Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From silicon reactant having at least one...
Reexamination Certificate
1999-04-20
2001-08-07
Moore, Margaret G. (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From silicon reactant having at least one...
C428S447000, C351S16000R, C623S005110, C623S006120
Reexamination Certificate
active
06271332
ABSTRACT:
The present invention describes a polymer and a precursor thereof; a prepolymer made essentially from a macromer that is, for example, crosslinked via its free hydroxy groups with a polyisocyanate, a macromer being made essentially from a polysiloxane and a polyol component; methods of producing such prepolymers and polymers; the use of such polymers, for example as artificial corneas, as moulded articles, especially as contact lens material; also the use of a prepolymer or polymer for coating surfaces, especially functionalised polymer surfaces.
JP 62/068 820 and JP 63/139 106 (Kao Corporation) describe a polymer consisting of a polysiloxane that carries at least one primary amino group via which the polysiloxane has been modified by a sugar radical. Such modified polysiloxanes are recommended as additives for haircare products.
WO 83/01617 (Minnesota Mining) describes inter alia a macromer that is a methacryl-amidoacyl or acrylamidoacyl derivative of a polysiloxane. According to that publication, such siloxane derivatives can be used as coatings or films.
EP 362 145 (Ciba-Geigy) describes a contact lens that is produced by reacting a polydialkylsiloxane prepolymer containing terminal isocyanate with a polydialkylsiloxane di- or poly-alkanol.
R. Stadler et al. (Macromolecules 28, 17-24 (1995)) describe polysiloxanes having pendant gluconamide or maltoheptaoneamide groups, the synthesis of which starts, for example, from the corresponding peracylated N-allylaldoneamides which are added to a Si—H group of a corresponding polysiloxane by hydrosilylation using a rhodium or platinum catalyst.
JP 52/29084 (Toray Industries) describes a polyurethane resin that is used as an electro-photographic recording layer. The polyurethane in that specification is made up of a poly-siloxane containing, terminally or pendently, at least two hydroxy groups, a polyisocyanate, especially a diisocyanate, and a polyol, such as ethylene glycol or propylene glycol, as a chain extending agent.
Contact lens materials having a high siloxane content are known and are valued because, as a rule, those materials have the high oxygen permeability required of a contact lens material. However, they often bring with them the following disadvantageous properties: loss of comfort for the contact lens wearer owing to mechanical rigidity, reduction in oxygen permeability when the material used has a relatively high water content, and a refractive index that is too low for good optical properties. Contact lens materials having relatively low refractive indices are thicker than those having relatively high refractive indices and are therefore less comfortable to wear. In addition, the frightening suction-cup effect of a lens can occur, restricting the ability of the lens to move on the eye.
The problem mentioned is solved by the disclosure of polymers that are obtainable, for example, by the thermal polymerisation of a polysiloxane/polyol macromer with a polyisocyanate, such a macromer being made from an amino- or hydroxy-alkylated polysiloxane linked to at least one polyol component and, in some cases, via a bifunctional organic radical. A special property of polysiloxane/polyol macromers is that they undergo microphase separation and that crosslinking via urethane groups takes place exclusively in the polyol phase. The microphase separation, which is hydrophilic/hydrophobic, is in the range <200 nm, with the result that the materials have a high degree of optical clarity and photopermeability. Reversible physical interactions, such as hydrogen bridging, have an additional stabilising effect. The continuous siloxane phases existing in a composite phase produce a surprisingly high degree of oxygen permeability. The second microphase, consisting mainly of polyol, is capable of storing water, with the result that the material as a whole acquires a hydrophilic character but does not lose its optical clarity and high oxygen permeability. In addition, the stored water generally has a positive effect on the mechanical relaxation properties of the material.
The present invention relates to a polymer comprising a polymerisation product of at least one macromer that comprises at least one section of formula (I)
-a-Z-b- (I),
wherein
(a) is a polysiloxane segment containing at least one primary amino group or at least one hydroxy group,
(b) is a polyol segment containing at least 4 carbon atoms,
Z is a segment (c) or a group X
1
,
segment (c) being defined as X
2
—R—X
2
wherein R is a bivalent radical of an organic compound having up to 25 carbon atoms and each X
2
independently of the other is a bivalent radical having at least one carbonyl group, and X
1
having the same meaning as X
2
; with a polyisocyanate.
A polysiloxane segment (a) is derived from a compound of formula (II)
wherein n is an integer from 5 to 500; 99.8-25% of the radicals R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are each independently of the others alkyl and 0.2-75% of the radicals R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are each independently of the others partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, Alk-NH-Alk-NH
2
or Alk-(OCH
2
CH
2
)
m
—(O CH
2
)
p
—OR
7
, wherein R
7
is hydrogen or lower alkyl, Alk is alkylene, m and p are each independently of the other an integer from 0-10; and a molecule contains at least one primary amino group or at least one hydroxy group.
The alkyleneoxy groups —(OCH
2
CH
2
)
m
— and —(OCH
2
)
p
— in a ligand Alk-(OCH
2
CH
2
)
m—(OCH
2
)
p
—OR
7
are distributed either randomly or as blocks in a chain.
A polysiloxane segment (a) is linked a total of 1-50 times, preferably 2-30 times, and especially 4-10 times, via a group Z to a segment (b) or to a further segment (a), Z in an a-Z-a sequence always being a segment (c).
In a segment (a) the site of linkage to a group Z is an amino or hydroxy group reduced by a hydrogen atom.
In a preferred definition, a polysiloxane segment is derived from a compound of formula (II) wherein the radicals R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are a total of 1-50 times, preferably 2-30 times and especially 2-10 times, each independently of the others either terminal or pendant aminoalkyl or hydroxyalkyl and wherein the remaining variables are as defined hereinbefore.
In a preferred embodiment, a polysiloxane segment is derived from a compound of formula (II) wherein 95-29% of the radicals R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are each independently of the others alkyl and 5-71% of the radicals R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are each independently of the others partially fluorinated alkyl, aminoalkyl, alkenyl, aryl, cyanoalkyl, Alk-NH-Alk-NH
2
or Alk-(OCH
2
CH
2
)
m
—(OCH
2
)
p
—OR
7
, and wherein the other variables are as defined hereinbefore.
In another preferred embodiment, a polysiloxane segment is derived from a compound of formula (II) wherein 95-29% of the radicals R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are each independently of the others lower alkyl and 5-71% of the radicals R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are each independently of the others partially fluorinated alkyl, aminoalkyl or hydroxyalkyl.
In a preferred definition, n is an integer from 5 to 400, preferably from 10 to 250 and especially from 12 to 125.
In a preferred definition, the two terminal radicals R
1
and R
6
are aminoalkyl or hydroxyalkyl, the other variables being as defined hereinbefore.
In a further preferred definition, the radicals R
4
and R
5
are 1-50 times, preferably 2-30 times and especially 4-10 times, pendant aminoalkyl or hydroxyalkyl, the other variables being as defined hereinbefore.
In a further preferred definition, the radicals R
1
, R
2
, R
3
, R
4
, R
5
and R
6
are a total of 1-50 times, preferably 2-30 times and especially 2-10 times, each independently of the others either terminal or pendant aminoalkyl or hydroxyalkyl, the other variables being as defined hereinbefore.
In a further preferred definition, the radicals R
1
and R
6
are a total of 1-2 times and especially 1.5 times, terminal aminoalkyl or hydroxyalkyl, the other variables being as de
Domschke Angelika
Hopken Jens
Lohmann Dieter
Gorman Jr. Robert J.
Meece R. Scott
Moore Margaret G.
Novartis AG
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