Preparation method of bromo-pyrrolecarbonitrile grafted block type acrylic acid self-polishing resin and environmentally-friendly marine antifouling composition

A technology of bromopyrrole nitrile and acrylic silicone resin, which is applied in antifouling/underwater coatings, biocide-containing paints, coatings, etc., can solve the problems that copper-containing antifouling agents affect human health and ecological safety, and achieve Good stability, uniform distribution, anti-fouling effect

Active Publication Date: 2021-04-06
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, copper-containing antifouling agents in coatings can still af

Method used

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  • Preparation method of bromo-pyrrolecarbonitrile grafted block type acrylic acid self-polishing resin and environmentally-friendly marine antifouling composition
  • Preparation method of bromo-pyrrolecarbonitrile grafted block type acrylic acid self-polishing resin and environmentally-friendly marine antifouling composition
  • Preparation method of bromo-pyrrolecarbonitrile grafted block type acrylic acid self-polishing resin and environmentally-friendly marine antifouling composition

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Effect test

preparation example Construction

[0075] A kind of preparation method of bromopyrrole nitrile graft block type acrylic acid isobornyl resin, comprises the following steps:

[0076] 1) Preparation of bromopyrrolenitrile-modified isocyanate: under the protection of inert gas, mix ethyl acetate and bromopyrrolenitrile evenly, then add dropwise to isophorone diisocyanate, heat up to 40-50°C for reaction, and Remove 40-60% of ethyl acetate under conditions, add xylene with a mass ratio of (40-60):(15-20) to the remaining ethyl acetate to obtain bromopyrrole nitrile-modified isocyanate. The mass ratio of ethyl acetate, bromopyrrole nitrile and isophorone diisocyanate is 100:(20-30):(15-20).

[0077] 2) Preparation of block-type isobornyl acrylate resin: Mix initiator, molecular weight modifier, isobornyl methacrylate and xylene under the protection of an inert gas, heat up to 65-75°C and react for 20-30 hours, then add formaldehyde The mixed solution of butyl acrylate, hydroxyethyl acrylate, xylene and initiator wa...

Embodiment 1

[0114] Embodiment 1: Preparation (A) of bromopyrrole nitrile modified isocyanate

[0115] Add 16.7g isophorone diisocyanate (IPDI), 100g dry ethyl acetate and 25g bromopyrrole nitrile homogeneous mixture in the four-necked flask equipped with high-purity argon protection, stirrer, reflux condenser and thermometer Add it dropwise into the system, raise the temperature to 45°C to continue the reaction, measure the content of NCO groups in the system by di-n-butylamine titration method, after reaching the theoretical value, remove 50g of ethyl acetate under vacuum conditions, add 18.3g of dry xylene to obtain bromopyrrole nitrile modified isocyanate (A).

[0116]

[0117] Preparation of Bromopyrrole Nitrile Modified Isocyanate (A)

Embodiment 2

[0118] Embodiment 2: the preparation of block type acrylic acid isobornyl resin (B1)

[0119] Add 0.6g of azobisisobutyronitrile (AIBN), 1.2g of mercaptoethanol, 45g of isobornyl methacrylate (IBOMA), and 51g of xylene in a 1L four-necked flask equipped with a stirrer, a reflux condenser, and nitrogen protection. After 24 hours of reaction, add 18g of butyl methacrylate (BMA), 27g of hydroxyethyl acrylate (HEA), 51g of xylene and 0.6g of AIBN, continue the reaction for 24 hours, cool to room temperature, and complete the reaction . The measured solid content was 47.2%. According to the GPC test, the number average molecular weight of the resin is 34287, the weight average molecular weight is 111775, and the dispersion degree is 3.26.

[0120]

[0121] Preparation of Block Type Acrylic Isobornyl Resin (B1)

[0122] The batching weight (g) of the block type acrylic isobornyl resin of more different monomer ratios is as follows:

[0123]

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Abstract

The invention relates to the field of polymer synthesis, and discloses a preparation method of bromo-pyrrolecarbonitrile grafted block type acrylic acid self-polishing resin and an environmentally-friendly marine antifouling composition. The bromo-pyrrolecarbonitrile grafted block type acrylic acid self-polishing resin is a block type polymer and contains a block easy to hydrolyze and a block difficult to hydrolyze. According to the invention, after the resin is applied to the surface of a marine facility (such as the bottom of a ship) as a coating material component, a unique dynamic hydration layer can be formed after the block easy to hydrolyze meets water, so that the effect of actively inhibiting fouling can be achieved; an anti-fouling agent bromo-pyrrolecarbonitrile is grafted on the block difficult to hydrolyze, so that fouling can be passively eliminated and inhibited; and the marine antifouling composition can effectively reduce the use amount of cuprous oxide, can also be applied to a copper-free tin-free self-polishing system, and is environmentally-friendly.

Description

technical field [0001] The invention relates to the field of polymer synthesis, in particular to a preparation method of a bromopyrrole nitrile grafted block type acrylic self-polishing resin and a low-copper marine antifouling composition. Background technique [0002] Marine biofouling refers to the biofouling formed by the adsorption, growth and reproduction of marine microorganisms, plants and animals on the surface of ships and marine facilities (such as the bottom of ships), which brings many disadvantages to human beings engaged in marine activities. Applying antifouling paint is recognized as the most effective and economical means to deal with biofouling. Organotin (TBT) antifouling coatings, which used to be used as special effects weapons, were banned globally in 2008 because of their great harm to the ecological environment. In the post-TBT era, copper-containing antifouling agents are generally used to replace organotin, and a compound coating system with cupro...

Claims

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Application Information

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IPC IPC(8): C08F8/32C08F293/00C09D153/00C09D5/16
CPCC08F8/32C08K2003/2248C08L2205/03C09D5/1618C09D5/1625C09D5/1662C09D153/00C08F293/005C08L93/04C08L47/00C08K13/02C08K3/22C08K5/0091C08K5/39
Inventor 胡建坤张庆华詹晓力
Owner ZHEJIANG UNIV
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