Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From silicon reactant having at least one...
Reexamination Certificate
2002-07-25
2004-05-04
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...
C528S038000, C556S408000, C556S425000
Reexamination Certificate
active
06730766
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to organopolysiloxane polymers bearing quaternary ammonium groups (“quaternized polysiloxanes”) and to processes for the preparation of these compounds.
2. Background Art
Quaternized polysiloxanes have been known for a long time from the literature. In this connection, various methods are described for their preparation. DE-A-1493384 can be given by way of example for the preparation of lateral quaternary siloxanes. Lateral epoxy group-containing siloxanes are reacted with secondary amines such as dimethylamine and alkylated in a further step with corresponding alkylating agents, such as methyl chloride. &agr;,&ohgr;-quaternary polysiloxanes have likewise been described widely, such as, for example, in EP-A-17121, in which &agr;,&ohgr;-quaternary polysiloxanes are prepared by reacting corresponding epoxy-functionalized polysiloxanes with tertiary amines in the presence of an acid. In addition, EP-A-606159 discloses the preparation of &agr;,&ohgr;-quaternary polysiloxanes by two different procedures, first by the reaction of &agr;,&ohgr;-chloroalkyl group-containing polysiloxanes with tertiary amines, and second by the reaction of allyl-containing tertiary amines with Si-H-containing siloxanes and subsequent quaternization of the tertiary nitrogen.
In the field of polyquaternary polysiloxanes which contain the quaternized nitrogen in the siloxane backbone, reference should be made, for example, to U.S. Pat. No. 4,533,714 and the corresponding DE-A 33 40 708, which describe polyquaternary polysiloxanes having two quaternary ammonium groups per repeating unit, where the nitrogen atoms are bonded to silicon atoms exclusively via —(CH
2
)
1-6
bridges. In addition, EP-A-282720 discloses polysiloxane polymers having, in each case, two quaternary ammonium groups per unit, bonded via a hydroxyl group-containing hydrocarbon bridge which may also contain oxygen atoms or nitrogen atoms. For the purposes of the present invention, the term “organopolysiloxanes” is intended to include polymers, oligomers and also dimeric siloxanes.
SUMMARY OF THE INVENTION
The present invention pertains to processes for the manufacture of quaternized polysiloxanes by reaction of epoxy-functional polysiloxane III
Y—(SiR
2
—O)
b
—SiR
2
—Y (III)
as defined hereafter, with an amine salt or an amine, followed by quaternization. Process varients can be used to control the relative numbers of epoxy and quaternized amino groups as well as the viscosity of the resulting product.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
The invention provides organopolysiloxanes having quaternary ammonium groups and containing units of the general formula
—[R
2
—(SiR
2
—O)
b
—SiR
2
—R
2
—N
+
R
1
2
]
n
—·nX
−
(I′)
where
R is identical or different and is a monovalent, SiC-bonded, optionally substituted hydrocarbon radical having 1 to 12 carbon atoms,
R
1
is identical or different and is a monovalent, optionally substituted hydrocarbon radical having 1 to 12 carbon atoms, or is a constituent of a bridging alkylene radical,
X
−
is an organic or inorganic anion,
R
2
is a divalent hydrocarbon radical having at least 4 carbon atoms which contains at least one hydroxyl group and is optionally interrupted by one or more oxygens,
b is an integer from 1 to 200 and
n is an integer from 1 to 50.
The organopolysiloxanes having quaternary ammonium groups according to the invention may be cyclic, linear or branched compounds which, apart from the units of the formula (I′), may have in the chain any other units, such as, for example, R
3
SiO
1/2
, RSiO
3/2
or SiO
4/2
units, where R has the meaning given above, in the chain.
The organopolysiloxanes having quaternary ammonium groups according to the invention are preferably those of the general formula
D
1
a
—[R
2
—(SiR
2
—O)
b
—SiR
2
—R
2
—N
+
R
1
2
]
n
—D
2
a
·nX
−
(I)
where
R is identical or different and is a monovalent, SiC-bonded, optionally substituted hydrocarbon radical having 1 to 12 carbon atoms,
R
1
is identical or different and is a monovalent, optionally substituted hydrocarbon radical having 1 to 12 carbon atoms or is a constituent of a bridging alkylene radical,
X
−
is an organic or inorganic anion,
R
2
is a divalent hydrocarbon radical having at least 4 carbon atoms which contains at least one hydroxyl group and is optionally interrupted by one or more oxygens,
a is 0 or 1,
b is an integer from 1 to 200,
n is an integer from 1 to 50,
D
1
is a hydrogen atom, hydroxyl radical, halide radical, NH
2
radical or a monovalent organic radical and
D
2
is a group of the formula
—R
2
—(SiR
2
O)
b
—SiR
2
—R
2
—D
1
(II)
where R, R
2
, D1 and b have the meanings given above.
Organopolysiloxanes having quaternary ammonium groups according to the invention of the general formula (I) may be cyclic compounds, i.e. where a is in each case 0, and also linear compounds where a is in each case 1. In preferred compounds, a has the value 1.
Examples of radicals R and R
1
are alkyl radicals such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and isooctyl radicals such as the 2,2,4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as the n-decyl radical, dodecyl radicals such as the n-dodecyl radical; alkenyl radicals such as the vinyl and the allyl radical; cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; aryl radicals such as the phenyl and the naphthyl radicals; alkaryl radicals such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; aralkyl radicals such as the benzyl radical, and the &agr;- and &bgr;-phenylethyl radicals;
If the radicals R and R
1
are substituted hydrocarbon radicals, preferred substituents are hydroxyl groups. The radical R is preferably a hydrocarbon radical having 1 to 6 carbon atoms, most preferably the methyl radical. The radical R
1
is preferably a hydrocarbon radical having 1 to 8 carbon atoms, most preferably an alkyl radical having 1 to 6 carbon atoms or a benzyl radical. The radical R
1
can, however, also be a divalent radical derived therefrom, so that, for example, two radicals R
1
may form a ring with the nitrogen atom.
Examples of anion X
−
are organic anions, such as carboxylate ions, enolate ions and sulfonate ions, and inorganic anions such as sulfate ions and halide ions, for example, chloride ions, bromide ions and iodide ions. The anion X
−
is preferably a carboxylate ion or a halide ion, more preferably a chloride ion or acetate ion.
Examples of radical R
2
are divalent linear, cyclic or branched, saturated or unsaturated hydrocarbon radicals having at least 4 carbon atoms, which contain at least one hydroxyl group and are optionally interrupted once or more than once by oxygen atoms, such as all alkylene radicals having at least 4 carbon atoms and at least one hydroxyl group, arylene radicals having at least one hydroxyl group,
—(CH
2
)
3
OCH
2
—CH(OH)—CH
2
— and —(CH
2
)
3
OCH
2
—CH
2
—CH(OH)—, where Me is the methyl radical.
The radical R
2
is preferably an alkylene radical having at least 4 carbon atoms and at least one hydroxyl group, most preferably —(CH
2
)
3
OCH
2
—CH(OH)—CH
2
— and —(CH
2
)
3
OCH
2
—CH
2
—CH(OH)—. In Formula I, b is preferably an integer from 1 to 100, and n is preferably an integer from 1 to 20, more preferably from 2 to 20.
Examples of radicals D
1
, where D
1
is an organic radical, are alkyl radicals, alkoxy radicals, nitrogen-containing organic radicals such as amines, sulfur-containing organic radicals such as sulfonate radicals, or organic or inorganic anions attached to carbon, for example carboxylates and halogenated hydrocarbon radicals. The radical D
1
is preferably a hydrogen ato
Messner Michael
Minigshofer Renate
Richter Evelyn
Schattenmann Wolfgang
Moore Margaret G.
Wacker-Chemie GmbH
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