Silicon resin composition as well as preparation method and application thereof

Abstract

The invention discloses a silicon resin composition as well as a preparation method and application thereof, and relates to the technical field of high polymer materials. The silicon resin composition disclosed by the invention is prepared from alpha, omega-dihydroxy polydimethylsiloxane, a ketoxime cross-linking agent, a treating agent and an auxiliary agent, the treating agent comprises alcohol anhydride oleate. According to the silicon resin composition, migration of a ketoxime cross-linking agent is avoided, the problem of oil production of an existing silicon resin product is solved, meanwhile, in the presence of the filler, the dispersity of the filler in a system can be improved through the use of the alcohol anhydride oleate, and the obtained silicon resin composition is good in mechanical property and adhesive property and good in mechanical property. Compared with the conventional ketoxime type sealant (RTV-1), the ketoxime type sealant has the advantages that the oil outlet phenomenon is reduced, and the ketoxime type sealant is high in mechanical property and adhesion and suitable for door and window sealing or electronic and electric appliance sealing.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a silicone resin composition and a preparation method and application thereof. Background Art

[0002] Silicone resin is mainly composed of siloxane bonds to form the main chain, and organic groups are connected to silicon atoms. This unique chemical structure gives silicone resin a variety of excellent properties. Among them, moisture-hardening silicone resin is a silicone resin that uses moisture in the air to initiate curing. It has excellent resistance to ultraviolet light, weathering and high temperature and humidity. Compared with other types of silicone resins as sealants, its durability under harsh conditions is more prominent, especially single-component room temperature curing silicone sealant (RTV-1), which has excellent aging resistance due to the more stable silicon oxygen bonds in its structure. Ketoxime RTV-1 glue is one of the most widely used silicone sealant varieties. However, due to the poor compatibility of ketoxime crosslinkers with α, ω-dihydroxy polysiloxane, ketoxime crosslinkers are easy to migrate and precipitate during storage, resulting in oiling, especially when using hard packaging such as HDPE, the oiling phenomenon is more obvious, which not only affects the use of the product, but also the precipitation of ketoxime crosslinkers will reduce the performance of the product to a certain extent. Summary of the invention

[0003] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the purpose of the present invention is to provide a silicone resin composition, which uses alcohol anhydride oleate as a treating agent to improve the compatibility of the ketone oxime crosslinking agent with the system, effectively reduce the migration and precipitation of the ketone oxime crosslinking agent, and avoid oiling of the product.

[0004] The second aspect of the present invention is to provide a method for preparing a silicone resin composition.

[0005] A third aspect of the present invention is to provide a sealant.

[0006] The fourth aspect of the present invention is to provide an application of a silicone resin composition or a sealant.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is:

[0008] The first aspect of the present invention provides a silicone resin composition, comprising α,ω-dihydroxypolydimethylsiloxane, a ketoxime crosslinking agent, a treating agent and an auxiliary agent; the treating agent comprises alcohol anhydride oleate.

[0009] The silicone resin composition of the present invention belongs to a moisture-curing silicone resin composition. The present invention adopts an alcohol anhydride oleate with specific emulsification ability as a treating agent, so that the α,ω-dihydroxy polydimethylsiloxane system and the ketoxime crosslinking agent form an oil-in-water (w / o) structure, thereby improving the compatibility of the ketoxime crosslinking agent with the α,ω-dihydroxy polysiloxane system, effectively reducing the slow migration of the ketoxime crosslinking agent during storage, eliminating the oil leakage problem of the silicone resin composition, and the obtained silicone resin composition has good mechanical properties and adhesion.

[0010] In some embodiments of the present invention, the amount of the treating agent is 2 to 30% of the mass of the ketoxime cross-linking agent.

[0011] In some embodiments of the present invention, the amount of the treating agent is 8-25% of the mass of the ketoxime cross-linking agent.

[0012] In some specific embodiments of the present invention, the amount of the treating agent is 10-25% of the mass of the ketoxime cross-linking agent.

[0013] In some examples of the present invention, the amount of the treating agent is 15-25% of the mass of the ketoxime cross-linking agent.

[0014] By further adjusting the amount of the treating agent, the oil yield of the silicone resin composition can be reduced, and its mechanical properties, such as elongation at break, can be improved. However, a high amount of the treating agent is not conducive to the adhesion of the silicone resin composition, and is not conducive to its application as a sealant and in the sealing field.

[0015] In some embodiments of the present invention, the silicone resin composition comprises the following components in parts by mass:

[0016] 20-70 parts of α,ω-dihydroxypolydimethylsiloxane;

[0017] 1 to 10 parts of ketoxime cross-linking agent;

[0018] Treatment agent 0.1-2 parts;

[0019] 10 to 100 parts of additives.

[0020] In some embodiments of the present invention, the silicone resin composition comprises the following components in parts by mass:

[0021] 20-60 parts of α,ω-dihydroxy polydimethylsiloxane;

[0022] 3-7 parts of ketoxime cross-linking agent;

[0023] Treatment agent 0.1-2 parts;

[0024] 10 to 100 parts of additives.

[0025] In some specific embodiments of the present invention, the silicone resin composition comprises the following components in parts by mass:

[0026] 20 to 50 parts of α,ω-dihydroxypolydimethylsiloxane;

[0027] 4-6 parts of ketoxime cross-linking agent;

[0028] 0.5-1 part of treatment agent;

[0029] 10 to 100 parts of additives.

[0030] In some embodiments of the present invention, the auxiliary agent includes at least one of a filler, a plasticizer, a coupling agent, and a catalyst.

[0031] In some embodiments of the present invention, the auxiliary agent includes a filler, a plasticizer, a coupling agent and a catalyst.

[0032] In some embodiments of the present invention, the auxiliary agent includes 10 to 70 parts of filler, 0 to 20 parts of plasticizer, 0 to 5 parts of coupling agent and 0 to 5 parts of catalyst in parts by mass.

[0033] In some embodiments of the present invention, the silicone resin composition comprises the following components in parts by mass:

[0034] 20-70 parts of α,ω-dihydroxypolydimethylsiloxane;

[0035] 1 to 10 parts of ketoxime cross-linking agent;

[0036] Treatment agent 0.1-2 parts;

[0037] 10 to 70 parts of filler;

[0038] Plasticizer 0-20 parts;

[0039] Coupling agent 0-5 parts;

[0040] Catalyst 0-5 parts.

[0041] In some embodiments of the present invention, the amount of the plasticizer, coupling agent and catalyst is not zero.

[0042] In some embodiments of the present invention, the additives include 10 to 70 parts of filler, 1 to 20 parts of plasticizer, 0.1 to 5 parts of coupling agent and 0.01 to 5 parts of catalyst in parts by mass.

[0043] In some embodiments of the present invention, the additives include 30 to 70 parts of filler, 5 to 10 parts of plasticizer, 0.5 to 2 parts of coupling agent and 0.01 to 1 part of catalyst in parts by mass.

[0044] In some specific embodiments of the present invention, the additives include 35-65 parts of filler, 6-8 parts of plasticizer, 0.8-1.5 parts of coupling agent and 0.05-0.2 parts of catalyst in parts by mass.

[0045] When fillers are added to the silicone resin composition of the present invention, the alcohol anhydride oleate can also act as a surfactant, effectively improving the dispersibility of the filler in the α,ω-dihydroxypolydimethylsiloxane system, thereby improving the strength of the silicone resin composition, reducing the modulus, and increasing the elongation at break.

[0046] In some embodiments of the present invention, the viscosity of the α,ω-dihydroxypolydimethylsiloxane at 25° C. is 1 to 150 Pa·s.

[0047] In some embodiments of the present invention, the viscosity of the α,ω-dihydroxypolydimethylsiloxane at 25° C. is 10 to 100 Pa·s.

[0048] In some specific embodiments of the present invention, the viscosity of the α,ω-dihydroxypolydimethylsiloxane at 25° C. is 20 to 50 Pa·s.

[0049] In some embodiments of the present invention, the ketoxime crosslinking agent comprises a ketoxime-based silane.

[0050] In some embodiments of the present invention, the ketoxime crosslinking agent includes at least one of methyltributylacetoximine silane, vinyltributylacetoximine silane, and tetrabutylketoxime silane.

[0051] In some specific embodiments of the present invention, the ketoxime crosslinking agent includes at least two of methyltributylacetoximine silane, vinyltributylacetoximine silane and tetrabutylketoxime silane.

[0052] In some examples of the present invention, the ketoxime crosslinking agent includes methyltributylacetoximine silane and vinyltributylacetoximine silane; the mass ratio of the methyltributylacetoximine silane to the vinyltributylacetoximine silane is (3-4):1.

[0053] In some embodiments of the present invention, the anhydride oleate comprises sorbitan monooleate.

[0054] Sorbitan monooleate is a bio-based raw material that is renewable, sustainable and environmentally friendly.

[0055] In some embodiments of the present invention, the filler includes at least one of calcium carbonate, diatomaceous earth, quartz sand, and white carbon black.

[0056] In some embodiments of the present invention, the plasticizer includes at least one of alkyl aromatic hydrocarbons, mineral oil, and dimethyl silicone oil.

[0057] In some embodiments of the present invention, the viscosity of the plasticizer at 25° C. is 0.1 to 5 Pa·s.

[0058] In some embodiments of the present invention, the viscosity of the plasticizer at 25° C. is 0.2-0.5 Pa·s.

[0059] In some specific embodiments of the present invention, the viscosity of the plasticizer at 25° C. is 0.3-0.4 Pa·s.

[0060] In some embodiments of the present invention, the coupling agent includes at least one of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, γ-(glycidoxy)propylmethyltrimethoxysilane, and γ-(glycidoxy)propylmethyltriethoxysilane.

[0061] In some embodiments of the present invention, the coupling agent includes at least two of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, γ-(glycidoxy)propylmethyltrimethoxysilane, and γ-(glycidoxy)propylmethyltriethoxysilane.

[0062] In some embodiments of the present invention, the catalyst includes at least one of dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dimethyltin diceneodecanoate, and dibutyltin acetylacetonate.

[0063] The second aspect of the present invention is to provide a method for preparing the silicone resin composition according to the first aspect of the present invention, comprising the following steps:

[0064] The α,ω-dihydroxy polydimethylsiloxane, the ketoxime crosslinking agent, the treating agent and the auxiliary agent are degassed and mixed to obtain the silicone resin composition.

[0065] In some embodiments of the present invention, the mixing is performed in a mixer.

[0066] The third aspect of the present invention is to provide a sealant comprising the silicone resin composition described in the first aspect of the present invention.

[0067] The fourth aspect of the present invention is to provide an application of the silicone resin composition described in the first aspect of the present invention or the sealant described in the third aspect of the present invention in sealing in the fields of new energy vehicles, batteries, construction, industry or electronic appliances.

[0068] The sealing in the new energy field can be, for example, plane sealing. The sealing in the construction field includes the sealing of building materials, such as door and window sealing.

[0069] Compared with the prior art, the present invention has the following beneficial effects:

[0070] The silicone resin composition of the present invention is a moisture-hardening silicone resin. By adopting alcohol anhydride oleate with specific emulsification ability, the compatibility of the ketoxime crosslinking agent and the α,ω-dihydroxy polysiloxane system is improved, the slow migration of the ketoxime crosslinking agent during the storage process is effectively reduced, and the problem of oil release of the product caused by the migration of the ketoxime crosslinking agent in the existing silicone resin is solved. At the same time, in the presence of fillers, the use of alcohol anhydride oleate can also improve the dispersibility of the filler in the system, thereby improving the strength of the silicone resin composition and reducing the modulus.

[0071] The silicone resin composition of the present invention can be used as a sealant to effectively avoid the oil leakage problem of conventional ketoxime sealants (RTV-1), and has good mechanical properties and strong adhesion, and is suitable for sealing in the fields of new energy vehicles, batteries, construction, industry or electronic appliances. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Figure 1 This is a picture showing the oil leakage from the sealant head formed by the silicone resin composition in Comparative Example 1. DETAILED DESCRIPTION

[0073] The present invention is further described in detail below by specific examples. Unless otherwise specified, the raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial sources or can be obtained by prior art methods. Unless otherwise specified, the experiments or test methods are conventional methods in the art.

[0074] Some of the raw materials used in the following examples and comparative examples of the present invention are described as follows:

[0075] α,ω-dihydroxypolydimethylsiloxane-1: viscosity at 25°C is 20000 mPa·s (20 Pa·s);

[0076] α,ω-dihydroxypolydimethylsiloxane-2: viscosity at 25°C is 50000 mPa·s (50 Pa·s);

[0077] Dimethyl silicone oil: viscosity is 350mPa·s at 25°C;

[0078] Sorbitan monooleate: Span 80.

[0079] Calcium carbonate treated with stearic acid: commonly available in the market.

[0080] The following is a detailed description with reference to specific embodiments and comparative examples.

[0081] Example 1

[0082] A silicone resin composition, the formula of which is shown in Table 1.

[0083] The preparation method of the silicone resin composition comprises the following steps:

[0084] α,ω-dihydroxypolydimethylsiloxane, dimethyl silicone oil, calcium carbonate treated with stearic acid, methyltributylacetoximate silane, vinyltributylacetoximate silane, aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, sorbitan monooleate (Span 80) and dibutyltin dilaurate are degassed and mixed in a universal mixer to obtain a silicone resin composition.

[0085] Embodiments 2 to 4

[0086] A silicone resin composition, the formula of which is shown in Table 1, and the preparation method is the same as that of Example 1.

[0087] Table 1 Silicone resin composition formula of Examples 1 to 4 (parts by mass)

[0088]

[0089]

[0090] In Example 2, the viscosity (25° C.) of the mixture of α,ω-dihydroxypolydimethylsiloxane-1 and α,ω-dihydroxypolydimethylsiloxane-2 was 35 Pa·s.

[0091] Comparative Example 1

[0092] A silicone resin composition, compared with Example 1, does not add sorbitan monooleate, and the rest is the same as Example 1, and the preparation method is the same as Example 1.

[0093] Results

[0094] The silicone resin composition obtained in the above embodiments and comparative examples was used as a sealant, and an H-type adhesive test piece was prepared according to the method provided in Chapter 7 of GB / T13477.8-2002, with the substrates being glass and aluminum, to obtain a glass-aluminum adhesive piece; the test piece was cured by vulcanization for 7 days in an environment at a temperature of 23±2°C and a relative humidity of 50±5%; a tensile test was performed using a tensile testing machine to obtain tensile strength, elongation at break and modulus; a butterfly test (refer to the test process in Appendix D.4.3 of GB 16776-2005) was performed, and then the hard packaging (i.e., HDPE plastic tube) was cut open, and the oil leakage was judged based on whether the paper was oily or not.

[0095] Among them, the tensile test is to fix the glass and aluminum and stretch them, which can also be used to reflect the bonding performance.

[0096] The test results are shown in Table 2 below.

[0097] Table 2 Performance of the silicone resin compositions of the embodiments and comparative examples as sealants

[0098] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Tensile strength / MPa 1.35 1.12 1.41 1.30 1.22 Elongation at break / % 410 300 450 350 350 100% modulus / MPa 0.60 0.56 0.76 0.66 0.68 Oil output none none none none Oil out of head and tail

[0099] From the results in Table 2, it can be seen that the silicone resin composition of the present invention, as a sealant, effectively solves the oil leakage problem of the product and ensures good mechanical properties and adhesion. After bonding the glass and aluminum, the tensile test showed that the tensile strength was not less than 1.1 MPa, the elongation at break was not less than 300%, and the modulus was not less than 0.56 MPa, indicating good mechanical properties and adhesion. The mechanical properties of Example 2 are slightly inferior to those of Examples 1, 3 and 4 because the amount of polysiloxane used in Example 2 is lower than that of other examples, and the basic mechanical properties are lower. Comparative Example 1 does not add alcohol anhydride oleate, and although the mechanical properties are not inferior to those of Example 2, according to Figure 1 Meanwhile, by comparing Example 1 with Comparative Example 1, under the same other conditions, the use of alcohol anhydride oleate in Example 1 can not only improve the tensile strength and reduce the modulus, but also has good bonding performance.

[0100] In summary, the silicone resin composition of the present invention avoids the migration of the ketoxime crosslinking agent and solves the problem of oil leakage in existing silicone resin products. At the same time, in the presence of fillers, the use of alcohol anhydride oleate can also improve the dispersibility of the filler in the system. The obtained silicone resin composition has good mechanical properties and adhesion. Compared with conventional ketoxime sealants (RTV-1), the use of the silicone resin composition as a sealant effectively avoids the oil leakage problem, and has strong mechanical properties and adhesion, and is suitable for door and window sealing or electronic appliance sealing.

[0101] 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. A silicone resin composition, characterized in that: The invention comprises α,ω-dihydroxy polydimethylsiloxane, ketoxime crosslinking agent, treating agent and auxiliary agent; the treating agent comprises alcohol anhydride oleate.

2. The silicone resin composition according to claim 1, characterized in that The amount of the treating agent used is 2-30% of the mass of the ketoxime cross-linking agent.

3. The silicone resin composition according to claim 1, characterized in that The silicone resin composition comprises the following components in parts by mass: 20 to 70 parts of α,ω-dihydroxypolydimethylsiloxane; 1 to 10 parts of ketoxime cross-linking agent; Treatment agent 0.1-2 parts; 10 to 100 parts of additives.

4. The silicone resin composition according to claim 3, characterized in that: The auxiliary agent includes at least one of a filler, a plasticizer, a coupling agent and a catalyst.

5. The silicone resin composition according to claim 4, characterized in that The auxiliary agent comprises, by weight, 10 to 70 parts of filler, 0 to 20 parts of plasticizer, 0 to 5 parts of coupling agent and 0 to 5 parts of catalyst.

6. The silicone resin composition according to claim 1, characterized in that The viscosity of the α,ω-dihydroxy polydimethylsiloxane at 25° C. is 1 to 150 Pa·s; And / or, the ketoxime crosslinking agent comprises ketoxime silane.

7. The silicone resin composition according to claim 4 or 5, characterized in that: The filler includes at least one of calcium carbonate, diatomaceous earth, quartz sand and white carbon black; And / or, the plasticizer includes at least one of alkyl aromatic hydrocarbons, mineral oil, and dimethyl silicone oil; And / or, the coupling agent includes at least one of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, γ-(glycidoxy)propylmethyltrimethoxysilane, and γ-(glycidoxy)propylmethyltriethoxysilane; And / or, the catalyst includes at least one of dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dimethyltin diceneodecanoate, and dibutyltin acetylacetonate.

8. A method for preparing the silicone resin composition according to any one of claims 1 to 7, characterized in that: The following steps are involved: The α,ω-dihydroxy polydimethylsiloxane, the ketoxime crosslinking agent, the treating agent and the auxiliary agent are degassed and mixed to obtain the silicone resin composition.

9. A sealant, characterized in that: The silicone resin composition comprises the silicone resin composition according to any one of claims 1 to 7.

10. Use of the silicone resin composition according to any one of claims 1 to 7 or the sealant according to claim 9 in sealing in the fields of new energy vehicles, batteries, construction, industry or electronic appliances.

Images