CN101775086B - Preparation method for ethylene homopolymer and copolymer - Google Patents

Preparation method for ethylene homopolymer and copolymer Download PDF

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CN101775086B
CN101775086B CN 200910076325 CN200910076325A CN101775086B CN 101775086 B CN101775086 B CN 101775086B CN 200910076325 CN200910076325 CN 200910076325 CN 200910076325 A CN200910076325 A CN 200910076325A CN 101775086 B CN101775086 B CN 101775086B
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catalyst
polymerization
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titanium
compound
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CN101775086A (en )
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付义
何书艳
匡洞庭
姜涛
宁英男
张丽洋
张怀志
杨国兴
王立娟
罗明检
赵增辉
赵成才
邹恩广
郎笑梅
陈洪侠
韦德帅
高宇新
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中国石油天然气股份有限公司
大庆石油学院
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Abstract

The invention relates to a preparation method for ethylene homopolymers and copolymers. The preparation method adopts liquid phase polymerization or gas phase polymerization; the polymerization conditions are as follows: the reaction temperature is 80 DEG C, and the total reaction pressure is 0.73MPa; a ball-like particle ethylene polymer is prepared; magnesium chloride is dissolved in an isooctanol solvent at a dissolving temperature of 50 to 130 DEG C to obtain a liquid magnesium compound, and the liquid magnesium compound is interacted with triethyl phosphate to obtain a product; the product is contacted with titanium tetrachloride to be heated to 50 to 120 DEG C to precipitate solid as a catalyst; counted in per mole of magnesium chloride in the magnesium compound, the amount of a isooctanol compound is 0.1 to 10.0 mole, the amount of triethyl phosphate is 0.05 to 0.35 mole, and the amount of titanium tetrachloride is 30 to 40 mole; the catalyst is mixed with triethylaluminium or triisobutyl aluminium; and the molar ratio of aluminum to titanium is 20 to 200. The activity and the particle form of the catalyst are improved, so that the particle form of the polymer is improved, and the sensibility to hydrogen regulation is better.

Description

一种乙烯均聚合与共聚合的制备方法 An ethylene polymerization method are co-polymerization

技术领域 FIELD

[0001] 本发明涉及一种用于乙烯均聚合或乙烯与其他α -烯烃共聚合的制备方法。 [0001] The present invention relates to an ethylene homo polymerization of ethylene with other α or for - producing an olefin copolymerization. 背景技术 Background technique

[0002] 乙烯聚合高效Ziegler-Natta催化剂的制备方法是众所周知的,主要是由MgCl2 或SiO2负载的钛的卤化物组成。 [0002] The ethylene polymerization method of efficiently preparing Ziegler-Natta catalysts are well known, mainly by MgCl2 or SiO2 supported titanium halide composition. 如JP 4951378中公开的乙烯聚合和共聚合的催化剂的制备方法是:经研磨粉碎的二氯化镁与乙醇反应生成MgCl2 WC2H5OH醇合物浆液,再与一氯二乙基铝发生酯化反应,最后和TiCl4进行载钛反应,得到MgCl2载体负载的钛系催化剂。 The method for preparing an ethylene polymerization and copolymerization catalyst is disclosed in JP 4951378: grinding comminuted by reaction of magnesium dichloride with ethanol production MgCl2 WC2H5OH alcoholates slurry, and then an esterification reaction with the diethylaluminum chloride, and finally TiCl4 for the reaction of the titanium, to obtain a titanium-based catalyst supported MgCl2 support. 这种催化剂制备方法简单,反应条件温和,催化剂催化乙烯聚合时活性很高。 This catalyst preparation method is simple, mild reaction conditions, the polymerization of ethylene catalyzed by highly active. 但这种制备方法存在载体氯化镁在矿物油中不能溶解,氯化镁在浆液反应体系中存在原研磨粉碎时产生的不规则片状颗粒,导致得到的固体催化剂颗粒形态较差,粗细不均勻,因而聚合物形态也不好,细粉较多,易产生静电并容易堵塞管道。 However, this production method does not dissolve the magnesium chloride support in the presence of mineral oil, magnesium chloride tabular grain irregularities generated when the original grind in a slurry reaction system, resulting in poor morphology of the solid catalyst particles obtained, uneven thickness, and therefore the polymerization morphology is not good, more powder, easy to produce static and easy to plug the pipeline. 同时该催化剂在聚合时溶剂中的低聚物含量较多,为后处理带来了较大的麻烦。 Meanwhile, the higher the oligomer content of the catalyst in the polymerization solvent, brought greater trouble after treatment.

[0003] 专利CN1M9092公开了一种用于乙烯聚合和共聚合的催化剂体系,该催化剂体系包括:(1)含Ti的固体催化剂组分,(2)烷基铝化合物,其中含Ti的固体催化剂组分是由卤化镁溶于有机环氧化合物和有机磷化合物形成均相溶液,加入乙醇处理已溶解的卤化镁, 然后该溶液与四卤化钛混合,在沉淀剂如有机酸酐、有机酸、醚、酮等化合物存在下,析出固体物,得到固体催化剂。 [0003] Patent CN1M9092 discloses a catalyst system for the polymerization and copolymerization of ethylene, the catalyst system comprising: (1) a solid catalyst component containing Ti, (2) an alkyl aluminum compound, wherein the Ti-containing solid catalyst component from a magnesium halide is dissolved in an organic epoxy compound and organic phosphorus compound to form a homogeneous solution, adding the magnesium halide dissolved in ethanol, and the solution is then mixed with a titanium tetrahalide, in a precipitant such as organic anhydrides, organic acids, ethers , the presence of a ketone compound, a solid precipitate was obtained a solid catalyst. 该催化剂体系用于乙烯聚合时,所得聚合物细粉含量较多、催化剂活性较低、氢调性能差,不适于制备双峰聚合物,难以替代现有的高活性乙烯淤浆聚合催化齐U。 The catalyst system used for ethylene polymerization, the resulting polymer is more fines content, low catalyst activity and poor hydrogen transfer properties, a bimodal polymer suitable for the preparation, it is difficult to replace conventional high activity ethylene polymerization catalyst slurry homogeneous U . 同时聚合物的堆密度也略低于现有催化剂的水平。 While the bulk density of the polymer is also slightly lower than the conventional catalyst.

[0004] 专利CN1140722公开了一种固体钛催化剂组分及其制备工艺,主要采用低碳醇来溶解卤化镁,并加入烷烃稀释剂和硅烷类给电子体化合物,然后与卤化钛作用,析出固体催化剂。 [0004] Patent CN1140722 discloses a solid titanium catalyst component and its preparation process, mainly lower alcohol to dissolve the magnesium halide and the added alkane diluent and a silane electron donor compound, and then with a titanium halogen action precipitated solid was catalyst. 尽管该催化剂用于乙烯聚合时能制得具有优良的颗粒性能的乙烯聚合物,但其催化活性和低聚物含量仍不尽人意。 It can be prepared having excellent particle properties although ethylene polymer of the catalyst used for ethylene polymerization, but the catalytic activity is still unsatisfactory and oligomer content.

发明内容 SUMMARY

[0005] 本发明的目的是提供一种以固体钛为催化剂组分的乙烯均聚合与共聚合的制备方法,用该催化剂组分能使乙烯聚合具有较高的活性,并使制得的乙烯聚合物具有类球形的颗粒形态。 [0005] The object of the present invention is to provide a solid titanium catalyst component are ethylene polymerization method of co-polymerization, using the catalyst components can have a higher activity for ethylene polymerization, and obtained by polymerization of ethylene having a spherical particle morphology.

[0006] 本方法采用液相聚合或气相聚合;聚合条件为:反应温度80°C、反应总压0. 73MPa ;制得具有类球形颗粒形态的乙烯聚合物;它是由一种液态的镁化合物与一种无活性氢的有机磷化合物相互作用,它们的产物与四氯化钛相接触,析出的固体为催化剂; [0006] In this method, a liquid phase polymerization or gas phase polymerization; polymerization conditions are: a reaction temperature of 80 ° C, the total reaction pressure of 0. 73MPa; prepared ethylene polymer having a spherical particle shape; it is a liquid magnesium the organic phosphorus compound having no active hydrogen compounds with one interaction product thereof in contact with titanium tetrachloride, and the precipitated solid catalyst;

[0007] 其中所述的液态镁化合物是将氯化镁溶解在异辛醇溶剂中所得到的产物; [0007] wherein said liquid magnesium compound is magnesium chloride product was dissolved in a solvent, isooctyl alcohol obtained;

[0008] 所述的无活性氢原子的有机磷化合物选用磷酸三乙酯; [0008] The organic phosphorus compound having no active hydrogen atoms according to the selection of triethyl phosphate;

[0009] 以镁化合物中的每摩尔氯化镁计,异辛醇化合物用量为:0. 1〜10. 0摩尔,磷酸三乙酯用量为0. 05〜0. 35摩尔,四氯化钛用量为30〜40摩尔。 [0009] In the magnesium compound per mole of magnesium chloride basis, isooctyl alcohol compound in an amount of:... 0 0 1~10 mol of triethyl phosphate in an amount of 0.5 mol 05~0 35, an amount of titanium tetrachloride 30 to 40 mol. [0010] 催化剂配三烷基铝化合物,铝与钛的摩尔比为20〜200。 [0010] catalyst with a trialkyl aluminum compound, the molar ratio of aluminum to titanium is 20~200.

[0011] 制备固体钛催化剂: [0011] Preparation of Solid titanium catalyst:

[0012] 本发明的催化剂组分可采用以下的方法制备: [0012] The catalyst components of the present invention can be prepared by the following method:

[0013] (1)制备液态镁化合物 [0013] (1) Preparation of liquid magnesium compound

[0014] 将将氯化镁溶解在异辛醇溶剂中,在溶剂体系中加入惰性稀释剂,形成均勻溶液, 溶解温度50〜130°C ;在形成溶液的过程中或溶液形成后加入无活性氢原子的有机磷化合 [0014] The magnesium chloride is dissolved in a solvent and isooctyl alcohol, an inert diluent is added in a solvent system to form a homogeneous solution, the dissolution temperature of 50~130 ° C; no active hydrogen atom is added or a solution after the solution is formed during the formation of organic phosphorus

物磷酸三乙酯。 It was triethyl phosphate.

[0015] (2)制备固体钛催化剂 [0015] (2) Preparation of solid titanium catalyst

[0016] 将上述溶液与钛化合物进行接触反应,无活性氢原子的有机磷化合物磷酸三乙酯也可以在(1)步骤中的溶液与钛化合物进行接触反应时加入,并将混合物缓慢升温至50〜 120°C,固体物逐渐析出并形成颗粒,反应一定的时间后,除去未反应物和溶剂,并采用惰性稀释剂洗涤,得到本发明的催化剂组分。 [0016] The above solution was subjected to contact reaction with a titanium compound, an active hydrogen atom-free organic phosphorus compound triethyl phosphate may also be added to the reaction in the contact step (1) with a titanium compound in a solution, and the mixture was slowly warmed to 50~ 120 ° C, the solid was gradually precipitated and formed into particles, after a certain reaction time, to remove unreacted materials and solvent, and washed with an inert diluent, to give the catalyst components of the invention.

[0017] 配以三乙基铝或三异丁基铝为好。 [0017] together with triethylaluminum or triisobutylaluminum as well. 其中组份铝与组分钛的摩尔比为5〜500,优选20 〜200。 Wherein the molar ratio of aluminum component ingredients titanium is 5~500, preferably 20 ~ 200.

[0018] 聚合时可采用液相聚合,也可以采用气相聚合。 [0018] The polymerization can be liquid phase polymerization, gas phase polymerization can be employed. 液相聚合介质包括:异丁烷、己烷、 庚烷、环己烷、石脑油、抽余油、加氢汽油、煤油、苯、甲苯、二甲苯等饱和脂肪烃或芳香烃等惰性溶剂。 Liquid polymerization medium comprising: isobutane, hexane, heptane, cyclohexane, naphtha, other than pumping oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene and the like saturated aliphatic or aromatic hydrocarbon inert solvent . 聚合条件为:反应温度80°C、反应总压0. 73MPa。 The polymerization conditions are: a reaction temperature of 80 ° C, the total reaction pressure of 0. 73MPa.

[0019] 本发明的催化剂由于采用无活泼氢的有机磷化合物为助析剂,因此在催化剂制备时很容易析出类球形的催化剂颗粒。 [0019] The catalyst of the present invention, since active hydrogen-free organic phosphorus compound as promoter analysis agent, catalyst preparation therefore easily precipitated spheroidal catalyst particles. 而且在载钛过程中不需要使用大量的四氯化钛来促使沉淀的析出,也不需要多次使用四氯化钛来处理沉淀,因此四氯化钛的加入量大大减少。 And does not require a large amount of titanium contained in the titanium tetrachloride during the precipitation to cause precipitation, does not require the use of multiple processing of titanium tetrachloride to precipitate, thus reducing the large amount of titanium tetrachloride was added. 同时有机磷化合物的加入还有助于提高催化剂的活性和催化剂的颗粒形态的改善,从而进一步改善聚合物的颗粒形态。 While adding an organic phosphorus compound also helps to improve the catalyst activity and improve the particle morphology of the catalyst, thereby further improving the particle morphology of the polymer. 该催化剂用于乙烯聚合时,表现出较好的氢调敏感性。 The catalyst is used for ethylene polymerization, exhibits good hydrogen response.

具体实施方式 detailed description

[0020] 下面以实施例来说明本发明,但并非限制发明范围。 [0020] In the following examples illustrate the invention, but not limit the scope of the invention.

[0021] 实施例1 [0021] Example 1

[0022] 把4. 76克(50mmol)无水氯化镁、75毫升癸烷和16. 3克(125mmol)异辛醇加热至130°C,使之反应3小时,得到一种均相溶液。 [0022] The 4.76 g (50mmol) of anhydrous magnesium chloride, 75 ml of decane and 16.3 g (125mmol) isooctanol are heated to 130 ° C, reacted for 3 hours to obtain a homogeneous solution. 向该溶液中加入15mmol的磷酸三乙酯并在50°C下搅拌2小时以使磷酸三乙酯溶解于该溶液。 To this solution was added to 15mmol of triethyl phosphite and stirred at 50 ° C 2 hours to triethylphosphite was dissolved in the solution. 将上述得到的所有均相溶液冷却至室温,然后在1小时内边搅拌边将其滴加到温度保持为0°C的150mL四氯化钛中。 All above-obtained homogeneous solution was cooled to room temperature and then stirring over 1 hour with stirring in dropwise added 150mL of titanium tetrachloride, maintaining the temperature of 0 ° C in. 滴完后使混合物温度在0°C下保持1小时,然后在搅拌下在2小时内把温度提至120°C,并将此温度保持2小时。 After finishing the dropping temperature of the mixture was maintained at 0 ° C 1 hour and then stirred for 2 hours under the temperature raised to 120 ° C, and this temperature was maintained for 2 hours. 当2小时反应结束后,对生成的固体进行热过滤分离。 After the end of the two hours of reaction, a solid produced was separated by hot filtration. 分别用己烷和癸烷对固体催化剂进行充分洗涤,直至在清洗液中检测不出析出的钛化合物,经干燥后得到一种固体钛催化剂组分。 Respectively, of the solid catalyst was sufficiently washed with hexane and decane until no precipitated titanium compound is detected in the washing liquid, to obtain a solid titanium catalyst component after drying.

[0023] 乙烯聚合 [0023] Ethylene Polymerization

[0024] 容积为2L的不锈钢反应釜,经高纯氮气充分置换后,加入己烷IL和浓度lmol/L 的三乙基铝1. OmL,用注射器加入准确称量上述制备的催化剂,升温至75°C,通入氢气使釜内压力达到0. 28MPa,再通入乙烯使釜内总压达到0. 73MPa (表压),在80°C条件下聚合2小时,聚合结果见表1。 [0024] The volume of 2L stainless steel reactor, high purity after sufficiently replaced with nitrogen, was added IL of hexane and the concentration of lmol / L triethylaluminum 1. OmL, accurately weighed was added via syringe catalyst prepared above was heated to 75 ° C, hydrogen was introduced into the autoclave pressure reaches 0. 28MPa, and then ethylene was fed so that the total pressure became 0. 73MPa (gauge pressure) inside the autoclave at 80 ° C for polymerization for 2 hours, the polymerization results in table 1. [0025] 实施例2 [0025] Example 2

[0026] 同实施例1,不同之处在于磷酸三乙酯的加入量为20mmol。 [0026] The same as in Example 1, except that the amount of triethyl phosphate 20mmol. 聚合结果见表1。 The polymerization results are shown in Table 1.

[0027] 实施例3 [0027] Example 3

[0028] 同实施例1,不同之处在于磷酸三乙酯的加入量为lOmmol。 [0028] in Example 1, except that the amount of triethyl phosphate lOmmol. 聚合结果见表1。 The polymerization results are shown in Table 1.

[0029] 实施例4同实施例1,不同之处在于癸烷的加入量为50mL。 [0029] Example 4 with Example 1, except that the amount of decane was added to 50mL. 聚合结果见表1。 The polymerization results are shown in Table 1.

[0030] 对比例1 [0030] Comparative Example 1

[0031] 同实施例1。 [0031] The same as in Example 1. 不同之处在于含磷化合物改为四乙氧基硅烷,乙烯聚合结果见表1。 Except that the tetraethoxysilane was changed to phosphorus-containing compound, an ethylene polymerization results are shown in Table 1.

[0032] 对比例2 [0032] Comparative Example 2

[0033] 同实施例1。 [0033] The same as in Example 1. 只是不加磷酸三乙酯。 Except that no triphosphate ester. 催化剂析出成型困难,析出粒子极细,难于沉降,抽滤时全被抽走,未能形成催化剂。 Difficulty in molding the catalyst precipitation, fine precipitated particles, settling is difficult, when suction is pumped full, unable to form the catalyst.

[0034] 对比例3 [0034] Comparative Example 3

[0035] 催化剂的合成按CN1M9092实施例1所述方法制备。 [0035] The synthesis catalyst prepared according to the procedure of Example 1 CN1M9092 embodiment.

[0036] 在经高纯氮气充分置换的反应器中,依次加入0. 042mol无水MgCl2 (约4g) ,60ml 甲苯、0. 032mol环氧氯丙烷、0. 022mol磷酸三丁酯、0. 017mol乙醇,搅拌下升温至80°C,并维持15分钟固体完全溶解,形成均勻溶液,然后加入邻苯二甲酸酐0. 0074mol,再维持1小时,将该溶液冷却至_25°C,再将0. 5mol四氯化钛(约55ml)滴入其内,然后缓慢升温至80°C,反应3小时,过滤后分别用甲苯和己烷洗涤3次,真空干燥,得到固体催化剂。 [0036] In the high purity nitrogen gas was sufficiently purged reactor were successively added 0. 042mol anhydrous MgCI2 (about 4g), 60ml of toluene, 0. 032mol epichlorohydrin, 0. 022mol tributyl phosphate, 0. 017mol ethanol, under stirring warmed to 80 ° C, 15 minutes and maintaining the solid was completely dissolved to form a homogeneous solution, followed by addition of phthalic anhydride 0. 0074mol, was maintained for 1 hour, the solution was cooled to _25 ° C, and then 0. 5mol titanium tetrachloride (55 ml of approximately) was added dropwise therein, and then slowly warmed to 80 ° C, reacted for 3 hours, filtered and was washed three times with toluene and hexane, and dried in vacuo to obtain a solid catalyst. 乙烯聚合条件同实施例1,聚合结果见表1。 Ethylene polymerization conditions as in Example 1, the polymerization results in Table 1.

[0037] 对比例4 [0037] Comparative Example 4

[0038] 催化剂的合成按JP49-51378实施例所述方法制备。 [0038] JP49-51378 synthesis catalyst prepared according to the method described in Example.

[0039] 在经高纯氮气充分置换的反应器中,加入市售无水MgCl2IOm0I,悬浮在IOL己烷中,室温下,滴入60mol乙醇,搅拌30分钟。 [0039] in high purity by a reactor thoroughly purged with nitrogen was added a commercially available anhydrous MgCl2IOm0I, IOL was suspended in hexane, at room temperature, 60mol ethanol was added dropwise, stirred for 30 minutes. 维持体系的温度不超过40°C条件下滴入31mol 一氯二乙基铝,搅拌30分钟,加入5molTiCl4,体系维持在60°C,搅拌反应6小时。 Maintaining the temperature of the system does not exceed 31mol added dropwise diethylaluminum monochloride 40 ° C under conditions of stirring for 30 minutes, 5molTiCl4, the system was maintained at 60 ° C, the reaction was stirred for 6 hours. 经过过滤、己烷洗涤后得到固体催化剂。 After filtration and washed with hexane to obtain a solid catalyst. 乙烯聚合条件同实施例1,聚合结果见表1。 Ethylene polymerization conditions as in Example 1, the polymerization results in Table 1.

[0040] 表1 [0040] TABLE 1

[0041] [0041]

Figure CN101775086BD00051

Claims (1)

  1. 1. 一种乙烯均聚合与共聚合的制备方法,其特征在于:采用液相聚合或气相聚合;聚合条件为:反应温度80°C、反应总压0. 73MPa ;制得具有类球形颗粒形态的乙烯聚合物;催化剂为:将氯化镁溶解在异辛醇溶剂中所得的液态镁化合物与磷酸三乙酯相互作用,溶解温度50〜130°C ;相互作用的产物与四氯化钛相接触,升温至50〜120°C析出的固体;以镁化合物中的每摩尔氯化镁计,异辛醇化合物用量为:0. 1〜10. 0摩尔,磷酸三乙酯用量为0. 05〜0. 35摩尔,四氯化钛用量为30〜40摩尔;催化剂配三乙基铝或三异丁基铝;铝与钛的摩尔比为20〜200。 CLAIMS 1. A method of co-polymerization of ethylene are polymerized, characterized in that: a liquid phase polymerization or gas phase polymerization; polymerization conditions are: a reaction temperature of 80 ° C, the total reaction pressure of 0. 73MPa; prepared having a spherical particle morphology ethylene polymers; catalyst: magnesium chloride obtained by dissolving a liquid magnesium compound with triethylphosphite in a solvent interactions isooctanol, dissolution temperature of 50~130 ° C; product of interaction in contact with titanium tetrachloride, heated to 50~120 ° C and the precipitated solid; magnesium compound per mole of magnesium chloride basis, isooctyl alcohol compound in an amount of: 0 0 1~10 mol of triethyl phosphate in an amount of 35 mol 0. 05~0... titanium tetrachloride in an amount of 30 to 40 moles; catalyst with triethylaluminum or triisobutylaluminum; molar ratio of aluminum to titanium is 20~200.
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