CN102268160A - Polybutene alloy material and preparation method thereof - Google Patents
Polybutene alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polybutene alloy material and a preparation method thereof, and belongs to the field of polyolefin material, specifically relates to a polybutene alloy material and a preparation method thereof. The polybutene alloy material provided by the present invention comprises, by mass, 50-99% of poly-1-butene, 1-40% of polypropylene and 0-10% of a butane-propylene copolymer. The preparation method is characterized by: adopting a TiCl4/MgCl2 supported titanium catalyst for synthesis of the polybutene alloy material through a two-phase polymerization method. The polybutene alloy material provided by the present invention has a core-shell structure, and has advantages of the combination of the excellent impact resistance of the poly-1-butene, the heat resistance and creep property of the poly-1-butene, the low shrinkage rate of the poly-1-butene, the high modulus of the polypropylene, the high surface hardness of the polypropylene, the rapid shaping of the polypropylene, and the like, such that the polybutene alloy material can replace the partial use of the poly-1-butene and the polypropylene. In addition, the polybutene alloy material can be applicable for preparation of the pipe and the pipe fitting, toughening modification of the polypropylene, or the polybutene alloy material can be used as the general polyolefin material.
Description
Technical field
The present invention relates to a kind of new type polyolefin material field, particularly a kind of preparation method of polybutene alloy and the polybutene polypropylene alloy material for preparing by this method.
Background technology
Usually, polypropylene has characteristics such as density is little, price is low, processibility is good, and its yield strength, tensile strength, surface hardness and Young's modulus are all more excellent.But under the PP low temperature poor, the molding shrinkage of impact resistance big, easily aging, heat-resisting creep properties is poor, has limited its some range of application greatly.
Entirely with polybutene be a kind of by 1-butylene as monomeric semicrystalline polymer, the full characteristic that has with poly-1-butylene comprises high flexing resistance, outstanding anti-creep shape and the tensile strength under the high temperature.But the poly-1-butylene resin solidification time is long, often needs several days to present stable performance to tens talentes.
In view of above 2 points, prepare novel polybutene alloy material and just have important practical significance, promptly under the prerequisite that does not influence poly-1-butylene resin high-temperature creep resistance and flexibility, shorten shaping cycle as far as possible, improve its intensity and modulus etc.Polybutene and polypropylene physical blending exist two-phase scattering problem and interface problem, thereby influence the performance of polybutene alloy product.In-situ polymerization prepares the polybutene alloy in the still, not only can effectively improve the two-phase scattering problem, the original position of minor amounts of copolymerized thing is synthesized the phase interface problem that can obviously improve alloy, the parameters such as component concentration, molecular weight and distribution thereof that also can regulate alloy by the adjusting of polymerization technique parameter simultaneously.Therefore in-situ polymerization prepares the polybutene alloy and can better embody polybutene and polyacrylic original performance in the still.
In order to reduce the heat-sealing temperature of poly-1-butylene, Chinese patent (publication number: CN1090855A), Japanese Patent (spy opens clear 61-108615 and 60-38414), United States Patent (USP) (US4048419,3944529) has proposed 1-butylene and other alpha-olefin copolymers prepare the polybutene copolymer elastomerics.Japanese Patent (spy opens clear 61-108647 and the clear 61-118449 of Te Kai) and United States Patent (USP) 655397 are made the polybutene composition with propylene copolymer and butene-1 copolymer blend.
Mitsui Chemicals (Chinese patent ZL 01144854.7) has reported that polybutene resin is by forming melt flow rate (MFR) 0.01-10g/10min with the alpha-olefin unit (20mol% is following) of carbon atom 2-10 more than 1-butylene unit 80～100mol%.United States Patent (USP) (US 6998458) has been reported the preparation of a kind of 1-butylene homopolymer or butene-1 copolymer.Chinese patent (ZL 03800736.3, Basel's polyolefins company) has reported and has adopted the synthetic 1-butylene homopolymer of solution polymerization process or contain the butene-1 copolymer of other alpha-olefins of 20wt% at the most that Mw/Mn is less than 6, and melt strength is greater than 2.8g.(grant number ZL 99800235.6 for Chinese patent, Meng Teer technology company) reported and adopt solution polymerization process or the synthetic 1-butylene homopolymer of gaseous polymerization or contain the butene-1 copolymer of other alpha-olefins of 20wt% at the most, Mw/Mn is greater than 6, and polymkeric substance is fit to preparation tubing very much.
Above-mentioned polybutene or polybutene composition reduce the fusing point of polybutene by copolymerization, but also reduce the performances such as modulus, intensity and heat-drawn wire of material.
Carry out the polymer architecture regulation and control from the angle of polymer chain regularity, Chinese patent (publication number CN1989199A, Basel's polyolefins company) reported that the employing metallocene catalyst synthesizes the 1-butylene polymer composition, said composition comprises isotaxy 1-butylene based polyalcohol and atactic 1-butylene based polyalcohol, wherein, isotaxy 1-butylene based polyalcohol molecular weight distribution mw/mn is equal to or less than 4.Chinese patent (CN101044172A, Basel's polyolefins company) reported that the employing metallocene catalyst synthesizes a kind of butene-1 copolymer, randomly contain 0～30mol% ethene, propylene or other alpha-olefin derived monomeric units, this butene-1 copolymer molecular weight distribution mw/mn is less than 4, according to (190 ℃ of ISO1133,2.16kg) melt flow rate (MFR) 200～1000 measured, be lower than 0.8dl/g with naphthane in the limiting viscosity of 135 ℃ of mensuration.Metallocene catalyst synthetic polybutene composition molecular weight distribution is narrower, and molecular weight is not high, and synthetic polybutene taxis is not high.
Poly-1-butylene resin combination of Mitsui Chemicals (Chinese patent ZL 01142929.1) report and preparation method thereof.Poly-1-butylene composition comprises the butylene-alpha olefin copolymer of 90-99.95 weight % and the acrylic resin of 0.05-10 weight %, prepares by the screw extrusion press blend.
Chinese patent (publication number CN 1032172A, Neste OY) has reported that the liquid hydrocarbon that contains 5-12 carbon atom carries out pre-polymerization earlier, with this pre-polymerized catalyst composition, polymerization in the 1-butylene gas phase, obtains the poly-1-butylene of high-crystallinity.The poly-1-butylene of this high-crystallinity is made up of 1-butylene and the multipolymer that other unsaturated monomer unit that are lower than 10% are formed.
Qingdao University of Science and Technology (Chinese patent ZL 200710013587.X) has reported the new polymerization technique of the synthetic polybutene (chevron) of employing bulk precipitation polymerization method.
The present invention relates to polybutene alloy material and preparation method thereof, this material is complete in poly-1-butylene by a) 50～99 (weight) %'s, b) 1～40 (weight) % isotatic polypropylene, c) 0～10 (weight) %1-butylene-propylene copolymer composition.A) entirely with content 85～99%, b) entirely with content 85～99%, c) be random copolymers.The present invention reduces the content of random copolymers as far as possible to guarantee the modulus of polybutene alloy, adopt the synthetic polybutene alloy of two-stage method, polybutene alloy of the present invention is powdery or the spherical product with nucleocapsid structure, have excellent impact resistance energy, heat-resisting creep property, low-shrinkage and the polyacrylic high-modulus of poly-1-butylene concurrently, advantage such as high surface hardness, fast shaping, can instead of part polyethylene and polypropylene purposes: be used to make tubing and pipe fitting, polyacrylic toughening modifying, or use as the general purpose polyolefin material.
Summary of the invention
One of purpose of the present invention is the performance deficiency that exists at present single polyolefine example, long set time as polybutene, withstand voltage properties is not ideal enough etc., and poor mechanical property under the polypropylene low temperature, molding shrinkage are big, easily aging, heat-resisting creep properties is poor, has limited its scope of application greatly.Preparation polybutene alloy can make up polybutene and polyacrylic advantage.
Two of purpose of the present invention provides the synthetic method of polybutene alloy.Providing a kind of adopts single heterogeneous Ziegler-Natta catalyst to prepare the method for polybutene alloy carrying out polymerization stage by stage.
Three of purpose of the present invention provides a kind of novel polybutene alloy.
The present invention is by adopting heterogeneous Ziegler-Natta catalyst, catalysis 1-butylene and propylene carry out polymerization stage by stage, thereby original position has been synthesized the polybutene alloy, and because heterogeneous Ziegler-Natta has many active centre and good hydrogen-sensitivity, prepared polybutene alloy has wider molecular weight distribution, simultaneously can also be by add the molecular weight that hydrogen comes telomerized polymer in propylene or 1-butylene polymerization.By the bulk precipitation polymerization technology or the slurry polymerization processes of propylene section and butylene section, synthesized pulverous polybutene polypropylene alloy material.
The structure and the performance of the polybutene alloy that the present invention can regulate in a big way by the enforcement of polymerization technique.By controlling two elementary reaction times, monomeric initial charge etc., in a big way, regulate each components contents in the polybutene alloy, thus the adjustable polybutene alloy of the structure of obtaining and performance.
A kind of polybutene alloy material and preparation method thereof is characterized in that: poly-1-butylene mass content is 50%-99% in the described polybutene alloy, polypropylene mass content 1%-40%, and 1-butylene-propylene copolymer mass content is 0-10%.
Described poly-1-butylene is complete in poly-1-butylene,, entirely with content 85～99%, 115～129 ℃ of fusing points; Described polypropylene is an isotatic polypropylene, entirely with content 85～99%, and 155～169 ℃ of fusing points.Described 1-butylene-propylene copolymer is a random copolymers.
Described polybutene alloy molecular weight distribution mw/mn=3-20,210 ℃ of 2.16Kg melting flow index 0.01-100g/10min.
The preparation method of polybutene alloy of the present invention carries out according to the following steps:
One of preparation method of described polybutene alloy, can synthesize according to the following steps:
(1) add aluminum alkyls or aikyl aluminum halide, external electron donor, heterogeneous Ziegler-Natta catalyst and propylene, hydrogen successively in reactor, the mass polymerization of carrying out propylene obtains alfon; Or
In reactor, add the alkane of 5～10 carbon atoms and/or aromatic hydrocarbon organic solvent, aluminum alkyls or aikyl aluminum halide, external electron donor, heterogeneous Ziegler-Natta catalyst and propylene, the hydrogen of 5～10 carbon atoms successively, the slurry polymerization that carries out propylene obtains alfon, and wherein the mass ratio of propylene and organic solvent is 1～1000: 100;
Polymeric reaction temperature when carrying out above-mentioned mass polymerization or slurry polymerization is 0 ℃～80 ℃, and hydrogen and propylene volume ratio are 0～30: 100, and the mol ratio of Ti element and propylene is 1～1000 * 10 in the heterogeneous Ziegler-Natta catalyst
-7The mol ratio of Ti element is 40～200: 1 in Al element in aluminum alkyls or the aikyl aluminum halide and the heterogeneous Ziegler-Natta catalyst, the Al element in aluminum alkyls or the aikyl aluminum halide and the mol ratio of external electron donor are 0.1～50, and the homopolymerization time is 0.1～6 hour;
(2) after the homopolymerization time of the reaction system of step (1) reaches any time point in 0.1～6 hour, residue propylene monomer and solvent are removed in decompression, in reactor, add 1-butylene monomer and hydrogen, carry out the 1-butylene slurry polymerization as solvent with the 1-butylene monomer.
Or
After the homopolymerization time of step (1) reaction system reached any time point in 0.1～6 hour, the residue propylene monomer was removed in decompression, added 1-butylene monomer and hydrogen in reactor, carried out the 1-butylene slurry polymerization.
When carrying out above-mentioned polymerization, hydrogen and 1-butylene volume ratio are 0～30: 100, the monomer mass ratio of the propylene of 1-butylene and step (1) is 1～200: 1, and make the heterogeneous Ziegler-Natta catalyst in the step (1) continue to cause the 1-butylene polymerization, polymerization temperature is 0 ℃～70 ℃, and polymerization time is 1～24 hour; Remove butene monomers etc., obtain the polybutene alloy.Two sections polymerizations can be to carry out in a reactor, also can carry out in two or more reactors.
The preparation method's of described polybutene alloy two, can synthesize according to the following steps:
(1) add aluminum alkyls or aikyl aluminum halide, external electron donor, heterogeneous Ziegler-Natta catalyst and 1-butylene, hydrogen successively in reactor, the mass polymerization of carrying out 1-butylene obtains the 1-butylene homopolymer;
Or
In reactor, add the alkane of 5～10 carbon atoms and/or aromatic hydrocarbon organic solvent, aluminum alkyls or aikyl aluminum halide, external electron donor, heterogeneous Ziegler-Natta catalyst and 1-butylene, the hydrogen of 5～10 carbon atoms successively, the slurry polymerization that carries out butylene obtains chevron, and wherein the mass ratio of butylene and organic solvent is 1～1000: 100;
When carrying out above-mentioned polymerization, polymeric reaction temperature is 0 ℃～70 ℃, and hydrogen and 1-butylene volume ratio are 0～30: 100, and the mol ratio of Ti element and 1-butylene is 1～1000 * 10 in the heterogeneous Ziegler-Natta catalyst
-7The mol ratio of Ti element is 40～200: 1 in Al element in aluminum alkyls or the aikyl aluminum halide and the heterogeneous Ziegler-Natta catalyst, the Al element in aluminum alkyls or the aikyl aluminum halide and the mol ratio of external electron donor are 0.1～50, and the homopolymerization time is 1～24 hour;
(2) after the homopolymerization time of the reaction system of step (1) reached any time point in 1～24 hour, residue butene monomers and solvent were removed in decompression, add propylene monomer and hydrogen, catalyzing propone bulk precipitation polymerization in reactor;
Or
After the homopolymerization time of the reaction system of step (1) reached any time point in 1～24 hour, the residue butene monomers was removed in decompression, adds propylene monomer and hydrogen in reactor, and catalyzing propone carries out slurry polymerization;
When carrying out above-mentioned polymerization, hydrogen and propylene volume ratio are 0～30: 100, the monomer mass ratio of the 1-butylene of propylene and step (1) is 1: 1～200, and make the heterogeneous Ziegler-Natta catalyst in the step (1) continue to cause propylene polymerization, polymerization temperature is 0 ℃～80 ℃, and polymerization time is 0.1～6 hour; Remove propylene monomer etc., obtain the polybutene alloy.Two sections polymerizations can be to carry out in a reactor, also can carry out in two or more reactors.
When adopting propylene as first section reaction monomers, this section can be bulk precipitation polymerization or slurry polymerization, temperature of reaction is 0-80 ℃, optimal conditions is under 50-70 ℃, directly obtains polypropylene GRANULES, and second section polymerization reaction monomer is 1-butylene, this section is a slurry polymerization, temperature of reaction is 0-70 ℃, and optimal conditions is 5-30 ℃, realizes the coating growth of polybutene on polypropylene GRANULES.
When adopting 1-butylene as first section reaction monomers and reaction medium, this section can be mass polymerization or slurry polymerization, and temperature of reaction is 0-70 ℃, and optimal conditions is under 5-30 ℃, and 1-butylene polymkeric substance nucleation is precipitated out, and dissolving or swelling do not take place.Second section polymerization reaction monomer is propylene, and this section can be bulk precipitation polymerization or slurry polymerization, and polymeric reaction temperature is 0-80 ℃, and optimal conditions is 50-70 ℃, realizes the coating growth of second section polypropylene on the polybutene particle.
Described aluminum alkyls is triethyl aluminum or triisobutyl aluminium; Described aikyl aluminum halide is a kind of in dimethyl monochlor(in)ate aluminium, monomethyl al dichloride, diethyl monochlor(in)ate aluminium, an ethylaluminum dichloride, diisobutyl monochlor(in)ate aluminium or the isobutyl-al dichloride.
Described heterogeneous Ziegler-Natta catalyst is to be the catalyzer that contains titanium compound and internal electron donor of carrier with magnesium halogenide, wherein, the Ti element account for Ziegler-Natta catalyst total mass 1%～5%, internal electron donor account for Ziegler-Natta catalyst total mass 0.5%～20%.
Described magnesium halogenide is selected from MgCl
2, MgBr
2Or MgI
2In a kind of;
Described titanium compound is selected from TiCl
4, TiBr
4Or TiI
4In a kind of;
Described internal electron donor is ester class, ethers, ketone, anhydrides compound, a kind of in preferred phenylformic acid, anisic acid, paraethoxybenxoic acid, toluylic acid, o-benzene butyl phthalate ester, phthalic acid dibutyl ester, benzoquinones, methyl benzoate, the ethyl benzoate etc.
Described external electron donor is selected from silicon compound, preferred silicon compound is a cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane, uncle's hexyl Trimethoxy silane, diisopropyl dimethoxy silane, methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, 1,1,1-trifluoro propyl-2-ethyl piperidine base-dimethoxy silane, ethyl trimethoxy silane, propyl trimethoxy silicane, phenyltrimethoxysila,e, a kind of in the dicyclohexyl dimethoxy silane etc.;
Described polybutene alloy is powdery or the spherical product with nucleocapsid structure, have the advantages such as excellent impact resistance energy, heat-resisting creep property, low-shrinkage and polyacrylic high-modulus, high rigidity, fast shaping of poly-1-butylene concurrently, can the instead of part polyethylene and the polypropylene purposes be used to make tubing and pipe fitting, polyacrylic toughening modifying, or use as the general purpose polyolefin material.
The present invention adopts heterogeneous Ziegler-Natta catalyst to prepare the polybutene alloy to have following characteristics:
1. the present invention relates to the synthetic polybutene alloy branch of two kinds of methods: first method is first polypropylene, feeds butene reaction again, and obtaining polypropylene is the polybutene alloy of shell for the poly-1-butylene of nuclear; Second method is first polymerization 1-butylene, feeds the propylene reaction again, and obtaining poly-1-butylene is the polybutene alloy of shell for the nuclear polypropylene.
2. the present invention realizes the preparation of polyolefin alloys by two sections polymerizations: carry out first section polybutene or polyacrylic polyreaction, not under the prerequisite of completely dissolve, feed the monomer propylene or the 1-butylene of second-stage reaction at catalyst activity.But the temperature of reaction of two-stage reaction and time conditions free adjustment, and then obtain the controlled novel polybutene alloy material of relative content easily, product is Powdered or spherical product, particle diameter is 10 microns～1 centimetre.
3. polymerization equipment of the present invention is a voltage-resistant reactor, furtherly, can adopt for example conversion unit of bulk polypropylene, to satisfy two sections common needs of polymeric, directly carries out the production of polybutene alloy.
4. the method for polybutene alloy of the present invention helps suitability for industrialized production, and during the polymerization of propylene section, degree of isotacticity can reach more than 85%, 155～169 ℃ of fusing points; During the polymerization of butylene section, degree of isotacticity can reach more than 85%, 115～129 ℃ of fusing points.
Embodiment:
Embodiment 1
1L fully-closed magnetic agitation stainless steel pressure polymeric kettle, pump drainage and with after the high pure nitrogen displacement for several times, in reactor, be metered into triethyl aluminum (Al), external electron donor dimethoxydiphenylsilane (Si) and supported titanium catalyst (Ti) 0.25g successively, add propylene 0.05Kg, Al/Ti=50 (mol ratio) wherein, Al/Si=10 (mol ratio).60 ℃ are stirred polymerization 20min, and cooling and emptying propylene add 1-butylene 0.2Kg in reactor subsequently, and 30 ℃ of reaction 6h stop directly obtaining polymer powder polybutene alloy 141g after the drying.
The polybutene alloy characteristic sees Table 1.
Embodiment 2
1L fully-closed magnetic agitation stainless steel pressure polymeric kettle, pump drainage and with after the high pure nitrogen displacement for several times, in reactor, be metered into hexane 100ml, triethyl aluminum (Al), external electron donor cyclohexyl trimethoxy silane and supported titanium catalyst (Ti) 0.25g successively, add propylene 0.05Kg, Al/Ti=80 (mol ratio) wherein, Al/Si=20 (mol ratio).70 ℃ are stirred polymerization 20min, and cooling and emptying propylene add 1-butylene 0.2Kg in reactor subsequently, and 35 ℃ of reaction 8h stop directly obtaining polymer powder polybutene alloy 172g after the drying.
The polybutene alloy characteristic sees Table 1.
Embodiment 3
10L fully-closed magnetic agitation stainless steel pressure polymeric kettle, pump drainage and with after the high pure nitrogen displacement for several times, in reactor, be metered into heptane 150ml, triethyl aluminum (Al), external electron donor dimethoxydiphenylsilane (silicon Si compound) and supported titanium catalyst (Ti) 1.0g successively, add propylene 0.5Kg, Al/Ti=50 (mol ratio) wherein, Al/Si=20 (mol ratio).60 ℃ are stirred polymerase 10 .5hr, and cooling and emptying propylene and solvent heptane add 1-butylene 4.0Kg in reactor subsequently, and 40 ℃ of reaction 6h stop directly obtaining polymer powder polybutene alloy 3.3Kg after the drying.The polybutene alloy characteristic sees Table 1.The polybutene alloy can the instead of part polyethylene and the polypropylene purposes be used to make tubing and pipe fitting or use as the general purpose polyolefin material.
Embodiment 4
2 10L fully-closed magnetic agitation stainless steel pressure polymeric kettles, pump drainage and with after the high pure nitrogen displacement for several times, in No. 1 reactor, be metered into triethyl aluminum (Al), external electron donor dimethoxydiphenylsilane (silicon Si compound) and supported titanium catalyst (Ti) 1.0g successively, add propylene 0.5Kg, Al/Ti=20 (mol ratio) wherein, Al/Si=10 (mol ratio).Add hydrogen 40mL, 60 ℃ are stirred polymerization 20min, subsequently in mass transport to 2 reactor, the emptying propylene adds 1-butylene 4Kg in No. 2 reactors, add hydrogen 0.1L, 40 ℃ of reaction 12h stop directly obtaining polymer powder polybutene alloy 3.5Kg after the drying.
The polybutene alloy characteristic sees Table 1.
Embodiment 5
1L fully-closed magnetic agitation stainless steel pressure polymeric kettle, pump drainage and with after the high pure nitrogen displacement for several times, in reactor, be metered into triethyl aluminum (Al), external electron donor tert-butyl trimethoxy silane and supported titanium catalyst (Ti) 0.25g successively, add 1-butylene 0.3Kg, Al/Ti=50 (mol ratio) wherein, Al/Si=20 (mol ratio).Add hydrogen 10mL, 30 ℃ are stirred polymerization 6hr, and the emptying butylene adds propylene 0.01Kg in reactor, add hydrogen 0.3NL, and 70 ℃ of reaction 40min stop directly obtaining polymer powder polybutene alloy 241g after the drying.The polybutene alloy characteristic sees Table 1.
Embodiment 6
1L fully-closed magnetic agitation stainless steel pressure polymeric kettle, pump drainage and with after the high pure nitrogen displacement for several times, in reactor, be metered into triethyl aluminum (Al), external electron donor uncle hexyl Trimethoxy silane and supported titanium catalyst (Ti) 0.25g successively, add 1-butylene 0.3Kg, Al/Ti=80 (mol ratio) wherein, Al/Si=20 (mol ratio).Add hydrogen 0.01L, 25 ℃ are stirred polymerization 8hr, and the emptying butylene adds propylene 0.02Kg in reactor, add hydrogen 3mL, and 65 ℃ of reaction 1h stop directly obtaining polymer powder polybutene alloy 265g after the drying.The polybutene alloy characteristic sees Table 1.
Embodiment 7
1000L fully-closed magnetic agitation stainless steel pressure polymeric kettle, pump drainage and with after the high pure nitrogen displacement for several times, in reactor, be metered into triethyl aluminum (Al), external electron donor diisopropyl dimethoxy silane (Si compound) and supported titanium catalyst (Ti) 80g successively, add 1-butylene 500Kg, Al/Ti=10 (mol ratio) wherein, Al/Si=10 (mol ratio).Add hydrogen 6L, 25 ℃ are stirred polymerization 12hr, and the emptying butylene adds propylene 300Kg in reactor, add hydrogen 3L, and 70 ℃ of reaction 3h stop directly obtaining polymer powder polybutene alloy 456Kg after the drying.The polybutene alloy characteristic sees Table 1.
Embodiment 8
1000L fully-closed magnetic agitation stainless steel pressure polymeric kettle, pump drainage and with after the high pure nitrogen displacement for several times, in reactor, be metered into triethyl aluminum (Al), external electron donor methylcyclohexyl dimethoxy silane (silicon Si compound) and supported titanium catalyst (Ti) 80g successively, add propylene 300Kg, Al/Ti=10 (mol ratio) wherein, Al/Si=10 (mol ratio).60 ℃ are stirred polymerization 2h, and the emptying propylene adds hydrogen 5L, add 1-butylene 500Kg in reactor, add hydrogen 10L, and 30 ℃ of reaction 8h stop directly obtaining polymer powder polybutene alloy 430Kg after the drying.The polybutene alloy characteristic sees Table 1.
The polybutene alloy physical parameter of table 1 embodiment 1～8
| Embodiment | The polybutene alloy, kg | Polybutene alloy boiling heptane insolubles content, wt% | Polybutene alloy boiling diethyl ether solubles content, wt% | Complete in poly-1-butylene components contents/wt% (entirely with content 99%) | Isotatic polypropylene components contents/wt% (entirely with content 99%) | The molecular weight distribution M of polybutene alloy w/M n | The melt flow index of polybutene alloy (210 ℃, 2.16Kg) g/10min |
| 1 | 0.141 | 6 | 3 | 90 | 6 | 4.6 | 0.01 |
| 2 | 0.172 | 4 | 1 | 95 | 4 | 5.5 | 0.04 |
| 3 | 3.30 | 5.93 | 0.07 | 94 | 5.93 | 6.3 | 0.03 |
| 4 | 3.50 | 3 | 0.6 | 96.4 | 3 | 9.5 | 4.3 |
| 5 | 0.241 | 8 | 4 | 88 | 8 | 7.9 | 1.2 |
| 6 | 0.265 | 15 | 3 | 82 | 15 | 7.8 | 0.87 |
| 7 | 456.0 | 32 | 8 | 60 | 32 | 8.4 | 2.5 |
| 8 | 430.0 | 12.2 | 9.8 | 71 | 12.2 | 12 | 17 |
Claims (10)
1. polybutene alloy material and preparation method thereof is characterized in that: poly-1-butylene mass content is 50%-99% in the described polybutene alloy, polypropylene mass content 1%-40%, and butylene-propylene copolymer mass content is 0-10%.
2. the alloy material of polybutene described in the claim 1 is characterized in that: described poly-1-butylene for complete with poly-1-butylene, entirely with content 85-99%, 115～129 ℃ of fusing points; Described polypropylene is an isotatic polypropylene, entirely with content 85-99%, and 155～169 ℃ of fusing points.Described butylene-propylene copolymer is a random copolymers.
3. the alloy material of polybutene described in the claim 1 is characterized in that: described polybutene alloy molecular weight distribution mw/mn=3-20,210 ℃ of 2.16Kg melting flow index 0.01-100g/10min.
4. one of preparation method of the described polybutene alloy of claim 1 can synthesize according to the following steps, it is characterized in that:
(1) add aluminum alkyls or aikyl aluminum halide, external electron donor, heterogeneous Ziegler-Natta catalyst and propylene, hydrogen successively in reactor, the mass polymerization of carrying out propylene obtains alfon; Or
In reactor, add the alkane of 5～10 carbon atoms and/or aromatic hydrocarbon organic solvent, aluminum alkyls or aikyl aluminum halide, external electron donor, heterogeneous Ziegler-Natta catalyst and propylene, the hydrogen of 5～10 carbon atoms successively, the slurry polymerization that carries out propylene obtains alfon, and wherein the mass ratio of propylene and organic solvent is 1～1000: 100;
Polymeric reaction temperature when carrying out above-mentioned mass polymerization or slurry polymerization is 0 ℃～80 ℃, and hydrogen and propylene volume ratio are 0～30: 100, and the mol ratio of Ti element and propylene is 1～1000 * 10 in the heterogeneous Ziegler-Natta catalyst
-7The mol ratio of Ti element is 40～200: 1 in Al element in aluminum alkyls or the aikyl aluminum halide and the heterogeneous Ziegler-Natta catalyst, the Al element in aluminum alkyls or the aikyl aluminum halide and the mol ratio of external electron donor are 0.1～50, and the homopolymerization time is 0.1～6 hour;
(2) after the homopolymerization time of the reaction system of step (1) reaches any time point in 0.1～6 hour, residue propylene monomer and solvent are removed in decompression, in reactor, add 1-butylene monomer and hydrogen, carry out the 1-butylene slurry polymerization as solvent with the 1-butylene monomer.
Or
After the homopolymerization time of step (1) reaction system reached any time point in 0.1～6 hour, the residue propylene monomer was removed in decompression, added 1-butylene monomer and hydrogen in reactor, carried out the 1-butylene slurry polymerization.
When carrying out above-mentioned polymerization, hydrogen and 1-butylene volume ratio are 0～30: 100, the monomer mass ratio of the propylene of 1-butylene and step (1) is 1～200: 1, and make the heterogeneous Ziegler-Natta catalyst in the step (1) continue to cause the 1-butylene polymerization, polymerization temperature is 0 ℃～70 ℃, and polymerization time is 1～24 hour; Remove butene monomers etc., obtain the polybutene alloy.Two sections polymerizations can be to carry out in a reactor, also can carry out in two or more reactors.
5. the preparation method's of the described polybutene alloy of claim 1 two, can synthesize according to the following steps, it is characterized in that:
(1) add aluminum alkyls or aikyl aluminum halide, external electron donor, heterogeneous Ziegler-Natta catalyst and 1-butylene, hydrogen successively in reactor, the mass polymerization of carrying out 1-butylene obtains the 1-butylene homopolymer;
Or
In reactor, add the alkane of 5～10 carbon atoms and/or aromatic hydrocarbon organic solvent, aluminum alkyls or aikyl aluminum halide, external electron donor, heterogeneous Ziegler-Natta catalyst and 1-butylene, the hydrogen of 5～10 carbon atoms successively, the slurry polymerization that carries out butylene obtains chevron, and wherein the mass ratio of butylene and organic solvent is 1～1000: 100;
When carrying out above-mentioned polymerization, polymeric reaction temperature is 0 ℃～70 ℃, and hydrogen and 1-butylene volume ratio are 0～30: 100, and the mol ratio of Ti element and 1-butylene is 1～1000 * 10 in the heterogeneous Ziegler-Natta catalyst
-7The mol ratio of Ti element is 40～200: 1 in Al element in aluminum alkyls or the aikyl aluminum halide and the heterogeneous Ziegler-Natta catalyst, the Al element in aluminum alkyls or the aikyl aluminum halide and the mol ratio of external electron donor are 0.1～50, and the homopolymerization time is 1～24 hour;
(2) after the homopolymerization time of the reaction system of step (1) reached any time point in 1～24 hour, residue butene monomers and solvent were removed in decompression, add propylene monomer and hydrogen, catalyzing propone bulk precipitation polymerization in reactor;
Or
After the homopolymerization time of the reaction system of step (1) reached any time point in 1～24 hour, the residue butene monomers was removed in decompression, adds propylene monomer and hydrogen in reactor, and catalyzing propone carries out slurry polymerization;
When carrying out above-mentioned polymerization, hydrogen and propylene volume ratio are 0～30: 100, the monomer mass ratio of the 1-butylene of propylene and step (1) is 1: 1～200, and make the heterogeneous Ziegler-Natta catalyst in the step (1) continue to cause propylene polymerization, polymerization temperature is 0 ℃～80 ℃, and polymerization time is 0.1～6 hour; Remove propylene monomer etc., obtain the polybutene alloy.Two sections polymerizations can be to carry out in a reactor, also can carry out in two or more reactors.
6. method according to claim 4 is characterized in that: described aluminum alkyls is triethyl aluminum or triisobutyl aluminium; Described aikyl aluminum halide is a kind of in dimethyl monochlor(in)ate aluminium, monomethyl al dichloride, diethyl monochlor(in)ate aluminium, an ethylaluminum dichloride, diisobutyl monochlor(in)ate aluminium or the isobutyl-al dichloride.
7. method according to claim 4, it is characterized in that: described heterogeneous Ziegler-Natta catalyst is to be the catalyzer that contains titanium compound and internal electron donor of carrier with magnesium halogenide, wherein, the Ti element account for Ziegler-Natta catalyst total mass 1%～5%, internal electron donor account for Ziegler-Natta catalyst total mass 0.5%～20%.
8. method according to claim 6 is characterized in that: described magnesium halogenide is selected from MgCl
2, MgBr
2Or MgI
2In a kind of; Optimum is MgCl
2
Described titanium compound is selected from TiCl
4, TiBr
4Or TiI
4In a kind of; Optimum is TiCl4
Described internal electron donor is ester class, ethers, ketone, anhydrides compound, a kind of in preferred phenylformic acid, anisic acid, paraethoxybenxoic acid, toluylic acid, o-benzene butyl phthalate ester, phthalic acid dibutyl ester, benzoquinones, methyl benzoate, the ethyl benzoate etc.
9. method according to claim 4, it is characterized in that: described external electron donor is selected from silicon compound, preferred silicon compound is a cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane, uncle's hexyl Trimethoxy silane, diisopropyl dimethoxy silane, methylcyclohexyl dimethoxy silane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2-ethyl piperidine base-2-tertiary butyl dimethoxy silane, 1,1,1-trifluoro propyl-2-ethyl piperidine base-dimethoxy silane, ethyl trimethoxy silane, propyl trimethoxy silicane, phenyltrimethoxysila,e, a kind of in the dicyclohexyl dimethoxy silane etc.;
10. polybutene alloy for preparing by any described method of claim 1～9, it is characterized in that: described polybutene alloy is powdery or the spherical product with nucleocapsid structure, have excellent impact resistance energy, heat-resisting creep property, low-shrinkage and the polyacrylic high-modulus of poly-1-butylene concurrently, advantages such as high rigidity, fast shaping.
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