WO2012174965A1 - 一种基于多元共聚接枝反应的长支链聚丙烯的制备方法 - Google Patents

一种基于多元共聚接枝反应的长支链聚丙烯的制备方法 Download PDF

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WO2012174965A1
WO2012174965A1 PCT/CN2012/075794 CN2012075794W WO2012174965A1 WO 2012174965 A1 WO2012174965 A1 WO 2012174965A1 CN 2012075794 W CN2012075794 W CN 2012075794W WO 2012174965 A1 WO2012174965 A1 WO 2012174965A1
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chain branched
branched polypropylene
long
group
copolymerization reaction
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PCT/CN2012/075794
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English (en)
French (fr)
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辛忠
周帅
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华东理工大学
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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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/14—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers obtained by ring-opening polymerisation of carbocyclic compounds having one or more carbon-to-carbon double bonds in the carbocyclic ring, i.e. polyalkeneamers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92009—Measured parameter
    • B29C2948/922—Viscosity; Melt flow index [MFI]; Molecular weight
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92009—Measured parameter
    • B29C2948/92266—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92695—Viscosity; Melt flow index [MFI]; Molecular weight
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92761—Mechanical properties

Definitions

  • the present invention relates to the field of polypropylene technology, and more particularly to a process for preparing long-chain branched polypropylene based on a multicomponent copolymer grafting reaction.
  • PP is one of the most widely used resins in the world with the fastest growth in production. Compared with other thermoplastic resins, PP has the characteristics of low density, high melting point, wide source, low price, superior mechanical properties and good chemical stability. It has become a non-woven industry, such as packaging, light industry, construction, electronics, electrical appliances and automobiles. The lack of basic raw materials. Ordinary commodity PP, whether it is Ziegler-Natta or a metallocene catalyst-catalyzed polypropylene, is a linear structure of polypropylene (l inear PP, LPP), its molecular weight distribution is relatively narrow, resulting in the softening point and melting point of polypropylene Close, the melting range is shorter.
  • thermoforming process when the temperature is higher than the melting point, the melt viscosity drops sharply, and the strain hardening phenomenon does not occur when the molten state is stretched, thereby causing poor sag resistance of the polymer, and the wall thickness of the thermoformed product is not Both, extrusion coating, rolling edge curling, shrinkage, and collapse of the cells during extrusion foaming.
  • This shortcoming greatly limits the application of common polypropylene in thermoforming, foaming, extrusion coating, blow molding, and the like. Therefore, many countries have conducted in-depth research on the development of high-melt-strength polypropylene (HMSPP) in recent years, and have made breakthroughs in development, expanding the application area of PP and increasing its added value.
  • HMSPP high-melt-strength polypropylene
  • the only methods for developing HMSPP are: reactor modification, blend modification, and post reactor reform. Sex law. Its purpose is to increase its molecular weight, broaden its molecular weight distribution or introduce long-chain branched structures by various means.
  • the reactor modification method is to carry out a graft reaction in the polymerization process of propylene or in the late stage of polymerization, and directly synthesize polypropylene containing long-chain branches. The method is difficult to prepare and has a large investment. At present, Belgium and other countries have such technologies.
  • the blending modification method is to physically modify to increase the relative molecular weight distribution of PP, such as blending with polyethylene and elastomer.
  • the post-reactor modification method directly controls the grafting or partial crosslinking of the existing commercial PP by electron irradiation or melt grafting.
  • the method has less investment and relatively simple production process, and at the same time Maintain the various properties of polypropylene itself.
  • HMS PPs At present, there are several commercial HMS PPs, most of which are obtained by means of electron irradiation.
  • electronic radiation method some internationally renowned manufacturers have successively developed high melt strength polypropylenes for foaming, thermoforming and extrusion coating, such as Basell's Profax® and Boreal i s Daploy® models.
  • Current methods of electronic radiation are common in industrial production, electron radiation is limited by the depth of radiation and requires the protection of inert gases. At the same time, the equipment investment required is large and the products produced are expensive, which limits the method. Applications; Moreover, the branched structure introduced by electron radiation is only present in the amorphous phase region of the semi-crystalline PP, which greatly limits the number of branched chains. Therefore, people are keen to develop by reactive extrusion.
  • GMA G-grafted polypropylene
  • PP-gG G-grafted polypropylene
  • a polyfunctional chain extender with an amino group to carry out a reaction between functional groups to prepare LCB-PP.
  • Such a method not only requires a secondary high temperature reaction extrusion process to increase the control of the degradation of the polypropylene, but also causes the color of the product to yellow due to the presence of the amino group. So far, there has been no report on the preparation of LCB-PP by directly grafting long-chain macromonomers onto a polypropylene backbone by one-time reaction extrusion.
  • the object of the present invention is to overcome the deficiencies of the prior art and to provide a process for the preparation of long-chain branched polypropylene based on a multi-component copolymerization reaction.
  • a long-chain branched polypropylene based on a multi-copolymer grafting reaction the raw material composition of which is 100 parts by weight of polypropylene, 0.01 to 1 part of initiator, 0.1 to 5 parts of first grafting monomer, and second The grafting monomer is 0.1 to 5 parts.
  • the initiator is selected from the group consisting of a peroxide, an azo radical initiator or a combination thereof; specifically, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, azobis-iso-nitrile Or its combination
  • the first grafting monomer is selected from the group consisting of vinyl silicone oil
  • the vinyl silicone oil compound is a linear polysiloxane product which is kept in a liquid state at room temperature, and the structural formula is as shown in Formula I: wherein E1 to E5 are alkane A, an aryl group; E is an alkyl group, an aryl group, a hydrogen, a carbon functional group, a polyether chain, etc.; X is an alkyl group, an aryl group, an alkenyl group, an amino group, a hydrogen group, a hydroxyl group, an alkoxy group, an acetoxy group, Chlorine, carbon functional group and polyether chain; n, m 2 0, 1, 2, 3 ⁇ , where the value of n is selected according to the vinyl content required by the experiment, the vinyl quality of all types of vinyl silicone oil The percentage is 0. 01 ⁇ 15wt%;
  • the second grafting monomer of formula J is a C5 to C10 monoolefin or multiolefin compound such as T diene, piperylene, isoprene, cyclopentadiene, dicyclopentanyl Diene, norbornene anhydride, 1,3-hexadiene, 2,4-hexamethylene, 4-methyl-1,3 pentadiene, 1,4-pentadiene, 1,4-hexane One or more of alkene, styrene, and 1,4-heptadiene, octylene, ethylene oxide, decylene, and the like.
  • a preparation method of long-chain branched polypropylene based on multi-component copolymerization reaction wherein polypropylene, initiator, first grafting monomer, second grafting monomer are dry-mixed or solvent-mixed uniformly, and then fed into twin-screw extrusion Out of the machine, under the conditions of temperature control, screw speed and feed rate, melt reaction extrusion And granulating, preparing long-chain branched polypropylene with high melt strength; or adding polypropylene, initiator dry mixed or solvent mixed and added from the feeding port, and the first grafting monomer and the second grafting single
  • the body distribution is continuously fed from other feed ports of the extruder, melt-reacted and extruded, and granulated to prepare long-chain branched polypropylene having high melt strength;
  • the twin-screw extruder has a length to diameter ratio of 15 to 100, a rotation speed of 60 to 600 rpm, and a controllable temperature of 50 to 400 ° C.
  • the second heating section and the fourth heating section of the extruder are equipped with a lateral liquid feeding device, the liquid feed can be accurate to 0.1%.
  • a vacuum exhaust system with a condensing recovery unit at the exit section of the extruder at the end of the extruder can collect small molecules released during the reaction extrusion process, facilitating the analysis of the material composition during the reaction.
  • the twin-screw extruder has an aspect ratio ranging from 32 to 50.
  • each section of the extruder is controlled between 140 and 250 'C, wherein the temperature of the feed section is lower than the temperatures of the other sections.
  • the invention controls the degradation of the polypropylene in the graft modification process by controlling the ratio of the polypropylene, the initiator, the grafting monomer, the residence time and the reaction temperature, and the second grafting monomer, thereby obtaining a long-term property with good performance.
  • the product has its advantages in color, mechanical properties and processing properties, and is suitable for application fields such as foaming, thermoforming, film blowing and extrusion coating, and the preparation method is simple, easy to operate and easy to control. With the prospect of industrial implementation, it is easy to promote and apply.
  • Raw material components 100 parts of homopolypropylene, produced by Jiujiang Petrochemical Company, grade T30S; initiator is 0.8 parts of benzoyl peroxide; the first grafting monomer is substituted hydroxyvinyl silicone oil 2 parts The second grafting monomer is 2 parts of cyclopentadiene;
  • the extruder used is a co-rotating twin-screw extruder with a screw diameter of 30mm and a length to diameter ratio of 40. It adopts seven-stage heating and temperature control, and is the sixth in the extruder. The section is evacuated by vacuum.
  • Raw material components 100 parts of homopolypropylene, produced by Jiujiang Petrochemical Company, grade T30S; initiator is 0.8 parts of benzoyl peroxide; the first grafting monomer is substituted methyl vinyl silicone oil 2 a second grafting monomer is 2 parts of cyclopentadiene;
  • Raw material components 100 parts of homopolypropylene, produced by Jiujiang Petrochemical Company, grade T30S; initiator is 0.8 parts of benzoyl peroxide; the first grafting monomer is substituted amino group B 2 parts of alkenyl silicone oil; the second graft monomer is 2 parts of cyclopentadiene;
  • Raw material components 100 parts of homopolypropylene, produced by Jiujiang Petrochemical Company, grade T30S; initiator is 0.8 parts of benzoyl peroxide; the first grafting monomer is substituted acetoxy vinyl silicone oil 2 parts; the second grafting monomer is 2 parts of cyclopentadiene;
  • Example S The operation steps and implementation methods are the same as those in the first embodiment.
  • Example S
  • Raw material components 100 parts of homopolypropylene, produced by Jiujiang Petrochemical Company, grade T30S; initiator is 0.8 parts of benzoyl peroxide; the first grafting monomer is substituted chlorovinyl silicone oil 2 parts The second grafting monomer is 2 parts of cyclopentadiene;
  • Raw material components 100 parts of homopolypropylene, produced by Jiujiang Petrochemical Company, grade T30S; initiator is 0.5 parts of dicumyl peroxide; the first graft monomer is substituted phenyl vinyl silicone oil 0.5 parts; the second grafting monomer is 0.5 part of norbornene dianhydride;
  • Raw material components 100 parts of homopolypropylene, produced by Jiujiang Petrochemical Company, The grade T30S; the initiator is 0.5 parts of di-tert-butyl peroxide and 0.5 parts of azobis-iso-nitrile; the first graft monomer replaces 1 part of phenyl vinyl silicone oil and 1 part of substituted hydroxy vinyl silicone oil; The branch monomer is 0.5 parts of styrene and styrene;
  • Comparative Example 1 The raw material component contained only 100 parts of homopolypropylene, and the preparation process was the same as in Example 1. Comparative Example 2 The other components and preparation procedures were the same as in Example 1 except that the component first graft monomer was not contained. Comparative Example 3 The other components and preparation procedures were the same as in Example 1 except that the component second graft monomer was not contained. Comparative Example 4 The other components and preparation procedures were the same as in Example 1 except that the component initiator was not contained.
  • the measured rotation of the roller was 6 mm/ s 2 ; the number average molecular weight of the sample, the weight average molecular weight and the molecular weight distribution MWD 03 ⁇ 4/) were measured by a Waters 150C gel permeation chromatograph from the United States.
  • the measurement condition temperature was 150 ° C, and trichlorobenzene was used as a carrier solvent.
  • the Profax-814 sample in Table 1 is a high melt strength polypropylene product from Basell. It can be seen that the high melt strength polypropylene obtained by the method of the present invention has the same properties as those of the similar products of Basell, both in terms of melt strength and mechanical properties.
  • the invention overcomes the shortcomings existing in the prior art, and provides a method for preparing a gel-free, color-free, high-strength polypropylene having a long-chain branch by a one-step silane method with simple process, flexible operation and industrial implementation prospect.
  • the long-chain branched polypropylene material obtained by the invention is suitable for application fields such as foaming, thermoforming, film blowing and extrusion coating.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

本发明公开了一种基于多元共聚接枝反应的长支链聚丙烯的制备方法。接枝单体为双功能基团硅油类化合物与C5-C10类单烯烃或多烯烃类化合物，在反应挤出机中通过共聚接枝反应制备出具有高分子量、宽分子量分布、高熔体强度和高抗冲击强度的长支链聚丙烯。本发明提供了一种工艺简单、操作灵活、具有工业化实施前景的方法制备色泽良好的长支链高熔体强度聚丙烯；本发明得到的长支链聚丙烯材料适用于发泡、热成型、薄膜吹塑及挤出涂覆等应用领域。

Description

一种基于多元共聚接枝反应的长支链聚丙烯的制备方法
【技术领域】
本发明涉及聚丙烯技术领域，具体地说，是一种基于多元共聚接枝反 应的长支链聚丙烯的制备方法。 说
【背景技术】 书
PP 是目前世界上应用最为广泛， 产量增长最快的树脂之一。 与其他 热塑性树脂相比， PP 具有低密度、 高熔点、 来源广、 价格低以及机械性 能优越、 化学稳定性好等特点， 巳经成为包装、 轻工、 建筑、 电子、 电器 和汽车等行业不可缺少的基本原料。普通商品 PP，无论是 Ziegler-Natta 还是茂金属催化剂催化生产的聚丙烯， 均为线性结构的聚丙烯（l inear PP， LPP)， 其分子量分布相对较窄， 导致聚丙烯的软化点与熔点较接近， 熔程较短。这在热成型加工中表现为当温度高于熔点后，熔体粘度急剧下 降，熔融态下拉伸时不能出现应***化现象，进而导致聚合物的抗熔垂性 能差， 热成型制品壁厚不均， 挤出涂覆、压延时边缘卷曲、 收缩， 以及挤 出发泡时泡孔塌陷等问题。这一缺点极大地限制了普通聚丙烯在热成型加 工、 发泡、挤出涂覆、 吹塑等方面的应用。 因此， 许多国家近年来在开发 高熔体强度聚丙烯 （HMSPP) 进行了深入研究， 取得了突破进展， 扩大了 PP的应用领域， 使其附加值提高。
开发 HMSPP的只有方法有：反应器改性法、共混改性法和后反应器改 性法。其目的是通过各种途径来提高其分子量、加宽其分子量分布或者引 入长支链结构。反应器改性法是在丙烯聚合过程中或者聚合后期进行接枝 反应， 直接合成含有长支链的聚丙烯， 该方法制备难度大， 且投资大， 目 前比利时等国家拥有该类技术。 共混改性法是进行物理改性增大 PP的相 对分子量分布， 如与聚乙烯及弹性体等共混， 此法虽提高了 PP的熔体强 度，但其耐热性及易降解性也显著降低；后反应器改性法是直接对现有商 品化 PP通过电子辐射或者熔融接枝的方法进行可控接枝或部分交联， 该 类方法投资少、生产工艺相对简单，同时又能保持聚丙烯本身的各种性能。
目前，巳有好几种商业化 HMS PP , 其中的大部分是通过电子辐射的方 法得到的。通过电子辐射的方法，一些国际知名厂商巳经相继研发出可用 于发泡、 热成型和挤出涂敷等领域的高熔体强度聚丙烯， 如 Basell 的 Profax®和 Boreal i s 的 Daploy®型号。虽然目前在工业生产中， 电子辐 射的方法比较普遍，然而电子辐射法受限于辐射深度，且需要惰性气体的 保护， 同时所需的设备投资大从而所制备的产品价格昂贵，限制了此法的 应用； 而且， 由电子辐射引入的支链结构只是存在于半结晶 PP的非晶相 区域，这就大大限制了支化链的数目。于是人们热衷于采用反应挤出的方 法开发。
但目前， 采用反应挤出方法制备 HMSPP 巳实现工业化生产的报道很 少。只有北欧化工 (Boreal i s)公司曾报道用过氧化物和单体一起处理树脂: 在特殊的挤出机中进行接枝反应，制备了高熔体强度聚丙烯。 但文献报道 却很多，现有的文献报道采用的多官能团接枝单体主要是小分子单体，如 丙婦酸月旨类7¾， J" W. Yu, and C. Zhou, The preparation and rheology characterization of long chain branching polypropylene. Polymer, 2006. 47(23): p. 7962-7969],马来酸酐及其类似物 Y., X.M. Xie, and Β.Η. Guo, Study on styrene-assisted melt free-radical grafiing of maleic anhydride onto polypropylene. Polymer, 2001. 42(8): p. 3419-3425] , 乙烯基硅氧烷类 [Beltradn, M. and C. Mijangos, Silane grafting and moisture crosslinking of polypropylene. Polymer Engineering & Science, 2000. 40(7): p. 1534-1541 J 禾口苯乙婦及其类以物 "ZAfl g, Z" et at, A new grafting monomer for synthesizing long chain branched polypropylene through melt radical reaction. Polymer, 2011】。 采用小分子多官能团单体存在产物支化与分子量分布不 均一的特点。 还有些研究者利用功能化 PP和多官能团大分子化合物制备 了 LCB-PP , 例如， Li /L， S., et at, The melt grafiing preparation and rheological characterization of long chain branching polypropylene. Polymer, 2009. 50(25): p. 等采用反应挤出法以甲基丙烯酸缩水甘油酯
(GMA)为接枝单体先制备 G 接枝聚丙烯（PP-g-G )， 之后将其与带有 氨基的多官能团扩链剂再次采用反应挤出通过官能团之间的反应来制备 LCB-PP。此类方法不仅需要二次高温反应挤出过程加大了对聚丙烯降解的 控制， 同时由于氨基的存在会使产品的颜色变黄。到目前为止，还没有关 于采用一次反应挤出直接将长链大分子单体接枝到聚丙烯骨架上来制备 LCB-PP的报道。
【发明内容】
本发明的目的在于克服现有技术的不足，提供一种基于多元共聚接枝 反应的长支链聚丙烯的制备方法。
本发明的目的是通过以下技术方案来实现的： 一种基于多元共聚接枝反应的长支链聚丙烯，其原料组成的重量份数 为， 聚丙烯 100份， 引发剂 0.01〜1份， 第一接枝单体 0.1〜5份， 以及第 二接枝单体 0.1〜5份。
所述的引发剂选自过氧化物类、偶氮类自由基引发剂或其组合；具体 为氧化苯甲酰、过氧化二异丙苯、过氧化二叔 T基、偶氮二异 T腈或其组 合國
所述的第一接枝单体选自乙烯基硅油，乙烯基硅油类化合物为室温下 保持液体状态的线型聚硅氧烷产品， 结构式如式 I所示： 式中， E1〜E5为 烷基、 芳基； E为烷基、 芳基、 氢、 碳官能基及聚醚链等； X为烷基、 芳 基、 烷烯基、 氨基、 氢、 羟基、 烷氧基、 乙酰氧基、 氯、 碳官能基及聚醚 链等； n， m二 0、 1、 2、 3···， 其中 n值大小根据实验要求的乙烯基含量而 进行选择， 所有类型乙烯基硅油的乙烯基质量百分比都为 0. 01〜15wt%;
Rl 5 R3
CH2= CH— s Ii― 0 -t ΓSi— O jj S Ii—— X
I
k2 R R I 4 式 J 所述的第二接枝单体为 C5〜C10类单烯烃或多烯烃类化合物， 如 T 二烯、间戊二烯、异戊二烯、环戊二烯、双环戊二烯、降冰片烯酸酐、 1，3- 己二烯、 2，4-己二矯、 4-甲基 -1，3戊二烯、 1，4-戊二烯、 1，4-己二烯、 苯乙 烯、 和 1,4-庚二烯、 辛乙烯、 壬乙烯、 癸乙烯等中的一种或几种。 一种基于多元共聚接枝反应的长支链聚丙烯的制备方法， 将聚丙烯、 引发剂、第一接枝单体、第二接枝单体干混或溶剂混合均匀后喂入双螺杆 挤出机，在控制温度、螺杆转速和喂料速率的条件下，进行熔融反应挤出 并造粒，制备成具有高熔体强度的长支链聚丙烯； 或者将聚丙烯、引发剂 干混或溶剂混合后从喂料口加入，而第一接枝单体和第二接枝单体分布从 挤出机的其他进料口连续进料，进行熔融反应挤出并造粒，制备出具有高 熔体强度的长支链聚丙烯；
其中， 所述的双螺杆挤出机的长径比为 15〜100 的范围内， 转速为 60〜600rpm， 可控温度为 50〜400'C之间。挤出机第二加热段和第四加热 段配有侧向液体喂料装置， 其液体进料可以精确到 0.1%。 另外， 在挤出 机末端加热段靠出口位置带有冷凝回收装置的真空排气***，可以收集反 应挤出过程中释放的小分子物质， 便于反应过程中物料成分分析。
所述的双螺杆挤出机的长径比范围为 32〜50。
所述的挤出机的各段温度控制在 140〜250'C之间， 其中进料段的温 度低于其它各段的温度。
与现有技术相比， 本发明的积极效果是：
本发明通过控制聚丙烯、引发剂、接枝单体的比例、停留时间和反应 温度，并利用第二接枝单体控制接枝改性过程中聚丙烯的降解，从而获得 性能良好的含有长支链无凝胶的具有高熔体强度的长支链聚丙烯。该产品 在色泽、力学性能及加工性能等诸多方面均体现了其优越性，适用于发泡、 热成型、薄膜吹塑及挤出涂覆等应用领域，而且制备方法简单，操作容易， 便于控制， 具有工业化实施的前景， 易于推广应用。
【具体实施方式】
以下提供本发明一种基于多元共聚接枝反应的长支链聚丙烯的制备 方法的具体实施方式。 实施例 1
原材料组分（按重量份数）：均聚聚丙烯 100份， 九江石化公司生产， 牌号 T30S ; 引发剂为过氧化苯甲酰 0.8份； 第一接枝单体为取代羟基乙 烯基硅油 2份； 第二接枝单体为环戊二烯 2份；
双螺杆挤出机结构及功能： 所采用的挤出机为同向啮合双螺杆挤出 机， 螺杆直径为 30mm， 长径比为 40， 采用七段加热控温， 在挤出机的 第六段进行真空排气。
长支链聚丙烯的制备：将上述所有组分用高速混合机混合均匀，然后 加入双螺杆挤出机中进行反应挤出造粒即制得本发明产品。控制螺杆转速 为 150rpm,挤出机各段加热温度为： 165。C， 170。C， 180。C， 185。C， 190。C， 200。C， 200。C。 实施例 2
原材料组分（按重量份数）：均聚聚丙烯 100份， 九江石化公司生产， 牌号 T30S ; 引发剂为过氧化苯甲酰 0.8份； 第一接枝单体为取代甲基乙 烯基硅油 2份； 第二接枝单体为环戊二烯 2份；
其操作步骤及实施方法均同实施例 1。 实施例 3
原材料组分（按重量份数）：均聚聚丙烯 100份， 九江石化公司生产， 牌号 T30S ; 引发剂为过氧化苯甲酰 0.8份； 第一接枝单体为取代氨基乙 烯基硅油 2份； 第二接枝单体为环戊二烯 2份；
其操作步骤及实施方法均同实施例 1。 实施例 4
原材料组分（按重量份数）：均聚聚丙烯 100份， 九江石化公司生产， 牌号 T30S ; 引发剂为过氧化苯甲酰 0.8份； 第一接枝单体为取代乙酰氧 基乙烯基硅油 2份； 第二接枝单体为环戊二烯 2份；
其操作步骤及实施方法均同实施例 1。 实施例 S
原材料组分（按重量份数）：均聚聚丙烯 100份， 九江石化公司生产， 牌号 T30S ; 引发剂为过氧化苯甲酰 0.8份； 第一接枝单体为取代氯乙烯 基硅油 2份； 第二接枝单体为环戊二烯 2份；
其操作步骤及实施方法均同实施例 1。 实施例 6
原材料组分（按重量份数）：均聚聚丙烯 100份， 九江石化公司生产， 牌号 T30S ; 引发剂为过氧化二异丙苯 0.5份； 第一接枝单体为取代苯基 乙烯基硅油 0.5份； 第二接枝单体为降冰片烯二酸酐 0.5份；
其操作步骤及实施方法均同实施例 1。 实施例 7
原材料组分（按重量份数）：均聚聚丙烯 100份， 九江石化公司生产， 牌号 T30S ; 引发剂为过氧化二叔 T基 0.5份和偶氮二异 T腈 0.5份； 第一 接枝单体取代苯基乙烯基硅油 1份和取代羟基乙烯基硅油 1份;第二接枝 单体为和苯乙烯 0.5份；
其操作步骤及实施方法均同实施例 1。
对比实施例 1 原料组分只含有均聚聚丙烯 100份， 制备过程与实施例 1相同。 对比实施例 2 除不含组分第一接枝单体外， 其它组分与制备过程与实施例 1相同。 对比实施例 3 除不含组分第二接枝单体外， 其它组分与制备过程与实施例 1相同。 对比实施例 4 除不含组分引发剂外， 其它组分与制备过程与实施例 1相同。
由各实施例获得的材料性能见表 1。
表 1实施例制备的长支链聚丙烯的性能
弯曲模量 拉伸强度 冲击强度 结晶温度 瑢体强度 Mr Mr/M, 序号
CMpa) CMpa) Cj - m"1 ) CC ) CcN) C Kg/mo 1 ) 实施例 1 1282 35 156 128. 1 29. 2 384 7. 1 实施例 2 1296 35 141 126. 2 28. 1 379 6. 9 实施例 3 1267 36 157 126. 8 26. 9 368 6. 6 实施例 4 1296 36 158 127. 1 27. 3 372 6. 8 实施例 5 1264 34 148 128. 4 26. 8 367 6. 5 实施例 6 1278 37 146 124. 7 29. 1 383 7. 0 实施例 7 1289 33 152 125. 6 26. 5 365 6. 4
Profax-814 1215 33 128 127. 8 25. 9 359 6. 3 对比实施例 1 916 29 29 1 14. 1 2. 2 225 4. 4 对比实施例 2 1 178 37 66 127. 4 17. 1 306 5. 4 对比实施例 3 1 128 30 55 120. 6 3. 6 240 7. 1 对比实施例 4 958 28 55 1 14. 3 2. 5 225 4. 5 在表 1的数据中， 力学性能按照 ASTM的相应标准测定； 结晶温度通 过差示扫描量热仪进行测试， 测定时采用 20'C/m in的升降温速率； 熔体 强度以 EhedtenS71. 97 (德国， Gottfert)熔体强度测试仪测定， 滚轮转动 加速度为 6mm/S2 ; 样品的数均分子量 ， 重均分子量 以及分子量分布 MWD 0¾/ )用美国 Waters公司 150C型凝胶渗透色谱仪进行测定。测定条 件温度为 150°C， 用三氯苯作为载体溶剂。 表 1中的 Profax-814样品是 Basell 公司的高熔体强度聚丙烯产品。 可见， 以本发明方法得到的高熔 体强度聚丙烯， 无论是熔体强度还是力学性能， 都与 Basell公司的同类 产品的性能相当。
本发明克服现有技术中存在的缺点， 提供一种工艺简单、 操作灵活、 具有工业化实施前景的一步硅烷法制备无凝胶的、色泽良好、含长支链的 高熔体强度聚丙烯的方法。 本发明得到的长支链聚丙烯材料适用于发泡、 热成型、 薄膜吹塑及挤出涂覆等应用领域。

Claims

1. 一种基于多元共聚接枝反应的长支链聚丙烯， 其特征在于， 原料 组成的重量份数为，聚丙烯 100份，引发剂 0.01〜1份，第一接枝单体 0.1〜 5份， 以及第二接枝单体 0.1〜5份。
2. 如权利要求 1所述的一种基于多元共聚接枝反应的长支链聚丙烯， 权
其特征在于，所述的引发剂选自过氧化物、偶氮类自由基引发剂或其组合。
3. 如权利要求 2所述的一种基于多元共聚接枝反应的长支链聚丙烯， 其特征在于，所述的引发剂具体为氧化苯甲酰、过氧化二异丙苯、过氧化 二叔 T基、 偶氮二异 T腈或其组合。 书
4. 如权利要求 1所述的一种基于多元共聚接枝反应的长支链聚丙烯， 其特征在于， 所述的第一接枝单体选自乙烯基硅油。
5. 如权利要求 4所述的一种基于多元共聚接枝反应的长支链聚丙烯， 其特征在于，所述的乙烯基硅油化合物为室温下保持液体状态的线型聚硅 氧烷产品， 结构式如式 I所示： 式中， R1〜R5为烷基、 芳基； R为烷基、 芳基、 氢、 碳官能基及聚醚链； X为烷基、 芳基、 烷烯基、 氨基、 氢、 羟 基、 烷氧基、 乙酰氧基、 氯、 碳官能基及聚醚链； n， m=0、 1、 2、 3...， 其中 n值大小根据实验要求的乙烯基含量而进行选择，所有类型乙烯基硅 油的乙烯基质量含量都为 0.01〜15wt%;
Rl 5 R3
CH2= CH― s Ii― o -[ rSi— O jj S Ii—— X
I I
k2 R R4 式 I。
6. 如权利要求 1所述的一种基于多元共聚接枝反应的长支链聚丙烯， 其特征在于， 所述的第二接枝单体为 C5〜C10单烯烃或多烯烃化合物。
7. 一种基于多元共聚接枝反应的长支链聚丙烯的制备方法， 其特征 在于， 将聚丙烯、 引发剂、 第一接枝单体、 第二接枝单体干混或溶剂混合 均匀后喂入双螺杆挤出机， 在控制温度、 螺杆转速和喂料速率的条件下， 进行熔融反应挤出并造粒，制备成高熔体强度聚丙烯； 或者将聚丙烯、引 发剂干混或溶剂混合后从喂料口加入，而第一接枝单体和第二接枝单体分 别从挤出机的其他进料口连续进料，进行熔融反应挤出并造粒，制备出长 支链聚丙烯。
8. 如权利要求 7所述的一种基于多元共聚接枝反应的长支链聚丙烯 的制备方法，其特征在于，所述的双螺杆挤出机的长径比为 15〜100的范 围内， 转速为 60〜600rpm， 可控温度为 50〜400'C之间。
9. 如权利要求 7所述的一种基于多元共聚接枝反应的长支链聚丙烯 的制备方法， 其特征在于， 所述的双螺杆挤出机的长径比范围为 32〜50。
10. 如权利要求 7所述的一种基于多元共聚接枝反应的长支链聚丙烯 的制备方法， 其特征在于， 所述的挤出机的各段温度控制在 140〜250'C 之间， 其中进料段的温度低于其它各段的温度。
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