Process for polymerizing of cyclic olefins and a photopolymeriza

Details Process for polymerizing of cyclic olefins and a photopolymeriza Process for polymerizing of cyclic olefins and a photopolymeriza

1997-05-22

1998-10-13

Berman, Susan W.

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Compositions to be polymerized by wave energy wherein said...

522 29, 522184, 522186, 522167, 522168, 522172, 522173, 522180, 522182, 526113, 526170, 526172, 526256, 526258, 526266, 526279, 526308, 526309, C08F 246, C08F 248, C08F 468, C08F 3200

Patent

active

058212787

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to a process for the polymerization of cyclic olefins by photochemical ring-opening metathesis polymerization using catalytic amounts of a niobium or tantalum catalyst which contains at least two methyl groups or two monosubstituted methyl groups, without .alpha.-hydrogen atoms in the substituent, bound to the metal, and to compositions comprising these olefins together with a catalytic amount of this catalyst.
Thermally induced ring-opening metathesis polymerization using catalytic amounts of metal catalysts has already been known for a relatively long for example, Ivin, K. J., Olefin Metathesis 1-12, Academic Press, London (1983)!. Polymers which can be prepared in this manner are prepared industrially and are commercially obtainable. On the other hand, only little has been disclosed on photochemically induced ring-opening metathesis polymerization, and as yet there have been no commercial applications.
It is known from U.S. Pat. No. 4,060,468 to carry out an olefin metathesis polymerization by introducing a two-component mixture of a metal salt chosen from the group consisting of tungsten, molybdenum, rhenium and tantalum salts and a substituted phenol or benzyl alcohol as cocatalysts to a reaction vessel with the monomeric olefin, and then irradiating the entire reaction mixture with UV light. Olefins which are mentioned are only cyclic and acyclic hydrocarbons without functional groups or substituents. Separate storage of the catalyst components and the process step of mixing the catalyst components directly before the actual reaction render the known process industrially expensive and cumbersome. Letters 52: 4589-4592 (1977)! describe the catalyst system W(CO).sub.6 /CCl.sub.4, which, after irradiation with UV light, can be employed for metathesis polymerization of cyclopentene and norbornene. Metal carbonyls are volatile and toxic, so that their use requires expensive safety precautions for physiological reasons. Furthermore, a free radical addition reaction to form monomeric 1-chloro-2-trichloromethyl-cycloalkanes is observed as a competing reaction.
It is known from Thoi, H. H., Ivin, K. J., Rooney, J. J., J. Mol. Catal. 15:245-270 (1982)! that a tungsten pentacarbonyl-carbene complex of the formula ##STR1## is a thermal catalyst for ring-opening metathesis polymerization of dimethylnorbornene, and, together with phenylacetylene as a cocatalyst, is also a photocatalyst system for the same polymerization. This catalyst system has the serious disadvantage that it has only a low storage stability as the ready-to-use formulation, the carbonyl compound is physiologically unacceptable, and the tolerance towards functional groups in cycloolefins is too low. Progress in Inorganic Chemistry, 39:3-73 (1991)! describe molybdenum- and tungsten-alkylidene complexes which are thermal catalysts for the polymerization of cycloolefins which by themselves have only a weak action, but together with Lewis acids are active.
The known photochemically activatable catalysts thus always require a cocatalyst, which means that the quality of the polymers prepared can vary greatly due to the chosen nature and sequence of the reagents.
Polymers can be prepared from cyclic olefins by photochemical ring-opening metathesis polymerization by the known processes only with high expenditure and in an economically unsatisfactory manner. The lack of storage stability, which allows mixing of the components only directly before the preparation, the lack of tolerance towards functionalized cyclic olefins and the need to use two components as the catalyst system have been found to be particular disadvantages. There is therefore a need to provide a process, which is improved from the industrial, economic and ecological aspect and is generally usable, for the preparation of polymers from cyclic olefins by photochemical ring-opening metathesis polymerization.
WO 93/13171 describes air- and water-stable one-component and two-component catalysts based on molybdenum and tungsten compounds containing carbonyl groups

REFERENCES:
patent: 4060468 (1977-11-01), Castner
patent: 5198511 (1993-03-01), Brown-Wensley et al.
patent: 5371158 (1994-12-01), Brekner et al.
patent: 5616663 (1997-04-01), Imuta et al.

Affiliated with

Also associated with

Rating

Process for polymerizing of cyclic olefins and a photopolymeriza 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 polymerizing of cyclic olefins and a photopolymeriza, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for polymerizing of cyclic olefins and a photopolymeriza will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-313645