TW201319103A - Solution polymerization/co-polymerization of dienes, hydrogenation of dienerubbers and hydrogenated dienerubbers - Google Patents

Solution polymerization/co-polymerization of dienes, hydrogenation of dienerubbers and hydrogenated dienerubbers Download PDF

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TW201319103A
TW201319103A TW101122736A TW101122736A TW201319103A TW 201319103 A TW201319103 A TW 201319103A TW 101122736 A TW101122736 A TW 101122736A TW 101122736 A TW101122736 A TW 101122736A TW 201319103 A TW201319103 A TW 201319103A
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group
rhcl
diene
metal
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Matthias Soddemann
Sharon Guo
Zhen-Li Wei
qing-chun Liu
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Lanxess Deutschland Gmbh
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Abstract

The present invention relates to butadiene rubber polymers having low molecular weights and narrower molecular weight distributions than those known in the art. The present invention also relates to a metal-containing catalyst system, a solution polymerization process for the manufacture of said butadiene rubber, a one-pot process for the synthesis of the hydrogenated diene polymers, and a process for the hydrogenation of diene polymers.

Description

二烯之溶液聚合/共聚合、二烯橡膠之氫化及經氫化之二烯橡膠 Solution polymerization/copolymerization of diene, hydrogenation of diene rubber and hydrogenated diene rubber

本發明總體上涉及二烯的溶液聚合/共聚合反應，確切地說涉及一種用於二烯和乙烯基單體的溶液聚合/共聚合和/或基於所獲得的二烯橡膠的聚合物的氫化(以一鍋法或以兩步法)的催化劑體系，一種用於二烯以及乙烯基單體在金屬催化劑體系的存在下的溶液聚合/共聚合的方法，連同基於所獲得的二烯橡膠的聚合物的氫化(以一鍋法或以兩步法)，藉由基於所獲得的二烯橡膠的聚合物的溶液聚合和/或氫化(以一鍋法或以兩步法)所獲得的二烯橡膠聚合物。 The present invention relates generally to solution polymerization/copolymerization of dienes, and more particularly to solution polymerization/copolymerization of diene and vinyl monomers and/or hydrogenation of polymers based on the obtained diene rubber a catalyst system (one-pot or two-step process), a method for solution polymerization/copolymerization of a diene and a vinyl monomer in the presence of a metal catalyst system, together with a diene rubber based on Hydrogenation of a polymer (either in a one-pot process or in a two-step process) by solution polymerization and/or hydrogenation of a polymer based on the obtained diene rubber (one-pot or two-step process) Ene rubber polymer.

丁二烯橡膠(BR)係藉由1,3-二烯單體的聚合作用獲得的常見的合成橡膠。丁二烯橡膠通常是在溶液中聚合的丁二烯，包括陰離子聚合以及配位聚合。 Butadiene rubber (BR) is a common synthetic rubber obtained by polymerization of a 1,3-diene monomer. Butadiene rubber is typically butadiene polymerized in solution, including anionic polymerization and coordination polymerization.

苯乙烯-丁二烯橡膠(SBR)可以在溶液中聚合(例如陰離子聚合)，所謂的SSBR。苯乙烯-丁二烯橡膠(SBR)還可以在乳液中聚合，所謂的ESBR。 Styrene-butadiene rubber (SBR) can be polymerized in solution (for example anionic polymerization), the so-called SSBR. Styrene-butadiene rubber (SBR) can also be polymerized in emulsions, the so-called ESBR.

腈丁二烯橡膠(NBR)通常藉由自由基乳液聚合來生產。腈丁二烯橡膠(NBR)，其為包括至少一種共軛二烯，丁二烯，至少一種不飽和腈以及任外的共聚單體的共聚物係一特種橡膠，該橡膠具有良好的化學耐受性以及優異的耐油性。與橡膠的高水平機械性能(特別 是高耐磨損性)相結合，發現NBR除其他領域之外還在汽車(密封件、軟管、支承墊)、電氣(電纜外皮)、機械工程(輪胎、輥)和鞋業中之廣泛應用便不足為奇。 Nitrile butadiene rubber (NBR) is usually produced by free radical emulsion polymerization. Nitrile butadiene rubber (NBR), which is a copolymer comprising at least one conjugated diene, butadiene, at least one unsaturated nitrile and optionally a comonomer, which has a good chemical resistance Receptive and excellent oil resistance. High level of mechanical properties with rubber (special It is a combination of high wear resistance and found that NBR is widely used in automobiles (seals, hoses, support pads), electrical (cable outer skin), mechanical engineering (tires, rollers) and footwear, among other areas. It is not surprising that the application.

目前，NBR藉由自由基乳液聚合法製造，該方法生產了具有較寬的分子量分佈以及某種程度的乳化劑殘餘的NBR聚合物。總體上，藉由這種方法獲得的NBR具有在從30至90範圍內的慕尼粘度，在從80,000至150,000範圍內的Mn，在從250,000至350,000範圍內的Mw以及大於3.2的多分散性指數。 Currently, NBR is produced by a free radical emulsion polymerization process which produces an NBR polymer having a broad molecular weight distribution and some degree of emulsifier residue. In general, the NBR obtained by this method has a Mooney viscosity in the range of from 30 to 90, a Mn in the range of from 80,000 to 150,000, a Mw in the range of from 250,000 to 350,000, and a polydispersity of more than 3.2. index.

金屬化合物催化的溶液聚合法可以生產具有更高純度以及更高的受控分子結構的NBR。 Metal compound catalyzed solution polymerization can produce NBR with higher purity and higher controlled molecular structure.

此外，氫化的腈丁二烯橡膠聚合物(HNBR)藉由NBR在溶液法中的氫化來生產-NBR聚合物係首先從膠乳中凝結、清潔並且乾燥，然後溶解在用於氫化的溶劑中。當將NBR聚合物(其藉由自由基乳液聚合法製造)進行氫化時，HNBR聚合物的慕尼粘度將增加到高達60-120。 Further, the hydrogenated nitrile butadiene rubber polymer (HNBR) is produced by hydrogenation of NBR in a solution process - the NBR polymer system is first coagulated from the latex, cleaned and dried, and then dissolved in a solvent for hydrogenation. When the NBR polymer, which is produced by a free radical emulsion polymerization process, is hydrogenated, the Mooney viscosity of the HNBR polymer will increase up to 60-120.

因為NBR係在乳液聚合(E-NBR)後以膠乳形式生產的並且NBR在工廠生產中的氫化技術上僅可在有機溶液中進行，因此目前商業的HNBR的生產涉及許多繁雜的步驟以從該膠乳中獲得清潔的固體NBR並且隨後將該NBR溶解在有機溶劑中。而且，由於E-NBR最終處理過程的限制，用於製造低MV HNBR的低慕尼粘度(MV)NBR原料的供應受到限制；朗盛公司發展了 用於生產具有低MV的Therban AT的複分解法，用於改進加工性。然而，附加的複分解增加了生產成本。 Since the NBR is produced in the form of a latex after emulsion polymerization (E-NBR) and the hydrogenation technology of NBR in factory production can only be carried out in an organic solution, the production of commercial HNBR currently involves many complicated steps from A clean solid NBR is obtained in the latex and the NBR is subsequently dissolved in an organic solvent. Moreover, due to the limitations of the final processing of E-NBR, the supply of low Munni viscosity (MV) NBR raw materials for the manufacture of low MV HNBR is limited; LANXESS has developed A metathesis process for producing Therban AT with low MV for improving processability. However, additional metathesis increases production costs.

在過去的二十多年，受控的自由基聚合反應(CRP)，包括ATRP、NOMP、RAFT以及引發轉移終止劑(iniferter)已經引起了許多注意，因為它開啟了用於以較容易的方式生產具有精確設計分子構造的良好定義的聚合物的新途徑(不像現存的陰離子聚合反應中對濕度/空氣/雜質一樣敏感)(Chem.Rev.2001,101,2921-2990；Chem.Rev.2001,101,3689-3745；Chem.Rev.,2001,101,3661-3688；Prog.Polym.Sci.2007,32,93-146)。 Over the past two decades, controlled free radical polymerization (CRP), including ATRP, NOMP, RAFT, and inducing transfer terminators (iniferter) have attracted a lot of attention because it opens up in an easier way. A new way to produce well-defined polymers with precisely designed molecular structures (unlike the sensitivity of existing anionic polymerizations to humidity/air/impurities) (Chem. Rev. 2001, 101, 2921-2990; Chem. Rev. 2001, 101, 3689-3745; Chem. Rev., 2001, 101, 3661-3688; Prog. Polym. Sci. 2007, 32, 93-146).

總體上，與(甲基)丙烯酸乙烯基亞乙烯基型的單體相比，二烯被認為更難以藉由CRP進行聚合。僅存在幾個關於二烯之受控的自由基均聚或共聚作用的報告。((a)ATRP：J.Ind.Eng.Chem.,2005,11(6),911-917；J.Ind.Eng.Chem.,2006,12(2),241.；(b)RAFT：Macromolecules,2007,40,1408；J.Polymerk Sci.Part A：Polymer Chem.2007,45,4100；Macromol.Rapid Commun.2010,31,1616-1621.(c)NOMP：Macromolecules,1998,31,7559；Macromolecules,2000,33,363)。 In general, diene is considered to be more difficult to polymerize by CRP than the vinyl (vinyl) vinyl vinylidene type monomer. There are only a few reports of controlled free radical homopolymerization or copolymerization of dienes. ((a) ATRP: J. Ind. Eng. Chem., 2005, 11(6), 911-917; J. Ind. Eng. Chem., 2006, 12(2), 241 .; (b) RAFT: Macromolecules, 2007, 40, 1408; J. Polymerk Sci. Part A: Polymer Chem. 2007, 45, 4100; Macromol. Rapid Commun. 2010, 31, 1616-1621. (c) NOMP: Macromolecules, 1998, 31, 7559 ; Macromolecules, 2000, 33, 363).

所提到的聚合方法使用不同類型的金屬催化劑，需要提供用於二烯以及乙烯基單體的溶液聚合/共聚合反應的催化劑體系和/或基於所獲得的二烯橡膠的聚合 物，其以一鍋法或兩步法的氫化的催化劑體系，其具有受控的分子量，較窄的分子量分佈以及在從大於0至30、較佳的是大於1至30範圍內的慕尼粘度。 The polymerization process mentioned uses different types of metal catalysts, requires a catalyst system for solution polymerization/copolymerization of diene and vinyl monomers and/or polymerization based on the obtained diene rubber. a catalyst system of hydrogenation in a one-pot or two-step process having a controlled molecular weight, a narrow molecular weight distribution, and a muni range from greater than 0 to 30, preferably greater than 1 to 30. Viscosity.

總之，本發明的目的因此是提供用於生產腈丁二烯橡膠聚合物的溶液聚合/共聚合法，該橡膠聚合物具受控的分子量，比習知技術的已知者更低慕尼粘度以及更窄的分子量分佈。 In summary, it is therefore an object of the present invention to provide a solution polymerization/copolymerization process for producing a nitrile butadiene rubber polymer having a controlled molecular weight, a lower Mooney viscosity than known in the prior art and A narrower molecular weight distribution.

在第一方面，本發明提供了用於二烯的溶液聚合法和/或用於含二烯的聚合物氫化的含金屬的催化劑體系，該體系包括(1)含金屬的催化劑，(2)助催化劑，以及任選地(3)添加劑，其中(1)該含金屬的催化劑係選自MLnXm、MXm、MXm．pH2O、M(OC(O)R)m、或其任何組合，其中M代表選自Rh、Pd、Ru、Ir、 Mo、Co、Cu、Fe、或Ti的金屬，L係選自的基團，其中R1、R2、和R3可以是相同或不同的，並且R1、R2、和R3各自獨立地選自H、C1-C6烷基、C5-C7芳基或C3-C6環烷基、取代的C3-C6環烷基、取代的C5-C7芳基，其條件係R1、R2、和R3不全為H，X係鹵素，n係1至5的一整數，p係1至7的一整數，並且m係等於M的化合價；(2)該助催化劑係選自鹵化物、偶氮化合物或過氧化物；並且任選地 (3)該添加劑係選自由以下各項組成之群組：一級胺(R1-NH2)、二級胺(R1-NH-R2)、三級胺(N(R1)(R2)(R3))、、抗壞血酸、或銨鹽、或其任何組合，其中R1、R2、和R3如以上定義。 In a first aspect, the present invention provides a solution polymerization process for a diene and/or a metal-containing catalyst system for hydrogenation of a diene-containing polymer, the system comprising (1) a metal-containing catalyst, (2) a cocatalyst, and optionally (3) an additive, wherein (1) the metal-containing catalyst is selected from the group consisting of ML n X m , MX m , MX m . pH 2 O, M(OC(O)R) m , or any combination thereof, wherein M represents a metal selected from the group consisting of Rh, Pd, Ru, Ir, Mo, Co, Cu, Fe, or Ti, and the L is selected from the group consisting of a group wherein R 1 , R 2 , and R 3 may be the same or different, and R 1 , R 2 , and R 3 are each independently selected from H, C 1 -C 6 alkyl, C 5 -C a 7- aryl or C 3 -C 6 cycloalkyl group, a substituted C 3 -C 6 cycloalkyl group, a substituted C 5 -C 7 aryl group, the conditions of which are R 1 , R 2 , and R 3 are not all H, X is a halogen, n is an integer from 1 to 5, p is an integer from 1 to 7, and m is equal to the valence of M; (2) the cocatalyst is selected from a halide, an azo compound or a peroxide; And optionally (3) the additive is selected from the group consisting of a primary amine (R 1 -NH 2 ), a secondary amine (R 1 -NH-R 2 ), a tertiary amine (N(R) 1 )(R 2 )(R 3 )), , ascorbic acid, or an ammonium salt, or any combination thereof, wherein R 1 , R 2 , and R 3 are as defined above.

在第二方面，本發明提供了一種二烯的溶液聚合法，包括在至少一種本申請案的含金屬催化劑體系的存在下、在至少一種有機溶劑中將二烯均聚或二烯連同至少一種單體共聚。 In a second aspect, the present invention provides a solution polymerization process for a diene comprising homodimerizing a diene or a diene in at least one organic solvent in the presence of at least one metal-containing catalyst system of the present application Monomer copolymerization.

該溶液聚合提供了用於合成具有窄分子量分佈的低分子量腈橡膠的方法，是藉由將至少一種共軛二烯單體與至少一種α,β-不飽和腈以及任選地另外一或多種可共聚的單體在一或多種含金屬催化劑以及助催化劑與或不與一或多種適當的添加劑在有機溶劑中直接進行溶液共聚。 The solution polymerization provides a method for synthesizing a low molecular weight nitrile rubber having a narrow molecular weight distribution by reacting at least one conjugated diene monomer with at least one α,β-unsaturated nitrile and optionally one or more The copolymerizable monomer is directly solution copolymerized with one or more metal-containing catalysts and a cocatalyst with or without one or more suitable additives in an organic solvent.

本發明係針對具有在小於1000至300000 g/mol範圍內的Mn，自小於1至30的慕尼粘度(ML 1+4@100℃)以及小於5的多分散性指數的腈橡膠。 The present invention is directed to a nitrile rubber having a Mn in the range of less than 1000 to 300,000 g/mol, a Mooney viscosity (ML 1+4@100 ° C) of less than 1 to 30, and a polydispersity index of less than 5.

在第三方面，本發明提供了藉由溶液聚合反應獲得的二烯聚合物，包含在從40至85重量份範圍內的衍生自一或多種二烯的重複單元，在從0至70重量份範圍內的衍生自一或多種α,β-不飽和腈或苯乙烯或任何苯乙烯衍生物的重複單元，以及在從0至40重量份範圍內的衍生自任選的除α,β-不飽和腈或苯乙烯以及任何 苯乙烯衍生物之外的三單體的重複單元。 In a third aspect, the present invention provides a diene polymer obtained by solution polymerization comprising repeating units derived from one or more dienes in a range of from 40 to 85 parts by weight, from 0 to 70 parts by weight Repeating units derived from one or more α,β-unsaturated nitriles or styrene or any styrene derivative, and derived from the range of from 0 to 40 parts by weight, optionally from α,β- Saturated nitrile or styrene and any A repeating unit of three monomers other than the styrene derivative.

在第四方面，本發明提供了藉由本發明的溶液聚合法獲得的二烯聚合物在氫氣的以及基於Rh、Ru、和/或Pd催化劑的存在下在氫化作用中獲得氫化的二烯聚合物的用途。 In a fourth aspect, the present invention provides a hydrogenated diene polymer obtained by hydrogenation of a diene polymer obtained by the solution polymerization method of the present invention in the presence of hydrogen and based on a Rh, Ru, and/or Pd catalyst. the use of.

在第五方面，本發明提供了用於合成氫化的二烯聚合物的一鍋法，是藉由溶液聚合完成之後直接將氫氣引入到該反應器中並且在所欲的溫度下進行反應。 In a fifth aspect, the present invention provides a one-pot process for the synthesis of hydrogenated diene polymers by introducing hydrogen directly into the reactor after completion of solution polymerization and carrying out the reaction at the desired temperature.

在第六方面，本發明提供了氫化的二烯聚合物，它係藉由用於合成本發明的氫化的二烯聚合物的一鍋法所獲得的。 In a sixth aspect, the present invention provides a hydrogenated diene polymer obtained by a one-pot process for synthesizing the hydrogenated diene polymer of the present invention.

在第七方面，本發明提供了用於氫化二烯聚合物的方法，包括：a)在本發明的含金屬的催化劑體系的存在下、在至少一種有機溶劑中將二烯進行溶液均聚或二烯連同至少一種單體進行共聚以獲得二烯橡膠，b)在該溶液聚合完成之後直接將氫氣引入到步驟a)的混合物中，以獲得氫化的含二烯的聚合物。 In a seventh aspect, the present invention provides a process for hydrogenating a diene polymer comprising: a) solution homopolymerizing a diene in at least one organic solvent in the presence of a metal-containing catalyst system of the invention or The diene is copolymerized together with at least one monomer to obtain a diene rubber, and b) hydrogen is directly introduced into the mixture of step a) after completion of the polymerization of the solution to obtain a hydrogenated diene-containing polymer.

在第八方面，本發明提供了用於氫化二烯聚合物的方法，包括：a)將至少一種二烯聚合物溶解在高壓釜反應器中的至少一種有機溶劑中，b)將本發明的至少一種含金屬的催化劑體系加入在步驟a)中獲得的溶液中，c)將氫氣引入該高壓釜反應器中，並且將該高壓 釜反應器加熱到高達預定的溫度並持續預定的時間。 In an eighth aspect, the present invention provides a process for hydrogenating a diene polymer comprising: a) dissolving at least one diene polymer in at least one organic solvent in an autoclave reactor, b) At least one metal-containing catalyst system is added to the solution obtained in step a), c) hydrogen is introduced into the autoclave reactor, and the high pressure is applied The autoreactor is heated up to a predetermined temperature for a predetermined period of time.

在第九方面，本發明提供了用於氫化二烯聚合物的方法，包括：a)添加藉由本發明的溶液聚合法獲得的二烯均聚溶液或二烯共聚溶液，以及任選地至少一種有機溶劑，b)將氫氣直接引入到步驟a)的混合物中並且將其加熱到達到預定的溫度以獲得含氫化的二烯的聚合物。 In a ninth aspect, the present invention provides a process for hydrogenating a diene polymer, comprising: a) adding a diene homopolymer solution or a diene copolymer solution obtained by the solution polymerization method of the present invention, and optionally at least one The organic solvent, b) is introduced directly into the mixture of step a) and heated to a predetermined temperature to obtain a polymer containing hydrogenated diene.

在第十方面，本發明提供了氫化的二烯的聚合物，它係藉由用於合成本發明的含氫化的二烯的聚合物的一鍋法所獲得的。 In a tenth aspect, the present invention provides a hydrogenated diene polymer obtained by a one-pot process for synthesizing the hydrogenated diene-containing polymer of the present invention.

在第十一方面，本發明提供了本發明的催化劑體系在製造二烯聚合物中的用途。 In an eleventh aspect, the invention provides the use of a catalyst system of the invention in the manufacture of a diene polymer.

在第十二方面，本發明提供了本發明的催化劑體系在製造含氫化的二烯的聚合物中的用途。 In a twelfth aspect, the invention provides the use of a catalyst system of the invention in the manufacture of a hydrogenated diene containing polymer.

在第十三方面，本發明提供了玻璃管反應器和/或高壓釜在本發明的溶液聚合法或用於合成本發明的氫化的二烯聚合物的一鍋法中的用途。 In a thirteenth aspect, the invention provides the use of a glass tube reactor and/or autoclave in the solution polymerization process of the invention or in a one-pot process for the synthesis of the hydrogenated diene polymer of the invention.

在第十四方面，本發明提供了玻璃管反應器和/或高壓釜在用於合成本發明的氫化的二烯聚合物方法中的用途。 In a fourteenth aspect, the invention provides the use of a glass tube reactor and/or autoclave for the synthesis of the hydrogenated diene polymer process of the invention.

藉由本申請案的溶液聚合提供的二烯橡膠聚合物具有小於1000至300000 g/mol範圍內的Mn，小於1至30的慕尼粘度(ML 1+4@100℃)，以及小於5、 較佳的是在從1.1到5.0的範圍內並且特別是在從1.1至4.0範圍內，更佳的是在從1.1至2.0的範圍內的多分散性指數。同時，本申請案的溶液聚合提供的二烯橡膠聚合物可以直接在氫氣的存在下進行氫化。藉由本申請案的用於合成含氫化的二烯的聚合物的一鍋法或用於氫化二烯聚合物的方法所獲得的氫化的二烯橡膠聚合物具有小於1000至300000 g/mol範圍內的Mn，10至60的慕尼粘度(ML 1+4@100℃)，以及小於5、較佳的是在從1.1到5.0的範圍內並且特別是在從1.1至4.0範圍內，更佳的是在從1.1至3.0的範圍內，仍然更佳的是在從1.1至2.0的範圍內的多分散性指數。 The diene rubber polymer provided by solution polymerization of the present application has an Mn in the range of less than 1,000 to 300,000 g/mol, a Mooney viscosity of less than 1 to 30 (ML 1+4@100 ° C), and less than 5, It is preferably in the range from 1.1 to 5.0 and particularly in the range from 1.1 to 4.0, more preferably in the range of from 1.1 to 2.0. Meanwhile, the diene rubber polymer provided by the solution polymerization of the present application can be directly hydrogenated in the presence of hydrogen. The hydrogenated diene rubber polymer obtained by the one-pot method for synthesizing a hydrogenated diene-containing polymer or the method for hydrogenating a diene polymer of the present application has a range of less than 1,000 to 300,000 g/mol Mn, a Mui viscosity of 10 to 60 (ML 1+4@100 ° C), and less than 5, preferably in the range from 1.1 to 5.0 and especially in the range from 1.1 to 4.0, more preferably It is still in the range from 1.1 to 3.0, and still more preferably the polydispersity index in the range from 1.1 to 2.0.

發明詳細說明Detailed description of the invention

在整個本說明書中使用時，“腈橡膠”這一術語旨在具有較廣泛的含義並意在包括具有多個重複單元的共聚物，該等重複單元衍生自至少一種共軛的二烯、至少一種α,β-不飽和的腈、和任選地另外的一或多種可共聚的單體。 As used throughout this specification, the term "nitrile rubber" is intended to have a broader meaning and is intended to include copolymers having a plurality of repeating units derived from at least one conjugated diene, at least An alpha, beta-unsaturated nitrile, and optionally one or more copolymerizable monomers.

該共軛的二烯可以是任何已知的二烯，較佳為C4-C6共軛二烯。較佳的共軛的二烯包括：1,3-丁二烯、異戊二烯、2,3-二甲基丁二烯、1,3-戊二烯、或其混合物。更佳的C4-C6共軛二烯包括1,3-丁二烯、異戊二烯以及其混合物。最佳的C4-C6共軛二烯係1,3-丁二烯。 The conjugated diene may be any known diene, preferably a C 4 -C 6 conjugated diene. Preferred conjugated dienes include: 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, or mixtures thereof. More preferred C 4 -C 6 conjugated dienes include 1,3-butadiene, isoprene, and mixtures thereof. The most preferred C 4 -C 6 conjugated diene is 1,3-butadiene.

α,β-不飽和腈可以是任何已知的α,β-不飽和腈，較佳的是(C3-C5)α,β-不飽和腈。較佳的(C3-C5)α,β-不飽 和腈包括：丙烯腈、甲基丙烯腈、乙基丙烯腈或其混合物。最佳的(C3-C5)α,β-不飽和腈係丙烯腈。 The α,β-unsaturated nitrile may be any known α,β-unsaturated nitrile, preferably a (C 3 -C 5 )α,β-unsaturated nitrile. Preferred (C 3 -C 5 )α,β-unsaturated nitriles include: acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof. The most preferred (C 3 -C 5 ) α,β-unsaturated nitrile acrylonitrile.

本申請案提供的溶液聚合二烯橡膠聚合物具有在小於1000至300000 g/mol範圍內的Mn，小於1至30的慕尼粘度(ML 1+4@100℃)，以及小於5的多分散性指數，並且該氫化的二烯橡膠聚合物具有在小於1000至300000 g/mol範圍內的Mn，10至60的慕尼粘度(ML 1+4@100℃)，以及小於5的多分散性指數。 The solution polymerized diene rubber polymer provided by the present application has Mn in the range of less than 1,000 to 300,000 g/mol, a Mooney viscosity of less than 1 to 30 (ML 1+4@100 ° C), and a polydispersity of less than 5. Index, and the hydrogenated diene rubber polymer has Mn in the range of less than 1000 to 300,000 g/mol, a Mui viscosity of 10 to 60 (ML 1+4@100 ° C), and a polydispersity of less than 5. index.

為了本申請的目的，本發明的具體實例提供了本發明的用於二烯的溶液聚合法和/或用於含烯烴的聚合物的氫化的含金屬的催化劑體系，該體系包括(1)含金屬的催化劑，(2)助催化劑，以及(3)任選地添加劑，其中(1)該含金屬的催化劑係選自MLnXm、MXm、MXm．pH2O、M(OC(O)R)m、或其任何組合，其中M代表選自Rh、Pd、Ru、Ir、Mo、Co、Cu、Fe、或Ti的金屬，L係選自基團，其中R1、R2、和R3可以是相同或不同的，並且每個R1、R2、和R3各自獨立地選自H、C1-C6烷基、C5-C7芳基或C3-C6環烷基、經取代的C3-C6環烷基、經取代的C5-C7芳基，其條件係R1、R2、和R3不全為H，X係鹵素，n係1至5的整數，p係1至7的整數，並且m係等於M的化合價；(2)該助催化劑係選自鹵化物、偶氮化合物、或過 氧化物；並且任選地(3)該添加劑係選自由以下所組成之群組：一級胺(R1-NH2)、二級胺(R1-NH-R2)、三級胺(N(R1)(R2)(R3))、、抗壞血酸、或銨鹽、或其任何組合，其中R1、R2、和R3如以上定義。 For the purposes of this application, specific examples of the invention provide a solution polymerization process for a diene of the invention and/or a metal-containing catalyst system for the hydrogenation of an olefin-containing polymer, the system comprising (1) a metal catalyst, (2) a cocatalyst, and (3) an optional additive, wherein (1) the metal-containing catalyst is selected from the group consisting of ML n X m , MX m , MX m . pH 2 O, M(OC(O)R) m , or any combination thereof, wherein M represents a metal selected from the group consisting of Rh, Pd, Ru, Ir, Mo, Co, Cu, Fe, or Ti, and the L is selected from the group consisting of group Wherein R 1 , R 2 , and R 3 may be the same or different, and each of R 1 , R 2 , and R 3 is independently selected from H, C 1 -C 6 alkyl, C 5 -C 7 An aryl or C 3 -C 6 cycloalkyl group, a substituted C 3 -C 6 cycloalkyl group, a substituted C 5 -C 7 aryl group, the conditions of which are R 1 , R 2 , and R 3 are not all H , X is a halogen, n is an integer from 1 to 5, p is an integer from 1 to 7, and m is equal to the valence of M; (2) the cocatalyst is selected from a halide, an azo compound, or a peroxide; And optionally (3) the additive is selected from the group consisting of a primary amine (R 1 -NH 2 ), a secondary amine (R 1 -NH-R 2 ), a tertiary amine (N (R 1 ) )(R 2 )(R 3 )), , ascorbic acid, or an ammonium salt, or any combination thereof, wherein R 1 , R 2 , and R 3 are as defined above.

在較佳具體實例中，本發明的含金屬的催化劑體系，其中(1)在該含金屬的催化劑中，M代表一選自Rh、Pd、Ru、Ir或Mo的金屬，較佳的是Rh、Pd、Ru、Ir，X係選自Cl或Br，更佳的是Cl；在中，每個R1、R2、和R3獨立地選自苯基、C3-C6環烷基、經取代的C3-C6環烷基、苯基、經取代的苯基，較佳的是羧基取代的苯基、磺酸鈉取代的苯基，更佳的是PPh3，三環己基膦(PCy3)、 其中該磺酸鈉基團或羧基基團可以是在苯環的鄰位、間位或對位；(2)在該助催化劑中，該鹵化物係選自 、CH2Cl2、CHCl3、CCl4、二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)，其中每個R、R1、和R2各自獨立地是C1-C6烷基或C3-C6環烷基，並且R基團可以位於苯環的鄰位、間位或對位，並且每個X獨立地如以上定義，該偶氮化合物係選自：2,2’-偶氮雙異丁腈(AIBN)、2,2’-偶氮雙-(2-甲基丁腈(AMBN)、2,2’-偶氮雙-(2-甲基丁腈(AMBN)、2,2’-偶氮雙-(2-甲基丁腈(AMBN)、、2,2’-偶氮雙-(2-甲基丙酸二甲酯、1-氰基-1-甲基乙基偶氮甲醯胺，1,1’-偶氮雙(環己烷-1-腈(ACCN),2,2’-偶氮雙-(2-甲基丙醯胺)二鹽酸化物(AIBA)、或4,4’-偶氮雙-(4-氰基戊酸)(ACVA)，並且該過氧化物係選自：第三丁基過氧化氫、過氧化苯甲醯(BPO)或過氧化異丙苯；並且任選地(3)該添加劑係選自由以下所組成之群組：抗壞血酸、甲胺、乙胺、乙二胺、正丙胺、異丙胺、丙二胺、正丁胺、異丁胺、丁二胺、二丁胺、二甲胺、二乙胺、二異丙基胺、第三丁基胺、戊胺、環己胺、三乙醇胺、三甲胺、三乙胺、三正丙胺、三正丁胺、環庚胺、環戊胺、氯化甲基三正辛基銨(MTOAC)、或其任何組合，其中R1、R2、 和R3如以上定義。 In a preferred embodiment, the metal-containing catalyst system of the present invention, wherein (1) in the metal-containing catalyst, M represents a metal selected from the group consisting of Rh, Pd, Ru, Ir or Mo, preferably Rh. , Pd, Ru, Ir, X is selected from Cl or Br, more preferably Cl; Wherein each of R 1 , R 2 , and R 3 is independently selected from the group consisting of phenyl, C 3 -C 6 cycloalkyl, substituted C 3 -C 6 cycloalkyl, phenyl, substituted phenyl, Preferred is a carboxy substituted phenyl group, a sodium sulfonate substituted phenyl group, more preferably PPh 3 , tricyclohexylphosphine (PCy 3 ), Wherein the sodium sulfonate group or the carboxyl group may be ortho, meta or para to the phenyl ring; (2) in the cocatalyst, the halide is selected from , CH 2 Cl 2 , CHCl 3 , CCl 4 , dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), each of which R, R 1 , and R 2 are each independently C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl, and the R group may be ortho, meta or para to the phenyl ring, and each X independently as defined above, the azo compound is selected from the group consisting of: 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-(2-methylbutyronitrile (AMBN), 2,2'-azobis-(2-methylbutyronitrile (AMBN), 2,2'-azobis-(2-methylbutyronitrile (AMBN), 2,2'-azobis- (Dimethyl 2-methylpropionate, 1-cyano-1-methylethylazomethamine, 1,1'-azobis(cyclohexane-1-carbonitrile (ACCN), 2, 2'-Azobis-(2-methylpropionamide) dihydrochloride (AIBA), or 4,4'-azobis-(4-cyanovaleric acid) (ACVA), and the peroxide Is selected from the group consisting of: tert-butyl hydroperoxide, benzamidine peroxide (BPO) or cumene peroxide; and optionally (3) the additive is selected from the group consisting of ascorbic acid, methylamine ,ethylamine, ethylenediamine, n-propylamine, isopropylamine, propylenediamine, n-butylamine, isobutylamine, butanediamine Dibutylamine, dimethylamine, diethylamine, diisopropylamine, tert-butylamine, pentylamine, cyclohexylamine, triethanolamine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, Cycloheptylamine, cyclopentylamine, methyltri-n-octyl ammonium chloride (MTOAC), Or any combination thereof, wherein R 1 , R 2 , and R 3 are as defined above.

在一較佳的具體實例中，本發明的含金屬的催化劑體系，其中該含金屬的催化劑體系係選自：由(1)MClm(PPh3)n、(2)、2,2-二氯苯乙酮(DCAP)或氯化苄基、以及任選地(3)PPh3所組成之群組；由(1)MClm和/或MXm．pH2O、(2)2,2-二氯苯乙酮或氯化苄基(BCL)、以及任選地(3)PPh3所組成之群組；由(1)MClm(PPh3)n、(2)PhCH2Cl，、以及任選地(3)PPh3所組成之群組；由(1)MClm(PPh3)n、(2)二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)、CH2Cl2、CHCl3、CCl4之一，以及任選地(3)PPh3所組成之群組；由(1)MClm(PPh3)n、(2)Cl3CCOOCH2CH3、以及(3)PPh3所組成之群組；由(1)MClm(PPh3)n、(2)2,2’-偶氮雙異丁腈(AIBN)、2,2’-偶氮雙-(2-甲基丁腈(AMBN)、2,2’-偶氮雙-(2-甲基丁腈(AMBN)、2,2’-偶氮雙-(2-甲基丙酸二甲酯、1-氰基-1-甲基乙基偶氮甲醯胺、1,1’-偶氮雙(環己烷-1-腈(ACCN)、2,2’-偶氮雙-(2-甲基丙醯胺)二鹽酸化物(AIBA)、4,4’-偶氮雙-(4-氰基戊酸)(ACVA)中的至少一種，以及任選地(3)PPh3所組成之群組； 由(1)M(OAc)m、(2)CH2Cl2、CHCl3、CCl4中的至少一種，以及任選地(3)P(Ph)3所組成之群組；其中M係選自Rh、Pd、Ru、Ir、Mo，較佳的是選自Rh、Ru、Pd、和Ir，更佳的是選自Rh、Ru、和Pd，n係整數3，p係1至7的整數，並且m係等於M的化合價。 In a preferred embodiment, the metal-containing catalyst system of the present invention, wherein the metal-containing catalyst system is selected from the group consisting of: (1) MCl m (PPh 3 ) n , (2) a group consisting of 2,2-dichloroacetophenone (DCAP) or benzyl chloride, and optionally (3) PPh 3 ; from (1) MCl m and/or MX m . a group consisting of pH 2 O, (2) 2,2-dichloroacetophenone or benzyl chloride (BCL), and optionally (3) PPh 3 ; from (1) MCl m (PPh 3 ) a group consisting of n , (2) PhCH 2 Cl, and optionally (3) PPh 3 ; from (1) MCl m (PPh 3 ) n , (2) dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), one of CH 2 Cl 2 , CHCl 3 , CCl 4 , and optionally (3) PPh 3 a group consisting of (1) MCl m (PPh 3 ) n , ( 2 ) Cl 3 CCOOCH 2 CH 3 , and (3) PPh 3 ; (1) MCl m (PPh 3 ) n , ( 2) 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-(2-methylbutyronitrile (AMBN), 2,2'-azobis-(2-A Butyl nitrile (AMBN), 2,2'-azobis-(dimethyl 2-methylpropionate, 1-cyano-1-methylethylazomethamine, 1,1'-couple Nitrogen bis(cyclohexane-1-carbonitrile (ACCN), 2,2'-azobis-(2-methylpropionamide) dihydrochloride (AIBA), 4,4'-azobis-(4 At least one of -cyanovaleric acid (ACVA), and optionally (3) a group consisting of PPh 3 ; from (1) M(OAc) m , (2) CH 2 Cl 2 , CHCl 3 , at least one and CCl 4, and optionally (3) P (Ph) 3 the group consisting of Wherein M is selected from the group consisting of Rh, Pd, Ru, Ir, Mo, preferably selected from the group consisting of Rh, Ru, Pd, and Ir, more preferably selected from the group consisting of Rh, Ru, and Pd, and the n is an integer of 3, p. An integer from 1 to 7, and m is equal to the valence of M.

在一更佳的具體實例中，其中含金屬的催化劑體系係選自：由RhCl(PPh3)3、2,2-二氯苯乙酮(DCAP)、以及任選地PPh3所組成之群組；由RhCl3或RhCl3．3H2O、2,2-二氯苯乙酮、以及PPh3所組成之群組；由RhCl(PPh3)3、Cl3CCOOCH2CH3、以及任選地PPh3所組成之群組；由RhCl3或RhCl3．3H2O、Cl3CCOOCH2CH3以及PPh3所組成之群組；包括或由RhCl(PPh3)3、PhCH2Cl以及任選地PPh3組成的混合物；由RhCl3或RhCl3．3H2O、PhCH2Cl、以及PPh3所組成之群組；由PdCl2、2,2-二氯苯乙酮、以及PPh3所組成之群組；由PdCl2、氯化苄基、以及PPh3所組成之群組；由RhCl(PPh3)，CH2Cl2、CHCl3、CCl4中的至少一種，以及任選地PPh3所組成之群組； 由RhCl3或RhCl3．3H2O，CH2Cl2、CHCl3、CCl4中的至少一種，以及PPh3所組成之群組；由Pd(OAc)2，CH2Cl2、CHCl3、CCl4中的至少一種，以及PPh3所組成之群組；或由RhCl(PPh3)3、偶氮雙異庚腈(ABVN)、以及任選地PPh3所組成之群組。 In a more preferred embodiment, the metal-containing catalyst system is selected from the group consisting of RhCl(PPh 3 ) 3 , 2,2-dichloroacetophenone (DCAP), and optionally PPh 3 Group; by RhCl 3 or RhCl 3 . a group consisting of 3H 2 O, 2,2-dichloroacetophenone, and PPh 3 ; a group consisting of RhCl(PPh 3 ) 3 , Cl 3 CCOOCH 2 CH 3 , and optionally PPh 3 ; From RhCl 3 or RhCl 3 . a group consisting of 3H 2 O, Cl 3 CCOOCH 2 CH 3 and PPh 3 ; comprising or consisting of a mixture of RhCl(PPh 3 ) 3 , PhCH 2 Cl and optionally PPh 3 ; from RhCl 3 or RhCl 3 . a group consisting of 3H 2 O, PhCH 2 Cl, and PPh 3 ; a group consisting of PdCl 2 , 2,2-dichloroacetophenone, and PPh 3 ; PdCl 2 , benzyl chloride, and a group consisting of PPh 3 ; a group consisting of at least one of RhCl(PPh 3 ), CH 2 Cl 2 , CHCl 3 , CCl 4 , and optionally PPh 3 ; from RhCl 3 or RhCl 3 . 3H 2 O, at least one of CH 2 Cl 2 , CHCl 3 , CCl 4 , and a group consisting of PPh 3 ; at least one of Pd(OAc) 2 , CH 2 Cl 2 , CHCl 3 , CCl 4 , And a group consisting of PPh 3 ; or a group consisting of RhCl(PPh 3 ) 3 , azobisisoheptonitrile (ABVN), and optionally PPh 3 .

在一另外更佳的具體實例中，該含金屬的催化劑體系係按重量計選自由以下組成物所組成者：RhCl(PPh3)3：DCAP：PPh3=1：0.3-3.0：0-20；RhCl3：DCAP：PPh3=1：1.3-13：4.4-88；RhCl3．3H2O：DCAP：PPh3=1：1.0-10：3.0-63；RhCl(PPh3)3：Cl3CCOOCH2CH3：PPh3=1：0.3-3.0：0-20；RhCl3：Cl3CCOOCH2CH3：PPh3=1：1.3-3.9：4.4-88；RhCl3．3H2O：Cl3CCOOCH2CH3：PPh3=1：1.0-10：3.0-63；RhCl(PPh3)3：PhCH2Cl：PPh3=1：0.05-2.0：0-20；RhCl3：PhCH2Cl：PPh3=1：0.22-9.0：4.4-88；RhCl3．3H2O：PhCH2Cl：PPh3=1：0.2-7.0：3.0-63；PdCl2：DCAP：PPh3=1：0.3-3.0：0-20；RhCl(PPh3)3：CCl4：PPh3=1：0.1-3：0-20；RhCl3：CCl4：PPh3=1：0.4-13：4.4-88；RhCl3．3H2O：CCl4：PPh3=1：0.3-11：3.0-63； Pd(OAc)2：CCl4：PPh3=1：10-4-10-2：3.5-27；或RhCl(PPh3)3：ABVN：PPh3=0-1：1-10：2-20。 In an additional preferred embodiment, the metal-containing catalyst system is selected from the group consisting of RhCl(PPh 3 ) 3 : DCAP: PPh 3 = 1:0.3-3.0:0-20 ; RhCl 3 : DCAP: PPh 3 = 1: 1.3-13: 4.4-88; RhCl 3 . 3H 2 O: DCAP: PPh 3 = 1: 1.0-10: 3.0-63; RhCl(PPh 3 ) 3 : Cl 3 CCOOCH 2 CH 3 : PPh 3 = 1: 0.3-3.0: 0-20; RhCl 3 : Cl 3 CCOOCH 2 CH 3 : PPh 3 =1: 1.3-3.9: 4.4-88; RhCl 3 . 3H 2 O:Cl 3 CCOOCH 2 CH 3 :PPh 3 =1:1.0-10:3.0-63; RhCl(PPh 3 ) 3 :PhCH 2 Cl:PPh 3 =1:0.05-2.0:0-20; RhCl 3 :PhCH 2 Cl: PPh 3 = 1: 0.22-9.0: 4.4-88; RhCl 3 . 3H 2 O:PhCH 2 Cl:PPh 3 =1:0.2-7.0:3.0-63; PdCl 2 :DCAP:PPh 3 =1:0.3-3.0:0-20; RhCl(PPh 3 ) 3 :CCl 4 :PPh 3 =1: 0.1-3: 0-20; RhCl 3 : CCl 4 : PPh 3 = 1: 0.4-13: 4.4-88; RhCl 3 . 3H 2 O:CCl 4 :PPh 3 =1:0.3-11:3.0-63; Pd(OAc) 2 :CCl 4 :PPh 3 =1:10 -4 -10 -2 :3.5-27; or RhCl(PPh 3 ) 3 : ABVN: PPh 3 = 0-1: 1-10: 2-20.

在另一更佳的具體實例中，該含金屬的催化劑體系係按重量計選自由以下組成物所組成者：RhCl(PPh3)3：DCAP：PPh3=1：0.5-2.0：1-10；RhCl3：DCAP：PPh3=1：2.2-9.0：5.4-50；RhCl3．3H2O：DCAP：PPh3=1：2.0-8：4.0-44；RhCl(PPh3)3：Cl3CCOOCH2CH3：PPh3=1：0.5-2.0：1-10；RhCl3：Cl3CCOOCH2CH3：PPh3=1：2.2-9.0：54-50；RhCl3．3H2O：Cl3CCOOCH2CH3：PPh3=1：2.0-8：4.0-44；RhCl(PPh3)3：PhCH2Cl：PPh3=1：0.08-1.5：1-10；RhCl3：PhCH2Cl：PPh3=1：0.35-6.7：5.4-50；RhCl3．3H2O：PhCH2Cl：PPh3=1：0.3-6.0：4.0-44；PdCl2：DCAP：PPh3=1：0.5-2.0：1-10；RhCl(PPh3)3：CCl4：PPh3=1：0.2-2：1-10；RhCl3：CCl4：PPh3=1：0.9-9：5.4-50；RhCl3．3H2O：CCl4：PPh3=1：0.7-7：4.0-44；Pd(OAc)2：CCl4：PPh3=1：5＊10-4-5＊10-2：4.5-17；或RhCl(PPh3)3：ABVN：PPh3=0.2-0.5：0.5-2：0.5-4。 In another more preferred embodiment, the metal-containing catalyst system is selected from the group consisting of RhCl(PPh 3 ) 3 :DCAP:PPh 3 =1:0.5-2.0:1-10 ; RhCl 3 : DCAP: PPh 3 = 1: 2.2-9.0: 5.4-50; RhCl 3 . 3H 2 O: DCAP: PPh 3 = 1: 2.0-8: 4.0-44; RhCl(PPh 3 ) 3 : Cl 3 CCOOCH 2 CH 3 : PPh 3 = 1: 0.5-2.0: 1-10; RhCl 3 : Cl 3 CCOOCH 2 CH 3 : PPh 3 =1: 2.2-9.0: 54-50; RhCl 3 . 3H 2 O:Cl 3 CCOOCH 2 CH 3 :PPh 3 =1:2.0-8:4.0-44; RhCl(PPh 3 ) 3 :PhCH 2 Cl:PPh 3 =1:0.08-1.5:1-10; RhCl 3 :PhCH 2 Cl:PPh 3 =1:0.35-6.7:5.4-50; RhCl 3 . 3H 2 O:PhCH 2 Cl:PPh 3 =1:0.3-6.0:4.0-44; PdCl 2 :DCAP:PPh 3 =1:0.5-2.0:1-10; RhCl(PPh 3 ) 3 :CCl 4 :PPh 3 =1: 0.2-2: 1-10; RhCl 3 : CCl 4 : PPh 3 = 1: 0.9-9: 5.4-50; RhCl 3 . 3H 2 O:CCl 4 :PPh 3 =1:0.7-7:4.0-44; Pd(OAc) 2 :CCl 4 :PPh 3 =1:5 * 10 -4 -5 * 10 -2 :4.5-17; Or RhCl(PPh 3 ) 3 : ABVN: PPh 3 = 0.2-0.5: 0.5-2: 0.5-4.

在還更佳的具體實例中，該添加劑係選自由抗壞血 酸、氯化甲基三正辛基銨、正丙胺、異丙胺、丙二胺、正丁胺、異丁胺、正丁胺、二丁胺、三甲胺、三乙胺、三正丙胺、三正丁胺、或其組合所組成之群組。 In still more preferred embodiments, the additive is selected from the group consisting of ascorbic blood Acid, methyl tri-n-octyl ammonium chloride, n-propylamine, isopropylamine, propylenediamine, n-butylamine, isobutylamine, n-butylamine, dibutylamine, trimethylamine, triethylamine, tri-n-propylamine, three A group consisting of n-butylamine, or a combination thereof.

在另一具體實例中，本發明提供了一種二烯的溶液聚合法，包括在至少一種本發明的含金屬的催化劑體系的存在下在至少一種有機溶劑中將二烯進行均聚或二烯連同至少一種單體進行共聚。 In another embodiment, the invention provides a solution polymerization process for a diene comprising homopolymerizing a diene or a diene in at least one organic solvent in the presence of at least one metal-containing catalyst system of the invention At least one monomer is copolymerized.

在一較佳的具體實例中，該二烯係選自任何已知的二烯，較佳的是選自至少一種共軛的二烯，更佳的是C4-C6共軛二烯，包括1,3-丁二烯、異戊二烯、2,3-二甲基丁二烯、1,3-戊二烯或其混合物，並且最佳的是1,3-丁二烯、異戊二烯或其混合物。 In a preferred embodiment, the diene is selected from any known diene, preferably selected from at least one conjugated diene, more preferably a C 4 -C 6 conjugated diene, Including 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene or a mixture thereof, and most preferably 1,3-butadiene, different Pentadiene or a mixture thereof.

在一更佳的具體實例中，該至少一種單體係選自至少一種α,β-不飽和腈或基於苯乙烯的化合物，並且較佳的是該至少一種α,β-不飽和腈係選自任何已知的α,β-不飽和腈，更佳的是α,β-不飽和(C3-C5)腈，包括丙烯腈、甲基丙烯腈、乙基丙烯腈或其混合物，最佳的是丙烯腈；該基於苯乙烯的化合物係選自苯乙烯、α-甲基苯乙烯或乙烯基甲苯。在另一更佳的具體實例中，本發明的溶液聚合法，其中該至少一種單體係選自苯乙烯。 In a more preferred embodiment, the at least one single system is selected from the group consisting of at least one α,β-unsaturated nitrile or styrene-based compound, and preferably the at least one α,β-unsaturated nitrile is selected From any known α,β-unsaturated nitrile, more preferably α,β-unsaturated (C 3 -C 5 ) nitrile, including acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof, most Preferred is acrylonitrile; the styrene-based compound is selected from the group consisting of styrene, alpha-methyl styrene or vinyl toluene. In another more preferred embodiment, the solution polymerization process of the present invention, wherein the at least one single system is selected from the group consisting of styrene.

在另一更佳的具體實例中，該至少一種共聚單體進一步包括三單體(termonomer)，包括乙烯基單體、亞乙烯基單體以及α,β-不飽和單體，其係選自(甲基)丙烯酸、任何(甲基)丙烯酸酯、任何(甲基)丙烯酸鹽、任何 烯烴、以及任何不飽和的羧酸之至少一者，較佳的是(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁基酯、(甲基)丙烯酸第三丁基酯、乙烯、丙烯、亞乙烯基單體、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸2-氨乙酯、(甲基)丙烯酸2-二甲基氨基乙基酯、富馬酸、馬來酸、以及衣康酸之任一者。 In another more preferred embodiment, the at least one comonomer further comprises a termonomer comprising a vinyl monomer, a vinylidene monomer, and an alpha, beta-unsaturated monomer selected from the group consisting of (meth)acrylic acid, any (meth) acrylate, any (meth) acrylate, any At least one of an olefin and any unsaturated carboxylic acid is preferably n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, ethylene, Propylene, vinylidene monomer, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, benzene (meth) acrylate Any of an ester, 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, fumaric acid, maleic acid, and itaconic acid.

在另一更佳的具體實例中，該至少一種有機溶劑選自任何不與該催化劑反應或以其他方式干擾該反應的有機溶劑，較佳的是選自：苯、甲苯、環己烷、二甲亞碸(DMSO)、碳酸乙烯酯(EC)、四氫呋喃(THF)、1,4-二烷、一氯苯(MCB)、二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAC)、或其混合物，更佳的是選自一氯苯(MCB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)，進一步較佳的是選自一氯苯(MCB)和甲基乙基酮(MEK)，最佳的是一氯苯(MCB)。 In another more preferred embodiment, the at least one organic solvent is selected from any organic solvent that does not react with or otherwise interfere with the reaction, preferably selected from the group consisting of: benzene, toluene, cyclohexane, and Amidoxime (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4-two Alkane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone ( MEK), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), or a mixture thereof, more preferably selected from monochlorobenzene (MCB), methyl Ethyl ketone (MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC), further preferably selected from monochlorobenzene (MCB) and Methyl ethyl ketone (MEK), the most preferred is monochlorobenzene (MCB).

在一還更佳的具體實例中，其中該含金屬的催化劑體系係選自：由RhCl(PPh3)3：DCAP：PPh3所組成之群組，其中 按重量計的RhCl(PPh3)3：DCAP：PPh3=1：0.5-2.0：1-10；由RhCl3：DCAP：PPh3所組成之群組，其中按重量計的RhCl3：DCAP：PPh3=1：2.2-9.0：5.4-50；由RhCl3．3H2O：DCAP：PPh3所組成之群組，其中按重量計的RhCl3．3H2O：DCAP：PPh3=1：2.0-8：4.0-44；由PdCl2：DCAP：PPh3所組成之群組，其中按重量計的PdCl2：DCAP：PPh3=1：0.5-2.0：1-10；由Pd(OAc)2：CCl4：PPh3所組成之群組，其中按重量計的Pd(OAc)2：CCl4：PPh3=1：5＊10-4-5＊10-2：3.5-27；由RhCl(PPh3)3：PhCH2Cl：PPh3所組成之群組，其中按重量計的RhCl(PPh3)3：PhCH2Cl：PPh3=1：0.08-1.5：1-10；由RhCl3：PhCH2Cl：PPh3所組成之群組，其中按重量計的RhCl3：PhCH2Cl：PPh3=1：0.35-6.7：5.4-50；或由RhCl3．3H2O：PhCH2Cl：PPh3所組成之群組，其中按重量計的RhCl3．3H2O：PhCH2Cl：PPh3=1：0.3-6.0：4.0-44。 In a still more preferred embodiment, wherein the metal-containing catalyst system is selected from the group consisting of RhCl(PPh 3 ) 3 :DCAP:PPh 3 wherein RhCl(PPh 3 ) 3 by weight :DCAP:PPh 3 =1:0.5-2.0:1-10; a group consisting of RhCl 3 :DCAP:PPh 3 , wherein RhCl 3 :DCAP:PPh 3 =1:2.2-9.0:5.4 by weight -50; by RhCl 3 . 3H 2 O: group of DCAP: PPh 3 , of which RhCl 3 by weight. 3H 2 O: DCAP: PPh 3 =1: 2.0-8: 4.0-44; a group consisting of PdCl 2 :DCAP:PPh 3 wherein PdCl 2 :DCAP:PPh 3 =1:0.5- by weight 2.0: 1-10; a group consisting of Pd(OAc) 2 : CCl 4 :PPh 3 wherein Pd(OAc) 2 :CCl 4 :PPh 3 =1:5 * 10 -4 -5 by weight * 10 -2 : 3.5-27; a group consisting of RhCl(PPh 3 ) 3 : PhCH 2 Cl:PPh 3 wherein RhCl(PPh 3 ) 3 :PhCH 2 Cl:PPh 3 =1: 0.08-1.5: 1-10; a group consisting of RhCl 3 :PhCH 2 Cl:PPh 3 wherein RhCl 3 :PhCH 2 Cl:PPh 3 = 1:0.35-6.7:5.4-50 by weight; By RhCl 3 . 3H 2 O: group of PhCH 2 Cl: PPh 3 , wherein RhCl 3 by weight. 3H 2 O: PhCH 2 Cl: PPh 3 = 1:0.3-6.0: 4.0-44.

在仍然更佳的具體實例中，該二烯均聚物或共聚物具有的受控的Mn係從1,000至300,000，具有PDI係從1.0至5.0，較佳的是該受控的Mn係從3,000至 100,000，具有PDI係從1.1至4.0，更佳的是該受控的Mn係5,000至50,000，具有PDI係1.1至3.0，該二烯均聚物或共聚物中的ACN含量係從0至65 wt%，或該二烯共聚物中的苯乙烯含量係從0至80，較佳的是該二烯共聚物中的ACN含量係從10 wt%至63 wt%，或該二烯共聚物中的苯乙烯含量係從20 wt%至80 wt%，更佳的是，該二烯共聚物中的ACN含量係從30 wt%至60 wt%，或該二烯共聚物中的苯乙烯含量係從20 wt%至70 wt%，基於該二烯均聚物或共聚物的總重量。 In still still more preferred embodiments, the diene homopolymer or copolymer has a controlled Mn system from 1,000 to 300,000, and a PDI system from 1.0 to 5.0, preferably the controlled Mn system is from 3,000. to 100,000, having a PDI system from 1.1 to 4.0, more preferably the controlled Mn is from 5,000 to 50,000, having a PDI system of 1.1 to 3.0, and the ACN content in the diene homopolymer or copolymer is from 0 to 65 wt. %, or the styrene content in the diene copolymer is from 0 to 80, preferably the ACN content in the diene copolymer is from 10 wt% to 63 wt%, or in the diene copolymer The styrene content is from 20 wt% to 80 wt%, more preferably, the ACN content in the diene copolymer is from 30 wt% to 60 wt%, or the styrene content in the diene copolymer is from 20 wt% to 70 wt% based on the total weight of the diene homopolymer or copolymer.

在另外較佳的具體實例中，進行該聚合反應所使用該二烯的進料重量份係從約大於0至約小於100，並且該至少一種單體的進料重量份係從約小於100至約大於0。 In another preferred embodiment, the feed weight fraction of the diene used in the polymerization is from about greater than 0 to about less than 100, and the feed weight fraction of the at least one monomer is from less than about 100 to It is greater than 0.

特別地，進行該聚合反應所使用的α,β-不飽和腈單體的進料重量份係約4至約小於96，或該苯乙烯以及任何苯乙烯衍生物的進料重量百分比係從約小於96至約4，較佳的是該α,β-不飽和腈單體的進料重量份係約4至約小於90，或該苯乙烯以及任何苯乙烯衍生物的進料重量百分比係從約小於96至約10。 In particular, the feed weight fraction of the α,β-unsaturated nitrile monomer used in the polymerization is from about 4 to about less than 96, or the weight percent of the feed of the styrene and any styrene derivative is from about From less than 96 to about 4, preferably the feed weight fraction of the alpha, beta-unsaturated nitrile monomer is from about 4 to about less than 90, or the weight percent of the feed of the styrene and any styrene derivative is from It is less than about 96 to about 10.

更特別地，該聚合反應在10℃-160℃的溫度下進行了5-200小時，較佳的是在20℃-150℃的溫度下進行10-180小時，更佳的是在30℃-140℃的溫度下進行20-170小時，進一步較佳的是在40℃-140℃的溫度下進行10-150小時，仍然較佳的是在60℃-140℃ 的溫度下進行1-100小時，並且該二烯橡膠聚合物具有。 More specifically, the polymerization is carried out at a temperature of from 10 ° C to 160 ° C for from 5 to 200 hours, preferably from 20 ° C to 150 ° C for from 10 to 180 hours, more preferably at 30 ° C. It is carried out at a temperature of 140 ° C for 20 to 170 hours, further preferably at a temperature of 40 ° C to 140 ° C for 10 to 150 hours, still more preferably between 60 ° C and 140 ° C. The temperature is carried out for 1-100 hours, and the diene rubber polymer has.

在另外較佳的具體實例中，該溶液聚合方法進一步包括移除該含金屬的催化劑的步驟，較佳的是藉由使用如在EP 2 072 532 A1、EP 2 072 533 A1和CN101463096 A中描述的離子交換樹脂。較佳的是，在該共聚和/或氫化反應完成之後，將該反應混合物取出並且用離子交換樹脂在100℃下處理48小時並且然後在冷的甲醇中沉澱。 In a further preferred embodiment, the solution polymerization process further comprises the step of removing the metal-containing catalyst, preferably by using as described in EP 2 072 532 A1, EP 2 072 533 A1 and CN 101463096 A. Ion exchange resin. Preferably, after completion of the copolymerization and/or hydrogenation reaction, the reaction mixture is taken out and treated with an ion exchange resin at 100 ° C for 48 hours and then precipitated in cold methanol.

為了本申請案的目的，藉由溶液聚合的腈橡膠(NBR)係包含至少一種共軛的二烯、至少一種α,β-不飽和腈以及合適時一或多種可共聚單體的重複單元的共聚物或三元共聚物，並且其中併入聚合物中的二烯單元的C=C雙鍵已經被全部或某種程度上氫化。併入該聚合物中的二烯單元的氫化程度通常在從50%至100%的範圍內，較佳的是在從85%至100%的範圍內，並且特別佳的是在從95%至100%的範圍內。該共軛的二烯可以是任何類型的。較佳的是使用C4-C6共軛二烯。給予特別佳的是1,3-丁二烯、異戊二烯、2,3-二甲基丁二烯、1,3-戊二稀、或其混合物。給予特別佳的是1,3-丁二烯和異戊二烯或者其混合物。1,3-丁二烯係非常特別佳的。所使用的α,β-不飽和腈可以包含任何已知的α,β-不飽和腈，並且給予較佳的係C3-C5 α,β-不飽和腈，例如丙烯腈，甲基丙烯腈、乙基丙烯腈、或該等的混合物。丙烯腈係特別佳的。 For the purposes of this application, a solution polymerized nitrile rubber (NBR) comprises at least one conjugated diene, at least one alpha, beta-unsaturated nitrile and, as appropriate, repeating units of one or more copolymerizable monomers. Copolymer or terpolymer, and the C=C double bond of the diene unit incorporated into the polymer has been hydrogenated, in whole or in part. The degree of hydrogenation of the diene units incorporated into the polymer is generally in the range of from 50% to 100%, preferably in the range of from 85% to 100%, and particularly preferably from 95% to 100% range. The conjugated diene can be of any type. It is preferred to use a C4-C6 conjugated diene. Particularly preferred are 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentane dilute, or mixtures thereof. Particularly preferred are 1,3-butadiene and isoprene or mixtures thereof. The 1,3-butadiene system is very particularly good. The α,β-unsaturated nitrile used may comprise any known α,β-unsaturated nitrile, and a preferred C3-C5 α,β-unsaturated nitrile such as acrylonitrile, methacrylonitrile, Ethyl acrylonitrile, or a mixture of these. Acrylonitrile is particularly preferred.

特別佳的氫化的腈橡膠係由基於該等單體丙烯腈和1,3-丁二烯的氫化的共聚物而提供的。 A particularly preferred hydrogenated nitrile rubber is provided by a hydrogenated copolymer based on the monomers acrylonitrile and 1,3-butadiene.

與共軛的二烯和α,β-不飽和腈並行，還有可能使用熟習該項技術者已知的一或多種其他的單體，實例係α,β-不飽和單-或二羧酸、或者它們的酯或醯胺。這裡較佳的α,β-不飽和單羧酸或二羧酸係：丙烯酸、甲基丙烯酸、富馬酸、馬來酸、衣康酸。較佳所使用α,β-不飽和羧酸的酯係它們的烷基酯和烷氧基烷基酯。α,β-不飽和羧酸的特別佳的酯係丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸-2-乙基己酯、甲基丙烯酸-2-乙基己基酯、以及丙烯酸辛酯。 In parallel with the conjugated diene and the α,β-unsaturated nitrile, it is also possible to use one or more other monomers known to those skilled in the art, examples being α,β-unsaturated mono- or dicarboxylic acids. Or their esters or guanamines. Preferred α,β-unsaturated monocarboxylic or dicarboxylic acids are acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid. The esters of the α,β-unsaturated carboxylic acids preferably used are their alkyl esters and alkoxyalkyl esters. Particularly preferred esters of α,β-unsaturated carboxylic acids are methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate Ester, and octyl acrylate.

共軛的二烯與α,β-不飽和腈在待使用的HNBR聚合物中的比例可以寬泛地變化。基於總的聚合物，該共軛的二烯或該等共軛的二烯總體的比例通常在按重量計從40%至90%的範圍內，並且較佳的是在從55%至75%的範圍內。基於總的聚合物，該α,β-不飽和腈或該等α,β-不飽和腈總體的比例通常為按重量計從10%至60%，較佳的是為按重量計從25%至45%。該等單體的比例在各自的情況下給出了總和為以重量計100%。基於總的聚合物，該等另外單體能夠存在的量值係按重量計從0.1%至40%，較佳的是按重量計從1%至30%。在這種情況下，該或該等共軛的二烯的對應比例和該或該等α,β不飽和腈的對應比例分別由該等另外單體的比例來代替，並且這裡所有單體的比例在各自的情況下給出 了總和為按重量計100%。 The ratio of the conjugated diene to the α,β-unsaturated nitrile in the HNBR polymer to be used can vary widely. The proportion of the conjugated diene or the conjugated diene population is generally in the range of from 40% to 90% by weight, based on the total polymer, and preferably from 55% to 75%. In the range. The proportion of the α,β-unsaturated nitrile or the total α,β-unsaturated nitrile is generally from 10% to 60% by weight, based on the total polymer, preferably from 25% by weight. Up to 45%. The proportions of these monomers are given in each case as a total of 100% by weight. These additional monomers can be present in amounts ranging from 0.1% to 40% by weight, based on the total polymer, preferably from 1% to 30% by weight. In this case, the corresponding ratio of the or the conjugated diene and the corresponding proportion of the or the α,β unsaturated nitrile are respectively replaced by the ratio of the other monomers, and all of the monomers herein Proportions are given in their respective cases The sum is 100% by weight.

藉由聚合上述單體製備該等腈橡膠對於熟習該項技術者來說是眾所周知的並且廣泛描述在文獻中(Werner Hofmann,Nitrile Rubber[腈橡膠]，由美國化學會的橡膠化學分部出版，1964；CX Zhang、JS Huo等人，丙烯腈-丁二烯橡膠(主編：XH Cao、Synthetic Rubber Technology Series,Part 4[合成橡膠技術系列，第4部分])，由中國石化出版社出版，2010；C.S.Marvel,W.S.Anderson,Barbara H.Weil等人，Industrial and Engineering Chemistry[工業工程化學],1955,47(2),344-351；以及Harold P.Brown，Industrial and Engineering Chemistry[工業工程化學],1955,47(5),1006-1012)。 The preparation of such nitrile rubbers by polymerizing the above monomers is well known to those skilled in the art and is widely described in the literature (Werner Hofmann, Nitrile Rubber, published by the Chemical Chemistry Division of the American Chemical Society, 1964; CX Zhang, JS Huo et al., Acrylonitrile-butadiene rubber (Editor: XH Cao, Synthetic Rubber Technology Series, Part 4 [Synthetic Rubber Technology Series, Part 4]), published by China Petrochemical Press, 2010 ; CS Marvel, WS Anderson, Barbara H. Weil et al, Industrial and Engineering Chemistry, 1955, 47 (2), 344-351; and Harold P. Brown, Industrial and Engineering Chemistry [Industrial Engineering Chemistry] , 1955, 47 (5), 1006-1012).

以上描述的用於產生氫化的腈橡膠(A)的對該等腈橡膠的氫化作用能以熟習該項技術者已知的方式來進行。舉例而言，適當的方法係使用均相催化劑與氫氣反應，該催化劑例如被稱為“威爾金森(Wilkinson)”催化劑((PPh3)3RhCl)或其他。用於腈橡膠的氫化的方法係已知的。(參見，例如美國專利號3,700,637、DE-PS-2 539 132、EP-A-134 023、DE-A-35 41 689、DE-A-35 40 918、EP-A-298 386、DE-A-35 29 252、DE-A-34 33 392、美國專利號4,464,515以及美國專利號4,503,196)。 The hydrogenation of the nitrile rubbers described above for the production of hydrogenated nitrile rubber (A) can be carried out in a manner known to those skilled in the art. For example, a suitable method using a homogeneous catalyst system with hydrogen, the catalyst is for example called "Wilkinson (Wilkinson)" catalyst ((PPh 3) 3 RhCl) or other. Processes for the hydrogenation of nitrile rubber are known. (See, for example, U.S. Patent Nos. 3,700,637, DE-PS-2 539 132, EP-A-134 023, DE-A-35 41 689, DE-A-35 40 918, EP-A-298 386, DE-A -35 29 252, DE-A-34 33 392, U.S. Patent No. 4,464,515, and U.S. Patent No. 4,503,196.

用於均相氫化的適合的催化劑和溶劑在以下進行 描述並且亦在DE-A-25 39 132和EP-A-0 471 250中揭露。 Suitable catalysts and solvents for homogeneous hydrogenation are carried out in the following It is also described in DE-A-25 39 132 and EP-A-0 471 250.

可以例如在用於二烯的溶液聚合法和/或用於氫化含二烯的聚合物的含銠的催化劑的(含金屬的催化劑體系)的存在下來實現選擇性的氫化，該催化劑體系包括(1)含金屬的催化劑，(2)助催化劑，以及任選地(3)添加劑，其中該含金屬的催化劑係選自MLnXm、MXm、MXm．pH2O、M(OC(O)R)m、或其任何組合，其中M代表一選自Rh、Pd、Ru、Ir、Mo、Co、Cu、Fe、或Ti的金屬，L係選自的基團，其中R1、R2、和R3可以是相同或不同的，並且R1、R2、和R3各自獨立地選自H、C1-C6烷基、C5-C7芳基或C3-C6環烷基、經取代的C3-C6環烷基、經取代的C5-C7芳基，其條件係R1、R2、和R3不全為H，X係鹵素，n係1至5的整數，p係1至7的整數，並且m係等於M的化合價；該添加劑係選自以下各項所組成之群組：一級胺(R1-NH2)、二級胺(R1-NH-R2)、三級胺(N(R1)(R2)(R3))、、抗壞血酸、或銨鹽、或其任何組合，其中R1、R2、和R3如以上定義。 Selective hydrogenation can be achieved, for example, in the presence of a solution polymerization process for a diene and/or a metal-containing catalyst system for hydrogenating a diene-containing polymer, the catalyst system comprising 1) a metal-containing catalyst, (2) a cocatalyst, and optionally (3) an additive, wherein the metal-containing catalyst is selected from the group consisting of ML n X m , MX m , MX m . pH 2 O, M(OC(O)R) m , or any combination thereof, wherein M represents a metal selected from the group consisting of Rh, Pd, Ru, Ir, Mo, Co, Cu, Fe, or Ti, and the L is selected from the group consisting of a group wherein R 1 , R 2 , and R 3 may be the same or different, and R 1 , R 2 , and R 3 are each independently selected from H, C 1 -C 6 alkyl, C 5 -C a 7 aryl or C 3 -C 6 cycloalkyl group, a substituted C 3 -C 6 cycloalkyl group, a substituted C 5 -C 7 aryl group, the conditions of which are not all of R 1 , R 2 , and R 3 are H, X is a halogen, n is an integer from 1 to 5, p is an integer from 1 to 7, and m is equal to the valence of M; the additive is selected from the group consisting of a primary amine (R 1 - NH 2 ), a secondary amine (R 1 -NH-R 2 ), a tertiary amine (N(R 1 )(R 2 )(R 3 )), , ascorbic acid, or an ammonium salt, or any combination thereof, wherein R 1 , R 2 , and R 3 are as defined above.

較佳的催化劑係氯化參(三苯基膦)銠(I)、氯化參(三苯基膦)銠(III)、以及氯化參(二甲基亞碸)銠(III)、以及 還有氫化肆(三苯基膦)銠以及相應的化合物，其中該三苯基膦已被三環己基膦完全或在某一程度上取代了。可以使用小量的催化劑。適合的量基於該聚合物的重量係在按重量計從0.01%至1%的範圍內、較佳的是在按重量計從0.03%至0.5%的範圍內、並且特別佳的是在按重量計從0.1%至0.3%的範圍內。 Preferred catalysts are chlorinated ginseng (triphenylphosphine) ruthenium (I), chlorinated ginseng (triphenylphosphine) ruthenium (III), and chlorinated ginseng (dimethyl fluorene) ruthenium (III), and There is also hydrazine hydride (triphenylphosphine) ruthenium and the corresponding compound, wherein the triphenylphosphine has been completely or to some extent substituted by tricyclohexylphosphine. A small amount of catalyst can be used. A suitable amount is in the range of from 0.01% to 1% by weight, preferably from 0.03% to 0.5% by weight, based on the weight of the polymer, and particularly preferably by weight. It ranges from 0.1% to 0.3%.

通常將催化劑連同助催化劑一起使用是可行的。適當的助催化劑作為舉例在美國專利號4,631,315中找到。三苯膦為較佳的助催化劑。基於待氫化的腈橡膠的重量，助催化劑所使用的量值較佳的是以按重量計從0.3%至5%，較佳的是在按重量計從0.5%至4%的範圍內。更佳的是，含銠的催化劑與助催化劑的重量比在從1：3至1：55的範圍內，較佳的是在從1：5至1：45的範圍內。基於100重量份的待氫化的腈橡膠，適合的方法使用了從0.1至33重量份的助催化劑，較佳的是從0.5至20重量份，並且非常特別佳的是從1至5重量份，特別是大於2重量份但是小於5重量份的助催化劑。 It is generally feasible to use the catalyst together with a cocatalyst. Suitable cocatalysts are found by way of example in U.S. Patent No. 4,631,315. Triphenylphosphine is a preferred cocatalyst. The amount of the cocatalyst used is preferably from 0.3% by weight to 5% by weight, based on the weight of the nitrile rubber to be hydrogenated, preferably from 0.5% to 4% by weight. More preferably, the weight ratio of the rhodium-containing catalyst to the cocatalyst is in the range of from 1:3 to 1:55, preferably in the range of from 1:5 to 1:45. A suitable method uses from 0.1 to 33 parts by weight of a cocatalyst, preferably from 0.5 to 20 parts by weight, and very particularly preferably from 1 to 5 parts by weight, based on 100 parts by weight of the nitrile rubber to be hydrogenated. In particular more than 2 parts by weight but less than 5 parts by weight of cocatalyst.

熟習該項技術者從美國專利號6,683,136所熟知用於這種氫化的實際方法。在通常的方法中，將該待氫化的腈橡膠用氫在溶劑(如甲苯或一氯苯)中、在從100℃至150℃範圍內的溫度下以及從700至2,500 Psi的範圍壓力下處理從2至10小時。 A practical method for such hydrogenation is well known to those skilled in the art from U.S. Patent No. 6,683,136. In a usual method, the nitrile rubber to be hydrogenated is treated with hydrogen in a solvent such as toluene or monochlorobenzene at a temperature ranging from 100 ° C to 150 ° C and at a pressure ranging from 700 to 2,500 Psi. From 2 to 10 hours.

為了本發明的目的，氫化係起始腈橡膠中存在的 C=C雙鍵的反應，這種基於在該起始腈橡膠中存在的雙鍵的反應程度通常是至少50%、較佳的是70%、並且特別佳的是至少85%。 For the purposes of the present invention, hydrogenated starting nitrile rubber is present The reaction of the C=C double bond, which is usually at least 50%, preferably 70%, and particularly preferably at least 85%, based on the double bond present in the starting nitrile rubber.

在第三具體實例中，本發明提供了藉由溶液聚合反應獲得的二烯聚合物，包含在從40至85重量份範圍內的衍生自一或多種二烯的重複單元，在從0至70重量份範圍內的衍生自一或多種α,β-不飽和腈或苯乙烯或任何苯乙烯衍生物的重複單元，以及在從0至40重量份範圍內的衍生自任選的除α,β-不飽和腈或苯乙烯以及任何苯乙烯衍生物之外的三單體的重複單元。 In a third embodiment, the present invention provides a diene polymer obtained by solution polymerization comprising repeating units derived from one or more dienes in a range from 40 to 85 parts by weight, from 0 to 70 Repeating units derived from one or more α,β-unsaturated nitriles or styrene or any styrene derivative in parts by weight, and from the range of from 0 to 40 parts by weight derived from optional α,β - a repeating unit of a tri-monomer other than an unsaturated nitrile or styrene and any styrene derivative.

在第四具體實例中，本發明提供了藉由本發明的溶液聚合法獲得的二烯聚合物在氫氣的以及基於Rh、Ru、和/或Pd的催化劑的存在下在氫化作用中獲得氫化的二烯烴聚合物的用途。 In a fourth embodiment, the present invention provides a diene polymer obtained by the solution polymerization method of the present invention, which is hydrogenated in the presence of hydrogen and a Rh, Ru, and/or Pd-based catalyst. Use of olefin polymers.

在一較佳的具體實例中，該基於Rh、Ru、和/或Pd的含金屬的催化劑係選自金屬Rh、Ru或Pd，或在本發明的Rh、Ru、或Pd的含金屬的催化劑和PPh3。 In a preferred embodiment, the Rh, Ru, and/or Pd-containing metal-containing catalyst is selected from the group consisting of metals Rh, Ru, or Pd, or a metal-containing catalyst of Rh, Ru, or Pd of the present invention. And PPh 3 .

在第五具體實例中，本發明提供了用於合成氫化的二烯聚合物的一鍋法，包括在本發明溶液聚合完成之後直接將氫氣引入反應器中並且在所望的溫度下進行反應。 In a fifth specific embodiment, the present invention provides a one-pot process for the synthesis of hydrogenated diene polymers, including direct introduction of hydrogen into the reactor after completion of solution polymerization of the present invention and reaction at a desired temperature.

在一較佳的是具體實例中，該所希望的溫度係從60℃至200℃並且該氫化反應在100至3000 Psi的氫氣壓力下進行10分鐘至20小時，較佳的是該所希望的 溫度係從80℃至180℃並且該反應在200至2000 Psi的氫氣壓力下進行10分鐘至10小時，更佳的是該所希望的溫度係從100℃至160℃並且該反應在300-1500 Psi的氫氣壓力下進行30分鐘至5小時，進一步較佳的是該所希望的溫度係從120℃至150℃並且該反應在500至1000 Psi的氫氣壓力下進行30分鐘至3小時。 In a preferred embodiment, the desired temperature is from 60 ° C to 200 ° C and the hydrogenation reaction is carried out at a hydrogen pressure of from 100 to 3000 Psi for 10 minutes to 20 hours, preferably the desired The temperature is from 80 ° C to 180 ° C and the reaction is carried out at a hydrogen pressure of 200 to 2000 Psi for 10 minutes to 10 hours, more preferably the desired temperature is from 100 ° C to 160 ° C and the reaction is between 300 and 1500. The Psi is subjected to hydrogen pressure for 30 minutes to 5 hours, and it is further preferred that the desired temperature is from 120 ° C to 150 ° C and the reaction is carried out at a hydrogen pressure of 500 to 1000 Psi for 30 minutes to 3 hours.

在一更佳的具體實例中，該用於合成氫化的二烯聚合物的一鍋法進一步包括移除該含金屬的催化劑的步驟，較佳的是藉由使用如在EP 2 072 532 A1、EP 2 072 533 A1和CN101463096 A中描述的離子交換樹脂。較佳的是，該共聚和/或氫化反應完成之後，將該反應混合物取出並且用離子交換樹脂在100℃下處理48小時並且然後在冷的甲醇中沉澱。 In a more preferred embodiment, the one-pot process for synthesizing a hydrogenated diene polymer further comprises the step of removing the metal-containing catalyst, preferably by using as in EP 2 072 532 A1. The ion exchange resins described in EP 2 072 533 A1 and CN101463096 A. Preferably, after completion of the copolymerization and/or hydrogenation reaction, the reaction mixture is taken out and treated with an ion exchange resin at 100 ° C for 48 hours and then precipitated in cold methanol.

在第六具體實例中，本發明提供了藉由用於合成本發明的氫化的二烯聚合物的一鍋法所獲得的氫化的二烯聚合物。 In a sixth embodiment, the present invention provides a hydrogenated diene polymer obtained by a one-pot process for synthesizing the hydrogenated diene polymer of the present invention.

在第七具體實例中，本發明提供了用於二烯聚合物的氫化的方法，包括：a)在本發明的含金屬的催化劑體系的存在下在至少一種有機溶劑中將二烯烴進行溶液均聚或二烯烴連同至少一種共聚單體進行共聚以獲得二烯橡膠，b)在該溶液聚合完成之後直接將氫氣引入到步驟a)的混合物中，以獲得氫化的含二烯的聚合物。 In a seventh embodiment, the invention provides a process for the hydrogenation of a diene polymer comprising: a) subjecting a diolefin to a solution in at least one organic solvent in the presence of a metal-containing catalyst system of the invention The poly or diolefin is copolymerized together with at least one comonomer to obtain a diene rubber, and b) hydrogen is introduced directly into the mixture of step a) after completion of the polymerization of the solution to obtain a hydrogenated diene-containing polymer.

在一較佳的具體實例中，該二烯係選自任何已知的 二烯，較佳的是選自至少一種共軛的二烯以及至少一種非共軛的二烯，更佳的是一種C4-C6共軛二烯，包括1,3-丁二烯、異戊二烯、2,3-二甲基丁二烯、1,3-戊二烯或其混合物，或C4-C6非共軛二烯，包括1,2-丁二烯，並且最佳的是1,3-丁二烯、異戊二烯或其混合物；該至少一種有機溶劑選自任何不與該催化劑反應或以其他方式干擾該反應的有機溶劑，較佳的是選自：苯、甲苯、環己烷、二甲亞碸(DMSO)、碳酸乙烯酯(EC)、四氫呋喃(THF)、1,4-二烷、一氯苯(MCB)、二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAC)、或其混合物，更佳的是選自：一氯苯(MCB)、一溴苯(MBB)、二氯苯(DCB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)，進一步較佳的是選自一氯苯(MCB)和甲基乙基酮(MEK)，最佳的是一氯苯(MCB)。 In a preferred embodiment, the diene is selected from any known diene, preferably selected from at least one conjugated diene and at least one non-conjugated diene, more preferably a a C 4 -C 6 conjugated diene comprising 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene or a mixture thereof, or C 4 - a C 6 non-conjugated diene, including 1,2-butadiene, and most preferably 1,3-butadiene, isoprene or a mixture thereof; the at least one organic solvent is selected from any catalyst An organic solvent which reacts or otherwise interferes with the reaction, preferably selected from the group consisting of benzene, toluene, cyclohexane, dimethyl hydrazine (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1, 4 -two Alkane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone ( MEK), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), or a mixture thereof, more preferably selected from the group consisting of: monochlorobenzene (MCB), Bromobenzene (MBB), dichlorobenzene (DCB), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC) Further preferably, it is selected from the group consisting of monochlorobenzene (MCB) and methyl ethyl ketone (MEK), and most preferred is monochlorobenzene (MCB).

在一更佳的具體實例中，用於二烯聚合物的氫化的方法進一步包括移除該含金屬的催化劑的步驟，較佳的是藉由使用離子交換樹脂。該氫化反應完成之後，將該反應混合物取出並且用離子交換樹脂在100℃下處理48小時並且然後在冷的甲醇中沉澱。 In a more preferred embodiment, the method for hydrogenating a diene polymer further comprises the step of removing the metal-containing catalyst, preferably by using an ion exchange resin. After the hydrogenation reaction was completed, the reaction mixture was taken out and treated with an ion exchange resin at 100 ° C for 48 hours and then precipitated in cold methanol.

在第八具體實例中，本發明提供了一用於二烯聚合物的氫化的方法，包括： a)將至少一種二烯聚合物溶解在高壓釜反應器中的至少一種有機溶劑中，b)將本發明的至少一種含金屬的催化劑體系加入在步驟a)中獲得的溶液中，c)將氫氣引入到該高壓釜反應器中並且將該高壓釜反應器加熱到高達預定的溫度持續預定的時間。 In an eighth embodiment, the invention provides a method for the hydrogenation of a diene polymer comprising: a) dissolving at least one diene polymer in at least one organic solvent in the autoclave reactor, b) adding at least one metal-containing catalyst system of the invention to the solution obtained in step a), c) Hydrogen is introduced into the autoclave reactor and the autoclave reactor is heated to a predetermined temperature for a predetermined period of time.

在一較佳的具體實例中，該至少一種二烯聚合物係選自BR、NBR、SBR中的一或多種，較佳的是藉由溶液聚合獲得的BR NBR、SBR中的一或多種，並且該二烯聚合物中的ACN含量係從0至65 wt%，或該二烯共聚物中的苯乙烯含量係從0至80，較佳的是該二烯聚合物中的ACN含量係從10 wt%至63 wt%，或該二烯聚合物中的苯乙烯含量係從20 wt%至80 wt%，更佳的是，該二烯聚合物中的ACN含量係從30 wt%至60 wt%，或該二烯聚合物中的苯乙烯含量係從20 wt%至70 wt%，基於該二烯聚合物的總重量。 In a preferred embodiment, the at least one diene polymer is selected from one or more of BR, NBR, and SBR, preferably one or more of BR NBR and SBR obtained by solution polymerization. And the ACN content in the diene polymer is from 0 to 65 wt%, or the styrene content in the diene copolymer is from 0 to 80, preferably the ACN content in the diene polymer is from 10 wt% to 63 wt%, or the styrene content in the diene polymer is from 20 wt% to 80 wt%, and more preferably, the ACN content in the diene polymer is from 30 wt% to 60 wt% The wt%, or the styrene content in the diene polymer is from 20 wt% to 70 wt%, based on the total weight of the diene polymer.

至少一種含金屬的催化劑體系的量基於100重量份的該至少一種二烯聚合物係從0.000001至50重量份，較佳的是從0.00001至20重量份，更佳的是從0.0001至10重量份；該至少一種有機溶劑選自任何不與該催化劑反應或以其他方式干擾該反應的有機溶劑，較佳的是選自：苯、甲苯、環己烷、二甲亞碸(DMSO)、碳酸乙烯酯(EC)、四氫呋喃(THF)、1,4-二烷、一氯苯(MCB)、 二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAC)、或其混合物、更佳的是選自：一氯苯(MCB)、一溴苯(MBB)、二氯苯(DCB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)，進一步較佳的是選自一氯苯(MCB)和甲基乙基酮(MEK)，最佳的是一氯苯(MCB)。 The amount of the at least one metal-containing catalyst system is from 0.000001 to 50 parts by weight, preferably from 0.00001 to 20 parts by weight, more preferably from 0.0001 to 10 parts by weight, based on 100 parts by weight of the at least one diene polymer. The at least one organic solvent is selected from any organic solvent that does not react with or otherwise interfere with the reaction, and is preferably selected from the group consisting of benzene, toluene, cyclohexane, dimethyl hydrazine (DMSO), ethylene carbonate. Ester (EC), tetrahydrofuran (THF), 1,4-two Alkane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone ( MEK), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), or a mixture thereof, more preferably selected from the group consisting of: monochlorobenzene (MCB), Bromobenzene (MBB), dichlorobenzene (DCB), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC) Further preferably, it is selected from the group consisting of monochlorobenzene (MCB) and methyl ethyl ketone (MEK), and most preferred is monochlorobenzene (MCB).

該預定的溫度係從80℃至180℃並且該預定的時間係在200-2000 Psi的氫氣壓力下從10分鐘至10小時，更佳的是，該預定的溫度係從100℃至160℃並且該預定的時間係在300-1500 Psi的氫氣壓力下從30分鐘至5小時，進一步較佳的是該預定的溫度係從120℃至150℃並且該預定的時間係在500-1000 Psi的氫氣壓力下從30分鐘至3小時。 The predetermined temperature is from 80 ° C to 180 ° C and the predetermined time is from 10 minutes to 10 hours under a hydrogen pressure of 200 to 2000 Psi, and more preferably, the predetermined temperature is from 100 ° C to 160 ° C and The predetermined time is from 30 minutes to 5 hours under a hydrogen pressure of 300 to 1500 Psi, and it is further preferred that the predetermined temperature is from 120 ° C to 150 ° C and the predetermined time is between 500 and 1000 Psi of hydrogen. From 30 minutes to 3 hours under pressure.

該二烯聚合物具有的受控的Mn係從1,000至300,000，具有PDI係從1.0至5.0，較佳的是該受控的Mn係從3,000至100,000，具有PDI係從1.1至4.0，更佳的是該受控的Mn係5,000至50,000，具有PDI係1.1至3.0。 The diene polymer has a controlled Mn system of from 1,000 to 300,000, a PDI system of from 1.0 to 5.0, preferably a controlled Mn of from 3,000 to 100,000, and a PDI of from 1.1 to 4.0, more preferably. The controlled Mn is 5,000 to 50,000 and has a PDI of 1.1 to 3.0.

在一更佳的是具體實例中，進一步包括d)移除該含金屬的催化劑，較佳的是藉由使用離子交換樹脂。該含金屬的催化劑可以如在EP 2 072 532 A1、EP 2 072 533 A1、和CN101463096 A中描述的移除。 In a more preferred embodiment, further comprising d) removing the metal-containing catalyst, preferably by using an ion exchange resin. The metal-containing catalyst can be removed as described in EP 2 072 532 A1, EP 2 072 533 A1, and CN101463096 A.

在第九具體實例中，本發明提供了用於二烯聚合物的氫化的方法，包括a)加入本發明的溶液聚合法中獲得的二烯均聚反應或二烯共聚反應，以及任選地至少一種有機溶劑，b)將氫氣直接引入步驟a)的混合物中並且加熱到預定的溫度以獲得該氫化的含二烯的聚合物，其中該至少一種有機溶劑係選自任何不與該催化劑反應或以其他方式干擾該反應的有機溶劑，較佳的是選自：苯、甲苯、環己烷、二甲亞碸(DMSO)、碳酸乙烯酯(EC)、四氫呋喃(THF)、1,4-二烷、一氯苯(MCB)、二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAC)、或其混合物、更佳的是選自一氯苯(MCB)、一溴苯(MBB)、二氯苯(DCB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)，進一步較佳的是選自一氯苯(MCB)和甲基乙基酮(MEK)，最佳的是一氯苯(MCB)。 In a ninth embodiment, the invention provides a process for the hydrogenation of a diene polymer comprising a) addition of a diene homopolymerization reaction or a diene copolymerization reaction obtained in the solution polymerization process of the invention, and optionally At least one organic solvent, b) introducing hydrogen directly into the mixture of step a) and heating to a predetermined temperature to obtain the hydrogenated diene-containing polymer, wherein the at least one organic solvent is selected from any reaction that does not react with the catalyst Or an organic solvent which interferes with the reaction in other manners, preferably selected from the group consisting of benzene, toluene, cyclohexane, dimethyl hydrazine (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4- two Alkane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone ( MEK), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), or a mixture thereof, more preferably selected from monochlorobenzene (MCB), monobromo Benzene (MBB), dichlorobenzene (DCB), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC), Further preferably, it is selected from the group consisting of monochlorobenzene (MCB) and methyl ethyl ketone (MEK), and most preferred is monochlorobenzene (MCB).

在第十具體實例中，本發明提供了氫化的二烯橡膠，它係藉由用於合成本發明的氫化的含二烯的聚合物的一鍋法而獲得的。 In a tenth embodiment, the present invention provides a hydrogenated diene rubber obtained by a one-pot process for synthesizing the hydrogenated die-containing polymer of the present invention.

在第十一具體實例中，本發明提供了本發明的催化劑體系在製造二烯聚合物的用途。 In an eleventh embodiment, the invention provides the use of the catalyst system of the invention in the manufacture of a diene polymer.

在第十二具體實例中，本發明提供了本發明的催化劑體系在製造氫化的含二烯的聚合物的用途。 In a twelfth embodiment, the invention provides the use of a catalyst system of the invention in the manufacture of a hydrogenated die-containing polymer.

在第十三具體實例中，本發明提供了玻璃管反應器和/或高壓釜在本發明的溶液聚合法或本發明的用於合成氫化的二烯聚合物的一鍋法中的用途。 In a thirteenth embodiment, the invention provides the use of a glass tube reactor and/or autoclave in the solution polymerization process of the invention or the one-pot process of the invention for synthesizing hydrogenated diene polymers.

在第十四具體實例中，本發明提供了玻璃管反應器和/或高壓釜在本發明的用於合成氫化的二烯聚合物方法中的用途。 In a fourteenth embodiment, the invention provides the use of a glass tube reactor and/or autoclave in the process for the synthesis of hydrogenated diene polymers of the invention.

在本發明的方法中用作起始材料的溶液聚合的腈橡膠通常具有的重均分子量Mw係在從200,000至1,000,000範圍內，較佳的是在從200 000至400 000的範圍內並且特別佳的是在從200,000至300,000的範圍內。此外，它們具有多分散性指數D=Mw/Mn，其中Mw係重均分子量並且Mn係數均分子量，該多分散性指數在從1.1至6.0範圍內、較佳的是在從1.1至5.0的範圍內，並且特別係在從1.1至4.0的範圍內，更佳的是在從1.1至3.0的範圍內，仍然更佳的是在從1.1至2.0的範圍內。 The solution-polymerized nitrile rubber used as a starting material in the process of the present invention usually has a weight average molecular weight Mw in the range of from 200,000 to 1,000,000, preferably in the range of from 200,000 to 400,000 and particularly preferably It is in the range from 200,000 to 300,000. Further, they have a polydispersity index D = Mw / Mn, wherein Mw is a weight average molecular weight and a Mn coefficient average molecular weight, and the polydispersity index is in the range of from 1.1 to 6.0, preferably from 1.1 to 5.0. Within, and particularly in the range from 1.1 to 4.0, more preferably in the range from 1.1 to 3.0, still more preferably in the range from 1.1 to 2.0.

在分批法(即，分批流程)的情況下，操作係在攪拌的或非攪拌的反應器中進行的。 In the case of a batch process (i.e., a batch process), the operation is carried out in a stirred or non-stirred reactor.

本發明的溶液聚合法和/或氫化法可以在任何不與該催化劑發生反應或以其他方式干擾反應的適當的溶劑中進行。所使用的溶劑可以包括任何適合於HNBR的溶劑，例子係：苯、甲苯、環己烷、二甲亞碸(DMSO)、碳酸乙烯酯(EC)、四氫呋喃(THF)、1,4-二烷、一氯苯(MCB)、二氯苯(DCB)、三氯苯(TCB)、一溴苯 (MBB)、二溴苯(DBB)、三溴苯(TBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)、以及其混合物。一氯苯(MBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)係較佳的。一氯苯(MCB)和甲基乙基酮(MEK)、N,N-二甲基乙醯胺(DMAC)係更佳的。 The solution polymerization and/or hydrogenation process of the present invention can be carried out in any suitable solvent which does not react with or otherwise interfere with the reaction. The solvent used may include any solvent suitable for HNBR, examples being: benzene, toluene, cyclohexane, dimethyl hydrazine (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4-two Alkane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone ( MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC), and mixtures thereof. Monochlorobenzene (MBB), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC) is preferred. Monochlorobenzene (MCB) and methyl ethyl ketone (MEK) and N,N-dimethylacetamide (DMAC) are more preferred.

本發明的方法通常是在從10℃至200℃範圍內的溫度下進行的。已經發現了更高的溫度對於該聚合反應和/或氫化反應具有有利的作用。本發明的方法因此較佳的是在從20℃到160℃的範圍內的溫度下進行，更佳的是在從60℃到150℃的範圍內的溫度下進行。 The process of the invention is generally carried out at temperatures ranging from 10 ° C to 200 ° C. Higher temperatures have been found to have a beneficial effect on the polymerization and/or hydrogenation reaction. The process of the present invention is therefore preferably carried out at a temperature ranging from 20 ° C to 160 ° C, more preferably at a temperature ranging from 60 ° C to 150 ° C.

本發明的溶液聚合法通常在單體和有機溶劑的自然壓力下，在從10至100 Psi的範圍內，較佳的是在從15至75 Psi的範圍內進行。在本發明中，氫化過程通常是在100-3000 Psi的氫氣壓力下進行10分鐘至20小時，較佳的是所希望的溫度係從80℃至180℃並且該反應在200-2000 Psi的氫氣壓力下進行10分鐘至10小時，更佳的是該所希望的溫度係從100℃至160℃並且該反應在300-1500 Psi的氫氣壓力下進行30分鐘至5小時，進一步較佳的是該所希望的溫度係從120℃至150℃並且該反應在500-1000 Psi的氫氣壓力下進行30分鐘至3小時。 The solution polymerization method of the present invention is usually carried out at a natural pressure of a monomer and an organic solvent in the range of from 10 to 100 Psi, preferably from 15 to 75 Psi. In the present invention, the hydrogenation process is usually carried out under a hydrogen pressure of 100 to 3000 Psi for 10 minutes to 20 hours, preferably at a desired temperature of from 80 ° C to 180 ° C and the reaction is carried out at 200-2000 Psi of hydrogen. The pressure is carried out for 10 minutes to 10 hours, more preferably, the desired temperature is from 100 ° C to 160 ° C and the reaction is carried out at a hydrogen pressure of 300 to 1500 Psi for 30 minutes to 5 hours, further preferably The desired temperature is from 120 ° C to 150 ° C and the reaction is carried out at a hydrogen pressure of 500-1000 Psi for 30 minutes to 3 hours.

本發明的方法中獲得的該溶液聚合的橡膠以及氫化的腈橡膠的特徵係特別窄的分子量分佈以及對應地 低多分散性指數值。具有這種特性曲線的溶液聚合的橡膠以及氫化的腈橡膠迄今為止是未知的並且不可獲得的。 The solution-polymerized rubber and the hydrogenated nitrile rubber obtained in the process of the invention are characterized by a particularly narrow molecular weight distribution and correspondingly Low polydispersity index value. Solution polymerized rubbers having such a characteristic curve and hydrogenated nitrile rubber are hitherto unknown and not available.

因此，本發明提供了溶液聚合橡膠以及氫化的腈橡膠，該等橡膠具有小於或等於2，較佳的是小於2，特別佳的是小於1.9並且非常特別佳的是小於1.7的多分散性指數。具體地，該多分散性指數係大於1並且小於2.0，並且較佳的是大於1並且小於1.9。 Accordingly, the present invention provides solution polymerized rubbers and hydrogenated nitrile rubbers having a polydispersity index of less than or equal to 2, preferably less than 2, particularly preferably less than 1.9 and very particularly preferably less than 1.7. . Specifically, the polydispersity index is greater than 1 and less than 2.0, and is preferably greater than 1 and less than 1.9.

在本發明的方法中獲得的溶液聚合橡膠以及氫化的腈橡膠具有的重均分子量Mw係在從30,000至250,000範圍內，較佳的是在從30,000至150,000的範圍內並且特別佳的是在從30,000至100,000的範圍內。 The solution polymerized rubber obtained in the process of the present invention and the hydrogenated nitrile rubber have a weight average molecular weight Mw in the range of from 30,000 to 250,000, preferably in the range of from 30,000 to 150,000 and particularly preferably in the range of from 30,000 to 100,000.

在本發明的方法中獲得的溶液聚合橡膠和/或氫化的腈橡膠的慕尼粘度(ML 1+4 @ 100℃.)係在從大於0至50的範圍內，較佳的是在從1至40的範圍內，更佳的是在從10至40的範圍內。慕尼粘度於此是根據ASTM標準D1646確定的。 The Mooney viscosity (ML 1+4 @ 100 ° C.) of the solution-polymerized rubber and/or the hydrogenated nitrile rubber obtained in the process of the present invention is in the range of from more than 0 to 50, preferably from 1 In the range of up to 40, it is more preferably in the range of from 10 to 40. The Mooney viscosity is hereby determined according to ASTM Standard D1646.

本發明的具有低分子量以及窄分子量分佈的溶液聚合橡膠和/或氫化的腈橡膠具有非常好的可加工性。 The solution-polymerized rubber and/or hydrogenated nitrile rubber of the present invention having a low molecular weight and a narrow molecular weight distribution have very good workability.

該含金屬的催化劑可以在該聚合反應和/或氫化反應完成之後使用離子交換樹脂如在EP 2 072 532 A1、EP 2 072 533 A1、和CN101463096 A中描述的移除。 The metal-containing catalyst can be removed after the completion of the polymerization and/or hydrogenation reaction using an ion exchange resin as described in EP 2 072 532 A1, EP 2 072 533 A1, and CN101463096 A.

在該氫化的反應混合物中單體的濃度不是關鍵性的，但是應使得在如果該混合物太粘稠而不能在反應過程中有效地進行攪拌時也不會妨礙該反應。 The concentration of the monomer in the hydrogenated reaction mixture is not critical, but should be such that the reaction is not hindered if the mixture is too viscous to be effectively stirred during the reaction.

本發明藉由以下實施例進一步進行展示但不用於限制，其中除非另有具體指明，所有份數和百分數都是按重量計的。 The invention is further illustrated by the following examples, which are not intended to be limiting, and all parts and percentages are by weight unless otherwise specified.

實施例Example

以下實施例與以下示出的實驗條件展示了本發明的範圍而無意對其進行限制。 The following examples and experimental conditions shown below demonstrate the scope of the invention and are not intended to be limiting.

所有的聚合反應在氮氣中進行。1,3-丁二烯藉由從壓力瓶蒸餾到玻璃瓶中進行純化。將苯乙烯和苯乙烯衍生物，例如α-甲基苯乙烯、乙烯基甲苯和丙烯腈穿過活性氧化鋁柱以在使用之前除去該穩定劑。將三苯膦(PPh3)從乙醇中再結晶。其他化學物按接收時使用。 All polymerizations were carried out in nitrogen. The 1,3-butadiene was purified by distillation from a pressure bottle into a glass bottle. Styrene and styrene derivatives, such as alpha-methyl styrene, vinyl toluene, and acrylonitrile, are passed through an activated alumina column to remove the stabilizer prior to use. Triphenylphosphine (PPh 3 ) was recrystallized from ethanol. Other chemicals are used as received.

將含條形磁鐵並且用硬質橡膠停止件蓋帽的玻璃管在分別加入所要求量的溶劑、單體以及催化劑體系之前藉由重複的真空氮氣循環吹掃掉空氣。所有該等液體在氮氣下引入。將該等玻璃管在恒溫油浴中在所希望的溫度下加熱並且在反應過程中緩慢保持磁力攪拌。在所要求的反應時間之後，將樣品從該管中撤出。反應完成之後，將該管打開，並且將該等反應混合物取出並且然後在冷的甲醇中沉澱出。將該聚合物過濾掉並且在60℃下在真空中乾燥24小時。反應壓力係單體在反應溫度下的蒸汽壓力。在該等試驗中所使用的最高溫度出於安全的原因限制到80℃。 A glass tube containing a strip magnet and capped with a hard rubber stopper was purged of air by a repeated vacuum nitrogen cycle before separately adding the required amount of solvent, monomer, and catalyst system. All of these liquids were introduced under nitrogen. The glass tubes were heated in a constant temperature oil bath at the desired temperature and slowly maintained magnetically agitated during the reaction. After the required reaction time, the sample was withdrawn from the tube. After the reaction was completed, the tube was opened, and the reaction mixtures were taken out and then precipitated in cold methanol. The polymer was filtered off and dried in vacuo at 60 ° C for 24 hours. The reaction pressure is the vapor pressure of the monomer at the reaction temperature. The maximum temperature used in these tests was limited to 80 °C for safety reasons.

該含金屬的催化劑可以在該聚合反應和/或氫化反應完成之後使用離子交換樹脂如在EP 2 072 532 A1、EP 2 072 533 A1、CN101463096 A中描述的進行移除。 The metal-containing catalyst can be removed after the completion of the polymerization and/or hydrogenation reaction using an ion exchange resin as described in EP 2 072 532 A1, EP 2 072 533 A1, CN 101463096 A.

使用Parr高壓釜反應器用於以更大的規模並且在更高的溫度下進行共聚反應試驗和/或氫化試驗。在所要求的反應時間之後，將該等樣品從該反應器中撤出。該共聚和/或氫化反應完成之後，將該反應器打開，並且將該反應混合物取出並且用離子交換樹脂在100℃下處理48小時並且然後在冷的甲醇中沉澱。將該聚合物過濾掉並且在60℃下在真空中乾燥24小時。該反應壓力係在反應溫度下的單體或氫氣的蒸汽壓力。在該等試驗中所使用的溫度可以是在10℃至200℃，並且通常在室溫至160℃，即，氫化溫度。 A Parr autoclave reactor was used to carry out the copolymerization test and/or the hydrogenation test on a larger scale and at a higher temperature. The samples were withdrawn from the reactor after the required reaction time. After completion of the copolymerization and/or hydrogenation reaction, the reactor was opened, and the reaction mixture was taken out and treated with an ion exchange resin at 100 ° C for 48 hours and then precipitated in cold methanol. The polymer was filtered off and dried in vacuo at 60 ° C for 24 hours. The reaction pressure is the vapor pressure of the monomer or hydrogen at the reaction temperature. The temperature used in such tests may be from 10 ° C to 200 ° C, and usually from room temperature to 160 ° C, ie, the hydrogenation temperature.

該含金屬的催化劑可以在該聚合反應和/或氫化反應完成之後藉由使用離子交換橡膠如在EP 2 072 532 A1、EP 2 072 533 A1、CN101463096 A中描述的進行移除。 The metal-containing catalyst can be removed after the completion of the polymerization and/or hydrogenation reaction by using an ion exchange rubber as described in EP 2 072 532 A1, EP 2 072 533 A1, CN 101463096 A.

(a)確定最終的聚合轉化率 (a) Determine the final polymerization conversion rate

最終的聚合轉化率可以藉由重量法使用初始的單體總量以及最終的乾S-NBR的量來進行計算。 The final polymerization conversion can be calculated by gravimetric method using the total amount of initial monomers and the amount of final dry S-NBR.

(b)GPC、DSC、FT-IR和1HNMR測試 (b) GPC, DSC, FT-IR and 1 H NMR tests

表觀分子量和分佈係藉由Waters GPC系統進行測試的，該系統配備有Waters 1515高效液相層析泵、Waters 717 plus自動進樣器、PLgel 10 μm混 合B柱以及Waters 2414 RI檢測器。GPC測試係在40℃下使用THF作為沖提液以1 mL/min的流速來進行的，並且該GPC柱使用窄的PS標準樣品進行校準。 Apparent molecular weight and distribution were tested by the Waters GPC system equipped with a Waters 1515 high performance liquid chromatography pump, a Waters 717 plus autosampler, and a PLgel 10 μm mix. B column and Waters 2414 RI detector. The GPC test was performed at 40 ° C using THF as a rinse at a flow rate of 1 mL/min, and the GPC column was calibrated using a narrow PS standard sample.

Tg係該聚合物的玻璃化轉變溫度。Tg使用Netzsch DSC 2014F1示差掃描量熱計測量。DSC測試以下來進行：1)首先以10℃/min的加熱速率從-80℃加熱到60℃；2)在60℃保持3分鐘並且然後以20℃/min的冷卻速率冷卻到-80℃；3)在-80℃保持3分鐘，並且然後再以10℃/min的加熱速率加熱到60℃。Tg值係基於該第二加熱試驗進行測量的。 Tg is the glass transition temperature of the polymer. Tg was measured using a Netzsch DSC 2014F1 differential scanning calorimeter. The DSC test was carried out as follows: 1) first heated from -80 ° C to 60 ° C at a heating rate of 10 ° C / min; 2) held at 60 ° C for 3 minutes and then cooled to -80 ° C at a cooling rate of 20 ° C / min; 3) Hold at -80 ° C for 3 minutes, and then heat to 60 ° C at a heating rate of 10 ° C / min. The Tg value was measured based on this second heating test.

所獲得的橡膠的FT-IR圖譜在一台Perkin Elmer光譜100 FT-IR光譜儀上進行記錄。將該等聚合物樣品溶解在MCB中並且然後將該溶液流延到KBr盤中並且乾燥以形成用於IR測試的膜。根據ASTM(D 5670-95)方法藉由FT-IR分析來確定其氫化轉化率。 The FT-IR spectrum of the obtained rubber was recorded on a Perkin Elmer Spectrometer 100 FT-IR spectrometer. The polymer samples were dissolved in MCB and then the solution was cast into a KBr disk and dried to form a film for IR testing. The hydrogenation conversion ratio was determined by FT-IR analysis according to the ASTM (D 5670-95) method.

1H NMR表徵係在Bruker AV500機器上使用CDCl3或DMSO-d6作為溶劑並且TMS作為內標準進行的。 1 H NMR characterization was performed on a Bruker AV500 machine using CDCl 3 or DMSO- d 6 as solvent and TMS as an internal standard.

實施例1-3Examples 1-3

將含條形磁鐵並且用硬質橡膠塞蓋帽的該等玻璃管在分別加入所要求量的溶劑、單體以及催化劑體系之前藉由三次重複的真空氮氣循環吹掃掉空氣。將所要求量的含金屬的催化劑體系RhCl(PPh3)3(77 mg，0.083 mmol)、2,2-二氯苯乙酮(DCAP)(93 mg，69 uL，0.49 mmol)、PPh3(154 mg，0.59 mmol)、有機溶劑一氯苯(MCB)(14.1 mL),1,3-丁二烯(Bd)(2.4 g，44.4 mmol)、丙烯腈(ACN)(1.7 g，32.1 mmol)分別添加到三個玻璃管中。所有該等液體在氮氣下引入。將該等玻璃管在恒溫油浴中在60℃的溫度下加熱並且在該反應過程中緩慢保持這種磁力攪拌。所要求的反應時間，例如17、24和45小時之後，將該等管分別打開，並且將該反應混合物取出並且用離子交換樹脂在100℃下處理48小時並且然後分別在冷的甲醇中沉澱。將該聚合物過濾掉並且分別在60℃下在真空中乾燥24小時。該反應壓力係在反應溫度下的單體蒸氣壓。該等結果總結在表1中。 The glass tubes containing the strip magnets and capped with a hard rubber plug were purged of air by three repeated vacuum nitrogen cycles before separately adding the required amount of solvent, monomer, and catalyst system. The required amount of metal-containing catalyst system RhCl(PPh 3 ) 3 (77 mg, 0.083 mmol), 2,2-dichloroacetophenone (DCAP) (93 mg, 69 uL, 0.49 mmol), PPh 3 ( 154 mg, 0.59 mmol), organic solvent monochlorobenzene (MCB) (14.1 mL), 1,3-butadiene (Bd) (2.4 g, 44.4 mmol), acrylonitrile (ACN) (1.7 g, 32.1 mmol) Add to each of the three glass tubes. All of these liquids were introduced under nitrogen. The glass tubes were heated in a constant temperature oil bath at a temperature of 60 ° C and this magnetic stirring was slowly maintained during the course of the reaction. After the required reaction time, for example, after 17, 24 and 45 hours, the tubes were opened separately, and the reaction mixture was taken out and treated with an ion exchange resin at 100 ° C for 48 hours and then separately precipitated in cold methanol. The polymer was filtered off and dried in vacuo at 60 ° C for 24 hours. The reaction pressure is the monomer vapor pressure at the reaction temperature. These results are summarized in Table 1.

每個管：MCB，14.1 mL；Bd，2.4 g，44.4 mmol；ACN，1.7 g，32.1 mmol；DCAP 93 mg，69 uL，0.49 mmol；RhCl(PPh3)3，77 mg，0.083 mmol；PPh3，154 mg，0.59 mmol；60℃ Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl (PPh 3 ) 3 , 77 mg, 0.083 mmol; PPh 3 , 154 mg, 0.59 mmol; 60 ° C

該聚合反應對水不敏感。該聚合反應進行約10分鐘到150小時之後可以獲得該S-NBR橡膠。 The polymerization is not sensitive to water. The S-NBR rubber can be obtained after the polymerization is carried out for about 10 minutes to 150 hours.

圖1係實施例1-3的樣品的GPC曲線，其中數字1-3代表實施例1-3並且範圍係從右向左。可見，實施例1-3的表觀分子量隨著反應時間的增加逐漸增加。這 表明了藉由根據本發明的二烯的溶液聚合法獲得的聚合物的分子量可以藉由調節所要求的反應時間而進行控制。 Figure 1 is a GPC curve for the samples of Examples 1-3, with numbers 1-3 representing Examples 1-3 and ranges from right to left. It can be seen that the apparent molecular weight of Examples 1-3 gradually increases as the reaction time increases. This It is shown that the molecular weight of the polymer obtained by the solution polymerization method of the diene according to the present invention can be controlled by adjusting the required reaction time.

實施例4-6Example 4-6

使用與在實施例1-3中所用的相同的催化劑體系和單體，並且該聚合反應在如實施例1中相同的條件下進行，除了該反應在80℃的溫度下進行不同的時間，例如9.5小時、30小時和45小時。該等結果總結在表2中。 The same catalyst system and monomers as used in Examples 1-3 were used, and the polymerization was carried out under the same conditions as in Example 1, except that the reaction was carried out at a temperature of 80 ° C for different times, for example 9.5 hours, 30 hours and 45 hours. These results are summarized in Table 2.

每個管：MCB，14.1 mL；Bd，2.4 g，44.4 mmol；ACN，1.7 g，32.1 mmol；DCAP 93 mg，69 uL，0.49 mmol；RhCl(PPh3)3，77 mg，0.083 mmol；PPh3，154 mg，0.59 mmol；80℃ Each tube : MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl (PPh 3 ) 3 , 77 mg, 0.083 mmol; PPh 3 , 154 mg, 0.59 mmol; 80 ° C

類似地，該聚合反應對水不敏感。該聚合反應在約10℃至約160℃的溫度下進行約10分鐘到150小時之後也可以獲得該S-NBR橡膠。 Similarly, the polymerization is not sensitive to water. The S-NBR rubber can also be obtained after the polymerization is carried out at a temperature of from about 10 ° C to about 160 ° C for about 10 minutes to 150 hours.

圖2係實施例4-6的樣品的GPC曲線，其中數字4-6代表實施例4-6並且範圍係從右向左。可見，實施例4-6的表觀分子量隨著反應時間的增加逐漸增加。這也表明了藉由根據本發明的二烯和/或至少一種單體的溶液聚合法獲得的聚合物的分子量可以藉由調節所要 求的反應時間進行控制。同時，如果該聚合反應在更高的溫度下進行一相同的時間，則該反應的轉化率將增加。 Figure 2 is a GPC curve for the samples of Examples 4-6, with numbers 4-6 representing Examples 4-6 and ranges from right to left. It can be seen that the apparent molecular weight of Examples 4-6 gradually increases as the reaction time increases. This also indicates that the molecular weight of the polymer obtained by solution polymerization of the diene and/or at least one monomer according to the present invention can be adjusted by The reaction time is controlled. At the same time, if the polymerization is carried out at a higher temperature for the same time, the conversion of the reaction will increase.

實施例7-16Example 7-16

使用與在實施例1-3中所用的相同的催化劑體系和單體，並且該聚合反應係在如實施例3中相同的條件下進行，除了該反應在80℃的溫度下進行45小時之外，改變按重量計的Bd和CAN的進料比率，並且所有的樣品在45小時時撤出。該等結果總結在表3-4中。 The same catalyst system and monomers as used in Examples 1-3 were used, and the polymerization was carried out under the same conditions as in Example 3 except that the reaction was carried out at a temperature of 80 ° C for 45 hours. , changing the feed ratio of Bd and CAN by weight, and all samples were withdrawn at 45 hours. These results are summarized in Table 3-4.

＊每個管：DCAP 93 mg，69 uL，0.49 mmol；RhCl(PPh3)3，77 mg，0.083 mmol；PPh3，154 mg，0.59 mmol；添加MCB以達到20 mL的水平；80℃；總時間45小時；其中1,4-Bd代表在Bd的1,4-位置上發生聚合反應的聚合單元，並且1,2-Bd代表在Bd的1,2-位置上發生聚合反應的聚合單元。 * Each tube: DCAP 93 mg, 69 uL, 0.49 mmol; RhCl (PPh 3 ) 3 , 77 mg, 0.083 mmol; PPh 3 , 154 mg, 0.59 mmol; MCB added to reach 20 mL level; 80 ° C; The time is 45 hours; wherein 1,4-Bd represents a polymerization unit which undergoes polymerization at the 1,4-position of Bd, and 1,2-Bd represents a polymerization unit which undergoes polymerization at the 1,2-position of Bd.

＊在這個試驗中，使用16.1 mL的MCB、2.4 g的Bd、93 mg的DCAP、77 mg的RhCl(PPh3)3和154 mg of PPh3。 * In this test, 16.1 mL of MCB, 2.4 g of Bd, 93 mg of DCAP, 77 mg of RhCl (PPh 3 ) 3 and 154 mg of PPh 3 were used .

類似地，該聚合反應對水不敏感。圖3a係實施例6-15的樣品的Mn和PDI；圖3b係實施例6和8-15的樣品的轉化率；圖3c係實施例6-16的樣品的FT-IR圖譜；圖3d係實施例6-16的樣品的1HNMR圖譜；圖3e係單獨的實施例6的樣品的1HNMR圖譜；並且圖3f係實施例6-15的樣品的DBS曲線。 Similarly, the polymerization is not sensitive to water. Figure 3a is the Mn and PDI of the samples of Examples 6-15; Figure 3b is the conversion of the samples of Examples 6 and 8-15; Figure 3c is the FT-IR spectrum of the samples of Examples 6-16; Figure 3d is 1 H NMR spectrum of the samples of Examples 6-16; Figure 3e is a 1 H NMR spectrum of the sample of Example 6 alone; and Figure 3f is a DBS curve of the samples of Examples 6-15.

在圖3e中，1HNMR光譜中峰的判定(assignment)如下列出：5.2-5.8 ppm,Bd,1,4-(-C H =C H -)以及乙烯基(-C H =CH2)；4.9-5.2 ppm,Bd，乙烯基(-CH=C H 2)；2.5-3.1 ppm,>C H -CN；1.0-2.5 ppm，在主鏈上的 H ；其中Bd，1,4-(或1,4-Bd)代表在Bd的1,4-位置上發生聚合反應的聚合單元，並且乙烯基(或1,2-Bd)代表在Bd的1,2-位置上發生聚合反應的聚合單元。請考慮如果沒有其他具體定義的話之後，Bd，1,4-(或1,4-Bd)和乙烯基(或1,2-Bd)在此具有相同含義。 In Figure 3e, the assignment of peaks in the 1 H NMR spectrum is listed below: 5.2-5.8 ppm, Bd, 1,4-(-C H =C H -) and vinyl (-C H =CH 2 ) ; 4.9-5.2 ppm, Bd, vinyl (-CH=C H 2 ); 2.5-3.1 ppm, >C H -CN; 1.0-2.5 ppm, H in the main chain; where Bd, 1,4-( Or 1,4-Bd) represents a polymerized unit which undergoes polymerization at the 1,4-position of Bd, and the vinyl group (or 1,2-Bd) represents a polymerization which undergoes polymerization at the 1,2-position of Bd. unit. Please consider that Bd, 1,4- (or 1,4-Bd) and vinyl (or 1,2-Bd) have the same meaning here if there is no other specific definition.

見到的是首先該等樣品的Mn和PDI隨著實施例6-16中按重量計的ACN的進料百分比增加而逐漸增加，其次，該等樣品中的Mn和PDI在ACN的進料百 分比係從約41 wt%至61 wt%時達到了一最高範圍，並且然後該等實施例中的Mn和PDI隨著ACN的進料百分比的進一步增加而逐漸降低。而且，當該ACN的進料百分比係從約13 wt%至61 wt%時，該等實施例中的轉化率係處於從約28.6 wt%至30.8 wt%的更高水平。還見到的是，根據本發明的BD和ACN的溶液聚合法獲得的聚合物中的ACN含量係從約8.0 wt%至約62.2 wt%。 It is seen that first the Mn and PDI of the samples increase gradually with the increase in the percentage of ACN by weight in Examples 6-16, and secondly, the Mn and PDI in the samples are fed in the ACN. The fractional ratio reached a maximum range from about 41 wt% to 61 wt%, and then the Mn and PDI in these examples gradually decreased with a further increase in the percentage of ACN feed. Moreover, when the ACN feed percentage is from about 13 wt% to 61 wt%, the conversions in these examples are at a higher level from about 28.6 wt% to 30.8 wt%. It is also seen that the ACN content of the polymer obtained by the solution polymerization method of BD and ACN according to the present invention is from about 8.0 wt% to about 62.2 wt%.

如以上提及的，根據本發明的BD和ACN的溶液聚合法可以提供具有超高水平(大於55 wt%)的ACN的S-NBR橡膠。這種在S-NBR橡膠中超高水平(大於55 wt%)的ACN打破了藉由乳液聚合獲得的NBR橡膠的55 wt%的ACN含量的限制。 As mentioned above, the solution polymerization method of BD and ACN according to the present invention can provide an S-NBR rubber having an ultrahigh level (greater than 55 wt%) of ACN. This ultra-high level (greater than 55 wt%) of ACN in S-NBR rubber breaks the limit of 55 wt% ACN content of NBR rubber obtained by emulsion polymerization.

由於在根據本發明的溶液聚合法的ACN在S-NBR橡膠中之超高水平(大於55 wt%)，可以提供比常規的乳液聚合獲得的NBR橡膠優異的耐油性。 Due to the ultra-high level (greater than 55 wt%) of ACN in the solution polymerization method according to the present invention in the S-NBR rubber, it is possible to provide excellent oil resistance than the NBR rubber obtained by conventional emulsion polymerization.

實施例17-18Example 17-18

使用與在實施例1中所用的相同的催化劑體系和單體，並且該聚合反應係在如實施例1中相同的條件下進行的，除了該反應在不同溫度下進行不同的反應時間之外，並且所有的樣品在該反應時間之後迅速撤出。該等結果總結在表5中。1,4-Bd、1,2-Bd和ACN的含量係其聚合到S-NBR橡膠中的含量。 The same catalyst system and monomers as used in Example 1 were used, and the polymerization was carried out under the same conditions as in Example 1, except that the reaction was carried out at different temperatures for different reaction times. And all samples were quickly withdrawn after the reaction time. These results are summarized in Table 5. The contents of 1,4-Bd, 1,2-Bd and ACN are the amounts which are polymerized into the S-NBR rubber.

＊每個管：MCB，14.1 mL；Bd，2.4 g，44.4 mmol；ACN，1.7 g，32.1 mmol；DCAP 93 mg，69 uL，0.49 mmol；RhCl(PPh3)3，77 mg，0.083 mmol；PPh3，154 mg，0.59 mmol；其中1,4-Bd代表在Bd的1,4-位置上發生聚合反應的聚合單元，並且1,2-Bd代表在Bd的1,2-位置上發生聚合反應的聚合單元。 * Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl (PPh 3 ) 3 , 77 mg, 0.083 mmol; 3, 154 mg, 0.59 mmol; 1,4-Bd wherein polymerized units representative of polymerization occurs in the 1,4-position Bd, and 1,2-Bd representative of a polymerization reaction in 1,2-position on Bd Aggregate unit.

類似地，該聚合反應對水不敏感。該聚合反應在約10℃至約160℃的溫度下進行約10分鐘到150小時之後也可以獲得該S-NBR橡膠。 Similarly, the polymerization is not sensitive to water. The S-NBR rubber can also be obtained after the polymerization is carried out at a temperature of from about 10 ° C to about 160 ° C for about 10 minutes to 150 hours.

圖4a係實施例3、6、17和18的樣品的FT-IR圖譜；並且圖4b係實施例3、6、17和18的樣品的1HNMR圖譜。 Figure 4a is an FT-IR spectrum of the samples of Examples 3, 6, 17, and 18; and Figure 4b is a 1 H NMR spectrum of the samples of Examples 3, 6, 17, and 18.

在圖4b中，1HNMR光譜中峰的判定如下列出：5.2-5.8 ppm,Bd,1,4-(-C H =C H -)以及乙烯基(-C H =CH2)；4.9-5.2 ppm,Bd，乙烯基(-CH=C H 2)；2.5-3.1 ppm,>C H -CN；1.0-2.5 ppm，在主鏈上的 H ；其中1,4-Bd代表在Bd的1,4-位置上發生聚合反應的聚合單元，並且1,2-Bd代表在Bd的1,2-位置上發生聚合反應的聚合單元。 In Figure 4b, the determination of the peaks in the 1 H NMR spectrum is as follows: 5.2-5.8 ppm, Bd, 1,4-(-C H =C H -) and vinyl (-C H =CH 2 ); 5.2 ppm, Bd, vinyl (-CH=C H 2 ); 2.5-3.1 ppm, >C H -CN; 1.0-2.5 ppm, H in the main chain; where 1,4-Bd represents 1 in Bd a polymerization unit in which polymerization occurs at the 4-position, and 1,2-Bd represents a polymerization unit in which polymerization occurs at the 1,2-position of Bd.

它表明了該共聚單體ACN可以在不同的溫度下共聚到S-NBR橡膠中，並且如果該反應在更低的溫度下進行相同的反應時間的話，其轉化率將降低。如果該反應在更低的溫度下進行一段長的反應時間，該轉化率也將增加。聚合溫度似乎對該ACN含量具有輕度的影響。 It is shown that the comonomer ACN can be copolymerized into the S-NBR rubber at different temperatures, and if the reaction is carried out at a lower temperature for the same reaction time, the conversion rate will be lowered. If the reaction is carried out at a lower temperature for a longer reaction time, the conversion will also increase. The polymerization temperature seems to have a slight effect on the ACN content.

實施例19-21Example 19-21

使用如在實施例1-3中所用的該等單體，並且該聚合反應在與實施例3中相同的條件下進行，並且所有的樣品在該反應時間45小時之後迅速撤出，除了該催化劑體系不同。在該催化劑體系中，RhCl(PPh3)3和DCAP的含量與在實施例1中的那些相同，並且僅PPh3含量不同。該等結果總結在表6中。 The monomers as used in Examples 1-3 were used, and the polymerization was carried out under the same conditions as in Example 3, and all the samples were quickly withdrawn after 45 hours of the reaction time, except for the catalyst. The system is different. In the catalyst system, the contents of RhCl(PPh 3 ) 3 and DCAP were the same as those in Example 1, and only the PPh 3 content was different. These results are summarized in Table 6.

＊每個管：MCB，14.1 mL；Bd，2.4 g，44.4 mmol；ACN，1.7 g，32.1 mmol；DCAP 93 mg，69 uL，0.49 mmol；RhCl(PPh3)3，77 mg，0.083 mmol；0.59 mmol；60℃，45小時；其中，1,4-Bd代表在Bd的1,4-位置上發生聚合反應的聚合單元，並且1,2-Bd代表在Bd的1,2-位置上發生聚合反應的聚合單元。 * Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl (PPh 3 ) 3 , 77 mg, 0.083 mmol; Ment; 60 ° C, 45 hours; wherein 1,4-Bd represents a polymerized unit in which polymerization occurs at the 1,4-position of Bd, and 1,2-Bd represents polymerization at the 1,2-position of Bd. The polymerization unit of the reaction.

類似地，該聚合反應對水不敏感。該聚合反應在約10℃至約160℃的溫度進行約10分鐘到150小時之後 也可以獲得該S-NBR橡膠。 Similarly, the polymerization is not sensitive to water. The polymerization is carried out at a temperature of from about 10 ° C to about 160 ° C for about 10 minutes to 150 hours. The S-NBR rubber can also be obtained.

它表明了該單體ACN中能夠在在該催化劑體系中不同的PPh3含量下共聚到S-NBR橡膠中。如果該催化劑體系中PPh3的含量增加的話，則轉化率將降低並且Mn和Mw將增加。在催化劑體系中PPh3的含量似乎對S-NBR橡膠中的ACN含量沒有影響。 It is shown that the monomeric ACN can be copolymerized into the S-NBR rubber at different PPh 3 contents in the catalyst system. If the content of PPh 3 in the catalyst system is increased, the conversion will decrease and Mn and Mw will increase. The content of PPh 3 in the catalyst system appeared to have no effect on the ACN content in the S-NBR rubber.

實施例22-1至22-12Examples 22-1 to 22-12

使用如在實施例1-3中的單體，並且該聚合反應在如實施例3或6中相同的條件下進行，並且所有的樣品在該反應時間之後迅速撤出，除了該催化劑體系中的添加劑不同之外。該等結果總結在表7-9中。 The monomers as in Examples 1-3 were used, and the polymerization was carried out under the same conditions as in Example 3 or 6, and all the samples were quickly withdrawn after the reaction time, except in the catalyst system. Additives are different. These results are summarized in Tables 7-9.

在實施例22-1、22-1和22-3，該等催化劑體系包括77 mg的RhCl(PPh3)3、93 mg的DCAP、154 mg的PPh3，連同另外的MTOAC添加劑，正丁胺或二丁胺。該等結果總結在表7中。 In Examples 22-1, 22-1, and 22-3, the catalyst systems included 77 mg of RhCl(PPh 3 ) 3 , 93 mg of DCAP, 154 mg of PPh 3 , along with additional MTOAC additives, n-butylamine. Or dibutylamine. These results are summarized in Table 7.

＊每個管：MCB，14.1 mL；Bd，2.4 g，44.4 mmol；ACN，1.7 g，32.1 mmol；DCAP 93 mg，69 uL，0.49 mmol；RhCl(PPh3)3，77 mg，0.083 mmol；PPh3，154 mg，0.59 mmol； 其中1,4-Bd代表在Bd的1,4-位置上發生聚合反應的聚合單元，並且1,2-Bd代表在Bd的1,2-位置上發生聚合反應的聚合單元；MTOAC：甲基三正辛基銨氯化物，Aliquat® 336。 * Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl (PPh 3 ) 3 , 77 mg, 0.083 mmol; 3, 154 mg, 0.59 mmol; 1,4-Bd wherein polymerized units representative of polymerization occurs in the 1,4-position Bd, and 1,2-Bd representative of a polymerization reaction in 1,2-position on Bd Polymerization unit; MTOAC: methyl tri-n-octyl ammonium chloride, Aliquat® 336.

該聚合反應對水不敏感，並且在所有的樣品中也沒有巨-凝膠(macro-gel)發生。該聚合反應在約10℃至約160℃的溫度進行約10分鐘到150小時之後也可以獲得該S-NBR橡膠。 The polymerization was not sensitive to water and no macro-gel occurred in all of the samples. The S-NBR rubber can also be obtained after the polymerization is carried out at a temperature of from about 10 ° C to about 160 ° C for about 10 minutes to 150 hours.

圖5a係實施例22-1、22-2和22-3的樣品的1HNMR圖譜。見使用該催化劑體系與另外的添加劑MTOAC，正丁基胺或二丁基胺的樣品的轉化率比使用實施例6中的催化劑的水平更高，並且該聚合物中的ACN含量似乎比使用實施例6中催化劑的量些微更高。 Figure 5a is a 1 H NMR spectrum of the samples of Examples 22-1, 22-2, and 22-3. See that the conversion of the sample using the catalyst system with the additional additive MTOAC, n-butylamine or dibutylamine is higher than the level of the catalyst used in Example 6, and the ACN content in the polymer appears to be more than that used. The amount of catalyst in Example 6 was slightly higher.

＊MCB：14.1 mL；Bd：2.4 g；ACN：1.7 g；DCAP：93 mg。 * MCB: 14.1 mL; Bd: 2.4 g; ACN: 1.7 g; DCAP: 93 mg.

在實施例22-4至22-10和22-13中，該等催化劑體系包括RhCl(PPh3)3、DCAP、任選地PPh3，連同任選另外的維生素C添加劑。該等結果總結在表8中。圖5b係實施例22-7的樣品的1HNMR圖譜。實施例22-7的樣品的聚合物組成歸納在表9中。 In Examples 22-4 to 22-10 and 22-13, the catalyst systems include RhCl(PPh 3 ) 3 , DCAP, optionally PPh 3 , along with optionally additional vitamin C additives. These results are summarized in Table 8. Figure 5b is a 1 H NMR spectrum of the samples of Examples 22-7. The polymer compositions of the samples of Examples 22-7 are summarized in Table 9.

類似地，該聚合反應對水不敏感。該聚合反應在約10℃至約160℃的溫度下進行約10分鐘到150小時之後也可以獲得該S-NBR橡膠。 Similarly, the polymerization is not sensitive to water. The S-NBR rubber can also be obtained after the polymerization is carried out at a temperature of from about 10 ° C to about 160 ° C for about 10 minutes to 150 hours.

見到的是，使用了實施例3或6中的催化劑體系與另外的維生素C添加劑的樣品的轉化率，隨著維生素C的含量的增加而增加。此外，維生素C可以代替實施例3或6中的催化劑體系中的PPh3來使用。 It was found that the conversion of the sample using the catalyst system of Example 3 or 6 with the additional vitamin C additive increased as the content of vitamin C increased. Further, vitamin C may be used in place of PPh 3 in the catalyst system of Example 3 or 6.

此外，見到的是，使用了實施例1中的催化劑體系的該等樣品的轉化率隨著PPh3和/或RhCl(PPh3)3的含量的增加而增加。 Further, it is seen that the conversion of the samples using the catalyst system of Example 1 increases as the content of PPh 3 and/or RhCl(PPh 3 ) 3 increases.

實施例23-1至23-12Examples 23-1 to 23-12

使用如在實施例1-3中的單體，並且該聚合反應在與實施例3或6中相同的條件下進行，並且所有的樣品在該反應時間之後迅速撤出，除了該催化劑體系中的助催化劑不同。該等結果總結在表10-12中。 The monomers as in Examples 1-3 were used, and the polymerization was carried out under the same conditions as in Example 3 or 6, and all the samples were quickly withdrawn after the reaction time, except in the catalyst system. The cocatalyst is different. These results are summarized in Tables 10-12.

＊每個管：MCB,14.1 mL；Bd,2.4 g,44.4 mmol；ACN,1.7 g,32.1 mmol。 * Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol.

該聚合反應對不水敏感，並且在所有的樣品中也沒有巨-凝膠發生。該聚合反應在約10℃至約160℃的溫度下進行約10分鐘到150小時之後也可以獲得該S-NBR橡膠。 The polymerization was not water sensitive and there was no macro-gel formation in all samples. The S-NBR rubber can also be obtained after the polymerization is carried out at a temperature of from about 10 ° C to about 160 ° C for about 10 minutes to 150 hours.

圖6a-6c係實施例23-3、23-7以及23-10的樣品的1HNMR圖譜。助催化劑PhCH2Cl、CCl4、或Cl3CCOOCH2CH3可以用來代替實施例1-3或4-6中的催化劑體系中的DCAP，並且共聚物S-NBR可以藉由在催化劑體系中使用助催化劑PhCH2Cl、CCl4或Cl3CCOOCH2CH3代替DCAP來獲得。 Figures 6a-6c are 1 H NMR spectra of the samples of Examples 23-3, 23-7, and 23-10. The cocatalyst PhCH 2 Cl, CCl 4 , or Cl 3 CCOOCH 2 CH 3 may be used in place of DCAP in the catalyst system of Examples 1-3 or 4-6, and the copolymer S-NBR may be used in the catalyst system. It was obtained using a cocatalyst PhCH 2 Cl, CCl 4 or Cl 3 CCOOCH 2 CH 3 instead of DCAP.

＊每個管：MCB,14.1 mL；Bd,2.4 g,44.4 mmol；ACN,1.7 g,32.1 mmol；60℃，45小時。 * Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; 60 ° C, 45 hours.

＊每個管：MCB,14.1 mL；Bd,2.4 g,44.4 mmol；ACN,1.7 g,32.1 mmol。 * Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol.

見到的是使用了該催化劑體系與另外的添加劑偶氮雙異庚腈(ABVN)而沒有RhCl(PPh3)3的實施例23-11的轉化率與在實施例23-12中使用另外的添加劑偶氮雙異庚腈(ABVN)和金屬催化劑RhCl(PPh3)3的催化劑體系大致相同，ACN在實施例23-11中的含量比在實施例23-12中的稍微更高，並且在實施例23-11中的PDI比實施例23-12中的遠遠更高。這表明了該催化劑體系中RhCl(PPh3)3的金屬催化劑可以控制該S-NBR橡膠的分子量分佈並且似乎對S-NBR橡膠中的ACN含量具有輕微影響。 It is seen using the catalyst system further additives azobisisobutyronitrile heptanenitrile (ABVN) without RhCl (PPh 3) 3 conversion with the use of embodiments 23-11 further embodiment in the examples of 23-12 The catalyst system of the additive azobisisoheptanenitrile (ABVN) and the metal catalyst RhCl(PPh 3 ) 3 is substantially the same, and the content of ACN in Examples 23-11 is slightly higher than in Examples 23-12, and The PDI in Examples 23-11 was much higher than in Examples 23-12. This indicates that the metal catalyst of RhCl(PPh 3 ) 3 in the catalyst system can control the molecular weight distribution of the S-NBR rubber and seems to have a slight influence on the ACN content in the S-NBR rubber.

實施例24-1至24-6Examples 24-1 to 24-6

使用如在實施例1中的該等單體，並且該聚合反應係在如實施例3或6中相同的條件下進行，並且所有的樣品在該反應時間之後迅速撤出，除了該催化劑體系中的含金屬的催化劑以及反應時間係不同的之外。該等結果總結在表13-14中。 The monomers as in Example 1 were used, and the polymerization was carried out under the same conditions as in Example 3 or 6, and all the samples were quickly withdrawn after the reaction time, except in the catalyst system. The metal-containing catalyst and the reaction time are different. These results are summarized in Tables 13-14.

＊每個管：MCB,14.1 mL；Bd,2.4 g,44.4 mmol；ACN,1.7 g,32.1 mmol。 * Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol.

＊每個管：MCB,14.1 mL；Bd,2.4 g,44.4 mmol；ACN,1.7 g,32.1 mmol。 * Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol.

在實施例24-1至24-4中，使用含金屬的催化劑RhCl3．3H2O，代替催化劑體系中的RhCl(PPh3)3。在實施例24-4中，使用助催化劑CCl4代替DCAP。圖7a-7c係實施例24-1、24-3以及24-4的樣品的1HNMR圖譜。 In Examples 24-1 to 24-4, a metal-containing catalyst RhCl 3 was used . 3H 2 O instead of RhCl(PPh 3 ) 3 in the catalyst system. In Example 24-4, a cocatalyst CCl 4 was used instead of DCAP. Figures 7a-7c are 1 H NMR spectra of the samples of Examples 24-1, 24-3, and 24-4.

RhCl3．3H2O可以與PPh3反應以獲得RhCl(PPh3)3，並且然後可以藉由實施例1-3或4-6中的溶液聚合獲得共聚物S-NBR。這表明了根據本申請的溶液聚合反應係對水不敏感。此外，在所有的樣品中也沒有巨-凝膠發 生。 RhCl 3 . 3H 2 O can be reacted with PPh 3 to obtain RhCl(PPh 3 ) 3 , and then the copolymer S-NBR can be obtained by solution polymerization in Examples 1-3 or 4-6. This indicates that the solution polymerization reaction system according to the present application is not sensitive to water. In addition, no macro-gels occurred in all of the samples.

在實施例24-5至24-6中，使用含金屬的催化劑Pd(OAC)2(乙酸鈀(II))，代替催化劑體系中的RhCl(PPh3)3。圖7d係實施例24-5的樣品的1HNMR圖譜。當該反應在相同的溫度下進行相同的時間時，該溶液聚合的轉化率和PDI隨著催化劑體系的量的增加將增加。 In Examples 24-5 to 24-6, a metal-containing catalyst Pd(OAC) 2 (palladium(II) acetate) was used instead of RhCl(PPh 3 ) 3 in the catalyst system. Figure 7d is a 1 H NMR spectrum of the sample of Example 24-5. When the reaction is carried out at the same temperature for the same time, the conversion of the solution polymerization and the PDI will increase as the amount of the catalyst system increases.

實施例25Example 25

使用如在實施例1中的催化劑體系和單體，並且該聚合反應在與實施例3中相同的條件下進行，並且所有的樣品在該反應時間之後迅速撤出，除了該有機溶劑係不同的之外。該等結果總結在表15-16中。 The catalyst system and the monomer as in Example 1 were used, and the polymerization was carried out under the same conditions as in Example 3, and all the samples were quickly withdrawn after the reaction time, except that the organic solvent was different. Outside. These results are summarized in Tables 15-16.

＊此管：MEK,14.1 mL；Bd,2.4 g,44.4 mmol；ACN,1.7 g,32.1 mmol。 * This tube: MEK, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol.

在實施例25中，在該聚合反應系統中使用有機溶劑甲基乙基酮(MEK)代替一氯苯(MCB)。圖8係實施例25的樣品的1HNMR圖譜。表16顯示所獲得的S-NBR橡膠的組成。 In Example 25, an organic solvent methyl ethyl ketone (MEK) was used in place of monochlorobenzene (MCB) in the polymerization reaction system. Figure 8 is a 1 H NMR spectrum of the sample of Example 25. Table 16 shows the composition of the obtained S-NBR rubber.

在本申請案的溶液聚合反應中也可以使用其他有機溶劑，如二甲亞碸(DMSO)、N,N-二甲基乙醯胺(DMAc)和N,N-二甲基甲醯胺(DMF)。 Other organic solvents such as dimethyl hydrazine (DMSO), N,N-dimethylacetamide (DMAc) and N,N-dimethylformamide can also be used in the solution polymerization of the present application. DMF).

實施例26-1至26-2Examples 26-1 to 26-2

使用如在實施例1-3中的催化劑體系和有機溶劑，並且該聚合反應在與實施例3或6中相同的條件下進行，並且所有的樣品在該反應時間之後迅速撤出，除了該共聚單體係不同的之外。該等結果總結在表17-18中。 The catalyst system as in Examples 1-3 and an organic solvent were used, and the polymerization was carried out under the same conditions as in Example 3 or 6, and all the samples were quickly withdrawn after the reaction time, except for the copolymerization. The single system is different. These results are summarized in Tables 17-18.

＊每個管：MCB,14.1 mL；Bd,2.5 g,46.2 mmol；苯乙烯，1.7 g,16.3 mmol；DCAP 93 mg,69 uL,0.49 mmol；RhCl(PPh3)3,77 mg,0.083 mmol；PPh3,154 mg,0.59 mmol；45小時。 * Each tube: MCB, 14.1 mL; Bd, 2.5 g, 46.2 mmol; styrene, 1.7 g, 16.3 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl (PPh 3 ) 3 , 77 mg, 0.083 mmol; PPh 3 , 154 mg, 0.59 mmol; 45 hours.

其中，Bd，1,4-代表在Bd的1,4-位置上發生聚合反應的聚合單元，並且Bd，乙烯基代表在Bd的1,2-位置上發生聚合反應的聚合單元。 Wherein Bd, 1,4- represents a polymerized unit which undergoes polymerization at the 1,4-position of Bd, and Bd, vinyl represents a polymerized unit which undergoes polymerization at the 1,2-position of Bd.

在實施例26-1至26-2中，在聚合反應體系中使用共聚單體丁二烯(BD)和苯乙烯(St)代替丁二烯(BD)和丙烯腈(ACN)。圖9a係實施例26-2的樣品 的FT-IR圖譜；並且圖9b係實施例26-2的樣品的1HNMR圖譜。表18顯示所獲得的S-SBR橡膠的組成。 In Examples 26-1 to 26-2, comonomers butadiene (BD) and styrene (St) were used in the polymerization reaction system in place of butadiene (BD) and acrylonitrile (ACN). Figure 9a is an FT-IR spectrum of the sample of Example 26-2; and Figure 9b is a 1 H NMR spectrum of the sample of Example 26-2. Table 18 shows the composition of the obtained S-SBR rubber.

在圖9a中，FT-IR光譜中峰的判定如下列出：967 cm-1,Bd，反式-1,4；911 cm-1,Bd，乙烯基；1452 cm-1和699 cm-1，苯環，其中Bd，反式-1,4代表在Bd的1,4-位置上發生聚合反應並且是反式聚合反應的聚合單元，並且Bd，乙烯基代表在Bd的1,2-位置上發生聚合反應的聚合單元。 In Figure 9a, the peaks in the FT-IR spectrum are determined as follows: 967 cm -1 , Bd, trans -1 , 4; 911 cm -1 , Bd, vinyl; 1452 cm -1 and 699 cm -1 a benzene ring, wherein Bd, trans-1, 4 represents a polymerization unit which undergoes polymerization at the 1,4-position of Bd and is a trans-polymerization reaction, and Bd, vinyl represents a 1,2-position at Bd A polymerization unit on which polymerization occurs.

在圖9b中，1HNMR光譜中峰的判定如下列出：6.9-7.1 ppm，在苯環上的 H ；5.0-5.6 ppm，在1,4-Bd單元以及1,2-Bd單元上的 H ；4.8-5.0 ppm，在1,2-Bd單元上的 H 。 In Figure 9b, 1 HNMR spectrum peak determination are listed below: 6.9-7.1 ppm, H on the benzene ring; 5.0-5.6 ppm, H in the 1,4-Bd units and 1,2-Bd unit ; 4.8-5.0 ppm, H on 1,2-Bd units.

RhCl(PPh3)3/PPh3/DCAP催化劑體系可以催化Bd和St的溶液聚合以獲得S-SBR橡膠。並且，當該聚合反應在更低的溫度下進行時，S-SBR橡膠中的乙烯(St)含量增加。 The RhCl(PPh 3 ) 3 /PPh 3 /DCAP catalyst system can catalyze solution polymerization of Bd and St to obtain S-SBR rubber. Also, when the polymerization is carried out at a lower temperature, the ethylene (St) content in the S-SBR rubber increases.

實施例27-1至27-5Examples 27-1 to 27-5

使用如在實施例1-3中的催化劑體系和有機溶劑，並且該聚合反應係在與實施例6中相同的條件下進行的，並且所有的樣品在該反應時間之後迅速撤出，除了該共聚單體包含不同的三單體之外。該等結果總結在表19-24中。 The catalyst system and the organic solvent as in Examples 1-3 were used, and the polymerization was carried out under the same conditions as in Example 6, and all the samples were quickly withdrawn after the reaction time, except for the copolymerization. The monomers contain different three monomers. These results are summarized in Tables 19-24.

＊每個管：MCB，14.1 mL；Bd，2.4 g，44.4 mmol；ACN，1.7 g，32.1 mmol；DCAP 93 mg，69 uL，0.49 mmol；RhCl(PPh3)3，77 mg，0.083 mmol；PPh3，154 mg，0.59 mmol；80℃，45小時，其中對照試驗與實施例6相同，並且不存在三單體。 需要其中DMF作為洗脫液的＊＊GPC體系。n/a=不可用。 * Each tube: MCB, 14.1 mL; Bd, 2.4 g, 44.4 mmol; ACN, 1.7 g, 32.1 mmol; DCAP 93 mg, 69 uL, 0.49 mmol; RhCl (PPh 3 ) 3 , 77 mg, 0.083 mmol; 3 , 154 mg, 0.59 mmol; 80 ° C, 45 hours, wherein the control test was the same as in Example 6, and no three monomers were present. A ** GPC system in which DMF is used as an eluent is required. n/a= not available.

＊所有的值使用1H NMR圖譜計算。 * All values were calculated using 1 H NMR spectra.

表20係實施例6的樣品的對照試驗的組成。圖10a係實施例6的樣品的對照試驗的FT-IR圖譜；並且圖10b係實施例6的樣品的對照試驗的1HNMR圖譜。 Table 20 is the composition of the control test of the sample of Example 6. Figure 10a is an FT-IR spectrum of a control test of the sample of Example 6; and Figure 10b is a 1 H NMR spectrum of a control test of the sample of Example 6.

在圖10a中，FT-IR光譜中峰的判定如下列出：2237 cm-1,-CN；970 cm-1,Bd，反式-1,4；920 cm-1，Bd，乙烯基；722 cm-1,Bd，順式-1,4 In Figure 10a, the peaks in the FT-IR spectrum are determined as follows: 2237 cm -1 , -CN; 970 cm -1 , Bd, trans -1 , 4; 920 cm -1 , Bd, vinyl; 722 Cm -1 , Bd, cis -1 , 4

在圖10b中，1HNMR光譜中峰的判定如下列出： 5.2-5.8 ppm,Bd,1,4-(-C H =C H -)以及乙烯基(-C H =CH2)；4.9-5.2 ppm,Bd，乙烯基(-CH=C H 2)；2.6 ppm,>C H -CN。 In Figure 10b, the determination of the peaks in the 1 H NMR spectrum is as follows: 5.2-5.8 ppm, Bd, 1,4-(-C H =C H -) and vinyl (-C H =CH 2 ); 5.2 ppm, Bd, vinyl (-CH=C H 2 ); 2.6 ppm, >C H -CN.

表21係實施例27-1的具有三單體丙烯酸正丁基酯(n-BA)的樣品的組成。圖10c係實施例27-1的具有三單體丙烯酸正丁酯的樣品的FT-IR圖譜；並且圖10d係實施例27-1的具有三單體丙烯酸正丁酯的樣品的1HNMR圖譜。 Table 21 is the composition of the sample of Example 27-1 having a trimeric monomeric n-butyl acrylate (n-BA). Figure 10c is an FT-IR spectrum of a sample having three monomers of n-butyl acrylate of Example 27-1; and Figure 10d is a 1 H NMR spectrum of a sample having three monomers of n-butyl acrylate of Example 27-1.

在圖10c中，FT-IR光譜中峰的判定如下列出：1729 cm-1,>C=O；1164 cm-1,-COOC-。 In Figure 10c, the determination of the peaks in the FT-IR spectrum is as follows: 1729 cm -1 , >C=O; 1164 cm -1 , -COOC-.

在圖10d中，1HNMR光譜中峰的判定如下列出：4.1 ppm,n-BA單元的-COOC H 2-；0.8 ppm和1.4 ppm,n-BA單元的C H 2C H 3-。 In the FIG 10d, 1 HNMR spectrum peak determination are listed below: 4.1 ppm, -COOC H n- BA unit 2 -; C H 0.8 ppm and 1.4 ppm, n-BA unit 2 C H 3 -.

表22係實施例27-2的具有三單體甲基丙烯酸甲酯(MMA)的樣品的組成。圖10e係實施例27-2的具有三單體MMA的樣品的1HNMR圖譜；並且圖10f係實施例27-2的具有三單體MMA的樣品的1HNMR圖譜。 Table 22 is the composition of the sample of Example 27-2 having the tri-monomer methyl methacrylate (MMA). Figure 10e is a 1 H NMR spectrum of a sample with three monomers MMA of Example 27-2; and Figure 10f is a 1 H NMR spectrum of a sample with three monomers MMA of Example 27-2.

在圖10e中，FT-IR光譜中峰的判定為1729 cm-1,>C=O。 In Fig. 10e, the peak in the FT-IR spectrum was judged to be 1729 cm -1 , >C=O.

在圖10f中，1HNMR光譜中峰的判定如下列出：3.7 ppm,-COOC H 3；1.1 ppm,MMA單元的-C H 3。 In the FIG. 10f, 1 HNMR spectrum peak determination are listed below: 3.7 ppm, -COOC H 3; -C H 1.1 ppm, MMA unit 3.

表23係實施例27-3的具有三單體甲基丙烯酸(MAA)的樣品的組成。圖10g係實施例27-3的具有三單體MAA的樣品的FT-IR圖譜；並且圖10h-10i係實施例27-3的具有三單體MAA的樣品的1HNMR圖譜。 Table 23 is the composition of the sample of Example 27-3 with the tri-monomer methacrylic acid (MAA). Figure 10g is an FT-IR spectrum of a sample with three monomers MAA of Example 27-3; and Figures 10h-10i are 1 H NMR spectra of a sample with three monomers MAA of Example 27-3.

在圖10g中，FT-IR光譜中峰的判定為1701 cm-1,-COOH。 In Fig. 10g, the peak in the FT-IR spectrum was judged to be 1701 cm -1 , -COOH.

在圖10h-10i中，1HNMR光譜中峰的判定如下列出：1.0 ppm,MAA單元上的-C H 3；12.2 ppm,-COO H ；3.3 ppm,H2O；2.5 ppm,DMSO。 10h-10i in FIG, 1 HNMR spectrum peak determination are listed below: 1.0 ppm, -C H on MAA unit 3; 12.2 ppm, -COO H; 3.3 ppm, H 2 O; 2.5 ppm, DMSO.

IA含量的值不能藉由使用1H NMR圖譜計算。 在此ACN和Bd的總含量被認為是100%。 The value of the IA content cannot be calculated by using a 1 H NMR spectrum. The total content of ACN and Bd here is considered to be 100%.

表24係實施例27-4的具有三單體衣康酸(IA)的樣品的組成。圖10j係實施例27-4的具有三單體IA的樣品的FT-IR圖譜；並且圖10k-10l係實施例27-4的具有三單體IA的樣品的1HNMR圖譜。 Table 24 is the composition of the sample of Example 27-4 having the trimeric itaconic acid (IA). Figure 10j is an FT-IR spectrum of a sample with three monomers IA of Example 27-4; and Figures 10k-10l are 1 H NMR spectra of a sample with three monomers IA of Example 27-4.

在圖10j中，FT-IR光譜中峰的判定為1701 cm-1,-COOH。 In Fig. 10j, the peak in the FT-IR spectrum was judged to be 1701 cm -1 , -COOH.

在圖10k-10l中，1HNMR光譜中峰的判定如下列出：12.3 pm,-COO H ；3.3 ppm,H2O；2.5 ppm,DMSO。 In Figures 10k-10l, the determination of the peaks in the 1 H NMR spectrum is as follows: 12.3 pm, -COO H ; 3.3 ppm, H 2 O; 2.5 ppm, DMSO.

圖10m係實施例27-5的具有三單體丙烯醯胺的樣品的FT-IR圖譜。在圖10m中，FT-IR光譜中峰的判定如下列出：1671 cm-1,>C=O；3100-3500 cm-1,-NH2。 Figure 10m is an FT-IR spectrum of a sample with three monomers of acrylamide as in Examples 27-5. In Fig. 10m, the determination of the peaks in the FT-IR spectrum is as follows: 1671 cm -1 , >C=O; 3100-3500 cm -1 , -NH 2 .

見到的是三單體丙烯醯胺被共聚至NBR聚合物鏈。 It is seen that the trimeric acrylamide is copolymerized to the NBR polymer chain.

其他的三單體，例如乙酸乙烯酯、富馬酸以及類似物也可以在根據本發明的方法中進行溶液共聚。 Other three monomers, such as vinyl acetate, fumaric acid and the like, can also be solution copolymerized in the process according to the invention.

實施例28-1至28-4Examples 28-1 to 28-4

使用一台600 mL Parr的高壓釜反應器用於更大規模的共聚試驗。實驗條件和結果在表25，圖11a和11b中列出。 A 600 mL Parr autoclave reactor was used for larger scale copolymerization experiments. Experimental conditions and results are listed in Table 25, Figures 11a and 11b.

＊ n/a：不可用 * n/a: not available

發現了更高的溫度對於在更短的反應時間以更低的催化劑濃度獲得更高的聚合反應轉化率係有益的。 Higher temperatures have been found to be beneficial for obtaining higher polymerization conversions at lower catalyst concentrations in shorter reaction times.

BD與至少一種共聚單體在有機溶液中的聚合反應可以在更寬範圍的反應溫度(從10℃至用於氫化所使用的溫度例如160℃)下進行。較佳的是，該反應可以在室溫至150℃下進行，更佳的是在30℃至150℃，進一步較佳的是在60℃至150℃，更佳的是在80℃至150℃。 The polymerization of BD with at least one comonomer in an organic solution can be carried out at a wider range of reaction temperatures (from 10 ° C to temperatures used for hydrogenation, for example 160 ° C). Preferably, the reaction is carried out at from room temperature to 150 ° C, more preferably from 30 ° C to 150 ° C, still more preferably from 60 ° C to 150 ° C, more preferably from 80 ° C to 150 ° C. .

該聚合反應在更高的溫度下進行以藉由更少的催化劑來改進該共聚反應的生產率。 The polymerization is carried out at a higher temperature to improve the productivity of the copolymerization reaction by less catalyst.

將實施例28-2的樣品在高壓釜反應器中以一鍋法連續地進行氫化。該等氫化反應條件在以下實施例中列出。 The sample of Example 28-2 was continuously hydrogenated in a one-pot process in an autoclave reactor. These hydrogenation reaction conditions are listed in the examples below.

圖11a係以不同的反應時間進行的實施例28-1、和28-2的樣品的FT-IR圖譜，並且圖11b係實施例28-4的樣品的1HNMR圖譜。 Figure 11a is an FT-IR spectrum of the samples of Examples 28-1, and 28-2 at different reaction times, and Figure 11b is a 1 H NMR spectrum of the sample of Example 28-4.

實施例29Example 29

該聚合反應係在高壓釜反應器中進行的，並且其反應條件和結果在表26中列出，並且反應時間之後迅速 將樣品撤出，除了包括三單體丙烯酸正丁酯(n-BA)之該共聚單體之外。 The polymerization was carried out in an autoclave reactor, and the reaction conditions and results are listed in Table 26, and the reaction time was rapid The sample was withdrawn except for the comonomer comprising the tri-monomer n-butyl acrylate (n-BA).

見到的是，BD和ACN與三單體的溶液聚合反應也可以在高壓釜反應器中進行。 It is seen that solution polymerization of BD and ACN with three monomers can also be carried out in an autoclave reactor.

當n-BA(丙烯酸正丁酯)用作聚合反應的三單體時，在更短的時間獲得了更高分子量的NBR。與使用n-BA作為三單體藉由乳液聚合反應獲得的E-NBR產品相比，這種S-NBR產品具有窄得多的分子量分佈(PDI=2.04)。 When n-BA (n-butyl acrylate) is used as the tri-monomer of the polymerization reaction, a higher molecular weight NBR is obtained in a shorter time. This S-NBR product has a much narrower molecular weight distribution (PDI = 2.04) than the E-NBR product obtained by emulsion polymerization using n-BA as a tri-cell.

實施例30-1至30-7Examples 30-1 to 30-7

該一鍋溶液聚合反應以及氫化過程在600 mL Parr高壓釜反應器中進行。該溶液聚合完成之後，將過量的單體和/或DCAP在聚合溫度下從閥門排出。然後，將閥門關閉並且將溫度增加到氫化溫度並且將氫氣注入到該高壓釜反應器中。從丁二烯和丙烯腈到HNBR的一 鍋溶液聚合和氫化(HD)過程的方案如下在方案1中列出。實驗條件和結果在表27和圖12中示出。 The one-pot solution polymerization and hydrogenation were carried out in a 600 mL Parr autoclave reactor. After the solution polymerization is complete, excess monomer and/or DCAP is withdrawn from the valve at the polymerization temperature. Then, the valve was closed and the temperature was increased to the hydrogenation temperature and hydrogen was injected into the autoclave reactor. One from butadiene and acrylonitrile to HNBR The protocol for the pot solution polymerization and hydrogenation (HD) process is listed below in Scheme 1. Experimental conditions and results are shown in Table 27 and Figure 12.

類似地，從丁二烯和丙烯腈或其他共聚單體(例如苯乙烯)以及任選的三單體到氫化的三聚物、或氫化的丁二烯-苯乙烯共聚物、或氫化的丁二烯-苯乙烯三聚物的一鍋溶液聚合和氫化(HD)的方法也可以如在方案1中指出的藉由不同的單體進行合成。 Similarly, from butadiene and acrylonitrile or other comonomers (such as styrene) and optionally three monomers to hydrogenated terpolymers, or hydrogenated butadiene-styrene copolymers, or hydrogenated butyl The one-pot solution polymerization and hydrogenation (HD) method of the diene-styrene terpolymer can also be synthesized by different monomers as indicated in Scheme 1.

＊存在兩個階段：聚合(polym.)和氫化(HD)；n/a：不可用；No：沒有凝膠發生。 * There are two stages: polymerization (polym.) and hydrogenation (HD); n/a: not available; No: no gelation occurs.

圖12係S-NBR和氫化的S-NBR的FT-IR圖譜和1HNMR圖譜。FT-IR圖譜和1HNMR圖譜的判定在圖12中給出。 Figure 12 is a FT-IR spectrum and a 1 H NMR spectrum of S-NBR and hydrogenated S-NBR. The determination of the FT-IR spectrum and the 1 H NMR spectrum is given in FIG.

清楚的是一鍋聚合和氫化得以成功進行以直接從單體生產HNBR。因此，一鍋聚合和氫化的方案大大縮短了。即，本發明的催化劑體系不僅用作BD以及至少一種共聚單體的溶液聚合反應催化劑，而且還用作藉由溶液聚合反應獲得的聚合物的氫化催化劑。 It is clear that one-pot polymerization and hydrogenation are successfully carried out to produce HNBR directly from the monomer. Therefore, the one-pot polymerization and hydrogenation scheme is greatly shortened. That is, the catalyst system of the present invention is used not only as a solution polymerization catalyst for BD and at least one comonomer, but also as a hydrogenation catalyst for a polymer obtained by solution polymerization.

實施例31-1至31-4Examples 31-1 to 31-4

用於NBR聚合物固體的氫化法在600 mL Parr高壓釜反應器中進行。從NBR固體到HNBR的氫化(HD)過程的方案在方案2中列出。實驗條件和結果在表28-29和圖13中示出。 The hydrogenation process for NBR polymer solids was carried out in a 600 mL Parr autoclave reactor. The protocol for the hydrogenation (HD) process from NBR solids to HNBR is listed in Scheme 2. Experimental conditions and results are shown in Tables 28-29 and 13.

S-NBR固體產品的氫化在實施例31-1中進行。從 實施例28-4中的樣品獲得的S-NBR固體用於實施例31-1中的氫化試驗。將S-NBR固體溶解在有機溶劑(例如，MCB、MEK、DMAC、DEAC、特別是MCB)中。將所獲得的溶液混合物在含金屬的催化劑以及本發明的金屬催化劑體系的添加劑(例如RhCl(PPh3)3/PPh3)的存在下在所希望的氫氣壓力下進行氫化，實驗條件和結果在表28和圖13中列出。 Hydrogenation of the S-NBR solid product was carried out in Example 31-1. The S-NBR solid obtained from the sample in Example 28-4 was used in the hydrogenation test in Example 31-1. The S-NBR solid is dissolved in an organic solvent (eg, MCB, MEK, DMAC, DEAC, especially MCB). The obtained solution mixture is hydrogenated under the desired hydrogen pressure in the presence of a metal-containing catalyst and an additive of the metal catalyst system of the invention (for example, RhCl(PPh 3 ) 3 /PPh 3 ), the experimental conditions and results are Table 28 and Figure 13 are listed.

圖13係S-NBR和氫化的S-NBR的FT-IR圖譜FT-IR圖譜和1HNMR圖譜的判定在圖13中列出。 Figure 13 is a FT-IR spectrum of the S-NBR and hydrogenated S-NBR. The FT-IR spectrum and the 1 H NMR spectrum are determined in Figure 13.

此外，商用的NBR的氫化係在實施例31-2中在含金屬的催化劑以及本發明的金屬催化劑體系的添加劑(RhCl(PPh3)3/PPh3)以及有機溶劑(例如MCB)以及任選地助催化劑(例如DCAP)和單體(例如ACN和/或Bd)的存在下進行的。將商用NBR固體溶解在有機溶劑(例如，MCB、MEK、DMAC、DEAC、特別是MCB)中。將該溶液混合物在含金屬的催化劑以及本發明的金屬催化劑體系的添加劑(例如RhCl(PPh3)3/PPh3)的存在下在所希望的氫氣壓力下進行氫化。實驗條件和結果在表29中列出。 Further, the hydrogenation of commercial NBR is in the metal-containing catalyst of Example 31-2 and the additive of the metal catalyst system of the present invention (RhCl(PPh 3 ) 3 /PPh 3 ) and an organic solvent (for example, MCB) and optionally It is carried out in the presence of a cocatalyst such as DCAP and a monomer such as ACN and/or Bd. Commercial NBR solids are dissolved in an organic solvent (eg, MCB, MEK, DMAC, DEAC, especially MCB). The solution mixture is hydrogenated under the desired hydrogen pressure in the presence of a metal-containing catalyst and an additive of the metal catalyst system of the invention (e.g., RhCl(PPh 3 ) 3 /PPh 3 ). Experimental conditions and results are listed in Table 29.

在各個實施例中：MCB,170 mL；RhCl(PPh3)3,15 mg,0.016 mmol；PPh3,30 mg,0.11 mmol；氫氣壓力600 psi,120℃,1小時。 In various examples: MCB, 170 mL; RhCl (PPh 3 ) 3 , 15 mg, 0.016 mmol; PPh 3 , 30 mg, 0.11 mmol; hydrogen pressure 600 psi, 120 ° C, 1 hour.

發現在少量的單體(例如ACN和/或Bd)或助催化劑(例如DCAP)的存在下，該氫化可以實現高的轉化率，並且甚至在更大量的Bd單體(1 g NBR與5.5 g的Bd)的存在下，該NBR仍然可以被氫化。這個結果與在單體或任選地助催化劑和/或添加劑殘餘物的存在下的一鍋法方式中S-NBR直接以一鍋方式得到的氫化相同。 It has been found that in the presence of small amounts of monomers (for example ACN and/or Bd) or cocatalysts (for example DCAP), this hydrogenation can achieve high conversions and even in larger amounts of Bd monomers (1 g NBR and 5.5 g) The NBR can still be hydrogenated in the presence of Bd). This result is identical to the one-pot method of direct hydrogenation of S-NBR in a one-pot process in the presence of a monomer or optionally a cocatalyst and/or additive residue.

該含金屬的催化劑可以如在EP 2 072 532 A1、EP 2 072 533 A1、和CN101463096 A中描述的藉由使用離子交換樹脂進行移除。特別地，該共聚和/或氫化反應完成之後，將該反應混合物取出並且用離子交換樹脂在100℃下處理48小時並且然後在冷的甲醇中沉澱。 The metal-containing catalyst can be removed by using an ion exchange resin as described in EP 2 072 532 A1, EP 2 072 533 A1, and CN101463096 A. Specifically, after completion of the copolymerization and/or hydrogenation reaction, the reaction mixture was taken out and treated with an ion exchange resin at 100 ° C for 48 hours and then precipitated in cold methanol.

結論in conclusion

如以上提及的，該S-NBR法可以藉由直接以溶液形式提供NBR原料來簡化HNBR的生產。 As mentioned above, the S-NBR process can simplify the production of HNBR by providing the NBR feed directly in solution.

S-NBR(藉由在溶液中受控的自由基聚合而獲得的)作為原料以及用於HNBR生產的一鍋法具有以下優 點：1)簡化了製造過程，並且節省了加工時間和成本；2)提供了純的原料和純的HNBR產品；3)提供了具有控制分子量的HNBR，以及具有更低慕尼粘度的HNBR產品，而無需額外的成本/加工。 S-NBR (obtained by controlled radical polymerization in solution) as a raw material and a one-pot method for HNBR production has the following advantages Points: 1) simplifies the manufacturing process and saves processing time and cost; 2) provides pure raw materials and pure HNBR products; 3) provides HNBR with controlled molecular weight, and HNBR products with lower Mooney viscosity Without additional cost/processing.

該等結果清楚地表明瞭在各種操作條件下，有可能的是在含金屬的催化劑與適當的助催化劑和任選地的添加劑的催化劑的存在下合成具有受控的分子量以及窄的分子量分佈的腈橡膠聚合物。 These results clearly demonstrate that under various operating conditions it is possible to synthesize a nitrile having a controlled molecular weight and a narrow molecular weight distribution in the presence of a metal-containing catalyst with a suitable cocatalyst and optionally an additive catalyst. Rubber polymer.

儘管為了說明的目的，先前已對本發明進行了詳細描述，應該理解的是，這種詳述僅是為了說明的目的，除了當其可受到申請專利範圍的限制之外，熟習該項技術者在不背離本發明精神和範圍的條件下可以在其中做出多種改變。 Although the present invention has been described in detail for the purposes of illustration, it should be understood that this description is only for the purpose of illustration and description Many changes can be made therein without departing from the spirit and scope of the invention.

本發明的以上以及其他方面、特徵以及優點將從以下詳細說明結合附圖變得清楚，其中編號代表本文實施例的編號並且：圖1係實施例1-3的GPC曲線，其中編號1-3代表實施例1-3；圖2係實施例4-6的GPC曲線，其中編號4-6代表實施例4-6；圖3a係實施例6-15的Mn和PDI； 圖3b係實施例6和8-15的樣品的轉化率；圖3c係實施例6-16的樣品的FT-IR圖譜，其中編號6-16代表實施例6-16；圖3d係實施例6-16的樣品的1HNMR圖譜，其中編號6-16代表實施例6-16；圖3e係單獨的實施例6樣品的1HNMR圖譜；圖3f係實施例6-15的樣品的DSC曲線，其中編號6-15代表實施例6-15的樣品；圖4a係實施例3、6、17和18的樣品的FT-IR圖譜；圖4b係實施例3、6、17和18的樣品的1HNMR圖譜；圖5a係實施例22-1至22-3的樣品的1HNMR圖譜；圖5b係實施例22-7的樣品的1HNMR圖譜；圖6a-6c係實施例23-4、23-7以及23-10的樣品的1HNMR圖譜；圖7a-7c係實施例24-1、24-3以及24-4的樣品的1HNMR圖譜；圖7d係實施例24-5的樣品的1HNMR圖譜；圖8係實施例25的樣品的1HNMR圖譜；圖9a係實施例26-2的樣品的FT-IR圖譜；圖9b係實施例26-2的樣品的1HNMR圖譜；圖10a係實施例6的對照試驗的樣品的FT-IR圖譜；圖10b係實施例6的對照試驗的樣品的1HNMR圖譜； 圖10c係實施例27-1的具有三單體丙烯酸正丁酯的樣品的FT-IR圖譜；圖10d係實施例27-1的具有三單體丙烯酸正丁酯的樣品的1HNMR圖譜；圖10e係實施例27-2的具有三單體MMA樣品的FT-IR圖譜；圖10f係實施例27-2的具有三單體MMA樣品的1HNMR圖譜；圖10g係實施例27-3的具有三單體MAA樣品的FT-IR圖譜；圖10h-10i係實施例27-3的具有三單體MAA樣品的1HNMR圖譜；圖10j係實施例27-4的具有三單體IA樣品的FT-IR圖譜；圖10k-10l係實施例27-4的具有三單體IA樣品的1HNMR圖譜；圖10m係實施例27-5的具有三單體丙烯醯胺樣品的FT-IR圖譜；圖11a係進行不同的反應時間的實施例28-1和28-2的樣品的FT-IR圖譜；圖11b係實施例28-4的樣品的1HNMR圖譜；圖12係S-NBR和氫化的S-NBR的FT-IR圖譜和1HNMR圖譜；並且圖13係S-NBR和氫化的S-NBR的FT-IR圖譜。 The above and other aspects, features, and advantages of the present invention will become more apparent from the following detailed description of the appended claims. Representative Examples 1-3; Figure 2 is a GPC curve of Examples 4-6, wherein Numbers 4-6 represent Examples 4-6; Figure 3a is Mn and PDI of Examples 6-15; Figure 3b is Example 6 and sample rate conversion of 8-15; FIG. 3c-based FT-IR spectra of the samples of Examples 6-16 embodiment, wherein the representative Example No. 6-16 6-16; 6-16 sample of Example 3d-based embodiment of FIG. 1 H NMR spectrum, wherein numbers 6-16 represent Examples 6-16; Figure 3e is a 1 H NMR spectrum of a separate Example 6 sample; Figure 3f is a DSC curve for the samples of Examples 6-15, wherein number 6-15 represents implementation Samples of Examples 6-15; Figure 4a is an FT-IR spectrum of the samples of Examples 3, 6, 17, and 18; Figure 4b is a 1 H NMR spectrum of the samples of Examples 3, 6, 17, and 18; Figure 5a is an implementation 1 H NMR spectrum of the samples of Examples 22-1 to 22-3; Figure 5b is the 1 H NMR spectrum of the samples of Examples 22-7; Figures 6a-6c are the samples of Examples 23-4, 23-7, and 23-10 the 1 HNMR spectrum; Figures 7a-7c-based 1 HNMR chart of the sample of Example 24-1,24-3 and 24-4; Fig. 7d-based 1 HNMR chart of the sample of Example 24-5 embodiment; FIG. 8 line 1 HNMR spectrum of the sample of Example 25; FIG. 9a The FT-IR spectrum of the sample of Example 26-2; Figure 9b is the 1 H NMR spectrum of the sample of Example 26-2; Figure 10a is the FT-IR spectrum of the sample of the control test of Example 6; Figure 10b is an implementation 1 H NMR spectrum of the sample of the control test of Example 6; Fig. 10c is an FT-IR spectrum of the sample of the embodiment 37-1 having n-butyl butyl acrylate; Fig. 10d is the ternary of the sample of the embodiment 27-1 1 H NMR spectrum of a sample of n-butyl acrylate; Figure 10e is an FT-IR spectrum of a sample of a three-merate MMA of Example 27-2; Figure 10f is a 1 H NMR of a sample of a three-monomer MMA of Example 27-2 Figure 10g is an FT-IR spectrum of a three-cell MAA sample of Example 27-3; Figure 10h-10i is a 1 H NMR spectrum of a three-cell MAA sample of Example 27-3; Figure 10j is an example FT-IR spectrum of a sample of three monomers IA of 27-4; Figures 10k-10l are the 1 H NMR spectrum of the sample of the three monomer IA of Example 27-4; Figure 10m has three orders of the embodiment 27-5 Acrylamide sample FT-IR spectrum; Figure 11a is an FT-IR spectrum of the samples of Examples 28-1 and 28-2 for different reaction times; Figure 11b is a 1 H NMR spectrum of the sample of Example 28-4; FT-IR spectrum and 1 H NMR spectrum of -NBR and hydrogenated S-NBR; and Figure 13 is an FT-IR spectrum of S-NBR and hydrogenated S-NBR.

Claims (37)

一種含金屬之催化劑系統，其包括(1)含金屬的催化劑，(2)助催化劑，以及任選地(3)添加劑，係用於二烯的溶液聚合法和/或用於含二烯的聚合物的氫化作用，其中(1)該含金屬的催化劑係選自MLnXm、MXm、MXm．pH2O、M(OC(O)R)m、或其任何組合，其中M代表選自Rh、Pd、Ru、Ir、Mo、Co、Cu、Fe、或Ti的金屬，L係選自的基團，其中R1、R2、和R3可以是相同或不同的，並且R1、R2、和R3各自獨立地選自H、C1-C6烷基、C5-C7芳基或C3-C6環烷基、取代的C3-C6環烷基、取代的C5-C7芳基，其條件係R1、R2、和R3不全為H，X係鹵素，n係1至5的一整數，p係1至7的一整數，並且m係等於M的化合價；(2)該助催化劑係選自鹵化物、偶氮化合物或過氧化物；並且任選地(3)該添加劑係選自下組，該組由以下所組成：一級胺(R1-NH2)、二級胺(R1-NH-R2)、三級胺(N(R1)(R2)(R3))、、抗壞血酸、或銨鹽、或其任何組合，其中R1、R2、和R3如以上所定義。 A metal-containing catalyst system comprising (1) a metal-containing catalyst, (2) a cocatalyst, and optionally (3) an additive for solution polymerization of a diene and/or for a diene-containing Hydrogenation of a polymer wherein (1) the metal-containing catalyst is selected from the group consisting of ML n X m , MX m , MX m . pH 2 O, M(OC(O)R) m , or any combination thereof, wherein M represents a metal selected from the group consisting of Rh, Pd, Ru, Ir, Mo, Co, Cu, Fe, or Ti, and the L is selected from the group consisting of a group wherein R 1 , R 2 , and R 3 may be the same or different, and R 1 , R 2 , and R 3 are each independently selected from H, C 1 -C 6 alkyl, C 5 -C a 7- aryl or C 3 -C 6 cycloalkyl group, a substituted C 3 -C 6 cycloalkyl group, a substituted C 5 -C 7 aryl group, the conditions of which are R 1 , R 2 , and R 3 are not all H, X is a halogen, n is an integer from 1 to 5, p is an integer from 1 to 7, and m is equal to the valence of M; (2) the cocatalyst is selected from a halide, an azo compound or a peroxide; And optionally (3) the additive is selected from the group consisting of a primary amine (R 1 -NH 2 ), a secondary amine (R 1 -NH-R 2 ), a tertiary amine (N) (R 1 )(R 2 )(R 3 )), , ascorbic acid, or an ammonium salt, or any combination thereof, wherein R 1 , R 2 , and R 3 are as defined above. 如申請專利範圍第1項之含金屬之催化劑系統，其中(1)在該含金屬的催化劑中，M代表選自Rh、Pd、Ru、Ir、或Mo的金屬，較佳的是Rh、Pd、Ru、Ir，X係選自Cl或Br，更佳的是Cl；在中，每個R1、R2、和R3係獨立地選自：苯基、C3-C6環烷基、取代的C3-C6環烷基、苯基、取代的苯基，較佳的是羧基取代的苯基、磺酸鈉取代的苯基，更佳的是PPh3，三環己基膦(PCy3)、其中該磺酸鈉基團或羧基基團可以是在苯環的鄰位、間位或對位；(2)在該助催化劑中，該鹵化物係選自 、CH2Cl2、CHCl3、CCl4，其中R、R1、和R2各自獨立地是C1-C6烷基或C3-C6環烷基，並且R基團可以在苯環的鄰位、間位或對位，並且每個X獨立地如以上定義，該偶氮化合物係選自2,2’-偶氮雙異丁腈(AIBN)、2,2’-偶氮雙-(2-甲基丁腈(AMBN)、2,2’-偶氮二-(2-甲基丁腈(AMBN)、二甲 基2,2’-偶氮雙-(2-甲基丙酸酯、1-氰基-1-甲基乙基偶氮甲醯胺、1,1’-偶氮雙(環己烷-1-腈(ACCN)、2,2’-偶氮雙-(2-甲基丙醯胺)二鹽酸化物(AIBA)、或4,4’-偶氮雙-(4-氰戊酸)(ACVA)，並且該過氧化物係選自第三丁基過氧化氫、過氧化苯甲醯(BPO)或過氧化異丙苯；並且任選地(3)該添加劑係選自下組，該組由以下所組成：抗壞血酸、甲胺、乙胺、乙二胺、正丙胺、異丙胺、丙二胺、正丁胺、異丁胺、丁二胺、二丁胺、二甲胺、二乙胺、二異丙胺、第三丁胺、戊胺、環己胺、三乙醇胺、三甲胺、三乙胺、三正丙胺、三正丁胺、環庚胺、環戊胺、甲基三正辛基銨氯化物(MTOAC)、、或其任何組合，其中R1、R2、和R3如以上定義。 The metal-containing catalyst system of claim 1, wherein (1) in the metal-containing catalyst, M represents a metal selected from the group consisting of Rh, Pd, Ru, Ir, or Mo, preferably Rh, Pd. , Ru, Ir, X is selected from Cl or Br, more preferably Cl; Wherein each of R 1 , R 2 , and R 3 is independently selected from the group consisting of: phenyl, C 3 -C 6 cycloalkyl, substituted C 3 -C 6 cycloalkyl, phenyl, substituted phenyl, Preferred is a carboxy substituted phenyl group, a sodium sulfonate substituted phenyl group, more preferably PPh 3 , tricyclohexylphosphine (PCy 3 ), Wherein the sodium sulfonate group or the carboxyl group may be ortho, meta or para to the phenyl ring; (2) in the cocatalyst, the halide is selected from , CH 2 Cl 2 , CHCl 3 , CCl 4 , wherein R, R 1 , and R 2 are each independently C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl, and the R group may be in the phenyl ring Ortho, meta or para, and each X is independently as defined above, the azo compound is selected from the group consisting of 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azo double -(2-methylbutyronitrile (AMBN), 2,2'-azobis-(2-methylbutyronitrile (AMBN), dimethyl 2,2'-azobis-(2-methylpropane) Acid ester, 1-cyano-1-methylethylazomethamine, 1,1'-azobis(cyclohexane-1-carbonitrile (ACCN), 2,2'-azobis-( 2-methylpropionamide) dihydrochloride (AIBA), or 4,4'-azobis-(4-cyanovaleric acid) (ACVA), and the peroxide is selected from the group consisting of tert-butyl peroxidation Hydrogen, benzamidine peroxide (BPO) or cumene peroxide; and optionally (3) the additive is selected from the group consisting of ascorbic acid, methylamine, ethylamine, ethylenediamine , n-propylamine, isopropylamine, propylenediamine, n-butylamine, isobutylamine, butanediamine, dibutylamine, dimethylamine, diethylamine, diisopropylamine, tert-butylamine, pentylamine, cyclohexylamine , triethanolamine, trimethylamine, triethylamine, three positive Amine, n-butylamine, cycloheptyl amine, cyclopentyl amine, tri-n-octyl methyl ammonium chloride (MTOAC), Or any combination thereof, wherein R 1 , R 2 , and R 3 are as defined above. 如申請專利範圍第1-2項中一項或多項之含金屬之催化劑系統，其中該含金屬之催化劑系統係選自：由以下所組成的組：(1)MClm(PPh3)n、(2)、2,2-二氯苯乙酮(DCAP)或苄基氯、以及任選地(3)PPh3；由以下所組成的組：(1)MClm和/或MXm．pH2O、(2)2,2-二氯苯乙酮(DCAP)或苄基氯(BCL)、以及任選地(3)PPh3； 由以下所組成的組：(1)MClm(PPh3)n、(2)PhCH2Cl、以及任選地(3)PPh3；由以下所組成的組：(1)(MClm(PPh3)n、(2)CH2Cl2、CHCl3、CCl4之一、以及任選地(3)PPh3；由以下所組成的組：(1)MClm(PPh3)n、(2)Cl3CCOOCH2CH3、以及任選地(3)PPh3；由以下所組成的組：(1)MClm(PPh3)n、(2)2,2’-偶氮雙異丁腈(AIBN)、2,2’-偶氮雙-(2-甲基丁腈(AMBN)、2,2’-偶氮二-(2-甲基丁腈(AMBN)、二甲基2,2’-偶氮雙-(2-甲基丙酸酯、1-氰基-1-甲基乙基偶氮甲醯胺、1,1’-偶氮雙(環己烷-1-腈(ACCN)、2,2’-偶氮雙-(2-甲基丙醯胺)二鹽酸化物(AIBA)、4,4’-偶氮雙-(4-氰戊酸)(ACVA)中的至少之一、以及任選地(3)PPh3；或者由以下所組成的組：(1)M(OAc)m、(2)CH2Cl2、CHCl3、CCl4中的至少之一、以及任選地(3)P(Ph)3；其中M係選自Rh、Pd、Ru、Ir、Mo，較佳的是選自Rh、Ru、Pd、和Ir，更佳的是選自Rh、Ru、和Pd，n係整數3，p係1至7的整數並且m係等於M的化合價。 A metal-containing catalyst system as claimed in one or more of claims 1-2, wherein the metal-containing catalyst system is selected from the group consisting of: (1) MCl m (PPh 3 ) n , (2) 2,2-dichloroacetophenone (DCAP) or benzyl chloride, and optionally (3) PPh 3 ; a group consisting of: (1) MCl m and/or MX m . pH 2 O, (2) 2,2-dichloroacetophenone (DCAP) or benzyl chloride (BCL), and optionally (3) PPh 3 ; a group consisting of: (1) MCl m ( PPh 3 ) n , (2) PhCH 2 Cl, and optionally (3) PPh 3 ; a group consisting of: (1) (MCl m (PPh 3 ) n , (2) CH 2 Cl 2 , CHCl 3 , one of CCl 4 , and optionally (3) PPh 3 ; a group consisting of: (1) MCl m (PPh 3 ) n , (2) Cl 3 CCOOCH 2 CH 3 , and optionally ( 3) PPh 3 ; a group consisting of: (1) MCl m (PPh 3 ) n , (2) 2, 2'-azobisisobutyronitrile (AIBN), 2, 2'-azobis- (2-methylbutyronitrile (AMBN), 2,2'-azobis-(2-methylbutyronitrile (AMBN), dimethyl 2,2'-azobis-(2-methylpropionic acid) Ester, 1-cyano-1-methylethylazomethamine, 1,1'-azobis(cyclohexane-1-carbonitrile (ACCN), 2,2'-azobis-(2 At least one of -methylpropionamide) dihydrochloride (AIBA), 4,4'-azobis-(4-cyanovaleric acid) (ACVA), and optionally (3) PPh 3 ; a group consisting of: (1) at least one of M(OAc) m , (2) CH 2 Cl 2 , CHCl 3 , CCl 4 , and optionally (3) P(Ph) 3 ; Is selected from Rh, Pd, Ru, Ir, Mo, Is selected from Rh, Ru, Pd, and Ir, more preferably it is selected from Rh, Ru, and Pd, n an integer of 3 lines, line p is an integer of 1 to 7 and m is equal to the valence of M lines. 如申請專利範圍第1-3項中一項或多項之含金屬之催化劑系統，其中該含金屬之催化劑系統係選自：由以下所組成的組：RhCl(PPh3)3、2,2-二氯苯乙酮 (DCAP)、以及任選地PPh3；由以下所組成的組：RhCl3或RhCl3．3H2O、2,2-二氯苯乙酮、以及PPh3；由以下所組成的組：RhCl(PPh3)3、Cl3CCOOCH2CH3、以及任選地PPh3；由以下所組成的組：RhCl3或RhCl3．3H2O、Cl3CCOOCH2CH3以及PPh3；包括或由RhCl(PPh3)3、PhCH2Cl以及任選地PPh3組成的混合物；由以下所組成的組：RhCl3或RhCl3．3H2O、PhCH2Cl、以及PPh3；由以下所組成的組：PdCl2、2,2-二氯苯乙酮、以及PPh3；由以下所組成的組：PdCl2、苄基氯、以及PPh3；由以下所組成的組：RhCl(PPh3)，CH2Cl2、CHCl2、CCl4中的至少之一，以及任選地PPh3；由以下所組成的組：RhCl3或RhCl3．3H2O，CH2Cl2、CHCl3、CCl4中的至少之一，以及PPh3；由以下所組成的組：Pd(OAc)2，CH2Cl2、CHCl3、CCl4中的至少之一，以及PPh3；或由以下項組成的組：RhCl(PPh3)3、偶氮雙異庚腈(ABVN)、以及任選地PPh3。 A metal-containing catalyst system according to one or more of claims 1-3, wherein the metal-containing catalyst system is selected from the group consisting of RhCl(PPh 3 ) 3 , 2 , 2 Dichloroacetophenone (DCAP), and optionally PPh 3 ; a group consisting of RhCl 3 or RhCl 3 . 3H 2 O, 2,2-dichloroacetophenone, and PPh 3 ; a group consisting of RhCl(PPh 3 ) 3 , Cl 3 CCOOCH 2 CH 3 , and optionally PPh 3 ; Group: RhCl 3 or RhCl 3 . 3H 2 O, Cl 3 CCOOCH 2 CH 3 and PPh 3 ; a mixture comprising or consisting of RhCl(PPh 3 ) 3 , PhCH 2 Cl and optionally PPh 3 ; a group consisting of RhCl 3 or RhCl 3 . 3H 2 O, PhCH 2 Cl, and PPh 3 ; a group consisting of PdCl 2 , 2,2-dichloroacetophenone, and PPh 3 ; a group consisting of PdCl 2 , benzyl chloride, And PPh 3 ; a group consisting of RhCl (PPh 3 ), at least one of CH 2 Cl 2 , CHCl 2 , CCl 4 , and optionally PPh 3 ; a group consisting of RhCl 3 or RhCl 3 . At least one of 3H 2 O, CH 2 Cl 2 , CHCl 3 , CCl 4 , and PPh 3 ; a group consisting of: at least Pd(OAc) 2 , CH 2 Cl 2 , CHCl 3 , CCl 4 One, and PPh 3 ; or a group consisting of RhCl(PPh 3 ) 3 , azobisisoheptonitrile (ABVN), and optionally PPh 3 . 如申請專利範圍第1-4項中一項或多項之含金屬之催化劑系統，其中該含金屬之催化劑系統係選自由 按重量計的以下所組成的組合物：RhCl(PPh3)3：DCAP：PPh3=1：0.3-3.0：0-20；RhCl3：DCAP：PPh3=1：1.3-13：4.4-88；RhCl3．3H2O：DCAP：PPh3=1：1.0-10：3.0-63；RhCl(PPh3)3：Cl3CCOOCH2CH3：PPh3=1：0.3-3.0：0-20；RhCl3：Cl3CCOOCH2CH3：PPh3=1：1.3-3.9：4.4-88；RhCl3．3H2O：Cl3CCOOCH2CH3：PPh3=1：1.0-10：3.0-63；RhCl(PPh3)3：PhCH2Cl：PPh3=1：0.05-2.0：0-20；RhCl3：PhCH2Cl：PPh3=1：0.22-9.0：4.4-88；RhCl3．3H2O：PhCH2Cl：PPh3=1：0.2-7.0：3.0-63；PdCl2：DCAP：PPh3=1：0.3-3.0：0-20；RhCl(PPh3)3：CCl4：PPh3=1：0.1-3：0-20；RhCl3：CCl4：PPh3=1：0.4-13：4.4-88；RhCl3．3H2O：CCl4：PPh3=1：0.3-11：3.0-63；Pd(OAc)2：CCl4：PPh3=1：10-4-10-2：3.5-27；或RhCl(PPh3)3：ABVN：PPh3=0-1：1-10：2-20。 A metal-containing catalyst system according to one or more of claims 1-4, wherein the metal-containing catalyst system is selected from the group consisting of: RhCl(PPh 3 ) 3 : DCAP :PPh 3 =1:0.3-3.0:0-20; RhCl 3 :DCAP:PPh 3 =1:1.3-13:4.4-88; RhCl 3 . 3H 2 O: DCAP: PPh 3 = 1: 1.0-10: 3.0-63; RhCl(PPh 3 ) 3 : Cl 3 CCOOCH 2 CH 3 : PPh 3 = 1: 0.3-3.0: 0-20; RhCl 3 : Cl 3 CCOOCH 2 CH 3 : PPh 3 =1: 1.3-3.9: 4.4-88; RhCl 3 . 3H 2 O:Cl 3 CCOOCH 2 CH 3 :PPh 3 =1:1.0-10:3.0-63; RhCl(PPh 3 ) 3 :PhCH 2 Cl:PPh 3 =1:0.05-2.0:0-20; RhCl 3 :PhCH 2 Cl: PPh 3 = 1: 0.22-9.0: 4.4-88; RhCl 3 . 3H 2 O:PhCH 2 Cl:PPh 3 =1:0.2-7.0:3.0-63; PdCl 2 :DCAP:PPh 3 =1:0.3-3.0:0-20; RhCl(PPh 3 ) 3 :CCl 4 :PPh 3 =1: 0.1-3: 0-20; RhCl 3 : CCl 4 : PPh 3 = 1: 0.4-13: 4.4-88; RhCl 3 . 3H 2 O:CCl 4 :PPh 3 =1:0.3-11:3.0-63; Pd(OAc) 2 :CCl 4 :PPh 3 =1:10 -4 -10 -2 :3.5-27; or RhCl(PPh 3 ) 3 : ABVN: PPh 3 = 0-1: 1-10: 2-20. 如申請專利範圍第1-5項中一項或多項之含金屬之催化劑系統，其中該含金屬之催化劑系統係選自由按重量計的以下所組成的組合物：RhCl(PPh3)3：DCAP：PPh3=1：0.5-2.0：1-10；RhCl3：DCAP：PPh3=1：2.2-9.0：5.4-50； RhCl3．3H2O：DCAP：PPh3=1：2.0-8：4.0-44；RhCl(PPh3)3：Cl3CCOOCH2CH3：PPh3=1：0.5-2.0：1-10；RhCl3：Cl3CCOOCH2CH3：PPh3=1：2.2-9.0：54-50；RhCl3．3H2O：Cl3CCOOCH2CH3：PPh3=1：2.0-8：4.0-44；RhCl(PPh3)3：PhCH2Cl：PPh3=1：0.08-1.5：1-10；RhCl3：PhCH2Cl：PPh3=1：0.35-6.7：5.4-50；RhCl3．3H2O：PhCH2Cl：PPh3=1：0.3-6.0：4.0-44；PdCl2：DCAP：PPh3=1：0.5-2.0：1-10；RhCl(PPh3)3：CCl4：PPh3=1：0.2-2：1-10；RhCl3：CCl4：PPh3=1：0.9-9：5.4-50；RhCl3．3H2O：CCl4：PPh3=1：0.7-7：4.0-44；Pd(OAc)2：CCl4：PPh3=1：5＊10-4-5＊10-2：4.5-17；或RhCl(PPh3)3：ABVN：PPh3=0.2-0.5：0.5-2：0.5-4。 A metal-containing catalyst system according to one or more of claims 1-5, wherein the metal-containing catalyst system is selected from the group consisting of: RhCl(PPh 3 ) 3 : DCAP :PPh 3 =1:0.5-2.0:1-10; RhCl 3 :DCAP:PPh 3 =1:2.2-9.0:5.4-50; RhCl 3 . 3H 2 O: DCAP: PPh 3 = 1: 2.0-8: 4.0-44; RhCl(PPh 3 ) 3 : Cl 3 CCOOCH 2 CH 3 : PPh 3 = 1: 0.5-2.0: 1-10; RhCl 3 : Cl 3 CCOOCH 2 CH 3 : PPh 3 =1: 2.2-9.0: 54-50; RhCl 3 . 3H 2 O:Cl 3 CCOOCH 2 CH 3 :PPh 3 =1:2.0-8:4.0-44; RhCl(PPh 3 ) 3 :PhCH 2 Cl:PPh 3 =1:0.08-1.5:1-10; RhCl 3 :PhCH 2 Cl:PPh 3 =1:0.35-6.7:5.4-50; RhCl 3 . 3H 2 O:PhCH 2 Cl:PPh 3 =1:0.3-6.0:4.0-44; PdCl 2 :DCAP:PPh 3 =1:0.5-2.0:1-10; RhCl(PPh 3 ) 3 :CCl 4 :PPh 3 =1: 0.2-2: 1-10; RhCl 3 : CCl 4 : PPh 3 = 1: 0.9-9: 5.4-50; RhCl 3 . 3H 2 O:CCl 4 :PPh 3 =1:0.7-7:4.0-44; Pd(OAc) 2 :CCl 4 :PPh 3 =1:5 * 10 -4 -5 * 10 -2 :4.5-17; Or RhCl(PPh 3 ) 3 : ABVN: PPh 3 = 0.2-0.5: 0.5-2: 0.5-4. 如申請專利範圍第1-6項中一項或多項之含金屬之催化劑系統，其中該添加劑係選自下組，該組由以下所組成：抗壞血酸、甲基三正辛基銨氯化物、正丙胺、異丙胺、丙二胺、正丁胺、異丁胺、正丁胺、二丁胺、三甲胺、三乙胺、三正丙胺、三正丁胺、或其組合。 A metal-containing catalyst system as claimed in one or more of claims 1-6, wherein the additive is selected from the group consisting of ascorbic acid, methyl tri-n-octyl ammonium chloride, positive Propylamine, isopropylamine, propylenediamine, n-butylamine, isobutylamine, n-butylamine, dibutylamine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, or a combination thereof. 一種二烯的溶液聚合法，包括在至少一種如申請專利範圍第1-7項中一項或多項之含金屬之催化劑系 統的存在下在至少一種有機溶劑中將二烯進行均聚或二烯連同至少一種單體進行共聚。 A solution polymerization method for a diene comprising at least one metal-containing catalyst system according to one or more of claims 1-7 The diene is homopolymerized or the diene is copolymerized with at least one monomer in at least one organic solvent in the presence of a system. 如申請專利範圍第8項之溶液聚合法，其中該等二烯係選自任何已知的二烯，較佳的是選自至少一種共軛的二烯，更佳的是C4-C6共軛二烯，包括1,3-丁二烯、異戊二烯、2,3-二甲基丁二烯、1,3-戊二烯或其混合物，並且最佳的是1,3-丁二烯、異戊二烯或其混合物。 The solution polymerization method of claim 8, wherein the diene is selected from any known diene, preferably selected from at least one conjugated diene, more preferably C 4 - C 6 Conjugated diene, including 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene or a mixture thereof, and the most preferred is 1,3- Butadiene, isoprene or a mixture thereof. 如申請專利範圍第8-9項中一項或多項之溶液聚合法，其中該至少一種共聚單體係選自至少一種α,β-不飽和腈或基於苯乙烯的化合物，並且較佳的是該至少一種α,β-不飽和腈係選自任何已知的α,β-不飽和腈，更佳的是一種α,β-不飽和(C3-C5)腈，包括丙烯腈、甲基丙烯腈、乙基丙烯腈或其混合物，最佳的是丙烯腈；該基於苯乙烯的化合物係選自苯乙烯、α-甲基苯乙烯或乙烯基甲苯。 A solution polymerization process according to one or more of claims 8-9, wherein the at least one copolymerization system is selected from at least one α,β-unsaturated nitrile or styrene-based compound, and preferably The at least one α,β-unsaturated nitrile is selected from any known α,β-unsaturated nitrile, more preferably an α,β-unsaturated (C 3 -C 5 ) nitrile, including acrylonitrile, A The acrylonitrile, ethacrylonitrile or a mixture thereof is most preferably acrylonitrile; the styrene-based compound is selected from the group consisting of styrene, α-methylstyrene or vinyltoluene. 如申請專利範圍第8-10項中一項或多項之溶液聚合法，其中該至少一種共聚單體係選自苯乙烯。 A solution polymerization process according to one or more of claims 8-10, wherein the at least one copolymerization system is selected from the group consisting of styrene. 如申請專利範圍第8-11項中一項或多項之溶液聚合法，其中該至少一種共聚單體進一步包括三單體，包括：乙烯基單體、亞乙烯基單體以及α,β-不飽和的單體，該等單體係選自(甲基)丙烯酸、任何(甲基)丙烯酸酯、任何(甲基)丙烯酸鹽、任何烯烴、以及任何不飽和的羧酸中的至少之一，較佳的是(甲基) 丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、乙烯、丙烯、亞乙烯基單體、(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸環己基酯、(甲基)丙烯酸苯基酯、(甲基)丙烯酸2-胺基乙基酯、(甲基)丙烯酸2-二甲基胺基乙基酯、富馬酸、馬來酸以及衣康酸之任何者。 A solution polymerization process according to one or more of claims 8-11, wherein the at least one comonomer further comprises three monomers, including: a vinyl monomer, a vinylidene monomer, and an α,β- a saturated monomer selected from at least one of (meth)acrylic acid, any (meth) acrylate, any (meth) acrylate, any olefin, and any unsaturated carboxylic acid, Preferred is (methyl) N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, ethylene, propylene, vinylidene monomer, methyl (meth)acrylate, ethyl (meth)acrylate Ester, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylate Hydroxybutyl ester, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-aminoethyl (meth) acrylate, (meth) acrylate 2 Any of dimethylaminoethyl ester, fumaric acid, maleic acid, and itaconic acid. 如申請專利範圍第8-12項中一項或多項之溶液聚合法，其中該至少一種有機溶劑係選自不與該催化劑反應或以其他方式干擾該反應的任何有機溶劑，較佳的是選自：苯、甲苯、環己烷、二甲亞碸(DMSO)、碳酸乙烯酯(EC)、四氫呋喃(THF)、1,4-二烷一氯苯(MCB)、二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAC)、或其混合物，更佳的是選自：一氯苯(MCB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)，進一步較佳的是選自：一氯苯(MCB)和甲基乙基酮(MEK)，最佳的是一氯苯(MCB)。 A solution polymerization process according to one or more of claims 8-12, wherein the at least one organic solvent is selected from any organic solvent that does not react with or otherwise interfere with the reaction, preferably selected. From: benzene, toluene, cyclohexane, dimethyl hydrazine (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4-two Alkanochlorobenzene (MCB), Dichlorobenzene (DCB), Trichlorobenzene (TCB), Monobromobenzene (MBB), Dibromobenzene (DBB), Tribromobenzene (TBB), Methyl Ethyl Ketone (MEK) , N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), or a mixture thereof, more preferably selected from the group consisting of: monochlorobenzene (MCB), methyl Ethyl ketone (MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC), further preferably selected from the group consisting of: monochlorobenzene (MCB) And methyl ethyl ketone (MEK), the most preferred is monochlorobenzene (MCB). 如申請專利範圍第8-13項中一項或多項之溶液聚合 法，其中該含金屬之催化劑系統係選自由以下所組成的組：RhCl(PPh3)3：DCAP：PPh3，其中按重量計的RhCl(PPh3)3：DCAP：PPh3=1：0.5-2.0：1-10；由以下所組成的組：RhCl3：DCAP：PPh3，其中按重量計的RhCl3：DCAP：PPh3=1：2.2-9.0：5.4-50；由以下所組成的組：RhCl3．3H2O：DCAP：PPh3，其中按重量計的RhCl3．3H2O：DCAP：PPh3=1：2.0-8：4.0-44；由以下所組成的組：PdCl2：DCAP：PPh3，其中按重量計的PdCl2：DCAP：PPh3=1：0.5-2.0：1-10；由以下所組成的組：Pd(OAc)2：CCl4：PPh3，其中按重量計的Pd(OAc)2：CCl4：PPh3=1：5＊10-4-5＊10-2：3.5-27；由以下所組成的組：RhCl(PPh3)3：PhCH2Cl：PPh3，其中，按重量計的RhCl(PPh3)3：PhCH2Cl：PPh3=1：0.08-1.5：1-10；由以下所組成的組：RhCl3：PhCH2Cl：PPh3，其中，按重量計的RhCl3：PhCH2Cl：PPh3=1：0.35-6.7：5.4-50；或由以下所組成的組：RhCl3．3H2O：PhCH2Cl：PPh3，其中，按重量計的RhCl3．3H2O：PhCH2Cl：PPh3=1：0.3-6.0：4.0-44。 A solution polymerization process according to one or more of claims 8-13, wherein the metal-containing catalyst system is selected from the group consisting of RhCl(PPh 3 ) 3 : DCAP: PPh 3 , wherein by weight RhCl (PPh 3) 3 meter: DCAP: PPh 3 = 1: 0.5-2.0: 1-10; from the group consisting of: RhCl 3: DCAP: PPh 3 , wherein by weight RhCl 3: DCAP: PPh 3 =1: 2.2-9.0: 5.4-50; a group consisting of RhCl 3 . 3H 2 O: DCAP: PPh 3 , wherein RhCl 3 by weight. 3H 2 O: DCAP: PPh 3 = 1: 2.0-8: 4.0-44; a group consisting of PdCl 2 : DCAP: PPh 3 , wherein PdCl 2 : DCAP: PPh 3 = 1: 0.5 by weight -2.0: 1-10; the group consisting of the following: Pd (OAc) 2: CCl 4: PPh3, wherein by weight Pd (OAc) 2: CCl4: PPh3 = 1: 5 * 10-4-5 * 10 -2 : 3.5-27; a group consisting of RhCl(PPh 3 ) 3 :PhCH 2 Cl:PPh 3 , wherein RhCl(PPh 3 ) 3 :PhCH 2 Cl:PPh 3 =1 by weight : 0.08-1.5: 1-10; a group consisting of RhCl 3 :PhCH 2 Cl:PPh 3 , wherein RhCl 3 :PhCH 2 Cl:PPh 3 =1:0.35-6.7:5.4- by weight 50; or a group consisting of RhCl 3 . 3H 2 O: PhCH 2 Cl: PPh 3 , wherein RhCl 3 by weight. 3H 2 O: PhCH 2 Cl: PPh 3 = 1:0.3-6.0: 4.0-44. 如申請專利範圍第8-14項中一項或多項之溶液聚 合法，其中該二烯均聚物或共聚物具有的受控的Mn係從1,000至300,000，與PDI係從1.0至5.0，較佳的是該受控的Mn係從3,000至100,000，與PDI係從1.1至4.0，更佳的是該受控的Mn係5,000至50,000，與PDI係1.1至3.0，基於該二烯均聚物或共聚物的總重量，該二烯均聚物或共聚物中的ACN含量係從0至65 wt%，或該二烯共聚物中的苯乙烯含量係從0至80，較佳的是該二烯共聚物中的ACN含量係從10 wt%至63 wt%，或該二烯共聚物中的苯乙烯含量係從20 wt%至80 wt%，更佳的是，該二烯共聚物中的ACN含量係從30 wt%至60 wt%，或該二烯共聚物中的苯乙烯含量係從20 wt%至70 wt%。 Solution concentration as in one or more of claims 8-14 Legal, wherein the diene homopolymer or copolymer has a controlled Mn system from 1,000 to 300,000, and a PDI system from 1.0 to 5.0, preferably the controlled Mn system is from 3,000 to 100,000, with a PDI system. More preferably, from 1.1 to 4.0, the controlled Mn is from 5,000 to 50,000, and the PDI is from 1.1 to 3.0, based on the total weight of the diene homopolymer or copolymer, in the diene homopolymer or copolymer. The ACN content is from 0 to 65 wt%, or the styrene content in the diene copolymer is from 0 to 80, preferably the ACN content in the diene copolymer is from 10 wt% to 63 wt%. Or the styrene content in the diene copolymer is from 20 wt% to 80 wt%, more preferably, the ACN content in the diene copolymer is from 30 wt% to 60 wt%, or the diene The styrene content in the copolymer is from 20 wt% to 70 wt%. 如申請專利範圍第8-15項中一項或多項之溶液聚合法，其中進行該聚合反應所使用的該二烯的進料重量份係從約大於0至約小於100，並且該至少一種共聚單體的進料重量份係從約小於100至約大於0。 A solution polymerization method according to one or more of claims 8-15, wherein the diene has a feed weight fraction of from about greater than 0 to about less than 100, and the at least one copolymerization is carried out. The monomer feed weight fraction is from about less than 100 to about greater than zero. 如申請專利範圍第8-16項中一項或多項之溶液聚合法，其中進行該聚合反應所使用的α,β-不飽和腈單體的進料重量份係約4至約小於96，或該苯乙烯以及任何苯乙烯衍生物的進料重量百分比係從約小於96至約4，較佳的是該α,β-不飽和腈單體的進料重量份係約4至約小於90，或該苯乙烯以及任 何苯乙烯衍生物的進料重量百分比係從約小於96至約10。 a solution polymerization method according to one or more of claims 8-16, wherein the feed weight fraction of the α,β-unsaturated nitrile monomer used in the polymerization is from about 4 to about less than 96, or The styrene and any styrene derivative have a feed weight percentage of from about less than 96 to about 4, preferably from about 4 to about less than 90 parts by weight of the feed of the alpha, beta-unsaturated nitrile monomer. Or the styrene and any The weight percent of the feed of the styrene derivative is from about less than about 96 to about 10. 如申請專利範圍第8-17項中一項或多項之溶液聚合法，其中該聚合反應在10℃-160℃的溫度進行5-200小時，較佳的是在20℃-150℃的溫度進行10-180小時，更佳的是在30℃-140℃的溫度進行20-170小時，進一步較佳的是在40℃-140℃的溫度進行10-150小時，仍然較佳的是在60℃-140℃的溫度進行1-100小時，並且該二烯橡膠聚合物具有。 A solution polymerization process according to one or more of claims 8-17, wherein the polymerization is carried out at a temperature of from 10 ° C to 160 ° C for from 5 to 200 hours, preferably from 20 ° C to 150 ° C. More preferably, it is 10-180 hours, more preferably 30-170 hours at a temperature of 30 ° C - 140 ° C, still more preferably 10 - 150 hours at a temperature of 40 ° C - 140 ° C, still preferably 60 ° C. The temperature of -140 ° C is carried out for 1-100 hours, and the diene rubber polymer has. 如申請專利範圍第8-18項中一項或多項之溶液聚合法，進一步包括移除該含金屬的催化劑的步驟，較佳的是藉由使用離子交換樹脂。 The solution polymerization method as claimed in one or more of claims 8-18 further includes the step of removing the metal-containing catalyst, preferably by using an ion exchange resin. 一種藉由溶液聚合反應獲得的二烯聚合物，包含從40至85重量份範圍內的衍生自一或多種二烯的重複單元，從0至70重量份範圍內的衍生自一或多種α,β-不飽和腈的或苯乙烯或任何苯乙烯衍生物的重複單元，以及從0至40重量份範圍內的衍生自任選的除α,β-不飽和腈或苯乙烯以及任何苯乙烯衍生物之外的三單體的重複單元。 A diene polymer obtained by solution polymerization comprising repeating units derived from one or more dienes in a range of from 40 to 85 parts by weight, derived from one or more α in a range of from 0 to 70 parts by weight, a repeating unit of a β-unsaturated nitrile or styrene or any styrene derivative, and from 0 to 40 parts by weight derived from an optional α,β-unsaturated nitrile or styrene and any styrene derived A repeating unit of three monomers other than the substance. 藉由如申請專利範圍第8-19項中一項或多項所述之溶液聚合法獲得的二烯聚合物的用途，係在氫氣的以及基於Rh、Ru、和/或Pd的催化劑的存在下在氫化作用中獲得氫化的二烯聚合物。 Use of a diene polymer obtained by solution polymerization as described in one or more of claims 8-19, in the presence of hydrogen and a Rh, Ru, and/or Pd based catalyst A hydrogenated diene polymer is obtained in the hydrogenation. 如申請專利範圍第21項所述之用途，該基於Rh、Ru、和/或Pd的含金屬的催化劑係選自金屬Rh、Ru或Pd，或在申請專利範圍1-7中一項或多項中定義的Rh、Ru、或Pd的含金屬的催化劑以及PPh3。 The metal-containing catalyst based on Rh, Ru, and/or Pd is selected from the group consisting of metal Rh, Ru or Pd, or one or more of claims 1-7, as claimed in claim 21 of the patent application. A metal-containing catalyst of Rh, Ru, or Pd as defined in PPh 3 . 一種用於合成氫化的二烯聚合物的一鍋法，包括在如申請專利範圍第8-19中一項或多項的溶液聚合完成之後直接將氫氣引入到該反應器中並且在所希望的溫度下進行反應。 A one-pot process for the synthesis of hydrogenated diene polymers, comprising introducing hydrogen directly into the reactor after completion of solution polymerization as one or more of claims 8-19, and at a desired temperature The reaction is carried out. 如申請專利範圍第23項之用於合成氫化的二烯聚合物的一鍋法，其中該所希望的溫度係從60℃至200℃並且該氫化反應在100-3000 Psi的氫氣壓力下進行10分鐘至20小時，較佳的是該所希望的溫度係從80℃至180℃並且該反應在200-2000 Psi的氫氣壓力下進行10分鐘至10小時，更佳的是該所希望的溫度係從100℃至160℃並且該反應在300-1500 Psi的氫氣壓力下進行30分鐘至5小時，進一步較佳的是該所希望的溫度係從120℃至150℃並且該反應在500-1000 Psi的氫氣壓力下進行30分鐘至3小時。 A one-pot process for synthesizing a hydrogenated diene polymer according to claim 23, wherein the desired temperature is from 60 ° C to 200 ° C and the hydrogenation reaction is carried out under a hydrogen pressure of from 100 to 3000 Psi. From minute to 20 hours, preferably the desired temperature is from 80 ° C to 180 ° C and the reaction is carried out at a hydrogen pressure of 200-2000 Psi for 10 minutes to 10 hours, more preferably the desired temperature system. From 100 ° C to 160 ° C and the reaction is carried out at a hydrogen pressure of 300-1500 Psi for 30 minutes to 5 hours, further preferably the desired temperature is from 120 ° C to 150 ° C and the reaction is at 500-1000 Psi The hydrogen pressure is carried out for 30 minutes to 3 hours. 如申請專利範圍第23和24項中一項或多項之用於合成氫化的二烯聚合物的一鍋法，進一步包括移除該含金屬的催化劑的步驟，較佳的是藉由使用離子交換樹脂。 A one-pot process for synthesizing a hydrogenated diene polymer as claimed in one or more of claims 23 and 24, further comprising the step of removing the metal-containing catalyst, preferably by using ion exchange Resin. 一種氫化的二烯聚合物，藉由如申請專利範圍第 23-25項中一項或多項之用於合成氫化的二烯聚合物的一鍋法獲得。 a hydrogenated diene polymer by the scope of the patent application One-pot method for synthesizing hydrogenated diene polymers from one or more of items 23-25. 一種用於二烯聚合物的氫化之方法，包括：a)在如申請專利範圍第1-7項中任一項或多項述之含金屬的催化劑系統的存在下在至少一種有機溶劑中將二烯進行溶液均聚或二烯連同至少一種單體進行共聚以獲得二烯橡膠，b)在該溶液聚合完成之後直接將氫氣引入到步驟a)的混合物中，以獲得該氫化的含二烯的聚合物。 A method for hydrogenating a diene polymer, comprising: a) placing two in at least one organic solvent in the presence of a metal-containing catalyst system as described in any one or more of claims 1-7 The alkene is subjected to solution homopolymerization or diene copolymerization with at least one monomer to obtain a diene rubber, b) direct hydrogen is introduced into the mixture of step a) after completion of the solution polymerization to obtain the hydrogenated diene-containing polymer. 如申請專利範圍第27項之用於二烯聚合物的氫化之方法，其中該二烯係選自任何已知的二烯，較佳的是選自至少一種共軛的二烯以及至少一種非共軛的二烯，更佳的是C4-C6共軛二烯，包括1,3-丁二烯、異戊二烯、2,3-二甲基丁二烯、1,3-戊二烯或其混合物，或C4-C6非共軛的二烯，包括1,2-丁二烯，並且最佳的是1,3-丁二烯、異戊二烯或其混合物；該至少一種有機溶劑選自任何不與該催化劑反應或以其他方式干擾該反應的有機溶劑，較佳的是選自：苯、甲苯、環己烷、二甲亞碸(DMSO)、碳酸乙烯酯(EC)、四氫呋喃(THF)、1,4-二烷、一氯苯(MCB)、二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAC)、或其混合物，更佳的 是選自一氯苯(MCB)、一溴苯(MBB)、二氯苯(DCB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)，進一步較佳的是選自一氯苯(MCB)和甲基乙基酮(MEK)，最佳的是一氯苯(MCB)。 A method for hydrogenating a diene polymer according to claim 27, wherein the diene is selected from any known diene, preferably selected from at least one conjugated diene and at least one non- Conjugated diene, more preferably C 4 -C 6 conjugated diene, including 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentane a diene or a mixture thereof, or a C 4 -C 6 non-conjugated diene, including 1,2-butadiene, and most preferably 1,3-butadiene, isoprene or a mixture thereof; The at least one organic solvent is selected from any organic solvent that does not react with or otherwise interfere with the reaction, and is preferably selected from the group consisting of benzene, toluene, cyclohexane, dimethyl hydrazine (DMSO), and ethylene carbonate ( EC), tetrahydrofuran (THF), 1,4-two Alkane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone ( MEK), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), or a mixture thereof, more preferably selected from monochlorobenzene (MCB), monobromo Benzene (MBB), dichlorobenzene (DCB), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC), Further preferably, it is selected from the group consisting of monochlorobenzene (MCB) and methyl ethyl ketone (MEK), and most preferred is monochlorobenzene (MCB). 如申請專利範圍第27-28項中一項或多項之用於二烯聚合物的氫化之方法，進一步包括移除該含金屬的催化劑的步驟，較佳的是藉由使用離子交換樹脂。 The method for hydrogenating a diene polymer as claimed in one or more of claims 27-28 further includes the step of removing the metal-containing catalyst, preferably by using an ion exchange resin. 一種用於二烯聚合物的氫化之方法，包括：a)在高壓釜反應器中將至少一種二烯聚合物溶解至至少一種有機溶劑中，b)將如申請專利範圍第1-7項中任一項或多項之至少一種含金屬的催化劑系統加入到在步驟a)中獲得的溶液中，c)將氫氣引入到該高壓釜反應器中並且將該高壓釜反應器加熱到高達預定的溫度持續預定的時間。 A method for hydrogenating a diene polymer comprising: a) dissolving at least one diene polymer in at least one organic solvent in an autoclave reactor, b) as in claim 1-7 At least one metal-containing catalyst system of any one or more is added to the solution obtained in step a), c) introducing hydrogen into the autoclave reactor and heating the autoclave reactor up to a predetermined temperature Continue for a predetermined time. 如申請專利範圍第30項之用於二烯聚合物的氫化之方法，其中該至少一種二烯聚合物係選自BR、NBR、SBR中的一或多種，較佳的是藉由溶液聚合獲得的BR、NBR、SBR中的一或多種，並且基於該二烯聚合物的總重量，該二烯聚合物中的ACN含量係從0至65 wt%，或該二烯共聚物中的苯乙烯含量係從0至 80，較佳的是該二烯聚合物中的ACN含量係從10 wt%至63 wt%，或該二烯聚合物中的苯乙烯含量係從20 wt%至80 wt%，更佳的是，該二烯聚合物中的ACN含量係從30wt%至60 wt%，或該二烯聚合物中的苯乙烯含量係從20 wt%至70 wt%；基於100重量份的該至少一種二烯聚合物，至少一種含金屬的催化劑系統的量係從0.000001至50重量份，較佳的是從0.00001至20重量份，更佳的是從0.0001至10重量份；該至少一種有機溶劑係選自任何不與該催化劑反應或以其他方式干擾該反應的有機溶劑，較佳的是選自：苯、甲苯、環己烷、二甲基亞碸(DMSO)、碳酸乙烯酯(EC)、四氫呋喃(THF)、1,4-二烷、一氯苯(MCB)、二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAC)、或其混合物，更佳的是選自一氯苯(MCB)、一溴苯(MBB)、二氯苯(DCB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)，進一步較佳的是選自一氯苯(MCB)和甲基乙基酮(MEK)，最佳的是一氯苯(MCB)；該預定的溫度係從80℃至180℃並且該預定的時間係在200-2000 Psi的氫氣壓力下從10分鐘至10小 時，更佳的是，該預定的溫度係從100℃至160℃並且該預定的時間係在300-1500 Psi的氫氣壓力下從30分鐘至5小時，進一步較佳的是該預定的溫度係從120℃至150℃並且該預定的時間係在500-1000 Psi的氫氣壓力下從30分鐘至3小時；並且該二烯聚合物具有的受控的Mn係從1,000至300,000，與PDI係從1.0至5.0，較佳的是該受控的Mn係從3,000至100,000，與PDI係從1.1至4.0，更佳的是該受控的Mn係5,000至50,000，與PDI係1.1至3.0。 A method for hydrogenating a diene polymer according to claim 30, wherein the at least one diene polymer is selected from one or more of BR, NBR, and SBR, preferably obtained by solution polymerization. One or more of BR, NBR, SBR, and based on the total weight of the diene polymer, the ACN content in the diene polymer is from 0 to 65 wt%, or styrene in the diene copolymer The content is from 0 to 80, preferably the ACN content in the diene polymer is from 10 wt% to 63 wt%, or the styrene content in the diene polymer is from 20 wt% to 80 wt%. More preferably, the ACN content in the diene polymer is from 30% by weight to 60% by weight, or the styrene content in the diene polymer is from 20% by weight to 70% by weight; based on 100 parts by weight The at least one diene polymer, the amount of the at least one metal-containing catalyst system is from 0.000001 to 50 parts by weight, preferably from 0.00001 to 20 parts by weight, more preferably from 0.0001 to 10 parts by weight; the at least one The organic solvent is selected from any organic solvent that does not react with or otherwise interfere with the reaction, and is preferably selected from the group consisting of: , Toluene, cyclohexane, dimethyl sulfoxide (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF), 1,4- two Alkane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone ( MEK), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), or a mixture thereof, more preferably selected from monochlorobenzene (MCB), monobromo Benzene (MBB), dichlorobenzene (DCB), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC), Further preferably, it is selected from the group consisting of monochlorobenzene (MCB) and methyl ethyl ketone (MEK), most preferably monochlorobenzene (MCB); the predetermined temperature is from 80 ° C to 180 ° C and the predetermined time It is from 10 minutes to 10 hours under a hydrogen pressure of 200-2000 Psi, and more preferably, the predetermined temperature is from 100 ° C to 160 ° C and the predetermined time is from 30 to 1500 Psi of hydrogen pressure from 30 From minute to 5 hours, it is further preferred that the predetermined temperature is from 120 ° C to 150 ° C and the predetermined time is from 30 minutes to 3 hours under a hydrogen pressure of 500 to 1000 Psi; and the diene polymer has The controlled Mn is from 1,000 to 300,000, and the PDI is from 1.0 to 5.0, preferably the controlled Mn is from 3,000 to 1 00,000, and PDI are from 1.1 to 4.0, more preferably the controlled Mn is from 5,000 to 50,000, and the PDI is from 1.1 to 3.0. 如申請專利範圍第30-31項中一項或多項之用於二烯聚合物的氫化之方法，進一步包括d)移除該含金屬的催化劑，較佳的是藉由使用離子交換樹脂。 The method for hydrogenating a diene polymer as claimed in one or more of claims 30-31, further comprising d) removing the metal-containing catalyst, preferably by using an ion exchange resin. 一種用於二烯聚合物的氫化之方法，包括a)加入如申請專利範圍第8-19項中一項或多項所述之溶液聚合法獲得的二烯溶液均聚反應或二烯共聚反應，以及任選地至少一種有機溶劑，b)將氫氣直接引入到步驟a)的混合物中並且加熱到一預定的溫度以獲得該氫化的含二烯的聚合物，其中該至少一種有機溶劑係選自任何不與該催化劑反應或以其他方式干擾該反應的有機溶劑，較佳的是選自：苯、甲苯、環己烷、二甲亞碸(DMSO)、碳酸乙烯酯(EC)、四氫呋喃(THF)、1,4-二烷、一氯 苯(MCB)、二氯苯(DCB)、三氯苯(TCB)、一溴苯(MBB)、二溴苯(DBB)、三溴苯(TBB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺(DMAC)、或其混合物，更佳的是選自一氯苯(MCB)、一溴苯(MBB)、二氯苯(DCB)、甲基乙基酮(MEK)、N,N-二甲基甲醯胺(DMF)、或N,N-二甲基乙醯胺(DMAC)，進一步較佳的是選自一氯苯(MCB)和甲基乙基酮(MEK)，最佳的是一氯苯(MCB)。 A method for hydrogenating a diene polymer, comprising: a) adding a diene solution homopolymerization reaction or a diene copolymerization reaction obtained by a solution polymerization method as described in one or more of claims 8 to 19; And optionally at least one organic solvent, b) introducing hydrogen directly into the mixture of step a) and heating to a predetermined temperature to obtain the hydrogenated diene-containing polymer, wherein the at least one organic solvent is selected from Any organic solvent that does not react with or otherwise interfere with the reaction is preferably selected from the group consisting of benzene, toluene, cyclohexane, dimethyl hydrazine (DMSO), ethylene carbonate (EC), tetrahydrofuran (THF). ), 1,4-two Alkane, monochlorobenzene (MCB), dichlorobenzene (DCB), trichlorobenzene (TCB), monobromobenzene (MBB), dibromobenzene (DBB), tribromobenzene (TBB), methyl ethyl ketone ( MEK), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), or a mixture thereof, more preferably selected from monochlorobenzene (MCB), monobromo Benzene (MBB), dichlorobenzene (DCB), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), or N,N-dimethylacetamide (DMAC), Further preferably, it is selected from the group consisting of monochlorobenzene (MCB) and methyl ethyl ketone (MEK), and most preferred is monochlorobenzene (MCB). 一種氫化的二烯橡膠，藉由如申請專利範圍第27-29或如申請專利範圍30-33項中一項或多項之用於合成氫化的含二烯的聚合物的一鍋法獲得。 A hydrogenated diene rubber is obtained by a one-pot process for synthesizing a hydrogenated diene-containing polymer as claimed in claims 27-29 or one or more of claims 30-33. 一種如申請專利範圍第1-7項中任一項或多項之催化劑系統之用途，係用在製造二烯聚合物。 A use of a catalyst system according to any one or more of claims 1 to 7 for the manufacture of a diene polymer. 一種如申請專利範圍第1-7項中任一項或多項之催化劑系統之用途，係用在製造氫化的含二烯的聚合物。 A use of a catalyst system according to any one or more of claims 1 to 7 for the manufacture of a hydrogenated diene-containing polymer. 一種玻璃管反應器和/或反應釜之用途，其係用在如申請專利範圍第8-19項中一項或多項之溶液聚合法中、或用在如申請專利範圍第23-25中一項或多項中用於合成氫化的二烯聚合物的一鍋法、或用在如申請專利範圍第27-33項中一項或多項將二烯聚合物進行氫化的方法。 Use of a glass tube reactor and/or a reactor for use in a solution polymerization process according to one or more of claims 8-19, or in the application of claims 23-25 A one-pot method for synthesizing a hydrogenated diene polymer, or a method for hydrogenating a diene polymer, as used in one or more of claims 27-33.
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JP7251793B2 (en) * 2017-11-14 2023-04-04 日東化成株式会社 Curing catalyst for organic polymer or organopolysiloxane, moisture-curable composition, cured product and method for producing the same
EP3898706A1 (en) 2018-12-17 2021-10-27 ARLANXEO Deutschland GmbH Process for preparing hnbr solutions with alternative solvents
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Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3700637A (en) 1970-05-08 1972-10-24 Shell Oil Co Diene-nitrile rubbers
US3914210A (en) * 1974-09-26 1975-10-21 Firestone Tire & Rubber Co Process for polymerizing butadiene having a high proportion of syndiotactic 1,2-microstructure
DE2539132A1 (en) 1975-09-03 1977-03-17 Bayer Ag HYDROGENATION OF POLYMERS
CA1203047A (en) 1982-12-08 1986-04-08 Hormoz Azizian Polymer hydrogenation process
CA1220300A (en) 1982-12-08 1987-04-07 Polysar Limited Polymer hydrogenation process
DE3329974A1 (en) 1983-08-19 1985-02-28 Bayer Ag, 5090 Leverkusen MANUFACTURE OF HYDRATED NITRILE RUBBER
DE3433392A1 (en) 1984-09-12 1986-03-20 Bayer Ag, 5090 Leverkusen HYDROGENATION OF UNSATURATED POLYMER WITH NITRILE GROUPS
DE3529252A1 (en) 1985-08-16 1987-02-19 Bayer Ag METHOD FOR SELECTIVE HYDRATION OF UNSATURATED COMPOUNDS
DE3540918A1 (en) 1985-11-19 1987-05-21 Bayer Ag METHOD FOR SELECTIVE HYDRATION OF UNSATURATED COMPOUNDS
DE3541689A1 (en) 1985-11-26 1987-05-27 Bayer Ag METHOD FOR SELECTIVE HYDROGENATION OF UNSATURATED POLYMERS CONTAINING NITRILE GROUPS
US4816525A (en) 1987-07-06 1989-03-28 University Of Waterloo Polymer hydrogenation process
DE4025781A1 (en) 1990-08-15 1992-02-20 Bayer Ag Selected copolymer hydrogenation - using butadiene!-isoprene!-acrylonitrile! copolymers in organic solvent using metal (cpd.) catalyst under specified conditions
JP3016397B2 (en) * 1990-11-30 2000-03-06 三菱化学株式会社 Method for hydrogenating unsaturated copolymers containing nitrile groups
US5397851A (en) * 1993-11-09 1995-03-14 Polysar Rubber Corporation Process for cis-1,4-polybutadiene production with reduced gel formation
DE19832455A1 (en) * 1998-07-18 2000-01-27 Bayer Ag Polymerization of conjugated diene is carried out in aromatic vinyl compound as solvent and uses a catalyst containing cobalt and organoaluminum compounds and a modifier
CA2329844A1 (en) 2000-12-28 2002-06-28 Bayer Inc. Esbo enhanced hydrogenation
WO2004009652A1 (en) * 2002-07-22 2004-01-29 Jsr Corporation Process for producing crystalline 1,2-polybutadiene
US7666950B2 (en) * 2006-06-01 2010-02-23 Lanxess Deutschland Gmbh Process for preparing hydrogenated nitrile rubbers
CA2646056A1 (en) 2007-12-21 2009-06-21 Lanxess Deutschland Gmbh A process for removing ruthenium-containing catalyst residues from optionally hydrogenated nitrile rubber
EP2072532A1 (en) 2007-12-21 2009-06-24 Lanxess Deutschland GmbH A process for removing iron-residues, rhodium- and ruthenium-containing catalyst residues from optionally hydrogenated nitrile rubber

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