阅读说明：本技术 固体催化剂及其制备方法与应用 (Solid catalyst, preparation method and application thereof ) 是由 郭正阳 唐璐 刘萃莲 雷世龙 王迎 于 2019-10-28 设计创作，主要内容包括：本发明涉及烯烃聚合领域,公开了一种固体催化剂的制备方法,包括以下步骤：(1)将镁化合物溶解于包含有机环氧化合物、有机磷化合物和惰性稀释剂I的混合溶液中,进行第一反应得到均匀溶液；(2)在第一温度下,将助析出剂和钛化合物I加入所述均匀溶液中,升温至第二温度后,加入给电子体,进行第二反应,经过滤制得固体颗粒；(3)将所述固体颗粒用钛化合物II和惰性稀释剂II洗涤、干燥后得到所述固体催化剂；所述助析出剂的通式为：H-2C＝CR-1COOR-2,R-1为氢、C-1-C-6的烷基或苯基,R-2为C-1-C-(20)的烷基、环烷基、芳基、烷芳基或芳烷基；所述第一温度小于第一反应温度。该方法能够在保持催化剂的催化活性的前提下,降低制备过程中钛化合物的用量,降低生产的成本。(The invention relates to the field of olefin polymerization, and discloses a preparation method of a solid catalyst, which comprises the following steps: (1) dissolving a magnesium compound in a mixed solution containing an organic epoxy compound, an organic phosphorus compound and an inert diluent I, and carrying out a first reaction to obtain a uniform solution; (2) adding a precipitation aid and a titanium compound I into the uniform solution at a first temperature, heating to a second temperature, adding an electron donor, carrying out a second reaction, and filtering to obtain solid particles; (3) washing the solid particles with a titanium compound II and an inert diluent II, and drying to obtain the solid catalyst; the general formula of the precipitation aid is as follows: h 2 C＝CR 1 COOR 2 ，R 1 Is hydrogen, C 1 ‑C 6 Alkyl or phenyl of R 2 Is C 1 ‑C 20 Alkyl group of (A) or (B),Cycloalkyl, aryl, alkaryl, or aralkyl; the first temperature is less than the first reaction temperature. The method can reduce the dosage of the titanium compound in the preparation process and reduce the production cost on the premise of keeping the catalytic activity of the catalyst.)

1. A method for preparing a solid catalyst, wherein the method comprises the steps of:

(1) dissolving a magnesium compound in a mixed solution containing an organic epoxy compound, an organic phosphorus compound and an inert diluent I, and carrying out a first reaction to obtain a uniform solution;

(2) adding a precipitation aid and a titanium compound I into the uniform solution at a first temperature, heating to a second temperature, adding an electron donor, carrying out a second reaction, and filtering to obtain solid particles;

(3) washing the solid particles with a titanium compound II and an inert diluent II, and drying to obtain the solid catalyst;

wherein the general formula of the precipitation aid is as follows: h₂C＝CR₁COOR₂Wherein R is₁Is hydrogen, C₁-C₆Alkyl or phenyl of R₂Is C₁-C₂₀Alkyl, cycloalkyl, aryl, alkaryl or aralkyl groups of (a);

the first temperature is less than the first reaction temperature.

2. The preparation method according to claim 1, wherein per mole of the magnesium compound, the organic epoxy compound is 0.2 to 10 moles, the organic phosphorus compound is 0.1 to 3 moles, the inert diluent I is 5 to 25 moles, the precipitation assistant is 0.01 to 1 mole, the titanium compound I is 0.5 to 15 moles, the electron donor is 0.005 to 15 moles, the titanium compound II is 3 to 15 moles, and the inert diluent II is 5 to 25 moles;

preferably, per mole of the magnesium compound, the organic epoxy compound is 0.5-4 moles, the organic phosphorus compound is 0.3-1 mole, the inert diluent I is 10-20 moles, the precipitation assistant is 0.05-0.5 mole, the titanium compound I is 1-10 moles, the electron donor is 0.06-10 moles, the titanium compound II is 5-10 moles, and the inert diluent II is 10-20 moles.

3. The production method according to claim 1 or 2, wherein in the step (1), the magnesium compound comprises at least one of a halide of magnesium, an alcoholate of magnesium, and a haloalcoholate of magnesium, preferably a magnesium halide;

preferably, the organic epoxy compound comprises at least one of an oxide of an aliphatic olefin having 2 to 8 carbon atoms, an oxide of a halogenated aliphatic olefin, an oxide of a diene, a glycidyl ether and an internal ether, preferably at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene monoepoxide, butadiene diepoxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether;

preferably, the organophosphorus compound comprises at least one of a hydrocarbyl orthophosphate, a halogenated hydrocarbyl orthophosphate, a hydrocarbyl phosphite, and a halogenated hydrocarbyl phosphite, preferably at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzyl phosphite;

the inert diluent I and the inert diluent II are respectively and independently selected from at least one of hexane, heptane, octane, decane, benzene, toluene and xylene, and toluene is preferred.

4. The production method according to any one of claims 1 to 3, wherein in step (1), the reaction conditions of the first reaction include: the reaction temperature is 40-70 ℃, the reaction time is 0.5-3h, preferably, the reaction temperature is 45-65 ℃, and the reaction time is 1-2 h.

5. The production method according to any one of claims 1 to 4, wherein the general formulae of the titanium compound I and the titanium compound II are each independently Ti (OR)₃)_4-aX_aWherein R is₃Is C₁-C₁₄X is halogen, a is an integer from 1 to 4;

preferably, the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxytitanium trichloride, triethoxy titanium chloride, diethoxy titanium dichloride and ethoxytitanium trichloride;

preferably, the precipitation-aiding agent is at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, lauryl methacrylate and stearyl methacrylate; preferably at least one of methyl acrylate, methyl methacrylate and stearyl methacrylate;

preferably, the electron donor is at least one of an ester electron donor, an ether electron donor and a ketone electron donor; preferably at least one of alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, alkyl, cycloalkyl, aryl, alkaryl, alkyl esters, aliphatic ethers, cycloaliphatic ethers, aliphatic diethers, and aliphatic ketones of polyols; more preferably C₁-C₄Alkyl esters of saturated fatty carboxylic acids, C₇-C₈Alkyl esters of aromatic carboxylic acids, C₂-C₁₀Aryl esters of dihydric alcohols, C₂-C₆Fatty ethers, C₃-C₄Cyclic ether, C₅-C₂₀Aliphatic diethers and C₃-C₆At least one of saturated aliphatic ketones.

6. The method according to claim 5, wherein the electron donor is methyl formate, ethyl acetate, butyl acetate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, 3, 5-heptanediol dibenzoate, diethyl ether, hexyl ether, tetrahydrofuran, 2-R₄-2-R₅At least one of-1, 3-dimethoxypropane, acetone and methyl isobutyl ketone, wherein R₄And R₅Which may be the same or different, R₄And R₅Is hydrogen, C₁-C₁₆Straight chain alkyl or C₁-C₁₆A branched alkyl group;

preferably, the electron donor is at least one of di-n-butyl phthalate, diisobutyl phthalate, 3, 5-heptanediol dibenzoate and 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane;

more preferably, the electron donor is 3, 5-heptanediol dibenzoate and/or 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane.

7. The production method according to any one of claims 1 to 6, wherein, in the step (2), the first temperature is from-50 to 50 ℃, preferably from-30 to 20 ℃;

the second temperature is 60-110 ℃, and preferably 70-100 ℃;

the reaction conditions of the second reaction include: the reaction temperature is 60-110 ℃, and the reaction time is 0.5-3 h; preferably, the reaction temperature is 70-100 ℃ and the reaction time is 1-2 h.

8. A solid catalyst obtained by the production method according to any one of claims 1 to 7.

9. The solid catalyst according to claim 8, wherein the content of titanium in the solid catalyst is 0.8-4 wt%, preferably 1-3 wt%.

10. Use of a solid catalyst according to claim 8 or 9 in the polymerisation of olefins.

Technical Field

The invention relates to the field of olefin polymerization, in particular to a solid catalyst and a preparation method and application thereof.

Background

Due to the explosive development of the polyolefin industry and the wide demand for polyolefin products, research into catalysts for olefin polymerization or copolymerization has been continuously conducted. Research researches of researchers find that magnesium chloride and titanium trichloride have similar molecular structures, the specific surface area of the catalyst can be greatly improved by adopting the magnesium chloride as a carrier, the loading effect of an active titanium compound is better, the activity of the catalyst is obviously improved, and therefore, extensive research on a titanium-magnesium system catalyst is promoted.

The titanium-magnesium system catalyst has two types, one is a supported or supported titanium-magnesium catalyst, and the other is a coprecipitation or dissolution precipitation type titanium-magnesium catalyst. According to literature reports, the structure of the solution precipitation type titanium magnesium catalyst depends more on the preparation method of the catalyst. In general, the preparation process first obtains complex primary microcrystals generated by the reaction of magnesium halide, Lewis base and titanium tetrahalide, then under certain conditions, the primary microcrystals are aggregated and grown into secondary microcrystals, and the final catalyst is obtained after the aggregation and growth are carried out for a plurality of times.

CN85100997A discloses a method for preparing a catalyst system (N catalyst system) for olefin polymerization and copolymerization, wherein the necessity of the presence of a precipitation aid in the catalyst system is mentioned. In the system, if no precipitation aid is added in the precipitation process, only the polybasic carboxylic ester and the titanium tetrahalide are added, only a colloidal solution can be formed, but solid substances cannot be precipitated from a magnesium halide solution, and the solid substances can be precipitated from the solution only by adding the corresponding precipitation aid. This shows that the precipitation aid has a certain promoting effect on the growth of the titanium-magnesium complex microcrystal. The auxiliary precipitation agent comprises organic acid anhydride, organic acid, organic ether, organic ketone and other compounds, and specifically comprises the following components: acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, and the like. However, a large amount of titanium compound is used in the preparation process, and a large amount of titanium waste liquid is generated, so that the production cost is greatly increased.

Disclosure of Invention

The invention aims to solve the problem of overhigh dosage of a titanium compound when a solid catalyst is prepared in the prior art, and provides the solid catalyst, and a preparation method and application thereof.

In order to achieve the above object, a first aspect of the present invention provides a method for preparing a solid catalyst, wherein the method comprises the steps of:

(1) dissolving a magnesium compound in a mixed solution containing an organic epoxy compound, an organic phosphorus compound and an inert diluent I, and carrying out a first reaction to obtain a uniform solution;

(2) adding a precipitation aid and a titanium compound I into the uniform solution at a first temperature, heating to a second temperature, adding an electron donor, carrying out a second reaction, and filtering to obtain solid particles;

(3) washing the solid particles with a titanium compound II and an inert diluent II, and drying to obtain the solid catalyst;

wherein the general formula of the precipitation aid is as follows: h₂C＝CR₁COOR₂Wherein R is₁Is hydrogen, C₁-C₆Alkyl or phenyl of R₂Is C₁-C₂₀Alkyl, cycloalkyl, aryl, alkaryl or aralkyl of；

The first temperature is less than the first reaction temperature.

Preferably, per mole of magnesium compound, the organic epoxy compound is 0.2-10 moles, the organic phosphorus compound is 0.1-3 moles, the inert diluent I is 5-25 moles, the precipitation promoter is 0.01-1 mole, the titanium compound I is 0.5-15 moles, the electron donor is 0.005-15 moles, the titanium compound II is 3-15 moles, and the inert diluent II is 5-25 moles.

More preferably, per mole of the magnesium compound, the organic epoxy compound is 0.5 to 4 moles, the organic phosphorus compound is 0.3 to 1 mole, the inert diluent I is 10 to 20 moles, the precipitation promoter is 0.05 to 0.5 mole, the titanium compound I is 1 to 10 moles, the electron donor is 0.06 to 10 moles, the titanium compound II is 5 to 10 moles, and the inert diluent II is 10 to 20 moles.

Preferably, in step (1), the magnesium compound includes at least one of a halide of magnesium, an alcoholate of magnesium, and a haloalcoholate of magnesium, preferably a magnesium halide.

Preferably, the organic epoxy compound comprises at least one of an oxide of an aliphatic olefin having 2 to 8 carbon atoms, an oxide of a halogenated aliphatic olefin, an oxide of a diene, a glycidyl ether and an internal ether, and preferably at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene monoepoxide, butadiene diepoxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether.

Preferably, the organophosphorus compound includes at least one of a hydrocarbyl orthophosphate, a halogenated hydrocarbyl orthophosphate, a hydrocarbyl phosphite, and a halogenated hydrocarbyl phosphite, preferably at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzyl phosphite.

Preferably, the inert diluent I and the inert diluent II are each independently selected from at least one of hexane, heptane, octane, decane, benzene, toluene and xylene, preferably toluene.

Preferably, in step (1), the reaction conditions of the first reaction include: the reaction temperature is 40-70 ℃, and the reaction time is 0.5-3 h.

More preferably, the reaction temperature is 45-65 ℃ and the reaction time is 1-2 h.

Preferably, in step (2), the titanium compound I and the titanium compound II have the general formula of Ti (OR) independently₃)_{4- a}X_aWherein R is₃Is C₁-C₁₄X is halogen and a is an integer from 1 to 4.

More preferably, the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxytitanium trichloride, triethoxy titanium chloride, diethoxy titanium dichloride, and ethoxytitanium trichloride.

Preferably, the precipitation assistant is at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, lauryl methacrylate and stearyl methacrylate.

More preferably, the precipitation assistant is at least one of methyl acrylate, methyl methacrylate and stearyl methacrylate.

Preferably, the electron donor is at least one of an ester electron donor, an ether electron donor and a ketone electron donor; preferably at least one of alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, alkyl, cycloalkyl, aryl, alkaryl, alkyl esters, aliphatic ethers, cycloaliphatic ethers, aliphatic diethers, and aliphatic ketones of polyols; more preferably C₁-C₄Alkyl esters of saturated fatty carboxylic acids, C₇-C₈Alkyl esters of aromatic carboxylic acids, C₂-C₁₀Aryl esters of dihydric alcohols, C₂-C₆Fatty ethers, C₃-C₄Cyclic ether, C₅-C₂₀Aliphatic diethers and C₃-C₆At least one of saturated aliphatic ketones.

Preferably, the electron donor is methyl formate, ethyl acetate, butyl acetate, diisobutyl phthalate, phthalic acidDi-n-butyl ester, diisooctyl phthalate, 3, 5-heptanediol dibenzoate, diethyl ether, hexyl ether, tetrahydrofuran, 2-R₄-2-R₅At least one of-1, 3-dimethoxypropane, acetone and methyl isobutyl ketone, wherein R₄And R₅Which may be the same or different, R₄And R₅Is hydrogen, C₁-C₁₆Straight chain alkyl or C₁-C₁₆A branched alkyl group.

More preferably, the electron donor is at least one of di-n-butyl phthalate, diisobutyl phthalate, 3, 5-heptanediol dibenzoate, and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.

Still more preferably, the electron donor is 3, 5-heptanediol dibenzoate and/or 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane.

Preferably, in step (2), the first temperature is from-50 to 50 ℃, preferably from-30 to 20 ℃.

Preferably, the second temperature is 60 to 110 ℃, preferably 70 to 100 ℃.

Preferably, the reaction conditions of the second reaction include: the reaction temperature is 60-110 ℃, and the reaction time is 0.5-3 h; more preferably, the reaction temperature is 70-100 ℃ and the reaction time is 1-2 h.

In a second aspect, the present invention provides a solid catalyst obtained by the preparation method of the present invention.

Preferably, the titanium content of the solid catalyst is between 0.8 and 4 wt%, preferably between 1 and 3 wt%.

In a third aspect, the present invention provides a use of the solid catalyst of the present invention in olefin polymerization.

Through the technical scheme, the solid catalyst and the preparation method and application thereof provided by the invention have the following beneficial technical effects:

when the method is used for preparing the catalyst, the acrylic ester compound is added in the precipitation process as the precipitation aid to replace the conventional precipitation aid in the prior art, the catalyst for olefin polymerization can be prepared by adopting a specific preparation method, the use amount of the titanium compound in the precipitation process can be reduced on the premise of keeping the catalytic activity of the catalyst, the production cost can be reduced, and the generation of titanium-containing waste liquid can be reduced.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The first aspect of the present invention provides a method for preparing a solid catalyst, wherein the method comprises the steps of:

(1) dissolving a magnesium compound in a mixed solution containing an organic epoxy compound, an organic phosphorus compound and an inert diluent I, and carrying out a first reaction to obtain a uniform solution;

(2) adding a precipitation aid and a titanium compound I into the uniform solution at a first temperature, heating to a second temperature, adding an electron donor, carrying out a second reaction, and filtering to obtain solid particles;

(3) washing the solid particles with a titanium compound II and an inert diluent II, and drying to obtain the solid catalyst;

wherein the general formula of the precipitation aid is as follows: h₂C＝CR₁COOR₂Wherein R is₁Is hydrogen, C₁-C₆Alkyl or phenyl of R₂Is C₁-C₂₀Alkyl, cycloalkyl, aryl, alkaryl or aralkyl groups of (a);

the first temperature is less than the first reaction temperature.

In the invention, the general formula is H₂C＝CR₁COOR₂The auxiliary precipitating agent replaces the traditional auxiliary precipitating agent in the prior art, and when the method is used for preparing the solid catalyst, the method can obviously reduce the preparation time of the solid catalyst when obtaining the solid catalyst with similar or even higher catalytic activityThe required dosage of the titanium compound reduces the generation of titanium waste liquid in the preparation process of the catalyst and reduces the production cost.

According to the invention, per mole of magnesium compound, 0.2-10 moles of organic epoxy compound, 0.1-3 moles of organic phosphorus compound, 5-25 moles of inert diluent I, 0.01-1 mole of precipitation promoter, 0.5-15 moles of titanium compound I, 0.005-15 moles of electron donor, 3-15 moles of titanium compound II and 5-25 moles of inert diluent II are used.

Preferably, per mole of magnesium compound, the organic epoxy compound is 0.5-4 moles, the organic phosphorus compound is 0.3-1 mole, the inert diluent I is 10-20 moles, the precipitation assistant is 0.05-0.5 mole, the titanium compound II is 1-10 moles, the electron donor is 0.06-10 moles, the titanium compound II is 5-10 moles, and the inert diluent II is 10-20 moles.

According to the invention, in step (1), the magnesium compound comprises at least one of a halide of magnesium, an alcoholate of magnesium and a haloalcoholate of magnesium, preferably a magnesium halide.

According to the invention, the organic epoxy compound comprises at least one of an oxide of an aliphatic olefin having 2 to 8 carbon atoms, an oxide of a halogenated aliphatic olefin, an oxide of a diene, a glycidyl ether and an internal ether, preferably at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene monoepoxide, butadiene diepoxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether.

According to the present invention, the organophosphorus compound includes at least one of a hydrocarbyl orthophosphate, a halogenated hydrocarbyl orthophosphate, a hydrocarbyl phosphite, and a halogenated hydrocarbyl phosphite, and is preferably at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzyl phosphite.

According to the invention, the inert diluent I and the inert diluent II are each independently selected from at least one of hexane, heptane, octane, decane, benzene, toluene and xylene, preferably toluene.

According to the present invention, in step (1), the reaction conditions of the first reaction include: the reaction temperature is 40-70 ℃, and the reaction time is 0.5-3 h.

Preferably, the reaction temperature is 45-65 ℃ and the reaction time is 1-2 h.

According to the invention, in step (2), the titanium compound I and the titanium compound II are each independently of the other Ti (OR)₃)_4-aX_aWherein R is₃Is C₁-C₁₄X is halogen and a is an integer from 1 to 4.

Preferably, the titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxytitanium trichloride, triethoxy titanium chloride, diethoxy titanium dichloride and ethoxytitanium trichloride.

According to the invention, the precipitation-aiding agent is at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, lauryl methacrylate and stearyl methacrylate.

Preferably, at least one of methyl acrylate, methyl methacrylate, stearyl methacrylate.

According to the invention, the electron donor is at least one of an ester electron donor, an ether electron donor and a ketone electron donor; preferably at least one of alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, alkyl, cycloalkyl, aryl, alkaryl, alkyl esters, aliphatic ethers, cycloaliphatic ethers, aliphatic diethers, and aliphatic ketones of polyols; more preferably C₁-C₄Alkyl esters of saturated fatty carboxylic acids, C₇-C₈Alkyl esters of aromatic carboxylic acids, C₂-C₁₀Aryl esters of dihydric alcohols, C₂-C₆Fatty ethers, C₃-C₄Cyclic ether, C₅-C₂₀Aliphatic diethers and C₃-C₆At least one of saturated aliphatic ketones.

According to the invention, the electron donor is methyl formate, ethyl acetate, butyl acetate,Diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, 3, 5-heptanediol dibenzoate, diethyl ether, hexyl ether, tetrahydrofuran, 2-R₄-2-R₅At least one of-1, 3-dimethoxypropane, acetone and methyl isobutyl ketone, wherein R₄And R₅Which may be the same or different, R₄And R₅Is hydrogen, C₁-C₁₆Straight chain alkyl or C₁-C₁₆A branched alkyl group.

Preferably, the electron donor is at least one of di-n-butyl phthalate, diisobutyl phthalate, 3, 5-heptanediol dibenzoate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.

More preferably, the electron donor is 3, 5-heptanediol dibenzoate and/or 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane.

In a specific embodiment of the present invention, when the solid catalyst is prepared, the precipitation aid of the present invention is used to cooperate with the electron donor 3, 5-heptanediol dibenzoate and/or 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, which not only can significantly reduce the amount of titanium compound required in the preparation process and reduce the generation of titanium waste liquid in the catalyst preparation process, but also can improve the catalytic activity of the prepared solid catalyst.

In the invention, the inventor researches and discovers that the precipitation assistant can be added into a uniform solution containing a magnesium compound under the condition of low temperature, so that the reaction time can be shortened, the catalyst component can be still precipitated, and meanwhile, the higher catalytic activity can be maintained under the condition of less dropwise adding titanium.

Specifically, in the present invention, the first temperature is lower than the first reaction temperature.

Further, the inventors have studied and found that the amount of the titanium compound to be used can be further reduced when the first temperature is-50 to 50 ℃, preferably-30 to 20 ℃.

According to the invention, the second temperature is between 60 and 110 ℃, preferably between 70 and 100 ℃.

According to the invention, the reaction conditions of the second reaction comprise: the reaction temperature is 60-110 ℃, and the reaction time is 0.5-3 h; more preferably, the reaction temperature is 70-100 ℃ and the reaction time is 1-2 h.

In a second aspect, the present invention provides a solid catalyst obtained by the preparation method of the present invention.

According to the invention, the titanium content of the solid catalyst is between 0.8 and 4 wt.%, preferably between 1 and 3 wt.%.

In a third aspect, the present invention provides a use of the solid catalyst of the present invention in olefin polymerization.

The present invention will be described in detail below by way of examples. In the following examples, the titanium content of the solid catalyst was measured on a spectrophotometer and measured by a hydrogen peroxide colorimetry.

The catalytic activities of the solid catalysts of the present examples and comparative examples were obtained by calculating the ratio of the amount of the olefin polymer obtained in the polymerization experiment to the amount of the catalyst used.

The polymerization experimental conditions were as follows: a5-liter stainless steel autoclave fully purged with nitrogen was charged with 5 ml of a hexane solution of Triethylaluminum (TEA) having a concentration of 0.5 mol/liter and 1 ml of a hexane solution of methylcyclohexyldimethoxysilane (CMMS) having a concentration of 1 mol/liter and 10 mg of the catalyst prepared in example or comparative example, and then 10 ml of hexane was added to flush the feed line, 1 liter (in a standard state) of hydrogen and 2 liters of purified propylene were added, and the temperature was raised to 70 ℃ to make the hydrogen partial pressure 0.2 MPa, at which temperature the polymerization was carried out for 1 hour. After the reaction is finished, cooling the reaction kettle, stopping stirring, and discharging reaction products to obtain the olefin polymer.

The raw materials used in the examples and comparative examples are commercially available products.

In the following examples and comparative examples, the kinds and amounts of the precipitation aid and electron donor, the amount of titanium added to the mother solution of the catalyst, and the content of titanium in the catalyst are shown in Table 1, wherein MMA represents methyl methacrylate, MA represents acrylate, SMA represents octadecyl methacrylate, phthalic anhydride represents phthalic anhydride, DNPB represents di-n-butyl phthalate, glycol ester represents 3, 5-heptanediol dibenzoate, and diether represents 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.

Example 1

0.05mol of anhydrous magnesium chloride, 0.658mol of toluene, 0.051mol of epichlorohydrin and 0.046mol of tributyl phosphate are sequentially added into a reaction kettle repeatedly replaced by high-purity nitrogen, the reaction is carried out for 1.5 hours at the temperature of 62 ℃, 0.376mol of toluene is additionally added, the temperature is reduced to-28 ℃, 0.007mol of methyl methacrylate is added, 0.118mol of titanium tetrachloride is dropwise added, the temperature is increased to 85 ℃ within 5 hours, 0.004mol of di-n-butyl phthalate is added at the temperature of 80 ℃, the temperature is kept constant at 85 ℃ for 1 hour, mother liquor is filtered, the mother liquor is washed twice by toluene, 0.677mol of toluene and 0.436mol of titanium tetrachloride are added, the temperature is kept at 110 ℃ for 0.5 hour, the treatment is repeated twice after the filtration, then the washing is carried out for 3 times by hexane, the residual solid product is dried in vacuum to obtain a solid catalyst A1, and the catalytic activity of the solid catalyst is shown in Table 1.

Example 2

A solid catalyst was prepared by the same method as in example 1, except that: at 80 deg.C, 0.01mol of 3, 5-heptanediol dibenzoate was added to obtain solid catalyst A2, the catalytic activity of which is shown in Table 1.

Example 3

A solid catalyst was prepared by the same method as in example 1, except that: at 80 ℃, 0.007mol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane is added to prepare a solid catalyst A3, and the catalytic activity of the solid catalyst is shown in Table 1.

Example 4

A solid catalyst was prepared by the same method as in example 1, except that: after the temperature is reduced to-28 ℃, 0.009mol of methyl methacrylate is added, 0.091mol of titanium tetrachloride is added dropwise, and then 0.005mol of 3, 5-heptanediol dibenzoate and 0.004mol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane are added at 80 ℃ to prepare a solid catalyst A4, wherein the catalytic activity of the solid catalyst is shown in Table 1.

Example 5

A solid catalyst was prepared by the same method as in example 1, except that: after the temperature is reduced to-28 ℃, 0.011mol of methyl methacrylate is added, and then 0.005mol of 3, 5-heptanediol dibenzoate and 0.004mol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane are added at 80 ℃ to prepare a solid catalyst A5, wherein the catalytic activity of the solid catalyst is shown in Table 1.

Example 6

A solid catalyst was prepared by the same method as in example 1, except that: at 80 ℃, 0.008mol of di-n-butyl phthalate is added to prepare a solid catalyst A6, and the catalytic activity of the solid catalyst is shown in Table 1.

Example 7

A solid catalyst was prepared by the same method as in example 1, except that: 0.005mol of 3, 5-heptanediol dibenzoate and 0.004mol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane are added at 80 ℃ to prepare a solid catalyst A7, wherein the catalytic activity of the solid catalyst is shown in Table 1.

Example 8

A solid catalyst was prepared by the same method as in example 1, except that: after the temperature is reduced to minus 28 ℃, 0.008mol of methyl acrylate is added to prepare a solid catalyst A8, and the catalytic activity of the solid catalyst is shown in Table 1.

Example 9

A solid catalyst was prepared by the same method as in example 1, except that: after the temperature is reduced to-28 ℃, 0.006mol of octadecyl methacrylate is added and the temperature is kept constant for 0.5 hour, so as to prepare the solid catalyst A9, wherein the catalytic activity of the solid catalyst is shown in Table 1.

Comparative example 1

0.050mol of anhydrous magnesium chloride, 0.658mol of toluene, 0.051mol of epichlorohydrin and 0.046mol of tributyl phosphate are sequentially added into a reaction kettle repeatedly replaced by high-purity nitrogen, the reaction is carried out for 1.5 hours at the temperature of 62 ℃, 0.009mol of phthalic anhydride is added at the temperature of 55 ℃, 0.376mol of toluene is supplemented after the constant temperature is 0.5 hour, the temperature is reduced to-28 ℃, 0.51mol of titanium tetrachloride is dropwise added, the temperature is increased to 85 ℃ within 5 hours, 0.004mol of di-n-butyl phthalate is added at the temperature of 80 ℃, the constant temperature is kept at 85 ℃ for 1 hour, mother liquor is filtered out, toluene is used for washing twice, 0.677mol of toluene and 0.436mol of titanium tetrachloride are added, the constant temperature is kept at 110 ℃ for 0.5 hour, the treatment is repeated after the filtration, then hexane is used for washing 3 times, the residual solid product is subjected to vacuum drying, and the solid catalyst D1 is obtained, and the catalytic activity of the solid catalyst is.

Comparative example 2

A solid catalyst was prepared by the same method as in comparative example 1, except that: after the temperature is reduced to minus 28 ℃, 0.091mol of titanium tetrachloride is added dropwise to prepare a solid catalyst D2, and the catalytic activity of the solid catalyst is shown in Table 1.

Comparative example 3

A solid catalyst was prepared by the same method as in example 1, except that: after the temperature is reduced to-28 ℃, 0.007mol of phthalic anhydride is added, 0.118mol of titanium tetrachloride is added dropwise, 0.005mol of 3, 5-heptanediol dibenzoate and 0.004mol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane are added at 80 ℃, and a solid catalyst D3 is prepared, wherein the catalytic activity of the solid catalyst is shown in Table 1.

Comparative example 4

A solid catalyst was prepared by the same method as in example 1, except that: after the temperature is reduced to minus 28 ℃, 0.007mol of phthalic anhydride is added, after the temperature is kept for 0.5 hour, 0.118mol of titanium tetrachloride is added dropwise, the catalyst cannot be separated out, and the catalyst is not prepared.

Comparative example 5

A solid catalyst was prepared by the same method as in example 1, except that: 0.007mol of methyl methacrylate is added at 65 ℃, after the temperature is reduced to-28 ℃, 0.118mol of titanium tetrachloride is added dropwise to prepare a solid catalyst D5, and the catalytic activity of the solid catalyst is shown in Table 1.

TABLE 1

As can be seen from the data in the table, the target catalyst can be successfully prepared by using the acrylate compound represented by methyl methacrylate, octadecyl methacrylate and methyl acrylate instead of phthalic anhydride as the precipitation aid, and the catalyst with higher activity can be obtained only by adding a small amount of titanium compound in the precipitation process, so that the production cost can be reduced, and the generation of titanium-containing waste liquid can be reduced.

The solid catalysts provided in comparative example 1 and comparative example 5 were compared, and specifically, in comparative example 5, the first temperature at which the precipitation aid was added was higher than the first reaction temperature, whereas the solid catalyst provided in comparative example 5 had a significantly lower catalytic activity than that of example 1.

The solid catalysts provided by comparative examples 5 and 7, in example 5 in which the amount of the precipitation aid used is large, provide catalysts having more excellent catalytic activity.

Meanwhile, according to the catalytic activities of the solid catalysts provided in example 7, examples 2 to 3 and comparative example 3, it can be seen that when the glycols and the diether compounds are used together as an electron donor and are coordinated with the precipitation assistant described in the present application, the catalytic activity of the solid catalyst can be significantly improved.

In contrast, in comparative examples 1 to 2 in which phthalic anhydride was used as a precipitation assistant, since the solid catalyst was not prepared by the method defined in the present invention, a large amount of titanium compound had to be added during the preparation process in order to ensure that the solid catalyst obtained had good catalytic activity, and such an operation produced a large amount of titanium-containing waste liquid.

In comparative example 4, the solid catalyst was prepared according to the method of the present invention using phthalic anhydride as a precipitation aid, but the final precipitation aid, phthalic anhydride, did not cause the separation of the catalyst components and thus the catalyst could not be prepared.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.