Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From silicon reactant having at least one...
Reexamination Certificate
2001-01-02
2002-05-07
Dawson, Robert (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From silicon reactant having at least one...
C528S031000, C528S032000
Reexamination Certificate
active
06384172
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to the synthesis of polymers from polyfunctional monomers, and more particularly to the synthesis of branched polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof.
BACKGROUND OF THE INVENTION
Silicon-containing polymers, such as polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof, are typically synthesized from difunctional monomers to produce linear polymers, or from a combination of difunctional and polyfunctional monomers to prepare thermoset resins. Thermoplastic and thermoset polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof are used in a variety of applications. Liquid polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof are used as adhesives, lubricants, protective coatings, coolants, mold-release agents, dielectric fluids, heat transfer fluids, wetting agents, water-repellents, polishes, etc. Resinous polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof are used in coatings, molding compounds, sealants, room-temperature curing cements, modifiers for alkyd resins, etc. Elastomeric polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof are used for encapsulation of electronic parts, gaskets, surgical membranes, etc. However, there is a recognized need for branched, and more particularly for highly branched polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof. It is know that chemically similar polymers having different molecular architectures can exhibit different properties and advantages. For example, polymer-coating compositions comprising a highly branched polymer have a lower viscosity and better shear-thinning properties for coating applications than similar compositions containing a chemically similar linear polymer having the same molecular weight and same concentration.
One method of synthesizing branched polymers is to use polyfunctional monomers (i.e., monomers having three or more functional groups) during polymerization. However, this method may result in the production of gelled or thermoset cross-linked materials that do not exhibit good processability characteristics, and which are insoluble.
It has been suggested that dendrimers can be employed in certain applications to achieve improved properties, such as thermoplastic processing characteristics, lower viscosity, and improved rheology, as compared with linear polymers having similar chemistry and molecular weight. However, dendrimers are almost monodisperse (typically having a polydispersity of less than about 1.02), highly defined molecules that are prepared by a series of controlled stepwise growth reactions which generally involve protect-deprotect strategies and purification procedures at the conclusion of each step. As a consequence, synthesis of dendrimers is a tedious and expensive process that places a practical limitation on their applicability.
In contrast to dendrimers, hyperbranched polymers can be prepared in a one-step, one-pot procedure. This facilitates the synthesis of large quantities of materials, at high yields, and at a relatively low cost. Although the properties of hyperbranched polymers are different from those of dendrimers due to imperfect branching and larger polydispersities, hyperbranched polymers exhibit a degree of branching intermediate between that of linear polymers and dendrimers, and, therefore, exhibit thermoplastic processing and rheological properties that are comparable, or for some applications superior, to those of dendrimers. Accordingly, hyperbranched polymers have been perceived as being useful in certain applications as a lower cost alternative to dendrimers.
Heretofore, hyperbranched polymers, including hyperbranched polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof, have been prepared using a monomer having at least one functionality of one type (A), and at least two functionalities of another type (B), wherein functionalities of the same type are not reactive with each other, and functionalities of the first type are reactive with functionalities of the second type to form hyperbranched polymers via condensation or addition reactions. The monomers employed during synthesis of conventional hyperbranched polymers are generally designated as A
x
B
y
monomers, wherein A represents a functional group of a first type that does not react with itself, B represents a functional group of a second type that does not react with itself but reacts with the functional groups of the first type, x is at least 1, and y is at least 2. However, there are relatively few commercially available A
x
B
y
monomers, and synthesis of such monomers is generally more difficult than synthesis of monomers having a single type of functionality. As a result, the variety of hyperbranched polymers that can be synthesized from A
x
B
y
monomers is limited, and although they are generally less expensive than dendrimers they are often too expensive for many applications.
SUMMARY OF THE INVENTION
This invention provides hyperbranched polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof prepared from difunctional and/or polyfunctional monomers having functional groups of one type (A) without any other functional groups that react significantly during the polymerization process, and difunctional and/or polyfunctional monomers having functional groups of another type (B) that react with a functional group of the first type (A) without any other functional groups that react significantly during the polymerization process. More specifically, the hyperbranched copolymers of this invention are prepared by a process in which a monomer having the form A
x
is reacted with another monomer of the form B
y
, where A is a functional group that does not react with itself during the polymerization process, B is a functional group that does not react with itself during the polymerization process but participates in an addition or condensation reaction with a first functional group (A) to form a hyperbranched copolymer, x and y are integers which each have a value of at least 2, and at least one of x and y is an integer having a value of at least 3.
The process of this invention enables synthesis of hyperbranched polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof from comonomers, each of which has a single type of functional group, thereby providing greater flexibility in the preparation of a larger variety of different hyperbranched polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof. Because A
x
and B
y
type monomers are easier to synthesize than A
x
B
y
type monomers, the process of this invention also enables hyperbranched polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof to be prepared at a lower cost than with conventional synthesis processes.
These and other features, advantages and objects of the present invention will be further understood and appreciated by those skilled in the art by reference to the following specification and claims.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention is directed to hyperbranched polycarbosilanes, polycarbosiloxanes, polycarbosilazenes and copolymers thereof prepared by reacting at least two different monomers, each of which will not react with itself, but will react with the other monomer, wherein at least one of the monomers includes at least three functional groups, and the other monomer is at least difunctional. It should be understood that the A
x
and B
y
monomers may contain other groups that are potentially reactive in other ways. Accordingly, it will be understood that an A
x
monomer does not include any functional groups, other than the A-functional groups, that will react appreciably or significantly during polymerization reaction. Similarly, the B
y
monomers will not contain any functional groups, other than the B-functional groups, that will react appreciably o
Dvornic Petar R.
Hu Jin
Meier Dale J.
Nowak Robert M.
Dawson Robert
Michigan Molecular Institute
Price Heneveld Cooper DeWitt & Litton
Zimmer Marc S.
LandOfFree
Hyperbranched polycarbosilanes, polycarbosiloxanes,... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Hyperbranched polycarbosilanes, polycarbosiloxanes,..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Hyperbranched polycarbosilanes, polycarbosiloxanes,... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2876402