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CN-121108423-B - Tree-shaped cross-linked structure fluorine-free oil-proof agent and preparation method thereof

CN121108423BCN 121108423 BCN121108423 BCN 121108423BCN-121108423-B

Abstract

The invention discloses a fluorine-free oil-proof agent with a tree-shaped cross-linked structure and a preparation method thereof, comprising the following steps of copolymerizing vinyl siloxane monomer, hydrogen-containing siloxane monomer and unsaturated double bond organic monomer to obtain silicon resin with a tree-shaped structure, and mixing the silicon resin with the tree-shaped structure and a solvent to obtain the fluorine-free oil-proof agent with the tree-shaped cross-linked structure; the molecular weight of the vinyl siloxane monomer is 1000-3000, the molecular weight of the hydrogen-containing siloxane monomer is 1000-3000, and the unsaturated double bond organic monomer is any one or combination of vinyl aromatic monomer and olefin monomer. The dendritic structural silicone resin combines the advantages of the dendrimer and the silicone resin through unique molecular structure design, and has excellent comprehensive performance. The high heat resistance enables stable use under high temperature environments.

Inventors

  • XU JIANMIN
  • WANG LIHUA
  • LU WEI

Assignees

  • 天津日津科技股份有限公司
  • 深圳市日博电子科技有限公司
  • 天津日津新材料有限公司

Dates

Publication Date
20260508
Application Date
20251113

Claims (8)

  1. 1. The preparation method of the fluorine-free oil-proof agent with the tree-shaped cross-linked structure is characterized by comprising the following steps: S1, under the protection of inert gas, mixing vinyl siloxane monomer, unsaturated double bond organic monomer and initiator, heating and carrying out polymerization reaction to obtain mixed solution; s2, adding a hydrogen-containing siloxane monomer and a catalyst into the mixed solution in the step S1, heating to react, and after the reaction is finished, performing aftertreatment to obtain a dendritic structural silicone resin, and preparing a fluorine-free oil-proof agent with a dendritic cross-linked structure by using a solvent; The molecular weight of the vinyl siloxane monomer is 1000-3000; The molecular weight of the hydrogen-containing siloxane monomer is 1000-3000; The unsaturated double bond organic monomer is any one or combination of vinyl aromatic monomer or olefin monomer; The mass of the hydrogen-containing siloxane monomer is 3-10% of the total mass of the prepared tree-structured silicone resin.
  2. 2. The method for preparing a fluorine-free oil repellent agent with a tree-like cross-linked structure according to claim 1, wherein the olefin monomer is one or more selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, vinyl acetate, propylene and butadiene.
  3. 3. The method for preparing a fluorine-free oil repellent agent with a tree-like cross-linked structure according to claim 1, wherein the vinyl aromatic monomer is one or more selected from the group consisting of styrene, 1-methyl vinyl benzene and divinylbenzene.
  4. 4. The method for preparing a fluorine-free oil-proofing agent with a tree-shaped cross-linked structure according to claim 1, wherein the mass ratio of vinyl siloxane monomer to unsaturated double bond organic monomer is 9-11:1.
  5. 5. The method for preparing a fluorine-free oil repellent agent with a tree-like cross-linked structure according to claim 1, wherein the inert gas in the step S1 is one or more selected from nitrogen and argon; the initiator in the step S1 is selected from one or two of azodiisobutyronitrile and benzoyl peroxide; The mass of the initiator is 0.1-0.5% of the total mass of the vinyl siloxane monomer, the hydrogen-containing siloxane monomer and the unsaturated double bond organic monomer; the temperature for polymerization reaction is 50-100 ℃ after the temperature rise in the step S1; The polymerization reaction is carried out at a temperature rise in the step S1 for 1 to 5 hours.
  6. 6. The method for preparing a fluorine-free oil-proofing agent with a tree-shaped cross-linked structure according to claim 1, wherein the catalyst in the step S2 is chloroplatinic acid; The reaction temperature of the hydrogen-containing siloxane monomer and the catalyst in the step S2 is 30-50 ℃ and the reaction time is 3-6h; The mass of the catalyst is 0.03% -0.1% of the total mass of vinyl siloxane monomer, hydrogen-containing siloxane monomer and unsaturated double bond organic monomer.
  7. 7. The method for producing a fluorine-free oil repellent agent having a tree-like crosslinked structure according to claim 1, wherein the post-treatment in step S2 comprises subjecting the reaction product to distillation under reduced pressure; the mass fraction of the dendritic silicone resin in the fluorine-free oil-proof agent with the dendritic cross-linked structure prepared in the step S2 is 4-10%.
  8. 8. The fluorine-free oil-proofing agent with a tree-shaped cross-linked structure prepared by the preparation method of the fluorine-free oil-proofing agent with a tree-shaped cross-linked structure as claimed in any one of claims 1 to 7, which is characterized in that the fluorine-free oil-proofing agent with the tree-shaped cross-linked structure comprises a solvent and a tree-shaped structure silicon resin.

Description

Tree-shaped cross-linked structure fluorine-free oil-proof agent and preparation method thereof Technical Field The invention belongs to the technical field of functional materials, and particularly relates to a fluorine-free oil-proof agent with a tree-shaped cross-linked structure and a preparation method thereof. Background At present, intelligent devices have become indispensable tools in life, such as intelligent household appliances including mobile phones, watches, headphones, intelligent sound boxes and the like. The acoustic and electrical components inside the above-mentioned devices are very fragile and are susceptible to intrusion by water, oil, solid particles (dust, waste, dangerous debris), resulting in damage to the devices. The main solution is to add a protective layer at the position of the external through hole, and the protective layer is usually made of gauze, steel mesh and film materials to ensure air permeability, and meanwhile, a barrier is formed at the position of the through hole to effectively isolate dirt and dust. However, the oil stain resistance of the materials is weak, so that the materials need to be subjected to oleophobic modification treatment. Indeed, superoleophobic coatings developed to date all use fluorinated compounds with a large number of CF 2- and CF 3- groups, such as PTFE, perfluorosilanes and perfluoropolymers. In view of the limitations of the inherent surface tension of materials, essentially previous high oleophobic coatings were based on fluorinated materials with surface energy. CN118930763a discloses a fluorine-free waterproofing agent, its preparation method is that acrylic ester is added with active groups such as long-chain alkyl and epoxy, so that it is convenient to react with active groups on the surface of fabric to enhance washing resistance, and at the same time, provides better hand feeling. The formula takes acrylic esters as a main body, has higher surface tension, takes water resistance as a main body, and cannot reach the oil-proof level. CN116854888a discloses a dendritic structural resin formed by crosslinking trimethylolpropane, IPDI and diethanolamine to achieve a waterproof effect, but the polymer of the resin contains a large amount of formate bonds, ether bonds, hydroxyl groups, ionic bonds and other hydrophilic bonds, has high surface tension, is poor in compatibility with a PTFE film, and repels the surface of the PTFE film, so that the hydrophilic bonds are arranged outwards, the tension of the film surface is integrally improved, and the waterproof and oil-proof properties are affected. Disclosure of Invention In view of the above, the present invention aims to provide a fluorine-free oil-repellent agent with a tree-shaped cross-linked structure and a preparation method thereof, so as to solve at least one technical problem in the background art. In order to achieve the above purpose, the technical scheme of the invention is realized as follows: the preparation process of the fluorine-free oil-proof agent with tree cross-linked structure includes the steps of copolymerizing vinyl siloxane monomer, hydrogen-containing siloxane monomer and unsaturated double bond organic monomer to obtain tree-structured silicone resin, and mixing the tree-structured silicone resin with solvent to obtain the fluorine-free oil-proof agent with tree cross-linked structure; The molecular weight of the vinyl siloxane monomer is 1000-3000; The molecular weight of the hydrogen-containing siloxane monomer is 1000-3000; The unsaturated double bond organic monomer is any one or combination of vinyl aromatic monomer or olefin monomer. The vinyl siloxane monomer has a chemical formula of Vi- (Me 2 SiO) m (Vi-MeSiO) nSiMeVi and a vinyl content of 3%; The structural formula of the hydrogen-containing silicone oil monomer is Me 3SiO(Me2SiO)m(MeHSiO)nSiMe3, and the hydrogen content is 0.5%. Further, the olefin monomer is selected from one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, vinyl acetate, propylene and butadiene. Further, the vinyl aromatic monomer is selected from one or more of styrene, 1-methyl vinyl benzene and divinylbenzene. Further, the mass of the hydrogen-containing siloxane monomer is 3-10% of the total mass of the prepared tree-structured silicone resin. Further, the mass ratio of the vinyl siloxane monomer to the unsaturated double bond organic monomer is 9-11:1. A preparation method of a fluorine-free oil-proof agent with a tree-shaped cross-linked structure comprises the following steps: S1, mixing vinyl siloxane monomer, unsaturated double bond organic monomer and initiator under the protection of inert gas, heating to perform polymerization reaction to obtain mixed solution, and introducing branched organic groups on a siloxane main chain through unsaturated bond addition reaction to form a primary branched structure. And S2, adding a hydr