KR101800195B1 - Polycyclo-olefinic block polymers and pervaporation membranes made therefrom - Google Patents

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. Their use in the preparation of such block polymers and in the production of membranes exhibiting specific separation properties are also disclosed. Specifically, membranes as disclosed herein are useful for the separation of organic volatiles such as butanol, phenol and the like from biomass and / or organic wastes.

Description

POLYCYCLO-OLEFINIC BLOCK POLYMERS AND PERVAPORATION MEMBRANES MADE THEREFROM < RTI ID = 0.0 >

Cross-reference to related application

This application claims priority to U.S. Provisional Application No. 62 / 037,823, filed on August 15, 2014, U.S. Provisional Application No. 62 / 037,828, filed on August 15, 2014, and U.S. Provisional Application No. 62 / 073,013 filed on October 31, The entire contents of these applications are incorporated herein by reference.

Field of invention

The present invention relates to a block polymer series derived from cyclo-olefin monomers. More specifically, the present invention relates to a block polymer series derived from various functionalized norbornene-type monomers. The present invention also relates to pervaporation membranes formed from such block polymers and to the use of such membranes in a pervaporation process.

Cyclic olefin polymers such as polynorbornene (PNB) are widely used in various electronic applications, optoelectronic applications, and other applications, and accordingly, the method of manufacturing such PNBs on an industrial scale is becoming more important. It is well known in the literature that various functionalized PNBs can be synthesized by addition polymerization using a variety of transition metal catalysts and procatalysts using suitable starting norbornene monomers. See, for example, U.S. Patent 7,989,570, the relevant portion of which is incorporated herein by reference.

However, in order to produce functionalized PNBs on an industrial scale, there is a need for catalysts or catalyst systems that will meet certain desirable characteristics. Some of these properties include, inter alia, the following a) to f): a) living catalytic polymerization systems, i.e., catalysts, even reach very high levels of chain growth leading to ultra high molecular weight polymers But retains its activity; b) High activity of the catalyst system, even at very high monomers: catalyst molar ratio; c) effective chain transfer to control molecular weight; d) good catalyst stability during polymerization, including thermal and chemical stability, i.e. no termination of polymerization activity; e) high-speed polymerization kinetics, i.e., high-speed chain propagation, preferably at about room temperature; And f) a component that is stable to storage, such as a stable A and B component, for a highly reactive catalyst system.

U.S. Patent No. 6,936,672 discloses various catalysts, catalysts, and catalyst systems for the polymerization of polycyclic olefins. However, these catalyst systems may not be suitable for the preparation of highly ordered block copolymers as described herein.

Accordingly, it is an object of the present invention to provide a series of substituted or unsubstituted bicycloalkene-palladium compounds having utility as an addition polymerization catalyst as a single component or two component system.

It is also an object of the present invention to provide a process for preparing substituted bicycloalkene-palladium compounds as disclosed herein.

In addition, it is an object of the present invention to provide a novel series of block copolymers for the formation of membranes having specific properties for various applications and having specific properties for various applications in the fabrication of electronic and optoelectronic devices.

Other objects and further scope of applicability of the present invention will become apparent from the following detailed description.

Advantageously, it has been found to be advantageous to the present invention that various block copolymers as described herein can be prepared by several organo-palladium compounds as described herein and other various catalysts known in the art. The block copolymers of the present invention provide specific advantages and are therefore useful in a variety of applications including, but not limited to, the formation of film materials, and in a variety of other optical and electronics applications It is further disclosed that the present invention finds that the present invention is not limited thereto. Membranes formed from block copolymers are useful, for example, for the separation of organic matter from biomass or other organic wastes.

Accordingly, block copolymers of formula (VI) are provided:

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

M and n may be in the range of 20 to 4000, or 50 to 3000 or 100 to 2000, and in other embodiments, m and n may be in the range of May be higher than 4000 depending on the purpose of use;

b represents the bond between two blocks of homopolymer A and B;

A and B are different from each other and independently selected from repeating units represented by the formula (IVA), wherein the repeating units are derived from monomers of the formula (IV)

(IVA)

(IV)

(IVA)

(IV)

Wherein:

는 또 다른 반복단위와의 결합위치를 나타내며;

Represents a bonding position with another repeating unit;

p is an integer of 0, 1 or 2;

(C ₁ -C ₁₆ ) alkyl, hydroxy (C ₁ -C ₁₆ ) alkyl, perfluoro (C ₁ -C ₁₆ ) alkoxy, and the like, wherein R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each independently of one another is hydrogen, straight or branched (C ₁ -C ₁₂₎ alkyl, (C ₃ -C ₁₂₎ cycloalkyl, (C ₆ -C ₁₂₎ bicycloalkyl, (C ₇ -C ₁₄₎ tricycloalkyl, (C ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, perfluoro (C ₆ -C ₁₀₎ aryl, perfluoroalkyl (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, di (C ₁ -C ₂ ) alkylmaleimido (C ₃ -C ₆ ) alkyl, di (C ₁ -C ₂ ) alkylmaleimide (C ₂ -C ₆ ) alkoxy (C ₁ -C ₂ ) alkyl, (C ₁ -C ₁₂₎ alkoxy, (C ₃ -C ₁₂₎ cycloalkoxy, (C ₆ -C ₁₂₎ bicyclo alkoxy, (C ₇ -C ₁₄₎ tricycloalkyl alkoxy, (C ₆ -C ₁₀₎ aryloxy (C ₁ -C ₃ ) alkyl, (C ₅ -C ₁₀ ) heteroaryloxy (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₀ ) aryloxy, (C ₅ -C ₁₀ ) heteroaryloxy or C ₁ -C ₆₎ is selected from acyloxy, each of the foregoing substituents here are halogen or a hydroxyl Is a group selected from optionally substituted.

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

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

Where m, n and b are as defined above and o is an integer of at least 15, but in other embodiments o may range from 20 to 4000, or from 50 to 3000 or from 100 to 2000, and in other embodiments, , O may also be higher than 4000 depending on the intended use of the block polymer. C is the same or different from A or B and is independently selected from repeating units represented by the formula (IVA), wherein the repeating units are derived from monomers of the formula (IV) as defined herein.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments according to the present invention will be described below with reference to the accompanying drawings and / or images. Where a drawing is provided, it is a simplified illustration of various embodiments of the invention and is provided for illustrative purposes only.
Figure 1 shows a pervaporation module according to an embodiment of the invention.
2 is a cross- 1 shows a pervaporation system in accordance with an embodiment of the invention.
Figures 3 through 5 illustrate the results of a comparison between the membrane formed from BuNB-HFANB (1: 2) block copolymer (Figure 3), the BuNB-HFANB (2: 1) block copolymer (Figure 4) and HFANB-BuNB-HFANB (AFM) of a film formed from a 1: 1: 1 block copolymer (FIG. 5).
Figure 6 (a) shows the schematic relationship between the separation factor (SF) of HFANB (W _HFANB ) and various weight fractions for one vinyl adduct block copolymer (a-BCP) W _HFANB ) and the various weight fractions.
Figure 6 (b) shows the schematic relationship between the swelling ratio of HFANB (W _HFANB ) and various weight fractions in one vinyl adduct block copolymer (a-BCP) of an embodiment of the invention.
7 (a) is a graph showing the results of a comparison between a block copolymer (r-BCP81) and a random vinyl addition copolymer (a-RCP81) prepared by a ring opening metathesis polymerization (ROMP) And the normalization flux and separation factor SF obtained for one (a-BCP81).
FIG. 7 (b) is a graph showing the results of a comparison between the block copolymer (r-BCP81) and the random vinyl addition copolymer (a-RCP81) prepared by ring opening metathesis polymerization (ROMP) The swelling ratio observed for one (a-BCP81) is shown.

The terms used herein have the following meanings:

As used herein, the articles " a "," an ", and " the " include plural referents unless the context clearly dictates otherwise.

All numbers, values and / or expressions referring to quantities of ingredients, reaction conditions, etc., as used herein and in the claims appended hereto are subject to various uncertainties in the metrics encountered in obtaining such values, Unless otherwise indicated, are to be understood as being modified in all instances by the term " about. &Quot;

Where numerical ranges are disclosed herein, such ranges are contiguous, including both the minimum and maximum values of the range and all values between such minimum and maximum values. Also, when a range refers to an integer, all integers between the minimum and maximum of such range are included. In addition, when multiple ranges are provided to describe a feature or characteristic, such ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all sub-ranges subsumed therein. For example, a specified range of " 1 to 10 " should be considered to include any and all subranges between a minimum value of 1 and a maximum value of 10. Exemplary subranges from 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10, and the like.

”는 또 다른 반복단위 또는 또 다른 원자 또는 분자 또는 기 또는 모이어티와, 필요에 따라서는 나타낸 바와 같은 기의 구조와 결합이 일어나는 위치를 나타낸다.
As used herein, the symbol "

Quot; refers to another repeating unit or another atom or molecule or group or moiety, and where necessary the structure of the group as indicated and the position at which the bond takes place.

As used herein, " hydrocarbyl " refers to radicals of groups containing carbon and hydrogen atoms, and non-limiting examples are alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The term " halohydrocarbyl " refers to a hydrocarbyl group in which at least one of the hydrogens is replaced by halogen. The term " perhalocarbyl "refers to a hydrocarbyl group in which all hydrogens are substituted by halogen.

As used herein, the phrase " (C ₁ -C ₆ ) alkyl " includes methyl and ethyl groups and straight or branched chain propyl, butyl, pentyl and hexyl groups. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyl and tert-butyl. Derived phrases, such as "(C ₁ -C ₄₎ alkoxy", "(C ₁ -C ₄₎ thioalkyl""(C ₁ -C ₄₎ alkoxy (C ₁ -C ₄₎ alkyl", "hydroxy ( C ₁ -C ₄₎ alkyl _{"," (C 1 -C 4} ) alkyl-carbonyl _{"," (C 1 -C 4} ) alkoxycarbonyl (C ₁ -C ₄₎ alkyl "," (C ₁ -C ₄₎ alkoxycarbonyl "," amino (C ₁ -C ₄₎ - alkyl "," (C ₁ -C ₄₎ alkylamino "," (C ₁ -C ₄₎ alkyl, carbamoyl (C ₁ -C ₄₎ (C ₁ -C ₄ ) dialkylcarbamoyl- (C ₁ -C ₄ ) alkyl "," mono- or di- (C ₁ -C ₄ ) alkylamino (C ₁ -C ₄ ) alkyl " , "amino (C ₁ -C ₄₎ alkylcarbonyl""diphenyl (C ₁ -C ₄₎ alkyl", "phenyl (C ₁ -C ₄₎ alkyl", "phenyl-carbonyl (C ₁ -C ₄ Quot; alkyl " and " phenoxy- (C ₁ -C ₄ ) alkyl "

As used herein, the phrase " cycloalkyl " includes all of the known cyclic radicals. Representative examples of " cycloalkyl " include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Derived terms such as " cycloalkoxy "," cycloalkylalkyl "," cycloalkylaryl ", and " cycloalkylcarbonyl "

As used herein, the phrase " (C ₂ -C ₆ ) alkenyl " includes ethenyl and straight or branched chain propenyl, butenyl, pentenyl, and hexenyl groups. Likewise, the phrase " (C ₂ -C ₆ ) alkynyl " includes ethynyl and propynyl, and straight or branched chain butyryl, pentynyl and hexynyl groups.

As used herein, the phrase "(C ₁ -C ₄ ) acyl" has the same meaning as "(C ₁ -C ₄ ) alkanoyl" and may also be structurally represented as "R-CO-" and, wherein R is a (C ₁ -C ₃₎ alkyl as defined herein. Additionally, "(C ₁ -C ₃ ) alkylcarbonyl" has the same meaning as (C ₁ -C ₄ ) acyl. Specifically, "(C ₁ -C ₄ ) acyl" means formyl, acetyl or ethanoyl, propanoyl, n-butanoyl and the like. Derived terms such as " (C ₁ -C ₄ ) acyloxy " and " (C ₁ -C ₄ ) acyloxyalkyl "

As used herein, the phrase " (C ₁ -C ₆ ) perfluoroalkyl " means that all of the hydrogen atoms in the alkyl group are replaced by fluorine atoms. Illustrative examples include trifluoromethyl and pentafluoroethyl, and straight or branched heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, and tridecafluorohexyl groups. Derived phrase " (C ₁ -C ₆ ) perfluoroalkoxy " is to be interpreted appropriately according to the situation.

As used herein, the phrase " (C ₆ -C ₁₀ ) aryl " means substituted or unsubstituted phenyl or naphthyl. Specific examples of the substituted phenyl or naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, do. &Quot; Substituted phenyl " or " substituted naphthyl " also includes any of the possible substituents as defined further herein or those known in the art. Derived word " (C ₆ -C ₁₀ ) arylsulfonyl " shall be construed accordingly.

As used herein, the phrase "(C ₆ -C ₁₀ ) aryl (C ₁ -C ₄ ) alkyl" refers to a radical of the formula (C ₆ -C ₁₀ ) aryl, as defined herein, ₁ -C ₄₎ means that the attachment in addition to the alkyl. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like. It should also be noted that the phrases " arylalkyl " and " aralkyl " are used interchangeably. Thus, the phrase "(C ₆ -C ₁₀ ) aryl (C ₁ -C ₄ ) alkyl" can also be interpreted as "(C ₆ -C ₁₄ ) aralkyl".

As used herein, the phrase " heteroaryl " includes all of the known heteroatom-containing aromatic radicals. Representative 5-membered heteroaryl radicals include furanyl, thienyl or thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl and the like. Representative 6-membered heteroaryl radicals include pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl radical, and the like. Representative examples of bicyclic heteroaryl radicals include benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl radicals And the like.

As used herein, the phrase " heterocycle " includes all of the known reduced heteroatom-containing cyclic radicals. Representative 5-membered heterocycle radicals include tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, and the like. Representative 6-membered heterocycle radicals include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like. Other various heterocycle radicals include, without limitation, aziridinyl, azepanyl, diazepanyl, diazabicyclo [2.2.1] hept-2-yl, and triazocanyl and the like.

&Quot; Halogen " or " halo " means chloro, fluoro, bromo and iodo.

In a broad sense, the term " substitution " is considered to include all permissible substituents of organic compounds. In some specific embodiments as disclosed herein, the term "substituted" is C _1-6 alkyl, C _2-6 alkenyl, C _1-6 perfluoroalkyl, phenyl, hydroxy, -CO ₂ H, an ester, amides, C ₁ -C ₆ alkoxy, C ₁ -C ₆ thioalkyl, C ₁ -C _6, a perfluoroalkoxy, -NH _2, Cl, Br, I, F, lower alkyl, -NH-, and -N (lower Alkyl) < RTI ID = 0.0 > _{2. &} Lt; / RTI > However, any of the other suitable substituents known to those skilled in the art may also be used in these embodiments.

It should be noted that any atom with an unmet valence in the text, schemes, examples and tables herein is presumed to have the appropriate number of hydrogen atoms or atoms to satisfy such valence.

As used herein, the term " living polymerization " refers to chain growth polymerization in which the terminating ability of the growing polymer chain is removed. In other words, both the chain termination and chain transfer reactions are absent in this system and the rate of chain initiation is also much greater than the rate of chain propagation, which leads to the growth of polymer chains at a more constant rate than is seen in traditional chain polymerization And their lengths remain very similar (ie, they have a very low polydispersity index PDI).

As used herein, the term " block copolymer " or " block polymer " is used interchangeably and means that the same, i.e., two or more homopolymer subunits are linked by covalent bonds. Thus, a " diblock copolymer " may be represented by - (A) _m -b- (B) _n - wherein the homopolymer of Formula A is linked by a single bond to the homopolymer of Formula B, And n is the number of each of the monomer repeat units. Thus, in the "diblock copolymer" designation "b" indicates that the "block" of the preceding homopolymer (A) _m is linked to the homopolymer (B) _n following the covalent bond. Therefore, the symbol designation " -b- " must be interpreted as a bond between designated polymer blocks. Likewise, " triblock copolymers "," tetrablock copolymers ", and the like should be construed accordingly. Also, " diblock copolymer " or " diblock polymer " is used interchangeably.

As used herein, the terms "polymer composition", "copolymer composition", "terpolymer composition" or "templated polymer composition" are used interchangeably herein and refer to at least one of the synthetic polymers, Is meant to include terpolymers or terpolymers, and residues from initiators, solvents or other elements involved in the synthesis of such polymers, wherein such residues are not necessarily covalently incorporated therein. However, some catalysts or initiators may also be covalently bonded at the start and / or ends of the polymer chain to a portion of the polymer chain. Such residues and other elements which are contemplated as part of a "polymer" or "polymer composition" are typically mixed or co-mixed with the polymer such that they tend to remain with the polymer when they are moved between containers or between solvents or dispersion media co-mingled. The polymer composition may also include a material added after synthesis of the polymer to provide or modify certain properties of such a composition. Such materials include, but are not limited to, solvent (s), antioxidant (s), photoinitiator (s), photosensitizers and other materials as will be discussed in more detail below.

The phrase " monomer repeating unit is derived from " means that the polymer repeating unit is polymerized (formed) from, for example, a polycyclic norbornene-type monomer wherein the resulting polymer is a norbornene Lt; / RTI > is formed by two or three human enchainment of type-monomers:

Catalyst / polymerization initiator

Accordingly, in accordance with the practice of the present invention, there is provided a compound of formula I:

(I)

(I)

In this formula,

는 (C₅-C₁₀)시클로알켄, (C₇-C₁₂)비시클로알켄 또는 (C₈-C₁₂)트리시클로알켄 기이고;

It is (C ₅ -C ₁₀₎ cycloalkene, (C ₇ -C ₁₂₎ alkene or bicyclo (C ₈ -C ₁₂₎ tricycloalkyl alkenyl group;

M is nickel, palladium or platinum;

LB is a Lewis base;

는 약하게 배위하는 음이온이며;Z

Is a weakly coordinating anion;

Y is PR ₃ or O = PR ₃ wherein R is methyl, ethyl, (C ₃ -C ₆ ) alkyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀₎ aralkyl, methoxy, ethoxy, (C ₃ -C ₆₎ alkoxy, substituted or non-substituted (C ₃ -C ₇₎ cycloalkoxy, (C ₆ -C ₁₀₎ aryl oxy or (C ₆ -C ₁₀₎ independently selected from aralkyloxy;

R ₁ is methyl, ethyl, straight or branched (C ₃ -C ₆ ) alkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀ ) aralkyl or R ₂ CO, wherein R ₂ is methyl , ethyl, or (C ₃ -C ₆₎ alkyl.

기로서 사용될 수 있다. (C₅-C₁₀)시클로알켄 기의 대표적인 예는 제한 없이, 시클로펜텐, 시클로헥센, 시클로헵텐, 시클로옥텐, 시클로노넨 또는 시클로데센을 포함한다. 그러나, 시클로운데센, 시클로도데센 등을 포함한 다른 적합한 시클로알켄 기가 또한 사용될 수 있다. (C₇-C₁₂)비시클로알켄 기의 대표적인 예는 제한 없이, 비시클로[2,2,1]헵텐, 비시클로[3,2,1]옥텐, 비시클로[2,2,2]옥텐, 비시클로[3,2,2]노넨, 비시클로[3,3,1]노넨, 1,2,3,3a,4,6a-헥사히드로펜탈렌, 3a,4,5,6,7,7a-헥사히드로-1H-인덴, 1,2,3,4,4a,5,8,8a-옥타히드로나프탈렌, 2,3,4,4a,5,6,9,9a-옥타히드로-1H-벤조[7]아눌렌 등을 포함한다. (C₈-C₁₂)트리시클로알켄 기의 대표적인 예는 제한 없이, 디시클로펜타디엔, (4s,7s)-3a,4,5,6,7,7a-헥사히드로-1H-4,7-에타노인덴 등을 포함한다. 또한, 전술한 것의 치환 시클로알켄, 비시클로알켄 또는 트리시클로알켄 중 임의의 것이 또한 사용될 수 있다.
In another embodiment of the invention, a variety of cycloalkene, bicycloalkene or tricycloalkene groups are present in the compounds of formula (I)

. Representative examples of (C ₅ -C ₁₀ ) cycloalkene groups include, without limitation, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene or cyclodecene. However, other suitable cycloalkene groups, including cyclodecene, cyclododecene, and the like, may also be used. Representative examples of (C ₇ -C ₁₂ ) bicycloalkene groups include, but are not limited to, bicyclo [2,2,1] heptene, bicyclo [3,2,1] octene, bicyclo [ , Bicyclo [3,2,2] nonene, bicyclo [3,3,1] nonene, 1,2,3,3a, 4,6a- hexahydropentalene, 3a, 4,5,6,7, Hexahydro-1H-indene, 1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3,4,4a, 5,6,9,9a-octahydro-1H- Benzo [7] asulene, and the like. Representative examples of (C ₈ -C ₁₂ ) tricycloalkane groups include, without limitation, dicyclopentadiene, (4s, 7s) -3a, 4,5,6,7,7a-hexahydro-1H- Ethenoindene, and the like. In addition, any of the substituted cycloalkene, bicycloalkene, or tricycloalkene of the foregoing may also be used.

In another embodiment of the present invention, M may be other than nickel, palladium or platinum. Suitable M comprises any of the Group X transition metals or Group IX metals, such as cobalt, rhodium or iridium.

In another embodiment of the present invention, the compound of formula (I) comprises a Lewis base which is coordinately bound to a metal atom M. That is, the Lewis base is bonded to the metal atom by sharing both sides of its lone pair. Any of the Lewis bases known in the art may be used for this purpose. Advantageously, it is advantageous to the present invention that Lewis bases, which are easily dissociable under polymerization conditions as described in further detail below, provide a more suitable compound of formula (I) as a polymerization catalyst, i. It turned out. Thus, in one aspect of the present invention, the wise selection of Lewis bases will provide control of the catalytic activity of the compounds of the present invention.

Thus, suitable LB's that may be used include, without limitation, substituted and non-substituted nitriles including alkylnitriles, arylnitriles or aralkyl nitriles; Phosphine oxides including various combinations of substituted and non-substituted trialkylphosphine oxides, triarylphosphine oxides, triaralkylphosphine oxides, and alkyl, aryl, and aralkylphosphine oxides; Substituted and non-substituted pyrazines; Substituted and non-substituted pyridines; Phosphites including various combinations of substituted and unsubstituted trialkyl phosphites, triaryl phosphites, triaralkyl phosphites, and alkyl, aryl, and aralkyl phosphites; And phosphines including various combinations of substituted and unsubstituted trialkylphosphines, triarylphosphines, triaralkylphosphines, and alkyl, aryl, and aralkylphosphines. . Other various LBs that may be used include various ethers, alcohols, ketones, amines and anilines, arsine, stibine, and the like.

In some embodiments of the present invention, LB is selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (C ₆ H ₅ CN), 2,4,6-trimethylbenzonitrile, phenyl acetonitrile _{(C 6 H 5 CH 2 CN} ), pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, Di-t-butylpyridine, 2-methoxypyridine, 3-methoxypyridine, 2-methoxypyridine, 2-methoxypyridine, Benzophenones such as methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, , Triphenylphosphine oxide, triphenyl phosphate or the formula PR ₃ wherein R is methyl, ethyl, (C ₃ -C ₆ ) alkyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl, (C to ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aralkyl, methoxy, Ethoxy, (C ₃ -C ₆₎ alkoxy, substituted or non-substituted (C ₃ -C ₇₎ cycloalkoxy, (C ₆ -C ₁₀₎ aryloxy and (C ₆ -C ₁₀₎ independently selected from aralkyloxycarbonyl ) Phosphine or phosphite. Representative examples of PR ₃ include, but are not limited to, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tri-iso-propylphosphine, tri-n-butylphosphine, tri- tri-n-propyl phosphite, tri-n-butyl phosphine, tricyclopentyl phosphine, triallyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, trimethyl phosphite, triethyl phosphite, Propylphosphite, tri-n-butylphosphite, tri-iso-butylphosphite, tri-tert-butylphosphite, tricyclopentylphosphite, triallylphosphite, tricyclohexylphosphite, triphenylphosphite . It should be noted, however, that various other known LBs that will bring about the intended activity may also be used in this embodiment of the invention.

The phosphine ligand can also be selected from phosphine compounds which are water-soluble and consequently impart solubility in the aqueous medium to the resulting catalyst. This type of selected phosphine is selected from carboxylic acid-substituted phosphines such as 4- (diphenylphosphine) benzoic acid and 2- (diphenylphosphine) benzoic acid, sodium 2- (dicyclohexylphosphino) ethanesulfonate, 4 , 4 '- (phenylphosphinidene) bis (benzenesulfonic acid) diphosphate, 3,3', 3 "-phosphinidine tris (benzenesulfonic acid) trisodium salt, 4- (dicyclohexylphosphino) 1,1-dimethylpiperidinium chloride, and 4- (dicyclohexylphosphino) -1,1-dimethylpiperidinium iodide, and quaternary amine-functionalized salts of phosphines, such as 2- N, N, N-trimethylethanaminium chloride, 2,2 '- (cyclohexylphosphinene) bis [N, N, N-trimethylethanaminium dichloride, 2,2' (N, N, N-trimethylethanaminium) diiodide, and 2- (dicyclohexylphosphino) -N, N, N-trimethylethanaminium iodide Including but not limited to Neunda.

Other examples of organic phosphorus compounds suitable as LB include phosphinite and phosphonate ligands. Representative examples of phosphinite ligands include, but are not limited to, methyldiphenylphosphonite, ethyldiphenylphosphonite, isopropyldiphenylphosphonite, and phenyldiphenylphosphonite. Representative examples of phosphonate ligands include, but are not limited to, diphenyl phenyl phosphonite, dimethyl phenyl phosphonite, diethyl methyl phosphonite, diisopropyl phenyl phosphonite, and diethyl phenyl phosphonite Do not.

을 갖는 화학식(I)의 화합물은 보다 양호한 촉매(즉, 개시제) 활성을 제공한다는 것이 본 발명에 이르러 비로서 밝혀졌다. 즉, WCA는 양이온 착체에 오직 약하게 배위되는 음이온이다. 중성 루이스 염기, 용매 또는 단량체에 의하여 치환되기에 충분히 불안정하다. 보다 구체적으로, WCA 음이온은 양이온 착체에 대한 안정화 음이온으로서 기능하며 금속 원자 M과 공유결합을 형성하지 않는다. WCA 음이온은 비-산화성, 비-환원성 및 비-친핵성이라는 점에서 비교적 불활성이다.
In a further aspect of the invention, a counter anion Z (WCA), which is a weakly coordinating anion

(I. E., Initiator) activity of the compound of formula (I) having the formula < RTI ID = 0.0 > (I) < / RTI > That is, WCA is an anion that is only weakly coordinated to the cation complex. It is sufficiently unstable to be substituted by neutral Lewis base, solvent or monomer. More specifically, the WCA anion functions as a stabilizing anion for the cation complex and does not form a covalent bond with the metal atom M. WCA anions are relatively inert in that they are non-oxidizing, non-reducing and non-nucleophilic.

Generally, the WCA can be selected from borate, phosphate, arsenate, antimonate, aluminate, borate benzene anion, carboran, halocarborane anion, sulfonamidate and sulfonate.

Generally speaking, suitable borate anions may be represented by formula A, phosphate, arsenate and antimonate anions may be represented by formula B, and aluminate anions may 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

In formula A, M _a is boron, and in formula B M _b is phosphorus, arsenic or antimony, and in formula C M _c is aluminum. R _a , R _b , R _c , R _d , R _e and R _f are independently selected from the group consisting of fluorine, straight and branched C ₁ -C ₁₀ alkyl, linear and branched C ₁ -C ₁₀ alkoxy, linear and branched C ₃ -C ₅ haloalkenyl, linear and branched C ₃ -C ₁₂ trialkyl siloxy, C ₁₈ -C ₃₆ triaryl siloxy, substituted and non-substituted C ₆ -C ₃₀ aryl, and substituted and non-substituted C _{6 to 30} aryloxy groups, wherein all of R _a to R _f can not simultaneously represent an alkoxy or aryloxy group. When substituted, the aryl group may be mono- or poly-substituted, wherein the substituents are selected from the group consisting of straight and branched C ₁ -C ₅ alkyl, straight and branched C ₁ -C ₅ haloalkyl, straight and branched C ₁ -C ₅ Alkoxy, straight-chain and branched C ₁ -C ₅ haloalkoxy, straight and branched chain C ₁ -C ₁₂ trialkylsilyl, C ₆ -C ₁₈ triarylsilyl, and halogen selected from chlorine, bromine and fluorine .

Representative borate anions of formula A include tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tetrakis Tetrakis (3-fluorophenyl) borate, tetrakis (4-fluorophenyl) borate, tetrakis (3,5-difluorophenyl) (3,4,5,6-tetrafluorophenyl) borate, tetrakis (3,4,5,6-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) (Perfluorophenyl) borate, tetrakis (1,2,2-trifluoroethylenyl) borate, tetrakis (4-tri- i -propyl a silyl-tetra fluorophenyl) borate, tetrakis (4-dimethyl - tert - butyl silyl Tris (pentafluorophenyl) borate, tetrakis [3,5-bis [1-methoxy-2 (trifluoromethyl) , 2,2-trifluoro-1- (trifluoromethyl) ethyl] phenyl] borate, tetrakis [3- [1-methoxy-2,2,2-trifluoro- Methyl] ethyl] -5- (trifluoromethyl) phenyl] borate, and tetrakis [3- [2,2,2-trifluoro-1- (2,2,2-trifluoroethoxy) 1- (trifluoromethyl) ethyl] -5- (trifluoromethyl) phenyl] borate.

Representative phosphates of formula B, arsenate, antimonate include hexafluorophosphate, hexaphenyl phosphate, hexakis (pentafluorophenyl) phosphate, hexakis (3,5-bis (trifluoromethyl) phenyl) phosphate , Hexafluoroarsenate, hexaphenyl arsenate, hexakis (pentafluorophenyl) arsinate, hexakis (3,5-bis (trifluoromethyl) phenyl) arsinate, hexafluoroanthene (Pentafluorophenyl) antimonate, hexakis (3,5-bis (trifluoromethyl) phenyl) antimonate, and the like, but are not limited thereto.

Representative aluminate anions of formula C include tetrakis (pentafluorophenyl) aluminate, tris (nonafluorobiphenyl) fluoroaluminate, (octyloxy) tris (pentafluorophenyl) aluminate, tetrakis 5-bis (trifluoromethyl) phenyl) aluminate, and methyltris (pentafluorophenyl) aluminate.

는 B(C₆F₅)₄

, B[C₆H₃(CF₃)₂]₄

, B(C₆H₅)₄

, [Al(OC(CF₃)₂C₆F₅)₄]

, BF₄

, PF₆

, AsF₆

, SbF₆

, (CF₃SO₂)N

및 CF₃SO₃

로부터 선택된다.
In an embodiment of the present invention, suitable Z

B (C ₆ F ₅ ) ₄

, B [C ₆ H ₃ (CF ₃ ) ₂ ] ₄

_{, B (C 6 H 5)} 4

_{, [Al (OC (CF 3} ) 2 C 6 F 5) 4]

, BF ₄

, PF ₆

, AsF ₆

, SbF ₆

, (CF ₃ SO ₂₎ N

And CF ₃ SO ₃

.

In another embodiment of the invention, the compounds of formula (I) have the following substituents:

는 시클로옥텐, 비시클로[3,3,0]옥텐, 비시클로[2,2,1]헵트-2-엔, 비시클로[2,2,2]옥트-2-엔 또는 트리시클로[5,2,1,0^2,6]데크-3-엔이고;

Is selected from the group consisting of cyclooctene, bicyclo [3,3,0] octene, bicyclo [2,2,1] hept-2-ene, bicyclo [2,2,2] 2,1,0 ^2,6 ] dec-3-ene;

M is palladium;

LB is acetonitrile, tert- butynyl, C ₆ H ₅ CN, 2,4,6- trimethyl-benzonitrile, pyridine, 4-methylpyridine, 3,5-dimethylpyridine, 4-methoxypyridine, a benzophenone or Triphenylphosphine oxide;

는 B(C₆F₅)₄

, B[C₆H₃(CF₃)₂]₄

, (CF₃SO₂)N

또는 CF₃SO₃

로부터 선택되며;Z

B (C ₆ F ₅ ) ₄

, B [C ₆ H ₃ (CF ₃ ) ₂ ] ₄

, (CF ₃ SO ₂₎ N

Or CF ₃ SO ₃

Lt; / RTI >

Y is PR ₃ or O = PR ₃ where R is isopropyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert- Cyano, phenoxy or benzyloxy;

R ₁ is methyl, ethyl, isopropyl, sec-butyl, tert-butyl, phenyl, phenoxy or acetyl (CH ₃ CO).

In another embodiment of the present invention, the compounds of the present invention are represented by formula (II): < EMI ID =

(II)

(II)

In this formula,

LB is selected from pyridine, acetonitrile or C ₆ H ₅ CN;

은 B(C₆F₅)₄

, B(C₆H₅)₄

, BF₄

또는 CF₃SO₃

로부터 선택되며;Z

B (C ₆ F ₅ ) ₄

_{, B (C 6 H 5)} 4

, BF ₄

Or CF ₃ SO ₃

Lt; / RTI >

R is methyl, ethyl, (C ₃ -C ₆₎ alkyl, substituted or non-substituted (C ₃ -C ₇₎ cycloalkyl, (C ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aralkyl, methoxy (C ₃ -C ₆ ) alkoxy, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkoxy, (C ₆ -C ₁₀ ) aryloxy or (C ₆ -C ₁₀ ) aralkyloxy Independently selected;

R ₁ is methyl, ethyl, straight or branched (C ₃ -C ₆ ) alkyl, (C ₆ -C ₁₀ ) aralkyl or R ₂ CO wherein R ₂ is methyl, ethyl or (C ₃ -C ₆₎ ) Alkyl.

In a further embodiment of the invention, the compound of formula (II) has the following substituents:

LB is acetonitrile;

는 B(C₆F₅)₄

이며;Z

B (C ₆ F ₅ ) ₄

;

R is n-propyl, isopropyl, tert-butyl or phenyl;

R ₁ is n-propyl, isopropyl, tert-butyl or -COCH ₃ .

In another embodiment of the invention, the compounds of the present invention are represented by formula (IIA)

(IIA)

(IIA)

Wherein:

LB is acetonitrile or pyridine;

는 B(C₆F₅)₄

또는 BF₄

로부터 선택되며;Z

B (C ₆ F ₅ ) ₄

Or BF ₄

Lt; / RTI >

R ₁ is isopropyl or -COCH ₃ .

In this aspect of the embodiment, the compound of formula (IIA) has a substituent as follows:

는 B(C₆F₅)₄

또는 BF₄

이며; R₁은 이소프로필이다.
LB is acetonitrile or pyridine; Z

B (C ₆ F ₅ ) ₄

Or BF ₄

; R ₁ is isopropyl.

In another embodiment of the invention, the compounds of the present invention are represented by formula (IIB): < EMI ID =

(IIB).

(IIB).

In another embodiment of the present invention, the compounds of the present invention are represented by formula (IIC):

(IIC)

(IIC)

In the above formula, Py is pyridine.

In another embodiment of the present invention, the compounds of the present invention are represented by formula (IID): < EMI ID =

(IID)

(IID)

In the above formula, Py is pyridine.

In another aspect of the invention, compounds of formula (III) are also provided:

(III)

(III)

In this formula,

는 (C₅-C₁₀)시클로알켄, (C₇-C₁₂)비시클로알켄 또는 (C₈-C₁₂)트리시클로알켄 기이고;

It is (C ₅ -C ₁₀₎ cycloalkene, (C ₇ -C ₁₂₎ alkene or bicyclo (C ₈ -C ₁₂₎ tricycloalkyl alkenyl group;

M is nickel, palladium or platinum;

X is halogen, triflate, mesylate or tosylate;

Y is PR ₃ or O = PR ₃ where R is methyl, ethyl, (C ₃ -C ₆ ) alkyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀₎ aralkyl, methoxy, ethoxy, (C ₃ -C ₆₎ alkoxy, substituted or non-substituted (C ₃ -C ₇₎ cycloalkoxy, (C ₆ -C ₁₀₎ aryl oxy or (C ₆ -C ₁₀₎ independently selected from aralkyloxy;

R ₁ is methyl, ethyl, straight or branched (C ₃ -C ₆ ) alkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀ ) aralkyl or R ₂ CO wherein R ₂ is methyl , ethyl, or (C ₃ -C ₆₎ alkyl;

Provided that when R is phenyl, R < ₁ > is not methyl.

이 디시클로펜타디에닐 또는 시클로옥테닐 기이고 R₁이 메톡시이며, M이 팔라듐이며, X가 염소 또는 브롬이며, Y가 트리페닐 포스핀인 화학식(III)의 화합물은 문헌[Crociani et al., J. Chem. Soc. A (1968) 2869]에 개시되어 있다. 따라서, 하기 화합물은 화학식(III)의 화합물로부터 제외된다:It should be noted that some of the compounds of formula (III) are known. More specifically,

Compounds of formula (III) wherein d is a dicyclopentadienyl or cyclooctenyl group and R ₁ is methoxy, M is palladium, X is chlorine or bromine and Y is triphenylphosphine can be prepared according to Crociani et al , J. Chem. Soc. A (1968) 2869. Accordingly, the following compounds are excluded from the compounds of formula (III): <

[Pd (C ₈ H ₁₂ .OCH ₃ ) (P (C ₆ H ₅ ) ₃ ) Cl];

_{[Pd (C 8 H 12 .OCH} 3) (P (C 6 H 5) 3) Br];

_{[Pd (C 10 H 12 .OCH} 3) (P (C 6 H 5) 3) Cl];

_{[Pd (C 10 H 12 .OCH} 3) (P (C 6 H 5) 3) Br];

[Pt (C ₈ H ₁₂ .OCH ₃ ) (P (C ₆ H ₅ ) ₃ ) Cl];

[Pt (C ₈ H ₁₂ .OCH ₃ ) (P (C ₆ H ₅ ) ₃ ) Br];

_{[Pt (C 10 H 12 .OCH} 3) (P (C 6 H 5) 3) Cl]; And

_{[Pt (C 10 H 12 .OCH} 3) (P (C 6 H 5) 3) Br].

In one embodiment of the present invention, the compound of formula (III) has the following substituents:

은 시클로옥텐, 비시클로[3,3,0]옥텐, 비시클로[2,2,1]헵트-2-엔, 비시클로[2,2,2]옥트-2-엔 또는 트리시클로[5,2,1,0^2,6]데크-3-엔이고, 후자는 디시클로펜타디엔으로 통칭되며;

Bicyclopenta [2,2,1] hept-2-ene, bicyclo [2,2,2] oct-2-ene or tricyclo [5, 2,1,0 ^2,6 ] dec-3-ene, the latter being referred to as dicyclopentadiene;

M is palladium;

X is chlorine or triflate;

Y is PR ₃ or O = PR ₃ where R is isopropyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert- Cyano, phenoxy or benzyloxy;

R ₁ is methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, phenyl or acetyl.

In another embodiment of the invention, the compound of this aspect of the invention is represented by formula (IIIA)

(IIIA)

(IIIA)

Wherein:

X is chlorine or triflate;

R ₁ is n-propyl, isopropyl or -COCH ₃ .

In a further embodiment of the invention, the compound of formula (III) is that wherein R &_lt; ₁ > is isopropyl; Or R &_lt; ₁ > is n-propyl; Or it includes R ₁ is -COCH _3.

Non-limiting exemplary compounds of formula (III) may be represented by formula (IIIB), (IIIC) or (IIID):

(IIIB).

(IIIB).

(IIIC).

(IIIC).

(IIID).

(IIID).

In another embodiment of the present invention, other representative compounds included in the compounds of formula (III) may be represented by formula (IIIE)

(IIIE)

(IIIE)

Wherein R and X are as defined above. R _g is selected from acetoxy, methoxy, ethoxy, phenoxy and substituted or unsubstituted phenyl. Substituents include any of the moieties known to those skilled in the art. Non-limiting examples of suitable substituents include (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) alkoxy, (C ₇ -C ₁₀ ) aralkyl, (C ₆ -C ₁₀ ) aralkyloxy, _6, and the like -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aralkyloxy. In another embodiment, compounds of formula (IIIE) are those wherein X is Cl, Br or I; R is independently isopropyl, tert-butyl or phenyl; R _g is acetoxy, methoxy or phenyl. In another embodiment, compounds of formula (IIIE) are those wherein X is Cl, Br or I; R is independently isopropyl, tert-butyl or phenyl; And R _g is methoxyphenyl.

In a further aspect of the invention, a series of compounds useful as a precatalyst of formula (IIIX) or (IIIY) is also provided:

(IIIX) (IIIY)

Wherein R, R _g and X are as defined above. R _h is a suitable functional group to assist chain propagation by insertion into the olefin undergoing polymerization. Examples of such groups include hydroxy, alkenyl groups such as vinyl and the like.

The compounds of the present invention can be synthesized by any of the procedures known to those skilled in the art. Specifically, as mentioned above, some of the compounds of formula (III), and some of the starting materials used in the preparation of the compounds of the present invention, are known or are themselves commercially available. Some of the compounds and precursor compounds of the present invention may also be prepared by the methods used in the preparation of similar compounds as reported in the literature and as further described herein. See, for example, J. Chatt, et al., J. Chem. Soc. (1957) 3413-3416; M. Green, et al., J. Chem. Soc. (A) (1967) 2054-2057; And K. Hiraki, et al., Bull. Chem. Soc. Japan, 53, 1980, 1976-1981; The relevant portions of both of these documents are incorporated herein by reference.

More specifically, the compounds disclosed herein may be synthesized according to the following procedures of Schemes 1 and 2, wherein R, R ₁ , LB, M, X and Y are as defined in Formulas I and III, respectively, Respectively.

Scheme 1

In Step 1 of Scheme I, a suitable cyclodiene complexed metal compound of formula (IA) is reacted with a suitable alcohol or acid to form a compound of formula (IB). The reaction can be carried out by any of the procedures known in the art. For example, a solution of a compound of formula (IA) may be reacted with a suitable alcohol or acid at room temperature or at a higher temperature to form a compound of formula (IB). In step 2 of scheme 1, the compound of formula (IB) is further reacted with a suitable phosphine or phosphine oxide to form a compound of formula (III). The reaction may also be carried out using any of the known literature procedures. Typically, such a reaction is carried out in a suitable solvent at room temperature or above. Finally, in step 3 of Scheme I, the compound of formula (III) is reacted with a suitable salt of a weakly coordinating anion of formula AZ to form a compound of formula (I) wherein A is any suitable cation such as An alkali metal cation which readily exchanges anion Z with X of the compound of formula (III), and the like.

Scheme 2 illustrates the synthesis of some of the specific compounds listed herein. In particular, the compounds of formula (II) and their precursors, compounds of formula (IIC), can be synthesized from dicyclopentadiene complexes / Pd (II) salts of formula (IIA). (IIA) with various alcohols or carboxylic acids (i.e., R ₁ OH, wherein R ₁ is alkyl, aryl, or acetyl as defined herein) as illustrated in Scheme 2, Step 1, At room temperature or at elevated temperature to give compounds of formula (IIB). In step 2 of scheme 2, the compound of formula (IIB) is reacted with a suitable phosphine or phosphite of formula PR ₃ to give the compound of formula (IIC). The reaction may also be carried out in a suitable solvent at room temperature or above to give the compound of formula (IIC). Finally, in step 3 of Scheme 2, the compound of formula (IIC) is further reacted with a suitable salt of a weakly coordinating anion, for example the lithium salt LiZ, to form a compound of formula (II). Typically, such a reaction is carried out in a suitable solvent at room temperature. It should be noted that all of these reaction steps are carried out in an inert atmosphere such as, for example, nitrogen, helium or argon. Alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol and the like; Alkane solvents such as hexane, heptane or petroleum ether; And solvents, including, but not limited to, combinations thereof, can be used in these reactions.

Scheme 2

As described herein, the compounds of the present invention, particularly the compounds of formula (I), more particularly the compounds of formula (II), are further described in detail below and described below as the single component vinyl moiety It is very effective as a polymerization catalyst. Likewise, compounds of formula (III), more particularly compounds of formula (IIG), and more particularly compounds of formula (IIIA) to (IIIE), (IIIX) and (IIIY) The following is effective as a two-component catalyst for the vinyl addition polymerization of various olefins as explained by specific examples.

polymer

The compounds of the present invention can be used as vinyl addition polymerization initiators for the preparation of various cyclic olefin addition polymers. In one aspect of the present invention, by using a compound of the present invention of formula (I) or (II) as a single component system, the compound is characterized in that the initiation group, such as Pd-C bond, ≪ / RTI > Accordingly, the polydispersity is likely to decrease and the number of active centers increases in both solution polymerization and bulk polymerization. In contrast, some of the compounds known to date, such as Pd-allyl complexes, require switching from a sigma pi-sigma bonding configuration, so that the catalyst center is replaced by an inserted cycloalkyl structural unit such as norbornene If the cycloolefin monomer used is a norbornyl structural unit, it should be produced. Thus, the compounds of the present invention provide unprecedented benefits as initiators for the preparation of certain cyclo-olefin polymers as described herein.

In another aspect of the present invention, a compound of formula (III) is mixed in-situ with a particular compound of formula (VI) to form a highly active two-component catalyst system which is further activated do. It has surprisingly been found that such a catalyst system is very useful for preparing various polymers from certain cycloolefin monomers as described herein and avoids external ligands such as acetonitrile.

Accordingly, there is provided a polymeric composition comprising a compound of formula (I) and a monomer of formula (IV)

The compound of formula (I)

(I)

(I)

In this formula,

은 (C₅-C₁₀)시클로알켄, (C₇-C₁₂)비시클로알켄 또는 (C₈-C₁₂)트리시클로알켄 기이고;

It is (C ₅ -C ₁₀₎ cycloalkene, (C ₇ -C ₁₂₎ alkene or bicyclo (C ₈ -C ₁₂₎ tricycloalkyl alkenyl group;

M is nickel, palladium or platinum;

LB is a Lewis base;

는 약하게 배위하는 음이온이며;Z

Is a weakly coordinating anion;

Y is PR ₃ or O = PR ₃ where R is methyl, ethyl, (C ₃ -C ₆ ) alkyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀₎ aralkyl, methoxy, ethoxy, (C ₃ -C ₆₎ alkoxy, substituted or non-substituted (C ₃ -C ₇₎ cycloalkoxy, (C ₆ -C ₁₀₎ aryl oxy or (C ₆ -C ₁₀₎ independently selected from aralkyloxy;

R ₁ is methyl, ethyl, straight or branched (C ₃ -C ₆ ) alkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀ ) aralkyl or R ₂ CO wherein R ₂ is methyl , ethyl, or (C ₃ -C ₆₎ alkyl.

Monomers of formula (IV):

(IV)

(IV)

Wherein:

p is an integer of 0, 1 or 2;

(C ₁ -C ₁₆ ) alkyl, hydroxy (C ₁ -C ₁₆ ) alkyl, perfluoro (C ₁ -C ₁₆ ) alkyl, and the like, wherein R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each independently of one another is hydrogen, straight or branched (C ₁ -C ₁₂₎ alkyl, (C ₃ -C ₁₂₎ cycloalkyl, (C ₆ -C ₁₂₎ bicycloalkyl, (C ₇ -C ₁₄₎ tricycloalkyl, (C ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, perfluoro (C ₆ -C ₁₀₎ aryl, perfluoroalkyl (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, di (C ₁ -C ₂ ) alkylmaleimido (C ₃ -C ₆ ) alkyl, di (C ₁ -C ₂ ) alkylmaleimide (C ₂ -C ₆ ) alkoxy (C ₁ -C ₂ ) alkyl, (C ₁ -C ₁₂₎ alkoxy, (C ₃ -C ₁₂₎ cycloalkoxy, (C ₆ -C ₁₂₎ bicyclo alkoxy, (C ₇ -C ₁₄₎ tricycloalkyl alkoxy, (C ₆ -C ₁₀₎ aryloxy (C ₁ -C ₃ ) alkyl, (C ₅ -C ₁₀ ) heteroaryloxy (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₀ ) aryloxy, (C ₅ -C ₁₀ ) heteroaryloxy or C ₁ -C ₆₎ is selected from acyloxy, each of the foregoing substituents here are halogen or a hydroxyl Is a group selected from optionally substituted.

It should be noted that in this aspect of the invention all of the compounds of formula (I), including all of the compounds of formula (II) as described herein, can be used without limitation. It is further noted that any of the known monomers of formula (IV) may be used in this aspect of the invention. Representative examples of monomers of formula (IV) include, but are not limited to:

Bicyclo [2.2.1] hept-2-ene (NB);

5-methylbicyclo [2.2.1] hept-2-ene (MeNB);

5-ethylbicyclo [2.2.1] hept-2-ene (EtNB);

5-n-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-decylbicyclo [2.2.1] hept-2-ene (DecNB);

5-trifluoromethyl-bicyclo [2.2.1] hept-2-ene (CF ₃ NB);

5-perfluoroethyl-bicyclo [2.2.1] hept-2-ene (C ₂ F ₅ NB);

A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);

5-perfluoro hexyl actual bicyclo [2.2.1] hept-2-ene (C ₆ F ₁₃ NB);

5-perfluorooctylbicyclo [2.2.1] hept-2-ene (OctNB);

5-perfluorodecylbicyclo [2.2.1] hept-2-ene (perfluoro DecNB);

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

5 - ((2- (2-methoxyethoxy) ethoxy) methyl) bicyclo [2.2.1] hept-2-ene (NBTON);

1- (bicyclo [2.2.1] hept-5-en-2-yl) -2,5,8,11-tetraoxadodecane (NBTODD);

5- (2- (2-ethoxyethoxy) ethyl) bicyclo [2.2.1] hept-2-ene;

5- (2- (2- (2-propoxyethoxy) ethoxy) ethoxy) bicyclo [2.2.1] hept-2-ene;

1- (bicyclo [2.2.1] hept-5-en-2-ylmethyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (MeDMMINB);

1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);

1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);

2 - ((bicyclo [2.2.1] hept-5-en-2-ylmethoxy) methyl) oxirane (MGENB);

2- (bicyclo [2.2.1] hept-5-en-2-yl) oxirane;

2- (7- (bicyclo [2.2.1] hept-5-en-2-yl) heptyl) oxirane;

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB);

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (also referred to herein as NBANB);

Ethyl 3- (bicyclo [2.2.1] hept-2-en-2-yl) propanoate (EPEsNB); And

2- (bicyclo [2.2.1] hept-5-en-2-yl) -5-phenyl-bicyclo [2.2.1] heptane (also referred to herein as NBNBAPh).

In one embodiment, the polymerizable composition of the present invention comprises a compound of formula (I) selected from the group consisting of:

(IIB);

(IIB);

(IIC); 및

(IIC); And

(IID)

(IID)

Wherein Py is pyridine; The polymerizable monomer

Bicyclo [2.2.1] hept-2-ene (NB);

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

5-hexylbicyclo- [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-decylbicyclo [2.2.1] hept-2-ene (DecNB);

5-perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);

1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);

1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); And

(Bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In a further aspect of the invention there is also provided a polymeric composition comprising a compound of formula (III), a compound of formula (V) and a monomer of formula (IV)

A compound of formula (III):

(III)

(III)

In this formula,

는 (C₅-C₁₀)시클로알켄, (C₇-C₁₂)비시클로알켄 또는 (C₈-C₁₂)트리시클로알켄 기이고;

It is (C ₅ -C ₁₀₎ cycloalkene, (C ₇ -C ₁₂₎ alkene or bicyclo (C ₈ -C ₁₂₎ tricycloalkyl alkenyl group;

M is nickel, palladium or platinum;

X is halogen, triflate, mesylate or tosylate;

Y is PR ₃ or O = PR ₃ wherein R is methyl, ethyl, (C ₃ -C ₆ ) alkyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀₎ aralkyl, methoxy, ethoxy, (C ₃ -C ₆₎ alkoxy, substituted or non-substituted (C ₃ -C ₇₎ cycloalkoxy, (C ₆ -C ₁₀₎ aryl oxy or (C ₆ -C ₁₀₎ independently selected from aralkyloxy;

R ₁ is methyl, ethyl, straight or branched (C ₃ -C ₆ ) alkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀ ) aralkyl or R ₂ CO wherein R ₂ is methyl , ethyl, or (C ₃ -C ₆₎ alkyl.

A compound of formula (V):

Z

;M _d

Z

;

In this formula,

는 리튬, 나트륨, 칼륨, 세슘, 바륨, 암모늄 또는 직쇄 또는 분지쇄 테트라(C₁-C₄)알킬 암모늄으로부터 선택된 양이온이며;M _d

Is lithium, sodium, potassium, cesium, barium, ammonium or straight-chain or branched-tetra (C ₁ -C ₄₎ a cation selected from alkyl ammonium;

는 B(C₆F₅)₄

, B[C₆H₃(CF₃)₂]₄

, B(C₆H₅)₄

, [Al(OC(CF₃)₂C₆F₅)₄]

, BF₄

, PF₆

, AsF₆

, SbF₆

, (CF₃SO₂)N

또는 CF₃SO₃

으로부터 선택된 약하게 배위하는 음이온이다.Z

B (C ₆ F ₅ ) ₄

, B [C ₆ H ₃ (CF ₃ ) ₂ ] ₄

_{, B (C 6 H 5)} 4

_{, [Al (OC (CF 3} ) 2 C 6 F 5) 4]

, BF ₄

, PF ₆

, AsF ₆

, SbF ₆

, (CF ₃ SO ₂₎ N

Or CF ₃ SO ₃

≪ / RTI > is a weakly coordinating anion.

Monomers of formula (IV):

(IV)

(IV)

Wherein:

p is an integer of 0, 1 or 2;

(C ₁ -C ₁₆ ) alkyl, hydroxy (C ₁ -C ₁₆ ) alkyl, perfluoro (C ₁ -C ₁₆ ) alkyl, and the like, wherein R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each independently of one another is hydrogen, straight or branched (C ₁ -C ₁₂₎ alkyl, (C ₃ -C ₁₂₎ cycloalkyl, (C ₆ -C ₁₂₎ bicycloalkyl, (C ₇ -C ₁₄₎ tricycloalkyl, (C ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, perfluoro (C ₆ -C ₁₀₎ aryl, perfluoroalkyl (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, di (C ₁ -C ₂ ) alkylmaleimido (C ₃ -C ₆ ) alkyl, di (C ₁ -C ₂ ) alkylmaleimide (C ₂ -C ₆ ) alkoxy (C ₁ -C ₂ ) alkyl, (C ₁ -C ₁₂₎ alkoxy, (C ₃ -C ₁₂₎ cycloalkoxy, (C ₆ -C ₁₂₎ bicyclo alkoxy, (C ₇ -C ₁₄₎ tricycloalkyl alkoxy, (C ₆ -C ₁₀₎ aryloxy (C ₁ -C ₃ ) alkyl, (C ₅ -C ₁₀ ) heteroaryloxy (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₀ ) aryloxy, (C ₅ -C ₁₀ ) heteroaryloxy or C ₁ -C ₆₎ is selected from acyloxy, each of the foregoing substituents here are halogen or a hydroxyl Is a group selected from optionally substituted.

In this aspect of the invention, the polymerizable composition comprises a compound of formula (III) selected from the group consisting of:

(IIIB);

(IIIB);

(IIIC); 및

(IIIC); And

(IIID).

(IIID).

In addition, compounds of formula (V) are selected from the group consisting of:

Lithium tetrafluoroborate;

Lithium triflate;

Lithium tetrakis (pentafluorophenyl) borate;

Lithium (diethyl ether) tetrakis (pentafluorophenyl) borate _{([Li (OEt 2) 2.5} ] [B (C 6 F 5) 4]) (LiFABA);

Lithium tetraphenylborate;

Lithium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate;

Lithium tetrakis (2-fluorophenyl) borate;

Lithium tetrakis (3-fluorophenyl) borate;

Lithium tetrakis (4-fluorophenyl) borate;

Lithium tetrakis (3,5-difluorophenyl) borate;

Lithium hexafluorophosphate;

Lithium hexaphenyl phosphate;

Lithium hexakis (pentafluorophenyl) phosphate;

Lithium hexafluoroarsenate;

Lithium hexaphenyl arsenate;

Lithium hexakis (pentafluorophenyl) arsenate;

Lithium hexacis (3,5-bis (trifluoromethyl) phenyl) arsenate;

Lithium hexafluoroantimonate;

Lithium hexaphenyl antimonate;

Lithium hexakis (pentafluorophenyl) antimonate;

Lithium hexakis (3,5-bis (trifluoromethyl) phenyl) antimonate;

Lithium tetrakis (pentafluorophenyl) aluminate;

Lithium tris (nonafluorobiphenyl) fluoroaluminate;

Lithium (octyloxy) tris (pentafluorophenyl) aluminate;

Lithium tetrakis (3,5-bis (trifluoromethyl) phenyl) aluminate; And

Lithium methyl tris (pentafluorophenyl) aluminate.

On the other hand, any of the polymerizable monomers as described herein can be used. For example, the polymerizable monomer is selected from the group consisting of:

Bicyclo [2.2.1] hept-2-ene (NB);

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

5-hexylbicyclo- [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-decylbicyclo [2.2.1] hept-2-ene (DecNB);

5-perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);

1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);

1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); And

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

As mentioned, the polymerization reaction can be carried out in neat (bulk polymerization) or in solution. That is, by the practice of the present invention, various polymers containing at least one functionalized norbornene monomer (i.e., a compound of formula (IV)) can be combined with a single component (i. E. II) in the presence of a catalyst or a two-component catalyst (i.e., a compound of formula (III) in combination with a compound of formula (V)). When a two-component catalyst is used, the compound of formula (III) can generally be referred to as a precatalyst and the compound of formula (V) is generally referred to as an activator. However, various other compounds which will function effectively as catalysts, procatalysts and / or activators may also be used in combination with the compounds of formulas (III) and (V) when the two-component catalyst is used.

It has also been found that the compounds of the present invention as single component or two component catalyst compositions are highly active. Therefore, it is possible to produce a high-quality polymer by using a small amount of the catalyst in the present invention. Thus, in one embodiment, the addition polymerization can be effectively carried out using a monomer: single component catalyst molar ratio of at least 100: 1, based on the total number of moles of monomers and catalyst used. That is, 100 moles of the monomer is used per 1 mole of the single component catalyst. In another embodiment, the molar ratio of monomer: catalyst is 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, When a two-component catalyst system is used, the molar ratio of monomer: precatalyst: activator may be at least 100: 1: 1. In another embodiment, the molar ratio of monomer: precatalyst: activator is 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: In some embodiments, the activator is used in excess of the molar amount of the precatalyst used, for example, the molar ratio of the precatalyst: activator may be 1: 1 to 1: 6.

As mentioned, the bulk polymerization can be carried out with a catalyst and a monomer without a solvent. Advantageously, such polymerization can also be carried out at a suitable temperature in the mold to form a three-dimensional polymeric product. In general, the reaction temperature may be a sub-ambient temperature such as below 0 DEG C to the boiling point range of the monomers, but it is recommended that the components of the reaction vessel or mold are not heated above the flash point of one or more of the monomers . Generally, the bulk polymerization is carried out at a temperature range of from about 10 DEG C to 300 DEG C, and in some other embodiments, the temperature range is from about 10 DEG C to 200 DEG C; Or about 20 < 0 > C to 100 < 0 > C.

Since the polymerization reaction is exothermic, the temperature in the mold during the polymerization is generally higher than the temperature of the feed, unless a cooled mold is used. Thus, the initial mold temperature is generally from about-20 캜 to about 300 캜; Or from about 0 C to about 200 C; Or in the range of 20 < 0 > C to 100 < 0 > C. The temperature distribution in the mold is influenced by such factors as the geometry, the heat sink or heat supply means, the nature of the mold, the reactivity of the catalyst and the monomers. To some extent, the selection of suitable temperature and heat exchange conditions will be based on experience with a given system of molds, feeds and catalysts.

After completion of the polymerization reaction, the molded article is heated at a temperature in the range of about 100 캜 to 300 캜 for about 15 minutes to 24 hours; Or may be subjected to an additional post-curing treatment for 1 to 2 hours. Such post-curing treatments can enhance polymer properties including glass transition temperature (T _g ) and heat distortion temperature (HDT). Post-curing is also preferred, but not necessary, to lead the samples to their final stable dimensional state, minimize residual odors, and improve final properties.

The vinyl addition polymerization can also be carried out in the presence of a single component catalyst (i.e. a compound of formula (I) or (II)) or a two-part catalyst (i.e., a compound of formula (III) ≪ / RTI > In this embodiment, a solution of the catalyst is suitably mixed with one or more preferred solutions of monomers (i.e., compounds of formula (IV)) under conditions known in the art to form the polymers of the present invention. Suitable polymerization solvents include, but are not limited to, alkanes and cycloalkane solvents such as pentane, hexane, heptane, and cyclohexane; Halogenated alkane solvents such as dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1- chloropropane, 2- chloropropane, 1- chlorobutane, 2- , 1-chloro-2-methylpropane, and 1-chloropentane; Ethers such as THF and diethyl ether; Aromatic solvents such as benzene, xylene, toluene, mesitylene, chlorobenzene, and o- dichlorobenzene; And halo carbon solvents such as Freon ( ^R) 112; And any combination thereof.

The solution polymerization temperature may be a subatmospheric temperature, for example, below 0 [deg.] C to the boiling range of the solvent used. Generally, solution polymerization is carried out in a temperature range of from about 10 DEG C to 200 DEG C, and in some other embodiments, the temperature range is from about 10 DEG C to 150 DEG C; Or about 20 < 0 > C to 100 < 0 > C.

Polymers formed in accordance with the present invention generally exhibit a number average molecular weight (M _n ) of at least about 3,000. In another embodiment, the polymers of the present invention have a M _n of at least about 5,000. In another embodiment, the polymers of the present invention have a M _n of at least about 10,000. In another embodiment, the polymers of the present invention have a M _n of at least about 20,000. In another embodiment, the polymers of the present invention have a M _n of at least about 50,000. In some other embodiments, the polymers of this invention have a M _n of at least about 100,000. In another embodiment, the polymers of the present invention has a high M _n than 100,000, and in some other embodiments may be higher than 500,000. The number average molecular weight (M _n ) of the polymer can be determined by any known technique, for example, by gel permeation chromatography (GPC) with a suitable detector and calibration standard, such as a differential refractive index detector calibrated to a narrow distribution polystyrene standard . As mentioned, the polymers of the present invention show typically a weight average molecular weight (M _w) to number average molecular weight ratio polydispersity index (PDI) is very low in the (M _n). Generally, the PDI of the polymers of the present invention is less than two. In some embodiments, the 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, the PDI may be higher than 2, e.g., higher than 3.

Block copolymer

Advantageously, the various compounds of formula (I), (II) or (III) are effective as catalysts for the formation of a block copolymer series comprising at least one norbornene-type compound of formula (IV) It has also been found out that the functioning of the present invention has been achieved. Block copolymers such as those described herein may also be prepared by any other catalyst known in the art. The block copolymers of the present invention provide specific advantages and are therefore useful in a variety of applications including, but not limited to, the formation of film materials, and in various other optical and electronic applications Have been found to further extend the present invention. Membranes formed from block copolymers are useful, for example, for the separation of organic matter from biomass or other organic wastes.

Accordingly, block copolymers of formula (VI) are provided:

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

M and n may be in the range of 20 to 4000, or 50 to 3000 or 100 to 2000, and in other embodiments, m and n may be in the range of May be higher than 4000 depending on the purpose of use;

b represents the bond between two blocks of homopolymer A and B;

A and B are different from each other and independently selected from repeating units represented by the formula (IVA), wherein the repeating units are derived from monomers of the formula (IV)

(IVA)

(IV)

(IVA)

(IV)

Wherein:

는 또 다른 반복단위와의 결합위치를 나타내며;

Represents a bonding position with another repeating unit;

p is an integer of 0, 1 or 2;

(C ₁ -C ₁₆ ) alkyl, hydroxy (C ₁ -C ₁₆ ) alkyl, perfluoro (C ₁ -C ₁₆ ) alkoxy, and the like, wherein R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each independently of one another is hydrogen, straight or branched (C ₁ -C ₁₂₎ alkyl, (C ₃ -C ₁₂₎ cycloalkyl, (C ₆ -C ₁₂₎ bicycloalkyl, (C ₇ -C ₁₄₎ tricycloalkyl, (C ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, perfluoro (C ₆ -C ₁₀₎ aryl, perfluoroalkyl (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, di (C ₁ -C ₂ ) alkylmaleimido (C ₃ -C ₆ ) alkyl, di (C ₁ -C ₂ ) alkylmaleimide (C ₂ -C ₆ ) alkoxy (C ₁ -C ₂ ) alkyl, (C ₁ -C ₁₂₎ alkoxy, (C ₃ -C ₁₂₎ cycloalkoxy, (C ₆ -C ₁₂₎ bicyclo alkoxy, (C ₇ -C ₁₄₎ tricycloalkyl alkoxy, (C ₆ -C ₁₀₎ aryloxy (C ₁ -C ₃ ) alkyl, (C ₅ -C ₁₀ ) heteroaryloxy (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₀ ) aryloxy, (C ₅ -C ₁₀ ) heteroaryloxy or C ₁ -C ₆₎ is selected from acyloxy, each of the foregoing substituents here are halogen or a hydroxyl Is a group selected from optionally substituted.

In one embodiment of the present invention, the block polymer of the present invention further comprises a third type of repeat unit represented by formula (VII): < EMI ID =

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

Where m, n and b are as defined above and o is an integer of at least 15, but in other embodiments, o may range from 20 to 4000, or from 50 to 3000 or from 100 to 2000, and in other embodiments, , o may also be higher than 4000 depending on the intended use of the block polymer. C is the same or different from A or B and is independently selected from repeating units represented by the formula (IVA), wherein the repeating units are derived from monomers of the formula (IV) as defined herein. In other words, the block copolymers of the present invention can exist as diblocks or as triblocks. However, any number of additional blocks can be formed by sequentially adding one or more other monomers of formula (IV) to form a multiblock copolymer of the present invention. For example, diblock polymers are typically formed by first polymerizing a first monomer of formula (IV) in the presence of a suitable catalyst, and then the second monomer, which is the same as the first monomer or a second different monomer, Can be added to the polymerization reaction mixture to form a diblock copolymer. Generally, the polymerization is carried out in solution at a suitable polymerization reaction temperature as described above. That is, any of the solvents as described above may be used to form the diblock copolymer in the presence of one or more suitable polymerization catalysts. The reaction temperature is generally in the vicinity of ambient conditions, i.e., near room temperature. However, a super-ambient, i.e. a temperature above room temperature of about 25 ° C to 150 ° C, or a subatmospheric, ie, room temperature below about 25 ° C to room temperature, or even lower, temperature can be used. Polymerization can also be carried out neat, i. E. Bulk polymerization, without solvent. The triblock polymer is likewise formed by the polymerization of the second monomer followed by the addition of the third monomer. Multiblock polymers are formed by the sequential addition of additional monomers. As mentioned, the same monomers or different monomers can be used to form block copolymers to form different blocks as needed, and at various molar ratios of the monomers.

Thus, in one embodiment, there is provided a diblock copolymer wherein the block molar ratio of A: B is from 1: 1 to 1: 4. In another embodiment, the block molar ratio of A: B is from 1: 1 to 1: 2. In another embodiment, the block molar ratio of A: B is 1: 1. In another embodiment, the block polymer is a triblock polymer wherein the block molar ratio of A: B: C is from 1: 1: 1 to 1: 4: 1 to 1: 1: 4. In a further embodiment, the block molar ratio of A: B: C is 1: 1: 1; In another embodiment, the block molar ratio of A: B: C is 1: 2: 1. In this regard, the size of the block may also be controlled by the respective weight fraction of the block. That is, in the diblock polymer AbB, the weight fraction of monomer A may range from 0.1 to 1, expressed as W _A. A variety of triblock or other multiblock polymers may likewise be prepared using different monomers of different weight fractions to be used.

In general, any of the monomers included in formula (IV) can be used to form the block polymer of the present invention. For example, non-limiting examples of repeating units of A may be derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-perfluoroethyl-bicyclo [2.2.1] hept-2-ene (C ₂ F ₅ NB);

A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);

5-perfluoro hexyl actual bicyclo [2.2.1] hept-2-ene (C ₆ F ₁₃ NB);

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);

1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); And

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In another embodiment, non-limiting examples of repeating units B are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-perfluoroethyl-bicyclo [2.2.1] hept-2-ene (C ₂ F ₅ NB);

A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);

5-perfluoro hexyl actual bicyclo [2.2.1] hept-2-ene (C ₆ F ₁₃ NB);

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);

1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); And

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

Finally, non-limiting examples of repeating units C are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

5-octylbicyclo [2.2.1] hept-2-ene (OctNB);

5-perfluoroethyl-bicyclo [2.2.1] hept-2-ene (C ₂ F ₅ NB);

A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);

5-perfluoro hexyl actual bicyclo [2.2.1] hept-2-ene (C ₆ F ₁₃ NB);

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);

1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);

5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);

5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); And

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In another embodiment, representative examples of repeating units A are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB); And

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In another embodiment, representative examples of repeating units B are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB); And

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

In another embodiment, representative examples of repeating units C are derived from monomers selected from the group consisting of:

5-butylbicyclo [2.2.1] hept-2-ene (BuNB);

5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);

A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);

1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB); And

2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).

Non-limiting examples of block copolymers of the present invention are selected from the group consisting of:

(HexNB-2) derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan- b-HFANB);

A block copolymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB- b-HFANB);

A block copolymer derived from 5-benzylbicyclo [2.2.1] hept-2-ene and 5-n-perfluorobutylbicyclo [2.2.1] hept-2-ene (BnNB-bC ₄ F ₉ NB );

2.2.1] hept-2-ene and 1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3, 4-pentafluorobutylbicyclo [ - (C ₄ F ₉ NB-b-BuDMMINB) derived from dimethyl-1H-pyrrole-2,5-dione;

2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2 .1] heptane (HFANB-b-NBANB); And

Block copolymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2- yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB).

In one embodiment, the block polymers of the present invention are selected from the group consisting of:

2,2'-hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo [2.2. 1] hept-2-ene (BuNB-b-HFANB-b-BuNB);

Benzylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en- 2-yl) bicyclo [2.2.1] heptane (BuNB-b-BnNB-b-NBANB); And

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept- Block polymer derived from fluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

The block polymers of the present invention can be prepared by any of the procedures known in the art. In general, the polymerization is carried out in solution and in the presence of a suitable metal catalyst. In some embodiments of the present invention, a metal catalyst in combination with a suitable catalyst, initiator or pro-initiator, or a suitable compound that may function as an activator, is preferred to provide a process for preparing the block polymer of the present invention . However, as noted, any of the other approaches known in the art may also be used.

Thus, a block copolymer of formula (VI) as described herein, comprising reacting any of A of formula (IV), a first monomer as described herein, with a palladium compound to form a first polymer block Is provided. Then, B of formula (IV), which is a second monomer different from A of formula (IV) which is the first monomer, is added to the polymerization reaction mixture to form a block containing a diblock copolymer having a different molar ratio of monomer repeating units A and B To form a copolymer.

In another embodiment, there is further provided a process for preparing a triblock polymer, comprising reacting a third monomer, C, of formula (IV) to form a block polymer of formula (VII)

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

Wherein m, n, o, b, A, B and C are as defined herein. It should be noted that the monomer repeating unit C may be the same as or different from A or B and is independently selected from the repeating units represented by the formula (IVA), wherein the repeating units are monomers of the formula (IV) . Again, as noted above, the block polymer of formula (VII) is thus referred to as a triblock polymer and may have a variety of different molar ratios of repeating units of formula A, B or C as described above.

Palladium compounds that can be used in the process of the present invention include all of the compounds of formulas (I), (II) and (III) as described herein.

Advantageously, it has been found to be advantageous to the present invention that a wide variety of other palladium compounds can also be used in the process of the present invention. Such a palladium compound suitable for forming the block polymer of the present invention is represented by the following formula:

_{(Allyl) Pd (P (Q 3)} ) (L 1) or _{(methyl) Pd (P (Q 3)} ) (L 1)

Wherein Q, which may be the same or different, is independently selected from isopropyl, tert-butyl, neopentyl and cyclohexyl; L ₁ is selected from halogen, trifluoroacetate and trifluoromethanesulfonate (triflate). Non-limiting examples of such palladium compounds include:

Allylpalladium (triisopropylphosphine) chloride, [Pd (allyl) (triisopropylphosphine) Cl];

Allylpalladium (tri-tert-butylphosphine) chloride, [Pd (allyl) (tri-tert-butylphosphine) Cl];

Allylpalladium (diisopropyl-tert-butylphosphine) chloride, [Pd (allyl) (diisopropyl-tert-butylphosphine) Cl];

Allylpalladium (isopropyl-di-tert-butylphosphine) chloride, [Pd (allyl) (isopropyl-di-tert-butylphosphine) Cl];

Allylpalladium (ditert-butyl-cyclohexylphosphine) chloride, [Pd (allyl) (ditert-butyl-cyclohexylphosphine) Cl];

Allylpalladium (ditert-butyl-neopentylphosphine) chloride, [Pd (allyl) (ditert-butyl-neopentylphosphine) Cl];

(Allyl) palladium (tricyclohexylphosphine) triflate, [Pd (allyl) (tricyclohexylphosphine) triflate];

(Allyl) palladium (triisopropylphosphine) triflate, [Pd (allyl) (triisopropylphosphine) triflate];

(Allyl) palladium (tricyclohexylphosphine) trifluoroacetate, [Pd (allyl) (tricyclohexylphosphine) trifluoroacetate];

(Allyl) palladium (triisopropylphosphine) trifluoroacetate, [Pd (allyl) (triisopropylphosphine) trifluoroacetate];

Methylpyridinium (triisopropylphosphine) chloride, [Pd (methyl) (triisopropylphosphine) Cl];

Methylpyridinium (tri-tert-butylphosphine) chloride, [Pd (methyl) (tri-tert-butylphosphine) Cl];

Methylpyridinium (diisopropyl-tert-butylphosphine) chloride, [Pd (methyl) (diisopropyl-tert-butylphosphine) Cl];

Methylpyridinium (isopropyl-di-tert-butylphosphine) chloride, [Pd (methyl) (isopropyl-di-tert-butylphosphine) Cl];

Methyl palladium (ditert-butyl-cyclohexylphosphine) chloride, [Pd (methyl) (ditert-butyl-cyclohexylphosphine) Cl];

Methyl palladium (tricyclohexylphosphine) chloride, [Pd (methyl) (tricyclohexylphosphine) Cl], also abbreviated to as _{[(Me-Pd-PCy 3} ) Cl] ( where Cy is cyclohexyl (C ₆ H ₁₁ ));

Methylpalladium (dicyclohexyl-tert-butylphosphine) chloride, [Pd (methyl) (dicyclohexyl-tert-butylphosphine) Cl];

Methyl palladium (cyclohexyl-di (tert-butyl) phosphine) chloride, [Pd (methyl) (cyclohexyl-di (tert-butyl) phosphine) Cl]; Etc.

Another class of palladium compounds that may also be used in the formation of the block polymers of the present invention may be represented by the formula:

Wherein R x is substituted (C ₈ -C ₁₆ ) aryl, such as 2,5-diisopropylbenzene, mesityl, etc., and L ₁ is as defined above. Non-limiting examples of such palladium compounds include:

Allyl (palladium) (1,3-bis (2,6-diisopropylphenyl) -2,3-dihydro-1H-imidazole) Cl;

Allyl (palladium) (1,3-bis (2,6-diisopropylphenyl) imidazolidine) Cl; And

Allyl (palladium) (1,3-dimesityl-2,3-dihydro-1H-imidazole) Cl.

Some of the palladium compounds described above are commercially available or can be prepared using any of the procedures known in the literature and known in the literature.

Also as mentioned above, the palladium compounds as described above are generally used in combination with additional compounds that function as cocatalysts, initiators, developmental reagents or activators. For example, any of the compounds of formula (V) as described above may be used for this purpose. In one embodiment, the ratio of such an activator compound-limiting examples of lithium tetrakis (pentafluorophenyl) borate etherate _{(LiFABA - [Li (OEt 2} ) 2.5] [B (C 6 F 5) 4] ) And N, N-dimethylanilinium tetrakis (pentafluorophenyl) -borate (DANFABA).

It should thus be noted that the palladium-containing catalyst useful for the block copolymer preparation of the present invention can be prepared as a preformed monocomponent catalyst, or the palladium-containing precatalyst can be prepared by reacting the desired polymer (s) (Or in the system) by mixing with an activator (or a cocatalyst, initiator or development agent as described above) situ .

Therefore, the preformed catalyst can be prepared by mixing a catalyst precursor such as a catalyst and an activator (or a cocatalyst, an initiator or a development agent) in an appropriate solvent, conducting the reaction under an appropriate temperature condition, And isolating the product. Catalyst refers to a palladium-containing compound that is converted to an active catalyst by reaction with a cocatalyst, activator, initiator or development reagent compound. Further descriptions and synthesis of representative procatalyst and activator compounds can be found in U.S. Patent 6,455,650, the relevant portion of which is incorporated herein by reference.

The block copolymers formed according to the invention generally have a number average molecular weight (M _n ) of at least about 2,000 for each of the blocks formed. Each M _n of the block can be tailored based on the desired properties and end use of the block copolymer. Thus, In another embodiment, one of the blocks of the block copolymer of the present invention have a M _n of at least about 20,000. In another embodiment, one of the blocks of the block copolymer of the present invention have a M _n of at least about 50,000. In some other embodiments, one of the blocks of the block copolymer of the present invention have a M _n of at least about 100,000. In another embodiment, one block has a M _n of at least 5,000 and one block of the diblock copolymer has an M _n of at least 20,000. In some other embodiments, any one of the blocks of the block polymer of the present invention has a M _n greater than 100,000, greater than 200,000, or greater than 500,000. As already mentioned above, the number average molecular weight (M _n ) of the block copolymer can be determined by any of the known techniques, for example, as a differential refractive index (RI) detector or a polygonal laser light scattering (LS) detector calibrated to a narrowly distributed polystyrene standard Can be determined by gel permeation chromatography (GPC) with suitable detectors and calibration standards. As also mentioned, each of the block copolymers of the present invention typically exhibits a very low polydispersity index (PDI = M _w / M _n ). Generally, the PDI of each block of the block copolymer of the present invention is less than two. In some embodiments, the 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, the PDI may be higher than 2, e.g., higher than 3.

In one embodiment, a variety of diblock polymers can be formed by practicing the methods of the present invention. Non-limiting examples of such biblock polymers formed from the process of the present invention can be listed as follows:

(HexNB-2) derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan- b-HFANB);

A block copolymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB- b-HFANB);

2.2.1] hept-2-ene and 1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl- Pyrrole-2,5-dione (C ₄ F ₉ NB-b-BuDMMINB);

2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2 .1] heptane (HFANB-b-NBANB);

Block copolymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2- yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB); And

A block copolymer derived from 5-benzylbicyclo [2.2.1] hept-2-ene and 5-n-perfluorobutylbicyclo [2.2.1] hept-2-ene (BnNB-bC ₄ F ₉ NB ).

In another embodiment, various triblock polymers can be formed by practicing the methods of the present invention. Non-limiting examples of such triblock polymers formed from the process of the present invention can be listed as follows:

2,2'-hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo [2.2. 1] hept-2-ene (BuNB-b-HFANB-b-BuNB);

Benzylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2- A) Block polymer derived from bicyclo [2.2.1] heptane (BuNB-b-BnNB-b-NBANB); And

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept- Block polymer derived from fluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

Pervaporation membrane application

As mentioned, the block polymers of the present invention exhibit several specific properties and are therefore useful in several different applications, especially including membrane materials for separation, electronics and / or optoelectronics applications.

With growing interest in the production of biological fuels such as ethanol, butanol and the like, there is a growing interest in the development of an environmentally friendly separation process that economically separates organic materials from water. Isolation of organic products from aqueous fermentation broths designed to form various organic solvents through purification and biological processes of polluted water streams by industrial processes, such as the broth of a fermentation reactor or other biologically formed broth, such as algae The need for isolation of phenol from broth is also increasing. There is also an increasing interest in the separation of value-added products from biological and industrial wastes, including any biomass-derived wastes. Although it is well known to carry out such separation using processes such as distillation and stripping, these conventional processes, particularly distillation, generally characterize high capital and energy costs, and thus often result in such conventional processes being problematic For example, it is noted that over 60% of the calorific value of biofuels such as butanol can be " wasted " when conventional separation processes are employed.

More importantly, organic products, especially organic solvents prepared by the above-described bioprocesses or extracted from organic wastes, are becoming increasingly industrial applications. For example, about half of the produced n-butanol and its esters (for example, n-butyl acetate) are used as solvents in paint-making, including solvents for dyes, for example printing inks. Other well-known applications of butyl esters of dicarboxylic acids, phthalic anhydrides and acrylic acids include but are not limited to the use as additives in plasticizers, rubber additives, dispersants, semisynthetic lubricants, abrasives and detergents such as floor cleaners and stain removers, and hydraulic fluids Applications. Butanol and its esters are also used as solvents, including as drugs and extracts in the production of natural products such as antibiotics, hormones, vitamins, alkaloids and campo. Other various uses of butanol and its esters and ethers are also found in a wide variety of other applications as solubilizers in the textile industry, for example as additives in spinning baths or as plastics coloring supports, additives in thawing liquids, As additives in gasoline, as feedstocks for the production of glycol ethers.

Therefore, an alternate process for performing such separation, known as pervaporation, has received considerable attention as a solution to the aforementioned " waste ". In the pervaporation process, a charge liquid, typically a mixture of two or more liquids, such as a fermentation broth, is brought into contact with a film of film having properties that allow the film to preferentially permeate through one component of the feed. The permeate is then removed as vapor from the downstream side of the membrane film, typically by applying a vacuum to the permeate side of the membrane. In particular, the pervaporation process has proven to be an optimal method for the separation of liquid mixtures with similar volatilities, e. G., Azeotropic mixtures, which are difficult to separate by conventional methods. Polymers such as polyimide, polyether-polyamide, polydimethylsiloxane, and the like have been used to some extent in the formation of pervaporation membranes successfully, but none of the essential properties required for commercially feasible membrane materials have been demonstrated to date. For example, pervaporation membranes such as PERVAP 1060 (made of poly (dimethylsiloxane), PDMS), PERVAP 1070 (made of zeolite, ZSM-5, filled PDMS) (Sulzer Chemtech Membrane Systems AG, And PEBA (block copolymer polyether-polyamide, GKSS-Forschungszentrum Geesthacht GmbH, Geesthacht, Germany) are available for the separation of various low-volatile organic compounds from aqueous mixtures. However, there is still a need to develop membranes with better performance that can provide efficient separation of organics from aqueous mixtures with lower capital and reduced operating costs.

The present invention encompasses pervaporation membrane embodiments that advantageously provide for the separation of organic materials that have hitherto not been achievable from monomers, polymer composition embodiments, film and film composite embodiments, and various mixtures including, among others, fermentation broth, industrial waste formed therefrom ≪ / RTI > are disclosed herein.

Exemplary embodiments of the present invention will be described below. Various modifications, adaptations, or variations of such exemplary embodiments may become apparent to those skilled in the art as set forth above. It is to be understood that all such variations, adaptations or variations that rely on the teachings of the present invention and that those teachings are within the scope of the present invention are intended to come within the scope of the invention. For example, while the exemplary embodiments described herein generally refer to the separation of butanol and / or phenol from aqueous feeds, they are not meant to limit the present invention to embodiments for butanol and / or phenol separation . Accordingly, some embodiments of the present invention include the separation of any organic material from an aqueous feedstock where a suitable pervaporation membrane can be formed from the block copolymer of the present invention. For example, some embodiments include the separation of a hydrophobic organic material from a hydrophilic input using a suitable pervaporation membrane as disclosed herein. Another embodiment of the present invention involves the separation of non-polar and polar organic materials. Examples of such separations include the separation of aromatic materials such as benzene or toluene from water-miscible alcohols such as methanol or ethanol and the separation of non-polar hydrocarbyl-based materials such as hexane and heptane from polar heterocellular materials, But are not limited to them. Other various organic materials also include volatile organic solvents such as tetrahydrofuran (THF), ethyl acetate (EA), acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) Or in industrial waste.

The expected behavior of a pervaporation membrane made of a hydrophobic polymer is that it plasticizes and / or swells as the organic concentration increases. Plasticizations and / or swelling membranes generally result in an undesirable increase in the permeability of both the organic material and water, with the permeability generally increasing relative to the organic permeability, resulting in a decrease in the separation factor. Unexpectedly, the pervaporation membranes made of the block polymers of the present invention, which are generally hydrophobic, exhibit the opposite behavior as would normally be expected. Pervaporation membranes as described herein have a dramatically increasing separation factor depending on the increasing feed concentration (i.e., the increase in the organic matter concentration of the feed stream).

In pervaporation, a multi-component liquid stream is typically passed through a pervaporation membrane that preferentially permeates at least one of the components. As the multicomponent liquid stream flows across the pervaporation membrane surface, the preferentially permeated components pass through the pervaporation membrane and are removed as permeate vapor. Transport through the pervaporation membrane is induced by maintaining a vapor pressure lower than the vapor pressure of the multicomponent liquid stream on the permeate side of the pervaporation membrane. The vapor pressure differential can be achieved, for example, by maintaining the multicomponent liquid stream at a temperature higher than the temperature of the permeate stream. In this example, a multi-component liquid stream is supplied with latent heat during evaporation of the permeate component to maintain the feed temperature and to continue the pervaporation process. Alternatively, the vapor pressure difference is typically achieved by operating below the atmospheric pressure on the permeate side of the pervaporation module. Partial vacuum at the permeate side of the polynorbornene pervaporation membrane can be achieved by either: depending on the pressure drop resulting from cooling and condensation in the condenser unit, and / or the use of a vacuum pump By means of. Any sweep gas on the permeate side can promote the pervaporation process by lowering the concentration of the permeating component. The vapor pressure of the feed liquid may optionally be raised by heating the fermentation broth. Polynorbornene pervaporation membranes have already been disclosed in U.S. Patent No. 8,215,496, the disclosure of which is incorporated herein by reference, and although such membranes have achieved some success, the block copolymer pervaporation membranes disclosed and claimed herein are not such prior ≪ / RTI > which is apparent from the following disclosure.

Accordingly, there is provided a pervaporation membrane comprising a block polymer of formula (VI) or (VII) as disclosed herein. That is, any of the diblock or triblock polymers of the present invention can be used to form the pervaporation membrane of the present invention. In one embodiment, the pervaporation membrane of the present invention comprises a diblock copolymer of formula (VI) of the present invention. In another embodiment, the pervaporation membrane of the present invention comprises a triblock polymer of formula (VII) of the present invention.

In another embodiment, the pervaporation membrane of the present invention is made from a diblock copolymer selected from the group consisting of:

(HexNB-2) derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan- b-HFANB);

A block copolymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB- b-HFANB);

2.2.1] hept-2-ene and 1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl- Pyrrole-2,5-dione (C ₄ F ₉ NB-b-BuDMMINB);

2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2 .1] heptane (HFANB-b-NBANB); And

Block copolymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2- yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB).

In another embodiment, the pervaporation membrane of the present invention is made from a triblock polymer selected from the group consisting of:

2,2'-hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo [2.2. 1] hept-2-ene (BuNB-b-HFANB-b-BuNB); And

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept- A block copolymer derived from fluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

The pervaporation membranes of the present invention can be readily formed by any of the techniques known in the art. For example, a suitable diblock or triblock polymer of formula (VI) or (VII) of the present invention comprising the preferred repeat units of a polycycloalkyl norbornene-type monomer of formula (IVA) And dissolved to form a solution. The polymer solution is then generally filtered with a suitable filter to remove any residual contaminants. After filtration, the trapped gas can be removed. The polymer solution may then be formed into a film by any of the methods known in the art. For example, a polymer solution is poured onto a substrate and pulled to form a film. If necessary, the film is subsequently dried and removed from the substrate, ready for use. Films formed in this manner are generally considered as a single thickness film, and specific examples of such embodiments are described in more detail below. In some embodiments, the film is cast as a dual thickness film by forming a second layer of film over the first formed film. In some other embodiments, a polymer solution is applied to a polymeric web to form a reinforcing film, i. E., Applied to a sheet to form a backing film or to a substrate panel to form a non-supporting film. In another embodiment, the polymer solution may be suitably cast to form a tubular composite or hollow fiber. Thus, in one embodiment, the pervaporation membrane of the present invention is in the form of a tubular composite, a hollow fiber, a dense film flat sheet, or a thin film composite.

The pervaporation membrane of the present invention may be of any suitable form for carrying out the separation of the desired material, for example butanol, from the fermentation broth. Examples include spiral wound modules, fibrous membranes including hollow fibers, tubular membranes, and flat sheet membranes, such as flat sheet membranes in the form of plates and frames, supported or non-supported dense membranes, or thin film composites.

When the block polymer pervaporation membrane is used in a non-supported dense film form, the dense film thickness is from about 1 micron to about 500 microns. In another embodiment, the thickness of the dense film is from about 5 microns to about 100 microns.

When the pervaporation membrane is used in the form of a thin film composite, such a membrane may be thinner than the non-supporting membrane, for example, by about 0.1 micron. Additionally, the membrane comprises at least one layer of a block polymer and at least one layer of a non-block polymer component. Such a composite may comprise multiple layers of a block polymer film and multiple layers of non-block polymer components. Examples of non-block polymer components include various other polymers and inorganic materials. Examples of such polymers are polyethylene, polypropylene, polyester, polyimide, polycarbonate, polytetrafluoroethylene, polyvinylidene fluoride (PVDF), poly (methyl methacrylate) (PMMA) , Polyacrylonitrile (PAN), their mixed copolymers and terpolymers, and the like. Examples of inorganic materials include zeolite, glass frit, carbon powder, metal sheaves, metal screens, metal frit, and the like.

Figure 1 shows a schematic diagram of the pervaporation process. As shown, feeds containing multiple species are fed into the pervaporation module 100 and into the liquid chamber 102 on the feed side thereof. The permeate side vapor chamber 104 is separated from the liquid chamber 102 by a pervaporation membrane 106. The vapor phase is extracted from the feed liquid through a selective permeate membrane 106 and an optional permeate vapor 106 for a given permeate which is enriched relative to the feed liquid, Is removed from the evaporation module (100).

Using block polymeric pervaporation membranes, pervaporation can be employed to treat fermentation broth containing, for example, biobutanol, ethanol or phenol and one or more other miscible components. More specifically, a fermentation broth can be added to the liquid chamber 102, thereby placing it in contact with one side of the pervaporation membrane 106 while applying vacuum or gas purging to the vapor chamber 104. The fermentation broth may be heated or non-heated. The components in the fermentation broth are adsorbed onto / onto the pervaporation membrane 106 and then vaporized into vapor phase. The resulting vapor or permeate, for example butanol (or phenol), is then condensed and collected. Even low concentrations of ingredients in the feed can be highly concentrated in the permeate due to the different species in the fermentation broth with different affinities for the pervaporation membrane and the different diffusion rates through the membrane. Thus, in one embodiment, a pervaporation membrane with preferential permeability to volatile organics in preference to water is provided. The permeability of the volatile organic material through the pervaporation membrane of the present invention generally increases with increasing organic concentration of the feed stream. In another embodiment, such volatile organics include, but are not limited to, butanol, phenol, and the like.

FIG. 2 shows an example of a method for separating butanol or other desirable materials from a crude fermentation broth (or aqueous industrial waste or other waste containing biomass-waste) containing valuable organic compounds such as biobutanol or phenol An exemplary pervaporation system 200 is shown. The crude fermentation broth (or other waste including industrial and / or biomass waste) as the feed stream 210 from the feed tank 205 is pumped through the pump 215 and passes through the heater 220 to raise its temperature . The fermentation broth is then introduced under pressure into a pervaporation module 225 containing a pervaporation membrane. A permeate vapor 230 containing butanol (or phenol) is obtained from the pervaporation module 225 by applying a vacuum (using a vacuum pump 245), wherein the butanol vapor (or phenol vapor) (235) and collected at the collector (240). The residual fermentation broth or residue stream 250 that does not pass through the polynorbornene pervaporation membrane may be discharged (255) from the system 200 or may be sent to the recycling stream 260 and returned to the feed tank 205.

Supplementary methods to complement the pervaporation process include removing solids from the fermentation broth by centrifugation, filtration, tilt separation, deflagration, and the like; And increasing the concentration of butanol in the permeate using adsorption, distillation or liquid-liquid extraction.

Butanol from biomass is often referred to as biobutanol. Biobutanol can be produced by fermentation of biomass by an acetone-butanol-ethanol fermentation (ABE) process. For example, SY Li, et al. Biotechnol. Prog. 2011, vol. 27 (1), 111-120). The process utilizes bacteria from the genus Clostridium , such as Clostridium acetobutylicum , but also uses Saccharomyces cerevisiae , Zymomonas mobilis , host lithium Thermo dihydro alcohol Puri glutamicum (Clostridium thermohydrosulfuricum), the Sherry Escherichia coli can be used, including other things (Escherichia coli), Pseudomonas Candida Tropical faecalis (Candida pseudotropicalis), and Clostridium bay yerin key (Clostridium beijerinckii). Biobutanol can also be prepared using transgenic yeast for the production of biobutanol from cellulosic materials. The crude fermentation broth containing biobutanol is advantageously processed by the pervaporation membrane shown in Figure 1 and / or the pervaporation system shown in Figure 2 to provide concentrated butanol compared to the butanol concentration in the crude broth . It should further be noted that the pervaporation membranes of the present invention are also useful for the separation of various alcohols other than butanol, including ethanol and phenol from each fermentation broth or industrial or biomass waste.

Fermentation broths generally contain a variety of carbon substrates. In addition to the carbon source, the fermentation broth may contain suitable minerals, salts, cofactors, buffers, and other ingredients known to those skilled in the art, suitable for promoting the growth of the cultures and the enzymatic pathways required for butanol production. Examples of commercially available fermentation broths include Luria Bertani (LB) broth, Sabouraud Dextrose (SD) broth, or yeast medium (YM) broth. Any of these known fermentation broths may be used in the present invention to separate volatile organics from such broth.

Similarly, it should be noted that other various organic products are selectively formed from the fermentation process. For example, phenols, sometimes referred to as " green phenols ", can be formed by using suitable biological organisms to effect fermentation from suitable wastes, including biological wastes or industrial wastes, and selectively to phenol. Phenol can be selectively produced from a recombinant strain of the solvent-resistant bacteria Pseudomonas putida S12 (see, for example, L. Heerema, et al., Desalination, 200 (2006), pp 485-487) Was reported. Other various yeast strains have also been reported to produce phenol, all of which are bacteria of the genus Saccharomyces such as Saccharomyces cerevisiae rf bajanus, EP 171 Lalvin ( Saccharomyces cerevisiae rf bayanus , EP 171 Lalvin); Sakaromayses Baranus, Ever ( Saccharomyces bayanus , Ever); Ceparo 20, Castelli ( Saccharomyces ellipsoideus, Ceppo 20 Castelli ); Cepamoises o bifomis , Ceppo 838 Castelli ( Saccharomyces oviformis, Ceppo 838 Castelli ); Sakaromayses Selivijia rf < / RTI > Serveiiae, K1 Lalvin ( Saccharomyces cerevisiae rf cerevisiae , K1 Lalvin); And saccharomyces D254 Lalvin ( Saccharomyces cerevisiae , D254 Lalvin) is used. These organisms can produce a different amount of phenolic material from a synthetic and / or natural organic source source where the major carbon source is glucose. [M. Giaccio, J. Commodity Science (1999), 38 (4), 189-200). Generally, " green phenol " as used herein refers to phenols produced by fermentation broth containing from about 0.1% to about 6% phenol. In another embodiment, the fermentation broth contains about 0.5% to about 3% phenol.

As used herein, " butanol " generically refers to n-butanol and its isomers. In some embodiments, according to the present invention, the fermentation broth contains about 0.1% to about 10% butanol. In another embodiment, the fermentation broth contains about 0.5% to about 6% butanol. In some other embodiments, the fermentation broth contains about 1% to about 3% butanol. Generally, the pervaporation membrane described herein is effective in separating volatile organics such as butanol, ethanol or phenol from a fermentation broth containing relatively low to high levels of volatile organics, and in some embodiments, the fermentation broth is at least about Contains 1% volatile organic matter.

It should be further noted that some of the " green phenol " feedstock may also be produced using phenolic resins such as novolak resins. Such a feed stream may also be used in the pervaporation process of the present invention in which phenol can be separated and / or condensed from the waste stream. Further, various such phenol streams may also contain certain inorganic and organic salts as impurities. As a result, it is difficult to remove such inorganic salts from the feed stream and it is difficult to obtain the phenol in pure concentrated form. Surprisingly, however, it has been found that the pervaporation membrane of the present invention can separate such inorganic and organic salts. Representative examples of inorganic salts include, without limitation, salts of lithium, sodium, potassium, magnesium, calcium, barium and the like. Salts of these metals with any counter anion can be used in the present invention. Examples of non-limiting anions include phosphates, sulfates, acetates, benzoates, and the like. However, other anions such as methanesulfonate (mesylate), trifluoromethanesulfonate (triflate), p-toluenesulfonate (tosylate), and halides such as fluoride, chloride, bromide and iodide It can also be separated from the feed stream.

In one embodiment, there is provided a process for separating an organic product from a feedstock selected from fermentation broth or industrial waste containing organic products such as butanol, ethanol, phenol, THF, ethyl acetate, acetone, toluene, MEK, MIBK, . In some embodiments, the fermentation broth is introduced into a pervaporation module containing a pervaporation membrane formed by any one of the block polymers as described herein. The permeate vapor containing the organic product is then collected from the pervaporation module. In the process, it may be advantageous to heat the crude fermentation broth feed to a temperature that promotes the passage of organic products through the pervaporation membrane of the present invention. In one embodiment, the crude fermentation broth feed is heated to a temperature of from about 30 캜 to about 110 캜. In another embodiment, the crude fermentation broth feed is heated to a temperature of from about 40 째 C to about 90 째 C. In another embodiment, the crude fermentation broth feed is heated to a temperature of from about 50 째 C to about 70 째 C. It should be noted that the desired temperature can depend on the type of organics being separated. For example, relatively lower temperatures are used for the separation of butanol, while slightly higher temperatures are preferred for the separation of phenol. Thus, in one embodiment, the fermentation broth containing the butanol feed is heated to a temperature in the range of about 30 캜 to about 90 캜. In another embodiment, the fermentation broth containing the phenol feed is heated to a temperature in the range of about 40 캜 to about 110 캜.

In order to facilitate pervaporation, a suitable vacuum can be applied to the vapor chamber of the pervaporation module. In one embodiment, the applied vacuum is from about 0.1 in Hg to about 25 in Hg. In another embodiment, the applied vacuum is from about 0.15 in Hg to about 5 in Hg. In another embodiment, the applied vacuum is from about 0.2 in Hg to about 4 in Hg.

Other processes include methods for increasing the separation factor for organic products such as butanol, phenol or ethanol as the concentration of the organic product increases in the pervaporative feed stream. Such a method involves the use of a pervaporation membrane to separate the organic product from the pervaporation feed stream.

As used herein, " SF " is a separation factor that is a measure of the quality of separation of a first species versus a second species and is defined as the ratio of the ratio of permeate composition to the feed composition.

As used herein, a flux is an amount that flows through a unit area of a membrane per unit time.

Flux and SF can also be described by the following equation:

Thus, the efficiency of the pervaporation membrane can be evaluated in at least two aspects of the separation factor (the ratio of the concentration obtained when the liquid mixture permeates through the membrane) and the flux through which the liquid mixture permeates the polymer membrane. Therefore, the higher the separation factor and flux of the membrane, the higher the separation efficiency of such membrane. Of course, this is a superanneal analysis since low separation factors can often be overcome through the use of a multi-stage membrane process, and when the flux coefficient of the membrane is low, it is often possible to overcome the low flux by forming such a membrane with a high surface area. Thus, although separation and flux coefficients are important considerations, other factors such as film strength, resilience, stain resistance during use, thermal stability, free volume, etc., are also important considerations in selecting the best polymer for pervaporation film formation .

The pervaporation membranes of the present invention can be used to produce volatile organics such as butanol, phenol or ethanol for providing effective means of removing volatile organics, such as butanol, phenol or ethanol, from fermentation broths as described herein or other wastes, (SF). ≪ / RTI > In one embodiment, the pervaporation membrane has a SF of at least about 5 for volatile organics such as butanol, phenol or ethanol. In another embodiment, the pervaporation membrane has a SF of at least about 10 for volatile organics such as butanol, phenol or ethanol. In another embodiment, the pervaporation membrane has a SF of at least about 15 for volatile organics such as butanol, phenol or ethanol. In another embodiment, the pervaporation membrane has a SF of at least about 20, at least about 25, or at least about 30 for volatile organics such as butanol, phenol or ethanol. When the concentration of volatile organic compounds in the feed stream such as butanol, phenol or ethanol is 0.5% or more, 1% or more, 2% or more, 3% or more, or 4% or more, or 5% or more, or 6% SF can be achieved.

Suitable fluxes for volatile organics such as butanol, phenol or ethanol can be achieved using the inventive block polynorbornene pervaporation membranes to provide an effective means of removing volatile organics such as butanol, phenol or ethanol from the fermentation broth. have. In one embodiment, a flux of at least about 100 g / m ² / hr for volatile organics such as butanol, phenol or ethanol can be achieved using such block polynorbornene pervaporation membranes. Using such a block polynorbornene pervaporation membrane, in another embodiment, a flux of at least about 150 g / m ² / hr for volatile organics such as butanol, phenol or ethanol can be achieved; In another embodiment, a flux of at least about 200 g / m ² / hr for volatile organics such as butanol, phenol or ethanol may be achieved, and in another embodiment, a volatile organics such as butanol, phenol or ethanol A flux of at least about 250 g / m < ² > / hr can be achieved. Moreover, unlike what is commonly found using previously known non-polynorbornene pervaporation membranes, the concentration of volatile organics such as butanol, phenol or ethanol in the feed stream is greater than 0.5%, greater than 1%, greater than 2%, greater than 3 % Or more, or 4% or more, or 5% or more, or 6% or more of the above-described fluxes.

Surprisingly, it has been found that various block polymers as described herein are suitable for use in pervaporation film formation. (E.g., glass transition temperature (T _g ), modulus, free volume, hydrophobicity, hydrolytic stability, etc.) of the polymer resulting from a suitable combination of diblock copolymers or triblock terpolymers as described herein, And tailoring of pervaporation properties (e. G., SF and flux). ≪ / RTI > It should further be noted that the block polymers of the present invention may be prepared to exhibit a relatively high glass transition temperature and the block polymers of the present invention may be prepared as pervaporation membranes at temperatures higher than is possible for currently known membranes. It is possible to provide an operational capability.

Advantageously, it has been found to be advantageous to the present invention that a combination of different types of blocks comprising different polynorbornene repeat units provides a membrane characterized by a favorable flux and separation factor. Thus, for example, a diblock polymer having a relatively alcoholphilic block containing monomeric repeat units derived from a monomer such as HFANB in combination with a relatively hydrophobic block containing monomer repeat units such as BuNB When used, diblock polymer HFANB-b-BuNB with surprising properties is provided. Such block polymers can be prepared to form micro-phase separated membranes characterized by specific properties in separating organic products from feedstocks such as those described above and below. More specifically, it is possible to control the performance of a film produced therefrom by increasing the molar ratio (i.e., weight fraction) of the alcohol affinity block (e.g., HFANB) to the present invention. For example, it has been found that the increase in the weight fraction of the alcohol affinity block generally increases not only the separation factor but also the flux, leading to the present invention. Thus, in one embodiment, the weight fraction of alcohol affinity block, for example diblock polymer HFANB-b-BuNB HFANB weight fractions W of _HFANB in the 0.5 to 0.95; From about 0.6 to about 0.85 in another embodiment; And in another embodiment 0.7 to 0.8. In some embodiments, the weight fraction of alcohol affinity block, for example diblock polymer HFANB-b-BuNB HFANB weight fractions W of _HFANB in 0.5.

Likewise, triblock polymers can be prepared by various combinations of alcohol affinity blocks and hydrophobic blocks, such as alcohol affinity block-hydrophobic block-alcohol affinity block; Hydrophobic block - alcohol affinity block - hydrophobic block; Hydrophobic block - hydrophobic block - alcohol affinity block; Alcohol affinity block-alcohol affinity block-hydrophobic block, and the like.

Thus, in one embodiment, a method is provided for separating an organic product from a feedstock selected from a fermentation broth or waste containing an organic product, comprising the steps of:

Feeding a feedstock to a pervaporation module containing a pervaporation membrane formed from the polymer of claim 1; And

Collecting permeate vapors containing organic products from the pervaporation module.

As already mentioned, pervaporation can be carried out at any desired temperature. Thus, in one embodiment, pervaporation is performed when the fermentation broth is fed to the pervaporation module at a temperature of from about 30 [deg.] C to about 110 [deg.] C. In this embodiment, the vacuum applied to the pervaporation module may range from about 0.1 in Hg to about 25 in Hg.

In this aspect of the process of the present invention, the pervaporation membrane is formed from a polymer selected from the following:

(HexNB-2) derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan- b-HFANB);

A block copolymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB- b-HFANB);

2.2.1] hept-2-ene and 1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl- Pyrrole-2,5-dione (C ₄ F ₉ NB-b-BuDMMINB);

2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2 .1] heptane (HFANB-b-NBANB); And

Block copolymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2- yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB).

In another embodiment, the method of this aspect of the invention comprises a pervaporation membrane formed of a polymer selected from the following:

2,2'-hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo [2.2. 1] hept-2-ene (BuNB-b-HFANB-b-BuNB); And

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept- A block terpolymer derived from fluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

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

In another aspect of the present invention, there is also provided a process for separating such volatile organic products, such as butanol or phenol, from a feedstock selected from volatile organics such as fermentation broth or wastes containing butanol or phenol. The method includes:

Feeding the feedstock to a pervaporation module containing a pervaporation membrane formed from a polymer selected from:

(HexNB-2) derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan- b-HFANB);

A block copolymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB- b-HFANB);

2.2.1] hept-2-ene and 1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl- Pyrrole-2,5-dione (C ₄ F ₉ NB-b-BuDMMINB);

2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2 .1] heptane (HFANB-b-NBANB);

Block copolymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2- yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB);

2,2'-hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo [2.2. 1] hept-2-ene (BuNB-b-HFANB-b-BuNB); And

2-trifluorobutyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept- A block terpolymer (HFANB-b-BuNB-b-HFANB) derived from romethyl-3,3,3-trifluoropropan-2-ol; And

Collecting the permeate vapor containing butanol or phenol from the pervaporation module.

In a further aspect of the invention there is provided a process for forming a film comprising the steps of pouring a solution of a block polymer of formula (VI) or (VII) as described herein onto a suitable substrate and drying the substrate at a suitable temperature to form a film A method is also provided. As already mentioned above, the drying of the so formed film can be carried out at any temperature to obtain the intended result. Typically, drying is performed at a temperature in the range of from about 30 ° C to about 120 ° C, and in some other embodiments, the drying temperature is from about 50 ° C to 100 ° C, or from 70 ° C to 90 ° C. The time required to dry the membrane may range from about 10 minutes to 1 day, or from 30 minutes to 20 hours, or from 1 hour to 16 hours.

Any of the inventive block polymers as described herein can be used to form membranes in this aspect of the invention. Non-limiting examples of such diblock copolymers can be listed as follows:

(HexNB-2) derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan- b-HFANB);

A block copolymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB- b-HFANB);

2.2.1] hept-2-ene and 1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl- Pyrrole-2,5-dione (C ₄ F ₉ NB-b-BuDMMINB);

2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2 .1] heptane (HFANB-b-NBANB); And

Block copolymers derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2- yl) bicyclo [2.2.1] heptane (HexNB-b-NBANB).

In another embodiment of this method of the invention, non-limiting examples of such triblock polymers that can be used to form the membranes of the present invention can be listed as follows:

2,2'-hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo [2.2. 1] hept-2-ene (BuNB-b-HFANB-b-BuNB); And

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept- A block terpolymer derived from fluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB).

Surprisingly, phase separation occurs when a solution of the block polymer is formed and dried in a suitable solvent or solvent mixture, which can be attributed to some of the excellent properties observed during the selective separation of organic volatiles from biomass or organic waste It came to light when it came to the invention. It has been observed for the present invention that a suitable choice of solvent or mixture of solvents to dissolve the block polymer results in such phase separation as observed by different surface morphologies. Examples of suitable solvents for dissolving the block polymer include hydrocarbon solvents such as toluene and other ether solvents such as tetrahydrofuran (THF). It has surprisingly been found that the use of a mixture of solvents, such as hydrocarbon solvents and ethers, such as toluene and THF, brings about a significant change in the surface morphology of the film formed therefrom.

The molar ratio of BuNB-HFANB of diblock film atomic force micrograph formed from the copolymer (FIG. 3) and the weight fraction W _HFANB of HFANB is 0.48 (: This aspect is the weight fraction W _HFANB of HFANB a 0.78 (21) 3 and 4, respectively, showing atomic force micrographs (FIG. 4) of membranes formed from a 2: 1 molar ratio of BuLB copolymers of BuNB-HFANB. (1: 2) molar ratio of a BuLB-HFANB diblock copolymer is formed using toluene as a solvent. (2: 1) molar ratio of BuLB-HFANB diblock copolymer is formed using THF as a solvent. As is apparent from Figures 3 and 4, these two films do not exhibit any nanoscale structure, i.e., any observable phase separation of the block. On the other hand, FIG. 5 shows an atomic force micrograph of a film formed from a (1: 1: 1) molar ratio of tri-block polymer of HFANB-BuNB-HFANB. This film is formed using a mixture of toluene and THF. It is very clear that it clearly shows the nanoscale structure demonstrating membrane phase separation. As described in more detail below, by using the membrane of FIG. 5 in the pervaporation process of the present invention, a much higher flux can be obtained than in the membranes of FIGS. 3 and 4, relative to the present invention (see Table 4). This clearly illustrates at least one of the surprising beneficial effects obtainable from the practice of the present invention.

The micro-phase separated form of the membrane can also be obtained by using a mixture of solvents in a modified procedure. Thus, in another embodiment of the present invention, the block polymer of the present invention is dissolved in a mixture of non-polar and polar solvents and cast on a suitable support to form a film, followed by evaporation of the solvent mixture to give a micro- . Examples of non-polar solvents include any hydrocarbon solvents such as hexane, heptane, toluene, trifluorotoluene (TFT), and mixtures thereof. Examples of polar solvents are ether solvents such as tetrahydrofuran (THF) and diethyl ether; Alcohols, such as butanol, pentanol, hexanol or heptanol (or C ₈ -C ₁₂ alcohol), and mixtures thereof. In general, membranes are prepared by solution casting methods as described herein in this aspect of the invention. That is, typically the block polymer is dissolved in a mixture of solvents such as toluene, TFT and THF, the solution thus formed is coated on a polyacrylonitrile (PAN) film, and then THF vapor annealing is performed. The annealing may be performed by any method known in the art, for example, by exposing the film in a THF chamber at a preferred temperature. In general, the membrane formed in this manner contains a uniform and dense layer of block polymer on the porous PAN support membrane and functions as a selective layer for the pervaporation separation of organic products in aqueous solution, such as biobutanol.

The following examples are a detailed description of specific compounds / monomers, polymers and compositions of the present invention and how they are prepared and used. The detailed preparation is within the scope of the more generally described manufacturing method described above and serves to illustrate the same. The embodiments are presented for illustrative purposes only and are not intended as limitations on the scope of the invention. As used throughout the examples and specification, the ratio of monomer to catalyst is mole to mole basis.

Example

The following abbreviations are used hereinbefore and hereinafter in describing some of the compounds, apparatus and / or methods employed to describe certain embodiments of the invention:

HFANB: norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol; HexNB: 5-hexylbicyclo- [2.2.1] hept-2-ene; C ₄ F ₉ NB: 5-perfluorobutylbicyclo [2.2.1] hept-2-ene; BuDMMINB: 1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione; PGMEA: propylene glycol methyl ether acetate; PTFE: polytetrafluoroethylene; TFT: alpha, alpha, alpha -trifluorotoluene; THF: tetrahydrofuran; RT - room temperature.

The reaction is generally carried out under a nitrogen atmosphere, if necessary in a dry box or using a standard Schlenk tube / airless transfer technique. Generally, the solvent is dried over molecular sieves or magnesium sulphate or distilled from the drying agent and purged with nitrogen prior to use. Various other known techniques for drying the solvent may also be used.

The following examples describe procedures used in the preparation of various compounds as disclosed herein, including the specific starting materials used in the preparation of the compounds of the present invention. It should be noted, however, that these embodiments are intended to illustrate the present disclosure without limiting its scope.

Example 1

Bis (iso-propoxy-dicyclopentadienyl) dichlorodipalladium [Pd (i-PrO-DCPD) Cl] ₂

The title compound was prepared according to Chatt et al., J. Chem. Soc. (1957) 3413] was prepared as follows using a slightly modified procedure. Sodium chloropalladite [Na ₂ PdCl ₄ ] (3 g, 10.2 mmol) was suspended in isopropyl alcohol anhydride (15 ml) under nitrogen atmosphere and stirred at ambient temperature. To the suspension was added dicyclopentadiene (2.7 g, 20.4 mmol) and the mixture was stirred continuously at ambient temperature for 5 days. The resulting mixture was filtered, washed with heptane (3 times with 5 ml), and dried to give 3.8 g of a yellow powder.

Under ambient conditions, 1 g of the yellow powder obtained above was suspended in heptane (15 ml), isopropyl alcohol (15 ml) was added to the suspension with stirring, and the mixture was stirred continuously at ambient temperature for 2 days Respectively. The mixture was then filtered and the solids washed with heptane to give the title compound as a yellowish yellow powder, 1.1 g. The title compound was characterized by ¹ H NMR and found to be essentially pure: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm) 6.46 (1 H), 5.88 (1 H), 3.72 H), 1.17 (1 H), and 1.12 (6 H), 2.1 (2 H) ).

Example 2

Bis (acetoxy-dicyclopentadienyl) dichlorodipalladium [Pd (AcO-DCPD) Cl] ₂

Under ambient atmospheric conditions toluene (20 ml) was added to a mixture of [Pd (DCPD) Cl] ₂ (0.5 g, 1.6 mmol) and silver acetate (AgOAc) (0.27 g, 1.6 mmol) with stirring. The resulting yellow suspension was stirred at ambient temperature for 1 hour. The resulting brown solution was filtered and the filtrate was evaporated to dryness to give an orange oil which was washed with 30 ml of ether and filtered to give the yellowish pink title compound. The title compound was characterized by ¹ H NMR and found to be essentially pure: ¹ H NMR (CD ₂ Cl ₂ , δ ppm), 6.51 (1 H), 5.93 (1 H), 4.87 2 H), 2.85 (1 H), 2.68 (3 H), 2.33 (1 H), 2.22 (2 H), and 1.96 (3 H).

Example 3

Bis (n-propoxy-dicyclopentadienyl) dichlorodipalladium [Pd (n-PrO-DCPD) Cl] ₂

Under a nitrogen atmosphere, n-propanol (25 ml) was added via cannula to a solid mixture of [Na ₂ PdCl ₄ ] (1 g, 3.4 mmol) and dicyclopentadiene (0.9 g, 6.8 mmol) with stirring. The resulting reddish brown suspension was stirred at ambient temperature for 1 day. The resulting pale beige suspension was filtered, washed three times with hexane (5 ml each) and dried under vacuum to give 1.5 g of the title compound. The title compound was characterized by ¹ H NMR and found to be essentially pure: ¹ H NMR (CD ₂ Cl ₂ , δ ppm), 6.48 (1 H), 5.87 (1 H), 3.59 1 H), 3.3 (1 H), 3.21 (1 H), 3.02 (1 H), 2.83 ), 1.6 (1H), 1.58 (4H), 1.06 (1H), 0.88 (3H).

Example 4

(I-PrO-DCPD) Cl (Pi-Pr ₃ )] (Pd (i-PrO-DCPD)

The compound [Pd (i-PrO-DCPD) Cl] ₂ (1 g, 1.5 mmol) of Example 1 was suspended in tetrahydrofuran (30 ml) under nitrogen atmosphere and stirred. To this suspension was added dropwise a solution of triisopropylphosphine (0.48 g, 3 mmol) in tetrahydrofuran (10 ml) via a cannula. At the end of the addition the suspension became clear and the solution was stirred for an additional 15 minutes, then concentrated to 10 ml and then filtered. The resulting yellow filtrate was stirred overnight and concentrated to dryness to give 1.25 g of the title compound as a yellow solid. The title compound was characterized by ¹ H NMR and ³¹ P NMR and found to be essentially pure: ¹ H NMR (toluene-d ₈ ,? Ppm), 7.59 (1 H), 7.15 ), 3.47 (1 H), 2.76 (1 H), 2.53 (4 H), 2.28 (2 H), 2.1 (2 H), 1.81 1.24 (18 H), 1.05 (6 H); ³¹ P NMR (toluene-d ₈ ,? Ppm) 50.93.

Example 5

(Pd (i-PrO-DCPD) Cl (PPh ₃ )] (chloropalladium) (triphenylphosphine)

(230 ml) was added to a mixture of Example 1 [Pd (i-PrO-DCPD) Cl] ₂ (3 g, 4.5 mmol) and triphenylphosphine (2.6 g, 9.9 mmol) Respectively. The resulting brown suspension was stirred at ambient temperature for 24 h, filtered, washed with ether, and then dried to yield 4.1 g of the title compound as a brown powder. The title compound was characterized by ¹ H NMR and ³¹ P NMR and found to be essentially pure: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm), 7.67 (6 H), 7.48 (9 H), 6.89 ), 3.88 (1H), 3.33 (1H), 2.93 (1H) 1.54 (1H), 1.27 (1H), 1.09 (1H), 0.99 (3H), 0.79 (3H); ³¹ P NMR (CD ₂ Cl ₂ ,? Ppm) 30.76.

Example 6

(n- propoxy-dicyclopentadienyl) chloro palladium (triisopropylphosphine) phosphine [Pd (n-PrO-DCPD ) Cl (Pi-Pr 3)]

Pd (n-PrO-DCPD) Cl] ₂ (0.5 g, 1.5 mmol) was suspended in tetrahydrofuran (15 ml) and stirred under nitrogen atmosphere. To this suspension was added dropwise a solution of triisopropylphosphine (0.24 g, 1.5 mmol) in tetrahydrofuran (5 ml) via a cannula. At the end of the addition the suspension became clear and the solution was stirred overnight and then filtered using a 0.45 mm polytetrafluoroethylene (PTFE) syringe filter. The filtrate was concentrated to dryness to give a yellow oil which was taken in petroleum ether (3 ml) and sonicated for 3 minutes to precipitate the title compound as a solid. The title compound was then filtered off and dried under vacuum (0.26 g). The title compound was characterized by ¹ H NMR and ³¹ P NMR and found to be essentially pure: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm), 7.05 (1 H), 6.78 (1 H), 3.61 ), 3.36 (1 H), 3.18 (1 H), 2.89 (2 H), 2.64 (5 H), 2.35 1.47 (3 H), 1.34 (18 H); ³¹ P NMR (CD ₂ Cl ₂ ,? Ppm) 50.16.

Example 7

(I-PrO-DCPD) (Pi-Pr ₃ ) (OTf)] (tri-isopropyl) phosphine palladium triflate

The compound [Pd (i-PrO-DCPD) Cl (Pi-Pr ₃ )] (0.25 g, 0.5 mmol) of Example 4 was dissolved in dichloromethane (3 ml) and stirred under an inert atmosphere of nitrogen in a dry box . To this stirring solution was added a suspension of silver triflate AgOTf (0.13 mg, 5 mmol) in dichloromethane (2 ml) followed by a suspension of silver triflate AgOTf (0.13 mg, 5 mmol) in tetrahydrofuran , Resulting in a milky pale yellow suspension. The mixture was stirred for 10 minutes and then filtered through a 0.45 mm polytetrafluoroethylene (PTFE) syringe filter. The yellow filtrate thus obtained was concentrated to dryness to give an oily residue which was dissolved in diethyl ether (2 ml) and dried in vacuo to give 0.14 g of the title compound as a beige-white foamy solid Respectively. The title compound was characterized essentially as pure by characterization by ¹ H, ³¹ P and ¹⁹ F NMR: ¹ H NMR (toluene-d ₈ ,? Ppm), 7.3 (1 H), 6.8 (1 H), 3.55 1 H), 1.41 (1 H), 1.51 (1 H), 1.16 (1 H), 2.41 ), 1.06 (9H), 0.98 (6H), 0.86 (1H); ³¹ P NMR (toluene-d ₈ ,? Ppm), 50; ¹⁹ F NMR (toluene-d ₈ ,? Ppm), -77.3.

Example 8

(I-PrO-DCPD) (Pi-Pr ₃ ) (CH (CH ₃ ) ₂ ) (tri-isopropyl) phosphine (acetonitrile) palladium tetrakis (pentafluorophenyl) ₃ CN)] FABA

Was added with stirring in a nitrogen atmosphere, in Example 4 the compounds [Pd (i-PrO-DCPD ) Cl (Pi-Pr 3)] (5.1 g, 10.2 mmol) in toluene (25ml). To this solution was added a solution of lithium tetrakis (pentafluorophenyl) borate (LiFABA) (8.92 g, 10.2 mmol) in acetonitrile (25 ml) via a cannula. The clear yellow solution became cloudy, stirred overnight and then filtered through celite. The filtrate was concentrated to obtain a thick slurry mass. To the slurry mass was added pentane (50 ml) and ether (50 ml) to give a yellow solid which was filtered, washed with pentane (25 ml) and dried in vacuo to give 9.9 g (yield: 82% ≪ / RTI > The title compound was characterized essentially as pure by ¹ H and ³¹ P NMR: ¹ H NMR (acetone-d ₆ ,? Ppm), 7.17 (1 H), 6.76 (1 H), 3.85 , 2.72 (2 H), 2.1 (1 H), 1.56 (1 H), 1.42 (1 H) (18 H), 1.18 (1 H), 1.09 (6 H); ³¹ P NMR (acetone-d ₆ ,? Ppm), 52.19.

Example 9

(P-PrO-DCPD) (Pi-Pr ₃ ) (p) (tri-isopropyl) phosphine (pyridine) palladium tetrakis (pentafluorophenyl) ] FABA

Under nitrogen, it was subjected to Example 8 dissolved in the compound [Pd (i-PrO-DCPD ) (Pi-Pr 3) (CH 3 CN)] FABA (0.25 g, 0.212 mmol) in toluene (5 ml) and stirred. Pyridine (90 ml) was added via syringe to the solution, resulting in a pale yellow solution. The solution was concentrated to dryness to give a yellow oil which was dissolved in diethyl ether (1 ml) then evaporated to dryness to afford 0.18 g of the title compound as a white foamy solid. The title compound was characterized essentially as pure by ¹ H and ³¹ P NMR: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm), 8.54 (2 H), 7.92 (1 H), 7.54 (2 H) , 7.08 (1 H), 5.41 (1 H), 3.82 (1 H), 3.72 (1 H), 3.06 (2 H), 2.75 (6 H), 1.65 (1 H), 1.39 (18 H), 1.18 (6 H); ³¹ P NMR (CD ₂ Cl ₂ ,? Ppm), 50.35.

Example 10

(Iso-propoxy-dicyclopentadienyl) (triisopropyl) phosphine (acetonitrile) borate to palladium tetrafluoroborate [Pd (i-PrO-DCPD ) (Pi-Pr 3) (CH 3 CN)] BF ₄

In a dry box, the compound [Pd (i-PrO-DCPD) Cl (Pi-Pr ₃ )] (1 g, 2 mmol) of Example 4 was suspended in toluene (10 ml) with stirring under an inert atmosphere of nitrogen. To this suspension was added a solution of silver tetrafluoroborate AgBF ₄ (0.4 g, 2 mmol) in acetonitrile (5 ml) via a pipette. The suspension quickly cleared, a gray solid precipitated, stirring continued for 5 minutes, and then filtered through a 0.45 mm polytetrafluoroethylene (PTFE) syringe filter. The filtrate was concentrated to dryness to give a yellow oily residue which was washed twice with pentane (5 ml) and then taken up in diethyl ether (5 ml). The resulting solution was concentrated to dryness to give 820 mg of the title compound as a pale pale foam solid. The title compound was characterized by ¹ H NMR and ³¹ P NMR and found to be essentially pure: ¹ H NMR (CDCl ₃ ,? Ppm), 7.21 (1 H), 6.51 (1 H), 3.77 3.67 (1H), 2.96 (2H), 2.71 (2H), 2.46 (7H), 2.21 (2H), 1.58 (2H); ³¹ P NMR (CD ₂ Cl ₂ ,? Ppm), 52.49.

Example 11

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB)

Homopolymer

Example 11 illustrates the high catalytic activity of the compounds of the present invention as compared to the palladium catalyst reported in the literature, some of the comparative examples are provided below as Comparative Example 1 and Comparative Example 2, Were carried out under essentially the same conditions to show differences in the respective catalytic activities of the compounds used.

A suitable reaction vessel was charged with HFANB (1 g, 3.7 mmol) and toluene (3 g), sparged with nitrogen for 30 min and then heated to 80 < 0 > C. To this solution was added a solution of the compound of Example 8 (0.022 g, 0.018 mmol) in toluene (1 ml). The mixture was stirred for 30 minutes and then cooled to room temperature. A solution of ((phenylphosphandiyl) bis (ethane-2,1-diyl)) bis (diphenylphosphane), tripos (0.04 g, 0.06 mmol) in dichloromethane (0.3 ml) Respectively. The mixture was then poured into excess ethanol (10 mL) to precipitate the polymer to give 1 g of polymer (100% conversion). The polymer was characterized by GPC: M _w = 60,600; M _n = 16,700; PDI = 3.6.

Examples 12 to 15

The homopolymerization of the compound of Example 4

Except that various different monomers as listed in Table 1 were used in a 100: 1: 1 molar ratio of monomer: catalyst: LiFABA in combination with the compound of Example 4 and lithium tetrakis (pentafluoroborate) LiFABA as polymerization catalysts. In Examples 12 to 15, Example 11 was substantially repeated. The reaction was stopped at the end of the indicated reaction time and the solvent was evaporated. The residual mass was dissolved in THF and filtered. The polymer solution was then poured into water or acetone to precipitate the polymer. The thus obtained powdery polymer was subsequently collected, dissolved in THF, and then the solution was poured into water or acetone to precipitate again twice.

The GPC data of the monomers used in each of Examples 12 to 15, the solvent used, the temperature of the polymerization reaction, the reaction time, the conversion rate and the resultant polymer are summarized in Table 1.

[Table 1]

Examples 15A to E

The following Examples 15A-E provide the procedures for preparing the various methyl (palladium) phosphine compounds used in the preparation of the living polymer of the present invention.

Example 15A

[(CH ₃ ) Pd (P ^t Bu ₃ ) (Cl)]

See K. The title compound was prepared using a slightly modified procedure as described in Nozaki et al., Organometallics, 2006, 4588. [(1,5-Cyclooctadiene) Pd (CH ₃ ) (Cl)] (2.5 g, 9.43 mmol) was dissolved in anhydrous methylene chloride (2.5 ml) and stirred at -78 ° C under a nitrogen atmosphere. To this solution was added tri-tert-butylphosphine (1.91 g, 9.43 mmol) in methylene chloride solution (2 mL) and the mixture was kept stirring at -78 ° C for 5 minutes. The mixture solution was then allowed to warm to ambient temperature and continued stirring for 15 minutes. The resulting mixture was filtered, washed with n-pentane (3 x 10 ml), and dried to give 2.73 g of the title compound as a yellow powder.

The title compound was characterized essentially as pure by characterizing by ¹ H NMR and ³¹ P-NMR: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm) 1.75 (s, 3 H), 1.52 (d, 12 Hz, 27 H ). 31 P-NMR (CD ₂ Cl ₂ , 隆 ppm) 69.5

Example 15B

_{[(CH 3) Pd (P} (t Bu) 2 (Cy)) (Cl)]

_{[(1,5-cyclooctadiene) Pd (CH 3) (Cl} )] (300 mg, 1.1 mmol) and di -tert- butyl-cyclohexyl phosphine except that the pin (260 mg, 1.1 mmol) Was carried out substantially as in Example 15A to give 280 mg of the title compound as a pale yellow powder.

The title compound was characterized essentially as pure by characterizing by ¹ H NMR and ³¹ P-NMR: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm) 2.35 (m, 2H), 1.75 1.52 (m, 18 H), 1.30 (m, 4 H), 0.82 (s, 3 H). ³¹ P-NMR (CD ₂ Cl ₂ ,? Ppm) 71.5

Example 15C

[(CH ₃ ) Pd (P ( ^t Bu) ₂ ( ⁱ Pr)) (Cl)]

But using propyl phosphine (320 mg, 1.7 mmol) - [(1,5- _{cyclooctadiene) Pd (CH 3) (Cl} )] (430 mg, 1.62 mmol) and di -tert- butyl-iso The procedure of Example 15A was followed substantially to yield 380 mg of the title compound as a pale yellow powder.

The title compound was characterized by ¹ H NMR and ³¹ P-NMR and found to be essentially pure: ¹ H NMR (CDCl ₃ ,? Ppm) 2.8 (m, 1H), 1.54 (m, 24 H) 0.79 , 3H). _{^{31 P-NMR (CDCl 3,}} δ ppm) 71.5.

Example 15D

_{[(CH 3) Pd (P} (Cy) 3) (Cl)]

_{[(1,5-cyclooctadiene) Pd (CH 3) (Cl} )] (600 mg, 2.3 mmol) and tri-cyclohexyl-phosphine (630 mg, 2.3 mmol) and Example 15A but using To give 350 mg of the title compound as a pale yellow powder.

The title compound was characterized by ¹ H NMR and ³¹ P-NMR and found to be essentially pure: ¹ H NMR (CDCl ₃ ,? Ppm) 1.8 (m, 23 H), 1.32 (m, 10 H), 0.79 s, 3H). _{^{31 P-NMR (CDCl 3,}} δ ppm) 47.

Example 15E

_{[(CH 3) Pd (P} (i Pr) 3) (Cl)]

_{[(1,5-cyclooctadiene) Pd (CH 3) (Cl} )] (210 mg, 0.8 mmol) and tri-in Example 15A except that isopropyl phosphine (130 mg, 0.8 mmol) To give 180 mg of the title compound as a pale yellow powder.

The title compound was characterized essentially as pure by characterizing by ¹ H NMR and ³¹ P-NMR: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm) 2.40 (m, 3 H), 1.42 (m, 18 H) 0.72 (s, 3 H). ³¹ P-NMR (CD ₂ Cl ₂ , 隆 ppm, 50 属 C) 56.6.

Example 15F

[(CH ₃ ) Pd (P ( ⁱ Pr) ₂ ( ^t Bu)) (Cl)]

Except that 500 mg (1.9 mmol) of [(1,5-cyclooctadiene) Pd (CH ₃ ) (Cl)] and di-isopropyl-tert- butylphosphine Was carried out substantially as in Example 15A to give 510 mg of the title compound as a pale yellow powder.

The title compound was characterized essentially as pure by characterizing by ¹ H NMR and ³¹ P-NMR: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm) 2.55 (m, 2 H), 1.52 (m, (s, 3 H). ³¹ P-NMR (CD ₂ Cl ₂ , 隆 ppm, RT) 66.5.

Example 15AA to AI

The following Examples 15AA through 15 AI provide procedures for preparing various allyl (palladium) phosphine and imidazole compounds used in the preparation of the living polymer of the present invention.

Example 15AA

[(? ³ -allyl) Pd (P ( ⁱ Pr) ₃ ) (Cl)]

[(Η ³ -Allyl) Pd (Cl)] ₂ (4 g, 10.9 mmol) was dissolved in anhydrous toluene (100 ml) and stirred at -78 ° C under a nitrogen atmosphere. To this solution was added tri-iso-propylphosphine (3.68 g, 23 mmol) in toluene solution (50 mL) and the mixture was stirred continuously at-78 C for 5 min. The mixture was then allowed to warm to ambient temperature and then continued stirring for 2 days. The resulting mixture was evaporated to dryness and the resulting solid was dissolved in THF (48 ml). After stirring for 5 hours, the solution was filtered to remove any metal and then evaporated to dryness. The resulting solid was washed with diethyl ether (3 x 20 ml) and dried to give 5.7 g of the title compound as a pale yellow powder.

The title compound was characterized essentially as pure by characterizing by ¹ H NMR and ³¹ P-NMR: ¹ H NMR (CDCl ₃ ,? 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). _{^{31 P-NMR (CDCl 3,}} δ ppm) 53.

Example 15AB

[(? ³ -allyl) Pd (P ( ^t Bu) ₃ ) (Cl)]

The procedure of Example 15AA was substantially carried out except that tri-tert-butylphosphine (420 mg, 2.08 mmol) in toluene solution (15 mL) was used to obtain 310 mg of the title compound as yellow powder.

The title compound was characterized essentially as pure by characterizing by ¹ H NMR and ³¹ P-NMR: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm) 5.48 (m, 1H), 4.65 (m, 4.23 (m, 1H), 3.78 (m, 1H), 2.75 (m, 1H), 1.60 (m, 27H). ³¹ P-NMR (CD ₂ Cl ₂ , 隆 ppm) 88.

Example 15AC

[(? ³ -allyl) Pd (P (Cy) ( ^t Bu) ₂ ) (Cl)]

The procedure of Example 15AA was substantially carried out except that di-tert-butylcyclohexylphosphine (620 mg, 2.73 mmol) in toluene solution (15 mL) was used to obtain 350 mg of the title compound as a pale yellow powder Respectively.

The title compound was characterized essentially as pure by characterizing by ¹ H NMR and ³¹ P-NMR: ¹ H NMR (CD ₂ Cl ₂ ,? Ppm) 5.48 (m, 1H), 4.65 (m, 4.23 (m, 1H), 3.78 (m, 1H), 2.75 (m, 1H), 1.80-1.40 (m, 29H). ³¹ P-NMR (CD ₂ Cl ₂ , 隆 ppm) 72.

Example 15AD

[(? ³ -allyl) Pd (P ( ⁱ Pr) ( ^t Bu) ₂ ) (Cl)

The procedure of Example 15AA was substantially carried out except that di-tert-butyl-isopropylphosphine (510 mg, 2.73 mmol) in toluene solution (10 mL) was used to obtain 480 mg of the title compound as a pale yellow powder .

The title compound was characterized essentially as pure by characterizing by ¹ H NMR and ³¹ P-NMR: ¹ H NMR (CDCl ₃ ,? 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). _{^{31 P-NMR (CDCl 3,}} δ ppm) 71.8.

Example 15AE

[(? ³ -allyl) Pd (P ( ⁱ Pr) ₂ ( ^t Bu)) (Cl)]

The procedure of Example 15AE was substantially followed except that tert-butyl-diisopropylphosphine (480 mg, 2.73 mmol) in toluene solution (10 mL) was used to obtain 490 mg of the title compound as a pale yellow powder Respectively.

The title compound was characterized essentially as pure by characterizing by ¹ H NMR and ³¹ P-NMR: ¹ H NMR (CDCl ₃ ,? 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, 2H). _{^{31 P-NMR (CDCl 3,}} δ ppm) 63.2.

The following palladium compound was purchased from Johnson Matthey and used as such:

Example 15 AF

Example 15 AG

Example 15AH

Example 15AI

Example 16A

Homopolymer of 5-butyl-2-norbornene (BuNB)

BuNB (1.2 g, 7.98 mmol), toluene (22.32 g) and alpha, alpha, alpha -trifluorotoluene (TFT) (0.48 g) purged with nitrogen were placed in a suitable reaction vessel. To this solution was added a solution of the compound of Example 15A (30 mg, 0.79 mmol) and lithium tetrakis (pentafluoroborate) LiFABA (70 mg, 0.79 mmol). After polymerization for 20 minutes, the reaction solution was sampled and then inactivated with toluene / CH ₃ CN solution. The polymer was characterized by GPC: M _w = 34,509; M _n = 30,752; PDI = 1.1.

Examples 16B to 16R

Homopolymerization of functionalized norbornene using the compounds of Examples 15A to 15E

Homopolymerization of the various norbornene monomers and the Example 15A to 15E to the palladium compound was carried out using substantially the same procedure as described in Example 16A. The GPC data of the norbornene, the solvent used, the reaction time, the conversion rate and the resultant polymer used in each of these Examples 16B to 16R are summarized in Table 1A. In each of these Examples, the molar ratio of the Pd compound, LiFABA and norbornene monomer was Pd compound / LiFABA / NB monomer = 1/1/100.

[Table 1A]

Example 16AA

Homopolymer of 5-butyl-2-norbornene (BuNB)

BuNB (1.2 g, 7.98 mmol), toluene (22.32 g) and alpha, alpha, alpha -trifluorotoluene (TFT) (0.48 g) purged with nitrogen were placed in a suitable reaction vessel. To this solution was added a solution of the compound of Example 15AA (31 mg, 0.079 mmol) and lithium tetrakis (pentafluoroborate) LiFABA (70 mg, 0.079 mmol). After 20 minutes, the reaction solution was sampled and inactivated with toluene / CH ₃ CN solution. The polymer was isolated and characterized by GPC: M _w = 25,239, M _n = 22,243, PDI = 1.1.

Example 16 AB to AS

Example 15 < RTI ID = 0.0 > Homopolymerization < / RTI >

Homopolymerization of the various norbornene monomers and the Example 15AA to 15AI into the palladium compound was carried out using substantially the same procedure as described in Example 16A. GPC data of the norbornene, solvent used, reaction time, conversion rate and resultant polymer used in each of these Examples 16AB to 16AS are summarized in Table 1B. In each of these Examples, the molar ratio of the Pd compound, LiFABA and norbornene monomer (Pd compound / LiFABA / NB monomer) was 1/1/100.

[Table 1B]

From the above data, it can be seen that, as summarized in Tables 1A and 1B above, the allyl (palladium) phosphine compounds of Examples 15AA-AI generally have a higher (methylphenyl) phosphine compound than the corresponding methyl (palladium) phosphine compounds of Example 15AE Reactive and more living-like characteristic. ≪ RTI ID = 0.0 >

Examples 16 to 20

Diblock polymer

Example 11 was substantially repeated in these Examples 16 to 20, except that the biprolox polymer was formed using various different monomers as listed in Table 2. < tb >< TABLE > In all of these examples, a bipolar polymer was obtained by polymerizing the first monomer and then adding the second monomer to the resulting polymer mixture. The polymerization catalysts used in these Examples 16 to 20 were: Monomer 1: Monomer 2: Catalyst: LiFABA < RTI ID = 0.0 > [Pd (allyl) (triisopropylphosphine) Cl] with lithium tetrakis (pentafluoroborate), LiFABA at 100: 100: 1: The solvent used in each of these examples was toluene and the polymerization was carried out at room temperature, except that in Example 20 a 50:50 (v / v) mixture of toluene and trifluorotoluene was used. The resulting residual mass was re-precipitated by dissolving in THF as described in Examples 12-15 and filtering the solution followed by reprecipitation in water or acetone.

GPC data of the monomers used in each of these Examples 16 to 20, the monomer ratio in the resulting polymer, the reaction time, the conversion rate and the resultant polymer are summarized in Table 2.

[Table 2]

Examples 21 to 24

Diblock polymer

Example 11 was substantially repeated in these Examples 21 to 24 except that a biproton polymer was formed using various different monomers as listed in Table 3. [ In all of these examples, a bipolar polymer was obtained by polymerizing the first monomer and then adding the second monomer to the resulting polymer mixture. The polymerization catalysts used in these Examples 21 to 24 were the same as in Example 23, except that in Example 23, the monomer 1: monomer 2: catalyst: LiFABA molar ratio was 500: 500: 1: (Pd (methyl) (triisopropylphosphine) Cl] with lithium tetrakis (pentafluoroborate) LiFABA in a molar ratio of 100: 100: 1: 1. Polymerization was carried out at room temperature, except that the solvent used in each of these examples was toluene, except that trifluoro toluene was used in Example 24, and in Example 24 polymerization was carried out at 45 ° C. As in Examples 12 to 15, the polymerization was terminated at the end of the indicated reaction time and the solvent was evaporated to isolate the polymer. The resulting residual mass was re-precipitated by dissolving in THF as described in Examples 12-15 and filtering the solution followed by reprecipitation in water or acetone.

GPC data of the monomers used in each of these Examples 21 to 24, the monomer ratio in the resulting polymer, the time, the conversion rate and the resultant polymer are summarized in Table 3.

[Table 3]

Example 25

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

Except that the polymerization catalyst used in this Example was the compound of Example 4 with lithium tetrakis (pentafluoroborate), LiFABA in a ratio of 100: 100: 1: 1 of monomer 1: monomer 2: catalyst: LiFABA In Example 25, Example 11 was substantially repeated. The polymerization was carried out in a 50:50 (v / v) mixture of toluene and trifluorotoluene at room temperature. Monomer 1, HFANB, was first polymerized at room temperature for 60 minutes, then the polymer sample was analyzed by GPC, the number average molecular weight M _n was found to be 49,000, the PDI was 1.2, and the conversion was 89%. Monomer 2, BuNB, was then added to the reaction mixture and polymerization continued for 15 minutes, at which time the monomer conversion was 100%. The procedure was then substantially followed as described in Examples 12 to 15 to terminate the polymerization and isolate the polymer. The resulting diblock polymer HFANB-b-BuNB showed 102,000 M _n with a PDI of 1.2 according to GPC.

Example 26

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

Example 11 was substantially repeated in this Example 26 except that BuNB and HFANB monomers were used to form the title triblock polymer. First monomer 1, BuNB was first polymerized, followed by addition of monomer 2, HFANB to the resulting polymer mixture to form a diblock polymer, and in the final step monomer 3, BuNB was added to form the title triblock polymer . The polymerization catalyst used in this Example 26 was a mixture of lithium tetrakis (pentafluoroborate) and LiFABA in the ratio of 100: 100: 100: 1: 1 of the monomer 1: monomer 2: monomer 3: catalyst: LiFABA, Triisopropylphosphine) chloride, and [Pd (allyl) (triisopropylphosphine) Cl]. The solvent used was toluene and the polymerization was carried out at room temperature. A first polymerization to BuNB was conducted for 9 minutes, 97% conversion, M _n = 35,000, PDI is 1.1; The second polymerization to HFANB was carried out for 60 minutes with a 95% conversion, M _n = 80,000, PDI 1.1; Final polymerization with BuNB was carried out for 3 minutes with 97% conversion, M _n = 108,000, PDI 1.2.

Examples 26A to C

Other various diblock and triblock polymers

In these Examples 26A to 26C, a bubble rock and a triblock polymer were synthesized by sequentially adding respective norbornene monomers at room temperature under a nitrogen atmosphere. The total monomer concentration was 4 wt%. Representative procedures for the preparation of BuNB- b- HFANB, Example 26A included: _{(T -Bu 3 P) PdMeCl (} 12 mg, 0.033 mmol), LiFABA (29 mg, 0.033 mmol), toluene (6 g), and the TFT (6 g) a magnetic stir bar was placed in a 250 mL round bottom flask equipped with a , And the mixture was stirred for 5 minutes. BuNB (0.5 g, 3.3 mmol) was injected into the flask at once under vigorous stirring. After complete consumption of BuNB (30 min), a small aliquot of the reaction mixture was quenched with acetonitrile for GPC analysis of the poly (BuNB) block. HFANB (1.8 g, 6.6 mmol) in toluene / TFT (44 g, 50/50 wt%) was then added to the reaction flask. HFANB was polymerized for 2 days. The block copolymer was recovered by repeated precipitation into methanol / H ₂ O (50/50 vol%). The resulting polymer was dissolved in THF and the solution was stirred on charcoal followed by passing through an alumina plug to remove the residual Pd catalyst. The resulting filtrate was precipitated in methanol / H ₂ O (50/50 vol%) and subsequently dried at 60 ° C under vacuum. The other two block polymers BnNB-bC ₄ F ₉ NB (Example 26B) and a BuNB-b-BnNB-b- NBANB ( Example 26C), the ratio of each monomer, solvent, reaction times, percent conversion, M _n, and The PDI was prepared using the same procedure, except for summarizing in Table 3A.

[Table 3A]

^a polymerization from 4 wt% of each monomer in each solvent; ^b Tol = toluene; ^c TFT = alpha, alpha, alpha -trifluorotoluene; ^d NMR; ^e Measured by GPC using a differential refractive index (RI) detector calibrated with a narrow distribution polystyrene standard (THF)

Examples 26D to G

Block copolymers of HFANB-b-BuNB (different monomer ratios)

These Examples 26D-G illustrate in more detail the preparation of diblock polymers having different monomer ratios (i.e., molar ratios) of HFANB and BuNB using ( η ³ -allyl) Pd ( i -Pr ₃ P) Cl.

Representative procedures for the preparation of BuNB- b- HFANB, Example 26D included the following. BuNB (0.99 g, 6.6 mmol) and toluene / TFT (19 g, 50/50 wt%) were charged to a suitable reaction vessel equipped with a magnetic stir bar and the mixture was stirred for 5 minutes before the injection of the initiator solution. 0.23 mL of a 0.50 M solution of ( ? ³ -allyl) Pd ( i- Pr ₃ P) Cl in a TFT (39 mg, 0.12 mmol) and a solution of TFT (100 mg, 0.12 mmol) in a vial equipped with a magnetic stirrer bar 0.23 mL of a 0.50 M solution of LiFABA was added and stirred for 20 minutes to activate the Pd development reagent. 0.30 mL of (η ³ - _{allyl) Pd (i -Pr 3 P)} Cl / Li [FABA] solution ((η ³ - allyl) Pd (P i -Pr ₃₎ Cl and Li [FABA] 0.075 mmol with respect to each ) Was injected into a flask containing BuNB solution at once under vigorous stirring. After complete consumption of BuNB (15 min), a small aliquot of the reaction mixture was quenched with acetonitrile for GPC analysis of the first poly BuNB block. HFANB (4.4 g, 16 mmol) in toluene / TFT (83 g, 50/50 wt%) was then added to the reaction flask. HFANB was polymerized for 3 hours. The block copolymer was recovered by repeated precipitation into MeOH / H ₂ O (50/50 vol%). The polymer so obtained was dissolved in THF, the solution was stirred on activated carbon and then passed through an alumina plug to remove the residual Pd catalyst. The resulting filtrate was precipitated in MeOH / H ₂ O (50/50 vol%) and subsequently dried under vacuum at 60 ° C. Other block copolymers of BuNB-b-HFANB were prepared using substantially the same procedure, varying the monomer feed composition, the weight fraction of _HFANB , and _HFANB as summarized in Table 3B. Table 3B also shows the number average molecular weight M _n measured by GPC using a mole ratio of the block polymer, the degree of polymerization DP, a polyhedral laser light scattering (LS) detector (THF), and a differential refractive index ) Detector to determine the polydispersity PDI measured by GPC.

[Table 3B]

These results again demonstrate that ( η ³ -allyl) Pd ( i- Pr ₃ P) Cl is a more reactive initiator resulting in a higher molecular weight polymer as summarized in Table 3B. All of the polymers of Examples 26D to 26G were also characterized by differential scanning calorimetry (DSC). No glass transition from DSC to 200 占 폚 was detected for any of the polymers of Examples 26D to 26G.

Example 27

Manufacture of membranes

Single Thick Film or Thin Film Composite (TFC) Membrane: A solution is prepared by dissolving a polymer formed according to the present invention, specifically as exemplified in any one of Examples 16 to 26, in an organic solvent, followed by filtration . After filtration, the trapped gas is removed. The polymer is poured onto a substrate, pulled to form a film, and dried to be ready for use. In some cases, the film may be dried and removed from the substrate and used as a non-supporting film.

Specifically, a polymer (10 g) formed in Example 16 was dissolved in THF (100 g) to prepare a solution, which was then filtered with a 5 micron nylon filter. After filtration, the solution was rolled on a jar roller overnight to remove trapping gas introduced during filtration. The polymer solution was poured into a PAN ultrafiltration substrate and pulled using a Gardner film casting knife to form a film having an essentially uniform thickness. The film was dried in air for 1 hour, followed by annealing at 60 DEG C for 10 minutes to form a TFC film. In parallel, the film was coated on a glass substrate and the thickness was measured using a Dektak profilometer.

Double Thick Film: A double thickness film is prepared in a similar manner to a single film, except that the second layer of solution is provided on the first film and then the second film is pulled before removing the first film from the substrate . After pulling the second film, the dual film is dried, then removed from the substrate and ready for use.

For example, after about 5 hours from the first film casting, a second aliquot of the polymer solution is poured over the first film, and the second layer is provided by pooling it with a Gardner film casting knife as above A single thick film example is performed. After pulling the second film, the film is dried in air overnight.

Example 27A

The membranes of the polymers of Examples 26D to G

A thin film composite membrane having a dense polymer coating layer of the block polymer of Examples 26D to G was prepared on the upper surface by a simple blade coating method using a PAN membrane as a support. A 10 wt% solution was prepared by dissolving the block polymers of Examples 26D-G in a toluene / TFT / THF mixture (40/40/20 wt%) and filtered through a 0.45 μm pore PTFE filter. Each of the polymer solutions thus formed was poured into a PAN membrane supported by a glass plate and pulled with a film casting knife (25 μm gap height) to form a film of uniform thickness. The coating was slowly dried and annealed in a THF chamber for 2 hours to effect micro-phase separation of the block copolymer. After the film was dried on a hot plate at 60 DEG C for 1 hour, the film was then dried under vacuum at 60 DEG C overnight.

Example 28

Pervaporation test

The membrane was cut into 2-inch diameter circles for placement in capsules and then placed in a pervaporation test apparatus. The feed liquid in the test apparatus was heated to the desired temperature to circulate in the bypass mode and then circulated in the membrane housing at 450 mL / min in continuous mode to check for leaks. After completion of the check, the vacuum was pulled to the dry side of the membrane and the permeate was collected in a cooling trap (cooled with liquid nitrogen). The system was run for 3 hours and the collected permeate was evaluated by warming to room temperature.

Evaluation of permeate

The room temperature permeate collected / recovered as described above was separated into two phase liquids. MeOH was added to the permeate to make the phase miscible, thereby providing a single phase permeate. The single phase permeate (1 g) was added to a GC sampling vial containing 0.02 g PGMEA and mixed thoroughly. Subsequently, a sample from the vial was injected into the gas chromatograph where% butanol or% phenol was determined by evaluating the area of the butanol or phenol peak relative to the PGMEA standard.

In addition to forming a flat sheet membrane supported on the PAN ultrafiltration substrate, the likelihood of forming a hollow fiber including the inventive block polymer embodiments can be assessed. The following procedure is used to successfully form hollow fibers for further evaluation.

Example 29

Manufacture of Hollow Fiber Film

For example, the block polymer formed in accordance with the present invention, as specifically disclosed in any one of Examples 16-26, is dissolved in an organic solvent and filtered to remove the particles. The solution is then pressure-transferred through the outer bore of the spinneret while the solvent and salt mixture is pressure-transferred through the inner bore of the spinneret. These pressure transferred materials are passed straight through the settling bath to provide hollow fibers. The dimensions of the hollow fiber can be controlled by the size and pressure of the inner and outer diameters to which the solution is transferred.

For example, the block copolymer BuNB-b-HFANB (1: 1) of Example 18 is dissolved in THF at 10 wt% and the particles are removed by filtration through a 100 micron filter. The solution was then pressure-transferred through an external bore of a double-bore spinneret having an outer diameter of 1.0 mm and an inner diameter of 0.5 mm while simultaneously spraying a mixture of 20/80 MeOH / 5 wt% LiCl (aq.) Solution in the spinneret Pressure is transferred through the bore. These pressure-transferred materials are passed straight through a settling bath (20/80 MeOH / water), where the hollow fibers are observed and evaluated. The dimensions of the hollow fiber removed from the bath can be confirmed by SEM.

Example 30

Formation of thin film composite hollow fiber

Generally speaking, polymers formed in accordance with the present invention, such as those specifically disclosed in any one of Examples 16-26, may be used in a concentration (e.g., 10 wt%) suitable for a suitable solvent (e.g., THF) ≪ / RTI > and filtered through a 100 micron filter to remove the particles. A hollow microfiltration or ultrafiltration membrane (e.g., 0.1 micron PVDF or 3000 MWCO polysulfone) blocking the inner lumen is immersed in the block polymer solution and then removed from the solution. The solvent is removed by drying the fibers under suitable conditions (e.g., from about 23 to about 60 < 0 > C for about 0.5 to about 12 hours). The dimensions of the hollow fiber removed from the bath can be checked by SEM.

Example 31

The different block polymer compositions of the present invention and other polymers

Comparative manipulability of single thickness films

Comparison of the block polymers and random polymer compositions of the present invention was performed to observe the selective separation performance of n-butanol in the pervaporation test. The two dependent variables tested were% organic in flux and permeate. The feed solution concentration gave a change (1%). The feed solution was heated to 65 占 폚 using a heat bath. Through heat loss, it gives a housing temperature of about 60 ° C. To collect permeate samples, vacuum traps in liquid nitrogen were used. The vacuum was 0.4 in Hg (10 Torr). The feed solution was pumped into the system at 450 mL / min by a diaphragm pump. Samples were collected using a 3 hour test. Several different block polymers of BuNB / HFANB prepared according to Example 18 were compared with 1: 1 random copolymers of BuNB / HFANB, all of which were used as thin film composite membranes prepared according to the procedure described in Example 26 . The thickness of the film was varied and was from about 2 microns to about 4 microns. The flux numbers in Table 4 were normalized to a film thickness of 3 μm. The results are summarized in Table 4.

[Table 4]

Membrane Sample No. 6 formed from the triblock copolymer of HFANB-b-BuNB-b-HFANB (1: 1: 1) exhibits much better separation performance than Membrane Sample No. 1 formed from a 1: 1 random copolymer of BuNB / HFANB Is very clear from Table 4. Particularly noteworthy is that, as summarized in Table 4, when compared to films of similar thickness formed from a random copolymer (BuNB / HFANB random copolymer of membrane sample # 1), the triblock polymers at the same butanol concentration in the permeate (HFANB-b-BuNB-b-HFANB), a significantly higher flux was achieved. It should further be noted that only the film formed from the triblock polymer, i.e., film sample 6, showed phase separation as observed by atomic force microscopy (AFM) (Figure 5) The different surface morphologies are clearly shown when compared to the AFM of BuNB-b-HFANB (2: 1), Sample 3 (FIG. 4), and BuNB-b-HFANB (1: 2), Sample 5 Where both sample 3 and sample 5 did not exhibit phase separation under the conditions under which these samples were prepared and thus did not characterize the nanoscale structure. On the other hand, the film formed from the triblock polymer HFANB-b-BuNB-b-HFANB, Sample No. 6, FIG. 5 shows an ordered structure, which may be the cause of the high flux observed especially among other factors.

Example 32

The pervaporation test carried out with the membrane of Example 27A

The membrane formed from Example 27A was tested substantially as described in Example 28 except for the following. The effective area of the membrane was 13.38 cm ² . The permeation flux and separation factor were measured using a 1 wt% n- BuOH aqueous solution as feed. The feed flow rate was controlled by the diaphragm pump to 450 mL min ^-1 . The feed temperature was controlled by a heat exchanger connected to a temperature-adjustable water circulator. The feed was circulated for 30 minutes without a film to be heated to the desired temperature. The feed was circulated for 1 minute in the presence of a membrane to check for leaks and then the permeate was collected in a cold trap that was immersed in liquid nitrogen using a vacuum pump. The pressure on the permeate side of the membrane was monitored by a vacuum gauge and maintained below 10 Torr. We calculated the total flux ( J ) before and after the pervaporation experiment by weighing the cold trap. The composition of the permeate was determined by ¹ H NMR using acetone-d ₆ as solvent; A small amount of anhydrous ethanol was added to the permeate to make the phases miscible, thereby providing a single-phase solution prior to NMR analysis. Three different membranes were prepared for each of the polymers of Examples 26D-26G and analyzed under the same experimental conditions to ensure the reliability of the results. For stability testing, the permeate was alternatively collected using two cold traps, and the permeate through the membrane was replenished into the feed to maintain the n- BuOH feed concentration at 1 wt%. The permeate flux ( J ) and separation factor (SF) were calculated using the formula given above.

Pervaporation experiments were carried out at 37 ° C and 60 ° C. Higher temperatures and 60 ° C resulted in higher flux and separation coefficients in the feed solution. The measured flux for each of the film samples was normalized using the formula J '= J x (t / 2) where J' is the normalized flux, J is the measured flux, and t is the film film thickness. The normalization flux removes the effect of the different film thicknesses on the flux. Figure 6 (a) shows the normalization flux and separation factor (SF) obtained for each of the membranes formed from the polymers of Examples 26D-26G, labeled as a-BCPs (vinyl adduct block copolymer) _HFANB is the weight fraction of HFANB in each of the polymers of Examples 26D to 26G. Figure 6 (a) also shows the normalized flux and SF obtained for the homopolymer poly-HFANB (where W _HFANB is 1.0) and the homopolymer poly-BuNB (where W _HFANB is 0.0). From the _{data it} is _clear that the polymer with the W _HFANB of 0.81, the polymer of Example 26E (HFANB: BuNB = 70:30 molar ratio) shows a maximum separation factor of 21.2 at 60 ° C. The flux thus decreases gradually, as shown in Figure 6 (b), possibly due to the decreasing W _HFANB due to the reduction of the swell ratio. The observed separation factor (SF) for the poly-HFANB membrane was found to be only 13.7, presumably due to its relatively large swelling in a 1 wt% n- BuOH aqueous solution, which increases the permeation of water molecules b)).

The following two Comparative Examples 1 and 2 are provided herein to illustrate that certain known catalysts listed in the literature exhibit poor catalytic activity compared to the catalytic activity of the compounds of the present invention under similar reaction conditions.

Comparative Example 1

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB)

Homopolymer

The catalyst is a palladium used (acetoxy (bis (tri-isopropyl-phosphine)) (acetonitrile) tetrakis (pentafluorophenyl) borate [Pd (OAc) (Pi- Pr 3) 2 (CH 3 CN)] FABA The conversion of the monomer was found to be only 25%. The polymer was characterized by GPC: M _w = 12,000; M _n = 6,600; PDI = 3.6.

Comparative Example 2

Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB)

Homopolymer

The catalyst is a palladium used (acetylacetonato) (triisopropyl phosphine)) (acetonitrile) tetrakis (pentafluorophenyl) borate [Pd (acac) (Pi- Pr 3) (CH 3 CN)] FABA of Example 11 was substantially repeated in the comparative example 2 except for the above. Polymerization did not occur under these conditions.

Comparative Example 3

ROMP poly HFANB-b-poly BuNB (r-BCP81)

The ROMP block copolymer (r-BCP81) of HFANB and BuNB was synthesized by sequential addition of monomers at room temperature under nitrogen atmosphere. Block copolymer was designated as r-BCP81, where each "r" represent a "R OMP polymer", and "BCP" shows the "b lock c o p olymer (block copolymer)", '81 'Represents the weight composition (81 wt%) of the HFANB monomer units in the polymer. The initial monomer concentration was 4 wt%, and the subsequent HFANB monomer addition was carried out as a 4 wt% solution. BuNB (0.8 g, 5.3 mmol) and toluene (19 g) were placed in a 250 mL round bottom flask equipped with a magnetic stir bar and the mixture was stirred for 5 minutes before the injection of the initiator solution. (Tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride (0.034 g, 0.05 mmol), tricyclohexylphosphine (PCy ₃ , 0.057 g, 0.2 mmol) and Toluene (4 mL) was added and stirred for 5 minutes. The initiator solution was injected into the flask containing the BuNB solution at once under vigorous stirring. After complete consumption of BuNB (1 hour), a small aliquot of the reaction mixture was taken and terminated with excess ethyl vinyl ether for GPC analysis of the first poly BuNB block. HFANB (3.4 g, 12 mmol) in toluene (81 g) was then added to the reaction flask. HFANB was polymerized for 6 hours. The block copolymer was terminated with excess ethyl vinyl ether and recovered by evaporation of the solvent under N ₂ flow. The polymer so obtained was dissolved in a 1 L cyclohexane / THF mixture (95/5 vol%) and then charged into a 2 L Parr reactor. Using a Pd (0) heterogeneous catalysts supported on CaCO ₃ (8 g) was carried out the hydrogenation reaction for 2 days at 100 ℃ and 400 to 500 psig H _2. The progress of the reaction was followed by ¹ H NMR and saturation of more than 99.9% of the olefin double bonds was confirmed. After filtration of the catalyst, the resulting filtrate was concentrated and precipitated into MeOH / H ₂ O (50/50 vol%) and subsequently dried at 60 ° C under vacuum.

Comparative Example 4

A random vinyl addition copolymer (a-RCP81) of HFANB / BuNB

The vinyl-added random copolymer (a-RCP81) of HFANB and BuNB was synthesized by separating BuNB solution into reaction flask several times under nitrogen atmosphere at room temperature during the polymerization. It was named a random copolymer as a-RCP81, where each of 'a'is' vinyl a ddition polymer (a vinyl addition polymer), a display, and "RCP" is "r andom c o p olymer (random copolymer), , And '81' represents the weight composition (81 wt%) of the HFANB monomer units in the polymer. The initial monomer concentration was 5 wt%, and all subsequent BuNB addition was performed as a 5 wt% solution. To a 250 mL round bottom flask equipped with a magnetic stir bar was added HFANB (4.4 g, 16 mmol), BuNB (0.5 g, 3.3 mmol) and toluene / TFT (94 g, 50/50 wt% Lt; / RTI > for 5 minutes. 0.23 mL of a 0.50 M solution of ( ? ³ -allyl) Pd ( i- Pr ₃ P) Cl in a TFT (39 mg, 0.12 mmol) in a vial equipped with a magnetic stirrer bar and a solution of Li 0.23 mL of a 0.5 M solution of [FABA] was added and stirred for 20 minutes to activate the Pd development reagent. 0.30 mL of (η ³ - _{allyl) Pd (i -Pr 3 P)} Cl / Li [FABA] solution ((η ³ - allyl) Pd (P i -Pr ₃₎ for each of the Cl and Li [FABA] 0.075 mmol) were injected into a flask containing a monomer solution at once under vigorous stirring. Subsequent BuNB solutions (0.2, 0.15, 0.10, and 0.05 g BuNB) were then added to the reaction flask at 10, 30, 45, and 60 minutes after initiator injection, respectively. The monomers were polymerized for 3 hours. The random copolymer was recovered by repeated precipitation into MeOH / H ₂ O (50/50 vol%). The polymer so obtained was dissolved in THF, the solution was stirred on activated carbon and then passed through an alumina plug to remove the residual Pd catalyst. The resulting filtrate was precipitated into MeOH / H ₂ O (50/50 vol%) and subsequently dried at 60 ° C under vacuum.

Comparative Example 5

Pervaporation test with r-BCP81, a-RCP81 and a-BCP81

Films were prepared using the polymer from Comparative Examples 3 and 4 substantially as described in Example 27A, followed by following the procedure as described in Example 32 for the separation of 1 wt% n-BuOH . The results obtained in Fig. 7 (a) are shown. As is apparent from Fig. 7 (a), the film of Comparative Example 3 formed from ROMP polymer, r-BCP81 leads to a very low separation factor of 5.1. This may be due to the fact that the ROMP polymer with flexible skeleton structure r-BCP81 leads to a large swelling (about 31%) in the 1 wt% n-BuOH aqueous solution as shown in Fig. 7 (b).

Although the flux of a-BCP81, which is a film formed from the polymer of Example 26E, is slightly lower than that of a-RCP81 membranes formed from the polymer of Comparative Example 4, the separation factor of the a-BCP81 membrane (21.2) (18.5). It is clear that this is due to the microphase separation of a-BCP81 as described herein. The phase-separated polyBNB domain in a-BCP81 effectively inhibits the swelling of the polyHFANB domain, whereas the randomly distributed BuNB segment in a-RCP81 is sufficient for poly HFANB swelling due to molecular dilution of BuNB in the polyHFANB matrix (Fig. 7 (b)). Accordingly, it should be noted that it is important to enhance the selectivity in the high T _g butanol skeleton structure and a block copolymer architecture (architecture) of the pervaporation process of the present invention the polymer.

Although the invention has been described by means of specific preceding embodiments, it should not be construed as being limited thereto; Rather, the present invention encompasses a comprehensive field as disclosed above. Various modifications and embodiments can be made without departing from the spirit and scope of the present invention.

Claims (39)

Block polymer of formula (VI):
(A) _m -b- (B) _n (VI);
Wherein m and n are integers of at least 15;
b represents a bond;
A and B are different from each other and independently selected from repeating units represented by the formula (IVA), wherein the repeating units are derived from monomers of the formula (IV)

(IVA)

(IV)
Wherein:

Represents a bonding position with another repeating unit;
p is an integer of 0, 1 or 2;
(C ₁ -C ₁₆ ) alkyl, hydroxy (C ₁ -C ₁₆ ) alkyl, perfluoro (C ₁ -C ₁₆ ) alkoxy, and the like, wherein R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each independently of one another is hydrogen, straight or branched (C ₁ -C ₁₂₎ alkyl, (C ₃ -C ₁₂₎ cycloalkyl, (C ₆ -C ₁₂₎ bicycloalkyl, (C ₇ -C ₁₄₎ tricycloalkyl, (C ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, perfluoro (C ₆ -C ₁₀₎ aryl, perfluoroalkyl (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, di (C ₁ -C ₂ ) alkylmaleimido (C ₃ -C ₆ ) alkyl, di (C ₁ -C ₂ ) alkylmaleimide (C ₂ -C ₆ ) alkoxy (C ₁ -C ₂ ) alkyl, (C ₁ -C ₁₂₎ alkoxy, (C ₃ -C ₁₂₎ cycloalkoxy, (C ₆ -C ₁₂₎ bicyclo alkoxy, (C ₇ -C ₁₄₎ tricycloalkyl alkoxy, (C ₆ -C ₁₀₎ aryloxy (C ₁ -C ₃ ) alkyl, (C ₅ -C ₁₀ ) heteroaryloxy (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₀ ) aryloxy, (C ₅ -C ₁₀ ) heteroaryloxy or C ₁ -C ₆₎ is selected from acyloxy, each of the foregoing substituents here are halogen or a hydroxyl Is a group selected from optionally substituted. The block copolymer of claim 1, wherein the block polymer further comprises a third repeating unit and is represented by formula (VII):
(A) _m -b- (B) _n -b- (C) _o (VII);
Wherein A, B, m, n and b are as defined in claim 1, and o is an integer of at least 15;
C is the same or different from A or B and is independently selected from repeating units represented by the formula (IVA), wherein the repeating units are derived from monomers of the formula (IV) as defined in claim 1. The block polymer of claim 1, wherein the block molar ratio of A: B is from 1: 1 to 1: 4. The block polymer of claim 1, wherein the block molar ratio of A: B is from 1: 1 to 1: 2. The block polymer of claim 1 wherein the block molar ratio of A: B is 1: 1. The block polymer of claim 2, wherein the block molar ratio of A: B: C is from 1: 1: 1 to 1: 4: 1 to 1: 1: 4. The block polymer of claim 2, wherein the block molar ratio of A: B: C is 1: 1: 1. The block polymer of claim 2, wherein the block molar ratio of A: B: C is 1: 2: 1. 2. The block copolymer of claim 1, wherein A is a block polymer derived from a monomer selected from the group consisting of:
5-butylbicyclo [2.2.1] hept-2-ene (BuNB);
5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);
5-octylbicyclo [2.2.1] hept-2-ene (OctNB);
5-perfluoroethyl-bicyclo [2.2.1] hept-2-ene (C ₂ F ₅ NB);
A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);
5-perfluoro hexyl actual bicyclo [2.2.1] hept-2-ene (C ₆ F ₁₃ NB);
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);
1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);
1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);
5-phenethylbicyclo [2.2.1] hept-2-ene (PENB); And
2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB). The composition of claim 1, wherein B is a block polymer derived from a monomer selected from the group consisting of:
5-butylbicyclo [2.2.1] hept-2-ene (BuNB);
5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);
5-octylbicyclo [2.2.1] hept-2-ene (OctNB);
5-perfluoroethyl-bicyclo [2.2.1] hept-2-ene (C ₂ F ₅ NB);
A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);
5-perfluoro hexyl actual bicyclo [2.2.1] hept-2-ene (C ₆ F ₁₃ NB);
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);
1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);
1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);
5-phenethylbicyclo [2.2.1] hept-2-ene (PENB); And
2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB). The composition of claim 2, wherein C is a block polymer derived from a monomer selected from the group consisting of:
5-butylbicyclo [2.2.1] hept-2-ene (BuNB);
5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);
5-octylbicyclo [2.2.1] hept-2-ene (OctNB);
5-perfluoroethyl-bicyclo [2.2.1] hept-2-ene (C ₂ F ₅ NB);
A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);
5-perfluoro hexyl actual bicyclo [2.2.1] hept-2-ene (C ₆ F ₁₃ NB);
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);
1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);
1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);
5-phenethylbicyclo [2.2.1] hept-2-ene (PENB); And
2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB). 2. The block copolymer of claim 1, wherein A is a block polymer derived from a monomer selected from the group consisting of:
5-butylbicyclo [2.2.1] hept-2-ene (BuNB);
5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);
A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB); And
2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB). The composition of claim 1, wherein B is a block polymer derived from a monomer selected from the group consisting of:
5-butylbicyclo [2.2.1] hept-2-ene (BuNB);
5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);
A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB); And
2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB). The composition of claim 2, wherein C is a block polymer derived from a monomer selected from the group consisting of:
5-butylbicyclo [2.2.1] hept-2-ene (BuNB);
5-hexylbicyclo [2.2.1] hept-2-ene (HexNB);
A 5-n- perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB); And
2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB). The block polymer of claim 1 selected from the group consisting of:
A block polymer derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HexNB-b -HFANB);
A block polymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB-b -HFANB);
2.2.1] hept-2-ene and 1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl- A block polymer derived from pyrrole-2,5-dione (C ₄ F ₉ NB-b-BuDMMINB);
2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2 .1] heptane (HFANB-b-NBANB); And
Block polymer derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane HexNB-b-NBANB). The block polymer of claim 2 selected from the group consisting of:
2,2'-hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo [2.2. 1] hept-2-ene (BuNB-b-HFANB-b-BuNB); And
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept- Block polymer derived from fluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB). Reacting the first monomer with a palladium compound to form a first polymer block; And
Reacting a second monomer different from the first monomer to form a block polymer.
Process for preparing block polymers of formula (VI)
(A) _m -b- (B) _n (VI);
Wherein m and n are integers of at least 15;
b represents a bond;
A and B are each independently selected from the repeating units represented by the formula (IVA) which are different from each other and wherein the repeating units are selected from the group consisting of first and second monomers independently derived from the respective first and second monomers of formula (IV) 2 monomer repeating unit:

(IVA)

(IV)
Wherein:

Represents a bonding position with another repeating unit;
p is an integer of 0, 1 or 2;
(C ₁ -C ₁₆ ) alkyl, hydroxy (C ₁ -C ₁₆ ) alkyl, perfluoro (C ₁ -C ₁₆ ) alkoxy, and the like, wherein R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each independently of one another is hydrogen, straight or branched (C ₁ -C ₁₂₎ alkyl, (C ₃ -C ₁₂₎ cycloalkyl, (C ₆ -C ₁₂₎ bicycloalkyl, (C ₇ -C ₁₄₎ tricycloalkyl, (C ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, perfluoro (C ₆ -C ₁₀₎ aryl, perfluoroalkyl (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, di (C ₁ -C ₂ ) alkylmaleimido (C ₃ -C ₆ ) alkyl, di (C ₁ -C ₂ ) alkylmaleimide (C ₂ -C ₆ ) alkoxy (C ₁ -C ₂ ) alkyl, (C ₁ -C ₁₂₎ alkoxy, (C ₃ -C ₁₂₎ cycloalkoxy, (C ₆ -C ₁₂₎ bicyclo alkoxy, (C ₇ -C ₁₄₎ tricycloalkyl alkoxy, (C ₆ -C ₁₀₎ aryloxy (C ₁ -C ₃ ) alkyl, (C ₅ -C ₁₀ ) heteroaryloxy (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₀ ) aryloxy, (C ₅ -C ₁₀ ) heteroaryloxy or C ₁ -C ₆₎ is selected from acyloxy, each of the foregoing substituents here are halogen or a hydroxyl Is a group selected from optionally substituted. 18. The method of claim 17, further comprising the step of reacting a third monomer to form a block polymer of formula (VII)
(A) _m -b- (B) _n -b- (C) _o (VII);
Wherein A, B, m, n and b are as defined in claim 17 and o is an integer of at least 15;
C is the same or different from A or B and is independently selected from repeating units represented by the formula (IVA), wherein the repeating units are derived from monomers of the formula (IV) as defined in claim 17. 18. The method of claim 17, wherein the formed block polymer is selected from the group consisting of:
A block polymer derived from 5-hexylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HexNB-b -HFANB);
A block polymer derived from 5-butylbicyclo [2.2.1] hept-2-ene and norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (BuNB-b -HFANB);
2.2.1] hept-2-ene and 1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl- A block polymer derived from pyrrole-2,5-dione (C ₄ F ₉ NB-b-BuDMMINB);
2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2 .1] heptane (HFANB-b-NBANB); And
Block polymer derived from 5-hexylbicyclo [2.2.1] hept-2-ene and 2- (bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane HexNB-b-NBANB). 19. The method of claim 18, wherein the polymer formed is selected from the group consisting of:
2,2'-hept-2-ene, norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol and 5-butylbicyclo [2.2. 1] hept-2-ene (BuNB-b-HFANB-b-BuNB); And
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol, 5-butylbicyclo [2.2.1] hept- Block polymer derived from fluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB-b-BuNB-b-HFANB). The compound of formula (I)

(I)
(Wherein,

It is (C ₅ -C ₁₀₎ cycloalkene, (C ₇ -C ₁₂₎ alkene or bicyclo (C ₈ -C ₁₂₎ tricycloalkyl alkenyl group;
M is nickel, palladium or platinum;
LB is a Lewis base;
Z

Is a weakly coordinating anion;
Y is PR ₃ or O = PR ₃ wherein R is methyl, ethyl, (C ₃ -C ₆ ) alkyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀₎ aralkyl, methoxy, ethoxy, (C ₃ -C ₆₎ alkoxy, substituted or non-substituted (C ₃ -C ₇₎ cycloalkoxy, (C ₆ -C ₁₀₎ aryl oxy or (C ₆ -C ₁₀₎ independently selected from aralkyloxy;
R ₁ is methyl, ethyl, straight or branched (C ₃ -C ₆ ) alkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀ ) aralkyl or R ₂ CO, wherein R ₂ is methyl , ethyl, or (C ₃ -C ₆₎ alkyl); And
Monomers of formula (IV):

(IV)
(Wherein:
p is an integer of 0, 1 or 2;
(C ₁ -C ₁₆ ) alkyl, hydroxy (C ₁ -C ₁₆ ) alkyl, perfluoro (C ₁ -C ₁₆ ) alkoxy, and the like, wherein R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each independently of one another is hydrogen, straight or branched (C ₁ -C ₁₂₎ alkyl, (C ₃ -C ₁₂₎ cycloalkyl, (C ₆ -C ₁₂₎ bicycloalkyl, (C ₇ -C ₁₄₎ tricycloalkyl, (C ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, perfluoro (C ₆ -C ₁₀₎ aryl, perfluoroalkyl (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, di (C ₁ -C ₂ ) alkylmaleimido (C ₃ -C ₆ ) alkyl, di (C ₁ -C ₂ ) alkylmaleimide (C ₂ -C ₆ ) alkoxy (C ₁ -C ₂ ) alkyl, (C ₁ -C ₁₂₎ alkoxy, (C ₃ -C ₁₂₎ cycloalkoxy, (C ₆ -C ₁₂₎ bicyclo alkoxy, (C ₇ -C ₁₄₎ tricycloalkyl alkoxy, (C ₆ -C ₁₀₎ aryloxy (C ₁ -C ₃ ) alkyl, (C ₅ -C ₁₀ ) heteroaryloxy (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₀ ) aryloxy, (C ₅ -C ₁₀ ) heteroaryloxy or C ₁ -C ₆₎ is selected from acyloxy, each of the foregoing substituents here are halogen or a hydroxyl Is a group selected from optionally substituted.) Polymerizing a composition comprising a. 22. The method of claim 21,
The compound of formula (I)

(IIB);

(IIC); And

(IID)
(Wherein Py is pyridine);
The monomer of formula (IV)
Bicyclo [2.2.1] hept-2-ene (NB);
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
5-hexylbicyclo- [2.2.1] hept-2-ene (HexNB);
5-octylbicyclo [2.2.1] hept-2-ene (OctNB);
5-decylbicyclo [2.2.1] hept-2-ene (DecNB);
5-perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);
1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);
1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);
1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);
5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);
5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); And
2-bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB). A compound of formula (III):

(III)
(Wherein,

It is (C ₅ -C ₁₀₎ cycloalkene, (C ₇ -C ₁₂₎ alkene or bicyclo (C ₈ -C ₁₂₎ tricycloalkyl alkenyl group;
M is nickel, palladium or platinum;
X is halogen, triflate, mesylate or tosylate;
Y is PR ₃ or O = PR ₃ wherein R is methyl, ethyl, (C ₃ -C ₆ ) alkyl, substituted or unsubstituted (C ₃ -C ₇ ) cycloalkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀₎ aralkyl, methoxy, ethoxy, (C ₃ -C ₆₎ alkoxy, substituted or non-substituted (C ₃ -C ₇₎ cycloalkoxy, (C ₆ -C ₁₀₎ aryl oxy or (C ₆ -C ₁₀₎ independently selected from aralkyloxy;
R ₁ is methyl, ethyl, straight or branched (C ₃ -C ₆ ) alkyl, (C ₆ -C ₁₀ ) aryl, (C ₆ -C ₁₀ ) aralkyl or R ₂ CO wherein R ₂ is methyl , ethyl, or (C ₃ -C ₆₎ alkyl);
A compound of formula (V):
M _d

Z

(V)
(Wherein,
M _d

Is lithium, sodium, potassium, cesium, barium, ammonium, and straight-chain or branched-tetra (C ₁ -C ₄₎ a cation selected from alkyl ammonium;
Z

B (C ₆ F ₅ ) ₄

, B [C ₆ H ₃ (CF ₃ ) ₂ ] ₄

_{, B (C 6 H 5)} 4

_{, [Al (OC (CF 3} ) 2 C 6 F 5) 4]

, BF ₄

, PF ₆

, AsF ₆

, SbF ₆

, (CF ₃ SO ₂₎ N

Or CF ₃ SO ₃

Lt; / RTI > is a weakly coordinating anion selected from < RTI ID = 0.0 > And
Monomers of formula (IV):

(IV)
(Wherein:
m is an integer of 0, 1 or 2;
(C ₁ -C ₁₆ ) alkyl, hydroxy (C ₁ -C ₁₆ ) alkyl, perfluoro (C ₁ -C ₁₆ ) alkyl, and the like, wherein R ₃ , R ₄ , R ₅ and R ₆ are the same or different and each independently of one another is hydrogen, straight or branched (C ₁ -C ₁₂₎ alkyl, (C ₃ -C ₁₂₎ cycloalkyl, (C ₆ -C ₁₂₎ bicycloalkyl, (C ₇ -C ₁₄₎ tricycloalkyl, (C ₆ -C ₁₀₎ aryl, (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, perfluoro (C ₆ -C ₁₀₎ aryl, perfluoroalkyl (C ₆ -C ₁₀₎ aryl (C ₁ -C ₃₎ alkyl, di (C ₁ -C ₂ ) alkylmaleimido (C ₃ -C ₆ ) alkyl, di (C ₁ -C ₂ ) alkylmaleimide (C ₂ -C ₆ ) alkoxy (C ₁ -C ₂ ) alkyl, (C ₁ -C ₁₂₎ alkoxy, (C ₃ -C ₁₂₎ cycloalkoxy, (C ₆ -C ₁₂₎ bicyclo alkoxy, (C ₇ -C ₁₄₎ tricycloalkyl alkoxy, (C ₆ -C ₁₀₎ aryloxy (C ₁ -C ₃ ) alkyl, (C ₅ -C ₁₀ ) heteroaryloxy (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₀ ) aryloxy, (C ₅ -C ₁₀ ) heteroaryloxy or C ₁ -C ₆₎ is selected from acyloxy, each of the foregoing substituents here are halogen or a hydroxyl Is a group selected from optionally substituted.) Polymerizing a composition comprising a. 24. The method of claim 23,
The compound of formula (III)

(IIIB);

(IIIC); And

(IIID); < / RTI >
The compound of formula (V)
Lithium tetrafluoroborate;
Lithium triflate;
Lithium tetrakis (pentafluorophenyl) borate;
Lithium tetraphenylborate;
Lithium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate;
Lithium tetrakis (2-fluorophenyl) borate;
Lithium tetrakis (3-fluorophenyl) borate;
Lithium tetrakis (4-fluorophenyl) borate;
Lithium tetrakis (3,5-difluorophenyl) borate;
Lithium hexafluorophosphate;
Lithium hexaphenyl phosphate;
Lithium hexakis (pentafluorophenyl) phosphate;
Lithium hexafluoroarsenate;
Lithium hexaphenyl arsenate;
Lithium hexakis (pentafluorophenyl) arsenate;
Lithium hexacis (3,5-bis (trifluoromethyl) phenyl) arsenate;
Lithium hexafluoroantimonate;
Lithium hexaphenyl antimonate;
Lithium hexakis (pentafluorophenyl) antimonate;
Lithium hexakis (3,5-bis (trifluoromethyl) phenyl) antimonate;
Lithium tetrakis (pentafluorophenyl) aluminate;
Lithium tris (nonafluorobiphenyl) fluoroaluminate;
Lithium (octyloxy) tris (pentafluorophenyl) aluminate;
Lithium tetrakis (3,5-bis (trifluoromethyl) phenyl) aluminate; And
Lithium methyl tris (pentafluorophenyl) aluminate;
The monomer of formula (IV)
Bicyclo [2.2.1] hept-2-ene (NB);
Norbornenyl-2-trifluoromethyl-3,3,3-trifluoropropan-2-ol (HFANB);
5-hexylbicyclo- [2.2.1] hept-2-ene (HexNB);
5-octylbicyclo [2.2.1] hept-2-ene (OctNB);
5-decylbicyclo [2.2.1] hept-2-ene (DecNB);
5-perfluorobutyl [2.2.1] hept-2-ene (C ₄ F ₉ NB);
1- (3- (bicyclo [2.2.1] hept-5-en-2-yl) propyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);
1- (4- (bicyclo [2.2.1] hept-5-en-2-yl) butyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);
1- (6- (bicyclo [2.2.1] hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);
5-phenethylbicyclo [2.2.1] hept-2-ene (PENB);
5-benzylbicyclo [2.2.1] hept-2-ene (BnNB); And
2-bicyclo [2.2.1] hept-5-en-2-yl) bicyclo [2.2.1] heptane (NBANB).


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