Polypyrrole-graphene/polyurethane antifouling coating as well as preparation method and application thereof

Patent metadata

Field	Value
Publication number	US-12227671-B2
Application number	US-202217951125-A
Country	US
Kind code	B2
Filing date	Sep 23, 2022
Priority date	Oct 26, 2021
Publication date	Feb 18, 2025
Grant date	Feb 18, 2025

Abstract

A polypyrrole-graphene/polyurethane antifouling coating as well as a preparation method and an application thereof are provided. The polypyrrole-graphene/polyurethane antifouling coating includes component A and component B, wherein the component A mainly includes the following raw materials in parts by weight: 500 parts of group-hydrolyzable polyurethane prepolymer, 25-50 parts of bentonite, 25-50 parts of titanium dioxide, 60-120 parts of zinc oxide, 15-30 parts of talcum powder, and 15-30 parts of polypyrrole-graphene nanofiller; and the component B mainly includes the following raw materials in parts by weight: 5-7 parts of leveling agent, 5-7 parts of defoamer, 6-15 parts of chain extender, 10-25 parts of silane coupling agent, and 1-2 parts of catalyst. The two-component polyurethane coating of the present invention has relatively good adhesion, collision resistance and cracking resistance, and the antifouling property and the antifouling durability can be improved.

First claim

What is claimed is:

1. A polypyrrole-graphene/polyurethane antifouling coating, comprising a first component and a second component, wherein the first component comprises the following raw materials in parts by weight:
500 parts of a group-hydrolyzable polyurethane prepolymer, 25 parts-50 parts of bentonite, 25 parts-50 parts of titanium dioxide, 60 parts-120 parts of zinc oxide, 15 parts-30 parts of a talcum powder, and 15 parts-30 parts of a polypyrrole-graphene nanofiller, wherein the group-hydrolyzable polyurethane prepolymer is grafted with pyridine-triphenylborane; and
the second component comprises the following raw materials in parts by weight:
5 parts-7 parts of a leveling agent, 5 parts-7 parts of a defoamer, 6 parts-15 parts of a chain extender, 10 parts-25 parts of a silane coupling agent, and 1 part-2 parts of a catalyst.

2. The polypyrrole-graphene/polyurethane antifouling coating of claim 1 , wherein the group-hydrolyzable polyurethane prepolymer is prepared by the following method:
adding xylene and tetrahydrofuran to a four-necked flask with a mechanical stirring device, a thermometer, a constant-pressure dropping funnel, and a condenser pipe, and adding a carboxyl-containing diol to obtain a system,
heating the system to 50° C.-60° C. and dripping isophorone diisocyanate (IPDI) into the system to obtain a first mixed system, mixing the first mixed system and heating the first mixed system to a temperature of 80° C.-85° C., and maintaining the temperature for 0.5 h-1 h after the first mixed system reaches to a clarified status;
cooling the first mixed system to 50° C.-60° C., adding dehydrated polyether polyol to the first mixed system to obtain a second mixed system, mixing the second mixed system and heating the second mixed system to 80-85° C., and keeping a first reaction for 1.5 h-2.5 h; when a viscosity of the second mixed system increases and a —NCO content decreases to 0.5%, cooling the second mixed system to 50° C.-60° C., dripping the IPDI to the second mixed system to obtain a third mixed system, mixing the third mixed system and heating the third mixed system to 80° C.-85° C., and keeping a second reaction for 2 h-3 h;
adding the pyridine-triphenylborane (PTPB) in first batches to the third mixed system to obtain a fourth mixed system, keeping a reaction temperature at 70° C.-85° C., adding a second batch of the PTPB after a third reaction is completed and the fourth mixed system becomes clear from turbid, and keeping a fourth reaction for 1 h-2.5 h;
dripping polyisocyanate after final feeding is completed, and keeping the temperature at 80° C.-85° C. for 2 h-3 h until a fifth reaction is completed.

3. The polypyrrole-graphene/polyurethane antifouling coating of claim 1 , wherein the polypyrrole-graphene nanofiller is prepared by the following method:
dispersing ammonium persulfate and cetyl trimethyl ammonium bromide in a hydrochloric acid solution at a molar ratio of (2.5-4):1 to obtain a first resulting solution,
ultrasonically dispersing a graphene in the first resulting solution to obtain a second resulting solution,
dripping a pyrrole monomer under stirring to the second resulting solution to obtain a third resulting solution, wherein a mass ratio of the graphene to the pyrrole monomer is 1/50-1/200, and the third resulting solution changes from milky white to black blue and eventually to black; upon completion, filtrating the third resulting solution, washing filter cakes with distilled water and ethanol, and performing a vacuum drying to obtain the polypyrrole-graphene nanofiller.

4. The polypyrrole-graphene/polyurethane antifouling coating of claim 1 , wherein in use, the first component and the second component are mixed at a mass ratio of (30-45):1, heated and cured.

5. The polypyrrole-graphene/polyurethane antifouling coating of claim 1 , wherein the silane coupling agent is at least one of γ-aminopropyl triethoxysilane, γ-aminopropyl trimethoxy silane, bis-(γ-trimethoxysilylpropyl)amine, N-phenyl-γ-aminopropyl trimethoxy silane, N-phenyl-γ-aminopropyl triethoxysilane, N-butyl-γ-aminopropyl trimethoxy silane, and N-butyl-γ-aminopropyl triethoxysilane.

6. The polypyrrole-graphene/polyurethane antifouling coating of claim 1 , wherein the chain extender is a liquid amine chain extender.

7. The polypyrrole-graphene/polyurethane antifouling coating of claim 1 , wherein the catalyst is at least one of dibutyltin dilaurate and dibutyltin diacetate.

8. A method for preparing polypyrrole-graphene/polyurethane antifouling coating, wherein the polypyrrole-graphene/polyurethane antifouling coating, comprise a first component and a second component, wherein the first component comprises the following raw materials in parts by weight:
500 parts of a group-hydrolyzable polyurethane prepolymer, 25 parts-50 parts of bentonite, 25 parts-50 parts of titanium dioxide, 60 parts-120 parts of zinc oxide, 15 parts-30 parts of a talcum powder, and 15 parts-30 parts of a polypyrrole-graphene nanofiller, wherein the group-hydrolyzable polyurethane prepolymer is grafted with pyridine-triphenylborane; and
the second component comprises the following raw materials in parts by weight:
5 parts-7 parts of a leveling agent, 5 parts-7 parts of a defoamer, 6 parts-15 parts of a chain extender, 10 parts-25 parts of a silane coupling agent, and 1 part-2 parts of a catalyst, the method comprising the following steps:
S1, adding the raw materials of the first component to a high-speed dispersion machine, and performing a first high-speed dispersion for 15 min-45 min to prepare the first component; and
S2, adding the raw materials of the second component to the high-speed dispersion machine, and performing a second high-speed dispersion for 15 min-30 min to prepare the second component.

9. The method for preparing the polypyrrole-graphene/polyurethane antifouling coating of claim 8 , wherein the group-hydrolyzable polyurethane prepolymer is prepared by the following method:
adding xylene and tetrahydrofuran to a four-necked flask with a mechanical stirring device, a thermometer, a constant-pressure dropping funnel, and a condenser pipe, and adding a carboxyl-containing diol to obtain a system,
heating the system to 50° C.-60° C. and dripping isophorone diisocyanate (IPDI) into the system to obtain a first mixed system, mixing the first mixed system and heating the first mixed system to a temperature of 80° C.-85° C., and maintaining the temperature for 0.5 h-1 h after the first mixed system reaches to a clarified status;
cooling the first mixed system to 50° C.-60° C., adding dehydrated polyether polyol to the first mixed system to obtain a second mixed system, mixing the second mixed system and heating the second mixed system to 80-85° C., and keeping a first reaction for 1.5 h-2.5 h; when a viscosity of the second mixed system increases and a —NCO content decreases to 0.5%, cooling the second mixed system to 50° C.-60° C., dripping the IPDI to the second mixed system to obtain a third mixed system, mixing the third mixed system and heating the third mixed system to 80° C.-85° C., and keeping a second reaction for 2 h-3 h;
adding the pyridine-triphenylborane (PTPB) in first batches to the third mixed system to obtain a fourth mixed system, keeping a reaction temperature at 70° C.-85° C., adding a second batch of the PTPB after a third reaction is completed and the fourth mixed system becomes clear from turbid, and keeping a fourth reaction for 1 h-2.5 h;
dripping polyisocyanate after final feeding is completed, and keeping the temperature at 80° C.-85° C. for 2 h-3 h until a fifth reaction is completed.

10. The method for preparing the polypyrrole-graphene/polyurethane antifouling coating of claim 8 , w

Assignees

• Univ Harbin Eng

Inventors

• Wang Jun
• Tang Jiawei
• Chen Rongrong
• Liu Qi
• Liu Jingyuan
• Yu Jing
• Zhu Jiahui
• Sun Gaohui
• Liu Peili

Classifications

• C09D175/04

  Polyurethanes · CPC title

• C09D5/1662

  Synthetic film-forming substance · CPC title

• C08K9/08

  Ingredients agglomerated by treatment with a binding agent · CPC title

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08K3/042

  Graphene or derivatives, e.g. graphene oxides · CPC title