WO2014075381A1 - Procédé de préparation de poly-1-butène isotactique - Google Patents

Procédé de préparation de poly-1-butène isotactique Download PDF

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Publication number
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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WIPO (PCT)
Prior art keywords
butene
polymerization reactor
group
nucleating agent
liquid
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PCT/CN2013/000837
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English (en)
Chinese (zh)
Inventor
王秀绘
刘宾元
李建忠
张宝军
王亚丽
刘智博
贺德福
张莉
王桂芝
吴之禄
薛大庆
徐显明
陈谦
张德顺
任合刚
李群英
王力搏
于部伟
黄付玲
韩雪梅
高飞
曾群英
李文鹏
孙淑坤
韩云光
刘丽君
刘丽莹
张婧元
白玉洁
段兆磊
Original Assignee
中国石油天然气股份有限公司
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Publication of WO2014075381A1 publication Critical patent/WO2014075381A1/fr

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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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un procédé de préparation de poly-1-butène isotactique. Ledit procédé comprend les étapes consistant à ajouter un agent de nucléation dans un réacteur de polymérisation en masse contenant du 1-butène et à mettre en œuvre une polymérisation en masse sur le 1-butène en utilisant un système catalyseur Ziegler-Natta. Grâce au présent procédé, la cristallinité du poly-1-butène est améliorée, de même que sa vitesse de cristallisation et ses résultats en matière de résistance au choc, et la durée de passage de la forme cristalline II à la forme cristalline I est raccourcie.
PCT/CN2013/000837 2012-11-16 2013-07-11 Procédé de préparation de poly-1-butène isotactique WO2014075381A1 (fr)

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CN201210461456.9 2012-11-16
CN201210461456.9A CN103819596B (zh) 2012-11-16 2012-11-16 一种等规聚1-丁烯的制备方法

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Cited By (1)

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WO2019241043A1 (fr) * 2018-06-12 2019-12-19 Dow Global Technologies Llc Formulations d'activateur-nucléateur

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CN104193870B (zh) * 2014-08-26 2017-06-16 河北工业大学 一种高等规度聚丁烯‑1粉料制备方法
CN106147044B (zh) * 2016-07-07 2019-05-14 山西省化工研究所（有限公司） 一种等规聚丁烯-1与二元酸二酰胺类成核剂的组合物及其制备
CN106147045B (zh) * 2016-07-07 2019-07-30 山西省化工研究所（有限公司） 一种等规聚丁烯-1与二元酸金属盐类成核剂的组合物及其制备
CN106046573A (zh) * 2016-07-07 2016-10-26 山西省化工研究所（有限公司） 一种等规聚丁烯‑1与二元酸金属盐类成核剂的组合物及其制备
CN106147046A (zh) * 2016-07-07 2016-11-23 山西省化工研究所（有限公司） 一种等规聚丁烯‑1与二元酸二酰胺类成核剂的组合物及其制备
CN110684288B (zh) * 2019-11-11 2021-12-10 太原科技大学 一种用于提高聚丁烯-1晶型转化速率的专用助剂制备方法及专用助剂的应用
CN110791028B (zh) * 2019-11-11 2022-02-08 太原科技大学 一种用于高效诱导聚丁烯-1晶型转变的专用助剂制备方法及专用助剂的应用
CN113493584A (zh) * 2020-03-18 2021-10-12 天津大学 一种通过降温速率调控等规聚1-丁烯晶型iii含量的方法
CN114989334A (zh) * 2022-05-31 2022-09-02 山东京博石油化工有限公司 一种原位成核等规聚丁烯-1及其制备方法
CN115819648B (zh) * 2023-02-20 2023-05-09 山东东方宏业新材料科技有限公司 一种基于连续法的聚丁烯-1的生产工艺及生产系统

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WO2019241043A1 (fr) * 2018-06-12 2019-12-19 Dow Global Technologies Llc Formulations d'activateur-nucléateur
CN112166128A (zh) * 2018-06-12 2021-01-01 陶氏环球技术有限责任公司 活化剂-成核剂配制物
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