US 12,168,217 B2
Polyorganic functional groups modified silica, processes to make and use thereof
John Robert Wilson, Essex (GB)
Assigned to SI-NOVATION LTD, Hubei (CN)
Appl. No. 15/755,562
Filed by SI-NOVATION LTD, Hubei (CN)
PCT Filed Aug. 1, 2016, PCT No. PCT/CN2016/092663
§ 371(c)(1), (2) Date Feb. 27, 2018,
PCT Pub. No. WO2017/036268, PCT Pub. Date Mar. 9, 2017.
Claims priority of application No. 1515414 (GB), filed on Aug. 29, 2015.
Prior Publication US 2019/0176124 A1, Jun. 13, 2019
Int. Cl. B01J 20/26 (2006.01); B01D 53/02 (2006.01); B01J 20/32 (2006.01); B01J 31/06 (2006.01); B01J 37/02 (2006.01); B01J 47/00 (2017.01); C02F 1/28 (2023.01); C02F 1/42 (2023.01); C02F 1/72 (2023.01); C02F 101/20 (2006.01); C02F 101/30 (2006.01); C07F 7/18 (2006.01); C08G 77/28 (2006.01); C08K 3/36 (2006.01); C08K 9/06 (2006.01)
CPC B01J 20/265 (2013.01) [B01D 53/02 (2013.01); B01J 20/3204 (2013.01); B01J 20/3219 (2013.01); B01J 20/3231 (2013.01); B01J 31/069 (2013.01); B01J 37/0219 (2013.01); B01J 47/00 (2013.01); C02F 1/285 (2013.01); C02F 1/42 (2013.01); C02F 1/725 (2013.01); C07F 7/1804 (2013.01); C08G 77/28 (2013.01); B01D 2253/202 (2013.01); B01D 2253/25 (2013.01); B01J 2231/005 (2013.01); B01J 2531/004 (2013.01); C02F 2101/20 (2013.01); C02F 2101/30 (2013.01); C08K 3/36 (2013.01); C08K 9/06 (2013.01)] 6 Claims
 
1. Compositions of General Formula I:
[Y]y[A]a[B1]1b[B2]2b[C1]1c[C2]2c[C3]3c[C4]4c[D1]1d[D2]2d[D3]3d[D4]4d[D5]5d[D6]6d[E]e[F]f[G]g[H]h[J]j[K]k[M]m[P]p[U]u[V]v[W]w[X]x  General Formula I
wherein:
Y is Si(O4/2);
W is RZR1Si(Oq/2);
X is (O3/2)SiC3H6SH;
A is [(O3/2)Si(CH2)2SCH2CH2S—CH2CH2CH2SR]a1 [(O3/2)Si(CH2)2SCH2CH2SCH2CH2CH2S(CH2)2Si(O3/2)]a2 [(O3/2)Si(CH2)2SCH2CH2—CH2SCH2CH2SR]a3;
B1 is [(O3/2)Si(CH2)3SCH2CH2CH2SH]b1 [(O3/2)Si(CH2)3SCH2CH2CH2SCH2CH2—SH]b2 [(O3/2)Si(CH2)3SCH2CH2CH2SCH2CH2SCH2CH2CH2S(CH2)3Si(O3/2)]b3;
B2 is [(O3/2)Si(CH2)3—SCH2CH2CH2SH]b1 [(O3/2)Si(CH2)3SCH2CH2CH2SCH2CH2CH2SH]b2 [(O3/2)Si(CH2)3SCH2CH2CH2S—CH2CH2CH2SCH2CH2CH2S(CH2)3Si(O3/2)]b3;
C1 is [(O3/2)Si(CH2)2SCH2CH2SCH2CH2SCH2CH2SH]c1 [(O3/2)Si(CH2)2SCH2CH2SCH2CH2SCH2CH2S(CH2)2Si(O3/2)]c2;
C2 is [(O3/2)Si(CH2)2SCH2CH2CH2S—CH2CH2SCH2CH2CH2SH]c1 [(O3/2)Si(CH2)2SCH2CH2CH2SCH2CH2SCH2CH2CH2S(CH2)2Si(O3/2)]c2;
C3 is [(O3/2)Si(CH2)3SCH2CH2CH2SCH2CH2SCH2CH2CH2SR]c1 [(O3/2)Si(CH2)3SCH2CH2CH2SCH2CH2S—CH2CH2CH2S(CH2)3Si(O3/2)]c2;
C4 is [(O3/2)Si(CH2)3SCH2CH2CH2SCH2CH2CH2SCH2CH2CH2SR]c1 [(O3/2)Si(CH2)3SCH2CH2CH2SCH2CH2CH2SCH2CH2CH2S(CH2)3Si(O3/2)]c2;
D1 is [(O3/2)Si(CH2)2S—CH2CH2SCH2CH2CH2SH]d1 [(O3/2)Si(CH2)2SCH2CH2S(CH2)2Si(O3/2)]d2;
D2 is [(O3/2)Si(CH2)2SCH2—CH2CH2SCH2CH2CH2SH]d1 [(O3/2)Si(CH2)2SCH2CH2CH2S(CH2)2Si(O3/2)]d2;
D3 is [(O3/2)Si(CH2)2S—CH2CH2SCH2CH2CH2SCH2CH2SH]d1 [(O3/2)Si(CH2)2SCH2CH2S(CH2)2Si(O3/2)]d2;
D4 is [(O3/2)Si(CH2)2SCH2CH2SCH2CH2CH2SCH2CH2CH2SH]d1 [(O3/2)Si(CH2)2SCH2CH2S(CH2)2Si(O3/2)]d2;
D5 is [(O3/2)Si(CH2)2SCH2CH2CH2SCH2CH2CH2SCH2CH2SH]d1 [(O3/2)Si(CH2)2SCH2CH2CH2S(CH2)2—Si(O3/2)]d2;
D6 is [(O3/2)Si(CH2)2SCH2CH2CH2SCH2CH2CH2SCH2CH2CH2SH]d1 [(O3/2)Si(CH2)2S—CH2CH2CH2S(CH2)2Si(O3/2)]d2;
E is [(O3/2)Si(CH2)3SCH2CH2CH2NR3R4];
F is [(O3/2)Si(CH2)nSCH2—CH2CH2SR]f1[(O3/2)Si(CH2)nSCH2CH2CH2S(CH2)nSi(O3/2)]f2;
G is [(O3/2)Si(CH2)nSCH2CH2SR]g1 [(O3/2)Si(CH2)nSCH2CH2S(CH2)nSi(O3/2)]g2;
H is [(O3/2)Si(CH2)nSCH2CH2S(CH2)3NZR];
J is [(O3/2)Si(CH2)nSCH2CH2CH2S(CH2)3NZR];
K is [(O3/2)Si(CH2)nSCH2CH2S((CH2)3NZ(CH2)3SCH2CH2S)xR]k1 [(O3/2)Si(CH2)nSCH2CH2S((CH2)3NZ(CH2)3SCH2CH2S)v(CH2)nSi(O3/2)]k2 [(O3/2)Si(CH2)nSCH2CH2S—((CH2)3NZ(CH2)3SCH2CH2S)i(CH2)3NZR]k3;
M is [(O3/2)Si(CH2)nSCH2CH2CH2S((CH2)3NZ(CH2)3S—CH2CH2CH2S)xR]m1[(O3/2)Si(CH2)nSCH2CH2CH2S ((CH2)3NZ(CH2)3SCH2CH2CH2S)v(CH2)nSi(O3/2)]m2 [(O3/2)Si(CH2)nSCH2CH2CH2S((CH2)3NZ(CH2)3SCH2CH2CH2S)i(CH2)3NZR]m3;
P is [(O3/2)Si(CH2)nS—CH2CH2CH2S((CH2)2T(CH2)2SCH2CH2CH2S)xR]p1 [(O3/2)Si(CH2)nSCH2CH2CH2S((CH2)2T(CH2)2S—CH2CH2CH2S)v(CH2)nSi(O3/2)]p2 [(O3/2)Si(CH2)nSCH2CH2CH2S((CH2)2T(CH2)2SCH2CH2CH2S)i(CH2)2-TR]p3;
U is [(O3/2)Si(CH2)3S(CH2)3NHC(═S)NH2;
V is [O3/2Si(CH2)nS[(CH2)n1S]n2R9
wherein:
in the above Z is CONHR5;
RZ is C1-22-aryl group;
T is an optionally substituted C2-22-cycloalkyl group, C2-22-aryl group, C2-22-heteroaryl group and a C2-22-alkylaryl group;
R is selected from a hydrogen, C1-22-alkyl group, C2-22-alkenyl group, C1-22-aryl group, C1-22-alkylaryl group and an acyl group CO R2;
R1 is alkyl polyalkyl amine group;
R2 is independently selected from a hydrogen, C1-22-alkyl group, C2-22-alkenyl group and a C1-22-aryl group;
R5 is hydrogen;
R3 and R4 are either independently selected from a hydrogen, C1-22-alkyl group, C1-22-aryl group, C1-22-heteroaryl group, C1-22-alkylaryl group, alkyl amine group, alkyl polyalkyl amine group, a trialkyl ammonium group or both part of a C3-12-cyclic alkyl or hetero alkyl or aromatic group;
R9 is a mixture of (CH2)3N+(L1)(CH3)2CH2CH2CH3, (CH2)3N+(L1)(CH3)2CH2CHCH2 and a compound of General Formula III;
n3 is an integer between 1 and 100;
L1 is an anion including but not limited to a halide, nitrate, sulfate, carbonate, phosphate, chromate, permanganate, borohydride, cyanoborohydride;

OG Complex Work Unit Chemistry
wherein:
n and n1 are integers independently either 2 or 3;
n2 is an integer between 0 and 100;
i, x and v are independent integers from 1 to 100;
q is an integer from 1 to 3,
z is an integer from 0 to 2
such that q+z=3;
a, a1, a2, a3, 1b, 1b1, 1b2, 1b3, 2b, 2b1, 2b2, 2b3, 1c, 1c1, 1c2, 2c, 2c1, 2c2, 3c, 3c1, 3c2, 4c, 4c1, 4c2, 1d, 1d1, 1d2, 2d, 2d1, 2d2, 3d, 3d1, 3d2, 4d, 4d1, 4d2, 5d, 5d1, 5d2, 6d, 6d1, 6d2, e, f, f1, f2, g, g1, g2, h, j, k, k1, k2, k3, m, m1, m2, m3, p, p1, p2, p3, u, u1, u2, u3, v, x, w and y are integers
such that the ratio of:
y:a+(1 to 2)b+(1 to 4)c+(1 to 6)d+e+f+g+h+j+k+m+v+w+x is from 0.01 to 10,000;
y:a+(1 and 2)b+(1 to 4)c+(1 to 6)d+e+f+g+v+w+x is from 0.01 to 10,000;
y:f+g+h+j+k+m+v+w+x is from 0.01 to 10,000;
y:e+f+g+w+x is from 0.01 to 10,000;
y:f+g+h+j+p+u+v+w+x is from 0.01 to 10,000; and
respectively each of the following ratios a1:a3; a1:a2+a3; 1b2:1b1+1b3; 2b2:2b1+2b3; 1c1:1c2; 2c1:2c2; 3c1:3c2; 4c1:4c2; 1d1:1d2; 2d1:2d2; 3d1:3d2; 4d1:4d2; 5d1:5d2; 6d1:6d2; f1:f2; g1:g2; k1:k3; k1:k2+k3; m1:m3; m1:m2+m3; p1:p3; p1:p2+p3 vary independently between 0.01 to 100; and
wherein:
in General Formula I, component Y and at least one of the following components K, M and P are present, and the composition optionally comprises at least one of the following components A, B1-2, C1-4, D1-6, E, F, G, H, J, U, W and X.