CN106866849B - Vinyl polymerization major catalyst and preparation method thereof, the ethylene rolymerization catalyst containing the major catalyst - Google Patents
Vinyl polymerization major catalyst and preparation method thereof, the ethylene rolymerization catalyst containing the major catalyst Download PDFInfo
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- CN106866849B CN106866849B CN201510917781.5A CN201510917781A CN106866849B CN 106866849 B CN106866849 B CN 106866849B CN 201510917781 A CN201510917781 A CN 201510917781A CN 106866849 B CN106866849 B CN 106866849B
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of vinyl polymerization major catalyst and containing its catalyst.The major catalyst includes magnesium compound, double solvents, dicarboxylic acid monoester compound and titanium compound；Preparation method includes the following steps: to mix magnesium compound and double solvents, forms clear solution；By the clear solution, monoester compound and titanium compound are mixed to precipitating completely respectively, obtain major catalyst suspension；The major catalyst suspension is subjected to slaking reaction；Major catalyst suspension after the curing is washed, is dried, major catalyst is obtained.Catalyst of the present invention includes above-mentioned major catalyst and organo-aluminum compound.Major catalyst of the invention has very high activity, the particle size of good particle shape and very narrow size distribution, the most prominent feature catalyst is larger, and polymerizate fine powder is less, and there is good copolymerization performance with alpha-olefin, be suitble to prepare the resins such as haloflex PP Pipe Compound.
Description
Technical field
The present invention relates to olefin polymerization catalysis field more particularly to a kind of vinyl polymerization major catalyst and its preparation sides
Method, and the ethylene rolymerization catalyst containing the major catalyst.
Background technique
From the seventies after efficient Zigler-Natta ethylene rolymerization catalyst is succeeded in developing, world's polyethylene industry is had occurred
Great change.Over nearly more than 20 years, with the development of ethene polymerization process, the catalyst to match with polymerization technique also achieves considerable
Progress, wherein Ziegler-Natta catalyst is catalyzed by its excellent polymerization and mature application technology in polyethylene
Agent still occupies an important position in field, still has a large amount of patent application to occur in recent years.In these patent applications, announce
The ethylene rolymerization catalysts of many different performances, such as the active lifetime of some catalyst are long, some catalyst can be prepared
The polyethylene of broad peak or bimodal molecular weight distribution.It is analyzed from technical standpoint, the Ziegler-Natta announced in these patents is urged
Agent is mainly used for the preparation of a certain quasi-polyethylene PP Pipe Compound, and the performance of catalyst is to meet such polyethylene special-purpose material
It is required that and design.
At present in ethylene slurry polymerization processes industrially, the average grain of the Ziegler-Natta catalyst used
Size is substantially at 10.0 microns or less.Such as in Chinese patent CN1229092 and CN102875708, the catalyst of preparation
Average particle size particle size is between 5.0-10.0 microns.Form when according to Ziegler-Natta catalyst catalyzed ethylene polymerization is multiple
Effect processed, polyethylene particle will grow formation on the basis of catalyst granules, necessarily cause small catalyst particles particle shape in this way
At small polyethylene resin particles, final result is exactly in the ethene polymerization process caused industrially, polyvinyl resin
Fine powder content is higher, brings difficulty to the steady operating of technique, more seriously, such catalyst would be unavailable for production pair
Polyvinyl resin powder has some PP Pipe Compounds of strict demand, such as haloflex PP Pipe Compound.Due to the poly- second for chlorination
Alkene powder will complete the chlorination reaction of polyethylene in water phase using chlorine, after excessive fine powder content will cause water phase and chlorination
The separation of polyethylene powder is difficult.Therefore, special dedicated for haloflex it is necessary to prepare a kind of catalyst of bulky grain
The production of materials.
Chinese patent CN1229092 discloses the preparation method of a kind of vinyl polymerization or copolymerization catalyst, in patent
Catalyst is to be dissolved in organic epoxy compound object, organic phosphorus compound and alcohol compound by magnesium halide to form homogeneous solution,
The halide effect with a kind of benzene compound anhydride as precipitation additive effect and transition metals Ti obtains again.It is precipitated helping
Under the effect of agent benzene compound anhydride, obtained catalyst average particle size lower than 10.0 microns, and particle shape compared with
Difference.In Chinese patent CN102875708, using organosilicon compound instead of benzene compound anhydride, the particle of catalyst
Form is improved, but the average particle size particle size of catalyst still is below 10.0 microns.
Summary of the invention
The purpose of the present invention is to provide a kind of vinyl polymerization major catalyst and preparation method thereof, which has catalysis
The big advantage of active height, uniform particle sizes, average particle size particle size, copolymerization performance is excellent, is suitable for producing haloflex PP Pipe Compound
Equal products.
Another object of the present invention is to provide a kind of ethylene rolymerization catalysts containing above-mentioned vinyl polymerization major catalyst.
In order to achieve the above objectives, the present invention provides a kind of vinyl polymerization major catalyst, by magnesium chloride, double solvents, carboxylic acid
Monoester compound and TiCl4 are made, the molar ratio of the magnesium chloride, double solvents, dicarboxylic acid monoester compound and TiCl4 are as follows: 1:
1.1-10:0.05-2:0.5-50；The average particle size particle size D50 of the vinyl polymerization major catalyst is 5-50 microns；
The double solvents includes tributyl phosphate, epoxychloropropane and ethyl alcohol, and the dosage of the double solvents is often to rub
That magnesium compound meter, tributyl phosphate are 0.3-3.5 moles, and epoxychloropropane is 0.3-3.5 moles, and ethyl alcohol rubs for 0.5-3.0
You；
The dicarboxylic acid monoester compound is methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, first
Base hydroxy-ethyl acrylate, ethyl methacrylate, butyl methacrylate, methyl methacrylate or ethyl acetate.
Vinyl polymerization major catalyst of the present invention, wherein the double solvents preferably further includes inertia dispersing agent, institute
Stating inertia dispersing agent is preferably hydro carbons and/or halogenated hydrocarbon.
Vinyl polymerization major catalyst of the present invention, wherein the inertia dispersing agent be preferably selected from by hexane, heptane,
At least one of octane, toluene, dimethylbenzene, 1,2- dichloroethanes, chlorocyclohexane and the formed group of chlorobenzene.
Vinyl polymerization major catalyst of the present invention, wherein the average particle size particle size D50 of the vinyl polymerization major catalyst
Preferably 10-30 microns.
In order to achieve the above objectives, the present invention also provides a kind of preparation methods of above-mentioned vinyl polymerization major catalyst, including with
Lower step:
S1: at 25-100 DEG C, magnesium chloride and double solvents being mixed, and formed within sustained response 10 minutes to 20 hours transparent molten
Liquid；
S2: at -10 DEG C to 50 DEG C, clear solution obtained in step S1 being mixed with dicarboxylic acid monoester compound and TiCl4,
TiCl4 is added drop-wise in clear solution in 30 minutes to 5 hours, and then reaction obtains major catalyst suspension；
S3: at 25 DEG C to 150 DEG C, it is small that major catalyst suspension obtained in step S2 is subjected to slaking reaction 0.5 to 15
When；
S4: the major catalyst suspension after curing in step S3 is washed with atent solvent, is dried, main catalytic is obtained
Agent.
The preparation method of vinyl polymerization major catalyst of the present invention, wherein in step S3, preferred slaking reaction 1 to 5
Hour.
The preparation method of vinyl polymerization major catalyst of the present invention, wherein in step S4, the atent solvent is best
Selected from by least one of iso-butane, pentane, hexane, heptane and the formed group of hexamethylene.
In the preparation method of vinyl polymerization major catalyst of the present invention, TiCl4Charge temperature and charging rate pair
Critically important to the form control of solid particle, higher charge temperature and faster charging rate will be unfavorable for regular solid particle
Formation, therefore define TiCl in step S24Addition temperature and time；There is the grain shape of catalyst in the slaking reaction
Favorable influence, slaking reaction time and temperature defined by the present invention can make the size distribution narrow of catalyst, while
The intensity of catalyst particle can be improved, to reduce particle fragmentation phenomenon of catalyst during catalyzed ethylene polymerization.
In order to achieve the above objectives, the present invention also provides a kind of ethylene rolymerization catalysts, including following components:
Above-mentioned vinyl polymerization major catalyst or the vinyl polymerization major catalyst as made from above-mentioned method；
Organo-aluminum compound is general formula AlRgX3-gAt least one of shown compound, in formula, R C1-C20Hydrocarbon
Base, X are halogen, and g is integer and 1 < g 3.
Ethylene rolymerization catalyst of the present invention, wherein the organo-aluminum compound is preferably by AlEt3, Al (iso-
Bu) 3, at least one of Al (n-C6H13) 3, Al (n-C8H17) 3 and the formed group of AlEt2Cl.
The invention has the benefit that ethylene rolymerization catalyst average particle size particle size is larger, and there is good particle
Form and very narrow size distribution, in the copolymerization of ethylene and other alpha-olefins, the insertion rate of comonomer obviously compared with
It is high.Catalyst of the invention is suitable for the slurry polymerization processes of ethylene, is suitable for preparing the production of haloflex PP Pipe Compound.
Detailed description of the invention:
Fig. 1 is the stereoscan photograph of catalyst prepared by embodiment 1.
Specific embodiment
The present invention is further illustrated by the following examples, and however, the present invention is not limited to these examples.
The test of the average grain diameter and its size distribution of catalyst
In hexane by catalyst sample dispersion, using Malvern Instruments Ltd. company, Britain
The size distribution curve of Mastersizer laser particle size analyzer test sample, wherein
The average grain diameter of catalyst is provided with D (50)；
Size distribution Span=(D (90)-D (10))/D (50) of catalyst；
D (50) is whole particles in the size distribution curve of Mastersizer laser particle size analyzer test in formula
50% diameter is lower than the diameter value of the value；D (10) is that 10% diameter of whole particles is lower than the diameter value of the value；D(90)
It is that 90% diameter of whole particles is lower than the diameter value of the value.
Ethylene homo closes
The major catalyst of 1L hexane, 1mmol triethyl aluminum (co-catalyst) and 10mg is added to 2L stainless steel stirred tank
In, temperature is then risen to 80 DEG C, is added at one time the hydrogen of 0.2MPa, is then maintained the gross pressure of system with ethylene
1.0MPa carries out polymerization reaction, after reaction 2 hours, stops that ethylene, cooling, pressure release, polyethylene powder weighing is added.With polyethylene
The weight of powder calculates the activity of catalyst divided by the dosage of major catalyst.
Ethylene and butene-1 combined polymerization
The major catalyst of 1L hexane, 1mmol triethyl aluminum (co-catalyst), 20ml butene-1 and 10mg are added to 2L not
It becomes rusty in steel stirred tank, temperature is then risen to 80 DEG C, is added at one time the hydrogen of 0.2MPa, then with ethylene by the stagnation pressure of system
Power maintains 1.0MPa and carries out polymerization reaction, after reaction 2 hours, stops that ethylene, cooling, pressure release, polyethylene powder weighing is added.
The activity of catalyst is calculated divided by the dosage of major catalyst with the weight of polyethylene powder.
Embodiment 1
In the reactor being sufficiently displaced from by nitrogen, magnesium dichloride 4.0g, toluene 60ml, ethyl alcohol are sequentially added
6.0ml, tributyl phosphate 3.0ml, epoxychloropropane 2.0ml, are warming up to 65 DEG C, are stirred continuously until that solid is completely dissolved to be formed
Uniform solution.- 15 DEG C are then cooled to, 0.5ml hydroxyethyl methacrylate is added, 30ml was slowly added dropwise within the used time 1 hour
TiCl4, after being added dropwise to complete, it is warming up to 85 DEG C and is stirred to react 2h.After the reaction was completed, stop stirring, staticly settle, filter, then use
After hexane washs 4 times, it is dried to obtain solid main catalyst particle.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, size distribution, activity and the polymerization of catalyst
The characterization result of resin is as shown in table 1.
Embodiment 2
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 0.4ml ethyl acrylate,
The suspension of last catalyst is stirred to react at 85 DEG C, 0.5h, and other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 3
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 0.5ml methacrylic acid second
The suspension of ester, last catalyst is stirred to react 15h at 85 DEG C, and other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 4
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 0.5ml methacrylic acid fourth
The suspension of ester, last catalyst is stirred to react 1h at 85 DEG C, and other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 5
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 0.4ml ethyl acetate, most
The suspension of rear catalyst is stirred to react 5h at 85 DEG C, and other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 6
0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is adjusted to 1.0ml, last catalyst
Suspension be stirred to react 2h at 85 DEG C, other conditions are same as Example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Embodiment 7
The charging sequence of 0.5ml hydroxyethyl methacrylate in the preparation of 1 major catalyst of embodiment is changed to drip at -15 DEG C
Add 30ml TiCl4After completing and stirring 0.5h, the suspension of last catalyst is stirred to react 5h, other conditions and reality at 85 DEG C
It is identical to apply example 1.
The characterization result of the size distribution of catalyst, activity and polymer resin is as shown in table 1.
Comparative example 1
In the reactor being sufficiently displaced from by nitrogen, magnesium dichloride 4.0g, toluene 60ml, ethyl alcohol are sequentially added
6.0ml, tributyl phosphate 3.0ml, epoxychloropropane 2.0ml, are warming up to 65 DEG C, are stirred continuously until that solid is completely dissolved to be formed
Uniform solution.It is then warming up to 85 DEG C and is stirred to react 2h.After the reaction was completed, stop stirring, staticly settle, filter, then use oneself
After alkane washs 4 times, it is dried to obtain solid main catalyst particle.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, size distribution, activity and the polymerization of catalyst
The characterization result of resin is as shown in table 1.
Comparative example 2
In the reactor being sufficiently displaced from by nitrogen, magnesium dichloride 4.0g, toluene 60ml, ethyl alcohol are sequentially added
6.0ml, tributyl phosphate 3.0ml, epoxychloropropane 2.0ml, are warming up to 65 DEG C, are stirred continuously until that solid is completely dissolved to be formed
Uniform solution.The phthalic anhydride of 1.1g is then added, is warming up to 85 DEG C and is stirred to react 2h.After the reaction was completed, stop stirring
It mixes, staticly settles, filter, then after washing 4 times with hexane, be dried to obtain solid main catalyst particle.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, size distribution, activity and the polymerization of catalyst
The characterization result of resin is as shown in table 1.
Comparative example 3
The phthalic anhydride of 1.1g in the preparation of 2 major catalyst of comparative example is adjusted to tetraethoxysilane 3.4ml,
His condition is identical as comparative example 2.
Major catalyst and co-catalyst triethyl aluminum collectively constitute catalyst, size distribution, activity and the polymerization of catalyst
The characterization result of resin is as shown in table 1.
Table 1
From the data of table 1 it is found that the catalyst average particle size in embodiment is all larger than 10.0 microns, and granularity point
Cloth is relatively narrow, and Span value is respectively less than 1.3.Catalyst of the invention closes and when combined polymerization being catalyzed ethylene homo, obtained polymerization
The molecular weight distribution of product is significantly greater than comparative example, and when being catalyzed ethylene and butene-1 combined polymerization, the insertion rate of butene-1 is obvious
Higher than comparative example.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (8)
1. a kind of vinyl polymerization major catalyst, which is characterized in that by magnesium chloride, double solvents, dicarboxylic acid monoester compound and TiCl4
It is made, the double solvents includes tributyl phosphate, epoxychloropropane and ethyl alcohol, and dosage of each component is with every mole of magnesium compound
Meter, tributyl phosphate are 0.3-3.5 moles, and epoxychloropropane is 0.3-3.5 moles, and ethyl alcohol is 0.5-3.0 moles；The chlorination
Magnesium, double solvents include the sum of tributyl phosphate, epoxychloropropane and ethyl alcohol total amount, dicarboxylic acid monoester compound and TiCl4Rub
That ratio are as follows: 1:1.1-10:0.05-2:0.5-50；The average particle size particle size D50 of the vinyl polymerization major catalyst is 5-50 microns；
The dicarboxylic acid monoester compound is methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl-prop
Olefin(e) acid hydroxyl ethyl ester, ethyl methacrylate, butyl methacrylate, methyl methacrylate or ethyl acetate；
The preparation method of the vinyl polymerization major catalyst the following steps are included:
S1: at 25-100 DEG C, magnesium chloride and double solvents are mixed, 10 minutes to 20 hours formation clear solutions of sustained response；
S2: at -15 DEG C, by clear solution obtained in step S1 and dicarboxylic acid monoester compound and TiCl4Mixing, TiCl4Several times
Clear solution is added in 30 minutes to 5 hours, obtains major catalyst suspension；
S3: at 25 DEG C to 150 DEG C, major catalyst suspension obtained in step S2 is carried out slaking reaction 0.5 to 15 hour；
S4: the major catalyst suspension after curing in step S3 is washed with atent solvent, is dried, major catalyst is obtained.
2. vinyl polymerization major catalyst according to claim 1, which is characterized in that the double solvents further includes inertia point
Powder, the inertia dispersing agent are hydro carbons and/or halogenated hydrocarbon.
3. vinyl polymerization major catalyst according to claim 2, which is characterized in that the inertia dispersing agent is selected from by oneself
At least one of alkane, heptane, octane, toluene, dimethylbenzene, 1,2- dichloroethanes, chlorocyclohexane and the formed group of chlorobenzene.
4. vinyl polymerization major catalyst according to claim 1, which is characterized in that the vinyl polymerization major catalyst is averaged
Particle size D50 is 10-30 microns.
5. vinyl polymerization major catalyst according to claim 1, which is characterized in that in step S3, slaking reaction 1 to 5 is small
When.
6. vinyl polymerization major catalyst according to claim 1, which is characterized in that in step S4, the atent solvent choosing
At least one of free iso-butane, pentane, hexane, heptane and the formed group of hexamethylene.
7. a kind of ethylene rolymerization catalyst, which is characterized in that including following components:
Vinyl polymerization major catalyst described in any one of claims 1-6；
Organo-aluminum compound is general formula AlRgX3-gAt least one of shown compound, in formula, R C1-C20Alkyl, X is
Halogen, g are integer and 1 < g ￡ 3.
8. ethylene rolymerization catalyst according to claim 7, which is characterized in that the organo-aluminum compound is by AlEt3、
Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3And AlEt2At least one of formed group of Cl.
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| CN101173014A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Catalyst for polymerization of ethylene or combined polymerization, producing method and application of the same |
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