WO1987007265A1 - Acylation and sulfonation of silylketene acetals - Google Patents

Acylation and sulfonation of silylketene acetals Download PDF

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Publication number
WO1987007265A1
WO1987007265A1 PCT/US1987/001158 US8701158W WO8707265A1 WO 1987007265 A1 WO1987007265 A1 WO 1987007265A1 US 8701158 W US8701158 W US 8701158W WO 8707265 A1 WO8707265 A1 WO 8707265A1
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product
hydrocarbyl
acrylic
polymers
polymeric
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PCT/US1987/001158
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English (en)
French (fr)
Inventor
Gordon Mark Cohen
Hans Jurgen Reich
Harry Joseph Spinelli
Clyde Spencer Hutchins
Timothy David Costello
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E.I. Du Pont De Nemours And Company
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Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to KR1019880700093A priority Critical patent/KR910002674B1/ko
Publication of WO1987007265A1 publication Critical patent/WO1987007265A1/en
Priority to DK042688A priority patent/DK42688A/da
Priority to NO880368A priority patent/NO880368L/no
Priority to NO911451A priority patent/NO911451D0/no

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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
    • 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

Definitions

  • This invention relates to durable epoxy (meth)acrylic polymers with oxirane-containing
  • Epoxy resins are widely used today in surface coatings, adhesives, castings, laminates, and encapsulation of electronic parts. Most of these epoxy resins are prepared by the reaction of 2,2-bis( 4'-hydroxyphenyl)propane [bisphenol A] and
  • the epoxides have good tensile strengths, excellent electrical insulating properties, and have outstanding adhesion to many
  • the bisphenol A-based epoxides are well known and are items of commerce (e.g., the Epon resins from Shell and the family of DER epoxides from Dow) .
  • the cyclic epoxides have also been commercially available (e.g. Union Carbide's ERL-4221, a cycloaliphatic diepoxide).
  • Methacrylate copolymers that use randomly distributed GMA have been used in the coatings industry (US Patents 3,817,946; 4,027,066; 3,730,930; 4,346,144). However, no patents or publications have been identified that report ABA triblock methacrylate polymers with GMA in the A segments.
  • GTP Group Transfer Polymerization
  • a co-catalyst which is a source of fluoride, bifluoride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selected oxyanion.
  • a co-catalyst which is a source of fluoride, bifluoride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selected oxyanion.
  • the aforesaid patents and applications also disclose capping of "living" silylketene acetal groups with agents containing capping functions such as -CHO, -C(O)-, -NCO, -Br, -Cl and
  • R is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms, or a "polymeric radical containing at least
  • Initiators which are useful in GTP- include the silicon-containing initiators of United States Patents 4,414,372; 4,524,196;
  • Initiators which are preferred for use herein are of the formula selected from (R 1 ) 3 MZ, (R 1 ) 2 M(Z 1 ) 2 and 0[M(R 1 ) 2 X 1 ] 2 wherein: R is as defined above;
  • Z is an activating substituent selected from the group consisting of
  • X'R is 2, 3 or 4; n is 3, 4 or 5;
  • M is Si, Sn or Ge, provided, however,
  • M is Sn or Ge; and each of R 2 and R3 is independently selected from H and hydrocarbyl, defined as for R a,,- above; (a) at least one of any R, R 2 and R3 in the initiator optionally containing one or more initiating substituents of the formula -Z 2-M(R1) 3 wherein
  • R 2, R3, X', Z', and n are as
  • M is Sn or Ge, (b) R 2 and R3 taken together are
  • Z 2 is -C(R 2 )-CX'
  • Electron-withdrawing substituents such as -COOR attached to the double bond of silylketene acetals are known to promote reaction with acyl chlorides and anhydrides; -CF 3 is strongly electron-withdrawing.
  • Japanese Patent Application 53/034-719 discloses the preparation of alpha-hydroxysuccinic acid esters by reaction of non-polymeric silylketene acetals with alpha-ketocarboxylic
  • A. Wissner, J. Org. Chem., 4_4_(25), 4617 (1979) discloses a similar reaction to that of Burlachenko et al., and further shows that acid-catalyzed hydrolysis of the enol ester provides a beta-ketoester.
  • the reactions of Burlachenko et al. and Wissner require that the silylketene acetal contain an olefinic hydrogen atom, which is released during the reaction as HCl.
  • G. Rousseau et al. Tetrahedron Lett.,
  • 26_(35), 4191 (1985) disclose the C-acylation of non-polymeric silylketene acetals with acryloyl and mono-substituted acryloyl chlorides to form beta-ketoesters.
  • the reaction is catalyzed by Lewis acids such as zinc bromide.
  • beta-ketoesters are produced without Lewis acid catalysis when alpha-beta unsaturated acyl chlorides are used, the reaction involving addition to carbon-carbon double bonds, not to carbonyl.
  • the acylating and sulfonylating agents and silylketene acetals employed in the invention which will be described in greater detail hereinbelow are known or obvious compounds.
  • the polymeric silylketene acetal reactants are "living" polymers prepared by Group Transfer Polymerization, supra.
  • the invention which will be described in greater detail hereinbelow also is concerned with ABA triblock polymers that have glycidyl methacrylate (GMA) as the A segments and standard (meth)acrylate monomers as the B segment.
  • GMA glycidyl methacrylate
  • These methacrylate triblock polymers have now been synthesized with epoxy groups located only at the ends of the polymer chain. Because their backbone is a (meth)acrylate (meaning acrylate and/or methacrylate) structure, these epoxy resins should be significantly more durable than conventional bisphenol A based epoxides. These new polymers should have better final properties than the cyclic epoxides because the backbone is polymeric in nature. They should be better than conventional GMA polymers that have a random distribution of epoxy groups because all of the epoxy groups are now located at the end of the chains, similar to bisphenol A epoxides.
  • the invention resides in a process for the preparation of an ABA block copolymer having a center segment between two end segments, each end segment being an oxirane- containing acrylic or methacrylic moiety, said center segment being an acrylic or methacrylic moiety not containing oxirane groups, by reacting the ingredients by Group Transfer Polymerization (GTP) techniques.
  • GTP Group Transfer Polymerization
  • the invention also is concerned with the preparation of ABA triblock polymers that have glycidyl (meth)acrylate (GMA or GA) as the A segments and standard (meth)acrylate monomers as the B segment.
  • GMA glycidyl (meth)acrylate
  • GA glycidyl (meth)acrylate
  • B segment standard (meth)acrylate monomers
  • These methacrylate triblock polymers have now been synthesized with epoxy groups located only at the ends of the polymer chain. Because their backbone is a (meth)acrylate structure, these epoxy resins should be significantly more durable than conventional bisphenol A based epoxides. These new polymers should have better final properties than the cyclic epoxides because the backbone is polymeric in nature. They should be better than conventional GMA polymers that have a random distribution of epoxy groups because all of the epoxy groups are now located at the end of the chains, similar to bisphenol A epoxides.
  • the invention still further resides in a process for preparing beta-ketoesters or beta-sulfonylesters, the process comprising contacting and reacting a silylketene acetal with a selected acyl or sulfonyl compound in the presence of a catalyst which is a source of a selected anion or oxyanion.
  • a catalyst which is a source of a selected anion or oxyanion.
  • each Q independently, is selected from
  • each R 1 independently, is a hydrocarbyl or substituted hydrocarbyl radical
  • RR 3 is H, hydrocarbyl or substituted ..- hydrocarbyl; each R and R , independently, is hydrocarbyl, substituted hydrocarbyl, or a polymeric radical.
  • the acyl or sulfonyl compound is selected from 2Q [XC(0)] n R 5 and [YS(0) 2 - n R 5 wherein:
  • X is a silicon activating group
  • Y is -F or -OAr
  • Ar is aryl or substituted aryl
  • R is a hydrocarbyl, substituted
  • the invention also resides in the beta-ketoester and beta-sulfonylester having the formulas [R 2 0 2 C-C(R 3 )(R 8 )-C(0) ] a R 5 [C(0)X] n _ a and 0 [R 2 0 2 C-C(R 3 )(R 8 )-S(0) 2 ] a R 5 [S(0) 2 Y] n _ a , respectively, wherein: 2 R is a hydrocarbyl, substituted hydrocarbyl, or a polymeric radical;
  • R R 3 is H, hydrocarbyl or substituted hydrocarbyl; 5 5 R is a hydrocarbyl, substituted hydrocarbyl or polymeric radical, of valence n; g
  • R is a polymeric radical comprised of acrylic monomer units, preferably methacrylic units;
  • X is a silicon activating group;
  • Y is -F or -OAr
  • Ar is aryl or substituted aryl; n is an integer of at least 1; and a is an integer of at least 1 but not greater than n.
  • the invention also resides in block and chain-extended polymers prepared from the above-formulated products.
  • ABA polymers There are at least four major approaches to making ABA polymers according to the invention. They are: (1) start with a monofunctional initiator and polymerize in three steps, GMA first, which makes the first A segment, followed by methyl methacrylate (MMA) which adds onto the A segment and makes an AB polymer, and finally GMA again which completes the ABA structure; (2) start with a difunctional initiator and polymerize the monomers in two steps, MMA first, which creates the middle B segment, followed by GMA which will add onto both ends simultaneously because of the difunctional initiator, making the ABA polymer; (3) start with monofunctional initiator, polymerize in two steps, GMA first, making the A segment, followed by MMA, making an AB polymer, and finally coupling the polymer to unite the two AB polymers at the B end and create an ABA polymer; (4) start with an epoxy containing initiator, the A segment, polymerize the MMA, making an AB polymer, and finally, couple the polymer which unites the
  • Monomers which can be used to prepare the center section include, for example, alkyl methacrylates and acrylates that can be used to prepare acrylic polymers. Included are methyl methacrylate, ethyl methacrylate, butyl methacrylate (BMA), hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, propyl methacrylate, phenyl methacrylate, isobornyl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, cycl
  • Both the end and center sections can include other functionality, such as for crosslinking, so long as it does not interfere with polymerization.
  • Example 1 describes (3), supra, how one might make GMA//BMA//GMA using monofunctional initiator, two monomer feeds, and a coupling agent.
  • Example 2 describes (4), supra, how one might make GMA//BMA//GMA using an epoxy initiator, a monomer feed, and a coupling agent.
  • the coupling agent is preferably diphenyl terephthalate, but it could be other suitable materials.
  • acyl is meant the moiety which remains after removal of a hydroxy group from an organic carboxylic acid.
  • sulfonyl is meant the moiety which remains after removal of a hydroxy group from an organic sulfonic acid.
  • hydrocarbyl radical is meant a radical consisting essentially of hydrogen and up to about 20 carbon atoms.
  • substituted hydrocarbyl radical hydrocarbyl which contains one or more functional substituents that are inert under reaction conditions and/or one or more ether oxygen atoms within aliphatic segments thereof.
  • polymeric radical is meant a polymeric radical containing more than 20 carbon atoms; the radical may contain the intra-chain heteroatoms 0, N or S and/or non-functional or functional substituents that are inert under reaction conditions.
  • aryl is meant an aromatic radical having at least six carbon atoms.
  • substituted aryl is meant aryl which contains one or more aliphatic substituents or functional substituents that are inert under reaction conditions.
  • a selected anion or oxyanion is meant a fluoride, difluorotrimethylsilicate, bifluoride, cyanide or azide anion, or an oxyanion defined as in U. S. Patent 4,588,795, or the radical X from the acyl compound or Y from the sulfonyl compound.
  • the selected anion or oxyanion catalysts also include the Group Transfer Polymerization catalysts described in the aforesaid GTP patents and applications, especially in U. S. Patents 4,508,880 and 4,588,795.
  • silicon activating group (X) is meant a leaving group which is capable of displacing silicon from the silylketene acetal under reaction conditions.
  • Suitable silicon activating groups which include the groups -F, g -OAr or -OC(0)R , also function as catalysts in the invention process, thus reducing the amount of added catalyst required to sustain the reaction.
  • R is hydrocarbyl or substituted hydrocarbyl.
  • silylketene acetals which are useful herein are those wherein:
  • Q is -R , and R is C, deliberately alkyl or aryl, most preferably methyl; 2 R is C.
  • R is a polymeric radical, more preferably a substituted polymeric radical; still more preferably the substituent is ester or protected ' hydroxyl; preferably the polymeric radical is comprised of acrylic monomer units, most preferably methyl methacrylate units.
  • silylketene acetals are most preferred.
  • Preferred acyl or sulfonyl compounds are ⁇ those of the formula [XC(O)] R wherein: X is -F, -OAr or -OC(0)R 6 wherein Ar is g phenyl or substituted phenyl, and R is C 1 _ a alkyl, aryl or substituted aryl; 5 R is C, g hydrocarbyl; and n is 1 or 2; most preferably 2;
  • Preferred catalysts are sources of fluoride, bifluoride or selected oxyanions; bi-oxyanions, especially biacetate, are most preferred.
  • the beta-ketoester or beta-sulfonylester products of the invention process are of the formulas [R 2 0 2 C-C(R 3 ) (R 4 )-C(0) ] a R 5 [C(0)X] n __ and [R 2 0 2 C-C(R 3 )(R 4 )-S(0) 2 ] a R 5 [S(0) 2 Y] n _ a , respectively, wherein the symbols are defined as above; preferably a is 1 or 2.
  • the ketoester or sulfonylester products wherein R 4 is limited to R8, defined above as a polymer radical comprised of acrylic monomer units, are believed to be novel.
  • a is essentially equal to n.
  • Products prepared by employing a stoichiometric excess of acyl or sulfonyl compound will contain -C(0)X or -S(0) 2 Y groups (n > a), provided n is at least 2. These groups are then available for subsequent reaction with other, different, silylketene acetals and/or with other reagents, as discussed hereinafter. Silylketene acetals are "capped",
  • Coupled or branched, or combinations thereof, by reaction with acyl or sulfonyl compounds according to the invention process, depending on the magnitude of n, and on the molar ratios of the reactants employed, as discussed hereinafter.
  • Especially preferred polymers can be prepared by coupling protected hydroxyl-functional polymeric silylketene acetals (SKA) by means of diacyl compounds wherein n is 2, or by capping polymeric SKA with monoacyl compounds wherein n is 1.
  • SKA protected hydroxyl-functional polymeric silylketene acetals
  • R is hydrocarbyl other than aryl and R is defined as above.
  • SKA are "living" acrylic polymers prepared by Group Transfer Polymerization, as described in the foregoing patents and applications, the disclosures of which have been incorporated herein by reference.
  • Particularly useful polymeric SKA of this type also contain terminal silyl ether groups at non-living ends; these groups are introduced, e.g., by use of an appropriate GTP initiator containing at least one SKA moiety of the formula
  • a solvent is desirable but is not essential unless neither reactant is a liquid.
  • Suitable solvents are those described in the aforesaid GTP patents and applications; aprotic liquids such as tetrahydrofuran (THF), toluene, benzene and the glymes are preferred. Solvent mixtures may be especially suitable.
  • Total reactant concentration should be at least about 1% (w/v), preferably in the range 5-60% (w/v).
  • the process of the invention is carried out at a temperature of about -100°C to +150°C, preferably about -15°C to about 80°C, most preferably 10° to 60°C.
  • Silylketene actel concentration can vary from about 0.1% to 100% (w/w) .
  • Polymeric SKA which are viscous liquids or solids can be used at concentrations of about 25-80% (w/w), depending on molecular weight.
  • the acyl or sulfonyl compound can be used at a concentration such that the molar ratio of acyl or sulfonyl compound to SKA is about 0.01 to about 100, preferably about 0.25 to about 10, more preferably about 0.5 to about 5.
  • Catalyst concentration can be about 0.0001 to about 50 mol% of the SKA present, preferably about 0.001 to about 10 mol%.
  • the invention process leads to capping and/or coupling of SKA molecules, depending on functionality and concentration of acylating or sulfonating compound employed.
  • a monofunctional (n is 1) acylating or sulfonating compound is employed at a molar ratio to SKA of at least 1:1.
  • a polyfunctional (n is 2 or more) acylating or sulfonating compound is employed at a molar ratio to SKA of not more than 1:2.
  • a mixture of capped and coupled SKA products can be produced by employing a functionally mixed acylating or sulfonating compound.
  • Preferred telechelic polymers are prepared in the present invention process by coupling a polymeric SKA containing a suitable functional group, such as a protected hydroxyl, e.g. trialkylsiloxy, as described above, using a difunctional acyl or sulfonyl compound in the molar ratio to SKA of about 1:2 in the presence of catalyst.
  • the polymer product contains approximately two trialkylsiloxy groups per molecule; these can be converted to hydroxyl by hydrolysis with, e.g. hydrochloric acid in ethanol.
  • the telechelic polymer is recovered by precipitation in non-solvent.
  • the telechelic polymer prepared by SKA coupling, as described above but with difunctional compound in slight molar excess of 1:2 can, before precipitation, be "finished” to give more precisely two terminal functions per molecule by following the above acylation-coupling procedure with the addition of a stoichiometric excess of a -C(0)X or -S(0)-Y reactive compound such as ethylene glycol, to convert residual -C(0)X or -S(0) 2 Y polymer end groups to OH, together with an organic base such as an amine to consume by-product HX or HY, thus driving the reaction to completion.
  • a stoichiometric excess of a -C(0)X or -S(0)-Y reactive compound such as ethylene glycol
  • -C(0)X or -S(0) 2 Y ends introduced by capping a SKA with a stoichiometric excess of di- or polyfunctional acylating compound can also be used to provide other functional end groups, e.g., OH, C0 2 H, SH and NH 2 , for later use in chain extension or coupling, by subsequent reaction of -C(0)X or -S(0) 2 Y ends with appropriate reagents such as glycols, water, di ercaptans, aminoalcohols and diamines.
  • -C(0)x or -S(0) 2 Y end groups can also be reacted ("finished") by use of monofunctional reagents containing the above functions. Such reactions will be well known to those skilled in the art.
  • Telechelic polymers can also be prepared by a combination of coupling and finishing wherein the SKA is reacted with slightly more than 0.5 mole of difunctional acylating compound per mole of SKA. -C(0)X or -S(0) 2 Y groups present in the product are then finished as described above. If only -C(0)X groups are required, with minimal coupling, the SKA can be reacted with a large excess of acylating agent, followed by sufficient finishing agent to react all -C(0)X ends plus residual acylating compound. In general, such reactions are preferably carried out in solution.
  • the flask is cooled to 10°C.
  • Tetrabutylammonium m-chlorobenzoate TBACB (200 ⁇ l of a 1.0 M solution in acetonitrile) is injected into the flask.
  • Feed I consists of glyme (3.0 g) and tetrabutylammonium m-chlorobenzoate (200 ⁇ l of a 1.0 M solution). It is started 10 minutes after the first injection of TBACB. It is added over 56 minutes.
  • Feed II is methyl methacrylate (20.0 g, 0.20 mole). It is started simultaneously with the start of the feed I. Feed II is added over 35 minutes. Twenty 5 minutes after feed II is completed, diphenyl terephthalate (1.54 g, 0.0048 mole) is added and the reaction is allowed to remain at room temperature overnight. This couples living polymer chains 10 together. Then methanol (4.0 g) is added. This should be an ABA block polymer (GMA//MMA//GMA 4//40//4) with 4 epoxy groups on each end of the polymer chains.
  • Feed II is methyl methacrylate (20.0 g, 0 0.20 mole). It is started simultaneously with Feed I and is added over 30 minutes. Twenty minutes after Feed II is completed, diphenyl terephthalate (1.08 g, 0.005 mole) is added and the reaction is allowed to remain at room temperature overnight. 5 This couples the living polymer chains together. This should be an ABA block polymer (GMA//MMA//GMA 1//40//1) with one epoxy group on each end of every polymer chain.
  • Glassware was assembled while hot, flushed with argon with additional external heating, and then maintained at room temperature (RT) under a slightly positive pressure of argon.
  • the joints of the glassware were connected without grease and wrapped with Parafil M laboratory film.
  • Serum caps, for syringe introduction of solvents and reagents, were secured onto openings in the glassware by tightly-wrapped nylon ties.
  • Methyl methacrylate (MMA, Aldrich Chemical Co.) was purified and dried by passage through a column of anhydrous alumina, neutral grade (Woelm) , exiting the column through a syringe needle into a serum-capped bottle kept under a slightly positive pressure of argon.
  • Tetrahydrofuran THF was dried over sodium and distilled from sodium benzophenone ketyl immediately before use.
  • Acetonitrile was dried by distillation from P 2 °5 4 Initiators were distilled in a 12-inch spinning band column. Dried solvents, initiators, and catalyst solutions were stored in "Aldrich" bottles in drierite-packed desiccators. Analyses
  • H-NMR spectra were recorded with a 5 Nicolet 360WB spectrometer.
  • Molecular weights were determined by gel permeation chromatography (GPC) using a Waters Associates GPC with a 590 pump, 401 R.I. detector and 4 Microstyrogel columns, 100,000, 10,000, 500, and 100.
  • Hydroxy-PMMA and a, ⁇ -dihydroxy-PMMA content of the product was determined by high pressure liquid chromatography, employing a Du Pont 5 Instruments Series 800 Gradient Controller and Chromatographic Pump and a Waters Associates R401 refractive index detector.
  • a 100-ml 3-neck r.b. flask was outfitted with a magnetic stirring bar, argon inlet adapter, - serum cap, and thermowell. The apparatus was dried as usual and maintained under a slight positive pressure of argon. To the flask were added dry THF
  • Example 3 The reaction described in Example 3 was repeated except that acetyl fluoride (Aldrich) was used in place of benzoyl fluoride and 1 M tris(dimethylamino)sulfonium bifluoride (TASHF 2 )/CH 3 CN (40 ⁇ l , 0.5 ol %) in place of biacetate.
  • acetyl fluoride Aldrich
  • TASHF 2 tris(dimethylamino)sulfonium bifluoride
  • CH 3 CN 40 ⁇ l , 0.5 ol %
  • Example 5 Benzoyl Fluoride Capping of Polymeric SKA Methyl methacrylate (25 ml) was polymerized by Group Transfer polymerization (GTP) in a 250-ml, 4-neck r.b. flask, equipped with an argon inlet, thermocouple well, serum cap, and magnetic stirring bar, charged with dry THF (75 ml), [ (2-methyl-l-[2-(trimethylsiloxy)ethoxy]-l- propenyl)oxy]trimethylsilane (TTEB) (2.5 ml, 7.9 mmol), 0.5 M (8 ⁇ l , 0.051 mol % of TTEB).
  • GTP Group Transfer polymerization
  • the MMA was added by syringe pump at 0.5 ml/min only after an incubation period of 20 min. Upon addition of MMA, the temperature rose from 24.2°C to 39.4°C in 36 min (18 ml MMA added) and declined slowly thereafter to 38.8°C.
  • the precipitate was filtered on a vacuum filter funnel, rinsed three times with hexane, partially dried on the funnel, and dried overnight in an evaporating dish in a fume hood.
  • a sample was dissolved in CDC1-, for proton nmr analysis, the remainder dried for 24 h at 65°C in a vacuum oven, to constant weight.
  • the dry sample was weighed and a portion dissolved in THF for GPC analysis.
  • the weight of recovered poly(methyl methacrylate) (PMMA) was 21.08 g, the calculated TTEB residue 1.7 g.
  • the MMA conversion was thus 83.7%, theor.
  • Mn (100% basis) was 3260.
  • the MMA/benzoyl-capped end ratio was calculated from proton nmr spectra, by comparing peak areas for the MMA resonance at ⁇ 3.55 ppm (MeO) and benzoyl 5 resonance at ⁇ 7.2-7.7 ppm (Ph). As an internal check, the MMA/initiator fragment ratio was also calculated from ⁇ 3.55 ppm (MeO) and the initiator fragment's ⁇ 0.1 (Me 3 SiO) peaks.
  • 25 monomer/end-group ratio was calculated from nmr resonances for MMA at ⁇ 3.55 (MeO), acetyl cap at ⁇ 2.05 (overlapping slightly with polymer resonances), and initiator fragment at ⁇ 0.1 (Me 3 SiO) .
  • Example 5 The procedure of Example 5 was repeated with the following changes: MMA was polymerized using 50 ⁇ l of 0.045 M Bu 4 NOAc-HOAc/THF, all of
  • MMA was fed in over a 55-min period, from a pressure-equalizing dropping funnel instead of a syringe pump.
  • the polymer solution was stirred thereafter for 4 h and then capped by a solution of 3.1 g phenyl benzoate (15.6 mmol) in 25 ml of very dry THF, transferred by cannula.
  • the temperature rose very little and more catalyst was added (100 ⁇ l of 0/045 M Bu 4 NOAc «HOAc/THF and 100 ⁇ l of 0.2 M Bu 4 NOAc-HOAc/CH,CN) .
  • the temperature rose 0.5°C and the solution slowly acquired a slight yellow color.
  • Total recovered PMMA was 25.0 g, a 93.3% MMA conversion.
  • the theoretical MMA/end-group ratio was 29.4 (100% conversion basis) and nmr on polymer purified by re-precipitation gave 41.3 for MMA/capping fragment (MeO/Ph) and 35.6 for MMA/initiator fragment (MeO/Me 3 SiO).
  • Example 5 The procedure described in Example 5 was repeated with the following changes: MMA was polymerized using 35 ⁇ l of 0.04 M Bu 4 NOAc «HOAc «6 H 2 0/THF and MMA was fed in over a 65 min period, from a pressure-equalizing dropping funnel. The polymer solution was stirred thereafter for 2-1/2 hours and then capped by a solution of 3.6 g benzoic anhydride (15.9 mmol) dissolved in 10 ml of very dry THF and transferred by cannula. After 200 ⁇ l catalyst was added, the temperature rose 2.3°C.
  • the recovered PMMA 32.6 g, was dried only at room temperature (RT), then dissolved in 70 ml ethyl acetate and mixed with 2.3 g KOH in 70 ml deionized water, to remove unreacted benzoic anhydride. After vigorous stirring for 30 min., the mixture was shaken in a separatory funnel and the aqueous phase removed. The ethyl acetate layer was extracted with three 70- ⁇ tl portions of deionized water, dried 2 h over anhydrous MgS0 4 and filtered. The filtrate was poured into well-stirred hexane to precipitate the polymer. The polymer was dried only at RT and after 3 days weighed 26.7 g.
  • the theoretical MMA/end-group ratio was 29.4 and nmr gave 32.7 for MMA/capping fragment (MeO/Ph) and 66.8 for MMA/initiator fragment (MeO/Me 3 SiO) ; the high latter value arose from hydrolytic loss of Me 3 Si end groups caused by KOH treatment.
  • Example 9 Example 9
  • the product from the third sublimation was recrystallized overnight from 70 ml dry toluene/150 ml petroleum ether.
  • the mother liquor was removed from the solid by transferring it via a cannula to a serum-capped flask, under argon.
  • the solid was rinsed five times with 50-ml portions of 1:2.2 toluene-petroleum ether, the rinsings removed each time by cannula transfer to the mother liquor.
  • the solid was blown dry by a nitrogen sweep through the flask used for the recrystallization. A second crop was taken by concentrating the combined mother liquor plus rinsings with a nitrogen sweep applied to the heated liquid.
  • the volume of the concentrate was tripled by the addition of petroleum ether, and the solution allowed to cool to RT and then set aside for 3 days.
  • the product/solvent mixture was chilled 1 h in ice water and the mother liquor transferred away by cannula.
  • the solid was rinsed at RT with four 30-ml portions of petroleum ether and dried as above. The crops were weighed and portions placed in melting point tubes, in a dry box.
  • Methyl methacrylate was polymerized as follows:
  • a 250-ml 4-neck r.b. flask was outfitted with a magnetic stirring bar, pressure-equalizing dropping funnel, thermowell (for thermocouple), and argon inlet tube. After being heated with a heat-gun under argon flush, the apparatus was allowed to cool to RT and kept under a slight argon pressure.
  • Biacetate catalyst solution 200 ⁇ l was added to the stirred mixture and a 3.5°C temperature rise observed over the next 13 minutes. The reaction was left to stir an additional 1 h, then left unstirred at RT for 16 h. The solution slowly yellowed.
  • Example 9B The procedure of Example 9B was repeated but without adding more biacetate catalyst during coupling. The temperature rose only 0.3°C during coupling. Recovered PMMA (dried 48 h in a 65°C vacuum oven) weighed as follows (excluding 0.3g remaining on glassware): A- 1.2 g, B- 24.8 g. The overall MMA conversion was 94.5%. GPC Analysis:
  • Example 11 Diphenyl Terephthalate Coupling of Polymeric SKA
  • MMA was polymerized with 50 ⁇ l of 0.033 M Bu 4 NOAcHOAc6 H 2 0/THF catalyst, all of which was added at the start, and MMA feed took 1 h.
  • Coupling was started 2 h after the completion of MMA feed, with 2.50 g diphenyl terephthalate (7.85 mmol) in 150 ml of very dry THF. The solution yellowed but there was little exotherm.
  • Biacetate catalyst solution 100 ⁇ l , 0.033 M was added and the color darkened and the temperature rose 0.4°C over the next 5 min.
  • Example A All the polymer (sample A) was isolated, washed, and dried; recovery 26.1 g; 93.8% MMA conversion. Twenty g of A were dissolved in 100 ml of very dry THF and converted to ⁇ , ⁇ -dihydroxy-PMMA (sample B) by treatment with 5.1 ml of 10% (w/w) HCl/methanol for 3 h at RT. The polymer was isolated by precipitation in excess hexane, washing, and drying at RT and in a 65°C vacuum oven.
  • the solid was dissolved in 200 ml hot benzene and left at RT for 2-1/2 days.
  • the first crop was obtained by vacuum filtration.
  • the mother liquor was concentrated to about 150 ml and a second crop obtained by filtration.
  • a third crop was obtained after concentrating the mother liquor to ca. 75 ml.
  • an unusual melting point behavior of the samples suggests decomposition.
  • the solids melt at about 140-150°C and resolidify, melting again only at about 5 280-310°C.
  • a slight amount of melting occurs at ca. 140°C, but most melts only at 280-320°C.
  • Example 9B The procedure of Example 9B was repeated with the following changes: MMA was polymerized 0 with 2.5 ml TTEB initiator (7.9 mmol) and 20 ⁇ l 0.04 M Bu 4 NOAc•HOAc•6 H 2 0/THF catalyst, and MMA feed took 55 min. Coupling was started 3 h thereafter, with 1.47 g of TDB (first crop, 3.93 mmol) in 60 ml of very dry THF. The temperature 5 rose 0.1°C, and 0.2 ml of biacetate catalyst was added. The temperature rose another 0.1°C. No aliquot was removed before hydrolysis to hydroxyl ends. Recovered PMMA (dried 48 h in a 65°C vacuum oven), 23.8 g. 0 GPC Analysis:
  • Example 12B The procedure of Example 12B was repeated except that coupling was begun 2.5 h after the MMA feed with 1.60 g of solid DNPT (7.9 mmol). Additional biacetate catalyst (100 ⁇ l ) caused the temperature to rise 0.2°C and a yellow color to appear temporarily. Much of the solid did not dissolve even overnight. The solid was filtered off and the polymer hydrolyzed to diol and isolated as usual. No aliquot was removed before hydrolysis.
  • Example 12B The procedure of Example 12B was repeated except that 35 l of 0.04 M Bu 4 NOAc- * HOAc-6 H 2 0/THF was used for polymerization, MMA feed took 45 min and coupling was started 4.75 h after the MMA feed with 1.1 ml triethylamine (Fisher, 99%, 7.8 mmol) and 0.82 g terephthaloyl chloride (Aldrich, 97%, 3.9 mmol) in 16 ml of very dry THF. The solution turned yellow.
  • the mixed sulfonic-carboxylic dianhydride, terephthaloyl bis(p-toluenesulfonate) was prepared according to C. G. Overberger and E. Sarlo, J. Am. Chem. Soc, 8_5, 2446 (1963). A pure sample, mp 173-6°C (lit. 174-6°C) was obtained.
  • Example 12B The procedure of Example 12B was repeated in a 500-ml r.b. flask, except that coupling was begun 3.5 h after the MMA feed with 1.86 g of the mixed anhydride described above (3.9 mmol) in 190 ml of very dry THF. The temperature rose 1.1°C. When 0.2 ml of biacetate solution was added, there was no further exotherm and so another 0.8 ml was added over the next 10 min, without an effect on temperature.
  • Example 12B The procedure of Example 12B was repeated except for the use of 35 ⁇ l of 0.04 M
  • Example 12B The procedure of Example 12B was repeated except for the use of 35 ⁇ l of 0.04M Bu.NOAcHOAc-6 H 2 0/THF and a 70-min MMA feed.
  • the polymer solution was treated with 1.34 g of TF 2 (7.9 mmol) in 10 ml of very dry THF, 4.5 h after the MMA feed. After 0.2 ml of biacetate was added, the temperature rose 2.0°C and the solution yellowed slightly. The flask was stirred 1 h and left unstirred 17 h.
  • the a 7.7 multiplet represents TF 2 coupling and perhaps half of the protons of the TF 2 -capping moieties.
  • the a 8.05 multiplet represents TF 2 -capping.
  • a tared, dry 50-ml r.b. flask was stoppered with a serum-cap and cooled under argon.
  • About 0.60 ml of molten bis(p-isocyanatophenyl)- methane (MDI, Upjohn, Isonate 125 M) was injected into the flask with a syringe pre-warmed in the same oven.
  • the weight of MDI, 0.622 g was obtained by re-weighing the r.b. flask.
  • a,ca-Dihydroxy-PMMA, sample B prepared above after drying for 3 days in a 65°C vacuum oven, was weighed out quickly while hot.
  • the stopper was briefly removed from the flask while 8.57 g of PMMA (ca. 1:1 mole ratio) and a magnetic stirring bar were introduced. Stoppered again, and under argon, the flask was charged with 10 ml of very dry THF.
  • the flask was stirred for 15 min to dissolve all ingredients and then 4 drops of dibutyltin dilaurate (T-12 Catalyst, M and T Chemical Co.), were added by disposable Pasteur pipette. No viscosity increase was seen after 5 min, but stirring was difficult after 15 min.
  • a sample (C) was removed from the flask with a spatula.
  • the reaction flask was connected to a dried short-path still head and receiving flask, the assembly kept under argon.
  • the reaction flask was heated to reflux to drive off the THF and then held in an oil bath at 115°C for 0.5 h and at 107°C for 3 h. It was then left at RT ' for 12 h.
  • the results show that the dihydroxy-PMMA substrate contained a sufficient number of difunctional hydroxyl-terminated chains to be extended to high molecular weight polymer by reaction with MDI.
  • the mixture was slightly acidified with 10% aq HCl.
  • a fine solid precipitated which was isolated by vacuum filtration, rinsed twice with water on the funnel, and dried in part on the funnel.
  • the slightly wet, waxy crude product weighed 66.2 g (theory, 49.2 g) .
  • the product was tested with a variety of recrystallization solvents, then 31.7 g thereof was dissolved in 50 ml of THF and solid impurities removed by gravity filtration of the hot solution. Mixing with 500 ml of water gave 28 g of precipitate which was redissolved in about 80 ml of THF, the solution filtered through Celite to remove additional solid impurities.
  • the clear THF solution was concentrated to about 50 ml and, still hot, brought to the point of just becoming cloudy by adding about 25 ml of methanol.
  • the product which crystallized overnight was isolated by vacuum filtration, rinsed twice with 2:1 methanol/THF, and dried 1 h in a 65°C vacuum oven. This first crop weighed 9.35 g.
  • the filtrate was concentrated to 20 ml and 10 ml methanol were added.
  • the second crop obtained from overnight crystallization was isolated as above and weighed 1.57 g.
  • the products were further purified by dissolving both crops in 50 ml of hot ethyl acetate, filtering out impurities, concentrating to about 15 ml, and adding 8 ml of hexane to reach the cloud point. Solids began to appear in 1 h and were voluminous in 3 h. The solid was isolated by vacuum filtration, rinsed with 2:1 ethyl acetate/hexane, and dried on the filter and then for 1 h in a 65°C vacuum oven with slight nitrogen bleed. It weighed 4.3 g (18.3% yield), its elemental analysis and proton NMR spectrum consistent with theory. Calcd.
  • the analyses indicate coupling.
  • a solution of 32.6 g of 2,4-dichlorophenol (0.20 moles) in 100 ml of dry pyridine was dripped into the stirred mixture over 15 min, causing a 1.3°C exotherm. The mixture thickened and turned white. It was stirred 6 h more and left unstirred overnight.
  • Example 9B The procedure of Example 9B was repeated with the following changes.
  • MMA was polymerized with 2.5 ml TTEB initiator (7.9 mmol) and 30 microlitres of 0.04 M Bu 4 NOAc « HOAc-6H 2 0/THF catalyst, and MMA feed took 80 min. Coupling was begun 3 h thereafter with 1.80 g (3.9 mmol) of the first crop of recrystallized DCPT in 250 ml of very dry THF and 0.2 ml of 0.04 M biacetate catalyst, the temperature rising 1°C because of the warmth of the DCPT solution. After 18 h, the polymer was hydrolyzed to hydroxyl end-groups by stirr-ing 1 h at room temperature with 5 ml of 10% HCl/methanol. No aliquot was removed prior to hydrolysis. The recovered, 65°C vacuum oven-dried PMMA weighed 28.5 g.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
PCT/US1987/001158 1986-05-29 1987-05-21 Acylation and sulfonation of silylketene acetals WO1987007265A1 (en)

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KR1019880700093A KR910002674B1 (ko) 1986-05-29 1987-05-21 실릴케텐 아세탈의 아실화
DK042688A DK42688A (da) 1986-05-29 1988-01-28 Acylering og sulfonering af silylketenacetaler
NO880368A NO880368L (no) 1986-05-29 1988-01-28 Acylering og sulfonering av silylketenacetaler.
NO911451A NO911451D0 (no) 1986-05-29 1991-04-12 Fremgangsmaate for fremstilling av en aba-blokk-kopolymer med et midtsegment mellom to endesegmenter.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012229354A (ja) * 2011-04-27 2012-11-22 Hitachi Chemical Co Ltd 両末端にポリグリシジルブロックを有するアクリル樹脂及びその製造方法、それを用いた樹脂組成物
US10588694B1 (en) 2007-01-19 2020-03-17 Joseph Neev Devices and methods for generation of subsurface micro-disruptions for biomedical applications

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DE1076133B (de) * 1958-01-11 1960-02-25 Wolfen Filmfab Veb Verfahren zur Herstellung von ª‡,ª‡'-(Diacyl)-bis-ketocarbon-saeureestern
GB842725A (en) * 1955-10-27 1960-07-27 Spofa Spojene Farmaceuticke Zd Methods of preparing diketodicarboxylic acid esters, and diketodicarboxylic acid esters when prepared by said methods
CA701643A (en) * 1965-01-12 W. Kluiber Rudolph .beta.-DIKETONE ESTERS AND PROCESS FOR PREPARING SAME
US4388448A (en) * 1981-02-23 1983-06-14 E. I. Du Pont De Nemours And Company Glycidyl methacrylate polymers, their preparation and solvolysis products
DE3302847A1 (de) * 1982-04-26 1983-11-03 Koppers Co., Inc., 15219 Pittsburgh, Pa. Verfahren zur herstellung eines delta-ketocarbonsaeureesters
US4414372A (en) * 1982-06-17 1983-11-08 E. I. Du Pont De Nemours & Co. Process for preparing living polymers
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JPS59213701A (ja) * 1983-05-19 1984-12-03 Nippon Paint Co Ltd 反応性アクリル重合体組成物
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CA701643A (en) * 1965-01-12 W. Kluiber Rudolph .beta.-DIKETONE ESTERS AND PROCESS FOR PREPARING SAME
GB842725A (en) * 1955-10-27 1960-07-27 Spofa Spojene Farmaceuticke Zd Methods of preparing diketodicarboxylic acid esters, and diketodicarboxylic acid esters when prepared by said methods
DE1076133B (de) * 1958-01-11 1960-02-25 Wolfen Filmfab Veb Verfahren zur Herstellung von ª‡,ª‡'-(Diacyl)-bis-ketocarbon-saeureestern
US4388448A (en) * 1981-02-23 1983-06-14 E. I. Du Pont De Nemours And Company Glycidyl methacrylate polymers, their preparation and solvolysis products
US4417034A (en) * 1981-06-30 1983-11-22 E. I. Du Pont De Nemours & Co. Living polymers and process for their preparation
DE3302847A1 (de) * 1982-04-26 1983-11-03 Koppers Co., Inc., 15219 Pittsburgh, Pa. Verfahren zur herstellung eines delta-ketocarbonsaeureesters
US4414372A (en) * 1982-06-17 1983-11-08 E. I. Du Pont De Nemours & Co. Process for preparing living polymers
US4524196A (en) * 1982-06-17 1985-06-18 E. I. Du Pont De Nemours And Company Process for preparing "living" polymers
JPS59213701A (ja) * 1983-05-19 1984-12-03 Nippon Paint Co Ltd 反応性アクリル重合体組成物
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CHEMICAL ABSTRACTS, Volume 61, No. 33, issued August 1964 (Columbus, Ohio, USA, GELIN, RENE et al, "Preparation of beta-Oxo Diesters and beta-Diketone Esters", the Abstract No. 4209, Compt. Rend. 258(19), 4783-4 (1964). *
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10588694B1 (en) 2007-01-19 2020-03-17 Joseph Neev Devices and methods for generation of subsurface micro-disruptions for biomedical applications
JP2012229354A (ja) * 2011-04-27 2012-11-22 Hitachi Chemical Co Ltd 両末端にポリグリシジルブロックを有するアクリル樹脂及びその製造方法、それを用いた樹脂組成物

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AU612581B2 (en) 1991-07-18
DK42688A (da) 1988-03-29
NO880368D0 (no) 1988-01-28
AU626496B2 (en) 1992-07-30
DK42688D0 (da) 1988-01-28
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NO911451D0 (no) 1991-04-12
KR910002674B1 (ko) 1991-05-03
NO880368L (no) 1988-03-28
EP0272285A4 (en) 1990-04-10

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