WO2014036678A1 - 一种丙烯多相共聚体系、聚合方法及聚丙烯釜内合金 - Google Patents
一种丙烯多相共聚体系、聚合方法及聚丙烯釜内合金 Download PDFInfo
- Publication number
- WO2014036678A1 WO2014036678A1 PCT/CN2012/001761 CN2012001761W WO2014036678A1 WO 2014036678 A1 WO2014036678 A1 WO 2014036678A1 CN 2012001761 W CN2012001761 W CN 2012001761W WO 2014036678 A1 WO2014036678 A1 WO 2014036678A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- propylene
- ethylene
- polypropylene
- formula
- polymerization
- Prior art date
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 109
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 102
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 88
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 51
- 239000000956 alloy Substances 0.000 title claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 46
- -1 polypropylene Polymers 0.000 title claims description 109
- 229920001155 polypropylene Polymers 0.000 title claims description 99
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 229920001577 copolymer Polymers 0.000 claims abstract description 47
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004711 α-olefin Substances 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229920005604 random copolymer Polymers 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 71
- 238000000034 method Methods 0.000 claims description 34
- 239000010936 titanium Substances 0.000 claims description 33
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 claims description 14
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 claims description 7
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000011949 solid catalyst Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- PKDYVBBBBHQJIZ-UHFFFAOYSA-N 1-but-3-enyl-4-ethenylbenzene Chemical compound C=CCCC1=CC=C(C=C)C=C1 PKDYVBBBBHQJIZ-UHFFFAOYSA-N 0.000 claims description 4
- ZXLAFQNTMMFLSA-UHFFFAOYSA-N 1-ethenyl-4-[2-(4-ethenylphenyl)ethyl]benzene Chemical compound C1=CC(C=C)=CC=C1CCC1=CC=C(C=C)C=C1 ZXLAFQNTMMFLSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical group CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims 1
- 230000009977 dual effect Effects 0.000 claims 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 abstract description 21
- 150000001993 dienes Chemical class 0.000 abstract description 18
- 238000004220 aggregation Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract description 4
- 229920005630 polypropylene random copolymer Polymers 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 239000012798 spherical particle Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 3
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 114
- 239000012071 phase Substances 0.000 description 43
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 13
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 13
- 229940095674 pellet product Drugs 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000008188 pellet Substances 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000000284 extract Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- ZJUIDERQBIMMAK-UHFFFAOYSA-N CO[SiH2]OC.CC1=CCCCC1 Chemical compound CO[SiH2]OC.CC1=CCCCC1 ZJUIDERQBIMMAK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/02—Ziegler natta catalyst
Definitions
- Polypropylene multiphase copolymerization system Polymerization method and polypropylene in-cylinder alloy
- the invention relates to a propylene heterogeneous copolymerization system, a polymerization method and an alloy in a polypropylene kettle.
- Polypropylene is an indispensable synthetic material in our life. It is also one of the most widely used and fastest growing resins. It has the advantages of low density, high melting point, easy processing, excellent impact resistance and good insulation properties. It has become the most synthetic resin with the fastest growth in output, the most varieties and the most versatile.
- Heterogeneous copolymerization of propylene refers to the use of high-efficiency MgCl 2 supported catalysts with good particle shape control ability in the fourth and fifth generations. After homopolymerization of propylene, it is supplemented with ethylene-propylene random copolymerization to form in situ in the reactor. A polypropylene/ethylene-propylene copolymer reactor alloy with excellent impact properties.
- the polymerization system usually includes a catalyst, a cocatalyst, an external electron donor, propylene, ethylene, hydrogen, etc.; the polymerization process is mostly a multi-step process: first, propylene homopolymerization is carried out in the first-stage reactor to obtain a homopolypropylene.
- One object of the present invention is to provide a propylene heterogeneous copolymerization system whereby the mutual fusion and aggregation of the dispersed phase of the ethylene-propylene random copolymer in the alloy of the polypropylene/ethylene-propylene random copolymer is suppressed.
- the propylene heterogeneous copolymerization system provided by the present invention, in addition to conventional propylene catalysts, cocatalysts, external electron donors, propylene, ethylene, higher alpha olefins having a carbon number of more than 3, etc.,
- a double alpha-olefin monomer having the structural formula of any one of formulas I - IV:
- the monomer of formula IV is divinylbenzene and includes three isomers: ortho-divinylbenzene, meta-divinylbenzene, para-divinylbenzene.
- the bis- ⁇ -olefin monomer is preferably a double ⁇ -olefin having a strong coordination polymerization ability of both ⁇ -olefin double bonds, such as 1, 5-hexadiene, 1,7-octadiene, 1,9 - decadiene, 4-(3-butenyl)styrene, divinylbenzene isomer, 1,2-bis(4-vinylphenyl)ethane, most preferably 1,5-hexane Alkene, 1, 7-octadiene or 1,9-decadiene.
- a double ⁇ -olefin having a strong coordination polymerization ability of both ⁇ -olefin double bonds such as 1, 5-hexadiene, 1,7-octadiene, 1,9 - decadiene, 4-(3-butenyl)styrene, divinylbenzene isomer, 1,2-bis(4-vinylphenyl)ethane, most preferably 1,5
- Still another object of the present invention is to provide a propylene heterophasic copolymer product (i.e., a polypropylene in-cylinder alloy) obtained by polymerizing the above propylene heterogeneous copolymerization system.
- a propylene heterophasic copolymer product i.e., a polypropylene in-cylinder alloy
- the polypropylene in-cylinder alloy provided by the invention has a multi-phase structure, the polypropylene homopolymer is a continuous phase matrix, and the ethylene-propylene or ethylene-high-grade ⁇ containing a double ⁇ -olefin monomer unit having a branched or crosslinked structure
- An olefin binary random copolymer or an ethylene-propylene-higher alpha-olefin ternary random copolymer is a dispersed phase.
- the above ethylene-propylene random copolymer containing a bis-olefin monomer unit may have a branched or crosslinked structure represented by the following structural formula:
- R in the formula: Formula VI is selected from the group consisting of bis-olefins represented by the following structural formula:
- ⁇ is an integer greater than one.
- the present invention also provides a process for preparing the above propylene heterophasic copolymer product (polypropylene in-cavity alloy).
- the polymerization method of the propylene heterophasic copolymer product provided by the present invention is a multi-reactor polymerization process catalyzed by a commercial fourth-generation or fifth-generation Ziegler-Natta catalyst having a spherical or porous particle form, and the polymerization process is typical.
- the two-stage or multi-stage polymerization process of propylene includes Spheripol process (liquid phase bulk-gas phase method), Unipol process (Unipol gas phase method) and Catalloy process.
- the specific method is as follows: First, propylene homopolymerization is carried out in a first-stage reactor to obtain a homopolypropylene, which is then transferred to a next-stage reactor, while ethylene and propylene are fed to copolymerize, and a double ⁇ -olefin is added.
- the monomer directly forms an ethylene-propylene-bis- ⁇ -olefin ternary random copolymer in a polypropylene matrix to form a branched or crosslinked rubber phase structure.
- the polypropylene homopolymer is transferred to a mixed monomer of ethylene and propylene mixed in a certain ratio, and the double ⁇ -olefin is added to carry out copolymerization reaction to obtain an alloy in the polypropylene kettle.
- the catalyst in the polymerization system of the present invention is a fourth and fifth generation high-efficiency spherical MgCl 2 supported Ziegler-Natta catalyst, and the cocatalyst is an alkyl aluminum compound, including triethyl aluminum, triisobutyl aluminum, and tributyl aluminum.
- an external electron donor is a compound of the formula R4. n Si (OR':> n , wherein l n 3, R and R' are each selected from an alkyl group, a cycloalkyl group. And any one of the aryl groups.
- dimethyldimethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, diphenyldimethoxysilane, diphenyl is preferred.
- Diethoxysilane or methylcyclohexene dimethoxysilane is used as an external electron donor.
- the polymerization method of the present invention is suitable for the production of the more mature and large-scale Spheripol process, Unipol process and Catalloy process, and the preparation process does not need to make major changes to the mature process flow.
- the propylene heterophasic copolymer product has a good particle morphology.
- the branched or crosslinked rubber phase propylene heterophasic copolymer, homopolypropylene and ethylene-propylene
- the mass ratio of the bis-olefin ternary copolymer is 30.0 to 99.0: 1.0-70.0
- the ratio of the three monomer units (molar ratio) in the ethylene-propylene-bis- ⁇ -olefin terpolymer is 5 to 95: 2-95: 1-30, and the preferred ratio is 27 to 69: 63-30 : 10-1 , the ratio of the two double bonds in the double ⁇ -olefin participating in the polymerization reaction is 3 to 97%.
- the catalyst for propylene polymerization includes, but is not limited to, a Ziegler-Natta catalyst.
- the Ziegler-Natta catalyst used has been widely disclosed, preferably a catalyst having high stereoselectivity and having a good copolymerization ability of an olefin monomer, and the "high stereoselective Ziegler-Natta catalyst" described herein means that the isotacticity can be prepared.
- Such a catalyst comprises the following components: 1) an active solid catalyst component, preferably a titanium-containing solid catalyst active component; 2) an organoaluminum compound cocatalyst component; 3) an external electron donor component and a hydrogen component.
- an active solid catalyst component preferably a titanium-containing solid catalyst active component
- an organoaluminum compound cocatalyst component preferably a titanium-containing solid catalyst active component
- an organoaluminum compound cocatalyst component preferably an external electron donor component and a hydrogen component.
- the molar ratio of A1 in the organoaluminum compound to Ti in the active component of the titanium-containing solid catalyst is preferably 100:1.
- Figure 1 is a Fourier infrared spectrum of the heterophasic copolymer polypropylene prepared in Examples 4, 5, 6 and 7.
- Figure 2 is a Fourier infrared spectrum of heptane extract (rubber phase) in the heterophasic copolymer polypropylene prepared in Examples 4, 5, 6 and 7.
- Figure 3 is a DSC scan curve of the heterophasic copolymer polypropylene prepared in Examples 4, 5, 6 and 7 (temperature rising rate 10 ° C / min).
- Figure 4 is a DSC scan curve (heating rate 10 °C/min) of heptane extract (rubber phase) in the heterophasic copolymer polypropylene prepared in Examples 4, 5, 6 and 7.
- Figure 5 is a graph showing the DMA loss tangent versus temperature for the heterophasic copolymer polypropylene prepared in Examples 4, 5, 6 and 7.
- Figure 6 is a graph showing the relationship of the storage modulus of the DMA rubber platform of the heterophasic copolymer polypropylene prepared in Examples 11, 12, 13 and 14.
- Figure 7 is a scanning electron micrograph of the rubber phase of the ethylene-propylene random copolymer etched after the heterogeneous copolymer polypropylene of Examples 4, 5, 6 and 7 was subjected to melt hot pressing at 200 ° C for 15 min.
- the holes in the figure are formed by etching off the ethylene-propylene random copolymer by xylene
- Figures a , b, c and d represent Cases 4, 5, 6 and 7, respectively. It can be seen from the figure that the addition of the diene monomer can effectively inhibit the mutual fusion of the ethylene-propylene random copolymer in the molten state.
- the structure of the branched or crosslinked ethylene-propylene-bis- ⁇ -olefin terpolymer is shown in the following figure.
- n is an integer greater than one. It is preferred that the two ⁇ -olefin double bonds have a strong coordination polymerization ability of a double ⁇ -olefin, such as 1, 5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4- (3-butenyl)styrene, divinylbenzene isomer, 1,2-bis(4-vinylphenyl)ethane, preferably 1,5-hexadiene, 1, 7-octyl Diene or 1,9-decadiene, and the like.
- a double ⁇ -olefin such as 1, 5-hexadiene, 1,7-octadiene, 1,9-decadiene, 4- (3-butenyl)styrene, divinylbenzene isomer, 1,2-bis(4-vinylphenyl)ethane, preferably 1,5-hexadiene, 1, 7-octyl Diene or 1,9-
- the propylene heterogeneous copolymerization polymerization method is as follows:
- a propylene monomer is polymerized by a fourth or fifth generation Ziegler-Natta catalyst to obtain a polypropylene homopolymer having a particle form;
- the polymer After completion of the homopolymerization reaction, the polymer is transferred to a mixed monomer of ethylene and propylene in a certain ratio, and a double ⁇ -olefin is added to carry out copolymerization to obtain a polypropylene in-cylinder alloy.
- composition and properties of ethylene-propylene-bis- ⁇ -olefin ternary random copolymer were determined by FTIR and DSC.
- the FTIR and DMA characterization confirmed the branching and crosslinking of ethylene-propylene-bis- ⁇ -olefin ternary random copolymer.
- the existence of structure, and DSC is used to characterize the melting point of medium-sized polypropylene in multiphase copolymerized polypropylene alloy And melting ⁇ .
- the ethylene content of the branched and crosslinked structure in the alloy can be adjusted by changing the copolymerization reaction time to adjust the content of the ethylene-propylene copolymer in the heterophasic copolymer polypropylene alloy, changing the polymerization temperature and the amount of the added double ⁇ -olefin monomer.
- the Ziegler-Natta catalyst used in the following examples was prepared as follows: Under the protection of dry high purity nitrogen, 150 ml of TiCl 4 was added to a 500 ml reactor with a sand core filter and mechanical stirring at the bottom, and cooled. To -20 ° C, 7.05 g of a spherical carrier MgCl 2 was added and reacted for 1 hour. The temperature was raised to 60 ° C, 1.335 g of 9,9-bis(methoxymethyl)phosphonium (BMMF) was added, and the temperature was slowly raised to 120 ° C. After 2 hours of reaction, the first filtration was carried out, and the TiCl 4 solution was filtered off. .
- BMMF 9,9-bis(methoxymethyl)phosphonium
- the propylene gas in the above step (1) is vented, and then an ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced, and when the polymerization system pressure is lata, 1 ml of 1,9-decadiene is added.
- the mixture was subjected to ethylene-propylene copolymerization in a hexane solvent system, and the polymerization temperature was controlled at 60 ° C, the pressure was 0.4 MPa, and the copolymerization reaction was carried out for 5 minutes. After the completion of the polymerization, the pressure of the gas in the autoclave was released, and the polymerization product was poured into a 10% by volume solution of ethanol-hydrochloric acid to terminate the reaction, and washed for 1 hour. Finally, it was filtered and dried to obtain 22.3 g of an alloy in a solid pellet product polypropylene.
- the propylene gas in the above step (1) is vented, and then an ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced, and when the system pressure is lata, 3 ml of 1,9-decadiene is rapidly injected.
- Monomer, copolymerization of ethylene-propylene and diene monomer was carried out directly in a hexane solvent system, the polymerization temperature was controlled at 60 ° C, the pressure was 0.4 MPa, and the copolymerization reaction was carried out for 5 minutes.
- the propylene gas in the above step (1) was vented, and the hexane solvent in the polymerization system was evacuated by a vacuum pump to have a vacuum of about 5 mmHg and a pumping time of about 5 minutes. After the hexane solvent was removed, a mixture of ethylene and propylene having a gas molar ratio of 1:1 was quickly introduced into the kettle. When the pressure in the reactor was lata, 1 ml of the 1,9-decadiene monomer was rapidly injected, and the copolymerization of the gas phase ethylene-propylene and the diene monomer was carried out in the polymerization reactor.
- Example 4 (Comparative Example): (1) Propylene homopolymerization
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 5 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced. , conducting gas phase ethylene-propylene copolymerization.
- the polymerization temperature is controlled at 80 to 90 ° C, the pressure is 0.4 MPa, and the polymerization reaction is carried out for 10 minutes.
- the gas pressure in the autoclave is released, and the polymerization product is poured into a 10% (volume ratio) ethanol-hydrochloric acid solution. In the middle, stop the reaction, and wash for 1 hour. Finally, it was filtered and dried to obtain 25.0 g of an alloy in a solid pellet product polypropylene.
- DSC characterization and compositional characterization of the product and its heptane solubles are shown in Table 1.
- the Fourier infrared spectrum of the prepared heterophasic copolymer polypropylene is shown in Fig. 1.
- the Fourier transform infrared spectrum of the heptane extract (rubber phase) in the prepared heterophasic copolymer polypropylene is shown in Fig. 2.
- the DSC scan curve (heating rate 10 ° C / min) of the prepared heterophasic copolymer polypropylene is shown in Fig. 3.
- the DSC scan curve (heating rate 10 °C/min) of the heptane extract (rubber phase) in the prepared heterophasic copolymer polypropylene is shown in Fig. 4.
- the relationship between the DMA loss tangent and the temperature of the prepared heterophasic copolymer polypropylene is shown in Fig. 5.
- the propylene gas in the above step (1) was vented, and the hexane solvent in the polymerization system was evacuated by a vacuum pump for about 5 minutes. Then, an ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced, and when the pressure in the autoclave is lata, 3 ml of 1,9-decadiene monomer is rapidly injected to carry out gas phase ethylene-propylene and diene. Monomer copolymerization.
- the polymerization temperature is controlled at 70 to 80 ° C, the pressure is 0.4 MPa, and the polymerization reaction is carried out for 10 minutes. After the polymerization is completed, the gas pressure in the autoclave is released.
- the polymerization product was poured into a 10% by volume solution of ethanol-hydrochloric acid, the reaction was terminated, and washed for 1 h. Finally, it was filtered and dried to obtain 31.0 g of an alloy in a solid pellet product polypropylene.
- the product and its heptane solubles were characterized by DSC and composition. The data are shown in Table 1.
- the Fourier infrared spectrum of the prepared heterophasic copolymer polypropylene is shown in Fig. 1.
- the Fourier transform infrared spectrum of the heptane extract (rubber phase) in the prepared heterophasic copolymer polypropylene is shown in Fig. 2.
- the DSC scan curve (heating rate 10 ° C / min) of the prepared heterophasic copolymer polypropylene is shown in Fig. 3.
- the DSC scan curve (heating rate 10 °C/min) of the heptane extract (rubber phase) in the prepared heterophasic copolymer polypropylene is shown in Fig. 4.
- the relationship between the DMA loss tangent and the temperature of the prepared heterophasic copolymer polypropylene is shown in Fig. 5.
- Example 6 Example 6:
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 5 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced.
- the pressure in the autoclave was lata, 5 ml of the 1,9-decadiene monomer was rapidly injected to carry out copolymerization of the gas phase ethylene-propylene and the diene monomer.
- the polymerization temperature is controlled at 85 to 90 ° C, the pressure is 0.4 MPa, and the polymerization reaction is carried out for 10 minutes.
- the Fourier infrared spectrum of the prepared heterophasic copolymer polypropylene is shown in Fig. 1.
- the Fourier infrared spectrum of the heptane extract (rubber phase) in the prepared heterophasic copolymer polypropylene is shown in Fig. 2.
- the DSC scan curve (heating rate 10 ° C / min) of the prepared heterophasic copolymer polypropylene is shown in Fig. 3.
- the DSC scan curve (heating rate 10 ° C / min) of the heptane extract (rubber phase) in the prepared heterophasic copolymer polypropylene is shown in Fig. 4.
- the relationship between the DMA loss tangent and the temperature of the prepared heterophasic copolymer polypropylene is shown in Fig. 5.
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 5 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced.
- the pressure in the autoclave was lata, 7 ml of 1,9-decadiene monomer was rapidly injected to carry out copolymerization of the gas phase ethylene-propylene and diene monomers.
- the polymerization temperature was controlled at 85 to 90 ° C, the pressure was 0.4 MPa, and the polymerization was carried out for 10 minutes.
- the Fourier infrared spectrum of the prepared heterophasic copolymer polypropylene is shown in Fig. 1.
- the Fourier transform infrared spectrum of the heptane extract (rubber phase) in the prepared heterophasic copolymer polypropylene is shown in Fig. 2.
- the DSC scan curve (heating rate 10 ° C / min) of the prepared heterophasic copolymer polypropylene is shown in Fig. 3.
- the DSC scan curve (heating rate 10 °C/min) of the heptane extract (rubber phase) in the prepared heterophasic copolymer polypropylene is shown in Fig. 4.
- the relationship between the DMA loss tangent and the temperature of the prepared heterophasic copolymer polypropylene is shown in Fig. 5.
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 5 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced.
- the pressure in the autoclave was lata
- 10 ml of the 1,9-decadiene monomer was rapidly injected to carry out copolymerization of the gas phase ethylene-propylene and the diene monomer.
- the polymerization temperature is controlled at 70 to 85 ° C, the pressure is 0.4 MPa, and the polymerization reaction is carried out for 10 minutes.
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 5 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced.
- the pressure in the autoclave was lata, 5 ml of the 1,9-decadiene monomer was rapidly injected to carry out copolymerization of the gas phase ethylene-propylene and the diene monomer.
- the polymerization temperature was controlled at 95 ° C, the pressure was 0.4 MPa, and the polymerization was carried out for 10 minutes, and finally 29.5 g of the alloy in the polypropylene kettle was obtained.
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 5 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced.
- the pressure in the autoclave was lata, 3 ml of the 1,9-decadiene monomer was rapidly injected to carry out copolymerization of the gas phase ethylene-propylene and the diene monomer.
- the polymerization temperature was controlled at 85 to 90 ° C, the pressure was 0.4 MPa, and the polymerization was carried out for 10 minutes.
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 5 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced.
- the pressure in the autoclave is lata, 1 ml of the 1,9-decadiene monomer is rapidly injected to carry out copolymerization of the gas phase ethylene-propylene and the diene monomer.
- the polymerization temperature is controlled at about 110 ° C, the pressure is 0.4 MPa, and the polymerization reaction is carried out for 10 min.
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 5 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced.
- the pressure in the autoclave was lata, 3 ml of the 1,9-decadiene monomer was rapidly injected to carry out copolymerization of the gas phase ethylene-propylene and the diene monomer.
- the polymerization temperature was controlled at 95 to 105 ° C, the pressure was 0.4 MPa, and the polymerization was carried out for 10 minutes.
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 3 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced.
- the pressure in the autoclave was lata, 5 ml of the 1,9-decadiene monomer was rapidly injected to carry out copolymerization of the gas phase ethylene-propylene and the diene monomer.
- the polymerization temperature was controlled at 70 to 80 ° C, the pressure was 0.4 MPa, and the polymerization was carried out for 20 minutes.
- the propylene gas in the above step (1) is vented, and the hexane solvent in the polymerization system is vacuum pumped for 3 minutes to remove the hexane solvent, and then the ethylene-propylene mixture having a gas molar ratio of 1:1 is introduced.
- the pressure in the autoclave was lata, 7 ml of 1,9-decadiene monomer was rapidly injected to carry out copolymerization of the gas phase ethylene-propylene and diene monomers.
- the polymerization temperature was controlled at 94 to 98 ° C, the pressure was 0.4 MPa, and the polymerization was carried out for 20 minutes.
- the propylene heterogeneous copolymerization system and the polymerization method provided by the invention have the advantages of low cost, simple implementation and convenient scale production.
- the heterophasic copolymerized polypropylene alloy resin branched or crosslinked by the rubber dispersed phase obtained by the method has a reduced mobility of the rubber phase due to branching and crosslinking of the rubber phase, and is advantageous for suppressing the aggregation of the rubber phase during the processing, and toughening The effect is more obvious.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种丙烯多相共聚体系、聚合方法及产品。该丙烯多相共聚体系使聚丙烯/乙丙无规共聚物反应器合金中乙丙无规共聚物分散相的相互融合、聚集作用得到有效的抑制。本发明中提供的丙烯多相共聚体系,除常规的丙烯催化剂、助催化剂、外给电子体等组分外,关键组分是一种脂肪族或芳香族对称二烯烃单体,实现对乙丙共聚物分散相的稳定化。聚合工艺采用典型的丙烯两段或多段聚合工艺进行,适用于工业上较成熟的聚合工艺。同时,本发明中提供的聚合产品粒子呈球形,具有多相结构,分散相为具有支化或交联结构的含有双α-烯烃单体单元的乙烯-丙烯三元无规共聚物。
Description
一种丙烯多相共聚体系、 聚合方法及聚丙烯釜内合金 技术领域
本发明涉及一种丙烯多相共聚体系、 聚合方法及聚丙烯釜内合金。
背景技术
聚丙烯是我们生活中必不可少的合成材料, 也是应用最为广泛、 产量增 长最快的树脂之一, 它具有低密度、 高熔点、 易加工、 抗冲击性能优、 绝缘 性能佳等优点, 近年来, 已成为产量增长最快、 品种牌号最多、 用途最广的 一种合成树脂。
丙烯多相共聚是指利用第四代、 第五代具有良好颗粒形态控制能力的高 效 MgCl2载体催化剂,在丙烯均聚后辅以乙烯-丙烯无规共聚, 从而在反应器 内原位生成具有优良抗冲性能的聚丙烯 /乙丙共聚物反应器合金。聚合体系通 常包括催化剂、 助催化剂、 外给电子体、 丙烯、 乙烯、 氢气等等; 聚合工艺 多为一种多步骤过程: 首先在第一级反应器中进行丙烯均聚合, 得到均聚聚 丙烯, 然后将其转移到下一级反应器中, 同时通入乙烯和丙烯进行共聚合, 在聚丙烯基体中生成乙烯-丙烯无规共聚物。由于橡胶态的乙丙无规共聚物作 为橡胶相分散在聚丙烯基体中,赋予聚丙烯树脂良好的抗冲击性能。近年来, 全球范围内随着可持续经济的发展, 节能减排和低碳经济的呼声越来越高, 研发以多相共聚聚丙烯反应器合金为代表的组成范围宽广、 性能可调性强的 高性能聚丙烯树脂, 替代高耗能的机械物理共混方法, 成为适应社会发展对 高分子材料加工制备提出的绿色环保要求的最佳选择。
在聚丙烯-乙丙无规共聚物反应器合金中, 由于乙烯 -丙烯无规共聚物和 聚丙烯热力学上不相容(Macromolecules, 1999, 32(10): 3227) , 因此, 在高 温加工过程中, 乙烯-丙烯无规共聚物作为分散相在热和剪切力的作用下容易 相互融合, 形成尺寸较大的软相相畴。 文献报道聚丙烯反应器合金经过熔融 加工后, 在聚丙烯基体中乙烯-丙烯无规共聚物相畴尺寸能够增大到 ΙΟμηι以 上 (Journal of Polymer Science Part B: Polymer Physics, 1994, 32(7): 1205. Polymer, 2011, 52(13): 2956) , 显著地降低了作为橡胶相乙丙无规共聚物对 聚丙烯基体树脂的增韧作用。 因此, 有必要抑制聚丙烯 /乙丙无规共聚物反应 器合金中, 乙烯-丙烯无规共聚物在熔融态下的相互融合、聚集, 充分发挥其 对聚丙烯基体树脂的增韧作用。
发明公开
本发明的目的之一是提供一种丙烯多相共聚体系, 从而使聚丙烯 /乙丙无 规共聚物釜内合金中乙丙无规共聚物分散相的相互融合、聚集作用得到抑制。
本发明所提供的丙烯多相共聚体系, 除包括常规的丙烯催化剂、 助催化 剂、 外给电子体、 丙烯、 乙烯、 碳数大于 3的高级 α -烯烃等组分外, 其关键 在于还包括一种双 α -烯烃单体, 其结构通式为式 I -式 IV中任一所示:
(式 I ) (式 II ) (式 III) (式 IV) 其中, 式 I -式 IV中 η均为大于 1的整数。
式 IV所示的单体为二乙烯基苯, 包括三种异构体: 邻位二乙烯基苯、 间位二乙烯基苯、 对位二乙烯基苯。
所述双 α -烯烃单体优选两个 α -烯烃双键均具有强的配位聚合能力的双 α -烯烃, 如 1, 5-己二烯, 1,7-辛二烯、 1,9-癸二烯、 4- (3-丁烯基)苯乙烯、 二乙烯基苯异构体、 1, 2-二 (4-乙烯基苯基) 乙烷, 最优选为 1, 5-己二烯, 1, 7-辛二烯或 1, 9-癸二烯等。
本发明的再一个目的是提供上述丙烯多相共聚体系聚合得到的丙烯多相 共聚物产品 (即聚丙烯釜内合金) 。
本发明所提供的聚丙烯釜内合金具有多相结构, 聚丙烯均聚物为连续相 基体, 具有支化或交联结构的含有双 α -烯烃单体单元的乙烯-丙烯或乙烯-高 级 α -烯烃二元无规共聚物或乙烯 -丙烯 -高级 α -烯烃三元无规共聚物为分散 相。
上述含有双 α -烯烃单体单元的乙烯-丙烯无规共聚物可具有如下结构式 所示的支化或交联结构:
本发明还提供了制备上述丙烯多相共聚物产品 (聚丙烯釜内合金) 的方 法。
本发明提供的丙烯多相共聚物产品的聚合方法是一种多反应器聚合过 程, 由具有球形、 多孔颗粒形态的商品化第四代或第五代 Ziegler-Natta催化 剂催化, 聚合工艺采用典型的丙烯两段或多段聚合工艺进行, 包括 Spheripol 工艺 (液相本体-气相法) 、 Unipol工艺 (Unipol气相法) 以及 Catalloy工艺 等。 具体方法如下: 首先在第一级反应器中进行丙烯均聚合, 得到均聚聚丙 烯后, 将其转移到下一级反应器中, 同时通入乙烯和丙烯进行共聚, 并且加 入双 α -烯烃单体,在聚丙烯基体中直接生成乙烯-丙烯-双 α -烯烃三元无规共 聚物, 形成支化或交联的橡胶相结构。
所述方法的详细步骤如下:
1 )首先使丙烯单体在第四代或第五代 Ziegler-Natta催化剂的作用下进行 均聚反应, 得到具有颗粒形态的聚丙烯均聚物;
2 )在均聚反应完成后,将聚丙烯均聚物转移至按一定比例混合的乙烯和 丙烯混合单体中, 并加入所述双 α -烯烃, 进行共聚合反应, 得到聚丙烯釜内 合金。
本发明所述的聚合体系中催化剂为第四、 五代高效的球形 MgCl2负载的 Ziegler-Natta催化剂, 助催化剂为烷基铝化合物, 包括三乙基铝、 三异丁基 铝、 三丁基铝、 一氯二乙基铝等, 外给电子体为结构通式为 R4.nSi(OR':>n的化 合物, 其中, l n 3, R与 R'均选自烷基、 环烷基和芳基中的任意一种。 本 发明中, 优选二甲基二甲氧基硅烷、三甲基甲氧基硅烷、 甲基三甲氧基硅烷、 二苯基二甲氧基硅烷、 二苯基二乙氧基硅烷或甲基环己烯二甲氧基硅烷作为 外给电子体。
本发明所述的聚合方法适合目前较成熟且规模化的 Spheripol工艺、 Unipol工艺以及 Catalloy工艺进行生产, 制备过程无需对成熟的工艺流程作 大的改动。
所述的丙烯多相共聚物产品具有良好的颗粒形态。
所述的支化或交联的橡胶相丙烯多相共聚物中, 均聚聚丙烯与乙烯 -丙烯
-双 α -烯烃的三元共聚物的质量比为 30.0〜99.0: 1.0-70.0
所述的乙烯-丙烯-双 α -烯烃三元共聚物中三种单体单元比例 (摩尔比) 依次为 5〜95: 2-95: 1-30, 优选比例为 27〜69: 63-30: 10-1 , 双 α -烯烃中 两个双键均参与聚合反应的比例为 3〜97%。
本发明提供的制备上述丙烯多相共聚物产品 (即聚丙烯反应器合金) 的 方法中, 丙烯聚合的催化剂包括但不限于 Ziegler-Natta催化剂。 使用的 Ziegler-Natta催化剂已被大量公开, 优选具有高立构选择性且具有较好烯烃 单体共聚能力的催化剂, 此处所述的 "高立构选择性的 Ziegler-Natta催化剂" 是指可以制备全同立构指数大于 95%的丙烯均聚物的催化剂。 此类催化剂包 括以下组分: 1 ) 活性固体催化剂组分, 优选为含钛的固体催化剂活性组分; 2)有机铝化合物助催化剂组分; 3 )外给电子体组分和氢气组分。 本发明所 用的 Ziegler-Natta催化剂中,有机铝化合物中的 A1与含钛的固体催化剂活性 组分中的 Ti的摩尔比优选为 100: 1。
附图说明
图 1是实施例 4、 5、 6和 7中制备的多相共聚聚丙烯的傅里叶红外光谱 图。
图 2是实施例 4、 5、 6和 7制备的多相共聚聚丙烯中庚烷抽提物(橡胶 相) 的傅里叶红外光谱图。
图 3是实施例 4、 5、 6和 7制备的多相共聚聚丙烯的 DSC扫描曲线(升 温速率 10°C/min) 。
图 4是实施例 4、 5、 6和 7制备的多相共聚聚丙烯中庚烷抽提物(橡胶 相) 的 DSC扫描曲线 (升温速率 10°C/min)。
图 5是实施例 4、 5、 6和 7中制备的多相共聚聚丙烯的 DMA损耗正切 同温度的关系曲线。
图 6是实施例 11、 12、 13和 14中制备的多相共聚聚丙烯的 DMA橡胶 平台储能模量的关系曲线。
图 7是实施例 4、 5、 6和 7中制备多相共聚聚丙烯经过 200°C熔融热压 15min后刻蚀掉乙烯 -丙烯无规共聚物橡胶相的扫描电镜图。 图中的孔洞是二 甲苯刻蚀掉乙烯-丙烯无规共聚物后形成的, 图 a、 b、 c和 d分别代表案例 4、 5、 6和 7。从图中可以看出二烯单体的加入能够有效地抑制乙烯 -丙烯无规共 聚物在熔融态下的相互融合。
实施发明的最佳方式
本发明中, 支化或交联的乙烯-丙烯-双 α -烯烃三元共聚物的结构如下图 所示。
支化三元共聚物结构 交联三元共聚物结构 其中, R选自由以下结构通式代表的双 体单元:
其中, n均为大于 1的整数。 优选两个 α -烯烃双键均具有强的配位聚合 能力的双 α -烯经, 如 1, 5-己二烯, 1,7-辛二烯、 1,9-癸二烯、 4- (3-丁烯基) 苯乙烯、 二乙烯基苯异构物、 1, 2-二(4-乙烯基苯基) 乙烷, 最好为 1, 5-己 二烯, 1, 7-辛二烯或 1, 9-癸二烯等。
丙烯多相共聚聚合方法如下:
1 )首先使丙烯单体在第四代或第五代 Ziegler-Natta催化剂的作用下进行 聚合反应, 得到具有颗粒形态的聚丙烯均聚物;
2)在均聚反应完成后,将聚合物转移至按一定比例混合的乙烯和丙烯混 合单体中, 并加入双 α -烯烃, 进行共聚合反应, 得到聚丙烯釜内合金。
通过 FTIR和 DSC来确定乙烯-丙烯-双 α -烯烃三元无规共聚物的组成与 性质,利用 FTIR和 DMA表征确认乙烯-丙烯-双 α -烯烃三元无规共聚物支化 和交联结构的存在,并用 DSC表征多相共聚聚丙烯合金中等规聚丙烯的熔点
和熔融焓。 可以通过改变共聚合反应时间来调节多相共聚聚丙烯合金中乙丙 共聚物的含量,改变聚合温度和加入的双 α -烯烃单体的量来调节合金中支化 和交联结构的乙烯-丙烯-双 α -烯烃三元无规共聚物的含量。 下面结合具体实施案例对本发明作进一步的阐述, 但本发明不限于以下 实施案例, 所述方法如无特别说明均为常规方法。 所述材料如无特别说明均 能从公开商业途径获得。
下述实施例中所用的 Ziegler-Natta催化剂是按照以下所述方法制备: 干燥的高纯氮气保护下, 在底部带有砂芯过滤器和机械搅拌的 500ml反 应器中加入 150ml的 TiCl4, 冷却到 -20°C, 加入 7.05g球形载体 MgCl2, 反应 1小时。 升温至 60°C, 加入 1.335g的 9,9-二 (甲氧基甲基)芴 (BMMF) , 缓慢升温至 120°C, 反应 2小时后, 进行第一次过滤, 滤掉 TiCl4溶液。 然后 再加入 150ml的热的 TiCl4, 与 110°C反应 2小时, 60°C用干燥的己烷洗涤产 物, 得到聚合用催化剂。 测得比表面积: 8.4m2/g, 电子显微镜下观察形态为 球形颗粒状, 直径在 ΙΟμηι到 ΙΟΟμηι之间, 测得组成为: Ti的质量百分含量 为 4.1%, 内给电子体 BMMF的质量百分含量为 5.4%。 实施例 1 :
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的正己烷,再依次加 入浓度为 1.8mol/L的三乙基铝 1ml,上述制备的 Ziegler-Natta催化剂 19.6mg, 保持铝钛比: Al:Ti=100:l (摩尔比) , 然后通入丙烯气体, 于 60°C, 0.4MPa 压下聚合反应 15min, 得到聚丙烯颗粒, 直接进行下一步反应。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 然后再通入气体摩尔比例是 1 :1的 乙烯-丙烯混合气, 并且在聚合体系压力为 lata时, 加入 lml的 1,9-癸二烯 单体, 在己烷溶剂体系中进行乙丙共聚合, 聚合温度控制在 60°C, 压力为 0.4MPa, 共聚合反应 5分钟。 待聚合完成后, 放掉高压釜中的气体压力, 将 聚合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤, 干燥得到固体颗粒产物聚丙烯釜内合金 22.3g。
实施例 2:
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的正己烷,再依次加 入浓度为 1.8mol/L的三乙基铝 1ml,上述制备的 Ziegler-Natta催化剂 24.0mg, 保持铝钛比: Al:Ti=100: l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒, 直接进行下一步反应。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 然后再通入气体摩尔比例是 1 :1的 乙烯-丙烯混合气, 在体系压力为 lata时, 快速地注射入 3ml的 1,9-癸二烯 单体, 直接在己烷溶剂体系中进行乙烯-丙烯及二烯单体的共聚合, 聚合温度 控制在 60°C, 压力为 0.4MPa, 共聚合反应 5分钟。 待聚合完成后, 放掉高 压釜中的气体压力, 将聚合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤, 干燥得到固体颗粒产物聚丙烯釜内合金 29.9g。 实施例 3 :
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的正己烷,再依次加 入浓度为 1.8mol/L的三乙基铝 1.5ml, 上述制备的 Ziegler-Natta催化剂 27.1mg, 保持铝钛比: Al:Ti=100: 1 (摩尔比)左右, 然后通入丙烯气体, 于 60 °C , 0.4MPa压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 )中的丙烯气体放空, 并用真空泵将聚合体系中的己烷溶 剂抽除, 真空度约为 5mmHg, 抽除时间约 5min。 抽除掉己烷溶剂后, 再将 气体摩尔比例是 1 :1的乙烯-丙烯混合气迅速通入釜内。 当反应器内压力为 lata时, 迅速注入 lml的 1,9-癸二烯单体, 在聚合反应釜中进行气相乙烯- 丙烯及二烯单体的共聚合反应。 聚合温度控制在 70〜90°C, 压力为 0.4MPa, 聚合反应 10分钟。待聚合完成后, 放掉高压釜中的气体压力,将聚合产物倒 入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过 滤, 干燥得到固体颗粒产物聚丙烯釜内合金 25.5g。 实施例 4 (对比例) :
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的正己烷,再依次加 入浓度为 1.8mol/L的三乙基铝 1ml,上述制备的 Ziegler-Natta催化剂 20.0mg, 保持铝钛比: Al:Ti=100: l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 5min, 除掉己烷溶剂,然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 进行气相乙烯 -丙烯共聚合反应。 聚合温度控制在 80〜90°C, 压力为 0.4MPa, 聚合反应 10min, 待聚合完成后, 放掉高压釜中的气体压力, 将聚 合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤,干燥得到固体颗粒产物聚丙烯釜内合金 25.0g。对产物及其庚烷可 溶物进行 DSC表征和组成表征, 数据见表 1。
所述制备的多相共聚聚丙烯的傅里叶红外光谱图见图 1。 所制备的多相 共聚聚丙烯中庚烷抽提物(橡胶相) 的傅里叶红外光谱图见图 2。 所制备的 多相共聚聚丙烯的 DSC扫描曲线(升温速率 10°C/min)见图 3。 所制备的多 相共聚聚丙烯中庚烷抽提物(橡胶相) 的 DSC扫描曲线 (升温速率 10°C/min) 见图 4。所制备的多相共聚聚丙烯的 DMA损耗正切同温度的关系曲线见图 5。 实施例 5:
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的正己烷,再依次加 入浓度为 1.8mol/L的三乙基铝 1ml,上述制备的 Ziegler-Natta催化剂 23.6mg, 保持铝钛比: Al:Ti=200: 1 (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽除掉己烷溶剂, 约为 5min。 然后再通入气体摩尔比例是 1 :1的乙烯- 丙烯混合气, 当釜内压力为 lata时, 快速地注射入 3ml的 1,9-癸二烯单体, 进行气相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 70〜80°C, 压 力为 0.4MPa, 聚合反应 10min, 待聚合完成后, 放掉高压釜中的气体压力,
将聚合产物倒入 10% (体积比)的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。最后过滤, 干燥得到固体颗粒产物聚丙烯釜内合金 31.0g。对产物及其庚 烷可溶物进行 DSC表征和组成表征, 数据见表 1。
所述制备的多相共聚聚丙烯的傅里叶红外光谱图见图 1。 所制备的多相 共聚聚丙烯中庚烷抽提物(橡胶相) 的傅里叶红外光谱图见图 2。 所制备的 多相共聚聚丙烯的 DSC扫描曲线(升温速率 10°C/min)见图 3。 所制备的多 相共聚聚丙烯中庚烷抽提物(橡胶相) 的 DSC扫描曲线 (升温速率 10°C/min) 见图 4。所制备的多相共聚聚丙烯的 DMA损耗正切同温度的关系曲线见图 5。 实施例 6:
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的正己烷,再依次加 入浓度为 1.8mol/L的三乙基铝 1ml,上述制备的 Ziegler-Natta催化剂 20.7mg, 保持铝钛比: Al:Ti=100: 1 (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 5min, 除掉己烷溶剂,然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 当釜内压力为 lata时, 快速地注射入 5ml的 1,9-癸二烯单体, 进行气 相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 85〜90°C, 压力为 0.4MPa, 聚合反应 10min, 待聚合完成后, 放掉高压釜中的气体压力, 将聚 合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤,干燥得到固体颗粒产物聚丙烯釜内合金 29.6g。对产物及其庚烷可 溶物进行 DSC表征和组成表征, 数据见表 1。
所述制备的多相共聚聚丙烯的傅里叶红外光谱图见图 1。 所制备的多相 共聚聚丙烯中庚烷抽提物(橡胶相) 的傅里叶红外光谱图见图 2。 所制备的 多相共聚聚丙烯的 DSC扫描曲线(升温速率 10°C/min)见图 3。 所制备的多 相共聚聚丙烯中庚烷抽提物(橡胶相) 的 DSC扫描曲线 (升温速率 10°C/min) 见图 4。所制备的多相共聚聚丙烯的 DMA损耗正切同温度的关系曲线见图 5。 实施例 Ί:
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的己烷,再依次加入 浓度为 1.8mol/L的三乙基铝 lml, 上述制备的 Ziegler-Natta催化剂 20.1mg, 保持铝钛比: Al:Ti=100:l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 5min, 除掉己烷溶剂,然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 当釜内压力为 lata时, 快速地注射入 7ml的 1,9-癸二烯单体, 进行气 相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 85〜90°C, 压力为 0.4MPa, 聚合反应 10min。 待聚合完成后, 放掉高压釜中的气体压力, 将聚 合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤,干燥得到固体颗粒产物聚丙烯釜内合金 26.4g。对产物及其庚烷可 溶物进行 DSC表征和组成表征, 数据见表 1。
所述制备的多相共聚聚丙烯的傅里叶红外光谱图见图 1。 所制备的多相 共聚聚丙烯中庚烷抽提物(橡胶相) 的傅里叶红外光谱图见图 2。 所制备的 多相共聚聚丙烯的 DSC扫描曲线(升温速率 10°C/min)见图 3。 所制备的多 相共聚聚丙烯中庚烷抽提物(橡胶相) 的 DSC扫描曲线 (升温速率 10°C/min) 见图 4。所制备的多相共聚聚丙烯的 DMA损耗正切同温度的关系曲线见图 5。
由图 1可知, 1,9-癸二烯单体成功地共聚入乙烯 -丙烯无规共聚物主链中。 由图 2可知, 部分交联的乙烯-丙烯无规共聚物中, 未反应完全的双键的含量 随着二烯单体的加入而增加。 由图 3可知, 在 110°C附近有微微鼓起的短链 聚乙烯结晶峰。 由图 4可知, 交联或部分交联的乙烯-丙烯无规共聚物随着二 烯单体的加入, 玻璃化转变温度有所提高。 由图 5中 DMA谱图中可知, 交 联或部分交联的乙烯-丙烯无规共聚物的玻璃化转变温度提高,并且损耗正切 峰峰值, 随着交联程度或者二烯单体的加入量而显著增加。 实施例 8:
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的正己烷,再依次加 入浓度为 1.8mol/L的三乙基铝 1ml,上述制备的 Ziegler-Natta催化剂 23.0mg,
保持铝钛比: Al:Ti=100:l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 5min, 除掉己烷溶剂,然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 当釜内压力为 lata时, 快速地注射入 10ml的 1,9-癸二烯单体, 进行 气相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 70〜85°C, 压力为 0.4MPa, 聚合反应 10min, 待聚合完成后, 放掉高压釜中的气体压力, 将聚 合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤,干燥得到固体颗粒产物聚丙烯釜内合金 29.8g。对产物及其庚烷可 溶物进行 DSC表征和组成表征, 数据见表 1。 实施例 9:
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的己烷,再依次加入 浓度为 1.8mol/L的三乙基铝 1.5ml,上述制备的 Ziegler-Natta催化剂 26.4mg, 保持铝钛比: Al:Ti=100:l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 5min, 除掉己烷溶剂,然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 当釜内压力为 lata时, 快速地注射入 5ml的 1,9-癸二烯单体, 进行气 相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 95°C, 压力为 0.4MPa, 聚合反应 10min, 最终得到聚丙烯釜内合金 29.5g。 实施例 10:
( 1 ) 、 丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的己烷,再依次加入 浓度为 1.8mol/L的三乙基铝 1.2ml,上述制备的 Ziegler-Natta催化剂 25.6mg, 保持铝钛比: Al:Ti=100:l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 、 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 5min, 除掉己烷溶剂,然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 当釜内压力为 lata时, 快速地注射入 3ml的 1,9-癸二烯单体, 进行气 相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 85〜90°C, 压力为 0.4MPa, 聚合反应 10min。 待聚合完成后, 放掉高压釜中的气体压力, 将聚 合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤, 干燥得到固体颗粒产物聚丙烯釜内合金 27.7g。 实施例 11 :
( 1 ) 、 丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的己烷,再依次加入 浓度为 1.8mol/L的三乙基铝 1.5ml,上述制备的 Ziegler-Natta催化剂 27.2mg, 保持铝钛比: Al:Ti=100:l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 、 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 5min, 除掉己烷溶剂,然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 当釜内压力为 lata时, 快速地注射入 lml的 1,9-癸二烯单体, 进行气 相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 110°C左右, 压力为 0.4MPa, 聚合反应 10min, 待聚合完成后, 放掉高压釜中的气体压力, 将聚 合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤,干燥得到固体颗粒产物聚丙烯釜内合金 40.7g。产物的熔点和熔融 焓的 DSC表征数据见表 1。
所述制备的多相共聚聚丙烯的 DMA橡胶平台储能模量的关系曲线见图
6。橡胶平台储能模量的升高另一角度说明交联橡胶相的存在,储能模量同交 联程度成正比。 实施例 12:
( 1 )丙烯均聚合
在 500ml干燥的高压反应釜中,首先加入 50ml干燥的己烷,再依次加入
浓度为 1.8mol/L的三乙基铝 1.5ml,上述制备的 Ziegler-Natta催化剂 27.1mg, 保持铝钛比: Al:Ti=100:l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 5min, 除掉己烷溶剂, 然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 当釜内压力为 lata时, 快速地注射入 3ml的 1,9-癸二烯单体, 进行气 相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 95〜105°C, 压力为 0.4MPa, 聚合反应 10min。 待聚合完成后, 放掉高压釜中的气体压力, 将聚 合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤,干燥得到固体颗粒产物聚丙烯釜内合金 41.0g。产物的熔点和熔融 焓的 DSC表征数据见表 1。
所述制备的多相共聚聚丙烯的 DMA橡胶平台储能模量的关系曲线见图 6。橡胶平台储能模量的升高另一角度说明交联橡胶相的存在, 储能模量同交 联程度成正比。 实施例 13 :
( 1 ) 丙烯均聚合
在 500ml干燥的高压反应釜中, 首先加入 50ml干燥的己烷, 再依次加入 浓度为 1.8mol/L的三乙基铝 1.5ml,上述制备的 Ziegler-Natta催化剂 27.7mg, 保持铝钛比: Al:Ti=100:l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到均聚聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 3min, 除掉己烷溶剂, 然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 当釜内压力为 lata时, 快速地注射入 5ml的 1,9-癸二烯单体, 进行气 相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 70〜80°C, 压力为 0.4MPa, 聚合反应 20min。 待聚合完成后, 放掉高压釜中的气体压力, 将聚 合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤,干燥得到固体颗粒产物聚丙烯釜内合金 38.9g。产物的熔点和熔融 焓的 DSC表征数据见表 1。
所述制备的多相共聚聚丙烯的 DMA橡胶平台储能模量的关系曲线见图 6。橡胶平台储能模量的升高另一角度说明交联橡胶相的存在, 储能模量同交 联程度成正比。 实施例 14:
( 1 ) 丙烯均聚合
在 500ml干燥的高压反应釜中, 首先加入 50ml干燥的己烷, 再依次加入 浓度为 1.8mol/L的三乙基铝 1.5ml,上述制备的 Ziegler-Natta催化剂 28.0mg, 保持铝钛比: Al:Ti=100:l (摩尔比)左右,然后通入丙烯气体,于 60°C, 0.4MPa 压下聚合反应 30min, 得到均聚聚丙烯颗粒。
(2) 乙烯 -丙烯共聚合
将上面步骤(1 ) 中的丙烯气体放空, 并将聚合体系中的己烷溶剂, 用真 空泵抽 3min, 除掉己烷溶剂, 然后再通入气体摩尔比例是 1 :1的乙烯-丙烯混 合气, 当釜内压力为 lata时, 快速地注射入 7ml的 1,9-癸二烯单体, 进行气 相乙烯 -丙烯及二烯单体的共聚合反应。 聚合温度控制在 94〜98°C, 压力为 0.4MPa, 聚合反应 20min。 待聚合完成后, 放掉高压釜中的气体压力, 将聚 合产物倒入 10% (体积比) 的乙醇-盐酸的溶液中, 终止反应, 并且洗涤 lh。 最后过滤, 干燥得到固体颗粒产物聚丙烯釜内合金 37.5 g。 产物的熔点和熔 融焓的 DSC表征数据见表 1。
所述制备的多相共聚聚丙烯的 DMA橡胶平台储能模量的关系曲线见图
6。橡胶平台储能模量的升高另一角度说明交联橡胶相的存在, 储能模量同交 联程度成正比。
在一定温度下, 橡胶平台储能模量越高, 体系的平均交联度越高, 由图 6 可知, 随着二烯单体加入量的增加, 多相共聚聚丙烯体系的平均交联度增加, 交联的乙烯-丙烯无规共聚物增加。
7 18.02 160.7 36.6 -49.59 14.2
11 32.93 159.4 52.0 -46.04 10.4
12 29.35 157.2 48.0 -40.37 11.6
13 30.88 157.3 51.0 -44.54 17.2
14 21.66 157.1 54.8 -42.47 22.3 工业应用
本发明所提供的丙烯多相共聚体系及聚合方法, 成本低廉, 实施简便, 便于规模化生产。 利用该方法得到的橡胶分散相支化或交联的多相共聚聚丙 烯合金树脂, 由于橡胶相支化和交联使其运动能力降低, 有利于抑制加工过 程中橡胶相的聚集, 使增韧效果更明显。
Claims
1、 一种丙烯多相共聚体系, 其组成包括单体和催化剂, 所述单体包括丙 烯、 乙烯和 /或碳数大于 3的 α -烯烃; 其特征在于: 所述单体还包括双 α -烯 烃单体。
(式 I ) (式 II ) (式 III) (式 IV ) 其中, 式 I -式 IV中 η均为大于 1的整数;
所述双 α -烯烃单体优选 1, 5-己二烯, 1,7-辛二烯、 1,9-癸二烯、 4- (3- 丁烯基)苯乙烯、 二乙烯基苯异构体或 1, 2-二(4-乙烯基苯基) 乙烷, 最优 选为 1, 5-己二烯, 1, 7-辛二烯或 1, 9-癸二烯。
3、根据权利要求 1或 2所述的丙烯多相共聚体系, 其特征在于: 所述催 化剂为具有球形、 多孔颗粒形态的 Ziegler-Natta催化剂;
所述 Ziegler-Natta催化剂包括下述组分 1 )和 2)或 1 ) 、 2)和 3 ) : 1 ) 活性固体催化剂组分, 优选为含钛的固体催化剂活性组分, 最优选为球形 MgCl2负载的 TiCl4固体催化剂活性组分; 2)有机铝化合物助催化剂组分; 3 ) 外给电子体组分和氢气组分;
所述有机铝化合物优选为烷基铝化合物, 所述烷基铝化合物优选自下述 至少一种: 三乙基铝、 三异丁基铝、 三丁基铝和一氯二乙基铝;
所述外给电子体为结构通式为 R4.nSi(;OR';)n的化合物,其中, l n 3, 与 R'均选自烷基、 环烷基和芳基中的任意一种; 所述外给电子体优选二甲基 二甲氧基硅烷、 三甲基甲氧基硅烷、 甲基三甲氧基硅烷、 二苯基二甲氧基硅 烷、 二苯基二乙氧基硅烷或甲基环己烯二甲氧基硅烷。
4、一种聚丙烯釜内合金, 由作为连续相基体的聚丙烯均聚物和作为分散 相的具有支化和 /或交联结构的含有双 α -烯烃单体单元的下述任意一种共聚 物组成: 乙烯-丙烯二元无规共聚物、 乙烯-碳数大于 3的 α -烯烃二元无规共 聚物和乙烯-丙烯-碳数大于 3的 α -烯烃三元无规共聚物。
(式 I ) (式 II ) (式 III) (式 IV) 其中, 式 I -式 IV中 η均为大于 1的整数;
所述双 α -烯烃单体优选 1, 5-己二烯, 1,7-辛二烯、 1,9-癸二烯、 4- (3- 丁烯基)苯乙烯、 二乙烯基苯异构体或 1, 2-二(4-乙烯基苯基) 乙烷, 最优 选为 1, 5-己二烯, 1, 7-辛二烯或 1, 9-癸二烯。
6、根据权利要求 4所述的聚丙烯釜内合金, 其特征在于: 所述含有双 α -烯
(式 V ) (式 VI)
所述式 V和式 VI中的 R选自由以下结构通式代表的双 ci -烯烃所形成的 单体单元:
7、根据权利要求 4-6中任一项所述的聚丙烯釜内合金, 其特征在于: 所 述聚丙烯釜内合金中连续相与分散相的质量比为 30.0〜99.0: 1.0-70.0 c
8、根据权利要求 4-7中任一项所述的聚丙烯釜内合金, 其特征在于: 所 述分散相为具有支化或交联结构的含有双 α -烯烃单体单元的乙烯-丙烯二元
无规共聚物, 其中乙烯、 丙烯、 双 α -烯烃三种单体的摩尔比为 5〜95: 2-95: 1-30, 优选摩尔比为 27〜69: 63-30: 10-1; 所述双 α -烯烃单体中两个双键 均参与聚合反应的比例为 3〜97%。
9、 根据权利要求 4-8中任一项所述的聚丙烯釜内合金, 其特征在于: 所 述聚丙烯釜内合金是按照下述方法制备得到的: 以权利要求 1-3中任一项所 述的丙烯多相共聚体系为反应体系,采用丙烯两段或多段聚合工艺进行制备, 得到所述聚丙烯釜内合金;其中,所述丙烯两段或多段聚合工艺优选 Spheripol 工艺、 Unipol工艺或 Catalloy工艺。
10、 根据权利要求 9所述的聚丙烯釜内合金, 其特征在在于: 所述方法 至少包括下述步骤:
1 )使丙烯气体在权利要求 1-3中任一项所述的丙烯多相共聚体系中催化 剂的作用下进行聚合反应, 得到聚丙烯均聚物;
2) 在均聚反应完成后, 将聚合物转移至乙烯和丙烯的混合单体中, 并 加入所述双 α -烯烃, 进行共聚合反应, 得到聚丙烯釜内合金。
11、 一种制备权利要求 4-8中任一项所述的聚丙烯釜内合金的方法, 是 以权利要求 1-3中任一项所述的丙烯多相共聚体系为反应体系, 采用丙烯两 段或多段聚合工艺进行制备, 得到所述聚丙烯釜内合金; 其中, 所述工艺优 选 Spheripol工艺、 Unipol工艺或 Catalloy工艺。
12、根据权利要求 11所述的方法, 其特征在在于: 所述方法至少包括下 述步骤:
1 )使丙烯气体在权利要求 1-3中任一项所述的丙烯多相共聚体系中催化 剂的作用下进行聚合反应, 得到聚丙烯均聚物;
2) 在均聚反应完成后, 将聚合物转移至乙烯和丙烯的混合单体中, 并 加入所述双 α -烯烃, 进行共聚合反应, 得到聚丙烯釜内合金。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210324326.0A CN102838701B (zh) | 2012-09-04 | 2012-09-04 | 一种丙烯多相共聚体系、聚合方法及聚丙烯釜内合金 |
CN201210324326.0 | 2012-09-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014036678A1 true WO2014036678A1 (zh) | 2014-03-13 |
Family
ID=47366447
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2012/001761 WO2014036678A1 (zh) | 2012-09-04 | 2012-12-28 | 一种丙烯多相共聚体系、聚合方法及聚丙烯釜内合金 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN102838701B (zh) |
WO (1) | WO2014036678A1 (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102838701B (zh) * | 2012-09-04 | 2014-12-10 | 中国科学院化学研究所 | 一种丙烯多相共聚体系、聚合方法及聚丙烯釜内合金 |
CN103804795B (zh) * | 2014-03-06 | 2016-03-09 | 中国科学院化学研究所 | 具有长链支化结构特征的高熔体强度聚丙烯树脂的制备方法 |
CN103992560B (zh) * | 2014-04-30 | 2016-08-24 | 中国科学院化学研究所 | 一种可用于3d打印的高橡胶含量的聚丙烯多相共聚物树脂及其制备方法和应用 |
CN105623077B (zh) * | 2014-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | 一种高熔体强度的抗冲聚丙烯材料及其制备方法 |
CN106832583B (zh) * | 2016-01-31 | 2020-04-24 | 浙江大学 | 高乙烯含量流动性好的抗冲聚丙烯及其制备方法 |
CN110804117A (zh) * | 2018-07-20 | 2020-02-18 | 中国科学院化学研究所 | 一种交联乙丙共聚物及其制备方法和应用 |
CN111944234B (zh) * | 2019-05-17 | 2022-01-11 | 中国科学院化学研究所 | 用于制备聚烯烃釜内合金的方法及其制备的聚烯烃釜内合金 |
CN113683837B (zh) * | 2020-05-19 | 2023-11-28 | 中国石油天然气股份有限公司 | 一种抗冲共聚聚丙烯及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101208391A (zh) * | 2005-06-22 | 2008-06-25 | 埃克森美孚化学专利公司 | 多相聚合物共混物及其制备方法 |
CN101553509A (zh) * | 2006-12-22 | 2009-10-07 | 埃克森美孚化学专利公司 | 制备聚合物共混物的方法 |
CN102174225A (zh) * | 2011-01-28 | 2011-09-07 | 中国科学院化学研究所 | 一种多相共聚聚丙烯釜内合金及其制备方法 |
CN102838701A (zh) * | 2012-09-04 | 2012-12-26 | 中国科学院化学研究所 | 一种丙烯多相共聚体系、聚合方法及聚丙烯釜内合金 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1328310C (zh) * | 2004-11-05 | 2007-07-25 | 中国科学院化学研究所 | 聚烯烃复合材料及其制备方法 |
CN100427509C (zh) * | 2006-12-30 | 2008-10-22 | 中国石化扬子石油化工有限公司 | 一种聚烯烃合金的制备方法 |
-
2012
- 2012-09-04 CN CN201210324326.0A patent/CN102838701B/zh active Active
- 2012-12-28 WO PCT/CN2012/001761 patent/WO2014036678A1/zh active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101208391A (zh) * | 2005-06-22 | 2008-06-25 | 埃克森美孚化学专利公司 | 多相聚合物共混物及其制备方法 |
CN101553509A (zh) * | 2006-12-22 | 2009-10-07 | 埃克森美孚化学专利公司 | 制备聚合物共混物的方法 |
CN102174225A (zh) * | 2011-01-28 | 2011-09-07 | 中国科学院化学研究所 | 一种多相共聚聚丙烯釜内合金及其制备方法 |
CN102838701A (zh) * | 2012-09-04 | 2012-12-26 | 中国科学院化学研究所 | 一种丙烯多相共聚体系、聚合方法及聚丙烯釜内合金 |
Also Published As
Publication number | Publication date |
---|---|
CN102838701A (zh) | 2012-12-26 |
CN102838701B (zh) | 2014-12-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2014036678A1 (zh) | 一种丙烯多相共聚体系、聚合方法及聚丙烯釜内合金 | |
CN102268160B (zh) | 一种聚丁烯合金材料及其制备方法 | |
CN106832583B (zh) | 高乙烯含量流动性好的抗冲聚丙烯及其制备方法 | |
CN108659151B (zh) | 一种有机硅烷的应用以及聚丙烯及其制备方法 | |
EP3192817B1 (en) | Method for producing olefin (co)polymer containing constituent unit derived from 1-butene | |
JP7455426B2 (ja) | プロピレン共重合体の製造方法 | |
CN104761834A (zh) | 一种高等规聚烯烃合金材料及其制备方法 | |
EP1810991B1 (en) | Method for producing a polyolefin composite material | |
CN114507311B (zh) | 乙烯聚合物及其制备方法 | |
CN109929185B (zh) | 一种生产聚丙烯组合物的方法 | |
TW201428007A (zh) | 丙烯聚合物的製備方法 | |
CN103288993A (zh) | 高等规度球形聚丁烯-1及其制备方法 | |
CN106893020B (zh) | 一种球形聚丁烯-1的制备方法 | |
CN111944079B (zh) | 聚烯烃釜内合金及其制备方法 | |
WO2007115993A1 (en) | Controlled distribution of active sites in ziegler-natta catalyst systems. | |
CN111944234B (zh) | 用于制备聚烯烃釜内合金的方法及其制备的聚烯烃釜内合金 | |
CN111087503B (zh) | 1-丁烯聚合物及1-丁烯淤浆聚合方法 | |
CN108707289B (zh) | 一种聚烯烃合金材料及其制备方法 | |
CN111087509A (zh) | 一种柔性1-丁烯聚合物及其制备方法 | |
CN104761833A (zh) | 一种聚烯烃合金材料及其制备方法 | |
CN114621379B (zh) | 乙烯聚合物及其制备方法 | |
WO2022161400A1 (zh) | 淤浆聚合连续生产超高分子量聚乙烯的方法 | |
CN113087826B (zh) | 外给电子体组合物、烯烃聚合催化剂及其应用以及聚烯烃及其制备方法 | |
CN106432570B (zh) | 一种丙烯丁烯共聚物材料及立构控制聚合的合成方法 | |
CN115926331A (zh) | 一种聚丁烯-1合金及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12884224 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12884224 Country of ref document: EP Kind code of ref document: A1 |