CN115850586A - Comb-shaped ethylene-propylene copolymer, cross-linked comb-shaped ethylene-propylene copolymer and preparation method thereof - Google Patents
Comb-shaped ethylene-propylene copolymer, cross-linked comb-shaped ethylene-propylene copolymer and preparation method thereof Download PDFInfo
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- CN115850586A CN115850586A CN202211648075.1A CN202211648075A CN115850586A CN 115850586 A CN115850586 A CN 115850586A CN 202211648075 A CN202211648075 A CN 202211648075A CN 115850586 A CN115850586 A CN 115850586A
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- ethylene
- propylene
- macromonomer
- catalyst
- comb
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 ethylene, propylene Chemical group 0.000 claims abstract description 58
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims description 105
- 238000007334 copolymerization reaction Methods 0.000 claims description 47
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 43
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 38
- 239000003960 organic solvent Substances 0.000 claims description 24
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 150000004291 polyenes Chemical class 0.000 claims description 19
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 claims description 12
- 229920005604 random copolymer Polymers 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 9
- 239000012968 metallocene catalyst Substances 0.000 claims description 7
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 7
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012005 post-metallocene catalyst Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- ZAAMQANODYDRDF-UHFFFAOYSA-N 3-tert-butyl-2-hydroxybenzoic acid Chemical compound CC(C)(C)C1=CC=CC(C(O)=O)=C1O ZAAMQANODYDRDF-UHFFFAOYSA-N 0.000 claims description 5
- GDBLZKMJBVGZTR-UHFFFAOYSA-K Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl Chemical compound Cl[Ti](OC1=C(C=CC=C1)C1=CC=CC=C1)(C1(C(=C(C(=C1C)C)C)C)C)Cl GDBLZKMJBVGZTR-UHFFFAOYSA-K 0.000 claims description 5
- 125000006312 cyclopentyl amino group Chemical group [H]N(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- PYTPZZGJNMQOKN-UHFFFAOYSA-N C1=CC2=CC=CC=C2C1[Zr](C)(C)C1C2=CC=CC=C2C=C1 Chemical compound C1=CC2=CC=CC=C2C1[Zr](C)(C)C1C2=CC=CC=C2C=C1 PYTPZZGJNMQOKN-UHFFFAOYSA-N 0.000 claims description 4
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 claims description 3
- BGGKSZPSSRGVTP-UHFFFAOYSA-L 2-methyl-1h-inden-1-ide;zirconium(4+);dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C1=CC=C2[CH-]C(C)=CC2=C1.C1=CC=C2[CH-]C(C)=CC2=C1 BGGKSZPSSRGVTP-UHFFFAOYSA-L 0.000 claims description 3
- YNZVRGAKCHKLMI-UHFFFAOYSA-N C1(=CC=CC=C1)P(C=1C=CC=C2CCC(NC=12)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)CC1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)P(C=1C=CC=C2CCC(NC=12)[Zr](CC1=CC=CC=C1)(CC1=CC=CC=C1)CC1=CC=CC=C1)C1=CC=CC=C1 YNZVRGAKCHKLMI-UHFFFAOYSA-N 0.000 claims description 3
- KGWXYUFIQHXOIL-UHFFFAOYSA-K CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O[Ti](Cl)(Cl)C1(C)C(C)=C(C)C(C)=C1C KGWXYUFIQHXOIL-UHFFFAOYSA-K 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
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- GVILDFZVSFXAIF-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr+2]C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr+2]C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 GVILDFZVSFXAIF-UHFFFAOYSA-L 0.000 claims description 3
- FFAYLXSITFDGCE-UHFFFAOYSA-L [Cl-].[Cl-].C[Si](C1=C(C(CC2=C(C=C(C=C2F)F)[Ti+2]C2=C(C(=CC(=C2)F)F)CC=2C(O)=C(C=CC2)[Si](C)(C)C)=CC=C1)O)(C)C Chemical compound [Cl-].[Cl-].C[Si](C1=C(C(CC2=C(C=C(C=C2F)F)[Ti+2]C2=C(C(=CC(=C2)F)F)CC=2C(O)=C(C=CC2)[Si](C)(C)C)=CC=C1)O)(C)C FFAYLXSITFDGCE-UHFFFAOYSA-L 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- IVTQDRJBWSBJQM-UHFFFAOYSA-L dichlorozirconium;indene Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C2=CC=CC=C2C=C1 IVTQDRJBWSBJQM-UHFFFAOYSA-L 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- YQRRFEPNTPQQHU-UHFFFAOYSA-L [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 Chemical compound [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 YQRRFEPNTPQQHU-UHFFFAOYSA-L 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 claims 2
- RBQGALRSGWYFMO-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)[Zr+2]C1=CC=CC=2C3=CC=CC=C3CC1=2 Chemical compound [Cl-].[Cl-].C1(C=CC=C1)[Zr+2]C1=CC=CC=2C3=CC=CC=C3CC1=2 RBQGALRSGWYFMO-UHFFFAOYSA-L 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 abstract description 14
- 229920002725 thermoplastic elastomer Polymers 0.000 abstract description 8
- 229920001155 polypropylene Polymers 0.000 abstract description 6
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- 239000004698 Polyethylene Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
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- 238000006243 chemical reaction Methods 0.000 description 36
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- 239000007789 gas Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000004711 α-olefin Substances 0.000 description 9
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 8
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 8
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Abstract
The invention discloses a comb-shaped ethylene-propylene copolymer, a cross-linked comb-shaped ethylene-propylene copolymer and a preparation method thereof, wherein the comb-shaped ethylene-propylene copolymer takes an ethylene-propylene polymer with adjustable ethylene content as a side chain and an amorphous ethylene-propylene copolymer as a main chain, and firstly an ethylene-propylene macromonomer is prepared through a first reactor and is subjected to ternary polymerization of ethylene, propylene and the ethylene-propylene macromonomer in a second reactor through a cascade catalytic system to synthesize the comb-shaped ethylene-propylene olefin polymer. The comb-shaped ethylene propylene olefin polymer prepared by the invention can be used in various application fields such as thermoplastic elastomers and polyethylene polypropylene phase compatilizers, and has high industrial value.
Description
Technical Field
The invention belongs to the technical field of preparation of high-performance polyolefin, and relates to a comb-shaped ethylene propylene olefin polymer and a preparation method thereof.
Background
Polyolefin thermoplastic elastomers (TPE-Os) are high performance polyolefins consisting of two phases, plastic and rubber. TPE-Os has better chemical stability, transparency, re-processability and electrical insulation properties compared to other thermoplastic elastomers, thereby making it useful in a wide range of applications. The Dow company, USA, developed a constrained geometry metallocene catalyst (CGC) with the trade name ENGAGE in 1993 TM The ethylene/alpha-olefin copolymer-polyolefin elastomer (POE) is used as a high-end product in TPE-O, and the product POE has good processability and light transmission performance. Subsequently, POE production processes were developed in Exxonmobil Chemical (ExxonMobil Chemical), mitsui Petrochemical (Mitsui Petrochemical), LG Chemical (LG Chemical), and Lyondelbasell (Lyondelbasell), respectively. Currently, the market demand for POE is increasing year by year. In order to improve the mechanical and thermal properties of POE with higher alpha-olefin content (low melting temperature and poor mechanical strength), dow further developed OBC (International Business machines corporation) with a chain shuttling polymerization technology in 2006 under the trade name of INFUSE TM . The alternating soft and hard segments provide the OBC with a well distributed crystalline morphology compared to POE of the same alpha-olefin composition. Thus, OBCs exhibit better mechanical properties and thermal stability than POE, which makes OBCs a promising alternative in pharmaceutical packaging and other sophisticated applications.
There are three methods for industrially producing an ethylene/α -olefin copolymer at present, namely, a solution method, a gas phase method and a slurry method (prog.polym.sci.2001, 26, 1287-1336.). However, in the production of POE with high alpha-olefin content, each company adopts a high-temperature solution process. The POE product obtained by the solution method has obviously better product performance, including toughness and elasticity, than the product obtained by the gas phase method. Although there is a patent report (US 5770664) for producing POE by a slurry process, since POE has a low melting point, it is easily swollen in a solvent, and the product is easily melted and agglomerated, there is no industrial example of producing POE by a slurry process. In addition, the chain structure can be better regulated and controlled in the polymerization process by utilizing solution polymerization, and products with different properties can be synthesized by combining the design of the chain structure and the regulation of the polymerization process.
However, the synthesis and separation costs of α -olefins are high, and it is difficult to control the raw material costs and transportation costs in the actual production process using α -olefins as comonomers.
Disclosure of Invention
The invention aims to provide a preparation method of a novel comb-shaped ethylene-propylene olefin polymer aiming at the defects of the existing products and technologies.
The purpose of the invention is realized by the following technical scheme:
the first aspect of the embodiment of the invention provides a comb-shaped ethylene-propylene copolymer, wherein the main chain of the comb-shaped ethylene-propylene copolymer is an ethylene-propylene random copolymer, and the comb-shaped branched chain is the ethylene-propylene random copolymer; wherein the ethylene-propylene random copolymer of the main chain has a weight average molecular weight (M) W ) 20000-500000g/mol, and the mol fraction of propylene is 5% -95%; the weight average molecular weight of the ethylene-propylene random copolymer with propylene mole fraction side chain is 2000-20000mol, the side chain propylene mole fraction is 5% -95%, and the grafting amount is 0.1-20.
The second aspect of the embodiments of the present invention provides a preparation method of a comb-shaped ethylene-propylene copolymer, including the following steps:
(1) Under the anhydrous and anaerobic conditions, adding ethylene, propylene, a macromonomer catalyst, a cocatalyst and an organic solvent into a first reactor, and carrying out polymerization reaction to obtain an ethylene-propylene copolymerized macromonomer; the polymerization temperature is 60-300 ℃, and the polymerization pressure is 0.1-5MPa; the concentration of the macromonomer catalyst is 0.1-100 mu mol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 50-10000; the proportion of terminal double bonds of the prepared ethylene-propylene copolymer macromonomer is 50-100%, the ethylene-propylene copolymer macromonomer has no melting point, and the glass transition temperature is-90-0 ℃;
(2) The solution after the polymerization reaction in the first reactor enters a second reactor, and ethylene, propylene, a copolymerization catalyst, a cocatalyst and an organic solvent are added into the second reactor under the anhydrous and oxygen-free conditions to carry out the ternary polymerization of ethylene/propylene/a macromonomer; the polymerization temperature is 60-300 ℃, and the polymerization pressure is 0.1-5MPa; the concentration of the copolymerization catalyst is 0.1-100 mu mol/L based on the volume of the organic solvent in the second reactor, the molar ratio of the copolymerization catalyst to the macromonomer catalyst is 50.
The third aspect of the embodiment of the invention provides a crosslinkable comb-shaped ethylene-propylene copolymer, wherein the main chain of the crosslinkable comb-shaped ethylene-propylene copolymer is an ethylene-propylene polyene monomer random copolymer, the comb-shaped branched chain is an ethylene-propylene polyene monomer random copolymer, the weight-average molecular weight of the ethylene-propylene polyene monomer random copolymer of the main chain is 20000-500000g/mol, and the molar content of propylene is 5% -95%; in the crosslinkable comb-shaped ethylene-propylene copolymer, the molar content of crosslinking groups is 0.001-10%; the weight average molecular weight of the side chain ethylene-propylene polyene monomer random copolymer is 2000-20000mol, the side chain propylene mole fraction is 5% -95%, the mole content of the crosslinking group is 0.001-10%, and the grafting number is 0.1-20.
The fourth aspect of the embodiment of the invention provides a preparation method of a comb-shaped ethylene-propylene copolymer capable of being crosslinked, which is characterized by comprising the following steps:
(1) Under the anhydrous and anaerobic conditions, adding ethylene, propylene, polyene monomers, a macromonomer catalyst, a cocatalyst and an organic solvent into a first reactor, and carrying out polymerization reaction to obtain an ethylene-propylene-polyene copolymerized macromonomer; the polymerization temperature is about 60-300 ℃, and the polymerization pressure is about 0.1-5MPa; the concentration of the macromonomer catalyst is 0.1-100 μmol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 50-10000, the molar ratio of the ethylene to propylene is 200; the proportion of terminal double bonds of the prepared macromonomer is 50-100%, the macromonomer has no melting point, the glass transition temperature is-90-0 ℃, and the molar content of crosslinking groups is 0.001-10%;
(2) The solution after the polymerization reaction in the first reactor enters a second reactor, and ethylene, propylene, a polyene monomer, a copolymerization catalyst, a cocatalyst and an organic solvent are added into the second reactor under the anhydrous and oxygen-free conditions to carry out the quadripolymer of ethylene/propylene/macromonomer/polyene monomer; the polymerization temperature is 60-300 ℃, and the polymerization pressure is 0.1-5MPa. The concentration of the copolymerization catalyst is 0.1-100 mu mol/L based on the volume of the organic solvent in the second reactor, the molar ratio of the copolymerization catalyst to the macromonomer catalyst is 50.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a comb-shaped ethylene-propylene olefin polymer and a preparation method thereof, the comb-shaped olefin polymer takes an ethylene-propylene polymer with adjustable ethylene content as a side chain and an amorphous ethylene-propylene copolymer as a main chain, and an ethylene-propylene macromonomer is prepared by a first reactor through a cascade catalysis system, and the ethylene-propylene macromonomer is subjected to ternary polymerization of ethylene, propylene and the ethylene-propylene macromonomer in a second reactor to synthesize the comb-shaped ethylene-propylene olefin polymer.
According to the invention, through the design of a topological structure of a copolymer chain, an ethylene-propylene copolymer macromonomer with a terminal double bond is synthesized firstly as a side chain of the polymer, and ethylene-propylene is copolymerized with the macromonomer, so that the ethylene-propylene copolymer macromonomer with the side chain can replace the function of an alpha-olefin branched chain, and finally, the novel comb-shaped ethylene-propylene olefin polymer is synthesized.
The invention firstly uses the macromonomer catalyst to catalyze ethylene-propylene mixed gas to generate ethylene-propylene macromonomer, and the macromonomer is copolymerized with ethylene-propylene to obtain a product, wherein the content of propylene in the main chain and the side chain has a large adjustable range, can replace expensive alpha-olefin, can be used in various application fields such as thermoplastic elastomers and the like, and has high industrial value.
Drawings
FIG. 1 is a structural formula of a comb-shaped ethylene-propylene copolymer;
FIG. 2 is a structural formula of a crosslinkable comb-shaped ethylene-propylene copolymer.
Detailed Description
The present invention is illustrated by the following specific examples, but the scope of the present invention is not limited to the following examples.
The embodiment of the invention provides a comb-shaped ethylene-propylene copolymer, wherein the main chain of the comb-shaped ethylene-propylene copolymer is an ethylene-propylene random copolymer, and the comb-shaped branched chain of the comb-shaped ethylene-propylene copolymer is an ethylene-propylene random copolymer. The weight-average molecular weight of the ethylene-propylene random copolymer of the main chain is 20000-500000g/mol, and the mole fraction of propylene is 5% -95%; preferably, the backbone propylene mole fraction is 10% to 70%. The weight average molecular weight of the ethylene-propylene random copolymer of the side chain is 2000-20000mol, the mole fraction of the side chain propylene is 5% -95%, and the grafting amount is 0.1-20; preferably, the grafting amount is from 0.5 to 8. The comb-shaped ethylene-propylene copolymer has no melting point and the glass transition temperature of-90-0 ℃.
The structural formula of the comb-shaped ethylene-propylene copolymer is shown in figure 1, wherein a is the number of ethylene repeating units in a polymer main chain, b is the number of propylene repeating units in the polymer main chain, c is the number of macromonomer repeating units in the polymer main chain, w is the number of ethylene propylene macromonomer composition units in the polymer main chain, x is the number of ethylene repeating units in a polymer side chain, y is the number of propylene repeating units in the polymer side chain, z is the number of ethylene propylene units in the polymer side chain, and n is more than or equal to 0.
The second aspect of the embodiment of the invention provides a preparation method of a comb-shaped ethylene-propylene copolymer, which is characterized by comprising the following steps:
(1) Under the anhydrous and anaerobic condition, adding ethylene, propylene, a macromonomer catalyst, a cocatalyst and an organic solvent into a first reactor, and carrying out polymerization reaction to obtain the ethylene-propylene copolymerized macromonomer. The polymerization temperature is about 60-300 ℃, and the polymerization pressure is about 0.1-5MPa. The concentration of the macromonomer catalyst is 0.1-100 μmol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 50-10000, the molar ratio of the ethylene to propylene is 200. The proportion of the terminal double bond of the prepared macromonomer is 50-100%, the macromonomer has no melting point, and the glass transition temperature is-90-0 ℃; preferably, the proportion of terminal double bonds of the resulting macromonomer is 80 to 100%. The weight average molecular weight of the ethylene propylene macromonomer is preferably 6000 to 10000g/mol.
(2) The solution after the polymerization reaction in the first reactor enters a second reactor, and ethylene, propylene, a copolymerization catalyst, a cocatalyst and an organic solvent are added into the second reactor under the anhydrous and oxygen-free conditions to carry out the ternary polymerization of ethylene/propylene/a macromonomer; the polymerization temperature is 60-300 ℃, and the polymerization pressure is 0.1-5MPa. The concentration of the copolymerization catalyst is 0.1-100 mu mol/L based on the volume of the organic solvent in the second reactor, the molar ratio of the copolymerization catalyst to the macromonomer catalyst is 50. The step 2 ethylene to propylene ratio is preferably 5.
The macromonomer catalyst is a single-active-center metallocene catalyst or a post-metallocene catalyst, and is selected from rac-ethenylene bridged bis-indenyl zirconium dichloride, rac-dimethylsilane bridged bis (2-methylindenyl) zirconium dichloride, rac-dimethylsilane bridged bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, rac-dimethylsilane bridged bis-indenyl dimethyl hafnium, meso-diphenylmethyl bridged-cyclopentadienyl-fluorenyl-zirconium dichloride, dimethylsilane bridged- (3, 5-diisopropylcyclopentadienyl) - (4-isopropylcyclopentadienyl) zirconium dichloride, dimethylsilane bridged-fluorenyl-tert-butylamino-dimethyl titanium, bis [ N- (3-tert-butylsalicylic acid) cyclopentylamino ] zirconium dichloride and bis (3-trimethylsilylsalicyl-3, 5-difluorophenyl) titanium dichloride.
The copolymerization catalyst is a single-active-center metallocene catalyst or a post-metallocene catalyst, and is selected from biscyclopentadienylhafnium dimethyl, bisindenyl zirconium dimethyl, vinylidene bridged bisindenyl zirconium dichloride, dimethylsilyl bridged-bisindenyl zirconium dichloride, diphenylcarbon bridged-cyclopentadienyl-fluorenyl zirconium dichloride, dimethylsilyl bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, bisindenyl zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, biscyclopentadienyl-bisphenoxy zirconium, dimethylsilyl bridged-bisindenyl zirconium dimethyl, diphenylcarbon-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarbon bridged-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, dimethylsilyl bridged-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride, dimethylsilyl-3-pyrrolyl-tert-butylamino-dimethyl titanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride, bis (3-dimethylaminochloro-ylidene-3-bis (3-dimethylaminoylidene) -indenyl titanium dichloride, and salicylanilinium, [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenylimine ] titanium trichloride, (2, 3, 4-trihydro-8-diphenylphosphino-quinolyl) tribenzylzirconium.
The cocatalyst is selected from methylaluminoxane, modified methylaluminoxane, a tri (pentafluorophenyl) boron compound, a tetra (pentafluorophenyl) boron compound, triisobutyl aluminum, triethyl aluminum and trimethyl aluminum.
The organic solvent is straight-chain alkane, isoparaffin, cycloparaffin or aromatic alkane with 4-10 carbon atoms. Preferably, the solvent is n-butane, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene, xylene.
The following description will discuss the preparation of comb-like ethylene-propylene copolymers with reference to examples 1-1 to 1-14, wherein examples 1-1 to 1-14 are two-pot tandem continuous solution polymerizations conducted in two 300ml polymerization reactors. The feed molar concentrations to be used in examples 1-1 to 1-14 of the present invention refer to initial concentrations of ethylene and propylene monomers in a solution when they enter a reaction vessel in terms of the volume of an organic solvent, and the feed molar ratio refers to an initial molar fraction ratio of ethylene to propylene monomers when they enter the reaction vessel.
Examples 1 to 1
In the experiment, a macromonomer catalyst adopts rac-dimethylsilicon bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, a copolymerization catalyst adopts dimethylsilicon bridged-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride, a cocatalyst adopts methylaluminoxane, a solvent is Isopar E, mixed gas ethylene propylene is fed in a molar ratio of 7. Prior to the experiment, the autoclave and tubing were purged with a solution of triisobutylaluminum and Isopar E to remove water oxygen. Weighing quantitative macromonomer catalyst, copolymerization catalyst and cocatalyst, transferring under the protection of nitrogen atmosphere, preparing solutions with Isopar E respectively, and storing the solutions in respective storage tanks, wherein the solvent Isopar E is also stored in a solvent storage tank.
The experimental steps are as follows: opening the reaction kettle and the pipeline oil bath, raising the temperature of the kettle 1 to 140 ℃, raising the temperature of the kettle 2 to 140 ℃, and setting the stirring speed to be 1000rpm; opening the feed valve and the discharge valve of the two kettles, opening the No. 1-5 high-pressure chemical metering pumps, continuously inputting the five metering pumps into the reaction kettle according to the set flow rate, wherein the ethylene-propylene mixed gas, the macromonomer catalyst, the cocatalyst and the solvent continuously enter the kettle 1, the discharge of the kettle 1, the copolymerization catalyst, the cocatalyst and the solvent continuously enter the kettle 2, and the pressure relief discharge of the kettle 2 is carried out to obtain the final product. The pressure in the reaction kettle is controlled by a proportional valve, when the pressure in the kettle 1 is stabilized at 18bar and the pressure in the kettle 2 is stabilized at 15bar, the system is stable, the concentration of the macromonomer catalyst in the kettle 1 is 2 mu mol/L, the concentration of the cocatalyst is 10mmol/L, the molar ratio of the cocatalyst to the main catalyst is 5000, the temperature in the kettle is controlled at 140 ℃ in a steady state, the pressure in the kettle is controlled at 18bar, and the retention time of the material in the kettle is 8min; the concentration of the copolymerization catalyst in the kettle 2 is 20 mu mol/L, the concentration of the cocatalyst is 20mmol/L, the molar ratio of the cocatalyst to the main catalyst is 1000, the molar ratio of the ethylene to the propylene is 7, the temperature in the kettle is controlled at 140 ℃ in a steady state, the pressure in the kettle is controlled at about 15bar, and the retention time of the materials in the reaction kettle is 10min; the continuously flowing-out material is washed for a plurality of times by a large amount of acidified ethanol, filtered, pumped to dryness and dried in vacuum at 70 ℃ for more than 8 hours.
The molecular weights (Mw and Mn) of the polymers and their distribution indices (PDI) were determined by high temperature gel permeation chromatography (PL-GPC 220). 1,2, 4-trichlorobenzene is used as a solvent to prepare 0.1 to 0.3 weight percent of polymer solution at the temperature of 150 ℃, polystyrene with narrow molecular weight distribution is used as a standard sample to measure at the temperature of 150 ℃, and the flow rate of the solvent is 1.0ml/min. The parameter K =17.5 × 10 was used for all PS standards -4 α =0.67, pe parameter K =59.1 × 10 -4 ，α＝0.69。
The melting point (Tm) of the copolymer was determined by TA Instruments Q200. Taking 5.0-7.0 mg of polymer sample, heating to 200 ℃ at 30 ℃/min, keeping the temperature for 5min to eliminate thermal history, then cooling to-90 ℃ at 10 ℃/min, keeping the temperature for 3min, heating to 200 ℃ at 10 ℃/min, and obtaining the melting point of the polymer from the second heating curve.
Average composition of comonomer in copolymer Using NMR (C.R.), ( 13 C NMR) was measured at 125 ℃ and the instrument model was Bruker AC 400. The polymer is prepared into a deuterated o-dichlorobenzene solution with the mass fraction of 10% at 150 ℃, and the deuterated o-dichlorobenzene solution is dissolved in advance for 3 to 4 hours, so that the sample solution is uniform. The instrument parameters are optimized to be pulse angle of 90 degrees, reverse proton decoupling, pulse delay time of 8s, collection time of 1.3s and spectrum width of 8000Hz, and the average scanning times are not less than 5000 times.
Examples 1 to 2
The experimental conditions were: after the system reaches a steady state, the reaction temperature in the kettle 1 is 70 ℃, the concentration of the macromonomer catalyst is 0.5 mu mol/L, the concentration of the cocatalyst is 5mmol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 10000, the reaction temperature in the kettle 2 is 70 ℃, and other experimental conditions are the same as those in example 1-1.
Examples 1 to 3
The experimental conditions were: after the system reaches a steady state, the reaction temperature in the kettle 1 is 290 ℃, the concentration of the macromonomer catalyst is 95 μmol/L, the concentration of the cocatalyst is 47.5mmol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 50, the reaction temperature in the kettle 2 is 290 ℃, and other experimental conditions are the same as those in example 1-1.
Examples 1 to 4
The experimental conditions were: after the system reaches a steady state, the concentration of the copolymerization catalyst in the kettle 2 is 0.5 mu mol/L, the concentration of the cocatalyst is 5mmol/L, the molar ratio of the cocatalyst to the main catalyst is 10000, and other experimental conditions are the same as those in example 1-1.
Examples 1 to 5
The experimental conditions were: after the system reaches a steady state, the concentration of the copolymerization catalyst in the kettle 2 is 95 mu mol/L, the concentration of the cocatalyst is 47.5mmol/L, the molar ratio of the cocatalyst to the main catalyst is 50, and other experimental conditions are the same as those in example 1-1.
Examples 1 to 6
The experimental conditions were: after the system reached steady state, the ethylene-propylene feed molar ratio in tank 1 was 5, the operating pressure was 48bar, the ethylene-propylene feed molar ratio in tank 2 was 5.
Examples 1 to 7
The experimental conditions were: after the system reached steady state, the ethylene propylene feed molar ratio in tank 1 was 2, the operating pressure was 0.5bar, the ethylene propylene feed molar ratio in tank 2 was 1, the operating pressure was 0.3bar, and other experimental conditions were the same as in example 1-1.
Examples 1 to 8
The experimental conditions were: changing the macromonomer catalyst to be bis [ N- (3-tert-butylsalicylic acid) cyclopentylamino ] zirconium dichloride, changing the copolymerization catalyst to be bis-indenyl dimethyl zirconium, wherein the residence time of the kettle 1 is 3min, and the residence time of the kettle 2 is 3 min. Other experimental conditions were the same as in example 1-1.
Examples 1 to 9
The experimental conditions were: changing the macromonomer catalyst to be dimethyl silicon bridged- (3, 5-diisopropyl cyclopentadienyl) - (4-isopropyl cyclopentadienyl) zirconium dichloride, changing the copolymerization catalyst to be dimethyl silicon bridged bis indenyl dimethyl zirconium, wherein the residence time of the kettle 1 is 57min, and the residence time of the kettle 2 is 57 min. Other experimental conditions were the same as in example 1-1.
Examples 1 to 10
The experimental conditions were: the cocatalyst of the kettle 1 is changed into modified methylaluminoxane, the cocatalyst of the kettle 2 is changed into a tri (pentafluorophenyl) boron compound, and the solvent is changed into n-hexane. Other experimental conditions were the same as in example 1-1. Examples 1-11 were carried out as batch copolymerizations in a 500ml olefin batch polymerization reactor.
Examples 1 to 11
In the experiment, a macromonomer catalyst adopts dimethyl silicon bridged-fluorenyl-tert-butylamino-dimethyl titanium, a copolymerization catalyst adopts pentamethyl cyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, a cocatalyst adopts triisobutylaluminum, a solvent is toluene, and monomers are ethylene and propylene. Polymerization experiments were conducted in a batch solution system. Before the experiment, the reaction kettle is repeatedly vacuumized and replaced by nitrogen at 110 ℃ for 6 hours, and then vacuumized and replaced by ethylene-propylene mixed gas for three times, so that the whole pipeline and the inside of the reaction kettle meet the requirements of sealing, water-free and oxygen-free.
The experimental steps are as follows: the method comprises the following steps of reducing the temperature of a reaction kettle to 140 ℃, then opening a liquid feed valve, adding 440ml of solvent toluene and 10mmol of cocatalyst into the reaction kettle, then immediately closing the liquid feed valve, opening and stirring to 1000 r/min, adding a macromonomer catalyst into the reaction kettle through pressure difference after the temperature in the kettle is raised to the reaction temperature, rapidly increasing the pressure in the kettle to 1.5MPa, and then continuously replenishing the consumption amount of ethylene-propylene mixed gas in the kettle through a pressure reducing valve in the reaction process to ensure that the pressure in the kettle is constant. Reacting at constant temperature and constant pressure for 10min, adding the copolymerization catalyst into the reaction kettle by pressure difference, continuing to react for 20min, closing the gas feed valve, opening the gas vent valve to release pressure, then opening the liquid discharge valve, and pouring the materials into a beaker filled with a large amount of acidified ethanol. The polymer was filtered and washed several times with acidified ethanol and dried under vacuum at 70 ℃ for more than 8 hours.
In the experiment, the concentration of the macromonomer catalyst in the reactor is 2. Mu. Mol/L, the concentration of the copolymerization catalyst promoter is 10. Mu. Mol/L, and the feeding molar ratio of ethylene to propylene is 7. All materials used in the experiment were subjected to water removal and oxygen removal.
Table 1: results of a tandem catalytic solution copolymerization experiment
Note: ENGAGE 8150 represents a POE industrial sample from DOW
As shown in the table 1, a series of novel comb-shaped ethylene-propylene olefin polymers are prepared by the invention, and the mechanical properties show that the polymers all show the properties of typical thermoplastic elastomers. The elastomer possessed similar or even higher strength and elongation at break than the industrial sample ENGAGE 8150. Because the polymer contains long-chain branches, the high-viscosity-free-cutting polypropylene composite material has higher zero-cut viscosity and melt index, has obvious shear thinning phenomenon in the processing process, and is beneficial to processing and molding. Meanwhile, the method embodies obvious compatibilization in the blending process of polyethylene and polypropylene, and effectively eliminates a phase interface. Showing lower cost and wider use than POE.
The third aspect of the embodiments of the present invention provides a crosslinkable comb-shaped ethylene-propylene copolymer, in which a main chain of the crosslinkable comb-shaped ethylene-propylene copolymer is an ethylene-propylene polyene monomer random copolymer, and a comb-shaped branched chain of the crosslinkable comb-shaped ethylene-propylene copolymer is an ethylene-propylene polyene monomer random copolymer. The weight-average molecular weight of the ethylene-propylene polyene monomer random copolymer of the main chain is 20000-500000g/mol, and the propylene molar content is 5-95%; preferably, the main chain propylene molar content is 10% -70%, and in the crosslinkable comb-shaped ethylene-propylene copolymer, the molar content of crosslinking groups is 0.001-10%. The weight average molecular weight of the ethylene-propylene-polyene monomer random copolymer of the side chain is 2000-20000mol, the mole fraction of the side chain propylene is 5% -95%, the mole content of the crosslinking group is 0.001-10%, and the grafting quantity is 0.1-20; preferably, the grafting amount is from 0.5 to 8. The crosslinkable comb-shaped ethylene-propylene copolymer has no melting point and the glass transition temperature of-90-0 ℃.
The structural formula of the crosslinkable comb-shaped ethylene-propylene copolymer is shown in figure 2, wherein a is the number of ethylene repeating units in a polymer main chain, b is the number of propylene repeating units in the polymer main chain, c is the number of ethylene-propylene polyene macromonomer repeating units in the polymer main chain, d is the number of polyene monomer repeating units in the polymer main chain, e is the number of polyene monomer repeating units in a polymer side chain, w is the number of ethylene propylene macromonomer polyene forming units in the polymer main chain, x is the number of ethylene repeating units in the polymer side chain, y is the number of propylene repeating units in the polymer side chain, z is the number of ethylene propylene polyene units in the polymer side chain, and n is more than or equal to 0.
The fourth aspect of the embodiments of the present invention provides a crosslinkable comb-like ethylene-propylene copolymer and a preparation method thereof, comprising the following steps:
(1) Under the anhydrous and oxygen-free conditions, adding ethylene, propylene, polyene monomers, a macromonomer catalyst, a cocatalyst and an organic solvent into a first reactor, and carrying out polymerization reaction to obtain the ethylene-propylene-polyene copolymerized macromonomer. The polymerization temperature is about 60-300 ℃ and the polymerization pressure is about 0.1-5MPa. The concentration of the macromonomer catalyst is 0.1-100 μmol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 50-10000, the molar ratio of the ethylene to propylene is 200. The proportion of the terminal double bonds of the prepared macromonomer is 50-100%, the macromonomer has no melting point, the glass transition temperature is-90-0 ℃, and the molar content of crosslinking groups is 0.001-10%; preferably, the proportion of terminal double bonds of the macromonomer produced is 80 to 100%. The weight average molecular weight of the prepared ethylene-propylene-polyene comonomer is preferably 6000 to 10000g/mol.
(2) The solution after the polymerization reaction in the first reactor enters a second reactor, and ethylene, propylene, a polyene monomer, a copolymerization catalyst, a cocatalyst and an organic solvent are added into the second reactor under the anhydrous and oxygen-free conditions to carry out the quadripolymer of ethylene/propylene/macromonomer/polyene monomer; the polymerization temperature is 60-300 ℃, and the polymerization pressure is 0.1-5MPa. The concentration of the copolymerization catalyst is 0.1-100 μmol/L based on the volume of the organic solvent in the second reactor, the molar ratio of the copolymerization catalyst to the macromonomer catalyst is 50; the feeding molar ratio of the polyene monomer to the propylene is 1-25.
The crosslinkable macromonomer catalyst is a single-active-center metallocene catalyst or a post-metallocene catalyst, and is selected from rac-ethenylene bridged bis-indenyl zirconium dichloride, rac-dimethylsilane bridged bis (2-methylindenyl) zirconium dichloride, rac-dimethylsilane bridged bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, rac-dimethylsilane bridged bis-indenyl hafnium dimethyl, meso-diphenylmethyl bridged-cyclopentadienyl-fluorenyl-zirconium dichloride, dimethylsilane bridged- (3, 5-diisopropylcyclopentadienyl) - (4-isopropylcyclopentadienyl) zirconium dichloride, dimethylsilane bridged-fluorenyl-tert-butylamino-dimethyl titanium dichloride, bis [ N- (3-tert-butylsalicylic acid) cyclopentylamino ] zirconium dichloride and bis (3-trimethylsilylsalicyl-3, 5-difluorophenyl) titanium dichloride.
The copolymerization catalyst is a single-active-center metallocene catalyst or a post-metallocene catalyst, and is selected from biscyclopentadienyl hafnium dimethyl, bisindenyl zirconium dimethyl, vinylidene bridged bisindenyl zirconium dichloride, dimethylsilyl bridged-bisindenyl zirconium dichloride, diphenylcarbon bridged-cyclopentadienyl-fluorenyl zirconium dichloride, dimethylsilyl bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, bisindenyl zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, biscyclopentadienyl-bisphenoxyzirconium, dimethylsilyl-bridged bis-indenyl-dimethylzirconium, diphenylcarbon-bridged-cyclopentadienyl-fluorenyl-dimethylzirconium, diphenylcarbon-bridged-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride, dimethylsilyl-bridged-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride, bis (3-methylsalicylidene-pentafluorobenzimidino) titanium dichloride, bis (salicylidene-phenylimino) titanium dichloride, dimethylsilyl-bridged-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium dichloride, [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenylimine ] titanium trichloride, (2, 3, 4-trihydro-8-diphenylphosphino-quinolyl) tribenzylzirconium.
The cocatalyst is selected from methylaluminoxane, modified methylaluminoxane, a tri (pentafluorophenyl) boron compound, a tetra (pentafluorophenyl) boron compound, triisobutylaluminum, triethylaluminum and trimethylaluminum.
The organic solvent is straight-chain alkane, isoparaffin, cycloparaffin or aromatic alkane with 4-10 carbon atoms. Preferably, the solvent is n-butane, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene, xylene.
The polyene monomer includes a straight chain type diene monomer, a cyclic diene monomer, a straight chain triene monomer, a cyclic triene monomer, a alkene having a benzene ring and the like, and preferably butadiene, 1, 5-hexadiene, 1, 4-hexadiene, 1, 7-octadiene, 1, 9-decadiene, 1, 4-isoprene, cyclopentadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinylbicyclo [2.2.1] hept-2-ene, styrene, cyclohexadiene and the like.
The following description of the preparation of the crosslinkable comb-like ethylene-propylene olefin polymers is given in conjunction with examples 2-1 to 2-14, examples 2-1 to 2-14 being two-pot series continuous solution polymerizations carried out in two 300ml polymerization reactors. The feed molar concentrations to be used in examples 2-1 to 2-14 of the present invention refer to initial concentrations of ethylene and propylene monomers in a solution when they enter a reaction vessel in terms of the volume of an organic solvent, and the feed molar ratio refers to an initial molar fraction ratio of ethylene, propylene and polyene monomers when they enter the reaction vessel.
Example 2-1
In the experiment, a macromonomer catalyst adopts rac-dimethylsilicon-bridged-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, a copolymerization catalyst adopts dimethylsilicon-bridged-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride, a cocatalyst adopts methylaluminoxane, a solvent is Isopar E, mixed gas of ethylene and propylene is fed according to a molar ratio of 7, and the feeding molar ratio of 1, 9-decadiene to propylene is 0.05. The polymerization experiments were carried out in a two-pot series continuous solution system. Prior to the experiment, the autoclave and tubing were purged with a solution of triisobutylaluminum and Isopar E to remove water oxygen. Weighing quantitative macromonomer catalyst, copolymerization catalyst and cocatalyst, transferring under the protection of nitrogen atmosphere, preparing solutions with Isopar E respectively, and storing the solutions in respective storage tanks, wherein the solvent Isopar E is also stored in a solvent storage tank.
The experimental steps are as follows: opening the reaction kettle and the pipeline oil bath, raising the temperature of the kettle 1 to 140 ℃, raising the temperature of the kettle 2 to 140 ℃, and setting the stirring speed to 1000rpm; opening the feed valve and the discharge valve of the two kettles, opening the No. 1-5 high-pressure chemical metering pump, continuously inputting the five metering pumps into the reaction kettle according to the set flow rate, wherein the ethylene-propylene mixed gas, the polyene monomer, the macromonomer catalyst, the cocatalyst and the solvent continuously enter the kettle 1, the discharge of the kettle 1, the ethylene-propylene mixed gas, the polyene monomer, the copolymerization catalyst, the cocatalyst and the solvent continuously enter the kettle 2, and the pressure relief and the discharge of the kettle 2 are carried out to obtain the final product. The pressure in the reaction kettle is controlled by proportional valves, when the pressure in the kettle 1 is stabilized at 18bar and the pressure in the kettle 2 is stabilized at 15bar, the system is stable, the concentration of the macromonomer catalyst in the kettle 1 is 2 mu mol/L, the concentration of the cocatalyst is 10mmol/L, the molar ratio of the cocatalyst to the main catalyst is 5000, the temperature in the kettle is controlled at 140 ℃ in a stable state, the pressure in the kettle is controlled at 18bar, and the retention time of materials in the kettle is 8min; the concentration of a copolymerization catalyst in the kettle 2 is 20 mu mol/L, the concentration of a cocatalyst is 20mmol/L, the molar ratio of the cocatalyst to a main catalyst is 1000, the molar ratio of the ethylene to propylene to be fed is 7, 3,1, 9-decadiene to propylene is 0.05, the temperature in the kettle is controlled at 140 ℃ in a steady state, the pressure in the kettle is controlled at about 15bar, and the retention time of materials in the reaction kettle is 10min; the continuously flowing-out material is washed for several times by a large amount of acidified ethanol, filtered, pumped to dryness and dried under vacuum at 70 ℃ for more than 8 hours.
The molecular weights (Mw and Mn) of the polymers and their distribution indices (PDI) were determined by high temperature gel permeation chromatography (PL-GPC 220). 1,2, 4-trichlorobenzene is used as solvent to prepare 0.1-0.3 wt% polymer solution at 150 deg.C, polystyrene with narrow molecular weight distribution is used as standard sample at 150 deg.CThe flow rate of the solvent was 1.0ml/min, measured at DEG C. The parameter K =17.5 × 10 was used for all PS standards -4 α =0.67, pe parameter K =59.1 × 10 -4 ，α＝0.69。
The melting point (Tm) of the copolymer was determined by TA Instruments Q200. Taking 5.0-7.0 mg of polymer sample, heating to 200 ℃ at 30 ℃/min, keeping the temperature for 5min to eliminate thermal history, then cooling to-90 ℃ at 10 ℃/min, keeping the temperature for 3min, heating to 200 ℃ at 10 ℃/min, and obtaining the melting point of the polymer from the second heating curve.
Average composition of comonomer in copolymer Using NMR (C.R.), ( 13 C NMR) was measured at 125 ℃ and the instrument model was Bruker AC 400. The polymer is prepared into a deuterated o-dichlorobenzene solution with the mass fraction of 10% at 150 ℃, and the deuterated o-dichlorobenzene solution is dissolved in advance for 3 to 4 hours, so that the sample solution is uniform. The instrument parameters are optimized to be pulse angle of 90 degrees, reverse proton decoupling, pulse delay time of 8s, collection time of 1.3s and spectrum width of 8000Hz, and the average scanning times are not less than 5000 times.
Examples 2 to 2
The experimental conditions were: after the system reaches a steady state, the reaction temperature in the kettle 1 is 70 ℃, the concentration of the macromonomer catalyst is 0.5 mu mol/L, the concentration of the cocatalyst is 5mmol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 10000, the reaction temperature in the kettle 2 is 70 ℃, and other experimental conditions are the same as those in example 2-1.
Examples 2 to 3
The experimental conditions were: after the system reaches a steady state, the reaction temperature in the kettle 1 is 290 ℃, the concentration of the macromonomer catalyst is 95 μmol/L, the concentration of the cocatalyst is 47.5mmol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 50, the reaction temperature in the kettle 2 is 290 ℃, and other experimental conditions are the same as those in example 2-1.
Examples 2 to 4
The experimental conditions were: after the system reaches a steady state, the concentration of the copolymerization catalyst in the kettle 2 is 0.5 mu mol/L, the concentration of the cocatalyst is 5mmol/L, the molar ratio of the cocatalyst to the main catalyst is 10000, and other experimental conditions are the same as those in example 2-1.
Examples 2 to 5
The experimental conditions were: after the system reaches a steady state, the concentration of the copolymerization catalyst in the kettle 2 is 95 mu mol/L, the concentration of the cocatalyst is 47.5mmol/L, the molar ratio of the cocatalyst to the main catalyst is 50, and other experimental conditions are the same as those in example 2-1.
Examples 2 to 6
The experimental conditions were: after the system reached steady state, the ethylene propylene feed molar ratio in tank 1 was 5, 2,1, 9-decadiene to propylene feed molar ratio was 20, the operating pressure was 48bar, the ethylene propylene feed molar ratio in tank 2 was 5, the operating pressure was 45bar, and other experimental conditions were the same as in example 2-1.
Examples 2 to 7
The experimental conditions were: after the system reached steady state, the ethylene propylene feed molar ratio in tank 1 was 2, the polyene monomer was changed to 1, 5-hexadiene, the 1, 5-hexadiene to propylene feed molar ratio was 0.1, the operating pressure was 0.5bar, the ethylene propylene feed molar ratio in tank 2 was 1.
Examples 2 to 8
The experimental conditions were: changing the macromonomer catalyst to be bis [ N- (3-tert-butylsalicylic acid) cyclopentylamino ] zirconium dichloride, changing the copolymerization catalyst to be bis-indenyl dimethyl zirconium, wherein the residence time of the kettle 1 is 3min, and the residence time of the kettle 2 is 3 min. Other experimental conditions were the same as in example 2-1.
Examples 2 to 9
The experimental conditions were: changing the macromonomer catalyst to be dimethyl silicon bridged- (3, 5-diisopropyl cyclopentadienyl) - (4-isopropyl cyclopentadienyl) zirconium dichloride, changing the copolymerization catalyst to be dimethyl silicon bridged bis indenyl dimethyl zirconium, wherein the residence time of the kettle 1 is 57min, and the residence time of the kettle 2 is 57 min. Other experimental conditions were the same as in example 2-1.
Examples 2 to 10
The experimental conditions were: the cocatalyst of the kettle 1 is changed into modified methylaluminoxane, the cocatalyst of the kettle 2 is changed into a tri (pentafluorophenyl) boron compound, and the solvent is changed into n-hexane. Other experimental conditions were the same as in example 1. Example 11 was a batch copolymerization conducted in a 500ml olefin batch polymerization reactor.
Examples 2 to 11
In the experiment, a macromonomer catalyst adopts dimethyl silicon bridged-fluorenyl-tert-butylamino-dimethyl titanium, a copolymerization catalyst adopts pentamethyl cyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, a cocatalyst adopts triisobutyl aluminum, a solvent is toluene, and monomers are ethylene, propylene and 1, 9-decadiene. Polymerization experiments were conducted in a batch solution system. Before the experiment, the reaction kettle is repeatedly vacuumized and replaced by nitrogen at 110 ℃ for 6 hours, and then vacuumized and replaced by ethylene-propylene mixed gas for three times, so that the whole pipeline and the inside of the reaction kettle meet the requirements of sealing, water-free and oxygen-free.
The experimental steps are as follows: the method comprises the following steps of firstly reducing the temperature of a reaction kettle to 140 ℃, then opening a liquid feed valve, adding 440ml of solvent toluene, 30ml of 1, 9-decadiene and 10mmol of cocatalyst into the reaction kettle, then immediately closing the liquid feed valve, opening and stirring to 1000 r/min, adding a macromonomer catalyst into the reaction kettle through pressure difference after the temperature in the kettle is raised to the reaction temperature, rapidly increasing the pressure in the kettle to 1.5MPa, and continuously supplying the consumption of ethylene-propylene mixed gas in the kettle through a pressure reducing valve in the reaction process so as to ensure constant pressure in the kettle. Reacting at constant temperature and constant pressure for 10min, adding the copolymerization catalyst into the reaction kettle by pressure difference, continuing to react for 20min, closing the gas feed valve, opening the gas vent valve to release pressure, then opening the liquid discharge valve, and pouring the materials into a beaker filled with a large amount of acidified ethanol. The polymer was filtered and washed several times with acidified ethanol and dried under vacuum at 70 ℃ for more than 8 hours.
In this experiment, the concentration of the macromonomer catalyst in the reactor was 2. Mu. Mol/L, the concentration of the copolymerization catalyst promoter was 10. Mu. Mol/L, and the feed molar ratio of ethylene to propylene was 7, 3,1, 9-decadiene to propylene was 0.84. All materials used in the experiment were subjected to water removal and oxygen removal.
Table 2: results of a tandem catalytic solution copolymerization experiment
Note: ENGAGE 8150 represents a POE industrial sample from DOW
As shown in the above Table 2, a series of crosslinkable comb-shaped ethylene-propylene olefin polymers are prepared by the invention, and the mechanical properties show that the polymers all show the properties of typical crosslinked thermoplastic elastomers. Compared with the industrial sample ENGAGE 8150, the elastomer has similar or even higher strength and elongation at break. Because the polymer contains crosslinking points, the high breaking strength is shown, and simultaneously, the obvious compatibilization effect is shown in the blending process of polyethylene and polypropylene, and the phase interface is effectively eliminated. Showing lower cost and wider use than POE.
The above embodiments are only used for illustrating the design idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention accordingly, and the protection scope of the present invention is not limited to the above embodiments. Therefore, all equivalent changes or modifications based on the principles and design concepts disclosed herein are intended to be included within the scope of the present invention.
Claims (10)
1. The comb-shaped ethylene-propylene copolymer is characterized in that the main chain of the comb-shaped ethylene-propylene copolymer is an ethylene-propylene random copolymer, and the comb-shaped branched chain is an ethylene-propylene random copolymer; wherein the ethylene-propylene random copolymer of the main chain has a weight average molecular weight (M) W ) 20000-500000g/mol, and the mol fraction of propylene is 5% -95%; the weight average molecular weight of the ethylene-propylene random copolymer with propylene mole fraction side chain is 2000-20000mol, the side chain propylene mole fraction is 5% -95%, and the grafting amount is 0.1-20.
2. The comb ethylene-propylene copolymer according to claim 1, wherein the propylene mole fraction in the main chain is 10% to 70%; the grafting amount is 0.5-8; the glass transition temperature is-90-0 ℃.
3. A method for preparing a comb-like ethylene-propylene copolymer according to claim 1, characterized in that the method comprises the following steps:
(1) Under the anhydrous and anaerobic conditions, adding ethylene, propylene, a macromonomer catalyst, a cocatalyst and an organic solvent into a first reactor, and carrying out polymerization reaction to obtain an ethylene-propylene copolymerized macromonomer; the polymerization temperature is 60-300 ℃, and the polymerization pressure is 0.1-5MPa; the concentration of the macromonomer catalyst is 0.1-100 mu mol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 50-10000; the proportion of terminal double bonds of the prepared ethylene-propylene copolymer macromonomer is 50-100%, the ethylene-propylene copolymer macromonomer has no melting point, and the glass transition temperature is-90-0 ℃;
(2) The solution after the polymerization reaction in the first reactor enters a second reactor, and ethylene, propylene, a copolymerization catalyst, a cocatalyst and an organic solvent are added into the second reactor under the anhydrous and oxygen-free conditions to carry out the ternary polymerization of ethylene/propylene/a macromonomer; the polymerization temperature is 60-300 ℃, and the polymerization pressure is 0.1-5MPa; the concentration of the copolymerization catalyst is 0.1-100 mu mol/L based on the volume of the organic solvent in the second reactor, the molar ratio of the copolymerization catalyst to the macromonomer catalyst is 50.
4. The method for preparing the comb-shaped ethylene-propylene copolymer according to claim 3, wherein the proportion of the terminal double bonds of the macromonomer prepared in the step (1) is 80-100%; the weight average molecular weight of the ethylene propylene macromonomer prepared in the step (1) is 6000-10000g/mol; the molar ratio of the ethylene to the propylene in the step (2) is 5.
5. The process for preparing a comby ethylene-propylene copolymer according to claim 3, wherein the macromonomer catalyst in step (1) is a single site metallocene catalyst or post metallocene catalyst selected from rac-vinylidene bridged bis-indenyl zirconium dichloride, rac-dimethylsilane bridged bis (2-methylindenyl) zirconium dichloride, rac-dimethylsilane bridged bis (2-methyl-4-phenyl-indenyl) zirconium dichloride, rac-dimethylsilane bridged bis-indenyl hafnium dimethyl, meso-diphenylmethyl bridged cyclopentadienyl-fluorenyl-zirconium dichloride, dimethylsilane bridged- (3, 5-diisopropylcyclopentadienyl) - (4-isopropylcyclopentadienyl) zirconium dichloride, bridged fluorenyl-tert-butylamino-dimethyltitanium, bis [ N- (3-tert-butylsalicylic acid) cyclopentylamino ] zirconium dichloride, bis (3-trimethylsilylsalicyl-3, 5-difluorophenyl) titanium dichloride.
6. The process for the preparation of combed ethylene-propylene copolymers according to claim 3, wherein the copolymerization catalyst in step (2) is a single-site metallocene or post-metallocene catalyst selected from biscyclopentadienylhafnium dimethyl, bisindenyl zirconium dimethyl, vinylidene-bridged bisindenyl zirconium dichloride, dimethylsilyl-bridged bisindenyl zirconium dichloride, diphenylcarbon-bridged cyclopentadienyl-fluorenyl zirconium dichloride, dimethylsilyl-bridged tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, bisindenyl zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, biscyclopentadienyl-bisphenoxyzirconium, dimethylsilyl-bridged bis-indenyl-dimethylzirconium, diphenylcarbobridged-cyclopentadienyl-fluorenyl-dimethylzirconium, diphenylcarbobridged-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-titanium dichloride, dimethylsilyl-bridged-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride, bis (3-methylsalicylidene-pentafluoroimino) titanium dichloride, bis (salicylidene-phenylimino) titanium dichloride, dimethylsilyl-bridged-3-pyrrolylindenyl-tert-butylamino-dimethyl titanium, [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenylimine ] titanium trichloride, (2, 3, 4-trihydro-8-diphenylphosphino-quinolyl) tribenzylzirconium.
7. The method for preparing a comb-shaped ethylene-propylene copolymer according to claim 3, wherein the cocatalyst used in the steps (1) and (2) is selected from the group consisting of methylalumoxane, modified methylalumoxane, tris (pentafluorophenyl) boron compound, tetrakis (pentafluorophenyl) boron compound, triisobutylaluminum, triethylaluminum, trimethylaluminum; the organic solvent in the step (1) and the step (2) is straight-chain alkane, isoparaffin, cycloalkane or arene with 4-10 carbon atoms; the organic solvent is preferably n-butane, n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene, xylene.
8. The crosslinkable comb-shaped ethylene-propylene copolymer is characterized in that the main chain of the crosslinkable comb-shaped ethylene-propylene copolymer is an ethylene-propylene polyene monomer random copolymer, the comb-shaped branched chain is the ethylene-propylene polyene monomer random copolymer, the weight average molecular weight of the ethylene-propylene polyene monomer random copolymer of the main chain is 20000-500000g/mol, and the propylene molar content is 5% -95%; in the crosslinkable comb-shaped ethylene-propylene copolymer, the molar content of crosslinking groups is 0.001-10%; the weight average molecular weight of the side chain ethylene-propylene polyene monomer random copolymer is 2000-20000mol, the side chain propylene mole fraction is 5% -95%, the mole content of the crosslinking group is 0.001-10%, and the grafting number is 0.1-20.
9. A process for preparing a comb-like ethylene-propylene copolymer crosslinkable by crosslinking according to claim 8, comprising the steps of:
(1) Under the anhydrous and oxygen-free conditions, adding ethylene, propylene, a polyene monomer, a macromonomer catalyst, a cocatalyst and an organic solvent into a first reactor, and carrying out polymerization reaction to obtain an ethylene-propylene-polyene copolymerized macromonomer; the polymerization temperature is about 60-300 ℃, and the polymerization pressure is about 0.1-5MPa; the concentration of the macromonomer catalyst is 0.1-100 μmol/L, the molar ratio of the cocatalyst to the macromonomer catalyst is 50-10000, the molar ratio of the ethylene to propylene is 200; the proportion of terminal double bonds of the prepared macromonomer is 50-100%, the macromonomer has no melting point, the glass transition temperature is-90-0 ℃, and the molar content of crosslinking groups is 0.001-10%;
(2) The solution after the polymerization reaction in the first reactor enters a second reactor, and ethylene, propylene, a polyene monomer, a copolymerization catalyst, a cocatalyst and an organic solvent are added into the second reactor under the anhydrous and oxygen-free conditions to carry out the quadripolymer of ethylene/propylene/macromonomer/polyene monomer; the polymerization temperature is 60-300 ℃, and the polymerization pressure is 0.1-5MPa. The concentration of the copolymerization catalyst is 0.1-100 mu mol/L based on the volume of the organic solvent in the second reactor, the molar ratio of the copolymerization catalyst to the macromonomer catalyst is 50.
10. The process for preparing comb-shaped crosslinkable ethylene-propylene copolymer according to claim 8, wherein the ratio of terminal double bonds of the macromonomer obtained in step (1) is 80-100%.
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