CN107880180B

CN107880180B - Catalyst component for olefin polymerization, preparation method thereof and catalyst

Info

Publication number: CN107880180B
Application number: CN201610874981.1A
Authority: CN
Inventors: 王世波; 周俊领; 黄廷杰; 刘东兵; 张磊; 吕新平; 周歆; 张长礼
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2016-09-30
Filing date: 2016-09-30
Publication date: 2020-12-18
Anticipated expiration: 2036-09-30
Also published as: CN107880180A

Abstract

The invention provides a catalyst component for olefin polymerization, a preparation method thereof and a catalyst. The catalyst component comprises the reaction product of at least one organomagnesium compound, at least one liquid titanium-containing compound, at least one hydroxyl-containing compound, at least one chlorine-containing phosphorus-containing compound, and at least one additive, wherein the additive is a polystyrene block polymethylmethacrylate block-based polymer. The catalyst provided by the invention not only has good hydrogen regulation performance, but also has good particle shape and distribution, thereby being more beneficial to the use of the catalyst on polymerization process devices such as gas phase, slurry and the like.

Description

Catalyst component for olefin polymerization, preparation method thereof and catalyst

Technical Field

The invention belongs to the field of catalysts for olefin polymerization, and relates to a catalyst component for olefin polymerization, a preparation method thereof and a catalyst.

Background

In recent 20 years, with the development of olefin polymerization process, catalyst matched with olefin polymerization has been advanced, wherein high-efficiency catalyst has important position in the field of olefin polymerization by virtue of excellent catalytic performance and mature application technology. Through research and research for many years, the preparation method of the Mg-Ti series high-efficiency catalyst is developed into a chemical reaction method from a co-grinding method and a suspension impregnation method. Chinese patents CN158136, CN1795213 and US patents US4508843, US4921920 and US5124296 disclose that various catalysts of different types are prepared by using organic metal magnesium compound, chlorinating agent and transition metal titanium compound, and the like, and in the process of preparing the catalysts in these patents, the problem of difficulty in controlling the forming step exists, and further the morphology of the catalyst particles is affected. Recent studies have found that the particle morphology of the catalyst obtained can be improved by adding a substance like an emulsifier to a dispersion in which the catalyst precursor comprises a magnesium/titanium compound, forming an emulsion, and then precipitating the catalyst particles by reaction, and the use of perfluoropolyethers is disclosed in European patent No. 0258089 and perfluorooctane is disclosed in Chinese patent No. CN1537118, but the processes disclosed in these patents are complicated in forming steps and difficult to control, the morphology of the catalyst particles obtained is also difficult to control, and the substances used are expensive and costly.

Despite the considerable research work that has been done in the area of ziegler-natta catalysts, there is still a need for new or improved processes for the preparation of ZN catalysts with higher performance requirements.

Disclosure of Invention

The inventor finds out through repeated experiments that the synthesis process of the catalyst can be simple and easy by selecting proper additives, catalyst particles with good shapes and narrow particle size distribution can be obtained, and the catalyst has high catalytic activity and hydrogen regulation sensitivity.

It is a first object of the present invention to provide a catalyst component for the polymerization of olefins.

The catalyst component for olefin polymerization provided by the invention comprises the reaction product of components 1), 2), 3), 4) and 5), wherein the component 1) is at least one organic magnesium compound; component 2) is at least one titanium-containing compound, preferably a liquid titanium-containing compound; component 3) is at least one hydroxyl-containing compound; the component 4) is at least one chlorine-containing phosphorus-containing compound; and component 5) is at least one additive which is a polystyrene block polymethylmethacrylate block polymer (PS-b-PMMA).

According to a preferred embodiment of the present invention, the organomagnesium compound has the general formula (I) MgR¹ _nCl_2-nIn the formula, R¹Is C₂-C₂₀Alkyl, n is more than 0 and less than or equal to 2.

According to a preferred embodiment of the invention, the titanium-containing compound has the formula (II) Ti (OR)²)_nCl_4-nIn the formula, R²Is C₂-C₂₀Alkyl, m is more than or equal to 0 and less than or equal to 4.

According to a preferred embodiment of the invention, the hydroxyl group containing compound has the formula (III) HOR³In the formula, R³Is C₂-C₂₀A hydrocarbyl group.

According to a preferred embodiment of the invention, the chlorine-and phosphorus-containing compound is PCl₅Or a general formula of (IV) O_pPR⁴ _qCl_3-qIn the formula, R⁴Is C₂-C₂₀Alkyl or C₂-C₂₀Alkoxy, q is more than or equal to 0 and less than 3, and p is 0 or 1;

according to a preferred embodiment of the invention, the polystyrene block polymethylmethacrylate block polymer is selected from diblock, triblock and derivatives thereof, and may be in the form of other blocks, linear, branched and the like, branched and may include star, comb, dendritic and the like. Preferably, the polystyrene mass content of the polystyrene block polymethyl methacrylate block polymer is 5 wt% -95 wt%, preferably 10 wt% -90 wt%.

According to the invention, the hydrocarbon groups include alkyl, alkenyl and alkynyl groups, and may be linear, branched or cyclic. Said C is₂-C₂₀Examples of the hydrocarbon group of (1) include C₂-C₂₀Straight chain alkyl, C₃-C₂₀Branched alkyl radical, C₃-C₂₀Cycloalkyl radical, C₂-C₂₀Straight chain alkenyl, C₃-C₂₀Branched alkenyl, C₃-C₂₀Cycloalkenyl radical, C₂-C₂₀Straight chain alkynyl, C₃-C₂₀Branched alkynyl groups, and the like.

According to a preferred embodiment of the present invention, in the organomagnesium compound, R¹Is C₂-C₂₀Alkyl, particular compounds such as MgCl₂、MgEtCl、MgBu₂. Preferably, the organomagnesium compound is selected from at least one of dibutylmagnesium, diisobutylgagnesium, dioctylmagnesium, butyloctylmagnesium, ethylmagnesium chloride, and butylmagnesium chloride.

According to a preferred embodiment of the present invention, the titanium-containing compound is a tetravalent titanium compound, because the tetravalent titanium compound is generally in a liquid state at normal temperature and has good compatibility with a solvent. Preferably, the titanium-containing compound is at least one of titanium tetrachloride, tetraethyl titanate, and tetrabutyl titanate, more preferably titanium tetrachloride.

According to a preferred embodiment of the present invention, the hydroxyl group-containing compound is an aliphatic alcohol or an aromatic alcohol, preferably at least one of n-butanol, n-hexanol, isooctanol, benzyl alcohol and phenethyl alcohol.

According to a preferred embodiment of the present invention, the chlorine-containing phosphorus-containing compound is at least one selected from the group consisting of phosphorus methyl dichloride, phosphorus ethyl dichloride, phosphorus butyl dichloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, methyl dichlorophosphate, ethyl dichlorophosphate and butyl dichlorophosphate, preferably at least one selected from the group consisting of phosphorus trichloride, phosphorus pentachloride and phosphorus oxychloride.

It is a second object of the present invention to provide a process for preparing said catalyst component comprising the steps of:

1) reacting an organic magnesium compound with a hydroxyl-containing compound to obtain a transparent solution;

2) dispersing the additive in C₄-C₂₀Alkane or C₆-C₂₀Forming a solution in an aromatic hydrocarbon solvent, and mixing the solution with the transparent solution obtained in the step 1) to obtain a mixed solution;

3) sequentially adding chlorine-containing phosphorus-containing compound and titanium-containing compound into the mixed liquid obtained in the step 2) to obtain the catalyst component.

Preferably, in the preparation of said catalyst component, the proportions of the components are such that the titanium-containing compound is present in an amount of 0.01 to 10 moles, preferably 0.05 to 5 moles, per mole of organomagnesium compound; 0.1 to 20 moles, preferably 0.2 to 10 moles of a hydroxyl group-containing compound; 0.1-50 mol of chlorine-containing phosphorus-containing compound, preferably 0.5-20 mol; the concentration of the additive in the reaction system is 0.001-100g/L, preferably 0.01-50 g/L.

In step 1), the reaction temperature of the organomagnesium compound and the alcohol is advantageously selected to be relatively high, preferably below the boiling point of the reactants, and is generally not higher than 90 ℃ and generally not higher than 70 ℃. The time of reaction depends on the nature of the reactants and the operating conditions, and the time required is generally from 5 minutes to 2 hours, preferably from 10 minutes to 1 hour. After the reaction of the organomagnesium compound and the alcohol, the resulting solution can be used in admixture with an inert diluent, which is generally selected from aliphatic hydrocarbons, such as isobutane, pentane, hexane, heptane or cyclohexane and mixtures thereof, hexane or heptane being generally suitable inert solvents.

In the step 2), the modifying additive is dispersed in C₄-C₂₀Alkane or C₆-C₂₀The solvent is preferably dispersed in hexane, heptane or toluene and the mixture solvent thereof to form a solution, and then mixed with the transparent solution obtained in step 1) sufficiently, the solution preparation concentration is controlled to be 0.1-100 g/l, preferably 1-50g/l, according to the kind and property of the additive, and the amount added is such that the concentration of the additive in the reaction system is controlled to be 0.001-100g/l, preferably 0.01-50 g/l. The mixing temperature is generally below the boiling point of the system and is generally chosen, for convenience, between 0 and 90 c, preferably between 10 and 50 c. The mixing time of the two is generally selected from 0.5 minutes to 5 hours, preferably from 10 minutes to 1 hour.

In the step 3), the uniform mixing of all the substances is rapidly completed at a certain temperature, firstly the solution system obtained in the first two steps is reduced to a certain temperature, the solution still keeps clear and transparent at the temperature, the turbidity or the precipitation is not generated, the temperature can be controlled between-90 ℃ and 30 ℃, preferably between-70 ℃ and 0 ℃, then the chlorine-containing phosphorus-containing compound and the titanium-containing compound are gradually and slowly added in sequence, the full stirring is usually carried out in the feeding process so as to be beneficial to the full mixing of various substances, and the feeding speed is usually selected on the basis of not causing obvious reaction or obviously increasing the temperature of the system. After thorough mixing, the temperature can be raised by any known suitable method, such as slow, gradual, rapid or programmed temperature raising, and different temperature raising methods can obtain catalysts with different performance characteristics, during the temperature raising process, the system will change from clear to turbid and precipitate is separated out, in the precipitation reaction step, the reaction time of the precipitation step should be long enough to obtain complete precipitation, and the reaction time can last from 1 minute to 10 hours, preferably from 3 minutes to 5 hours.

It has been found that the aging treatment after the precipitation step at a certain temperature for a certain period of time is advantageous for the particle shape of the catalyst, and it can improve the strength of the catalyst particles, thereby reducing the particle breakage of the catalyst during the polymerization. The temperature of the aging treatment is generally equal to or higher than the final temperature of the precipitation reaction, and the time of the aging reaction may be controlled to 0.5 to 10 hours, preferably 1 to 5 hours.

After the maturation, washing is generally carried out to remove excess reactants and by-products formed during the preparation, any inert solvent can be used for this washing step, for example isobutane, pentane, hexane, heptane, cyclohexane, toluene or various aromatic hydrocarbons and mixtures thereof can be chosen, and in the experiments it was generally chosen to wash twice with toluene and then thoroughly with hexane. After washing, the catalyst suspension was dried under nitrogen to obtain a catalyst powder.

The catalyst prepared by the method has good hydrogen regulation performance and good particle shape and distribution, thereby being more beneficial to the use of the catalyst on polymerization process devices such as gas phase, slurry and the like.

A third object of the present invention is to provide a catalyst for olefin polymerization comprising the reaction product of:

a) the catalyst component of the present invention;

b) at least one of the general formula is AlR'₃Wherein R' "are the same or different C₁-C₈Wherein one or both alkyl groups may be substituted with chlorine.

According to an embodiment of the catalyst of the present invention, one or more kinds of alkylaluminum may be selected and used in combination, preferably AlEt₃、Al(iso-Bu)₃、Al(n-C₆H₁₃)₃、Al(n-C₈H₁₇)₃Or AlEt₂At least one of Cl.

The catalyst is used in a manner well known in the art for Ziegler-Natta catalysts, such as with another cocatalyst or electron donor, and the catalyst may also be used in combination with one or more Ziegler-Natta catalysts or non-Ziegler-Natta catalysts.

A fourth object of the invention is to provide the use of said catalyst in olefin polymerization reactions.

The catalyst provided by the invention is suitable for various olefins capable of carrying out coordination polymerization, and comprises homopolymerization of one olefin or copolymerization of a plurality of olefins, wherein the olefin is preferably alpha-olefin such as ethylene, propylene, butylene and the like, or a mixture of ethylene, propylene, butylene and one or more alpha-olefins. The preferred comonomer is C₂-C₁₂Olefins, preferably C₄-C₁₀Olefins such as 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methyl-1-pentene, dienes such as butadiene, 1, 4-hexadiene and 1, 7-octadiene, cycloalkenes such as norbornene, and any mixtures thereof.

The catalysts of the present invention are suitable for use in polymerization reactions, including gas phase, slurry and bulk polymerization reactions, which may be batch or continuous polymerization processes, in one or more polymerization reactors using conventional polymerization techniques.

For slurry or bulk reactors, the reaction temperature is 40 to 130 ℃, preferably 60 to 110 ℃; the reactor pressure is 0.2-8MPa, preferably 1-6 MPa; the residence time is generally from 0.2 to 6 hours, preferably from 0.5 to 3 hours. Aliphatic hydrocarbons having a boiling point in the range from-70 to 100 ℃ are generally selected for use as diluents, and the polymerization can be carried out under supercritical conditions, if desired.

For gas phase reactors, the reaction temperature is 60 to 130 ℃, preferably 70 to 110 ℃; the reactor pressure is generally between 0.5 and 4MPa, preferably between 1 and 3 MPa; the residence time is from 0.5 to 10 hours, preferably from 1 to 8 hours. If desired, the polymerization can be carried out under condensed conditions by using an appropriate aliphatic hydrocarbon as a diluent.

The amount of catalyst generally depends on the nature of the catalyst, the type of reactor and the operating conditions and the properties required for the polymer product, and conventional amounts of catalyst are generally selected.

The catalyst of the present invention has high catalytic activity, high hydrogen sensitivity and excellent comprehensive performance.

Detailed Description

The test method comprises the following steps:

1. particle size distribution of support and catalyst: MASTERSIZE particle size distribution instrument with n-hexane as dispersant, and has measurement range of 0.02-2000 μm.

2. Relative weight percentages of metals (mainly titanium, magnesium) in the catalyst system: plasma emission spectroscopy (ICP).

3. Morphology of catalyst and polymer: scanning Electron Microscopy (SEM).

4. Melt index MI_2.16The determination of (1): ASTM-D1238.

4. Measurement of bulk density BD: DIN-53194.

The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

Example 1

Taking 30ml of toluene, 3.15ml of dibutyl magnesium hexane solution (1M) and 1.0ml of isooctanol in sequence, heating to 50 ℃, maintaining stirring and reacting for half an hour to obtain a transparent solution, then adding 2ml of toluene solution (10g/L) of polystyrene block polymethyl methacrylate copolymer (polystyrene content is 48 wt%), cooling to-50 ℃, adding 0.6 ml of phosphorus trichloride and 0.35ml of titanium tetrachloride in sequence, after the materials are added, quickly heating to 50 ℃ within 10 minutes, and maintaining the reaction for 2 hours. Cooling the catalyst suspension to room temperature, standing, settling, washing with toluene three times, wherein the amount of toluene is 50 ml each time, washing with hexane twice, wherein the amount of hexane is 50 ml each time, and drying to obtain brown solid flowable powder with the average particle size of 20.6 microns after washing.

Elemental analysis (ICP): 10.11 wt% of Ti and 16.20 wt% of Mg.

Evaluation of ethylene polymerization: 1L of hexane, 1mmol of triethylaluminum and a certain amount of catalyst are added into a 2L stainless steel stirring kettle, then the temperature is raised to 85 ℃, 0.18MPa of hydrogen is added at a time, then the total pressure of the system is maintained at 1.03MPa by using ethylene for polymerization reaction, after 2 hours of reaction, the addition of ethylene is stopped, the temperature is reduced, the pressure is relieved, polyethylene powder is weighed, the activity of the catalyst is calculated, and the bulk density and the melt index under the load of 2.16Kg of the polyethylene powder are tested, and the results are shown in Table 1.

Example 2

The catalyst component used in the preparation of the catalyst was changed to 1ml of titanium tetrachloride under the same conditions as in example 1 except that the average particle diameter of the catalyst component was 26.9. mu.m.

Elemental analysis (ICP): 12.28 wt% of Ti and 19.45 wt% of Mg.

The evaluation conditions for slurry polymerization of ethylene in the catalyst were the same as in example 1, and the polymerization results are shown in Table 1.

Example 3

1.0ml of isooctanol in the preparation process of the catalyst is changed into 3.0ml of isooctanol, the temperature is quickly raised to 50 ℃ within 10 minutes, the temperature is naturally and slowly raised to room temperature, then the temperature is raised to 50 ℃, the other conditions are the same as the example 1, and the average particle size of the catalyst component is 22.6 microns.

Elemental analysis (ICP): 11.64 wt% of Ti and 16.27 wt% of Mg.

Comparative example 1

The toluene solution (10g/L) of polystyrene block polymethyl methacrylate copolymer (polystyrene content: 48 wt%) added during the catalyst preparation was removed under the same conditions as in example 1, and the average particle size was 64.76 μm, and the particle size distribution was broad and multimodal.

Elemental analysis (ICP): 10.07 wt% of Ti and 13.16 wt% of Mg.

Comparative example 2

30ml of hexane, 3.15ml of dibutyl magnesium hexane solution (1M) and 1.0ml of isooctanol are taken in sequence, the temperature is raised to 50 ℃, stirring reaction is maintained for half an hour, a transparent solution is obtained, 3ml of Kraton FG1901 hexane solution (10g/L) is added, the temperature is lowered to-50 ℃, 0.6 ml of phosphorus trichloride and 0.35ml of titanium tetrachloride are added in sequence, after the materials are added, the temperature is raised to 50 ℃ rapidly within 10 minutes, and the reaction is maintained for 2 hours. The catalyst suspension was cooled to room temperature, allowed to stand, settled, washed three times with 50 ml of hexane each time, and after washing, dried to give a brown solid flowable powder having an average particle size of 17.6 microns.

Elemental analysis (ICP): 9.86% by weight of Ti and 12.69% by weight of Mg.

TABLE 1

As can be seen from the experimental data of the examples and comparative examples in Table 1, when the polystyrene block polymethyl methacrylate block polymer additive is used in the preparation process of the catalyst, the obtained catalyst and polymer have good particle morphology, the Bulk Density (BD) of the polymer resin is higher, and the melt index of the polymer is high under the same polymerization conditions, which indicates that the catalyst has good hydrogen regulation performance. The catalyst has excellent comprehensive performance.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims

1. A catalyst component for the polymerization of olefins comprising the reaction product of components 1), 2), 3), 4) and 5), wherein component 1) is at least one organomagnesium compound; component 2) is at least one titanium-containing compound; component 3) is at least one hydroxyl-containing compound; the component 4) is at least one chlorine-containing phosphorus-containing compound; and component 5) is at least one additive, the additive is a polystyrene block polymethyl methacrylate block polymer, the polystyrene content in the polystyrene block polymethyl methacrylate block polymer is 5 wt% -95 wt%, and the titanium-containing compound accounts for 0.01-10 mol per mol of the organic magnesium compound; 0.2-10 mol of hydroxyl-containing compound; 0.5-20 mol of chlorine-containing phosphorus-containing compound; the concentration of the additive in the reaction system is 0.001-100 g/L.

2. The catalyst component according to claim 1 in which the organomagnesium compound has the general formula (I) MgR¹ _nCl_2-nIn the formula, R¹Is C₂-C₂₀Alkyl, n is more than 0 and less than or equal to 2.

3. The catalyst component according to claim 2 in which R is in the formula¹Is C₂-C₂₀And n is more than 0 and less than or equal to 2.

4. The catalyst component according to claim 3 in which the organomagnesium compound is chosen from at least one of dibutylmagnesium, diisobutylgagnesium, dioctylmagnesium, butyloctylmagnesium, ethylmagnesium chloride and butylmagnesium chloride.

5. The catalyst component according to claim 1 in which the titanium-containing compound has the formula (II) Ti (OR)²)_mCl_4-mIn the formula, R²Is C₂-C₂₀Alkyl, m is more than or equal to 0 and less than or equal to 4.

6. The catalyst component according to claim 5 in which the titanium-containing compound is a tetravalent titanium compound.

7. The catalyst component of claim 6 wherein the titanium-containing compound is at least one of titanium tetrachloride, tetraethyl titanate, and tetrabutyl titanate.

8. The catalyst component according to claim 1 in which the hydroxyl group containing compound has the formula (III) HOR³In the formula, R³Is C₂-C₂₀A hydrocarbyl group.

9. The catalyst component according to claim 8 in which the hydroxyl group containing compound is selected from at least one of n-butanol, n-hexanol, isooctanol, benzyl alcohol and phenethyl alcohol.

10. The catalyst component according to claim 1 in which the chlorine-and phosphorus-containing compound is PCl₅Or a general formula of (IV) O_pPR⁴ _qCl_3-qIn the formula, R⁴Is C₂-C₂₀Alkyl or C₂-C₂₀Alkoxy, q is more than or equal to 0 and less than 3, and p is 0 or 1.

11. The catalyst component according to claim 10 in which the chlorine-containing phosphorus-containing compound is at least one selected from the group consisting of phosphorus methyl dichloride, phosphorus ethyl dichloride, phosphorus butyl dichloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, methyl dichlorophosphate, ethyl dichlorophosphate and butyl dichlorophosphate.

12. The catalyst component of claim 10 in which the phosphorus-containing compound is at least one of phosphorus trichloride, phosphorus pentachloride and phosphorus oxychloride.

13. The catalyst component according to any of claims 1 to 12 in which the polystyrene block polymethylmethacrylate block polymer comprises di-and tri-blocks and derivatives thereof.

14. The catalyst component according to any of claims 1 to 12 in which the polystyrene block polymethylmethacrylate block polymer is in linear, branched or star form.

15. The catalyst component according to any of claims 1 to 12 in which the polystyrene content of the polystyrene block polymethylmethacrylate block polymer is between 10% and 90% by weight.

16. A process for preparing the catalyst component of any one of claims 1 to 15, comprising the steps of:

17. The method as set forth in claim 16, wherein the titanium-containing compound is present in an amount of 0.05 to 5 moles per mole of the organomagnesium compound; 0.2-10 mol of hydroxyl-containing compound; 0.5-20 mol of chlorine-containing phosphorus-containing compound; the concentration of the additive in the reaction system is 0.01-50 g/L.

18. A catalyst for the polymerization of olefins comprising the reaction product of:

a) the catalyst component of any one of claims 1 to 15 or obtained according to the process of claim 16 or 17;

19. Use of the catalyst of claim 18 in olefin polymerization reactions.

20. Use according to claim 19, wherein the olefin is an alpha-olefin.

21. The use according to claim 20, wherein the olefin is at least one of ethylene, propylene, butene and octene.