CN105622801A - Catalyst component for ethylene polymerization, catalyst for ethylene polymerization, and preparation method of catalyst component - Google Patents
Catalyst component for ethylene polymerization, catalyst for ethylene polymerization, and preparation method of catalyst component Download PDFInfo
- Publication number
- CN105622801A CN105622801A CN201410637373.XA CN201410637373A CN105622801A CN 105622801 A CN105622801 A CN 105622801A CN 201410637373 A CN201410637373 A CN 201410637373A CN 105622801 A CN105622801 A CN 105622801A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- titanium
- compound
- catalytic component
- vinyl polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention provides a catalyst component for ethylene polymerization, wherein magnesium halide is dissolved in an alcohol compound and an organic epoxy compound to form a uniform solution, and the obtained uniform solution acts with a titanium compound in the presence of a thioester compound so as to obtain the catalyst component. According to the present invention, the catalyst provides characteristics of high polymerization activity, good hydrogen response, good copolymerization performance, and good bulk density when the catalyst is used for ethylene polymerization at a high temperature; the thioester compound is added so as to improve the particle morphology of the catalyst, and improve the hydrogen response and the copolymerization performance of the catalyst; and the use of a lot of titanium tetrachloride to promote precipitate precipitation and the multiple uses of titanium tetrachloride to treat the precipitate are not required, such that the addition amount of titanium tetrachloride is substantially reduced so as to improve the production efficiency and the production benefits of the catalyst.
Description
Technical field
The present invention relates to a kind of catalyst for olefinic polymerization, the preparation method being particularly used for the catalytic component of vinyl polymerization, catalyst and this catalyst.
Background technology
It is known that the caltalyst containing Ti/Mg complex ties up in the industrialized production of polyethylene occupies leading position, its research focus concentrates on particle shape and the particle size distribution etc. of the polymerization activity of catalyst, hydrogen response, copolymerization performance and catalyst. And in the slurry polymerization processes of ethylene, except requiring catalyst and should having higher catalysis activity, hydrogen response and the copolymerization performance of catalyst are most important. It may be said that, in the slurry polymerization process of ethylene, above-mentioned performance directly decides the destiny of a catalyst, and the application of its commercial introduction is had direct impact, particularly in when producing the PP Pipe Compound trade mark, the above-mentioned performance improving polyethylene catalysts just becomes more urgent. Along with the increase of the various costs of material such as ethylene, the PP Pipe Compound trade mark of exploitation high added value is fallen over each other to increase benefit in each big petrochemical plant commercial city. And these PP Pipe Compound trades mark are higher, harsher to performance requirements such as the hydrogen response of catalyst and copolymerization performances, petrochemical industry manufacturer even can in order to improve the above-mentioned performance sacrificial section catalysis activity of catalyst.
Hydrogen response, its essence is and weigh the size of the macromolecular chain transferance that hydrogen (or hydrogen atom) is risen in olefin polymerization process. Copolymerization performance, its essence is that in ethylene polymerisation process, comonomer coordination accesses the ability of ethylene molecule chain. In actual research and production, introduce various component generally in the catalyst to improve the above-mentioned performance of catalyst. In the slurry polymerization processes of ethylene, except requiring catalyst and should having the active and good distribution of particles of higher catalysis, in order to produce the Alathon or copolymer with better performance, also require that catalyst has good hydrogen response, namely hydrogen dividing potential drop is passed easily through in polymerization process to regulate the melt index of final polymer, to obtain the polyvinyl resin of different commercial grades; Additionally, the copolymerization trade mark of quite a few trade mark especially some high added values needs catalyst to provide the copolymerization performance of excellence to meet its demand. A kind of catalytic component disclosed in Chinese patent CN1229092A, it is with magnesium chloride for carrier, titanium tetrachloride is active component, and the preparation method of catalyst is as follows: first by MgCl2Be dissolved in dicyandiamide solution, formed homogeneous transparent solution, then precipitation additive phthalic anhydride exist and low temperature under with TiCl4Reaction, by the precipitation solid catalyst that slowly heats up. When the catalytic component prepared is for vinyl polymerization, the catalysis activity of catalyst is unsatisfactory, and hydrogen response is then more undesirable, and copolymerization performance is not known where to begin yet. Meanwhile, the Organic substances such as phthalic anhydride need to be adopted to promote the precipitation of precipitation as precipitation additive when synthesizing this catalyst and it needs to add substantial amounts of titanium tetrachloride. Therefore not only catalyst is had adverse effect on by the existence of anhydride, simultaneously the use of substantial amounts of titanium tetrachloride, will also result in substantial amounts of waste and pollution. In Chinese patent CN1958620A, it is with magnesium chloride for carrier, and titanium tetrachloride is active component, and the preparation method of catalyst is as follows: first by MgCl2It is dissolved in dicyandiamide solution, forms homogeneous transparent solution, then precipitation additive silicon ester compound and TiCl at low temperatures4Reagentia, by the precipitation solid catalyst that slowly heats up. When the catalytic component prepared is for vinyl polymerization, the catalysis activity of catalyst is higher, although its hydrogen response and copolymerization performance also relatively the catalyst in Chinese patent CN1229092A have clear improvement, but be still difficult to fully meet the demand of some PP Pipe Compound trades mark of commercial production.
Therefore, it is highly desirable to provide a kind of catalyst for ethylene homo conjunction or copolymerization, it is particularly well-suited to ethylene slurry polymerization processes, being especially adapted for use in the ethylene slurry polymerization processes under higher temperature and pressure, not only catalysis activity is higher and have good hydrogen response, excellent copolymerization performance and narrower particle size distribution for it.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of for the catalytic component of vinyl polymerization, its preparation method and catalyst thereof. Owing to introducing sulfur ester, improve the particle shape of catalyst, improve hydrogen response and the copolymerization performance of catalyst.
A kind of catalytic component for vinyl polymerization, including the product of following components: (1) magnesium halide; (2) alcoholic compound; (3) organic epoxy compound thing; (4) titanium compound; (5) sulfur ester;
Described magnesium halide in magnesium dihalide, the water of magnesium dihalide or the complex of alcohol, magnesium dihalide molecular formula one of them halogen atom by the replaced derivant of alkyl or halogen oxyl;
Described organic epoxy compound thing selected from carbon number 2��8 aliphatic alkene, at least one in alkadienes or halogenated aliphatic alkene or the oxide of alkadienes, glycidyl ether and inner ether;
Described titanium compound formula is Ti (OR)aXb, in formula, R is aliphatic group or the aryl of C1��C14, and X is halogen, and a is 0,1 or 2, b is the integer of 0 to 4, a+b=3 or 4;
Specifically, described magnesium halide is selected from magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride. Described halogenated magnesium compound can be used alone or as a mixture.
Described alcohol includes the alcohol of straight chain, side chain or cycloalkyl that carbon number is 1��10 or carbon number is 6��20 alcohol containing aryl. The example of alcohol includes fatty alcohol: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, glycerol, hexanol, 2-methyl anyl alcohol, 2-ethyl butanol, n-heptanol, n-octyl alcohol, isooctanol, decanol etc.; Cyclic alkanol, such as Hexalin, methyl cyclohexanol etc.; Aromatic alcohol, as benzyl alcohol, methylbenzyl alcohol ,-methylbenzyl alcohol ,-dimethylphenylcarbinol etc. Wherein preferred alcohol, butanol, 2-Ethylhexyl Alcohol, glycerol. Preferred alcohol and isooctanol.
Described organic epoxy compound thing is selected from oxirane, expoxy propane, epoxy butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether etc.
In order to make dissolving more abundant, this dicyandiamide solution can be optionally added inert diluent, usual this inert diluent includes arene compounds or alkane derivative, and arene compounds includes benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and derivant thereof; Alkane includes a kind of in the linear paraffin of 3��20 carbon, branched paraffin or cycloalkane or their mixture, such as butane, pentane, hexane, hexamethylene, heptane etc., as long as what contribute to that magnesium halide dissolves can use. Above-mentioned inert diluent can be used alone, it is possible to combination uses.
Described titanium compound can be the one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanous chloride., dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium or its mixture, it is preferable that titanium tetrachloride.
Described sulfur ester is selected from S-butyl sulfo-chloro-formate; S-isobutyl sulfo-chloro-formate; S-phenyl isobutyrate; S-methyl thiobutyrate; Chloro dithiocarbonic acid pentafluorophenyl group ester; Sulfo-chloro-carbonic acid-S-isopropyl ester; Furfuryl thiopropionate; Thio-ethyl chloride; N-butanimide-3-acetylthiopropionate; S-propyl chloride thiocarboxylic; S-sec-butyl sulfo-chloro-formate; S-t-butylthio chloro-formate; S-ethyl-N, N-dipropyl thiocarbamate; 1,4-succinimide mercaptans oxalic acid; The pungent two mercaptan diacetate esters of 1,8-. Preferred S-butyl sulfo-chloro-formate, 1,8-pungent two mercaptan diacetate esters, S-ethyl-N, N-dipropyl thiocarbamate and thio-ethyl chloride. In the present invention, sulfur ester is except using as precipitation additive, should contain the sulfur ester of q.s to improve the combination property of catalyst in the solid-state finally given or liquid titanium catalyst component.
In the catalytic component for vinyl polymerization or combined polymerization of the present invention, ratio between each reactant is in every mole of magnesium halide, and alcoholic compound is: 0.1��10.0mol, organic epoxy compound thing: 0.5��5.0mol, sulfur ester: 1.0��10.0ml, it is preferable that 1.0��5.0ml; Organo-aluminum compound is 0��5.0 mole, and titanium compound is 1.0��15.0 moles.
The compositing range of gained catalytic component of the present invention is: Ti:2.0��10.0wt%, Mg:15.0��25.0wt%, Cl:50.0��70.0wt%, S:0.2��1.2wt%, OR:4.0��10.0wt%, Al:0��1.0wt%.
The above-mentioned catalytic component of the present invention can adopt following method to prepare:
1. magnesium halide is dissolved in the dicyandiamide solution containing alcohol compound and machine epoxide, preferred dicyandiamide solution adds inert diluent, forms homogeneous solution, solution temperature preferably 50��90 DEG C, it is subsequently adding or is not added with organo-aluminum compound, react the regular hour;
2. at a lower temperature, preferably in-40 DEG C-20 DEG C, above-mentioned solution and titanium compound are carried out haptoreaction, sulfur ester can solution in (1) step carry out haptoreaction with titanium compound after add, also can add before the solution in (1) step and titanium compound carry out haptoreaction, it is preferable that the solution in (1) step and titanium compound add before carrying out haptoreaction. After above-mentioned reacting completely, mixture is to slowly warm up to 50-120 DEG C, solids precipitates out gradually and forms granule, after the reaction regular hour, remove unreacted reactant and solvent, and adopt inert diluent to wash, obtain the catalytic component of the present invention, catalytic component can be solid-state, it is also possible to be liquid.
Present invention also offers the catalyst of the copolymerization of a kind of equal polyreaction for ethylene or ethylene and other alpha-olefin, alpha-olefin therein includes propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, styrene, methyl styrene etc.; This catalyst comprises the catalytic component of (1) the above-mentioned present invention; (2) formula is AlRnX3-nThe product of organo-aluminum compound, in formula, R can be hydrogen, carbon number be the alkyl of l��20, particularly alkyl, aralkyl, aryl; X is halogen, particularly chlorine and bromine; N is the number of 0 < n��3. Particular compound such as aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethylmercury chloride aluminum, ethyl aluminum dichlorides, wherein preferably triethyl aluminum, triisobutyl aluminium. Wherein in component (2), aluminum is 5��500 with the mol ratio of titanium in component (1), it is preferable that 20��200.
Liquid phase polymerization can be adopted, it would however also be possible to employ gas-phase polymerization during polymerization.
Liquid polymerization medium includes: iso-butane, hexane, heptane, hexamethylene, Petroleum, raffinate oil, the atent solvent such as aliphatic saturated hydrocarbon or aromatic hydrocarbon such as hydrogasoline, kerosene, benzene,toluene,xylene.
In order to regulate the molecular weight of final polymer, hydrogen is adopted to make molecular weight regulator.
The catalytic component of the present invention introduces sulfur ester, therefore catalyst granules it is readily formed when prepared by catalytic component, improve bulk density, it is not necessary to using substantial amounts of titanium tetrachloride to promote the molding of catalyst granules, therefore the addition of titanium tetrachloride greatly reduces. The simultaneously addition of sulfur ester also contributes to the catalyst improvement in the activity of high temperature ethylene polymerization and the particle shape of catalyst. When catalyst is for ethylene polymerization at high temperatures, show good hydrogen response.
Detailed description of the invention
Following example are that present invention citing specifically is described, but the invention is not limited in these embodiments.
Embodiment 1
(1) preparation of catalytic component: in the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into 6.0g magnesium dichloride, toluene 90ml, ethanol 9.0ml, epoxychloropropane 6.0ml, 70 DEG C it are warming up to, when solid is completely dissolved and forms that after homogeneous solution, under 70 DEG C of conditions, reaction 1 is little under stirring. Then this system is cooled to-10 DEG C, adds S-butyl sulfo-chloro-formate 5.0ml, be then slowly added dropwise 80ml titanium tetrachloride, react 1��2 hour. It is to slowly warm up to 80 DEG C, reacts 2 hours. Stopping stirring, stand, toluene washing twice, hexanes wash four times, high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution. Catalyst forms in Table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M, adds the hexane solution of catalyst (containing the 0.4 milligram of titanium) solid of above-mentioned preparation, is warming up to 100 DEG C, passing into hydrogen makes pressure in still reach 0.28Mpa, passing into ethylene again makes stagnation pressure in still reach 0.45Mpa (gauge pressure), is polymerized 2 hours under 100 DEG C of conditions, and polymerization result is in Table 2.
Embodiment 2
(1) synthesis of catalyst is with embodiment 1. S-butyl sulfo-chloro-formate consumption changes 4.0ml into.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
Embodiment 3
(1) synthesis of catalyst is with embodiment 1, S-butyl sulfo-chloro-formate consumption simply changes into 2.0ml, and adds before titanium tetrachloride.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
Embodiment 4
(1) preparation of catalytic component: in the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into 6.0g magnesium dichloride, toluene 70ml, ethanol 10.0ml, epoxychloropropane 6.0ml, 70 DEG C it are warming up to, when solid is completely dissolved and forms that after homogeneous solution, under 70 DEG C of conditions, reaction 1 is little under stirring. Then this system is cooled to-10 DEG C, adds 1,8-pungent two mercaptan diacetate esters 8.0ml, be then slowly added dropwise 60ml titanium tetrachloride, react 1��2 hour, be to slowly warm up to 80 DEG C, react 2 hours. Stopping stirring, stand, toluene washing twice, hexanes wash four times, high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution. Catalyst forms in Table 1.
(2) vinyl polymerization is with embodiment 1. Polymerization result is in Table 2.
Embodiment 5
(1) synthesis of catalyst is with embodiment 4. Simply the pungent two mercaptan diacetate esters consumptions of 1,8-change 5.0ml into.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
Embodiment 6
(1) synthesis of catalyst is with embodiment 4. Simply the pungent two mercaptan diacetate esters consumptions of 1,8-change 3.0ml into.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
Embodiment 7
(1) preparation of catalytic component: in the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into 8.0g magnesium dichloride, toluene 90ml, ethanol 9.0ml, epoxychloropropane 6.0ml, 70 DEG C it are warming up to, when solid is completely dissolved and forms that after homogeneous solution, under 70 DEG C of conditions, reaction 1 is little under stirring. Then this system is cooled to-10 DEG C, adds S-ethyl-N, N-dipropyl thiocarbamate 6.0ml, be then slowly added dropwise 80ml titanium tetrachloride, react 1��2 hour. It is to slowly warm up to 80 DEG C, reacts 2 hours. Stopping stirring, stand, toluene washing twice, hexanes wash four times, high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution. Catalyst forms in Table 1.
Embodiment 8
(1) synthesis of catalyst is with embodiment 7. S-ethyl-N, N-dipropyl thiocarbamate consumption changes 3.0ml into.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
Embodiment 9
(1) synthesis of catalyst is with embodiment 7. S-ethyl-N, N-dipropyl thiocarbamate consumption changes 4.0ml into, and adds before dropping titanium tetrachloride.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
Embodiment 10
(1) preparation of catalytic component: in the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into 6.0g magnesium dichloride, toluene 70ml, ethanol 10.0ml, epoxychloropropane 6.0ml, 70 DEG C it are warming up to, when solid is completely dissolved and forms that after homogeneous solution, under 70 DEG C of conditions, reaction 1 is little under stirring. Then this system is cooled to-10 DEG C, adds thio-ethyl chloride 6.0ml, be then slowly added dropwise 70ml titanium tetrachloride, react 1��2 hour, be to slowly warm up to 80 DEG C, react 2 hours. Stopping stirring, stand, toluene washing twice, hexanes wash four times, high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution. Catalyst forms in Table 1.
(2) vinyl polymerization is with embodiment 1. Polymerization result is in Table 2.
Embodiment 11
(1) synthesis of catalyst is with embodiment 10. Simply thio-ethyl chloride consumption changes 4.0ml into.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
Embodiment 12
(1) synthesis of catalyst is with embodiment 10. Simply thio-ethyl chloride consumption changes 3.0ml into.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
Comparative example 1
(1) synthesis of catalyst is with embodiment 1, is not added with S-butyl sulfo-chloro-formate or 1,8-pungent two mercaptan diacetate esters, and catalyst cannot precipitate out.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
Comparative example 2
(1) synthesis of catalyst: in the reactor being sufficiently displaced from through high pure nitrogen, it is sequentially added into 6.0g magnesium dichloride, toluene 70ml, epoxychloropropane 6.0ml, tributyl phosphate 7ml, ethanol 5.0ml, 70 DEG C it are warming up to, when solid is completely dissolved and forms that after homogeneous solution, under 70 DEG C of conditions, reaction 1 is little under stirring. Being cooled to 30 DEG C, dropping 5.0ml concentration is the aluminium diethyl monochloride of 2.2M, and maintains reaction 1 hour at 30 DEG C. This system is cooled to-5 DEG C, is slowly added dropwise 60ml titanium tetrachloride, be subsequently adding 5.0ml tetraethyl orthosilicate, react 1 hour. This system is cooled to-5 DEG C, is slowly added dropwise 50ml titanium tetrachloride, be subsequently adding 6.5ml tetraethyl orthosilicate, react 1 hour. It is to slowly warm up to 80 DEG C, reacts 2 hours. Stopping stirring, stand, toluene washing twice, hexanes wash four times, high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.
(2) vinyl polymerization is with embodiment 1. Catalyst composition and polymerization result are in Table 1 and table 2.
The catalyst investigating hydrogen response employing is embodiment 1, embodiment 4 and comparative example 2. It is the stainless steel cauldron of 2L at volume, after high pure nitrogen is sufficiently displaced from, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M, add the hexane solution of catalyst (containing the 0.4 milligram of titanium) solid of above-mentioned preparation, be warming up to 100 DEG C, pass into ethylene and hydrogen, and change the mol ratio of hydrogen and ethylene, it is polymerized 2 hours under 100 DEG C of conditions. Wherein, the mol ratio of hydrogen and ethylene is respectively as follows: 0.28/0.45; 0.38/0.35; 0.48/0.25; 0.58/0.15; 0.68/0.05. Concrete result of investigating is in Table 3.
The catalyst investigating copolymerization performance employing is embodiment 7, embodiment 10 and comparative example 2. It is the stainless steel cauldron of 2L at volume, after high pure nitrogen is sufficiently displaced from, add hexane 1L, the triethyl aluminum 1.0ml of concentration 1M, add the hexane solution of catalyst (containing the 0.4 milligram of titanium) solid of above-mentioned preparation, be warming up to 100 DEG C, pass into the ethylene and 1-butylene gas-phase (co-) polymerisation that prepare according to fixed proportion, the volume ratio of 1-butylene and ethylene respectively 5/100,10/100, and pass into modifying polymerization with hydrogen thing molecular weight; When hexene makes comonomer, being separately added into 5ml, 10ml hexene, other is with 1-butylene copolymerization. The density of polymerization resulting polymers is measured according to GB GB/T1033.2-2010. Concrete result of investigating is in Table 4.
Table 1 catalyst forms
| Numbering | Ti (wt%) | Mg (wt%) | Cl (wt%) | OR (wt%) |
| Example 1 | 6.5 | 18.7 | 59.7 | 7.6 |
| Example 2 | 6.2 | 17.5 | 58.3 | 6.9 |
| Example 3 | 6.7 | 17.8 | 61.3 | 5.9 |
| Example 4 | 5.5 | 15.7 | 59.2 | 6.9 |
| Example 5 | 5.7 | 17.3 | 60.7 | 6.1 |
| Example 6 | 5.1 | 17.5 | 58.1 | 5.6 |
| Example 7 | 5.3 | 17.8 | 61.2 | 7.5 |
| Example 8 | 5.6 | 18.1 | 58.9 | 6.7 |
| Example 9 | 5.4 | 16.3 | 60.1 | 5.9 |
| Example 10 | 6.1 | 16.8 | 58.5 | 7.1 |
| Example 11 | 5.9 | 17.7 | 59.8 | 6.5 |
| Example 12 | 5.7 | 15.3 | 60.3 | 5.7 |
| Contrast 2 | 5.7 | 15.6 | 60.2 | 5.7 |
Table 2 polymer performance
From the aggregated data of table 2 it can be seen that under same polymerizing condition, the catalyst activity of the present invention is higher, bulk density is high, centralized particle diameter.
The particle shape of table 3 catalyst
| Numbering | Catalyst mean diameter D (0.5) | Catalyst particle size distribution (SPAN value) |
| Example 1 | 11.9 | 1.05 |
| Example 2 | 9.8 | 1.46 |
| Example 3 | 9.1 | 1.66 |
| Example 4 | 12.3 | 1.01 |
| Example 5 | 10.5 | 1.78 |
| Example 6 | 11.3 | 1.69 |
| Example 7 | 13.8 | 1.13 |
| Example 8 | 12.1 | 1.54 |
| Example 9 | 10.5 | 1.89 |
| Example 10 | 14.5 | 1.07 |
| Example 11 | 12.3 | 1.39 |
| Example 12 | 4.1 | 0.31 |
| Contrast 2 | 3.2 | 0.32 |
From the data of table 3 it can be seen that the catalyst particle size narrow distribution of the present invention, particle shape is good, and the mean diameter of catalyst is bigger.
Table 4 hydrogen response
From the data of table 4 it can be seen that the catalyst of present invention hydrogen response under higher polymerization temperature is significantly improved; The catalyst of the present invention that more prominent is is when high hydrogen ethylene ratio, and the hydrogen response of catalyst is better, and the bulk density of polymer is higher.
Table 5 copolymerization performance
From the data of table 5 it can be seen that catalyst its density when 1-butylene and hexene are as comonomer has to a certain degree reduces, it was shown that the copolymerization performance of catalyst improves.
Claims (12)
1. for a catalytic component for vinyl polymerization, including the product of following components: (1) magnesium halide; (2) alcoholic compound; (3) organic epoxy compound thing; (4) titanium compound; (5) sulfur ester;
Described magnesium halide in magnesium dihalide, the water of magnesium dihalide or the complex of alcohol, magnesium dihalide molecular formula one of them halogen atom by the replaced derivant of alkyl or halogen oxyl;
Described organic epoxy compound thing selected from carbon number 2��8 aliphatic alkene, at least one in alkadienes or halogenated aliphatic alkene or the oxide of alkadienes, glycidyl ether and inner ether;
Described titanium compound formula is Ti (OR)aXb, in formula R to be carbon number be 1��14 aliphatic group or aryl, X is halogen, and a is 0,1 or 2, b is the integer of 0 to 4, a+b=3 or 4.
2. the catalytic component for vinyl polymerization, it is characterized in that the ratio between each reactant is in every mole of magnesium halide, alcoholic compound is: 0.1��10.0mol, organic epoxy compound thing: 0.5��5.0mol, sulfur ester: 1.0��10.0ml, it is preferable that 1.0��5.0ml; Organo-aluminum compound is 0��5.0 mole, and titanium compound is 1.0��15.0 moles.
3. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterized in that described sulfur ester is selected from S-butyl sulfo-chloro-formate, S-isobutyl sulfo-chloro-formate, S-phenyl isobutyrate, S-methyl thiobutyrate, chloro dithiocarbonic acid pentafluorophenyl group ester, sulfo-chloro-carbonic acid-S-isopropyl ester, furfuryl thiopropionate, thio-ethyl chloride, N-butanimide-3-acetylthiopropionate, S-propyl chloride thiocarboxylic, S-sec-butyl sulfo-chloro-formate, S-t-butylthio chloro-formate, S-ethyl-N, N-dipropyl thiocarbamate, 1, 4-succinimide mercaptans oxalic acid and 1, the pungent two mercaptan diacetate esters of 8-.
4. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterized in that described sulfur ester selected from S-butyl sulfo-chloro-formate, 1, the pungent two mercaptan diacetate esters of 8-, S-ethyl-N, N-dipropyl thiocarbamate and thio-ethyl chloride.
5. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterised in that described magnesium halide is selected from magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination butoxy magnesium.
6. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterised in that described organic epoxy compound thing is selected from oxirane, expoxy propane, epoxy butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether and diglycidyl ether.
7. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterised in that described titanium compound is selected from the one in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanous chloride., dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium or its mixture.
8. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterised in that described alcoholic compound is 6��20 alcohol containing aryl selected from alcohol or the carbon number of the straight chain that carbon number is 1��10, side chain or cycloalkyl.
9. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterised in that described alcoholic compound is selected from ethanol, butanol, 2-Ethylhexyl Alcohol and glycerol.
10. a kind of catalytic component for vinyl polymerization according to claim 1, it is characterised in that containing Ti:2.0��10.0wt%, Mg:15.0��25.0wt%, Cl:50.0��70.0wt%, S:0.2��1.2wt%, OR:4.0��10.0wt%, Al:0��1.0wt%.
11. the preparation method of a kind of catalytic component for vinyl polymerization that one of claim 1-10 is described, comprise the following steps:
(1) magnesium halide is dissolved in the dicyandiamide solution containing alcohol compound and machine epoxide, dicyandiamide solution adds inert diluent, forms homogeneous solution, be subsequently adding or be not added with organo-aluminum compound, react the regular hour;
(2) under low temperature, above-mentioned solution and titanium compound are carried out haptoreaction, sulfur ester solution in step (1) and titanium compound add after carrying out haptoreaction, or the solution in step (1) and titanium compound carry out haptoreaction before add, add before carrying out haptoreaction preferably in the solution in step (1) and titanium compound, after above-mentioned reacting completely, mixture is to slowly warm up to solids precipitate out and form granule, after the reaction regular hour, remove unreacted reactant and solvent, and adopt inert diluent to wash, obtain the catalytic component of the present invention.
12. for a catalyst for vinyl polymerization, including:
(1) catalytic component for vinyl polymerization described for one of claim 1-10;
(2) organo-aluminum compound;
In component (2), aluminum is 5��500 with the mol ratio of titanium in component (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410637373.XA CN105622801B (en) | 2014-11-06 | 2014-11-06 | A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410637373.XA CN105622801B (en) | 2014-11-06 | 2014-11-06 | A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105622801A true CN105622801A (en) | 2016-06-01 |
| CN105622801B CN105622801B (en) | 2018-08-17 |
Family
ID=56038178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410637373.XA Active CN105622801B (en) | 2014-11-06 | 2014-11-06 | A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105622801B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072809A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN111072812A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN111072810A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN112759678A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and olefin polymerization method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348472A (en) * | 1999-03-03 | 2002-05-08 | 伊斯曼化学公司 | Process for producing polyethylene |
| US20030069372A1 (en) * | 2001-10-09 | 2003-04-10 | Formosa Plastics Corporation, U.S.A. | Olefin polymerization catalyst and process for preparing polyolefins with said catalyst |
| CN103772555A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
| CN103772554A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
-
2014
- 2014-11-06 CN CN201410637373.XA patent/CN105622801B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1348472A (en) * | 1999-03-03 | 2002-05-08 | 伊斯曼化学公司 | Process for producing polyethylene |
| US20030069372A1 (en) * | 2001-10-09 | 2003-04-10 | Formosa Plastics Corporation, U.S.A. | Olefin polymerization catalyst and process for preparing polyolefins with said catalyst |
| CN103772555A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
| CN103772554A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Ingredients of catalyst for vinyl polymerization and catalyst |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111072809A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN111072812A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN111072810A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN111072810B (en) * | 2018-10-19 | 2022-05-24 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN111072809B (en) * | 2018-10-19 | 2022-05-24 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN111072812B (en) * | 2018-10-19 | 2022-05-24 | 中国石油化工股份有限公司 | Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method |
| CN112759678A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst and olefin polymerization method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105622801B (en) | 2018-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103772554B (en) | A kind of catalyst component for polymerization of ethylene and catalyst thereof | |
| JP2004527633A (en) | Method for producing olefin polymer and selected catalyst | |
| CN101633704B (en) | Catalyst component used for ethylene polymerization reaction and catalyst thereof | |
| CN102295717B (en) | Catalyst compound used for vinyl polymerization reaction and catalyst thereof | |
| CN105622801A (en) | Catalyst component for ethylene polymerization, catalyst for ethylene polymerization, and preparation method of catalyst component | |
| CN106478850B (en) | The preparation method and ethylene rolymerization catalyst of catalytic component for vinyl polymerization | |
| JP6706582B2 (en) | Method for preparing catalyst component for olefin polymerization | |
| JP2011157561A (en) | Ziegler-natta catalyst for polyolefin | |
| CN104974282B (en) | A kind of catalytic component for ethylene polymerization, preparation method and catalyst | |
| CN105482002B (en) | Catalytic component, catalyst for vinyl polymerization and preparation method thereof | |
| CN103772553B (en) | A kind of catalyst for vinyl polymerization and preparation method thereof | |
| CN102993343B (en) | Catalyst component for ethylene polymerization, and catalyst thereof | |
| CN109694423A (en) | Catalytic component for vinyl polymerization and preparation method thereof and catalyst for vinyl polymerization | |
| CN102040685B (en) | Catalyst component for ethylene polymerization and catalyst | |
| CN106467583B (en) | A kind of catalytic component, preparation method and application for vinyl polymerization | |
| CN106467588B (en) | A kind of catalytic component, preparation method and application for vinyl polymerization | |
| CN105199024B (en) | A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof | |
| JP2007505970A (en) | Ziegler-Natta catalyst for polyolefin | |
| CN103772555A (en) | Ingredients of catalyst for vinyl polymerization and catalyst | |
| CN102993344B (en) | A kind of catalyst component for vinyl polymerization and catalyzer | |
| ZA200304674B (en) | Catalyst for polymerization and copolymerization of ethylene. | |
| CN114426605B (en) | Catalyst component for olefin polymerization and preparation method and application thereof | |
| CN111057168B (en) | Catalyst for olefin polymerization and preparation method and application thereof | |
| CN112661885B (en) | Titanium magnesium-based catalyst component for olefin polymerization, preparation method, catalyst and application | |
| CN111057169B (en) | Catalyst for olefin polymerization and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |