CN106632781A - A preparing method of an ethylene/propylene copolymer having a branched structure and the copolymer - Google Patents
A preparing method of an ethylene/propylene copolymer having a branched structure and the copolymer Download PDFInfo
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- CN106632781A CN106632781A CN201510724648.8A CN201510724648A CN106632781A CN 106632781 A CN106632781 A CN 106632781A CN 201510724648 A CN201510724648 A CN 201510724648A CN 106632781 A CN106632781 A CN 106632781A
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Abstract
The invention relates to a preparing method of an ethylene/propylene copolymer having a branched structure. The method includes polymerizing ethylene and propylene. A poly(metallocene) catalyst includes a metallocene compound and a cocatalyst. The structure of the metallocene compound is Q2Si(2-R1-4-R2-Ind)(2-R<1><'>-4-R<2><'>-Ind)MX2, wherein the Q is C1-C6 alkyl, the R1 and the R<1><'> are respectively methyl, ethyl, propyl or isopropyl and are different, the R2 and the R<2><'> are respectively hydrogen, isopropyl, phenyl or naphthyl and are different or same, the M is zirconium or hafnium, the X is halogen or C1-C5 alkyl which is methyl preferably, and the Ind is indenyl. The invention also relates to the copolymer prepared by the method.
Description
Technical field
The present invention relates to a kind of preparation method of copolymer, more particularly to a kind of preparation side of high-molecular copolymer
Method.The invention further relates to copolymer obtained by this method.
Background technology
Polypropylene is the general-purpose plastics for using in a large number.The a small amount of vinyl monomer of copolymerization can significantly change in polypropylene
The transparency of kind resin, cryogenic property also has improvement.One major defect of acrylic resin is that melt strength is low,
Which has limited the application of acrylic resin：In blown film field, in order to avoid bubbles burst, high score is generally used
The acrylic resin of son amount, but the viscosity of molecular weight high resin melt is also big, causes production efficiency to reduce, energy consumption
Increase.
In order to improve melt strength, there is several methods that in document：1) polypropylene is processed using free radical, is formed
Long chain branched.2) propylene and alkadienes copolymerization.3) propylene and macromonomer occur under given conditions
Copolyreaction, prepares long-chain branching polypropylene.
But comprehending at free radical causes the degraded or crosslinking of polypropylene chains, for producing the peroxide of free radical
Compound can also make product have smell.The subject matter of propylene and alkadienes copolymerization process is the amount ratio of alkadienes
Relatively it is difficult to control to, alkadienes somewhat excessively may result in product crosslinking, and operation difficulty is very big in actual production,
Simultaneously the residual of alkadienes also results in the odor problem of product.
The copolymerization of propylene and macromonomer does not have a shortcoming of first two method, but propylene and macromonomer
Copolyreaction is also relatively difficult.Existing document (Macromolecular Rapid Communications, 2000,21,
1103；Macromolecular Rapid Communications, 2001,22,1488) disclose a kind of using specific
Metallocene catalyst, propylene polymerization first generates polypropylene macromers, then in second step using same
The copolyreaction of catalyst propylene and macromonomer, prepares branched p 0 lypropylene.However, this method
Needs are reacted at 120 DEG C, and this temperature is far above generally industrial propylene polymerization temperature, and this
The activity of metallocene catalyst can also be subject to extreme influence, therefore this method to be difficult to industrially in fact at a temperature of one
Now apply.
(2002,35,3838) Macromolecules has found to be prepared by macromonomer copolymerization process document
The branched structure of branched p 0 lypropylene exist13On C NMR spectras chemical shift be 44.88,44.74,44.08
There is formant with the position of 31.74ppm.
Also the research having uses complex catalyst system, and first by a kind of catalyst preparation macromonomer is gone out,
Then using another catalyst olefinic monomer and macromonomer copolymerization, long chain branching polymerization is prepared
Thing, but this method is operationally more complicated, simultaneously because the polymer molecular weight that two kinds of catalyst are generated
Generally not fully consistent, the molecular weight distribution for causing copolymer broadens.Therefore, it is optimal to prepare branched polymeric
The method of thing should use a kind of catalyst, and carry out under relatively industrial reaction condition.
The content of the invention
In order to solve above-mentioned problems of the prior art, the present inventor exceeds through many experiments
Expect ground to find, the polymerisation of propylene/ethylene is catalyzed using specific metallocene compound catalyst, can be with
One step is obtained the ethylene/propene copolymer with branched structure.
The invention provides a kind of method for preparing the ethylene/propene copolymer with branched structure, methods described makes
Propylene and ethene are catalyzed with metallocene catalyst carries out polymerisation, and the metallocene catalyst includes metallocene
Compound and co-catalyst, the structure of the metallocene compound is
Q2Si(2-R1-4-R2-Ind)(2-R1’-4-R2’-Ind)MX2,
Wherein, Q represents the alkyl that carbon number is 1-6, preferably methyl；R1And R1' be respectively methyl,
Ethyl, propyl group or isopropyl, and R1And R1' different；R2And R2' it is respectively hydrogen, isopropyl, phenyl or naphthalene
Base, R2And R2' identical or different；M is zirconium or hafnium；X is halogen or carbon number for the alkyl of 1-5, institute
State alkyl and be preferably methyl；Ind is indenyl.
In the present invention, the ethylene/propene copolymer with branched structure is under olefin polymerization conditions, to incite somebody to action
Propylene, ethene and metallocene catalyst carry out in organic solvent the random copolymer that haptoreaction is obtained.At this
Invention one preferred embodiment in, on the basis of the total mole number of mixture, the content of propylene is
80-99.5 mole of %, the content of ethene is 0.5-20 mole of %.
The present invention has no particular limits to the feed postition of comonomer in copolymerization system.As a rule, normal
Under normal temperature and pressure, propylene and ethene are all gaseous, propylene and ethene can be mixed by fixed proportion and persistently be led to
Enter in copolymerization system, be 0.1-4MPa, the propylene and ethene list by controlling the pressure of reaction system
Body is constantly dissolved in reaction system and polymerisation occurs.
One of the present invention preferred embodiment in, the metallocene compound and co-catalyst can be loaded
To on granular carrier, make load metallocene catalyst and use, the carrier can be inorganic porous
Bead-type substrate, including but not limited to magnesium chloride, talcum, zeolite, aluminum oxide, silica gel etc., preferably silica gel.
The present invention one preferred embodiment in, the present invention to catalyst system described in reaction system
Content is not particularly limited, and with elemental metal, the metallocene compound in the catalyst mixes with described
The mol ratio of the total mole number of thing can be 1:104-106, more preferably 1:104-105。
The present invention one preferred embodiment in, in polymerization process, propylene is gas phase or liquid phase
, or be dissolved in solvent.In the state of liquid propene, directly can be polymerized using liquid propene
Reaction.
The present invention one preferred embodiment in, the metallocene compound be selected from dimethyl-silicon bridging (2-
Methyl 4-phenyl-indenyl) (2- isopropyl -4- pheny-indenylzirconiums) zirconium dichloride and/or dimethyl-silicon bridging (2- first
Base -4- pheny-indenylzirconiums) (2- isopropyl -4- pheny-indenylzirconiums) zirconium dimethyl.
The present invention one preferred embodiment in, the co-catalyst can be metallocene catalyst system
Middle conventional various co-catalysts, for example, can be alkylaluminoxane.Usually, in the alkylaluminoxane
Alkyl can be C1-C12Alkyl, preferably C1-C5Alkyl.Preferably, the alkylaluminoxane can be with
One kind in MAO, ethylaluminoxane, isobutyl aluminium alkoxide and alkyl-modified MAO or
It is various.Wherein, the alkyl-modified MAO refers to MAO and C2-C5Alkylaluminoxane
Mixture or by trimethyl aluminium and C2-C5Alkyl aluminum mixture be hydrolyzed obtained from methyl alumina
Alkane, for example：Ethyl modified methylaluminoxane, isobutyl group modified methylaluminoxane.Most preferably, the alkyl
Aikyiaiurnirsoxan beta is MAO and/or alkyl-modified MAO.The alkyl-modified MAO can be with business
Buy, it would however also be possible to employ well known to a person skilled in the art method is prepared.
One of the present invention preferred embodiment in, the co-catalyst includes alkylaluminoxane and/or boric acid
Ester type compound.Alkyl in the alkylaluminoxane can be C1-C12Alkyl, preferably C1-C5Alkane
Base.Preferably, the alkylaluminoxane can be selected from MAO, ethylaluminoxane, isobutyl aluminium alkoxide
With one or more in alkyl-modified MAO.Wherein, the alkyl-modified MAO is nail
Base aikyiaiurnirsoxan beta and C2-C5Alkylaluminoxane mixture or by trimethyl aluminium and C2-C5Alkyl aluminum
Mixture be hydrolyzed obtained from MAO, for example：Ethyl modified methylaluminoxane, isobutyl group are modified
MAO.Most preferably, the alkylaluminoxane is MAO and/or alkyl-modified MAO.
The alkyl-modified MAO is commercially available, it would however also be possible to employ well known to a person skilled in the art method
Prepare.
One of the present invention preferred embodiment in, the method according to the invention for co-catalyst, preferably
Consumption for alkylaluminoxane is not particularly limited, and can be the conventional amount used of this area.Preferably, the cyclopentadienyl
The mol ratio of the aluminium in transition metal and alkylaluminoxane in metallic catalyst is 1:100 to 1:10000, it is more excellent
Elect 1 as:100 to 1:5000, most preferably 1:100 to 1:4000.
The present invention one preferred embodiment in, the mol ratio of ethene and propylene is in the polymerisation
1:1 to 1:100.
One of the present invention preferred embodiment in, the reaction temperature of the polymerisation is 60-80 DEG C.
Polymeric reaction temperature is too high, can cause the destruction of catalytic active center, reduces polymerization activity, while compared with
High reaction also makes plus thermal energy consumption increases.
The present invention one preferred embodiment in, the polymerisation is carried out in an inert atmosphere.It is described
Inert atmosphere refers to any one gas or admixture of gas that chemical reaction does not occur with reactant and product, such as nitrogen
One or more in gas and periodic table of elements zero group gas, preferably nitrogen.
The present invention one preferred embodiment in, the condition of the polymerisation can be this area routine
Polymerisation condition.General, the polymerizing condition includes：Temperature can be 0-100 DEG C, and pressure can
Think 0.1-4MPa, the time can be 0.1-3 hours；Preferably, the polymeric reaction condition includes：Temperature
It can be 30-80 DEG C, pressure can be 0.1-3MPa, and the time can be 0.1-2 hours.
One of the present invention preferred embodiment in, the organic solvent can be conventional for field of olefin polymerisation
Various solvents, such as various aromatic hydrocarbon, alkane or its mixture, it is preferable that the solvent can selected from toluene,
One or more in dimethylbenzene, hexane and heptane.The present invention is to the consumption of the organic solvent without especially
Limit, as long as meeting concentration of the metallocene compound in the organic solvent for 1 × 10-8To 1 × 10-3MM/
Rise, more preferably 2 × 10-5To 5 × 10-5MM/l.
It is a further object of the invention to provide having the ethene of branched structure according to obtained in above-mentioned method
/ propylene copolymer, it is characterised in that the copolymer carbon-13 magnetic resonance (13C NMR) on spectrogram
There is characteristic peak at 45.1ppm, 44.9ppm, 44.3ppm and 31.9ppm.
The present invention one preferred embodiment in, the number-average molecular weight of the copolymer is at least
5000g/mol, preferred number average molecular weight is 20000-500000g/mol, and the molecular weight distribution of the copolymer is
2-5。
The present invention one preferred embodiment in, the ethylene unit (ethene in polymer chain in copolymer
Unit) content be 0.5-10 mole of %.
The present invention one preferred embodiment in, the branch point content of the copolymer is not less than 3/10000
C。
The beneficial effects of the present invention is：It is prepared for branched structure under the reaction condition for being suitable to commercial Application
Ethylene/propene copolymer, due to the presence of branched structure, the copolymer of the present invention has more preferable processing characteristics.
Description of the drawings
Fig. 1 is ethylene/propene copolymer obtained in embodiment 213C NMR spectras.
Specific embodiment
With reference to non-limiting specific embodiment, the invention will be further described, but the protection model of the present invention
Enclose and be not limited to following embodiments.
The method of testing and condition that following examples and comparative example are related to is as follows：
1st, the molecular weight of propylene copolymer
The molecular weight of polymer is determined using gel permeation chromatography method, wherein, gel permeation chromatography test exists
Carry out on gel permeation chromatograph commercially available from model PL-GPC 220 of PL companies of Britain, wherein, flowing
It is mutually 1,3,5- trichloro-benzenes, flow velocity is 1mL/min, and test temperature is 150 DEG C.
2nd, nuclear magnetic resonance spectroscopy
Core is carried out on the nuclear magnetic resonance chemical analyser of model AVANCE400 commercially available from Bruker companies of Switzerland
Magnetic resonance carbon analysis of spectrum, branch point in the molar content and copolymer of ethylene comonomer in detection propylene copolymer
Content, wherein, solvent for use be o-dichlorohenzene-d4, temperature be 125 DEG C, the sampling time be 5.0 seconds, sweep
Number of times is retouched for 5000 times.The chemical shift of the formant of the medium rule five-tuple of polypropylene segment in spectrogram is set to
21.86ppm, as benchmark the chemical shift of each formant in spectrogram is determined.
Embodiment 1-5
Embodiment 1-5 is used for the preparation of the propylene copolymer for illustrating present invention offer.
Polymer reactor is purged with nitrogen, then with propylene and the gaseous mixture of ethene (mol ratio is as shown in table 1)
Displacement nitrogen.The temperature of reactor is set to the temperature (as shown in table 1) needed for polymerization, 45mL is added
The toluene solution (concentration of MAO is 1.4mol/L) of toluene, MAO, and stir 10 minutes.
Then the gaseous mixture of propylene and ethene alkene is passed through with the pressure of 0.1MPa, and respectively according to the amount be given in table 1
Metallocene compound is added in reactor.Propylene is kept to be 0.1MPa with the pressure of ethene, respectively in table 1
Polyase 13 0min at shown temperature.After reaction terminates, pour product into 200mL ethanol and (contain 10
The concentrated hydrochloric acid of volume %) in, and filtered, the propylene copolymer of white solid powder is obtained, and use 100mL
After ethanol and 200mL water washings three times, by the propylene copolymer for obtaining temperature be 50 DEG C, pressure be -0.1MPa
It is dried in the baking oven of (gauge pressure).
The architectural feature of reaction condition and copolymer is as shown in table 1.
Data from table 1 can be seen that the branch point of the ethylene/propene copolymer prepared using the inventive method
Density is not less than 3/10000C.Accompanying drawing 1 is the copolymer that embodiment 2 is obtained13C NMR spectras, from figure
In as can be seen that chemical shift be 31.9ppm, 44.3ppm, 44.9ppm and 45.1ppm at have branched knot
The formant of structure.
Comparative example 1
Other conditions are same as Example 2, the difference is that only, the reaction temperature of polymerisation is increased to
100℃.Polymerization results are listed in Table 1 below.
Result from table 1 can be seen that reaction temperature and be increased to 100 DEG C from 70 DEG C, polymerization activity from
9.7x106G/mol falls below 1.3x106g/mol。
Table 1
Catalyst：1：Dimethyl-silicon bridging (2- methyl 4-phenyls-indenyl) (2- isopropyl -4- pheny-indenylzirconiums) dichloro
Change zirconium
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (10)
1. a kind of method for preparing the ethylene/propene copolymer with branched structure, methods described uses metallocene
Catalyst being catalyzed propylene and ethene carries out polymerisation, the metallocene catalyst include metallocene compound and
Co-catalyst, the structure of the metallocene compound is
Q2Si(2-R1-4-R2-Ind)(2-R1’-4-R2’-Ind)MX2,
Wherein, Q represents the alkyl that carbon number is 1-6, preferably methyl；R1And R1' be respectively methyl,
Ethyl, propyl group or isopropyl, and R1And R1' different；R2And R2' it is respectively hydrogen, isopropyl, phenyl or naphthalene
Base, R2And R2' identical or different；M is zirconium or hafnium；X is halogen or carbon number for the alkyl of 1-5, institute
State alkyl and be preferably methyl；Ind is indenyl.
2. method according to claim 1, it is characterised in that in polymerization process, propylene is
Gas phase or liquid phase, or be dissolved in solvent.
3. method according to claim 1 and 2, it is characterised in that the metallocene compound is selected from
Dimethyl-silicon bridging (2- methyl 4-phenyls-indenyl) (2- isopropyl -4- pheny-indenylzirconiums) zirconium dichloride and/or two
Methyl silicon bridging (2- methyl 4-phenyls-indenyl) (2- isopropyl -4- pheny-indenylzirconiums) zirconium dimethyl.
4. the method according to any one in claim 1-3, it is characterised in that the co-catalyst bag
Include alkylaluminoxane and/or boric acid ester compound.
5. the method according to any one in claim 1-4, it is characterised in that in the polymerisation
The mol ratio of ethene and propylene is 1:1 to 1:100.
6. the method according to any one in claim 1-5, it is characterised in that the polymerisation
Reaction temperature is 60-80 DEG C.
7. there is the ethylene/propylene of branched structure obtained in the method according to any one in claim 1-6
Alkene copolymer, it is characterised in that 45.1ppm of the copolymer on carbon-13 magnetic resonance spectrogram, 44.9ppm,
There is characteristic peak at 44.3ppm and 31.9ppm.
8. copolymer according to claim 7, it is characterised in that the number-average molecular weight of the copolymer
At least 5000g/mol, preferred number average molecular weight is 20000-500000g/mol, the molecular weight of the copolymer
It is distributed as 2-5.
9. the copolymer according to claim 7 or 8, it is characterised in that ethylene unit in copolymer
Content is 0.5-10 mole of %.
10. the copolymer according to any one in claim 7-9, it is characterised in that the copolymer
Branch point content is not less than 3/10000C.
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| CN1103067A (en) * | 1993-06-07 | 1995-05-31 | 三井石油化学工业株式会社 | Novel transition metal compound, olefin polymerization catalyst component comprising said compound, olefin polymerization catalyst containing said catalyst component, process for olefin polymeri...... |
| CN1103405A (en) * | 1993-06-07 | 1995-06-07 | 三井石油化学工业株式会社 | Transition metal compound, olefin polymerization catalyst, olefin polymerization process, and propylene polymer |
| CN1151172A (en) * | 1994-05-24 | 1997-06-04 | 埃克森化学专利公司 | Articles made from polypropylene-high 'alpha' olefin copolymers |
| CN1361795A (en) * | 1998-12-21 | 2002-07-31 | 埃克森化学专利公司 | Branched semi-crystalline ethylene-propylene compositions |
| CN1433435A (en) * | 1999-12-23 | 2003-07-30 | 巴塞尔聚烯烃有限公司 | Transition metal compound, ligand system, catalyst system and the use of the latter for the polymerisation and copolymerisation of olefins |
| CN101018815A (en) * | 2004-04-15 | 2007-08-15 | 埃克森美孚化学专利公司 | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
| CN101506296A (en) * | 2006-08-25 | 2009-08-12 | 博里利斯技术有限公司 | Extrusion coated substrate |
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2015
- 2015-10-29 CN CN201510724648.8A patent/CN106632781B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103067A (en) * | 1993-06-07 | 1995-05-31 | 三井石油化学工业株式会社 | Novel transition metal compound, olefin polymerization catalyst component comprising said compound, olefin polymerization catalyst containing said catalyst component, process for olefin polymeri...... |
| CN1103405A (en) * | 1993-06-07 | 1995-06-07 | 三井石油化学工业株式会社 | Transition metal compound, olefin polymerization catalyst, olefin polymerization process, and propylene polymer |
| CN1151172A (en) * | 1994-05-24 | 1997-06-04 | 埃克森化学专利公司 | Articles made from polypropylene-high 'alpha' olefin copolymers |
| CN1361795A (en) * | 1998-12-21 | 2002-07-31 | 埃克森化学专利公司 | Branched semi-crystalline ethylene-propylene compositions |
| CN1433435A (en) * | 1999-12-23 | 2003-07-30 | 巴塞尔聚烯烃有限公司 | Transition metal compound, ligand system, catalyst system and the use of the latter for the polymerisation and copolymerisation of olefins |
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| CN101506296A (en) * | 2006-08-25 | 2009-08-12 | 博里利斯技术有限公司 | Extrusion coated substrate |
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