CN106589199B - Olefin polymer and preparation method thereof - Google Patents
Olefin polymer and preparation method thereof Download PDFInfo
- Publication number
- CN106589199B CN106589199B CN201510660975.1A CN201510660975A CN106589199B CN 106589199 B CN106589199 B CN 106589199B CN 201510660975 A CN201510660975 A CN 201510660975A CN 106589199 B CN106589199 B CN 106589199B
- Authority
- CN
- China
- Prior art keywords
- formula
- monomer
- copolymer
- molar ratio
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application discloses a copolymer with a syndiotactic structure, and a repeating structural unit of the copolymer comprises a structural unit shown as a formula I and a structural unit shown as a formula II. According to the copolymer provided by the invention, the melting point is high. The application also discloses a method for preparing the syndiotactic copolymer, which has simple preparation process and high conversion rate.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and relates to a copolymer of allylcyclopentane and allylcyclohexane and a preparation method thereof.
Background
Single-site transition metal catalysts for olefin polymerization have been the focus of research in metallo-organic chemistry, catalytic chemistry, polymer chemistry and materials science for decades. By using the catalyst, the olefin polymer with uniform molecular weight distribution and chemical composition distribution can be obtained, and the molecular structure and the molecular weight of the polymer can be highly controlled by adjusting the structure of the catalyst. By means of a single-site catalyst, olefin polymers which are not obtainable by conventional Ziegler-Natta catalysts can be obtained.
Syndiotactic olefin polymers were first disclosed in U.S. patent No. 3258455, which is syndiotactic polypropylene produced by Natta et al by catalysis with titanium trichloride and diethylaluminum chloride, and subsequently, syndiotactic polypropylene was produced by Natta et al using a vanadium-based catalyst in the presence of an organoaluminum compound (US 3305538). In the patent document US 3364190, syndiotactic polypropylene is prepared using a mixed system of titanium and vanadium in the presence of various aluminium compounds and other lewis bases.
The so-called syndiotactic polypropylene is significantly different from conventional isotactic polypropylene in structure and properties. The main difference in structure is the position of the methyl group, as assumed to constitute the methylene group (CH) of the main chain2) And methine (CH) are in the same plane, then the branched methyl (CH) groups of the isotactic polypropylene3) Are all positioned at one side of the plane, namely both positioned above or below the plane; and the branched methyl group (CH) of syndiotactic polypropylene3) The planes are staggered in sequence above and below the plane. Expressed using the fischer projection formula, isotactic polypropylene can be expressed as:
wherein the letter "m" indicates that the relationship of adjacent two propylene units is isotactic.
And syndiotactic polypropylene is represented by:
wherein the letter "r" indicates that the relationship of adjacent two propylene units is syndiotactic.
This structure is currently commonly passed through nuclear magnetic resonance C13Spectrum (A)13C-NMR), the tacticity of polypropylene can be generally expressed by n-tuple, such as binary m and r, and ternary mm, mr and rr.
In the molecular chain of polypropylene, stereoregular defects such as an insertion conformation error and an insertion direction error are generally present. For example, in isotactic polymerization, one possible insertion conformational error can cause a stereodefect that can be expressed as:
wherein, when a propylene unit is inserted incorrectly, the next propylene molecule will continue to be inserted in the original correct way, i.e. the incorrect insertion is corrected, and two consecutive syndiotactic conformations "rr" are generated on the propylene sequence, and the insertion is used as an active center to control the polymerization. While the misinsertion of another constellation can be expressed as:
in this case, when a propylene unit is inserted incorrectly, the next propylene molecule will not continue to be inserted in the correct manner as it was, but will continue to be inserted in the opposite manner to that which was the case, resulting in an isolated syndiotactic conformation "r" in the propylene sequence, which is the chain-end controlled polymerization. Therefore, the study of the polymer chain structure and sequence distribution analysis has important implications for the polymerization mechanism. In the case of active-center-controlled polymerization, "r" appears in pairs, with few isolated "r" conformations.
Another type of stereoregularity is caused by insertion direction errors. In general, the insertion of propylene molecules is in the 1, 2-direction, i.e., in a head-to-tail manner. However, there is a 2,1 insertion of individual propylene molecules resulting in head-to-head and tail-to-tail linkages, and the structure can be expressed as:
as indicated above, the propylene molecules with "", are the 2, 1-trans insertions.
When polypropylene has a high stereoregularity, whether isotactic or syndiotactic, the polymer may form crystals due to its stereoregularity, and thus have a melting point. The melting point of polypropylene depends on the type of tacticity (isotactic or syndiotactic), the level of tacticity and the number of defects. The same stereoregularity type, the higher the regularity, the higher the melting point; the fewer defects, the higher the melting point.
In 1980, Zambelli published (Macromolecules,1980,13,267) characterized the syndiotactic structure of polypropylene using 13C-NMR. In 1988, the literature (CN 89104461.2, J Am Chem Soc,1988,110,6255) disclosed metallocene catalysts for the preparation of syndiotactic polyolefins, with which it was possible to successfully prepare polypropylene of high syndiotactic degree ([ rrrr [ ]]0.86). In 1990, patent US5132381 discloses the preparation of syndiotactic polypropylene using metallocene catalysts. Patent CN91103928 discloses a process for the preparation of syndiotactic copolymers of propylene with non-conjugated dienes using metallocene catalysts. In 1991, patent US 5369196 used metallocene catalysts to prepare syndiotactic polypropylene, syndiotactic poly (4-methyl-1-pentene) and syndiotactic poly (3-methyl-1-butene), wherein the melting point of syndiotactic polypropylene was 145 ℃ and the melting points of both syndiotactic poly (4-methyl-1-pentene) and syndiotactic poly (3-methyl-1-butene) were over 200 ℃. In 1993, patent 5391672 disclosed the preparation of syndiotactic poly (1-butene), poly (4-methyl-1-pentene), poly (4-methyl-1-hexene), poly (4-methyl-1, 3-pentadiene) using metallocene catalysts, wherein the melting point of poly (4-methyl-1-pentene) was 196.6 ℃ and the melting point of poly (4-methyl-1-hexene) was 146.6 ℃. In 1997, the use of iPr (Cp) (flu) ZrCl was reported in the literature (Macromolecules 1997,30,2197)2The type of comonomer and the amount in the copolymer, which catalyze the copolymerization of propylene and other olefins, including ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, have an influence on the melting point of the polymer. In 2006, patent CN201110128933 discloses a preparation method of a syndiotactic propylene copolymer, and comonomers are ethylene and 1-butene. In 2007, patent CN200780034550 discloses a method of syndiotactic polypropylene copolymer, the comonomers comprising ethylene, 1-butene and a non-conjugated diene. In 2010, patent CN201080058413 discloses a process for preparing liquid poly (α -olefins) with syndiotactic structure, such as 1-decene, using a transition metal catalyst, which can be used as synthetic base oil. In 2010, patent CN201080057591 discloses a process for the preparation of syndiotactic copolymers of 4-methyl-1-pentene and propylene. [ r ] of]A98% homopolymer of 4-methyl-1-pentene had a melting point of 204 ℃. But do notThe activity is very low, only 0.22kg/mol-Zr/hr, the melting point of the polymer can be obviously reduced by inserting a small amount of ethylene units, and when the ethylene content is not more than 1 mol%, the melting point is between 190 and 200 ℃, and the polymerization activity is improved. In 2003, Me2C(η5-C5H4)(η5-C13H8)ZrCl2、Me2C(η5-C5H4)(η5-C29H36)ZrCl2And Me2Si(η1-N-tBu)(η1-C29H36)ZrCl2·OEt2As a catalyst and for the polymerization of propylene and 4-methyl-1-pentene (J Am Chem Soc 2005,127,9972), the propylene polymer syndiotactic pentad [ rrrr]Up to 99%, corresponding to a polymer melting point of 165 ℃, 4-methyl-1-pentene polymer syndiotactic pentads [ rrrr]Up to 97%, corresponding to a polymer melting point of 215 ℃. Later studies (Macromolecules 2007,40,5662) investigated the copolymerization of propylene with higher olefins, including 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, etc., using these three catalysts, [ rrrr ] with increasing comonomer content]Decrease, [ rmrr]The content is increased, and]remain substantially unchanged. The melting point is lowered depending on the catalyst, the type of monomer and the monomer content.
The research mainly focuses on the polymerization of propylene and 4-methyl-1-pentene, the melting point of the propylene polymer is generally lower than 170 ℃, and the melting point of the 4-methyl-1-pentene polymer is far higher than that of the propylene polymer, but the conversion rate is lower.
Disclosure of Invention
In view of the deficiencies of the prior art, the present application provides a syndiotactic copolymer formed from monomers comprising allylcyclohexane and allylcyclopentane, the syndiotactic copolymer having a relatively high melting point. The invention also provides a preparation method of the copolymer, the copolymer is prepared by using a catalytic system consisting of a metallocene compound and alkylaluminoxane, and the preparation method has the advantages of high conversion rate and the like.
According to one aspect of the present invention, there is provided a copolymer of syndiotactic structure comprising recurring structural units comprising structural units represented by formula I and structural units represented by formula II,
according to a particular embodiment of the copolymer of the invention, the molar ratio of the structural unit of formula I to the unit of formula II is from 100:1 to 1:100, preferably from 10:1 to 1: 10.
According to another embodiment of the copolymer of the present invention, the copolymer further comprises structural units of other comonomers. Wherein the further comonomer is selected from olefins having not more than eighteen carbon atoms, preferably ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexadecene and 1-octadecene. The molar ratio of structural units belonging to the other comonomer to structural units of formula I is from 1:100 to 1: 2. In a specific example, the molar ratio of structural units of the other comonomer to units of formula I is from 1:5 to 1: 7.
According to another embodiment of the copolymer according to the present invention, the copolymer has a weight average molecular weight of 1 to 40 ten thousand, such as 2 to 520 ten thousand. The copolymer has a molecular weight distribution index (Mw/Mn in the present invention) of 1.5 to 3.5, preferably 2.0 to 3.0.
In a specific embodiment, the molar proportion of the monomer unit represented by formula I is 0.01 to 99%, preferably 0.1 to 90%, such as 70 to 90%; the molar proportion of the monomer units of the formula II is from 0.01 to 99%, preferably from 0.1 to 90%, for example from 10 to 20%. The molar proportion of the structural units of the other comonomers is 0-50%, such as 0-20%, such as 0-10%.
According to the invention, the copolymer of syndiotactic structure has a high melting point. The copolymer is a heat-resistant high polymer material.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned copolymer having a syndiotactic structure, comprising adding an allylcyclohexane monomer and an allylcyclopentane monomer to a system, and then copolymerizing the monomers under a catalyst system of a transition metal compound to obtain the copolymer having the syndiotactic structure, wherein the catalyst system comprises the transition metal compound represented by formula III and alkylaluminoxane,
wherein R is1Is a hydrocarbon group, preferably C5-C15Aryl or C1-C10Wherein two R are1Can be bonded into a ring or not; r2And R3Independently a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom or C1-C6Alkyl groups of (a); x is a halogen atom or an alkyl group.
Wherein R is1Is a hydrocarbon radical in which two R are1Can be bonded into a ring or not; r2And R3Independently a hydrogen atom or a hydrocarbon group; x is a halogen atom or an alkyl group.
According to another preferred embodiment of the process of the invention, R1Is C5-C15Aryl or C1-C10Alkyl of (2) may be, for example, C5-C10Aryl or C1-C6Alkyl group of (1). Specific examples are phenyl, pyridyl, quinolyl, methyl, ethyl, propyl or isopropyl. When two R are1When bonded to form a ring, the ring may be bonded to form a 3-to 10-membered ring, preferably a 5-to 6-membered ring.
According to another preferred embodiment of the process of the invention, R2And R3Independently is a hydrogen atom or C1-C6Alkyl groups of (a); x is halogen or C1-C6Alkyl group of (1). Said C is1-C6Such as methyl, ethyl, propyl, isobutyl, butyl, isobutyl, tert-butyl, pentyl or hexyl and the like. Halogen such as fluorine, chlorine, bromine or iodine.
According to a particular embodiment of the process of the present invention, the alkylaluminoxane is represented by formula IV or V,
wherein R is alkyl; n is an integer of 2 to 30.
In a preferred embodiment, in the alkylaluminoxane, R is C1-C6Alkyl groups of (a); n is an integer of 10 to 30. The alkylaluminoxane, such as methylaluminoxane, ethylaluminoxane, and the like. All the commonly used alkylaluminoxanes can be used in the present invention. Preferably, the molar ratio of the alkylaluminoxane to the transition metal compound is 100:1 to 10000:1, preferably 100:1 to 500: 1.
According to a preferred embodiment of the process according to the invention, the molar ratio of the allylcyclohexane monomer and the allylcyclopentane monomer is from 1:100 to 100:1, preferably from 1:10 to 10: 1.
According to a preferred embodiment of the process according to the invention, further comonomers are added to the system. The further comonomer is selected from the group consisting of 1-olefins having not more than eighteen carbon atoms, preferably ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexadecene and 1-octadecene. Preferably the molar ratio of the further comonomer to the allylcyclopentane monomer is from 1:100 to 1:2, such as from 1:5 to 1: 7.
According to a preferred embodiment of the process of the present invention, the concentration of the transition metal compound in the polymerization system is 1X10-8mol/L to 1x10-2mol/L, preferably 1X10-6mol/L to 1x10-2mol/L. The polymerization temperature is-20 ℃ to 120 ℃, preferably 0 ℃ to 80 ℃.
According to the method provided by the invention, the conversion rate of the monomer is high, and the copolymer with a syndiotactic structure can be obtained. The copolymer with the syndiotactic structure provided by the invention has high melting point, good thermal stability and high heat resistance, and can be used as a heat-resistant polymer material in the field of automotive resin.
Drawings
FIG. 1 shows the DSC curve of the polymer of example 1;
FIG. 2 shows the DSC curve of the polymer of example 2;
FIG. 3 shows the DSC curve of the polymer of example 3;
FIG. 4 shows the DSC curve of the polymer of example 4;
FIG. 5 shows the polymer of example 613C-NMR spectrum.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but do not limit the present invention.
The analysis in the present invention is characterized as follows:
(1) thermal analysis: the melting point of the polymer was determined using a differential scanning calorimetry analyzer (DSC, Q100, American TA instruments) according to ASTM D3418. (ii) a
(2) Determination of molecular weight and distribution: waters Alliance GPCV2000 was used with 1,2, 4-trichlorobenzene as the mobile phase. (ii) a
(3) Composition and Structure determination (13C-NMR): the relaxation time, measured at 125 ℃ using Bruker AVANCE III-400MHz, deuterated o-dichlorobenzene as solvent, was 10 s.
EXAMPLE 1 allylcyclopentane and allylcyclohexane copolymerization
Magnetic stirring was turned on, and 0.8ml of allylcyclopentane, 0.2ml of allylcyclohexane, 6ml of 10% (by weight) methylaluminoxane solution containing 20. mu. mol of the metallocene compound Ph, and 0.2ml of 10% (by weight) methylaluminoxane were sequentially added to a 100ml polymerization flask purged with nitrogen three times2C(Cp)(Flu)ZrCl2After 24 hours at 20 ℃, the mixture obtained after the reaction was poured into ethanol containing hydrochloric acid, stirred for 6 hours, and then filtered and washed with ethanol to obtain a polymer. Finally, vacuum drying was carried out at 60 ℃ for 24 hours to obtain 0.80g of a dried polymer, the conversion of the monomer weight>99％。
The dried polymer was determined to have a melting point of 195 deg.C, a weight average molecular weight of 47000 and a molecular weight distribution index of 2.3.
EXAMPLE 2 allylcyclopentane copolymerisation with allylcyclohexane
Magnetic stirring was turned on, and 0.6ml of allylcyclopentane, 0.4ml of allylcyclohexane, 6ml of 10% (by weight) methylaluminoxane solution containing 20. mu. mol of the metallocene compound Ph, and 6ml of a 10% (by weight) methylaluminoxane solution were sequentially added to a 100ml polymerization flask purged with nitrogen three times2C(Cp)(Flu)ZrCl21ml of toluene solution at 20 DEG CThe reaction was continued for 24 hours, after which the mixture obtained after the reaction was poured into ethanol containing hydrochloric acid, stirred for 6 hours, and then filtered and washed with ethanol to obtain a polymer. Finally, vacuum drying was carried out at 60 ℃ for 24 hours to give 0.79g of dried polymer, the conversion by weight of the monomer being 99%.
The dried polymer was determined to have a melting point of 170 ℃, a weight average molecular weight of 58000 and a molecular weight distribution index of 2.2.
Example 3
Allylcyclopentane and allylcyclohexane copolymerization
Magnetic stirring was turned on, and 0.4ml of allylcyclopentane, 0.6ml of allylcyclohexane, 6ml of 10% (by weight) methylaluminoxane solution containing 20. mu. mol of the metallocene compound Ph, and 6ml of a 10% (by weight) methylaluminoxane solution were sequentially added to a 100ml polymerization flask purged with nitrogen three times2C(Cp)(Flu)ZrCl2After 24 hours at 20 ℃, the mixture obtained after the reaction was poured into ethanol containing hydrochloric acid, stirred for 6 hours, and then filtered and washed with ethanol to obtain a polymer. Finally, vacuum drying was carried out at 60 ℃ for 24 hours to obtain 0.80g of a dried polymer, the conversion of the monomer weight>99％。
The dried polymer was determined to have a melting point of 153 ℃, a weight average molecular weight of 54000 and a molecular weight distribution index of 2.5.
Example 4
Allylcyclopentane and allylcyclohexane copolymerization
Magnetic stirring was turned on, and 0.2ml of allylcyclopentane, 0.8ml of allylcyclohexane, 6ml of 10% (by weight) methylaluminoxane solution containing 20. mu. mol of the metallocene compound Ph, and a solution of allylcyclopentane, allylcyclohexane, and methylaluminoxane were sequentially charged into a 100ml polymerization flask purged with nitrogen three times2C(Cp)(Flu)ZrCl2After 24 hours at 20 ℃, the mixture obtained after the reaction was poured into ethanol containing hydrochloric acid, stirred for 6 hours, and then filtered and washed with ethanol to obtain a polymer. Finally, vacuum drying was carried out at 60 ℃ for 24 hours to obtain 0.81g of a dried polymer, the conversion of the monomer weight>99％。
The dried polymer was determined to have a melting point of 178 ℃, a weight average molecular weight of 55000, and a molecular weight distribution index of 2.2.
Example 5
Copolymerization of allylcyclopentane with allylcyclohexane and 4-methyl-1-pentene
Magnetic stirring was turned on, and 0.8mL of allylcyclopentane, 0.2mL of allylcyclohexane, 0.1mL of 4-methyl-1-pentene, 6mL of 10% (by weight) methylaluminoxane solution containing 20. mu. mol of the metallocene compound Ph, were added in this order to a 100mL polymerization flask which had been purged with nitrogen three times2C(Cp)(Flu)ZrCl2After 24 hours at 20 ℃, the mixture obtained after the reaction was poured into ethanol containing hydrochloric acid, stirred for 6 hours, and then filtered and washed with ethanol to obtain a polymer. Finally, vacuum drying was carried out at 60 ℃ for 24 hours to obtain 0.82g of a dried polymer, the conversion of the monomer weight>99％。
The dried polymer was determined to have a melting point of 186 ℃, a weight average molecular weight of 49000, and a molecular weight distribution of 2.3. The polymer contained 73 mol% of allylcyclopentane units, 17 mol% of allylcyclohexane units and 10 mol% of 4-methyl-1-pentene.
Example 6
Copolymerization of allylcyclopentane and allylcyclohexane
Magnetic stirring was turned on, and 1.0ml of allylcyclopentane, 0.1ml of allylcyclohexane, 6ml of 10% (by weight) methylaluminoxane solution containing 20. mu. mol of the metallocene compound Ph, and 1.0ml of allylcyclopentane, 0.1ml of allylcyclohexane, and 6ml of a 10% (by weight) methylaluminoxane solution were sequentially added to a 100ml polymerization flask purged with nitrogen three times2C(Cp)(Flu)ZrCl2After 24 hours at 20 ℃, the mixture obtained after the reaction was poured into ethanol containing hydrochloric acid, stirred for 6 hours, and then filtered and washed with ethanol to obtain a polymer. Finally, vacuum drying was carried out at 60 ℃ for 24 hours to obtain 0.87g of a dried polymer, the conversion of the monomer weight>99％。
The dried polymer was determined to have a melting point of 217 ℃, a weight average molecular weight of 53000, and a molecular weight distribution of 2.1. The polymer contained 87 mol% of allylcyclopentane units and 13 mol% of allylcyclohexane units. It can be further confirmed from fig. 5 that the polymer is a copolymer of a syndiotactic structure.
The olefin polymer with a syndiotactic structure, which contains the allyl cyclohexane unit and the allyl cyclopentane unit as the repeating structures, has a very high melting point, can reach 224 ℃ at most and has a high conversion rate (> 99%).
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (18)
1. A method for preparing a copolymer with a syndiotactic structure comprises the steps of adding an allyl cyclohexane monomer and an allyl cyclopentane monomer into a system, and then carrying out copolymerization in the presence of a catalyst system of a transition metal compound to obtain the copolymer with the syndiotactic structure, wherein the catalyst system comprises the transition metal compound shown in a formula III and alkyl aluminoxane,
wherein R is1Is phenyl; r2And R3Is a hydrogen atom; x is a halogen atom;
wherein the repeating structural unit of the copolymer with the syndiotactic structure comprises a structural unit shown in a formula I and a structural unit shown in a formula II,
2. the method of claim 1, wherein the alkylaluminoxane is represented by formula IV or V,
wherein R is alkyl; n is an integer of 2 to 30.
3. The method of claim 2, wherein R is C1-C6Alkyl groups of (a); n is an integer of 10 to 30.
4. The method of claim 2, wherein the alkylalumoxane is methylalumoxane and/or ethylalumoxane.
5. The method of claim 2, wherein the molar ratio of the alkylalumoxane to the transition metal compound is from 100:1 to 10000: 1.
6. The method of claim 1, wherein the molar ratio of allylcyclohexane monomer to allylcyclopentane monomer is from 100:1 to 1: 100.
7. The method of claim 1, wherein the molar ratio of allylcyclohexane monomer to allylcyclopentane monomer is from 10:1 to 1: 10.
8. The method of claim 1, wherein other comonomers selected from olefins having no more than eighteen carbon atoms are added to the system.
9. The process according to claim 8, characterized in that the other comonomer is selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexadecene and 1-octadecene.
10. The process of claim 8, wherein the molar ratio of the other comonomer to the allylcyclopentane monomer is from 1:100 to 1: 2.
11. The method according to claim 1, wherein the concentration of the transition metal compound in the polymerization system is 1x10-8mol/L to 1x10-2mol/L; and/or the temperature of the polymerization is from-20 ℃ to 120 ℃.
12. The method according to claim 1, wherein the concentration of the transition metal compound in the polymerization system is 1x10-6mol/L to 1x10-2mol/L; and/or the temperature of the polymerization is from 0 ℃ to 80 ℃.
13. The method according to claim 1, wherein the molar ratio of the structural unit of formula I to the unit of formula II is from 100:1 to 1: 100.
14. The method according to claim 1, wherein the molar ratio of the structural unit of formula I to the unit of formula II is from 10:1 to 1: 10.
15. The method of claim 1, wherein the copolymer comprises structural units of other comonomers selected from olefins having no more than eighteen carbon atoms.
16. The method of claim 15, wherein the other comonomer is selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexadecene, and 1-octadecene.
17. The method of claim 15, wherein the molar ratio of structural units of the additional comonomer to units of formula I is from 1:100 to 1: 2.
18. The method of claim 1, wherein the copolymer has a weight average molecular weight of 1 to 40 ten thousand and a molecular weight distribution index of 1.5 to 3.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510660975.1A CN106589199B (en) | 2015-10-14 | 2015-10-14 | Olefin polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510660975.1A CN106589199B (en) | 2015-10-14 | 2015-10-14 | Olefin polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106589199A CN106589199A (en) | 2017-04-26 |
| CN106589199B true CN106589199B (en) | 2019-12-24 |
Family
ID=58552064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510660975.1A Active CN106589199B (en) | 2015-10-14 | 2015-10-14 | Olefin polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589199B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922516B (en) * | 2018-09-20 | 2022-12-30 | 中国石油化工股份有限公司 | Ethylene copolymer and preparation method thereof |
| CN112646258B (en) * | 2019-10-12 | 2023-01-03 | 中国石油化工股份有限公司 | High-barrier polyethylene composition, preparation method thereof, polyethylene film and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB999722A (en) * | 1960-08-11 | 1965-07-28 | Eastman Kodak Co | Polyolefin fibres, yarns and fabrics |
| US3294771A (en) * | 1963-08-27 | 1966-12-27 | Grace W R & Co | Polymerization of allyl cyclopentane with a friedel-crafts catalyst |
| EP0487278A2 (en) * | 1990-11-20 | 1992-05-27 | Mitsubishi Chemical Corporation | Functionalized olefin polymers |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB999723A (en) * | 1960-08-11 | 1965-07-28 | Eastman Kodak Co | A mono-ª‡-olefin and polymers and copolymers thereof |
| GB999772A (en) * | 1960-11-30 | 1965-07-28 | Gulf Research Development Co | Process of hydrogenating esters of diarylketone carboxylic acid |
-
2015
- 2015-10-14 CN CN201510660975.1A patent/CN106589199B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB999722A (en) * | 1960-08-11 | 1965-07-28 | Eastman Kodak Co | Polyolefin fibres, yarns and fabrics |
| US3294771A (en) * | 1963-08-27 | 1966-12-27 | Grace W R & Co | Polymerization of allyl cyclopentane with a friedel-crafts catalyst |
| EP0487278A2 (en) * | 1990-11-20 | 1992-05-27 | Mitsubishi Chemical Corporation | Functionalized olefin polymers |
Non-Patent Citations (1)
| Title |
|---|
| Homo- and Copolymerization of Vinylcyclohexane with α-Olefins in the Presence of Heterogeneous and Homogeneous Catalytic Systems;L.A.Rishina et al.;《Polymer Science》;20061231;第48卷(第1期);第18-25页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106589199A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5651588B2 (en) | Polymacromonomer and method for producing the same | |
| EP1401896B1 (en) | Polymerization process for producing propylene copolymers | |
| US6177377B1 (en) | Polymer blends and process for preparation | |
| JP4334053B2 (en) | Propene polymer, method for producing the same, and method for using the same | |
| KR101154508B1 (en) | Hybrid supported metallocene catalysts, method for preparing the same, and method for preparing the polyolefins using the same | |
| US6566294B2 (en) | Multi-donor catalyst system for the polymerization of olefins | |
| JP4119607B2 (en) | Polydispersed propylene polymer and process for producing the same | |
| CN108137748B (en) | Process for preparing polyolefins having one or more pendant functional groups | |
| MXPA05001171A (en) | Polyolefin block copolymers. | |
| CN106589182B (en) | Polymer with syndiotactic structure and preparation method thereof | |
| JP2018505946A5 (en) | ||
| CN106589199B (en) | Olefin polymer and preparation method thereof | |
| Li et al. | Progress in the catalyst for ethylene/α‐olefin copolymerization at high temperature | |
| US8569434B2 (en) | Ethylene copolymers, catalyst system and process for preparing the same | |
| EP1448633A1 (en) | Two-step polymerization process | |
| Pellecchia et al. | Ethylene—styrene copolymerization | |
| KR101610879B1 (en) | A silica support and preparation method of metallocene catalyst using the same | |
| Kim et al. | Copolymerization of propene and 1-hexene with isospecific and syndiospecific metallocene catalysts | |
| CN102766229B (en) | Catalytic system for preparing polyolefin material containing polar monomer | |
| CN110922516B (en) | Ethylene copolymer and preparation method thereof | |
| KR100242208B1 (en) | Metallocene catalysts and process for preparing polypropylene | |
| CN105566545A (en) | Olefin copolymer and preparation method thereof | |
| US9546230B2 (en) | Methods for stereoselective coordinative chain transfer polymerization of olefins | |
| CN114716599B (en) | Olefin copolymer and preparation method and application thereof | |
| CN106589183A (en) | Olefin polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |