Aminomethylene functional siloxanes
Organopolysiloxanes containing pendent silicon-bonded aminomethylene groups may be prepared by reaction of hydroxy-functional siloxanes or polysiloxanes with aminomethylalkoxysilanes. By adjusting the functionalities of the siloxane and silane, branched siloxanes with aminomethylene functionality may be obtained, as may also organopolysiloxanes of high amine number, reflecting numerous chain-pendent aminomethylene groups. The products are easily emulsifyable in water.
1 - 9 . (canceled)
10 . An amino-functional organosiloxane of formula I
(SiO 4/2 ) k (RSiO 3/2 ) m (R 2 SiO 2/2 ) p (R 3 SiO 1/2 ) q (O 1/2 H) t [(O f/2 R 1 3-f SiCR 2 2 ) 3-g NR g 4 ] s (I)
in which
R each, independently, is hydrogen or a monovalent Si—C-bonded C 1 -C 20 -hydrocarbon radical or C 1 -C 15 -hydrocarbonoxy radical, each of which is optionally substituted by —CN, —NCO, —NR x 2 , —COOH, —COOR x , -halogen, -acryloyl, -epoxy, —SH, —OH or —CONR x 2 , and in each of which one or more non-adjacent methylene units may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —S—, or —NR x — groups, and in each of which one or more non-adjacent methine units may be replaced by —N═, —N═N— or —P═ groups,
R 1 each, independently is hydrogen or a monovalent Si—C-bonded C 1 -C 20 -hydrocarbon radical or C 1 -C 15 -hydrocarbonoxy radical which is optionally substituted by —CN, —NCO, —COOH, —COOR x , -halogen, -acryloyl, —SH, —OH or —CONR x 2 , and in each of which one or more non-adjacent methylene units may be replaced by —O—, —CO—, —COO—, —OCO—, —OCOO—, —S—, or —NR x — groups, and in each of which one or more non-adjacent methine units may be replaced by —N═, —N═N— or —P═ groups,
R x each, independently, is hydrogen or a C 1 -C 10 -hydrocarbon radical optionally substituted by —CN or halogen,
R 2 each, independently, is hydrogen or a C 1 -C 20 -hydrocarbon radical optionally substituted by —CN or halogen,
R 4 each, independently, is hydrogen or a C 1 -C 20 -hydrocarbon radical optionally substituted by —CN or halogen,
k, m, p, q are each, independently, an integer from 0 to 100,000,
f is an integer of 1, 2 or 3,
g is an integer of 0, 1 or 2,
s is an integer of at least 1 and
t is 0 or a positive integer, where the sum of
k+m+p+q is at least 1, and the amino-functional organosiloxane contains at least one pendent aminomethylene group.
11 . The amino-functional organosiloxane of claim 10 , wherein R is a C 1 -C 10 -alkyl radical or phenyl radical.
12 . The amino-functional organosiloxane of claim 10 , wherein R 1 is a C 1 -C 6 -alkyl radical.
13 . The amino-functional organosiloxane of claim 11 , wherein R 1 is a C 1 -C 6 -alkyl radical.
14 . The amino-functional organosiloxane of claim 10 , wherein R 2 is a C 1 -C 3 -alkyl radical or hydrogen.
15 . The amino-functional organosiloxane of claim 11 , wherein R 2 is a C 1 -C 3 -alkyl radical or hydrogen.
16 . The amino-functional organosiloxane of claim 12 , wherein R 2 is a C 1 -C 3 -alkyl radical or hydrogen.
17 . The amino-functional organosiloxane of claim 10 , wherein each R 4 independently is a C 1 -C 12 -alkyl or aryl radical or hydrogen.
18 . The amino-functional organosiloxane of claim 11 , wherein each R 4 independently is a C 1 -C 12 -alkyl or aryl radical or hydrogen.
19 . The amino-functional organosiloxane of claim 12 , wherein each R 4 independently is a C 1 -C 12 -alkyl or aryl radical or hydrogen.
20 . The amino-functional organosiloxane of claim 14 , wherein each R 4 independently is a C 1 -C 12 -alkyl or aryl radical or hydrogen.
21 . The amino-functional organosiloxane of claim 10 , wherein p has a value of from 3 to 1000.
22 . The amino-functional organosiloxane of claim 10 , wherein the sum k+m is 0.
23 . The amino-functional organosiloxane of claim 10 , wherein the sum k+m+p+q is at least 2.
24 . A process for preparing an amino-functional organosiloxane of formula I of claim 10 , comprising reacting siloxanes of formula (II)
(SiO 4/2 ) k (RSiO 3/2 ) m (R 2 SiO 2/2 ) p (R 3 SiO 1/2 ) q (O 1/2 H) r (II),
with amino-functional silanes of formula (III)
[(R 3 O) f R 1 3-f SiCR 2 2 ] 3-g NR g 4 (III),
where
R 3 is hydrogen or a C 1 -C 20 -hydrocarbon radical which is optionally substituted by —CN or halogen,
r is an integer of at least 1 and
t is less than r.
25 . The process of claim 24 wherein at least one siloxane of the formula II is an α,ω-bis(hydroxy)-terminated disiloxane or polysiloxane, and at least one aminosilane of formula (III) is an optionaly N-substituted aminomethyl dialkoxy or trialkoxy silane.