Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1995-07-05
1997-03-18
Schofer, Joseph L.
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
526242, 526328, 526343, 526344, 526346, 526319, 526348, 526341, 526335, 526 82, C08F 434, C08F 238
Patent
active
056124309
DESCRIPTION:
BRIEF SUMMARY
The invention relates to a method of radically (co)polymerizing monomers in the presence of unsaturated organic peroxide chain transfer agents to thereby control the molecular weights of the resulting (co)polymers, to (co)polymers and shaped objects containing (co)polymers produced by the instant polymerization methods, and to the use of said unsaturated organic peroxides as chain transfer agents.
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 unsaturated group therein have been employed for this purpose.
Perhaps one of the earlier disclosures of such a chain transfer agent is to be found in U.S. Pat. No. 3,248,374, wherein the use of a cyclomonoolefin as a polymerization modifier is disclosed. The presence of these modifiers during the copolymerization of vinylidene chloride with other olefinic materials rendered the resultant polymer more water soluble. Successively, the following compounds have been disclosed as chain transfer agents: cyclic ethers and vinyl ethers (U.S. Pat. No. 3,726,832), allyl halides, benzyl halides or tertiary aliphatic halide compounds (U.S. Pat. No. 4,176,219), and unsaturated ethers, thioethers, amines, and acrylates and thioacrylates of acrylamides (U.S. Pat. No. 4,405,742).
Very recent publications in this area are PCT applications WO 91/06535 and WO 91/07387 disclosing unsaturated organic peroxide compounds substituted with an activating group capable of enhancing the reactivity of the olefinic unsaturation towards free radical addition.
These peroxide compounds may be used as chain transfer agents in the polymerization of monomers. However, they are attended with the disadvantage that severe retardation occurs during the polymerization reaction in their presence thereby resulting in low monomer conversions.
The present invention relates to a method of radically (co)polymerizing monomers with a polymerization initiator in the presence of an effective amount of at least one unsaturated organic peroxide chain transfer agent, characterized in that the unsaturated organic peroxide is selected from the group represented by the following formula: ##STR1## wherein R.sub.1 is an activating group capable of enhancing the reactivity of the olefinic unsaturation towards free radical addition; R.sub.2 is selected from the group of hydrogen, C.sub.1 -C.sub.18 alkyl, C.sub.3 -C.sub.18 alkenyl, C.sub.3 -C.sub.18 alkynyl, C.sub.7 -C.sub.22 aralkyl, and C.sub.3 -C.sub.18 saturated or unsaturated carbocyclic and heterocyclic rings; and R.sub.3 is selected from the group of hydrogen, C.sub.1 -C.sub.18 alkyl, C.sub.3 -C.sub.18 alkenyl, C.sub.6 -C.sub.18 aryl, C.sub.6 -C.sub.22 alkaryl and C.sub.7 -C.sub.22 aralkyl, or R.sub.1 and R.sub.3 may combine to form a C.sub.5 -C.sub.10 ring; all of groups R.sub.1, R.sub.2, and R.sub.3 may be linear or branched and may be optionally substituted with one or more groups selected from hydroxy, alkoxy, aryloxy, epoxy, halogen, acid, ester, nitrile, ketone, and amido.
.beta.-tert-Butyl monoperoxyitaconate, for which in formula I R.sub.1 is COOH, R.sub.2 is tert-butyl and R.sub.3 is hydrogen, is known from Fedorova et al., Ukr. Khim. Zh. (Russ. Ed.), 52 (9), 1986, pp. 966-8. In this article the kinetics of the hydrolysis of this monoperester are described. Although mention is made of the possibility to use this monoperester as a radical initiator in polymerization processes, molecular weight regulation ability is not disclosed.
Furthermore, Fedorova et al, Izv. Vyssh. Uchebn. Zaved, Khim. Khim. Tekhnol., 19 (10), 1976, pp. 1504-6, discloses .alpha.-tert-butyl monoperoxy-.beta.-methylitaconate. This, however, is not a peroxide used in the process according to the present invention. Neither is the use of this particular peroxide in polymerization processes or its potential ability to act as a molecular weight regulator, disclosed herein.
Finally, German patent application
REFERENCES:
patent: 3248374 (1966-04-01), Covington
patent: 3560529 (1971-02-01), Blumbergs et al.
patent: 3726832 (1973-04-01), Komatsu et al.
patent: 4176219 (1979-11-01), Makino et al.
patent: 4405742 (1983-09-01), Musch et al.
patent: 5292839 (1994-03-01), Vertommen et al.
Fedorova et al., Ukr. Khim Zh. (Russ. Ed.), 52 (9), 1986, pp. 966-8.
Fedorova et al., Izv. Vyssh. Uchebn. Zaved, Khim. Khim Tekhnol., 19 (10), 1976, pp. 1504-1506.
Fedorova et al., Visn. L'viv Polithekh. Inst., 149, 1981, pp. 43-47.
Maillard Bernard J.
Nijhuis Walter H. N.
Talma Auke G.
Vertommen Luc L. T.
Akzo Nobel nv
Cheng Wu C.
Mancini Ralph J.
Morris Louis A.
Schofer Joseph L.
LandOfFree
Process for molecular weight regulation in (co)polymers does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Process for molecular weight regulation in (co)polymers, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for molecular weight regulation in (co)polymers will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-1707184