CN106574008A

CN106574008A - Polycyclo-olefinic block polymers and pervaporation membranes made therefrom

Info

Publication number: CN106574008A
Application number: CN201580043759.0A
Authority: CN
Inventors: A·贝尔; O·布托夫; 滝川圭美
Original assignee: Sumitomo Bakelite Co Ltd; Promerus LLC
Current assignee: Sumitomo Bakelite Co Ltd
Priority date: 2014-08-15
Filing date: 2015-08-17
Publication date: 2017-04-19
Anticipated expiration: 2035-08-17
Also published as: JP6225294B2; CN106574008B; KR101800195B1; WO2016025942A1; KR20170036799A; JP2017525808A

Abstract

A series of vinyl addition block polymers derived from functionalized norbornene monomers are disclosed and claimed. Specifically, a series of diblock and triblock polymers derived from norbornene monomers are disclosed. Also disclosed are the method of preparation of such block polymers, and their use in the fabrication of membranes which exhibit unique separation properties. Specifically, the membranes as disclosed herein are useful in the separation of organic volatiles from biomass and/or organic waste, including butanol, phenol, and the like.

Description

Polycyclic alkene block polymer and the osmotic evaporation film being produced from it

Cross-reference to related applications

The application advocates U.S. Provisional Patent Application the 62/037,823rd, in August, 2014 filed in August in 2014 15 days U.S. Provisional Patent Application filed in 15 days the 62/037,828th and US provisional patent Shen filed in 31 days October in 2014 Please the preference of the 62/073rd, No. 013, contents of these applications is used as with reference to quoting in this article.

Technical field

The present invention relates to a series of block polymers derived from cycloolefin monomers.More particularly it relates to spread out It is conigenous a series of block polymers of the norbornene-type monomers of various functionalizations.The invention further relates to by this block polymer The purposes of the osmotic evaporation film of formation and this film in pervaporation processes.

Background technology

Cyclic olefin polymer such as polynorbornene (PNB) etc be widely used in various electronics, photoelectron and other should With in, therefore it is more and more important to manufacture the method for this PNB on an industrial scale.In the literature it is well known that, using various transition gold Metal catalyst and major catalyst (procatalyst), by the addition polymerization using suitable starting norbornene monomer, can Synthesize the PNB of various functionalizations.U.S. Patent No. 7,989,570 is see, for example, its relevant portion is by reference to being introduced into this Wen Zhong.

However, the PNB in order to manufacture functionalization on an industrial scale, needs catalyst or catalyst system, to meet some Desired characteristic.Wherein several such characteristics include：A) active catalyst polymerization system, i.e. even if catalyst is reaching It is directed to still keep its activity after the chain growth of the very high degree of very high molecular weight polymer present；Even if b) in very high list Body:Also it is highly active catalyst system under the mol ratio of catalyst；C) it is used to control the effective chain tra nsfer of molecular weight；D) wrap Include the good catalyst stability during the thermally and chemically polymerization of stability, i.e. polymerization activity does not terminate；E) rapid polymerization Kinetics, i.e. the quick chain preferably near room temperature increases；And f) for the stable storing group of high response catalyst system Point, such as stable A and B component.

No. 6,936,672 disclosures of U.S. Patent No. are used for the various catalyst of polymerization of polycyclic olefin, major catalyst and urge Agent system.However, these catalyst systems are possible to the block copolymer for being unsuitable for preparing the high-sequential as described in text.

The content of the invention

The invention technical task to be solved

Therefore, it is an object of the invention to provide having and being urged as addition polymerization as one-component or bicomponent system A series of substituted or unsubstituted bicyclic alkene-palladium compound of the serviceability of agent.

In addition, it is an object of the invention to provide a kind of prepare substituted bicyclic alkene-palladium compound disclosed herein Technique.

The present invention also aims to provide for formed have for various applications unique property film and Series of new block copolymer with the unique property for being used for various applications in electronics, the manufacture of opto-electronic device.

The other purposes and further scope of the suitability of the present invention will become clear and definite from detailed description below.

For solving the means of technical task

Advantageously, it has now been found that various block copolymers as herein described can be by the way that as described herein some be organic Palladium compound and various other catalyst known in the art are prepared.It has furthermore been found that the block copolymer of the present invention Unique advantage is provided, therefore can be used for various applications, including but not limited to the formation of membrane material and various other optics and Electronic application.The film formed by block copolymer is useful for example to separating Organic substance from biomass or other organic waste materials.

Therefore it provides the block copolymer of logical formula (VI)：

(A)_m-b-(B)_n (VI)

Wherein, m and n are at least 15 integer, but in other embodiments, m and n can be 20 to 4000 or 50 to 3000 Or in the range of 100 to 2000, and in other embodiments, according to expected purposes, m and n can also be higher than 4000；

B represents the key between homopolymer A and two blocks of B；

A and B are different from each other, and independently selected from the repetitives represented by formula (IVA), the repetitives derive The monomer of self-drifting (IV)：

Wherein：

The position that representative is bonded with another repetitives；

P is 0,1 or 2 integer；

R₃、R₄、R₅And R₆It is identical or different, and each is independently from each other hydrogen, straight or branched (C₁-C₁₆) alkyl, Hydroxyl (C₁-C₁₆) alkyl, perfluor (C₁-C₁₂) alkyl, (C₃-C₁₂) cycloalkyl, (C₆-C₁₂) bicyclic alkyl, (C₇-C₁₄) three cycloalkanes Base, (C₆-C₁₀) aryl, (C₆-C₁₀) aryl (C₁-C₃) alkyl, perfluor (C₆-C₁₀) aryl, perfluor (C₆-C₁₀) aryl (C₁-C₃) alkane Base, two (C₁-C₂) alkyl maleimide (C₃-C₆) alkyl, two (C₁-C₂) alkyl maleimide (C₂-C₆) alkoxyl (C₁- C₂) alkyl, hydroxyl, (C₁-C₁₂) alkoxyl, (C₃-C₁₂) cycloalkyloxy, (C₆-C₁₂) bicycloalkyloxy, (C₇-C₁₄) three cycloalkanes oxygen Base, (C₆-C₁₀) aryloxy group (C₁-C₃) alkyl, (C₅-C₁₀) heteroaryloxy (C₁-C₃) alkyl, (C₆-C₁₀) aryloxy group, (C₅-C₁₀) miscellaneous Aryloxy group or (C₁-C₆) acyloxy, wherein, each above-mentioned substituent group be optionally selected from halogen or hydroxyl in substituent group.

In another aspect of this invention, the triblock polymer represented by logical formula (VII) is also provided：

(A)_m-b-(B)_n-b-(C)_o(VII)；

Wherein, as defined above, and o is at least 15 integer for m, n and b, but in other embodiments, o can 20 to 4000 or 50 to 3000 or 100 to 2000 scope, and in other embodiments, according to the expected use of block polymer On the way, o can also be higher than 4000.C and A or B are identical or different, and independently selected from the repetitives represented by formula (IVA), The repetitives are derived from the monomer for leading to formula (IV) as defined herein.

Description of the drawings

Below, refer to the attached drawing and/or iamge description be according to the embodiment of the present invention.When drawing is provided, it will be made For the drawing of the simplified part of the various embodiments of the present invention, and provide merely for illustrative purpose.

Fig. 1 describes pervaporation component according to the embodiment of the present invention.

Fig. 2 describes pervaporation system according to the embodiment of the present invention.

Fig. 3 to Fig. 5 is represented respectively by BuNB-HFANB (1:2) block copolymer formed film (Fig. 3), by BuNB-HFANB (2:1) block copolymer formed film (Fig. 4) and by HFANB-BuNB-HFANB (1:1:1) film (figure that block copolymer is formed 5) atomic force micrograph (AFM).

Fig. 6 (a) represents HFANB (W in the block polymer in one embodiment of the present invention_HFANB) normalized flux (normalized flux) and the graphics relationship between various weight fractions and vinyl addition block copolymer (a-BCP) Middle HFANB (W_HFANB) separation factor (separation factor, SF) and the graphics relationship between various weight fractions.

Fig. 6 (b) represents HFANB in vinyl addition block copolymer (a-BCP) in one embodiment of the present invention (W_HFANB) swelling ratio and various weight fractions between graphics relationship.

Fig. 7 (a) is represented and the block polymer (r-BC P81) and nothing manufactured by ring-opening metathesis polymerization (ROMP) method Rule vinyl addition block copolymer (a-BCP81) compare, to the present invention vinyl addition block copolymer in one (a-BCP81) normalized flux for obtaining and separation factor (SF).

Fig. 7 (b) is represented and the block polymer (r-BC P81) and nothing manufactured by ring-opening metathesis polymerization (ROMP) method Rule vinyl addition copolymer (a-RCP81) compare, to the present invention vinyl addition copolymer in one (a-RCP81) The swelling ratio of observation.

Specific embodiment

Term used herein has following meanings：

As used herein, unless be limited to a denoted object explicitly in addition, otherwise article " a ", " an " and " the " includes multiple denoted objects.

Due to all quantity, the number of amount, the reaction condition of quantity relating used herein and in appended claims etc. Value and/or statement are subject to the uncertainty for obtaining the various measurements that aforementioned value is run into, unless otherwise specified, otherwise should be understood that To be modified by term " about (about) " under Suo You Qing Condition.

When a numerical range disclosed herein, above range is considered as continuously, and the minima including the scope and most Big value, and each value between this minima and maximum.Further, when scope refers to integer, including the model Each integer between the minima enclosed and maximum.Additionally, when multiple scope Expressive Features or characteristic is provided, Ke Yihe And the scope.In other words, unless otherwise specified, all scopes otherwise disclosed herein are understood to include and are wherein included into Any and all subrange.For example, should be regarded as including between minima 1 and maximum 10 from the specified range of " 1 to 10 " Any and all subrange.The Exemplary scope of scope 1 to 10 include but is not limited to 1 to 6.1,3.5 to 7.8,5.5 to 10 etc..

As used herein, symbolRepresent with another repetitives or another atom or molecule or group or A part occurs the position of bonding, such as suitably have the structure of shown group.

As used herein, " alkyl (hydrocarbyl) " refers to the group containing carbon atom and hydrogen atom, non-limiting Example is alkyl, cycloalkyl, aryl, aralkyl, alkaryl and thiazolinyl.Term " halohydrocarbyl (halohydrocarbyl) " is Refer to the alkyl that at least one hydrogen is optionally substituted by halogen.Term " perhalogeno alkyl (perhalocarbyl) " is all of hydrogen by halogen Substituted alkyl.

As used herein, " (C is stated₁-C₆) alkyl " and include methyl and ethyl and straight or branched propyl group, butyl, Amyl group and hexyl.Specific alkyl is methyl, ethyl, n-pro-pyl, isopropyl and the tert-butyl group.Derivative statement such as " (C₁-C₄) alcoxyl Base ", " (C₁-C₄) sulfanyl ", " (C₁-C₄) alkoxyl (C₁-C₄) alkyl ", " hydroxyl (C₁-C₄) alkyl ", " (C₁-C₄) alkyl-carbonyl Base ", " (C₁-C₄) alkoxy carbonyl (C₁-C₄) alkyl ", " (C₁-C₄) alkoxy carbonyl ", " amino (C₁-C₄)-alkyl ", " (C₁- C₄) alkyl amino ", " (C₁-C₄) alkylcarbamoyl group (C₁-C₄) alkyl ", " (C₁-C₄) dialkyl carbamyl-(C₁-C₄) alkane Base ", " single-or two-(C₁-C₄) alkyl amino (C₁-C₄) alkyl ", " amino (C₁-C₄) alkyl-carbonyl ", " diphenyl (C₁-C₄) alkane Base ", " phenyl (C₁-C₄) alkyl ", " phenyl carbonic acyl radical (C₁-C₄) alkyl " and " phenoxy group-(C₁-C₄) alkyl " should make corresponding Explain.

As used herein, stating " cycloalkyl " includes all known cyclic groups.The representative example of " cycloalkyl " Include cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl etc. without any restriction.Derivative statement such as " cycloalkanes oxygen Base ", " cycloalkyl-alkyl ", " cycloalkylaryl ", " naphthene base carbonyl " should make corresponding explanation.

As used herein, " (C is stated₂-C₆) thiazolinyl " include vinyl and straight or branched acrylic, cyclobutenyl, amylene Base and hexenyl.Similarly, " (C is stated₂-C₆) alkynyl " and include acetenyl and propinyl and straight or branched butynyl, penta Alkynyl and hexin base.

As used herein, " (C is stated₁-C₄) acyl group " should have and " (C₁-C₄) alkanoyl " identical implication, it also may be used To be expressed as in structure " R-CO- ", wherein R is (C as defined herein₁-C₃) alkyl.Additionally, " (C₁-C₃) alkyl oxycarbonyl Base " should have and (C₁-C₄) acyl group identical implication.Specifically, " (C₁-C₄) acyl group " answer fingernail acyl group, acetyl group (acetyl or ethanoyl), propiono, positive bytyry etc..Derivative statement such as " (C₁-C₄) acyloxy " and " (C₁-C₄) acyloxy Alkyl " should make corresponding explanation.

As used herein, " (C is stated₁-C₆) perfluoroalkyl " refer to all of hydrogen atom in the alkyl by fluorine atom Replace.Illustrative example includes trifluoromethyl and pentafluoroethyl group and straight or branched heptafluoropropyl, nine fluorine butyl, 11 fluorine Amyl group and ten trifluoro hexyls.Derivative statement " (C₁-C₆) perfluoro alkoxy " corresponding explanation should be made.

As used herein, " (C is stated₆-C₁₀) aryl " refer to substituted or unsubstituted phenyl or naphthyl.Substituted benzene The concrete example of base or naphthyl includes o-, p-, m- tolyl, 1,2-, 1,3-, 1,4- xylyl, 1- methyl naphthyls, 2- first Base naphthyl etc.." substituted phenyl " or " substituted naphthyl " also include definition herein further or it is as known in the art it is any can The substituent group of energy.Derivative statement " (C₆-C₁₀) aryl sulfonyl " corresponding explanation should be made.

As used herein, " (C is stated₆-C₁₀) aryl (C₁-C₄) alkyl " refer to (C as defined herein₆-C₁₀) virtue Base is further connected to (C as defined herein₁-C₄) alkyl.Representative example includes benzyl, phenylethyl, 2- phenyl third Base, 1- naphthyl methyls, 2- naphthyl methyls etc..It should be further noted that, statement " aryl alkyl " and " aralkyl " refers to identical It is used interchangeably.Therefore, " (C is stated₆-C₁₀) aryl (C₁-C₄) alkyl " " (C can also be construed to₆-C₁₄) aralkyl ".

As used herein, " heteroaryl " is stated including all known containing heteroatomic aromatic group.It is representative 5- unit's heteroaryls group includes furyl, thienyl (thienyl or thiophenyl), pyrrole radicals, different pyrrole radicals, pyrazolyl, miaow Oxazolyl, oxazolyl, thiazolyl, isothiazolyl etc..Representative 6- unit's heteroaryls group includes pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazine The groups such as base, triazine radical.The representative example of bicyclic heteroaryl group includes benzofuranyl, benzothienyl, indyl, quinoline The bases such as base, isoquinolyl, cinnolines base (cinnolyl), benzimidazolyl, indazolyl, pyrido furyl, pyrido thienyl Group.

As used herein, " heterocycle " is stated including all known containing also former heteroatomic cyclic group.It is representative 5- circle heterocycles group includes tetrahydrofuran base, tetrahydro-thienyl, pyrrolidinyl, 2- thiazolinyls, tetrahydro-thiazoles base, Si Qing oxazoles Base etc..Representative 6- circle heterocycles group includes piperidyl, piperazinyl, morpholinyl, thio-morpholinyl etc..Various other heterocyclic radicals Group unrestrictedly includes '-aziridino, nitrogen heterocyclic heptyl (azepanyl), Diazesuberane base, diazabicyclo [2.2.1] hept- 2- base and three Azacyclooctane bases (triazocanyl) etc..

" halogen " or " halo " refers to chlorine, fluorine, bromine and iodine.

Broadly, term is " substituted " it is contemplated that including all permissible substituent group of organic compound.Such as In some specific embodiments disclosed herein, term " substituted " is referred to by more than one independently selected from C_1-6Alkyl, C_2-6Thiazolinyl, C_1-6Perfluoroalkyl, phenyl, hydroxyl ,-CO₂H, ester, amide, C₁-C₆Alkoxyl, C₁-C₆Sulfanyl, C₁-C₆Perfluor alkane Epoxide ,-NH₂, Cl, Br, I, F ,-NH- low alkyl groups and-N (low alkyl group)₂In substituent group replace.However, art technology Any other suitable substituent group known to personnel can also be used for these embodiments.

It should be noted that any atom in the text, scheme, embodiment and table in this paper with unsaturated valence state is assumed to be With proper number so that the hydrogen atom of this valence state saturation.

As used herein, term " living polymerization " refers to the chain life that the ability that the polymer chain of growth terminates has been removed Long polymerization.In other words, in the system, there is no chain termination and chain transfer reaction, and chain trigger rate also compares rate of chain growth Much bigger, this is caused polymer chain and is grown with the more constant speed than seeing in traditional chain polymerization, and their length Keep closely similar (that is, they have low-down polydispersity index, PDI).

As used herein, term " block copolymer " or " block polymer " are used interchangeably and represent identical, i.e., Plural homopolymer subunit is by covalently bonded.Therefore, " diblock copolymer " can be by-(A)_m-b-(B)_n- represent, The homopolymer of its formula of A is connected by singly-bound with the homopolymer of Formula B, and m and n is the respective number of monomeric repeating unit Amount.Therefore, in the expression of " diblock copolymer ", " b " represents aforementioned homopolymers (A)_m" block " by covalent bond with Homopolymer (B) described later_nConnection.Therefore, mark "-b- " should be interpreted that the key between the polymer blocks specified.Similarly, " triblock copolymer ", " Tetrablock copolymer " etc. according to circumstances should be explained suitably.In addition, " diblock copolymer " or " diblock polymer " is used interchangeably.

As used herein, term " polymer " compositionss ", " copolymer compositions, " " binary polymerization compositions " or " four-element polymerization compositions " are used interchangeably herein, and it refers to polymer, copolymer, the ternary including at least one synthesis Polymer or quadripolymer and from initiator, solvent or with this polymer synthesis other compositions remnants Thing, it refers to, this residue is interpreted as being not necessarily intended to and the polymer covalent bonding.But, some catalyst or initiator Sometimes can be in the top of polymer chain and/or a part of covalent bonding of end and polymer chain.Be considered " polymer " or This residue of the part of " polymer composition " and other compositions typically with polymer mixed or blending so that when this A little between containers or when shifting between solvent or disperse medium, they are intended to be kept together with polymer.Polymer group Compound can also be included in the material added after synthetic polymer, to provide or change the special properties of this compositionss.This Plant material and include but is not limited to solvent, antioxidant, light trigger, sensitizer and other materials, will be in further detail below Discussion.

Term " derivative monomer repetitives " refers to polymer repeat unit by for example multi-ring norbornene-type monomers polymerization (formation), wherein resulting polymers are formed by 2,3 matchings connection (ench ainment) of norbornene-type monomers, as follows It is shown：

Therefore, enforcement of the invention, there is provided compounds of formula I：

Wherein：

For (C₅-C₁₀) cycloalkenyl group, (C₇-C₁₂) bicyclic alkene base or (C₈-C₁₂) tricyclene alkyl；

M is nickel, palladium or platinum；

LB is lewis base (Lewis Base)；

For Weakly coordinating anions；

Y is PR₃Or O=PR₃, wherein, R is independently selected from methyl, ethyl, (C₃-C₆) alkyl, substituted or unsubstituted (C₃-C₇) cycloalkyl, (C₆-C₁₀) aryl, (C₆-C₁₀) aralkyl, methoxyl group, ethyoxyl, (C₃-C₆) alkoxyl, replace or not (the C for replacing₃-C₇) cycloalkyloxy, (C₆-C₁₀) aryloxy group or (C₆-C₁₀) aralkoxy；And

R₁For methyl, ethyl, straight or branched (C₃-C₆) alkyl, (C₆-C₁₀) aryl, (C₆-C₁₀) aralkyl or R₂CO, its Middle R₂For methyl, ethyl or (C₃-C₆) alkyl.

In another embodiment of the present invention, various cycloalkenyl groups, bicyclic alkene base or tricyclene alkyl can serve as In the compound of logical formula (I)Group.(C₅-C₁₀) cycloalkenyl group representative example without any restriction include ring penta Alkene, cyclohexene, cycloheptene, cyclo-octene, cyclonoene or cyclodecene.It is also possible, however, to use including ring endecatylene, the carbon of ring 12 Other suitable cycloalkenyl groups of alkene etc..(C₇-C₁₂) bicyclic alkene base representative example without any restriction include it is bicyclic [2, 2,1] heptene, bicyclic [3,2,1] octene, bicyclic [2,2,2] octene, bicyclic [3,2,2] nonene, bicyclic [3,3,1] nonene, 1,2, 3,3a, 4,6a- hexahydro pentalene, 3a, 4,5,6,7,7a- hexahydro -1H- indenes, 1,2,3,4,4a, 5,8,8a- octahydro naphthalenes, 2, 3,4,4a, 5,6,9,9a- octahydro -1H- benzos [7] annulene etc..(C₈-C₁₂) tricyclene alkyl representative example it is without any restrictions Ground includes bicyclopentadiene, (4s, 7s) -3a, 4,5,6,7,7a- hexahydro -1H-4,7- ethano- indenes etc..In addition it is also possible to make With aforesaid any substituted cycloolefins, bicyclic alkene or tricyclene hydrocarbon.

In another embodiment of the present invention, M can not be nickel, palladium or platinum.Suitable M includes any X races transition gold Category or IX races metal, such as cobalt, rhodium or iridium.

In another embodiment of the present invention, leading to the compound of formula (I) includes lewis base, and it matches somebody with somebody with metallic atom M Position bonding.That is, lewis base is bonded by sharing two lone pair electron with metallic atom.Any Louis known in the art Alkali is used equally to the purpose.Advantageously, it has been found that under polymerizing condition elaborated further below, can easily solve From lewis base it is the commonly provided more suitably lead to formula (I) compound be initiator as polymerization catalyst.Therefore, at this Bright one side, advisably selects lewis base to provide the regulation of the catalysis activity of the compound of the present invention.

Therefore, it has been found that the suitable LB that can be used without any restriction include replace and unsubstituted nitrile, including Alkyl nitrile, aryl nitrile or aralkyl nitrile；Phosphine oxide, including replace and unsubstituted trialkyl phosphine, triaryl phosphine oxide, The various combinations of three aralkyl phosphine oxides and alkyl, aryl and aralkyl phosphine oxide；Replace and unsubstituted pyrazine；Take Generation and unsubstituted pyridine；Phosphite ester, including replace and unsubstituted trialkyl phosphite, triaryl phosphorous acid The various combinations of ester, three aralkyl phosphite esters and alkyl, aryl and aralkyl phosphite ester；Phosphine, including replace and not Substituted trialkyl phosphine, triaryl phosphine, the various combinations of tris aralkyl phosphine and alkyl, aryl and alkyl aryl phosphine.Can use Various other LB include various esters, alcohol, ketone, amine and aniline, arsenic hydride (arsine), antimonous hydride (stibine) etc..

In certain embodiments of the present invention, LB is selected from acetonitrile, propionitrile, n-Butyronitrile, tertiary butyronitrile, benzonitrile (C₆H₅CN)、2, 4,6- trimethyl benzonitriles, phenylacetonitrile (C₆H₅CH₂CN) pyridine, 2- picolines, 3- picolines, 4- picolines, 2,3- bis- Picoline, 2,4- lutidines, 2,5- lutidines, 2,6- lutidines, 3,4- lutidines, 3,5- diformazans Yl pyridines, 2,6 di tert butyl pyridine, 2,4- di-tert-butyl pyridines, 2- methoxypyridines, 3-Methoxy Pyridine, 4- methoxyl group pyrroles Pyridine, pyrazine, 2,3,5,6- tetramethyl base pyrazines, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, Pentamethylene oxide., two Benzophenone, triphenylphosphine oxide, formula PR₃Triphenyl or phosphine or phosphite ester, wherein, R independently selected from methyl, Ethyl, (C₃-C₆) alkyl, substituted or unsubstituted (C₃-C₇) cycloalkyl, (C₆-C₁₀) aryl, (C₆-C₁₀) aralkyl, methoxy Base, ethyoxyl, (C₃-C₆) alkoxyl, substituted or unsubstituted (C₃-C₇) cycloalkyloxy, (C₆-C₁₀) aryloxy group and (C₆-C₁₀) Aralkoxy.PR₃Representative example without any restriction include trimethyl-phosphine, triethyl phosphine, three n-pro-pyl phosphines, triisopropyl Phosphine, tri-n-butyl phosphine, tri isobutyl phosphine, tri-butyl phosphine, three cyclopenta phosphines, triallyl phosphine, tricyclohexyl phosphine, triphenyl Phosphine, trimethyl phosphite, triethyl phosphorite, three n-pro-pyl phosphite esters, tri isopropyl phosphorite, three normal-butyls are sub- Phosphate ester, triisobutyl phosphite ester, tri-tert phosphite ester, three cyclopenta phosphite esters, triallyl phosphite ester, three Cyclohexyl phosphite ester, triphenyl phosphite etc..It should be noted, however, that can also make in the embodiment of the present invention With the various other known LB by expection activity is produced.

Phosphine ligands can also be selected from then water solublity and give gained catalyst deliquescent phosphine in an aqueous medium Compound.Selected such phosphine include but is not limited to carboxyl replacement phosphine, such as 4- (diphenylphosphine) benzoic acid and 2- (diphenylphosphine) benzoic acid, 2- (dicyclohexyl phosphino-) ethyl sulfonic acid sodium, double (benzenesulfonic acid) dipotassiums of 4,4'- (phenyl phosphinidene) Salt, 3,3', 3 "-phosphinidyne three (benzenesulfonic acid) trisodium salt, 4- (dicyclohexyl phosphino-) -1,1- dimethylpiperidine chlorides, 4- (two Cyclohexylphosphino) -1,1- lupetidine iodide, the salt of the quatemary-amine-functional of phosphine, such as 2- (dicyclohexyl phosphino-)-N, N, N- Trimethyl second ammonium chloride, 2,2'- (cyclohexyl-phosphinidene) double [N, N, N- trimethyl second ammonium dichloride, 2,2'- (cyclohexyl Phosphinidene)-bis- (N, N, N- trimethyl second ammonium) diiodides and 2- (dicyclohexyl phosphino-)-N, N, N- trimethyl second ammonium iodate Thing.

Being suitable as the other examples of the organic phosphorus compound of LB includes phosphinous acid ester (phosphinite) and phosphonate ester Part.The representative example of phosphinite ligands includes but is not limited to methyldiphenyl base phosphinous acid ester, ethyl diphenyl Phosphinous acid ester, isopropyl diphenyl base phosphinous acid ester and phenyl diphenyl phosphinous acid ester.Phosphinate (phosphonite) The representative example of part includes but is not limited to diphenyl phenylphosphite ester, 3,5-dimethylphenyl phosphinate, diethyl first Base phosphinate, diisopropyl phenyl phosphinate and diethyl phenyl phosphinate.

In the further aspect of the present invention, it has been found that with counter anion(it is Weakly coordinating anions (WCA) compound of logical formula (I)) provides preferably catalysis (that is, initiator) activity.That is, WCA for only with cationic complex The anion of weak coordination.It is fully unstable for being replaced by neutral Lewis base, solvent or monomer.More specifically, WCA aniones work as the stable anion to cationic complex, and not with metallic atom M formed covalent bond.WCA Anion is relative inertness, because it is non-oxidizable, irreducibility and non-affinity.

In general, WCA may be selected from borate, phosphate radical, arsenate, metaantimmonic acid root, aluminate, boron benzene (boratobenzene) anion, carborane, halocarborane anion, sulfamic acid root (sulfo namidate) and sulphur Acid group.

Broadly, suitable borate anion can represent by formula A, phosphate radical, arsenate and metaantimmonic acid root it is cloudy from Son can be represented by Formula B, and aluminate anion can be represented by formula C：

[M_a(R_a)(R_b)(R_c)(R_d)] A

[M_b(R_a)R_b)(R_c)(R_d)(R_e)(R_f)] B

[M_c(OR_a)(OR_b)(OR_c)(OR_d)] C

Wherein, the M in formula A_aFor boron, the M in Formula B_bFor phosphorus, arsenic or antimony, the M in formula C_cFor aluminum.R_a、R_b、R_c、 R_d、R_eAnd R_fIndependently represent fluorine, straight chain and side chain C₁-C₁₀Alkyl, straight chain and side chain C₁-C₁₀Alkoxyl, straight chain and side chain C₃-C₅ Haloalkenyl group, straight chain and side chain C₃-C₁₂Trialkylsiloxy, C₁₈-C₃₆Triaryl siloxy, replace and do not take The C in generation₆-C₃₀Aryl and substituted and unsubstituted C₆-C₃₀Aryloxy group, wherein R_aTo R_fAll can not represent simultaneously alkoxyl or Aryloxy group.When replacing, aryl can be with monosubstituted or polysubstituted, and wherein substituent group is independently selected from straight chain and side chain C₁-C₅Alkane Base, straight chain and side chain C₁-C₅Haloalkyl, straight chain and side chain C₁-C₅Alkoxyl, straight chain and side chain C₁-C₅Halogenated alkoxy, straight chain With side chain C₁-C₁₂Trialkylsilkl, C₆-C₁₈Diarye silyl and the halogen in chlorine, bromine and fluorine.

The representative borate anion of formula A include but is not limited to tetrafluoroborate, tetraphenylborate, four (five Fluorophenyl) borate, four (3,5- double (trifluoromethyl) phenyl) borates, four (2- fluorophenyls) borates, four (3- fluorophenyls) Borate, four (4- fluorophenyls) borates, four (3,5- difluorophenyls) borates, four (2,3,4,5- tetrafluoro phenyl) borates, Four (3,4,5,6- tetrafluoro phenyl) borates, four (3,4,5- trifluorophenyls) borates, methyl three (perfluorophenyl) borate, second Base three (perfluorophenyl) borate, phenyl three (perfluorophenyl) borate, four (1,2,2- trifluoro vinyls) borates, four (4- Triisopropylsilyl tetrafluoro phenyl) borate, four (4- dimethyl-t-butylsilyl tetrafluoro phenyl) borates, (three Phenylsilane epoxide) three (pentafluorophenyl group) borates, (octyloxy) three (pentafluorophenyl group) borate, four [double [the 1- methoxies of 3,5- Fluoro- 1- (trifluoromethyl) ethyls of base -2,2,2- three] phenyl] borate, the four [3- [fluoro- 1- (trifluoros of 1- methoxyl groups -2,2,2- three Methyl) ethyl] -5- (trifluoromethyl) phenyl] borate and four [3- [fluoro- 1- (2,2,2- the trifluoro ethoxies) -1- of 2,2,2- tri- (trifluoromethyl) ethyl] -5- (trifluoromethyl) phenyl] borate.

The representative phosphate radical of Formula B, arsenate, metaantimmonic acid root include but is not limited to hexafluoro-phosphate radical, hexaphenyl phosphoric acid Root, six (pentafluorophenyl group) phosphate radicals, six (3,5- double (trifluoromethyl) phenyl) phosphate radicals, hexafluoroarsenate root, hexaphenyl arsenate, Six (pentafluorophenyl group) arsenates, six (3,5- double (trifluoromethyl) phenyl) arsenates, hexafluoroantimonic anion, hexaphenyl metaantimmonic acid root, six (pentafluorophenyl group) metaantimmonic acid root, six (double (trifluoromethyl) phenyl of 3,5-) metaantimmonic acid roots etc..

The aluminate anion of representational formula C includes but is not limited to four (pentafluorophenyl group) aluminates, three (nine fluorine connection Benzene) fluoaluminic acid root, (octyloxy) three (pentafluorophenyl group) aluminate, four (double (trifluoromethyl) phenyl of 3,5-) aluminates and methyl three (pentafluorophenyl group) aluminate.

In embodiments of the present invention, suitablyIt is selected from And

In another embodiment of the present invention, the compound for leading to formula (I) has following substituent group：

For cyclo-octene, bicyclic [3,3,0] octene, bicyclic [2,2,1] hept-2-ene", bicyclic [2,2,2] oct-2-ene or Three rings [5,2,1,0^2,6] decyl- 3- alkene；

M is palladium；

LB is acetonitrile, tertiary butyronitrile, C₆H₅CN, 2,4,6- trimethyl benzonitrile, pyridine, 4- picolines, 3,5- dimethyl pyrazoles Pyridine, 4-methoxypyridine, benzophenone or triphenylphosphine oxide；

It is selected fromOr

Y is PR₃Or O=PR₃, wherein, R independently selected from isopropyl, sec-butyl, the tert-butyl group, cyclohexyl, phenyl, benzyl, Isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy group or benzyloxy；And

R₁For methyl, ethyl, isopropyl, sec-butyl, the tert-butyl group, phenyl, phenoxy group or acetyl group (CH₃CO)。

In another embodiment of the present invention, compound of the invention is represented by logical formula (II)：

Wherein：

LB is selected from pyridine, acetonitrile or C₆H₅CN；

It is selected fromOr

R is independently selected from methyl, ethyl, (C₃-C₆) alkyl, substituted or unsubstituted (C₃-C₇) cycloalkyl, (C₆-C₁₀) Aryl, (C₆-C₁₀) aralkyl, methoxyl group, ethyoxyl, (C₃-C₆) alkoxyl, substituted or unsubstituted (C₃-C₇) cycloalkanes oxygen Base, (C₆-C₁₀) aryloxy group or (C₆-C₁₀) aralkoxy；And

R₁For methyl, ethyl, straight or branched (C₃-C₆) alkyl, (C₆-C₁₀) aralkyl or R₂CO, wherein, R₂For methyl, Ethyl or (C₃-C₆) alkyl.

In the further embodiment of the present invention, the compound of logical formula (II) has following substituent group：

LB is acetonitrile；

For

R is n-pro-pyl, isopropyl, the tert-butyl group or phenyl；And

R₁For n-pro-pyl, isopropyl, the tert-butyl group or-COCH₃。

In another embodiment of the present invention, compound of the invention is represented by formula (IIA)：

Wherein：

LB is acetonitrile or pyridine；

It is selected fromOrAnd

R₁For isopropyl or-COCH₃。

In this aspect of the invention, the compound of formula (IIA) has following substituent group：

LB is acetonitrile or pyridine；ForOrAnd R₁For isopropyl.

In another embodiment of the invention, the compound of the present invention is represented by formula (IIB)：

In another embodiment of the invention, the compound of the present invention is represented by formula (IIC)：

Wherein, Py is pyridine.

In another embodiment of the invention, the compound of the present invention is represented by formula (IID)：

Wherein, Py is pyridine.

In another aspect of this invention, the compound of logical formula (III) is also provided：

Wherein：

M is nickel, palladium or platinum；

X is halogen, triflate, methanesulfonates or tosylate；

R₁For methyl, ethyl, straight or branched (C₃-C₆) alkyl, (C₆-C₁₀) aryl, (C₆-C₁₀) aralkyl or R₂CO, its Middle R₂For methyl, ethyl or (C₃-C₆) alkyl；And

When R is phenyl, R₁It is not methyl.

It should be noted that some compounds of logical formula (III) are known.More specifically, in Crociani et al., The compound of logical formula (III) is disclosed in J.Chem.Soc.A (1968) 2869, wherein,For dicyclopentadienyl or ring Octenyl, wherein, R₁It is palladium for methoxyl group, M, X is chlorine or bromine, and Y is triphenylphosphine.Therefore, following compound is from formula (III) exclude in compound：

[Pd(C₈H₁₂.OCH₃)(P(C₆H₅)₃)Cl]；

[Pd(C₈H₁₂.OCH₃)(P(C₆H₅)₃)Br]；

[Pd(C₁₀H₁₂.OCH₃)(P(C₆H₅)₃)Cl]；

[Pd(C₁₀H₁₂.OCH₃)(P(C₆H₅)₃)Br]；

[Pt(C₈H₁₂.OCH₃)(P(C₆H₅)₃)Cl]；

[Pt(C₈H₁₂.OCH₃)(P(C₆H₅)₃)Br]；

[Pt(C₁₀H₁₂.OCH₃)(P(C₆H₅)₃)Cl]；And

[Pt(C₁₀H₁₂.OCH₃)(P(C₆H₅)₃)Br]。

In one embodiment of the present invention, the compound for leading to formula (III) has following substituent group：

For cyclo-octene, bicyclic [3,3,0] octene, bicyclic [2,2,1] hept-2-ene", bicyclic [2,2,2] oct-2-ene or Three rings [5,2,1,0^2,6] decyl- 3- alkene, the latter is commonly known as bicyclopentadiene；

M is palladium；

X is chlorine or triflate；

R₁For methyl, ethyl, n-pro-pyl, isopropyl, sec-butyl, the tert-butyl group, phenyl or acetyl group.

In another embodiment of the present invention, the compound of this aspect of the invention is by representing formula (III A)：

Wherein：

X is chlorine or triflate；And

R₁For n-pro-pyl, isopropyl or-COCH₃。

In the further embodiment of the present invention, the compound for leading to formula (III) includes wherein R₁For isopropyl；Or its Middle R₁For n-pro-pyl；Or wherein R₁For-COCH₃。

The nonrestrictive exemplary compounds of logical formula (III) can be represented by formula (IIIB), (IIIC) or (IIID)：

In another embodiment of the present invention, other representative compounds are comprised in the compound of logical formula (III), its Can be represented by formula (IIIE)：

Wherein, R and X be as defined above.R_gSelected from acetoxyl group, methoxyl group, ethyoxyl, phenoxy group and substituted or do not take The phenyl in generation.Wherein, substituent group includes any part well known by persons skilled in the art.The non-limiting example of suitable substituent group Attached bag includes (C₁-C₆) alkyl, (C₁-C₆) alkoxyl, (C₇-C₁₀) aralkyl, (C₆-C₁₀) aralkoxy, (C₆-C₁₀) aryl, (C₆- C₁₀) aralkoxy etc..In another embodiment, the compound of formula (IIIE) includes following compound：Wherein, X is Cl, Br Or I；R independently is isopropyl, the tert-butyl group or phenyl；And R_gFor acetoxyl group, methoxyl group or phenyl.In another embodiment In, the compound of formula (IIIE) includes following compound：Wherein, X is Cl, Br or I；R independently be isopropyl, the tert-butyl group or Phenyl；And R_gFor methoxyphenyl.

In the further aspect of the present invention, the useful as major catalyst of formula (IIIX) or (IIIY) is also provided A series of compounds：

Wherein, R, R_gAnd X is as defined above.R_hFor suitable functional group, it passes through to be inserted into the alkene being polymerized And contribute to chain growth.The example of this group includes hydroxyl, thiazolinyl such as vinyl etc..

The compound of the present invention can be synthesized by any program well known by persons skilled in the art.Specifically, As described above, some compounds of logical formula (III) and several initial substances for preparing the compound of the present invention are known Or it is commercially available in itself.The compound and several precursor compounds of the present invention can also pass through as it is reporting in document and this The method for preparing similar compound further described in text is prepared.J.Chatt, et al. are see, for example, J.Chem.Soc.(1957)3413-3416；M.Green,et al.,J.Chem.Soc.(A)(1967)2054-2057； K.Hiraki,et al.,Bull.Chem.Soc.Japan,53,1980,1976-1981；The relevant portion of all these patents By reference to being introduced into herein.

More specifically, compound disclosed herein can be synthesized according to the following procedure of scheme 1-2, its In, R, R₁, LB, M, X and Y unless otherwise specified, otherwise respectively as mutual-through type I and III are defined.

Scheme 1

In 1 the step of scheme I, make the suitable cyclic diolefine complexation of formula (IA) metallic compound and appropriate alcohol or Acid reaction and form the compound of formula (IB).The reaction can be carried out by any program known in the art.For example, lead to The solution of the compound of formula (IA) can at room temperature or at higher temperatures react with suitable alcohol or acid and form formula (IB) Compound.In 2 the step of scheme 1, the compound of formula (IB) further with suitable phosphine or oxidation phosphine reaction and formed The compound of logical formula (III).The reaction is again able to be carried out using any of literature procedure.Typically, this reaction Carry out in room temperature or the suitable solvent higher than room temperature.Finally, in 3 the step of scheme I, lead to formula (III) compound with The suitable reactant salt of the Weakly coordinating anions of formula A-Z and form the compound of logical formula (I), wherein, A be any suitable sun Ion such as alkali metal cation etc., it easily exchanges anion Z with the compounds X of logical formula (III).

Scheme 2 illustrates the synthesis of some particular compounds lifted as set forth herein.Specifically, the compound of formula (II) is led to And its compound of precursor, formula (IIC) can be closed by the salt of the bicyclopentadiene complex of formula (IIA)/Pd (II) Into.Illustrated in such as 1 the step of scheme 2, the compound of formula (IIA) can in a suitable solvent, in room temperature or in liter At high temperature, with various alcohol or carboxylic acid (that is, R₁OH, wherein R₁For alkyl as defined herein, aryl or acetyl group) it is anti- Answer and the compound of acquisition formula (IIB).In 2 the step of scheme 2, compound and the formula PR of formula (IIB)₃It is suitable Phosphine or phosphite reactions and obtain the compound of formula (IIC).The reaction is again able in room temperature or suitable higher than room temperature Solvent in carry out and obtain the compound of formula (IIC).Finally, in 3 the step of scheme 2, the compound of formula (IIC) is made Further react and the compound of the logical formula (II) of formation with the suitable salt such as lithium salts LiZ of Weakly coordinating anions.Typically, this Planting reaction is carried out in a suitable solvent at room temperature.It should be noted that all these reactions steps are in inert atmosphere such as nitrogen Carry out in gas, helium or argon.Any solvent can be used in these reactions, including but not limited to alcohol, such as methanol, second Alcohol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, tert-butyl alcohol etc.；Alkane solvent, such as hexane, heptane or petroleum ether；They Combination.

Scheme 2

As described herein, the compound of the present invention especially leads to the compound of formula (I), more particularly leads to the change of formula (II) Compound gathers as the one-component vinyl addition illustrated by as further detailed below and following article specific embodiment It is highly effective to close catalyst.Similarly, the compound of logical formula (III), the more particularly compound of formula (IIG), more enter The compound of one step especially formula (IIIA) to (IIIE), (IIIX) and (IIIY) is used as to as further detailed below And the bicomponent catalyst of the vinyl addition polymerization of the various alkene illustrated by the specific embodiment of following article is effective.

Polymer

The compound of the present invention can act as preparing the vinyl addition polymerization initiator of various Progress in Catalysts for Addition Polymerization of Naphthenic things. In one aspect of the invention, the compound of the invention of logical formula (I) or (II) is used as single-component system (unicomponent System), the compound is considered as initiator, wherein initiating group such as Pd-C keys copy propagation species as closely as possible Characteristic.Therefore, polydispersity is likely to decrease, and in polymerisation in solution and polymerisation in bulk, the quantity in active center increases.Phase Than under, some hitherto known compounds such as Pd- allyl complexs need to be changed into σ bonding configurations from σ-π, then urge Agent center must produce the cyclic alkyl structure unit of insertion, if for example norborene is cycloolefin monomers, for norborene Construction unit.Therefore, compound of the invention provides the conduct that cannot be obtained so far and prepares some cyclenes as herein described The benefit of the initiator of hydrocarbon polymer.

In another aspect of this invention, lead to formula (III) compound mix with the compound in situ of some logical formula (VI)s and The two component catalyst system of great activity is formed, it passes through solvent or monomer is further activated.It has now been found, surprisingly, that this Catalyst system is highly useful to preparing various polymer by some cycloolefin monomers as herein described, and avoids exogenous part Such as acetonitrile.

Therefore it provides a kind of polymeric compositions, it is included：

The compound of logical formula (I),

Wherein：

M is nickel, palladium or platinum；

LB is lewis base；

For Weakly coordinating anions；

R₁For methyl, ethyl, straight or branched (C₃-C₆) alkyl, (C₆-C₁₀) aryl, (C₆-C₁₀) aralkyl or R₂CO, its In, R₂For methyl, ethyl or (C₃-C₆) alkyl；And

The monomer of logical formula (IV)：

Wherein：

P is 0,1 or 2 integer；

It should be noted that in this aspect of the invention, can be all of using including as described herein without any restriction The compound of all of logical formula (I) of the compound of logical formula (II).It shall also be noted that the monomer of any of logical formula (IV) is equal This aspect of the invention can be used in.The representative example of the monomer of logical formula (IV) includes without any restriction following：

Bicyclic [2.2.1] hept-2-ene" (NB)；

5- methyl bicycles [2.2.1] hept-2-ene" (MeNB)；

Bicyclic [2.2.1] hept-2-ene" (EtNB) of 5- ethyls；

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5-n- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- octyl groups；

Bicyclic [2.2.1] hept-2-ene" (DecNB) of 5- decyls；

Bicyclic [2.2.1] hept-2-ene" (CF of 5- trifluoromethyls₃NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro-ethyls₂F₅NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro hexyls₆F₁₃NB)；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- perfluoro capryls；

Bicyclic [2.2.1] hept-2-ene" (PerfluoroDecNB) of 5- perfluoro decyls；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

5- ((2- (2- methoxy ethoxy) ethyoxyl) methyl) bicyclic [2.2.1] hept-2-ene" (NBTON)；

1- (bicyclic [2.2.1] hept- 5- alkene -2- bases) the oxa- dodecanes (NBTODD) of -2,5,8,11- four；

5- (2- (2- ethoxy ethoxies) ethyl) bicyclic [2.2.1] hept-2-ene"；

5- (2- (2- (2- propoxyl group ethyoxyls) ethyoxyl) ethyoxyl) bicyclic [2.2.1] hept-2-ene"；

1- (bicyclic [2.2.1] hept- 5- alkene -2- ylmethyls) -3,4- dimethyl -1H- pyrrole-2,5-diones (MeDMMINB)；

1- (3- (bicyclic [2.2.1] hept- 5- alkene -2- bases) propyl group) -3,4- dimethyl -1H- pyrrole-2,5-diones (PrDMMINB)；

1- (4- (bicyclic [2.2.1] hept- 5- alkene -2- bases) butyl) -3,4- dimethyl -1H- pyrrole-2,5-diones (BuDMMINB)；

1- (6- (bicyclic [2.2.1] hept- 5- alkene -2- bases) hexyl) -3,4- dimethyl -1H- pyrrole-2,5-diones (HexDMMINB)；

2- ((bicyclic [2.2.1] hept- 5- alkene -2- ylmethoxies) methyl) oxirane (MGENB)；

2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) oxirane；

2- (7- (bicyclic [2.2.1] hept- 5- alkene -2- bases) heptyl) oxirane；

Bicyclic [2.2.1] hept-2-ene" (PENB) of 5- phenethyls；

Bicyclic [2.2.1] hept-2-ene" (BnNB) of 5- benzyls；

2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) bicyclic [2.2.1] heptane (referred to herein as NBANB)；

Ethyl 3- (bicyclic [2.2.1] hept-2-ene" -2- bases) propionic ester (EPEsNB)；And

2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) -5- phenyl-bicyclic [2.2.1] heptane (referred to herein as NBNBAPh)。

In one embodiment, the compound of polymerizable composition, polymerizable composition of the invention comprising logical formula (I), it is selected from following：

Wherein, Py is pyridine；And the polymerizable monomer is selected from following：

Bicyclic [2.2.1] hept-2-ene" (NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

5- hexyls are bicyclic-[2.2.1] hept-2-ene" (HexNB)；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- octyl groups；

Bicyclic [2.2.1] hept-2-ene" (DecNB) of 5- decyls；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro butyls₄F₉NB)；

Bicyclic [2.2.1] hept-2-ene" (PENB) of 5- phenethyls；

Bicyclic [2.2.1] hept-2-ene" (BnNB) of 5- benzyls；And

2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) bicyclic [2.2.1] heptane (NBANB).

In the further aspect of the present invention, polymeric compositions are also provided, it is included：

The compound of logical formula (III)：

Wherein：

M is nickel, palladium or platinum；

X is halogen, triflate, methanesulfonates or tosylate；

R₁For methyl, ethyl, straight or branched (C₃-C₆) alkyl, (C₆-C₁₀) aryl, (C₆-C₁₀) aralkyl or R₂CO, its Middle R₂For methyl, ethyl or (C₃-C₆) alkyl；

The compound of logical formula V：

Wherein,

It is selected from lithium, sodium, potassium, caesium, barium, ammonium or the (C of straight or branched four₁-C₄) cation in alkylammonium；

Be selected from Or In Weakly coordinating anions；And

The monomer of logical formula (IV)：

Wherein：

P is 0,1 or 2 integer；

In this aspect of the invention, compound of the polymerizable composition, polymerizable composition comprising logical formula (III), it is selected from following：

Additionally, the compound of logical formula V is selected from following：

LiBF4；

Trifluoromethanesulfonic acid lithium；

Four (pentafluorophenyl group) Lithium biborates；

(diethyl ether) four (pentafluorophenyl group) Lithium biborate ([Li (OEt₂)_2.5][B(C₆F₅)₄])(LiFABA)；

Tetraphenylboronic acid lithium；

Four (double (trifluoromethyl) phenyl of 3,5-) Lithium biborates；

Four (2- fluorophenyls) Lithium biborates；

Four (3- fluorophenyls) Lithium biborates；

Four (4- fluorophenyls) Lithium biborates；

Four (3,5- difluorophenyls) Lithium biborates；

Lithium hexafluoro phosphate；

Hexaphenyl lithium phosphate；

Six (pentafluorophenyl group) lithium phosphates；

Hexafluoroarsenate lithium；

Hexaphenyl arsenic acid lithium；

Six (pentafluorophenyl group) arsenic acid lithiums；

Six (double (trifluoromethyl) phenyl of 3,5-) arsenic acid lithiums；

Hexafluoro-antimonic acid lithium；

Hexaphenyl metaantimmonic acid lithium；

Six (pentafluorophenyl group) metaantimmonic acid lithiums；

Six (double (trifluoromethyl) phenyl of 3,5-) metaantimmonic acid lithiums；

Four (pentafluorophenyl group) lithium aluminates；

Three (nine fluorine biphenyl) fluoaluminic acid lithiums；

(octyloxy) three (pentafluorophenyl group) lithium aluminate；

Four (double (trifluoromethyl) phenyl of 3,5-) lithium aluminates；And

Methyl three (pentafluorophenyl group) lithium aluminate.

Furthermore it is possible to using any polymerizable monomer as described herein.For example, polymerizable monomer is selected from following：

Bicyclic [2.2.1] hept-2-ene" (NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

5- hexyls are bicyclic-[2.2.1] hept-2-ene" (HexNB)；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- octyl groups；

Bicyclic [2.2.1] hept-2-ene" (DecNB) of 5- decyls；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro butyls₄F₉NB)；

Bicyclic [2.2.1] hept-2-ene" (PENB) of 5- phenethyls；

Bicyclic [2.2.1] hept-2-ene" (BnNB) of 5- benzyls；And

As described above, polyreaction can pure (neat) (polymerisation in bulk) or carry out in the solution.That is, by implementing The present invention, can urge in one pack system as described herein (that is, leading to the compound of formula (I) or (II)) catalyst or bi-component now In the presence of agent (that is, leading to the combination of the compound with the compound of logical formula V of formula (III)), manufacture various containing at least one Plant the polymer of the norbornene monomer (that is, leading to the compound of formula (IV)) of functionalization.When using bicomponent catalyst, formula (III) compound may be generally referred to as major catalyst, and the compound of logical formula V is commonly referred to activator.However, when using double groups During divided catalyst, being effective as various other compounds that catalyst, major catalyst and/or activator work can also be with The compound of logical formula (III) and (V) is applied in combination.

The compound for also finding the present invention is high activity as one pack system or bi-component catalyst composition.Therefore, it is existing In the polymer that high-quality can be manufactured by using a small amount of catalyst.Therefore, in one embodiment, addition polymerization can The use of the total mole number based on monomer and used catalyst is at least 100:1 monomer:The mol ratio of single component catalyst is effective Carry out.That is, the single component catalyst using 100 moles of monomer to 1 mole.In other embodiments, monomer:Catalyst Mol ratio can be 1,000,000:1；500,000:1；100,000:1；20,000:1；10,000:1、1,000:1、500:1、 400:1、200:1 etc..When using two component catalyst system, monomer:Major catalyst:The mol ratio of activator can be at least 100:1:1.In other embodiments, monomer:Major catalyst:The mol ratio of activator can be 1,000,000:1:1；500, 000:1:1；100,000:1:1；20,000:1:1；10,000:1:1、1,000:1:1、500:1:1、400:1:1、200:1:1 Deng.In some embodiments, the consumption of activator exceedes the mole of major catalyst used, such as major catalyst:Activator Mol ratio can be 1:1 to 1:6.

As described above, bulk polymerization can be entered in the case of without any solvent using catalyst and monomer OK.Advantageously, this polyreaction also can be carried out in a mold at a suitable temperature, to form three dimensional polymeric product. In general, reaction temperature can be carried out in the range of the boiling point less than such as less than 0 DEG C to monomer of ambient temperature, however, The component of recommendation response container or mould is not heated beyond the lightning (flash point) of more than one monomer.Generally, Polymerisation in bulk is carried out within the temperature range of about 10 DEG C to 300 DEG C, and in some other embodiments, temperature range can be about 10 DEG C to 200 DEG C；Or about 20 DEG C to 100 DEG C.

Because polyreaction is heat release, except the mould of non-usage cooling, in the course of the polymerization process the temperature in mould is usual Higher than the temperature of charging.Therefore, initial mould temperature generally can be in about -20 DEG C to about 300 DEG C of scope；Or about 0 DEG C to about 200 ℃；Or 20 DEG C to 100 DEG C.Temperature Distribution in mould is by such as mould geometry, as radiator or heat supplying device The factor such as the reactivity of characteristic, catalyst and monomer of mould impact.To a certain extent, suitable temperature and heat exchange The selection of condition must be based on the experience of given mould, charging and catalyst system.

After polyreaction terminates, molded object can be carried out separately within the temperature range of about 100 DEG C to 300 DEG C Outer post curing treatment about 15 minutes to 24 hours, or 1 hour to 2 hours.This post curing treatment can strengthen polymer Matter, including glass transition temperature (T_g) and heat distortion temperature (HDT).Additionally, solidify afterwards are desirable, but it is not required , so that sample obtains its final stable dimensional state (dimensional state), so that the abnormal smells from the patient of residual is minimum Change, and improve final physical property.

Vinyl addition polymerization can also use single component catalyst as described herein (that is, to lead to the change of formula (I) or (II) Compound) or bicomponent catalyst (that is, the compound of logical formula (III) being combined with the compound of logical formula V) is in the solution Carry out.In this embodiment, the solution of catalyst (that is, is led to into the change of formula (IV) with monomer under conditions known in the art Compound) more than one desired solution suitably mix and formed the present invention polymer.Suitable polymer solvent without Any ground that limits includes alkane and cyclic alkane solvents, such as pentane, hexane, heptane and hexamethylene；Halogenated alkane solvents, such as dichloromethane Alkane, chloroform, carbon tetrachloride, ethyl chloride, 1,1- dichloroethanes, 1,2- dichloroethanes, n-propyl chloride, 2 cbloropropane isopropyl chloride, 1-chlorobutane, Sec-Butyl Chloride, 1- chloro-2-methyls propane and 1-chloropentane；Ether, such as THF and diethyl ether；Aromatic solvent, such as benzene, dimethylbenzene, first Benzene, sym-trimethylbenzene., chlorobenzene and o-dichlorohenzene；Halocarbon solvent, such as112；And the mixture of any combination of them.

Solution polymerization temperatures can be less than in the range of ambient temperature, such as less than 0 DEG C to solvent for use of boiling point.It is logical Often, polymerisation in solution is carried out within the temperature range of about 10 DEG C to 200 DEG C, and in some other embodiments, temperature range can be About 10 DEG C to 150 DEG C；Or about 20 DEG C to 100 DEG C.

Polymer formed according to the present invention generally shows at least about 3,000 number-average molecular weight (M_n).In another reality In applying mode, the polymer of the present invention has at least about 5,000 M_n.In another embodiment, polymer of the invention tool There is at least about 10,000 M_n.In another embodiment, polymer of the invention has at least about 20,000 M_n.Another In embodiment, the polymer of the present invention has at least about 50,000 M_n.In some other embodiments, the present invention's is poly- Compound has at least about 100,000 M_n.In another embodiment, polymer of the invention has the M higher than 100,000_n, And can be higher than 500,000 in some other embodiments.Number-average molecular weight (the M of polymer_n) can pass through any of Technology is for example suitable just like the differential refractive index detector calibrated with Narrow distribution polystyrene standard etc by being equipped with The gel permeation chromatography (GPC) of detector and calibration standard is measured.As described above, the polymer of the present invention is typically Low-down polydispersity index (PDI) is shown, it is weight average molecular weight (M_w) and number-average molecular weight (M_n) ratio.In general, The PDI of the polymer of the present invention is less than 2.In some embodiments, PDI is less than 1.5, less than 1.4, less than 1.3, less than 1.2 Or less than 1.1.It should be noted, however, that in some embodiments, PDI can be higher than 2, such as higher than 3.

Block copolymer

Advantageously, now it has also been found that the various compounds of logical formula (I), (II) or (III) for formation used as including As described herein a series of catalyst of block copolymers of more than one norbornene-type compound of logical formula (IV) has Effect ground function.As described herein block copolymer also can be by any other catalyst system known in the art It is standby.It has furthermore been found that the block copolymer of the present invention provides unique advantage, therefore can be used for various applications, including but do not limit In formation membrane material and various other optics and electronic application.The film formed by block copolymer for example to from biomass or its Organic substance is separated in his organic waste materials useful.

Therefore it provides the block copolymer of logical formula (VI)：

(A)_m-b-(B)_n (VI)

Wherein, m and n are at least 15 integer, but in other embodiments, m and n can 20 to 4000, or 50 to 3000, or 100 to 2000 scope, and in other embodiments, according to expected purposes, m and n can also be higher than 4000；

B represents the key between homopolymer A and two blocks of B；

Wherein：

The position that representative is bonded with another repetitives；

P is 0,1 or 2 integer；

In one embodiment of the present invention, block polymer of the invention is also comprising the 3rd represented by logical formula (VII) The repetitives of type：

(A)_m-b-(B)_n-b-(C)_o (VII)

Wherein, as defined above, and o is at least 15 integer for m, n and b, but in other embodiments, o can be 20 To 4000 or, 50 to 3000, or 100 to 2000 scope, and in other embodiments, according to expected from block polymer Purposes, o can also be higher than 4000.C and A or B are identical or different, and independently selected from the repetition list represented by formula (IVA) Unit, the repetitives are derived from the monomer for leading to formula (IV) as defined herein.In other words, block copolymer of the invention Can exist as diblock or as three block.However, the other monomers of the logical formula (IV) by adding more than one and Form the segmented copolymer of the present invention such that it is able to form any amount of other block.For example, diblock polymer allusion quotation Type ground is formed first by making the first monomer of logical formula (IV) be polymerized in the presence of suitable catalyst, then, can Using as being added in identical polymerization reaction mixture with the second comonomer of the first monomer identical or second different monomers And form diblock copolymer.In general, polymerization is entered in the solution under suitable polymeric reaction temperature as described above OK.That is, in the presence of more than one suitable polymerization catalyst, any solvent as described above can be used and two are formed Block copolymer.Reaction temperature generally about in environmental condition, i.e., near room temperature.It is also possible, however, to use being higher than environment (super-ambient) temperature more than i.e. about 25 DEG C to 150 DEG C of room temperature, or it is i.e. big less than environment (sub-ambient) Temperature below about 25 DEG C to 0 DEG C of room temperature, or even lower temperature.Polymerization also can be carried out purely, i.e. polymerisation in bulk Without solvent.Triblock polymer is formed again by Third monomer is added after making second comonomer be polymerized.Many blocks Polymer is formed by adding other monomer successively.As described above, block copolymer can be by using identical monomer Or different monomers and formed, with the monomer of different mol ratio to form different blocks as needed.

Therefore, diblock copolymer is provided in one embodiment, wherein, A:The block mol ratio of B is 1:1 to 1:4. In another embodiment, A:The block mol ratio of B is 1:1 to 1:2.In yet, A:The block mol ratio of B is 1: 1.In yet, block polymer is triblock polymer, wherein, A:B:The block mol ratio of C is 1:1:1 to 1: 4:1 to 1:1:4.In further embodiment, A:B:The block mol ratio of C is 1:1:1；And in another embodiment, A:B:The block mol ratio of C is 1:2:1.With regard to this, the size of block can also be controlled by the weight fraction of each block System.That is, in diblock polymer A-b-B, the weight fraction of monomer A can be expressed as W in 0.1 to 1 scope_A.Various three is embedding Section or other multi-block polymers equally can be prepared using the respective monomer used of Different Weight fraction.

In general, the arbitrary monomer included by logical formula (IV) can be used in forming the block polymer of the present invention.Example Such as, the non-limitative example of A repetitives can be derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- octyl groups；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro-ethyls₂F₅NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro hexyls₆F₁₃NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

Bicyclic [2.2.1] hept-2-ene" (PENB) of 5- phenethyls；

Bicyclic [2.2.1] hept-2-ene" (BnNB) of 5- benzyls；And

In another embodiment, the non-limitative example of repetitives B is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- octyl groups；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro-ethyls₂F₅NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro hexyls₆F₁₃NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

Bicyclic [2.2.1] hept-2-ene" (PENB) of 5- phenethyls；

Bicyclic [2.2.1] hept-2-ene" (BnNB) of 5- benzyls；And

Finally, the non-limitative example of repetitives C is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- octyl groups；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro-ethyls₂F₅NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro hexyls₆F₁₃NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

Bicyclic [2.2.1] hept-2-ene" (PENB) of 5- phenethyls；

Bicyclic [2.2.1] hept-2-ene" (BnNB) of 5- benzyls；And

In another embodiment, the representative example of repetitives A is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

1- (4- (bicyclic [2.2.1] hept- 5- alkene -2- bases) butyl) -3,4- dimethyl -1H- pyrrole-2,5-diones (BuDMMINB)；And

In yet, the representative example of repetitives B is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

In yet, the representative example of repetitives C is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

The non-limitative example of the block copolymer of the present invention is selected from following：

Derived from bicyclic [2.2.1] hept-2-ene" of 5- hexyls and norbornene -2- trifluoromethyl -3,3,3- trifluoro propyl-s 2- The block copolymer (HexNB-b-HFANB) of alcohol；

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl and norbornene -2- trifluoromethyl -3,3,3- trifluoro propyl-s 2- The block copolymer (BuNB-b-HFANB) of alcohol

Block derived from bicyclic [2.2.1] hept-2-ene" of 5- benzyls and bicyclic [2.2.1] hept-2-ene" of 5-n- perfluoro butyls Copolymer (BnNB-b-C₄F₉NB)；

Derived from bicyclic [2.2.1] hept-2-ene" of 5-n- perfluoro butyls and 1- (4- (bicyclic [2.2.1] hept- 5- alkene -2- bases) Butyl) -3,4- dimethyl -1H- pyrrole-2,5-diones block copolymer (C₄F₉NB-b-BuDMMINB)；

Derived from norbornene -2- trifluoromethyls -3,3,3- trifluoros propan-2-ol and 2- (bicyclic [2.2.1] hept- 5- alkene - 2- yls) bicyclic [2.2.1] heptane block copolymer (HFANB-b-NBANB)；And

It is bicyclic derived from bicyclic [2.2.1] hept-2-ene" of 5- hexyls and 2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) The block copolymer (HexNB-b-NBANB) of [2.2.1] heptane.

In one embodiment, block polymer of the invention is selected from following：

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl, norbornene -2- trifluoromethyl -3,3,3- trifluoro propyl-s 2- The block polymer (BuNB-b-HFANB-b-BuNB) of alcohol and bicyclic [2.2.1] hept-2-ene" of 5- butyl；

It is (bicyclic derived from bicyclic [2.2.1] hept-2-ene" of 5- normal-butyls, bicyclic [2.2.1] hept-2-ene" of 5- benzyls and 2- [2.2.1] hept- 5- alkene -2- bases) bicyclic [2.2.1] heptane block copolymer (BuNB-b-BnNB-b-NBANB)；And

Derived from norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols, bicyclic [2.2.1] hept- 2- of 5- butyl Block polymer (the HFANB-b-BuNB-b- of alkene and norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols HFANB)。

The block polymer of the present invention can be prepared by any program known in the art.In general, polymerization Carry out in the solution and in the presence of suitable metallic catalyst.In certain embodiments of the present invention, it is advantageously discovered that, Metallic catalyst with can as co-catalyst (co-catalyst), initiator or main initiator (pro-intiator) or activation The method that the suitable compound that agent is worked is combined and provides the block polymer for preparing the present invention.However, as described above, Any other method known in the art can be used.

Therefore it provides a kind of preparation technology of the block copolymer of formula (VI) logical as described herein, it includes following step Suddenly：Any one in the first monomer A for leading to formula (IV) as described herein is reacted with palladium compound and form first polymer Block.Then, the second comonomer B of the logical formula (IV) different from the first monomer A of logical formula (IV) is added to into polyreaction mixing The block copolymer of the diblock copolymer containing monomeric repeating unit A and B with different mol ratio is formed in thing.

In another embodiment, a kind of preparation technology of triblock polymer is also provided, it is included makes logical formula (IV) The step of Third monomer C reacts and forms the block polymer of logical formula (VII)：

(A)_m-b-(B)_n-b-(C)_o (VII)

Wherein, m, n, o, b, A, B and C be as defined herein.It should be noted that monomeric repeating unit C can be with A or B phases It is same or different, and independently selected from the repetitives represented by formula (IVA), the repetitives derive institute freely herein The monomer of the logical formula (IV) of definition.And, as described above, therefore the block polymer of logical formula (VII) is referred to as three block polymerization Thing, and can have the repetitives of formula A, B or C as above of various different mol ratios.

The palladium compound that can be used in the technique of the present invention includes logical formula (I), (II) and (III) as described herein All compounds.

Advantageously, it has been found that various other palladium compounds also can be used in the technique of the present invention.It is suitable for This palladium compound for forming the block polymer of the present invention is represented by the following general formula：

(pi-allyl) Pd (P (Q₃))(L₁) or (methyl) Pd (P (Q₃))(L₁)

Wherein, Q can be with identical or different, and independently selected from isopropyl, the tert-butyl group, neopentyl and cyclohexyl；And L₁ Selected from halogen, trifluoro-acetate and trifluoromethayl sulfonic acid ester (triflate).The non-limitative example of this palladium compound Including following：

Allylpalladium (tri isopropyl phosphine) chloride [Pd (pi-allyl) (tri isopropyl phosphine) Cl]；

Allylpalladium (tri-butyl phosphine) chloride [Pd (pi-allyl) (tri-butyl phosphine) Cl]；

Allylpalladium (diisopropyl-tert-butyl group phosphine) chloride [Pd (pi-allyl) (diisopropyl-tert-butyl group phosphine) Cl]；

Allylpalladium (isopropyl-di-t-butyl phosphine) chloride [Pd (pi-allyl) (isopropyl-di-t-butyl phosphine) Cl]；

Allylpalladium (di-t-butyl-cyclohexyl phosphine) chloride [Pd (pi-allyl) (di-t-butyl-cyclohexyl phosphine) Cl]；

Allylpalladium (di-t-butyl-neopentyl phosphine) chloride [Pd (pi-allyl) (di-t-butyl-neopentyl phosphine) Cl]；

(pi-allyl) palladium (tricyclohexyl phosphine) triflate [Pd (pi-allyl) (tricyclohexyl phosphine) trifluoromethanesulfonic acid Ester]；

(pi-allyl) palladium (tri isopropyl phosphine) triflate [Pd (pi-allyl) (tri isopropyl phosphine) trifluoromethanesulfonic acid Ester]；

(pi-allyl) palladium (tricyclohexyl phosphine) trifluoro-acetate [Pd (pi-allyl) (tricyclohexyl phosphine) trifluoro-acetate]；

(pi-allyl) palladium (tri isopropyl phosphine) trifluoro-ethylene ester [Pd (pi-allyl) (tri isopropyl phosphine) trifluoro-acetate]；

Methyl palladium (tri isopropyl phosphine) chloride [Pd (methyl) (tri isopropyl phosphine) Cl]；

Methyl palladium (tri-butyl phosphine) chloride [Pd (methyl) (tri-butyl phosphine) Cl]；

Methyl palladium (diisopropyl-tert-butyl group phosphine) chloride [Pd (methyl) (diisopropyl-tert-butyl group phosphine) Cl]；

Methyl palladium (isopropyl-di-t-butyl phosphine) chloride [Pd (methyl) (isopropyl-di-t-butyl phosphine) Cl]；

Methyl palladium (di-t-butyl-cyclohexyl phosphine) chloride [Pd (methyl) (di-t-butyl-cyclohexyl phosphine) Cl]；

Methyl palladium (tricyclohexyl phosphine) chloride [Pd (methyl) (tricyclohexyl phosphine) Cl], is also abbreviated by [(Me-Pd- PCy₃) Cl], wherein Cy is cyclohexyl (C₆H₁₁)；

Methyl palladium (dicyclohexyl-tert-butyl group phosphine) chloride [Pd (methyl) (dicyclohexyl-tert-butyl group phosphine) Cl]；

Methyl palladium (cyclohexyl-two (tert-butyl group) phosphine) chloride [Pd (methyl) (cyclohexyl-two (tert-butyl group) phosphine) Cl]；Deng Deng.

Another kind of palladium compound can also be used for forming the block polymer of the present invention, can be represented by the following general formula：

Wherein, Rx is the (C for replacing₈-C₁₆) aryl, such as 2,5- diisopropyl phenyls, sym-trimethylbenzene. base etc., L₁As above institute Definition.The non-limitative example of this palladium compound includes following：

Pi-allyl (palladium) (double (2,6- the diisopropyl phenyls) -2,3- dihydro -1H- imidazoles of 1,3-) Cl；

Pi-allyl (palladium) (double (2,6- diisopropyl phenyls) imidazolidines of 1,3-) Cl；And

Pi-allyl (palladium) (the sym-trimethylbenzene. base -2,3- dihydro -1H- imidazoles of 1,3- bis-) Cl.

Several above-mentioned palladium compounds are commercially available or known in the literature, and can be using known in document Any program be prepared.

As also described above, above-mentioned palladium compound generally with as co-catalyst, initiator, main initiator or activator play The other compound of function is used in combination.For example, any compound of logical formula V as described above can be used in the mesh 's.In one embodiment, the non-limitative example of this activator compound includes four (pentafluorophenyl group) boronation lithium ether (LiFABA-[Li(OEt₂)_2.5][B(C₆F₅)₄]) and N, accelerine four (pentafluorophenyl group)-borate (DANFABA) etc..

It should therefore be noted that for being conducive to the palladium-containing catalyst of the block copolymer for manufacturing the present invention to be prepared as Preformed one-component catalyst, or by the way that palladium major catalyst and activator will be contained in the presence of the monomer to be polymerized (or co-catalyst, initiator or main initiator as above) mixes and in situ preparation mixes.

Therefore, preformed catalyst can be by by (or the catalysis altogether of catalyst precarsor such as major catalyst and activator Agent, initiator or main initiator) mix in appropriate solvent so that reaction is carried out under the appropriate temperature conditions, and is separated Product, i.e., preformed catalyst product is preparing.Major catalyst refer to by with co-catalyst, activator, initiation Agent or main initiator compounds react and are converted into the containing palladium compound of active catalyst.Representative major catalyst and activator The further description of compound and synthesis can in U.S. Patent No. 6,455, No. 650 check that its relevant portion is by reference to quilt In being incorporated herein.

Block copolymer formed according to the present invention generally shows at least about 2,000 for each block for being formed Number-average molecular weight (M_n).The M of each block_nCan be by the property (property) desired by being appropriate to and based on block copolymerization The final use of thing and adjust.Therefore, in another embodiment, one of block of block copolymer of the invention has at least About 20,000 M_n.In yet, one of block of block copolymer of the invention has at least about 50,000 M_n.In some other embodiments, one of block of block copolymer of the present invention has at least about 100,000 M_n.Another In one embodiment, one of block of diblock copolymer has at least 5,000 M_n, and other blocks have at least 20,000 M_n.In some other embodiments, the arbitrary block of block polymer of the present invention has higher than 100,000, higher than 200, 000 or the M higher than 500,000_n.As described above, number-average molecular weight (the M of block copolymer_n) can be by any of skill Art, such as by being equipped with just like differential refractometer (RI) detector or multi-angle laser light with Narrow distribution polystyrene standard calibration The suitable detector of scattering (LS) detector etc and the gel permeation chromatography (GPC) of calibration standard are determined.Also It may be noted that every kind of block copolymer of the present invention typically shows low-down polydispersity index (PDI=M_w/M_n).It is general and Speech, the PDI of each block of the block copolymer of the present invention is less than 2.In some embodiments, PDI is less than 1.5, is less than 1.4th, less than 1.3, less than 1.2 or less than 1.1.It should be noted, however, that in some embodiments, PDI can be higher than 2, for example Higher than 3.

In one embodiment, various diblock polymers can be formed by implementing the technique of the present invention.By this The non-limitative example of this diblock polymer that bright technique is formed can be listed below：

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl and norbornene -2- trifluoromethyl -3,3,3- trifluoro propyl-s 2- The block copolymer (BuNB-b-HFANB) of alcohol；

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl and 1- (4- (bicyclic [2.2.1] hept- 5- alkene -2- bases) butyl) - Block copolymer (the C of 3,4- dimethyl -1H- pyrrole-2,5-diones₄F₉NB-b-BuDMMINB)；

Derived from norbornene -2- trifluoromethyls -3,3,3- trifluoros propan-2-ol and 2- (bicyclic [2.2.1] hept- 5- alkene - 2- yls) bicyclic [2.2.1] heptane block copolymer (HFANB-b-NBANB)；

It is bicyclic derived from bicyclic [2.2.1] hept-2-ene" of 5- hexyls and 2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) The block copolymer (HexNB-b-NBANB) of [2.2.1] heptane；And

Block derived from bicyclic [2.2.1] hept-2-ene" of 5- benzyls and bicyclic [2.2.1] hept-2-ene" of 5-n- perfluoro butyls Copolymer (BnNB-b-C₄F₉NB)。

In another embodiment, various triblock polymers can be formed by implementing the technique of the present invention.By this The non-limitative example of this triblock polymer that the technique of invention is formed can be listed below：

It is (bicyclic derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl, bicyclic [2.2.1] hept-2-ene" of 5- benzyls and 2- [2.2.1] hept- 5- alkene -2- bases) bicyclic [2.2.1] heptane block polymer (BuNB-b-BnNB-b-NBANB)；And

Osmotic evaporation film application

As described above, the block polymer of the present invention shows the property of several uniquenesses, therefore in several different applications In it is useful, including being used to separating as membrane material, electronics and/or optoelectronic applications.

With the increase of the care to such as producing the bio-fuels such as ethanol, butanol, exploitation is economically isolated from water The care more and more higher of the environmentally friendly separating technology of organic materials.Also exist current to being polluted by industrial process purification and Organic product is separated from the aqueous fermentation liquid for being designed to form various organic solvents by bioprocess, such as always from fermentation The meat soup of reactor or any other meat soup for being formed with bioanalysises, such as the demand of separating phenol is increasingly in algae meat soup It is high.Additionally, the detached care from biological and industrial waste (including the waste material of any biomass derived) by value-added product Increasing.Although the use of use as the techniques such as distillation and air stripping carry out this separation being known, these common process, especially It is to distill generally to be characterized with high capital and high-energy source cost, therefore this common process Jing often becomes problem, such as, it is known that such as Fruit uses conventional separation methods, then the caloric value more than 60% such as the bio-fuel of butanol etc is wasted.

Importantly, organic product, especially by above-mentioned bioprocess technology or preparation or extract from organic waste materials Organic solvent obtain increasing industrial application.For example, the n-butyl alcohol for being produced and its ester (for example, acetic acid N-butyl) about half be used as solvent in coatings industry, including the solvent as dyestuff such as printing-ink.Dicarboxylic acids, neighbour Other known applications of phthalate anhydride and acrylic acid butyl ester are included as plasticizer, rubber additive, dispersant, hemizygous Into the additive in lubricant, polishing agent and cleaning agent such as floor cleaner and detergent, and answering as hydraulic fluid With.Butanol and its ester also serve as solvent, including as medicine and natural product such as antibiotic, hormone, vitamin, alkaloid and Camphor tree Extractant in the production of brain.Various other purposes of butanol and its ester and its ether include as weaving in various other purposes Solubilizing agent in industry, such as adding as the additive in spinning bath or the carrier as coloured plastics, in as thawing solution Plus agent, as the additive in the gasoline of spark ignition engine, as producing the raw material of glycol ether.

Therefore, for carrying out being known as this detached alternative techniques of pervaporation as to above-mentioned " waste material " Solution and receive sizable concern.In pervaporation processes, feed liquid (charge liquid) (typically two is made Plant the mixture of above liquid, such as fermentation liquid) use with the film of the property with the preferential permeable membrane of a kind of component for allowing feed liquid Film (membrane film) is contacted.Then, generally by the per-meate side applying vacuum in film, using the penetrant as steam from The downstream of film film removes.Therefore, Pervaporation is had proven to similar volatile liquid mixture, example Such as it is difficult to selectable method in the separation by the detached azeotropic mixture of conventional method.Although such as polyimides, polyethers-poly- The polymer such as amide, polydimethylsiloxane have been successfully used to form to a certain extent osmotic evaporation film, but are so far Only the necessary characteristic needed for viable commercial membrane material which be not all proved to.For example, if PERVAP 1060 is (by gathering (dimethyl siloxane), PDMS manufacture), PERVAP 1070 (by zeolite, ZSM-5, filling PDMS manufacture) (Sulzer Chemtech Membrane Systems A.G., Nuo Yinjixing, Germany) and PEBA (block copolymer polyphenylene ether-polyamide, GKSS-Forschungszen trum Geesthacht GmbH, cover Si Tehahete, Germany) etc osmotic evaporation film can For separating various low volatile organics from aqueous mixture.It remains desirable, however, that film of the exploitation with more preferable performance, its Organic substance efficiently separating from aqueous mixture can be provided with lower capital and the operation cost for reducing.

Disclosed herein is according to the embodiment of the present invention, its cover monomer, the embodiment of polymer composition, film and The embodiment of film composite and formed by it, advantageously provide cannot realize so far from various mixture (bag Include fermentation liquid, industrial waste, other) in separate Organic substance osmotic evaporation film embodiment.

The illustrative embodiments of the present invention are described below.The various improvement of this illustrative embodiments, transformation (adaptation) or change be disclosed, therefore it will be apparent to those skilled in the art that.It should be appreciated that depending on The teachings of the present invention and these teaching made this area obtain progress all of this improvement, transformation or change be considered as It is in the scope of the present invention and objective.For example, although illustrative embodiments as herein described are usually directed to from aqueous feed liquid Middle separating butanol and/or phenol, but this does not imply that by present invention is limited only to be used for the embodiment party of separating butanol and/or phenol Formula.Therefore, some embodiments of the present invention include separating any organic materials from aqueous (aqueous based) feed liquid, Wherein appropriate osmotic evaporation film can be formed by the block copolymer of the present invention.For example, some embodiments are included using this Literary disclosed appropriate osmotic evaporation film is from separating hydrophobicity organic materials in hydrophilic feed liquid.Another other enforcements of the present invention Mode includes the separation of non-polar and polar organic materials.This detached example is included but is not limited to from water-soluble alcohol such as methanol Or separating aromatic compound such as benzene or toluene in ethanol, and from miscellaneous carbon-based (heterocarbyl-based) the class thing of polarity The material such as hexane and heptane of nonpolar alkyl (hydrocarbyl-based) class are separated in matter.Various other Organic substances are also Including volatile organic matter solvent, such as tetrahydrofuran (THF), ethyl acetate (EA), acetone, butanone (MEK), methyl-isobutyl Ketone (MIBK) etc., it is all these to may reside in fermentation liquid or industrial waste.

With the increase of organic concentration, the expected behavior of the osmotic evaporation film manufactured by hydrophobic polymer (expected behavior) is to become plasticising and/or swelling.Plasticising and/or swelling film typically results in Organic substance With infiltrative undesirable increase of both water, the infiltrative increase of water is generally relatively larger than the infiltrative increasing of Organic substance Plus, therefore cause the reduction of separation factor.Unexpectedly, generally in the hydrophobic block polymer manufacture by the present invention Osmotic evaporation film shows and generally desired contrary behavior.As described herein osmotic evaporation film has with input concentration Increase (that is, the increase of the organic concentration of feed stream) and the separation factor that sharply increases.

Typically in pervaporation, multicomponent liquid stream passes through osmotic evaporation film, the osmotic evaporation film to make more than one Component preferentially permeate.When multicomponent liquid stream flows through osmotic evaporation film surface, the component of preferential infiltration passes through osmotic evaporation film, And be removed as penetrant steam.By the vapour pressure on the penetrant side for keeping osmotic evaporation film less than multicomponent liquid stream Vapour pressure, induces the conveying through osmotic evaporation film.For example, can be by the way that multicomponent liquid stream be maintained above to permeate logistics Temperature and realize steam pressure difference.In this embodiment, the latent heat of penetrant component evaporation is supplied to multicomponent liquid stream, to keep Feeding temperature, and proceed pervaporation processes.Or, typically via on the penetrant side of pervaporation component Operate under subatmospheric, to realize steam pressure difference.Partial vacuum energy on the penetrant side of polynorbornene osmotic evaporation film Enough obtained by following either type：The pressure drop produced by the cooling due to occurring in the condenser unit and condensation, and/ Or by using vacuum pump.Optional purge gas (sweep gas) on penetrant side can be by reducing infiltration component Concentration promoting pervaporation processes.The vapour pressure of feed liquid can arbitrarily be improved by heating fermentation liquid.Poly- drop ice Piece alkene osmotic evaporation film has been disclosed in U.S. Patent No. 8,215,496, and its relevant disclosure is by reference to being introduced into this Wen Zhong, and in this film to a certain extent achieved with the case of successfully, block disclosed herein and advocating right is total to Polymers osmotic evaporation film provides significantly improving beyond disclosed film before this, and this is apparent from disclosure below.

Therefore it provides including logical formula (VI) as disclosed above or the osmotic evaporation film of the block polymer of (VII).That is, Any diblock or triblock polymer of the present invention can be used in forming the osmotic evaporation film of the present invention.In the present invention one is real In applying mode, the diblock copolymer of the logical formula (VI) of the osmotic evaporation film comprising the present invention of the present invention.In another embodiment In, the triblock polymer of the logical formula (VII) of the osmotic evaporation film comprising the present invention of the present invention.

In another embodiment, osmotic evaporation film of the invention is by the diblock copolymer manufacture in following：

In another embodiment, osmotic evaporation film of the invention is by the triblock polymer manufacture in following：

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl, norbornene -2- trifluoromethyl -3,3,3- trifluoro propyl-s 2- The block copolymer (BuNB-b-HFANB-b-BuNB) of alcohol and bicyclic [2.2.1] hept-2-ene" of 5- butyl；And

Derived from norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols, bicyclic [2.2.1] hept- 2- of 5- butyl Block copolymer (the HFANB-b-BuNB-b- of alkene and norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols HFANB)。

The osmotic evaporation film of the present invention can be formed easily by any technology known in the art.For example, will include The logical formula (VI) of the invention or (VII) of the desired repetitives of the polycyclic alkyl norbornene ene-type monomer of formula (IVA) Suitable diblock or triblock polymer be generally dissolved in suitable organic solvent and form solution.Then, polymer Solution is generally filtered by suitable filter and is removed the pollutant of any residual.After filtration, capture can be removed Gas (trapped gas).Then, polymer solution can be formed as by film by any of method in this area.Citing For, polymer solution is poured on base material and is stretched and is formed film.Then, by film be dried and from base material remove and it is standby With (if desired).The film for being formed by this way is typically considered single thickness film, the embodiment party described further below The concrete example of formula, in some embodiments, by forming the second tunic on the first shaping membrane, by film double thickness is cast into Film.In some other embodiments, polymer solution is applied on polymeric web and reinforcing membrane is formed, that is, be applied to sheet material Support membrane is above formed, or is applied on backing material plate and is formed unsupported film.In other embodiments, polymer solution energy It is enough to be suitably cast into tubular composites or doughnut.Therefore, in one embodiment, osmotic evaporation film of the invention is pipe The form of shape complex, doughnut, dense film plain film or film composite.

The osmotic evaporation film of the present invention can be any suitable form, to realize separating desired thing from fermentation liquid Matter such as butanol.Example include screw winding (piral wound) component, the fibrous membrane including hollow-fibre membrane, tubular film and Flat sheet membrane, support or unsupported dense film or film composite such as plate and frame structure.

When the form that block polymer osmotic evaporation film is unsupported dense film, the thickness of dense film is for about 1 micron To about 500 microns.In another embodiment, the thickness of dense film is for about 5 microns to about 100 microns.

When form of the osmotic evaporation film for film composite, this film can be thinner than unsupported film, for example, be as thin as about 0.1 micron.Additionally, film contains at least one of which block polymer and the non-block polymer component of at least one of which.This species complex can Containing multilamellar block polymer film and the non-block polymer component of multilamellar.The example of non-block polymer component includes various other Polymer and inorganic substances.The example of this polymer includes polyethylene, and it includesPolypropylene, polyester, polyamides are sub- Amine, Merlon, politef, poly- (vinylidene fluoride) (PVDF), poly- (methyl methacrylate) (PMMA), polyacrylonitrile (PAN), their mixed copolymer and ter-polymers etc..The example of inorganic substances includes zeolite, frit (glass Frit), carbon dust, metal screens (metal sieves), metal gauze (metal screen), metal glass material (metal Frit) etc..

By the schematic diagram of pervaporation processes in Fig. 1.As illustrated, the charging containing most species is encased in into infiltration In evaporative component 100, and it is filled in the liquid chamber 102 of its feed side.By osmotic evaporation film 106 by the vaporium of penetrant side 104 separate with liquid chamber 102.By extracting from feed liquid to the specified selective osmotic evaporation film 106 of penetrant Steam phase, and generally condensed by it, remove from pervaporation component 100 and specified infiltration is rich in relative to feed liquid The penetrant steam of thing.

Using block polymer osmotic evaporation film, can be processed using pervaporation containing such as biological butanol, ethanol or The fermentation liquid of phenol and more than one other miscible components.More specifically, fermentation liquid can be added in liquid chamber 102, Thus vacuum or gas purging are put on into vaporium 104 and is configured to the side contacts with osmotic evaporation film 106.Fermentation liquid can To heat or not heat.Component in fermentation liquid be adsorbed among osmotic evaporation film 106 and/or on, permeate and be evaporated to In steam phase.Then, gained steam or penetrant such as butanol (or phenol) is condensed and collected.Not jljl in due to fermentation liquid Kind there is different affinity and the different diffusion rate through film to osmotic evaporation film so that the even concentration in charging is non- Often low component also can be highly enriched in penetrant.Therefore, in one embodiment of the present invention, there is provided one kind infiltration Evaporating film, it can have preferential permeability compared to water to volatile organic matter.The present invention through osmotic evaporation film The permeability of volatile organic matter generally increases with the increase of the organic concentration of feed stream.In another embodiment, This volatile organic matter without any restriction include butanol, phenol, etc..

Fig. 2 depicts exemplary osmotic vapo(u)rization system 200, and it can be used in from containing valuable organic compound such as life In the thick hair zymotic fluid (or the aqueous industrial waste or other waste materials comprising biomass waste material) of thing butanol or phenol separating butanol or Material desired by other.From thick hair zymotic fluid (or including industry and/or other waste materials of the biomass) conduct of head tank 205 Feed stream 210, via pump 215 heater 220 is pumped through, to improve its temperature.Then, fermentation liquid is loaded under stress To in the pervaporation component 225 containing osmotic evaporation film.By applying vacuum (using vacuum pump 245), from pervaporation group The penetrant steam 230 containing butanol (or phenol) is obtained in part 225, wherein butanol steam (or phenol steam) is in condenser Condense in 235, and collect in catcher 240.The fermentation liquid of the residual of polynorbornene osmotic evaporation film cannot be passed through or oozed Excess stream (retentate stream) 250 can be discharged (255) from system 200, or be guided to recirculation flow 260, and be back to In head tank 205.

Improving the compensation process of pervaporation processes includes by centrifugation, filters, is decanted, segregating (dephle gmation) Deng removing solid from fermentation liquid；Increase the concentration of butanol in penetrant using absorption, distillation or liquid-liquid extraction etc..

The butanol Jing for carrying out authigenic material is commonly referred to as biological butanol.Biological butanol can be by using acetone-butanol-ethanol Fermentation (A.B.E.) technique fermentation of biomass and produce.S-Y Li, et al, Biotechnol.Prog.2011 are see, for example, vol.27(1),111-120.Technique uses fusobacterium (Clostri dium) antibacterial, such as clostridium acetobutylicum (Clostridium Acetobutylicum), but it is also possible to which using includes saccharomyces cerevisiae (Saccharomyces cerevisiae), motion fermentation list Born of the same parents bacterium (Zymomonas mobilis), Clostridium thermohydrosulfuricum (Clostridium thermohydrosulfuricum), large intestine Bacillus (Escherichia coli), candida pseudotropicalis (Candida pseudotropicalis) and Clostridium beijerinckii (Clostridium beijerinckii).Biological butanol can also be using the transgenic yeast of biological butanol production by fiber Plain material is manufacturing.Thick hair zymotic fluid containing biological butanol can be advantageous by the osmotic evaporation film and/or Fig. 2 shown in Fig. 1 Shown pervaporation system is processed to provide the butanol for being able to concentrate compared with the concentration in thick meat soup.Should also note Meaning, the present invention osmotic evaporation film can be also used for from respective fermentation liquid industry or biomass waste material in isolate butanol with Outer various alcohol, including ethanol and phenol.

Fermentation liquid usually contains various carbon matrix.In addition to carbon source, fermentation liquid can be containing suitable mineral, salt, auxiliary The factor, buffer and it is well known by persons skilled in the art be suitable to the growth of culture and promote production of butanol necessary to enzymatic pathway Other components.The example of commercially available fermentation liquid includes Luria Bertani (LB) meat soup, Sabouraud Dextrose (SD) Meat soup or Yeast Medium (YM) meat soup.Any these known fermentation liquids can be used for the present invention, so as to from this meat soup Middle separating volatile Organic substance.

Similarly, it should be noted that from the selectively formed various other organic products of fermentation technology.For example, commonly referred to as Phenol for " green phenol " can be formed by appropriate waste material, including biological waste or industrial waste, and by using suitable When biologic artifact come realize fermentation to be formed selectively phenol.Report that phenol can be false single by solvent resistant antibacterial stench Optionally produce in the recombinant bacterial strain of born of the same parents bacterium S12, see, for example, L.Heerema, et.al.Desalination, 200 (2006),pp 485-487.Also report that various other yeast strains also produce phenol, all these bacterial strains use Saccharomyces Antibacterial, such as saccharomyces cerevisiae (Saccharomyces cerevisiae) r.f bayanus, the Lalvin of EP 171；Yeast (Saccharomyces bayanus), Ever；Saccharomyces ellipsoideus (Saccharomyces ellipsoideus), Ceppo 20Castelli；Ellipsoideus yeast (Saccharomyces oviformis), the Castelli of Ceppo 838；Saccharomyces cerevisiae (Saccharomyces cerevisiae) r.f.cerevisiae, K1Lalvin；And saccharomyces cerevisiae (Saccharomyces Cerevisiae), D254Lalvin.These organisms can be from synthesis of the primary carbon source for glucose and/or natural organic source product The different amounts of phenol type substances of life.Referring to M.Giaccio, J.Commodity Science (1999), 38 (4), 189-200.One As for, as used herein, " green phenol " refer generally to using fermentation liquid produce phenol, it contains about 0.1% to about 6% Phenol.In other embodiments, fermentation liquid contains the phenol of about 0.5% to about 3%.

As used herein, " butanol " refers generally to n-butyl alcohol and its isomer.According to certain embodiments of the present invention In, fermentation liquid contains the butanol of about 0.1% to about 10%.In other embodiments, fermentation liquid contains about 0.5% to about 6% Butanol.In some other embodiments, fermentation liquid contains the butanol of about 1% to about 3%.Generally, infiltration as herein described Evaporating film is effectively from separating volatile Organic substance, such as fourth in the fermentation liquid containing relatively low at high-caliber volatile organic matter Alcohol, ethanol or phenol, and in some embodiments, fermentation liquid contains at least about 1% volatile organic matter.

It shall also be noted that some " green phenol " raw materials can also be produced using phenolic resin such as novolac resin etc. It is raw.This feed stream can be used for phenol can be from waste material flow separation and/or the pervaporation processes of the invention of enrichment.This Outward, various this phenol streams also contain some inorganic and organic salts as impurity.As a result, being difficult to remove this nothing from feed stream Machine salt, and be difficult to obtain the phenol of pure enriched form.However, it has now, surprisingly, been found that the infiltration of the present invention is steamed Sending out film can separate this inorganic and organic salt.The representative example of inorganic salt without any restriction include lithium, sodium, potassium, magnesium, The salt of calcium, barium etc..Can be used for the present invention with any counter anion of the salt of these metals.This non-limiting example of anion Attached bag includes phosphate, sulfate, acetate, benzoate etc..But, it is also possible to other aniones such as first is separated from feed stream Alkyl sulfonate (mesylate), trifluoro-methanyl sulfonate (fluoroform sulphonate), tosilate (toluene fulfonate) and Halogenide such as fluoride, chloride, bromide and iodide.

In one embodiment, there is provided separating from the raw material selected from the fermentation liquid containing organic product or industrial waste has The technique of machine product, the organic product is such as butanol, ethanol, phenol, THF, ethyl acetate, acetone, toluene, MEK, MIBK Deng.In some embodiments, fermentation liquid is encased in containing the infiltration formed by any one block polymer as herein described In the pervaporation component of evaporating film.Then, the penetrant steam of organic product is contained from pervaporation collect components.In the work In skill, it is possible to be advantageously heated to promoting organic product through the temperature of the osmotic evaporation film of the present invention by thick hair zymotic fluid. In one embodiment, the charging of thick hair zymotic fluid is heated to about 30 DEG C to about 110 DEG C of temperature.In another embodiment, will The charging of thick hair zymotic fluid is heated to about 40 DEG C to about 90 DEG C of temperature.In yet, the charging of thick hair zymotic fluid is heated to About 50 DEG C to about 70 DEG C of temperature.It should be noted that desired temperature is likely to be dependent on by the type of detached Organic substance. For example, temperature relatively low used in separating butanol, and slightly higher temperature is needed in separating phenol.Therefore, at this In a bright embodiment, the fermentation liquid fed containing butanol is heated to about into 30 DEG C of temperature to about 90 DEG C of scopes.Another In embodiment, the fermentation liquid fed containing phenol is heated to about into 40 DEG C of temperature to about 110 DEG C of scopes.

In order to promote pervaporation, suitable vacuum can be put on the vaporium of pervaporation component.In an embodiment party In formula, the vacuum of applying is for about 0.1in Hg to about 25in Hg.In another embodiment, the vacuum of applying is for about 0.15in Hg to about 5in Hg.In another embodiment, the vacuum of applying is for about 0.2in Hg to about 4in Hg.

Other techniques include increasing organic product such as fourth as the concentration of organic product in pervaporation feed stream increases The method of the separation factor of alcohol, phenol or ethanol.This method is directed to use with osmotic evaporation film, with from pervaporation feed stream Separate organic product.

As used herein, " SF " is separation factor, and this is weighing apparatus of first species relative to the disintegrate-quality of the second species Figureofmerit, it is defined as the ratio of the ratio of the ratio and feed composition of permeating compositions.

As used herein, flux is the amount that unit plane integrated membrane is flow through in time per unit.

Flux and SF can also be described by below equation：

Flux (J)=quality/(the area time)

Separation factor (SF)

Y=penetrant concentration, x=feed liquid concentrations

Therefore, it can evaluate the efficiency of osmotic evaporation film at least two aspects, separation factor is (when liquid mixture passes through The enrichment ratio obtained during membrane permeation) and the flux that permeated by polymeric film of liquid mixture.Therefore, the separation factor of film Higher with flux, then this membrane separation efficiency is higher.Certainly this is the analysis for simplifying very much, because by using Multistage Membranes work Skill Jing can often overcome low separation factor, and when the flux of film is relatively low, Jing be commonly formed high surface this film can gram Take small throughput.Therefore, although separation factor and flux factor are important Considerations, selecting to form osmotic evaporation film During best polymer, other factors, such as film strength, elasticity, resistance to soiling, heat stability, free volume when using It is important Consideration.

It has been found that the osmotic evaporation film of the present invention has to the suitable of volatile organic matter such as butanol, phenol or ethanol Separation factor (SF), remove volatile organic matter such as fourth from fermentation liquid or from other waste materials as described herein to provide Alcohol, phenol or ethanol effectively have a section.In one embodiment, osmotic evaporation film has to volatile organic matter such as butanol, benzene The SF of at least about the 5 of phenol or ethanol.In another embodiment, osmotic evaporation film has to volatile organic matter such as butanol, benzene The SF of at least about the 10 of phenol or ethanol.In yet, osmotic evaporation film has to volatile organic matter such as butanol, benzene The SF of at least about the 15 of phenol or ethanol.In another other embodiment, osmotic evaporation film has to volatile organic matter such as fourth The SF of at least about 20, at least about 25 or at least about the 30 of alcohol, phenol or ethanol.And, when the volatile organic matter in feed stream As butanol, phenol or ethanol concentration be 0.5% or higher, 1% or higher, 2% or higher, 3% or higher, 4% or higher, When 5% or higher, 6% or higher, any one in aforementioned SF can be realized.

Using the block polynorbornene osmotic evaporation film of the present invention, can realize to volatile organic matter such as butanol, benzene The suitable flux of phenol or ethanol, to provide the effective of volatile organic matter such as butanol, phenol or ethanol is removed from fermentation liquid There is section.In one embodiment, using this block polynorbornene osmotic evaporation film, can realize to volatile organic matter such as At least about 100g/m of butanol, phenol or ethanol²The flux of/hr.In another embodiment, can realize organic to volatility At least about 150g/m of thing such as butanol, phenol or ethanol²The flux of/hr；In yet, can realize to volatility At least about 200g/m of Organic substance such as butanol, phenol or ethanol²The flux of/hr, and in another embodiment, using this poly- Norborene osmotic evaporation film, can realize at least about 250g/m to volatile organic matter such as butanol, phenol or ethanol²/hr Flux.Additionally, non-polynorbornene osmotic evaporation film previously known from the use being generally found is different, when in feed stream The concentration of volatile organic matter such as butanol, phenol or ethanol is 0.5% or higher, 1% or higher, 2% or higher, 3% or more It is high, 4% or higher, 5% or higher, 6% or higher when, any one in aforementioned flux can be realized.

Surprisingly, it has been found that, as described herein various block polymers are suitable for forming osmotic evaporation film. It has further been observed, the suitable combination of diblock copolymer as herein described or three block ter-polymers is also suitable for adjusting Physical characteristics (for example, the glass transition temperature (T of whole resulting polymers_g), modulus, free volume, hydrophobicity, hydrolysis-stable Property etc.) and pervaporation characteristic (for example, SF and flux).It shall also be noted that the block polymer of the present invention can be adjusted, with Of a relatively high glass transition temperature is shown, it is being higher than what is be currently known that the block polymer of the present invention be able to may be provided As the ability of osmotic evaporation film work at the possibility temperature of film.

Advantageously, it has been found that the combination including the different types of block of different polynorbornene repetitives is carried For the film with desired flux and separation factor.Thus, for example using with containing the monomer derived from monomer such as HFANB The diblock polymer of the relatively close alcohol block of repetitives is embedding with the relative hydrophobicity containing monomeric repeating unit such as BuNB The diblock polymer of the combination of section, then can provide the HFANB-b-BuNB with surprising property.Following from as above addressing Raw material in when separating organic product, manufacturing this block polymer can form the microphase-separated being characterized with unique property Film.More specifically, by the mol ratio (that is, weight fraction) of close alcohol block (such as HFANB) of increase, can control now Make the performance of thus obtained film.For example, it has been found that the increase of the weight fraction of close alcohol block would generally increase logical Amount and separation factor.Therefore, in one embodiment, the weight fraction of close alcohol block, the weight fraction of such as HFANB W_HFANBIt is 0.5 to 0.95 in diblock polymer HFANB-b-BuNB；In other embodiments, it is for about 0.6 to 0.85； And in other embodiments, it is 0.7 to 0.8.In some embodiments, the weight fraction of close alcohol block, for example The weight fraction W of HFANB_HFANBIt is 0.5 in diblock polymer HFANB-b-BuNB.

Similarly, triblock polymer can have close alcohol block to combine with the various of hydrophobic block, such as close alcohol Block-hydrophobic block-parent's alcohol block；Hydrophobic block-parent's alcohol block-hydrophobic block；Hydrophobic block-hydrophobicity Block-parent's alcohol block；Close alcohol block-parent's alcohol block-hydrophobic block；Deng.

Therefore, in one embodiment of the present invention, there is provided from the fermentation liquid containing organic product or waste material The method that organic product is separated in raw material, methods described is comprised the steps of：

Raw material is encased in into the pervaporation containing the osmotic evaporation film formed by polymer according to claim 1 In component；And

The penetrant steam containing organic product is collected from pervaporation component.

As it was previously stated, pervaporation can be carried out at any desired temperature.Therefore, in one embodiment, exist Pervaporation is carried out when fermentation liquid is encased in pervaporation component at a temperature of about 30 DEG C to about 110 DEG C.In the enforcement In mode, the vacuum for putting on pervaporation component can be about the scope of 0.1in Hg to about 25in Hg.

In this aspect of the method for the present invention, osmotic evaporation film is formed by the polymer in following：

In another embodiment, the method for this aspect of the invention includes oozing for being formed by the polymer in following Saturating evaporating film：

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl, norbornene -2- trifluoromethyl -3,3,3- trifluoro propyl-s 2- The block ter-polymers (BuNB-b-HFANB-b-BuNB) of alcohol and bicyclic [2.2.1] hept-2-ene" of 5- butyl；And

Derived from norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols, bicyclic [2.2.1] hept- 2- of 5- butyl Block ter-polymers (the HFANB-b-BuNB-b- of alkene and norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols HFANB)。

In this aspect of the method for the present invention, detached organic product is butanol, ethanol from biomass or organic waste materials Or phenol.

In another aspect of this invention, a kind of separation method of volatility organic product is also provided, from selected from containing for example This volatile organic matter such as butanol or phenol are separated in raw material in the fermentation liquid or waste material of butanol or phenol.The method bag Containing following steps：

Raw material is encased in the pervaporation component containing osmotic evaporation film, the osmotic evaporation film is by following Polymer formed：

It is bicyclic derived from bicyclic [2.2.1] hept-2-ene" of 5- hexyls and 2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) The block copolymer (HexNB-b-NBANB) of [2.2.1] heptane；

Derived from norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols, bicyclic [2.2.1] hept- 2- of 5- butyl Block ter-polymers (the HFANB-b-BuNB-b- of alkene and norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols HFANB)；And

The penetrant steam containing butanol or phenol is collected from pervaporation component.

In the further aspect of the present invention, film forming method is also provided, it is comprised the steps of：Will be as described herein The solution of the block polymer of logical formula (VI) or (VII) is poured on suitable base material, and at a suitable temperature dry substrate and Form film.As described above, the drying of the film being thusly-formed can be carried out at any temperature and achieved desired results.Typical case Ground, be dried in the range of about 30 DEG C to about 120 DEG C at a temperature of carry out, in some other embodiments, baking temperature is About 50 DEG C to 100 DEG C, or 70 DEG C to 90 DEG C.Can be at about 10 minutes to 1 day the time required to desciccator diaphragm, or 30 minutes to 20 hours, Or in the range of 1 hour to 16 hours.

As of the invention described herein any one in block polymer can be used in forming this aspect of the invention In film.The non-limitative example of this diblock copolymer can be listed below：

In another embodiment of the method for the present invention, this three block that can be used in being formed the film of the present invention is gathered The non-limitative example of compound can be listed below：

It has now, surprisingly, been found that forming the solution of block polymer in suitable solvent or solvent mixture And be dried and cause to be separated, this may be attributed to from Selective Separation organic volatile in biomass or organic waste materials When some excellent properties for observing.Now it has been observed that the suitable solvent or solvent for dissolving block polymer Mixture selection, the phase separation arrived by different surface morphologic observations can be caused.For dissolving block polymer The example of suitable solvent includes hydrocarbon solvent such as toluene, and other ether solvents such as tetrahydrofuran (THF)., it is surprising that It has been found that using the mixture of solvent, such as hydrocarbon solvent and ether such as toluene and THF, can cause by the surface of its film for being formed The significant changes of form.

With regard to this aspect, illustrated by Fig. 3 and Fig. 4, it is represented respectively by the weight fraction W of HFANB_HFANBFor 0.78 (1:2) BuNB-HFANB of mol ratio diblock copolymer formed film atomic force micrograph (Fig. 3) and by HFANB Weight fraction W_HFANBFor 0.48 (2:1) atomic force of the film that the diblock copolymer of the BuNB-HFANB of mol ratio is formed shows Micro- photo (Fig. 4).Containing (1:2) film of the diblock copolymer of the BuNB-HFANB of mol ratio use toluene as solvent shape Into.Containing (2:1) film of the diblock copolymer of the BuNB-HFANB of mol ratio is formed using THF as solvent.From Fig. 3 and Fig. 4 is visible, and two kinds of films do not show any nanoscale structures, that is, do not show the observable phase separation of any block.However, Fig. 5 is represented by (1:1:1) atomic force microscopy of the film that the triblock polymer of the HFANB-BuNB-HFANB of mol ratio is formed shines Piece.The film is formed using the mixture of toluene and THF.It is obvious that film clearly illustrates the nanometer of phase separation of issuing a certificate Level structure.As described further below, in the pervaporation method of the present invention, by using film as shown in Figure 5, present energy It is enough to obtain the flux higher than the film of Fig. 3 and Fig. 4 (referring to table 4).This point is clearly demonstrated can be obtained from the enforcement of the present invention Surprising advantageous effects at least one effect.

The form of the microphase-separated of film can also be obtained by using the mixture of solvent with improved operation.Therefore, In another embodiment of the present invention, the block polymer of the present invention is dissolved in into nonpolar and polar solvent mixture In, and be cast after suitable supporter forms film, evaporate solvent mixture and form the form of microphase-separated.Non- pole Property solvent example include any hydrocarbon solvent, such as hexane, heptane, toluene, benzotrifluoride (TFT) and their mixture.Polarity The example of solvent includes ether solvents, such as tetrahydrofuran (THF) and diethyl ether；Alcohol, such as butanol, amylalcohol, hexanol or enanthol (or C₈- C₁₂Alcohol) and their mixture.Generally, in this aspect of the invention, manufactured by solution casting method as described herein Film.That is, typically block polymer is dissolved in the mixture such as the solvent of toluene, TFT and THF etc, will be thusly-formed Solution coating THF steam annealings are carried out on polyacrylonitrile (PAN) film, subsequently.Annealing can pass through known in the art Where method is carried out, such as in THF rooms, the exposed film at desired temperature.Generally, the film for being formed by this way is in porous Even compact layer containing block polymer on PAN support membranes, and as organic product in aqueous such as biology The pervaporation of butanol is detached to select layer function.

Following examples are described the preparation of some compound/monomer, polymer and the compositionss of the present invention in detail and are made Use method.Detailed preparation is fallen in the range of more broadly described preparation method mentioned above, and for illustrating.Institute The purpose that the embodiment of offer is merely to illustrate, rather than the scope of the invention is limited.Such as in embodiment and whole explanation It is used in book, monomer:The ratio of catalyst based on mole:Mole.

Embodiment

Hereinafter abridge and be used in the above and below description to illustrate some chemical combination of some embodiments of the present invention Thing, instrument and/or method.

HFANB：Norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols；HexNB：5- hexyls are bicyclic- [2.2.1] hept-2-ene"；C₄F₉NB：Bicyclic [2.2.1] hept-2-ene" of 5- perfluoro butyls；BuDMMINB：1- (4- (bicyclic [2.2.1] Hept- 5- alkene -2- bases) butyl) -3,4- dimethyl -1H- pyrrole-2,5-diones；PGMEA：Propylene glycol methyl ether acetate；PTFE：It is poly- Tetrafluoroethene；TFT：α, α, α-benzotrifluoride；THF：Tetrahydrofuran；R.T.-room temperature.

Reaction is generally carried out under nitrogen atmosphere, in drying baker or the Shu Lunke pipe/stuffy transfers using standard when needing (airless transfer) technology is carried out.In general, solvent is dried by molecular sieve or magnesium sulfate, or steam from desiccant Evaporate and purged with nitrogen using front.The various other known technology for being dried solvent can also be used.

The program for preparing various compounds disclosed herein is following examples set forth, including for preparing this Some initial substances of bright compound.It should be noted, however, that these embodiments be intended to illustrate the disclosure and not Limit its scope.

Embodiment 1

Double (isopropoxy-dicyclopentadienyl) palladiums of dichloro two [Pd (i-PrO-DCPD) Cl]₂

Using Chatt et al. are such as recorded in, prepared by the operation being slightly improved in J.Chem.Soc. (1957) 3413 Title compound.In a nitrogen atmosphere, by sodium chloropalladite [Na₂PdCl₄] (3g, 10.2mmol) be suspended in anhydrous isopropyl alcohol (15ml) in, and it is stirred at ambient temperature.Add bicyclopentadiene (2.7g, 20.4mmol) in the suspension, and Mixture is continued at ambient temperature stirring 5 days.Gained mixture is filtered, is gone forward side by side with heptane (three times are washed with 5ml) washing Row drying, has obtained 3.8g yellow powders.

Under environmental condition (ambient condition), the yellow powder that 1g is obtained as described above is suspended in into heptane (15ml) in, isopropanol (15ml) is stirred while be added in the suspension, and by mixture at ambient temperature after Continuous stirring 2 days.Then mixture is filtered, and uses heptane wash solid, obtain 1.1g as the yellow powder of whitish Title compound.Pass through¹H NMR are characterized, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ ppm) 6.46 (1H), 5.88 (1H), 3.72 (2H), 3.18 (1H), 3 (1H), 2.8 (1H), 2.6 (1H), 2.5 (1H), 2.17 (2H), 1.61 (1H), 1.17 (1H) and 1.12 (6H).

Embodiment 2

Double (acetoxyl group-dicyclopentadienyl) palladiums of dichloro two [Pd (AcO-DCPD) Cl]₂

Under Atmospheric Condition, toluene (20ml) is stirred while being added to [Pd (DCPD) Cl]₂(0.5g, 1.6mmol) and in the mixture of silver acetate (AgOAc) (0.27g, 1.6mmol).By gained yellow suspension at ambient temperature Stirring 1 hour.Gained brown solution is filtered, and filtrate is evaporated to dryness and orange oil is obtained, washed simultaneously with the ether of 30ml Filtered, obtained micro- yellowy pink title compound.Pass through¹H NMR are characterized, and find title compound base It is pure in sheet：¹H NMR(CD₂Cl₂, δ ppm), 6.51 (1H), 5.93 (1H), 4.87 (1H), 3.1 (2H), 2.85 (1H), 2.68 (3H), 2.33 (1H), 2.22 (2H) and 1.96 (3H).

Embodiment 3

Double (positive propoxy-dicyclopentadienyl) palladiums of dichloro two [Pd (n-PrO-DCPD) Cl]₂

In a nitrogen atmosphere, normal propyl alcohol (25ml) is stirred while being added to [Na by sleeve pipe₂PdCl₄] (1g, 3.4mmol) and in the solid mixture of bicyclopentadiene (0.9g, 6.8mmol).The reddish brown suspension of gained is existed Stirred at ambient temperature one day.Gained oldlace suspension is filtered, is washed three times with hexane (each 5ml), and entered under vacuo Row drying, obtains 1.5g title compounds.Pass through¹H NMR are characterized, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ ppm), 6.48 (1H), 5.87 (1H), 3.59 (1H), 3.45 (1H), 3.3 (1H), 3.21 (1H), 3.02 (1H), 2.83 (1H), 2.63 (1H), 2.56 (1H), 2.25 (1H), 2.18 (1H), 1.6 (1H), 1.58 (4H), 1.06 (1H), 0.88(3H)。

Embodiment 4

(isopropoxy-dicyclopentadienyl) Palladous chloride. (triisopropyl) phosphine [Pd (i-PrO-DCPD) Cl (P-i-Pr₃)]

In a nitrogen atmosphere, by the compound [Pd (i-PrO-DCPD) Cl] of embodiment 1₂(1g, 1.5mmol) is suspended in four In hydrogen furan (30ml), and it is stirred.By sleeve pipe to the triisopropyl in Deca tetrahydrofuran (10ml) in the suspension Phosphine (0.48g, 3mmol) solution.Suspension is changed into transparent at the end of the addition, solution is stirred for 15 minutes, then by it It is concentrated into 10ml and is filtered.Gained yellow filtrate is stirred all night, and is concentrated to dryness, obtain 1.25g solid as yellow The title compound of body.Pass through¹H NMR and³¹P NMR are characterized, it is found that title compound is substantially pure：¹H NMR (toluene-d₈, δ ppm), 7.59 (1H), 7.15 (1H), 3.71 (1H), 3.47 (1H), 2.76 (1H), 2.53 (4H), 2.28 (2H), 2.1 (2H), 1.81 (1H), 1.63 (1H), 1.4 (1H), 1.24 (18H), 1.05 (6H)；³¹P NMR (toluene-d₈, δ ppm)50.93。

Embodiment 5

(isopropoxy-dicyclopentadienyl) Palladous chloride. (triphenylphosphine) [Pd (i-PrO-DCPD) Cl

(PPh₃)]

In a nitrogen atmosphere, light petroleum ether (230ml) is added to into embodiment 1 [Pd (i-PrO-DCPD) Cl]₂(3g, 4.5mmol) and in the mixture of triphenylphosphine (2.6g, 9.9mmol).Gained brown suspension is stirred at ambient temperature 24 Hour, and filtered, washed with ether, then it is dried, 4.1g is obtained as the title compound of brown powder.It is logical Cross¹H NMR and³¹P NMR are characterized, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ ppm), 7.67 (6H), 7.48 (9H), 6.89 (1H), 3.88 (1H), 3.33 (1H), 2.93 (1H), 2.83 (1H), 2.67 (2H), 2.33 (1H), 2.21 (1H), 1.92 (1H), 1.54 (1H), 1.27 (1H), 1.09 (1H), 0.99 (3H), 0.79 (3H)；³¹P NMR(CD₂Cl₂, δppm)30.76。

Embodiment 6

(positive propoxy-dicyclopentadienyl) Palladous chloride. (triisopropyl) phosphine [Pd (n-PrO-DCPD) Cl (P-i-Pr₃)]

In a nitrogen atmosphere, by the compound [Pd (n-PrO-DCPD) Cl] of embodiment 3₂(0.5g, 1.5mmol) is suspended in In tetrahydrofuran (15ml), and it is stirred.By sleeve pipe to the triisopropyl in Deca tetrahydrofuran (5ml) in the suspension Phosphine (0.24g, 1.5mmol) solution.Suspension is changed into transparent at the end of the addition, and solution is stirred all night, and uses 0.45mm politef (PTFE) syringe type filter (syringe filter) is filtered.Concentrate the filtrate to do, Yellow oil is obtained, is taken into petroleum ether (3ml), and supersound process (sonicate) 3 minutes, make title compound As solid precipitation.Then, title compound is filtered, and is dried in a vacuum (obtain 0.26g).Pass through¹H NMR and³¹P NMR Characterized, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ ppm), 7.05 (1H), 6.78 (1H), 3.61 (1H), 3.36 (1H), 3.18 (1H), 2.89 (2H), 2.64 (5H), 2.35 (1H), 2.24 (1H), 2.09 (1H), 1.55 (4H), 1.47 (3H), 1.34 (18H)；³¹P NMR(CD₂Cl₂, δ ppm) and 50.16.

Embodiment 7

(isopropoxy-dicyclopentadienyl) (triisopropyl) phosphine trifluoromethanesulfonic acid palladium

[Pd(i-PrO-DCPD)(P-i-Pr₃)(OTf)]

In drying baker, under the inert atmosphere of nitrogen, by compound [Pd (i-PrO-DCPD) Cl (P-i- of embodiment 4 Pr₃)] (0.25g, 0.5mmol) is dissolved in dichloromethane (3ml), and be stirred.Add dichloromethane in the agitating solution The suspension of the silver trifluoromethanesulfonate AgOTf (0.13mg, 5mmol) in alkane (2ml), subsequently adds in tetrahydrofuran (2ml) The suspension of silver trifluoromethanesulfonate AgOTf (0.13mg, 5mmol), as a result produces the light yellow suspension of emulsus.Mixture is stirred Mix 10 minutes, and filtered by 0.45mm politef (PTFE) syringe type filter.By thus obtained yellow Filtrate is concentrated to dryness, and obtains oily residue, in being dissolved in diethyl ether (2ml), and is dried in a vacuum, obtains Title compounds of the 0.14g as cream-coloured-white foam solid.Pass through¹H,³¹P and¹⁹F NMR are characterized, and are found titled Compound is substantially pure：¹H NMR (toluene-d₈, δ ppm), 7.3 (1H), 6.8 (1H), 3.55 (1H), 3.41 (1H), 2.62 (1H), 2.45 (1H), 2.27 (6H), 2.03 (1H), 1.8 (1H), 1.5 (1H), 1.16 (9H), 1.06 (9H), 0.98 (6H), 0.86(1H)；³¹P NMR (toluene-d₈, δ ppm), 50；¹⁹F NMR (toluene-d₈, δ ppm), -77.3.

Embodiment 8

(isopropoxy-dicyclopentadienyl) (triisopropyl) phosphine (acetonitrile) four (pentafluorophenyl group) boric acid palladium

[Pd(i-PrO-DCPD)(P-i-Pr₃)(CH₃CN)]FABA

In a nitrogen atmosphere, by compound [Pd (i-PrO-DCPD) Cl (P-i-Pr of embodiment 4₃)] (5.1g, 10.2mmol) stir while being dissolved in toluene (25ml).Added in acetonitrile (25ml) in the solution by sleeve pipe Four (pentafluorophenyl group) Lithium biborate (LiFABA) (8.92g, 10.2mmol) solution.Clear yellow solution becomes muddy, stirs all night, And filtered by kieselguhr.Filtrate is concentrated, thick paste block (thick slurry mass) is obtained.Add in the lumps Pentane (50ml) and ether (50ml), obtain yellow solid, are filtered, and are washed and are dried in a vacuum with pentane (25ml), obtain Obtained 9.9g (82% yield) title compound.Pass through¹H and³¹P NMR are characterized, it is found that title compound is substantially pure 's：¹H NMR (acetone-d₆, δ ppm), 7.17 (1H), 6.76 (1H), 3.85 (1H), 3.72 (1H), 3.5 (2H), 2.94 (2H), 2.7 (5H), 2.4 (1H), 2.32 (2H), 2.1 (1H), 1.56 (1H), 1.42 (18H), 1.18 (1H), 1.09 (6H)；³¹P NMR (acetone-d₆, δ ppm), 52.19.

Embodiment 9

(isopropoxy-dicyclopentadienyl) (triisopropyl) phosphine (pyridine) four (pentafluorophenyl group) boric acid palladium

[Pd(i-PrO-DCPD)(P-i-Pr₃)(p)]FABA

In a nitrogen atmosphere, by compound [Pd (the i-PrO-DCPD) (P-i-Pr of embodiment 8₃)(CH₃CN)]FABA (0.25g, 0.212mmol) is dissolved in toluene (5ml), and is stirred.Pyridine is added in the solution by syringe (90ml), pale yellow solution is as a result produced.Solution is concentrated to dryness, yellow oil is obtained, diethyl ether (1ml) is dissolved in In, and be evaporated to dryness, 0.18g is obtained as the title compound of white foam solid.Pass through¹H and³¹P NMR carry out table Levy, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ ppm), 8.54 (2H), 7.92 (1H), 7.54 (2H), 7.08 (1H), 5.41 (1H), 3.82 (1H), 3.72 (1H), 3.06 (2H), 2.75 (1H), 2.65 (1H), 2.46 (1H), 2.34 (6H), 1.65 (1H), 1.39 (18H), 1.18 (6H)；³¹P NMR(CD₂Cl₂, δ ppm), 50.35.

Embodiment 10

(isopropoxy-dicyclopentadienyl) (triisopropyl) phosphine (acetonitrile) Tetrafluoroboric acid palladium

[Pd(i-PrO-DCPD)(P-i-Pr₃)(CH₃CN)]BF₄

In drying baker, under the inert atmosphere of nitrogen, by compound [Pd (i-PrO-DCPD) Cl (P-i- of embodiment 4 Pr₃)] (1g, 2mmol) is suspended under agitation in toluene (10ml).Added in acetonitrile (5ml) in the suspension by suction pipe Silver tetrafluoroborate AgBF₄(0.4g, 2mmol) solution.The rapid bleach of suspension, gray solid precipitation continues to stir 5 points Clock, is then filtered by 0.45mm politef (PTFE) syringe type filter.Concentrate the filtrate to do, obtain Huang Color oily residue, is used pentane (5ml) to wash twice, and is then taken into diethyl ether (5ml).Resulting solution is concentrated into It is dry, 820mg is obtained as the title compound of shallow pearl foaming solid.Pass through¹H NMR and³¹P NMR are characterized, It was found that title compound is substantially pure：¹H NMR(CDCl₃, δ ppm), 7.21 (1H), 6.51 (1H), 3.77 (1H), 3.67 (1H), 2.96 (2H), 2.71 (2H), 2.46 (7H), 2.21 (2H), 1.58 (26H)；³¹P NMR(CD₂Cl₂, δ ppm), 52.49.

Embodiment 11

The homopolymer of norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)

Embodiment 11 illustrates that compared with the palladium catalyst reported in document there is the compound of the present invention high catalysis to live Property, some comparative examples presented below are all these substantially to carry out under the same conditions as comparative example 1 and comparative example 2, with aobvious Show the difference of the respective catalysis activity of the compound for wherein using.

Add HFANB (1g, 3.7mmol) and toluene (3g) in suitable reaction vessel, and with nitrogen bubble 30 minutes, It is then heated to 80 DEG C.The compound (0.022g, 0.018mmol) of the embodiment 8 in the solution in addition toluene (1ml) is molten Liquid.Stir the mixture for 30 minutes, be subsequently cooled to room temperature.((Phenylphosphine alkane two in by adding dichloromethane (0.3ml) Base (phenylphosphanediyl)) double (ethane -2,1- diyls)) double (diphenylphosphine alkane), triphos (0.04g, Solution 0.06mmol) and stop polymerization.Then, by pouring the mixture into excessive ethanol (10mL) in and make polymer sink Form sediment, obtain 1g polymer (100% conversion ratio).Polymer is characterized by GPC：M_w=60,600；M_n=16,700； PDI=3.6.

Embodiment 12-15

With the homopolymerization of the compound of embodiment 4

Using a variety of monomers as listed in table 1 as polymerization catalyst with the compound and four (five fluorine of embodiment 4 Boric acid) lithium LiFABA is with monomer:Catalyst:LiFABA=100:1:1 mol ratio is used, in addition, in these embodiments Embodiment 11 is essentially repeated in 12 to embodiment 15.At the end of the specified response time, stopped reaction and evaporation solvent.Will The material of residual is dissolved in THF, and is filtered.Then, by pouring polymer solution into water or acetone in and make polymerization Thing is precipitated.Then, collect thus obtained polymer powder, and by being dissolved in THF in and pour solution into water or acetone In and precipitate again twice.

By when the monomer used respectively in these embodiments 12 to 15, solvent for use, the temperature of polyreaction, reaction Between, the GPC data of conversion ratio and resulting polymers be summarized in table 1.

Table 1

R.T.-room temperature；TFT-benzotrifluoride；

Embodiment 15A-E

Example 1 below 5A-E provides the various methyl used in the manufacture of the living polymer for manufacturing the present invention The program of (palladium) phosphine compound.

Embodiment 15A

[(CH₃)Pd(P^tBu₃)(Cl)]

Using the work being slightly improved such as being recorded in K.Nozaki et al., Organometallics, 2006,4588 Sequence prepares title compound.In a nitrogen atmosphere, by [(1,5- cyclo-octadiene) Pd (CH₃) (Cl)] (2.5g, 9.43mmol) molten Solution is stirred in anhydrous methylene chloride (2.5ml) at -78 DEG C.Add in dichloromethane (2mL) in the solution Tri-butyl phosphine (1.91g, 9.43mmol) solution, and mixture is continued at -78 DEG C stirring 5 minutes.Then, by mixture Solution heats up (warm up) to ambient temperature, and continues stirring 15 minutes.Gained mixture is filtered, (10ml tri- is used with pentane It is secondary) washing, and be dried, 2.73g has been obtained as the title compound of yellow powder.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ Ppm) 1.75 (s, 3H), 1.52 (d, 12Hz, 27H).31P-NMR(CD₂Cl₂, δ ppm) and 69.5

Embodiment 15B

[(CH₃)Pd(P(^tBu)₂(Cy))(Cl)]

Use [(1,5- cyclo-octadiene) Pd (CH₃) (Cl)] (300mg, 1.1mmol) and di-t-butyl-cyclohexyl phosphine (260mg, 1.1mmol), in addition, basically according to the program of embodiment 15A, has obtained 280mg as buff powder Title compound.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ Ppm) 2.35 (m, 2H), 1.75 (m, 5H), 1.52 (m, 18H), 1.30 (m, 4H), 0.82 (s, 3H).³¹P-NMR(CD₂Cl₂, δ ppm)71.5

Embodiment 15C

[(CH₃)Pd(P(^tBu)₂(ⁱPr))(Cl)]

Use [(1,5- cyclo-octadiene) Pd (CH₃) (Cl)] (430mg, 1.62mmol) and di-t-butyl-isopropyl phosphine (320mg, 1.7mmol), in addition, basically according to the program of embodiment 15A, has obtained 380mg as buff powder Title compound.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CDCl₃, δ Ppm) 2.8 (m, 1H), 1.54 (m, 24H), 0.79 (s, 3H).³¹P-NMR(CDCl₃, δ ppm) and 71.5.

Embodiment 15D

[(CH₃)Pd(P(Cy)₃)(Cl)]

Use [(1,5- cyclo-octadiene) Pd (CH₃) (Cl)] (600mg, 2.3mmol) and three-cyclohexyl phosphine (630mg, 2.3mmol), in addition, basically according to the program of embodiment 15A, 350mg has been obtained as the titled of buff powder Compound.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CDCl₃, δ Ppm) 1.8 (m, 23H), 1.32 (m, 10H), 0.79 (s, 3H).³¹P-NMR(CDCl₃, δ ppm) and 47.

Embodiment 15E

[(CH₃)Pd(P(ⁱPr)₃)(Cl)]

Use [(1,5- cyclo-octadiene) Pd (CH₃) (Cl)] (210mg, 0.8mmol) and tri isopropyl phosphine (130mg, 0.8mmol), in addition, basically according to the program of embodiment 15A, 180mg has been obtained as the titled of buff powder Compound.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ Ppm) 2.40 (m, 3H), 1.42 (m, 18H) 0.72 (s, 3H).³¹P-NMR(CD₂Cl₂, δ ppm, 50 DEG C) 56.6.

Embodiment 15F

[(CH₃)Pd(P(ⁱPr)₂(^tBu))(Cl)]

Use [(1,5- cyclo-octadiene) Pd (CH₃) (Cl)] (500mg, 1.9mmol) and diisopropyl-tert-butyl group phosphine (330mg, 1.9mmol), in addition, basically according to the program of embodiment 15A, has obtained 510mg as buff powder Title compound.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ Ppm) 2.55 (m, 2H), 1.52 (m, 21H) 0.80 (s, 3H).³¹P-NMR(CD₂Cl₂, δ ppm, RT) and 66.5.

Embodiment 15AA-AI

Example 1 below 5AA-AI is provided for the various allyls used in the living polymer manufacture for manufacturing the present invention The program of base (palladium) phosphine and imidazolium compoundss.

Embodiment 15AA

[(η³- pi-allyl) Pd (P (ⁱPr)₃)(Cl)]

Under nitrogen atmosphere, by [(η³- pi-allyl) Pd (Cl)]₂(4g, 10.9mmol) is dissolved in dry toluene (100ml), And be stirred at -78 DEG C.Add the tri isopropyl phosphine (3.68g, 23mmol) in toluene solution (50mL) in the solution, And mixture continues at -78 DEG C stirring 5 minutes.Then, mixture is warming up to into ambient temperature, and continues stirring 2 days.Will Gained mixture is evaporated to dryness, and gained solid THF (48ml) is dissolved.Afterwards filtering solution is any to remove within 5 hours for stirring Metal, is then evaporated to dryness.Gained solid is washed with diethyl ether (with 20ml tri- times), and is dried, obtained 5.7g conducts The title compound of buff powder.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CDCl₃, δ Ppm) 5.42 (m, 1H), 4.73 (m, 1H), 3.75 (m, 1H), 3.62 (m, 1H), 2.75 (m, 1H), 2.53 (m, 3H), 1.30 (m, 18H)。³¹P-NMR(CDCl₃, δ ppm) and 53.

Embodiment 15AB

[(η³- pi-allyl) Pd (P (^tBu)₃)(Cl)]

Using the tri-butyl phosphine (420mg, 2.08mmol) in toluene solution (15mL), in addition, basically according to The program of embodiment 15AA, has obtained 310mg as the title compound of yellow powder.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CD₂Cl₂, δ Ppm) 5.48 (m, 1H), 4.65 (m, 1H), 4.23 (m, 1H), 3.78 (m, 1H), 2.75 (m, 1H), 1.60 (m, 27H).³¹P-NMR (CD₂Cl₂, δ ppm) and 88.

Embodiment 15AC

[(η³- pi-allyl) Pd (P (Cy) (^tBu)₂)(Cl)]

Using di-t-butyl cyclohexyl phosphine (620mg, 2.73mmol) in toluene solution (15mL), in addition, substantially On according to embodiment 15AA program, obtained 350mg as the title compound of buff powder.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure.¹H NMR(CD₂Cl₂, δ Ppm) 5.48 (m, 1H), 4.65 (m, 1H), 4.23 (m, 1H), 3.78 (m, 1H), 2.75 (m, 1H), 1.80-1.40 (m, 29H).³¹P-NMR(CD₂Cl₂, δ ppm) and 72.

Embodiment 15AD

[(η³- pi-allyl) Pd (P (ⁱPr)(^tBu)₂)(Cl)]

Using the di-t-butyl in toluene solution (10mL)-isopropyl phosphine (510mg, 2.73mmol), in addition, substantially On according to embodiment 15AA program, obtained 480mg as the title compound of buff powder.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CDCl₃, δ Ppm) 5.40 (m, 1H), 4.73 (m, 1H), 3.82 (m, 1H), 3.70 (m, 1H), 3.25 (m, 1H), 2.75 (m, 1H), 1.63 (m, 24H)。³¹P-NMR(CDCl₃, δ ppm) and 71.8.

Embodiment 15AE

[(η³- pi-allyl) Pd (P (ⁱPr)₂(^tBu))(Cl)]

Using the tert-butyl group-diisopropyl phosphine (480mg, 2.73mmol) in toluene solution (10mL), in addition, substantially On according to embodiment 15AE program, obtained 490mg as the title compound of buff powder.

Pass through¹H NMR and³¹P-NMR is characterized, it is found that title compound is substantially pure：¹H NMR(CDCl₃, δ Ppm) 5.40 (m, 1H), 4.73 (m, 1H), 3.82 (m, 1H), 3.70 (m, 1H), 3.25 (m, 1H), 2.75 (m, 3H), 1.45 (m, 21H)。³¹P-NMR(CDCl₃, δ ppm) and 63.2.

Following palladium compound is purchased from Johnson Matthey companies, and uses as former state：

Embodiment 15AF

Embodiment 15AG

Embodiment 15AH

Embodiment 15AI

Embodiment 16A

The homopolymer of 5- butyl -2- norborene (BuNB)

Addition is purged with nitrogen in suitable reaction vessel BuNB (1.2g, 7.98mmol), toluene (22.32g) and α, α, α-benzotrifluoride (TFT) is (0.48g).Add the compound (30mg, 0.79mmol) and four of embodiment 15A in the solution The solution of (pentafluorophenyl group) boronation lithium LiFABA (70mg, 0.79mmol).Polymerization is afterwards sampled reaction solution for 20 minutes, and With toluene/CH₃CN solution inactivates it.Polymer is characterized by GPC：M_w=34,509；M_n=30,752；PDI= 1.1。

Embodiment 16B-16R

Using the homopolymerization of the norborene of the functionalization of the compound of embodiment 15A-15E

Using carrying out and various norbornene monomers and embodiment with the essentially identical program described in embodiment 16A The homopolymerization of the palladium compound of 15A～15E.By the norborene used respectively in these embodiments 16B-16R, solvent for use, The GPC data of response time, conversion ratio and resulting polymers is summarized in table 1A.These embodiments each in, Pd compounds, LiFABA, the mol ratio of norbornene monomer are Pd compounds/LiFABA/NB monomer=1/1/100.

Table 1A

Embodiment 16AA

The homopolymer of 5- butyl -2- norborene (BuNB)

BuNB (1.2g, 7.98mmol), toluene (22.32g) and the α purged with nitrogen to suitable reaction vessel addition, α, α-benzotrifluoride (TFT) is (0.48g).Add the compound (31mg, 0.079mmol) and four of embodiment 15AA in the solution The solution of (pentafluorophenyl group) boronation lithium LiFABA (70mg, 0.079mmol).After 20 minutes, reaction solution is sampled, and use first Benzene/CH₃CN solution inactivates it.Isolating polymer, and characterized by GPC：M_w=25,239, M_n=22,243, PDI= 1.1。

Embodiment 16AB-AS

With the homopolymerization of the compound of embodiment 15AA-AI

Using carrying out and various norbornene monomers and embodiment with the essentially identical program described in embodiment 16A The homopolymerization of the palladium compound of 15AA～15AI.By the norborene used respectively in these embodiments 16AB-16AS, used molten The GPC data of agent, response time, conversion ratio and resulting polymers is summarized in table 1B.These embodiments each in, Pd chemical combination Thing, LiFABA, the mol ratio (Pd compounds/LiFABA/NB monomers)=1/1/100 of norbornene monomer.

Table 1B

ND=undetermineds

Most clearly find out from above-mentioned data, as being summarized in above-mentioned table 1A and table 1B, embodiment 15AA-AI Pi-allyl (palladium) phosphine compound generally show the higher reaction of corresponding methyl (palladium) phosphine compound than embodiment 15AE Property and more living features (living-like characteristic).

Embodiment 16-20

Diblock polymer

Diblock polymer is formed using the various different monomers listed in such as table 2, in addition, in these embodiments 16 Embodiment 11 is essentially repeated into 20.In all these embodiments, then the polymerization of the first monomer mixes to resulting polymers Add second comonomer in compound, obtain diblock polymer.In embodiment 19, monomer 1:Monomer 2:Catalyst:LiFABA's Mol ratio is 250:250:1:1, in addition, the polymerization catalyst used in these embodiments 16 to 20 is monomer 1:Monomer 2:Catalyst:LiFABA=100:100:1:Four (pentafluorophenyl group) boronation lithium LiFABA of 1 mol ratio and Allylpalladium (tri isopropyl phosphine) chloride [Pd (pi-allyl) (tri isopropyl phosphine) Cl].The toluene used in embodiment 20 and benzotrifluoride 50:50 (v/v) mixture, in addition, these embodiments each used in solvent be toluene, and carry out at room temperature Polymerization.As described in embodiment 12-15, gained residuals by being dissolved in THF in and filtering solution after in water or acetone again Precipitate and carry out reprecipitation.

By when the monomer used in these embodiments 16 to 20 are respective, the monomer ratio in resulting polymers, reaction Between, the GPC data of conversion ratio and resulting polymers be summarized in table 2.

Table 2

* polymer is precipitated from reaction solution；N.m.-undetermined

Embodiment 21-24

Diblock polymer

Diblock polymer is formed using the various different monomers listed in such as table 3, in addition, in these embodiments 21 Embodiment 11 is essentially repeated into 24.In all these embodiments, then the polymerization of the first monomer mixes to resulting polymers Add second comonomer in compound, obtain diblock polymer.In embodiment 23, monomer 1:Monomer 2:Catalyst:LiFABA's Mol ratio is 500:500:1:1, in addition, the polymerization catalyst used in these embodiments 21 to 24 is monomer 1:Monomer 2:Catalyst:LiFABA=100:100:1:Four (pentafluorophenyl group) boronation lithium LiFABA of 1 mol ratio and methyl palladium (three Isopropyl phosphine) chloride, [Pd (methyl) (three-tert-butyl group phosphine) Cl].The benzotrifluoride used in embodiment 24, in addition, These embodiments each used in solvent be toluene, in embodiment 24, be polymerized at 45 DEG C, in addition in room It is polymerized under temperature.As in embodiment 12-15, at the end of the specified response time, stop polyreaction, and by steaming Send out solvent and isolating polymer.As described in embodiment 12-15, during gained residuals are by being dissolved in THF and after filter solvents The reprecipitation in water or acetone and carry out reprecipitation.

By monomer, the monomer ratio in resulting polymers, time, conversion used in these embodiments 21 to 24 are respective The GPC data of rate and resulting polymers is summarized in table 3.

Table 3

Embodiment 25

The diblock polymer (HFANB-b-BuNB) of HFANB and BuNB

The polymerization catalyst for using in this embodiment is monomer 1:Monomer 2:Catalyst:LiFABA=100:100:1:1 Mol ratio four (pentafluorophenyl group) boronation lithium LiFABA and the compound of embodiment 4, in addition, in this embodiment in 25 It is essentially repeated embodiment 11.It is aggregated in the 50 of toluene and benzotrifluoride:Carry out in the mixture of 50 (v/v), and in room temperature Under carry out.First, monomer 1HFANB is polymerized at room temperature 60 minutes, now polymer samples is analyzed by GPC, surveyed Make number-average molecular weight M_nFor 49,000, PDI is 1.2, and conversion ratio is 89%.Then, monomer 2BuNB is added to into reaction mixing In thing, continue to be polymerized 15 minutes, now monomer conversion is 100%.Now carry out the journey substantially as described in embodiment 12-15 Sequence come stop polymerization.Gained diblock polymer HFANB-b-BuNB shows 102,000 M by GPC_nPDI with 1.2.

Embodiment 26

Triblock polymer-BuNB-b-HFANB-b-BuNB (1:1:1 block ratio)

Title triblock polymer is formed using BuNB and HFANB monomers, in addition, in the embodiment 26 substantially Repeat embodiment 11.First, monomer 1BuNB is polymerized, monomer 2HFANB is then added in resulting polymers mixture And diblock polymer is formed, in final step, add the BuNB of monomer 3 and form title triblock polymer.In the enforcement Polymerization catalyst used in example 26 is monomer 1:Monomer 2:Monomer 3:Catalyst:LiFABA=100:100:100:1:1 rubs Four (pentafluorophenyl group) boronation lithium LiF ABA and Allylpalladium (tri isopropyl phosphine) chloride [Pd (pi-allyl) (three of your ratio Isopropyl phosphine) Cl].Solvent for use is toluene, and is polymerized at room temperature.Being polymerized with the first of BuNB is carried out 9 minutes, is turned Rate is 97%, M_n=35,000, PDI is 1.1；Being polymerized with the second of HFANB is carried out 60 minutes, and conversion ratio is 95%, M_n= 80,000, PDI is 1.1；With BuNB it is final be polymerized carry out 3 minutes, conversion ratio is 97%, M_n=108,000, PDI is 1.2.

Embodiment 26A-C

Various other diblocks and triblock polymer

In these embodiments 26A-C, in a nitrogen atmosphere, add respective norbornene monomer successively at room temperature and Synthesis diblock and triblock polymer.Total monomer concentration is 4wt%.For preparing the generation of BuNB-b-HFANB embodiments 26A Table operation includes following.By (t-Bu₃P) PdMeCl (12mg, 0.033mmol), LiFABA (29mg, 0.033mmol), toluene (6g) and TFT (6g) is added in the 250mL round-bottomed flasks equipped with magnetic stirring bar, and stir the mixture for 5 minutes.Will BuNB (0.5g, 3.3mmol) is disposably expelled to vigorous stirring in flask.Consume after BuNB (30 minutes) completely, be The gpc analysis of poly- (BuNB) block are carried out, a small amount of reactant mixture is taken out and is simultaneously quenched with acetonitrile.Then, by toluene/TFT During HFANB (1.8g, 6.6mmol) in (44g, 50/50wt%) is added to reaction flask.HFANB is polymerized 2 days.By weight Methanol/H is deposited to again₂Block copolymer is reclaimed in O (50/50vol%).Resulting polymers are dissolved in THF, and will be molten Liquid is stirred on the activated carbon, and the Pd catalyst of residual is subsequently removed by aluminium oxide plug (alumina plug).Gained is filtered Liquid precipitate is to methanol/H₂In O (50/50vol%), then at 60 DEG C, it is dried under vacuum.By the ratio of each monomer, Solvent, response time, % conversion ratios, M_nAnd PDI is summarized in table 3A, in addition, using identical operation other two kinds are prepared Block polymer BnNB-b-C₄F₉NB (embodiment 26B) and BuNB-b-BnNB-b-NBANB (embodiment 26C).

Table 3A

^aEach monomer 4wt% from respective solvent is polymerized；^bTol=toluene；^cTFT=α, α, α ,-fluoroform Benzene；^dIt is measured by NMR；^eUsing differential refractometer (RI) detection calibrated with Narrow distribution polystyrene standard (THF) Device, is measured by GPC

Embodiment 26D-G

The block copolymer (different monomer ratios) of HFANB-b-BuNB

These embodiments 26D-G further illustrate use (η³- pi-allyl) Pd (i-Pr₃P) Cl prepare have HFANB with The diblock polymer of the different monomers ratio (that is, mol ratio) of BuNB.

Representative operation for preparing BuNB-b-HFANB embodiments 26D includes following.To equipped with magnetic stirring apparatuss Suitable reaction vessel in add BuNB (0.99g, 6.6mmol) and toluene/TFT (19g, 50/50wt%), in injection initiation Before agent solution, 5 minutes are stirred the mixture for.Add in TFT (39mg, 0.12mmol) in the bottle for have magnetic stirring bar (η³- pi-allyl) Pd (i-Pr₃P) LiFABA in 0.50M solution 0.23mL and TFT (100mg, 0.12mmol) of Cl 0.50M solution 0.23mL, and stir 20 minutes and activate the main initiators of Pd.By (the η of 0.30mL³- pi-allyl) Pd (i-Pr₃P) Cl/Li [FABA] solution is (to (η³- pi-allyl) Pd (i-Pr₃P) Cl and Li [FABA] are respectively 0.075mmol) it is being stirred vigorously On be disposably expelled in the flask containing BuNB solution.After BuNB (15 minutes) is consumed completely, gather to carry out first The gpc analysis of BuNB blocks, take out a small amount of reactant mixture, and are quenched with acetonitrile.Then, by toluene/TFT (83g, 50/ During HFANB (4.4g, 16mmol) in 50wt%) is added to reaction flask.By HFANB polyase 13 hours.By repeating to be deposited to MeOH/H₂Block copolymer is reclaimed in O (50/50vol%).Such polymer for obtaining is dissolved in THF, and by solution Stir on the activated carbon, subsequently the Pd catalyst of residual is removed by aluminium oxide plug.Gained filtrate is deposited to into MeOH/H₂O (50/50vol%) in, then at 60 DEG C, it is dried under vacuum.Change monomer feed combination as being summarized in table 3B The weight fraction W of thing, HFANB_HFANB, using essentially identical operation other block copolymers of BuNB-b-HFANB are prepared.Table Also summarize in 3B the mol ratio of block polymer, the degree of polymerization, DP, using multi-angle laser light scattering (LS) detector (THF), Number-average molecular weight M determined by GPC_nAnd using the differential refractometer calibrated with Narrow distribution polystyrene standard (THF) (RI) detector, polydispersity PDI determined by GPC.

Table 3B

These results demonstrate again that, (η³- pi-allyl) Pd (i-Pr₃P more macromolecule is caused during) Cl is as being summarized in table 3B The more reactive initiator of weight polymers.To all polymer of embodiment 26D～26G also by differential scanning calorimetry (DSC) characterized.Any polymer of embodiment 26D～26G, glass transition is not detected by from DSC up to 200 DEG C.

Embodiment 27

The preparation of film

Single thickness film (Single Thickness Film) or Film laminated (TFC) film：By such as embodiment 16 to 26 In in any one specifically disclosed polymer formed according to the present invention be dissolved in organic solvent, form solution, then filter. After filtration, the gas of capture is removed.Polymer is poured on base material and is stretched and is formed film, it is dry and standby.In certain situation Under, film is dried, and can be removed from base material and be used as unsupported film.

Specifically, the polymer (10g) formed in embodiment 16 is dissolved in THF (100g) and manufactures solution, Passed through 5 micron nylon filters to be filtered.After filtration, solution is set to roll all night on pot type cylinder (jar roller) And remove the gas of the capture introduced during filtering.Polymer solution is poured on PAN ultrafiltration base materials and is used Gardner film streams Prolong knife (Gardner Film Casting Knife) stretching and form the film with substantially uniform thickness.By film in atmosphere It is dried one hour, subsequently anneals 10 minutes at 60 DEG C and form TFC films.Meanwhile, film is coated on glass baseplate, and use Dektak talysurves measure thickness.

Double thickness films (Double Thickness Film)：Before the first film is removed from base material, above carry in the first film For second layer solution, the second film is then stretched, in addition, to prepare double thickness films with single film similar mode.Stretching the After two times, duplicature is dried, is then removed and standby from base material.

For example, from the first film curtain coating second point of taken amount of polymer solution is poured on the first film, such as after about 5 hours Stretched as being carried out with Gardner film casting knifes above and the second layer is provided, in addition, carried out as above The example of single thickness film.After stretching second time, desciccator diaphragm all night in atmosphere.

Embodiment 27A

The film of the polymer of embodiment 26D-G

Using PAN films as supporter, by simple scraper for coating (simple blade coating) method in upper surface Prepare the thin-film composite membrane of the fine and close polymer coating of the block polymer with embodiment 26D-G.By embodiment 26D-G Block polymer is dissolved in toluene/TFT/THF mixture (40/40/20wt%) and prepares 10wt% solution, and by 0.45 μm pore PTFE filters are filtered.The each polymer solution being thusly-formed is poured on the PAN films supported by sheet glass, and Stretched with film casting knife (25 μm of clearance heights) and formed the film with uniform thickness.Coating is slowly dried, and in THF rooms Middle annealing 2 hours, makes block copolymer microphase-separated.Film is dried into 1 hour afterwards on 60 DEG C of hot plate, then at 60 DEG C Desciccator diaphragm all night in a vacuum.

Embodiment 28

Pervaporation is tested

In order to film is arranged in capsule, film is cut into into the circle of 2 inch diameters, is subsequently placed in pervaporation test device In.Temperature desired by feed liquid in test device is heated to circulating in bypass mode, then with even under 450mL/min Discontinuous Conduction mode cycles through film shell, to check for leaks.After the inspection terminates, the evacuation in the dried side of film, and will All penetrants collect cold-trap (being cooled down with liquid nitrogen).By system operation three hours, the penetrant collected is warming up to into room temperature And evaluated.

The evaluation of penetrant

The room temperature penetrant collected as described above is separated into into biphase liquid.To in the penetrant add MeOH and Make it is mutually miscible, so as to provide single-phase penetrant.Single-phase penetrant (1g) is added to into the samplings of the GC containing 0.02g PGMEA little In bottle, and it is sufficiently mixed.Then by the sample injection of bottle to gas chromatograph, wherein by marking relative to PGMEA Standard evaluates the peak area of butanol or phenol to determine % butanol or % phenol.

In addition to forming the flat sheet membrane being supported on PAN ultrafiltration base materials, can also evaluate to be formed including the embedding of the present invention The probability of the doughnut of section polymer embodiment.Using following operation, in having successfully formed for further evaluating Hollow fiber.

Embodiment 29

The manufacture of hollow-fibre membrane

By specifically disclosed block polymer dissolving formed according to the present invention in any one in such as embodiment 16 to 26 In organic solvent, and filtered and removed degranulation.Then, shift pressure by the exit orifice of spinning head the solution, together When shift pressure by the endoporus of spinning head with the mixture of salt solvent.The material of these pressure transfers is directed to precipitation Doughnut is provided in bath.The pressure that the size of doughnut can be shifted by the size of interior exit orifice and solvent is controlled System.

For example, by block copolymer B uNB-b-HFANB (1 of embodiment 18:1) it is dissolved in the THF of 10wt.%, and leads to The filter for crossing 100 microns is filtered and is removed degranulation.Then, by the solution by the external diameter with 1.0mm and 0.5mm The exit orifice of the diplopore spinning head of internal diameter shifts pressure, while by the mixture of 20/80MeOH/5wt.%LiCl (aq.) solution Pressure is shifted by the endoporus of spinning head.The material of these pressure transfers is directed to precipitating bath (20/80MeOH/ water), its In observe and doughnut and evaluated.The size of the doughnut taken out from bath can be confirmed by SEM.

Embodiment 30

The formation of Film laminated doughnut

Typically, by specifically disclosed polymer formed according to the present invention in any one in embodiment 16 to 26 closing Suitable concentration (for example, 10wt.%) is dissolved in suitable solvent (for example, THF), and is carried out by 100 micron filters Filter and remove degranulation.By the blocked doughnut microfiltration of inner chamber or ultrafilter membrane, (for example, 0.1 micron of PVDF or 3000MWCO gathers Sulfone) block polymer solution is impregnated in, then pull out from the solution.By in suitable condition (for example, at 23-60 DEG C Be dried 0.5-12 hours) under dry fiber and remove solvent.The size of the hollow fiber taken out from bath can be by SEM come really Recognize.

Embodiment 31

Operated by the comparison of the single thickness film of the different block polymeric compositions and other polymers manufacture of the present invention Property

The block polymer of the present invention and the comparison of atactic polymerization compositions are carried out, to observe in testing in pervaporation The Selective Separation performance of n-butyl alcohol.Two dependent variable for being checked are the % Organic substances in flux and penetrant.Change charging Solution concentration (1%).Using heating bath, feedstock solution is heated to into 65 DEG C.By heat loss, it brings about 60 DEG C of housing temperature Degree.In order to collect penetrant sample, using the vacuum trap in liquid nitrogen.Vacuum is 0.4in Hg (10Torr).Feedstock solution is led to Cross membrane pump to pump in system with 450mL/min.Sample is collected using test in three hours.By what is prepared according to embodiment 18 Several different block polymers of BuNB/HFANB and the 1 of BuNB/HFANB:1 random copolymer is compared, all these equal As the thin-film composite membrane prepared according to program as described in Example 26.Change the thickness of film, it is for about 2 microns to about 4 micro- Rice.Flux in table 4 is numbered into the film thickness standardization to 3 μm.Result is summarized in into table 4.

Table 4

To the pervaporation performance of 1% n-butyl alcohol charging

N.m.=is unmeasured

It is clear that from table 4, by HFANB-b-BuNB-b-HFANB (1:1:1) the film sample of triblock polymer manufacture Product numbering 6 is shown than 1 by BuNB/HFANBs:The more excellent separating property of membrane sample numbering 1 that 1 random copolymer is formed. Most notably, as summarized in table 4, when with by random copolymer (the BuNB/HFANB random copolymerizations of membrane sample numbering 1 Thing) film of similar thickness that formed when comparing, with the identical butanol concentration in penetrant triblock polymer (HFANB- uses B-BuNB-b-HFANB) realizing considerably higher flux.It shall also be noted that the film i.e. film for only being formed by triblock polymer Sample number into spectrum 6 as by atomic force micrograph (AFM) observe as show phase separation (Fig. 5), when with by diblock Copolymer BuNB-b-HFANB (2:1) film, the sample number into spectrum 3 (Fig. 4) and by BuNB-b-HFANB (1 for being formed:2) formed film, And the AFM of sample number into spectrum 5 (Fig. 3) is when comparing, different configurations of surface, wherein sample number into spectrum 3 and sample are clearly shown Both do not show phase separation to numbering 5 under conditions of these samples are prepared, therefore do not have nanoscale structures.On the other hand, The film that formed by triblock polymer HFANB-b-BuNB-b-HFANB, sample number into spectrum 6, Fig. 5 show ordered structure, and it may Especially observed high-throughout reason is in order in other factors.

Embodiment 32

Using the pervaporation test of the film of embodiment 27A

In addition to the film formed by embodiment 27A, substantially tested using the program described in embodiment 28.Film Effective area be 13.38cm².Using 1wt%n-BuOH aqueous solutions as charging, permeation flux and separation factor are determined.It is logical Membrane pump is crossed, feed stream speed is controlled to into 450mLmin^–1.Feeding temperature is by being connected to changing for the adjustable water circulator of temperature Hot device is controlled.Charging is set to circulate 30 minutes in the case of without film, to be heated to desired temperature.Charging is made in film In the presence of circulation 1 minute to check for leaks after, using vacuum pump by penetrant collect immersion liquid nitrogen in cold-trap In.Pressure on the penetrant side of film is monitored by vacuometer so as to be maintained at below 10Torr.Weigh cold-trap to calculate infiltration Total flux (J) before and after evaporation experiment.By using acetone-d₆As solvent, use¹H NMR determine the group of penetrant Into；By a small amount of dehydrated alcohol be added in penetrant and make it is miscible, so as to provide single phase soln before NMR is analyzed.It is right Each polymer of embodiment 26D～embodiment 26G prepares respectively three kinds of different films, in order to ensure result reliability and in phase It is analyzed under same experiment condition.For stability test, a collection penetrant is selected using two cold-traps, film will have been passed through Penetrant add to again charging in, n-BuOH input concentrations are maintained into 1wt%.Using equation meter provided above Calculate infiltration total flux (J) and separation factor (SF).

Pervaporation experiment is carried out at 37 DEG C and 60 DEG C.In the feed solution, obtain at 60 DEG C of higher temperature Higher flux and separation factor.Using equation J '=J x (t/2), rower will be entered to the flux of each membrane sample measurement Standardization, wherein, J ' is normalized flux, and J is the flux of Jing measurements, and t is the thickness of film.For standardized flux, eliminate Impact of the different film thicknesses to flux.Fig. 6 (a) is represented to by being labeled as a-BCPs's (vinyl addition block copolymer) Normalized flux and separation factor (SF) that each film that the polymer of embodiment 26D～26G is formed is obtained, wherein W_HFANBFor reality Apply the weight fraction of the HFANB in each polymer of 26D～26G.Also it is shown with Fig. 6 (a) to homopolymer, poly- HFANB (wherein W_HFANB1.0) and homopolymer, poly- BuNB (wherein W for_HFANBFor the normalized flux and SF of 0.0) acquisition.From the data As can be seen that as embodiment 26E polymer with 0.81 W_HFANBPolymer (HFANB:BuNB=70:30 rub You compare) highest separation factor 21.2 is shown at 60 DEG C.Then, as shown in Fig. 6 (b), due to the reduction of swelling ratio, flux With W_HFANBReduction and be gradually lowered.It was found that the separation factor (SF) observed to poly- HFANB films is only 13.7, this may It is to be caused due to relatively large swelling of its in 1wt%n-BuOH aqueous solutions, which increases infiltration (Fig. 6 of hydrone (b))。

Here provides following two comparative examples 1 and 2, to illustrate that catalyst is in similar reaction known to some of document Under the conditions of with the present invention compound catalysis activity compared with show poor catalysis activity.

Comparative example 1

The homopolymer (HFANB) of norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols

Used catalyst is palladium (acetoxyl group (double (tri isopropyl phosphines))) (acetonitrile) four (pentafluorophenyl group) borate [Pd (OAc)(P-i-Pr₃)₂(CH₃CN)] FABA, in addition, is essentially repeated embodiment 11.It was found that the conversion ratio of monomer is only 25%.Polymer is characterized by GPC：M_w=12,000；M_n=6,600；PDI=3.6.

Comparative example 2

Used catalyst is (pentafluorophenyl group) borate [Pd (acac) of palladium (acetylacetone,2,4-pentanedione) (tri isopropyl phosphine) (acetonitrile) four (P-i-Pr₃)(CH₃CN)] FABA, in addition, is essentially repeated embodiment 11 in comparative example 2.Do not produce under these conditions Raw polymerization.

Comparative example 3

The poly- BuNB of the poly- HFANB-b- of ROMP (r-BCP81)

In a nitrogen atmosphere, the ROMP block copolymerizations of HFANB and BuNB are synthesized by adding monomer successively at room temperature Thing (r-BCP81).Block copolymer is named as into r-BCP81, wherein ' r ' expression 'ROMP polymer ', ' BCP ' expression 'Block Copolymer', and ' 81 ' represent polymer in HFANB monomeric units weight combinations (81wt%).Initial monomer concentration is 4wt%, with 4wt% solution follow-up HFANB monomers are loaded.BuNB (0.8g, 5.3mmol) and toluene (19g) are added to and are matched somebody with somebody In having the 250mL round-bottomed flasks of magnetic stirring apparatuss, before agent solution is sent out in injection, 5 minutes are stirred the mixture for.To having magnetic Add double (tricyclohexyl phosphine) benzal ruthenium (IV) dichloride (0.034g, 0.05mmol), three rings in the bottle of power stirring rod Hexyl phosphine (PCy₃, 0.057g, 0.2mmol) and toluene (4mL), and stir 5 minutes.By initiator solution with vigorous stirring Secondary property is expelled in the flask containing BuNB solution.After BuNB (1h) is consumed completely, in order to carry out the first poly- BuNB blocks Gpc analysis, take out a small amount of reactant mixture, and ether capped with the ethyl vinyl of excess.Then, by toluene (81g) HFANB (3.4g, 12mmol) be added to reaction flask.HFANB is polymerized 6 hours.Sealed with excessive ethyl vinyl ether End block copolymer, and by N₂Solvent is set to evaporate and reclaim under flowing.Such polymer for obtaining is dissolved in into the ring of 1L In hexane/THF mixture (95/5vol%), in being then charged into 2L Parr reactors.Using being supported in CaCO₃(8g) Pd on (0) heterogeneous (heterogeneous) catalyst, at 100 DEG C and 400-500psig H₂Under carry out 2 days hydrogenations.Pass through¹H The progress of NMR tracking reactions, and confirm the saturation of olefinic double bonds more than 99.9%.After filtering catalyst, gained is filtered Liquid concentrates and is deposited to MeOH/H₂In O (50/50vol%), then under vacuo, it is dried at 60 DEG C.

Comparative example 4

Random ethylene base addition copolymer (a-RCP81) of HFANB/BuNB

In a nitrogen atmosphere, during being polymerized at room temperature, by the separation several times of BuNB solution and to reaction flask In loading synthesizing vinyl addition random copolymer (a-RCP81) of HFANB and BuNB.Random copolymer is named as into a- RCP81, wherein ' a ' represents ' vinyl-addition polymer ', ' RCP ' expression 'Random copolymer', and in ' 81 ' expression polymer HFANB monomeric units weight combinations (81wt%).Initial monomer concentration is 5wt%, loads all follow-up with 5wt% solution BuNB.HFANB (4.4g, 16mmol), BuNB (0.5g, 3.3mmol) and toluene/TFT (94g, 50/50wt%) are added to In equipped with the 250mL round-bottomed flasks of magnetic stirring apparatuss, before injection initiator solution, 5 minutes are stirred the mixture for.Xiang Bei There is (the η added in the bottle of magnetic stirring bar in TFT (39mg, 0.12mmol)³- pi-allyl) Pd (i-Pr₃P) 0.50M of Cl is molten The 0.5M solution 0.23mL of the Li [FABA] in liquid 0.23mL, TFT (100mg, 0.12mmol), and stir 20 minutes, to activate The main initiators of Pd.By (the η of 0.30mL³- pi-allyl) Pd (i-Pr₃P) Cl/Li [FABA] solution is (to (η³- pi-allyl) Pd (i- Pr₃P) Cl and Li [FABA] are respectively 0.075mmol) flask containing monomer solution is disposably expelled to vigorous stirring In.After injection initiator, by follow-up BuNB solution (0.2,0.15,0.10 and 0.05g BuNB) respectively 10,30, It is then injected in reaction flask when 45 and 60 minutes.By monomer polyase 13 h.By random copolymer by repeated precipitation to MeOH/ H₂Reclaimed in O (50/50vol%).Such polymer for obtaining is dissolved in THF, and by solution on the activated carbon Stirring, subsequently removes the Pd catalyst of residual by aluminium oxide plug.Gained filtrate is deposited to into MeOH/H₂O (50/50vol%) In, then under vacuo, it is dried at 60 DEG C.

Comparative example 5

Tested using the pervaporation of r-BCP81, a-RCP81 and a-BCP81

Using the polymer from comparative example 3 and 4, substantially film is manufactured using the program as shown in embodiment 27A, then In order to separate 1wt%n-BuOH, as the program according to embodiment 32 is tested.Fig. 7 (a) represents acquired results.From Fig. 7 A () is clear that, the film of the comparative example 3 formed by ROMP polymer r-BCP81 causes low-down separation factor 5.1.This It is probably due to the following fact：In 1wt%n- shown in ROMP polymer r-BCP81 such as Fig. 7 (b) with flexible backbone structure Cause in BuOH aqueous solutions a large amount of swelling (about 31%).

It was found that the film i.e. flux of a-BCP81 formed by the polymer of embodiment 26E is slightly below by the polymer of comparative example 4 The film of formation is the flux of a-RCP81 films, but the separation factor (21.2) of a-BCP81 films higher than a-a-RCP81 films separation because Sub (18.5).This should be attributed to the microphase-separated of a-BCP81 as described herein.The poly- BuNB of the phase separation in a-BCP81 Domain (domain) effectively suppresses the swelling of poly- HFANB domains, and the BuNB fragments of the random distribution in a-RCP81 because The molecular dilution of BuNB in poly- HFANB base materials and the abundant suppression (Fig. 7 (b)) swelling to poly- HFANB cannot be provided.Therefore, It should be noted that the high T of the polymer of the present invention_gFraming structure and block copolymer construction (architecture) for It is very important to increase in pervaporation processes for butanol selectivity.

Although being described the present invention by some previous embodiments, should not be construed as and be limited, and should manage Solve includes general range as disclosed for the present invention.Without departing from the spirit and scope of the present invention, can be with Make various improvement and materialization.

Claims

1. the block copolymer of formula (VI) is led to：

(A)_m-b-(B)_n(VI)；

Wherein, m and n are at least 15 integer；

B represents key；

A and B are different from each other, and independently selected from the repetitives represented by formula (IVA), the repetitives are derived from logical The monomer of formula (IV)：

Wherein：

The position that representative is bonded with another repetitives；

P is 0,1 or 2 integer；

R₃、R₄、R₅And R₆It is identical or different, and each is independently from each other hydrogen, straight or branched (C₁-C₁₆) alkyl, hydroxyl (C₁-C₁₆) alkyl, perfluor (C₁-C₁₂) alkyl, (C₃-C₁₂) cycloalkyl, (C₆-C₁₂) bicyclic alkyl, (C₇-C₁₄) tricyclic alkyl, (C₆-C₁₀) aryl, (C₆-C₁₀) aryl (C₁-C₃) alkyl, perfluor (C₆-C₁₀) aryl, perfluor (C₆-C₁₀) aryl (C₁-C₃) alkyl, Two (C₁-C₂) alkyl maleimide (C₃-C₆) alkyl, two (C₁-C₂) alkyl maleimide (C₂-C₆) alkoxyl (C₁-C₂) alkane Base, hydroxyl, (C₁-C₁₂) alkoxyl, (C₃-C₁₂) cycloalkyloxy, (C₆-C₁₂) bicycloalkyloxy, (C₇-C₁₄) three cycloalkyloxies, (C₆-C₁₀) aryloxy group (C₁-C₃) alkyl, (C₅-C₁₀) heteroaryloxy (C₁-C₃) alkyl, (C₆-C₁₀) aryloxy group, (C₅-C₁₀) heteroaryl Epoxide or (C₁-C₆) acyloxy, wherein, each above-mentioned substituent group be optionally selected from halogen or hydroxyl in substituent group.

2. copolymer according to claim 1, wherein, the polymer is also comprising the third repeating unit forming by formula (VII) the block ter-polymers for representing：

(A)_m-b-(B)_n-b-(C)_o(VII)；

Wherein, m, n and b are as defined in claim 1, and o is at least 15 integer；

C and A or B are identical or different, and independently selected from the repetitives represented by formula (IVA), the repetitives spread out It is conigenous the monomer for leading to formula (IV) as defined in claim 1.

3. block copolymer according to claim 1, wherein, A:The block mol ratio of B is 1:1 to 1:4.

4. block copolymer according to claim 1, wherein, A:The block mol ratio of B is 1:1 to 1:2.

5. block copolymer according to claim 1, wherein, A:The block mol ratio of B is 1:1.

6. block ter-polymers according to claim 2, wherein, A:B:The block mol ratio of C is 1:1:1 to 1:4:1 To 1:1:4.

7. block ter-polymers according to claim 2, wherein, A:B:The block mol ratio of C is 1:1:1.

8. block ter-polymers according to claim 2, wherein, A:B:The block mol ratio of C is 1:2:1.

9. block copolymer according to claim 1, wherein, A is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- octyl groups；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro-ethyls₂F₅NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro hexyls₆F₁₃NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

Bicyclic [2.2.1] hept-2-ene" (PENB) of 5- phenethyls；And

10. block copolymer according to claim 1, wherein, B is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- octyl groups；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro-ethyls₂F₅NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro hexyls₆F₁₃NB)

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

Bicyclic [2.2.1] hept-2-ene" (PENB) of 5- phenethyls；And

11. block ter-polymers according to claim 2, wherein, C is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (OctNB) of 5- octyl groups；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro-ethyls₂F₅NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Bicyclic [2.2.1] hept-2-ene" (C of 5- perfluoro hexyls₆F₁₃NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

Bicyclic [2.2.1] hept-2-ene" (PENB) of 5- phenethyls；And

12. block copolymers according to claim 1, wherein, A is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

13. block copolymers according to claim 1, wherein, B is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

14. block ter-polymers according to claim 2, wherein, C is derived from the monomer in following：

Bicyclic [2.2.1] hept-2-ene" (BuNB) of 5- butyl；

Bicyclic [2.2.1] hept-2-ene" (HexNB) of 5- hexyls；

Bicyclic [2.2.1] hept-2-ene" (C of 5-n- perfluoro butyls₄F₉NB)；

Norbornene -2- trifluoromethyls -3,3,3- trifluoro propan-2-ols (HFANB)；

15. block copolymers according to claim 1, it is selected from following：

Derived from bicyclic [2.2.1] hept-2-ene" of 5- hexyls and norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols Block copolymer (HexNB-b-HFANB)；

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl and norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols Block copolymer (BuNB-b-HFANB)；

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl and 1- (4- (bicyclic [2.2.1] hept- 5- alkene -2- bases) butyl) -3,4- Block copolymer (the C of dimethyl -1H- pyrrole-2,5-diones₄F₉NB-b-BuDMMINB)；

Derived from norbornene -2- trifluoromethyls -3,3,3- trifluoros propan-2-ol and 2- (bicyclic [2.2.1] hept- 5- alkene -2- Base) bicyclic [2.2.1] heptane block copolymer (HFANB-b-NBANB)；And

Derived from bicyclic [2.2.1] hept-2-ene" of 5- hexyls and 2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) bicyclic [2.2.1] heptan The block copolymer (HexNB-b-NBANB) of alkane.

16. block ter-polymers according to claim 2, it is selected from following：

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl, norbornene -2- trifluoromethyls -3,3,3- trifluoros propan-2-ol and The block copolymer (BuNB-b-HFANB-b-BuNB) of bicyclic [2.2.1] hept-2-ene" of 5- butyl；And

Derived from norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols, bicyclic [2.2.1] hept-2-ene" of 5- butyl and Block ter-polymers (the HFANB-b-BuNB-b- of norbornene -2- trifluoromethyl -3,3,3- trifluoro propan-2-ols HFANB)。

A kind of 17. techniques of the block copolymer for preparing logical formula (VI)：

(A)_m-b-(B)_n(VI)；

Wherein, m and n are at least 15 integer；

B represents key；

A and B are respectively the first and second monomeric repeating units different from each other, and separately derive self-drifting (IV) First and second monomers：

Wherein：

The position that representative is bonded with another repetitives；

P is 0,1 or 2 integer；

R₃、R₄、R₅And R₆It is identical or different, and each is independently from each other hydrogen, straight or branched (C₁-C₁₆) alkyl, hydroxyl (C₁-C₁₆) alkyl, perfluor (C₁-C₁₂) alkyl, (C₃-C₁₂) cycloalkyl, (C₆-C₁₂) bicyclic alkyl, (C₇-C₁₄) tricyclic alkyl, (C₆-C₁₀) aryl, (C₆-C₁₀) aryl (C₁-C₃) alkyl, perfluor (C₆-C₁₀) aryl, perfluor (C₆-C₁₀) aryl (C₁-C₃) alkyl, Two (C₁-C₂) alkyl maleimide (C₃-C₆) alkyl, two (C₁-C₂) alkyl maleimide (C₂-C₆) alkoxyl (C₁-C₂) alkane Base, hydroxyl, (C₁-C₁₂) alkoxyl, (C₃-C₁₂) cycloalkyloxy, (C₆-C₁₂) bicycloalkyloxy, (C₇-C₁₄) three cycloalkyloxies, (C₆-C₁₀) aryloxy group (C₁-C₃) alkyl, (C₅-C₁₀) heteroaryloxy (C₁-C₃) alkyl, (C₆-C₁₀) aryloxy group, (C₅-C₁₀) heteroaryl Epoxide or (C₁-C₆) acyloxy, wherein, each above-mentioned substituent group be optionally selected from halogen or hydroxyl in substituent group；

The technique is comprised the following steps：

First monomer is set to be reacted to form first polymer block with palladium compound；And make to be different from the first monomer The second comonomer is reacted to form block copolymer.

18. techniques according to claim 17, it also includes being reacted Third monomer to form the embedding of logical formula (VII) Section ter-polymers：

(A)_m-b-(B)_n-b-(C)_o(VII)；

Wherein, m, n and b are as defined in claim 17, and o is at least 15 integer；And

C and A or B are identical or different, and independently selected from the repetitives represented by formula (IVA), the repetitives spread out It is conigenous the monomer of logical formula (IV) as defined in claim 17.

19. techniques according to claim 17, wherein, the polymer for being formed is selected from following：

20. techniques according to claim 17, wherein, the polymer for being formed is selected from following：

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl, norbornene -2- trifluoromethyls -3,3,3- trifluoros propan-2-ol and The block ter-polymers (BuNB-b-HFANB-b-BuNB) of bicyclic [2.2.1] hept-2-ene" of 5- butyl；And

A kind of 21. osmotic evaporation films, it includes block copolymer according to claim 1.

A kind of 22. osmotic evaporation films, it includes block ter-polymers according to claim 2.

23. osmotic evaporation films according to claim 21, wherein, the copolymer is selected from following：

24. osmotic evaporation films according to claim 22, wherein, the polymer is selected from following：

25. osmotic evaporation films according to claim 21 or 22, its complex, doughnut, dense film plain film in a tubular form Or the form of film composite.

26. osmotic evaporation films according to claim 21 or 22, it can have to volatile organic matter compared to water Preferential permeability, the permeability increases with the increase of the organic concentration of feed stream.

27. osmotic evaporation films according to claim 26, wherein, the volatile organic matter includes butanol.

28. osmotic evaporation films according to claim 26, wherein, the volatile organic matter includes phenol.

29. osmotic evaporation films according to claim 27, during it is to taking the self-contained at least about fermentation liquid of 1 weight % butanol Butanol have at least about 100g/m²The flux of h, wherein, it is to flow through unit plane in time per unit (h) to the flux of butanol Product (m²) osmotic evaporation film butanol amount (g).

A kind of 30. methods that organic product is separated from raw material, the raw material is selected from the fermentation liquid containing organic product or waste material, The method comprising the steps of：

Raw material is encased in the pervaporation component containing the osmotic evaporation film described in good grounds claim 21 or 22；And

31. methods according to claim 30, wherein, the temperature of the fermentation liquid being encased in pervaporation component is for about 30 DEG C to about 110 DEG C.

32. methods according to claim 30, wherein, to pervaporation component application about 0.1in Hg to about 25in Hg Vacuum.

33. methods according to claim 30, wherein, the osmotic evaporation film is formed by the polymer in following：

34. methods according to claim 30, wherein, the osmotic evaporation film is formed by the polymer in following：

35. methods according to claim 30, wherein, the organic product is butanol, ethanol or phenol.

The method of a kind of 36. separating butanols from raw material or phenol, the raw material selected from the fermentation liquid containing butanol or phenol or Waste material, the method comprising the steps of：

Raw material is encased in the pervaporation component containing osmotic evaporation film, and

The penetrant steam containing butanol or phenol is collected from pervaporation component,

The osmotic evaporation film is formed by the polymer in following：

Derived from norbornene -2- trifluoromethyls -3,3,3- trifluoros propan-2-ol and 2- (bicyclic [2.2.1] hept- 5- alkene -2- Base) bicyclic [2.2.1] heptane block copolymer (HFANB-b-NBANB)；

Derived from bicyclic [2.2.1] hept-2-ene" of 5- hexyls and 2- (bicyclic [2.2.1] hept- 5- alkene -2- bases) bicyclic [2.2.1] heptan The block copolymer (HexNB-b-NBANB) of alkane；

Derived from bicyclic [2.2.1] hept-2-ene" of 5- butyl, norbornene -2- trifluoromethyls -3,3,3- trifluoros propan-2-ol and The block ter-polymers (BuNB-b-HFANB-b-BuNB) of bicyclic [2.2.1] hept-2-ene" of 5- butyl；Or

A kind of 37. forming methods of film, it is comprised the following steps：

By block copolymer according to claim 1 or the solution of block ter-polymers according to claim 2 It is poured on suitable base material；And

At a suitable temperature dry substrate is forming film.

38. methods according to claim 37, wherein, the block copolymer is selected from following：

39. methods according to claim 37, wherein, the block ter-polymers are selected from following：