CN106589199A - Olefin polymer and preparation method thereof - Google Patents
Olefin polymer and preparation method thereof Download PDFInfo
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- CN106589199A CN106589199A CN201510660975.1A CN201510660975A CN106589199A CN 106589199 A CN106589199 A CN 106589199A CN 201510660975 A CN201510660975 A CN 201510660975A CN 106589199 A CN106589199 A CN 106589199A
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Abstract
The invention discloses a copolymer of a syndiotactic structure. The constitutional repeating unit of the copolymer comprises a structural unit shown as the formula I and a structural unit shown as the formula II. According to the provided copolymer, the copolymer is high in melting point. The invention further discloses a method for preparing the copolymer of the syndiotactic structure. The preparation technology is simple and the conversion rate is high. The formulas are shown as the description.
Description
Technical field
The invention belongs to field of olefin polymerisation, is related to copolymer of a kind of allyl cyclopentane and allyl cyclohexane and preparation method thereof.
Background technology
The single centre transition-metal catalyst of olefin polymerization is always the study hotspot of Organometallic Chemistry, catalysis, polymer chemistry and materialogy in recent decades.Using this kind of catalyst, molecular weight distribution can be obtained and chemical composition is distributed all well-proportioned olefin polymer, while the molecular structure and molecular weight of polymer can be highly controllable by adjusting catalyst structure.By single-site catalysts, the not getable olefin polymer of traditional Ziegler-Natta catalyst can be obtained.
Between the olefin polymer advised most disclosed in United States Patent (USP) US 3258455, this is the syndiotactic polypropylene that Natta et al. is prepared by titanous chloride. and diethyl aluminum chloride catalysis, later, Natta et al. uses vanadium series catalyst again, and syndiotactic polypropylene (US 3305538) is prepared in the presence of organo-aluminum compound.In patent documentation US 3364190, using the mixed system of titanium vanadium, in the presence of various aluminium compounds and some other lewis base, syndiotactic polypropylene is prepared for.
So-called syndiotactic polypropylene, is visibly different with common isotactic polypropylene in structure and performance.The position that main difference is that methyl in structure is different, such as assumes to constitute the methylene (CH of 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.Expressed using Fischer projection formula, 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 generally passes through nuclear magnetic resonance, NMR C at present13Spectrum (13C-NMR) determine, the sequence of n propylene units composition in polypropylene is become n tuples generally, polyacrylic stereoregularity, such as binary m and r, tlv triple mm, mr and rr generally can be represented with n tuples.
In polyacrylic strand, it will usually there is stereoregular defect, such as insert the mistake of the mistake and direction of insertion of conformation.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 continued into according to original correct way, that is, corrected the insertion of mistake, cause in propylene sequences conformation is advised between continuous two " rr ", it is this to be inserted as active center control polymerization.And another kind of being erroneously inserted for conformation is represented by：
In this case, after a propylene units make a mistake insertion, next propylene molecules will not be continued into according to original correct way, and be to continue with according to continuing into original contrary mode, cause 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 distributional analysiss have critically important enlightenment to mechanism of polymerization.In the polymerization that active center controls, " r " it is occur in pairs, seldom occur what is isolated " r " conformation.
Another kind of stereoregular defect has direction of insertion mistake to cause.Generally propylene molecules, in insertion, are all that 1,2- directions are inserted, mode as from beginning to end.But have indivedual propylene molecules and 2,1 insertion occurs, cause head to link and connect with tail tail chain, structure is represented by：
As it appears from the above, carrying " * " propylene molecules be 2,1- anti-plugs.
When polypropylene have higher stereoregularity when, either isotactic or between advise, polymer all can form crystallization because of the order of its vertical structure, so as to fusing point.Polyacrylic fusing point depend on stereoregulated type (isotactic or syndiotactic), the height of regularity and defect number.Identical stereoregular type, regularity are higher, and fusing point is higher；Defect is fewer, and fusing point is higher.
1980, (Macromolecules, 1980,13,267) characterized polyacrylic syndiotactic structure using 13C-NMR to the document that Zambelli is delivered.1988, document (CN 89104461.2, J Am Chem Soc, 1988,110,6255) disclose the metallocene catalyst for preparing syndiotactic polyolefins, using the species catalyst, the polypropylene ([rrrr]=0.86) of normality between height can be successfully prepared.Nineteen ninety, patent US5132381 disclose and prepare 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, patent US 5369196 is prepared for syndiotactic polypropylene, a rule poly- (4-methyl-1-pentene) and a rule poly- (3-methyl-1-butene) using metallocene catalyst, wherein syndiotactic polypropylene fusing point is 145 DEG C, above 200 DEG C of the fusing point of a rule poly- (4-methyl-1-pentene) and a rule poly- (3-methyl-1-butene).1993, patent 5391672 is disclosed advises poly- (1-butylene), poly- (4-methyl-1-pentene), poly- (4- methyl isophthalic acids-hexene), poly- (4- methyl isophthalic acids using between metallocene catalyst preparation, 3- pentadienes) method, 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, (2197) Macromolecules 1997,30 reported and uses iPr (Cp) (Flu) ZrCl document2Catalysis propylene and other alpha-olefinic copolymerizations, including ethylene, 1-butylene, 1- amylenes, 1- hexenes, 4-methyl-1-pentene, the species of co-monomer and content in the copolymer all can be had an impact to melting point polymer.2006, patent CN201110128933 disclosed the preparation method of syndiotactic propylene copolymer, and comonomer is ethylene and 1-butylene.2007, the method that patent CN200780034550 discloses syndiotactic polypropylene copolymer, comonomer included ethylene, 1-butylene and non-conjugated diene.2010, patent CN201080058413 disclosed the method for preparing the liquid poly- (alpha-olefin) with syndiotactic structure using transition-metal catalyst, and such as 1-decene, this material can serve as synthetic base oil.2010, patent CN201080057591 disclosed the preparation method of the syndiotactic copolymer of 4-methyl-1-pentene and propylene.It is 204 DEG C that [r] is the homopolymer 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 when ethylene contents are less than 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·OEt2For catalyst and carry out polymerization (the J Am Chem Soc 2005 of propylene and 4-methyl-1-pentene, 127,9972), five-tuple [rrrr] is advised between acrylic polymers and reaches as high as 99%, correspondence melting point polymer is 165 DEG C, five-tuple [rrrr] is advised between 4-methyl-1-pentene polymer and reaches as high as 97%, correspondence melting point polymer is 215 DEG C.Research (Macromolecules 2007 later, 40,5662) using these three catalyst researches propylene and higher alkene combined polymerization, including 4-methyl-1-pentene, 1- hexenes, 1- octenes, 1-decene etc., with the increase of co-monomer content, [rrrr] is reduced, and [rmrr] content increases, and [rmmr] is held essentially constant.The reduction of fusing point and catalyst, 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 generally below 170 DEG C, and 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, this application provides a kind of copolymer of the syndiotactic structure of the formation of the monomer comprising allyl cyclohexane and allyl cyclopentane, the copolymer of the syndiotactic structure is with higher fusing point.Present invention also offers the preparation method of the copolymer, the catalyst system and catalyzing preparation that the copolymer is constituted using metallocene compound and alkylaluminoxane, have the advantages that high conversion rate.
According to an aspect of the invention, there is provided a kind of copolymer of syndiotactic structure, its constitutional repeating unit includes the construction unit shown in construction unit and formula II shown in formula I,
According to a specific embodiment of copolymer of the present invention, the mol ratio of unit shown in the construction unit and Formula II shown in the Formulas I is 100:1 to 1:100, preferably 10:1-1:10.
According to another specific embodiment of copolymer of the present invention, the construction unit in the copolymer also including other comonomers.Wherein, alkene of described other comonomers selected from not more than 18 carbon atoms, optimal ethylene, propylene, 1-butylene, 4-methyl-1-pentene, cetene and 1- vaccenic acids.The construction unit for belonging to other comonomers is 1 with the mol ratio of construction unit described in Formulas I:100 to 1:2.In an instantiation, the construction unit of other comonomers is 1 with the mol ratio of unit shown in Formulas I:5-1:7.
According to another specific embodiment of copolymer of the present invention, the weight average molecular weight of the copolymer is 1 ten thousand to 40 ten thousand, such as 20,000-520 ten thousand.The molecular weight distributing index (middle finger Mw/Mn of the present invention) of the copolymer is 1.5 to 3.5, preferred 2.0-3.0.
In a specific embodiment, the molar ratio shown in the Formulas I shared by monomeric unit be 0.01-99%, preferred 0.1-90%, such as 70-90%；Molar ratio shown in the Formula II shared by monomeric unit be 0.01-99%, preferred 0.1-90%, such as 10-20%.Molar ratio shared by the construction unit of other comonomers be 0-50%, such as 0-20%, such as 0-10%.
According to the present invention, the copolymer fusing point of the syndiotactic structure is high.Macromolecular material of the copolymer for thermostability.
Outer one side of the invention, additionally provide a kind of method of the copolymer for preparing above-mentioned syndiotactic structure, including, allyl cyclohexane monomer and allyl cyclopentane monomer are added in system, then copolymerization is carried out under the catalyst system of transistion metal compound, obtain the copolymer of the syndiotactic structure, wherein, the catalyst system includes transistion metal compound and alkylaluminoxane shown in formula III
Wherein, R1For alkyl, preferably C5-C15Aromatic radical or C1-C10Alkyl, two of which R1Bonding cyclization or not cyclization；R2And R3It independently is hydrogen atom or alkyl, preferably hydrogen atom or C1-C6Alkyl；X is halogen atom or alkyl.
Wherein, R1For alkyl, two of which R1Bonding cyclization or not cyclization；R2And R3It independently is hydrogen atom or alkyl；X is halogen atom or alkyl.
According to another preferred embodiment of the inventive method, R1For C5-C15Aromatic radical or C1-C10Alkyl, can for example be C5-C10Aromatic radical or C1-C6Alkyl.Instantiation such as phenyl, pyridine radicals, quinolyl, methyl, ethyl, propyl group or isopropyl.As two R1It is during bonding cyclization, bonding into 3-10 yuan of rings, 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 such as methyl, ethyl, propyl group, isobutyl group, butyl, isobutyl group, the tert-butyl group, amyl group or hexyl etc..Halogen such as fluorine, chlorine, bromine or iodine.
According to a specific embodiment of the inventive method, the alkylaluminoxane as shown in formula IV or V,
In formula, R is alkyl；Integers of the n for 2-30.
In a preferred embodiment, in the alkylaluminoxane, R is C1-C6Alkyl；Integers of the n for 10-30.The alkylaluminoxane, such as MAO, ethylaluminoxane etc..All conventional alkylaluminoxanes are used equally to the present invention.It is preferred that the alkylaluminoxane is 100 with the mol ratio of the transistion metal compound:1 to 10000:1, preferably 100:1-500:1.
It is 1 according to the mol ratio of a preferred embodiment of the method for the invention, the allyl cyclohexane monomer and allyl cyclopentane monomer:100 to 100:1, preferably 1:10-10:1.
According to a preferred embodiment of the method for the invention, other comonomers in the system, are additionally added.1- alkene of described other comonomers selected from not more than 18 carbon atoms, optimal ethylene, propylene, 1-butylene, 4-methyl-1-pentene, cetene and 1- vaccenic acids.It is preferred that described other comonomers are 1 with the mol ratio of allyl cyclopentane monomer:100 to 1:2, such as 1:5-1:7.
According to a preferred embodiment of the method for the invention, concentration of the transistion metal compound in polymerization system is 1x10-8Mol/L to 1x10-2Mol/L, preferred 1x10-6Mol/L to 1x10-2mol/L.- 20 DEG C to 120 DEG C, preferably 0 DEG C to 80 DEG C of the temperature of the polymerization.
According to the method that the present invention is provided, the high conversion rate of monomer can obtain the copolymer of syndiotactic structure.The copolymer of the syndiotactic structure provided according to the present invention, its fusing point is high, heat stability is good, and thermostability is high, can act as 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 polymer in embodiment 613C-NMR spectrograms.
Specific embodiment
Technical scheme is described further with reference to embodiment, but does not constitute any limitation of the invention.
Analysis and characterization in the present invention is as follows：
(1) heat analysis：Melting point polymer uses differential scanning calorimetric analysis instrument (DSC, Q100, U.S.'s TA instruments), is determined according to ASTM D 3418.；
(2) molecular chain conformation is determined：Using Waters Alliance GPCV2000, with 1,2,4- trichloro-benzenes are mobile phase.；
(3) composition with structure determination (13C-NMR)：Using Bruker AVANCE III-400MHz, deuterated o-dichlorohenzene is solvent, is determined at 125 DEG C, and slack time is 10s.
1 allyl cyclopentane of embodiment and allyl cyclohexane combined polymerization
Open magnetic agitation, polymerization bottle to a 100ml for blowing row through three nitrogen sequentially adds allyl cyclopentane 0.8ml, allyl cyclohexane 0.2ml, the methylaluminoxane solution 6ml of 10% (weight ratio), containing 20 μm of ol metallocene compound Ph2C(Cp)(Flu)ZrCl2Toluene solution 1ml, at 20 DEG C react 24 hours, afterwards the mixture obtained after reaction is poured in the ethanol containing hydrochloric acid, stir 6 hours, then filter and use washing with alcohol, obtain polymer.It is last to be vacuum dried 24 hours at 60 DEG C, obtain dry polymer 0.80g, monomer weight conversion ratio>99%.
Jing is determined, and dry polymer fusing point is 195 DEG C, and weight average molecular weight is 47000, and molecular weight distributing index is 2.3.
2 allyl cyclopentane of embodiment and allyl cyclohexane combined polymerization
Open magnetic agitation, polymerization bottle to a 100ml for blowing row through three nitrogen sequentially adds allyl cyclopentane 0.6ml, allyl cyclohexane 0.4ml, the methylaluminoxane solution 6ml of 10% (weight ratio), containing 20 μm of ol metallocene compound Ph2C(Cp)(Flu)ZrCl2Toluene solution 1ml, at 20 DEG C react 24 hours, afterwards the mixture obtained after reaction is poured in the ethanol containing hydrochloric acid, stir 6 hours, then filter and use washing with alcohol, obtain polymer.It is last to be vacuum dried 24 hours at 60 DEG C, dry polymer 0.79g is obtained, monomer weight conversion ratio is 99%.
Jing is determined, and dry polymer fusing point is 170 DEG C, and weight average molecular weight is 58000, and molecular weight distributing index is 2.2.
Embodiment 3
Allyl cyclopentane and allyl cyclohexane combined polymerization
Open magnetic agitation, polymerization bottle to a 100ml for blowing row through three nitrogen sequentially adds allyl cyclopentane 0.4ml, allyl cyclohexane 0.6ml, the methylaluminoxane solution 6ml of 10% (weight ratio), containing 20 μm of ol metallocene compound Ph2C(Cp)(Flu)ZrCl2Toluene solution 1ml, at 20 DEG C react 24 hours, afterwards the mixture obtained after reaction is poured in the ethanol containing hydrochloric acid, stir 6 hours, then filter and use washing with alcohol, obtain polymer.It is last to be vacuum dried 24 hours at 60 DEG C, obtain dry polymer 0.80g, monomer weight conversion ratio>99%.
Jing is determined, and dry polymer fusing point is 153 DEG C, and weight average molecular weight is 54000, and molecular weight distributing index is 2.5.
Embodiment 4
Allyl cyclopentane and allyl cyclohexane combined polymerization
Open magnetic agitation, polymerization bottle to a 100ml for blowing row through three nitrogen sequentially adds allyl cyclopentane 0.2ml, allyl cyclohexane 0.8ml, the methylaluminoxane solution 6ml of 10% (weight ratio), containing 20 μm of ol metallocene compound Ph2C(Cp)(Flu)ZrCl2Toluene solution 1ml, at 20 DEG C react 24 hours, afterwards the mixture obtained after reaction is poured in the ethanol containing hydrochloric acid, stir 6 hours, then filter and use washing with alcohol, obtain polymer.It is last to be vacuum dried 24 hours at 60 DEG C, obtain dry polymer 0.81g, monomer weight conversion ratio>99%.
Jing is determined, and dry polymer fusing point is 178 DEG C, and weight average molecular weight is 55000, and molecular weight distributing index is 2.2.
Embodiment 5
The combined polymerization of allyl cyclopentane and allyl cyclohexane and 4-methyl-1-pentene
Open magnetic agitation, polymerization bottle to a 100ml for blowing row through three nitrogen sequentially adds allyl cyclopentane 0.8ml, allyl cyclohexane 0.2ml, 4-methyl-1-pentene 0.1mL, the methylaluminoxane solution 6ml of 10% (weight ratio), containing 20 μm of ol metallocene compound Ph2C(Cp)(Flu)ZrCl2Toluene solution 1ml, at 20 DEG C react 24 hours, afterwards the mixture obtained after reaction is poured in the ethanol containing hydrochloric acid, stir 6 hours, then filter and use washing with alcohol, obtain polymer.It is last to be vacuum dried 24 hours at 60 DEG C, obtain dry polymer 0.82g, monomer weight conversion ratio>99%.
Jing is determined, and dry polymer fusing point is 186 DEG C, weight average molecular weight 49000, molecular weight distribution 2.3.Allyl cyclopentane unit content 73mol% in polymer, allyl cyclohexane unit content 17mol%, 4-methyl-1-pentene content 10mol%.
Embodiment 6
The combined polymerization of allyl cyclopentane and allyl cyclohexane
Open magnetic agitation, polymerization bottle to a 100ml for blowing row through three nitrogen sequentially adds allyl cyclopentane 1.0ml, allyl cyclohexane 0.1ml, the methylaluminoxane solution 6ml of 10% (weight ratio), containing 20 μm of ol metallocene compound Ph2C(Cp)(Flu)ZrCl2Toluene solution 1ml, at 20 DEG C react 24 hours, afterwards the mixture obtained after reaction is poured in the ethanol containing hydrochloric acid, stir 6 hours, then filter and use washing with alcohol, obtain polymer.It is last to be vacuum dried 24 hours at 60 DEG C, obtain dry polymer 0.87g, monomer weight conversion ratio>99%.
Jing is determined, and dry polymer fusing point is 217 DEG C, weight average molecular weight 53000, molecular weight distribution 2.1.Allyl cyclopentane unit content 87mol% in polymer, allyl cyclohexane unit content 13mol%.Can be further characterized by from Fig. 5, copolymer of the polymer for syndiotactic structure.
It is provided by the present invention comprising allyl cyclohexane unit and allyl cyclopentane unit for the syndiotactic structure of repetitive structure olefin polymer, with very high fusing point, reach as high as 224 DEG C and conversion ratio it is higher (>99%).
It should be noted that embodiment described above is only used for explaining the present invention, any limitation of the invention is not constituted.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive and explanatory vocabulary, rather than limited vocabulary.Within the scope of the claims the present invention can be modified by regulation, and the present invention be revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in which 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 can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of copolymer of syndiotactic structure, its constitutional repeating unit include construction unit and formula II shown in formula I
Shown construction unit,
2. copolymer according to claim 1, it is characterised in that construction unit shown in the Formulas I and
The mol ratio of unit shown in Formula II is 100:1 to 1:100, preferably 10:1-1:10.
3. copolymer according to claim 1 and 2, it is characterised in that the copolymer includes other
The construction unit of comonomer, alkene of described other comonomers selected from not more than 18 carbon atoms, preferably
Ethylene, propylene, 1-butylene, 4 Methyl-1-pentenes, cetene and 1- vaccenic acids, described other copolymerization
The construction unit of monomer is 1 with the mol ratio of unit shown in Formulas I:100 to 1:2.
4. copolymer according to claim 1 and 2, it is characterised in that the Weight-average molecular of the copolymer
Measure as 1 ten thousand to 40 ten thousand, molecular weight distributing index is 1.5-3.5.
5. a kind of method of the copolymer for preparing any one syndiotactic structure in claim 1-4, including,
Allyl cyclohexane monomer and allyl cyclopentane monomer are added in system, then in transistion metal compound
Copolymerization is carried out under catalyst system, the copolymer of the syndiotactic structure is obtained, wherein, the catalyst system bag
The transistion metal compound and alkylaluminoxane shown in formula III is included,
Wherein, R1For alkyl, preferably C5-C15Aromatic radical or C1-C10Alkyl, two of which R1Can
Bonding cyclization or not cyclization；R2And R3It independently is hydrogen atom or alkyl, preferably hydrogen atom or C1-C6Alkane
Base；X is halogen atom or alkyl.
6. method according to claim 5, it is characterised in that R1For C5-C10Aromatic radical or C1-C6
Alkyl, preferably phenyl, pyridine radicals, quinolyl, methyl, ethyl, propyl group or isopropyl；And/or two
R13-10 yuan of rings are bonded to, 5-6 yuan of rings are preferably bonded to；And/or X is halogen atom or C1-C6Alkyl.
7. the method according to claim 5 or 6, it is characterised in that the alkylaluminoxane such as formula IV
Or shown in V,
In formula, R is alkyl, preferably C1-C6Alkyl；Integers of the n for 2-30, preferably 10-30's
Integer, more preferably described alkylaluminoxane are MAO and/or ethylaluminoxane；It is preferred that the alkyl alumina
Alkane is 100 with the mol ratio of the transistion metal compound:1 to 10000:1.
8. the method according to claim 6 or 7, it is characterised in that the allyl cyclohexane monomer and
The mol ratio of allyl cyclopentane monomer is 100:1 to 1:100, preferably 10:1-1:10.
9. the method according to any one in claim 6-8, it is characterised in that in the system also plus
Enter other comonomers, alkene of described other comonomers selected from not more than 18 carbon atoms, optimal ethylene,
Propylene, 1-butylene, 4 Methyl-1-pentenes, cetene and 1- vaccenic acids, preferably described other copolymerization
Monomer is 1 with the mol ratio of allyl cyclopentane monomer:100 to 1:2.
10. the method according to any one in claim 6-9, it is characterised in that the transition metal
Concentration of the compound in polymerization system is 1x10-8Mol/L to 1x10-2Mol/L, preferred 1x10-6Mol/L is arrived
1x10-2mol/L；And/or, the temperature of the polymerization is -20 DEG C to 120 DEG C, preferably 0 DEG C to 80 DEG C.
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| 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 |
| CN112646258A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | High-barrier polyethylene composition, preparation method thereof, polyethylene film and application |
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Cited By (2)
| 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 |
| CN112646258A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | High-barrier polyethylene composition, preparation method thereof, polyethylene film and application |
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