An acrylate-modified polyether block silicone oil and its preparation method
By preparing polyether block silicone oil with (meth)acrylate and epoxy functional groups, the problems of large volume shrinkage and insufficient anchoring performance of UV-curable silicone release agents on high-temperature resistant substrates were solved, achieving rapid curing and high residual adhesion.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HUIZHOU YONGZHUO TECH CO LTD
- Filing Date
- 2024-10-10
- Publication Date
- 2026-06-30
AI Technical Summary
Existing UV-curable silicone release agents suffer from large volume shrinkage and insufficient anchoring performance when cured on substrates that are not resistant to high temperatures, and their synthesis process is complex or has poor compatibility.
By reacting epoxy polyether monomers with hydrogen-containing silicone oil to generate intermediate epoxy polyether block silicone oil, and then reacting it with (meth)acrylic acid, and adding polymerization inhibitors and catalysts, a polyether block silicone oil with (meth)acrylate and epoxy functional groups is prepared, which improves anchoring performance and reduces curing volume shrinkage.
It achieves rapid curing on high-temperature resistant substrates and improves residual adhesion, avoiding the problem of poor compatibility and improving anchoring performance and curing efficiency.
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Abstract
Description
Technical Field
[0001] This invention relates to polyether block silicone oils, and more particularly to an acrylate-modified polyether block silicone oil and its preparation method. Background Technology
[0002] Based on their crosslinking systems, silicone release agents are mainly classified into condensation-type and addition-type release agents. Furthermore, with technological advancements, new types of silicone release agents, such as UV-curable ones, have emerged. Currently, addition-type silicone release agents are the mainstream in the market, but UV-curable silicone release agents offer significant advantages for curing on substrates that are not heat-resistant.
[0003] Epoxy acrylic resins are widely used in coatings, inks, and adhesives due to their excellent adhesion, gloss retention, color retention, outdoor durability, and chemical resistance. However, in some applications, such as those requiring good mold release properties, the performance of epoxy acrylic resin alone may be insufficient. Therefore, combining epoxy acrylic resin with silicone oil to prepare epoxy acrylic release silicone oil combines the advantages of both.
[0004] Existing UV-curable silicone release agents are classified into free radical and cationic types according to their curing method. Free radical type release agents are mainly classified by grafting acrylate groups onto the end groups or side chains of the prepolymer, while cationic type release agents are mainly classified by grafting epoxy groups onto the end groups or side chains of the prepolymer. Free radical type release agents cure faster but are more susceptible to oxygen inhibition and have a larger volume shrinkage rate, while cationic type release agents are not affected by oxygen inhibition and have a smaller volume shrinkage rate, but cure more slowly. Therefore, grafting acrylate groups onto a portion of the end-side silicone oil and epoxy groups onto another portion can combine the advantages of both.
[0005] Patent CN103030810A discloses the method of obtaining acrylic acid-modified polysiloxane by adding acrylic acid to epoxy polysiloxane at both ends under the catalysis of sodium hydroxide. However, this structure only has acrylate groups at both ends, so the anchoring performance is slightly worse.
[0006] Patent CN115584204B discloses a method of first obtaining partially hydrogen-containing silicone oils with hexamethyldisiloxane, octamethylcyclotetrasiloxane, and tetramethylcyclotetrasiloxane under the catalysis of sulfuric acid, then grafting the partially hydrogen-containing silicone oils with allyl glycidyl ether, and finally obtaining epoxy acrylic acid modified silicone oils with acrylic acid under the catalysis of tetrabutylammonium bromide. However, the synthesis of this epoxy acrylic acid modified silicone oil uses sulfuric acid, a strong acid, and the synthesis process is complex.
[0007] Patent CN111500189B discloses a method of blending silicone oil with acrylate grafted at both ends and silicone oil with acrylate grafted on some sides to obtain UV-curable acrylate silicone oil. However, this method has the problem of poor compatibility between the two. Summary of the Invention
[0008] To address the shortcomings and deficiencies of existing technologies, one objective of this invention is to provide an acrylate-modified polyether block silicone oil that can improve the anchoring performance to the substrate and reduce the volume shrinkage rate of the acrylate silicone release agent after curing, thereby increasing the residual adhesion rate.
[0009] One of the objectives of this invention is achieved through the following technical solution:
[0010] An acrylate-modified polyether block silicone oil, wherein the acrylate-modified polyether block silicone oil has the following structural formula:
[0011]
[0012] The second objective of this invention is to provide a method for preparing acrylate-modified polyether block silicone oil.
[0013] This can be achieved through the following technical solution:
[0014] A method for preparing an acrylate-modified polyether block silicone oil, characterized by comprising the following steps:
[0015] 1) Mix and stir epoxy polyether monomer and catalyst A, heat to 70-100℃, add hydrogen-containing silicone oil, and react for 5-20 hours to obtain intermediate epoxy polyether block silicone oil.
[0016] The epoxy polyether monomer has the following structural formula:
[0017]
[0018] 2) In step 1), add an inhibitor to the epoxy polyether block silicone oil, stir, heat to 30-70°C, add a mixture of (meth)acrylic acid and catalyst B, heat to 70-120°C, react for 5-30 hours, remove unreacted (meth)acrylic acid by vacuum distillation, and then filter to obtain acrylate-modified polyether block silicone oil with formula (Ⅰ).
[0019] In step 1), the Si-H molar ratio of epoxy polyether monomer to hydrogen-containing silicone oil is 1.5 to 1:1, and catalyst A is a chloroplatinic acid catalyst with a concentration of 5000 ppm and a Pt concentration of 10 to 20 ppm.
[0020] In step 2):
[0021] The amount of polymerization inhibitor is 0 to 5% of the mass of (meth)acrylic acid.
[0022] The molar ratio of epoxy functional groups in the (meth)acrylic acid and epoxy polyether block silicone oil is 1 to 2:1.
[0023] The polymerization inhibitor is an alkylphenol, such as 1,4-hydroquinone, p-methoxyphenol, 2,6-di-tert-butylhydroxytoluene, 4,4'-dioxodiphenol, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 3-methyl-4-isopropylphenol, 2,4,5-trihydroxybenzophenone, 2,6-di-tert-butylphenol, 2,5-di-tert-pentylhydroquinone, 2,5-di-tert-butylhydroquinone, 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butyl-α-dimethyl-p-cresol, 4,4'-bis(2,6-dibutylphenol), 2 One of the following: 2'-methylene-bis(4-ethyl-6-tert-butylphenol), 2,2'-methylene-(2,6-di-tert-butylphenol), 4,4'-methylene-(2,6-di-tert-butylphenol), 4,4'-butylene(3-methyl-6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 4,4'-thiobis(6-tert-butyl-o-cresol), and 2,2'-thiobis(4-methyl-6-tert-butylphenol).
[0024] Catalyst B accounts for 0-5% of the total mass of the reaction system.
[0025] The catalyst B is one of the following: chromium acetylacetone, chromium 2-ethylhexanoate, chromium acrylate, benzyltriethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium bromide, tetraethylammonium bromide, hexadecyltrimethylammonium bromide, trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, triethylbenzylammonium bromide, triethylamine, N,N-dimethylethanolamine, N,N-dimethylbenzylamine, triphenylphosphine, sodium hydroxide, potassium hydroxide, etc.
[0026] The beneficial effects of this invention are:
[0027] It combines the advantages of acrylate-modified silicone oil and epoxy-modified silicone oil, such as the short curing time of acrylate functional groups and the lack of oxygen inhibition of epoxy functional groups. The polyether unit is directly grafted into the silicone oil structure, avoiding the problem of poor compatibility between polyether diluent monomers and acrylate-modified silicone oil.
[0028] Epoxy polyether group modification can improve anchoring performance on film / paper substrates. End-position and side-position acrylic modification has higher reactivity than single acrylic modified silicone oil, which can improve curing efficiency, increase crosslinking degree, and thus improve residual adhesion. Detailed Implementation
[0029] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. Unless otherwise specified, the methods described are conventional methods. Unless otherwise specified, the materials described are all available from publicly available commercial sources.
[0030] The acrylate-modified polyether block silicone oil provided by this invention has the following structural formula:
[0031]
[0032] The epoxy polyether monomer used in this invention has the following structural formula:
[0033]
[0034] Example 1
[0035] 1) 49.28 parts of allyl glycidyl polyether (p=0, q=1) and 10 ppm of chloroplatinic acid with a platinum concentration were stirred evenly, and 100 parts of hydrogen-containing silicone oil (m=3, n=20) were slowly added dropwise to the mixture at 70°C. The reaction was carried out for 6 hours. After the reaction was completed, the intermediate epoxy polyether block silicone oil was obtained by vacuum distillation.
[0036] 2) Stir 100 parts of intermediate and 1% of p-methoxyphenol by mass of acrylic acid in step 1) until homogeneous. Heat to 30°C and dropwise add 13.92 parts of a mixture of acrylic acid and 0.5% of tetrabutylammonium bromide by mass of the total reactants. After the dropwise addition is completed, raise the temperature to 70°C and react for 20 hours. The reaction mixture is then distilled under reduced pressure at 100°C and filtered to obtain acrylate-modified polyether block silicone oil. Example
[0037] 1) 177.84 allyl glycidyl polyether (p=5, q=20) and 10 ppm platinum concentration of chloroplatinic acid were stirred evenly, and 100 parts of hydrogen-containing silicone oil (m=3, n=50) were slowly added dropwise to 70℃ and reacted for 6 hours. After the reaction was completed, the intermediate was obtained.
[0038] 2) Stir 100 parts of intermediate from step 1) and 1% of 1,4-hydroquinone by mass of acrylic acid evenly, heat to 40°C and dropwise add 3.42 parts of a mixture of acrylic acid and 0.5% of triethylamine by mass of the feed. After the dropwise addition is completed, raise the temperature to 80°C and react for 16 hours. The reaction mixture is then distilled under reduced pressure at 100°C and filtered to obtain acrylate-modified polyether block silicone oil. Example
[0039] 1) 149.63 parts of allyl glycidyl polyether (p=50, q=0) and 10 ppm of chloroplatinic acid catalyst were stirred evenly, and 100 parts of hydrogen-containing silicone oil (m=3, n=100) were slowly added dropwise to 70℃ and reacted for 6 hours. After the reaction was completed, the intermediate was obtained.
[0040] 2) Stir 100 parts of the intermediate from step 1) and 1% of 4-hydroxymethyl-2,6-di-tert-butylphenol by weight of acrylic acid until homogeneous. Heat the mixture to 50°C and add dropwise a mixture of 2.06 parts of acrylic acid and 0.5% of triethylbenzylammonium bromide by weight of the feed. After the addition is complete, raise the temperature to 90°C and react for 10 hours. The reaction mixture is then distilled under reduced pressure at 100°C and filtered to obtain acrylate-modified polyether block silicone oil. Example
[0041] 1) 143.2 parts of allyl glycidyl polyether (p=25, q=25) and 10 ppm of chloroplatinic acid catalyst were stirred evenly, and 10 parts of hydrogen-containing silicone oil (m=10, n=20) were slowly added dropwise to 70℃ and reacted for 6 hours. After the reaction was completed, the intermediate was obtained.
[0042] 2) Stir 100 parts of the intermediate from step 1) and 1% of 4,4'-bis(2,6-dibutylphenol) by mass of acrylic acid until homogeneous. Heat to 30°C and add dropwise 2.79 parts of a mixture of acrylic acid and 1% of chromium acetylacetone by mass of the feed. After the addition is complete, raise the temperature to 100°C and react for 20 hours. The reaction mixture is then distilled under reduced pressure at 100°C and filtered to obtain acrylate-modified polyether block silicone oil. Example
[0043] 1) Stir 150.76 parts of allyl glycidyl ether and 10 ppm of chloroplatinic acid catalyst evenly, heat to 70℃ and slowly add 20 parts of hydrogen-containing silicone oil (m=8, n=50) dropwise for 6 hours. After the reaction is completed, the intermediate is obtained.
[0044] 2) Stir 100 parts of the intermediate from step 1) and 1% of 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol) by mass of acrylic acid until homogeneous. Heat to 40°C and add dropwise 2.5 parts of a mixture of acrylic acid and 1% of N,N-dimethylbenzylamine by mass of the feed. After the addition is complete, raise the temperature to 80°C and react for 16 hours. The reaction mixture is then distilled under reduced pressure at 100°C and filtered to obtain acrylate-modified polyether block silicone oil. Example
[0045] 1) 188.4 parts of allyl glycidyl polyether (p=35, q=15) and 10 ppm of chloroplatinic acid catalyst were stirred evenly, and 50 parts of hydrogen-containing silicone oil (m=10, n=100) were slowly added dropwise to 70℃ and reacted for 6 hours. After the reaction was completed, the intermediate was obtained.
[0046] 2) Stir 100 parts of the intermediate from step 1) and 1% of 2,5-di-tert-butylhydroquinone by mass of acrylic acid until homogeneous. Heat to 50°C and add dropwise a mixture of 2.49 parts of acrylic acid and 1% of triphenylphosphine by mass of the feed. After the addition is complete, raise the temperature to 90°C and react for 20 hours. The reaction mixture is then distilled under reduced pressure at 100°C and filtered to obtain acrylate-modified polyether block silicone oil.
[0047] Comparative Example 1
[0048] 1) Stir 3.52 parts of allyl glycidyl ether and 10 ppm of chloroplatinic acid catalyst evenly, heat to 70℃ and slowly add 100 parts of hydrogen-containing silicone oil (0.028% hydrogen content) at both ends and react for 6 hours. After the reaction is completed, distill under reduced pressure to obtain the intermediate.
[0049] 2) Stir 100 parts of intermediate from step 1) and 1% of 1,4-hydroquinone by mass of acrylic acid evenly, heat to 30°C and dropwise add 2.15 parts of a mixture of acrylic acid and 1% of triphenylphosphine by mass of feed. After the dropwise addition is completed, raise the temperature to 90°C and react for 20 hours. The reaction mixture is then distilled under reduced pressure at 100°C and filtered to obtain acrylate-modified polyether block silicone oil.
[0050] Comparative Example 2
[0051] 1) Stir 8.41 parts of allyl glycidyl ether and 10 ppm of chloroplatinic acid catalyst evenly, heat to 70℃ and slowly add 100 parts of partially hydrogen-containing side-chain silicone oil (hydrogen content 0.067%) and react for 6 hours. After the reaction is completed, distill under reduced pressure to obtain the intermediate.
[0052] 2) Stir 100 parts of intermediate and 1% of 1,4-hydroquinone (by mass of acrylic acid) from step 1) evenly, heat to 30°C and dropwise add 4.93 parts of a mixture of acrylic acid and 1% of triphenylphosphine (by mass of feed). After the dropwise addition is completed, raise the temperature to 90°C and react for 20 hours. The reaction mixture is then distilled under reduced pressure at 100°C and filtered to obtain acrylate-modified polyether block silicone oil.
[0053] Performance testing
[0054] Take 100 parts of acrylate-modified polyether block silicone oil from Examples 1-6 and Comparative Examples 1-2 respectively, add 2 parts of 1173 photoinitiator, stir evenly at room temperature, then coat it on a clean PET film with a 1.5μm wire rod, expose it with 365nm wavelength ultraviolet light for 3s, and prepare for performance testing.
[0055] The methods for testing peel strength at room temperature, residual adhesion of release agent, and anchoring properties are as follows:
[0056] I. Room Temperature Peel Strength Test Method for Release Agent: Apply TESA 7475 tape to the silicone-coated release paper to be tested according to the standard method, cut it into long strips according to the tape shape, and then press it back and forth three times with a 2kg rubber roller. Then, test the treated tape with a 20g / cm... 2 The standard stainless steel strip is pressed at room temperature for 20 hours and left at room temperature for 4 hours. Then, it is tested with a release force tester. The tensile force at a tensile speed of 30 cm / min and a tensile angle of 180 degrees is the room temperature peel force.
[0057] II. Test method for residual adhesion rate of release agent:
[0058] (1) Apply Nitto 31B tape to the silicone-coated release paper to be tested according to the standard method, cut it into strips according to the tape shape, and then press it back and forth three times with a 2kg rubber roller. Then, apply 20g / cm... 2 The standard stainless steel strips are pressed in a 70℃ oven for 20 hours, then removed and left to stand for 1 hour.
[0059] (2) Tear the Nitto 31B tape off the release paper and apply it to a clean PET film using the standard method. After 1.5 hours, test the release force with a release force tester at a tensile speed of 30 cm / min and a tensile angle of 180°. Record the obtained peel force value. Repeat the experiment multiple times and calculate the average value of the release force, which is recorded as f2.
[0060] (3) Apply Nitto 31B tape directly to a clean PET film using the standard method. After 1.5 hours, test the release force using a peel force tester at a tensile speed of 30 cm / min and a tensile angle of 180°. Record the release force value. Repeat the experiment multiple times and calculate the average peel force value, which is denoted as f1.
[0061] (4) Residual adhesion rate = f2 / f1 × 100%.
[0062] III. Anchorage Testing Methods:
[0063] Place the cured release film flat on a horizontal table, then rub it back and forth 20 times with your index finger at a 45° angle. If the silicone peels off severely after less than 20 times, the anchoring is poor. If the silicone does not peel off or peels off slightly after 20 times, the anchoring is good.
[0064] The performance test results for Examples 1 to 3 and the comparative examples are as follows:
[0065]
[0066] In summary, the acrylate-modified polyether block silicone release films obtained in Examples 1-6 all exhibited room-temperature peel strengths between 20 and 100 g / 25 mm as measured by the 180° peel method, with residual adhesion rates exceeding 90%. Comparative Example 1 showed a room-temperature peel strength of 6 g / 25 mm, but suffered severe silicone shedding, with a residual adhesion rate below 90%. Comparative Example 2 showed a room-temperature peel strength of 40 g / 25 mm, with a residual adhesion rate below 90% and slight silicone shedding.
[0067] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.
Claims
1. An acrylate-modified polyether-blocked silicone oil characterized by, The acrylate-modified polyether block silicone oil has the following structural formula:
2. The method for preparing the acrylate-modified polyether block silicone oil according to claim 1, characterized in that, Includes the following steps: 1) Mix and stir epoxy polyether monomer and catalyst A, heat to 70-100℃, add hydrogen-containing silicone oil, and react for 5-20 hours to obtain intermediate epoxy polyether block silicone oil. The epoxy polyether monomer has the following structural formula: Where m+n = 20 to 300, and m and n are both integers; 2) In step 1), the epoxy polyether block silicone oil is mixed with a polymerization inhibitor, stirred, heated to 30-70°C, and a mixture of (meth)acrylic acid and catalyst B is added. The mixture is heated to 70-120°C and reacted for 5-30 hours. Unreacted (meth)acrylic acid is removed by vacuum distillation, and then filtered to obtain acrylate-modified polyether block silicone oil.
3. The method for preparing acrylate-modified polyether block silicone oil according to claim 2, characterized in that, In step 1), the Si-H molar ratio of epoxy polyether monomer to hydrogen-containing silicone oil is 1.5 to 1:1, and catalyst A is a chloroplatinic acid catalyst with a concentration of 5000 ppm and a Pt concentration of 10 to 20 ppm.
4. The method for preparing acrylate-modified polyether block silicone oil according to claim 2, characterized in that, In step 2), the amount of the polymerization inhibitor is 0 to 5% of the mass of (meth)acrylic acid.
5. The method for preparing acrylate-modified polyether block silicone oil according to claim 2, characterized in that, In step 2), the molar ratio of the epoxy functional groups in the (meth)acrylic acid and the epoxy polyether block silicone oil is 1 to 2:
1.
6. The method for preparing acrylate-modified polyether block silicone oil according to claim 2, characterized in that, In step 2), the polymerization inhibitor is an alkylphenol, 1,4-hydroquinone, p-methoxyphenol, 4,4'-dioxophenol, or 2,4,5-trihydroxybenzophenone.
7. The method for preparing acrylate-modified polyether block silicone oil according to claim 6, characterized in that, In step 2), the alkylphenols include 2,6-di-tert-butylhydroxytoluene, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 3-methyl-4-isopropylphenol, 2,6-di-tert-butylphenol, 2,5-di-tert-pentylhydroquinone, 2,5-di-tert-butylhydroquinone, 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butyl-α-dimethyl-p-cresol, 4,4'-bis(2,6-dibutylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), 2,2'-methylene- Any one of (2,6-di-tert-butylphenol), 4,4'-methylene-(2,6-di-tert-butylphenol), 4,4'-butylidene (3-methyl-6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), bis(3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 4,4'-thiobis(6-tert-butyl-o-cresol) and 2,2'-thiobis(4-methyl-6-tert-butylphenol).
8. The method for preparing acrylate-modified polyether block silicone oil according to claim 2, characterized in that, In step 2), catalyst B accounts for 0-5% of the total mass of the reaction system.
9. The method for preparing acrylate-modified polyether block silicone oil according to claim 2, characterized in that, In step 2), the catalyst B is one of the following: chromium acetylacetone, chromium 2-ethylhexanoate, chromium acrylate, benzyltriethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium bromide, tetraethylammonium bromide, hexadecyltrimethylammonium bromide, trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, triethylbenzylammonium bromide, triethylamine, N,N-dimethylethanolamine, N,N-dimethylbenzylamine, triphenylphosphine, sodium hydroxide, and potassium hydroxide.