TWI504623B - Terminal-modified copolymer of conjugated diene and vinyl aromatic hydrocarbon and the synthesis method thereof - Google Patents
Terminal-modified copolymer of conjugated diene and vinyl aromatic hydrocarbon and the synthesis method thereof Download PDFInfo
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本發明是有關於一種烯烴聚合物,且特別是有關於一種末端改質的共軛二烯-乙烯基芳香烴共聚物。This invention relates to an olefin polymer, and more particularly to a terminally modified conjugated diene-vinyl aromatic copolymer.
末端改質的共軛二烯-乙烯基芳香烴共聚物可用來製造輪胎,因此,為了節約能源及行車安全之考量,其滾動阻力及耐濕滑性等性質非常重要。習知的作法是在末端改質的共軛二烯-乙烯基芳香烴共聚物中加入碳黑(carbon black),以增加輪胎之強度。The terminally modified conjugated diene-vinyl aromatic copolymer can be used to manufacture tires. Therefore, in order to save energy and drive safety considerations, the properties of rolling resistance and wet skid resistance are very important. It is a common practice to add carbon black to the terminally modified conjugated diene-vinyl aromatic copolymer to increase the strength of the tire.
習知用來改質共軛二烯-乙烯基芳香烴共聚物之改質劑為甲醯胺(formamide),此可改善輪胎之動態效果,然碳黑不易分散於甲醯胺改質之共軛二烯-乙烯基芳香烴共聚物,因此需要另尋改質劑,以得試用於製作輪胎之共軛二烯-乙烯基芳香烴共聚物。It is conventionally known that the modifier used to modify the conjugated diene-vinyl aromatic copolymer is formamide, which improves the dynamic effect of the tire, and the carbon black is not easily dispersed in the total modification of the methotrexate. The conjugated diene-vinyl aromatic copolymer requires an additional modifier to be tested for the conjugated diene-vinyl aromatic copolymer of the tire.
本發明提供一種末端改質的共軛二烯-乙烯基芳香烴共聚物及其合成方法,所合成的末端改質的共軛二烯-乙烯基芳香烴共聚物與碳黑具有良好的相容性,可製作具有良好耐濕滑性與低滾動阻力的輪胎。The invention provides a terminally modified conjugated diene-vinyl aromatic copolymer and a synthetic method thereof, wherein the synthesized terminal modified conjugated diene-vinyl aromatic copolymer has good compatibility with carbon black. Sex, can produce tires with good wet skid resistance and low rolling resistance.
本發明提供一種末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法,包括下列步驟:首先,以2:1~5:1的重量比使共軛二烯單體與乙烯基芳香烴單體在微結構調整劑與有機鹼金屬化合物的存在下進行反應,以生成具有活性端的共軛二烯-乙烯基芳香烴共聚物。接著,使具有活性端的共軛二烯-乙烯基芳香烴共聚物與第一改質劑進行反應,以生成中間產物。然後,使中間產物與第二改質劑進行反應,以生成末端改質的共軛二烯-乙烯基芳香烴共聚物。值得注意的是,第一改質劑可為含錫化合物,且第二改質劑可為含-CM-N<連結(linkage)基團的化合物,其中M為硫原子或氧原子。第一改質劑與第二改質劑之用量的莫耳比是1:4~4:1。The invention provides a method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer, which comprises the following steps: First, a conjugated diene monomer and a vinyl group are used in a weight ratio of 2:1 to 5:1. The aromatic hydrocarbon monomer is reacted in the presence of a microstructure control agent and an organic alkali metal compound to form a conjugated diene-vinyl aromatic copolymer having a living end. Next, the conjugated diene-vinyl aromatic copolymer having the active end is reacted with the first modifier to form an intermediate product. The intermediate product is then reacted with a second modifier to form a terminally modified conjugated diene-vinyl aromatic copolymer. It is to be noted that the first modifier may be a tin-containing compound, and the second modifier may be a compound containing a -CM-N<linkage group, wherein M is a sulfur atom or an oxygen atom. The molar ratio of the first modifier to the second modifier is 1:4 to 4:1.
在本發明的一實施例中,上述的末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法,其中以共軛二烯單體與乙烯基芳香烴單體的總量為100重量份計,第一改質劑與第二改質劑的總用量是0.001重量份~1重量份,所述第一改質劑和所述第二改質劑的總莫耳數與所述有機鹼金屬化合物的莫耳數的比值為0.95~1.05。In an embodiment of the invention, the method for synthesizing the terminally modified conjugated diene-vinyl aromatic copolymer, wherein the total amount of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer is 100 The total amount of the first modifier and the second modifier is 0.001 parts by weight to 1 part by weight, the total number of moles of the first modifier and the second modifier, and the The molar ratio of the organic alkali metal compound is 0.95 to 1.05.
在本發明的一實施例中,上述的末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法,其中微結構調整劑是選自四氫呋喃、 二乙醚、二噁烷、乙二醇二甲醚、乙二醇二丁醚、二乙二醇二甲醚、二乙二醇二丁醚、二甲氧基苯和2,2-雙(2-四氫呋喃基)丙烷所構成的群組中的至少一種。第一改質劑包括鹵化錫化合物或鹵化有機錫化合物。In an embodiment of the invention, the method for synthesizing the terminally modified conjugated diene-vinyl aromatic copolymer, wherein the microstructure adjusting agent is selected from the group consisting of tetrahydrofuran, Diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene and 2,2-dual (2 At least one of the group consisting of -tetrahydrofuranyl)propane. The first modifier includes a tin halide compound or a halogenated organotin compound.
在本發明的一實施例中,上述的末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法,其中鹵化有機錫化合物包括二乙基二氯化錫(diethyltin dichloride)、二丁基二氯化錫(dibutyltin dichloride)、氯化三丁錫(tributyltin chloride,TBSnCl)、二苯基二氯化錫(diphenyltin dichloride)或三苯基氯化錫(triphenyltin chloride)。In an embodiment of the invention, the method for synthesizing the terminal modified conjugated diene-vinyl aromatic copolymer, wherein the halogenated organotin compound comprises diethyltin dichloride, dibutyl Dibutyltin dichloride, tributyltin chloride (TBSnCl), diphenyltin dichloride or triphenyltin chloride.
在本發明的一實施例中,上述的末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法,其中第二改質劑包括醯胺類化合物、醯亞胺類化合物、內醯胺類化合物、尿素類化合物或異三聚氰酸衍生物。In one embodiment of the present invention, the method for synthesizing the terminally modified conjugated diene-vinyl aromatic copolymer, wherein the second modifier comprises a guanamine compound, a quinone imine compound, and a ruthenium An amine compound, a urea compound or an isocyanuric acid derivative.
本發明亦提供一種末端改質的共軛二烯-乙烯基芳香烴共聚物,其由(A)共軛二烯單體及(B)乙烯基芳香烴單體聚合生成共軛二烯-乙烯基芳香烴共聚物後,經(C)第一改質劑後再與(D)第二改質劑改質而產生。末端改質的共軛二烯-乙烯基芳香烴共聚物中,由(A)共軛二烯單體所構成的重複單元與所述(B)乙烯基芳香烴單體所構成的重複單元的重量比為2:1~5:1。(C)第一改質劑是含錫化合物。(D)第二改質劑是含-CM-N<連結基團(linkage)的化合物,其中M為硫原子或氧原子。(C)第一改質劑與(D)第二改質劑的莫耳比是1:4~4:1。The present invention also provides a terminally modified conjugated diene-vinyl aromatic copolymer which is polymerized from (A) a conjugated diene monomer and (B) a vinyl aromatic hydrocarbon monomer to form a conjugated diene-ethylene After the base aromatic hydrocarbon copolymer is modified by (C) the first modifier, and (D) the second modifier is produced. In the terminally modified conjugated diene-vinyl aromatic copolymer, a repeating unit composed of (A) a conjugated diene monomer and a repeating unit composed of the (B) vinyl aromatic hydrocarbon monomer The weight ratio is 2:1~5:1. (C) The first modifier is a tin-containing compound. (D) The second modifier is a compound containing -CM-N <linkage, wherein M is a sulfur atom or an oxygen atom. (C) The molar ratio of the first modifier to the (D) second modifier is 1:4 to 4:1.
在本發明的一實施例中,上述的末端改質的共軛二烯-乙烯 基芳香烴共聚物,其中第一改質劑包括鹵化錫化合物或鹵化有機錫化合物。In an embodiment of the invention, the terminal modified conjugated diene-ethylene The aromatic hydrocarbon copolymer, wherein the first modifier comprises a tin halide compound or a halogenated organotin compound.
在本發明的一實施例中,上述的末端改質的共軛二烯-乙烯基芳香烴共聚物,其中鹵化錫化合物包括四氯化錫或四溴化錫。In an embodiment of the invention, the terminal modified conjugated diene-vinyl aromatic copolymer, wherein the tin halide compound comprises tin tetrachloride or tin tetrabromide.
在本發明的一實施例中,上述的末端改質的共軛二烯-乙烯基芳香烴共聚物,其中鹵化有機錫化合物包括二乙基二氯化錫、二丁基二氯化錫、氯化三丁錫、二苯基二氯化錫或三苯基氯化錫。In an embodiment of the invention, the terminal modified conjugated diene-vinyl aromatic copolymer, wherein the halogenated organotin compound comprises diethyltin dichloride, dibutyltin dichloride, chlorine Tributyltin, diphenyltin dichloride or triphenyltin chloride.
在本發明的一實施例中,上述的末端改質的共軛二烯-乙烯基芳香烴共聚物,其中第二改質劑包括醯胺類化合物、醯亞胺類化合物、內醯胺類化合物、尿素類化合物或異三聚氰酸衍生物。In an embodiment of the invention, the terminal modified conjugated diene-vinyl aromatic copolymer, wherein the second modifier comprises a guanamine compound, a quinone imine compound, an intrinsic amine compound , a urea compound or a derivative of isocyanuric acid.
本發明還提供一種橡膠組合物,其包括碳黑及上述的末端改質的共軛二烯-乙烯基芳香烴共聚物。The present invention also provides a rubber composition comprising carbon black and the above-mentioned terminal-modified conjugated diene-vinyl aromatic copolymer.
基於上述,本發明提出一種末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法。根據此方法合成的末端改質的共軛二烯-乙烯基芳香烴共聚物與碳黑具有良好的相容性。因此,這種末端改質的共軛二烯-乙烯基芳香烴共聚物適於製造輪胎,且其製成的輪胎能表現優秀的滾動阻力以及出色的耐濕滑性。Based on the above, the present invention proposes a method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer. The terminally modified conjugated diene-vinyl aromatic copolymer synthesized according to this method has good compatibility with carbon black. Therefore, such terminally modified conjugated diene-vinyl aromatic copolymer is suitable for the manufacture of tires, and the tires produced thereof can exhibit excellent rolling resistance and excellent wet skid resistance.
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。The above described features and advantages of the invention will be apparent from the following description.
以下將根據本發明之實施方式,詳細描述末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法。Hereinafter, a method of synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer will be described in detail according to an embodiment of the present invention.
在本說明書中,如果沒有特別指明某一基團是否經過取代,則該基團可表示經取代或未經取代的基團。例如,「烷基」可表示經取代或未經取代的烷基。另外,對某一基團冠以「Cx」來描述時,表示該基團之主鏈具有X個碳原子。In the present specification, if a group is not specifically indicated, whether or not a group is substituted, the group may represent a substituted or unsubstituted group. For example, "alkyl" can mean a substituted or unsubstituted alkyl group. Further, when a group crown is described by "Cx", it means that the main chain of the group has X carbon atoms.
在本說明書中,化合物結構有時以鍵線式(skeleton formula)表示。這種表示法可以省略碳原子、氫原子以及碳氫鍵。當然,結構式中有明確繪出官能基的,則以繪示者為準。In the present specification, the compound structure is sometimes represented by a skeleton formula. This representation can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, if the functional group is clearly drawn in the structural formula, the manufacturer will prevail.
在說明書中,有時以「phr(part per hundred rubber)」作為添加物用量的單位,其為橡膠合成領域中常見的術語,意指「每100(重量)份的橡膠中添加的重量份數」,且此處所謂的「橡膠」即指共軛二烯-乙烯基芳香烴共聚物。此外,在說明書中,關於聚合反應的部份是將共軛二烯-乙烯基芳香烴共聚物之重量與共軛二烯單體加上乙烯基芳香烴單體的重量之和視為相等。也就是說,聚合反應中用phr表示添加物用量時,其基準可以是100重量份的共軛二烯-乙烯基芳香烴共聚物,也可以是100重量份的共軛二烯單體與乙烯基芳香烴單體。In the specification, "phr (part per hundred rubber)" is sometimes used as a unit of the amount of additives, which is a common term in the field of rubber synthesis, and means "parts by weight per 100 parts by weight of rubber. The term "rubber" as used herein means a conjugated diene-vinyl aromatic copolymer. Further, in the specification, the portion relating to the polymerization reaction is considered to be equal to the sum of the weight of the conjugated diene-vinyl aromatic copolymer and the weight of the conjugated diene monomer plus the vinyl aromatic hydrocarbon monomer. That is, when the amount of the additive is represented by phr in the polymerization reaction, the reference may be 100 parts by weight of the conjugated diene-vinyl aromatic copolymer, or 100 parts by weight of the conjugated diene monomer and ethylene. Aromatic aromatic hydrocarbon monomer.
根據本發明之一實施例,末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法包括下列步驟:(a)使共軛二烯單體與乙烯基芳香烴單體進行反應以生成共軛二烯-乙烯基芳香烴共聚物;(b)使共軛二烯-乙烯基芳香烴共聚物與第一改質劑進行反應以生成中間產物;以及(c)使中間產物與第二改質劑進行反應以生成末端改質的共軛二烯-乙烯基芳香烴共聚物。According to an embodiment of the present invention, a method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer comprises the steps of: (a) reacting a conjugated diene monomer with a vinyl aromatic hydrocarbon monomer to Forming a conjugated diene-vinyl aromatic copolymer; (b) reacting the conjugated diene-vinyl aromatic copolymer with the first modifier to form an intermediate product; and (c) intermediate product The second modifier is reacted to form a terminally modified conjugated diene-vinyl aromatic copolymer.
以下詳細描述上述各個步驟:The above various steps are described in detail below:
步驟(a)Step (a)
可以任何習知的使共軛二烯單體與乙烯基芳香烴單體發生聚合反應的方法來執行步驟(a)。例如,可以在聚合起始劑的存在下使共軛二烯單體與乙烯基芳香烴單體聚合形成具有活性端的未改質的共軛二烯-乙烯基芳香烴共聚物。步驟(a)中,共軛二烯單體與乙烯基芳香烴單體的重量比為約2:1~5:1,因此上述該共聚物中包含上述共軛二烯單體所構成的共軛二烯重複單元以及上述乙烯基芳香烴單體所構成的乙烯基芳香烴單體單元的重量比同樣為約2:1~5:1。在一實施例中,共軛二烯單體在共軛二烯-乙烯基芳香烴共聚物中所佔的比例可以介於74重量%到84重量%之間,而乙烯基芳香烴結構單元在共軛二烯-乙烯基芳香烴共聚物 中所佔的比例可介於16重量%到26重量%之間。Step (a) can be carried out by any conventional method of polymerizing a conjugated diene monomer with a vinyl aromatic hydrocarbon monomer. For example, the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer can be polymerized in the presence of a polymerization initiator to form an unmodified conjugated diene-vinyl aromatic copolymer having a living end. In the step (a), the weight ratio of the conjugated diene monomer to the vinyl aromatic hydrocarbon monomer is from about 2:1 to 5:1, so that the copolymer comprises the above-mentioned conjugated diene monomer. The weight ratio of the conjugated diene repeating unit and the vinyl aromatic hydrocarbon monomer unit composed of the above vinyl aromatic hydrocarbon monomer is also about 2:1 to 5:1. In one embodiment, the proportion of the conjugated diene monomer in the conjugated diene-vinyl aromatic copolymer may be between 74% and 84% by weight, and the vinyl aromatic hydrocarbon structural unit is Conjugated diene-vinyl aromatic copolymer The proportion may be between 16% and 26% by weight.
聚合起始劑可為有機鹼金屬化合物,例如乙基鋰、正丙基鋰、異丙基鋰、正丁基鋰、正戊基鋰、苯基鋰、甲苯基鋰或其組合。The polymerization initiator may be an organic alkali metal compound such as ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium or a combination thereof.
共軛二烯單體可為1,3-丁二烯、異戊二烯、1,3-戊二烯、2-乙基-1,3-丁二烯、2,3-二甲基丁二烯、2-甲基戊二烯、4-甲基戊二烯、2,4-己二烯或其組合。The conjugated diene monomer may be 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutyl Diene, 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene or a combination thereof.
乙烯基芳香烴單體可為苯乙烯、α-甲基苯乙烯、二乙烯基苯(Divinylbenzene)或其組合。The vinyl aromatic hydrocarbon monomer can be styrene, alpha-methyl styrene, divinyl benzene, or a combination thereof.
在一實施例中,共軛二烯單體是1,3-丁二烯,而乙烯基芳香烴單體是苯乙烯。In one embodiment, the conjugated diene monomer is 1,3-butadiene and the vinyl aromatic hydrocarbon monomer is styrene.
經步驟(a)聚合而得的共軛二烯-乙烯基芳香烴共聚物包括共軛二烯結構單元與乙烯基芳香烴結構單元。此處所謂「結構單元」(或稱單體單元)是指前述的共軛二烯單體或乙烯基芳香烴單體經聚合反應而形成的重複結構。The conjugated diene-vinyl aromatic copolymer obtained by the polymerization of the step (a) includes a conjugated diene structural unit and a vinyl aromatic hydrocarbon structural unit. Here, the "structural unit" (or monomer unit) means a repeating structure in which the above-mentioned conjugated diene monomer or vinyl aromatic hydrocarbon monomer is polymerized.
共軛二烯結構單元可包括1,3-丁二烯結構單元、異戊二烯結構單元、1,3-戊二烯結構單元、2-乙基-1,3-丁二烯結構單元、2,3-二甲基丁二烯結構單元、2-甲基戊二烯結構單元、4-甲基戊二烯結構單元、2,4-己二烯結構單元或其組合。The conjugated diene structural unit may include a 1,3-butadiene structural unit, an isoprene structural unit, a 1,3-pentadiene structural unit, a 2-ethyl-1,3-butadiene structural unit, 2,3-dimethylbutadiene structural unit, 2-methylpentadiene structural unit, 4-methylpentadiene structural unit, 2,4-hexadiene structural unit or a combination thereof.
乙烯基芳香烴結構單元可包括苯乙烯結構單元、α甲基苯乙烯結構單元、二乙烯基苯結構單元或其組合。The vinyl aromatic hydrocarbon structural unit may include a styrene structural unit, an αmethylstyrene structural unit, a divinylbenzene structural unit, or a combination thereof.
於一實施例中,共軛二烯結構單元是1,3-丁二烯結構單 元,而乙烯基芳香烴結構單元是苯乙烯結構單元。In one embodiment, the conjugated diene structural unit is a 1,3-butadiene structure And the vinyl aromatic hydrocarbon structural unit is a styrene structural unit.
共軛二烯單體可進行1,4聚合及/或1,2聚合以形成1,4結構單元(或稱乙烯基1,4結構,以下簡稱1,4結構)及/或1,2結構單元(或稱乙烯基1,2結構,以下簡稱1,2結構)。詳言之,「1,4聚合」是指共軛二烯單體經由其1位置與4位置的碳與其他單體鍵結,藉由此方式聚合而成的1,4結構可進一步分成順式與反式;同理,「1,2聚合」是指共軛二烯單體經由其1位置與2位置的碳與其他單體鍵結,藉由1,2聚合形成的1,2結構則是一種乙烯基位於側鏈的結構。1,4結構與1,2結構可共存於聚合物鏈中。舉例來說,以1,3-丁二烯單體進行聚合時,可產生1,2-聚丁二烯結構單元或1,4-聚丁二烯結構單元。The conjugated diene monomer can be subjected to 1,4 polymerization and/or 1,2 polymerization to form 1,4 structural units (or vinyl 1,4 structures, hereinafter referred to as 1,4 structures) and/or 1,2 structures. Unit (or vinyl 1, 2 structure, hereinafter referred to as 1, 2 structure). In detail, "1,4 polymerization" means that the conjugated diene monomer is bonded to other monomers via its 1-position and 4-position carbon, and the 1,4 structure which is polymerized in this way can be further divided into Similarly, "1,2 polymerization" refers to a 1,2 structure in which a conjugated diene monomer is bonded to another monomer via its 1-position and 2-position carbons by polymerization of 1,2. It is a structure in which a vinyl group is located in a side chain. The 1,4 structure and the 1,2 structure may coexist in the polymer chain. For example, when polymerizing with a 1,3-butadiene monomer, a 1,2-polybutadiene structural unit or a 1,4-polybutadiene structural unit can be produced.
1,2結構在所有共軛二烯結構單元(即1,4結構單元以及1,2結構單元之和)中所佔的比例可介於10%到90%之間。在一實施例中,1,2結構佔共軛二烯結構單元的比例介於50%到90%之間,較佳為55%到70%之間。The ratio of the 1,2 structure to all of the conjugated diene structural units (i.e., the sum of the 1,4 structural units and the 1,2 structural units) may be between 10% and 90%. In one embodiment, the ratio of the 1,2 structure to the conjugated diene structural unit is between 50% and 90%, preferably between 55% and 70%.
步驟(a)的聚合反應可在溶劑的存在下進行。溶劑可包括非極性溶劑,例如(但不限於)戊烷、己烷、庚烷等脂肪族烴;環戊烷、環己烷、甲基環戊烷、甲基環己烷等脂環族烴;苯、甲苯、二甲苯等芳香族烴或前述溶劑的混合物。The polymerization of the step (a) can be carried out in the presence of a solvent. The solvent may include a non-polar solvent such as, but not limited to, an aliphatic hydrocarbon such as pentane, hexane or heptane; an alicyclic hydrocarbon such as cyclopentane, cyclohexane, methylcyclopentane or methylcyclohexane; An aromatic hydrocarbon such as benzene, toluene or xylene or a mixture of the foregoing solvents.
在本發明之一實施例中,上述末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法更包括在使共軛二烯單體與乙烯基芳香烴單體進行反應時,添加分歧劑,以增加單一分子鏈上可供改 質之活性點,使改質效果更佳。分歧劑可為多環氧基類(polyepoxides),如環氧化亞麻仁油(epoxidized linseed oil);多酯基類(polyesters),如己二酸二乙酯(diethyl adipate);多鹵化物(polyhalides),如四氯化矽(silicon tetrahalide);多異氰酸酯基類(polyisocyanates),如苯-1,2,4-三異氰酸酯(benzene-1,2,4-triisocyanate);多亞胺基類(polyimines),如三(1-氮丙啶基)氧化磷(tri(1-aziridinyl)phosphine oxide);多醛基類(polyaldehydes),如1,4,7-萘三羧醛(1,4,7-naphthalene tricarboxaldehyde);多酮基類(polyketones),如2,4,6-三庚酮(2,4,6-heptanetrione);多酸酐基類(polyanhydrides),如均苯四甲酸二酐(pyromellitic dianhydride);多乙烯基苯類化合物,如二乙烯基苯(divinylbenzene,DVB)或上述化合物的組合。本發明較佳為使用二乙烯基苯。In one embodiment of the present invention, the method for synthesizing the terminally modified conjugated diene-vinyl aromatic copolymer further comprises adding a conjugated diene monomer to a vinyl aromatic hydrocarbon monomer. Dividing agents to increase the availability of a single molecular chain The active point of the quality makes the modification effect better. The diverging agent may be polyepoxides such as epoxidized linseed oil; polyesters such as diethyl adipate; polyhalides ), such as silicon tetrahalide; polyisocyanates, such as benzene-1,2,4-triisocyanate; polyimine (polyimines) ), such as tris(1-aziridinyl)phosphine oxide; polyaldehydes such as 1,4,7-naphthalene tricarboxylic aldehyde (1,4,7) -naphthalene tricarboxaldehyde); polyketones such as 2,4,6-heptanetrione; polyanhydrides such as pyromellitic Dianhydride); a polyvinylbenzene compound such as divinylbenzene (DVB) or a combination of the above compounds. The present invention preferably uses divinylbenzene.
此外,共軛二烯單體與乙烯基芳香烴單體的聚合反應可在微結構調整劑的存在下進行。使用微結構調整劑能使共軛二烯單體與乙烯基芳香烴單體無規(randomly)共聚合。微結構調整劑可為極性化合物,且在一實施例中,其可作為乙烯化劑(vinylating agent)或1,2-乙烯結構化劑(1,2-vinyl configuration agent)。Further, the polymerization of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer can be carried out in the presence of a microstructure control agent. The use of a microstructure adjusting agent enables random copolymerization of a conjugated diene monomer with a vinyl aromatic hydrocarbon monomer. The microstructure modifier can be a polar compound and, in one embodiment, can act as a vinylating agent or a 1,2-vinyl configuration agent.
微結構調整劑包括(但不限於)四氫呋喃、二乙醚、二噁烷、乙二醇二甲醚、乙二醇二丁醚、二乙二醇二甲醚、二乙二醇二丁醚、二甲氧基苯、2,2-雙(2-四氫呋喃基)丙烷等醚類;四甲 基乙二胺、二哌啶乙烷、三甲胺、三乙胺、吡啶、奎寧環(quinuclidine)等三級胺化合物;第三戊醇鉀、第三丁醇鉀、第三丁醇鈉、第三戊醇鈉等鹼金屬烷醇鹽化合物;三苯基膦(triphenyl phosphine)等膦化合物;烷基磺酸化合物或芳基磺酸化合物等。上述極性化合物可單獨使用,或混合兩種或兩種以上極性化合物使用。Microstructural modifiers include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, two Ethers such as methoxybenzene and 2,2-bis(2-tetrahydrofuryl)propane; a tertiary amine compound such as ethylenediamine, dipiperidineethane, trimethylamine, triethylamine, pyridine, quinuclidine, potassium third potassium pentoxide, potassium butoxide, sodium butoxide, An alkali metal alkoxide compound such as sodium pentaerythritol; a phosphine compound such as triphenyl phosphine; an alkylsulfonic acid compound or an arylsulfonic acid compound. The above polar compounds may be used singly or in combination of two or more kinds of polar compounds.
微結構調整劑之使用量,可根據實際需求及其調整結構之效果進行選擇。通常,微結構調整劑相對於1莫耳的聚合起始劑實質上為0.01莫耳~100莫耳。在一實施例中,微結構調整劑的用量為0.05phr至0.5phr。根據所期望之1,2結構的量,可適量使用極性化合物(乙烯化劑)來作為微結構調節劑。The amount of microstructure control agent can be selected according to actual needs and the effect of adjusting the structure. Typically, the microstructure modifier is from 0.01 moles to 100 moles relative to 1 mole of polymerization initiator. In one embodiment, the microstructure modifier is used in an amount from 0.05 phr to 0.5 phr. A polar compound (vinylating agent) can be used as a microstructure adjusting agent in an appropriate amount according to the desired amount of the 1,2 structure.
此外,共軛二烯單體與乙烯基芳香烴單體的聚合反應後,可先添加足以和具有活性端的未改質的共軛二烯-乙烯基芳香烴共聚物反應的物質,使未改質的共軛二烯-乙烯基芳香烴共聚物失去活性後再添加改質劑,或者亦可以直接添加改質劑併作為聚合反應終止劑。較佳為在未改質的共軛二烯-乙烯基芳香烴共聚物具有活性端的時候添加改質劑。Further, after the polymerization of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer, a substance sufficient to react with the unmodified conjugated diene-vinyl aromatic copolymer having the active end may be added first. The conjugated diene-vinyl aromatic copolymer is deactivated and then added with a modifier, or a modifier can be added directly as a polymerization terminator. It is preferred to add a modifier when the unmodified conjugated diene-vinyl aromatic copolymer has an active end.
在一實施例中,步驟(a)所獲得的未改質的共軛二烯-乙烯基芳香烴共聚物的重量平均分子量可為800,000~1500,000,且較佳為900,000~1,300,000,更佳為970,000~1270,000。In one embodiment, the unmodified conjugated diene-vinyl aromatic copolymer obtained in the step (a) may have a weight average molecular weight of 800,000 to 1500,000, and preferably 900,000 to 1,300,000, more preferably It is 970,000~1270,000.
步驟(b)Step (b)
在步驟(b)中,使步驟(a)獲得的共軛二烯-乙烯基芳香烴共聚物與第一改質劑進行反應以生成中間產物。In the step (b), the conjugated diene-vinyl aromatic copolymer obtained in the step (a) is reacted with the first modifier to form an intermediate product.
第一改質劑可為含錫化合物,例如鹵化錫化合物或鹵化有機錫化合物(halogenated organotin)。鹵化錫化合物包括四氯化錫、四溴化錫或其類似物。鹵化有機錫化合物包括二乙基二氯化錫、二丁基二氯化錫、氯化三丁錫、二苯基二氯化錫、三苯基氯化錫或其類似物。鑑於加工及儲存之安全性,第一改質劑較佳為鹵化程度低之錫化合物,例如氯化三丁錫或三苯基氯化錫。The first modifier may be a tin-containing compound such as a tin halide compound or a halogenated organotin. The tin halide compound includes tin tetrachloride, tin tetrabromide or the like. The halogenated organotin compound includes diethyltin dichloride, dibutyltin dichloride, tributyltin chloride, diphenyltin dichloride, triphenyltin chloride or the like. In view of the safety of processing and storage, the first modifier is preferably a tin compound having a low degree of halogenation, such as tributyltin chloride or triphenyltin chloride.
上述第一改質劑可單獨使用,或混合兩種或兩種以上第一改質劑使用。The above first modifying agent may be used singly or in combination of two or more kinds of first modifying agents.
在一實施例中,第一改質劑的用量是0.01phr~0.3phr,較佳為0.08phr~0.3phr,且更佳為0.08phr~0.12phr。In one embodiment, the first modifier is used in an amount of from 0.01 phr to 0.3 phr, preferably from 0.08 phr to 0.3 phr, and more preferably from 0.08 phr to 0.12 phr.
步驟(c)Step (c)
在步驟(c)中,使步驟(b)中獲得的中間產物與第二改質劑進行反應,以生成末端改質的共軛二烯-乙烯基芳香烴共聚物。In the step (c), the intermediate product obtained in the step (b) is reacted with a second modifier to form a terminally modified conjugated diene-vinyl aromatic copolymer.
第二改質劑可為含-CM-N<連結基團的化合物,其中M為硫原子或氧原子。含-CM-N<連結基團化合物例如是醯胺類化合物、醯亞胺類化合物、內醯胺類化合物、尿素類化合物或異三聚氰酸衍生物。The second modifier may be a compound containing -CM-N < linking group, wherein M is a sulfur atom or an oxygen atom. The -CM-N<linking group-containing compound is, for example, a guanamine compound, a quinone imine compound, an indoleamine compound, a urea compound or a heterocyanuric acid derivative.
醯胺類化合物包括甲醯胺(formamide)、二甲基甲醯胺 (N,N-dimethylformamide)、乙醯胺(acetamide)、N,N-二甲基胺基乙醯胺(N,N-dimethylaminoacetamide)、N,N-二甲基-N',N'-二甲基胺基乙醯胺(N,N-dimethyl-N',N'-dimethylaminoacetamide)、N,N-二甲基-N'-乙基乙醯胺(N,N-dimethyl-N'-ethylaminoacetamide)、丙烯醯胺(acrylamide)、N,N-二甲基丙烯醯胺(N,N-dimethylacrylamide)、N,N-二甲基甲基丙烯醯胺(N,N-dimethylmethacrylamide)、菸鹼醯胺(nicotinamide)、異菸鹼醯胺(isonicotinamide)、吡啶甲酸醯胺(picolinic acid amide)、N,N-二甲基異菸鹼醯胺(N,N-dimethylisonicotinamide)、琥珀醯胺(succinic acid amide)、鄰苯二甲酸醯胺(phthalic acid amide)、N,N,N'N'-四甲基鄰苯二甲酸醯胺(N,N,N'N'-tetramethylphthalic acid amide)、草醯胺(oxamide)、N,N,N'N'-四甲基草醯胺(N,N,N'N'-tetramethyloxamide)、N,N-二甲基-2-呋喃甲酸醯胺(N,N-dimethyl-2-furan carboxylic acid amide)、喹啉-2-甲酸醯胺(quinoline-2-carboxylic acid amide)、N-乙基-N-甲基-喹啉-2-甲酸醯胺(N-ethyl-N-methyl-quinoline carboxylic acid amide)或其類似物。Indoleamines include formamide, dimethylformamide (N, N-dimethylformamide), acetamide, N,N-dimethylaminoacetamide, N,N-dimethyl-N', N'-di N,N-dimethyl-N', N'-dimethylaminoacetamide, N,N-dimethyl-N'-ethylacetamide (N,N-dimethyl-N'-ethylaminoacetamide ), acrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, nicotine oxime Nicotinamide, isonicotitinamide, picolinic acid amide, N,N-dimethylisonicotinamide, succinic acid Amide), phthalic acid amide, N,N,N'N'-tetramethylphthalic acid amide, grass carp Oxamide, N, N, N'N'-tetramethyloxamide (N, N, N'N'-tetramethyloxamide), N,N-dimethyl-2-furancarboxylic acid decylamine (N, N-dimethyl-2-furan carboxylic acid amide), quinoline-2-carboxylic acid amide, N-ethyl-N-methyl-quinoline-2-carboxylic acid hydrazine (N-ethyl-N-methyl-quinoline carboxylic acid amide) or the like.
醯亞胺類化合物包括琥珀醯亞胺(succinic imide)、N-甲基琥珀醯亞胺(N-methylsuccinic imide)、馬來醯亞胺(maleimide)、鄰苯二甲醯亞胺(phthalimide)、N-甲基鄰苯二甲醯亞胺(N-methylphthalimide)、1,2-環己烷二羧基亞醯胺(1,2-cyclohexanedicarboxyimide)或其類似物。The quinone imines include succinic imide, N-methylsuccinic imide, maleimide, phthalimide, N-methylphthalimide, 1,2-cyclohexanedicarboxyimide or the like.
內醯胺類化合物包括ε-己內醯胺(ε-caprolactam)、N- 甲基-ε-己內醯胺(N-methyl-ε-caprolactam)、2-吡咯酮(2-pyrrolidone)、N-甲基-2-吡咯酮(N-methyl-2-pyrrolidone)、2-哌啶酮(2-piperidone)、N-甲基-2-哌啶酮(N-methyl-2-piperidone)、2-喹啉酮(2-quinolone)、N-甲基-2-喹啉酮(N-methyl-2-quinolone)或其類似物。Indoleamines include ε-caprolactam (N-caprolactam), N- Methyl-ε-caprolactam, 2-pyrrolidone, N-methyl-2-pyrrolidone, 2- 2-piperidone, N-methyl-2-piperidone, 2-quinolone, N-methyl-2-quinolinone (N-methyl-2-quinolone) or an analogue thereof.
尿素類化合物包括尿素(urea)、N,N'-二甲基尿素(N,N'-dimethylurea)、N,N'-二乙基尿素(N,N'-diethylurea)、N,N,N',N'-四甲基尿素(N,N,N',N'-tetramethylurea)、N,N-二甲基-N',N'-二苯基尿素(N,N-dimethyl-N',N'-diphenylurea)或其類似物。胺基甲酸衍生物包括胺甲酸甲酯(methyl carbamate)、N,N-二甲基胺甲酸甲酯(N,N-dimethyl methyl carbamate)或其類似物。異三聚氰酸衍生物包括異三聚氰酸(isocyanuric acid)或其類似物。Urea compounds include urea (urea), N, N'-dimethylurea (N, N'-dimethylurea), N, N'-diethyl urea (N, N'-diethylurea), N, N, N ',N'-tetramethylurea (N,N,N',N'-tetramethylurea), N,N-dimethyl-N',N'-diphenylurea (N,N-dimethyl-N' , N'-diphenylurea) or an analogue thereof. The urethane derivative includes methyl carbamate, N, N-dimethyl methyl carbamate or the like. The isomeric cyanuric acid derivative includes isocyanuric acid or the like.
上述第二改質劑可單獨使用,或混合兩種或兩種以上第二改質劑使用。The above second modifying agent may be used singly or in combination of two or more kinds of second modifying agents.
在一實施例中,第二改質劑的用量是0.001phr~1phr,較佳為0.001phr~0.5phr,且更佳為0.01phr~0.05phr。In one embodiment, the second modifier is used in an amount of from 0.001 phr to 1 phr, preferably from 0.001 phr to 0.5 phr, and more preferably from 0.01 phr to 0.05 phr.
在一實施例中,第一改質劑與第二改質劑之用量的莫耳比可為1:4~4:1,較佳為1:1~5:2,且更佳為3:1~7:3~。In one embodiment, the molar ratio of the first modifier to the second modifier may be 1:4 to 4:1, preferably 1:1 to 5:2, and more preferably 3: 1~7:3~.
在一實施例中,改質劑的總莫耳數(第一改質劑與第二改質劑之用量的和)與聚合起始劑(如有機鹼金屬化合物)用量的莫耳數的比值可為0.95~1.05,且較佳為0.98~1.02。In one embodiment, the ratio of the total number of moles of the modifier (the sum of the amount of the first modifier to the second modifier) to the molar amount of the polymerization initiator (eg, an organic alkali metal compound) It can be from 0.95 to 1.05, and preferably from 0.98 to 1.02.
完成步驟(c)以後,可在反應系統中添加末端改質的共 軛二烯-乙烯基芳香烴共聚物的不良溶劑,例如醇類(如甲醇、乙醇或異丙醇),使末端改質的共軛二烯-乙烯基芳香烴共聚物析出,或以高於溶劑沸點溫度之熱水或以水蒸汽去除溶劑,而從混合物中分離出末端改質的共軛二烯-乙烯基芳香烴共聚物。After completion of step (c), a total of end-modifications can be added to the reaction system. A poor solvent of the conjugated diene-vinyl aromatic copolymer, such as an alcohol (such as methanol, ethanol or isopropanol), precipitates the terminally modified conjugated diene-vinyl aromatic copolymer, or is higher than The terminally modified conjugated diene-vinyl aromatic copolymer is separated from the mixture by hot water at the boiling point of the solvent or by removing the solvent with water vapor.
在一實施例中,末端改質的共軛二烯-乙烯基芳香烴共聚物的合成方法是在使共軛二烯單體與乙烯基芳香烴單體進行反應,以生成具有活性末端的共軛二烯-乙烯基芳香烴共聚物後,再添加第一或第二改質劑。In one embodiment, the terminally modified conjugated diene-vinyl aromatic copolymer is synthesized by reacting a conjugated diene monomer with a vinyl aromatic hydrocarbon monomer to form a total of active ends. After the conjugated diene-vinyl aromatic copolymer, a first or second modifier is added.
在一實施例中,末端改質的共軛二烯-乙烯基芳香烴共聚物由(A)共軛二烯單體及(B)乙烯基芳香烴單體聚合生成共軛二烯-乙烯基芳香烴共聚物後,再經(C)第一改質劑與(D)第二改質劑改質而產生。在進行聚合反應時,(A)共軛二烯單體與(B)乙烯基芳香烴單體的重量比為2:1~5:1。(C)第一改質劑可為含錫化合物。(D)第二改質劑可為含-CM-N<基團化合物,其中M為硫原子或氧原子。以(A)共軛二烯單體與(B)乙烯基芳香烴單體的總量為100重量份計,(C)第一改質劑與(D)第二改質劑的用量分別是0.001重量份~1重量份與0.001重量份~1重量份。In one embodiment, the terminally modified conjugated diene-vinyl aromatic copolymer is polymerized from (A) a conjugated diene monomer and (B) a vinyl aromatic hydrocarbon monomer to form a conjugated diene-vinyl group. After the aromatic hydrocarbon copolymer is modified by (C) the first modifier and (D) the second modifier. When the polymerization reaction is carried out, the weight ratio of the (A) conjugated diene monomer to the (B) vinyl aromatic hydrocarbon monomer is from 2:1 to 5:1. (C) The first modifier may be a tin-containing compound. (D) The second modifier may be a compound containing -CM-N<, wherein M is a sulfur atom or an oxygen atom. The amount of the (C) first modifier and the (D) second modifier are respectively, based on 100 parts by weight of the total of the (A) conjugated diene monomer and the (B) vinyl aromatic hydrocarbon monomer. 0.001 parts by weight to 1 part by weight and 0.001 parts by weight to 1 part by weight.
在一實施例中,末端改質的共軛二烯-乙烯基芳香烴共聚物的重量平均分子量為800,000~1500,000,數目平均分子量為450,000~900,000。多分散度為1.5~2.0。In one embodiment, the terminally modified conjugated diene-vinyl aromatic copolymer has a weight average molecular weight of from 800,000 to 1,500,000 and a number average molecular weight of from 450,000 to 900,000. The polydispersity is 1.5~2.0.
本發明另提供一種橡膠組合物的製造方法。在一實施例中,橡膠組合物的製造方法包括:混練橡膠與碳黑以得到橡膠組合物,其中橡膠包括前文詳細闡述的任一種末端改質的共軛二烯-乙烯基芳香烴共聚物。在一實施例中,橡膠包括末端改質的共軛二烯-乙烯基芳香烴共聚物與另一未改質的共軛二烯-乙烯基芳香烴共聚物。值得注意的是,所述另一未改質的共軛二烯-乙烯基芳香烴共聚物,可相同或相異於用以形成末端改質的共軛二烯-乙烯基芳香烴共聚物的未改質的共軛二烯-乙烯基芳香烴共聚物。The present invention further provides a method of producing a rubber composition. In one embodiment, a method of making a rubber composition includes kneading rubber and carbon black to obtain a rubber composition, wherein the rubber comprises any of the terminally modified conjugated diene-vinyl aromatic copolymers as described in detail above. In one embodiment, the rubber comprises a terminally modified conjugated diene-vinyl aromatic copolymer and another unmodified conjugated diene-vinyl aromatic copolymer. It is noted that the other unmodified conjugated diene-vinyl aromatic copolymer may be the same or different from the conjugated diene-vinyl aromatic copolymer used to form the terminal modification. Unmodified conjugated diene-vinyl aromatic copolymer.
所述末端改質的共軛二烯-乙烯基芳香烴共聚物與另一未改質的共軛二烯-乙烯基芳香烴共聚物可分別包含共軛二烯結構單元以及乙烯基芳香烴結構單元,其中共軛二烯結構單元包含乙烯基結構(1,2結構)。The terminally modified conjugated diene-vinyl aromatic copolymer and another unmodified conjugated diene-vinyl aromatic copolymer may respectively comprise a conjugated diene structural unit and a vinyl aromatic hydrocarbon structure. A unit in which a conjugated diene structural unit contains a vinyl structure (1, 2 structure).
在一實施例中,末端改質的共軛二烯-乙烯基芳香烴共聚物中的乙烯基結構,在其共軛二烯結構單元中所佔的百分比,實質上相同於另一未改質的共軛二烯-乙烯基芳香烴共聚物中的乙烯基結構於共軛二烯結構單元中所佔的百分比。In one embodiment, the vinyl structure in the terminally modified conjugated diene-vinyl aromatic copolymer has a percentage in its conjugated diene structural unit that is substantially the same as another unmodified. The percentage of the vinyl structure in the conjugated diene-vinyl aromatic copolymer in the conjugated diene structural unit.
根據需要,應用本發明末端改質的共軛二烯-乙烯基芳香烴共聚物的橡膠組合物還可視需要添加橡膠工業領域中常添加的各種藥劑或添加劑。可添加至橡膠組合物者包括填充材料、抗氧化劑、偶聯劑、硫化反應活化劑、硫化促進劑、硫化劑、防老劑、操作油等。The rubber composition to which the terminal-modified conjugated diene-vinyl aromatic copolymer of the present invention is applied may be optionally added with various chemicals or additives which are often added in the rubber industry as needed. Those which can be added to the rubber composition include a filler, an antioxidant, a coupling agent, a vulcanization reaction activator, a vulcanization accelerator, a vulcanizing agent, an antioxidant, a process oil, and the like.
填充材料可為碳黑,碳黑用量可以是以所用橡膠計之10 至100重量份,以20至90重量份為佳。The filling material can be carbon black, and the amount of carbon black can be 10% of the rubber used. It is preferably from 20 to 90 parts by weight to 100 parts by weight.
抗氧化劑包括至少有一受阻酚(hindered phenol)官能基的苯酚系化合物(例如:CIBA製造的Ix-1076);三亞磷酸二烷基苯酯型(dialkylphenyl triphosphite)抗氧化劑;萘胺(naphthylamines)、二苯胺(diphenylamines)或對苯二胺(p-phenylenediamines)的胺化抗氧化劑;三烷基酚(trialkyl phenols)、對苯二酚(hydroquinones)或多酚的酚類抗氧化劑,或上述化合物的組合。抗氧化劑用量可以是以所用橡膠計之0.2至1重量份。The antioxidant includes a phenolic compound having at least one hindered phenol functional group (for example, Ix-1076 manufactured by CIBA); a dialkylphenyl triphosphite antioxidant; naphthylamines, Aminated antioxidants of diphenylamines or p-phenylenediamines; phenolic antioxidants of trialkyl phenols, hydroquinones or polyphenols, or combinations of the foregoing . The antioxidant may be used in an amount of from 0.2 to 1 part by weight based on the rubber used.
偶聯劑包括雙-3-(三乙氧基甲矽烷基丙基)四硫化物(bis-(3-triethoxysilylpropyl)tetrasulfide)、雙-3-(三乙氧基甲矽烷基丙基)二硫化物(bis-(3-triethoxysilylpropyl)disulfide)、雙-(2-三乙氧基甲矽烷基乙基)四硫化物(bis-(2-triethoxysilylethyl)tetrasulfide)、3-巰基丙基三乙氧基矽烷(3-mercaptopropyltriethoxysilane)、3-三乙氧基甲矽烷基丙基-N,N-二甲基硫代胺基甲醯基四硫化物(3-triethoxysilyl propyl-N,N-dimethylthiocarbamoyl tetrasulfide)、3-三乙氧基甲矽烷基丙基苯並噻唑四硫化物(3-triethoxysilylpropyl benzothiazole tetrasulfide)或其類似物。偶聯劑用量可以是以所用橡膠計之1至15重量份,以5至10重量份為佳。The coupling agent includes bis-(3-triethoxysilylpropyl)tetrasulfide, bis-3-(triethoxymethanealkylpropyl) disulfide Bis-(3-triethoxysilylpropyl)disulfide, bis-(2-triethoxysilylethyl)tetrasulfide, 3-mercaptopropyltriethoxylate 3-mercaptopropyltriethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide or an analogue thereof. The coupling agent may be used in an amount of from 1 to 15 parts by weight, based on the rubber used, preferably from 5 to 10 parts by weight.
硫化助劑包括硫化反應活化劑以及硫化促進劑。The vulcanization aid includes a vulcanization reaction activator and a vulcanization accelerator.
硫化反應活化劑例如為氧化鋅或硬脂酸。The vulcanization reaction activator is, for example, zinc oxide or stearic acid.
硫化促進劑可為巰基苯並噻唑(mercapto-benzthiazoles)、次磺醯胺(sulfenamides)、胍(guanidines)、二硫代胺基甲酸酯(dithiocarbamates)、硫脲(thioureas)或硫代碳酸酯(thiocarbonates)。硫化促進劑較佳為次磺醯胺硫化促進劑(sulfenamide accelerators),其中次磺醯胺硫化促進劑例如是環己基苯並噻唑次磺醯胺(cyclohexylbenzothiazole-sulfenamide)、二環己基苯並噻唑次磺醯胺(dicyclohexylbenzothiazole-sulfenamide)、丁基苯並噻唑次磺醯胺(butylbenzo-thiazolesulfenamide)或上述化合物的組合。硫化促進劑更佳為N-環己基-2-苯並噻唑次磺醯胺(N-cyclohexyl-2-benzo thiazolesulphenamide,CBS)、二苯胍(Diphenyl Guanidine,DPG)或上述化合物的組合。The vulcanization accelerator may be mercapto-benzthiazoles, sulfenamides, guanidines, dithiocarbamates, thioureas or thiocarbonates. (thiocarbonates). The vulcanization accelerator is preferably a sulfenamide accelerator, wherein the sulfoximine vulcanization accelerator is, for example, cyclohexylbenzothiazole-sulfenamide or dicyclohexylbenzothiazole. Dicyclohexylbenzothiazole-sulfenamide, butylbenzo-thiazolesulfenamide or a combination of the above compounds. The vulcanization accelerator is more preferably N-cyclohexyl-2-benzothiazole sulphide (CBS), diphenylguanidine (DPG) or a combination of the above compounds.
硫化劑例如硫或有機硫提供者。所述硫化助劑(硫化反應活化劑、硫化促進劑)和硫化劑之總用量可以是以所用橡膠計之0.1至15重量份,以0.5至5重量份為佳。A vulcanizing agent such as sulfur or an organic sulfur supplier. The total amount of the vulcanization aid (vulcanization reaction activator, vulcanization accelerator) and vulcanizing agent may be 0.1 to 15 parts by weight, preferably 0.5 to 5 parts by weight, based on the rubber used.
防老劑例如是N-(1,3-二甲基丁基)-N'-苯基對苯二胺)(6PPD)。防老劑用量可以是以所用橡膠計之1至10重量份。The antioxidant is, for example, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD). The antioxidant may be used in an amount of from 1 to 10 parts by weight based on the rubber used.
首先,將8公斤之環己烷加入反應槽中當作溶劑,並將反應系統的溫度維持於45℃。接著,取6.4克之2,2-雙(2-四氫呋 喃基)丙烷(2,2-di(2-tetrahydrofuryl)propane,DTHFP)加入反應槽中,做為微結構調整劑。然後,取0.8克之正丁基鋰(n-butyllithium,n-BL)加入反應槽中做為聚合反應的起始劑。在此,微結構調整劑相對於聚合起始劑的莫耳比實質上約為2:1。接著,取447公克的苯乙烯(styrene)做為乙烯基芳香烴單體、1683公克的丁二烯(butadiene)做為共軛二烯單體,加入反應槽中進行聚合反應。之後,加入74.6克的丁二烯單體進行反應。此時,取樣並且去除樣品的溶劑後,利用IR或NMR測量共聚物中1,2結構之含量,結果發現1,2結構在所有丁二烯結構單元中所佔比例為63%。此共聚物的苯乙烯結構單元約佔整體丁二烯結構單元與苯乙烯結構單元的21重量%,且丁二烯結構單元約佔整體丁二烯結構單元與苯乙烯結構單元的79重量%。First, 8 kg of cyclohexane was added to the reaction tank as a solvent, and the temperature of the reaction system was maintained at 45 °C. Next, take 6.4 g of 2,2-bis(2-tetrahydrofuran) 2,2-di(2-tetrahydrofuryl) propane (DTHFP) was added to the reaction vessel as a microstructure modifier. Then, 0.8 g of n-butyllithium (n-BL) was added to the reaction tank as a starter for the polymerization. Here, the molar ratio of the microstructure control agent to the polymerization initiator is substantially about 2:1. Next, 447 g of styrene was used as the vinyl aromatic hydrocarbon monomer, and 1683 g of butadiene was used as the conjugated diene monomer, and was added to the reaction vessel for polymerization. Thereafter, 74.6 g of butadiene monomer was added to carry out the reaction. At this time, after sampling and removing the solvent of the sample, the content of the 1,2 structure in the copolymer was measured by IR or NMR, and it was found that the ratio of the 1,2 structure in all the butadiene structural units was 63%. The styrene structural unit of the copolymer accounts for about 21% by weight of the entire butadiene structural unit and the styrene structural unit, and the butadiene structural unit accounts for about 79% by weight of the entire butadiene structural unit and the styrene structural unit.
待反應槽中的反應物進行反應約15分鐘後,加入0.12phr(2.6克)的氯化三丁錫(tin tetrachloride,TBSnCl)做為第一改質劑。接著,反應15分鐘後,再加入0.004phr(0.09克)的甲醯胺(formamide)做為第二改質劑。第一改質劑的用量為8.00×10-3 mole(=2.6/325.51);第二改質劑的用量為2×10-3 mole(=0.09/45);並且兩者的莫耳數比為8:2。After the reaction in the reaction tank was reacted for about 15 minutes, 0.12 phr (2.6 g) of tin tetrachloride (TBSnCl) was added as the first modifier. Next, after 15 minutes of reaction, 0.004 phr (0.09 g) of formamide was further added as a second modifier. The amount of the first modifier is 8.00×10 -3 mole (=2.6/325.51); the amount of the second modifier is 2×10 -3 mole (=0.09/45); and the molar ratio of the two It is 8:2.
接著,可使用醇類(如甲醇、乙醇或異丙醇)析出粗產物,或以水蒸汽去除溶劑來獲得粗產物。將上述粗產物乾燥後,即可得到無油的實施例1的末端改質的共軛二烯-乙烯基芳香烴共聚物。Next, the crude product may be precipitated using an alcohol such as methanol, ethanol or isopropanol, or the solvent may be removed with water vapor to obtain a crude product. After drying the above crude product, the oil-free terminal modified conjugated diene-vinyl aromatic copolymer of Example 1 was obtained.
實施例2-3與比較例4-6的末端改質的共軛二烯-乙烯基芳香烴共聚物是以與實施例1相同的步驟來製備。惟,不同之處在於:第一改質劑與第二改質劑之使用量(如表1所示)。The terminally modified conjugated diene-vinyl aromatic copolymer of Examples 2-3 and Comparative Examples 4-6 was prepared in the same manner as in Example 1. However, the difference is the amount of the first modifier and the second modifier (as shown in Table 1).
比較例7的末端改質的共軛二烯-乙烯基芳香烴共聚物是以與實施例1相同的步驟來製備。惟,不同之處在於氯化三丁錫(TBSnCl)與甲醯胺(formamide)之使用量為5:5與實施例3相同,但是改質反應順序顛倒(先以甲醯胺(formamide)做為第一改質劑、再以氯化三丁錫(tin tetrachloride,TBSnCl)做為第二改質劑)。The terminally modified conjugated diene-vinyl aromatic copolymer of Comparative Example 7 was prepared in the same manner as in Example 1. However, the difference is that the amount of tributyltin chloride (TBSnCl) and formamide used is 5:5, which is the same as in Example 3, but the order of the modification reaction is reversed (first made with formamide). It is the first modifier, and then tin tetrachloride (TBSnCl) is used as the second modifier.
首先,取上述實施例1無油的末端改質的共軛二烯-乙烯基芳香烴共聚物790克(100phr)與以下物質進行混練,以製得橡膠組合物。在橡膠中投入碳黑(HAF 330;50phr,395公克)、油(Treated Distillate Aromatic Extract,TDAE,5.0phr,39.5g)、ZnO(3phr,23.7公克)、硬酯酸混合(1.5phr,11.9公克),待溫度上升至150℃出料後,常溫老化24小時。如此一來,便可獲得混膠。上述之程序是以班伯里(banbury)式混合機完成。出料後之混膠在滾動(roll)式混合機中添加1.25phr的N-環己基-2-苯並噻唑次磺醯胺、1.75phr的硫後進行硫化,以製得橡膠組合物。製備橡膠組合物使用之材料的資訊如下所示。First, 790 g (100 phr) of the oil-free terminal-modified conjugated diene-vinyl aromatic copolymer of the above Example 1 was kneaded with the following to prepare a rubber composition. Carbon black (HAF 330; 50 phr, 395 g), oil (Treated Distillate Aromatic Extract, TDAE, 5.0 phr, 39.5 g), ZnO (3 phr, 23.7 g), and stearic acid (1.5 phr, 11.9 g) were placed in the rubber. After the temperature rises to 150 ° C, the material is aged at room temperature for 24 hours. In this way, the glue can be obtained. The above procedure is done with a banbury mixer. The discharged rubber was vulcanized by adding 1.25 phr of N-cyclohexyl-2-benzothiazole sulfenamide, 1.75 phr of sulfur in a roll mixer to obtain a rubber composition. Information on the materials used in the preparation of the rubber composition is as follows.
碳黑:HAF 300,由中國橡膠合成製造。Carbon black: HAF 300, manufactured by China Rubber.
油:由Treated Distillate Aromatic Extract,TDAE,Vivtec 500,H&R製造。Oil: Manufactured by Treated Distillate Aromatic Extract, TDAE, Vivtec 500, H&R.
氧化鋅:ZnO,由HA製造。Zinc oxide: ZnO, manufactured from HA.
N-環己基-2-苯並噻唑次磺醯胺:N-cyclohexyl-2-benzo thiazolesulphenamide,CBS,由FLEXSYS製造。N-cyclohexyl-2-benzothiazole sulfoximine: N-cyclohexyl-2-benzothiazolesulphenamide, CBS, manufactured by FLEXSYS.
硫:三角牌。Sulfur: Triangle.
硬酯酸:TPSA1865,由CV.Pacific Indochem製造。Stearic acid: TPSA 1865, manufactured by CV. Pacific Indochem.
實驗例2-實驗例3的橡膠組合物是以與實驗例1相同的步驟來製備。惟,不同之處在於:實驗例2以及實驗例3的橡膠組合物是分別以實施例2以及實施例3的末端改質的共軛二烯-乙烯基芳香烴共聚物取代實施例1的末端改質的共軛二烯-乙烯基芳香烴共聚物來製備。Experimental Example 2 - The rubber composition of Experimental Example 3 was prepared in the same manner as in Experimental Example 1. However, the difference was that the rubber compositions of Experimental Example 2 and Experimental Example 3 were replaced with the terminal modified conjugated diene-vinyl aromatic hydrocarbon copolymer of Example 2 and Example 3, respectively, in place of the end of Example 1. A modified conjugated diene-vinyl aromatic copolymer is prepared.
實驗例4-實驗例7的橡膠組合物是以與實驗例1相同的步驟來製備。惟,不同之處在於:實驗例4-實驗例7的橡膠組合物是分別以比較例4-比較例7的末端改質的共軛二烯-乙烯基芳香烴共聚物取代實施例1的末端改質的共軛二烯-乙烯基芳香烴共聚物來製備。Experimental Example 4 - The rubber composition of Experimental Example 7 was prepared in the same manner as in Experimental Example 1. However, the difference was that the rubber composition of Experimental Example 4 - Experimental Example 7 was replaced with the terminal modified conjugated diene-vinyl aromatic copolymer of Comparative Example 4 - Comparative Example 7, respectively, in place of the end of Example 1. A modified conjugated diene-vinyl aromatic copolymer is prepared.
1.黏度Viscosity
摩尼黏度:以Alpha Technology公司型號MV-2000的機器參照ASTM D-1646方式量測,量測溫度條件為100℃,量測時間為1+4分鐘,分別測定共聚物(實施例與比較例)、橡膠(實驗例)組合物的摩尼黏度(混膠黏度(mooney)、橡膠組合物黏度以及前述兩者之黏度差△Mooney)。摩尼黏度越低表示該橡膠組成物的加工性(processability)越佳,△Mooney表示加工後黏度增加幅度越低,越易加工。Mooney viscosity: measured by Alpha Technology model MV-2000 with reference to ASTM D-1646, measuring temperature conditions of 100 ° C, measuring time of 1 + 4 minutes, respectively measuring copolymers (examples and comparative examples) ), rubber (experimental example) composition of the Mooney viscosity (mixey viscosity (mooney), rubber composition viscosity and the difference between the two ΔMooney). The lower the Mooney viscosity, the better the processability of the rubber composition. △Mooney indicates that the lower the viscosity increase after processing, the easier it is to process.
2.耐磨耗度2. Wear resistance
耐磨耗度是以耐磨耗試驗機GT-7012-D參照DIN53 516之方式量測,試片大小為29cm(直徑)×12.5mm(厚度)。耐磨耗度之值越小,表示耐磨損的能力越好。The wear resistance was measured by the wear resistance tester GT-7012-D with reference to DIN 53 516, and the test piece size was 29 cm (diameter) × 12.5 mm (thickness). The smaller the value of the wear resistance, the better the resistance to wear.
3.動態儲存彈性模數差(△E')3. Dynamic storage elastic modulus difference (△E')
使用TA儀器公司製造,型號為DMA Q800的黏彈性測定裝置來測定橡膠組成物的動態儲存彈性模數。測定模式為拉伸模式,測定頻率為20Hz。測定動態儲存彈性模數(E)的溫度設定在60℃,測定的形變程度為0.5%至10%。在形變程度0.5%測得的動態儲存彈性模數減去在形變程度10%測得的動態儲存彈性模數即為動態儲存彈性模數差(△E'),單位為MPa。△E'也稱為佩恩效應(Payne Effect),△E'的數值愈小,表示橡膠組成與碳黑的相容性愈好。The dynamic storage elastic modulus of the rubber composition was measured using a viscoelasticity measuring device manufactured by TA Instruments, Model DMA Q800. The measurement mode is the tensile mode, and the measurement frequency is 20 Hz. The temperature at which the dynamic storage elastic modulus (E) was measured was set at 60 ° C, and the degree of deformation was measured to be 0.5% to 10%. The dynamic storage elastic modulus measured at a deformation degree of 0.5% minus the dynamic storage elastic modulus measured at 10% of the deformation degree is the dynamic storage elastic modulus difference (ΔE'), and the unit is MPa. △E' is also called the Payne Effect, and the smaller the value of ΔE', the better the compatibility of the rubber composition with carbon black.
4.損失正切(Tan δ(0℃)及Tan δ(60℃))4. Loss tangent (Tan δ (0 ° C) and Tan δ (60 ° C))
使用TA儀器公司製造,型號為DMA Q800的黏彈性測定裝置來測定橡膠組成物的損失正切(tan δ)。測定損失正切時的溫度選擇在0℃與60℃,且測定損失正切的升溫速度為每分鐘3℃。在0℃的測試可以視為模擬輪胎在結冰路面上的表現,其損失正切越高,代表橡膠組合物之耐濕滑性越好;在60℃的測試則 可以視為模擬輪胎在高速行駛時的表現,其損失正切越低,代表橡膠組合物之滾動阻力越低。The loss tangent (tan δ) of the rubber composition was measured using a viscoelasticity measuring device manufactured by TA Instruments, model DMA Q800. The temperature at which the loss tangent was measured was selected at 0 ° C and 60 ° C, and the rate of temperature rise for measuring the loss tangent was 3 ° C per minute. The test at 0 °C can be regarded as the performance of the simulated tire on the icy road surface, the higher the loss tangent, the better the wet skid resistance of the rubber composition; the test at 60 ° C It can be regarded as the performance of the simulated tire at high speed, and the lower the loss tangent, the lower the rolling resistance of the rubber composition.
實施例1-實施例6以及比較例1-比較例3之混膠、橡膠組合物的評價結果如表2所示。The evaluation results of the rubber mixture and the rubber composition of Example 1 - Example 6 and Comparative Example 1 - Comparative Example 3 are shown in Table 2.
請參看表2,實驗例4為僅使用第二改質劑來製備的橡膠組合物。相較於此,實驗例1-實驗例3使用第一改質劑以及第二改質劑來製備的橡膠組合物。從實驗結果來看,實驗例4的黏度、耐磨耗度以及動態儲存彈性模數差(△E')高於實驗例1-實驗例3,且實驗例4的損失正切Tan δ(60℃)低於實驗例1-實驗例3。由此可知,僅使用第二改質劑來製備的橡膠組合物的加工性、耐濕滑性以及與碳黑的相容性不佳。Referring to Table 2, Experimental Example 4 is a rubber composition prepared using only the second modifier. In contrast, Experimental Example 1 - Experimental Example 3 used a rubber composition prepared by using a first modifier and a second modifier. From the experimental results, the viscosity, wear resistance and dynamic storage elastic modulus difference (ΔE') of Experimental Example 4 were higher than Experimental Example 1 - Experimental Example 3, and the loss tangent Tan δ of Experimental Example 4 (60 ° C) ) is lower than Experimental Example 1 - Experimental Example 3. From this, it is understood that the rubber composition prepared using only the second modifier has poor processability, wet skid resistance, and compatibility with carbon black.
實驗例6為僅使用第一改質劑來製備的橡膠組合物。從實驗結果來看,實驗例6的黏度以及動態儲存彈性模數差(△E')高於實驗例1-實驗例3。由此可知,僅使用第一改質劑來製備的橡膠組合物的加工性以及與碳黑的相容性不佳。Experimental Example 6 is a rubber composition prepared using only the first modifier. From the experimental results, the viscosity and dynamic storage elastic modulus difference (ΔE') of Experimental Example 6 were higher than those of Experimental Example 1 - Experimental Example 3. From this, it is understood that the rubber composition prepared using only the first modifier has poor processability and compatibility with carbon black.
實驗例5為使用第一改質劑與第二改質劑(其莫耳比為0.5:9.5)來製備的橡膠組合物。相較於此,實施例1-實驗例3為使用第一改質劑與第二改質劑(其莫耳比為5:5至8:2)來製備的橡膠組合物。從實驗結果來看,實驗例5的耐磨耗度以及動態儲存彈性模數差(△E')高於實驗例1-實驗例3,且實驗例5的損失正切Tan δ(0℃)低於實驗例1-實驗例3。由此可知,使用第一改質劑與第二改質劑的莫耳比為0.5:9.5的共軛二烯-乙烯基芳香烴共聚物來製備的橡膠組合物,其耐濕滑性以及與碳黑的相容性不佳。Experimental Example 5 is a rubber composition prepared using a first modifier and a second modifier (having a molar ratio of 0.5:9.5). In contrast, Example 1 - Experimental Example 3 is a rubber composition prepared using a first modifier and a second modifier (having a molar ratio of 5:5 to 8:2). From the experimental results, the wear resistance and dynamic storage elastic modulus difference (ΔE') of Experimental Example 5 were higher than Experimental Example 1 - Experimental Example 3, and the loss tangent Tan δ (0 ° C) of Experimental Example 5 was low. In Experimental Example 1 - Experimental Example 3. It can be seen that the rubber composition prepared by using the conjugated diene-vinyl aromatic copolymer having a molar ratio of the first modifier to the second modifier of 0.5:9.5 has wet skid resistance and The compatibility of carbon black is not good.
實驗例7為使用改質反應順序不同的末端改質的共軛二烯-乙烯基芳香烴共聚物來製備的橡膠組合物相較於此,實驗例1-實驗例3為先使用第一改質劑再使用第二改質劑來進行改值的末端改質的共軛二烯-乙烯基芳香烴共聚物來製備的橡膠組合物。從實驗結果來看,實驗例7的動態儲存彈性模數差(△E')高於實驗例1-實驗例3,且實驗例7的損失正切Tan δ(0℃)低於實驗例1-實驗例3。由此可知:改質反應順序不同的末端改質的共軛二烯-乙烯基芳香烴共聚物來製備的橡膠組合物,其耐濕滑性以及與碳黑的相容性不佳。Experimental Example 7 is a rubber composition prepared by using a terminally modified conjugated diene-vinyl aromatic copolymer having different upgrading reaction sequences, and Experimental Example 1 - Experimental Example 3 is the first use of the first modification. A rubber composition prepared by using a second modified agent to carry out a modified terminally modified conjugated diene-vinyl aromatic copolymer. From the experimental results, the dynamic storage elastic modulus difference (ΔE') of Experimental Example 7 is higher than Experimental Example 1 - Experimental Example 3, and the loss tangent Tan δ (0 ° C) of Experimental Example 7 is lower than Experimental Example 1 Experimental Example 3. From this, it was found that the rubber composition prepared by modifying the terminally modified conjugated diene-vinyl aromatic copolymer having different order of modification reaction has poor wet skid resistance and compatibility with carbon black.
綜上所述,本發明提出一種末端改質的共軛二烯-乙烯基 芳香烴共聚物的合成方法,其中以含錫化合物以及含-CM-N<連結基團的化合物作為改質劑。根據此方法合成的末端改質的共軛二烯-乙烯基芳香烴共聚物不僅與碳黑具有良好的相容性,也具有良好的加工性。一種可能的原因是於合成期間在共軛二烯-乙烯基芳香烴共聚物的末端引入了-CM-N<連結基團,以增加與碳黑的混練均勻性。因此,這種末端改質的共軛二烯-乙烯基芳香烴共聚物適於製造輪胎,且其製成的輪胎在高速行駛時表現優秀的滾動阻力,在結冰路面上則能表現出色的耐濕滑性。In summary, the present invention proposes a terminally modified conjugated diene-vinyl group. A method for synthesizing an aromatic hydrocarbon copolymer, wherein a tin-containing compound and a compound containing a -CM-N<linking group are used as a modifier. The terminally modified conjugated diene-vinyl aromatic copolymer synthesized according to this method not only has good compatibility with carbon black, but also has good processability. One possible reason is that a -CM-N <linking group is introduced at the end of the conjugated diene-vinyl aromatic copolymer during the synthesis to increase the kneading uniformity with the carbon black. Therefore, such terminally modified conjugated diene-vinyl aromatic copolymer is suitable for the manufacture of tires, and the tires produced thereof exhibit excellent rolling resistance at high speeds and excellent performance on icy road surfaces. Wet slip resistance.
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.
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