A kind of vinyl-terminated amphiphilic fluorine-containing graft polymer composite photocurable coating and preparation method

A technology of grafting polymers and curing coatings, applied in epoxy resin coatings, coatings, etc., can solve the problems of low reaction temperature, poor solubility of fluoropolymers and solvents, limited modification effect, etc., to improve hydrophobicity. sexual effect

Active Publication Date: 2015-11-18
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although fluoropolymers have so many advantages, there are also limitations in practical application, which are mainly reflected in: 1) the solubility of fluoropolymers and solvents is very poor, and it is difficult to find suitable compatible solvents; 2) Fluoropolymers have poor compatibility with other polymers, and it is difficult to achieve the purpose of modifying other polymers by means of physical blending or compounding
3) Although fluorine-containing polymers can reach a temporary compatible state with other polymers in a suitable compatible solvent, as the solvent volatilizes or other polymers undergo cross-linking and curing, fluorine-containing polymers often Separates to the surface and is difficult to retain for a long time
4) In addition, fluoropolymers are expensive
However, these traditional living polymerization methods have disadvantages such as harsh polymerization conditions, low reaction temperature, and difficult removal of catalysts, making it difficult to realize industrial control and production.
In addition, although the introduction of hydrophilic groups can improve the compatibility of fluoropolymers with other polymers, it only improves the modification effect of physical blending or compounding. This modification effect is very limited. Far from realizing the chemical reaction between polymer molecules to achieve the best modification effect

Method used

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  • A kind of vinyl-terminated amphiphilic fluorine-containing graft polymer composite photocurable coating and preparation method
  • A kind of vinyl-terminated amphiphilic fluorine-containing graft polymer composite photocurable coating and preparation method
  • A kind of vinyl-terminated amphiphilic fluorine-containing graft polymer composite photocurable coating and preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043](1) Carboxyl-terminated hexafluorobutyl methacrylate polymer is prepared by the following method: 1 mass part of tert-butyl malonate, 100 mass parts of toluene and 5 mass parts of tetrabutylammonium hydroxide aqueous solution with a concentration of 25wt% Mix well, react at 50°C for 10 hours, remove toluene under reduced pressure, then add 60 parts by mass of tetrahydrofuran and 6 parts by mass of hexafluorobutyl methacrylate, react for 1 hour, remove tetrahydrofuran under reduced pressure, and place the obtained product in Hydrolyze in a mixed solution of 8 parts by mass of trifluoroacetic acid and 60 parts by mass of dioxane at 80°C for 10 hours to obtain a carboxyl-terminated hexafluorobutyl methacrylate polymer.

[0044] Through gel permeation chromatography (GPC) analysis, the number average molecular weight M of the polymer is measured n =3240.

[0045] (2) The amphiphilic fluorine-containing graft polymer terminated by hydroxyl groups is prepared by the following...

Embodiment 2

[0052] (1) Carboxy-terminated dodecafluoroheptyl acrylate polymer was prepared by mixing 1 mass part of tert-butyl malonate, 100 mass parts of toluene and 5 mass parts of a 25 wt% tetrabutylammonium hydroxide aqueous solution Evenly, react at 50°C for 10h, remove toluene under reduced pressure, then add 60 parts by mass of tetrahydrofuran and 15 parts by mass of dodecafluoroheptyl acrylate, react for 1h, remove tetrahydrofuran under reduced pressure, and place the obtained product at 80°C 8 mass parts of trifluoroacetic acid and 60 mass parts of dioxane mixed solution were hydrolyzed for 10 h to obtain dodecafluoroheptyl carboxy-terminated acrylate polymer. Number average molecular weight M measured by gel permeation chromatography (GPC) n =3680

[0053] (2) Amphiphilic fluorine-containing graft polymers terminated by hydroxyl groups are prepared by the following method: 100 parts by mass of dodecafluoroheptyl acrylate polymers terminated with carboxyl groups, polypropylene g...

Embodiment 3

[0058] (1) Carboxy-terminated trifluoroethyl acrylate polymer was prepared by the following method: 1 mass part of tert-butyl malonate, 100 mass parts of toluene and 5 mass parts of tetrabutylammonium hydroxide aqueous solution with a concentration of 25wt% were uniformly mixed , reacted at 50°C for 10h, removed toluene under reduced pressure, then added 60 parts by mass of tetrahydrofuran and 3 parts by mass of trifluoroethyl acrylate, reacted for 1h, removed tetrahydrofuran under reduced pressure, and placed the obtained product in 8 mass parts at 80°C Parts of trifluoroacetic acid and 60 parts by mass of dioxane mixed solution were hydrolyzed for 10 hours to obtain carboxyl-terminated trifluoroethyl acrylate polymer. Number average molecular weight M measured by gel permeation chromatography (GPC) n =1870

[0059] (2) The amphiphilic fluorine-containing graft polymer terminated by hydroxyl groups is prepared by the following method: 100 parts by mass of carboxyl-terminated...

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Abstract

The invention belongs to the field of paints in chemical industry, and discloses a photocuring composite paint containing vinyl-terminated fluorosilicone graft copolymer. The preparation method comprises the following steps: sequentially adding 0.01-20 parts by mass of vinyl-terminated fluorosilicone graft copolymer, 0-500 parts by mass of organic solvent, 2-20 parts by mass of active dilute monomer, 2-30 parts by mass of filler, 0.5-5 parts by mass of film former, 0.1-4 parts by mass of defoaming agent and 0.5-8 parts by mass of photoinitiator into 100 parts by mass of epoxy acrylic resin, wherein another reaction raw material is added every time after a reaction raw material is added and uniformly stirred; and carrying out ultraviolet irradiation to obtain the composite photocuring paint containing vinyl-terminated fluorosilicone graft copolymer. The paint has the advantages of excellent water resistance, excellent stain resistance, excellent aging resistance, excellent corrosion resistance and the like. The paint can be used in the fields of ship stain resistance, indoor and outdoor surface application, surface protection coatings for various plastic and steel plate products, and the like.

Description

technical field [0001] The invention belongs to the field of chemical coatings, and relates to a compound light-curing coating of terminal vinyl group-containing amphiphilic fluorine-containing graft polymer and a preparation method thereof. Background technique [0002] Epoxy acrylic resin coatings are widely used because of their low price, abundant sources, high hardness, and good transparency, but there are also problems such as weather resistance, corrosion resistance, and poor water resistance, especially because epoxy acrylic resins are relatively high. The surface tension of the prepared epoxy resin coating has a high surface energy, which limits its use in fields such as highly hydrophobic special antifouling coatings. [0003] Due to the small atomic radius and high polarizability of fluorine atoms, fluoropolymers exhibit excellent chemical stability, flame retardancy, extremely low surface energy, high temperature resistance, and corrosion resistance. Therefore, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C09D163/10C09D187/00C08G81/02C08F220/22C08F8/12
Inventor 刘伟区闫振龙
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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