Terminated silane Michael polyaddition polymer

Details Terminated silane Michael polyaddition polymer Terminated silane Michael polyaddition polymer

1999-06-29

2001-04-24

Dawson, Robert (Department: 1712)

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

Synthetic resins

From silicon reactant having at least one...

C528S028000, C556S413000, C556S437000

Reexamination Certificate

active

06221994

ABSTRACT:

This invention pertains to a new type of polymer, which is produced by reacting an appropriate organic derivative of silicon with the terminal groups of linear or branched polymers that are obtained from the reaction of Michael addition of organic compounds that contain at least two active hydrogens to organic compounds that contain at least two double ethylene bonds that are activated by the presence, in the alpha position with regard to each ethylene bond, of an electronegative group. The terminated silane polymer that is obtained, in the form of a viscous fluid that is stable under conditions of absence of moisture, for example, by simple exposure to air and without further additions of other substances at the time of use, quickly increases its viscosity until it turns into a solid product, which can be hard and tough like a resin or elastic and flexible like a rubber. These products can be used as coatings and sealers.
The reaction of Michael addition of monofunctional nucleophilic compounds to double bonds that are activated by electronegative groups in the alpha position with regard to the ethylene bond has been known for some time, and the polymers that are obtained by polyaddition of bifunctional nucleophilic molecules such as diols, diamines, and dithiols to activated diolefins such as diacrylic derivatives, dimethyacrylic derivatives (e.g., esters and amides), dinitroolefins, divinylsulfones, and divinylsulfoxides are known and described in the literature. Let us cite, in a list that is certainly not exhaustive: Bayer, O.
Angew. Chem
. 61, 229 (1949); Hulse, G. E. U.S. Pat. No. 2,759,913 (1956); Mallik, K. L., Das, M. N. Z.
Phys. Chem
. 25, 205 (1960); Nogudu, H., Rembaum, A.
J. Polym. Sci., Part B
, 7, 383 (1969); Danusso, F., Ferruti,
P. Polymer
11, 88 (1970); Imai, Y. et al.
Makromol. Chem. Rapid Commun
. 1, 659 (1980); Imai, Y. et al.
J. Polym. Sci., Polym. Chem. Ed
. 19 583 (1981); Imai, Y. et al.
Polym. J
. 13 803 (1981); Mathias, L. J., Kress, A. O.
Polymer
29, 302 (1988); Nuyken, O., Volkel, T.
Makromol. Chem
. 191, 2465 (1990); Ferruti, P., Ranucci, E.
Polym. J
. 23 541 (1991).
The polyaddition reaction proceeds readily at ambient temperature or at moderate temperature, producing polymers that are predominantly characterized by a structure of the anti-Markovnikov type when the reaction is catalyzed by a base or by a Markovnikov-type structure when the reaction is catalyzed by an acid, as in the case where dithiols are added to divinyl ethers.
The polyaddition reaction has the charactistics of a staged reaction. The mean numerical degree of polymerization {overscore (P
n
+L )} is given by:
P
n
_
=
1
+
r
1
-
2
⁢
pr
+
r
where:
r=the ratio between the quantity of compound in deficit and that of the compound in surplus;
p=degree of conversion of the compound in deficit.
When p=1, i.e., the conversion of the deficit product is quantitative, this becomes:
P
n
_
=
1
+
r
1
-
r
and the mean degree of polymerization depends solely on the monomer ratio r.
When the monomers are made to react in an equimolar quantity, i.e., when the ratio between the quantities of the monomers is equal to one (r=1), the polymers that are obtained are products of extremely high (theoretically infinite) molecular weight with very little presence of free functional groups (theoretically none). In all the cases of equimolar reactions described in the literature, and in particular in U.S. Pat. No. 2, 759,913, very good agreement is observed between the elementary analysis of the polymers obtained and the theoretically calculated values. When the molecular ratio between the monomers is other than one (r≠1), the mean numerical degree of polymerization {overscore (P
n
+L )} is derived directly from the selected ratio, and the polymers that are obtained have terminal groups of the monomer in surplus. Examples of such polymers can be found in the literature cited: in all these cases very good agreement can be observed between the experimental data and the theoretically calculated mean molecular weights of the polymers obtained.
It can therefore be said that the reaction of polyaddition of organic compounds with at least two active hydrogens to compounds with at least two activated ethylene bonds in which process the molecular ratio between the monomers is other than one (r≠1) is a good way to obtain polymers and oligomers that have pre-established molecular weights and terminal groups. In addition, unlike reactions induced by radicals, there are no reticulation or chain-extension phenomena.
For the purposes of this invention, all of the polymers that are obtained with a ratio between the quantities of the monomers of other than one (r≠1) are usable since they are characterized by the presence of free functional groups that are required for subsequent silanization.
Polymers and oligomers from Michael polyaddition that are obtained with a ratio between the quantities of the monomers of other than one (r≠1) and terminate with functional groups such as amino, mercapto, activated ethylene, etc. do not have direct application in the area of coatings and sealers, but can be used only when mixed with other substances that have a functionality of greater than or equal to two and are able to react with the functional groups of the polymer or oliogmer. By way of example, let us mention the polyaddition polymers which terminate with a mercapto group and which can be reticulated by reacting with an epoxy resin, exploiting the reactivity of the nucleophilic mercapto group with regard to the oxyranic ring. The terminated mercapto polycondensation polymer acts as a chain extender of the epoxy resin and, if the chain is long enough, also of the flexibilizer of the resin itself. The reaction, which is catalyzed by a tertiary amine, takes place at as low as ambient temperature.
Other examples, which are well known to one skilled in the art, can be cited. Therefore these polymers find practical application only as parts of a bi-component system in which a product A, which has a well-defined weight or volume, must be accurately mixed with a product B, also having a well-defined weight or volume, and the A+B mixture must be used within a certain time, generally no more than one or two hours. It is also evident even to one not skilled in the art that the bi-component products have more than a few drawbacks with regard to their use: the metering of the products has to be very precise, the mixing has to be perfect, the time available for manipulation before it hardens is always limited, and it is impossible to recover the material in surplus.
There are, consequently, considerable advantages to using mono-component materials that do not have any of the drawbacks indicated above.
The object of this invention is to transform polyaddition polymers that are obtained by Michael addition, base-catalyzed, of organic compounds that have at least two active hydrogens to organic compounds that have at least two activated ethylene bonds, whereby the molecular ratio between the quantities of the monomers is other than one (r≠1), into polymers that reticulate completely and move from the fluid state to the solid state simply by being exposed to the humidity of the air and without further additions of other reactive substances, i.e., to transform them into mono-component products.
For this purpose since the polyaddition polymers are terminated with activated amine, mercaptane, or ethylene groups, these polymers are made to react with organic silicon derivatives which have either a reactive functional group that is suitable for reacting with the terminal functional group of the polyaddition polymer or suitable groups that can be easily hydrolyzed and condensed. The terminated silane polymers that are thus obtained are stable and retain their state as viscous fluids under anhydrous conditions but, if exposed to atmospheric humidity, are transformed into solid materials owing to the reticulation that is produced by the hydrolysis and subsequent addition of the groups to the t

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