WO2014075381A1 - Method for preparing isotactic poly-1-butene - Google Patents
Method for preparing isotactic poly-1-butene Download PDFInfo
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- WO2014075381A1 WO2014075381A1 PCT/CN2013/000837 CN2013000837W WO2014075381A1 WO 2014075381 A1 WO2014075381 A1 WO 2014075381A1 CN 2013000837 W CN2013000837 W CN 2013000837W WO 2014075381 A1 WO2014075381 A1 WO 2014075381A1
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- butene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
Definitions
- the invention relates to a preparation method of isotactic poly-1-butene for controlling crystallinity and crystal transformation of polybutene in a nucleating agent in a kettle.
- High-precision 1-butene is called "gold in plastic” and has outstanding high temperature creep resistance, low temperature resistance, environmental stress crack resistance, wear resistance and good toughness. Therefore, it is suitable for flexible pipes, especially for building hot water pipes such as floor heating. Its pipes are light, flexible and impact resistant. It can be used at temperatures below 95 °C for a long time. It is the best pipe in the world. one.
- the long-term use of hoop stress is 1.6 times of PPR and 1.3 times of PEX.
- the minimum water flow pressure loss is one-fifth of PPR, one-half of PEX tube, and the thermal expansion coefficient is three-quarters of PPR. It is three-fifths of PEX.
- Isotactic 1-butene has five crystal forms, namely Form I, Form II, Form III, Form and Form II, of which Form I, Form II, Form III and The melting point of the crystal form is 121 C ⁇ 136 °C, 100 X ⁇ 120 V, 96 °C and 95 °C ⁇ 109 °C, and the crystal form III and the crystal form are unstable, when the temperature is heated to near the melting temperature.
- the time crystal form III and the crystal form of the twin form are converted into the form II.
- Form II is a metastable crystal form. After standing at room temperature for several days to several weeks, metastable Form II will be converted to a stable Form I, thereby making isotactic polybutene.
- the physicochemical properties are constantly improving. Therefore, how to accelerate the transformation of the crystal form to the crystal form I becomes a focus of research on the industrial development of poly 1-butene.
- Chinese patent CN1330088A discloses a process for preparing highly crystalline polypropylene in a kettle.
- the method consists of a synthetic nucleating agent, i.e., at least one organometallic salt nucleating agent and an inorganic nucleating agent.
- the disadvantage of this method is that two nucleating agents are used and the amount of nucleating agent is large.
- Chinese Patent No. CN 101 429 259 A discloses a method of preparing a ⁇ -crystalline polypropylene by adding a nucleating agent to a kettle.
- a rare earth ⁇ crystal nucleating agent is added to a kettle to obtain a polypropylene powder, which is subjected to extrusion granulation to obtain a polypropylene resin having a crystal content of 3.
- the disadvantage of this method is the use of rare earth nucleating agents, which are costly.
- the above patents only refer to the polypropylene process, and the patent for the preparation of poly 1-butene by adding a nucleating agent to the kettle has not yet been reported.
- the object of the present invention is to provide a nucleating agent in a kettle to regulate the isotactic polymerization of polybutene-butene crystallinity and crystal form transformation.
- 1 Preparation method of butene; Add a small amount of nucleating agent in the polymerization process of 1-butene to increase the crystallinity of poly-1-butene, accelerate the crystallization rate, improve the impact resistance of poly-1-butene and shorten the crystal form II The time is changed to Form I.
- the method for preparing an isotactic polybutene which modulates the crystallinity and crystal form of polybutene in the in-cylinder nucleating agent according to the present invention comprises the following steps:
- nucleating agent Adding a nucleating agent to a bulk polymerization reactor containing 1 butene, and using a Ziegler-Natta catalyst system to catalyze bulk polymerization of 1-butene to prepare a poly 1-butene and a nucleating agent compound;
- the composite prepared in the step 1 is directly subjected to heat-melting treatment or extrusion granulation to obtain a nucleating agent-containing polybutene resin.
- the bulk polymerization is carried out as follows:
- the polymerization reactor Prior to the start of the polymerization, the polymerization reactor is purged with high purity nitrogen to ensure removal of air and traces of water from the polymerization reactor;
- step 2) adding hydrogen and liquid 1-butene to the polymerization reactor of step 1), wherein the liquid 1-butene is 0.1 to 2.0 kg, the hydrogen is 0 to 0.3 MPa, and the stirring is performed at a rotation speed of 100 to 600 rpm/min;
- step 5 Add 5 ⁇ 30mg of MgCl 2 /TiC supported Ziegler-Natta catalyst to the feeder in the upper part of the polymerization reactor, and use the liquid 1-butene to charge the MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst in the feeder. Rushing into the polymerization reactor of step 1), the amount of liquid 1-butene in the final polymerization reactor is 0.2 ⁇ 3kg ;
- the temperature of the polymerization reactor of the step 1) is raised to 30 to 80 ° C, and the polymerization is allowed to proceed for 1 to 3 hours to terminate the reaction.
- the MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst component comprises a compound consisting of titanium, magnesium, halogen, an electron donor, and the like.
- the bismuth-based aluminum compound has the formula of AlR n X( 3 . n ), wherein R is an alkyl group having 1 to 20 carbon atoms, an aryl fluorenyl group, an aryl group or the like; X is a halogen; 0 ⁇ n ⁇ 3 Integer; trimethylaluminum, triethylaluminum, triisobutylaluminum, monohydrogenethylaluminum, diethylaluminum dichloride, dichloroethylaluminum, and the like. Among them, triethylaluminum, triisobutylaluminum is preferred.
- the silicone-based outer embankment to the electron donor is a compound of formula RnSi (OR0 4 ⁇ C1 ⁇ C10 wherein R is an alkyl group, cycloalkyl group or aryl embankment; is an alkyl group having 1 ⁇ 4 carbon atoms, for example.
- Phenyltrimethoxysilane phenyl Triethoxysilane (PTES), diphenyldimethoxysilane (DPDMS), diphenyldiethoxysilane (DPDES), dicyclopentyldimethoxysilane (DCPDMS), ring Hexylmethyldimethoxysilane (CHMDMS), diisobutyldimethoxysilane (DIBDMS), diisopropyldimethoxysilane (DIPDMS), preferably cyclohexylmethyldimethoxy .
- PTES phenyl Triethoxysilane
- DDMS diphenyldimethoxysilane
- DPDES diphenyldiethoxysilane
- DCPDMS dicyclopentyldimethoxysilane
- CHMDMS ring Hexylmethyldimethoxysilane
- DIBDMS diisobutyldimethoxysilane
- DIPDMS
- the nucleating agent is an inorganic salt compound.
- zinc sulfate, calcium sulfate whiskers silicon carbide, silicon nitride, titanium dioxide, zinc oxide, magnesium oxide, cerium oxide, cerium oxide, aluminum oxide, calcium hydrogencarbonate, calcium phosphate, calcium hydrogen phosphate, and the like.
- the nucleating agent is a carboxylic acid and a salt thereof, such as sodium stearate, calcium stearate, potassium stearate, magnesium stearate, barium stearate, sodium benzoate, sodium adipate. , magnesium adipate, calcium adipate, potassium adipate, barium adipate, sodium succinate, magnesium succinate, calcium succinate, potassium succinate, bis(4-butylbenzoic acid) Hydroxyl aluminum
- the nucleating agent is a sorbitol compound having the formula -
- R 2 is independently H or an alkyl group of 1 to 4 carbon atoms, a decyloxy group or a halogen such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, fluoro, Chlorine, bromine, etc.
- a methyl group, an ethyl group and a chlorine atom are preferred.
- 1,3:2,4-di(benzylidene)-D-sorbitol D-sorbitol
- 1,3:2,4-p-fluorodibenzylidene sorbitol 1,3:2,4-p-chloro Dibenzylidene sorbitol (CDBS)
- 1,3:2,4-p-bromodibenzylidene sorbitol 1,3:2,4-di(p-ethylbenzylidene) sorbitol (EDBS)
- DBS 1,3:2,4-di(benzylidene)-D-sorbitol
- CDBS 1,3:2,4-p-fluorodibenzylidene sorb
- the nucleating agent is an organic phosphate compound.
- organic phosphate compound For example, 2,2-methylene-bis(4,6-di-n-butylphenol) sodium phosphate (NA-11), sodium bis(2,4-di-tert-butylphenyl)phosphate (NA-10), Sodium (p-butylphenyl)phosphate (MARK 2018) and the like.
- the nucleating agent is an amide compound.
- amide compound for example, hydrazine, ⁇ '-diphenylmalonamide, hydrazine, hydrazine, -diphenyl cis-butane dimethylamide, hydrazine, ⁇ '-diphenyl adipamide, hydrazine, ⁇ '-dicyclohexyl-p-phenylene Formamide, hydrazine, ⁇ '-dicyclohexylphthalamide, hydrazine, ⁇ '-dicyclopentyl terephthalamide, hydrazine, ⁇ '-dicyclopentyl phthalamide, hydrazine, hydrazine, - Dicyclohexyl-2,6-naphthalamide, hydrazine, hydrazine, -dicyclopentyl-2,6-naphthalamide, hydrazine, hydrazine, -diphenyl succ
- the nucleating agent is a class of fused ring compounds.
- ⁇ -quinacridone ⁇ 3 ⁇
- triphenyldithiazide TPDT
- diphenylamine sulfide MBIM
- hydrazine phenanthrene
- ⁇ -quinacridone organic dye (solubilin golden, gray, brown, Purple red), quinacridone oxime, bisazo yellow, etc.
- the polymerization was carried out by the bulk polymerization method described above.
- the air in the polymerization reactor and the trace amount of water were removed, and 200 g of butene, 0.15 MPa H 2 , 4 mg of inorganic nucleating agent silica, and 2 mL of triethyl ether having a concentration of 1 mol/L were sequentially added to the polymerization reactor.
- Base aluminum 1.25mL of 0.05mol/L external electron donor cyclohexylmethyldimethoxysilane was added to the upper feeder of the polymerization reactor, and 25g of liquid 1-butene was used to nucleating agent and cocatalyst.
- the external electron donor was flushed into the polymerization reactor and stirred at a rotation speed of 450 rpm/min.
- 10 mg of MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst was added to the feeder in the upper part of the polymerization reactor, and 25 g of liquid butene was charged into the polymerization reactor, and polymerization was carried out at 30 ° C for reaction time. It is 2 hours. After the completion of the reaction, the remaining 1-butene was discharged, and the reaction was terminated to obtain a composite of poly-1-butene and a nucleating agent.
- Example 2 The same bulk polymerization method as in Example 1 was employed except that the nucleating agent silica of Example 1 was changed to 4 mg of nano calcium carbonate, talc, calcium sulfate whisker, magnesium oxide, and trioxide, respectively.
- NA-11 sodium bis(2,4-di-tert-butylphenyl)phosphate ( ⁇ -10), hydrazine, ⁇ '-diphenylmalonamide, hydrazine, hydrazine, dicyclohexyl-2, 6-naphthalamide, cyclohexamide phthalate, cyclohexamide naphthalene dicarboxylate, hydrazine, hydrazine, dicyclopentylglutalamide, ⁇ -quinacridone ( ⁇ 3 ⁇ ), triphenyldithiazide TPDT), diphenylamine sulfide, quinacridonequinone.
- the polymerization was carried out by the bulk polymerization method described above.
- the air in the polymerization reactor and the trace amount of water were removed, and 200 g of butene, 0.15 MPa 3 ⁇ 4 was sequentially added to the polymerization reactor, 2 mL of triethyl aluminum having a concentration of 1 mol/L, and a concentration of 1.25 mL of 0.05 mol/L.
- the external electron donor cyclohexylmethyldimethoxysilane is added to the upper feeder of the polymerization reactor, and the promoter and the external electron donor are flushed into the polymerization reactor with 25 g of liquid 1-butene at the rotation speed. Stir at 450 rpm/min.
- the isotacticity of the composite is determined by diethyl ether extraction. The specific steps are as follows: Weigh 0.1 ⁇ 0.2g of poly-1-butene composite, cut it, put it into the Soxhlet extractor with filter paper, extract it in boiling ether for 48 hours, take it out and put it in vacuum drying oven. Dry to constant weight, weigh, and calculate the insoluble content. The insoluble matter is isotactic polybutene, and the insoluble content is used to indicate the isotacticity of poly-1-butene.
- the melting point, crystallinity, and the like of the composite were tested by DSC.
- the specific conditions are as follows: Under the protection of nitrogen, the poly-1-butene composite containing the nucleating agent is heated to 200 Torr for 5 minutes, and after cooling to room temperature, the temperature is raised and lowered again, and then allowed to stand for 7 days, and then heated and cooled once. In the DSC test, the heating and cooling rates were 10 ° C / min, and the melting point and crystallinity of the polybutene resin were measured after heating and cooling for 7 days.
- the crystallization rate of the composite can be evaluated by a polarizing microscope test.
- the specific method is as follows: The sample is heat treated on a polarizing microscope hot table at 20 CTC for 3 min, completely melted on a glass slide, covered with a cover glass, and naturally cooled, and the objective lens is enlarged to a desired multiple to observe the crystal form of the polymer.
- Example 26 ⁇ -quinacridone 17000 98.8 128.9 54.4 98.3
- Example 27 Triphenyldithiazide 13200 98.6 128.5 49.2 97.9
- Example 28 Diphenylamine Sulfide 7700 95.3 126.2 49.7 96.8
- Example 29 Quinacridone ⁇ 14500 98.5 127.9 50.4 94.3 Comparative example
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Abstract
A method for preparing isotactic poly-1-butene. The method comprises: adding a nucleating agent in a bulk polymerization reaction kettle with 1-butene, and performing bulk polymerization on 1-butene by using a Ziegler-Natta catalyst system. By means of the method, the crystallinity of the poly-1-butene is improved, the crystallization rate is improved, the shock resistance performance is improved, and the time of transiting the crystal form II to the crystal form I is shorted.
Description
一种等规聚 1 -丁烯的制备方法 Method for preparing isotactic poly-1-butene
技术领域 Technical field
本发明涉及一种釜内成核剂调控聚卜丁烯结晶度和晶型转变的等规聚 1 -丁烯的 制备方法。 The invention relates to a preparation method of isotactic poly-1-butene for controlling crystallinity and crystal transformation of polybutene in a nucleating agent in a kettle.
背景技术 Background technique
高等规聚 1-丁烯被称为"塑料中的黄金"， 具有突出的耐高温蠕变性、 耐低温性、 耐环境应力开裂性、 耐磨性和良好的韧性。 因此它适合于作挠性管材， 尤其适用于地 板采暖等建筑热水管， 其管道质轻、 柔韧、 抗冲击性好， 可在 95 °C以下长期使用， 是当今世界上性能最好的管材之一。 其长期使用环向应力是 PPR的 1.6倍以上、 是 PEX的 1.3倍以上， 最小水流压力损失是 PPR的五分之一、 是 PEX管的二分之一， 热膨胀系数是 PPR的四分之三、 是 PEX的五分之三。 High-precision 1-butene is called "gold in plastic" and has outstanding high temperature creep resistance, low temperature resistance, environmental stress crack resistance, wear resistance and good toughness. Therefore, it is suitable for flexible pipes, especially for building hot water pipes such as floor heating. Its pipes are light, flexible and impact resistant. It can be used at temperatures below 95 °C for a long time. It is the best pipe in the world. one. The long-term use of hoop stress is 1.6 times of PPR and 1.3 times of PEX. The minimum water flow pressure loss is one-fifth of PPR, one-half of PEX tube, and the thermal expansion coefficient is three-quarters of PPR. It is three-fifths of PEX.
等规聚 1-丁烯具有五种晶体型态， 分别为晶型 I、 晶型 II、 晶型 III、 晶型 Γ和晶 型 II，， 其中晶型 I、 晶型 II、 晶型 III和晶型 Γ熔点分别为 121 C〜136 °C、 100 X〜 120 V、 96 °C和 95 °C〜109 °C， 而且晶型 III和晶型 Γ结构不稳定， 当温度加热到 接近熔融温度时晶型 III和晶型 Γ晶型会转变成晶型 II。但晶型 II是一种亚稳态晶型， 其在室温下放置几天到几个星期后， 亚稳态晶型 II会转变为稳定的晶型 I， 从而使等 规聚 1 -丁烯的物理化学性能都不断的提升。 从而如何加快晶型 Π向晶型 I的转变成 为聚 1-丁烯工业发展研究的一个重点。 Isotactic 1-butene has five crystal forms, namely Form I, Form II, Form III, Form and Form II, of which Form I, Form II, Form III and The melting point of the crystal form is 121 C~136 °C, 100 X~120 V, 96 °C and 95 °C~109 °C, and the crystal form III and the crystal form are unstable, when the temperature is heated to near the melting temperature. The time crystal form III and the crystal form of the twin form are converted into the form II. However, Form II is a metastable crystal form. After standing at room temperature for several days to several weeks, metastable Form II will be converted to a stable Form I, thereby making isotactic polybutene. The physicochemical properties are constantly improving. Therefore, how to accelerate the transformation of the crystal form to the crystal form I becomes a focus of research on the industrial development of poly 1-butene.
中国专利 CN1330088A公开了一种釜内制备高结晶聚丙烯的方法。该方法采用复 合成核剂， 即至少一种有机金属盐类成核剂和一种无机成核剂组成。该方法的缺点是 采用了两种成核剂，且成核剂的用量大。中国专利 CN101429259A公开了一种釜内添 加成核剂制备 β晶型聚丙烯的方法。该方法通过在釜内添加稀土类的 β晶成核剂， 得 到聚丙烯粉料，通过挤出造粒后得到具有 3晶含量的聚丙烯树脂。该方法的缺点是采、 用稀土类的成核剂， 成本较高。 上述专利都只涉及到聚丙烯工艺， 而对于釜内添加成 核剂制备聚 1-丁烯的专利， 目前还尚未有报到。 Chinese patent CN1330088A discloses a process for preparing highly crystalline polypropylene in a kettle. The method consists of a synthetic nucleating agent, i.e., at least one organometallic salt nucleating agent and an inorganic nucleating agent. The disadvantage of this method is that two nucleating agents are used and the amount of nucleating agent is large. Chinese Patent No. CN 101 429 259 A discloses a method of preparing a β-crystalline polypropylene by adding a nucleating agent to a kettle. In this method, a rare earth β crystal nucleating agent is added to a kettle to obtain a polypropylene powder, which is subjected to extrusion granulation to obtain a polypropylene resin having a crystal content of 3. The disadvantage of this method is the use of rare earth nucleating agents, which are costly. The above patents only refer to the polypropylene process, and the patent for the preparation of poly 1-butene by adding a nucleating agent to the kettle has not yet been reported.
目前， 工业上使用的聚 1-丁烯产品， 都是经过加热熔融后， 放置一段时间后才 能加工使用。 从而延长了从生产聚 1-丁烯到制成成品之间的过程， 增加了生产成本。 发明内容 At present, the poly-1-butene products used in the industry are heated and melted and allowed to be processed for a period of time. This extends the process from the production of polybutene to the finished product, increasing production costs. Summary of the invention
本发明的目的是提供一种釜内成核剂调控聚 1-丁烯结晶度和晶型转变的等规聚
1 丁烯的制备方法； 在 1-丁烯聚合过程中添加少量成核剂， 提高聚 1-丁烯结晶度， 加快结晶速度， 同时提高聚 1-丁烯的抗冲击性能和缩短晶型 II向晶型 I转变时间。 The object of the present invention is to provide a nucleating agent in a kettle to regulate the isotactic polymerization of polybutene-butene crystallinity and crystal form transformation. 1 Preparation method of butene; Add a small amount of nucleating agent in the polymerization process of 1-butene to increase the crystallinity of poly-1-butene, accelerate the crystallization rate, improve the impact resistance of poly-1-butene and shorten the crystal form II The time is changed to Form I.
本发明所述的釜内成核剂调控聚 1-丁烯结晶度和晶型转变的等规聚 1-丁烯的制 备方法， 包括以下步骤： The method for preparing an isotactic polybutene which modulates the crystallinity and crystal form of polybutene in the in-cylinder nucleating agent according to the present invention comprises the following steps:
1. 在装有 1 丁烯的本体聚合反应釜中加入成核剂， 利用 Ziegler-Natta催化剂体 系催化 1-丁烯进行的本体聚合， 制备聚 1-丁烯与成核剂复合料； 1. Adding a nucleating agent to a bulk polymerization reactor containing 1 butene, and using a Ziegler-Natta catalyst system to catalyze bulk polymerization of 1-butene to prepare a poly 1-butene and a nucleating agent compound;
2. 将步骤 1制备得到的复合料直接加热熔融处理或经挤出造粒， 得到含成核剂 聚 1-丁烯树脂。 2. The composite prepared in the step 1 is directly subjected to heat-melting treatment or extrusion granulation to obtain a nucleating agent-containing polybutene resin.
所述的本体聚合按以下步骤进行： The bulk polymerization is carried out as follows:
1 ) 聚合开始之前， 用高纯氮气吹扫聚合反应釜， 以确保除掉聚合反应釜中的空 气和痕量的水； 1) Prior to the start of the polymerization, the polymerization reactor is purged with high purity nitrogen to ensure removal of air and traces of water from the polymerization reactor;
2)向步骤 1 )的聚合反应釜中加入氢气和液体 1-丁烯，其中液体 1-丁烯为 0.1〜 2.0kg, 氢气为 0〜0.3MPa， 在转速为 100〜600rpm/min下搅拌； 2) adding hydrogen and liquid 1-butene to the polymerization reactor of step 1), wherein the liquid 1-butene is 0.1 to 2.0 kg, the hydrogen is 0 to 0.3 MPa, and the stirring is performed at a rotation speed of 100 to 600 rpm/min;
3 ) 将 4〜200mg成核剂、 l〜200mmol垸基铝助催化剂、 0.5〜133mmol硅垸类 外给电子体加入步骤 1 ) 的聚合反应釜上部的加料器中； 3) 4 to 200 mg of a nucleating agent, 1 to 200 mmol of a mercapto aluminum cocatalyst, and 0.5 to 133 mmol of a silicon germanium external electron donor are added to the feeder in the upper portion of the polymerization reactor of the step 1);
4) 用液体 1-丁烯将步骤 3 ) 加料器中的成核剂、 垸基铝助催化剂、 硅烷类外给 电子体全部冲入到步骤 1 ) 的聚合反应釜中； 4) using the liquid 1-butene, the nucleating agent, the ruthenium-based aluminum co-catalyst, and the silane-based external electron donor in the step 3) are all flushed into the polymerization reactor of the step 1);
5 ) 将 MgCl2/TiC 负载型 Ziegler-Natta催化剂 5〜30mg加入到聚合反应釜上部 的加料器中， 用液体 1-丁烯将加料器中的 MgCl2/TiCl4负载型 Ziegler-Natta催化剂全 部冲入到步骤 1 )的聚合反应釜中，最终聚合反应釜中的液体 1-丁烯的量为 0.2〜3kg; 5) Add 5~30mg of MgCl 2 /TiC supported Ziegler-Natta catalyst to the feeder in the upper part of the polymerization reactor, and use the liquid 1-butene to charge the MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst in the feeder. Rushing into the polymerization reactor of step 1), the amount of liquid 1-butene in the final polymerization reactor is 0.2~3kg ;
6)将步骤 1 )的聚合反应釜温度升至 30〜80°C，聚合反应 1〜3小时，终止反应。 所述的垸基铝助催化剂： MgCl2/TiCl4负载型 Ziegler-Natta催化剂：硅烷类外给电 子体三者的摩尔比为 100〜500： 1〜20： 10〜40。 6) The temperature of the polymerization reactor of the step 1) is raised to 30 to 80 ° C, and the polymerization is allowed to proceed for 1 to 3 hours to terminate the reaction. The bismuth-based aluminum promoter: MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst: the molar ratio of the silane external electron donor is 100~500: 1~20: 10~40.
所述的 MgCl2/TiCl4负载型 Ziegler-Natta催化剂组分包括钛、 镁、 卤素、 给电子 体等组成的化合物。 The MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst component comprises a compound consisting of titanium, magnesium, halogen, an electron donor, and the like.
所述的垸基铝化合物通式为 AlRnX(3.n)， 式中 R为碳原子数 1〜20的烷基、 芳垸 基、 芳基等； X为卤素； 0≤n≤3的整数； 三甲基铝， 三乙基铝， 三异丁基铝， 一氢二 乙基铝， 一氯二乙基铝， 二氯一乙基铝等。 其中优选三乙基铝， 三异丁基铝。 The bismuth-based aluminum compound has the formula of AlR n X( 3 . n ), wherein R is an alkyl group having 1 to 20 carbon atoms, an aryl fluorenyl group, an aryl group or the like; X is a halogen; 0 ≤ n ≤ 3 Integer; trimethylaluminum, triethylaluminum, triisobutylaluminum, monohydrogenethylaluminum, diethylaluminum dichloride, dichloroethylaluminum, and the like. Among them, triethylaluminum, triisobutylaluminum is preferred.
所述的硅垸类外给电子体化合物通式为 RnSi(OR04^式中 R为 C1〜C10的烷基、 环垸基或芳基； 是含 1〜4个碳原子的烷基。例如苯基三甲氧基硅垸 (PTMS), 苯基
三乙氧基硅烷 (PTES),二苯基二甲氧基硅垸 (DPDMS),二苯基二乙氧基硅垸 (DPDES), 二环戊基二甲氧基硅垸 (DCPDMS), 环己基甲基二甲氧基硅烷 (CHMDMS), 二异丁基 二甲氧基硅垸 (DIBDMS), 二异丙基二甲氧基硅垸 (DIPDMS),优选环己基甲基二甲氧 基 院。 The silicone-based outer embankment to the electron donor is a compound of formula RnSi (OR0 4 ^ C1~C10 wherein R is an alkyl group, cycloalkyl group or aryl embankment; is an alkyl group having 1 ~ 4 carbon atoms, for example. Phenyltrimethoxysilane (PTMS), phenyl Triethoxysilane (PTES), diphenyldimethoxysilane (DPDMS), diphenyldiethoxysilane (DPDES), dicyclopentyldimethoxysilane (DCPDMS), ring Hexylmethyldimethoxysilane (CHMDMS), diisobutyldimethoxysilane (DIBDMS), diisopropyldimethoxysilane (DIPDMS), preferably cyclohexylmethyldimethoxy .
所述的成核剂为一种无机盐类化合物。 例如纳米碳酸钙、 碳酸钡、 碳酸镁、 钛白 粉、 滑石粉、 二氧化硅、 氧化钙、 炭黑、 云母、 高岭土、 硫酸镁、 硫酸钡 The nucleating agent is an inorganic salt compound. For example, nano calcium carbonate, barium carbonate, magnesium carbonate, titanium dioxide, talc, silica, calcium oxide, carbon black, mica, kaolin, magnesium sulfate, barium sulfate
、 硫酸锌、 硫酸钙晶须、 炭化硅、 氮化硅、 二氧化钛、 氧化锌、 氧化镁、 氧化锑、 氧 化钡、 三氧化二铝、 碳酸氢钙、 磷酸钙、 磷酸氢钙等。 , zinc sulfate, calcium sulfate whiskers, silicon carbide, silicon nitride, titanium dioxide, zinc oxide, magnesium oxide, cerium oxide, cerium oxide, aluminum oxide, calcium hydrogencarbonate, calcium phosphate, calcium hydrogen phosphate, and the like.
所述的成核剂为一种羧酸及其盐类化合物，例如硬脂酸钠、硬脂酸钙、硬脂酸钾、 硬脂酸镁、 硬脂酸钡、 苯甲酸钠、 己二酸钠、 己二酸镁、 己二酸钙、 己二酸钾、 己二 酸钡、 丁二酸钠、 丁二酸镁、 丁二酸钙、 丁二酸钾、 二 (4-丁基苯甲酸)羟基铝 The nucleating agent is a carboxylic acid and a salt thereof, such as sodium stearate, calcium stearate, potassium stearate, magnesium stearate, barium stearate, sodium benzoate, sodium adipate. , magnesium adipate, calcium adipate, potassium adipate, barium adipate, sodium succinate, magnesium succinate, calcium succinate, potassium succinate, bis(4-butylbenzoic acid) Hydroxyl aluminum
(A1-PTBBA), 二环 [2.2.1]庚垸二羧酸盐 (HPN-68)、 二环 [2.2.1]庚烷 -2,3-二羧酸钠盐 (HPN-68L); 以及硬脂酸盐与其它物质的混合体系， 例如硬脂酸钙与庚二酸体系等。 (A1-PTBBA), bicyclo [2.2.1] heptane dicarboxylate (HPN-68), bicyclo [2.2.1] heptane-2,3-dicarboxylate sodium salt (HPN-68L); And a mixture of stearates and other substances, such as calcium stearate and pimelic acid systems.
所述的成核剂为一种山梨醇类化合物， 其通式为- The nucleating agent is a sorbitol compound having the formula -
所述的成核剂为一种酰胺类化合物。例如 Ν，Ν'-二苯基丙二酰胺、 Ν，Ν，-二苯基顺 丁二甲酰胺、 Ν，Ν'-二苯基己二酰胺、 Ν,Ν'-二环己基对苯二甲酰胺、 Ν,Ν'-二环己基邻 苯二甲酰胺、 Ν,Ν'-二环戊基对苯二酰胺、 Ν,Ν'-二环戊基邻苯二酰胺、 Ν,Ν，-二环己基 -2,6-萘二甲酰胺、 Ν，Ν，-二环戊基 -2,6-萘二甲酰胺、 Ν，Ν，-二苯基丁二酰胺、 Ν，Ν，-二苯 基戊二酰胺、苯二甲酸环己酰胺、萘二甲酸环己酰胺、 Ν,Ν'-二环己基丙二酰胺、 Ν，Ν，- 二环戊基丙二酰胺、 Ν，Ν，-二环己基丁二酰胺、 Ν，Ν'-二环戊基丁二酰胺、 Ν，Ν，-二环己 基戊二酰胺、 Ν,Ν'-二环戊基戊二酰胺、 Ν,Ν'-二环己基己二酰胺、 Ν,Ν'-二环戊基己二 酰胺等。 The nucleating agent is an amide compound. For example, hydrazine, Ν'-diphenylmalonamide, hydrazine, hydrazine, -diphenyl cis-butane dimethylamide, hydrazine, Ν'-diphenyl adipamide, hydrazine, Ν'-dicyclohexyl-p-phenylene Formamide, hydrazine, Ν'-dicyclohexylphthalamide, hydrazine, Ν'-dicyclopentyl terephthalamide, hydrazine, Ν'-dicyclopentyl phthalamide, hydrazine, hydrazine, - Dicyclohexyl-2,6-naphthalamide, hydrazine, hydrazine, -dicyclopentyl-2,6-naphthalamide, hydrazine, hydrazine, -diphenyl succinic acid, hydrazine, hydrazine, - two Phenylglutaramide, cyclohexamide phthalate, cyclohexamide naphthalene dicarboxylate, hydrazine, Ν'-dicyclohexylmalonamide, hydrazine, hydrazine, -dicyclopentylmalonamide, hydrazine, hydrazine, - Dicyclohexyl succinamide, hydrazine, Ν'-dicyclopentyl succinamide, hydrazine, hydrazine, -dicyclohexylglutaramide, hydrazine, Ν'-dicyclopentylglutaminamide, hydrazine, Ν'- Dicyclohexyl adipamide, hydrazine, Ν'-dicyclopentyl adipamide, and the like.
所述的成核剂为一类稠环类化合物。例如 γ -喹吖啶酮 (Ε3Β)、三苯二噻嗪 (TPDT)、 硫化二苯胺 (MBIM)、 蒽、 菲、 δ -喹吖啶酮、 有机染料 (溶靛素金黄、 灰、 棕、 紫红)、 喹吖啶酮醌、 双偶氮黄等。 The nucleating agent is a class of fused ring compounds. For example, γ-quinacridone (Ε3Β), triphenyldithiazide (TPDT), diphenylamine sulfide (MBIM), hydrazine, phenanthrene, δ-quinacridone, organic dye (solubilin golden, gray, brown, Purple red), quinacridone oxime, bisazo yellow, etc.
所述的催化剂的活性 (g/gCat)= 合产物的质量 (gy催化剂的质量 (m)。 The activity of the catalyst (g/gCat) = the mass of the combined product (mass of the gy catalyst (m).
具体实施方式 实施例 1 DETAILED DESCRIPTION OF THE INVENTION Example 1
采用上述的本体聚合法进行聚合反应。除去聚合反应釜中的空气和痕量的水， 向 聚合反应釜中依次加入 200g卜丁烯， 0.15MPa H2， 将 4mg的无机成核剂二氧化硅， 2mL浓度为 lmol/L的三乙基铝， 1.25mL浓度为 0.05mol/L的外给电子体环己基甲基 二甲氧基硅垸加入聚合反应釜上部的加料器中， 用 25g液体 1-丁烯将成核剂、 助催 化剂、 外给电子体冲入到聚合反应釜中， 在转速为 450rpm/min 下搅拌。 将 10mg MgCl2/TiCl4负载型 Ziegler-Natta催化剂加入到聚合反应釜上部的加料器中， 用 25g 液体卜丁烯将其冲入聚合反应釜中， 在 30°C下进行聚合反应， 反应时间为 2小时。 反应结束后， 排出剩余的 1-丁烯， 终止反应， 得到聚 1-丁烯与成核剂的复合料。 实施例 2〜29 The polymerization was carried out by the bulk polymerization method described above. The air in the polymerization reactor and the trace amount of water were removed, and 200 g of butene, 0.15 MPa H 2 , 4 mg of inorganic nucleating agent silica, and 2 mL of triethyl ether having a concentration of 1 mol/L were sequentially added to the polymerization reactor. Base aluminum, 1.25mL of 0.05mol/L external electron donor cyclohexylmethyldimethoxysilane was added to the upper feeder of the polymerization reactor, and 25g of liquid 1-butene was used to nucleating agent and cocatalyst. The external electron donor was flushed into the polymerization reactor and stirred at a rotation speed of 450 rpm/min. 10 mg of MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst was added to the feeder in the upper part of the polymerization reactor, and 25 g of liquid butene was charged into the polymerization reactor, and polymerization was carried out at 30 ° C for reaction time. It is 2 hours. After the completion of the reaction, the remaining 1-butene was discharged, and the reaction was terminated to obtain a composite of poly-1-butene and a nucleating agent. Example 2~29
采用与实施例 1相同的本体聚合方法，不同之处是将实施例 1中的成核剂二氧化 硅分别改为 4mg的纳米碳酸钙、 滑石粉、 硫酸钙晶须、 氧化镁、 三氧化二铝、 硬脂 酸钙、 苯甲酸钠、 丁二酸钙、 硬脂酸钙与庚二酸混合体系、 二 (4-丁基苯甲酸)羟基铝 (A1-PTBBA)、二环 [2.2.1]庚垸二羧酸盐 (HPN-68)、 1,3:2,4-二 (亚苄基) -D-山梨醇 (DBS)、
1 ,3:2,4-对氯二苄叉山梨醇 (CDBS)、 1,3:2,4-二 (对乙基苄叉)山梨醇 (EDBS)、 1,3:2,4-二The same bulk polymerization method as in Example 1 was employed except that the nucleating agent silica of Example 1 was changed to 4 mg of nano calcium carbonate, talc, calcium sulfate whisker, magnesium oxide, and trioxide, respectively. Aluminum, calcium stearate, sodium benzoate, calcium succinate, calcium stearate and pimelic acid mixed system, bis(4-butylbenzoic acid) hydroxy aluminum (A1-PTBBA), bicyclo[2.2.1] Glyoxime dicarboxylate (HPN-68), 1,3:2,4-di(benzylidene)-D-sorbitol (DBS), 1, 3:2,4-p-chlorodibenzylidene sorbitol (CDBS), 1,3:2,4-di(p-ethylbenzylidene) sorbitol (EDBS), 1,3:2,4-di
(3,4-二甲基亚苄基)山梨醇 (DMDBS)、 1，3:2,4-二 (对甲氧基苄基） 山梨醇 (DOS)、 1,3- (对 氯亚苄基) -2,4- (对甲基亚苄基) -D-山梨醇、 2，2-亚甲基-二 (4,6-二正丁基苯酚)磷酸钠(3,4-dimethylbenzylidene) sorbitol (DMDBS), 1,3:2,4-di(p-methoxybenzyl) sorbitol (DOS), 1,3-(p-chlorobenzylidene) -2,4-(p-methylbenzylidene)-D-sorbitol, 2,2-methylene-bis(4,6-di-n-butylphenol) sodium phosphate
(NA- 11)、双 (2,4-二叔丁基苯基)磷酸钠 (ΝΑ-10)、 Ν,Ν'-二苯基丙二酰胺、 Ν，Ν，-二环己 基 -2,6-萘二甲酰胺、苯二甲酸环己酰胺、萘二甲酸环己酰胺、 Ν，Ν，-二环戊基戊二酰胺、 γ -喹吖啶酮 (Ε3Β)、 三苯二噻嗪 (TPDT)、 硫化二苯胺、 喹吖啶酮醌。 (NA-11), sodium bis(2,4-di-tert-butylphenyl)phosphate (ΝΑ-10), hydrazine, Ν'-diphenylmalonamide, hydrazine, hydrazine, dicyclohexyl-2, 6-naphthalamide, cyclohexamide phthalate, cyclohexamide naphthalene dicarboxylate, hydrazine, hydrazine, dicyclopentylglutalamide, γ-quinacridone (Ε3Β), triphenyldithiazide TPDT), diphenylamine sulfide, quinacridonequinone.
对比实例 1 Comparative example 1
采用上述的本体聚合法进行聚合反应。除去聚合反应釜中的空气和痕量的水， 向 聚合反应釜中依次加入 200g卜丁烯， 0.15MPa ¾， 将 2mL浓度为 lmol/L的三乙基 铝， 1.25mL浓度为 0.05mol/L的外给电子体环己基甲基二甲氧基硅垸加入聚合反应釜 上部的加料器中， 用 25g液体 1-丁烯将助催化剂、 外给电子体冲入到聚合反应釜中， 在转速为 450rpm/min下搅拌。 将 lOmg MgCl2/TiCl4负载型 Ziegler-Natta催化剂加入 到聚合反应釜上部的加料器中， 用 25g液体 1-丁烯将其冲入聚合反应釜中， 在 30°C 下进行聚合反应， 反应时间为 2小时。 反应结束后， 排掉剩余的 1-丁烯， 终止反应， 得到聚 1-丁烯产品。 工业实用性 The polymerization was carried out by the bulk polymerization method described above. The air in the polymerization reactor and the trace amount of water were removed, and 200 g of butene, 0.15 MPa 3⁄4 was sequentially added to the polymerization reactor, 2 mL of triethyl aluminum having a concentration of 1 mol/L, and a concentration of 1.25 mL of 0.05 mol/L. The external electron donor cyclohexylmethyldimethoxysilane is added to the upper feeder of the polymerization reactor, and the promoter and the external electron donor are flushed into the polymerization reactor with 25 g of liquid 1-butene at the rotation speed. Stir at 450 rpm/min. 10 mg MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst was added to the feeder in the upper part of the polymerization reactor, and 25 g of liquid 1-butene was used to flush it into the polymerization reactor, and polymerization was carried out at 30 ° C for reaction time. It is 2 hours. After the end of the reaction, the remaining 1-butene was drained off and the reaction was terminated to obtain a poly-1-butene product. Industrial applicability
所述的复合料的等规度采用***抽提法。 具体步骤为： 称取 0.1〜0.2g聚 1-丁烯 复合料， 剪碎后用滤纸包好放入索氏提取器中， 在沸腾的***中抽提 48小时， 取出 后在真空干燥箱中干燥至恒重， 称重， 计算不溶物含量。 不溶物为等规聚 1-丁烯， 采 用不溶物含量来表示聚 1-丁烯的等规度。 The isotacticity of the composite is determined by diethyl ether extraction. The specific steps are as follows: Weigh 0.1~0.2g of poly-1-butene composite, cut it, put it into the Soxhlet extractor with filter paper, extract it in boiling ether for 48 hours, take it out and put it in vacuum drying oven. Dry to constant weight, weigh, and calculate the insoluble content. The insoluble matter is isotactic polybutene, and the insoluble content is used to indicate the isotacticity of poly-1-butene.
所述的复合料的熔点、 结晶度等通过 DSC进行测试。 具体条件为： 在氮气保护 下， 将含有成核剂的聚 1-丁烯复合料升温至 200Ό熔融 5分钟， 冷却至室温后， 再一 次升温、 降温， 然后放置 7天后再升温、 降温一次。 DSC测试， 升温和降温速率为 10°C/min， 取放置 7天后升温和降温结果测得聚卜丁烯树脂的熔点、 结晶度。 The melting point, crystallinity, and the like of the composite were tested by DSC. The specific conditions are as follows: Under the protection of nitrogen, the poly-1-butene composite containing the nucleating agent is heated to 200 Torr for 5 minutes, and after cooling to room temperature, the temperature is raised and lowered again, and then allowed to stand for 7 days, and then heated and cooled once. In the DSC test, the heating and cooling rates were 10 ° C / min, and the melting point and crystallinity of the polybutene resin were measured after heating and cooling for 7 days.
所述的复合料的结晶速度可以通过偏光显微镜测试， 进行评估。 具体方法为： 试 样在偏光显微镜热台上 20CTC热处理 3min， 使其完全熔融在载玻片上， 盖上盖玻片， 自然冷却， 将物镜放大到所需的倍数， 观察聚合物结晶形态。 The crystallization rate of the composite can be evaluated by a polarizing microscope test. The specific method is as follows: The sample is heat treated on a polarizing microscope hot table at 20 CTC for 3 min, completely melted on a glass slide, covered with a cover glass, and naturally cooled, and the objective lens is enlarged to a desired multiple to observe the crystal form of the polymer.
所述的聚 1-丁烯复合料的晶型 II向晶型 I的转变快慢， 可以通过 X射线衍射法 (XRD法)进行表征。 利用 2Θ=9.8°和 2Θ=11.6°处晶型 I和晶型 II的特征衍射峰的高度 比来计算各晶型的相对含量 =H9.8/(H9.8+Hu.6))和 尸 Hn.6/(H9.8+ HU .6))。 我们
将加热熔融的聚卜丁烯产品在室温下放置 7天后，测定晶型 I所占的比例，从而确定 晶型 II向晶型 I的转变快慢。 晶型 I所占的比例越大， 说明晶型 Π向晶型 I的转变越 快。 表一本体聚合法釜内制备聚 1-丁烯产品物性一览表 The conversion of Form II of the polybutene-butene composite to Form I is fast and can be characterized by X-ray diffraction (XRD). Calculate the relative content of each crystal form using the height ratio of the characteristic diffraction peaks of Form I and Form II at 2Θ=9.8° and 2Θ=11.6°=H 9 . 8 /(H 9 . 8 +Hu. 6 )) And the corpse H n . 6 / (H 9 . 8 + HU . 6 )). Us After the heat-melted polybutene product was allowed to stand at room temperature for 7 days, the proportion of the crystalline form I was measured to determine the transition speed of the crystalline form II to the crystalline form I. The larger the proportion of crystal form I, the faster the transition of crystal form to crystal form I. Table 1 Physical Properties of Polybutene-butene Products Prepared in Bulk Polymerization Process
1，3:2,4-二 (3,4-二 1,3:2,4-two (3,4-two
实施例 16 甲基亚苄基)山 11300 96.8 126.4 50.5 97.6 梨醇 Example 16 Methylbenzylidene) Mountain 11300 96.8 126.4 50.5 97.6 Pearol
1,3 :2,4-二 (对甲 1,3:2,4-two (pair
实施例 17 氧基苄基） 山梨 13200 98.4 130.2 55.6 98.5 醇 Example 17 Oxybenzyl) Yamanashi 13200 98.4 130.2 55.6 98.5 Alcohol
1 ,3- (对氯亚苄 1 ,3- (p-chlorobenzylidene)
实施例 18 基) -2,4- (对甲基 13100 98.9 128.7 56.2 98.7 亚苄基) --山梨醇 Example 18 Base) -2,4-(p-methyl 13100 98.9 128.7 56.2 98.7 benzylidene) - sorbitol
2,2-亚甲基-二 2,2-methylene-di
实施例 19 (4，6-二正丁基苯 12500 95.4 125.9 47.5 97.6 酚:)磷酸钠 Example 19 (4,6-di-n-butylbenzene 12500 95.4 125.9 47.5 97.6 phenol:) sodium phosphate
双 (2,4-二叔丁基 Double (2,4-di-tert-butyl)
实施例 20 13000 95.5 126.3 50.2 97.4 苯基)磷酸钠 Example 20 13000 95.5 126.3 50.2 97.4 Phenyl) sodium phosphate
Ν,Ν'-二苯基丙 Ν,Ν'-diphenyl propyl
实施例 21 7900 95.1 125.6 53.4 98.6 二酰胺 Example 21 7900 95.1 125.6 53.4 98.6 Diamide
Ν，Ν'-二环己基 Ν,Ν'-dicyclohexyl
实施例 22 8600 94.6 125.9 50.9 96.9 Example 22 8600 94.6 125.9 50.9 96.9
-2,6-萘二甲酰胺 -2,6-naphthalocyanamide
苯二甲酸环己酰 Cyclohexanoyl phthalate
实施例 23 9680 95.3 126.5 51.3 96.3 胺 Example 23 9680 95.3 126.5 51.3 96.3 Amine
萘二甲酸环己酰 Naphthyl naphthalate
实施例 24 10800 95.1 126.8 50.5 96.9 胺 Example 24 10800 95.1 126.8 50.5 96.9 Amine
Ν,Ν'-二环戊基 Ν,Ν'-dicyclopentyl
实施例 25 14600 96.3 127.8 50.6 93.2 戊二酰胺 Example 25 14600 96.3 127.8 50.6 93.2 glutaramide
实施例 26 γ-喹吖啶酮 17000 98.8 128.9 54.4 98.3 实施例 27 三苯二噻嗪 13200 98.6 128.5 49.2 97.9 实施例 28 硫化二苯胺 7700 95.3 126.2 49.7 96.8 实施例 29 喹吖啶酮醌 14500 98.5 127.9 50.4 94.3
对比实例 Example 26 γ-quinacridone 17000 98.8 128.9 54.4 98.3 Example 27 Triphenyldithiazide 13200 98.6 128.5 49.2 97.9 Example 28 Diphenylamine Sulfide 7700 95.3 126.2 49.7 96.8 Example 29 Quinacridone 醌 14500 98.5 127.9 50.4 94.3 Comparative example
12000 97.7 125.1 40.1 89.2 12000 97.7 125.1 40.1 89.2
1 由表一可知，加入成核剂后能够显著提高聚 1-丁烯的结晶度、并且能够加速晶型 II向晶型 I的转变。 由附图 1、 2、 3、 4的对比能够发现， 加入成核剂后能够显著加 快结晶速度， 并且加入成核剂后 "黑十字"球晶清晰程度变弱， 晶粒变小， 晶粒变得 完善且尺寸均一， 从而能够显著提高聚 1-丁烯的抗冲击性能。
1 It can be seen from Table 1 that the addition of a nucleating agent can significantly increase the crystallinity of poly-1-butene and accelerate the conversion of Form II to Form I. From the comparison of Figures 1, 2, 3, and 4, it can be found that the crystallization rate can be significantly accelerated after the addition of the nucleating agent, and the "black cross" spherulites become weaker and the grains become smaller after adding the nucleating agent. It is perfected and uniform in size, so that the impact resistance of poly-1-butene can be significantly improved.
Claims
1 . 一种等规聚 1-丁烯的制备方法， 其特征在于： What is claimed is: 1. A method for preparing isotactic poly 1-butene, characterized by:
1 ) 向聚合反应釜中加入氢气和液体 1 丁烯， 其中液体卜丁烯为 0.1〜2.0kg， 氢 气为 0〜0.3MPa， 在转速为 100〜600rpm/min下搅拌； 1) adding hydrogen and liquid 1 butene to the polymerization reactor, wherein the liquid buprene is 0.1 to 2.0 kg, the hydrogen gas is 0 to 0.3 MPa, and the stirring is performed at a rotation speed of 100 to 600 rpm/min;
2 ) 将 4〜200mg成核剂、 〜 200mmol垸基铝助催化剂、 0.5〜133mmol硅垸类 外给电子体加入聚合反应釜上部的加料器中； 2) 4~200mg nucleating agent, ~200mmol sulfhydryl aluminum cocatalyst, 0.5~133mmol silicon germanium external electron donor is added to the feeder in the upper part of the polymerization reactor;
3 )用液体卜丁烯将加料器中的成核剂、 垸基铝助催化剂、 硅烷类外给电子体全 部冲入到聚合反应釜中； 3) flushing the nucleating agent, the ruthenium-based aluminum co-catalyst, and the silane-based external electron donor in the feeder into the polymerization reactor with the liquid butene;
4) 将 MgCl2/TiCl4负载型 Ziegler-Natta催化剂 5〜30mg加入到聚合反应釜上部 的加料器中， 用液体 1 -丁烯将加料器中的 MgCl2/TiCl4负载型 Ziegler-Natta催化剂全 部冲入到的聚合反应釜中， 最终聚合反应釜中的液体 1-丁烯的量为 0.2〜3.0kg; 4) Add 5 ~30mg of MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst to the feeder in the upper part of the polymerization reactor, and use the liquid 1-butene to charge the MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst in the feeder. All rushed into the polymerization reactor, the amount of liquid 1-butene in the final polymerization reactor is 0.2~3.0kg;
5 ) 将聚合反应釜温度升至 30〜80°C， 聚合反应 1〜3小时， 终止反应。 5) The temperature of the polymerization reactor is raised to 30 to 80 ° C, and the polymerization is allowed to proceed for 1 to 3 hours to terminate the reaction.
2.根据权利要求 1所述的等规聚 1-丁烯的制备方法， 其特征在于： Ziegler-Natta 催化剂体系的助催化剂垸基铝化合物选自通式 AlRnX(3-n)， 式中 R为碳原子数为 1〜 20的垸基、 环垸基、 芳烷基或芳基； X为卤素； n为 0〜3的整数。 The method for preparing isotactic 1-butene according to claim 1, wherein the promoter of the Ziegler-Natta catalyst system is selected from the group consisting of the general formula AlR n X( 3 - n ), Wherein R is an indenyl group, a cyclodecyl group, an aralkyl group or an aryl group having 1 to 20 carbon atoms; X is a halogen; and n is an integer of 0 to 3.
3. 根据权利要求 1 所述的等规聚 1-丁烯的制备方法， 其特征在于： 所述的 Ziegler-Natta催化剂体系的外给电子体是选自通式 RnSi(OR 4^的硅氧垸类化合物， 式中 R为 C1〜C10的垸基、 环垸基或芳基； Rt是含 1〜4个碳原子的垸基。 The method for preparing isotactic 1-butene according to claim 1, wherein the external electron donor of the Ziegler-Natta catalyst system is selected from the group consisting of R n Si (OR 4 ^) A siloxane compound, wherein R is a C1 to C10 fluorenyl group, a cycloalkyl group or an aryl group; and R t is a fluorenyl group having 1 to 4 carbon atoms.
4. 根据权利要求 1所述的等规聚 1-丁烯的制备方法， 其特征在于： 所述的成核 剂包括无机盐类、 羧酸及其盐类、 山梨醇类、 有机磷酸盐类、 酰胺类或稠环芳烃类能 起到成核作用的物质。 The method for preparing an isotactic polybutene according to claim 1, wherein the nucleating agent comprises an inorganic salt, a carboxylic acid and a salt thereof, a sorbitol, an organic phosphate , amides or fused aromatic hydrocarbons can act as nucleating substances.
5. 根据权利要求 1所述的等规聚 1-丁烯的制备方法， 其特征在于： 所述的烷基 铝助催化剂： MgCl2/TiCl4负载型 Ziegler-Natta催化剂：硅垸类外给电子体三者的摩尔 比为 100〜500： 〜 20: 10〜40。
The method for preparing isotactic polybutene according to claim 1, wherein: the aluminum alkyl promoter: MgCl 2 /TiCl 4 supported Ziegler-Natta catalyst: silicon germanium externally The molar ratio of the three electron bodies is 100 to 500: ~ 20: 10 to 40.
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| CN201210461456.9A CN103819596B (en) | 2012-11-16 | 2012-11-16 | A kind of preparation method of isotactic poly-1-butylene |
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| WO2019241043A1 (en) * | 2018-06-12 | 2019-12-19 | Dow Global Technologies Llc | Activator-nucleator formulations |
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| CN104193870B (en) * | 2014-08-26 | 2017-06-16 | 河北工业大学 | A kind of powder preparation method of high isotactic polybutene 1 |
| CN106147046A (en) * | 2016-07-07 | 2016-11-23 | 山西省化工研究所（有限公司） | The compositions of a kind of isotactic polybutene 1 and binary acid diamide nucleator and preparation thereof |
| CN106046573A (en) * | 2016-07-07 | 2016-10-26 | 山西省化工研究所（有限公司） | Composition with isotactic polybutylene-1 and dibasic acid metal salt nucleating agent and preparation of composition |
| CN106147045B (en) * | 2016-07-07 | 2019-07-30 | 山西省化工研究所（有限公司） | A kind of composition and its preparation of isotactic PB Polybutene-1 and binary acid metallic salt nucleating agent |
| CN106147044B (en) * | 2016-07-07 | 2019-05-14 | 山西省化工研究所（有限公司） | A kind of composition and its preparation of isotactic PB Polybutene-1 and binary acid diamide nucleating agent |
| CN110791028B (en) * | 2019-11-11 | 2022-02-08 | 太原科技大学 | Preparation method and application of special aid for efficiently inducing crystal form transformation of polybutene-1 |
| CN110684288B (en) * | 2019-11-11 | 2021-12-10 | 太原科技大学 | Preparation method and application of special aid for improving polybutene-1 crystal form conversion rate |
| CN113493584A (en) * | 2020-03-18 | 2021-10-12 | 天津大学 | Method for regulating and controlling content of isotactic poly-1-butene crystal form III through cooling rate |
| CN114989334A (en) * | 2022-05-31 | 2022-09-02 | 山东京博石油化工有限公司 | In-situ nucleation isotactic polybutene-1 and its prepn |
| CN115819648B (en) * | 2023-02-20 | 2023-05-09 | 山东东方宏业新材料科技有限公司 | Continuous-process-based polybutene-1 production process and production system |
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| US4663394A (en) * | 1984-06-20 | 1987-05-05 | Sumitomo Chemical Company, Limited | Crystalline polybutene-1 compositions |
| CN1032172A (en) * | 1987-07-15 | 1989-04-05 | 奈斯特公司 | High-crystallinity poly-1-butylene and preparation method thereof and the used catalyzer of this method |
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