted available being expressed as：
In this case, after a propylene units make a mistake insertion, next propylene molecules will not be according to original
First correct way is continued into, and is to continue with, according to continuing into original contrary mode, causing in propylene sequences
One it is isolated between advise conformation " r ", it is this be inserted as chain end control polymerization.So, Study Polymer Melts chain structure and sequence are divided
Cloth is analyzed, and has critically important enlightenment to mechanism of polymerization.In the polymerization of activated centre control, " r " it is occur in pairs, seldom occur
Isolated " r " conformation.
Another kind of stereoregular defect has direction of insertion mistake to cause.Generally propylene molecules, in insertion, are all 1,
2- directions are inserted, mode as from beginning to end.But have indivedual propylene molecules and occur 2,1 and insert, cause head to link and
Tail tail chain connects, and structure is represented by：
As it appears from the above, carrying " * " propylene molecules be 2,1- anti-plugs.
When polypropylene has higher stereoregularity, either isotactic or between advise, polymer all can be vertical because of it
The order of structure and crystallization can be formed, so as to fusing point.Polyacrylic fusing point depend on stereoregulated type (isotactic or
Between advise), the height of regularity and defect number.Identical stereoregular type, regularity is higher, and fusing point is higher；Defect
Fewer, fusing point is higher.
1980, (Macromolecules, 1980,13,267) used the document that Zambelli is delivered13C-NMR is characterized
Polyacrylic syndiotactic structure.1988, (CN 89104461.2, J Am Chem Soc, 1988,110,6255) disclosed document
The metallocene catalyst of syndiotactic polyolefins is prepared, using the species catalyst, the polypropylene of normality between height can be successfully prepared
([rrrr]=0.86).Nineteen ninety, patent US5132381 is disclosed and prepares syndiotactic polypropylene using metallocene catalyst.Patent
CN91103928 discloses the method for preparing propylene and the syndiotactic copolymer of non-conjugated diene using metallocene catalyst.1991
Year, patent US 5369196 is prepared for syndiotactic polypropylene, a rule poly- (4-methyl-1-pentene) and a rule using metallocene catalyst
Poly- (3-methyl-1-butene), wherein syndiotactic polypropylene fusing point are 145 DEG C, a rule poly- (4-methyl-1-pentene) and advise poly- (3-
Methyl isophthalic acid-butylene) fusing point be above 200 DEG C.1993, patent 5391672 was disclosed using between metallocene catalyst preparation
Poly- (1- butylene), poly- (4-methyl-1-pentene), poly- (4- methyl isophthalic acids-hexene), the method for poly- (4- methyl isophthalic acids, 3- pentadienes) are advised,
The fusing point of wherein poly- (4-methyl-1-pentene) is 196.6 DEG C, and the fusing point of poly- (4- methyl isophthalic acids-hexene) is 146.6 DEG C.1997,
Document (Macromolecules 1997,30,2197) report is usediPr(Cp)(Flu)ZrCl2Catalysis propylene and other alkene are total to
Polymerization, including ethene, 1- butylene, 1- amylenes, 1- hexenes, 4-methyl-1-pentene, the species of co-monomer and containing in the copolymer
Amount all can have an impact to melting point polymer.2006, patent CN201110128933 disclosed the preparation of syndiotactic propylene copolymer
Method, comonomer is ethene and 1- butylene.2007, patent CN200780034550 disclosed syndiotactic polypropylene copolymer
Method, comonomer includes ethene, 1- butylene and non-conjugated diene.2010, patent CN201080058413 was disclosed and used
Transition-metal catalyst prepares the method for the liquid poly- (alpha-olefin) with syndiotactic structure, such as 1- decene, and this material can be with
As synthetic base oil.2010, patent CN201080057591 disclosed the syndiotactic copolymer of 4-methyl-1-pentene and propylene
Preparation method.It is 204 DEG C that [r] is the homopolymers fusing point of 98% 4-methyl-1-pentene.But show activity is very low, only
0.22kg/mol-Zr/hr, the insertion of a small amount of ethylene unit can significantly reduce the fusing point of polymer, and ethylene contents are less than
During 1mol%, between 190-200 DEG C, polymerization activity increases fusing point.2003, document was with Me2C(η5-C5H4)(η5-
C13H8)ZrCl2、Me2C(η5-C5H4)(η5-C29H36)ZrCl2And Me2Si(η1-N-tBu)(η1-C29H36)ZrCl2·OEt2To urge
Agent and carry out polymerization (the J Am Chem Soc 2005,127,9972), between acrylic polymers of propylene and 4-methyl-1-pentene
Rule five-tuple [rrrr] reach as high as 99%, and correspondence melting point polymer is 165 DEG C, and five yuan are advised between 4-methyl-1-pentene polymer
Group [rrrr] reaches as high as 97%, and correspondence melting point polymer is 215 DEG C.Research later (Macromolecules 2007,40,
5662) using these three catalyst researches propylene and higher alkene combined polymerization, including 4-methyl-1-pentene, 1- hexenes, 1-
Octene, 1- decene etc., with the increase of co-monomer content, [rrrr] is reduced, and [rmrr] content increases, and [rmmr] keeps substantially
It is constant.The reduction and catalyst of fusing point, monomeric species and content of monomer are all relevant.
Research is concentrated mainly on the polymerization of propylene and the polymerization of 4-methyl-1-pentene, and the melting point polymer of propylene is typically low
In 170 DEG C, 4-methyl-1-pentene melting point polymer is significantly larger than acrylic polymers, but conversion ratio is relatively low.
The content of the invention
For deficiency of the prior art, the application is desirable to provide a kind of polymer of syndiotactic structure.The polymer has
Higher fusing point and decomposition temperature.Present invention also offers the preparation method of the polymer, the polymer of the syndiotactic structure is used
It is prepared by the catalyst system and catalyzing of the olefinic polymerization of metallocene compound and alkylaluminoxane composition.Allyl cyclohexane is removed in the polymer
Outward, other olefinic monomers are also alternatively included.
According to an aspect of the invention, there is provided a kind of polymer of syndiotactic structure, its structural formula is included shown in Formulas I
Monomeric unit and optional Formula II shown in monomeric unit,
R is the alkyl of hydrogen atom or 1 to 30 carbon atoms in formula.
According to a specific embodiment of polymer of the present invention, R is the alkyl of hydrogen atom or 1 to 16 carbon atoms,
Such as the alkyl of 2-16 carbon atom.In a preferred example, R is hydrogen, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl
Base, the tert-butyl group, decyl or cetyl.
According to the present invention, " optional " is referred to and may or may not be present.Such as, " the knot shown in optional Formula II
Structure unit " refers to the monomeric unit that can have shown in Formula II, it is also possible to without the monomeric unit shown in Formula II.When containing Formula II institute
During the monomeric unit for showing, the syndiotactic polymer in the present invention, is a kind of syndiotactic copolymer.In a specific embodiment, institute
The monomeric unit and the mol ratio of the monomeric unit shown in Formulas I stated shown in Formula II is 0:1 to 1:1, preferably 1:100 to 1:1, such as 1:
99 to 1:4.
According to another specific embodiment of Inventive polymers, the polymer average molecular weight is 10,000 to 500,000, excellent
Select 20,000-20 ten thousand.Molecular weight distributing index (middle finger Mw/Mn of the present invention) is 1.5-3.5, preferred 2.0-3.0.
According to the polymer of syndiotactic structure provided by the present invention, its fusing point is high, and higher than 180 DEG C, and heat endurance is good, heat
Weightless decomposition temperature is high.The polymer is the macromolecular material of heat resistance.
According to another aspect of the present invention, a kind of method of the polymer for preparing above-mentioned syndiotactic structure is additionally provided,
Including by allyl cyclohexane and optional CH2CHR compounds are polymerized in the presence of catalyst system, obtain it is described between
The copolymer of rule structure, the catalyst system includes the transistion metal compound and alkylaluminoxane shown in formula III,
Wherein, R1For alkyl, two of which R1It is bonding cyclic or not cyclic；R2And R3It independently is hydrogen atom or alkyl；
X is halogen atom or alkyl；The restriction of R is with above-mentioned polymer.
According to another preferred embodiment of the inventive method, R1For C5-C15Aromatic radical or C1-C10Alkyl, for example
Can be C5-C10Aromatic radical or C1-C6Alkyl.Instantiation for example phenyl, pyridine radicals, quinolyl, methyl, ethyl, propyl group or
Isopropyl.As two R1It is bonding into 3-10 yuan of rings when bonding cyclic, preferably it is bonded to 5-6 yuan of rings.
According to another preferred embodiment of the inventive method, R2And R3It independently is hydrogen atom or C1-C6Alkyl；X is
Halogen or C1-C6Alkyl.The C1-C6Alkyl for example methyl, ethyl, propyl group, isobutyl group, butyl, isobutyl group, the tert-butyl group, penta
Base or hexyl etc..Halogen such as fluorine, chlorine, bromine or iodine.
According to a specific embodiment of the inventive method, the CH2The mol ratio of CHR compounds and allyl cyclohexane
For 0:1 to 1:1, preferably 1:100 to 1:1.In a specific example, the mol ratio is 1:99 to 1:4.
According to a specific embodiment of the inventive method, the alkylaluminoxane as shown in formula IV or V,
In formula, R4For alkyl；N is the integer of 2-30.
In a preferred embodiment, in the alkylaluminoxane, R4For C1-C6Alkyl；N is the integer of 10-30.
The alkylaluminoxane, such as MAO, ethylaluminoxane.All conventional alkylaluminoxanes are used equally to this
It is bright.
In the present invention, catalyst system used is the custom catalystses system for preparing syndiotactic polymer, the catalysis
The composition and consumption of agent system is conventional composition and consumption.In a specific embodiment of the inventive method, the alkyl
Aikyiaiurnirsoxan beta is 100 with the mol ratio of the transistion metal compound:1 to 10000:1, preferably 100:1 to 500:1.The catalysis
Concentration of the agent system in polymerization system is 1x10-6Mole often it is raised to 1x10-2Mole per liter.
According to another specific embodiment of the inventive method, 0 to 120 DEG C of the temperature of the polymerization.The polymerization when
Between be 5 minutes to 24 hours.
According to the method that the present invention is provided, the high conversion rate of monomer can obtain the polymer of syndiotactic structure.
The polymer of the syndiotactic structure provided according to the present invention, its fusing point is high, heat endurance is good, and heat resistance is high, Neng Gouyong
Make heat-proof macromolecule material, for automobile-used resin art.
Description of the drawings
Fig. 1 shows the DSC curve of polymer in embodiment 1；
Fig. 2 shows the DSC curve of polymer in embodiment 2；
Fig. 3 shows the DSC curve of polymer in embodiment 3；
Fig. 4 shows the DSC curve of polymer in embodiment 4；
Fig. 5 shows the thermogravimetric curve of polymer in embodiment 1；
Fig. 6 shows the thermogravimetric curve of polymer in embodiment 2
Fig. 7 shows the thermogravimetric curve of polymer in embodiment 3；
Fig. 8 shows the thermogravimetric curve of polymer in embodiment 4.
Specific embodiment
With reference to specific embodiment, the present invention will be further described, but does not constitute any limitation of the invention.
Method of testing：
1. heat analysis：Melting point polymer uses differential scanning calorimetric analysis instrument (DSC, Q100, U.S.'s TA instruments), according to
ASTM D 3418 are determined；Thermal weight loss is determined using the C Jupiter synchronous solvings of STA 449.
2. molecular chain conformation is determined：Using Waters Alliance GPCV2000, with 1,2,4- trichloro-benzenes are flowing
Phase.
Embodiment 1
Allyl cyclohexane is polymerized
100 milliliters of polymerization bottles, magnetic agitation 20 DEG C, is vacuumized, inflated with nitrogen, repeatedly for three times.Sequentially add pi-allyl hexamethylene
1 milliliter of alkane, 6 milliliters of the methylaluminoxane solution of 10% (weight ratio), containing 20 micromole metallocene compound Ph2C(Cp)
(Flu)ZrCl21 milliliter of toluene solution (Al/Zr=500), catalyst concn is 2.5x10-6Mole per liter, start timing.24
After hour, stop reaction, reactant mixture poured in the ethanol containing hydrochloric acid, stir 6 hours, filter and washed with ethanol,
Obtain polymer.It is vacuum dried 24 hours at 60 DEG C, obtains 0.81 gram of dry polymer, conversion ratio>99%.Jing DSC are determined, and are gathered
211 DEG C of compound fusing point.380 DEG C of heat decomposition temperature, weight average molecular weight 37000, molecular weight distribution 2.5.
Embodiment 2
Allyl cyclohexane and 4-methyl-1-pentene combined polymerization
100 milliliters of polymerization bottles, magnetic agitation 20 DEG C, is vacuumized, inflated with nitrogen, repeatedly for three times.Sequentially add pi-allyl hexamethylene
1 milliliter of alkane, (allyl cyclohexane is 8.3 with the mol ratio of 4-methyl-1-pentene to 0.1 milliliter of 4-methyl-1-pentene:1), 10%
6 milliliters of the methylaluminoxane solution of (weight ratio), containing 20 micromole metallocene compound Ph2C(Cp)(Flu)ZrCl2Toluene
1 milliliter of solution (Al/Zr=500), catalyst concn is 2.5x10-3Mole per liter, start timing.After 24 hours, stop reaction,
Reactant mixture is poured in the ethanol containing hydrochloric acid, is stirred 6 hours, filtered and washed with ethanol, obtain polymer.At 60 DEG C
Vacuum drying 24 hours, obtains 0.88 gram of dry polymer, conversion ratio>99%.Jing DSC are determined, 185 DEG C of melting point polymer.Heat
376 DEG C of decomposition temperature, weight average molecular weight 39000, molecular weight distribution 2.2.
Embodiment 3
Allyl cyclohexane is closed with 1- hervene copolymers
100 milliliters of polymerization bottles, magnetic agitation 20 DEG C, is vacuumized, inflated with nitrogen, repeatedly for three times.Sequentially add pi-allyl hexamethylene
1 milliliter of alkane, (allyl cyclohexane is 8.2 with the mol ratio of 1- hexenes to 0.1 milliliter of 1- hexenes:1), the methyl of 10% (weight ratio)
6 milliliters of aluminoxanes solution, containing 20 micromole metallocene compound Ph2C(Cp)(Flu)ZrCl21 milliliter of toluene solution, start
Timing.After 24 hours, stop reaction, reactant mixture is poured in the ethanol containing hydrochloric acid, stir 6 hours, filter and use second
Alcohol is washed, and obtains polymer.It is vacuum dried 24 hours at 60 DEG C, obtains 0.88 gram of dry polymer, conversion ratio>99%.Jing DSC
Determine, 190 DEG C of melting point polymer.293 DEG C of heat decomposition temperature, weight average molecular weight 41000, and molecular weight distribution, 2.7.
Embodiment 4
Allyl cyclohexane and 1- vaccenic acid combined polymerizations
100 milliliters of polymerization bottles, magnetic agitation 20 DEG C, is vacuumized, inflated with nitrogen, repeatedly for three times.Sequentially add pi-allyl hexamethylene
1 milliliter of alkane, (allyl cyclohexane is 23 with the mol ratio of 1- vaccenic acids to 0.1 milliliter of 1- vaccenic acids:1), 10% (weight
Than) 6 milliliters of methylaluminoxane solution, containing 20 micromole metallocene compound Ph2C(Cp)(Flu)ZrCl2Toluene solution 1
Milliliter, starts timing.After 24 hours, stop reaction, reactant mixture is poured in the ethanol containing hydrochloric acid, stir 6 hours, mistake
Filter is simultaneously washed with ethanol, obtains polymer.It is vacuum dried 24 hours at 60 DEG C, obtains 0.89 gram of dry polymer, conversion ratio>
99%.Jing DSC are determined, 190 DEG C of melting point polymer.391 DEG C of heat decomposition temperature, weight average molecular weight 49000, molecular weight distribution 2.6.
Syndiotactic polymer, high conversion rate, higher than 99% are prepared according to the method that the present invention is provided.The syndiotactic polymerization for obtaining
Thing, fusing point is high, and heat decomposition temperature is high, thermally-stabilised good.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limit.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.By regulation the present invention can be made within the scope of the claims
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, this
It is bright to can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of polymer of syndiotactic structure, its structural formula is included shown in the monomeric unit shown in Formulas I and optional Formula II
Monomeric unit,
R is the alkyl of hydrogen atom or 1 to 30 carbon atoms in formula.
2. polymer according to claim 1, it is characterised in that R is the alkyl of hydrogen atom or 1 to 16 carbon atoms, excellent
Elect hydrogen, methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, decyl or cetyl as.
3. polymer according to claim 1 and 2, it is characterised in that the monomeric unit shown in the Formula II with shown in Formulas I
Monomeric unit mol ratio be 0:1 to 1:1,1:100 to 1:1, preferably 1:99 to 1:4.
4. the polymer according to any one in claim 1-3, it is characterised in that the polymer average molecular weight is
10000 to 500,000, molecular weight distributing index is 1.5-3.5.
5. a kind of method for preparing the polymer of syndiotactic structure described in any one in claim 1-4, including by allyl basic ring
Hexane and optional CH2CHR compounds are polymerized in the presence of catalyst system, obtain the copolymerization of the syndiotactic structure
Thing, the catalyst system includes the transistion metal compound and alkylaluminoxane shown in formula III,
Wherein, R1For alkyl, preferably C5-C15Aromatic radical or C1-C10Alkyl, two of which R1It is bonding cyclization or not into
Ring；R2And R3It independently is hydrogen atom or alkyl, preferably hydrogen atom or C1-C6Alkyl；X is halogen atom or alkyl；R's
Limit with claim 1 or 2.
6. method according to claim 5, it is characterised in that the R1For C5-C10Aromatic radical or C1-C6Alkyl, it is excellent
Elect phenyl, pyridine radicals, quinolyl, methyl, ethyl, propyl group or isopropyl as；And/or two R13-10 yuan of rings are bonded to, preferably
It is bonded to 5-6 yuan of rings；And/or X is halogen atom or C1-C6Alkyl.
7. the method according to claim 5 or 6, it is characterised in that the CH2CHR compounds rub with allyl cyclopentane
You are than being 0:1 to 1:1,1:100 to 1:1, preferably 1:99 to 1:4.
8. the method according to any one in claim 5-7, it is characterised in that the alkylaluminoxane such as formula IV or V
It is shown,
In formula, R4For alkyl, preferably C1-C6Alkyl；N is the integer of 2-30, the preferably integer of 10-30；It is preferred that the alkane
Base aikyiaiurnirsoxan beta is MAO and/or ethylaluminoxane；It is preferred that the alkylaluminoxane and the transistion metal compound
Mol ratio is 100:1 to 10000:1.
9. the method according to any one in claim 5-8, it is characterised in that the transistion metal compound is in polymerization
Concentration in system is 1x10-6To 1x10-2Mole per liter.
10. the method according to any one in claim 5-9, it is characterised in that the temperature of the polymerization is 0 to 120
℃。
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| CN110922516A (en) * | 2018-09-20 | 2020-03-27 | 中国石油化工股份有限公司 | Ethylene copolymer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686615A (en) * | 2009-12-21 | 2012-09-19 | 三井化学株式会社 | Process for production of syndiotactic alpha-olefin polymer |
| CN104558345A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686615A (en) * | 2009-12-21 | 2012-09-19 | 三井化学株式会社 | Process for production of syndiotactic alpha-olefin polymer |
| CN104558345A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymer and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110922516A (en) * | 2018-09-20 | 2020-03-27 | 中国石油化工股份有限公司 | Ethylene copolymer and preparation method thereof |
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