Reactive organosilicon polymer and preparation method and application thereof

Abstract

The invention provides a reactive organosilicon polymer, and a preparation method and application thereof. The preparation method comprises the following steps: (1) reacting linear silicone oil with two ends containing hydrogen with allyl methacrylate in the presence of a noble metal catalyst and a polymerization inhibitor to prepare modified silicone oil with two ends functionalized by acrylate; (2) telomerization is carried out on the modified silicone oil with two ends functionalized by acrylate in the step (1) and high-hydrogen-content silicone oil and / or a siloxane ring body to obtain side chain hydrogen-containing silicone oil; and (3) carrying out hydrosilylation reaction on the side chain hydrogen-containing silicone oil obtained in the step (2) and allyl polyether and / or allyl methacrylate to obtain the reactive organosilicon polymer. The organosilicon polymer prepared by the invention is used as a slipping and leveling auxiliary agent of radiation curing coating or printing ink, can effectively prevent Benard vortexes from being generated, and has the functions of leveling and shrinkage cavity inhibition.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon polymer technology, and specifically relates to a reactive organosilicon polymer, its preparation method, and its applications. Background Technology

[0002] Radiation curing technology, including ultraviolet (UV) and electron beam (EB) curing, is a surface treatment technology that utilizes UV / EB to initiate the rapid polymerization and cross-linking of chemically active liquid materials, resulting in instantaneous curing into a film. Due to its rapid curing, high production efficiency, energy saving, and environmental friendliness, the products are mainly in the form of coatings, inks, adhesives, printing plates, and electronic chemicals, and are widely used in building materials and furniture, printing and packaging, advertising and decoration, electronics and information technology, automobiles, machinery, and medical and health fields. Radiation curing has been recognized as a green industrial project by the Ministry of Industry and Information Technology.

[0003] With the rapid development of UV / EB radiation-curable coatings and inks, the requirements for the additives used in them are becoming increasingly stringent. Traditional organic-modified polysiloxanes can no longer meet the needs of radiation curing systems and are gradually being replaced by UV / EB-curable acryloyl-modified polysiloxanes. Acrylic-modified silicones combine the advantages of silicones and acrylics, exhibiting cross-linking and non-migrating properties, and significantly improving properties such as flowability, leveling, substrate wetting, degassing, smoothing, non-stickiness, and scratch resistance.

[0004] Existing methods for preparing acryloyl-modified polysiloxanes include hydrosilylation, esterification, hydrolysis, condensation to remove smaller molecules (such as alcohols, hydrogen chloride, sodium chloride, etc.), and non-equilibrium active anionic polymerization end-capping routes. For example, US Patent 6211322B1 mentions the addition of 1,1,1,-trimethylolpropane monoallyl ether to linear hydrogen-containing silicone oil, followed by esterification and dehydration with excess acrylic acid at 65°C in the presence of trifluoromethanesulfonic acid as a catalyst. The resulting mixture is neutralized with sodium carbonate solution, filtered, and distilled. This process is relatively cumbersome, and the expensive monomer 1,1,1,-trimethylolpropane monoallyl ether is not conducive to industrial production. US Patent 6288129B1 describes the synthesis of acryloyl- and polyether co-modified polysiloxanes from hydroxyl-terminated polyether-modified organosilicon via transesterification with butyl acrylate for use in radiation-cured coatings; however, the hydroxyl conversion rate is only 57-65%. EP0237757 describes a UV-curable elastomer coating made from acryloyl-alkyl functionalized siloxanes, which also contains mercapto groups. Mercaptosiloxanes are expensive, difficult to prepare and process, and have an unpleasant odor. US6548568B1, CN101089031, and others describe the hydrosilylation addition of hydrogen-containing polysiloxanes with unsaturated monomers containing epoxy groups, followed by epoxide ring opening with (meth)acrylic acid to obtain acryloyl-modified polysiloxanes. However, the final esterification reaction is energy-intensive, and the double bonds in (meth)acrylic acid pose a risk of self-polymerization during esterification and dehydration. US4978726A, US4675346A, and US5863966A introduce the application of difunctional or polyfunctional acrylate-modified organosilicones in sheet carriers, release agents, and printing inks, but they do not introduce tunable hydrophilic and lipophilic polyether segments, limiting the widespread application of these additives in various radiation curing systems. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a simple and controllable method for preparing reactive organosilicon polymers. The reactive organosilicon polymers prepared by this method are polyethers with acryloyl side chains at both ends or polyethers co-modified with acryloyl groups. They have broad system compatibility and excellent comprehensive performance as additives for radiation-cured (UV / EB) coatings and inks.

[0006] To solve the above technical problems, the present invention adopts the following technical solution:

[0007] This invention provides a method for preparing a reactive organosilicon polymer, the method comprising the following steps:

[0008] (1) A modified silicone oil with acrylate functionalized ends was prepared by reacting linear silicone oil containing hydrogen at both ends with allyl methacrylate in the presence of a noble metal catalyst and a polymerization inhibitor.

[0009] (2) The modified silicone oil with acrylate functionalized ends in step (1) is telomerized with high hydrogen content silicone oil and / or siloxane cyclic polymer to obtain side-chain hydrogen content silicone oil.

[0010] (3) The side-chain hydrogen-containing silicone oil from step (2) is hydrosilylated with allyl polyether and / or allyl methacrylate to obtain the reactive organosilicon polymer.

[0011] Preferably, the silane-hydrogen value of the hydrogen-containing silicone oil at both ends of the linear junction is 0.05% to 0.1%, for example, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.1%.

[0012] Preferably, the hydroxyl value of the side-chain hydrogen-containing silicone oil is 0.1% to 0.3%, for example, 0.1%, 0.15%, 0.2%, 0.25%, or 0.3%.

[0013] Preferably, the reactive organosilicon polymer does not have silicon-hydrogen bonds.

[0014] Preferably, the high-hydrogen-content silicone oil includes one or more of methyl fully hydrogen-containing silicone oil and methyl phenyl hydrogen-containing silicone oil.

[0015] Preferably, the siloxane cyclic compound comprises one or more of tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexaalkylcyclotrisiloxane, hexaphenylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, and tetramethyltetraphenylcyclotetrasiloxane.

[0016] Preferably, the allyl polyether has the following structural formula:

[0017]

[0018] Where m and n are integers and the number average molecular weight of the allyl polyether is 200–10000, and R4 is H, a straight-chain alkyl group containing 1–18 carbons, a branched alkyl group containing 3–18 carbons, or an acyl group containing 2–5 carbons.

[0019] The allyl polyether has an HLB value of 1 to 18.

[0020] Preferably, the noble metal catalyst includes one or more of platinum-based catalysts, rhodium-based catalysts, or cobalt-based catalysts.

[0021] Preferably, the polymerization inhibitor includes one or more of quinones, phenols, aromatic amines, or metal halide polymerization inhibitors.

[0022] Preferably, the noble metal catalyst comprises C7H5Cl2NPt, [(CH3)2-CH=CH2]3Pt2, H2PtCl6·6H2O, C8H18 One or more of OPtSi, PtCl2(PPh3)2, Pt(PPh3)4, RhCl(PPh3)3, RhCl2(PPh3)2, Cl2(Pcy3)2Ru=CHPh, and Co(CO)8.

[0023] Preferably, 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-butyl-p-cresol, or CuCl2.

[0024] Preferably, the reaction temperature in step (1) is 80–90°C.

[0025] Preferably, the reaction temperature in step (2) is 40–60°C.

[0026] Preferably, the reaction temperature in step (3) is 80–90°C.

[0027] The reactive organosilicon polymer prepared by the above method is also within the scope of protection of this invention, and the reactive organosilicon polymer has the following structural formula:

[0028]

[0029] Where R1 and R2 are alkyl groups containing 1 to 4 carbon atoms or unsubstituted phenyl groups, and R1 and R2 may be the same or different.

[0030] A is R3 is H or methyl.

[0031] B is R4 is H, a straight-chain alkyl group containing 1 to 18 carbons, a branched alkyl group containing 3 to 18 carbons, or an acyl group containing 2 to 5 carbons; m is an integer from 0 to 100; n is an integer from 0 to 150; m and n are not both 0.

[0032] x takes integers from 0 to 300, y takes integers from 0 to 20, and z takes integers from 1 to 100.

[0033] This invention also provides the application of the above-mentioned reactive organosilicon polymer as an aid in the preparation of radiation curing systems.

[0034] Preferably, the radiation curing system includes unsaturated polyester coatings or inks, epoxy acrylic coatings or inks, polyurethane acrylic coatings or inks, polyester acrylic coatings or inks, polyether acrylic coatings or inks, and acrylic coatings or inks.

[0035] Preferably, the reactive silicone polymer is used in the radiation curing system at an amount of 0.1 to 0.5 wt%.

[0036] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0037] This invention yields a specific polysiloxane structure containing acryloyl-terminated side chains at both ends, or a polyether co-modified with acryloyl groups, through equilibrium and hydrosilylation reactions. By introducing polyether segments, a polyether-modified polysiloxane surface control agent with acryloyl-terminated ends is obtained, exhibiting broad compatibility. This agent can meet the flow control requirements of various radiation-cured systems, including unsaturated polyesters, epoxy acrylics, polyurethane acrylics, polyester acrylics, polyether acrylics, and acrylates. As a slip and leveling agent for radiation-cured coatings or inks, it effectively prevents the formation of Bénard vortices, providing leveling and suppressing pinholes. This invention provides a simpler, more controllable synthesis process that is relatively lower in cost, safer, and more environmentally friendly. Attached Figure Description

[0038] Figure 1 The infrared spectrum of the product of Example 2;

[0039] Figure 2 The images show the effects of foam suppression (shaking for 10 minutes), early defoaming (shaking for 10 minutes and then standing for 10 minutes), late defoaming (shaking for 10 minutes and then standing for 30 minutes), and clarity (shaking for 10 minutes and then standing for 1 hour) of the products of Examples 1 to 4, Comparative Example 1, and Comparative Example 2 in epoxy modified acrylic varnish from left to right.

[0040] Figure 3 The images show the effects of foam suppression (shaking for 10 minutes), early defoaming (shaking for 10 minutes and then standing for 10 minutes), late defoaming (shaking for 10 minutes and then standing for 30 minutes), and clarity (shaking for 10 minutes and then standing for 1 hour) of the products of Examples 1 to 4, Comparative Example 1, and Comparative Example 2 in polyester-modified acrylic varnish from left to right.

[0041] Figure 4The images show the effects of foam suppression (shaking for 10 minutes), early defoaming (shaking for 10 minutes and then standing for 10 minutes), late defoaming (shaking for 10 minutes and then standing for 30 minutes), and clarity (shaking for 10 minutes and then standing for 1 hour) of the products of Examples 1 to 4, Comparative Example 1, and Comparative Example 2 in polyurethane modified acrylic varnish from left to right. Detailed Implementation

[0042] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific applications, and the implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0043] Unless otherwise specified, the raw materials used in the following examples and comparative examples were purchased from commercial sources.

[0044] Example 1

[0045] This embodiment provides a reactive organosilicon polymer, the preparation method of which is as follows:

[0046] In a 500ml four-necked flask equipped with a stirrer, thermometer, and condenser, 360 parts of a double-ended hydrogen-containing polysiloxane (Mw = 2500, silane-hydrogen value 0.08%) and 0.16 parts of a 2% chloroplatinic acid acetate solution were added. The temperature was raised to 80℃, and 40 parts of allyl methacrylate and 0.16 parts of hydroquinone premix were added dropwise over 1 hour with stirring. After the addition was complete, the mixture was kept at 80-90℃ for 2 hours until the SiH characteristic peak completely disappeared. Then, the mixture was evacuated at 80℃ until the solid content (120℃) was >98%, yielding a colorless, low-viscosity, transparent liquid A.

[0047] 87.3 parts of A and 12.7 parts of high-hydrogen silicone oil 202 (domestic, 1.5% hydroxyl content) were added to a four-necked flask equipped with a stirrer, thermometer, and condenser. The mixture was stirred and heated to 50°C under a nitrogen atmosphere. 0.88 parts of 10% trifluoromethanesulfonic acid ethyl acetate solution were added. After reacting for 5 hours, 0.10 parts of triethylamine were added. After stirring for another 30 minutes, the mixture was cooled to room temperature and filtered to obtain a colorless and transparent liquid B (0.19% hydroxyl content).

[0048] 31.4 parts of B and 0.04 parts of 2% chloroplatinic acid acetate solution were added to a four-necked flask equipped with a stirrer, thermometer, and condenser. Under nitrogen atmosphere protection, the mixture was stirred and heated to 80°C. 68.6 parts of allyl polyether (MW=1000, EO:PO=3:1, terminal methyl) were added dropwise over 2 hours. After the addition was completed, the mixture was kept at the temperature until the SiH characteristic peak completely disappeared. Vacuum was applied at 80°C until the solid content (120°C) was >98%. The mixture was then cooled and discharged to obtain a pale yellow transparent liquid, which is the target product.

[0049] Example 2

[0050] This embodiment provides another reactive organosilicon polymer, the preparation method of which is as follows:

[0051] In a four-necked flask equipped with a stirrer, thermometer, and condenser, 83.4 parts of A (from Example 1) and 16.6 parts of high-hydrogen silicone oil 202 (domestic, 1.5% hydroxyl content) were added respectively. Under nitrogen atmosphere protection, the mixture was stirred and heated to 50°C. Then, 0.88 parts of 10% trifluoromethanesulfonate ethyl acetate solution were added. After reacting at 50-60°C for 5 hours, 0.10 parts of triethylamine were added. After stirring for another 30 minutes, the mixture was cooled to room temperature and filtered to obtain a colorless and transparent liquid C (0.25% hydroxyl content).

[0052] In a four-necked flask equipped with a stirrer, thermometer, and condenser, 33.44 parts of C and 0.04 parts of a 2% ethyl chloroplatinate solution were added. Under a nitrogen atmosphere, the mixture was stirred and heated to 80°C. Over 2 hours, 63.5 parts of allyl polyether (M) were added dropwise. W =1000, EO:PO=3:1, terminal is methyl), after the addition is completed and kept warm for 2 hours, 3.04 parts of allyl methacrylate are added, and the temperature is kept at 90℃ until the SiH characteristic peak disappears completely. Vacuum is drawn at 80℃ until the solid content (120℃) is >98%, and a light yellow transparent liquid is obtained, which is the target product.

[0053] Example 3

[0054] This embodiment provides another reactive organosilicon polymer, the preparation method of which is as follows:

[0055] In a 500ml four-necked flask equipped with a stirrer, thermometer, and condenser, 371.6 parts of a self-made double-ended hydrogen-containing polysiloxane (Mw=4000, SiH value 0.05%) and 0.16 parts of a 2% chloroplatinic acid acetate solution were added. The temperature was raised to 80℃, and after stirring for about 2 hours, 28.4 parts of allyl methacrylate and 0.16 parts of hydroquinone premix were added dropwise. After the addition was complete, the temperature was maintained at 80-90℃ for 2 hours until the SiH characteristic peak completely disappeared. Then, the solid content (120℃) was evacuated at 80℃ until it was >98%, resulting in a colorless, low-viscosity, transparent liquid D.

[0056] 91.4 parts of D and 8.6 parts of high-hydrogen silicone oil 202 (domestic, 1.5% hydroxyl content) were added to a four-necked flask equipped with a stirrer, thermometer, and condenser. The mixture was stirred and heated to 50°C under a nitrogen atmosphere. 0.88 parts of 10% trifluoromethanesulfonate ethyl acetate solution were added. After reacting for 5 hours, 0.10 parts of triethylamine were added. After stirring for another 30 minutes, the mixture was cooled to room temperature and filtered to obtain a colorless and transparent liquid E (0.13% hydroxyl content).

[0057] 52.7 parts of E and 0.04 parts of 2% ethyl chloroplatinate solution were added to a four-necked flask equipped with a stirrer, thermometer, and condenser. The mixture was stirred and heated to 80°C under a nitrogen atmosphere. 47.3 parts of allyl polyether (MW=600, all EO, terminal acetyl) were added dropwise over 2 hours. After the addition was completed, the mixture was kept at the temperature until the SiH characteristic peak completely disappeared. Vacuum was applied at 80°C until the solid content (120°C) was >98%. The mixture was then cooled and discharged to obtain a pale yellow transparent liquid, which is the target product.

[0058] Example 4

[0059] This embodiment provides another reactive organosilicon polymer, the preparation method of which is as follows:

[0060] 310.5 parts of self-made double-ended hydrogen-containing polysiloxane (Mw=1050, SiH value 0.19%) and 0.16 parts of 2% ethyl chloroplatinate solution were added to a 500ml four-necked flask equipped with a stirrer, thermometer, and condenser. The temperature was raised to 80℃, and 89.5 parts of allyl methacrylate and 0.16 parts of hydroquinone premix were added dropwise over about 3 hours with stirring. After the addition was complete, the temperature was maintained at 80-90℃ until the SiH characteristic peak completely disappeared. Then, the solid content (120℃) was evacuated at 80℃ until it was >98%, resulting in a colorless, low-viscosity, transparent liquid F.

[0061] 70 parts of F and 20 parts of high-hydrogen silicone oil 202 (domestic, 1.5% hydroxyl value) and 10 parts of octamethylcyclotetrasiloxane were added to a four-necked flask equipped with a stirrer, thermometer, and condenser. The mixture was stirred and heated to 50°C under a nitrogen atmosphere. 0.88 parts of 10% trifluoromethanesulfonate ethyl acetate solution were added. After reacting for 5 hours, 0.10 parts of triethylamine were added. The mixture was stirred for another 30 minutes and then cooled to room temperature. The mixture was filtered to obtain a colorless and transparent liquid G (0.30% hydroxyl value).

[0062] 26.6 parts of G and 0.04 parts of 2% chloroplatinic acid acetate solution were added to a four-necked flask equipped with a stirrer, thermometer, and condenser. Under nitrogen atmosphere protection, the mixture was stirred and heated to 80°C. 73.4 parts of allyl polyether (MW=800, EO:PO=3:1, methyl-terminated) were added dropwise over 2 hours. After the addition was completed, the mixture was kept at the temperature until the SiH characteristic peak completely disappeared. Vacuum was applied at 80°C until the solid content (120°C) was >98%. The mixture was then cooled and discharged to obtain a pale yellow transparent liquid, which is the target product.

[0063] Comparative Example 1

[0064] In a 250ml four-necked flask equipped with a stirrer, thermometer, and condenser, 90 parts of a double-ended hydrogen-containing polysiloxane (Mw = 2500, SiH value 0.08%) and 0.04 parts of a 2% ethyl chloroplatinate solution were added. The temperature was raised to 80℃, and 10 parts of allyl methacrylate and 0.04 parts of hydroquinone premix were added dropwise over 1 hour with stirring. After the addition was complete, the temperature was maintained at 80-90℃ for 2 hours until the SiH characteristic peak completely disappeared. Then, the flask was evacuated at 80℃ until the solid content (120℃) was >98%, resulting in a colorless, low-viscosity, transparent liquid.

[0065] Comparative Example 2

[0066] In a 250ml four-necked flask equipped with a stirrer, thermometer, and condenser, 31.19 parts of a self-made double-ended hydrogen-containing polysiloxane with side chains (Mw = 2860, SiH value 0.28%) and 0.04 parts of a 2% ethyl chloroplatinate solution were added. Under a nitrogen atmosphere, 65.5 parts of allyl polyether (MW = 1000, EO:PO = 3:1, terminal methyl) were added dropwise over 2 hours. After the addition was completed, the temperature was raised to 130℃ and held for 2 hours. Then, the temperature was lowered to 80℃ and 3.31 parts of allyl methacrylate and 0.04 parts of hydroquinone premix were added dropwise. After the addition was completed, the temperature was maintained at 80℃ until the Si-H characteristic peaks completely disappeared. Vacuum was then applied until the solid content (120℃) was >98%. The product was cooled and discharged to obtain a pale yellow transparent liquid.

[0067] Product application performance testing:

[0068] The products of Examples 1 to 4, and the products of Comparative Example 1 and Comparative Example 2 were added to different UV varnish systems at an addition amount of 0.3 wt% (with the same effective fraction). After sealing, the products were shaken in a shaker for 10 minutes and then observed and their application performance was evaluated.

[0069] The UV varnish formulation is shown in Table 1.

[0070] Table 1

[0071]

[0072] Note: Except for 1173D, which is supplied by BASF, all other raw materials mentioned in the above formulations are supplied by Changxing Special Materials (Suzhou) Co., Ltd. 621A-80: Epoxy acrylate; EM221: 1,6-hexanediol diacrylate; EM231: Trimethylolpropane triacrylate; 1173D: Photoinitiator; 6420-TF: Tertiary amine co-initiator; 6316: Modified polyester acrylate; TPGDA: Tripropylene glycol diacrylate; 611B-85: Polyurethane acrylate.

[0073] The application performance evaluation methods and standards are as follows:

[0074] Defoaming performance: The liquid level before shaking is recorded as H0, and the final bubble height after shaking is recorded as the liquid level height H1. The liquid level height change rate (%) = (H1-H0) / H0*100%. The defoaming ability is evaluated based on the liquid level height change rate. Defoaming ability level classification standard: 1: 0-1%; 2: 1-5%; 3: 5-15%; 4: 15-30%; 5: >30%; +: better; -: worse; where the smaller the value, the better the defoaming effect, and the larger the value, the worse the defoaming effect.

[0075] Defoaming performance: After the above-mentioned shaken test samples were left to stand for 1 hour, the bubble condition was observed and graded. The grading criteria were as follows: A: No bubbles at all; B: Almost no bubbles; C: Few bubbles, only some bubbles in the upper liquid layer; D: Many bubbles and not very dense; E: Many bubbles, no liquid visible; +: Better; -: Worse.

[0076] Clarity (Compatibility Performance): After standing until no more bubbles remain, observe the light transmission and grade it according to the following criteria: 1: Clear and transparent; 2: Cloudy, hazy, but light-transmitting, objects on the other side can be seen through the bottle; 3: Severely cloudy, but still partially transparent; 4: Cloudy, the bottom of the bottle can be slightly seen when looking down; 5: Cloudy and completely opaque; +: Better; -: Worse.

[0077] Leveling and anti-cavity tests:

[0078] The varnish containing the test sample was scraped onto the polyester sheet using a 60μm wire rod.

[0079] The leveling evaluation criteria are as follows: Level 1: The coating is smooth, continuous, and flat; Level 2: The coating is relatively smooth and continuous, but upon close inspection, there may be slight unevenness; Level 3: The coating surface is not very smooth or flat; Level 4: The coating has orange peel or orange texture; Level 5: The coating has pinholes.

[0080] The criteria for evaluating and classifying shrinkage cavities are: presence or absence.

[0081] Slip rating: The smaller the number, the better the slip.

[0083] The evaluation results of defoaming, foam suppression, leveling and pinholes of the products of Examples 1 to 4, Comparative Example 1 and Comparative Example 2 on different UV clear varnish systems are summarized in Tables 2 to 4.

[0084] Table 2

[0085]

[0086] Table 3

[0087]

[0088] Table 4

[0089]

[0090] According to the results in Tables 2 to 4, the product of Example 2 has the best overall performance in different UV varnish systems, followed by the product of Example 1. Then, in order of overall performance from highest to lowest, the products of Example 3, Example 4, Comparative Example 1, and Comparative Example 2 are listed below.

[0091] Water contact angle test

[0092] The products of Examples 1 to 4, Comparative Example 1, and Comparative Example 2 were added to different UV clear varnish system spray plates at an addition amount of 0.2%, and the water contact angle was tested using a contact angle meter. The blank was the UV clear varnish without the above products. The test results are shown in Table 5.

[0093] Table 5

[0094]

[0095] Table 4 shows that, among the various UV varnish systems, the varnish containing the product of Example 2 has the largest water contact angle, followed by the varnish containing the product of Example 1, and then the varnish containing the product of Example 3, the varnish containing the product of Example 4, the varnish containing the product of Comparative Example 1, and the varnish containing the product of Comparative Example 2.

[0096] The application evaluation results above show that the reactive organosilicon polymer with a special structure prepared by the method of this invention has broad system compatibility. It exhibits advantages such as good wetting and leveling properties, anti-cratering, strong reduction of coating surface tension while maintaining long-term smoothness, and rapid defoaming in different varnish systems. The preparation method of this invention is simple, controllable, relatively lower in cost, safer, and more environmentally friendly.

[0097] The present invention has been described in detail above, with the aim of enabling those skilled in the art to understand and implement the invention. However, this description should not be construed as limiting the scope of protection of the invention. All equivalent changes or modifications made in accordance with the spirit and essence of the invention should be included within the scope of protection of the invention.

Claims

1. A method for preparing a reactive organosilicon polymer, characterized in that, The preparation method includes the following steps: (1) A modified silicone oil with acrylate functionalized ends was prepared by reacting linear silicone oil containing hydrogen at both ends with allyl methacrylate in the presence of a noble metal catalyst and a polymerization inhibitor. (2) The modified silicone oil with acrylate functionalized ends in step (1) is telomerized with high hydrogen content silicone oil and / or siloxane cyclic polymer to obtain side-chain hydrogen content silicone oil. (3) The side-chain hydrogen-containing silicone oil from step (2) is hydrosilylated with allyl polyether and / or allyl methacrylate to obtain the reactive organosilicon polymer.

2. The preparation method according to claim 1, characterized in that, The hydrogen silane content of the linear end-hydrogen-containing silicone oil is 0.05% to 0.1%; And / or, the silane-hydrogen value of the side-chain hydrogen-containing silicone oil is 0.1% to 0.3%; And / or, the reactive organosilicon polymer has no silane-hydrogen bonds.

3. The preparation method according to claim 1, characterized in that, The high-hydrogen-content silicone oil includes one or more of methyl fully hydrogen-containing silicone oil and methyl phenyl hydrogen-containing silicone oil; And / or, the siloxane cyclic body comprises one or more of tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexaalkylcyclotrisiloxane, hexaphenylcyclotrisiloxane, trimethyltriphenylcyclotrisiloxane, and tetramethyltetraphenylcyclotetrasiloxane; And / or, the allyl polyether has the following structural formula: Where m and n are integers and the number average molecular weight of the allyl polyether is 200–10000, and R4 is H, a straight-chain alkyl group containing 1–18 carbons, a branched alkyl group containing 3–18 carbons, or an acyl group containing 2–5 carbons. The allyl polyether has an HLB value of 1 to 18.

4. The preparation method according to claim 1, characterized in that, The noble metal catalyst includes one or more of platinum-based catalysts, rhodium-based catalysts, or cobalt-based catalysts; And / or, the polymerization inhibitor includes one or more of quinones, phenols, aromatic amines, or metal halide polymerization inhibitors.

5. The preparation method according to claim 1, characterized in that, The noble metal catalyst includes C7H5Cl2NPt, [(CH3)2-CH=CH2]3Pt2, H2PtCl6·6H2O, and C8H 18 One or more of the following: OPtSi, PtCl2(PPh3)2, Pt(PPh3)4, RhCl(PPh3)3, RhCl2(PPh3)2, Cl2(Pcy3)2Ru=CHPh, and Co(CO)8; And / or, the polymerization inhibitor includes one or more of p-methoxyphenol, hydroquinone, phenothiazine, 2,4-diisobutyl-6-methylphenol, p-tert-butylcatechol, p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, or CuCl2.

6. The preparation method according to claim 1, characterized in that, The reaction temperature of step (1) is 80-90°C; and / or the reaction temperature of step (2) is 40-60°C; and / or the reaction temperature of step (3) is 80-90°C.

7. The reactive organosilicon polymer prepared by the preparation method according to any one of claims 1 to 6, characterized in that, The reactive organosilicon polymer has the following structural formula: Where R1 and R2 are alkyl groups containing 1 to 4 carbon atoms or unsubstituted phenyl groups, and R1 and R2 may be the same or different. A is R3 is H or methyl. B is R4 is H, a straight-chain alkyl group containing 1 to 18 carbons, a branched alkyl group containing 3 to 18 carbons, or an acyl group containing 2 to 5 carbons; m is an integer from 0 to 100; n is an integer from 0 to 150; m and n are not both 0. x takes integers from 0 to 300, y takes integers from 0 to 20, and z takes integers from 1 to 100.

8. The application of the reactive organosilicon polymer as described in claim 7 as an aid in the preparation of radiation curing systems.

9. The application according to claim 8, characterized in that, The radiation curing system includes unsaturated polyester coatings or inks, epoxy acrylic coatings or inks, polyurethane acrylic coatings or inks, polyester acrylic coatings or inks, polyether acrylic coatings or inks, and acrylic coatings or inks.

10. The application according to claim 8, characterized in that, The reactive organosilicon polymer is used in the radiation curing system at an amount of 0.1–0.5 wt%.

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