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CN-117700707-B - Cationic polycarbonate resin and preparation method and application thereof

CN117700707BCN 117700707 BCN117700707 BCN 117700707BCN-117700707-B

Abstract

The invention discloses a cationic polycarbonate resin and a preparation method and application thereof. The cationic polycarbonate resin contains the following structural units: wherein R1, R2 and R3 are respectively and independently selected from H, methyl, ethyl or propyl, and R4 is selected from: R5 and R6 are respectively and independently selected from H, methyl, ethyl, propyl, -CH 2 NH 2 、-CH 2 CH 2 NH 2 or-CH 2 CH 2 CH 2 NH 2 , n is a positive integer, n is more than or equal to 100, x=0.7-0.9, y=0.1-0.3, x+y=1, and z=0, 1 or 2. The cationic polycarbonate resin prepared by the invention has a surface degradation mechanism, and the paint film is linearly thinned, so that the surface can be continuously updated and kept smooth and complete all the time, thereby making marine organisms difficult to adhere.

Inventors

  • PAN KAI
  • LIN YIJUN
  • XI ZHIWEI
  • WANG LIJIE
  • HUANG CHUNFANG

Assignees

  • 中国电建集团中南勘测设计研究院有限公司

Dates

Publication Date
20260505
Application Date
20231130

Claims (12)

  1. 1. A cationic polycarbonate resin, characterized in that the cationic polycarbonate resin consists of structural units of: ; wherein R1, R2 and R3 are each independently selected from H, methyl, ethyl or propyl; R4 is selected from: ; R5 and R6 are each independently selected from H, methyl, ethyl, propyl, -CH 2 NH 2 、-CH 2 CH 2 NH 2 or-CH 2 CH 2 CH 2 NH 2 ; n is a positive integer, n is greater than or equal to 100, x=0.7 to 0.9, y=0.1 to 0.3, x+y=1, z=0, 1 or 2.
  2. 2. The cationic polycarbonate resin according to claim 1, wherein the molar content of the structural unit where R4 is located is 10% -30% of the total structural unit content.
  3. 3. The method for preparing the cationic polycarbonate resin according to claim 1 or 2, which is characterized in that a compound containing hydroxyl is used as an initiator, cyclic carbonate containing double bonds and hexacyclic carbonate are subjected to ring-opening copolymerization under the condition of no water and no oxygen to obtain a functional polymer, and then thiolate containing amino and the functional polymer are subjected to post-polymerization modification through 'thiol-ene' click chemistry to obtain the cationic polycarbonate resin.
  4. 4. A process according to claim 3, wherein the six-membered cyclic carbonate comprises one or more of 1, 3-dioxan-2-one or 2, 2-dimethyltrimethylene cyclic carbonate or 5-methyl-5-propyl-1, 3-dioxan-2-one.
  5. 5. The process according to claim 3, wherein the cyclic carbonate having a double bond comprises one or more of 5-methyl-5-allyloxycarbonyl-1, 3-dioxan-2-one, 5-allyloxy-1, 3-dioxan-2-one, 2- (methacrylamide) trimethylene carbonate and 5-methyl-5-acryloyloxy-1, 3-dioxan-2-one.
  6. 6. The method according to claim 3, wherein the cyclic carbonate containing double bonds is 10 to 30% of the total molar content of the functional polymer.
  7. 7. The method according to claim 3, wherein the compound containing a hydroxyl group comprises one or more of benzyl alcohol, isopropyl alcohol, and propylene glycol.
  8. 8. The method according to claim 3, wherein a catalyst is further added to the ring-opening copolymerization, and the catalyst comprises one or two of stannous octoate and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
  9. 9. A method of preparation according to claim 3 wherein the amino group-containing thiolate is one or more of 2- (diethylamino) ethylthiolate, 2- (dimethylamino) ethylthiolate, cysteamine hydrochloride, 3-mercapto-1-propanamine hydrochloride, 2- [ (3-aminopropyl) amino ] ethanethiol dihydrochloride.
  10. 10. The method according to claim 3, wherein the amount of the amino group-containing thiolate added is 1 to 5 times the molar content of the double bond-containing cyclic carbonate.
  11. 11. An antifouling paint comprising the cationic polycarbonate resin according to claim 1 or 2.
  12. 12. The antifouling paint according to claim 11, wherein the antifouling paint comprises, by mass, 15-30 parts of cationic polycarbonate resin, 0-10 parts of rosin, 2-10 parts of a synthetic antifouling agent, 0-1 part of a natural antifouling agent, 0-30 parts of cuprous oxide, 20-35 parts of a pigment filler, 0.5-1 part of a dispersing agent, 0.5-1 part of a defoaming agent, 0-1 part of a leveling agent, 0.5-2 parts of a plasticizer, 0.5-1 part of a thixotropic agent and 10-18 parts of an organic solvent.

Description

Cationic polycarbonate resin and preparation method and application thereof Technical Field The invention belongs to the field of coatings, and particularly relates to cationic polycarbonate resin and a preparation method and application thereof. Background Marine equipment and engineering facilities have been faced with marine biofouling problems. Biological scale formed by fouling organisms on the surface of marine facilities/platforms can cause huge economic losses and potential safety hazards. For example, biofouling can increase frictional resistance of a ship body, so that energy consumption is increased, acidic substances secreted by marine organisms can aggravate equipment corrosion, shorten service life of the equipment and increase maintenance cost, and adhesion of the biofouling can cause instability of a marine floating body or a platform, block pipelines and filters and seriously affect water taking efficiency of facilities such as a nuclear power station. After 2008, tin-free self-polishing type, fouling-desorption type, biodegradable antifouling paint and the like are becoming development emphasis in the field of marine antifouling. At present, tin-free acrylic acid self-polishing paint is used as a mainstream in the industry, copper, zinc and silicon are used for replacing organic tin, the antifouling mechanism is similar to that of the organic tin paint, and the side group of the resin contains a hydrolyzable or ion exchange chain segment and can gradually fall off from the surface of the coating under the flushing of water flow, and meanwhile, the internal antifouling agent is released. The paint is mainly suitable for ocean vessels, and has great influence on antifouling performance in the aspects of course, speed and stall ratio. This is because the hydrolysis and polishing rates are severely dependent on water flow scouring and the antifouling properties are not ideal in static or low speed conditions. In addition, most acrylic polymers have backbones that can only rely on hydrophobic to hydrophilic conversion, are removed after swelling with water, and cannot be degraded, and the removed fragments are prone to form particles (microplastic) in the ocean, resulting in "white pollution". The emerging fouling desorption type antifouling paint usually uses organic silicon or/and organic fluorine as film forming resin, and the marine organisms are difficult to adhere due to the lower surface energy and the high-elasticity and smooth surface of the film forming resin, and even if the marine organisms adhere slightly, the marine organisms can fall off under the scouring of high-speed water flow. However, the fouling desorption type antifouling paint has generally lower mechanical strength, limited adhesive force, high construction requirement, expensive price and great limitation on practical application. Although the industry has derived a number of tin-free antifouling paint products, there is room for improvement in performance. For example, the anti-fouling agent has high content and high toxicity, the resin is not degraded thoroughly, the surface self-cleaning is excessively dependent on the relative shearing of water flow, and the anti-fouling effect of static ocean facilities such as offshore drilling platforms/wind power bases and the like is limited. Based on such problems, some researchers have attempted to develop biodegradable antifouling paints, which use a degradable polyester typified by Polycaprolactone (PCL) or polylactic acid (PLA), and which are continuously degraded and peeled off by a paint layer, so that fouling organisms cannot adhere to an unstable surface. However, polyester degradation speed tends to be high and uneven, holes are easily formed in the resin during degradation, and the surface is rough, which is likely to accelerate excessive degradation of the coating and release of the anti-fouling agent, which is unfavorable for long-term anti-fouling. Disclosure of Invention The invention aims to provide a cationic polycarbonate resin capable of degrading surface layer by layer, and a preparation method and application thereof. In order to solve the technical problems, the technical scheme of the invention is as follows: a cationic polycarbonate resin, which comprises a resin, the cationic polycarbonate resin contains the following structural units: wherein R1, R2 and R3 are each independently selected from H, methyl, ethyl or propyl; R4 is selected from: R5 and R6 are each independently selected from H, methyl, ethyl, propyl, -CH 2NH2、-CH2CH2NH2 or-CH 2CH2CH2NH2; n is a positive integer, n is greater than or equal to 100, x=0.7 to 0.9, y=0.1 to 0.3, x+y=1, z=0, 1 or 2. The unique backbone structure of the cationic polycarbonate resin determines the ability of the resin to achieve surface degradation. When the surface degradation occurs, the molecular chain of the surface layer of the material breaks and breaks down into oligomer or monomer, the inner chain segment