US 12,017,959 B2
Amphipathic multifunctional hybrid nanoparticle, and preparation method therefor and application thereof
Xin Shu, Nanjing (CN); Qianping Ran, Nanjing (CN); Yong Yang, Nanjing (CN); Xiumei Wang, Nanjing (CN); Jinzhi Liu, Nanjing (CN); Jiangang Zhang, Nanjing (CN); and Hongxia Zhao, Nanjing (CN)
Assigned to SOBUTE NEW MATERIALS CO., LTD., Nanjing (CN); NANJING BOTE NEW MATERIALS CO., LTD., Nanjing (CN); and BOTE NEW MATERIALS TAIZHOU JIANGYAN CO., LTD., Taizhou (CN)
Appl. No. 17/044,292
Filed by SOBUTE NEW MATERIALS CO., LTD., Nanjing (CN); NANJING BOTE NEW MATERIALS CO., LTD., Nanjing (CN); and BOTE NEW MATERIALS TAIZHOU JIANGYAN CO., LTD., Taizhou (CN)
PCT Filed Mar. 8, 2019, PCT No. PCT/CN2019/077457
§ 371(c)(1), (2) Date Sep. 30, 2020,
PCT Pub. No. WO2019/144973, PCT Pub. Date Aug. 1, 2019.
Claims priority of application No. 201810529704.6 (CN), filed on May 29, 2018.
Prior Publication US 2021/0155542 A1, May 27, 2021
Int. Cl. C04B 28/04 (2006.01); C04B 14/06 (2006.01); C04B 20/10 (2006.01); C04B 28/02 (2006.01); C04B 40/00 (2006.01); C08F 292/00 (2006.01); C08K 9/04 (2006.01); C08K 9/06 (2006.01); C08K 9/08 (2006.01); C09C 1/30 (2006.01); C09C 3/12 (2006.01)
CPC C04B 28/04 (2013.01) [C04B 14/06 (2013.01); C04B 20/1051 (2013.01); C04B 28/02 (2013.01); C04B 40/0028 (2013.01); C09C 1/3081 (2013.01); C01P 2004/61 (2013.01); C08F 292/00 (2013.01); C08K 9/04 (2013.01); C08K 9/06 (2013.01); C08K 9/08 (2013.01); C09C 1/30 (2013.01); C09C 3/12 (2013.01)] 5 Claims
OG exemplary drawing
 
1. An amphiphilic multifunctional hybrid nanoparticle having a detachable hydrophilic organic polymer with both a water-soluble chain and a hydrophobic hydrocarbon functional group attached to its surface, wherein a core of the nanoparticle is a silica or an organofunctional group substituted silicon dioxide or an organofunctional group substituted silicon-oxygen bond network, and the nanoparticle contains a free organosiloxane with hydrophobic hydrocarbon functional groups and a fatty acid or fatty acid ester or fatty acid aluminum complex with hydrophobic hydrocarbon functional groups;
the nanoparticle has an average diameter of not more than 1000 nm,
wherein the nanoparticle is prepared through a polymerization-hydrolysis reaction using polymerizable monomer A, polymerizable siloxane B, siloxane C with hydrophobic hydrocarbon functional groups that does not undergo free radical polymerization, siloxane D, and organic component A, B, C, D, and E are effective reactants; one end of the polymerizable monomer A has a double bond that can participate in free radical polymerization reactions, and the other end has a water-soluble chain; the organic component E consists of one or more arbitrary mixtures of saturated or unsaturated fatty acids or fatty acid esters F, and aluminum complexes G of saturated or unsaturated fatty acids with fatty bases;
polymerizable monomer A is one of or any combination of more than one of structures represented by the following formula (1) and formula (2),

OG Complex Work Unit Chemistry
where R1, R2, R3 and R4 each independently represent H or CH3, X represents —OCH2CH2—, —OCH2CH2CH2CH2—, or saturated alkyl with 1 to 4 carbon atoms, and Y represents —NH— or —O—; a and b represent the average molar adduct numbers of ethoxy and isopropoxy in the side chain, respectively, the value of (a+b) ranges from 8 to 114 (8 and 114 are included), and the value of a/(a+b) is not more than ⅓;
the polymerizable siloxane B is any one of or a mixture of more than one of methacryloxypropyltrimethoxysilane (MAPTMS), methacryloxypropyltriethoxysilane (MAPTES), methacryloxymethyltriethoxysilane (AAPTES), acryloyloxymethyltrimethoxysilane (AAMTMS), and acryloxypropyltrimethoxysilane (AAPTMS);
the non-radical polymerizable siloxane C having hydrophobic hydrocarbon functional groups is one of or any combination of more than one of siloxanes having a structure of the following formula (3),

OG Complex Work Unit Chemistry
where R5 represents a hydrocarbon functional group with 4 to 22 carbon atoms, R6, R7 and R8 each independently represent saturated alkyl with 1 to 4 carbon atoms, and R5, as a source of hydrophobicity of the particle;
the siloxane or organofunctional group substituted siloxane D is one of or any combination of more than one of siloxanes having a structure of the following general formula (4),

OG Complex Work Unit Chemistry
where R9 and R10 each independently represent saturated alkyl with 1 to 6 carbon atoms or saturated alkoxy with 1 to 4 carbon atoms, and Ru and Rig each independently represent saturated alkyl with 1 to 4 carbon atoms;
the saturated or unsaturated fatty acid or fatty acid ester F is one or more than any one of saturated or unsaturated fatty acid or fatty acid esters having a structure of the following formula (5),

OG Complex Work Unit Chemistry
where the functional group R13 represents a hydrocarbon functional group with 5 to 21 carbon atoms, and R14 represents H or saturated alkyl with 1 to 22 carbon atoms;
the aluminum complex G of the saturated or unsaturated aliphatic fatty acid is one of or any combination of more than one of aluminum complexes of formula Al(R15COO)3 or Al(OH)(R16COO)2, where R15 and R16 each independently represent a saturated or unsaturated hydrocarbon functional group with 8 to 18 carbon atoms;
the polymerizable monomer A accounts for 5-20% of the total mass of the effective reactants; the total mass of B and D accounts for 20-75% of the total mass of the effective reactants (A+B+C+D+E), and the mass of B accounts for 5-10% of the total mass of B and D; the total mass of C and E accounts for 20-75% of the total mass of the effective reactants (A+B+C+D+E), and the mass of C accounts for 20-80% of the total mass of C and E (C+E); the ratio of F to G in the organic component E is arbitrary.