Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1993-04-28
1994-03-08
Schofer, Joseph L.
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
5262325, 5263184, 5263292, 526335, 526341, 549427, 549501, 560183, 568567, C08F 432
Patent
active
052928390
DESCRIPTION:
BRIEF SUMMARY
The invention relates to novel allyl peroxyketal chain transfer agents, methods of radically polymerizing monomers in the presence of said peroxyketals to thereby control the molecular weights of the resulting polymers and to polymers and shaped objects containing polymers produced by the instant polymerization methods.
The general concept of employing a molecular weight regulating agent, also known as a chain transfer agent, as an additive during polymerization reactions has been known for a long time. A number of different chain transfer agents having an olefinic group therein, have been employed for this purpose.
Perhaps one of the earlier disclosures of such a polymerization modifying material can be found in U.S. Pat. No. 3,248,374 published on 24 Jun. 1966, wherein the use of an olefin of the formula I as a polymerization modifier is disclosed. ##STR1## wherein R is hydrogen, halogen or a saturated aliphatic radical and X is halogen, cyanide, phenyl, carboxyl, carbonate, phenyloxy, --CONH.sub.2, --CONH-alkyl or --CON-dialkyl. The presence of these olefinic materials during the polymerization of vinylidene chloride with other olefinic materials rendered the resultant polymer more water soluble.
U.S. Pat. No. 3,726,832 published on 10 Apr. 1973, discloses the use of a cyclic ether or a vinyl ether as a molecular weight regulator for the polymerization of dienes.
U.S. Pat. No. 4,176,219 published on 27 Nov. 1979, discloses the use of allyl halides, benzyl halides or a tertiary aliphatic halide compound as molecular weight regulators for the production of 1,2-polybutadiene.
U.S. Pat. 4,405,742, published on 20 Sep. 1983, discloses the use as a regulator, of unsaturated ethers, thioethers, amines, and acrylates and thioacrylates of acrylamides for the purpose of polymerizing chloroprene to produce an improved polychloroprene product.
PCT patent application WO 88/04304 published on 16 Jun. 1988 discloses the use of compounds of the formula (II) for the purpose of controlling the molecular weight and end group functionality of polymers. ##STR2## wherein R.sub.1 is hydrogen or a group capable of activating the vinylic carbon towards free radical addition; Y is OR.sub.2 or CH.sub.2 X(R.sub.2).sub.n, where R.sub.2 is an optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted saturated or unsaturated carbocyclic or heterocyclic ring; X is an element other than carbon selected from Groups IV, V, VI or VII of the Periodic Table or a group consisting of an element selected from Groups IV, V or VI to which is attached one or more oxygen atoms; and n is a number from 0 to 3 such that the valency of X is satisfied and, when n is greater than 1, the groups represented by R.sub.2 may be identical or different.
Finally, PCT patent application WO 91/06535 published on 16 May 1991 discloses the use of compounds of the formula (III) for the purpose of controlling the molecular weight and end group functionality of polymers. ##STR3## wherein R.sup.1 is hydrogen, chlorine, an alkyl group or a group capable of activating the vinylic carbon towards free radical addition; R.sup.2 is hydrogen or an optionally substituted alkyl, alkenyl, aryl, cycloalkenyl or cycloalkyl group or the group --COZ, where Z is R.sup.3 or OR.sup.3, where R.sup.3 is hydrogen or an optionally substituted alkyl, alkenyl or aryl group. X is a hydrogen atom, an optionally substituted alkyl, alkenyl halogen, and the two X groups may be the same or different.
The present invention relates to organic peroxides useful as chain transfer agents in radical polymerization of monomers characterized in that said organic peroxides are represented by the following formula: ##STR4## wherein R.sub.1 and R.sub.2 are independently selected from hydrogen, lower alkyl, alkenyl and aryl; R.sub.3 is represented by the formula V: ##STR5## wherein R.sub.4, R.sub.5 and R.sub.6 are independently selected from optionally substituted lower alkyl, alkenyl, aryl and hydrogen, whereby R.sub.4 and R.sub.5 cannot be hydroge
REFERENCES:
patent: 3069474 (1962-12-01), Rieche et al.
patent: 3248374 (1966-04-01), Covington
patent: 3726832 (1973-04-01), Komatsu et al.
patent: 4176219 (1979-11-01), Makino et al.
patent: 4405742 (1983-09-01), Musch et al.
International Search Report dated Jan. 31, 1992.
"Alkylated Perepoxides: Peroxonium vs. Phenonium Intermediates from Beta-Haloalkyl tert-Butyl Peroxides and Silver Trifluoroacetate" 1 Org Chem., vol., 51, pp. 1790-1793 (1986).
"An Olefination-Based Route To Unsaturated Hydroperoxides", Tetrahedron Letters, vol. 31, No. 36, pp. 5117-5120 (1990).
"Deplacements Homolytiques Intramoleculaires: III--Decomposition Du Peroxyde D`Allyle Et De t-Butyle Dans Les Ethers Et Les Cyclanes: Expoxy-2,3 Propanation De Ces Solvants"; Tetrahdron Letters, vol. 41, No. 21, pp. 5039-5043. (1985).
Maillard Bernard J.
Meijer John
Vertommen Luc L. T.
Akzo N.V.
Mancini Ralph J.
Morris Louis A.
Schofer Joseph L.
Smith Jeffrey T.
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