IIIUS005760149A United States Patent (19) 11 Patent Number: 5,760,149 Sanchez et al. 45) Date of Patent: Jun. 2, 1998 54 POLY(MONOPEROXYCARBONATES) 5,446,191 8/1995 Suyama et al. 5,455,321 10/1995 Cummings et al. 75 Inventors: Jose Sanchez, Grand Island; John Salvatore Yormick, Kenmore, both of OTHER PUBLICATIONS N.Y.; Jerome Wicher, Collegeville; 92:164324 Chem. Abs. Jun. 1980 Ladousse et al. Kenneth George Malone, Plymouth 71:123928 Chem. Abs. Dec. 1969 Komai et al. Meeting, both of Pa. 99:88729 Chem. Abs. Nov. 1983 Sanken Kako Co. 73) Assignee: Ef Atochem North America, Inc. Primary Examiner-Michael G. Ambrose Philadelphia, Pa. Attorney, Agent, or Firm-Stanley A. Marcus; Royal E. Bright 22 Filed: Aug. 8, 1997 Poly(monoperoxycarbonates) of the structure: Related U.S. Application Data O 60 Provisional application No. 60/025.206 Sep. 23, 1996. ----- (51 Int. C. ... C08F 4/36; C08F 4/38; CO8F 8/00; C07C 69/96 -- .. where R. R' and n are defined in the summary of the 52 U.S. Cl. ...................... 5:53, invention such aS 1,1,1-tris (t- 8 Field of S 525/451; 8/2 558/263 butylperoxycarbonyloxymethyl)ethane, intermediates 58) ield of Search ......................... 558/263; 526/230.5, for their preparation as well as processes for their 526/346; 525/313,387, 451 preparation and use are disclosed. The monoperoxy carbonate compounds are useful in initiating the poly 56 References Cited merization of ethylenically unsaturated monomers. par U.S. PATENT DOCUMENTS ticularly styrene, curing of unsaturated polyester resins, and in modifying the molecular weight of polymers 4,136,1053,652,631 3/19721/1979 Sanchez.Stevens et al.. such as by crosslinking or controlled chain degradation. 5,266,603 11/1993 Holzmeier et al. 5,314,970 5/1994 MacLeay et al.. 20 Claims, No Drawings 5,760,149 1 POLY(MONOPEROXYCARBONATES) This Application claims priority from Provisional Appli cation Ser. No. 60/025,206, filed Aug. 23, 1996. (where R' and Rare alkyl up to 10 carbons, optionally BACKGROUND OF THE INVENTION substituted with halogen or nitro groups, and R is the a) Field of the Invention divalent residue of an organic diol containing up to 12 This invention relates to new and novel compositions of carbon atoms and up to three ether linkages), matter classified in the art of chemistry as poly 10 t-amyl hydroperoxide or t-hexyl hydroperoxide and bis (monoperoxycarbonate) compounds of Structure A: (chloroformates) and the use of these compositions to poly merize monomers such as styrene. The bis O A. (monoperoxycarbonate) composition. 1,5-bis(t- Ri-oo-C-O-R butylperoxycarbonyloxy)-3-oxapentane, is covered by U.S. 15 Pat. No. 3,652,631. The applicants of the instant invention The definitions of n, R and R' are given in the SUM found that the novel poly(monoperoxycarbonate) composi MARY OF THE INVENTION), to processes for their prepa tions of Structure A were better initiators for polymerizing ration and use and to intermediates used in the preparation styrene than 1,5-bis(t-butylperoxycarbonyloxy)-3- processes. oxapentane as they produced polystyrenes with significantly There is a need in the polymer industry for efficient, increased molecular weights under the same polymerization free-radical initiators for polymerizing ethylenically unsat conditions. urated monomers, such as styrene, at faster production rates U.S. Pat. No. 4,136,105, Jan. 23, 1979 (to Pennwalt while retaining polymer molecular weight and polymer Corp.) discloses O-alkyl OO-t-octyl monoperoxycarbonates physical properties, e.g., tensile properties. In general, use of 2. more active free-radical initiators and increase of polymer 25 ization temperatures to enhance production rates of poly mers (e.g., polystyrene) result in the desired enhancement of CH CH O 2 production rates but also undesirably result in reduced CH-C-CH-C-OO-C-O-H-R polymer molecular weights and reduced tensile properties. There also is a need to increase the molecular weight of 30 CH CH commercial polymers in order to enhance polymer physical properties. Reduction of polymerization temperatures, (where n is an integer from 1 to 4, preferably 1; when n reduction in initiator use levels and use of less active is 1, R is selected from alkyl of 1-16 carbons, initiators generally achieve the goal of increasing polymer cycloalkyl of 5-12 carbons, aryl of 6 to 14 carbons, molecular weight, however, polymer production rates are 35 aralkyl of 7-14 carbons, alkenyl of 3-10 carbons, reduced. In the 1980s, the art of polymerizing styrene was cycloalkenyl of 5-10 carbons, and alkynyl of 3-14 advanced. Use of diperoxyketals, such as 1.1-bis(t- carbons; when n is 2, R is selected from alkylene of butylperoxy)cyclohexane, as initiators in place of standard 2-12 carbons, cycloalkylene of 4-12 carbons, arylene initiators, such as dibenzoyl peroxide and t-butyl of 6-14 carbons, alkenylene of 2-12 carbons, alky peroxybenzoate, for commercial styrene polymerizations nylene of 4-12 carbons, methylenephenylmethylene, resulted in enhanced polystyrene molecular weight and/or methylenecyclohexylmethylene, -R'XR'-, and enhanced production of polystyrene. The current applicants -RYR-, where R' is alkylene of 2-6 carbons, R further advanced the art and found that the novel poly is phenylene, X is -O- or -S-, and Y is -O-, (monoperoxycarbonate) compositions of Structure A of this -S-, -CH2- or -COCH)-; when n is 3. R is invention can be used as initiators for polymerizing ethyl 45 RC(CH-), -CH(CH-), and -CHCH(-) enically unsaturated monomers to produce polymers (e.g., CHCHCHCH-, where R is alkyl of 1-5 carbons; polystyrene) having significantly increased polymer and when n is 4, R is C(CH-)) molecular weights while simultaneously retaining or and the use of these compositions for initiating the poly increasing polymerization rates or to produce polymers at merization of vinyl monomers and for curing of unsaturated significantly enhanced rates while retaining polymer polyester resins. This art covers tris- and tetrakis(mono-t- molecular weights, and that the compositions of the instant octylperoxycarbonates) derived from t-octyl hydroperoxide invention were superior to diperoxyketals, such as 1.1-bis but does not disclose the novel poly(monoperoxycarbonate) (t-butylperoxy)cyclohexane. Thus, the novel poly compositions of the instant invention that are derived from (monoperoxycarbonate) compositions of the instant inven t-butyl and t-amyl hydroperoxides. tion are capable of satisfying the polymerization needs of 55 U.S. Pat. No. 5314,970, (to Elf Atochem, May 24, 1994) polymer industry. discloses OO-t-alkyl O-poly caprolactone There also is a need in the polyester industry for free monoperoxycarbonates, i.e., polycaprolactones end-capped radical initiators that cure unsaturated polyester resins faster with OO-t-alkylperoxycarbonate groups 3 derived from and/or at lower temperatures. The novel poly t-alkyl hydroperoxides and chloroformates of (monoperoxycarbonate) compositions of the instant inven tion are also capable of satisfying this polymer industry (A-XR-e-X-B). 3 need. b) Description of the Prior Art O U.S. Pat. No. 3,652,631 (to PPG, Mar. 28, 1972) discloses 65 bis(monoperoxycarbonates 1 derived from t-butyl (where A is H-E-O-(CH2C, B is hydroperoxide, 5,760,149 3 4 -continued U.S. Pat No. 5.455.321 (to The Dow Chemical Company, O O R Oct. 3, 1995) discloses a process for producing a monovi I nylidene aromatic polymer (e.g., polystyrene) having +C-(CH, orC -oo--R, molecular weight greater than 275,000 which comprises R3 polymerizing a monovinylidene aromatic monomer (e.g., styrene) in the presence of, a) 10 to 2000 ppm by weight of m is an integer from 0 to 3, n is an integer from 1 to 4, at least one free-radical generating, branching polymeriza m+n is an integer from 1 to 4. R' andR are the same tion initiator of the structure: or different and are alkyl of 1 to 4 carbons, R is alkyl of 1 to 12 carbons or alkynyl of 2 to 12 carbons, y is O R(CO)OOR), an integer from 0 to about 10,000, x is an integer from 4 to about 22,000, (y)(m)+(x)(n) is an integer from 4 to about 22,000, X and X are independently selected from where n is 0 or 1, m is 3 to 6, R is a multifunctional -O- or -N(R-), R' being hydrogen, substituted organic radical of up to 25 non-hydrogen atoms, and R or unsubstituted aliphatic of 1 to 20 carbons, substi 15 is C-1 tertiary alkyl or Cs tertiary aralkyl groups, tuted or unsubstituted acyclic of 5 to 18 carbons, and b) 10 to 2000 ppm of one or more organic substituted or unsubstituted aromatic of 6-14 carbons, gel-reducing agents selected from the group consisting and substituted or unsubstituted araliphatic of 7 to 22 of I) mercaptans, terpenes, halocarbons and halohydro carbons, and R is a substituted or unsubstituted carbons having up to 20 carbons, ii) a recycle liquid aliphatic, alicyclic aromatic or araliphatic radical, 20 generated by devolatilization of the polymerized mono diradical, triradical or tetraradical), mer mixture, and, iii) mixture of the organic gel hydroxy-terminated polycapirolactones and the use of these reducing agents from I) and ii). A preferred free-radical compositions for initiating the polymerization of vinyl generating, branching polymerization initiator was 2.2- monomers, for curing of unsaturated polyester resins, for bis(44-di-t-butylperoxycyclohexyl)propane: preparing polycaprolactone block copolymers, for crosslink 25 ing polyolefins, for curing of elastomers, for modifying t-CH-OO CHCH, CH, CHCH2 OO-t-CH polypropylene, for grafting polycaprolactone blocks onto N / N polyolefins, for preparation of interpenetrating polymer C -C-CH C networks, and for preparation of graft polyols.