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WO2005085297A1 - Polymeres telecheliques contenant des groupes fonctionnels reactifs - Google Patents

Polymeres telecheliques contenant des groupes fonctionnels reactifs Download PDF

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WO2005085297A1
WO2005085297A1 PCT/US2004/004584 US2004004584W WO2005085297A1 WO 2005085297 A1 WO2005085297 A1 WO 2005085297A1 US 2004004584 W US2004004584 W US 2004004584W WO 2005085297 A1 WO2005085297 A1 WO 2005085297A1
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polymer
vinyl
telechelic
initiator
functional groups
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Tze-Chiang Chung
Han Hong
Masahiko Oka
Katsuyoshi Kubo
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Penn State Research Foundation
Daikin Institute of Advanced Chemistry and Technology Inc
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Penn State Research Foundation
Daikin Institute of Advanced Chemistry and Technology Inc
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Priority to PCT/US2004/004584 priority patent/WO2005085297A1/fr
Priority to JP2006554066A priority patent/JP2007522333A/ja
Publication of WO2005085297A1 publication Critical patent/WO2005085297A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to telechelic polymers having reactive functional groups and their preparation.
  • the present invention relates to the preparation of polymers having two functional groups on one end of the polymer by cycloborane initiators.
  • the processes disclosed herein are applicable to the preparation of the telechelic block polymers with controlled copolymer composition, and narrow molecular weight distribution.
  • Telechelic polymers possessing reactive functional group(s) situated at the polymer chain end(s), are an importance class of polymeric materials. They find applications as prepolymers for inclusion into final products with well-specified properties by the reaction of their functional groups.
  • One early example of the commercial use of such telechelic polymers is in the formation of polyurethanes, which can be pe ⁇ ared by coupling reaction between hydroxyl-terminated prepolymers with diisocyanates. This example introduced new perspectives on making materials with a wide array of physical properties by controlling the molecular architecture of the polymers.
  • a telechelic polymer was considered a polymer containing two reactive end-groups, one group at each end.
  • telechelic polymers include all polymers that contain one or more reactive end-group(s), which can undergo chemical reactivity with itself or another functional group in another molecule.
  • the polymer that possesses only one reactive end-group is now referred to as a "monotelechelic” and the original telechelic having two opposing reactive end-groups is commonly called a "ditelechelic".
  • Those telechelic polymers having more than two reactive end-groups are designated as tritelechelic, tetratelechelic, or polytelechelic.
  • the most important commercial telechelic polymers are monotelechelic and ditelechelic polymers.
  • Telechelic polymers with higher functionality usually result in materials having a polymer network structure.
  • An important consideration in the use of telechelic polymers is their average functionality, i.e., the average functionality of a monotelechelic polymer should be 1.0 and that of a ditelechelic polymer should be 2.0.
  • end-group linking reactions are highly sensitive to accurate end group stoichiometry.
  • the quality of graft and multi-block copolymers employing telechelics depend upon the preciseness of their functionality, 1.0 and 2.0, respectively.
  • N-diethyldithiocarbamate derivatives (Otsu, et al., Macromol chem.,Rapid Commun., 3, 133, 1982, Ewr. P ⁇ lym. J., 25, 643, 1989).
  • the first robust living radical polymerization was observed in reaction involving a stable nitroxyl radical, such as 2,2,6,6-tetramethylpiperidinyl-l-oxy (TEMPO), that does not react with monomers but forms a reversible end-capped propagating chain end (see, Georges, et al., U. S. Patents 5,322,912 and 5,401,804).
  • TEMPO 2,2,6,6-tetramethylpiperidinyl-l-oxy
  • the formed covalent bonds reduce the overall concentration of free radical chain ends, which leads to a lower occurrence of unwanted coupling and disproportionation termination reactions.
  • the reaction has to be carried out at an elevated temperature (>100° C). Relatively high energy is needed in the cleavage of the covalence bond, which maintains a sufficient concentration of propagating radicals for monomer insertion. This living radical polymerization, however, appears effective only with styrenic monomers.
  • the research objective was centered around the functionalization of polyolefins by first inco ⁇ orating borane groups into a polymer chain, which was then selectively oxidized by oxygen to form the mono-oxidized borane moieties that initiate free radical graft-form polymerization at ambient temperature to produce polyolefm graft and block copolymers (Chung, et al., U. S. Patents 5,286,800 and 5,401,805, Macromolecules, 26, 3467, 1993, Macromolecules, 31_, 5943, 1998, J. Am. Chem. Soc, 121, 6763 (1999)).
  • the chemistry is centered on an in situ chain transfer reaction during metallocene-mediated ⁇ -olefin polymerization using two reactive chain transfer (CT) agents, including dialkylborane (R 2 B-H) and styrenic molecule/H , to form polyolefm containing a reactive alkylborane and styrenic terminal group, respectively,
  • CT reactive chain transfer
  • R 2 B-H dialkylborane
  • styrenic molecule/H styrenic molecule/H
  • the monotelechelic polyolefm formed shows narrow molecular weight distribution (MW/Mn of 2) and the polymer molecular weight was inversely proportional to the molar ratio of (CT agent)/( ⁇ -olefin).
  • CT agent CT agent/( ⁇ -olefin).
  • ditelechelic polymers such as aliphatic polyesters with two opposing terminal acid or alcohol groups and polyethylene oxide and polypropylene oxide with two opposing terminal alcohol groups
  • ditelechelic vinyl polymers usually requires the combination of living polymerization and difunctional initiators or functionally substituted initiators.
  • This methodology has been applied to practically all vinyl polymerization techniques, including anionic, cationic, free radical, metathesis, and Ziegler-Natta, which evidence living polymerizations with stab>le propagating active sites that can be converted to the desired functional group at the chain end.
  • anionic living polymerization see, e.g., U. S.
  • An advantage of the present invention is a new class of telechelic polymers and their preparation. [013] Additional advantages, and other features of the present invention will be set forth in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from the practice of the present disclosure. The advantages may be realized and obtained as particularly pointed out in the appended claims. [014] According to the present invention, the foregoing and other advantages are achieved in part by a process for preparing a telechelic polymer containing two reactive functional groups at one end of the polymer.
  • the process comprises combining a cycloborane initiator, at least one free r-adical polymerizable monomer and oxygen.
  • the initiator starts the polymerization of the monomer to form a polymer segment having a borane residue at one end of the segment.
  • the residue is the result of the cycloborane initiator.
  • Polymerization continues until all of the monomer is inco ⁇ orated into the polymer segment or until the reaction is halted.
  • the terminal borane residue can be converted to at least two functional groups to form the telechelic polymer having at least two functional groups at the same chain end.
  • Another advantage of the present invention is a telechelic polymer comprising a polymer segment derived from free radical polymerizable monomers and having two functional groups at the same chain end.
  • FIG. 1 illustrates (top) GPC curves of telechelic PMMA samples (Examples
  • Fig. 2 illustrates (top) 1H and (bottom) 13 C NMR-DEPT 135 spectra of poly(trifluoroethylacrylate) prepared by 8-bora-indane/O in benzene at 0 °C. [019] Fig.
  • the present invention stems from the discovery that polymerization of vinyl monomers with a boron containing initiator results in a polymer having a boron residue at one end of the polymer, which can be converted to multiple functional groups.
  • the synthesis of well-defined telechelic polymers, with precise functionality and molecular weight, is an important subject in polymer science due to the desire of using such polymers as starting materials, i.e., prepolymers or macromers, to prepare products with custom physical properties.
  • the issue is particularly of interest in free radical polymerization because it is a preferred industrial process for producing vinyl polymers.
  • free radical initiators are useful with a broad range of vinyl monomers, including monomers containing polar groups.
  • a vinyl monomer means a compound having at least one unsaturated carbon-carbon double bond, which is susceptible to polymerization.
  • a free radical polymerizable monomer is a compound susceptible to free radical polymerization either with itself or other monomers and includes vinyl monomers.
  • a telechelic polymer comprising a polymer segment derived from one or more free radical polymerizable monomer and having two functional groups at the same chain end can be obtained.
  • a telechelic polymer can be obtained having the following formula:
  • the polymer segment is derived from one or more free radical polymerizable monomer, i.e., the polymer segment is the product of the polymerization of the monomers.
  • the polymer segment can be a homopolymer or copolymer prepared by borane-mediated living radical polymerization of vinyl monomers.
  • Such monomers include C 2 to Cis monomers having linear, branched or cyclic structures.
  • copolymer is meant to include polymers containing groups or units derived from two or more monomers with random, diblock, and multi-block microstructures.
  • copolymer is meant to include copolymers, te ⁇ olymers, tetrapolymers, etc.
  • the average molecular weight (i.e. number average molecular weight) of the polymer segment is typically above 300 g/mole.
  • the number average molecular weight of the polymer segment is from about 500 to about 1,000,000 g/mole, and most preferably from about 1,000 to about 300,000 g/mole.
  • the polymer segment, and consequently the telechelic polymer has a relatively narrow molecular weight distribution, e.g., no more than 5 and preferably less than 3.
  • the free radical polymerizable monomers contemplated for use in the present invention include, for example, vinyl monomers and dienes, such as vinyl halides, vinyl alcohols, vinyl ethers, vinyl esters, vinyl pyrrolidones, vinyl alkyls, vinyl aromatics, i.e. styrenes, acrylates, acrylic acids, acrylonitriles, and their cyclic form.
  • the monomers can be substituted with one or more halogen, alkyl or polar group.
  • Examples of such monomers include, without limitation: methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacylate, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, acrylic acid, maleic anhydride, vinyl acetate, acrylonitrile, acrylamide, vinyl chloride, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3- pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 3-(perfluorobutyl)-2- hydroxypropyl methacrylate, 3-(perfluorohexyl)-2-hydroxypropyl methacrylate, 3- (perfluorooctyl)-2-hydroxypropyl methacrylate,
  • a telechelic polymer is prepared by initiating polymerization of a free radical polymerizable monomer.
  • the initiator is preferably a cycloborane initiator, in which all three C-B bonds are part of the cyclic structure, as illustrated below:
  • R] R 2 , and R 3 are independently linear or branched alkyl groups with a carbon count of from 2 to about 15, and preferably from 2 to 10.
  • Each pair of Ri, R 2 , and R 3 can be chemically bridged to each other with a linking group shared by the two alkyl groups to form a cyclic ring structure that includes the boron atom.
  • Particularly suitable cycloborane initiators include: 8-boraindane (IN), 9- boradecalin (V), 1-boraadamantane (VI), and perhydro-9b-boraphenalene (Nil), which are shown below.
  • IV (V) (VI) (VII)
  • cycloborane initiator one or more types of radical polymerizable monomer and oxygen are combined.
  • the initiator and monomer are combined fi-rst in an oxygen free atmosphere.
  • the components can be combined in an oxygen atmosphere and the amount of oxygen adjusted until the desired ratio of components are achieved.
  • a controlled amount of oxygen can be reduced or introduced to the mixture to form a mono-oxidized t>orane compound. It is believed that this oxidized borane can in situ initiate living radical polymerization to produce vinyl polymers, including homopolymers and copolymers.
  • the following scheme illustrates the believed mechanism of in situ oxidation and polymerization process involving a clycoborane initiator with an acrylic monomer in the presence of oxygen.
  • the example provided above shows the preparation of telechelic polymethylmethacrylate (PMMA) having a PMMA segment, where n is the number of repeat units, and with two terminal OH groups at the beginning of polymer chain.
  • the scheme shows the polymerization of the polymer segment by using the 8-boraindane (IN) initiator.
  • a trialkylborane (BR 3 ) is initially oxidized at one of the there B-C bonds to form a peroxide compound, i.e., R 2 B-O- O-C, when exposed to a stoichmetric amount of oxygen at ambient temperature. See Chung et al., U. S.
  • the B-O-O-C species that is formed further decomposes at ambient temperature to an alkoxyl radical (C-O*) and a borinate radical (B- O*).
  • the alkoxyl radical is believed active in initiating polymerization of monomers.
  • the borinate radical (B-O*) is believed too stable to initiate polymerization due to the back-donating of electrons to the empty p-orbital of boron.
  • this "dormant" borinate radical may form a reversible bond with the radical at the growing chain end to prolong the lifetime of the propagating radical.
  • this 8-boraindane (IV) case shown in the above scheme
  • one of three cyclic B-C bonds is oxidized and initiates radical MMA polymerization, and the partially oxidized cycloborane residue remains bonded to the beginning of polymer chain, despite the continuous growth of the polymer chain.
  • the two unreacted cyclic B-C bonds in the borane residue can be completely interconverted to functional groups, such as two OH groups by NaOH/H O 2 reagent.
  • the resulting PMMA polymer has two OH groups located at the beginning of polymer chain, as well as having a controlled molecular weight and narrow molecular weight distribution.
  • the chemistry is applicable to many monomers, including fluoro-monomers.
  • This new class of diol macromonomer can be used to introduce additional physical properties into a material made by condensation processes, such as polyurethanes and polyesters.
  • the combination of a cycloborane initiator, monomer and oxygen is useful for preparing homoploymers and random copolymers containing two reactive terminal functional groups at the same polymer chain end.
  • Mi, M 2 and M 3 are the same or different monomer units chosen from free radical polymerizable monomers. It is understood that the polymer segments shown above have at least two function groups on a terminus of the polymer chain. These radical polymerizable monomers can be used either singly or as a combination of two or more monomers.
  • the numbers x, y and z represent the number of repeating monomer units in each polymer block, and typically x, y and z, independently, would be from about 10 to about 100,000. Preferably, x, y, and z, independently, would be from about 20 to about 30,000, most preferably from about 30 to about 10,000.
  • the borane residue located at the polymer chain can be completely converted to two reactive functional groups.
  • R' and R" are, in one form or another, the fragments of the borane initiator.
  • one of the carbon-boron bonds is believed broken and eventually the carbon atom forms part of the polymer chain end.
  • the remaining carbon fragment of the initiator is believed to be retained on the polymer chain.
  • R' can be O, or -CH O-
  • R" can be a C 7 alkyl group or a C 8 alkyl ring with or without methylene groups attached to functional groups.
  • R' and R" in formula (I) above can be a combination of the R ls R 2 , and R 3 groups of the initiator of formulae (II) and (III) and R' and R" are intended to include such groups.
  • R' is an ether linkage, or a substituted or unsubstituted linear or branched alkyl, or alkyl ether linage and R" is a substituted or unsubstituted linear, branched, or cyclic alkyl group, such as a C M5 substituted or unsubstituted linear, branched, or cyclic alkyl group.
  • R" is a C - ⁇ o substituted or unsubstituted linear, branched, or cyclic alkyl group.
  • R' and R" can also be chemically linked together to form a long linear structure or with a direct chemical bond between the two alkyl groups or to form a cyclic ring structure.
  • the terminal functional groups (X 1 and X") can be a primary or secondary functional group. These groups include hydroxyl, amino, aldehyde, anhydride, halogen, carboxylic acid, etc. end groups.
  • the functional groups are formed by converting the borane residue on the end of the polymer segment. Such borane interconversion reactions are known in the art as for example those disclosed by H. C. Brown, "Organic Synthesis via Boranes,” Wiley-Interscience.
  • a telechelic polymer containing two OH terminal groups can be prepared by oxidizing the borane residue with a mixture of NaOH and peroxide.
  • telechelic polymers containing terminal amino functionality may be prepared by reaction of the borane-terminating polymer with NH OSO 3 R; polymers containing aldehyde functionality may be prepared by reaction of the borane-terminating polymer with a mixture of CO and K(i-C 3 H O) 3 BH; and polymer containing iodine functionality may be prepared by reaction of the borane-terminating polymer with a solution of Nal/chloramine-T-hydrate.
  • X is selected from the group consisting of OH, NH , COH, COOH, Br, I, and succinic anhydride. Any functional group capable of being derived from a borane is contemplated and included herein.
  • THF solution was added dropwise with 200 ml (1.0 M) of borane THF complex in THF solution. After the addition was complete, stirring continued for 1 hour at 0° C. Then the mixture was refluxed for 1 hour before THF was removed completely under vacuum at room temperature. The attained white solid was heated to 210°C for 3 hours then 9.6 g of 9-bora- indane (yield: 41%) was distilled from the mixture at about 50 °C to 60 °C (0.3 mmHg).
  • Example 3 Synthesis of 1-boraadamantane THF complex [042] Under Ar atmosphere and vigorous stirring, to 100 ml (1.0M) of allylmagnesium bromide in diethyl ether was added dropwise 4.8 g of borontrifloride diethyl ether. After refluxing for 30 min, the mixture was permitted to stand over night. The solution layer was transferred to another flask under Ar. The diethyl ether was removed by distillation at 60° C under normal pressure. The triallyl borane was distilled from the mixture under reduced pressure to yield 2.7g (60%). To a 100 ml flask preheated to 130 °C was added 2.7 g of triallyl borane.
  • the solution was then poured into 200 ml of well stirred methanol to quench the polymerization and precipitate PMMA polymer.
  • the isolated PMMA polymer was then re-dissolved in 20 ml THF before adding 0.2 ml (6N) NaOH solution, followed by dropwise 0.4 ml, 33% H 2 O 2 at 0° C.
  • the resulting mixture was heated up to 50° C for 1 hour to complete the oxidation.
  • the solution was purred into 200 ml of well stirred methanol.
  • the precipitated telechelic PMMA polymer was collected, washed, and dried in vacuum at 60°C for 2 days.
  • the terminal OH groups were examined by 1H and 13 C NMR-DEPT 135 spectra.
  • FIG. 1 GPC curves of telechelic PMMA samples (Examples No. 9, 11, and 13), and a plot of polymer molecular weight vs. monomer conversion (Examples No. 9-13) using 1/3 of (oxygen)/(borane) mole ratios, respectively. All the experimental conditions and results for the series of examples are summarized in Table 1 , where Mn represents number average molecular weight, Mw represents the weight average molecular weight, and PDI represents the polydispersity index. [049] Table 1. A summary of telechelic PMMA polymers prepared by 8-bora- indane/O 2 Example Oxygen Reaction Monomer Mn Mw PDI No.
  • the isolated PMMA polymer was then re-dissolved in 20 ml THF before adding 0.1 ml (6N) NaOH solution, followed by dropwise 0.2 ml, 33% H 2 O 2 at 0° C. The resulting mixture was heated up to 50° C for 1 hour to complete the oxidation. After cooling to room temperature, the solution was purred into 200 ml of well stirred methanol. The precipitated telechelic PMMA polymer was collected, washed, and dried in vacuum at 60°C for 2 days. The resulting telechelic PMMA polymers having two terminal OH groups were characterized by Gel Permeation Chromatography (GPC) and 1H and 13 C NMR-DEPT measurements.
  • GPC Gel Permeation Chromatography
  • Table 3 summarizes some experimental results for the series of examples.
  • Table 3 A summary of MMA polymerization in THF solvent by 8- bora-indane/O 2 Example Reaction Polymer Yield Mn Mw PDI No. Time (hr) (%) (g/mole) (g/mole) (Mw/Mn) 29 0.5 2.0 11,400 18,000 1.5 30 1.0 4.0 31 2.0 6.0 32 5.0 10.0 26,000 51,000 1.9 33 10.0 17.0 36,000 77,000 2.1 34 20.0 30.0 47,000 110,000 2.3
  • Examples 29-34 were carried out in benzene solvent to prepare telechelic PMMA polymers, except the amount of benzene (0.5 ml, 5ml, 15 ml, 35 ml, 55 ml) used in the reaction.
  • Example 40 Synthesis of telechelic poly(t-butyl acrylate) with two terminal OH groups by bulk process using 8-bora-indane/O 2 initiator [064] In a 100 ml flame-dried flask, 10.0 ml of t-butyl acrylate (purified by distillation over CaH 2 ) and 140 mg of 8-bora-indane were introduced under argon.
  • the solution was mixed by shaking the flask vigorously for about 5 minutes to initiate the polymerization reaction. The reaction was then maintained at room temperature for another 10 min before exposing to air to stop the polymerization and oxidize all borane moieties.
  • the solid polymer was dissolved in 60 ml THF solvent before pouring into 200 ml of well stirred methanol to precipitate polymer. The precipitated telechelic poly(t-butyl acrylate) was collected, washed, and dried in vacuum at 60°C for 2 days.
  • Example 41 Synthesis of telechelic poly(trifluoroethyl acrylate) with two terminal OH groups by bulk process using 8-bora-indane/O 2 initiator [067] The procedure of Example 36 was followed, except that 2',2',2'-trifluoroethyl acrylate (TFEA) monomer was used instead of t-butyl acrylate.
  • TFEA 2',2',2'-trifluoroethyl acrylate
  • the yield of telechelic poly(trifluoroethyl acrylate) was about 95%) with 10 min polymerization time.
  • Figure 2 shows 1H and 13 C NMR-DEPT 135 spectra of the resulting telechelic poly(trifluoroethyl acrylate) having two terminal OH groups.
  • the solution was then kept at a certain temperature for a certain time (shown in Table 6) before stopping the polymerization by pouring the solution into 50 ml methanol and precipitating PMMA polymer.
  • the isolated PMMA polymer was then re-dissolved in 20 ml THF before adding 0.5 ml (6N) NaOH solution, followed by dropwise 1 ml, 33% H 2 O 2 at 0° C. The resulting mixture was heated up to 50° C for 1 hour to complete the oxidation. After cooling to room temperature, the solution was poured into 200 ml of well stirred methanol.
  • Example 61 Synthesis of poly(methyl methacrylate-b-trifluoroethyl acrylate) diblock copolymer having two terminal OH groups in the beginning of the PMMA chain.
  • 5.0 ml (50 mmol) of MMA and 70 mg (0.6 mmol) of 9-bora-indane were mixed under argon.
  • 5.0 ml of O 2 (0.2 mmol) was injected, following by vigorous shaking to assure complete mixing.
  • the system was then kept at room temperature for 20 min, followed by removal of all the volatiles by vacuum distillation.
  • TFEA 2',2',2'-trifluoroethyl acrylate
  • the resulting telechelic poly(methyl methacrylate-b- trifluoroethyl acrylate) diblock copolymer was characterized by Gel Permeation Chromatography (GPC) and 1H and 13 C NMR-DEPT measurements.
  • Example 62 [080] Synthesis of poly(trifluoroethyl acrylate-b-methyl methacrylate) diblock copolymer having two terminal OH groups in the beginning of PTFEA chain. [081] The procedure of Example 61 was followed, except the sequence of monomer addition. 2',2',2'-Trifluoroethyl acrylate (TFEA) monomer was added first instead of methyl methacrylate.
  • TFEA Trifluoroethyl acrylate
  • the resulting telechelic poly(trifluoroethyl acrylate-b-methyl methacrylate) diblock copolymer having two terminal OH groups in the beginning of the PTFEA chain was characterized by Gel Permeation Chromatography (GPC) and 1H and 13 C NMR-DEPT measurements.
  • Table 7 compares the molecular weight of the first PTFEA block and the resulting PTFEA-b-PMMA diblock copolymer. [082] Table 7. A summary of PTFEA block and PTFEA-b-PMMA diblock copolymer.
  • Example 62 Mn Mw PD ⁇ MMA/TFEA (g/mole) (g/mole) (Mw/Mn) (mol/mol) PTFEA 41,000 78,000 1.9 PTFEA-b-PMMA 73,000 152,000 2.1 10/8

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  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne des polymères téléchéliques possédant deux groupes fonctionnels réactifs au niveau de la même extrémité de chaîne polymère. Ces polymères peuvent être préparés par la combinaison d'un amorceur cycloborane, d'au moins un monomère pouvant être traité par polymérisation radicalaire et d'oxygène pour former un segment polymère possédant un résidu borane à une extrémité, provenant de l'amorceur cycloborane; et par la transformation du résidu borane en au moins deux groupes fonctionnels, de manière que le polymère téléchélique de l'invention soit formé.
PCT/US2004/004584 2004-02-17 2004-02-17 Polymeres telecheliques contenant des groupes fonctionnels reactifs Ceased WO2005085297A1 (fr)

Priority Applications (3)

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EP04711824A EP1723181A4 (fr) 2004-02-17 2004-02-17 Polymeres telecheliques contenant des groupes fonctionnels reactifs
PCT/US2004/004584 WO2005085297A1 (fr) 2004-02-17 2004-02-17 Polymeres telecheliques contenant des groupes fonctionnels reactifs
JP2006554066A JP2007522333A (ja) 2004-02-17 2004-02-17 反応性官能基を含有するテレケリックポリマー

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WO2010091001A1 (fr) * 2009-02-04 2010-08-12 Dow Corning Corporation Procédé de formation d'un copolymère non aléatoire

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JP5031180B2 (ja) * 2004-03-29 2012-09-19 サンメディカル株式会社 重合開始剤、それを用いたラジカル重合体の製造方法、ラジカル重合体およびラジカル重合性組成物
JP2014136706A (ja) * 2013-01-15 2014-07-28 Hitachi Chemical Co Ltd 樹脂組成物、樹脂組成物の製造方法、樹脂組成物を含むレジスト組成物及びレジスト組成物を用いたパターン形成方法

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Publication number Priority date Publication date Assignee Title
WO2009077760A1 (fr) 2007-12-17 2009-06-25 Lux Innovate Limited Compositions et procédés pour l'entretien de systèmes d'acheminement et de confinement de fluides
WO2010091001A1 (fr) * 2009-02-04 2010-08-12 Dow Corning Corporation Procédé de formation d'un copolymère non aléatoire
US9080000B2 (en) 2009-02-04 2015-07-14 Dow Corning Corporation Method of forming a non-random copolymer

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EP1723181A4 (fr) 2009-01-21
JP2007522333A (ja) 2007-08-09
EP1723181A1 (fr) 2006-11-22

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