TWI503331B - 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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Description
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.
但近年來，由於石油能源逐漸枯竭及全球暖化等問題，輪胎業界開始研發以白煙(white carbon，其主成份為SiO2)取代碳黑的技術，以期改善輪胎的滾動阻力，達到減少能源損耗的目的。由於白煙相對於碳黑較不容易均勻分散於末端改質的共軛二烯-乙烯基芳香烴共聚物中，因此必須設法提高白煙與末端改質的共軛二烯-乙烯基芳香烴共聚物的相容性及混練均勻性。 However, in recent years, due to the gradual depletion of petroleum energy and global warming, the tire industry has begun to develop technology to replace carbon black with white carbon (the main component of which is SiO 2 ), in order to improve the rolling resistance of tires and reduce energy. The purpose of loss. Since white smoke is less likely to be uniformly dispersed in the terminally modified conjugated diene-vinyl aromatic copolymer relative to carbon black, it is necessary to seek to improve white smoke and terminally modified conjugated diene-vinyl aromatic hydrocarbons. Copolymer compatibility and kneading uniformity.
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白煙具有良好的相容性，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 white smoke. Sex, can produce tires with good wet skid resistance and low rolling resistance.
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，包括以下步驟。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進行反應，以生成共軛二烯-乙烯基芳香烴共聚物。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。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。第一改質劑是從式1與式2所表示的化合物中選出的任一者，第二改質劑是從式3與式4所表示的化合物中選出的任一者。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用量分別是0.001重量份~0.2重量份與0.001重量份~0.5重量份。 The present invention provides a method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer comprising the following steps. The conjugated diene monomer is reacted with a vinyl aromatic hydrocarbon monomer in a weight ratio of 2:1 to 5:1 to form a conjugated diene-vinyl aromatic copolymer. The conjugated diene-vinyl aromatic copolymer is reacted with a first modifier to form an intermediate product. The intermediate product is reacted with a second modifier to form a terminally modified conjugated diene-vinyl aromatic copolymer. The first modifying agent is any one selected from the compounds represented by Formula 1 and Formula 2, and the second modifying agent is any one selected from the compounds represented by Formula 3 and Formula 4. The amount of the first modifier and the second modifier is 0.001 parts by weight to 0.2 parts by weight and 0.001 parts by weight, respectively, based on 100 parts by weight of the total of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer. 0.5 parts by weight.
m為100至900的整數；n為1至50的整數；p為100至900的整數；q為1至50的整數。 m is an integer from 100 to 900; n is an integer from 1 to 50; p is an integer from 100 to 900; and q is an integer from 1 to 50.
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 an embodiment of the present invention, the method for synthesizing the terminally modified conjugated diene-vinyl aromatic copolymer further comprises reacting a conjugated diene monomer with a vinyl aromatic hydrocarbon monomer to form After the active terminal conjugated diene-vinyl aromatic copolymer, a first or second modifier is added.
在本發明之一實施例中，上述之第二改質劑是從式i至式vi所表示的化合物中選出的任一者。 In an embodiment of the invention, the second modifying agent is any one selected from the compounds represented by the formula i to the formula vi.
在本發明之一實施例中，第一改質劑與第二改質劑之用量的莫耳比是0.005~0.05。 In an embodiment of the invention, the molar ratio of the first modifier to the second modifier is from 0.005 to 0.05.
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，包括以下步驟。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進行反應，以生成 共軛二烯-乙烯基芳香烴共聚物。使共軛二烯-乙烯基芳香烴共聚物與含氮雜環矽烷化合物進行反應，以生成末端改質的共軛二烯-乙烯基芳香烴共聚物。含氮雜環矽烷化合物是從前述式3與式4所表示的化合物中選出的任一者，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，含氮雜環矽烷化合物的用量是0.01重量份至0.3重量份，較佳是0.08重量份至0.3重量份，最佳是0.08重量份~0.12重量份。 The present invention provides a method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer comprising the following steps. The conjugated diene monomer is reacted with a vinyl aromatic hydrocarbon monomer in a weight ratio of 2:1 to 5:1 to form Conjugated diene-vinyl aromatic copolymer. The conjugated diene-vinyl aromatic copolymer is reacted with a nitrogen-containing heterocyclodecane compound to form a terminally modified conjugated diene-vinyl aromatic copolymer. The nitrogen-containing heterocyclodecane compound is any one selected from the compounds represented by the above formulas 3 and 4, wherein the total amount of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer is 100 parts by weight, including The azacyclononane compound is used in an amount of from 0.01 part by weight to 0.3 part by weight, preferably from 0.08 part by weight to 0.3 part by weight, optimally from 0.08 part by part to 0.12 part by weight.
在本發明之一實施例中，上述含氮雜環矽烷化合物是從前述式i至式vi所表示的化合物中選出的任一者。 In one embodiment of the present invention, the nitrogen-containing heterocyclodecane compound is any one selected from the compounds represented by the above formulas i to vi.
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，添加微結構調整劑，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，微結構調整劑的用量是0.05重量份至0.5重量份，較佳是0.1重量份至0.4重量份，最佳是0.2重量份至0.4重量份。 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. a microstructure control agent, wherein the amount of the microstructure adjusting agent is 0.05 parts by weight to 0.5 parts by weight, preferably 0.1 parts by weight, based on 100 parts by total of the total of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer. It is preferably 0.2 parts by weight to 0.4 parts by weight to 0.4 parts by weight.
在本發明之一實施例中，上述微結構調整劑包括由醚類、三級胺化合物、鹼金屬烷醇鹽化合物、膦化合物以及烷基或芳基磺酸化合物中選出的至少一者。 In an embodiment of the invention, the microstructure adjusting agent comprises at least one selected from the group consisting of an ether, a tertiary amine compound, an alkali metal alkoxide compound, a phosphine compound, and an alkyl or arylsulfonic acid compound.
在本發明之一實施例中，上述共軛二烯單體包括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。 In one embodiment of the invention, the conjugated diene monomer comprises 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene. 2,3-Dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene or a combination thereof.
在本發明之一實施例中，上述乙烯基芳香烴單體包括苯乙烯、α甲基苯乙烯、二乙烯基苯或其組合。 In an embodiment of the invention, the above vinyl aromatic hydrocarbon monomer comprises styrene, alpha methyl styrene, divinyl benzene or a combination thereof.
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，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；其中(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)第一改質劑是從式1與式2所表示的化合物中選出的任一者，(D)第二改質劑是從式3與式4所表示的化合物中選出的任一者，且以(A)共軛二烯單體與(B)乙烯基芳香烴單體的總量計，(C)第一改質劑的用量是0.001重量份~0.2重量份，較佳是0.1重量份~0.2重量份，(D)第二改質劑的用量是0.001重量份~0.5重量份，較佳是0.01重量份~0.05重量份。 The present invention 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-vinyl aromatic After the hydrocarbon copolymer is further modified by (C) the first modifier and (D) the second modifier; wherein (A) the conjugated diene monomer and (B) the vinyl aromatic monomer The weight ratio is 2:1 to 5:1, (C) the first modifier is any one selected from the compounds represented by Formula 1 and Formula 2, and (D) the second modifier is from Formula 3 and Any one selected from the compounds represented by Formula 4, and based on the total amount of (A) conjugated diene monomer and (B) vinyl aromatic hydrocarbon monomer, (C) the amount of the first modifier is 0.001 parts by weight to 0.2 parts by weight, preferably 0.1 parts by weight to 0.2 parts by weight, and (D) the second modifier is used in an amount of 0.001 part by weight to 0.5 part by weight, preferably 0.01 part by weight to 0.05 parts by weight.
在本發明之一實施例中，(D)第二改質劑是由前述式i至式vi所表示的化合物中選出的任一者。 In an embodiment of the invention, the (D) second modifier is any one selected from the compounds represented by the above formulas i to vi.
在本發明之一實施例中，上述(A)共軛二烯單體聚合生成1,2結構單元與1,4結構單元，且所述1,2結構單元佔所述1,2結構單元與所述1,4結構單元之和的55%~70%。 In one embodiment of the present invention, the (A) conjugated diene monomer is polymerized to form 1, 2 structural units and 1, 4 structural units, and the 1, 2 structural units occupy the 1, 2 structural units and 55% to 70% of the sum of the 1,4 structural units.
在本發明之一實施例中，以所述共軛二烯-乙烯基芳香烴共聚物的總量計，所述(A)共軛二烯單體佔74重量%~84重量%，而所述(B)乙烯基芳香烴單體佔16重量%~26重量%。 In one embodiment of the present invention, the (A) conjugated diene monomer accounts for 74% by weight to 84% by weight based on the total amount of the conjugated diene-vinyl aromatic copolymer. The (B) vinyl aromatic hydrocarbon monomer accounts for 16% by weight to 26% by weight.
在本發明之一實施例中，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。 In one embodiment of the invention, 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.
在本發明之一實施例中，末端改質的共軛二烯-乙烯基芳香烴共聚物的多分散度為1.5~2.0。 In one embodiment of the invention, the terminally modified conjugated diene-vinyl aromatic copolymer has a polydispersity of from 1.5 to 2.0.
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白煙具有良好的相容性。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 white smoke. 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.
為讓本發明之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 present invention will be more 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 "C X ", 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 bond. 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.
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官能基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。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 terminal functional group. 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. 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 The proportion of the conjugated diene-vinyl aromatic copolymer 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. The term "structural unit" (or monomer unit) as used herein refers to the aforementioned conjugated diene. A repeating structure formed by polymerization of a monomer or a vinyl aromatic hydrocarbon monomer.
共軛二烯重複單元可包括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 repeating 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，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 structural unit, 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)。「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). "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 cis and trans. Similarly, "1,2 polymerization" means that the conjugated diene monomer is bonded to other monomers via its 1-position and 2-position carbon, and the 1,2 structure formed by the polymerization of 1,2 is an ethylene. The base is located in the structure of the 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.
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-結構(1,2-vinyl configuration)化劑。 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***、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(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；三苯基膦等膦化合物；烷基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; tetramethylethylenediamine, dipiperidineethane, trimethylamine, triethylamine, pyridine, quinuclidine, etc. Alkane compound; alkali metal alkoxide compound such as potassium third potassium pentoxide, potassium third potassium hydride, sodium butoxide or sodium tertiary pentoxide; phosphine compound such as triphenylphosphine; alkyl or aryl sulfonic acid Compounds, etc. 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。 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.
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。 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官能基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官能基的時候添加改質劑。 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 a reactive terminal functional group may be added first. The unmodified conjugated diene-vinyl aromatic copolymer is deactivated and then added with a modifier, or a modifier may be added directly as a polymerization terminator. It is preferred to add a modifier when the unmodified conjugated diene-vinyl aromatic copolymer has a living end functional group.
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.
第一改質劑是從式1與式2所表示的化合物中選出的任一者。 The first modifier is any one selected from the compounds represented by Formula 1 and Formula 2.
m為100至900的整數，n為1至50的整數，p為100至900的整數，且q為1至50的整數。 m is an integer of 100 to 900, n is an integer of 1 to 50, p is an integer of 100 to 900, and q is an integer of 1 to 50.
在一實施例中，第一改質劑的用量是0.001phr~0.2phr，較佳是0.1phr~0.2phr。 In one embodiment, the first modifier is used in an amount of from 0.001 phr to 0.2 phr, preferably from 0.1 phr to 0.2 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.
第二改質劑是從式3與式4所表示的化合物中選出的任一者。 The second modifier is any one selected from the compounds represented by Formula 3 and Formula 4.
舉例來說，第二改質劑可以是從式i至式vi所表示的化合物中選出的任一者。 For example, the second modifier may be any one selected from the compounds represented by the formula i to the formula vi.
在一實施例中，第二改質劑的用量是0.001phr~0.5phr，較佳是0.01phr~0.05phr。 In one embodiment, the second modifier is used in an amount of from 0.001 phr to 0.5 phr, 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0.005~0.05，較佳為0.0115~0.0287。 In one embodiment, the molar ratio of the first modifier to the second modifier may be from 0.005 to 0.05, preferably from 0.0115 to 0.0287.
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 poor solvent such as an alcohol (such as methanol, ethanol or isopropanol) of a terminally modified conjugated diene-vinyl aromatic copolymer may be added to the reaction system to effect terminal modification. Conjugated diene-ethylene The terminal aromatic hydrocarbon copolymer is precipitated, or the solvent is removed at a temperature higher than the boiling point of the solvent or the solvent is removed by steam, and the terminally modified conjugated diene-vinyl aromatic copolymer is separated from the mixture.
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(polydispersity index,PDI)Mw/Mn為1.5~2.0。 In one embodiment, the terminally modified conjugated diene-vinyl aromatic copolymer has a weight average molecular weight of 800,000 to 1500,000, a number average molecular weight of 450,000 to 900,000, and a polydispersity index (PDI) Mw. /Mn is 1.5 to 2.0.
在一實施例中，步驟(b)與步驟(c)的反應可能如以下反應式I所示。其中，連續曲線表示共聚物鏈段，第一改質劑是Dow Corning公司製造的SF-8411，第二改質劑是Gelest公司製造的SIB-1932.4。然而，以下所示反應只是一種可能的機制，本發明並不以此為限。 In one embodiment, the reaction of step (b) with step (c) may be as shown in Reaction Scheme I below. Among them, the continuous curve indicates a copolymer segment, the first modifier is SF-8411 manufactured by Dow Corning, and the second modifier is SIB-1932.4 manufactured by Gelest. However, the reactions shown below are only one possible mechanism, and the invention is not limited thereto.
根據本發明之另一實施例，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；以及 (c’)使共軛二烯-乙烯基芳香烴共聚物與含氮雜環矽烷化合物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 another embodiment of the present invention, a method for synthesizing a terminally modified conjugated diene-vinyl aromatic copolymer comprises the steps of: (a') conducting a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer; Reacting to form a conjugated diene-vinyl aromatic copolymer; (c') reacting a conjugated diene-vinyl aromatic copolymer with a nitrogen-containing heterocyclodecane compound to form a terminally modified conjugated diene-vinyl aromatic copolymer.
步驟(a’)可與前述步驟(a)相同。 Step (a') may be the same as the aforementioned step (a).
步驟(c’)中使用的含氮雜環矽烷化合物可與針對步驟(c)所述的第二改質劑相同，且其用量可在0.01phr~0.3phr之間，較佳為0.08phr~0.12phr之間。 The nitrogen-containing heterocyclodecane compound used in the step (c') may be the same as the second modifier described in the step (c), and may be used in an amount of from 0.01 phr to 0.3 phr, preferably 0.08 phr. Between 0.12 phr.
完成步驟(c’)以後，可使用前述方法使末端改質的共軛二烯-乙烯基芳香烴共聚物析出。注意在此實施例中，僅使用從式3與式4中選出的化合物進行改質，並未使用從式1與式2中選出的化合物進行改質。 After completion of the step (c'), the terminally modified conjugated diene-vinyl aromatic copolymer can be precipitated by the aforementioned method. Note that in this example, only the compounds selected from Formula 3 and Formula 4 were used for the modification, and the compounds selected from Formula 1 and Formula 2 were not used for the modification.
在一實施例中，步驟(c’)的反應可能如以下反應式II所示。其中，連續曲線表示共聚物鏈段，含氮雜環矽烷化合物是Gelest公司製造的SIB-1932.4。然而，以下所示反應只是一種可能的機制，本發明並不以此為限。 In one embodiment, the reaction of step (c') may be as shown in the following Reaction Scheme II. Among them, the continuous curve indicates a copolymer segment, and the nitrogen-containing heterocyclodecane compound is SIB-1932.4 manufactured by Gelest Corporation. However, the reactions shown below are only one possible mechanism, and the invention is not limited thereto.
根據本發明之再一實施例，提供一種末端改質的共軛二烯-乙烯基芳香烴共聚物。所述末端改質的共軛二烯-乙烯基芳香烴共聚物可以藉由執行步驟(a)至步驟(c)來合成，也可以藉由執行步驟(a’)與步驟(c’)來合成。 According to still another embodiment of the present invention, a terminally modified conjugated diene-vinyl aromatic copolymer is provided. The terminally modified conjugated diene-vinyl aromatic copolymer can be synthesized by performing steps (a) to (c), or by performing steps (a') and (c'). synthesis.
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)第一改質劑是從前述式1與式2所表示的化合物中選出的任一者。(D)第二改質劑是從前述式3與式4所表示的化合物中選出的任一者。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~0.2重量份與0.001重量份~0.5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 is any one selected from the compounds represented by the above formulas 1 and 2. (D) The second modifier is any one selected from the compounds represented by the above formulas 3 and 4. 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 0.2 parts by weight and 0.001 parts by weight to 0.5 parts 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物的製造方法。在一實施例中，橡膠物的製造方法包括混練橡膠組成與含矽材料以得到橡膠物，其中，橡膠組成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， 橡膠組成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，且此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 article. In one embodiment, the method for producing a rubber material comprises kneading a rubber composition and a niobium-containing material to obtain a rubber material, wherein the rubber composition comprises any of the terminally modified conjugated diene-vinyl aromatic copolymers as described in detail above. . In an embodiment, The rubber composition comprises a terminally modified conjugated diene-vinyl aromatic copolymer and another unmodified conjugated diene-vinyl aromatic copolymer, and this other unmodified conjugated diene - The vinyl aromatic hydrocarbon copolymer may be the same or different from the unmodified conjugated diene-vinyl aromatic copolymer used to form the terminally modified 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)。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。 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. unit. Wherein the conjugated diene structural unit contains a vinyl structure (1, 2 structure). 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。可添加至橡膠物者包括填充材料、抗氧化劑、偶聯劑、硫化反應活化劑(硫化助劑/氧化鋅、硬脂酸)、硫化促進劑、硫化劑、防老劑、操作油等。 The rubber of the terminally modified conjugated diene-vinyl aromatic copolymer of the present invention may be added as needed, and various chemicals or additives which are often added in the rubber industry may be added as needed. Those which can be added to the rubber include filler materials, antioxidants, coupling agents, vulcanization reaction activators (vulcanization aids/zinc oxide, stearic acid), vulcanization accelerators, vulcanizing agents, antioxidants, process oils, and the like.
在一實施例中，填充材料例如可以是含矽材料，例如為白煙，白煙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。還可以與白煙同時配合使用碳黑，碳黑用量可以是以所用橡膠計之2至100重量份，以5至90重量份為佳。適當的抗氧化劑可為至少有一受阻酚(hindered phenol)官能基的苯酚系化合物，例如：CIBA 製造的Ix-1076。或三亞磷酸二烷基苯酯型(dialkylphenyl triphosphite)抗氧化劑；選自萘胺(naphthylamines)、二苯胺(diphenylamines)及對苯二胺(p-phenylenediamines)的胺化抗氧化劑；選自三烷基酚(trialkyl phenols)、對苯二酚(hydroquinones)以及多酚的酚類抗氧化劑。抗氧化劑用量可以是以所用橡膠計之0.2至1重量份。 In one embodiment, the filler material may be, for example, a bismuth-containing material such as white smoke, and the amount of white smoke may be from 10 to 100 parts by weight, based on the rubber used, preferably from 20 to 90 parts by weight. It is also possible to use carbon black in combination with white smoke, and the amount of carbon black may be 2 to 100 parts by weight, preferably 5 to 90 parts by weight, based on the rubber used. Suitable antioxidants can be phenolic compounds having at least one hindered phenol functional group, for example: CIBA Made of Ix-1076. Or a dialkylphenyl triphosphite antioxidant; an aminated antioxidant selected from the group consisting of naphthylamines, diphenylamines and p-phenylenediamines; selected from trialkyl Phenolic antioxidants of trialkyl phenols, hydroquinones, and polyphenols. The antioxidant may be used in an amount of from 0.2 to 1 part by weight based on the rubber used.
偶聯劑例如為雙-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)di-sulfide)、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-triethoxysilylpropyl-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)等，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 is, for example, bis-(3-triethoxysilylpropyl)tetrasulfide, bis-3-(triethoxycarbamidopropyl)di Bis-(3-triethoxysilylpropyl)di-sulfide, bis-(2-triethoxysilylethyl)tetrasulfide, 3-mercaptopropyltri 3-mercaptopropyltriethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide , 3-triethoxysilylpropyl benzothiazole tetrasulfide, etc., the coupling agent may be used in an amount of from 1 to 15 parts by weight, based on the rubber used, from 5 to 10 parts by weight. It is better.
硫化反應活化劑例如為氧化鋅、硬脂酸等。 The vulcanization reaction activator is, for example, zinc oxide, stearic acid or the like.
適當的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)和硫代碳酸酯(thiocarbonates)。較佳是使用次磺醯胺硫化促進劑(sulfenamide accelerators)，如：環己基苯並噻唑次磺醯胺(cyclohexylbenzothiazole-sulfenamide)和/或 二環己基苯並噻唑次磺醯胺(dicyclohexylbenzothiazole-sulfenamide)和/或丁基苯並噻唑次磺醯胺(butylbenzo-thiazolesulfenamide)。較佳為n-環己基-2-苯並噻唑次磺酰胺(n-cyclohexyl-2-benzo thiazolesulphen-amide,CBS)以及二苯胍(Diphenyl Guanidine,DPG)。 Suitable vulcanization accelerators may be mercapto-benzthiazoles, sulfenamides, guanidines, dithiocarbamates, thioureas and thio Carbonate. Preferably, sulfenamide accelerators such as cyclohexylbenzothiazole-sulfenamide and/or cyclohexylbenzothiazole-sulfenamide are used. Dicyclohexylbenzothiazole-sulfenamide and/or butylbenzo-thiazolesulfenamide. Preferred is n-cyclohexyl-2-benzothiazole sulfonamide (CBS) and diphenylguanidine (DPG).
硫化劑例如硫或有機硫提供者。以上硫化反應加速劑和硫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 above sulfurization accelerator and sulfur may be used in an amount of from 0.1 to 15 parts by weight, based on the rubber used, preferably from 0.5 to 5 parts by weight.
防老劑例如是6PPD(N-(1,3-二甲基丁基)-N’-苯基對苯二胺)，防老劑用量可以是以所用橡膠計之1至10重量份。 The antioxidant may be, for example, 6PPD (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine), and the antioxidant may be used in an amount of from 1 to 10 parts by weight based on the rubber used.
實驗例1 Experimental example 1
首先，將800公克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0.64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0.08克之正丁基鋰(n-butyllithium)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44.7公克的苯乙烯(styrene)做為乙烯基芳香烴單體，168.3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7.46克的丁二烯單體參與反應。此時取樣去除溶劑後， 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, 800 g of cyclohexane was added to the reaction tank as a solvent, and the temperature of the reaction system was maintained at 45 °C. Next, 0.64 g of 2,2-di(2-tetrahydrofuryl)propane (DTHFP) was added to the reaction vessel as a microstructure control agent. Then, 0.08 g of n-butyllithium was added to the reaction tank as a starter for the polymerization reaction. Here, the molar ratio of the microstructure control agent to the polymerization initiator is substantially about 2:1. Next, 44.7 grams of styrene was used as the vinyl aromatic hydrocarbon monomer, and 168.3 grams of butadiene was used as the conjugated diene monomer, and was added to the reaction tank for polymerization. Then, 7.46 g of butadiene monomer was added to participate in the reaction. After sampling and removing the solvent, 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 to all of 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.
約15分鐘後，加入0.1phr(0.213克)的聚合物型式環氧官能基聚雙甲基矽氧烷(epoxy functional polydimethyl siloxane)做為第一改質劑，反應15分鐘後，再加入0.01phr(0.0213克)的環氮雜矽烷(cyclic azasilane)做為第二改質劑。反應後之生膠再與79.8公克(37.5phr)的TDAE(treated distillate aromatic extract)油混合。 After about 15 minutes, 0.1 phr (0.213 g) of a polymer type epoxy functional polydimethyl siloxane was added as the first modifier, and after 15 minutes, 0.01 phr was added. (0.0213 g) of cyclic azasilane was used as the second modifier. The raw rubber after the reaction was further mixed with 79.8 g (37.5 phr) of TDAE (treated distillate aromatic extract) oil.
接著，可使用醇類(如甲醇、乙醇或異丙醇)析出，或以水蒸汽去除溶劑，乾燥後，得到含油的末端改質的共軛二烯-乙烯基芳香烴共聚物。 Next, it can be precipitated using an alcohol such as methanol, ethanol or isopropanol, or the solvent can be removed with water vapor, and after drying, an oil-containing terminally modified conjugated diene-vinyl aromatic copolymer can be obtained.
實驗例1使用的第一改質劑為Dow Corning公司製造的SF-8411(Mw=70967，環氧基當量=3200)；第二改質劑為Gelest公司製造的SIB-1932.4(Mw=203.36)，得到的末端改質的共軛二烯-乙烯基芳香烴共聚物重量平均分子量為1100,000；數目平均分子量為650,000，多分散度為Mw/Mn=1.69。 The first modifier used in Experimental Example 1 was SF-8411 (Mw=70967, epoxy equivalent = 3200) manufactured by Dow Corning Co., Ltd.; the second modifier was SIB-1932.4 (Mw=203.36) manufactured by Gelest Corporation. The terminal modified conjugated diene-vinyl aromatic copolymer obtained had a weight average molecular weight of 1,100,000; a number average molecular weight of 650,000 and a polydispersity of Mw/Mn = 1.69.
實驗例1中，第一改質劑的用量為3.00×10-6mole(=0.213/70967)；第二改質劑的用量為1.047×10-4mole(=0.0213/203.36)；兩者的莫耳數比為0.0287。 In Experimental Example 1, the amount of the first modifier was 3.00×10 -6 mole (=0.213/70967); the amount of the second modifier was 1.047×10 -4 mole (=0.0213/203.36); The molar ratio is 0.0287.
實驗例2 Experimental example 2
除了以下列用量使用第一改質劑與第二改質劑以外，以與實驗例1相同的方式合成實驗例2的末端改質的共軛二烯-乙烯基芳香烴共聚物。 The terminally modified conjugated diene-vinyl aromatic copolymer of Experimental Example 2 was synthesized in the same manner as in Experimental Example 1, except that the first modifier and the second modifier were used in the following amounts.
實驗例2中，第一改質劑的用量為6.00×10-6mole(=0.426/70967)；第二改質劑的用量為5.237×10-4mole(=0.1065/203.36)；兩者的莫耳數比為0.0115。 In Experimental Example 2, the amount of the first modifier was 6.00×10 -6 mole (=0.426/70967); the amount of the second modifier was 5.237×10 -4 mole (=0.1065/203.36); The molar ratio is 0.0115.
實驗例3 Experimental example 3
實驗例3與實驗例1大致相同，差異在於，實驗例3並未使用SF-8411(第一改質劑)，而是直接添加0.1phr(0.213克)的環氮雜矽烷(cyclic azasilane)(SIB 1932.4)。實驗例3的整體反應過程如反應式II所示。 Experimental Example 3 was substantially the same as Experimental Example 1, except that Experimental Example 3 did not use SF-8411 (first modifier), but directly added 0.1 phr (0.213 g) of cyclic azasilane ( SIB 1932.4). The overall reaction process of Experimental Example 3 is shown in Reaction Scheme II.
比較例1 Comparative example 1
以與實驗例1相同的方式合成比較例1的末端改質的共軛二烯-乙烯基芳香烴共聚物，但僅使用0.1phr的第一改質劑(SF-8411)，未使用環氮雜矽烷(SIB 1932.4)作為第二改質劑。 The terminally modified conjugated diene-vinyl aromatic copolymer of Comparative Example 1 was synthesized in the same manner as Experimental Example 1, except that only 0.1 phr of the first modifier (SF-8411) was used, and no ring nitrogen was used. Heteroane (SIB 1932.4) acts as a second modifier.
比較例2 Comparative example 2
以與實驗例1相同的方式合成比較例2的末端改質的 共軛二烯-乙烯基芳香烴共聚物，但僅使用0.2phr的第一改質劑(SF-8411)，未使用環氮雜矽烷(cyclic azasilane)(SIB 1932.4)作為第二改質劑。 The terminal modified of Comparative Example 2 was synthesized in the same manner as Experimental Example 1. The conjugated diene-vinyl aromatic copolymer, but using only 0.2 phr of the first modifier (SF-8411), did not use cyclic azasilane (SIB 1932.4) as the second modifier.
比較例3 Comparative example 3
以與實驗例1相同的方式合成比較例3的末端改質的共軛二烯-乙烯基芳香烴共聚物，但僅使用0.3phr的第一改質劑(SF-8411)，未使用環氮雜矽烷(cyclic azasilane)(SIB 1932.4)作為第二改質劑。 The terminally modified conjugated diene-vinyl aromatic copolymer of Comparative Example 3 was synthesized in the same manner as Experimental Example 1, except that only 0.3 phr of the first modifier (SF-8411) was used, and no ring nitrogen was used. A cyclic azasilane (SIB 1932.4) was used as the second modifier.
實驗例4(橡膠物) Experimental Example 4 (rubber)
首先，使含油的末端改質的共軛二烯-乙烯基芳香烴共聚物756.66克(137.5重量份)與以下物質進行混練，以製得橡膠物。在橡膠組成中投入白煙(7000GR；70phr，385公克)、抗氧化劑(1phr，5.5公克)、防老劑(2phr，11公克)、碳黑(N-234：10phr，55公克)、偶聯劑(Si-69：5.6phr，30.8公克)、ZnO(3phr，16.5公克)、硬酯酸(2phr，11公克)並混合，待溫度上升至150℃出料後，常溫老化24小時。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1.8phr的n-環己基-2-苯並噻唑次磺酰胺、1.7phr的二苯胍、1.7phr的硫後進行硫化，以製得橡膠物。 First, 756.66 g (137.5 parts by weight) of an oil-containing terminal-modified conjugated diene-vinyl aromatic copolymer was kneaded with the following to obtain a rubber. In the rubber composition, white smoke (7000GR; 70phr, 385g), antioxidant (1phr, 5.5g), antioxidant (2phr, 11g), carbon black (N-234: 10phr, 55g), coupling agent (Si-69: 5.6 phr, 30.8 g), ZnO (3 phr, 16.5 g), stearic acid (2 phr, 11 g) and mixed. After the temperature was raised to 150 ° C, the material was aged at room temperature for 24 hours. The above procedure is done with a banbury mixer. After the discharge, the blend was added to a roll mixer to add 1.8 phr of n-cyclohexyl-2-benzothiazole sulfenamide, 1.7 phr of diphenyl hydrazine, 1.7 phr of sulfur, followed by vulcanization. Get rubber.
製備橡膠物使用之材料的資訊如下所示。 Information on the materials used to prepare the rubber is as follows.
白煙：ULTRASIL EVONIK製造 White smoke: manufactured by ULTRASIL EVONIK
油：Treated Distillate Aromatic Extract,TDAE，Vivtec 500，H&R製造 Oil: Treated Distillate Aromatic Extract, TDAE, Vivtec 500, H&R Manufacture
抗氧化劑：Ix-1076，CIBA製造 Antioxidant: Ix-1076, manufactured by CIBA
Si69：雙-3-(三乙氧基甲矽烷基丙基)四硫化物，Degussa AG製造 Si69: bis-3-(triethoxycarbamidopropyl) tetrasulfide, manufactured by Degussa AG
氧化鋅：ZnO，HA製造 Zinc oxide: ZnO, HA manufacturing
n-環己基-2-苯並噻唑次磺酰胺：n-cyclohexyl-2-benzo thiazolesulphenamide,CBS，FLEXSYS製造 N-cyclohexyl-2-benzothiazole sulfenamide: n-cyclohexyl-2-benzo thiazolesulphenamide, manufactured by CBS, FLEXSYS
硫：三角牌 Sulfur: triangle
硬酯酸：TPSA1865，CV.Pacific Indochem製造 Stearic acid: TPSA1865, manufactured by CV. Pacific Indochem
防老劑：N-(1,3-二甲基丁基)-N’-苯基對苯二胺，6PPD，創毅化學代理 Antioxidant: N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6PPD, Chuangyi Chemical Agent
碳黑：ISAF-HS N234，中國橡膠合成製造 Carbon black: ISAF-HS N234, China Rubber Synthetic Manufacturing
二苯胍：Diphenyl Guanidine,DPG，FLEXSYS製造 Diphenyl hydrazine: manufactured by Diphenyl Guanidine, DPG, FLEXSYS
橡膠物的性質是使用TA儀器公司製造，型號為DMA Q800的黏彈性測定裝置測定。測定模式為拉伸模式，測定頻率為20Hz。測定的項目有動態儲存彈性模數(E)以及損失正切(tanδ)。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’)。△E’的數值愈小，表示橡膠組合與白煙的相容性愈好。△E’也稱為佩恩效應(Payne Effect)。 The properties of the rubber were 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 items measured have a dynamic storage elastic modulus (E) and a loss tangent (tan δ). 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'). The smaller the value of ΔE', the better the compatibility of the rubber composition with white smoke. ΔE' is also called the Payne Effect.
測定損失正切(tanδ)時的升溫速度為每分鐘3℃，且測定損失正切時的溫度選擇在0℃與60℃。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，代表橡膠物之滾動阻力越低。 The temperature increase rate at the time of loss tangent (tan δ) was 3 ° C per minute, and the temperature at which the loss tangent was measured was selected to be 0 ° C and 60 ° C. The test at 0 ° C can be regarded as the performance of the simulated tire on the icy road surface, and the higher the loss tangent, the better the wet skid resistance of the rubber material. The test at 60 ° C can be regarded as the performance of the simulated tire at high speed, the lower the loss tangent, the lower the rolling resistance of the rubber.
測試結果示於表1。 The test results are shown in Table 1.
實驗例1~3中使用末端改質的共軛二烯-乙烯基芳香烴共聚物所製成的橡膠物，其佩恩效應與比較例1~3相比較小，表示實驗例1~3的橡膠組合與白煙的相容性較好。 In the rubber samples prepared by using the terminally modified conjugated diene-vinyl aromatic copolymer in Experimental Examples 1 to 3, the Penn effect was small compared with Comparative Examples 1 to 3, and the experimental examples 1 to 3 were shown. The rubber combination has good compatibility with white smoke.
在溫度0℃下，實驗例1~3中有使用末端改質的共軛二烯-乙烯基芳香烴共聚物所製成的橡膠物，其量測出的 損失正切(tanδ)大致上大於比較例1~3中單獨使用以具環氧基矽氧烷末端改質的共軛二烯-乙烯基芳香烴共聚物(即沒有使用第二改質劑)所製成的橡膠物的損失正切(tanδ)，顯示利用實驗例1~3的橡膠物相較於比較例1~3的橡膠物具有較佳之耐濕滑性。 At temperatures of 0 ° C, the rubbers made of the terminally modified conjugated diene-vinyl aromatic copolymer were used in the experimental examples 1 to 3, and the measured amounts thereof were measured. The loss tangent (tan δ) is substantially larger than that of the conjugated diene-vinyl aromatic copolymer (for example, without the use of the second modifier) used in the comparative examples 1 to 3 to be modified with an epoxy group. The loss tangent (tan δ) of the produced rubber material showed that the rubber materials of Experimental Examples 1 to 3 had better wet skid resistance than the rubber materials of Comparative Examples 1 to 3.
在溫度60℃下，實驗例1至實驗例2中有使用末端改質的共軛二烯-乙烯基芳香烴共聚物所製成的橡膠物，其量測出的損失正切(tanδ)大致上小於比較例1~3中沒有使用第二改質劑之末端改質的共軛二烯-乙烯基芳香烴共聚物所製成的橡膠物的損失正切(tanδ)，顯示利用實驗例1至實驗例3的橡膠物相較於比較例1~3的橡膠物具有較低之滾動阻力。 At a temperature of 60 ° C, in the experimental examples 1 to 2, there was a rubber material obtained by using a terminally modified conjugated diene-vinyl aromatic copolymer, and the measured loss tangent (tan δ) was substantially The loss tangent (tan δ) of the rubber material prepared by using the conjugated diene-vinyl aromatic copolymer having no terminal modification of the second modifier in Comparative Examples 1 to 3, showing the use of Experimental Example 1 to Experiment The rubber of Example 3 had lower rolling resistance than the rubber of Comparative Examples 1 to 3.
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。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白煙具有良好的相容性。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含矽基團，以增加與白煙的混練均勻性，但其他機制也是可能的。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 provides 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 white smoke. One possible reason is the introduction of a hydrazine-containing group at the end of the conjugated diene-vinyl aromatic copolymer during synthesis to increase the kneading uniformity with white smoke, but other mechanisms are also possible. 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，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，故本 發明之保護範圍當視後附之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 invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. this The scope of the invention is defined by the scope of the appended claims.
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