AU612581B2 - Acylation and sulfonation of silylketene acetals - Google Patents

Description

PCP

AU-AI-75128/81 WORLD INTELLECTUAL PROPERTY ORGANIZATION International Bureau 0 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 1 1 International Publication Number: WO 87/ 07265 CO7C 69/176, 69/738, 147/02 C07C 147/06, CO8G 2/24 A nteionaublication Date: 3 December 1987 (03.12.87) C08G 2/38 1 V I

I

(21) International Application Number: PCT/US87/01158 (22) International Filing Date: (31) Priority Application Numbers: 21 May 1987 (21.05.87) 868,083 008,960 048,958 May 1986 (29.05.86) January 1987 (30.01.87) 19 May 1987 (19.05.87) (32) Priority Dates: (33) Priority Country: 9

I

9586 Salem Terrace, Arlington, TN 38002 COS- TELLO, Timothy, David 224 East Court, Wilmington, DE 19810 (US).

(74) Agent: ROMBACH, Louis, E. I. Du Pont De Nemours Company, Legal Department, Patent Division, Wilmington, DE 19898 (US).

(81) Designated States: AT (European patent), AU, BE (European patent), BR, CH (European patent), DE (European patent), DK, FR (Europeain patent), GB (European patent,), IT (European patent), JP, KR, LU (European patent), NL (European patent), NO, SE (European patent), Published With international search report.

4 FEB 1988

AUSTRALIAN

2 2 DEC 1987 PATENT Q141 (71) Applicant: E, I, DU PONT DE NEMOURS COM- PANY [US/US]; 1007 Market Street, Wilmington, DE 19898 (US).

(72) Inventors: COHEN, Gordon, Mark 627 Greythorne Road, Wynnewood, PA 19096 REICH, Hans, Jurgen 514 Edward Street, Madison, WI 53711 (US), SPINELLI, Harry, Joseph 4604 Big Rock Drive, Wilmington, DE 19802 HUTCHINS, Clyde, Spencer L (54) Title: ACYLATION AND SULFONATION OF SILYLKETENE ACETALS (57) Abstract Process for the preparation of beta-ketoesters or beta-sulfonylesters wherein silylketene acetals, iecludir, "living" (meth)acrylic polymers prepared by Group Transfer Polymerization (GTP), are reacted with an acyl compoaid, such as diphenyl terephthalate, or a sulfonyl compound such as benzene bis-sulfnyl fluoride, in the presence or 'I TP-fffective (oxy)anion catalyst such as b!fluoride or m.chlorobenzoate. The keto- or sulfonylester products include capped 'iiving" polymers, telechelic polymers, sach as alpha, omega-dihydroxy polymethyl (meth)acrylatt, chain-extended polymers, and branched or block copolymers. Telechel- polymers are useful for preparing cioss-linked )r block polymers by reaction of the functional end groups. AB block liymers, for example from methyl methacrylate and n,,butyl acrylate, can also be prepared by coupling different polymeric silylketene acetals prepared by GTP with a dacyl Compound such as diphenyl terephthaate, ABA block copolymers can be prepared by first preparing an AB block polymeric silylketene acetal by GTP, then coupling with a diacyl compound as just described, Especially useful ABA block copolymers have end segments which are oxirane-containing (meth)acrylic moieties such as glycidyl methacrylate, separated by a central segment which is a (meth)acrylic moiety without oxirane groups, such as methyl mhoth-rylat AB block copolymers coniaining hard and soft segments provide tough, flexible materials for adhesives and coatings. An ABA block copolymer having epoxy groups at the ends of the polymer chain provides enhanced toughness, and the tribloak structure imparts improved outdoor durability in the use of these polymers as surface coatings, adhesives, castings, laminates and encapsulants for electronic parts.

i Lii iii i i :LIIi'": L iVO 87/07265 PCT/US87/01158 1

TITLE

Acylation and Sulfonation of Silylketene Acetals BACKGROUND OF THE INVENTION Field of the Invention This invention .eiates to durable epoxy (meth)acrylic polymers with oxirane-containing terminal groups; to processes for preparing beta-ketoesters and beta-sulfonylesters from silylketene acetals; and to block and chainextended polymers prepared therewith.

Background 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 epichlorohydrin. This generates a polymer with a backbone composed of ether links between bisphenol A structures and hydroxy propylene moieties. There is also one epoxy group (oxirane) at each end of the polymer backbone, These resins can be cured by reacting their epoxy groups with crosslinking agents, such as anhydrides, amines, and acids.

When cured, the epoxides have good tensile strengths, excellent electrical insulating properties, and have outstanding adhesion to many surfaces.

However, a major weakness of these conventional epoxy Yesins is their poor outdoor ii 'II WO 87/07265 PCT/US87/01158 2 durability. The ether links in their backbone as well as the aromatic rings lead to poor UV and oxidative stability. Because of this limitation, these epoxy resins cannot be used in systems that require long term outdoor exposure.

Previously, two approaches have been taken to make durable epoxides. One involves the synthesis and use of low molecular weight cyclic or acyclic diepoxides and the other involves the synthesis and use of copolymers of glycidyl methacrylate (GMA). Both of these approaches, though they generate epoxides that are more durable than bisphenol A based resins, have significant deficiencies. The cyclic-type of epoxides are not polymers and have only a very low molecular weight segments binding the two epoxy groups. These materials tend not to have the superior physical properties of conventional epoxides. The systems based on random copolymers of GMA do not have the controlled placement of the epoxy groups, That is, these copolymers have the epoxy groups distributed randomly along the entire backbone of the methacrylate chain. The placement of the epoxy groups at the end of the polymer chain, as seen in bisphenol A epoxides, imparts important properties such as toughness. The random placement of the epoxy groups lowers final properties.

The bisphenol A-based epoxides are well known and are items of commerce the Epon resins from Shell and the family of DER epoxides from Dow). The cyclic epoxides have also been commercially available 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; JI 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 segment.

Patents and publications concerning Group Transfer Polymerization (GTP) disclose the ability to make block structures using that process. However, none of these discloses the epoxy triblock structure, nor the advantages of that structure as a durable epoxy resin. For a detailed discussion of GTP see Webster et al., "Group Transfer Polynetizationi A New and Versatile Kind of Addition Polymerization", J. Am. Chem. Soc. 105, 5706 (1983); and United States Patents 4,414,372; 4,417,034; 4,508,880; 4,524,196; 4,581,428; 4,588,795; 4,598,161; 4,605,716; 4,622,372; 4,656,233; 4,711,942; 4,681,918; and 4,822,859. The 0e disclosures of these patents are hereby incorporated by reference. More 0 specifically, these patents disclose processes for polymerizing an acrylic or maleimide monomer to a "living" polymer in the presence of: an initiator having at least one initiating site and which is a .*k51 tetracoordinate organo (Si, Sn or Ge) compound, including such compound S having at least one oxygen, nitrogen or sulfur atom attached to Si; and 0 (ii) a co-catalyst which is a source of fluoride, biflouride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selected oxyanion.

-3- WQ 87/07265 PCT/US87/01158 The aforesaid patents -an application also disclose capping of "living" silylketene acetal groups with agents containing capping functions such as -CHO, -NCO, -Br, -Cl and -TiC13.

In GTP processes, the polymer produced is "living" in that the polymerization is characterized by the presence, in the growing and in the grown polymer, of a moiety containing the aforesaid metal at "living" ends and the activating substituent or diradical, or a tautomer thereof, at "nonliving" ends of the polymer.

Monomers which are useful in GTP are of the formula CH 2 =C(Y)X wherein: X is -CN, -CH=CHC(O)X' or Y is -CH 3 -CN or -CO 2 R, provided, however, when X is -CH=CHC(O)X', Y is -H or -CH3; X' is -OSi(Rl)3, -OR or -NR'R"; each R independently, is H or a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms, provided that at least one R group is not H; 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 carbon atoms, any of said radicals optionally containing one or more ether oxygen atoms within aliphatic segments thereof, optionally containing one or more functional WO 87/07265 S87/07265 PCT/US87/01158 substituents that are unreactive under polymerizing conditions, and optionally containing one or more reactive substituents of the formula

)=CH

2 wherein Y 1 is H or

CH

3 and Z' is O or NR'; and each of R' and R" is independently selected from CI_ 4 alkyl.

Initiators which are useful in GTP.

include the silicon-containing initiators of United States Patents 4,414,372; 4,524,196; 4,417,034; 4,508,880; 4,581,428; aaf4,656,233, -gigaa Seri.l.... 09 e 660,580 andr ,supra. Initiators which are preferred for use herein are of the formula selected from

(R)

3 MZ, (R 2

M(Z

1 2 and O[M(R 2

X

1 2 wherein: R is as defined above; Z is an activating substituent selected from the group consisting of 20 R2 R O 0 -C--CN -CN, 3 3 R" R 0 R 2

R

2 II II (CHJ L (CH R2

F

-N=C=C-R 3

-OC==C-R

2 2 X I t X' R Z'

S(CH

A

WO 87/07265 6 PCT/US87/01158, -0C =CR R, -OP(NR'R" 2 -OP(OR 1 21 -OP[OSi(R )312 and mixtures thereof wherein R, R R11, X' and Z' are as defined above; z is the activating substituent -OC=C-R 2

XIR

3 m is 2, 3 or 4; n is 3, 4 or M is Si, Sn or Ge, provided, however, when Z is 0 R2 11 2 Cr

-?~CH

2 o L(CH 4 PT is Sn or Ge; and each of R 2 and,- R 3 is itdependently selected from H and hydrocarbyl, defined as for R boe; at least one of any V, R2and R3 in the initiator optionally containing one ov more initiating substituents of the formula -~Z 2 )3 wherein and Rlare as defined above; Z2is an activating diradical selected from the group consisting of WO 87/07265 PCT/US87/O 1158 0 0R 2 it It P -C(R -Z'-C-C-I -Z-C=C(R 2)(R 3, 0- 0 2C 0-

Z

L(CH 2 0 '2r C C- -C--R2 and mixtures LCH 2 (H nc 2 3 thereof, wherein R R m and ni are as defined above provided however when z2is 0 itF C

C-,

(H2) M is Sn or Ge, R2and R3taken together are 3 CH-! CH 3 if Z is -C CX, or -OC=C(R 2 3 and/or Z 2 is R 3X 0 of 2)(R and ~l:lli ri.I WO 87/07265 PCT/US87/01158 X' and either R 2 or R taken together are O O 0 0 if Z is

R

1 0 if C CX' or -OC=C(R2)(R 3 and/or F I R

X'

0 p nI

Z

2 is -C(R 2

-CX'.

R. A. Olofson and J. Cuomo, Tetrahedron Lett., 21, 819 (1980) disclose fluoride ion catalyzed 0-acylation of silyl enol ethers with compounds of the type RXC(0)F where X is 0, NR' or a single bond, R is a cyclic or acyclic aliphatic radical and R' is methyl or, together with R, morpholino. C-acylation of silyl enol ethers is not reported.

United States Patent 4,482,729 discloses reactions of non-polymeric fluorine-containing silylketene acetals such as CF 3 CH=C(OSi(CH 3 3

)OCH

3 including reaction with a propionyl chloride, to 2form the alpha-trifluoromethyl-beta-ketoester

CH

3

CH

2 C(0)CH(CF 3

)CO

2

CH

3 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 esters in the presence of a Lewis acid catalyst.

i WPi 87/07265 PCT/US87/01 158 E. Colvin, "Silicon in organic Synthesis", page 234, Butterworths, Boston (1981); and M. W. Rathke and D. F. Sullivan, Tetrahedron Lett. 1297 (1973) show that even with amine promoters, acylation of silylketene acetals (SKA) does not occur with acyl chlorides when the SKA contains two at-substituents. Polymerizing methacrylate chain ends have two such substitueats.

These references further disclose that a stoichioinetric amount of amine is required even when less than two c-substituents are present.

Acylation of non-polymeric silyl enol ethers is well known. For example, Rl. Noyori, ec.

al., Tet., 37, 3899 (1981) disclose the acylation of silyl enol ethers in the presence of trimethylsilyl triflate as the (Lewis acid) catalyst. R. F. Tirpak et al., J. Org. Chem. 47, 5099 (1982) disclose acylation of silyl enol ethers with acyl chlorldes in the presence of Lewis acid promoters. K. P. Kramarova et all,, J* Gen. Chem.

USSR, 43( 1843 (1.973); ibid., 45, 469 (1975) disclose C-acylation, usually, of silyl enol ethers by reaction with acyl chlorides or anhydrides; the former require catalytic amnunts of mercuric chloride; the latter contain activating alpha-halogen atoms.4 G. S. Burlachenko et al., J, Gen. Chem., USSR, 43, 1708 (1973) disclose the reaction of alkyl silylketene acetals with acetyl chloride oe triethylsilylacetyl chloride. The veactiin produces alkylsilyl derivatives of acetoacetic enol, esters, e.g. CH COC. 2CH -C(OCfl)H (CH)

CH

3 C(O~i[C 2

H

5 13 )=CHIC 2 Cfl 3 A. Wissner, J, Org. Chem., 44(145), 1617 (1.979) discloses a similar reaction to that of Bi.rlachenko et al., and further shows that T 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 HC1.

G. Rousseau et al., Tetrahedron Lett., 2(35), 4191 (1985) disclose the C-acylation of non-polymeric silylketene acetals with acryloyl and monosubstituted acryloyl chlorides to form beta-ketoesters. The reaction is catalyzed by Lewis acids such as zinc bromide. Mainly, beta-ketoesters are produced S* without Lewis acid catalysis when alpha-beta unsaturated acyl chlorides are used, the reaction involving addition to carbon-carbon double bonds, not to carbonyl, :10' The acylating and sulfonylating agents and silylketene acetals employed in the invention which will be described in greater detail hereinbelGw are known or obvious compounds. The polymeric silylketene acetal reactants are "living" polymers prepared by Group Transfer Polymerization, supra.

SUMMARY OF THE INVENTION: 1 The irnvendon resides in a process for preparing beta-ketoesters or 4 0 00 10 1WO 87/07265 -1 II PCT/US87/0l 158 beta-sulfon-ylesters, the process comprising contacting arnd reacting a silylketene acetal with a selected acyJ. or sulfonyl compound in the presence of a catalyst which is a source of a selected anion or oxyaninn- The silylketene acetal is of the formula R3 ,-OSi 3 R il7 C.

0 NO 2 wherein: each Qf independentlyt is selected from F -O -N(fl 2 and SR1 each R independently, is a hydrocArbyl or substituted hydrocarbyl radical; 3 R Is H, hydrocarbyl or substituted each IR and R, t nd(-Pendently, is hydrocarbyl, substituted hydrocarbyl, or a polymeric radical.

The acyl or sulfonyl compound is selected from R, and. YS 5 wherein-, X is a silicon activatin5 group; Y is -FE or -OAr; At~ is aryl or~ substituted aryll a hydroc~irbylf suibstituted hydrocarby. or polymeric rical, of valence n; arl~ n is an integer of at least lo, The Invention also resides In the beta-ketoester and beta-su3lfonylester having ttNe formulas CR 20 2 C-.C(R 3)(Rn R 5 and (R 2 0 2 C-C(R 3 8 2 ]aR 5 (S(O) 2 Y~n-aO respectivel~y, wherein: R2 is a hyrcrysubstitut-d hydrocarbylp or a p vnier ic rNdi cal; Ris hydrocatbyl or %ubstituteoI hydrocarbyl;

R

5 is a hydrocarbyl, substituted hydrocarbyl or polymeric radical, of valence n; 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, 10i. Still further, the invention also resides in block and chain-extended 0.

polymers prepared from the above-formulated products.

Following are definitions of terms used in the Summary of the Invention, supra, By "acyl" is meant the moiety which remains Cfter removal of *o o *1 *e *o -V1? _i.-iL-F II- 'WO 87/07265 13 St PCT/US87/01158 a hydroxy group from an organic carboxylic acid.

By "sulfonyl" is meant the moiety which remains after removal of a hydroxy group from an organic sulfonic acid.

By "hydrocarbyl radical" is meant a radical consisting essentially of hydrogen and up to about 20 carbon atoms. By "substituted hydrocarbyl radical" is meant 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.

By "polymeric radical" is meant a polymeric radical containing more than 20 carbon atoms; the radical may contain the intra-chain heteruatoms 0, N or S and/or *atsebfe* s -fittftn l substituents that are inert under reaction conditions.

By "aryl" is meant an aromatic radical having at least six carbon atoms. By "substituted aryl" is meant aryl which contains one or more aliphatic substituents or substituents that are inert under reaction conditions.

By "a selected anion or oxyanion" is meant a fluoride, iiifluorotrimethylsilicate, 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 £fom the sulfonyl compound. The selected anion or oxyanion catalysts also include the Group Transfer olymerization catalysts described in the aforesaid GTP patents d=a especially in U. S.

Patents 4,508,880 and 4,588,795.

By "silicon activating group" is meant a leaving group which is capable of displacing silicon from the silylketene acetal y^J^A^Vu j i I WO 87/07265 PCT/US87/01158 under reaction conditions. SuitaL- silicon activating groups, which include the groups -F, -OAr or -OC(O)R also function as catalysts in the invention process, thus reducing the amount of added catalyst required to sustain the reaction.

In the formula R 6 is hydrocarbyl or substituted hydrocarbyl.

The following preferred embodiments are within the scope of the invention as described in the Summary of the Invention, supra.

Preferred silylketene acetals which are useful herein are those wherein: Q is -R 1 and R 1 is C_ 8 alkyl or aryl, most preferably methyl;

R

2 is C 1 8 hydrocarbyl;

R

3 is methyl; and

R

4 is a polymeric radical, more preferably a substituted polymeric radical; still more preferably the substituent is e.L er or protected hydroxyl; preferably the poll, cic radical is comprised of acrylic monomer units, most preferably methyl methacrylate units.

Most preferred silylketene acetals ars "living" acrylic polymers prepared by Group Transfer polymerization (GTP).

Preferred acyl or sulfonyl compounds are those of the formula nR 5 wherin: X is -OAr or -OC(O)R 6 wherein Ar is phenyl or substituted phenyl, and R 6 is C1_ 8 alkyl, aryl or substituted aryl; 5 R is C1-8 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.

ii^ IIl~ W 87/07265 PCT/US87/01158 The beta-ketoester or beta-sulfonylester products of the invention process are of the 2 3 4 C formulas [R 0 2 C-C(R3 )(R4 and [R202C-C(R3)(R4)-SO) 2 ]aR5[ S(O) 2

Y],

2 a 2 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 R 8 defined above as a polymer radical comprised of acrylic monomer units, are believed to be novel.

It is to be understood that, in the fully converted ketoester or sulfonylester products of a stoichiometric reaction between the acyl or sulfonyl compound and SKA, a is essentially equal to n. Products prepared by employing a stoichiometric excess of acyi or sulfonyl compound will contain -C(O)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 coiibinations 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 polymzer- cain 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.

Substituents that are, in most cases, unreactive under reaction conditions include, but are not limited to, -CO 2 R, -OC(O)R, 1 1 a 2 -C(O)N(R )2 -CN, -CH=CH 2 provided such groups are not conjugated with carbonyl or cyano groups, WO 87/07265 /A WO87/07265 PCT/US87/01158 -P(0)(OR1)2, -C(O)R and -OH and -C02H if chemically protected. In these substituents R is hydrocarbyl other than aryl and R is defined as above.

As indicated above, most preferred 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, by use of an appropriate GTP initiator containing at least one SKA moiety of the formula >C=C(OSi[Q]3)(OR 2 wherein Q and R 2 are defined as 2 above, the R group containing a trialkylsiloxy group. In the polymerization process, this group becomes located at a non-living end of the polymer chain. An example of such an initiator is (2-methyl-l-[2-(trimethylsiloxy)ethoxy)-lpropenyl)oxy]trimethylsilane (TTEB).

In the invention process, 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% preferably in the range 5-60% The process of the invention is carried out at a temperature of about -100C to +1500C, preferably about -15 C to about 80°C, most preferably 100 to 600C.

L

(WO 87/07265 S PCT/US87/01158 oceked Silylketene *aee\ concentration can vary from about 0.1% to 100% Polymeric SKA which are viscous liquids or solids can be used at concentrations of about 25-80% 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 mol%.

As already indicated, the invention process leads to capping and/or coupling of SKA molecules, depending on functionality and concentration of acylating or sulfonating compound employed. In general, to cap an SKA, a monofunctional (n is 1) acylating or sulfonating compound is employed at a molar ratio to SKA of at least 1:1. For coupling, a polyfunctional (n is 2 or more) acylating or sulfonating compound is employed at a mola. 4atio 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 sul" ting compound.

Prefr 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

F

WO 87/07265 DrTIi TC! 87/01158 hydrolysis with, e.g. hydrochloric acid in methanol. 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(O)X or

-S(O)

2 Y reactive compound such as ethylene glycol, to convert residual -C(O)X or -S(O ,jY 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.

-C(O)X or -S(O) 2 Y ends introduced by capping a SKA with a stoichiometric excess of dior polyfunctional acylating compound can also be used to provide other functional end groups, e.g., OH, CO 2 H, SH and NH 2 for later use in chain extension or coupling, by subsequent reaction of -C(O)X or -S(0) 2 Y ends with appropriate reagents such as glycols, water, dimercaptans, aminoalcohols and diamines. -C(0)X or -S(O) 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(O)X or -S(0) 2 Y groups present in the product are then finished as described above. If only -C(O)x groups are required, with minimal coupling, the SKA can be reacted with a large excess of acylating WO 87/0726$ \9 WO 8 7/0726 PCT/US87/01158 agent, followed by sufficient finishing agent to react all -C(O)X ends plus residual acylating compound. In general, such reactions are preferably carried out in solution.

The process of the invention is believed to proceed according to the following illustrative equation: a(R3)(R4)C=C(OSi[ )(OR2) [XC(O) R 5 cat.

)(R

4 R5[C(O)X]na a(Q) Si-X

C(O)(OR

2 It will be understood that the residual -C(O)X (or -S(0) 2 X) moitties can react with other SKA molecules in the presence of catalyst, or with other reagents as discussed above.

In the following examples of the invention process, and in comparative experiments, parts and percentages are by weight and temperatures are in degrees Celsius unless otherwise specified.

(GMA//MMA//GMA 4//40//4) Mono-Initiator, 2-Feed, Coupling Agent A 250 ml round bottom flask, ipped with a mechanical stirrer, thermome r, and nitrogen inlet, is charged with ,dmethoxyethane glyme (18.6 l-trimeth siloxy-l-i-butoxy-2methylpropene (2.1 g, 0 97 mole), and glycidyl methacrylate (5.6 g,.0394 mole). The flask is cooled to 10C. /etrabutylammonium m-chloroben ate TBACB (200 p# of a 1.0 M solution in acetpr itrile) is injected into the flask. Feed I consists of glyme (3.0 g) and tetrabutylammonium iJ-cho Qb-e-izat.J2-oliul 4af aaioHin) n Itt r i

I

~WO 87/07265 PCT/US87/01158 with one eoy-e u~p-oTrech end of every The following discussion is relevant to I Examples 4to 3-.\which are provided hereinbelow.

Drying of Equipment and Gases All glassware, including syringes, and syringe needles were dried in a 165°C oven overnight prior to use. Rubber septa, Teflon parts, and other polymeric materials were dried overnight in a vacuum oven at 65 0 C, with a slight nitrogen purge. Argon (Air Products) was purified by passage through a molecular sieve trap for drying and a reduced Girdler G-33 nickel oxide catalyst trap from United Catalyst, Inc., for removal of oxygen.

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 Parafilm M laboratory film. Serum caps, for syringe introduction of solvents and reagents, were secured onto openings in the glassware by tightly-wrapped nylon ties.

Chemicals 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 P2o 5 Initiators were distilled WO 87/07265 PCT/US87/01158, _24 in a 12-inch spinning band column. Dried solvents, initiators, and catalyst solutions were stored in "Aldrich" bottles in drierite-packed desiccators.

Analyses 1 H-NMR spectra were recorded with a Nicolet 360WB spectrometer. r_..cular 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. Polydispersity is given by the formula D Mw/Mn where Mw and Mn are, respectively, weight and number average molecular weight. Hydroxy-PMMA and a,w-dihydroxy-PMMA content of the product was determined by high pressure liquid chromatography, employing a Du Pont Instruments Series 800 Gradient Controller and Chromatographic Pump and a Waters Associates R401 refractive index detector.

Example Reaction of Benzoy Fluoride and [(l-methoxy-2-methyl-l-propenyl)oxy]trimethylsilane (MTS) 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 ml), MTS (1.6 ml, 8.0 mmol), benzoyl fluoride (0.87 ml, 8.0 mmol, Aldrich, 99% pure), and, last, 30.5 M tetrabutylammonium biacetate (Bu 4 NOAc'HOAc)/CH 3 CN (40 pi, 0.25 mol of MTS).

Within one minute, the temperature rose from to 36 0 C, then receded. Stirring was continued for 2 h, and then the solvent and volatile silyl 3fluoride by-product were removed with a rotary

K.

O 87/07265 4D O 8 PCTIUS87/01158 evaporator. The liquid product was dissolved in deuterochloroform (CDC1 3 for proton nmr analysis, which showed it to be virtually pure methyl 2-benzoylisobutyrate. NMR (CDC13, 8 ppm): 1.5 (s, H, CH 3 3.6 2.9 H, CH30), and 7.4, 7.5 and 7.8 5.1 H, C 6

H

5 Example Reaction of Acetyl Fluoride and MTS The reaction described in Example '-.3was 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 pi, 0.5 moA in place of biacetate. The acetyl fluoride was delivered from a cylinder into 15 ml of THF in a serum-capped Erlenmeyer flask. The amount of acid fluoride was measured by difference in weight, and thereby its concentration in solution determined. Thus, 1.37 g of reagent was added to the THF, which required 5.9 ml of solution to be syringed into the reaction flask in order to deliver 0.50 g of acetyl fluoride mmol).

The nmr of the liquid product showed it to be virtually pure methyl 2-acetyiisobutyrate.

NMP (CDC13, S ppm): 1.3 6.0 H, CH 3 2.1 (s, 3.3 H, CH 3 CO), and 3.65 3.0 H, Example 3 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 ml), [(2-methyl-l-[2-(trimethylsiloxy)ethoxy]-l- WO 87/07265 PCT/US87/01158 propenyl)oxy]trimethyl-silane (TTEB) (2.5 ml, 7.9 mmol), 0.5 M Bu 4 NOAc*HOAc/CH3CN (8 Cl, .051 mol of TTEB). The MMA was added by syringe pump at ml/min only after an incubation period of 20 min.

Upon addition of MMA, the temperature rose from 24.2 0 C to 39.4 0 C in 36 min (18 ml MMA added) and declined slowly thereafter to 38,80C.

The polymer solution was stirred for 1 h, and benzoyl fluoride (1.7 ml, 15.6 mmol, Aldrich, 99% pure) was syringed in. The temperature rose only from 24.5 0 C to 24.8 0 C, so an additional 30 pl of biacetate catalyst was added (net catalyst 0.24% of TTEB-derived living ends). Within 3 min, the temperature rose to 25.7 0 C, then declined very slowly thereafter, falling to 24.7 0 C 45 min after addition of the last measure of catalyst (55 min after benzoyl fluoride addition). The reaction was left unstirred overnight, concentrated to dryness on a rotary evaporator, dissolved in about 50 ml of

CH

2

CI

2 and precipitated in a large excess of stirred (magnetic bar) hexane (hexane:solution 10:1, v/v).

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 3 for proton nmr analysis, the remainder dried for 24 h at 650C 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. Rn (100% basis) was 3260. GPC analysis gave Mn=2840, Mw-3100, Mw/Mn1l.09.

Duplicate VPO (THF) gave Mn-3200. Compared with W 70265 6 P 8 the theoretical MMA/end-group value of 29.4, nmr cqave 34.4 (MeO/PhCO) and 37.2 (MeO/Me 3 SiO). The MMA/benzoyl-capped end ratio was calculated from proton nmr spectra, by comparing peak areas for the MMA resonance at 8 3.55 ppm (M4eo) and benzoyl resonance at 6 7.2-7.7 ppm (Ptk). As an internal check, the MMA/initiator fragment ratio was also cAlculato'd from S 3.55 ppm (MeD) and the initiator fragment's 0.1 'MaSio) peaks.

Example ~i Acet yl Fluoride Capping of Polymeric SIKA Thie procedure of th~i previous example was repeated except that 1.7 g (27.4 mmol) of acetyl fluoride dissolved in about 17 nib of TUF was used in p1,;ce of benzoyl fluoride. The acetyl. fluoride ctiused a temperature rise from 25,1 0 c to 2$.7 0 r-, After 10 mint the temperature began to decreasef and 30 p1 of biacetate was added, The tepmperature Zcose to a peak of 26.7 0 C in another 3 min, The recovered I'MMA weighed 23.81 ge a conversion of 96.7%. Theor. Mn (100%) Was 3200. GPC gave Mn-~2660, Vrw=28901 Mw/Mn-1,09# Compared with the theoretical MMA/end-group value of 29,41 nmr gave ca. 27 (MeO/CH 3 CQ) and 27.5 (tMeO/Me 3 SiO). The monomer/enid-group ratio was calculated from nmr resonances fo MMA at 3.5$ (MeO), %cetyl cap at 'S 2.05 (overlapping slightly with )olymet resonances), and inlltiatov fragment at 6 0,1 (Me 3

SIO).

Example 4' Phenyl Bentoate Capping of Polymeric SKA The procedure of EUarnp3e ei was repeated, with the following changes: MMA was polymerized, using 50 #1 of 0.045 M Bu 4 NOAC-fiOAc/THF, all of which was added at the start, mMA 'was fed in over WO 87/07265 PCT/US87/01158 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 "ery little and more catalyst was added (100 pl of 0.045 M Bu NOAc-HOAc/THF and 100 pu of 0.2 Bu NOAc-HOAc/CH 3 CN). The temperature rose and the solution slowly acquired a slight yellow color, Total recovered PMMA was 25,0 g, a 93.3% MMA conversion, Theor. Mn was 3260 and GPC gave Mn=2800, Mw=3200t Mw/Mnal.14. 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 8( Benzoic Anhydride Capping of Polymeric SKA The procedure described in Example *was repeated with the following changes: MMA was polymeried using 35 p~ of 0.04 M Bu 4 NOAc'HOAc'6 H 2 O/THF and MMA was fed in over a 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 pl catalyst was added, the temperature rose 2.3°C. The recovered PMMA, 32.6 g, was dried only at room temperature then dissolved in 70 ml ethyl acetate and mixed with 2,3 9 KOH in 70 ml deionized water, to remove unreacted WO 8707265PCI/US87/01 158 benzoic anhydride. After vig,. 3 stirring for min.t the mixture was shaken in a separatory funnel and the aqueous phase rimoved. The ethyl acetate layer was extracted with three 70-mi portions of d~eionized water, dried 2 h over anhydrous MgSO 4 ,nd filtered. Tha filtrate was pdiured into well.-stirred hexane to precipitate the polymet The polymer was dried only at RT and after 3 O'ays weighed 26.7 9.I Theor. Mn (100% basSis) was 3300 and GPQ gave Mn,=2900, Mn=3400, Mw/Mn=l.lS. The theoretical MMA/end-group ratio was 29.4 and nn'r gave 32.7 for MMA/capping fragment (MeO/Ph) and 66,8 for MKA,/iniitiator fragment (MeO/Me 3 SiQ); the high latter value arose from hydrolytic loss of Me 3 Si end groups caused by KOHI treatment.

Experiment 1 Aittempted Capping of Polymeric SKA with Benzoyl chloride The procedure of Example 4Wwas repeateO except foir the replaceament of benzoyl fluoride by 1.8 ml benzoyl !;hloridie g, 15.5 mmol). The temperaturiv~rrose from 27.4 to 27.6*C when the chloride was 4dded, but did not rise further upon addition of 30 p 1 of bliacetate catalyst solution.

The recovered PDMA weighed 23.8 g, a 95.4% conversion of MMA. Theor. Mn (100% basis) was 3260 and GPC gave Fin=2580, Mw-t2 t00, Mw NqMR analysis showed no resonance for a benzoyl cap at 8 7.2-7,7, indicating that acid chloride, which is usually m~ore reactive than acid 411v~oride, failed to react with SKA.

WO 87/07265 PCT/US87/01158 r, Example #"1 Coupling of Polymeric SKA with Terephthaloyl Fluoride (TF 2 A. Preparation of.terephthaloyl fluoride A 250-ml r.b. flask, fitted with magnetic stirring bar, serum cap, refiux condenser and argc inlet tube, was flushed with argon and then loaded with: anhydrous KF (Aldrich, 35.0 g, 0.602 mol); terephthaloyl chloride (Aldrich, 97%, 24.6 g, 0.118 mol); a solution of 18-Crown-6 (Aldrich, 99%, g, 0.011 mol), in CH 2 Cl 2 (Fisher, reagent grade, 60 ml), prepared in a bottle in the dry box.

When the mixture was stirred, it began to reflux.

It was maintained at reflux for two hours and stirred at RT for 1 h, under slight argon pressure.

The KF/KCl residue was removed by vacuum filtering the solution under nitrogen and rinsing the residue three times with 50-ml portions of

CH

2 C1 2 also under nitrogen. The solvent was removed from Ahe filtrate on a rotary evaporator with house vacuum. The solid was sublimed three times, under strong vacuum, at 100°C. The sublimer was assembled and disassembled in a glove bag, under nitrogen. The product from the respective sublimations was weighed and its m.p. measured: 20.5 g (90-108 0 20.0 g (115-123 0 and 18.1 g (115-124 0

C).

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 'WO 87/07265 PCT/US87/01158 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 coucentrate 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 portions of petroleum ether and dried as above. The crops were weighed and portions placed in melting point tubes, in a dry box.

1st crop: m.p. 122-123.5 0 C, 11.6 g 2nd crop: m.p. 121-123.5 0 C, 2.6 g The combined yield was 14.2 g, 71% of theory (20.0 g).

B. Preparation of a,w-Dihydroxy-PMMA 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.

The flask was charged with: THF (distilled from sodium benzophenone ketyl) 7 5 m l TTEB... 5.0 ml (15.7 mmol) 0.041 M Bu 4 NOAc'HOAc*6 H20 in THF..25 pi WO 87/07265 PCT/US87/01158 The mixture was stirred and 25 ml MMA was dripped in over a 50 min period, from the dropping funnel.

Additional biacetate solution (25 pl) was added min into the monomer addition. The mixture was stirred for an additional 4-1/2 h to complete polymerization (polymeric SKA) prior to the coupling reaction.

A solution of terephthaloyl fluoride (1.34 g, 7.88 mmol), prepared in Part A, in still-dried THF (10 ml) was cannula-transferred to the polymeric SKA prepared above and a 0.1°C temperature rise was observed.

Biacetate catalyst solution (200 pl) was added to the stirred mixture and a 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.

An aliquot of the a,o-di(trimethylsiloxy)-PMMA product was removed and precipitated in a 20-fold excess of hexane in a stirred beaker sample A.

The remaining solution was treated with ml of 10% HCl-MeOH and stirred for 3 h at RT to hydrolyze trimethylsiloxy end groups. The solution became colorless. The solution was concentrated and polymer precipitated when it was poured slowly into a 20-fold excess of hexane, rapidly stirred in a large beaker sample B.

Recovered weights (excluding 0.3g remaining on glassware)- A: 1.4 g; B: 24.2 g (dried 32 0 C/vac oven).

Overall MMA conversion was 93.2%.

GPC analysis: .9 l i, 1 'WO 87/07265 so PCT/US87/0 1158 A- Theor. Mn (100% conversion and 100% coupled)=3500. Mn=3400, Mw=4000, Mw/Mn= 1.19; B- Theor. Mn (100% basis)=33OO. Mn=3300, Mw=4000, Mw/Mn=1.19; HPLC Analysis: B- PMMA-OH 7.3% and H0-PMMA-OH 92.7%; NMR Analysis: A- Theoretical MMA/end-group d.p. before coupling =14.7; Theoretical MMA/coupling agent (assuming 100% coupling) =2 x d.p. before coupling 29.4 Actual MMA/end-group (from Meo at 8 3.55 and initiator Me 3 Sio fragment at 8 0.1) 15.7 Actual MMA/coupling agent (from MeQ at 8 3.55 and C 6

H

4 at 8 7.65) =33.0.

All three analyses demonstrate a high level of coupling.

Excample Coupling rf Polymeric S A with Terephthaloyl Fluoride The procedure of Example 41 was repeated but without adding more biacetate catalyst durinc coupling. The tem~perature rose only 0.3 0 C during coupling. Recovered PMMA (dried 48 h in a 65 0

C

vacuum oven) weighed as follows (excluding 0.3g remaining on glassware): A- 1.2 q, B- 24.8 q. The Overall MMA conversion was 94.5%.

GPC Analysis: A- Mn=3300, Mw=4000, Mw/Mn=1.20; B- Kfi=3200, Mw=3800, Mw/Mn=1.20; HPLC Analysis: B- PMMA-OH 14% and HO-PMMA-Ofl 86%; i WO 87/07265 3\ PCT/US87/01158

A

NMR Analysis: A- Actual MMA/end-group 14.6 (theor. 14.7) Actual MMA/coupling agent 36.6 (theor.

29.4) The three analyses show a substantial level of coupling even when no further catalyst is used for acylation.

q Example 3- Diphenyl Terephthalate Coupling of Polymeric SKA The procedure of Example 9BXwas repeated with the following changes: MMA was polymerized with 50 pl of 0.033 M Bu 4 NOAc-HOAc-6 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 pi, 0.033 M) was added and the color darkened and the temperature rose 0.4 0 r over the next 5 min.

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 a ,-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 0 C vacuum oven.

GPC Analysis: A- Mn=3200, Mw=3600, Mw/Mn=1.12; B- Mn=3000, Mw=3300, Mw/Mn=1.13; HPLC Analysis: B- PMMA-OH 9.3% and HO-PMMA-OH 90.7%;

I-

'WO 87/07265 'k PCT/US87/01158 NMR Analysis: A- Actual MMA/end-group 19.0 (theor. 14.7) Actual MMA/coupling agent 34.3 (theor.

29.4) The three analyses show substantial coupling.

I0 Example j Coupling of Polymeric SKA with Mixed Terephthalic/Benzoic Anhydride A. Preparation of Mixed Anhydride of Terephthalic Acid and Benzoic Acid (TDB) A 3-neck, 500-ml r.b. flask, equipped with a magnetic stirring bar, reflux condenser connected to nitrogen, and a pressure-equalizing dropping funnel, was flushed with nitrogen and held under a slightly positive nitrogen pressure. The flask was charged with 200 ml CHC1 3 Merck), 20.0 g terephthaloyl chloride (Aldrich, 97%, MW=203.0, 0.099 moles assuming 100% purity), and 24.1 g benzoic acid (Aldrich, MW=122.1, 0.197 moles). Triethylamire (20.0 g, Fisher, 0.198 moles) was dripped slowly into the stirred flask, and stirring continued 1-1/2 h thereafter. After 7 ml of solution was consumed in solubility tests, the remainder was extracted with three 250-ml portions of deionized water, the lower chloroform layer filtered. Concentrating the chloroform solution with a rotary evaporator gave 34.5 g of product (theor. yield 36.9 g).

After small-scale recrystallization trials, which consumed 1.4 g of product, 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 1

Y

0 e WO 87/07265 s PCT/US87/01158 after concentrating the mother liquor to ca. 75 ml.

In all cases, an unusual melting point behavior of the samples suggests decomposition. At fast heating rates, the solids melt at about 140-150 0

C

and resolidify, melting again only at about 280-310 0 C. At slow heating rates, a slight amount of melting occurs at ca. 140 0 C, but most melts only at 280-320 0

C.

First crop: 23.3 g, mp 145-150°C and 280-310°C 2nd crop: 0.5 g, mp 148-155°C and 290-310°C 3rd crop: 3.9 g, mp >90°C (never fully melts).

Elemental Analysis (first crop): C, 70.5%; H, 0, 26.2%.

Theory for C 22

H

14 0 6 C, 70.6%; H, 0, 25.6%.

H nmr (CD 2 C12, S ppm): 7,55 3.9H, C 6

H

5 -meta 7.7 (tt, 2.1 H, C 6

H

5 -para 8.15 H, C 6

H

5 -ortho), and 8.3 4.0 H, C 6

H

4 B. TDB Coupling of Polymeric SKA The procedure of Example 98 was repeated with the following changes: MMA was polymerized with 2.5 ml TTEB initiator (7.9 mmol) and 20 pu 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 amol) in 60 ml of very dry THF. The temperature rose 0.1 0 C, and 0.2 ml of biacetate catalyst was added. The temperature rose another 0.1 0 C. No aliquot was removed before hydrolysis to hydroxyl ends. Recovered PMMA (dried 48 h in a 65 0 C vacuum oven), 23.8 g.

GPC Analysis: Theor. Mn (100% conversion and coupling) S6400.

Mn 3700, Mw 4900, Mw/Mn 1.33; (lei -o 0/

/A

'WO 87/07265 PCT/US87/O158 HPLC Analysis: PMMA 1.0% PMMA-OH 60,2% and HO-PMMA-OH 38.8%.

The two analyses show that partial coupling occurred.

Example 13- Coupling of Polymeric SKA with Bis(p-Nitrophenyl)terephthalate A. Preparation of Bis(p-Nitrophenyl)terephthalate

(DNPT)

A 300-ml r.b. fask, equipped with a magnetic stirring bar was charged with 7.85 g sodium hydroxide (Fisher, 0.197 moles) in 75 ml of deionized water and then, to the stirred solution, 27.40 g of p-nitrophenol (Aldrich, 98%, 0.197 moles) was added. The solution turned orange and a considerable amount of yellow solid was present.

A solution of 20.04 g terephthaloyl chloride (Aldrich, 97%, 0.0987 moles assuming 100% purity) in methylene chloride was dripped into the flask from a dropping funnel. The flask was stirred another 15 min and the mixture filtered through a Whatman's #1 filter paper disk on a Buchner funnel.

The filtrate was almost clear and the solid on the filter was washed with a few portions of water in the funnel and with two small portions of acetone.

The solid was dried by briefly drawing air through it in the vacuum funnel and then, broken into finer pieces, in a 65°C vacuum oven. The -rude product weighed 36.1 g (theory, 40.2 g) and melted at 228-243 C.

Fifteen g of the product was dissolved in 2275 ml of THF at reflux; the solution was slightly cloudy. Solid slowly crystallized on the walls of the flask upon cooling to RT and a first crop was !Ir x WO 87/07265 5 PCT/US87/01158 obtained by vacuum filtration after leaving the flask overnight. The solid was dried 1 h in a 65 0

C

vacuum oven. A second crop was obtained by concentrating the mother liquor to about 200 ml and allowing the solution to cool.

First crop: 10.6 g, mp 245-7 0 C (lit. 242 0

C;

M. J. S. Dewar et al., J. Org.

Chem., 35, 2711 (1970)) Second crop: 1.4 g, mp 241-245.5°C Combiined yield (adjusted for use of only 15.0 g of the 36.1 g crude product), 71.8%.

Elemental analysis (first crop): C, 59.2%; H, N, 0, 30.2%.

Theory for C 20

H

12

N

2 0: C, 58.8%; H, N, 6.9%; 0, 31.4%.

1 H nmr (CD 2 Cl 2 6 ppm): 6 7.6 4.0 H, C 6

H

4

NO

2 H meta to NO 2 6 8.4 (d and s, 7,7 H, terephthaloyl and C6H 4

NO

2 H ortho to NO 2 B. DNPT Coupling of Polymeric SKA 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 pl) caused the temperature to rise 0.2 0 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.

GPC Analysis: Theor. Mn (100% conversion and coupling) 6400 Mn=3100, Mw=3900, Mw/Mn=a.26; HP1AC Analysis: Unknown 12.3%, PMMA-OH 70.4% and HO-PMMA-OH 17.2%.

V -2 CL<. f i i i 'WO 87/07265 c PCT/US87/01158 -3-9- The analyses indicate partial coupling.

\a Example Coupling of Polymeric SKA with _Diphenyl Isophthalate The procedure of Example 1a2Bwas repeated except that polymerization used 35 pl of 0.04 M Bu 4 NOAc*HOAc-6 H 2 0/THF, and coupling was begun h after the MMA feed, with 1.25 g diphenyl isophthalate (Polysciences, 3.9 mmol) in 12 ml of very dry THF. After a temperature rise of 0.1 0

C,

200 pl of biacetate solution was added and the temperature rose an additional 0.4 0 C and the solution yellowed slightly. Recovered PMMA (dried 32 h in a 65°C vacuum oven) weighed 25.0 g, a 98.1% conversion of MMA.

GPC Analysis: Theor. Mn (100% conversion and coupling) 6400 Mn=3600, Mw=4300, Mw/Mn=1.20; HPLC Analysis: PMMA PMMA-OH and HO-PMMA-OH These analyses indicate partial coupling.

Experiment 2 Attempted Coupling of Polymeric SKA with Terephthaloyl Chloride

\OB

The procedure of Example -A -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. There was a 0.1 0 C rise, but 0.2 ml t -1 i WO 87/07265 PCT/US87/01158 -4+0 of biacetate solution caused no further change, and 2 ml 0.04M Bu 4 NOAc (Fluka)/THF, added 1 h later, similarly caused no change. Recovered PMMA (dried 32 h in a 65 0 C vacuum oven) weighed 22.2 g, an 86.4% conversion of MMA.

GPC Analysis: Theor. Mn (100% basis) 6400 Mn=3000, Mw=3500, Mw/Mn=1.19; HPLC Analysis: PMMA 2.6% and PMMA-OH 97.4%.

These analyses show that no coupling occurred.

The above experiment was essentially repeated except that 4-dimethylaminopyridine in dry THF was used to absorb acidic by-products of a potential coupling reaction. Analysis of the recovered polymer again showed that no coupling had occurred.

Experiment 3 Attempted Coupling of Polymeric SKA with Terephthaloyl Bis(p-Toluenesulfonate) The mixed sulfonic-carboxylic dianhydride, terephthaloyl bis(p-toluenesulfonate), was prepared according to C. G. Overberger and E. Sarlo, J. Am. Chem. Soc., 85, 2446 (1963). A pure sample, mp 173-6 0 C (lit. 174-6 0 C) was obtained.

The procedure of Example ?2 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 ral of Cvry dry THF. The temperature rose 1.1 0

C.

When 0.2 ml of biacetate solution was added, there was no further exotherm and so another U.8 ml was added over the next 10 min, without an effect on temperature.

'WO 87/07265 W PCT/US87/01158 GPC Analysis: Theor. Mn (100% basis) 6400 Mn=3000, MW=3800, Mw/Mn=1.29; HPLC Analysis: PMMA 39% and PMMA-OH 61%; NMR Analysis: No Me 3 Si at 6 0-0.1 ppm.

These analyses show that no coupling occurred, and that MeSiO groups were quantitatively converted to

OH.

13 Sequential Terephthaloyl Fluoride Capping and Ethylene Glycol Finishing of Polymeric SKA The procedure of Example was repeated except for the use of 35 pl of 0.04 M Bu 4 NOAc*HOAc6 H 2 O/THF at the start of the MMA feed, and another 15 p1 10 min into the MMA feed, after 7 mL c MMA had been fed in. The MMA feed took 1 h.

Five hours after the MMA feed was completed, the solution was treated with 1.7g terephthaloyl fluoride (TF 2 (10.0 mmol) in 10 ml of very dry THF, The temperature rose 0.1 0 C, and 0.2 m of biacetate solution was added, causing the temperature to rise 1,5 0 C and the solution to yellow slightly. The reaction mixture was left unstirred for 17 h at RIT. Fo other purposes, ml of solution was removed by syringe.

The remaining solution was treated at RT with 1.8 mi ethylene glycol (EG) (32*3 mmol) and 1.2 mi triethylamine (8.6 mmol), causing a 2.4 0

C

temperature rise. The solution was stirred 7 h then left unstirred at RT overnight. The s-lution was then treated, while being stirred, with 4,.0 mi of 10% HC1/MeOH (11 mmol of dUCI, sufficient WO 87/07265 acm PCT/US87/01158 to render the mixture acidic. solids were removed by filtration and the solution was concentrated as usual and poured into well-stirred hexane to cause polymer to precipitate. The polymer, dried 48 h in a 65 0 C vacuum oven, weighed 12.3 g, Polymer from the 50 mL sample re-,oved earlier weighed 11.6 g.

Recovered PMMA was thus 23.9 g.

GPC Analysis: Theor. Mn (100% conversion and TF 2 and EG capping; no coupling) wt MMA/moles TTEB fragments of TTEB, TE 1 2 and EG =2950 132 132 61 =3300.

Mn=3400, Mw=4200t Mw/Mn=.24; HP.7C Analysis: PMMA 1.4%t PMMA-OH 6.3% and HO-PMMA-JHI 92.2%; the latter showed a double, peak representing diol by coupling and finishing.

NMR Analysis (ODC1 3 1 6 PPM): theor. MM4A/TF 2 end-group before capping 29.4 Actual MKA/TF' (Meo at 6 3.55 Vs. C6H 4 at 4 7.7 and 8.05) 24.0 The 6 7.7 multiplot represents

TF

2 -coUpling (cf, Example 95l), and perhaps half of the protons of the

TF

2 -capping moieties. The multiplet represents TF 2 capping.

These analyses show that much of the polymer is capped, some is coupled, and most chains have 2 OH termini..

'WVO 87/07265 4 O PCT/US87/0 1158 Example 4 Sequential TF Capping and 1, 4-Butanediol (BDO) Finishi.Ag apping of Polymeric SKA The procedure of Example was repeated except for the use of 35 p1 of 0.04M Bu 4 NOAc*HOAc*6

H

2 0/THF and a 70-mmn MNA feed.

The polymer solution was treated with 1.34 g of TE' 2 (7,9 mmol) in 10 ml of ver dry TFE', h after the MMA feed. Ifter 0.2 ml of biacetate was added, the temperature rose 2.0 0 C and the solution yellowed slightly. The flask was stirred 1 h and left unstirred 17 h.

The stirred solution was then treated with 2.8 ml BDO (Aldrich, 31.6 mmol) and 1.2 ml triethyl-,,nine (Fisher, 8.6 mmol) and stirred 1 h at RT. A 1-ml aliquot was removed by syringe, injected into 0.5 ml of 1Q$i HCl/MeQi, evaporated to dryness, ;7nd redissolved in CH C1 2 Polymer was isolated by filtration af Ite rprecipitation in excess hexane Sample A, The remaining solution was treattod wi h 1.1 mt (9.5 mmol) of Aldrich then hy'drolyzed with 1.0 ml of 10?, Hcl/M(A011 .nd s .Arred 1 h v T. it was cuncentr,,ted to dryness in a rotary avaporatot, the residtio disso],vod in 75 ml CHICl 2 extrzicted with three portions of deionized water arid then with $0 ml satutated aqueou.s Wadl. The CH, Cl 2 phaseo about nil in volume, was poured slowly into abou~t 1.5 1 of weil-stirred hexane to, precipitato polymer. The solid was vacuum filtered, washed 3 times with hexane and dried RT and then in a 6511Q vacuum oven for 56 h Sample 13.

The combined PMMA samples weighed 24.7 g, representing a 9181 conversion of MMA.

GP(C Analysis: WO 87/07265 WO 8707265PCT/US87/01158 Theor. Mn (100% conversion and TF 2 and BDO capping; no coupling) wt MMA/moles TTEB fragments of TTEB, TF 2 and BDO 2950 132 132 89 =3300.

A- Mn=3600, Mw=4600, Mw/rmn=1.27; B- Mn=3000, M,4=3700, Mw/Mn=1.24; HPLC Analysis: A- PMMVA or impurity PMMA-OH 4.1% and HO-PMMA-'H 92.9%: PMN4A or impurity PMMA-OH 5.2% and HO-PMZ4A-OH 92.3%. Two diol peaks representing capped and coupled products were obtained.

NMR Analysis (CDCl 3 a ppm): Theor. MMA/TF 2 end-group =29.4 B- Actual MMA/TF 2 (a 3.55 vs. A 7.7 and 8.05) 29t8 The ai 7.7 multiplet ,epy.*esents TF 2 coupling and perhaps half of the protons of the TF 2 capping moieties. The a 8.05 multiplet represents TIF 2 capping.

The analyses show that much of the polymer is capped, some is coupled, and most chains have hydroxyl groups at each end.

A separate experiment was run ti prove that the above tolechelic (dihydroxy) polymer can be chain-extended by coupling of the terminal hydroxyl groups.

A tared, dry 50-nil 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 stored, in a 50-60 0 C oven for 1 week, was injected into tho flask with a syringe pre-warmed in same overn.

The weight of MDI, U,~622 g, was obtained by re-weighing the r.b. flask. A,ra-Dihydroxy-PMMA, L_ dsuhdh WO 87/07265 PCT/US87/01158 L -4& sample B prepared above, after drying for 3 days in a 65 0 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 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 were added by disposable Pasteur pipette. No viscosity increase was seen after min, but stirring was difficult after 15 min.

After 1 h 20 min, a sample 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 solid residue was dissolved in the reaction flask in 25 ml THF. The solubility of the solid suggested that cross-linking reactions had largely been avoided. The solution was diluted further with 45 ml THF and dripped into 500 ml of well-stirred hexane, to precipitate polymer. The fibrous product was vacuum filtered and rinsed 3 times with hexane. After drying 40 h in a vacvum oven, this sample weighed 8.8 g.

Samples C and D had a combined weight of 9.5 g.

GPC Analysis: a,6-Dihydroxy-PMMA (sample Mn=3000, Mw=3700, Mw/Mn=l.24; 3- Mn=24,400, Mw=72,700, Mw/Mn=2.98; D- Mn=20,700, Mw=64,800, Mw/Mn=3.13; S/ t WO 87/07265 PCT/US87/01158 -46- Both C and D have low molecular weight peaks in the range of dihydroxy-PMMA representing about 5% of the peak area of the product. 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.

Example Coupling of Polymeric SKA with Bis(2,4-Dichlorophenyl Sebacate) A. Preparation of bis(2,4-dichlorophenyl sebacate) (DCPSeb) A 1000-ml round-bottom flask, equipped with a mechanical stirrer, pressure-equalizing dropping funnel, nitrogen inlet tube, and thermowell, was purged with and then held under a slightly positive pressure of nitrogen. The flask was charged with 300 ml of pyridine (dried over molecular sieves), and 23.2 ml of sebacyl chloride (0.10 moles, d=1.121 g/ml, MW=239.1, Aldrich, 92%) were syringed into the stirred solvent. A yellow solid precipitated. The dissolution of 32.92 g of 2,4-dichloro-phenol (0.2 moles, MW=163.0, Aldrich, 99%) in 100 ml of dry pyridine was accompanied by a small exotherm. The solution was dripped slowly into the flask from the dropping funnel, without heat evolution. The flask was stirred for 6 h thereafter and left unstirred another 72 h.

The mixture was slightly acidified with 10% aq HC1. 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 The product was tested with a variety of recrystallization _i 'WO 87/07265 lY- PCT/US87/01158 solvents, then 31.7 g thereof was dissolved in mi 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 wi:h 2:1 methanol/THF, and dried 1 h in a 65 0 C vacuum oven. This first crop weighed 9.35 g. The filtrate was concentrated to ml and 10 ml methanol were added. The second crop obtained from overnight crystallization was isolated as above and weighed 1.57 g. The 2 crops together weighed 10.9 g, a 46% yield (theoretical yield, 23.6 g, based on 31.7 g of crude product).

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 rea( 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 0

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.

for C 22

H

22 0 4 C1 4 C,53.7; H,4.5; 0,13.0; C1,28.8.

Found: C,54.2; H,4.7; 0, 13.1; C1,27.7. Proton NMR (CDC1 3 S ppm): 6 1.4 8.6 1.8 (pentet, 2.6 4.0 7.0 2.0 7.2 (dd, 2..2 7.4 1.8 Melting points: first crop-- 95-98.5 0 C, re-recrystallized, 97-98.5 0

C.

t"; 01 li- _X WO 87/07265 PCT/US87/01158 B. DCPSeb Coupling of Polymeric SKA The procedure of Example -9;was repeated twice, with changes noted below: TTEB initiator, ml (mmol) 0.04 M Bu 4 NOAc-HOAc- 6H 2 0/THF, pL MMA feed time, min Coupling begun after (h) Re-recrystd. DCPSeb/THF, g (mmol)/ml Temperature rise, °C 0.04 M Bu 4 NOAc-HOAc- 6H 2 0/THF, ml Additional temperature rise, °C Sample A 2.5 (7.9) 30 65 2.5 1.94 (3.9)/50 0 0.2 0.4 Sample B 2.5 (7.9) 9.94 (3.9)/20 0 1.1 The solutions were left for 18 h and then the polymer was hydrolyzed to hydroxyl end-groups by stirring each with 5 ml of 10% HCl/methanol for 1 h at room temperature. No aliquot was removed prior to hydrolysis. The polymer was precipitated and isolated as above and dried to constant weight in a 650C vacuum oven, yielding 24.6 g of Sample A.

Only a portion of Sample B was so isolated for GPC and HPLC analysis.

GPC Analysis: Theor. Mn (100% conversion and coupling) 6400 Sample A- Mn=3200, Mw=4500, Mw/Mn=1.38; Sample B- Mn=3600, Mw=4500, Mw/Mn=1.26; HPLC Analysis: Sample A- PMMA unknowns 31.7%, PMMA-OH 25.9% and HO-PMMA-OH 41.2%: Sample B- PMMA unknown 21.0%, M-A-OH 17.4% and HO-PMMA-OH 59.7%.

CeR v h -W O 87/ 726 5 L A I WO 87/07265 PCT/US87/01158 The analyses indicate coupling.

Example -8 Coupling of Polymeric SKA with Bis(2,4-Dichlorophenyl)terephthalate A. Preparation of bis(2,4-dichlorophenyl)terephthalate (DCPT) The nitrogen-purged apparatus described in Example/-?A for the preparaton of DCPSeb was charged with 300 ml of molecular sieves-dried pyridine and 20.3 g of terephthaloyl chloride (0.10 moles, MW=203.0, Aldrich, which gave a cloudy, yellow mixture. 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 ind left unstirred overnight. The mixture was slightly acidified with 10% aq HC1, the crude product isolated from it by vacuum filtration, then rinsed twice with ethanol on the funnel and dried on the funnel to 62 g of slightly wet solid. The product gave a hazy solution in 1200 ml of hot THF, which was filtered hot. After 2 h, a first crop of recrystallized solid was isolated by vacuum filtration and rinsed with a minimum of THF. More solids appeared in the filtrate after concentration to 200 ml. A second crop was taken as above after crystallization. The 2 crops were dried on their respective filtration funnels and then overnight at room temperature in a vacuum oven with a slight nitrogen bleed. The combined weight, 27.1 g, was of the theoretical 45.6 g. Elemental analysis is consistent with theory. Calcd, for C 20

H

1 0 0 4 C14: C, 52.7; H,2.2; Cl,31.1. Found: C,52.8; H,2.2; Cl,31.5.

WO 87/07265 7 PCT/US87/01158 Yields and melting points: first crop- 21.5 g, 220-221.5°C second crop- 5.6 g, 219-222.5°C B. DCPT Coupling of Polymeric SKA The procedure of Example 94Awas repeated with the following changes. MMA was polymerized with 2.5 ml TTEB initiator (7.9 mmol) and microlitres of 0.04 M Bu 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 stirring 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.

GPC Analysis: Theor. Mn (100% conversion and coupling) 6400 Mn=4800, Mw=5700, Mw/Mn=1.18; HPLC Analysis: PMMA unknown 22.5%, PMMA-OH 10.1% and HO-PMMA-OH 62.9%.

The analyses indicate coupling.

.i 1; -i L

Claims (26)

1. Process for preparing beta-ketoesters or beta-sulfonylesters comprising contacting and reacting a silylketene acetal with an acyl or sulfonyl compound in the presence of a catalyst which is a source of a selected anion or oxyanion, the silylketene acetal being of the formula 3 R OSi(Q) 3 C=C R4 \OR 2 wherein: each Q, independently, is selected from -R -OR -N(R 1 )2 and -SR1; each R, independently, is a hydrocarbyl or substituted hydrocarbyl radical; R is H, hydrocarbyl or substituted hydrocarbyl; 2 4 each of R and R 4 independently, is a hydrocarbyl, substituted hydrocarbyl, or a polymeric radical, the acy] or sulfonyl compound being selected from the group consisting of R5 and (YS(O) 2 R wherein: X is a silicon activating group; Y is -F or -OAr; Ar is aryl or substituted aryl; R is a hydrocarbyl, substituted hydroc.rbyl or polymeric radical, of valence n; and n is an integer of at least 1.

2. Process of Claim 1 wherein the silylketene acetal is reacted with the acyl compound R 5 i WO 87/07265 PCT/US87/01158

3. Process of Claim 2 wherein X is -F, -OAr or -OC(O)R 6 wherein R is hydrocarbyl or substituted hydrocarbyl.

4. Process of Claim 1 wherein wherein Q 1 2 in the silylketene acetal is R R is C1-8 3. hydrocarbyl and R is H or methyl. Process of Claim 4 wherein R 4 is a polymeric radical.

6. Process of Claim 5 wherein the polymeric radical is comprised of acrylic units.

7. Process of Claim 6 wherein the polymeric radical contains a -rte-i -F substituent.

8. Process of Claim 6 wherein the silylketene acetal is a "living" polymer prepared by Group Transfer Polymerization.

9. Process of Claim 8 wherein X is -F, -OAr or -OC(O)R 6 Process of Claim 9 wherein R 5 is C1-8 hydrocarbyl.

11. Process of Claim 10 wherein n is 1 or 2.

12. Process of Claim 11 wherein n is 2.

13. Process of Claim 12 wherein R 5 is 1,4-phenylene and X is -F or -OAr wherein Ar is phenyl.

14. Process of Claim 9 wherein the catalyst is fluoride, bifluoride or a selected oxyanion. Process of Claim 14 wherein the oxyanion is acetate, biacetate, m-chlorobenzoate, benzoate or bibenzoate.

16. Process of Claim 15 wherein the oxyanion is biacetate.

17. Process of Claim 11, wherein different polymeric silylketene acetals are coupled to form a block copolymer,

18. Process of Claim 9, wherein a stoichiometric excess of acyl or sulfonyl compound is employed.

19. Process of Claim 18, wherein n in the acyl or sulfonyl compound is at least 2, and -C(O)X or -S(0) 2 Y groups in the product are finished with a mono- or difunctional finishing agent.

20. Process of Claim 19, wherein the silylketene acetal contains a substituent, f 21, Process of Claim 20, wherein the finishing agent is a diol or aminoalcohol and the substituent is protected hydroxyL

22. Process of Claim 12, wherein R 4 contains a substituent and the acyl r sulfonyl compound is employed in a molar ratio to the silylketene acetal S not exceeding 1:2.

23. Process of Claitm 12, wherein R 4 contains a substituent and the acyl or sulfonyl compound is employed in a molar ratio to the silylketene acetal of 1:2 to 1:1. 24, Process of Claim 23, whereIn -C(O)X or -S(O)ZY groups in the *S product are finished with a montto- or difunctional finishing agent.

25. A compound being a ketoester or sulfonylester having the formula [r 2 o02C-c(r 3 )(r 8 5 oa It [r 02-c(r respectively, wherein: 2 is a hydrocarbyl, substituted hydrocarbyl, or a polymeric radical; r is h, hydrocarbyl or substituted hydrocarbyl; R 5 is a hydrocarbyl, substituted hydrocarbyl or polymeric radical, or Svalence n; 50 9 9. ai a 4' eIU 4Cce. 9 0 R 8 is a polymeric radical comprised of acrylic monomer units; X is a silicon activating group; Y is -F or -OAr; Ar is aryl or substituted aryl; I is an integer of at least 1; and a is an integer of at least 1 but not greater than it, 26, The compound of Claim 25, wherein a is equal to n.

27. The compound of Claim 25, wherein a is less than n.

28. The compound of Claim 27, wherein n is 2 and a is 1 or 2. 29, The compound of Claim 26, wherein R 8 contains a substituent The compound of Claim 27, wherein R 8 contains a substituent. 31, The compound of Claim 28, wherein R 8 contains a substituent, 32, Block copolymer formed by chain extension of the compound of

33. Block copolymer formed by chain extension of the compound of Claim 29, Claim 31. 34, with a mono- with a mono-

36. 37 Product of the process of finishing the compound of Claim 27 or difunctional finishing agent, Product of the process of finishing the compound of Claim or difunctional finishing agent, A compound whenever prepared by the process of Claim 19, Block copolymer formed by chain extension of the product of Claim

38. Process for preparing beta-ketoesters or beta-sulfonylesters which 51 F i I Is 0' process is substantially as herein described with reference to any one of the Examples but excluding the Comtparative Examples. DATED this 15th day of June 1990. S S C@ 5* 4 4* S. S S4* S S. I S.. Ed, DU PONT DE NEMOURS COMPANY By thieir Patent Attorneys: CALLINAN LAWRIE 4 OS S. S @0 4 4 0555 A. S A 5 C S I,' 52 Xq -KI 4,, K INTERNATIONAL SEARCH 'REPORT International Application PCT/US87 /01158 1. CLASS,'F-1CATION OF SUBJECT MATTER (it several classiIfcation symbols apply, idl ~,all)3 Accordirg to International Patent Classification (IPC) or to both National Classification and IPC IPC. 4 C07C 69/716, 738; 147/02, 147/06; C08G, 2/24, 2/38 11. FIEI.DS SEAR~CHED Minimum Documentation Sea- 4e Classification System Clasific~von Symbols U. S 560/145, 174, 176; 525/286, 299, 303, 308, 309 Documentation Searched other than Minimum Documentation to the Waent that such Documents are Included In the Fields Searched Ill. DOCUMENTS CONS!IERED TO 13E RELEVANT Caegr Citation ot Document, inl with Indicat Ion, where appr opriate, ot the relevant passages it Relevant to Claim No. isi A GB, A, 842,725 (SPOFA) 27 JULY 1960 SEE PAGE 25-28 1, LINES 19-34. A CA, A, 701,643 (KLUIBER) 12 JANUARY 1965 SEE 5, 6 and PAGE~ 4, LJINES 14-26. 25-28 A DE, A, 3,302,847 Al (KOPPERS CO. INC) 03 25-28 NOVEMBER 1983; SEE ABSTRACTt A PE, B, 1,076,133 (VEB FILMFABP,19) 25 FEBRUARY 25-28, 1960 SEE ABSTRACT. A CHEMICAL ABSTRACTS, VOLUME 61, NO, 33, ISSUED 25-28 ,NUGUST 1964 (COLUMBUS, OHIO, USA, GELIN, RENEj UT AL, "PREPARATION OF BETA-OXO DIESTERS AND BWTA-DIKETON2 ESTERS", THE ABSTRACT NO. 4209,i COMPT. REND. 258(19), 478.3-4 (1964). Y US, A, 4,388,448 (MELBY) 14 JUNE 1983 SEE 138-45 COLUMN 14, EXAMPLES 12 and 13, A US, A, 4,41.4,372 (FARNHAM ET A-L) 08 NOVEMBER 1-8 1983, SEE COLUMN 8, LINES 28-68. *Special categorles of cited ciicumentst 13 tater document published alte the international filing date ant efiingthegeneal tat ofthe rt hic Isnot or prioritv date and not in conflict 4ith the application but documnt ltnn h eea tt fteat~ hi o cited to kndqrstand the principle or theory underlying the consideared to be ot particular relevance invention "Ell 6.0flq docijrnent but published on or atter the International iIXII document of particular toloaence; the claimed invention filing date! cannot be considered novel of cannot bie conildered to i*L" docunment which may throw dloubts on priority claim(s) or involve an itirventlve step which is! cited to establish the publicatIon date of another "Y document ofl particular relevance, the claimed Invention citation or other special reason. (as specified) cannot be considered to Involve an inventive step when the I'O" document rate',,ng to an oral disclosure, use, exhibition or dqcument is comnbin~ed with one' or more other such docu. other means manta, such combination being obvious to a person skitted i4IP* document published prlq' to the International fillng dale but in the art, later than the priority dai, claimed document member of the tame patent family 0.14 or the AMiUaM Completion of the Inlernatlonal Search 11 Date of Mailing of this Interni onal Search Report J.ULY 1987 19 AUG ou Intrmionait Searching Authority 'Signature of Authorlaed Officer 1 ISA/US ROBERT SELLERS Forrii PCTjISA/21 0 (second sheet) (May I1980) PCT/UIS87 /olL58 International Application No. FURTHER INFORMATION CONTINUED FROM THE SCCZ SHEET VE OBSERVATIONS WHERE CERTAIN CLAIMS WERE FOUND UNSEARCHABLE in This International search report has no' booen established In respect of certain claims under Article 17(2) for the followng reasons' IQjj claim numbers because they relate to subject mutter V-1 not required to be searched by this Authoritys namelyt 2,iIZ claim numbers -because they relate to p4-, t the international application that do not comply Nith the prescribed require- ,ments to such an ertent that no meantr glut international search can be carried out 0, specificay, VIF-OBSERVATIONS WHERE UNITY OF INVENTION IS LACKING IL This International Searching Authority found multiple Inventions In this International application as follows-, I Claims 1-7, drawn to a process for the preparation of beta-ketoesters or beta-sul fony lesters, XI. Claims 8-16, directed to a process for the preparation of living polymers of beta-ketoesters or beta-sulfonylesters, Q AsI all required additional search fee. were timely paid by the applicant, this International search report covers all searchable claims of the International application, 2M As only some of the required additional search lees were tlmel paid by the applicant, this international search report covers only those claims of the International application for which tees were piad, specifdalty claims, No aequired additional search fees were ti1mely paid by the applicant. Consequently, this international search report Is restricted to the Invention first mentioned In the claims', it Is covered by claim niumbers: AIQj As all searchable claims could be searched without eflort justifying an additional fee, the International Searching Auithority did niot invite payment of any additional tee, Remark on Protest The additional search fees were accompanied by applicant's protest, SNo protest accompanied the payment of additional search lees, Form PCT/ISA/210 (supplemental cheat (May 1906) L FCT/US87/01158 Continuation of Suoplemental sheet III. Claims 17-37, drawn to a process for the preparation of block copolymk7,rs of beta-ketoesters or beta-sulfonylesters, and IV. Claims 38-45, directed to a process for the I preparation of an ABA block copolymer. -J. p r International Application No. PTU8Z15 Ill. DOCUMEN': CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category citation of Document, 16~ with indication, where appropriate, of the relevant passages 1 7 Relevant to Claim Y US, A, 4,417,034 (WEBSTER) 22 NOVEMBER 1983 38-45 SEE COLUMN 22, EXAMPLE

39. A US, A, 4,524,196 (FARNHAM ET AL) 18 JUNE 1985 1-8 AND SEE COLUMN 12, LINE 53 TO COLUMN 13, LINE 44. 38-45 A US, A, 4,588,795 (DICKER ET AL) 13 MAY 1986 14-16 SEE COLUMN 6, LINES 17-31. Y 12P, A, 59-213701 (NIPPON PAINT) 03 DECEMBER 38-45 1984, SEE ABSTRACT. No 18 Form PCT/ISA/21O (extra shoot) (May 1966)