Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1996-03-21
2001-07-10
Boykin, Terressa M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
active
06258895
ABSTRACT:
DESCRIPTION
The subject matter of the present application is a process for the manufacture of polymers having repeating units comprising spiro orthoester groups, the polymers obtained thereby and their use for the manufacture of strain free composites, high strength adhesives, additives to other monomer mixtures to control the amount of shrinkage or expansion upon polymerization and specifically in dental filling materials.
U.S. Pat. No. 4,387,215 already discloses that polymers formed by the polymerization of polycyclic ring-opening monomers, such as monomers comprising spiro orthoester groups, spiro orthocarbonate groups and polycyclic ketal lactone groups show near zero shrinkage or expansion during polymerization and are therefore usable for the manufacture of strain-free composites, high strength adhesive, precision castings and specifically binders for propellants.
The subject matter of DE-A-24 8 597 is a method for the manufacture of homopolymers comprising spiro orthoester groups of the following formula
wherein R
2
is hydrogen or methyl and X is halogen.
Said homopolymers are stated to be useful as adhesives, casting resins, protection coatings and for dental materials. The homopolymers are manufactured by the radical polymerization of 2-halomethyl-8,8-dimethyl-9-(meth)acryloyloxy- 1,4,6-trioxaspiro[4.4]nonanes. However, this process is not fully satisfying with respect both to the manufacture of the starting materials and their polymerization.
The object of the present invention therefore is the provision of an improved process for the manufacture of polymers having repeating units comprising spiro orthoester groups which provides the products from easily available starting products with high purity and high yields, novel polymers obtained thereby and their use.
The subject matter of the present application therefore is the process according to claim 1. The subclaims comprise preferred embodiments of this process, novel polymers obtainable by this process and the use of these polymers.
The subject matter of the present invention therefore is a process for the manufacture of polymers having repeating units comprising spiro orthoester groups of the following general formula I.
wherein
A is C
1-6
-alkylene, C
1-6
-alkyleneoxycarbonyl or an oxygen-carbon bond,
R
1
is hydrogen or methyl,
R
2
is C
1-6
-alkyl or C
1-6
-alkyl substituted by C
1-6
-alkoxy or aryloxy,
R
3
and R
4
independently are hydrogen or C
1-6
-alkyl,
R
5
is hydrogen or methyl,
R
6
is hydrogen, methyl, phenyl, carboxy, carboxy-C
1-6
-alkyl, carboxamido or cyano,
n is an integer >1 and
m is 0 or an integer ≧1, with the proviso that the molecular weight of the polymer is between 500 and 1,000,000,
which is characterized by reacting a polymer having repeating units comprising lactone groups of the following general formula II
wherein A, R
1
, R
3
, R
4
, R
5
, R
6
, n and m are as defined above, with an oxirane compound of the following general formula III
wherein R
2
is as defined above.
According to a preferred embodiment A is a methylene group, an ethylene oxycarbonyl group or an oxygen-carbon bond. R
1
preferably is methyl, R
2
preferably is C
1-6
-alkyl substituted by phenoxy and more preferably phenoxymethyl. R
3
and R
4
preferably are hydrogen or methyl. R
5
preferably is hydrogen or methyl. Preferably m is 0 and n is an integer such that the molecular weight of the polymer is between 500 and 500,000. more preferably between 1,000 and 50,000 and most preferably between 25,000 and 45,000.
According to a preferred embodiment of the process of the present invention the reaction is carried out in an organic solvent, such as benzene, dichloromethane, trichloroethylene, dichloroethylene, carbontetrachloride, chlorobenzene, nitrobenzene and cyclohexane, more preferably in anyone of the halogenated organic solvents inert to the reaction and most preferably in dichloromethane. The reaction of the starting material of formula (II) with the oxirane compound of the general formula (III) is preferably carried out in the presence of a catalyst or more preferably in the presence of a Lewis acid catalyst, such as boron trifluoride, boron trifluoride etherate, aluminum trichloride, tin dichloride, tin tetrachloride, titanium tetrachloride and iron trichloride. The reaction can be carried out at room temperature at a reaction time of 1 to 5 hours, preferably 2 to 4 hours.
According to a further preferred embodiment of the present invention, the starting compound of general formula (II) is manufactured by radical polymerization of a 2-oxo-tetrahydrofurane derivative of the following general formula (IV)
wherein A, R
1
, R
3
and R
4
are as defined above. For the manufacture of a copolymer of the above formula (I), wherein m is an integer of ≧1, the polymerization is carried out in the presence of a copolymerizable monomer of the following general formula (V)
wherein R
5
and R
6
are as defined above. Specifically preferred copolymerizable monomers of formula (V) are ethylene, propylene, (meth)acrylic acid and the esters thereof, acrylonitrile, acrylamide, styrene and the like.
The polymerization yielding the starting compounds of formula (II) is preferably carried out in solution in an inert organic solvent and in the presence of a radical forming catalyst. As the organic solvent preferably an aromatic solvent, such as toluene is used. As the catalyst a free radical forming catalyst useful for such polymerizations can be used, such as a peroxide catalyst or more preferably azobisisobutyronitrile.
The subject matter of the present application further are polymers having repeating units comprising spiro orthoester groups of the following general formula (I)
wherein A, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, m and n are as defined above. Specifically preferred polymers are homopolymers having repeating units comprising spiro orthoester groups of the following general formula VI
wherein
A is C
1-6
-alkylene. C
1-6
-alkyleneoxycarbonyl or an oxygen-carbon bond,
R
1
is hydrogen or methyl.
R
3
and R
4
independently are hydrogen or C
1-6
-alkyl,
n is an Integer ≧1 with the proviso that the molecular weight of the polymer is between 3,000 and 50,000.
The process of the present invention is specifically advantageous, in that the polymers having useful properties are easy to synthesize from readily available starting material and provides the products with high yield and high purity. The 2-oxo-tetrahydrofurane derivatives of the following general formula (IV)
wherein A, R
1
, R
3
and R
4
are as defined above, can be manufactured with ease by reacting the corresponding lactone of formula (VI)
with (meth)acryloyl chloride.
Specifically preferred polymers corresponding to the above general formula (I) are the following:
Homopolymers having repeating units comprising spiro orthoester groups of the following general formula VI
wherein
A is C
1-6
-alkylene. C
1-6
-alkyleneoxycarbonyl or an oxygen-carbon bond,
R
1
is hydrogen or methyl,
R
3
and R
4
independently are hydrogen or C
1-6
-alkyl,
n is an integer >1 with the proviso that the molecular weight of the polymer is between 3,000 and 50,000.
poly-{1-methyl-1-[2-(phenoxymethyl) -1,4,6-trioxaspiro[4.4]nonane-7-yl]methoxycarbonyl]ethylenes} having the formula 4
and a molecular weight in the range of 5,000 to 500,000, preferably 20,000 to 40,000.
poly-{1-methyl-1-[2-(phenoxymethyl)-1,4,6-trioxaspiro[4.4]nonane-7-yl]carbonyloxy-ethoxycarbonyl]ethylenes} having the formula 8
and a molecular weight in the range of 5,000 to 50,000, and
poly-{1-methyl-1-[2-(phenoxymethyl)-8,8-dimethyl-1,4,6-trioxaspiro[4.4]nonane-9-yl]oxycarbonyl]ethylenes} having the formula 12
and a molecular weight in the range of 5,000 to 500,000, preferably 20,000 to 40,000.
The above homopolymers preferably have a molecular weight in the range of 5,000 to 50,000, more preferably between 10,000 and 40,000 and even more preferred between 25,00
Hocker Hartwig
Zamzow Manfred
Boykin Terressa M.
Clark Karen F.
Dinsmore & Shohl
The Procter & Gamble & Company
Zea Betty J.
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