阅读说明：本技术 一种用于丙烯聚合的高效活性Ziegler-Natta催化剂的制备方法和应用 (A kind of preparation method and application of the high-efficiency activated Ziegler-Natta catalyst for propylene polymerization ) 是由 王磊 齐涛 张文泉 于 2019-09-19 设计创作，主要内容包括：本发明涉及一种用于丙烯聚合的高效活性Ziegler-Natta催化剂的制备方法和应用。取金属镁化合物和有机醇溶剂,于100～140℃恒温搅拌,得醇合物溶液；将所得醇合物溶液快速转入-20℃高速搅拌的环己烷溶剂中,搅拌后,过滤,洗涤,得镁醇合物载体；反应器中加入卤化钛,降温至-20℃,加入镁醇合物载体,加入完毕后,将体系温度缓慢升至90～120℃后,加入内给电子体化合物,恒温反应,得前驱体溶液；将所得前驱体溶液降温至60～100℃,加入助催化剂,恒温反应,所得产物洗涤,真空干燥,得目标产物。本发明合成原料少,工艺流程简单,能耗少,催化效率高,催化效果好。(The present invention relates to a kind of preparation method and application of high-efficiency activated Ziegler-Natta catalyst for propylene polymerization.Metal magnesium compound and organic alcohol solvent are taken, is stirred in 100~140 DEG C of constant temperature, obtains alcohol adduct solution；Gained alcohol adduct solution is quickly transferred in the cyclohexane solvent of -20 DEG C of high-speed stirreds, after stirring, is filtered, washing obtains magnesium alcoholate carrier；Halogenated titanium is added in reactor, is cooled to -20 DEG C, magnesium alcoholate carrier is added, after addition, after system temperature is slowly increased to 90~120 DEG C, internal electron donor compound is added, isothermal reaction obtains precursor solution；Gained precursor solution is cooled to 60~100 DEG C, co-catalyst, isothermal reaction is added, products therefrom washing is dried in vacuo, obtains target product.Synthesis material of the present invention is few, and process flow is simple, less energy consumption, high catalytic efficiency, excellent catalytic effect.)

1. a kind of preparation method of the high-efficiency activated Ziegler-Natta catalyst for propylene polymerization, which is characterized in that including Following steps:

1) it takes metal magnesium compound and organic alcohol solvent, after stirring and dissolving, hexamethylene is added, opens magnetic agitation, is warming up to 100 ~140 DEG C, 1~5h is stirred in 100~140 DEG C of constant temperature, obtains colorless and transparent alcohol adduct solution；

2) alcohol adduct solution obtained by step 1) is quickly transferred in the cyclohexane solvent of -20 DEG C of high-speed stirreds, after stirring 30min, Filtering, precipitating are washed with hexamethylene, obtain magnesium alcoholate carrier；

3) halogenated titanium is added in reactor, is cooled to -20 DEG C, opens stirring, magnesium alcoholate obtained by step 2) is added at -20 DEG C Carrier, after addition, after system temperature is slowly increased to 90~120 DEG C, addition internal electron donor compound, 90~120 DEG C 2~4h of isothermal reaction, obtains precursor solution；

4) precursor solution obtained by step 3) is cooled to 60~100 DEG C, co-catalyst, isothermal reaction 3 at 60~100 DEG C is added ~6h, products therefrom are washed with hexamethylene, and vacuum drying obtains target product.

2. preparation method according to claim 1, which is characterized in that in step 1), metal magnesium compound is being added and is having Before machine alcoholic solvent, reaction vessel is sufficiently displaced from high pure nitrogen.

3. preparation method according to claim 1, which is characterized in that be 1 by the molar ratio of magnesium and hydroxyl in step 1): (2.0~2.5) take metal magnesium compound and organic alcohol solvent.

4. preparation method according to claim 1, which is characterized in that the metal magnesium compound is selected from magnesium chloride, methoxy One of base magnesium chloride, ethyoxyl magnesium chloride, magnesium methoxide, magnesium ethylate and bromine (4- ethoxyl phenenyl) magnesium or two kinds or more Combination.

5. preparation method according to claim 1, which is characterized in that the organic alcohol solvent is selected from methanol, ethyl alcohol, isopropyl Alcohol, n-butanol, isobutanol, 1,4- butanediol or 1,3- propylene glycol.

6. preparation method according to claim 1, which is characterized in that the halogenated titanium is selected from TiCl₄、TiCl₃、TiBr₄、 TiF₄, methoxytitanium trichloride, ethyoxyl titanium trichloride, propoxyl group titanium trichloride or nbutoxytitanium trichloride one kind or two Kind or more combination.

7. preparation method according to claim 1, which is characterized in that the internal electron donor compound is selected from cyclobutyl- 1,1- diformazan diethylene glycol dimethyl ether, 2,2- diisobutyl -1,3- Propylene Glycol Dimethyl Ether, the third diether of 2,2- diisobutyl -1,3-, 2,2- bis- The third diether of hexyl -1,3-, the third diether of positive 1,3-, 2,2- dibutyl -1,3- Propylene Glycol Dimethyl Ether or dibutyl phthalate One or two or more kinds of combinations.

8. preparation method according to claim 1, which is characterized in that the co-catalyst is selected from trimethyl aluminium, triethyl group One or two or more kinds of combinations of aluminium, tri-n-n-propyl aluminum, three n-butylaluminums, tri-n-hexyl aluminum or tri-n-octylaluminium.

9. according to the Ziegler-Natta catalyst of the described in any item method preparations of claim 1-8 in catalysis propylene polymerization Application in reaction.

10. applying according to claim 9, which is characterized in that method is as follows: polymerization reaction kettle being dried in vacuo and uses nitrogen After gas and propylene are sufficiently displaced from, injected to reaction kettle according to the described in any item methods preparations of claim 1-8 with syringe The suspension of Ziegler-Natta catalyst and white oil is passed through hydrogen, opens and stirs and be added propylene liguid, is 50 in temperature ~80 DEG C, pressure is to react 1~2h under 0.5~1.5MPa.

Technical field

The present invention relates to a kind of preparation method of high-efficiency activated Ziegler-Natta catalyst for propylene polymerization, tools Body is related to the catalyst preparation that a kind of special internal electron donor is component.

Background technique

Polypropylene is a kind of crystalline polymer that molecular structure is very regular, and appearance white particle does not have peculiar smell, is nontoxic Harmless and lighter weight.With thermoplasticity, electrical insulation capability is high, and processing technology is simple, and impact strength is big and flex stiffiness The advantages that.In many-sided extensive use such as auto manufacturing, packaging industry, building material industry, Furniture manufacturing and household electrical appliance.Poly- third Alkene is divided into random polypropylene, syndiotactic polypropylene and three kinds of isotactic polypropylene by methyl arrangement position.The wherein methyl on strand Part is distributed in the polypropylene of main chain side, referred to as isotactic polypropylene.In the acrylic resin that general industry is produced, etc. Structural content is advised usually 95% or more, and remainder is random polypropylene or syndiotactic polypropylene.In the industrial production, isotactic Polypropylene is most widely used.

In the process flow of propylene polymerization, the preparation of catalyst is technology the most key in entire polyolefin industry. Ziegler-Natta catalyst is catalyst most widely used in current propylene polymerization process, Ziegler-Natta catalysis Agent experienced the development of several generations, and in 1989, Himont company invented a kind of using diether compound as the tune in activated centre Save agent.When the hydrogen of the 2nd carbon atom in 1,3- diether molecular structure is replaced by other substituent groups with steric hindrance, meeting Another relatively-stationary space conformation is formed, determines the direction of magnesium ethylate and titanium tetrachloride coordination to a certain extent, And then lead to the performance change of catalyst, the especially stereoselective of catalyst.It is given in addition, certain diether compounds are used as It when electron carries out propylene copolymerization, does not need to add external electron donor, the catalyst limitation before breaching makes synthesis material It reduces, side reaction reduces, and simplifies process flow.Two ethers catalyst are because have high activity, high hydrogen response, molecular weight A variety of advantages such as narrowly distributing, oligomer be low, are praised highly energetically.

Summary of the invention

The purpose of the present invention is to provide a kind of synthesis material is few, process flow is simple, less energy consumption, and high catalytic efficiency is urged Change the good high-efficiency activated Ziegler-Natta catalyst for propylene polymerization of effect.

The technical solution adopted by the present invention is that: a kind of high-efficiency activated Ziegler-Natta catalyst for propylene polymerization Preparation method, include the following steps:

1) it takes metal magnesium compound and organic alcohol solvent, after stirring and dissolving, hexamethylene is added, open magnetic agitation, heating To 100~140 DEG C, 1~5h is stirred in 100~140 DEG C of constant temperature, obtains colorless and transparent alcohol adduct solution；Preferably, temperature 130 ~140 DEG C, the reaction time is 2~3h.

2) alcohol adduct solution obtained by step 1) is quickly transferred in the cyclohexane solvent of -20 DEG C of high-speed stirreds, stirs 30min Afterwards, it filters, precipitating is washed with hexamethylene, obtains magnesium alcoholate carrier；

3) halogenated titanium is added in reactor, is cooled to -20 DEG C, opens stirring, magnesium alcohol obtained by step 2) is added at -20 DEG C Object carrier is closed, after addition, after system temperature is slowly increased to 90~120 DEG C, addition internal electron donor compound, 90~ 120 DEG C of 2~4h of isothermal reaction, obtain precursor solution；Preferably, temperature is 100~120 DEG C, and the reaction time is 3~4h.

4) precursor solution obtained by step 3) is cooled to 60~100 DEG C, co-catalyst, constant temperature at 60~100 DEG C is added 3~6h is reacted, products therefrom is washed with hexamethylene, is dried in vacuo, is obtained target product.Preferably, reaction temperature is 60~80 DEG C, Reaction time is 3~5h.

Further, in step 1), before metal magnesium compound and organic alcohol solvent is added, to reaction vessel with high-purity Nitrogen is sufficiently displaced from.

Further, it is 1:(2.0~2.5 by the molar ratio of magnesium and hydroxyl in step 1)), it takes metal magnesium compound and has Machine alcoholic solvent.

Further, the metal magnesium compound is selected from magnesium chloride, methoxy magnesium chloride, ethyoxyl magnesium chloride, methoxyl group One of magnesium, magnesium ethylate and bromine (4- ethoxyl phenenyl) magnesium or two kinds or more of combination.Further, the magnesium metal Compound is magnesium ethylate.

Further, the organic alcohol solvent is selected from methanol, ethyl alcohol, isopropanol, n-butanol, isobutanol, 1,4-butanediol Or 1,3- propylene glycol.Further, the organic alcohol solvent is n-butanol.

Further, the halogenated titanium is selected from TiCl₄、TiCl₃、TiBr₄、TiF₄, methoxytitanium trichloride, ethyoxyl three One or two or more kinds of combinations of titanium chloride, propoxyl group titanium trichloride or nbutoxytitanium trichloride.Further, described Halogenated titanium is TiCl₄。

Further, the internal electron donor compound is selected from cyclobutyl -1,1- diformazan diethylene glycol dimethyl ether, 2,2-, bis- isobutyl Base -1,3- Propylene Glycol Dimethyl Ether, the third diether of 2,2- diisobutyl -1,3-, the third diether of 2,2- dihexyl -1,3-, positive 1,3- the third two One or two or more kinds of combinations of ether, 2,2- dibutyl -1,3- Propylene Glycol Dimethyl Ether or dibutyl phthalate.More into one Step, the internal electron donor compound is 2,2- dibutyl -1,3-PD dimethyl ether.

Further, the co-catalyst is being selected from trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminums, three just One or two or more kinds of combinations of hexyl aluminium or tri-n-octylaluminium.Further, the co-catalyst is triethyl aluminum.

Application of the Ziegler-Natta catalyst prepared according to above-mentioned method in catalysis propylene polymerization.

Further, the method is as follows: after being dried in vacuo polymerization reaction kettle and being sufficiently displaced from nitrogen and propylene, with injection Device injects the suspension of the Ziegler-Natta catalyst and white oil that prepare according to above-mentioned method to reaction kettle, is passed through hydrogen, It opens and stirs and be added propylene liguid, be 50~80 DEG C in temperature, pressure is to react 1~2h under 0.5~1.5MPa.

The present invention has the advantage that the present invention uses diether compound as internal electron donor, without outer electron In the case of body, so that it may obtain high activated catalyst, and diether compound is with co-catalyst when being reacted, it will not be from catalysis Agent surface is replaced out, and the polymer isotacticity obtained from is high, and powder fine powder content is seldom, the injecting products coloring of processing Uniformly, it is in bright colors.The isotacticity of polypropylene catalyst reaches 99wt%, in catalyst transition metal load factor reached 8~ 12wt%, catalytic activity have reached 55000~62000gPE/g-cath.Catalyst stability prepared by the present invention is good, granularity Controllably, the service life is long, and the polypropylene catalyst in more domestic similar technique process units is had excellent performance.

Specific embodiment

The description being described in detail is done to the present invention below with reference to example, rather than limiting the invention.