CN102464748B - Propylene copolymer macromonomer and preparation method thereof - Google Patents
Propylene copolymer macromonomer and preparation method thereof Download PDFInfo
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- CN102464748B CN102464748B CN 201010547263 CN201010547263A CN102464748B CN 102464748 B CN102464748 B CN 102464748B CN 201010547263 CN201010547263 CN 201010547263 CN 201010547263 A CN201010547263 A CN 201010547263A CN 102464748 B CN102464748 B CN 102464748B
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229920001577 copolymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- -1 polypropylene Polymers 0.000 claims abstract description 19
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 26
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 239000004711 α-olefin Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 125000000746 allylic group Chemical group 0.000 claims description 10
- 239000012968 metallocene catalyst Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 5
- VTZSLRLGIGTMEP-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C(C(C)(C)C)=CC([Zr+2])C2=C1 Chemical compound [Cl-].[Cl-].C1=CC=C2C(C(C)(C)C)=CC([Zr+2])C2=C1 VTZSLRLGIGTMEP-UHFFFAOYSA-L 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 abstract description 14
- 239000004743 Polypropylene Substances 0.000 abstract description 11
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DZETZMSAJDMAKS-UHFFFAOYSA-L Cl[Zr]Cl.[CH]1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical compound Cl[Zr]Cl.[CH]1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 DZETZMSAJDMAKS-UHFFFAOYSA-L 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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Abstract
The invention provides a propylene copolymer macromonomer, which comprises a structural unit shown as a formula (1) and a structural unit shown as a formula (2), wherein the number average molecular weight of the propylene copolymer macromonomer is 1000-500,000 g/mol; the molar ratio of the structural unit shown as the formula (1) to the structural unit shown as the formula (2) is (3-100):1; at least a part of the terminal groups of the propylene copolymer macromonomer are allyl; the allyl accounts for 35-50 molar percent of the total weight of all terminal groups of the propylene copolymer macromonomer; and in the formula (2), R is alkyl with 2-18 carbon atoms. The invention further provides a preparation method of the propylene copolymer macromonomer. The propylene copolymer macromonomer provided by the invention has high allyl terminal group content, narrow molecular weight distribution and lower melting point than that of polypropylene.
Description
Technical field
The invention provides a kind of propylene copolymer macromonomer its preparation method.
Background technology
Propylene can be for the preparation of film, thermoplastic elastomer and the heat-sealable material etc. of excellent performance with the multipolymer that is different from the alpha-olefin of propylene.The research and development of propylene copolymer in recent years also come into one's own day by day.CN1151172A, CN1759128A and CN1957036A disclose the goods made from the propylene-alpha-olefin segmented copolymer, can be used for fields such as film, fiber, fabric.The film that the propylene-alpha-olefin segmented copolymer is made has excellent thermotolerance, low-temperature heat-sealing performance and the transparency.
Has the olefin polymer of allyl group end group because coming into one's own for the preparation of branched polymer.Disclose as CN1246127A and CN1246871A and a kind ofly to have the polyethylene of vinyl end or the macromonomer of its multipolymer, and to be used for preparing polyethylene be that side chain, polypropylene are the branched polymer of main chain.It is more difficult that preparation has the polypropylene macromers of allyl group end group, and its reason is in the propylene polymerization that chain transfer reaction is complicated and is difficult to control.CN1495209A uses the solid titanium catalyst catalyzing propone polymerization of Ziegler-Natta type, and then has just obtained containing the polypropylene macromers of acryl, methacryloyl or styryl end group through two-step reaction.CN1274367A, CN1278273A and CN1309669A disclose the method that a kind of preparation has polypropylene macromers and the branching propene polymer of vinyl ends, this method uses metallocene catalyst more than 90 ℃, even 110 ℃ high-temperature catalytic propylene polymerization is to obtain polypropylene macromers and to prepare the propene polymer of branching.
Because the polypropylene fusing point is higher, use polypropylene macromers to prepare branched polymer and will under very high temperature, react, be beneficial to polymkeric substance and in solvent, dissolve.Higher temperature of reaction can make the catalyst member inactivation and the activity of polyreaction is reduced, and has also influenced degree of isotacticity and the molecular weight of polypropylene backbone simultaneously.Therefore, it is very necessary developing the propylene copolymer macromonomer that a kind of fusing point is lower, polymeric reaction temperature is not high.
Summary of the invention
To the objective of the invention is to the higher shortcoming of propene polymer macromonomer fusing point that exists in the prior art in order overcoming, a kind of propylene copolymer macromonomer and preparation method thereof to be provided.
The invention provides a kind of propylene copolymer macromonomer, this propylene copolymer macromonomer contains formula, (1) structural unit shown in and formula, (2) structural unit shown in, the number-average molecular weight of this propylene copolymer macromonomer is 1000～500000g/mol, formula, (1) structural unit shown in and formula, the mol ratio of the structural unit (2) is 3～100: 1, the end group of at least part of this propylene copolymer macromonomer is allyl group, and the molar percentage that allylic content accounts for the total amount of the whole end groups of this propylene copolymer macromonomer is 35～50%
R in the formula (2) is the alkyl with 2～18 carbon atoms.
The present invention also provides a kind of preparation method of propylene copolymer macromonomer, this method comprises: under the olefin-copolymerization condition, with propylene and the alpha-olefin that is different from propylene with mol ratio 3～100: 1 ratio contacts in the presence of metallocene catalyst and solvent, and from contact the back products therefrom, isolate polymkeric substance, the condition of contact makes that the number-average molecular weight of isolated polymkeric substance is 1000～500000g/mol; Described metallocene catalyst contains Primary Catalysts and promotor, and described Primary Catalysts is for being selected from least a in the metallocene compound with following general formula (3),
R
2Y[3-R’-Ind]
2MCl
2 (3)
In the general formula (3), two R respectively do for oneself H or CH
3, Y is C or Si, R ' is H, CH
3, CH (CH
3)
2And C (CH
3)
3In a kind of, M is Zr or Hf, Ind is indenyl;
Described promotor is the alkylaluminoxane promotor, and the content of alkylaluminoxane is not less than 10 weight % in the alkylaluminoxane promotor, and the content of trialkylaluminium is not higher than 0.5 weight %.
The content height of allyl group end group in the propylene copolymer macromonomer provided by the invention, narrow molecular weight distribution, and its fusing point is lower than polypropylene, all below 140 ℃, do not need very high temperature when therefore utilizing propylene copolymer macromonomer of the present invention to carry out polyreaction, this not only more is conducive to the preparation of branched polymer, but also can bring into play the performance characteristics of propylene copolymer, regulates structure and the performance of branched polymer in the larger context.In addition, method operation of the present invention is simple, and polymeric reaction temperature is not high, is more suitable for industrial application.
Description of drawings
Fig. 1 is the embodiment of the invention 2
13The C-NMR spectrogram.
Fig. 2 is the embodiment of the invention 7
1The H-NMR spectrogram.
Embodiment
The invention provides a kind of propylene copolymer macromonomer, this propylene copolymer macromonomer contains formula, (1) structural unit shown in and formula, (2) structural unit shown in, wherein, the number-average molecular weight of this propylene copolymer macromonomer is 1000～500000g/mol, formula, (1) structural unit shown in and formula, the mol ratio of the structural unit (2) is 3～100: 1, the end group of at least part of this propylene copolymer macromonomer is allyl group, and the molar percentage that allylic content accounts for the whole end group total amounts of this propylene copolymer macromonomer is 35～50%
R in the formula (2) is the alkyl with 2～18 carbon atoms.
Under the preferable case, in aforesaid propylene multipolymer macromonomer, the molar percentage that allylic content accounts for the whole end group total amounts of this propylene copolymer macromonomer is 40～50%.Among the present invention, by
1The H-NMR mode determines that allylic content accounts for the molar percentage of the whole end group total amounts of this propylene copolymer macromonomer.
Under the preferable case, in aforesaid propylene multipolymer macromonomer, the mol ratio of the structural unit shown in the structural unit shown in the formula (1) and the formula (2) is 4～100: 1.Control in above-mentioned preferable range by the mol ratio that makes the structural unit shown in the structural unit shown in the formula (1) and the formula (2), can control the fusing point of multipolymer within the scope that requires.Among the present invention, by
13The C-NMR mode is determined in the propylene copolymer macromonomer, the mol ratio of the structural unit shown in the structural unit shown in the formula (1) and the formula (2).
Under the preferable case, the number-average molecular weight of aforesaid propylene multipolymer macromonomer is 1500～200000g/mol, molecular weight distribution is 1.5～5, and more preferably the number-average molecular weight of aforesaid propylene multipolymer macromonomer is 1500～50000g/mol, and molecular weight distribution is 2～4.
According to propylene copolymer macromonomer provided by the invention, wherein the structural unit shown in preferred most of described formula (2) and the structural unit key shown in the described formula (1) connect, and further the structural unit shown in the described formula (2) of preferred 95～100 moles of % and the structural unit key shown in the described formula (1) connect.Can pass through
13The C-NMR method defines structural unit and the structural unit key shown in the described formula (1) company shown in the described formula (2) of how many moles.
The present invention also provides a kind of preparation method of propylene copolymer macromonomer, this method comprises: under the olefin-copolymerization condition, with propylene and the alpha-olefin that is different from propylene with mol ratio 3～100: 1 ratio contacts in the presence of metallocene catalyst and solvent, and from contact the back products therefrom, isolate polymkeric substance, the condition of contact makes that the number-average molecular weight of isolated polymkeric substance is 1000～500000g/mol; Described metallocene catalyst contains Primary Catalysts and promotor, and described Primary Catalysts is for being selected from least a in the metallocene compound with following general formula (3),
R
2Y[3-R’-Ind]
2MCl
2 (3)
In the general formula (3), two R respectively do for oneself H or CH
3, Y is C or Si, R ' is H, CH
3, CH (CH
3)
2And C (CH
3)
3In a kind of, M is Zr or Hf, Ind is indenyl;
Described promotor is the alkylaluminoxane promotor, and the content of alkylaluminoxane is not less than 10 weight % in the alkylaluminoxane promotor, and the content of trialkylaluminium is not higher than 0.5 weight %.
In above-mentioned preparation method, the mol ratio of described Primary Catalysts and alkylaluminoxane promotor is preferably 1: 250～and 5000, more preferably 1: 500～2000.
Among the present invention, described metallocene compound is preferably and is selected from methylene bridge two (3-tertiary butyl indenyl) zirconium dichloride, sec.-propyl bridge two (3-tertiary butyl indenyl) zirconium dichloride and sec.-propyl bridge two (the 3-sec.-propyl indenyl) zirconium dichloride one or more.
Among the present invention, be not higher than 0.5 weight % by the content of controlling trialkylaluminium in the alkylaluminoxane promotor, can suppress the chain transfer reaction to trialkylaluminium that free alkyl aluminium causes, thereby obtain the propylene copolymer macromonomer of allyl capped.Usually, contain the alkylaluminoxane of 10～30 weight % and the trialkylaluminium of 1～6 weight % usually in the alkylaluminoxane as the promotor of metallocene catalyst.The content of the trialkylaluminium that uses among the present invention is not higher than the alkylaluminoxane promotor of 0.5 weight % can be by being that alkylaluminoxane promotor more than the 1 weight % carries out pre-treatment and obtains with trialkylaluminium content, described pretreated method is included under the pressure in gauge pressure position-0.1～0MPa, and described alkylaluminoxane promotor was heated under 30～100 ℃ temperature 2～24 hours.Under the preferable case, described pre-treatment comprises: counting-0.1 with gauge pressure～-pressure of 0.05MPa under, described alkylaluminoxane promotor was heated under 50～80 ℃ temperature 4～12 hours.
Kind for described alkylaluminoxane is not particularly limited, and can be the field of olefin polymerisation various alkylaluminoxanes that use as promotor commonly used.Alkyl in the alkylaluminoxane that uses among the present invention can be C
1～C
5Alkyl, be preferably and be selected from methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide and the modified methylaluminoxane one or more, more preferably methylaluminoxane and/or modified methylaluminoxane.Described modified methylaluminoxane refers to that the mixture of methylaluminoxane and other alkylaluminoxanes or trimethyl aluminium mix the alkylaluminoxane that the back hydrolysis obtains with the aluminum alkyls of other types, for example: ethyl modified methylaluminoxane, isobutyl-modified methylaluminoxane.Methylaluminoxane and modified methylaluminoxane be commercially available acquisition all.
In the preparation method of aforesaid propylene multipolymer macromonomer, described propylene is preferably 3～100 with the mol ratio that is different from the alpha-olefin of propylene: 1, more preferably 4～100: 1.
The described alpha-olefin that uses in the present invention can be 4～20 alpha-olefin as carbonatoms, is preferably 1-butylene, 1-hexene or 1-octene.
The described solvent that uses in the present invention can be field of olefin polymerisation all kinds of SOLVENTS commonly used, is preferably in toluene, dimethylbenzene, hexane and the heptane one or more; With respect to the Primary Catalysts of 1 weight part, use 10
3～10
8The solvent of weight part.
In the preparation method of aforesaid propylene multipolymer macromonomer, described olefin-copolymerization condition comprises that temperature can be 10～80 ℃, and the time can be 5～120min, and pressure can be 0.1～5MPa, and the concentration of described metallocene compound in solvent can be 10
-8～10
-3Mol/L.Under the preferable case, described olefin-copolymerization condition comprises that temperature is 30～70 ℃, and the time is 10～60min, and pressure is 0.1～4MPa, and the concentration of described metallocene compound in solvent is 10
-6～10
-4Mol/L.In the present invention, the described reaction times refers to add after the Primary Catalysts, extremely with reaction product time before the oxidation in dry air.
In the preparation method of aforesaid propylene multipolymer macromonomer, the method of isolating polymkeric substance from contact the back products therefrom can comprise washs the alcoholic solution of contact back products therefrom with ethanol solution hydrochloride, methanol hydrochloride solution or other mineral acids, thus residual promotor and catalyzer is removed.The volume ratio of mineral acid and alcohol can be 1: 5～20.
The propylene copolymer macromonomer that the present invention also provides the preparation method by aforesaid propylene multipolymer macromonomer to make.
The present invention is described in detail below in conjunction with embodiment.
In following examples, adopt the gel permeation chromatography method to measure polyolefinic molecular weight, wherein, the test condition of gel permeation chromatography comprises: using instrument is 1 as PL-GPC 220 gel permeation chromatographs, the moving phase of Britain PL company, 3,5-trichlorobenzene, flow velocity are 150 ℃ of 1mL/min, probe temperatures.Be that the differential scanning calorimeter of DiamondDSC is measured polyolefinic fusing point with the model of U.S. PE company.The nuclear magnetic resonance spectrometer that is respectively AVANCE300 and AVANCE400 with the model of Switzerland Bruker company carries out hydrogen nuclear magnetic resonance spectrum analysis and carbon-13 nmr spectra analysis (solvent is that deuterium is for orthodichlorobenzene).According to
13C-NMR is determined in the propylene copolymer macromonomer, the mol ratio of the structural unit shown in the structural unit shown in the formula (1) and the formula (2), and the structural unit shown in the formula (2) that connects with structural unit key shown in the formula (1) accounts for the mole % of the structural unit total amount shown in the formula (2).Wherein, embodiment 2
13The C-NMR spectrum as shown in Figure 1.In the present invention, adopt Guoqiang Fan and Jin-Yong Dong disclosed method in " Journal of Molecular Catalysis A:Chemical " rolled up 246 pages in 2005 the 236th, use
1Polymkeric substance stops the content of end group in the H-NMR analyzing polymers.Namely exist
1In the H-NMR spectrogram: 5.70ppm is the methyne in the polyacrylic allyl capped and the resonance peak of methylene radical respectively to the multiplet between the 5.90ppm and 4.90ppm to the triplet between the 5.10ppm; 4.70ppm and two of 4.75ppm place unimodal be the resonance peak of the methylene radical in the polyacrylic vinylidene end group; 3.30ppm the resonance peak to the methylene radical that to be polypropylene end of the chains link with hydroxyl of two multiplets between the 3.50ppm; 4.81ppm locate unimodal be the resonance peak of the methylene radical in the internal double bond structure in the middle of the polymer chain.Determine that according to the integral area of each resonance peak end group is the molar content of hydroxyl, vinylidene and allylic multipolymer in the multipolymer.Wherein, embodiment 7
1The H-NMR spectrum as shown in Figure 2.
Preparation example 1
The processing of methylaluminoxane
Adding 100mL concentration in the there-necked flask that is equipped with agitator is the methylaluminoxane promotor (U.S. Albemarle company of 10 weight %, wherein the content of methylaluminoxane is 8.5 weight %, the content of trimethyl aluminium is 1.5 weight %) toluene solution, stirring and vacuumizing (in gauge pressure, pressure is-0.08MPa) condition under, the toluene solution of methylaluminoxane slowly is heated to 50 ℃, after all disappearing, the liquid in the there-necked flask continued to vacuumize 8 hours, obtain 5.8g white powder material, and then adding 60mL toluene formation colourless transparent solution is standby.Warp
1H-NMR analyzes the existence that has detected less than trimethyl aluminium.
Embodiment 1～8
This embodiment is used for explanation propylene copolymer macromonomer of the present invention and preparation method thereof.
At first use the nitrogen purging polymerization reactor, with propylene and 1-butylene gas mixture displacement nitrogen, be set to required polymerization temperature then, the 3.6mL colourless transparent solution that obtains in 46mL toluene and the preparation example 1 is joined in the polymerization reactor; Under the polymerization temperature of setting, stirred 10 minutes, and the pressure in feeding aforesaid propylene and the 1-butylene gas mixture maintenance polymerization reactor, add Primary Catalysts, under the polymerization temperature of setting, stir certain hour, then with reaction product oxidation 2 hours in dry air, be 1: 10 ethanol solution hydrochloride precipitation then with the reactant volume ratio, filtration obtains the white solid powder, after ethanol (30mL * 3 time) washing, water (50mL * 2 time) washing again, dry in the baking oven that temperature is 50 ℃, pressure for-0.1MPa.Dried solid product is carried out the carbon-13 nmr spectra analysis, and analytical results confirms that the end group that has obtained an end is allylic propylene-1-butylene random copolymers macromonomer.Reaction conditions sees Table 1, and the constitutional features of polymkeric substance sees Table 3.
Comparative Examples 1
Adopt the method identical with embodiment 1 to carry out olefinic polymerization, different is, methylene bridge two (3-tertiary butyl indenyl) zirconium dichloride is replaced by dimethyl silicon bridge two (2-methyl-4-phenyl indenyl) zirconium dichloride, and reaction conditions sees Table 1, and the constitutional features of polymkeric substance sees Table 3.
Embodiment 9～13
This embodiment is used for explanation propylene copolymer macromonomer of the present invention and preparation method thereof.
At first use the nitrogen purging polymerization reactor, replace nitrogen with propylene then, be set to required polymerization temperature, according to the amount that provides in the table 2, the colourless transparent solution and the alpha-olefin that obtain in solvent, the preparation example 1 are joined in the polymerization reactor, and the reactant solution cumulative volume is 50mL; Under the polymerization temperature of setting, stirred 10 minutes, and the feeding propylene keeps the pressure in the polymerization reactor, add Primary Catalysts, stirring certain hour under the polymerization temperature of setting, with reaction product oxidation 2 hours in dry air, is that 1: 10 ethanol solution hydrochloride precipitates with the reactant volume ratio then then, filtration obtains the white solid powder, after ethanol (30mL * 3 time) washing, water (50mL * 2 time) washing again, at 50 ℃ of temperature, pressure be-baking oven of 0.1MPa in drying.Dried solid product is carried out the hydrogen nuclear magnetic resonance spectrum analysis, and analytical results confirms that the end group that has obtained an end is allylic propylene-1-hexene random copolymers macromonomer.Reaction conditions sees Table 2, and the constitutional features of polymkeric substance sees Table 3.
Comparative Examples 2
Adopt the method identical with embodiment 7 to carry out olefinic polymerization, different is, the methylaluminoxane promotor that obtains in the preparation example 1 by methylaluminoxane (available from U.S. Albemarle company, the trimethyl aluminium that wherein contains 1.5% weight) replaces, reaction conditions sees Table 2, and the constitutional features of polymkeric substance sees Table 3.
As shown in table 3, in prepared according to the methods of the invention propylene copolymer macromonomer, the molar percentage that allylic content accounts for the whole end group total amounts of this propylene copolymer macromonomer is 40～50%, and polyolefinic monomer distribution of the present invention is even, narrow molecular weight distribution, molecular weight distribution is in 1.94～2.85 scope, and its fusing point is lower than polypropylene, all below 140 ℃.Compare with the propylene copolymer macromonomer of embodiment 1 preparation, the propylene copolymer molecular weight of Comparative Examples 1 preparation is big, and does not have the allyl group end group.Compare with the propylene copolymer macromonomer of embodiment 7 preparations, the allyl group endgroup content of the propylene copolymer macromonomer of Comparative Examples 2 preparations has only 22.5%, is significantly less than the propylene copolymer macromonomer that adopts the inventive method preparation.
Claims (17)
1. propylene copolymer macromonomer, this propylene copolymer macromonomer contains the structural unit shown in the structural unit shown in the formula (1) and the formula (2), it is characterized in that, the number-average molecular weight of this propylene copolymer macromonomer is 1000～500000g/mol, the mol ratio of the structural unit shown in the structural unit shown in the formula (1) and the formula (2) is 3～100:1, the end group of at least part of this propylene copolymer macromonomer is allyl group, and the molar percentage that allylic content accounts for the total amount of the whole end groups of this propylene copolymer macromonomer is 35～50%
R in the formula (2) is the alkyl with 2～18 carbon atoms.
2. propylene copolymer macromonomer according to claim 1, wherein, the molar percentage that allylic content accounts for the whole end group total amounts of this propylene copolymer macromonomer is 40～50%.
3. propylene copolymer macromonomer according to claim 1 and 2, wherein, in described propylene copolymer macromonomer, the mol ratio of the structural unit shown in the structural unit shown in the formula (1) and the formula (2) is 4～100:1.
4. propylene copolymer macromonomer according to claim 1 and 2, wherein, the number-average molecular weight of described propylene copolymer macromonomer is 1500～200000g/mol, molecular weight distribution is 1.5～5.
5. propylene copolymer macromonomer according to claim 1 and 2, wherein, the structural unit key shown in the structural unit shown in the described formula (2) of 95～100 moles of % and the described formula (1) connects.
6. the preparation method of a propylene copolymer macromonomer, it is characterized in that, this method comprises: under the olefin-copolymerization condition, propylene and the alpha-olefin that is different from propylene are contacted in the presence of metallocene catalyst and solvent with the ratio of mol ratio 3～100:1, and from contact the back products therefrom, isolate polymkeric substance, the condition of contact makes that the number-average molecular weight of isolated polymkeric substance is 1000～500000g/mol; Described metallocene catalyst contains Primary Catalysts and promotor, and described Primary Catalysts is for being selected from least a in the metallocene compound with following general formula (3),
R
2Y[3-R’-Ind]
2MCl
2 （3）
In the general formula (3), two R respectively do for oneself H or CH
3, Y is C or Si, R ' is H, CH
3, CH (CH
3)
2And C (CH
3)
3In a kind of, M is Zr or Hf, Ind is indenyl;
Described promotor is the alkylaluminoxane promotor, and the content of alkylaluminoxane is not less than 10 weight % in the alkylaluminoxane promotor, and the content of trialkylaluminium is not higher than 0.5 weight %;
Described alkylaluminoxane promotor be by with trialkylaluminium content be alkylaluminoxane promotor more than the 1 weight % counting with gauge pressure-pressure of 0.1～0MPa under, under 30～100 ℃ temperature, heat and obtained in 2～24 hours.
7. method according to claim 6, wherein, the mol ratio of described Primary Catalysts and alkylaluminoxane promotor is 1:250～5000.
8. according to claim 6 or 7 described methods, wherein, described metallocene compound is for being selected from methylene bridge two (3-tertiary butyl indenyl) zirconium dichloride, sec.-propyl bridge two (3-tertiary butyl indenyl) zirconium dichloride and sec.-propyl bridge two (the 3-sec.-propyl indenyl) zirconium dichloride one or more.
9. according to claim 6 or 7 described methods, wherein, the alkyl in the described alkylaluminoxane is C
1～C
5Alkyl.
10. method according to claim 9, wherein, described alkylaluminoxane is to be selected from methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide and the modified methylaluminoxane one or more.
11. method according to claim 10, wherein, described alkylaluminoxane is methylaluminoxane and/or modified methylaluminoxane.
12. method according to claim 6, wherein, described propylene is 4～100:1 with the mol ratio that is different from the alpha-olefin of propylene.
13. according to claim 6 or 12 described methods, wherein, described alpha-olefin is that carbonatoms is 4～20 alpha-olefin.
14. method according to claim 13, wherein, described alpha-olefin is 1-butylene, 1-hexene or 1-octene.
15. method according to claim 6, wherein, described solvent is one or more in toluene, dimethylbenzene, hexane and the heptane.
16. method according to claim 6, wherein, described olefin-copolymerization condition comprises that temperature is 10～80 ℃, and the time is 5～120min, and pressure is 0.1～5MPa, and the concentration of described Primary Catalysts in solvent is 10
-8～10
-3Mol/L.
17. the propylene copolymer macromonomer that is made by any described method in the claim 6～16.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226894A (en) * | 1997-03-29 | 1999-08-25 | 蒙特尔技术有限公司 | Metallocene and olefin polymerization catalyst |
| CN1291986A (en) * | 1998-11-18 | 2001-04-18 | 蒙特尔技术有限公司 | Bis(tetrahydroindenyl) metallocenes as catalysts for olefin polymerization |
| CN101041701A (en) * | 2002-09-20 | 2007-09-26 | 埃克森美孚化学专利公司 | Polymer containing propylene and its use |
| CN101679556A (en) * | 2007-06-04 | 2010-03-24 | 埃克森美孚化学专利公司 | Super-solution homogeneous propylene polymerization |
-
2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1226894A (en) * | 1997-03-29 | 1999-08-25 | 蒙特尔技术有限公司 | Metallocene and olefin polymerization catalyst |
| CN1291986A (en) * | 1998-11-18 | 2001-04-18 | 蒙特尔技术有限公司 | Bis(tetrahydroindenyl) metallocenes as catalysts for olefin polymerization |
| CN101041701A (en) * | 2002-09-20 | 2007-09-26 | 埃克森美孚化学专利公司 | Polymer containing propylene and its use |
| CN101679556A (en) * | 2007-06-04 | 2010-03-24 | 埃克森美孚化学专利公司 | Super-solution homogeneous propylene polymerization |
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