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CN-122011397-A - Reactive organosilicon polymer and preparation method and application thereof

CN122011397ACN 122011397 ACN122011397 ACN 122011397ACN-122011397-A

Abstract

The invention provides a reactive organosilicon polymer and a preparation method and application thereof, and the reactive organosilicon polymer comprises the following steps of (1) reacting linear hydrogen-containing silicone oil at two ends with allyl methacrylate in the presence of a noble metal catalyst and a polymerization inhibitor to obtain acrylate functionalized modified silicone oil at two ends, (2) telomerizing the acrylate functionalized modified silicone oil at two ends of the step (1) with high hydrogen-containing silicone oil and/or siloxane ring to obtain side chain hydrogen-containing silicone oil, and (3) carrying out hydrosilation reaction on the side chain hydrogen-containing silicone oil of the step (2) with allyl polyether and/or allyl methacrylate to obtain the reactive organosilicon polymer. The organosilicon polymer prepared by the invention can be used as a slip and leveling auxiliary agent for radiation curing paint or ink, can effectively prevent generating benard vortex, and provides leveling and shrinkage cavity inhibiting functions.

Inventors

  • WANG ZHIJUN

Assignees

  • 埃夫科纳聚合物股份有限公司
  • 埃夫科纳(南充)特种聚合物有限公司

Dates

Publication Date
20260512
Application Date
20241111

Claims (10)

  1. 1. A method of preparing a reactive silicone polymer, the method comprising the steps of: (1) The linear two-end hydrogen-containing silicone oil and allyl methacrylate react in the presence of a noble metal catalyst and a polymerization inhibitor to prepare modified silicone oil with acrylate functionalization at two ends; (2) Telogenic the modified silicone oil functionalized by acrylic ester at two ends of the step (1) with high hydrogen silicone oil and/or siloxane ring bodies to obtain side chain hydrogen silicone oil; (3) And (3) carrying out hydrosilation reaction on the side chain hydrogen-containing silicone oil in the step (2) and allyl polyether and/or allyl methacrylate to obtain the reactive organosilicon polymer.
  2. 2. The preparation method according to claim 1, wherein the silicon hydrogen value of the linear two-terminal hydrogen-containing silicone oil is 0.05% -0.1%; and/or the silicon hydrogen value of the side chain hydrogen-containing silicone oil is 0.1% -0.3%; And/or, the reactive silicone polymer is free of silicon hydrogen bonds.
  3. 3. The preparation method according to claim 1, wherein the high hydrogen-containing silicone oil comprises one or more of methyl total hydrogen-containing silicone oil and methylphenyl hydrogen-containing silicone oil; And/or the siloxane ring body comprises one or more of tetramethyl cyclotetrasiloxane, hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, hexaalkyl cyclotrisiloxane, hexaphenyl cyclotrisiloxane, trimethyl triphenyl cyclotrisiloxane and tetramethyl tetraphenyl cyclotrisiloxane; and/or, the allyl polyether has the following structural formula: Wherein m and n are integers respectively and the number average molecular weight of the allyl polyether is 200 to 10000, R 4 is H, straight-chain alkyl containing 1 to 18 carbons, branched-chain alkyl containing 3 to 18 carbons or acyl containing 2 to 5 carbons, The HLB value of the allyl polyether is 1-18.
  4. 4. The method of preparation of claim 1, wherein the noble metal catalyst comprises one or more of a platinum-based catalyst, a rhodium-based catalyst, or a cobalt-based catalyst; And/or the polymerization inhibitor comprises one or more of quinone, phenol, aromatic amine or metal halide polymerization inhibitors.
  5. 5. The method of preparation of claim 1, wherein the noble metal catalyst comprises one or more of C 7 H 5 Cl 2 NPt、[(CH 3 ) 2 -CH＝CH 2 ] 3 Pt 2 、H 2 PtCl 6 ·6H 2 O、C 8 H 18 OPtSi、PtCl 2 (PPh 3 ) 2 、Pt(PPh 3 ) 4 、RhCl(PPh 3 ) 3 、RhCl 2 (PPh 3 ) 2 、Cl 2 (Pcy 3 ) 2 Ru＝CHPh、Co(CO) 8 ; And/or the polymerization inhibitor comprises one or more of p-methoxyphenol, hydroquinone, phenothiazine, 2, 4-diisobutyl-6-methylphenol, p-tert-butylcatechol, p-hydroxyanisole, 2, 6-di-tert-butylp-methylphenol or CuCl 2 .
  6. 6. The preparation method according to claim 1, wherein the reaction temperature of the step (1) is 80-90 ℃, and/or the reaction temperature of the step (2) is 40-60 ℃, and/or the reaction temperature of the step (3) is 80-90 ℃.
  7. 7. The reactive silicone polymer produced by the production method according to any one of claims 1 to 6, characterized in that the reactive silicone polymer has the following structural formula: Wherein R 1 、R 2 is an alkyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group, R 1 、R 2 are the same or different, A is R 3 is H or methyl, and the amino acid is H or methyl, B is R 4 is H, straight-chain alkyl containing 1-18 carbons, branched-chain alkyl containing 3-18 carbons or acyl containing 2-5 carbons, m is an integer of 0-100, n is an integer of 0-150, m and n are not simultaneously 0, X is an integer of 0 to 300, y is an integer of 0 to 20, and z is an integer of 1 to 100.
  8. 8. Use of the reactive silicone polymer of claim 7 in the preparation of an auxiliary for radiation curing systems.
  9. 9. The use according to claim 8, wherein the radiation-curable system comprises an unsaturated polyester coating or ink system, an epoxy acrylic coating or ink system, a polyurethane acrylic coating or ink system, a polyester acrylic coating or ink system, a polyether acrylic coating or ink system, an acrylate coating or ink system.
  10. 10. The use according to claim 8, characterized in that the reactive silicone polymer is used in an amount of 0.1-0.5 wt% in the radiation-curing system.

Description

Reactive organosilicon polymer and preparation method and application thereof Technical Field The invention belongs to the technical field of organosilicon polymers, and particularly relates to a reactive organosilicon polymer, a preparation method and application thereof. Background The radiation curing technology comprises Ultraviolet (UV) and Electron Beam (EB) curing, and is a material surface treatment technology for rapidly polymerizing and crosslinking and instantaneously curing a liquid material with chemical activity by using UV/EB. The product is widely used in the fields of building material furniture, printing package, advertisement decoration, electronic information, automobiles, machinery, medical sanitation and the like because of rapid solidification, high production efficiency, energy conservation, environmental protection, the product is in the forms of paint, ink, adhesive, printing plate material, electronic chemicals and the like. Light curing has been recognized by the industry as a green industry project. With the rapid development of UV/EB radiation-curable coatings and inks, the requirements for the additives used therein are also increasing, and the conventional organomodified polysiloxanes have failed to meet the requirements of the radiation-curing system, being gradually replaced by UV/EB curable acryl-modified polysiloxanes. The acrylate modified organosilicon combines the advantages of organosilicon and acrylic acid, has the characteristics of crosslinking and no migration, and greatly improves the performances of flow, leveling, substrate wetting, degassing, smoothness, non-sticking, scratch resistance and the like. The existing preparation method of the acryl-modified polysiloxane comprises a hydrosilylation method, an esterification method, a hydrolysis method, condensation and small molecule removal (such as alcohol, hydrogen chloride, sodium chloride and the like) and a non-equilibrium living anion polymerization end-capping route. For example, U.S. patent No. 6211322B1 mentions that the addition of 1, 1-trimethylol propane monoallyl ether to linear hydrogen-containing silicone oil followed by esterification dehydration with an excess of acrylic acid at 65 ℃ in the presence of a catalyst trifluoromethanesulfonic acid, the reaction mixture is neutralized with sodium carbonate solution, filtered and distilled, the process is cumbersome and the monomer 1, 1-trimethylol propane monoallyl ether is expensive and disadvantageous for industrial production. U.S. patent No. 6288129B1 describes the synthesis of acryl and polyether co-modified polysiloxanes with hydroxyl terminated polyether modified silicones by transesterification with butyl acrylate for radiation curable coatings, but with hydroxyl conversion of only 57-65%. EP0237757 describes UV-curable elastomeric coatings made from acryl-alkyl functional siloxanes which also contain mercapto groups, which are expensive to prepare and handle and which smell poorly. US6548568B1, CN101089031, etc. illustrate that after hydrosilylation of a hydrogen-containing polysiloxane with an unsaturated monomer having an epoxy group, the epoxy ring is opened with (meth) acrylic acid to obtain an acryl-modified polysiloxane, wherein the last step of the esterification reaction consumes a very high amount of energy, and the double bond in the (meth) acrylic acid has a risk of self-polymerization during the esterification and dehydration. US4978726A, US4675346A, US5863966a et al describe the application of difunctional or polyfunctional acrylate-modified silicones to sheet supports, release and printing inks, respectively, but without the introduction of regulatable hydrophilic lipophilic polyether segments, so that the auxiliaries cannot be used widely in a variety of radiation curing systems. Disclosure of Invention The invention aims to overcome the defects of the prior art and provide a preparation method of a reaction type organosilicon polymer which is simple and convenient to react and controllable, wherein the reaction type organosilicon polymer prepared by the method is polysiloxane with both ends containing side chain polyether of acryl or polyether and acryl co-modified, has wide system compatibility, and has excellent comprehensive performance as an additive of radiation curing (UV/EB) paint and printing ink. In order to solve the technical problems, the invention adopts the following technical scheme: the invention provides a preparation method of a reactive organosilicon polymer, which comprises the following steps: (1) The linear two-end hydrogen-containing silicone oil and allyl methacrylate react in the presence of a noble metal catalyst and a polymerization inhibitor to prepare modified silicone oil with acrylate functionalization at two ends; (2) Telogenic the modified silicone oil functionalized by acrylic ester at two ends of the step (1) with high hydrogen silicone oil and/or siloxane ring bodies to obtain side chain hydro