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    • 9. 发明公开
    • Process to make a diblock copolymer having a monovinylaromatic polymer block
    • Verfahren zur Herstellung eines Diblock-Copolymers mit einem Monovinylaroma-Polymerblock
    • EP2151457A1
    • 2010-02-10
    • EP08290732.0
    • 2008-07-28
    • Total Petrochemicals FranceCentre National de la Recherche Scientifique (CNRS)
    • Carpentier, Jean-FrançoisGuillaume, SophieHelou, MarionSarazin, YannDuc, Michel
    • C08F293/00C08F2/38C08L53/00
    • C08F293/005C08F293/00C08L53/00C08L2666/02C08L2666/24
    • The present invention is a process to make a composition comprising a block copolymer A-B and optionally a monovinylaromatic polymer, said process comprising :
      a) forming a mixture comprising:
      one or more cyclic component polymerizable by ring-opening polymerization (ROP) dispersed in at least one monovinylaromatic monomer,
      optionally a rubber dissolved in the monovinylaromatic monomer,

      b) contacting the mixture of step a) with a mixture of b1 and b2 such that :
      b1) is M[N(SiR 8 3 ) 2 ] x in which M is a metal, R 8 is an hydrocarbon group and x is the valency of the metal M, or
      a metal alkoxide M(OR 9 ) x in which M is a metal, R 9 is an hydrocarbon group and x is the valency of the metal M,
      or a mixture thereof,
      or a single-site metal catalyst component based upon a bulky β-diiminate ligands (BDI), represented by the following general formula:

      wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from hydrogen, unsubstituted or substituted hydrocarbyl, or inert functional group and wherein two or more of said groups can be linked together to form one or more rings, wherein X is an hydrocarbyl radical having from 1 to 12 carbon atoms, an alkoxide group OR*, an amido group NR** 2 or a borohydride group (BH 4 ).
      b2) a functional alcohol containing, besides its -OH function, another functionality Y enabling the growth or the grafting of a polyvinylaromatic, at conditions effective to produce by ROP of the cyclic component a block polymer A, having an -OH end and another function Y, dispersed in the monovinylaromatic monomer,

      c) polymerizing the solution obtained at step b) optionally in the presence of a free radical initiator, optionally in the presence of chain transfer agents, at conditions effective to produce:
      a monovinylaromatic block polymer B linked to the block polymer A by the aforementioned functionality Y such that H-A-O-R-Y-B or H-A-O-R-B-Y (referred in both cases as A-B to simplify) in which R is a linking group,
      optionally a monovinylaromatic polymer,

      d) optionally degassing the product of step c) to separate the optional unpolymerized monomers and comonomers and recovering optionally a composition comprising at least the block copolymer A-B, optionally a monovinylaromatic polymer and optionally a rubber.
      At step b2) advantageously the -OH function acts as the chain transfer agent during the ROP catalytic process.
    • 本发明是一种制备包含嵌段共聚物AB和任选的单乙烯基芳族聚合物的组合物的方法,所述方法包括:a)形成混合物,其包含:一个或多个可通过开环聚合(ROP)聚合的环状组分 一种单乙烯基芳族单体,任选的溶解在单乙烯基芳族单体中的橡胶,b)使步骤a)的混合物与b1和b2的混合物接触,使得:b1)是M [N(SiR 8 3)2] x,其中M是 金属,R 8为烃基,x为金属M或金属醇盐M(OR 9)x的化合价,其中M为金属,R 9为烃基,x为金属的价态 M或其混合物,或基于由以下通式表示的体积大的二 - 二亚胺配体(BDI)的单中心金属催化剂组分:其中R 1,R 2,R 3,R 4,R 5, R 6和R 7各自独立地选自氢,未取代或取代的烃基,或 惰性官能团,并且其中两个或更多个所述基团可以连接在一起以形成一个或多个环,其中X是具有1至12个碳原子的烃基,烷氧基基团OR *,酰胺基NR ** 2或 硼氢化物组(BH 4)。 b2)官能醇除了其-OH官能之外还含有另一功能Y,其能够在有效地通过环状组分的ROP生成具有-OH末端和另一功能的嵌段聚合物A的条件下生长或接枝聚乙烯基芳族化合物 Y,分散在单乙烯基芳族单体中,c)任选地在自由基引发剂存在下,任选地在链转移剂存在下,使步骤b)获得的溶液聚合,所述条件有效地产生:单乙烯基芳族嵌段聚合物B与 通过上述官能度Y使嵌段聚合物A使得HAORYB或HAORBY(在两种情况下都称为AB简化),其中R是连接基团,任选地是单乙烯基芳族聚合物,d)任选地将步骤c)的产物脱气以分离 任选的未聚合单体和共聚单体,并任选地回收包含至少嵌段共聚物AB,任选的单乙烯基芳族聚合物 r和任选的橡胶。 在步骤b2)有利地,在ROP催化过程中,-OH官能团用作链转移剂。