CN1099427C - Low-molecular-weight polyethylene with dual-peak distribution of molecular weight, and its preparing process and application - Google Patents
Low-molecular-weight polyethylene with dual-peak distribution of molecular weight, and its preparing process and application Download PDFInfo
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- CN1099427C CN1099427C CN98124351A CN98124351A CN1099427C CN 1099427 C CN1099427 C CN 1099427C CN 98124351 A CN98124351 A CN 98124351A CN 98124351 A CN98124351 A CN 98124351A CN 1099427 C CN1099427 C CN 1099427C
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Abstract
The present invention provides low molecular weight polyethylene. The number average molecular weight of the polymer is from 1500 to 6000, and molecular weight distribution Mw/Mn is from 20 to 50. The polyethylene simultaneously has the following characteristics that a molecular weight distribution curve measured by a gel permeation chromatography forms a double peak shape; melting ranges corresponding to double peaks on a curve measured by a differential heat scanning thermometric analysis method are respectively from 90 to 130DEGC and from 130 to 150 DEG C. The present invention also provides a preparing process of the polymer and the application of the polymer used as a xerography ink powder dispersing agent.
Description
Technical field
The present invention relates to a kind of low-molecular ethylene polymers, more particularly, relate to a kind of ethene polymers, the invention still further relates to this polyvinyl preparation method and as the application of electroscopic powder dispersion agent with bimodal distribution.
Background technology
Low molecular weight polyethylene mainly is to substitute traditional paraffin in actual applications, but compare with paraffin, because low molecular weight polyethylene has advantages such as fusing point height, high-temperature stability are good, so it is widely used in resin alloy, processing modified adjuvant, hot melt adhesive additive, printing-ink anti-wear agent, wax work properties-correcting agent, electroscopic powder carrier, cosmetics additive, cable coil and seals fields such as filling agent.
At present, many patent disclosures the have been arranged production method of low molecular weight polyethylene, wherein major part is to adopt High molecular weight polyethylene degraded to produce the technology of low molecular weight polyethylene, but the molecular weight of product is difficult to control, and adopt the polymeric method to prepare low molecular weight polyethylene, can control the molecular weight of product more easily, improve indexs such as product form and aspect.For example: EP 021700 discloses a kind of manufacture method of polyethylene wax, it adopts titanium-magnesium catalyst active constituent efficiently, the halogenide that is equipped with not halogen-containing alkylaluminium cpd and Al, Si or C is as catalyzer, the inert hydrocarbon compound is as solvent, temperature of reaction is 140～300 ℃, obtaining the low-molecular ethylene polymers number-average molecular weight is 500～6000, and molecular weight distribution is narrower.At present, still have nothing to do in the report of bimodal distribution low molecular weight polyethylene.
Summary of the invention
The object of the present invention is to provide a kind of new low-molecular ethylene polymers, this polymkeric substance is bimodal pattern through the molecular weight distribution curve of gel permeation chromatography, has shown better machining property.
Another object of the present invention provides a kind of preparation method of low-molecular ethylene polymers of the present invention.
A further object of the invention is with the application of low-molecular ethylene polymers of the present invention as the electroscopic powder dispersion agent.
The invention provides a kind of low-molecular ethylene polymers, the number-average molecular weight of this polymkeric substance is 1500～6000, molecular weight distribution mw/mn is between 20～50, and have following feature simultaneously: (1) is bimodal pattern by the molecular weight distribution curve of gel permeation chromatography, (2) on the curve by differential heat scanning analysis method mensuration, bimodal pairing melting range is respectively 90～130 ℃ and 130～150 ℃.
Preferred low-molecular ethylene polymers is: number-average molecular weight is 2000～5000, molecular weight distribution mw/mn is between 25～45, or on the curve by differential heat scanning analysis method mensuration, bimodal pairing melting range is respectively 120～130 ℃ and 130～140 ℃.
The number-average molecular weight of polymkeric substance and molecular weight distribution adopt gel permeation chromatography (GPC) to measure.For example, pure low-molecular ethylene polymers is dissolved in the solvent system of orthodichlorobenzene, under 135 ℃, measures with polystyrene standard.Can directly obtain number-average molecular weight and molecular weight distribution (distribution coefficient) from the GPC spectrogram, the molecular weight distribution curve of polymkeric substance of the present invention is bimodal pattern.
The melting point curve of polymkeric substance adopts differential heat scanning analysis method (DSC) to measure under nitrogen atmosphere, heat-up rate is 10～20 ℃/minute, on the DSC spectrogram, polymkeric substance of the present invention presents two fusing point peaks, the first fusing point peak is between 90～130 ℃, corresponding the part of lower molecular weight, the second fusing point peak between 130～150 ℃, corresponding the part of higher molecular weight.
The present invention also provides a kind of method for preparing low-molecular ethylene polymers of the present invention, and this method comprises: in the presence of inert solvent, 50～100 ℃ of temperature of reaction are preferably 65～95; Reaction pressure 0.8～2Mpa is preferably 1～1.6Mpa, and wherein the hydrogen dividing potential drop is 0.6～1.5Mpa, is preferably 0.8～1.4Mpa, and ethene carries out polyreaction in the presence of catalyzer, and the reaction times is 1～3 hour;
Described catalyzer is made up of titaniferous solid catalytic ingredient A and alkylaluminium cpd B, wherein titaniferous solid catalytic ingredient A is the solvent system formation homogeneous solution that magnesium halide is dissolved in organic epoxy compounds and organo phosphorous compounds, the mixture that this magnesium halide solution and titanium tetrahalide or derivatives thereof form is at first separated out solids in the presence of one or more precipitation additives, handle with the multi-carboxylate then, it is loaded on the solids, again with titanium tetrahalide and thinner and obtain; The ratio of component B and component A counts 20～500 with aluminium and titanium ratio.
The inert solvent that adopts among the preparation method of the present invention can be selected from one or more in pentane, hexane, heptane, octane, decane, kerosene, pentamethylene, methylcyclopentane, hexanaphthene, the methylcyclohexane, is preferably hexane or heptane.
Among the preparation method of the present invention, the titaniferous solid catalytic ingredient of component A----is prepared according to disclosed method in Chinese patent 85100997.2 specification sheetss in the catalyzer, to control for titanium content and ester content among the component A, titanium content is 1.5～3.0wt%, is preferably 2.0～2.8wt%; Ester content is 3～20wt%, is preferably 5.0～15wt%.
Magnesium halide is selected from one of them halogen atom in the complex compound, magnesium dihalide molecular formula of water, alcohol of magnesium dihalide, magnesium dihalide by in alkyl or the halogen-oxyl institute metathetical derivative one or more among the catalyst component A; Be preferably magnesium dichloride, dibrominated magnesium, two magnesium iodides.
Organic epoxy compounds is selected from carbonatoms one or more in oxide compound, glycidyl ether or the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine among the catalyst component A; Be preferably oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF).
Organo phosphorous compounds is selected from one or more in the halo hydrocarbyl carbonate of hydrocarbyl carbonate, ortho-phosphoric acid or phosphorous acid of ortho-phosphoric acid or phosphorous acid among the catalyst component A; Be preferably: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl.
The titanium tetrahalide or derivatives thereof is selected from one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium among the catalyst component A; Be preferably titanium tetrachloride, titanium tetrabromide, four titanium butoxide or purity titanium tetraethoxide.
Precipitation additive is selected from a kind of in organic acid, organic acid anhydride, organic ether, the organic ketone or their mixture among the catalyst component A.Concrete as: diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether.
The multi-carboxylate is selected from diethyl malonate among the catalyst component A, butyl ethyl malonate, diethylene adipate, Polycizer W 260, ethyl sebacate, Uniflex DBS, n-butyl phthalate, diisobutyl phthalate, dimixo-octyl phthalate, diethyl maleate, maleic acid n-butyl, the naphthalene dicarboxylic acids diethyl ester, the naphthalene dicarboxylic acids dibutylester, tributyl trimellitate, the benzene-1,2,3-tricarboxylic acid triethyl, the benzene-1,2,3-tricarboxylic acid tri-n-butyl, the pyromellitic acid tetra-ethyl ester, pyromellitic acid four butyl esters.
The alkylaluminium cpd of catalyst component B, its general formula are AlR
nX
3-n, R is that carbonatoms is 1～20 alkyl, particularly alkyl, aralkyl, aryl in the formula; X is halogen, particularly chlorine and bromine; N is the number of 0＜n＜3, particular compound such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, ethyl aluminum dichloride, sesquialter ethyl aluminum chloride; Wherein be preferably triethyl aluminum or triisobutyl aluminium.
The number-average molecular weight (Mn) of the low-molecular ethylene polymers of the present invention that obtains with aforesaid method can change in 1500～6000 scope, and molecular weight distribution (Mn/Mw) and is bimodal distribution between 20～50.Bimodal owing to having, therefore polymkeric substance of the present invention is highly suitable for the dispersion agent as electroscopic powder, and is better dispersed.In the prior art, adopt low-molecular ethylene polymers to occur such problem easily as the dispersion agent of electroscopic powder, when the fusing point of low-molecular ethylene polymers is higher, dispersion effect is bad, when the fusing point of low-molecular ethylene polymers hangs down, though dispersion effect is good, be easy to roll banding in the duplicating process.The softening temperature that has only strict control low-molecular ethylene polymers the problems referred to above could not occur in certain numerical range, but the softening temperature for polymkeric substance is to be difficult to control in polymerization process.Low-molecular ethylene polymers of the present invention is because molecular weight has bimodal distribution, be high-melting-point part and low melting point part, not only solved the problem of roll banding, and dispersion effect is fine, this may be because the high-melting-point part in the low-molecular ethylene polymers is better with the mixed with resin in the electroscopic powder, and the low melting point in low-molecular ethylene polymers part is mixed better with iron powder and carbon dust in the electroscopic powder, so has solved problems of the prior art.The add-on of low-molecular ethylene polymers of the present invention during as the dispersion agent of electroscopic powder is 2～10wt%.
Embodiment will be further understood that the present invention from following illustrative embodiment.
Embodiment 1 (1) Preparation of catalysts: titaniferous active constituent is prepared by embodiment 1 disclosed method and condition in Chinese patent 85100997.2 specification sheetss, obtain wherein titanium content 2.62% of solid catalyst, Mg content 17.01%, cl content 55.88%, ester content 14.36%.(2) vinyl polymerization: press in the stainless steel polymeric kettles in two risings that stirring and register are housed, fully replace with hydrogen, add one liter of heptane, above-mentioned solid catalyst 63.8mg, triethyl aluminum is 10ml, begin to heat up, during to 70 ℃, the heptane dividing potential drop is 0.04MPa, add hydrogen to 1.49Mpa (the hydrogen add-on is 11.6 standard liters), feeding ethene to stagnation pressure then is 1.6Mpa, continues to be warmed up to 86 ℃, keep this thermotonus after two hours, discharging obtains white polyethylene powder (the results are shown in Table 1).(3) test polymer: polymkeric substance apparent density BD is 0.27g/cm
3Catalyst efficiency is 151kg polymkeric substance/g titanium, adopt gel permeation chromatography on U.S. Waters150C instrument, the molecular weight and the molecular weight distribution of product have been tested, the number-average molecular weight of polymkeric substance is 3050, product is bimodal distribution (referring to Fig. 1), has done scintigram (referring to Fig. 2) in addition on PERKIN-ELMER differential scanning calorimeter DSC7.
The choosing of embodiment 2 (1) catalyzer is equipped with: with embodiment 1 (2) vinyl polymerization: stir and two the raising in the pressure stainless steel polymeric kettles of register being equipped with, fully replace with hydrogen, add one liter of heptane, above-mentioned solid catalyst 42mg, triethyl aluminum is 10ml, begin to heat up, during to 70 ℃, the heptane dividing potential drop is 0.04MPa, add hydrogen to 0.84Mpa (the hydrogen add-on is 6.4 standard liters), feeding ethene to stagnation pressure then is 1.0Mpa, continues to be warmed up to 86 ℃, keep this thermotonus after two hours, discharging obtains white polyethylene powder (the results are shown in Table 1).(3) test polymer: polymkeric substance apparent density BD is 0.30g/cm
3Catalyst efficiency is 140kg polymkeric substance/g titanium, produce the Waters150C instrument with the U.S., the molecular weight and the molecular weight distribution of product have been tested, the number-average molecular weight of polymkeric substance is 4874, molecular weight distribution is 25.56, and product is bimodal distribution (referring to Fig. 3), has done scintigram (referring to Fig. 4) in addition on PERKIN-ELMER differential scanning calorimeter DSC7.
The choosing of embodiment 3 (1) catalyst systems is equipped with: titaniferous active constituent is prepared by embodiment 7 disclosed methods and condition in Chinese patent 85100997.2 specification sheetss, obtain wherein titanium content 2.20% of solid catalyst, Mg content 17.86%, cl content 59.34%, ester content 5.9%.(2) vinyl polymerization: carry out ethylene polymerization with embodiment 2 same procedure, the results are shown in Table 1.(3) polymkeric substance test: polymkeric substance apparent density BD is 0.30g/cm
3Catalyst efficiency is 100kg polymkeric substance/g titanium, produce on the Waters150C instrument in the U.S., the molecular weight and the molecular weight distribution of product have been tested, the number-average molecular weight of polymkeric substance is 2980, product is bimodal distribution, has done scintigram in addition on PERKIN-ELMER differential scanning calorimeter DSC7, and fusing point is 128 ℃ and 142 ℃.
Embodiment 4 (1) Preparation of catalysts choosings is equipped with: with embodiment 3 (2) vinyl polymerizations: carry out ethylene polymerization with embodiment 1 same procedure, the results are shown in Table 1.(3) polymkeric substance test: polymkeric substance apparent density BD is 0.29g/cm
3Catalyst efficiency is 128kg polymkeric substance/g titanium, produce on the Waters150C instrument in the U.S., the molecular weight and the molecular weight distribution of product have been tested, the number-average molecular weight of polymkeric substance is 3265, product is bimodal distribution, has done scintigram in addition on PERKIN-ELMER differential scanning calorimeter DSC7, and fusing point is 129 ℃ and 140 ℃.
Table 1
| Numbering | Catalyst efficiency kgPE/g.Ti | The polymkeric substance number-average molecular weight | Polymer B D (g/cm 3) | Molecular weight distribution |
| Embodiment 1 | 151 | 3050 | 0.27 | 41.33 |
| Embodiment 2 | 140 | 4874 | 0.30 | 25.56 |
| Embodiment 3 | 100 | 2980 | 0.28 | 31.68 |
| Embodiment 4 | 128 | 3265 | 0.29 | 34.89 |
Claims (7)
1. low-molecular ethylene polymers, the number-average molecular weight of this polymkeric substance is 2000～5000, molecular weight distribution mw/mn is between 20～50, and have following feature simultaneously: (1) is bimodal pattern by the molecular weight distribution curve of gel permeation chromatography, (2) on the curve by differential heat scanning analysis method mensuration, bimodal pairing melting range is respectively 90～130 ℃ and 130～150 ℃.
2. low-molecular ethylene polymers according to claim 1 is characterized in that molecular weight distribution mw/mn is between 25～45.
3. low-molecular ethylene polymers according to claim 1 is characterized in that, on the curve by differential heat scanning analysis method mensuration, bimodal pairing melting range is respectively 120～130 ℃ and 130～140 ℃.
4. the preparation method of the described low-molecular ethylene polymers of one of claim 1～3, it is characterized in that: in the presence of inert solvent, 50～100 ℃ of temperature of reaction, reaction pressure 0.8～2Mpa, wherein the hydrogen dividing potential drop is 0.6～1.5Mpa, ethene carries out polyreaction in the presence of catalyzer, the reaction times is 1～3 hour;
Described catalyzer is made up of titaniferous solid catalytic ingredient A and alkylaluminium cpd B, wherein titaniferous solid catalytic ingredient A is the solvent system formation homogeneous solution that magnesium halide is dissolved in organic epoxy compounds and organo phosphorous compounds, the mixture that this magnesium halide solution and titanium tetrahalide or derivatives thereof form is at first separated out solids in the presence of one or more precipitation additives, handle with the multi-carboxylate then, it is loaded on the solids, again with titanium tetrahalide and thinner and obtain; Wherein titanium content is 1.5～3.0wt%, and ester content is 3～20wt%; The ratio of component B and component A counts 20～500 with aluminium and titanium ratio.
5. the preparation method of low-molecular ethylene polymers according to claim 4, it is characterized in that used inert solvent adopts one or more in pentane, hexane, heptane, octane, decane, kerosene, pentamethylene, methylcyclopentane, hexanaphthene, the methylcyclohexane.
6. the preparation method of low-molecular ethylene polymers according to claim 4 is characterized in that, temperature of reaction is 65～95 ℃, and reaction pressure is 1～1.6Mpa.
7. the described low-molecular ethylene polymers of one of claim 1～3 is as the application of electroscopic powder dispersion agent.
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| CN98124351A CN1099427C (en) | 1998-11-03 | 1998-11-03 | Low-molecular-weight polyethylene with dual-peak distribution of molecular weight, and its preparing process and application |
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| GB0425444D0 (en) * | 2004-11-18 | 2004-12-22 | Solvay | Multimodal composition for tapes, fibres and filaments |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100997A (en) * | 1985-04-01 | 1987-01-10 | 化工部北京化工研究院 | The catalyst system that is used for olefinic polymerization and copolymerization |
| CN1106613A (en) * | 1993-03-26 | 1995-08-09 | 博雷利丝·波利默斯公司 | Process for manufacturing olefin polymers and products prepared by the process |
| US5494872A (en) * | 1992-04-03 | 1996-02-27 | Toho Titanium Company, Ltd. | Catalyst and solid catalyst component for preparing polyolefins with broad molecular weight distribution |
| US5614456A (en) * | 1993-11-15 | 1997-03-25 | Mobil Oil Corporation | Catalyst for bimodal molecular weight distribution ethylene polymers and copolymers |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100997A (en) * | 1985-04-01 | 1987-01-10 | 化工部北京化工研究院 | The catalyst system that is used for olefinic polymerization and copolymerization |
| US5494872A (en) * | 1992-04-03 | 1996-02-27 | Toho Titanium Company, Ltd. | Catalyst and solid catalyst component for preparing polyolefins with broad molecular weight distribution |
| CN1106613A (en) * | 1993-03-26 | 1995-08-09 | 博雷利丝·波利默斯公司 | Process for manufacturing olefin polymers and products prepared by the process |
| US5614456A (en) * | 1993-11-15 | 1997-03-25 | Mobil Oil Corporation | Catalyst for bimodal molecular weight distribution ethylene polymers and copolymers |
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