TWI679237B - Dynamic crosslinked thermoplastic elastomer and its process - Google Patents
Dynamic crosslinked thermoplastic elastomer and its process Download PDFInfo
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Abstract
本發明係有關於一種動態交聯熱塑性彈性體及其製程。動態交聯熱塑性彈性體主要成分包括乙烯-丙烯-非-共軛二烯橡膠(EPDM),聚丙烯(PP),及兩種交聯劑,其係經由動態交聯反應製備所得之混合物。在製備此種動態交聯熱塑性彈性體時,先將第一交聯劑和一些聚丙烯,及乙烯-丙烯-非-共軛二烯橡膠混練,進行初步交聯反應,形成第一混合物,接著再將第二交聯劑和新一批聚丙烯,乙烯-丙烯-非-共軛二烯橡膠及內含第一交聯劑之第一混合物進行混練,以產生交聯程度較高,力學特性及加工性較佳之動態交聯熱塑性彈性體。當製備之有流動性問題時,可將部分聚丙烯以低分子量低立體規整性之聚丙烯(low molecular weight and low modulus polypropylene)取代,以改善動態交聯熱塑性彈性體(TPV)流動性偏低問題,使其相關加工成型方法和應用範圍更加寬廣。 The present invention relates to a dynamically crosslinked thermoplastic elastomer and its process. The main components of a dynamically crosslinked thermoplastic elastomer include ethylene-propylene-non-conjugated diene rubber (EPDM), polypropylene (PP), and two kinds of crosslinking agents, which are mixtures prepared through a dynamic crosslinking reaction. When preparing such a dynamically crosslinked thermoplastic elastomer, first the first crosslinking agent and some polypropylene, and ethylene-propylene-non-conjugated diene rubber are kneaded, and a preliminary crosslinking reaction is performed to form a first mixture, and then The second cross-linking agent and a new batch of polypropylene, ethylene-propylene-non-conjugated diene rubber and the first mixture containing the first cross-linking agent are mixed to produce a higher degree of cross-linking and mechanical properties. And a dynamically crosslinked thermoplastic elastomer with better processability. When the preparation has flowability problems, part of the polypropylene can be replaced with low molecular weight and low stereoregularity polypropylene (low molecular weight and low modulus polypropylene) to improve the dynamic crosslinked thermoplastic elastomer (TPV) with low flowability Problems, making its related processing and molding methods and applications wider.
Description
本發明涉及一種動態交聯熱塑性彈性體及其製程,特別涉及一種經雙重交聯劑反應所得之動態交聯熱塑性彈性體及其製程。。 The invention relates to a dynamically crosslinked thermoplastic elastomer and a process for the same, and in particular, to a dynamically crosslinked thermoplastic elastomer obtained through a reaction of a double crosslinker and a process for the same. .
熱塑性彈性體(Thermplastic Elastomer,TPE)又稱熱塑性橡膠,是近年合成橡膠原料中最受矚目的產品之一。熱塑性彈性體TPE結合了橡膠彈性特質,和塑膠加工條件,兼具兩者優勢。可用一般的熱塑性塑料成型機加工,快速製造成各式產品,應用於醫療、電子零件、工業建築、汽車配件、生活用品等,因此生產效率高。而加工過程所產生廢料及其成品,均可回收再利用,符合環保需求,且可降低成本。熱塑性彈性體還具有高伸長率、高回彈率、低壓縮永久變形率、及低脆化溫度等特性,可用於塑膠材料之增韌改質。 Thermoplastic elastomers (Thermplastic Elastomer, TPE), also known as thermoplastic rubber, is one of the most noticeable products in synthetic rubber raw materials in recent years. Thermoplastic elastomer TPE combines the elastic properties of rubber with the processing conditions of plastics. It can be processed by general thermoplastic molding machine and quickly manufactured into various products. It is used in medical, electronic parts, industrial construction, auto parts, daily necessities, etc., so the production efficiency is high. The waste materials and finished products produced during processing can be recycled and reused, which meets environmental protection requirements and can reduce costs. Thermoplastic elastomers also have high elongation, high rebound rate, low compression set, and low embrittlement temperature, which can be used to toughen and modify plastic materials.
常見的熱塑性彈性體(TPE)可分為六大類:熱塑性聚氨酯彈性體(Thermoplastic Urethane,TPU)、聚烯系彈性體(thermoplastic polyolefinelastomers,TPO)、動態交聯熱塑性彈性體(thermoplastic vulcanizate,TPV)、聚苯乙烯系彈性體(styrenic block copolymers,TPS)、聚醚酯彈性體(thermoplastic copolyester,TPC)、聚醯胺系彈性體(thermoplastic polyamides,TPA),近年來動態交聯熱塑性彈性體及尤其受到矚目,因其兼具傳統彈性體良好彈性,及熱塑性塑膠之可回收利用 性,為一環保高分子材料,所以廣泛應用於工業上,特別是汽車及船舶引擎等,需求量不斷成長,預計未來可取代丙烯酸酯(ACM)橡膠的市場。 Common thermoplastic elastomers (TPE) can be divided into six categories: thermoplastic polyurethane elastomers (TPU), thermoplastic polyolefin elastomers (TPO), dynamically crosslinked thermoplastic elastomers (thermoplastic vulcanizate, TPV), Polystyrenic block copolymers (TPS), polyetherester elastomers (thermoplastic copolyester, TPC), polyamidoamine-based elastomers (thermoplastic polyamides, TPA), have been dynamically crosslinked thermoplastic elastomers in recent years and are particularly affected by Attention, because it has the good elasticity of traditional elastomers and the recycling of thermoplastics It is an environmentally friendly polymer material, so it is widely used in industry, especially automotive and marine engines, and the demand is constantly growing. It is expected that it can replace the market of acrylic (ACM) rubber in the future.
為兼具塑膠與橡膠的特性,動態交聯熱塑性彈性體材料(thermoplastic vulcanizate,TPV)中要同時包含橡膠(彈性體)及塑膠(熱塑性樹脂類),而且在複合物中,橡膠的組成百分比通常遠高於塑膠。橡膠可與軟化油,增塑劑等配合使用。交聯劑和一些交聯助劑也是不可或缺。另外為了降低成本或者提高某些特定性能,有時也會添加一些無機填料。 In order to have the characteristics of both plastic and rubber, dynamic crosslinked thermoplastic elastomer materials (thermoplastic vulcanizate (TPV)) should contain both rubber (elastomer) and plastic (thermoplastic resin), and in the compound, the rubber composition percentage is usually Much higher than plastic. Rubber can be used with softening oil, plasticizer, etc. Cross-linking agents and some cross-linking aids are also indispensable. In addition, in order to reduce costs or improve some specific properties, some inorganic fillers are sometimes added.
製備動態交聯熱塑性彈性體時,將配方內含成分,如橡膠與塑膠、交聯劑等預先混合,在押出機內進行動態交聯,所謂動態交聯,係指橡膠與塑膠在熔融共混時,也就是讓橡膠分散在塑膠基質中的同時,使橡膠分子發生交聯,形成網狀結構,進而提升力學性能。交聯之橡膠微區主要提供共混體的彈性,塑膠基質則提供熱塑成型性。所謂橡膠的交聯/硫化係指橡膠大分子間彼此交叉鏈接,生成具有三維網絡結構的化學程序。經此程序,橡膠的化學結構改變,性能也提升。所以TPV為交聯橡膠微粒與塑膠的混合物,分散相為橡膠,連續相則為結晶性塑膠,提供尺寸安定性與熱可塑性,因此動態交聯熱塑性彈性體具有相當低的壓縮永久變形率,且性能逼近傳統硫化橡膠,這是其他種類TPE無法比擬。常見連續相通常是聚丙烯,而分散相通常是乙丙橡膠。這種材料橡膠特性顯著,相較於其他類別之熱塑性彈性體,這類熱塑性彈性體(TPV)具有良好的機械性,低壓縮永久變形量,耐熱性、抗化學腐蝕以及耐低溫性。 When preparing dynamically crosslinked thermoplastic elastomers, the ingredients contained in the formula, such as rubber, plastic, and crosslinker, are mixed in advance and dynamically crosslinked in the extruder. The so-called dynamic crosslinking refers to the melt blending of rubber and plastic. At the same time, the rubber is dispersed in the plastic matrix and the rubber molecules are crosslinked to form a network structure, thereby improving the mechanical properties. The crosslinked rubber micro-regions mainly provide the elasticity of the blend, while the plastic matrix provides thermoplastic moldability. The so-called crosslinking / vulcanization of rubber refers to a chemical program in which rubber macromolecules are cross-linked with each other to generate a three-dimensional network structure. After this procedure, the chemical structure of the rubber is changed, and its performance is also improved. Therefore, TPV is a mixture of crosslinked rubber particles and plastic, the dispersed phase is rubber, and the continuous phase is crystalline plastic, which provides dimensional stability and thermoplasticity. Therefore, dynamically crosslinked thermoplastic elastomers have a relatively low compression set, and Performance is similar to traditional vulcanized rubber, which is unmatched by other types of TPE. The common continuous phase is usually polypropylene and the dispersed phase is usually ethylene-propylene rubber. This material has remarkable rubber characteristics. Compared with other types of thermoplastic elastomers, this type of thermoplastic elastomer (TPV) has good mechanical properties, low compression set, heat resistance, chemical resistance and low temperature resistance.
一般市面上常用的彈性體包括天然橡膠、乙烯/丙烯共聚的二元乙丙橡膠(Ethylene-propylene monomer,EPM)、乙烯-丙烯-非-共軛二烯橡膠(三元乙丙橡膠,Ethylene Propylene-diene-monomer,EPDM)、苯乙烯系橡膠如苯乙烯/丁二烯共聚物(Styrene/Butadiene Copolymer,SBR)、苯乙烯乙烯/丁烯苯乙烯橡膠(Styrene Ethylene/Butylene Styrene rubber,SEBS)、丁腈橡膠(Nitrile Butadiene rubber,NBR)、丙烯酸酯橡胶(Acrylic rubber,ACM)、氯化聚乙烯(Chlorinated Polyethylene,CPE)等。而常見塑膠則有聚丙烯(polypropylene,PP)、聚乙烯(Polyethylene,PE)、尼龍(Polyamide,PA)、聚碳酸酯(Polycarbonate,PC)、丙烯腈-丁二烯-苯乙烯共聚物(Acrylonitrile Butadiene Styrene,ABS)、聚苯乙烯(Polystyrene,PS)、聚對苯二甲酸丁二酯(Polybutylene terephthalate,PBT)、聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)等,目前已經商業化的配方有EPDM/PP,NBR/PP,ACM/PP,SEBS/PS。 Elastomers commonly used in the market include natural rubber, ethylene / propylene copolymerized Ethylene-propylene monomer (EPM), ethylene-propylene-non-conjugated diene rubber (Ethylene Propylene, Ethylene Propylene) -diene-monomer (EPDM), styrene-based rubber such as styrene / butadiene copolymer (Styrene / Butadiene Copolymer, SBR), styrene ethylene / butene styrene rubber (Styrene Ethylene / Butylene Styrene rubber, SEBS) Nitrile Butadiene rubber (NBR), Acrylic rubber (ACM), Chlorinated Polyethylene (CPE), etc. The common plastics are polypropylene (PP), polyethylene (PE), nylon (Polyamide, PA), polycarbonate (Polycarbonate, PC), acrylonitrile-butadiene-styrene copolymer (Acrylonitrile Butadiene Styrene (ABS), Polystyrene (PS), Polybutylene terephthalate (PBT), Polyethylene terephthalate (PET), etc., have now been commercialized The formulations are EPDM / PP, NBR / PP, ACM / PP, SEBS / PS.
動態交聯熱塑性彈性體具有良好的彈性,抗壓縮變形,耐腐蝕,抗老化,耐候性,耐磨耐油易染色,較廣的應用溫度及硬度範圍,優良的加工性能,符合環保要求,比重輕。可用熱塑性塑料的加工方式進行加工如:模塑,射出,擠出成形等,無須添購新設備。這些特點,相較於傳統橡膠或塑料,在性能及成本上,都具一定優勢。 Dynamic crosslinked thermoplastic elastomer has good elasticity, resistance to compression deformation, corrosion resistance, aging resistance, weather resistance, wear resistance and oil resistance, easy dyeing, wide application temperature and hardness range, excellent processing performance, environmental protection requirements, light weight . It can be processed by thermoplastic processing methods such as molding, injection, extrusion, etc., without the need to purchase new equipment. Compared with traditional rubber or plastic, these characteristics have certain advantages in terms of performance and cost.
依所選用橡膠/塑膠/交聯劑組成成分不同,可得到不同性能的動態交聯熱塑性彈性體產品。其他會影響產品性質的因素還有技術條件,及混煉設備等。交聯劑可決定產品的動態交聯程度,及影響熱塑性彈性體之各種物理化學特性。交聯劑(又稱硫化劑)可分為硫磺硫化體系及 非硫磺硫化體系,包括過氧化物,酚醛樹脂,胺類,金屬氧化物,及輻射等。 Depending on the composition of the selected rubber / plastic / crosslinking agent, dynamic crosslinked thermoplastic elastomer products with different properties can be obtained. Other factors that affect product properties are technical conditions and mixing equipment. Crosslinking agents can determine the degree of dynamic crosslinking of the product and affect various physical and chemical characteristics of the thermoplastic elastomer. Crosslinking agents (also known as vulcanizing agents) can be divided into sulfur vulcanization systems and Non-sulfur vulcanization systems, including peroxides, phenolic resins, amines, metal oxides, and radiation.
硫磺硫化體系,雖然成本低廉,但硫化速度慢,時間長,產品有臭味,及高溫交聯不穩定。 Sulfur vulcanization system, although the cost is low, but the vulcanization speed is slow, the time is long, the product has an odor, and the high temperature crosslinking is unstable.
過氧化物,可使交聯反應在較低溫度下進行,經過氧化物硫化所得TPV產品有優越耐熱性及較低壓縮有優越耐熱性及較低壓縮變形,顏色較淺易著色,加工前不須乾燥,但過氧化物會造成塑膠/樹脂分子降解,產品物理機械性能較差(如產品拉伸強度低,撕裂強度,耐磨性能差)。 Peroxide can make the cross-linking reaction proceed at a lower temperature. The TPV product obtained through oxide vulcanization has superior heat resistance and lower compression. It has superior heat resistance and lower compression deformation. The color is lighter and easier to color. Dry, but the peroxide will cause the degradation of plastic / resin molecules, and the product has poor physical and mechanical properties (such as low tensile strength, poor tear strength and poor wear resistance).
而使用酚醛樹脂交聯劑所得,所以力學強度好,熔體強度及耐候性好,耐高溫,耐油性及抗化學品腐蝕。缺陷是速度較慢,一般硫化溫度較高,需要氯化物做活化劑,硫化工藝複雜,不同產品批次有輕微色差,有臭味問題,另材料具有很強的吸濕特性,加工之前需要乾燥。 The phenolic resin cross-linking agent is used, so it has good mechanical strength, good melt strength and weather resistance, high temperature resistance, oil resistance and chemical corrosion resistance. The disadvantage is that the speed is slow, the vulcanization temperature is generally high, chloride is required as an activator, the vulcanization process is complicated, there are slight color differences between different product batches, and there are odor problems. In addition, the material has strong hygroscopicity and needs to be dried before processing. .
因此使用不同交聯劑所生產之動態交聯熱塑性彈性體產品,各有其優缺點。所以如何選用合適橡膠塑膠組成分,具高交聯效率,低副作用之交聯劑,提高交聯程度,以改良動態交聯熱塑性彈性體之各種性能,如機械物性,拉伸特性,伸長率,壓縮變形及/或抗油性等,同時在力學性能和加工性兩者間取得平衡,實為動態交聯熱塑性彈性體業界所關注之重要議題。 Therefore, the dynamically crosslinked thermoplastic elastomer products produced by using different crosslinking agents have their own advantages and disadvantages. So how to choose a suitable rubber and plastic composition with high cross-linking efficiency and low side-effect cross-linking agents to improve the degree of cross-linking to improve various properties of dynamic cross-linked thermoplastic elastomers, such as mechanical properties, tensile properties, elongation, Compression deformation and / or oil resistance, etc., while achieving a balance between mechanical properties and processability, are important issues of concern for the dynamic crosslinked thermoplastic elastomer industry.
為符合上述需求,克服習知動態交聯熱塑性彈性體之缺點,因此本發明之一目的係提供一種使用雙重交聯劑製備之動態交聯熱塑性彈性體(TPV)及其製程,該動態交聯熱塑性彈性體(TPV)具有優異物性,及較高交聯程度。 In order to meet the above requirements and overcome the shortcomings of conventional dynamic crosslinked thermoplastic elastomers, it is an object of the present invention to provide a dynamically crosslinked thermoplastic elastomer (TPV) prepared by using a dual crosslinking agent and a process for the same. Thermoplastic elastomer (TPV) has excellent physical properties and a high degree of crosslinking.
本發明之另一目的,係提供一種動態交聯熱塑性彈性體(TPV),進一步包括低分子量低立體規整性之聚丙烯(low molecular weight and low modulus polypropylene),當所生產之動態交聯熱塑性彈性體發生流動性問題時,添加此類聚丙烯,可明顯改善及解決流動性問題。 Another object of the present invention is to provide a dynamically crosslinked thermoplastic elastomer (TPV), which further includes low molecular weight and low stereoregularity polypropylene (low molecular weight and low modulus polypropylene). When fluidity problems occur in the body, adding such polypropylene can obviously improve and solve the fluidity problems.
為達以上目的,本發明提供一動態交聯熱塑性彈性體(TPV),其係一混合物,包括彈性體,其係乙烯-丙烯-非-共軛二烯橡膠(EPDM),塑膠則為聚丙烯(PP),兩種交聯劑,及添加劑。 To achieve the above object, the present invention provides a dynamically crosslinked thermoplastic elastomer (TPV), which is a mixture including an elastomer, which is an ethylene-propylene-non-conjugated diene rubber (EPDM), and the plastic is polypropylene (PP), two crosslinking agents, and additives.
為達以上目的,本發明提供一動態交聯熱塑性彈性體(TPV)製程,首先將一部分聚丙烯(可為無規共聚合物及/或單聚合物),和一部分乙烯-丙烯-非-共軛二烯橡膠,加入萬馬力機(Banbury Mixer)中,待兩材料均勻熔融後,加入第一交聯劑-酚醛樹脂進行初步交聯反應,以形成第一混合物,當扭矩增加時,先暫時停止反應,故此第一混合物尚具有交聯反應性,下料,滾輪機出片。 To achieve the above objective, the present invention provides a process for dynamically crosslinking a thermoplastic elastomer (TPV). First, a part of polypropylene (which may be a random copolymer and / or a single polymer) and a part of ethylene-propylene-non-copolymer The yoke diene rubber is added to a Banbury Mixer. After the two materials are evenly melted, a first cross-linking agent, a phenolic resin, is added for a preliminary cross-linking reaction to form a first mixture. When the torque increases, first temporarily The reaction is stopped, so the first mixture still has cross-linking reactivity, and the material is discharged and rolled out by a roller.
接著再將另一部分聚丙烯,和另一部分乙烯-丙烯-非-共軛二烯橡膠,加入萬馬力機(Banbury Mixer)中,待兩材料均勻熔融後,加入紫外線安定劑、光穩定劑、抗氧化劑等等添加劑、第一混合物以及第二交聯劑-過氧化物;隨著扭矩增加至最大值後,再持續混合3分鐘,待反 應達平衡後,形成一第二混合物,即動態交聯熱塑性彈性體,下料將滾輪機出片。 Then add another part of polypropylene and another part of ethylene-propylene-non-conjugated diene rubber to a Banbury Mixer. After the two materials are evenly melted, add ultraviolet stabilizer, light stabilizer, Additives such as oxidants, the first mixture, and the second cross-linking agent-peroxide; after the torque increases to the maximum, continue to mix for 3 minutes, after the reaction reaches equilibrium, a second mixture is formed, that is, dynamic cross-linking Thermoplastic elastomer, the roller will be ejected from the blank.
當製備所得之動態交聯熱塑性彈性體(TPV),具有流動性不足問題時,可將部分聚丙烯以低分子量低立體規整性之聚丙烯(low molecular weight and low modulus polypropylene)取代製成後半部所加入之聚丙烯,或直接添加,亦即增加聚丙烯之總量。此低分子量聚丙烯具有低熔點、高流動性和柔軟性等特點,可改進動態交聯熱塑性彈性體的物性和加工性能。例如在特定加工溫度下,可解決動態交聯熱塑性彈性體流動性偏低問題,且不影響產品之壓縮永久變形率,或可增加最終產品之韌性,使其相關加工成型方法和應用範圍更加寬廣。 When the prepared dynamically crosslinked thermoplastic elastomer (TPV) has a problem of insufficient fluidity, part of the polypropylene can be replaced with low molecular weight and low modulus polypropylene (low molecular weight and low modulus polypropylene) to make the second half The added polypropylene may be added directly, that is, the total amount of polypropylene is increased. This low molecular weight polypropylene has the characteristics of low melting point, high fluidity and softness, which can improve the physical properties and processing properties of dynamically crosslinked thermoplastic elastomers. For example, at a specific processing temperature, it can solve the problem of low fluidity of dynamic crosslinked thermoplastic elastomers without affecting the compression set of the product, or it can increase the toughness of the final product, making its related processing and molding methods and applications wider. .
本發明之優點及技術特徵在於:在製備該動態交聯熱塑性彈性體(TPV),使用雙重交聯劑,同時在動態交聯熱塑性彈性體之製程中,先將第一交聯劑和部分聚丙烯,及乙烯-丙烯-非-共軛二烯橡膠混練,進行初步交聯反應,形成第一混合物,當扭矩增加時,先暫時停止反應,下料出片。再將第二交聯劑和剩餘聚丙烯,乙烯-丙烯-非-共軛二烯橡膠及內含第一交聯劑之第一混合物進行混練,待扭矩增加至最大值後,再持續混合3分鐘,待反應達平衡,產生交聯程度較高之動態交聯熱塑性彈性體。 The advantages and technical features of the present invention are as follows: in preparing the dynamically crosslinked thermoplastic elastomer (TPV), a dual crosslinking agent is used, and at the same time, in the process of dynamically crosslinking the thermoplastic elastomer, the first crosslinking agent and part of the polymer are firstly polymerized. Propylene and ethylene-propylene-non-conjugated diene rubber are kneaded, and a preliminary cross-linking reaction is performed to form a first mixture. When the torque is increased, the reaction is temporarily stopped first, and the sheet is discharged. The second cross-linking agent and then the remaining polypropylene, ethylene - propylene - non - the first diene rubber and a mixture of a first crosslinker containing conjugated kneaded until the torque increased to a maximum mixing continued 3 Minutes, when the reaction reaches equilibrium, a dynamically crosslinked thermoplastic elastomer with a higher degree of crosslinking is produced.
圖一、是本發明一實施例,在製備過程中,熔體溫度及扭矩隨時間之變化圖。 FIG. 1 is a graph showing changes in melt temperature and torque with time during the preparation process according to an embodiment of the present invention.
動態交聯熱塑性彈性體係介於橡膠(彈性體)與塑膠(樹脂)之間的一種新型高分子材料,兼具塑膠之熱塑性與橡膠之彈性且易於加工,適合取代傳統橡膠及塑料;一般包括至少一種彈性橡膠材料及至少一種熱塑性塑料。其中彈性橡膠係完全且均一地分散於熱塑性塑料中,熱塑性塑料為連續相,而彈性橡膠形成分散相。彈性橡膠粒子大小從0.1微米至約數微米,而交聯密度大於7×10-5mol/ml,粒子內部還含有其他添加劑。這些數目眾多的細小交聯橡膠粒子呈分散相散佈於塑料中,且粒子之間應沒有化學鍵接,因此動態交聯熱塑性彈性體具有高彈性,優異拉伸性能及良好的壓縮永久變形率。包覆在彈性橡膠粒子周圍的塑膠粒子則形成連續相,提供動態交聯熱塑性彈性體優良的熱流動性和重複成型加工性。所以動態交聯熱塑性彈性體像橡膠般耐壓可拉伸,如塑膠般熱塑加工,並具有穩定物理特性。 Dynamic crosslinked thermoplastic elastomer system is a new type of polymer material between rubber (elastomer) and plastic (resin). It has the flexibility of thermoplastic and rubber of plastic and is easy to process. It is suitable to replace traditional rubber and plastic; generally includes at least An elastic rubber material and at least one thermoplastic. The elastic rubber is completely and uniformly dispersed in the thermoplastic, the thermoplastic is a continuous phase, and the elastic rubber forms a dispersed phase. The size of the elastic rubber particles is from 0.1 micrometer to about several micrometers, and the cross-linking density is greater than 7 × 10 -5 mol / ml, and other additives are also contained inside the particles. These large numbers of finely crosslinked rubber particles are dispersed in the plastic in a dispersed phase, and there should be no chemical bonding between the particles. Therefore, the dynamically crosslinked thermoplastic elastomer has high elasticity, excellent tensile properties and good compression set. The plastic particles that surround the elastic rubber particles form a continuous phase, providing excellent thermal fluidity and repetitive processability of dynamically crosslinked thermoplastic elastomers. Therefore, the dynamically crosslinked thermoplastic elastomer is pressure-resistant and stretchable like rubber, and is processed like plastic, and has stable physical properties.
本發明所述之動態交聯熱塑性彈性體(TPV),其係一混合物,包括可交聯(硫化)之彈性橡膠,即油展或非油展之乙烯-丙烯-非-共軛二烯橡膠,分散於一熱塑性聚烯烴如聚丙烯之中,該聚丙烯可為無規共聚合物及/或單聚合物,以過氧化物和酚醛樹脂作為交聯劑(硫化劑),使乙烯-丙烯-非-共軛二烯橡膠經過特定製程,產生動態交聯反應,生成動態交聯熱塑性彈性體。另外,當動態交聯熱塑性彈性體產品有流動性問題 時,可加入低分子量聚烯烴共聚物,如低分子量低立體規整性之聚丙烯(low molecular weight and low modulus polypropylene)係作為改質劑,以改善動態交聯熱塑性彈性體之流動性和表面平滑性。 The dynamically crosslinked thermoplastic elastomer (TPV) according to the present invention is a mixture including a crosslinkable (vulcanizable) elastic rubber, that is, an oil-extended or non-oil-extended ethylene-propylene-non-conjugated diene rubber. It is dispersed in a thermoplastic polyolefin such as polypropylene. The polypropylene may be a random copolymer and / or a single polymer. Peroxide and phenolic resin are used as a crosslinking agent (vulcanizing agent) to make ethylene-propylene. -The non-conjugated diene rubber undergoes a specific process to produce a dynamic cross-linking reaction to form a dynamically cross-linked thermoplastic elastomer. In addition, when the dynamically crosslinked thermoplastic elastomer product has fluidity problems, low molecular weight polyolefin copolymers, such as low molecular weight and low stereoregularity polypropylene (low molecular weight and low modulus polypropylene), can be added as modifiers. To improve the fluidity and surface smoothness of dynamically crosslinked thermoplastic elastomers.
乙烯-丙烯-非-共軛二烯橡膠(EPDM)也可稱為三元乙丙橡膠,是乙烯、丙烯和非共軛二烯烴的三元共聚物,其特性為優越的抗氧化,抗臭氧和抗腐蝕性,低密度,高填充性。聚丙烯(PP)包括聚丙烯無規共聚合物(random copolymers of propylene)及/或聚丙烯單聚合物(又稱均聚合物)(homopolymer)。聚丙烯單聚合物為一半結晶性聚合物,具高結晶度,使其機械性質優良,如高剛性,高拉身強度,耐熱性佳。又因流動性良好,廣泛應用於各種加工。聚丙烯無規聚合物的結晶度較低,使其透明性良好、可提升產品外觀。使產品更加柔軟。相較於單聚合物,無規共聚合物的熔點與結晶溫度更低,使其更易加工成型。 Ethylene-propylene-non-conjugated diene rubber (EPDM), also known as ethylene-propylene diene rubber, is a terpolymer of ethylene, propylene, and non-conjugated diene . Its characteristics are superior oxidation resistance and ozone resistance. And corrosion resistance, low density, high filling . Polypropylene (PP) includes random copolymers of propylene and / or polypropylene monopolymers (also known as homopolymers). Polypropylene is a semi-crystalline polymer with high crystallinity, which makes it excellent in mechanical properties, such as high rigidity, high tensile strength, and good heat resistance. Because of its good fluidity, it is widely used in various processes. Polypropylene random polymer has low crystallinity, which makes it good in transparency and can improve product appearance. Makes the product softer. Compared with single polymers, random copolymers have lower melting points and crystallization temperatures, making them easier to process.
在一較佳實施例中,本發明所述之動態交聯熱塑性彈性體之製備程序包括,步驟A:先將一些聚丙烯,和乙烯-丙烯-非-共軛二烯橡膠,加入萬馬力機(Banbury Mixer)中,待兩材料均勻熔融後,加入第一交聯劑-酚醛樹脂進行初步交聯反應,形成第一混合物(參見表一),步驟B:當扭矩增加時,先暫時停止反應,故此第一混合物尚具有交聯反應性,下料將滾輪機出片。在混練時,橡膠和塑料兩相充分熔融共混,產生動態硫化,扭矩亦隨之上升,原因是,動態硫化時,在強機械剪切力和熱力作用下,橡膠互相高度交聯,粘度變大,此時需要更大剪切力和更高溫度以從連續相轉變為分散相,進而分佈在粘度較小的塑膠(樹脂)中。而且由於強剪切力作用,橡膠粒子變得更加細小,分散更為均勻,兩相 結合強度增大,所消耗的功率增大,以致為扭矩變大。製程中扭矩變化請參見圖一。 In a preferred embodiment, the preparation process of the dynamically crosslinked thermoplastic elastomer according to the present invention includes, Step A: firstly adding some polypropylene and ethylene-propylene-non-conjugated diene rubber to a ten thousand horsepower machine (Banbury Mixer), after the two materials are uniformly melted, the first cross-linking agent-phenolic resin is added for preliminary cross-linking reaction to form the first mixture (see Table 1). Step B: When the torque increases, stop the reaction temporarily. Therefore, the first mixture still has cross-linking reactivity, and the roller will be discharged out of the sheet. During kneading, the two phases of rubber and plastic are fully melted and blended, resulting in dynamic vulcanization, and the torque also increases. The reason is that during dynamic vulcanization, under the action of strong mechanical shear and heat, the rubbers are highly crosslinked with each other and the viscosity changes At this time, a larger shear force and a higher temperature are required to change from a continuous phase to a dispersed phase, and then be distributed in a plastic (resin) with a lower viscosity. Moreover, due to the strong shear force, the rubber particles become smaller and more uniformly dispersed, the two-phase bonding strength increases, and the power consumed increases, so that the torque becomes larger. See Figure 1 for torque changes during the process.
接著執行步驟C:再將另一部分,新一批丙烯及乙烯-丙烯-非-共軛二烯橡膠,加入萬馬力機(Banbury Mixer)中,待兩材料均勻熔融後,加入紫外線安定劑、光穩定劑、抗氧化劑等添加劑、第一混合物以及第二交聯劑-過氧化物,持續混練;步驟D:隨著扭矩增加至最大值後,再持續混合3分鐘,使反應達平衡,形成一第二混合物(參見表二),即動態交聯熱塑性彈性體(TPV),下料將滾輪機出片。 Then proceed to step C: add another batch of propylene and ethylene-propylene-non-conjugated diene rubber to a Banbury Mixer. After the two materials are evenly melted, add ultraviolet stabilizer, light Stabilizers, antioxidants and other additives, the first mixture and the second cross-linking agent-peroxide , continue to knead ; Step D: After the torque increases to the maximum, continue to mix for another 3 minutes, so that the reaction reaches equilibrium, forming a The second mixture (see Table 2), that is, the dynamically crosslinked thermoplastic elastomer (TPV), was cut out to roll out the tablet.
酚醛硫化樹脂是種表面活性劑,藉離子聚合反應,與乙烯-丙烯-非-共軛二烯橡膠內之雙鍵進行交聯反應。該酚醛硫化樹脂是指酚醛硫化樹脂的濃縮母粒。在製備動態交聯熱塑性彈性體過程中,所用塑膠原料有時會發生流動性問題,亦即在加熱時,塑膠分子會不易流動,以致較難熔融。當酚醛硫化樹脂直接與乙烯-丙烯-非-共軛二烯橡膠反應時,可改善乙烯-丙烯-非-共軛二烯橡膠之分散性,使動態交聯熱塑性彈性體其交聯反應過程穩定,產生優異的物性。酚醛樹脂可為帶有羥甲基的酚醛樹脂,烷基苯酚-甲醛樹脂,或鹵素取代的烷基取代的酚醛硫化樹脂,透過鹵素取代的苯酚、烷基取代的苯酚(較佳為對位取代)或未取代的苯酚與醛(較佳為甲醛)在鹼性介質中縮合來製備,或雙官能酚二醇的縮合來製備。 Phenolic vulcanizate is a kind of surfactant. It undergoes cross-linking reaction with double bonds in ethylene-propylene-non-conjugated diene rubber through ion polymerization. The phenolic vulcanized resin refers to a concentrated masterbatch of a phenolic vulcanized resin. In the process of preparing dynamically crosslinked thermoplastic elastomers, the plastic materials used sometimes have fluidity problems, that is, when heated, the plastic molecules will not flow easily, making it difficult to melt. When the phenolic vulcanized resin reacts directly with ethylene-propylene-non-conjugated diene rubber, the dispersibility of ethylene-propylene-non-conjugated diene rubber can be improved, and the crosslinking reaction process of the dynamically crosslinked thermoplastic elastomer is stable. , Resulting in excellent physical properties. The phenolic resin may be a phenolic resin with a methylol group, an alkylphenol-formaldehyde resin, or a halogen-substituted alkyl-substituted phenol vulcanization resin. The halogen-substituted phenol, the alkyl-substituted phenol (preferably para-substituted) ) Or an unsubstituted phenol and an aldehyde (preferably formaldehyde) are prepared by condensation in an alkaline medium, or a bifunctional phenol diol is prepared by condensation.
至於過氧化物,則是藉自由基使聚合物間產生交聯反應,反應過程中,過氧化物內的過氧化氫或生成之自由基會與飽和鍵、亞甲基鍵(-CH2)和甲基鍵(-CH3)作用,進行自由基接枝架橋反應。以有機過氧化物為交聯劑之動態加硫型烯烴系熱塑性彈性體(thermoplastic vulcanizate,TPV),交鏈後形成之-C-C-鍵,比傳統硫磺型交鏈劑所形成 之-C-Sx-C-鍵,較為安定,所以呈現較佳的耐熱抗老化性。適用於工業化生產的過氧化物為:二醯基過氧化物,叔烷基過氧酸酯,烷基氫過氧化物,二烷基過氧化物,二烷基過氧縮酮。其中常用者包括過氧化二異丙苯(DCP)、過氧化苯甲醯(BPO)、1,1-二叔丁基過氧基-3,3,5-三甲基環己烷(BPMC)、2,5-二甲基-2,5-雙(叔丁基過氧基)己烷(DBPMH)、1,3-雙(叔丁過氧異丙基)苯(BIPB)等。 As for peroxides, cross-linking reactions occur between polymers by free radicals. During the reaction, hydrogen peroxide or generated free radicals in peroxides will interact with saturated bonds and methylene bonds (-CH 2 ). It reacts with a methyl bond (-CH 3 ) to perform a free radical grafting and bridging reaction. A dynamically vulcanized olefin-based thermoplastic elastomer (thermoplastic vulcanizate (TPV)) using an organic peroxide as a cross-linking agent is formed with a -CC-bond after cross-linking, which is more than -C-Sx formed with a conventional sulfur-based cross-linking agent. -C-bond is more stable, so it shows better heat resistance and aging resistance. Peroxides suitable for industrial production are: difluorenyl peroxide, tertiary alkyl peroxyester, alkyl hydroperoxide, dialkyl peroxide, dialkyl peroxyketal. Commonly used ones include dicumyl peroxide (DCP), benzophenazine peroxide (BPO), 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane (BPMC) , 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane (DBPMH), 1,3-bis (tert-butylperoxyisopropyl) benzene (BIPB) and the like.
本發明所述之動態交聯熱塑性彈性體(TPV)之成分,可進一步包含低分子量低立體規整性聚丙烯(low molecular weight and low modulus polypropylene),具有低熔點、高流動性和柔軟性等特點,可改進TPV的物性和加工性能。例如在加工溫度下,動態交聯熱塑性彈性體(TPV)流動性偏低問題,且不影響產品之壓縮永久變形率,或增加最終產品之韌性,使相關加工成型方法和應用更加寬廣。 The components of the dynamically crosslinked thermoplastic elastomer (TPV) according to the present invention may further include low molecular weight and low stereoregular polypropylene (low molecular weight and low modulus polypropylene), which has the characteristics of low melting point, high fluidity, softness, and the like. , Can improve the physical properties and processing properties of TPV. For example, at the processing temperature, the fluidity of the dynamically crosslinked thermoplastic elastomer (TPV) is low, and it does not affect the compression set of the product, or increase the toughness of the final product, making the related processing and molding methods and applications more extensive.
第一實施例: First embodiment:
參見表三配方編號3號,取12g聚丙烯(無規共聚合物,單聚合物或其混合物),及20g乙烯-丙烯-非-共軛二烯橡膠(EPDM),在此實施例中為日本三井化學公司(Mitsui Chemicals,Inc.)製造之EPT-3045,利用萬馬力機(Banbury Mixer)進行均勻熔融,再加入4g第一交聯劑-酚醛樹脂(田岡化學工業製造之Tackirol 201),進行初步交聯反應,形成第一混合物,其組成物比例範圍,參見表一。 See Table 3 for Formula Number 3. Take 12 g of polypropylene (random copolymer, monopolymer, or mixture thereof), and 20 g of ethylene-propylene-non-conjugated diene rubber (EPDM), in this example: EPT-3045 manufactured by Mitsui Chemicals, Inc. of Japan was uniformly melted using a Banbury Mixer , and 4 g of a first cross-linking agent, a phenol resin (Tackirol 201, manufactured by Taoka Chemical Industries) was added. A preliminary cross-linking reaction is performed to form a first mixture, and its composition ratio range is shown in Table 1.
再取40g聚丙烯(無規共聚合物,單聚合物或其混合物),及100g乙烯-丙烯-非-共軛二烯橡膠,放入萬馬力機(Banbury Mixer)中,使其均勻熔融後,再加入2.5g第二交聯劑-過氧化物,20g第一混合物,及1.5g 添加劑(包括UV安定劑、光穩定劑、抗氧化劑),形成第二混合物,其組成物比例範圍,參見表二;隨著扭矩增加,持續混合3分鐘,待反應達平衡,得到本發明之動態交聯熱塑性彈性體。本發明之動態交聯熱塑性彈性體,其組成物比例範圍,請參見表三,其中20g第一混合物分拆為12g乙烯-丙烯-非-共軛二烯橡膠,6g聚丙烯及2g酚醛硫化樹脂(比例為60%,30%,及10%)。 Then take 40g of polypropylene (random copolymer, monopolymer or mixture thereof) and 100g of ethylene-propylene-non-conjugated diene rubber , put them into a Banbury Mixer, and make them melt uniformly. , And then add 2.5g of the second crosslinking agent-peroxide, 20g of the first mixture, and 1.5g of additives (including UV stabilizers, light stabilizers, antioxidants) to form a second mixture, the composition ratio range, see Table 2: As the torque increases, the mixing is continued for 3 minutes, and the reaction reaches equilibrium to obtain the dynamically crosslinked thermoplastic elastomer of the present invention. For the range of composition ratios of the dynamically crosslinked thermoplastic elastomer of the present invention, please refer to Table 3. 20g of the first mixture is divided into 12g of ethylene-propylene-non-conjugated diene rubber, 6g of polypropylene and 2g of phenolic vulcanizate. (Proportions are 60%, 30%, and 10%).
在本發明之一較佳實施例,該動態交聯熱塑性彈性體所包含乙烯-丙烯-非-共軛二烯橡膠之重量百分比為55-70%(wt%),聚丙烯(PP)之重量百分比係30-40%,交聯劑之重量百分比為1-7%,內含酚醛樹脂及過氧化物,重量百分比分別為0.3-4.2%,0.6-3.6%,添加劑之重量百分比係為0.6-3.6%。 In a preferred embodiment of the present invention, the weight percentage of ethylene-propylene-non-conjugated diene rubber contained in the dynamically crosslinked thermoplastic elastomer is 55-70% (wt%), and the weight of polypropylene (PP) The percentage is 30-40%, the cross-linking agent is 1-7% by weight, and it contains phenolic resin and peroxide. The weight percentages are 0.3-4.2% and 0.6-3.6%, and the weight percentage of additives is 0.6- 3.6%.
表4:使用配方類似但不同交聯劑所製成各動態交聯熱塑性彈性體(TPV)特性
對照實施例一(配方編號1號) Comparative Example 1 (Recipe No. 1)
製備程序同上述本發明之實施例一,但在步驟C:加入紫外線安定劑、光穩定劑、抗氧化劑等添加劑、第一混合物以及第二交聯劑時,完全不添加第二交聯劑過氧化物,改添加5g酚醛樹酯;所以本實施例只使用酚醛樹酯作為交聯劑。 The preparation procedure is the same as that of the first embodiment of the present invention, but in step C: when adding ultraviolet stabilizer, light stabilizer, antioxidant and other additives, the first mixture and the second crosslinking agent, the second crosslinking agent is not added at all. As an oxide, 5 g of phenolic resin is added; therefore, in this embodiment, only phenolic resin is used as the cross-linking agent.
對照實施例二(配方編號2號) Comparative Example 2 (Recipe No. 2)
製備程序同本發明實施例一,但省略前半段製作第一混合物之步驟A及步驟B,在後半段步驟C:加入紫外線安定劑、光穩定劑、抗氧化劑等添加劑、第一混合物以及第二交聯劑時,加入2.0g過氧化物作為交聯劑;也就是本實施例只使用過氧化物作為交聯劑。 The preparation procedure is the same as that of the first embodiment of the present invention, but the steps A and B of preparing the first mixture in the first half are omitted, and the step C of the second half is adding additives such as a UV stabilizer, a light stabilizer, an antioxidant, the first mixture, and When the cross-linking agent is used, 2.0 g of peroxide is added as the cross-linking agent; that is, only peroxide is used as the cross-linking agent in this embodiment.
第一實施例(配方編號3號) First embodiment (recipe number 3)
而配方編號3號即為本發明之第一實施例,包含前半段製作第一混合物之步驟A及B,使用酚醛樹酯作為交聯劑,而後半段製作第二混合物之步驟C和D,使用過氧化物作為交聯劑;也就是同時使用酚醛樹酯及過氧化物,雙重交聯劑。 Formula No. 3 is the first embodiment of the present invention, which includes steps A and B for preparing the first mixture in the first half, using phenolic resin as a crosslinking agent, and steps C and D for preparing the second mixture in the second half. Peroxide is used as the cross-linking agent; that is, phenolic resin and peroxide are used simultaneously, and the double-cross-linking agent is used.
參見表四,使用不同交聯劑,如酚醛樹酯,過氧化物,及其混合物,的所生產之動態交聯熱塑性彈性體(TPV)。由測試數據可知單獨使用酚醛樹脂作為交聯劑時,其產物物性為最佳(熔融指數除外),但交聯程度偏低,不易控制;而只使用過氧化物作為交聯劑時,其物性為最差;而結合酚醛樹酯和過氧化物兩種交聯劑,其所得動態交聯熱塑性彈性體物性,和酚醛樹脂相去不遠,但交聯程度大幅改善,增加至99%。 See Table 4. Dynamic crosslinked thermoplastic elastomers (TPV) produced using different crosslinking agents, such as phenolic resins, peroxides, and mixtures thereof. According to the test data, it is known that when phenolic resin is used alone as a cross-linking agent, its physical properties are the best (except for the melt index), but the degree of cross-linking is low and it is not easy to control; when only peroxide is used as the cross-linking agent, its physical properties It is the worst; and by combining two cross-linking agents of phenolic resin and peroxide, the physical properties of the dynamically cross-linked thermoplastic elastomer obtained are not far from those of phenolic resin, but the degree of cross-linking is greatly improved to 99%.
第二實施例(配方編號4號) Second embodiment (recipe number 4)
製備程序同本發明之第一實施例,但將配方/組成成分中所用的乙烯-丙烯-非-共軛二烯橡膠(EPDM),由日本三井化學公司之EPT-3045,改為中國陶氏化學公司(Dow chemical company)製造之NORDELTM EPDM IP 4640。 The preparation procedure is the same as the first embodiment of the present invention, but the ethylene-propylene-non-conjugated diene rubber (EPDM) used in the formula / composition is changed from EPT-3045 of Mitsui Chemicals of Japan to Dow of China NORDEL ™ EPDM IP 4640 manufactured by the Dow chemical company.
第三實施例(配方編號5號) Third embodiment (recipe number 5)
製備程序同本發明之第一實施例,但將配方/組成成分中所用的 乙烯-丙烯-非-共軛二烯橡膠(EPDM),由日本三井化學公司之EPT-3045,改為韓國錦湖化學公司(Kumho Polychem Co.,Ltd.)製造之KEP650。 The preparation procedure is the same as the first embodiment of the present invention, but the Ethylene-propylene-non-conjugated diene rubber (EPDM) was changed from EPT-3045 of Mitsui Chemicals Co., Ltd. of Japan to KEP650 manufactured by Kumho Polychem Co., Ltd. of Korea.
動態交聯熱塑性彈性體(TPV)組成成分會影響產品物性。因此使用不同廠商-日本三井,中國陶氏,及韓國錦湖化學公司生產,相當門尼黏度(Mooney viscosity)(ML(1+4)100℃)之非油展之乙烯-丙烯-非-共軛二烯橡膠(EPDM),製成動態交聯熱塑性彈性體,比較其物理性質,參見表五。動態交聯熱塑性彈性體之物性,以韓國錦湖和日本三井較佳,而熔融指數,則是日本三井較高。熔融指數(melt flow index,MI),亦稱熔體流動速率(MFR),是衡量材料,通常是橡膠或塑膠材料,在一定的溫度和壓力條件下,流動性的好壞的一個物性參數,MI值越大,表示流動性較好,反之越差,單位通常是g/10min。 The composition of the dynamically crosslinked thermoplastic elastomer (TPV) will affect the physical properties of the product. Therefore, different manufacturers-Japan's Mitsui, China's Dow, and Korea's Kumho Chemical Company-use ethylene-propylene-non-co-equivalent non-oil exhibition equivalent Mooney viscosity (ML (1 + 4) 100 ℃) The conjugated diene rubber (EPDM) is made into a dynamically crosslinked thermoplastic elastomer. For comparison of its physical properties, see Table 5. The physical properties of dynamically crosslinked thermoplastic elastomers are better in Kumho, Korea and Mitsui in Japan, while the melt index is higher in Mitsui, Japan. Melt flow index (MI), also known as melt flow rate (MFR), is a physical parameter that measures the quality of a material, usually a rubber or plastic material, under certain temperature and pressure conditions. The larger the MI value, the better the fluidity, and the worse it is, the unit is usually g / 10min.
硬度(Shore hardness,Shore A scale)是依據ASTM D2240所規定測試方法測得;壓縮永久變形率(Compression set(Cs))依據ASTM D395所規定測試方法測得;熔融指數(melt flow index,MI)依據ASTM D412所規定測試方法測得。 Shore hardness (Shore A scale) is measured according to the test method specified in ASTM D2240; Compression Set (Cs) is measured according to the test method specified in ASTM D395; melt flow index (MI) Measured in accordance with the test method specified in ASTM D412.
為了開發出適用於射出成型方法的動態交聯熱塑性彈性體(TPV),將製程中所加入,含有酚醛樹酯之第一混合物和過氧化物比例做調整,結果參見表六。 In order to develop a dynamic crosslinked thermoplastic elastomer (TPV) suitable for injection molding, the ratio of the first mixture containing phenolic resin and the peroxide added in the process was adjusted. The results are shown in Table 6.
第四實施例(配方編號6號) Fourth embodiment (recipe number 6)
製備程序同本發明之第一實施例,配方編號3號中所用的第一混合物重量不變,但過氧化物改為1g。 The preparation procedure is the same as that of the first embodiment of the present invention. The weight of the first mixture used in Formulation No. 3 is unchanged, but the peroxide is changed to 1 g.
第五實施例(配方編號7號) Fifth embodiment (recipe number 7)
製備程序同本發明之第一實施例,配方編號3號中所用的第一混合物重量不變,但過氧化物改為2g。 The preparation procedure is the same as that of the first embodiment of the present invention. The weight of the first mixture used in Formula No. 3 is unchanged, but the peroxide is changed to 2 g.
第六實施例(配方編號8號) Sixth embodiment (recipe number 8)
製備程序同本發明之第一實施例,配方編號3號中所用的第一混 合物重量不變,但過氧化物改為3g。 The preparation procedure is the same as that of the first embodiment of the present invention, and the first mixture used in Formulation No. 3 The weight of the compound was unchanged, but the peroxide was changed to 3 g.
第七實施例(配方編號9號) Seventh embodiment (recipe number 9)
製備程序同本發明之第一實施例,配方編號3號中所用的第一混合物重量改為30g,過氧化物改為1g。 The preparation procedure is the same as the first embodiment of the present invention. The weight of the first mixture used in Formula No. 3 is changed to 30 g, and the peroxide is changed to 1 g.
第八實施例(配方編號10號) Eighth embodiment (recipe number 10)
製備程序同本發明之第一實施例,配方編號3號中所用的第一混合物重量改為30g,過氧化物改為2g。 The preparation procedure is the same as the first embodiment of the present invention. The weight of the first mixture used in Formula No. 3 is changed to 30 g, and the peroxide is changed to 2 g.
第九實施例(配方編號11號) Ninth embodiment (recipe number 11)
製備程序同本發明之第一實施例,配方編號3號中所用的第一混合物重量改為30g,過氧化物改為3g。 The preparation procedure is the same as the first embodiment of the present invention. The weight of the first mixture used in Formula No. 3 is changed to 30 g, and the peroxide is changed to 3 g.
參見表六,由實驗數據可以得知,實施例8具有最佳壓縮永久變形率。由於配方8.之動態交聯熱塑性彈性體(TPV)之流動性是無法適用於射出成型,為解決此問題,添加低分子量低立體規整性之聚烯烴共聚物如低分子量低立體規整性之聚丙烯(low molecular weight and low modulus polypropylene),以改善流動性不佳狀況,同時仍能維持優異的壓縮永久變形率。參見表7中所列各實施例,由實驗數據可知添加低分子量低立體規整性之聚丙烯後,動態交聯熱塑性彈性體之流動性有顯著改善。 Referring to Table 6, it can be known from the experimental data that Example 8 has the best compression set. Since the fluidity of the dynamically crosslinked thermoplastic elastomer (TPV) of Formula 8. cannot be applied to injection molding, in order to solve this problem, a low molecular weight and low stereoregularity polyolefin copolymer such as a low molecular weight and low stereoregularity polymer is added. Propylene (low molecular weight and low modulus polypropylene) to improve poor fluidity, while still maintaining excellent compression set. Referring to the examples listed in Table 7, it can be known from the experimental data that after adding low molecular weight and low stereoregularity polypropylene, the fluidity of the dynamically crosslinked thermoplastic elastomer is significantly improved.
第十實施例(配方編號12號) Tenth embodiment (recipe number 12)
製備程序同本發明之第一實施例,在後半段製作第二混合物時,在將聚丙烯,和乙烯-丙烯-非-共軛二烯橡膠,加入萬馬力機(Banbury Mixer)之步驟中,聚丙烯重量減半,同時混入20g低分子量低立體規整性之聚丙烯(low molecular weight and low modulus polypropylene)。此處所用為日本出光興產株式會社(Idemitsu Kosan Co.,Ltd.)L-MODUTM,S400產品。 The preparation procedure is the same as that of the first embodiment of the present invention. When preparing the second mixture in the second half of the step, in the step of adding polypropylene and ethylene-propylene-non-conjugated diene rubber to a Banbury Mixer, The weight of polypropylene was halved, and at the same time, 20g of low molecular weight and low modulus polypropylene was mixed . As used herein, Idemitsu Kosan Co., Ltd. L-MODU ™ , S400 products are used.
第十一實施例(配方編號13號) Eleventh embodiment (recipe number 13)
製備程序同本發明之第一實施例,在後半段製作第二混合物時,在將聚丙烯,和乙烯-丙烯-非-共軛二烯橡膠,加入萬馬力機(Banbury Mixer)之步驟中,所用聚丙烯重量不變,同時再加入20g低分子量低立體規整性之聚丙烯。此處所用為日本出光興產株式會社(Idemitsu Kosan Co.,Ltd.)型號S400產品(L-MODUTM,S400)。 The preparation procedure is the same as that of the first embodiment of the present invention. When preparing the second mixture in the second half of the step, in the step of adding polypropylene and ethylene-propylene-non-conjugated diene rubber to a Banbury Mixer, The polypropylene used had the same weight, and at the same time 20 g of low molecular weight, low stereoregularity polypropylene was added. The model S400 (L-MODU ™ , S400) used by Idemitsu Kosan Co., Ltd. is used here.
參見表7中熔融指數的數據,第十實施例及第十一實施例流動性皆大幅改善。 Referring to the data of the melt index in Table 7, the tenth embodiment and the eleventh embodiment both greatly improved the fluidity.
惟上述各實施例係用以說明本創作之特點,其目的在使熟習該技術者能瞭解本創作之內容並據以實施,而非限定本創作之專利範 圍,故凡其他未脫離本創作所揭示之精神而完成之等效修飾或修改,仍應包含在以下所述之申請專利範圍中。 However, the above embodiments are used to explain the characteristics of this creation, and the purpose is to enable those skilled in the art to understand and implement the content of this creation, not to limit the patent scope of this creation. Therefore, all other equivalent modifications or modifications made without departing from the spirit disclosed in this creation should still be included in the scope of patent application described below.
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