CN103288993A - Spherical polybutylene-1 with high isotacticity and preparation method thereof - Google Patents
Spherical polybutylene-1 with high isotacticity and preparation method thereof Download PDFInfo
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- CN103288993A CN103288993A CN2013102684383A CN201310268438A CN103288993A CN 103288993 A CN103288993 A CN 103288993A CN 2013102684383 A CN2013102684383 A CN 2013102684383A CN 201310268438 A CN201310268438 A CN 201310268438A CN 103288993 A CN103288993 A CN 103288993A
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- polybutene
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- electron donor
- isotacticity
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 229920001748 polybutylene Polymers 0.000 claims description 36
- 238000011068 loading method Methods 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000007701 flash-distillation Methods 0.000 claims description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- 125000004494 ethyl ester group Chemical group 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 7
- -1 -isopropyl ethyl succinate Chemical compound 0.000 claims description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- HVTZPAKTPAZTBQ-UHFFFAOYSA-N bis(2-methylpropyl) 4-methylbenzene-1,2-dicarboxylate Chemical compound CC(C)COC(=O)C1=CC=C(C)C=C1C(=O)OCC(C)C HVTZPAKTPAZTBQ-UHFFFAOYSA-N 0.000 claims description 4
- QFDIPTVSUHQNNT-UHFFFAOYSA-N dibutyl 4-methylbenzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C)C=C1C(=O)OCCCC QFDIPTVSUHQNNT-UHFFFAOYSA-N 0.000 claims description 4
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- NXKGJIRLCQBHFD-UHFFFAOYSA-N CO[SiH](OC)CC(C)C Chemical compound CO[SiH](OC)CC(C)C NXKGJIRLCQBHFD-UHFFFAOYSA-N 0.000 claims description 3
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- NDUOKXVXMPVJRT-UHFFFAOYSA-N C[SiH2]C.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound C[SiH2]C.C1(=CC=CC=C1)C1=CC=CC=C1 NDUOKXVXMPVJRT-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 2
- OANIYCQMEVXZCJ-UHFFFAOYSA-N ditert-butyl(dimethoxy)silane Chemical compound CO[Si](OC)(C(C)(C)C)C(C)(C)C OANIYCQMEVXZCJ-UHFFFAOYSA-N 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-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
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000012798 spherical particle Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 14
- 229920001083 polybutene Polymers 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012725 vapour phase polymerization Methods 0.000 description 2
- 206010009866 Cold sweat Diseases 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Abstract
The invention discloses spherical polybutylene-1 with high isotacticity and a preparation method thereof as well as a catalyst used by the method. The method comprises the following steps: catalyzing the polymerization of a butene-1 monomer body to polymerize by using a loaded ziegler-giulio natta spherical catalyst system, wherein hydrogen is a molecular weight adjustor; adding an electron donor compound; implementing temperature-gradient polymerization in a temperature range from -10 DEG C to 50 DEG C, wherein polybutylene-1 suspends in the reaction system in form of spherical particles; and flashing to recover unpolymerized monomers to obtain spherical polybutylene-1. Spherical polybutylene-1 with high isotacticity can be obtained by adjusting the partial pressures of the electron donor and hydrogen, wherein the isotacticity is greater than 95%, the isotacticity is greater than 0.30g/cm<3> and the isotacticity is 0.1-30g/10min. The catalyst used in the method consists of a carrier, an active component, the electron donor and a promoter.
Description
Technical field
The present invention relates to a kind of high degree of isotacticity polybutene-1 polymkeric substance and preparation method thereof and the used catalyzer of this method, specifically, what the present invention relates to is a kind of degree of isotacticity greater than 95%, the polybutene-1 of form spherical in shape and preparation method thereof, relates to the special-purpose catalyst system of the spherical polybutene-1 of synthetic high degree of isotacticity simultaneously.
Background technology
High isotactic polybutene-1 has outstanding heat-resisting creep property and stress crack resistance performance, has very high heat-drawn wire, and its use temperature is-20
oC to 105
oC, can be under 100 degree life-time service, be excellent hot water pipe material.
The preparation method of high isotactic polybutene-1 comprises solution polymerization, slurry polymerization, vapour phase polymerization.United States Patent (USP) 3944529,5237013,6306996 all adopts solution polymerization, wherein United States Patent (USP) 5237013 adopts normal hexane to carry out the butene-1 solution polymerization as solvent, because the polybutene-1 polymer dissolution is in solvent, be faced with coagulating separating and reclaiming etc. of wadding, solvent and monomer of polymkeric substance after reaction finishes, complex process, efficient is low, cost is high.It is solvent that Shell company adopts excessive butene-1, because temperature of reaction is higher than 45
OC, polymer dissolution forms the solution of polybutene-1 in monomer.
United States Patent (USP) 5037908,3944529 reported that employing inert solvent Trimethylmethane carries out slurry polymerization as thinner, obtained isotaxy content greater than 94% polybutene-1.Because the boiling point of butene-1 and iso-butylene is very near (having only 0.6
oC), reaction finishes the back inert diluent and has difficulty separating of unreacted monomer.
United States Patent (USP) 4503203,5241024,3168484,3580898,3922322 have introduced the vapour phase polymerization of butene-1 monomer.In gas phase, generally there is rare gas element to have effectively avoid condensing of polymkeric substance also can in time take away polymerization reaction heat.
Bulk solution or slurry process, owing to there is not the existence of inert solvent, polymerization technique is simple, the production efficiency height.Chinese invention patent (ZL200710013587.x) has been reported the method for the synthetic isotactic polybutylene-1-1 of bulk precipitation polymerization, with butene-1 as monomer and reaction medium, at temperature of reaction 0-70
oUnder the condition of C, adopt supported titanium catalyst catalyzing butene-1, the polybutene-1 polymkeric substance of composite powder powder.This patent is owing to be the catalyzer that adopts constant temperature polymerization and grinding, and the particle form of the polybutene-1 polymkeric substance that obtains is very irregular, and very easily adhesion.Polymerization temperature is higher than 30
oDuring C, polybutene-1 is swelling in monomer whose, thereby system is clamminess, and causes the difficulty of mass transfer, heat transfer, and this has just limited in the polymerization process and can only stop when low-conversion, and production efficiency reduces, and the complicacy of production technique and production cost increase simultaneously.
Summary of the invention
One of purpose of the present invention provides a kind of polybutene-1, and the degree of isotacticity of described polybutene-1 is greater than 95% and have spheroidal particle form, tap density greater than 0.30g/cm
3, melting index is at 0.1-30 g/10min.
Preferably, the degree of isotacticity of described polybutene-1 greater than 96%, tap density is greater than 0.35g/cm
3And described polybutene has good flowing property.
Preferably, described polybutene-1 is by the following method or uses following Preparation of Catalyst.
Two of purpose of the present invention provides a kind of preparation method of polybutene-1, and this method comprises following method one or method two:
Method one
Add butene-1 monomer, aluminum alkyls, external electron donor compound, loading type Z-N spherical catalyst successively in tank reactor, hydrogen is as molecular weight regulator ,-10～50
oImplement the temperature-gradient method polymerization in the temperature range of C: namely-10～25
oC implements first section polymerization in preferred 0-20 ℃ the scope, polymerization time is 5～300 minutes, is warmed up to 30～50 then
oC implements second section polymerization, isothermal reaction 0.5～30 hour, and the flash distillation unreacted monomer directly obtains degree of isotacticity greater than 95% spherical polybutene-1;
Method two
Add butene-1 monomer, aluminum alkyls, external electron donor compound, loading type Z-N spherical catalyst successively in tank reactor, hydrogen is as molecular weight regulator ,-10～50
oImplement the temperature-gradient method polymerization in the temperature range of C: namely-10～25
oC, preferred 0-20
OCImplement first section polymerization in the scope, polymerization time is 5～300 minutes, is warmed up to 30～40 then
oC implements second section polymerization, and isothermal reaction 0.5～30 hour is warmed up to 41～50 then
oC implements three stage polymerization, isothermal reaction 0.5～5 hour, and the flash distillation unreacted monomer directly obtains degree of isotacticity greater than 95% spherical polybutene-1;
In described loading type Z-N spherical catalyst, carrier is spherical MgCl
2Or SiO
2, Primary Catalysts is TiCl
4Wherein the mass content of metal titanium in loading type Z-N spherical catalyst is 0.5-5%, internal electron donor is for being selected from Tetra hydro Phthalic anhydride, dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, dimixo-octyl phthalate, phthalic acid two (2-methoxyl group) ethyl ester, 2,3-di-isopropyl ethyl succinate, phenylformic acid (2-methoxyl group) ethyl ester, in 4-methylphthalic acid dibutylester and the 4-methylphthalic acid diisobutyl ester one or both, wherein, the mass content of described internal electron donor in loading type Z-N spherical catalyst is 0.15-20%;
Preferably, in described method, the metal titanium in the loading type Z-N spherical catalyst and the mol ratio of butene monomers are 1～100 * 10
-7: 1.
Preferably, in described method, described external electron donor is selected from the phenylbenzene dimethylsilane, vinyltriethoxysilane, vinyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, second, isobutyl dimethoxy silane, diisopropyl dimethoxy silane, dicyclopentyl dimethoxyl silane, cyclohexyl methyl dimethoxy silane, cyclohexyl trimethoxy silane, di-t-butyl dimethoxy silane, uncle's hexyl Trimethoxy silane, tert-butyl trimethoxy silane, in uncle's hexyl Trimethoxy silane and the Terpane one or both, external electron donor is preferably 0.01-250:1 with Primary Catalysts metal molar ratio.
In described method, hydrogen is as molecular weight regulator, and the control hydrogen partial pressure is 0.005-2.0MPa, and preferred hydrogen partial pressure is 0.01-1MPa.
Preferably, described aluminum alkyls is selected from one or both in triethyl aluminum, triisobutyl aluminium, diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium and the sesquialter ethylaluminium chloride, and the mol ratio of the metal titanium in the aluminium in the aluminum alkyls and the loading type Z-N spherical catalyst is preferably 10-200:1.
In described method, the degree of isotacticity of described polybutene-1 is greater than 96%, and tap density is greater than 0.30g/cm
3, be preferably greater than 0.35g/cm
3, melting index is 0.1-30 g/10min.
Three of purpose of the present invention provides a kind of catalyzer for the synthesis of described polybutene-1, and described catalyzer is loading type Z-N spherical catalyst, and wherein, carrier is spherical MgCl
2Or SiO
2, Primary Catalysts is TiCl
4Wherein the mass content of metal titanium in loading type Z-N spherical catalyst is 0.5-5%, promotor is aluminum alkyls, internal electron donor is for being selected from Tetra hydro Phthalic anhydride, dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, dimixo-octyl phthalate, phthalic acid two (2-methoxyl group) ethyl ester, 2,3-di-isopropyl ethyl succinate, phenylformic acid (2-methoxyl group) ethyl ester, 4-methylphthalic acid dibutylester, in the 4-methylphthalic acid diisobutyl ester one or both, wherein, the mass content of described internal electron donor in loading type Z-N spherical catalyst is 0.15-20%;
Preferably, described aluminum alkyls as mentioned above.
The catalytic efficiency of described catalyzer is 100-500kg polymkeric substance/gTi, and life of catalyst was greater than 30 hours.
Four of purpose of the present invention provides the application that a kind of described polybutene-1 is used for the hot water pipe material.
The polymerization process of the polybutene-1 for the synthesis of high degree of isotacticity and spherical morphology provided by the invention is simply effective, has solved the prepared polymkeric substance of current general catalyzer and has been difficult to regulate and control simultaneously the degree of isotacticity of polybutene and the problem of form.By the adjusting of external electron donor in stage feeding polymerization method and the catalyzer, the degree of isotacticity of polymkeric substance can be controlled greater than 95%, even greater than 96%, obtain good spherical morphology polybutene simultaneously.
Description of drawings
Fig. 1 is the Stereo microscope photo of the high isotactic polybutene of the embodiment of the present application 1.
Fig. 2 is the Stereo microscope photo of the high isotactic polybutene of the embodiment of the present application 3.
Fig. 3 is the Stereo microscope photo of the high isotactic polybutene of the embodiment of the present application 4.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Unless stated otherwise, the method and apparatus of the present invention's employing is ordinary method and the equipment of this area.
The test condition of relevant polymkeric substance is as follows:
Degree of isotacticity: the ether extracting is the shared weight percentage of insolubles after 48 hours;
Tap density: polybutene freely falls at the flare opening certain altitude and is full of graduated cylinder, measures the quality of the interior unit volume material of graduated cylinder under the loose condition (of surface), and tap density is to restrain every cubic centimetre of expression (g/cm
3).
Melting index: press GB/T3682-2000 and measure, load 2.16kg, 190 ℃ of probe temperatures.
Embodiment 1
1L stainless steel polymermaking autoclave (two ribbon stirring rake) pump drainage and with after the high pure nitrogen displacement for several times, in reactor, add 280 g butene-1 (Bt) monomers successively, (wherein, carrier is MgCl to the heterogeneous Ziegler-Natta catalyst of 9mmol triethyl aluminum, 0.1mmol vinyltriethoxysilane and 0.0383g
2, titanium compound is TiCl
4The mass content of titanium in catalyzer is 2.5%, internal electron donor is Tetra hydro Phthalic anhydride (mass content in catalyzer is 0.3%)), hydrogen partial pressure 0.03MPa, 0 ℃ of polymerase 10 .5h, 35 ℃ of constant temperature polyase 13 .5h then, polymerization finishes the unreacted monomer of back flash distillation, the polybutene 120g(that directly obtains spherical morphology sees Fig. 1), catalytic efficiency is 125.3Kg polymkeric substance/gTi, tap density 0.31 g/cm3, melting index 0.5 g/10min.Obtaining insolubles content by the diethyl ether extracting is 96%, and namely isotactic polybutene-1 content is 96%.
Embodiment 2
1L stainless steel polymermaking autoclave (two ribbon stirring rake) pump drainage and with after the high pure nitrogen displacement for several times, in reactor, add 280 g butene-1 (Bt) monomers successively, (wherein, carrier is MgCl to the heterogeneous Ziegler-Natta catalyst of 8mmol triethyl aluminum, 0.5mmol vinyltrimethoxy silane and 0.0292g
2, titanium compound is selected from TiCl4; Titanium is 2.5% with respect to the mass content of catalyzer, internal electron donor is Tetra hydro Phthalic anhydride (mass content in catalyzer is 1%)), hydrogen partial pressure 0.03MPa, 5 ℃ of polymerase 10 .5h, 40 ℃ of constant temperature polyase 13 .5h then, polymerization finishes the unreacted monomer of back flash distillation, directly obtain the polybutene 110g of spherical morphology, catalytic efficiency is 150Kg polymkeric substance/gTi, tap density 0.35 g/cm3, melting index 0.8 g/10min.Obtaining insolubles content by the diethyl ether extracting is 99.2%, and namely isotactic polybutene-1 content is 99.2%.
Embodiment 3
1L stainless steel polymermaking autoclave (two ribbon stirring rake) pump drainage and with after the high pure nitrogen displacement for several times, in reactor, add 280 g butene-1 (Bt) monomers successively, 7.8 the heterogeneous Ziegler-Natta catalyst of mmol triethyl aluminum, 0.1mmol second, isobutyl dimethoxy silane and 0.0296g (wherein, carrier is MgCl2, and titanium compound is selected from TiCl
4Titanium is 2.5% with respect to the mass content of catalyzer, internal electron donor is diisobutyl phthalate, (mass content in catalyzer is 2%)), hydrogen partial pressure 0.03MPa, 10 ℃ of polymerization 10min, 30 ℃ of constant temperature polyase 13 .5h then, polymerization finishes the unreacted monomer of back flash distillation, and the polybutene 100g(that directly obtains spherical morphology sees Fig. 2), catalytic efficiency is 135Kg polymkeric substance/gTi, tap density 0.29g/cm3, melting index 0.75 g/10min.Obtaining insolubles content by the diethyl ether extracting is 98%, and namely isotactic polybutene-1 content is 98%.
Embodiment 4
1L stainless steel polymermaking autoclave (two ribbon stirring rake) pump drainage and with after the high pure nitrogen displacement for several times, in reactor, add 200 g butene-1 (Bt) monomers successively, 6.7mmol (wherein, carrier is MgCl to the heterogeneous Ziegler-Natta catalyst of triethyl aluminum, 0.15mmol Terpane and 0.0286g
2, titanium compound is TiCl
4Titanium is 2.5% with respect to the mass content of catalyzer, internal electron donor is Tetra hydro Phthalic anhydride (mass content in catalyzer is 0.5%)), hydrogen partial pressure 0.5MPa, 20 ℃ of polymerization 1h, 45 ℃ of constant temperature polyase 13 .5h then, polymerization finishes the unreacted monomer of back flash distillation, the polybutene 150g(that directly obtains spherical morphology sees Fig. 3), catalytic efficiency is 210Kg polymkeric substance/gTi, tap density 0.37 g/cm
3, melting index 20 g/10min.Obtaining insolubles content by the diethyl ether extracting is 98%, and namely isotactic polybutene-1 content is 98%.
Embodiment 5
1L stainless steel polymermaking autoclave (two ribbon stirring rake) pump drainage and with after the high pure nitrogen displacement for several times, (wherein, carrier is MgCl to add the heterogeneous Ziegler-Natta catalyst of 250 g butene-1 (Bt) monomers, 5.5mmol triethyl aluminum, 0.15mmol cyclohexyl trimethoxy silane and 0.02g in the reactor successively
2, titanium compound is selected from TiCl
4Titanium is 2.5% with respect to the mass content of catalyzer, internal electron donor is dicyclohexyl phthalate, (mass content in catalyzer is 2%)), hydrogen partial pressure 0.03MPa, 10 ℃ of polymerization 1h, 30 ℃ of constant temperature polymerization 20h then, be warming up to 45 ℃ of constant temperature polyase 13 .5h, polymerization finishes the unreacted monomer of back flash distillation, directly obtains the polybutene 220g of spherical morphology, catalytic efficiency is 440Kg polymkeric substance/gTi, tap density 0.35 g/cm
3, melting index 0.5 g/10min.Obtaining insolubles content by the diethyl ether extracting is 99%, and namely isotactic polybutene-1 content is 99%.
Claims (10)
1. polybutene-1, the degree of isotacticity of described polybutene-1 is greater than 95% and have spheroidal particle form, tap density greater than 0.30g/cm
3, melting index is at 0.1-30 g/10min.
2. polybutene-1 as claimed in claim 1, wherein, the degree of isotacticity of described polybutene-1 greater than 96%, tap density is greater than 0.35g/cm
3
3. the preparation method of a polybutene-1, this method comprises following method one or method two:
Method one
Add butene-1 monomer, aluminum alkyls, external electron donor compound, loading type Z-N spherical catalyst successively in tank reactor, hydrogen is as molecular weight regulator ,-10～50
oImplement the temperature-gradient method polymerization in the temperature range of C: namely-10～25
oC implements first section polymerization in preferred 0-20 ℃ the scope, polymerization time is 5～300 minutes, is warmed up to 30～50 then
oC implements second section polymerization, isothermal reaction 0.5～30 hour, and the flash distillation unreacted monomer directly obtains degree of isotacticity greater than 95% spherical polybutene-1;
Method two
Add butene-1 monomer, aluminum alkyls, external electron donor compound, loading type Z-N spherical catalyst successively in tank reactor, hydrogen is as molecular weight regulator ,-10～50
oImplement the temperature-gradient method polymerization in the temperature range of C: namely-10～25
oC, preferred 0-20
OCImplement first section polymerization in the scope, polymerization time is 5～300 minutes, is warmed up to 30～40 then
oC implements second section polymerization, and isothermal reaction 0.5～30 hour is warmed up to 41～50 then
oC implements three stage polymerization, isothermal reaction 0.5～5 hour, and the flash distillation unreacted monomer directly obtains degree of isotacticity greater than 95% spherical polybutene-1;
In described loading type Z-N spherical catalyst, carrier is spherical MgCl
2Or SiO
2, Primary Catalysts is TiCl
4Wherein the mass content of metal titanium in loading type Z-N spherical catalyst is 0.5-5%, internal electron donor is for being selected from Tetra hydro Phthalic anhydride, dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, dimixo-octyl phthalate, phthalic acid two (2-methoxyl group) ethyl ester, 2,3-di-isopropyl ethyl succinate, phenylformic acid (2-methoxyl group) ethyl ester, in 4-methylphthalic acid dibutylester and the 4-methylphthalic acid diisobutyl ester one or both, wherein, the mass content of described internal electron donor in loading type Z-N spherical catalyst is 0.15-20%.
4. method as claimed in claim 3, wherein, the metal titanium in the described loading type Z-N spherical catalyst and the mol ratio of butene monomers are 1～100 * 10
-7: 1.
5. method as claimed in claim 3, wherein, described external electron donor is selected from the phenylbenzene dimethylsilane, vinyltriethoxysilane, vinyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, second, isobutyl dimethoxy silane, diisopropyl dimethoxy silane, dicyclopentyl dimethoxyl silane, cyclohexyl methyl dimethoxy silane, cyclohexyl trimethoxy silane, di-t-butyl dimethoxy silane, uncle's hexyl Trimethoxy silane, tert-butyl trimethoxy silane, in uncle's hexyl Trimethoxy silane and the Terpane one or both, external electron donor is preferably 0.01-250:1 with Primary Catalysts metal molar ratio.
6. as the described method of one of claim 3 to 5, wherein, in described method, hydrogen is as molecular weight regulator, and the control hydrogen partial pressure is 0.005-2.0MPa, and preferred hydrogen partial pressure is 0.01-1MPa.
7. as the described method of one of claim 3 to 5, wherein, described aluminum alkyls is selected from one or both in triethyl aluminum, triisobutyl aluminium, diethyl monochlor(in)ate aluminium, diisobutyl monochlor(in)ate aluminium and the sesquialter ethylaluminium chloride, and the mol ratio of the metal titanium in the aluminium in the aluminum alkyls and the loading type Z-N spherical catalyst is preferably 10-200:1.
8. as the described method of one of claim 3 to 5, wherein, in described method, the degree of isotacticity of described polybutene-1 is greater than 96%, and tap density is greater than 0.30g/cm
3, be preferably greater than 0.35g/cm
3, melting index is 0.1-30 g/10min.
9. catalyzer for the synthesis of claim 1 or 2 described polybutene-1s, described catalyzer is loading type Z-N spherical catalyst, wherein, carrier is spherical MgCl
2Or SiO
2, Primary Catalysts is TiCl
4Wherein the mass content of metal titanium in loading type Z-N spherical catalyst is 0.5-5%, promotor is alkylaluminium cpd, internal electron donor is for being selected from Tetra hydro Phthalic anhydride, dibutyl phthalate, diisobutyl phthalate, dicyclohexyl phthalate, dimixo-octyl phthalate, phthalic acid two (2-methoxyl group) ethyl ester, 2,3-di-isopropyl ethyl succinate, phenylformic acid (2-methoxyl group) ethyl ester, 4-methylphthalic acid dibutylester, in the 4-methylphthalic acid diisobutyl ester one or both, wherein, the mass content of described internal electron donor in loading type Z-N spherical catalyst is 0.15-20%.
10. a claim 1 or 2 described polybutene-1s are used for the application of hot water pipe material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610475A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization reaction |
| CN105482009A (en) * | 2016-01-12 | 2016-04-13 | 山东东方宏业化工有限公司 | Technology and device for producing polybutylene-1 through continuous method |
| CN106432559A (en) * | 2015-08-04 | 2017-02-22 | 山东省滕州瑞达化工有限公司 | Liquid phase synthesis method of high isotactic polybutene-1 |
| CN106893020A (en) * | 2015-12-17 | 2017-06-27 | 中国石油天然气股份有限公司 | A kind of preparation method of spherical PB Polybutene-1 |
| CN110894249A (en) * | 2018-09-12 | 2020-03-20 | 中国石油化工股份有限公司 | Homogeneous polymerization method and device for butene-1 |
| CN111234075A (en) * | 2020-03-26 | 2020-06-05 | 青岛科技大学 | Catalyst for synthesizing alloy in polybutylene kettle, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032172A (en) * | 1987-07-15 | 1989-04-05 | 奈斯特公司 | High-crystallinity poly-1-butylene and preparation method thereof and the used catalyzer of this method |
| CN1110281A (en) * | 1994-04-08 | 1995-10-18 | 中国科学院化学研究所 | Olefinic polymeric carrier catalyst system and preparation method thereof |
| US6998458B2 (en) * | 2002-05-29 | 2006-02-14 | Basell Poliolefine Italis S.P.A. | Butene-1 (co)polymers and process for their preparation |
| CN101914172A (en) * | 2010-08-25 | 2010-12-15 | 河北工业大学 | Spherical catalyst for 1-butene polymerization as well as preparation method and application thereof |
-
2013
- 2013-07-01 CN CN201310268438.3A patent/CN103288993B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032172A (en) * | 1987-07-15 | 1989-04-05 | 奈斯特公司 | High-crystallinity poly-1-butylene and preparation method thereof and the used catalyzer of this method |
| CN1110281A (en) * | 1994-04-08 | 1995-10-18 | 中国科学院化学研究所 | Olefinic polymeric carrier catalyst system and preparation method thereof |
| US6998458B2 (en) * | 2002-05-29 | 2006-02-14 | Basell Poliolefine Italis S.P.A. | Butene-1 (co)polymers and process for their preparation |
| CN101914172A (en) * | 2010-08-25 | 2010-12-15 | 河北工业大学 | Spherical catalyst for 1-butene polymerization as well as preparation method and application thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610475A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization reaction |
| CN106432559A (en) * | 2015-08-04 | 2017-02-22 | 山东省滕州瑞达化工有限公司 | Liquid phase synthesis method of high isotactic polybutene-1 |
| CN106432559B (en) * | 2015-08-04 | 2020-11-17 | 山东省滕州瑞达化工有限公司 | High isotactic polybutene-1 liquid phase synthesis process |
| CN106893020A (en) * | 2015-12-17 | 2017-06-27 | 中国石油天然气股份有限公司 | A kind of preparation method of spherical PB Polybutene-1 |
| CN106893020B (en) * | 2015-12-17 | 2019-10-11 | 中国石油天然气股份有限公司 | A kind of preparation method of spherical shape PB Polybutene-1 |
| CN105482009A (en) * | 2016-01-12 | 2016-04-13 | 山东东方宏业化工有限公司 | Technology and device for producing polybutylene-1 through continuous method |
| CN110894249A (en) * | 2018-09-12 | 2020-03-20 | 中国石油化工股份有限公司 | Homogeneous polymerization method and device for butene-1 |
| CN111234075A (en) * | 2020-03-26 | 2020-06-05 | 青岛科技大学 | Catalyst for synthesizing alloy in polybutylene kettle, preparation method and application thereof |
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