Acrylate modified polyether block silicone oil and preparation method thereof

Abstract

The invention discloses acrylate modified polyether block silicone oil and a preparation method thereof. The acrylate modified polyether block silicone oil is prepared by reacting an epoxy polyether monomer with hydrogen-containing silicone oil in the presence of a catalyst to synthesize epoxy polyether block silicone oil, the epoxy polyether block silicone oil reacts with (methyl) acrylic acid in the presence of a polymerization inhibitor and a catalyst to obtain the acrylate modified polyether block silicone oil. The acrylate modified polyether block silicone oil integrates the advantages of acrylate modified silicone oil and epoxy modified silicone oil, an acrylate functional group is short in curing time, an epoxy functional group is not subjected to oxygen inhibition and the like, and a polyether unit is directly grafted into a silicone oil structure, so that the problem of poor compatibility of a polyether diluting monomer and the acrylate modified silicone oil can be avoided. Epoxy polyether group modification can improve anchoring performance on a film / paper base material, end-position and side-position acrylic acid modification is higher in reaction activity compared with single acrylic acid modified silicone oil, curing efficiency can be improved, crosslinking degree can be increased, and residual adhesion rate can be increased.

Description

Technical Field

[0001] The invention relates to polyether block silicone oil, in particular to an acrylate modified polyether block silicone oil and a preparation method thereof. Background Art

[0002] Silicone release agents are mainly divided into condensation type and addition type according to different crosslinking systems. In addition, with the development of technology, new silicone release agents such as UV light curing have also emerged. At present, the mainstream on the market is still addition type silicone release agent, but UV light curing silicone release agent has obvious advantages in curing on substrates that are not resistant to high temperatures.

[0003] Epoxy acrylic resin is widely used in coatings, inks, adhesives and other fields due to its excellent adhesion, gloss retention, color retention, outdoor durability and chemical resistance. However, the performance of a single epoxy acrylic resin may not be sufficient to meet the needs in certain applications, such as those requiring good demolding properties. Therefore, epoxy acrylic resin is combined with silicone oil to prepare epoxy acrylic release silicone oil, which can combine the advantages of epoxy acrylic resin and silicone oil.

[0004] Existing UV light-curing silicone release agents are classified into free radical type and cationic type according to the type of curing. According to the free radical curing classification, it is mainly the grafting of acrylate groups on the end groups or side chains of the prepolymer, and according to the cationic type classification, it is mainly the grafting of epoxy groups on the end groups or side chains of the prepolymer. Among them, the free radical type cures faster, but is easily inhibited by oxygen and has a larger volume shrinkage rate. The cationic type cures without oxygen inhibition and has a small volume shrinkage rate, but cures slower. Therefore, grafting a part of the end side silicone oil with acrylic groups and a part of the end side silicone oil with epoxy groups can combine the advantages of both.

[0005] Patent CN103030810A discloses that acrylic acid-modified polysiloxane is obtained by adding acrylic acid to epoxy polysiloxane at both ends under the catalysis of sodium hydroxide. However, this structure has acrylate groups only at both ends, so the anchoring performance is slightly poor.

[0006] Patent CN115584204B discloses that hexamethyldisiloxane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, etc. are first used in the presence of sulfuric acid as a catalyst to obtain partially side-chain hydrogenated silicone oil, then allyl glycidyl ether is used to graft the partially side-chain hydrogenated silicone oil, and finally acrylic acid is used in the presence of tetrabutylammonium bromide as a catalyst to obtain epoxy acrylic acid-modified silicone oil. However, the epoxy acrylic acid-modified silicone oil uses strong acid such as sulfuric acid in the synthesis process, and the synthesis process is complicated.

[0007] Patent CN111500189B discloses that silicone oil grafted with acrylate at both ends is blended with silicone oil grafted with acrylate at some side chains to obtain UV-curable acrylate silicone oil. However, this method has the problem of poor compatibility between the two. Summary of the invention

[0008] In order to solve the shortcomings and deficiencies of the prior art, one of the objects of the present invention is to provide an acrylate-modified polyether block silicone oil, which can improve the anchoring performance to the substrate on the one hand, and reduce the volume shrinkage of the acrylate silicone release agent after curing on the other hand, thereby improving the residual bonding rate.

[0009] One of the purposes of the present invention is achieved through the following technical solutions:

[0010] An acrylate-modified polyether block silicone oil, wherein the acrylate-modified polyether block silicone oil has the following structural formula:

[0011]

[0012] Among them, x+y+z=20~300, x,z=3~20, and x, y and z are all integers.

[0013]

[0014] RH or CH3

[0015]

[0016] Wherein, p+q=1-50, and p and q are both integers.

[0017] A second object of the present invention is to provide a method for preparing acrylate modified polyether block silicone oil.

[0018] This is achieved through the following technical solutions:

[0019] A method for preparing an acrylate-modified polyether block silicone oil, characterized in that it comprises the following steps:

[0020] 1) The epoxy polyether monomer and catalyst A are mixed and stirred, the temperature is raised to 70-100° C., hydrogen-containing silicone oil is added, and the reaction is carried out for 5-20 hours to obtain an intermediate epoxy polyether block silicone oil;

[0021] Wherein, the epoxy polyether monomer structural formula is:

[0022]

[0023] Where p+q=1-50, p and q are both integers;

[0024] The structural formula of hydrogen silicone oil is:

[0025]

[0026] Wherein m+n=20-300, m and n are both integers;

[0027] 2) Add an inhibitor to the epoxy polyether block silicone oil in step 1), stir, heat to 30-70°C, add a mixed solution of (meth)acrylic acid and catalyst B, heat to 70-120°C, react for 5-30 hours, remove unreacted (meth)acrylic acid by distillation under reduced pressure, and then filter to obtain an acrylate-modified polyether block silicone oil having formula (I).

[0028] In the step 1), the Si-H molar ratio of the epoxy polyether monomer to the hydrogen-containing silicone oil is 1.5 to 1:1, the catalyst A is a chloroplatinic acid catalyst, 5000 ppm, and the Pt concentration is 10 to 20 ppm.

[0029] In the step 2):

[0030] The amount of the polymerization inhibitor is 0 to 5% of the mass of the (meth)acrylic acid.

[0031] The molar ratio of the (meth) acrylic acid to the epoxy functional group in the epoxy polyether block silicone oil is 1-2:1.

[0032] The polymerization inhibitor is an alkylphenol, such as 1,4-hydroquinone, p-methoxyphenol, 2,6-di-tert-butylhydroxytoluene, 4,4'-dioxydiphenol, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 3-methyl-4-isopropylphenol, 2,4,5-trihydroxybenzophenone, 2,6-di-tert-butylphenol, 2,5-di-tert-amylhydroquinone, 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-(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).

[0033] The catalyst B accounts for 0-5% of the total mass of the reaction system.

[0034] The catalyst B is one of chromium acetylacetonate, 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 and the like.

[0035] Beneficial effects of the present invention:

[0036] It can combine the advantages of acrylate-modified silicone oil and epoxy-modified silicone oil, such as the short curing time of acrylate functional group and the fact that epoxy functional group is not inhibited by oxygen. The polyether unit is directly grafted into the silicone oil structure to avoid the problem of poor compatibility between polyether diluent monomer and acrylate-modified silicone oil.

[0037] Epoxy polyether group modification can improve the anchoring performance on the film / paper substrate. The end and side acrylic acid modification has higher reactivity than single acrylic acid modified silicone oil, which can improve the curing efficiency, increase the cross-linking degree, and thus improve the residual bonding rate. DETAILED DESCRIPTION

[0038] The present invention is further described below in conjunction with specific examples, but the present invention is not limited to the following examples. The methods described are conventional methods unless otherwise specified. The materials described can be obtained from public commercial channels unless otherwise specified.

[0039] The acrylate-modified polyether block silicone oil provided by the present invention has the following structural formula:

[0040]

[0041] Among them, x+y+z=20~300, x,z=3~20, and x, y and z are all integers.

[0042]

[0043] R1H or CH3

[0044]

[0045] Wherein, p+q=1-50, and p and q are both integers.

[0046] The epoxy polyether monomer structural formula used in the present invention is:

[0047]

[0048] Where p+q=1-50, p and q are both integers;

[0049] The structural formula of the hydrogenated silicone oil used in the present invention is:

[0050]

[0051] Wherein m+n=20-300, m and n are both integers.

[0052] Example 1

[0053] 1) 49.28 parts of allyl glycidyl polyether (p=0, q=1) and 10 ppm platinum concentration of chloroplatinic acid were stirred evenly, the temperature was raised to 70°C, 100 parts of hydrogenated silicone oil (m=3, n=20) were slowly added dropwise, and 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.

[0054] 2) 100 parts of the intermediate of step 1) and 1% of p-methoxyphenol by weight of acrylic acid are stirred evenly, and the temperature is raised to 30° C., and a mixture of 13.92 parts of acrylic acid and 0.5% of the total weight of tetrabutylammonium bromide of the reactants is added dropwise. After the addition is completed, the temperature is raised to 70° C. and the reaction is carried out for 20 hours. The reaction mixture is distilled under reduced pressure at 100° C. and then filtered to obtain acrylate-modified polyether block silicone oil.

[0055] Example 2

[0056] 1) 177.84 allyl glycidyl polyether (p=5, q=20) and 10 ppm platinum concentration of chloroplatinic acid were stirred evenly, the temperature was raised to 70°C, 100 parts of hydrogenated silicone oil (m=3, n=50) were slowly added dropwise, and the reaction was carried out for 6 hours. After the reaction was completed, an intermediate was obtained.

[0057] 2) 100 parts of the intermediate of step 1) and 1% of 1,4-hydroquinone by weight of acrylic acid were stirred evenly, and the temperature was raised to 40° C., and a mixture of 3.42 parts of acrylic acid and 0.5% of triethylamine by weight of the feed was added dropwise. After the addition was completed, the temperature was raised to 80° C. and the reaction was carried out for 16 hours. The reaction mixture was distilled under reduced pressure at 100° C. and then filtered to obtain acrylate-modified polyether block silicone oil.

[0058] Example 3

[0059] 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 hydrogenated silicone oil (m=3, n=100) were slowly added dropwise at 70° C. and reacted for 6 hours to obtain an intermediate after the reaction was completed.

[0060] 2) 100 parts of the intermediate of step 1) and 1% of 4-hydroxymethyl-2,6-di-tert-butylphenol by weight of acrylic acid are stirred evenly, and the temperature is raised to 50° C., and a mixture of 2.06 parts of acrylic acid and 0.5% of triethylbenzylammonium bromide by weight of the feed is added dropwise. After the addition is completed, the temperature is raised to 90° C. and the reaction is carried out for 10 hours. The reaction mixture is distilled under reduced pressure at 100° C. and then filtered to obtain acrylate-modified polyether block silicone oil.

[0061] Example 4

[0062] 1) 143.2 parts of allyl glycidyl polyether (p=25, q=25) and 10 ppm of chloroplatinic acid catalyst were stirred evenly, the temperature was raised to 70°C, 10 parts of hydrogenated silicone oil (m=10, n=20) were slowly added dropwise, and the reaction was carried out for 6 hours. After the reaction was completed, an intermediate was obtained.

[0063] 2) 100 parts of the intermediate of step 1) and 1% of the mass of acrylic acid in 4,4'-bis(2,6-dibutylphenol) were stirred evenly, and the temperature was raised to 30°C, and a mixture of 2.79 parts of acrylic acid and 1% of the mass of chromium acetylacetonate was added dropwise. After the addition was completed, the temperature was raised to 100°C and the reaction was carried out for 20 hours. The reaction mixture was distilled under reduced pressure at 100°C, and then filtered to obtain acrylate-modified polyether block silicone oil.

[0064] Example 5

[0065] 1) 150.76 parts of allyl glycidyl ether and 10 ppm of chloroplatinic acid catalyst were stirred evenly, the temperature was raised to 70° C., 20 parts of hydrogenated silicone oil (m=8, n=50) were slowly added dropwise, and the reaction was carried out for 6 hours. After the reaction was completed, an intermediate was obtained.

[0066] 2) 100 parts of the intermediate of step 1) and 1% of the mass of acrylic acid 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol) were stirred evenly, and the temperature was raised to 40°C, and a mixture of 2.5 parts of acrylic acid and 1% of the mass of N,N-dimethylbenzylamine was added dropwise. After the addition was completed, the temperature was raised to 80°C and the reaction was carried out for 16 hours. The reaction mixture was distilled under reduced pressure at 100°C and then filtered to obtain acrylate-modified polyether block silicone oil.

[0067] Example 6

[0068] 1) 188.4 parts of allyl glycidyl polyether (p=35, q=15) and 10 ppm of chloroplatinic acid catalyst were stirred evenly, the temperature was raised to 70°C, 50 parts of hydrogenated silicone oil (m=10, n=100) were slowly added dropwise, and the reaction was carried out for 6 hours. After the reaction was completed, an intermediate was obtained.

[0069] 2) 100 parts of the intermediate of step 1) and 1% of 2,5-di-tert-butylhydroquinone by weight of acrylic acid were stirred evenly, and the temperature was raised to 50° C., and a mixture of 2.49 parts of acrylic acid and 1% of triphenylphosphine by weight of the feed was added dropwise. After the addition was completed, the temperature was raised to 90° C. and reacted for 20 hours. The reaction mixture was distilled under reduced pressure at 100° C. and then filtered to obtain acrylate-modified polyether block silicone oil.

[0070] Comparative Example 1

[0071] 1) 3.52 parts of allyl glycidyl ether and 10 ppm of chloroplatinic acid catalyst were stirred evenly, and the temperature was raised to 70° C. and 100 parts of hydrogenated silicone oil (hydrogen content 0.028%) were slowly added dropwise to react for 6 hours. After the reaction was completed, the intermediate was obtained by vacuum distillation.

[0072] 2) 100 parts of the intermediate of step 1) and 1% of 1,4-hydroquinone by weight of acrylic acid were stirred evenly, and the temperature was raised to 30° C., and a mixture of 2.15 parts of acrylic acid and 1% of triphenylphosphine by weight of the feed was added dropwise. After the addition was completed, the temperature was raised to 90° C. and reacted for 20 hours. The reaction mixture was distilled under reduced pressure at 100° C. and then filtered to obtain acrylate-modified polyether block silicone oil.

[0073] Comparative Example 2

[0074] 1) 8.41 parts of allyl glycidyl ether and 10 ppm of chloroplatinic acid catalyst were stirred evenly, the temperature was raised to 70° C., 100 parts of partially side-chain hydrogenated silicone oil (hydrogen content 0.067%) were slowly added dropwise, and the reaction was carried out for 6 hours. After the reaction was completed, the intermediate was obtained by vacuum distillation.

[0075] 2) 100 parts of the intermediate of step 1) and 1% of 1,4-hydroquinone by weight of acrylic acid were stirred evenly, and the temperature was raised to 30° C., and a mixture of 4.93 parts of acrylic acid and 1% of triphenylphosphine by weight of the feed was added dropwise. After the addition was completed, the temperature was raised to 90° C. and reacted for 20 hours. The reaction mixture was distilled under reduced pressure at 100° C. and then filtered to obtain acrylate-modified polyether block silicone oil.

[0076] Performance Testing

[0077] Take 100 parts of acrylate-modified polyether block silicone oil in Examples 1 to 6 and Comparative Examples 1 to 2 respectively, add 2 parts of 1173 photoinitiator, stir evenly at room temperature, then coat on a clean PET film with a 1.5 μm wire rod, expose with ultraviolet light of 365 nm wavelength for 3 seconds, and prepare for performance testing.

[0078] The room temperature peeling force test method, the residual adhesion rate of the release agent, and the anchoring test method are as follows:

[0079] 1. Test method for room temperature peeling force of release agent: stick TESA 7475 tape on the tested silicon-coated release paper according to the standard method, cut into strips according to the shape of the tape, and then press back and forth three times with a 2kg rubber roller. Press the treated tape with a 20g / cm2 standard stainless steel bar at room temperature for 20 hours, and then test it with a release force tester after 4 hours at room temperature. The tensile force at a tensile speed of 30cm / min and a tensile angle of 180 degrees is the room temperature peeling force.

[0080] 2. Test method for residual bonding rate of release agent:

[0081] (1) Stick Nitto 31B tape on the silicon-coated release paper to be tested according to the standard method, cut it into long strips according to the shape of the tape, and then press it back and forth three times with a 2kg rubber roller. Press the treated tape with a 20g / cm2 standard stainless steel bar in a 70℃ oven for 20 hours, take it out and let it stand for 1 hour.

[0082] (2) Remove the Nitto 31B tape from the release paper and stick it on a clean PET film according to the standard method. After 1.5 hours, test it with a release force tester. The tensile force at a tensile speed of 30 cm / min and a tensile angle of 180° is recorded. After repeating the experiment multiple times, the average release force value is calculated and recorded as f2.

[0083] (3) Apply Nitto 31B tape directly to a clean PET film according to the standard method. After 1.5 hours, test it with a peel force tester. The tensile force at a tensile speed of 30 cm / min and a tensile angle of 180° is recorded. After repeating the experiment multiple times, the average peel force value is calculated and recorded as f1.

[0084] (4) Residual bonding rate = f2 / f1×100%.

[0085] 3. Test method for anchorage:

[0086] Place the cured release film flat on a horizontal table, then rub the surface of the release film back and forth at 45 degrees with your index finger for a total of 20 times. If the silicon falls off severely below 20 times, it means the anchoring is poor; if the silicon does not fall off or falls off slightly after 20 times, it means the anchoring is good.

[0087] The performance test results of Examples 1 to 3 and the comparative example are as follows:

[0088]

[0089] In summary, the acrylate modified polyether block silicone release films obtained in Examples 1 to 6 have room temperature peeling forces measured by the 180° peeling method of 20 to 100 g / 25 mm, and the residual bonding rate is above 90%. The room temperature peeling force of Comparative Example 1 is 6 g / 25 mm, but the silicon is severely lost, and the residual bonding rate is less than 90%. The room temperature peeling force of Comparative Example 2 is 40 g / 25 mm, the residual bonding rate is less than 90%, and the silicon is slightly lost.

[0090] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An acrylate-modified polyether block silicone oil, characterized in that: The acrylate modified polyether block silicone oil has the following structural formula: Wherein, x+y+z=20-300, x, z=3-20, x, y and z are all integers; R1=H or CH3 Wherein, p+q=1-50, and p and q are both integers.

2. The method for preparing the acrylate-modified polyether block silicone oil according to claim 1, characterized in that: The following steps are involved: 1) The epoxy polyether monomer and catalyst A are mixed and stirred, the temperature is raised to 70-100° C., hydrogen-containing silicone oil is added, and the reaction is carried out for 5-20 hours to obtain an intermediate epoxy polyether block silicone oil; Wherein, the epoxy polyether monomer structural formula is: Where p+q=1-50, p and q are both integers; The structural formula of the hydrogen-containing silicone oil is: Wherein m+n=20-300, m and n are both integers; 2) Adding a polymerization inhibitor to the epoxy polyether block silicone oil in step 1), stirring, heating to 30-70° C., adding a mixed solution of (meth)acrylic acid and catalyst B, heating to 70-120° C., reacting for 5-30 hours, removing unreacted (meth)acrylic acid by vacuum distillation, and then filtering to obtain an acrylate-modified polyether block silicone oil.

3. The method for preparing the acrylate-modified polyether block silicone oil according to claim 2, characterized in that: In the step 1), the Si-H molar ratio of the epoxy polyether monomer to the hydrogen-containing silicone oil is 1.5 to 1:1, the catalyst A is a chloroplatinic acid catalyst, 5000 ppm, and the Pt concentration is 10 to 20 ppm.

4. The method for preparing the acrylate-modified polyether block silicone oil according to claim 2, characterized in that: In the step 2), the amount of the polymerization inhibitor is 0 to 5% of the mass of the (meth)acrylic acid.

5. The method for preparing the acrylate-modified polyether block silicone oil according to claim 2, characterized in that: In the step 2), the molar ratio of the (meth)acrylic acid to the epoxy functional group in the epoxy polyether block silicone oil is 1-2:

1.

6. The method for preparing the acrylate-modified polyether block silicone oil according to claim 2, characterized in that: In the step 2), the polymerization inhibitor is an alkylphenol.

7. The method for preparing the acrylate-modified polyether block silicone oil according to claim 2, characterized in that: In the step 2), the alkylphenols include 1,4-hydroquinone, p-methoxyphenol, 2,6-di-tert-butylhydroxytoluene, 4,4'-dioxydiphenol, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 3-methyl-4-isopropylphenol, 2,4,5-trihydroxybenzophenone, 2,6-di-tert-butylphenol, 2,5-di-tert-amylhydroquinone, 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-(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).

8. The method for preparing the acrylate-modified polyether block silicone oil according to claim 2, characterized in that: In the step 2), the catalyst B accounts for 0-5% of the total mass of the reaction system.

9. The method for preparing the acrylate-modified polyether block silicone oil according to claim 2, characterized in that: In the step 2), the catalyst B is one of chromium acetylacetonate, 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.

Images