CN115246992A - High-elasticity silica gel foam and application thereof - Google Patents
High-elasticity silica gel foam and application thereof Download PDFInfo
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- CN115246992A CN115246992A CN202111018498.0A CN202111018498A CN115246992A CN 115246992 A CN115246992 A CN 115246992A CN 202111018498 A CN202111018498 A CN 202111018498A CN 115246992 A CN115246992 A CN 115246992A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/0066—Use of inorganic compounding ingredients
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- C08J9/0085—Use of fibrous compounding ingredients
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2205/00—Foams characterised by their properties
- C08J2205/06—Flexible foams
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/05—Polysiloxanes containing silicon bound to hydrogen
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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Abstract
The invention provides high-elasticity silica gel foam which comprises the following raw materials in parts by weight: 60-80 parts of vinyl silicone oil, 30-40 parts of hydroxyl silicone oil, 8-12 parts of polymethylhydrosiloxane, 0.3-0.6 part of catalyst, 8-14 parts of filler, 3-9 parts of foaming agent and 0.1-0.5 part of inhibitor. Through the mutual matching and cooperation of the raw materials, the obtained silica gel foam has excellent elasticity and smaller relaxation stress, and the risk of failure caused by large compression deformation and softening is reduced; meanwhile, the silicon gel foam has excellent ultraviolet resistance, ozone resistance, extreme temperature resistance and flame retardance, has the advantage that the silicon gel foam can keep stable in performance under various environments, can be continuously used in the environment of-55 ℃ to 220 ℃, and has stronger sealing performance when forming a compact cell structure. The silica gel foam can be used for environmental sealing, dampproof and dustproof sealing of LED lamps, sealing of precision instrument gaskets, sealing of automobile engines and electronic components and sealing of high-temperature equipment.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to IPC class number C08L83/07, and more particularly relates to high-elasticity silica gel foam and application thereof.
Background
The silica gel foam integrates the characteristics of a foam material and an organic silicon material, has excellent comprehensive performance compared with a conventional high-molecular foam material, and is generally applied to the fields of aerospace, biomedicine, electronic equipment and the like. However, some silica gel foams on the market at present have insufficient cushioning and shock-absorbing performance, and cannot well play a sealing role when being used in certain extreme environments, so that the application of the silica gel foams is further limited.
Patent CN109651821A discloses a silicone foam and a preparation method thereof, the silicone foam prepared by the patent has high toughness, high elasticity and high ductility, and has good heat insulation and moisture resistance, but the silicone foam can only work continuously at-40-200 ℃ and cannot be used continuously at lower or higher limit temperature.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-elasticity silica gel foam which comprises the following raw materials in parts by weight:
in some embodiments, the vinyl silicone oil has a viscosity of 4000 to 6000cst at 25 ℃ and a vinyl content of 0.35 to 0.6mol%.
Preferably, the vinyl silicone oil has a viscosity of 4500-5500cst at 25 ℃ and a vinyl content of 0.45mol%.
The vinyl silicone oil is commercially available, including but not limited to from Zhiyou Silicone materials, inc., of Kindda, model number zy-5000.
In some embodiments, the hydroxy silicone oil has a hydroxyl content of 6 to 12mol%.
Preferably, the hydroxyl silicone oil has a hydroxyl group content of 9mol%.
The hydroxyl silicone oil may be commercially available, including but not limited to, from denna ryegrass chemical co.
In some embodiments, the polymethylhydrosiloxane is at 25 ℃The viscosity is 10-50mm 2 And/s, the hydrogen content is more than 1.2mol percent.
Preferably, the viscosity of the polymethylhydrosiloxane is 15-40mm at 25 DEG C 2 The hydrogen content is greater than 1.58mol%.
The polymethylhydrosiloxane is commercially available, including but not limited to, from Hubei Kowold chemical Co.
In some embodiments, the filler comprises one or more of white carbon black, calcium carbonate, talc, montmorillonite, mica powder, attapulgite, zinc oxide whiskers.
Preferably, the filler comprises a mixture of white carbon black, calcium carbonate and zinc oxide whiskers, and the weight ratio of the filler to the filler is 1: (1-1.8): (0.1-0.5).
More preferably, the filler comprises a mixture of precipitated white carbon black, calcium carbonate and zinc oxide whiskers, and the weight ratio of the precipitated white carbon black to the calcium carbonate is 1:1.5:0.3.
in some embodiments, the precipitated silica has a particle size of 1000 to 1500 mesh.
Preferably, the particle size of the precipitated silica is 1250 meshes.
In some embodiments, the calcium carbonate has a particle size of 1000 to 1500 mesh.
Preferably, the particle size of the calcium carbonate is 1250 meshes.
In some embodiments, the zinc oxide whiskers have a particle size of 0.1 to 10 μm.
Preferably, the grain diameter of the zinc oxide whisker is 0.5-5 μm.
The zinc oxide whiskers are commercially available, including but not limited to from ansamistar new carbon materials, changzhou limited.
In some embodiments, the inhibitor comprises ethynyl cyclohexanol.
In some embodiments, the blowing agent comprises one or more of azodicarbonamide, sodium bicarbonate, N-dinitrosopentamethylenetetramine.
Preferably, the blowing agent is azodicarbonamide.
In some embodiments, the raw material further comprises 0.5-2 parts by weight of a foaming aid.
Preferably, the foaming auxiliary agent is urea.
In some embodiments, the feedstock further comprises 8-16 parts of a functional material.
In some embodiments, the functional material comprises one or more of an ultraviolet absorber, an antioxidant, a flame retardant.
Preferably, the functional material comprises 2-5 parts by weight of ultraviolet absorbent, 1-3 parts by weight of antioxidant and 5-8 parts by weight of flame retardant.
In some embodiments, the ultraviolet light absorber comprises UV235 and UV531 in a weight ratio of 1:1.
in some embodiments, the antioxidant comprises at least one of antioxidant 1010, antioxidant 168, antioxidant 1076.
In some embodiments, the flame retardant comprises aluminum hydroxide.
Preferably, the particle size of the aluminum hydroxide is 1000-1500 meshes.
More preferably, the particle size of the aluminum hydroxide is 1250 mesh.
The applicant finds that specific vinyl silicone oil, hydroxyl silicone oil and polymethylhydrosiloxane are adopted and fillers in a specific proportion are added into the system, particularly the fillers are in a weight ratio of 1: (1-1.8): (0.1-0.5) the precipitated silica white, calcium carbonate and zinc oxide whisker have excellent buffering and damping performance, and the applicant considers that the probable reasons are that on one hand, vinyl silicone oil, hydroxyl silicone oil and polymethylhydrosiloxane with specific viscosity can form a more compact cross-linked structure under the action of a catalyst, and the foaming of the foaming agent and the foaming auxiliary agent in the application ensures that uniform cells are formed inside the silica gel foam, so that a compact cell structure is formed, and meanwhile, a specific filler is added to be uniformly dispersed into the structure, so that the elastic modulus and the yield stress of the silica gel foam are improved, the silica gel foam is endowed with excellent elasticity and smaller relaxation stress, the risk of failure caused by large compression deformation and softening is reduced, and the compact cell structure further promotes the sealing and high and low temperature resistance performance, so that the silica gel foam can continuously work at the limit temperature of-55-220 ℃. The applicant has also found that calcium carbonate, in particular calcium carbonate with a particle size of 1250 mesh, in the present application also produces a good synergistic effect with aluminium hydroxide, giving the silica gel foam better flame retardant properties.
The preparation method of the silica gel foam is not particularly limited, and in some embodiments, the preparation method of the silica gel foam comprises the following steps: adding vinyl silicone oil, hydroxyl silicone oil, polymethylhydrosiloxane, a catalyst, a filler, an inhibitor, a foaming aid and a functional material into a reaction kettle, stirring at the room temperature at the speed of 40-60rpm for 2-3h, then adding a foaming agent and a foaming aid, fully and uniformly mixing, then uniformly paving on the surface of the PET fluoroplastic release film, and placing in a drying oven at 130 ℃ for foaming.
The invention also provides application of the high-elasticity silica gel foam in environmental sealing, moisture-proof and dust-proof sealing of LED lamps, sealing of precision instrument gaskets, sealing of automobile engines and electronic components and sealing of high-temperature equipment.
Has the advantages that: through the mutual matching and cooperation of the raw materials, the obtained silica gel foam has excellent elasticity and smaller relaxation stress, and the risk of failure caused by large compression deformation and softening is reduced; meanwhile, the silicon gel foam has excellent ultraviolet resistance, ozone resistance, extreme temperature resistance and flame retardance, has the advantage that the silicon gel foam can keep stable performance in various environments, can be continuously used in the environment of-55 ℃ to 220 ℃, and has stronger sealing performance when forming a compact cell structure.
Detailed Description
Example 1
The embodiment provides a high-elasticity silica gel foam, which comprises the following raw materials in parts by weight:
70 parts of vinyl silicone oil;
35 parts of hydroxyl silicone oil;
10 parts of polymethylhydrosiloxane;
0.5 part of a catalyst;
12 parts of a filler;
6 parts of a foaming agent;
1 part of a foaming auxiliary agent;
0.3 part of inhibitor;
3 parts of an ultraviolet absorber;
2 parts of an antioxidant;
and 7 parts of a flame retardant.
The vinyl silicone oil is purchased from Zhiyou silicon materials Co., ltd, jiande, with the model number of zy-5000, the viscosity at 25 ℃ of 4500-5500cst, and the vinyl content of 0.45mol%.
The hydroxyl silicone oil is purchased from Jinan Ruiyuan chemical Co., ltd, and the hydroxyl content is 9mol%.
The polymethylhydrosiloxane is purchased from Hubei Kovesudade chemical Co., ltd, and the viscosity of the polymethylhydrosiloxane at 25 ℃ is 15-40mm 2 The hydrogen content is greater than 1.58mol%.
The filler comprises the mixture of precipitated white carbon black, calcium carbonate and zinc oxide whiskers, and the weight ratio of the filler to the filler is 1:1.5:0.3.
the precipitated white carbon black is purchased from New materials Co., ltd of Shandong Siricco, and the particle size is 1250 meshes.
The calcium carbonate is purchased from Xin Chang chemical industry, llc of Wuhan city, and has a particle size of 1250 meshes.
The particle size of the zinc oxide whisker is 0.5-5 mu m, and the zinc oxide whisker is purchased from Changzhou company of novel carbon material of Onsan.
The inhibitor is ethynyl cyclohexanol.
The foaming agent is azodicarbonamide.
The foaming auxiliary agent is urea.
The ultraviolet absorbent comprises UV235 and UV531, and the weight ratio is 1:1.
the antioxidant is 1010.
The flame retardant is aluminum hydroxide, is purchased from Jinan Supper-Italian chemical industry Co., ltd, and has a grain size of 1250 meshes.
Another aspect of this embodiment provides an application of a high elasticity silica gel foam for environmental sealing, LED lamp moisture and dust sealing, precision instrument gasket, automobile engine and electronic component sealing, high temperature equipment sealing.
Example 2
The embodiment provides a high-elasticity silica gel foam, which comprises the following raw materials in parts by weight:
60 parts of vinyl silicone oil;
30 parts of hydroxyl silicone oil;
8 parts of polymethylhydrosiloxane;
0.3 part of a catalyst;
8 parts of a filler;
3 parts of a foaming agent;
0.5 part of foaming auxiliary agent;
0.1 part of inhibitor;
2 parts of an ultraviolet absorber;
1 part of an antioxidant;
5 parts of a flame retardant.
The vinyl silicone oil is purchased from Zhiyou silicon materials Co., ltd, jiande, with the model number of zy-5000, the viscosity at 25 ℃ of 4500-5500cst, and the vinyl content of 0.45mol%.
The hydroxyl silicone oil is purchased from Jinan Ruiyuan chemical Co., ltd, and the hydroxyl content is 9mol%.
The polymethylhydrosiloxane is purchased from Hubei Kovesudade chemical Co., ltd, and the viscosity of the polymethylhydrosiloxane at 25 ℃ is 15-40mm 2 The hydrogen content is greater than 1.58mol%.
The filler comprises the mixture of precipitated white carbon black, calcium carbonate and zinc oxide whiskers, and the weight ratio of the filler to the filler is 1:1:0.1.
the precipitated white carbon black is purchased from New materials Co., ltd of Shandong Siricco, and the particle size is 1250 meshes.
The calcium carbonate is purchased from Xin Chang chemical industry, llc of Wuhan city, and has a particle size of 1250 meshes.
The particle size of the zinc oxide whisker is 0.5-5 mu m, and the zinc oxide whisker is purchased from Changzhou company of novel carbon material of Onsan.
The inhibitor is ethynyl cyclohexanol.
The foaming agent is azodicarbonamide.
The foaming auxiliary agent is urea.
The ultraviolet absorbent comprises UV235 and UV531, and the weight ratio is 1:1.
the antioxidant is 1010.
The flame retardant is aluminum hydroxide, is purchased from Jinan super meaning chemical Co., ltd, and has a grain size of 1250 meshes.
Another aspect of this embodiment provides an application of a high elasticity silica gel foam for environmental sealing, LED lamp moisture and dust sealing, precision instrument gasket, automobile engine and electronic component sealing, high temperature equipment sealing.
Example 3
The embodiment provides a high-elasticity silica gel foam, which comprises the following raw materials in parts by weight:
80 parts of vinyl silicone oil;
40 parts of hydroxyl silicone oil;
12 parts of polymethylhydrosiloxane;
0.6 part of a catalyst;
14 parts of a filler;
9 parts of a foaming agent;
2 parts of a foaming auxiliary agent;
0.5 part of inhibitor;
5 parts of an ultraviolet absorber;
3 parts of an antioxidant;
and 8 parts of a flame retardant.
The vinyl silicone oil is purchased from Zhiyou silicon materials Co., ltd, jiande, with the model number of zy-5000, the viscosity at 25 ℃ of 4500-5500cst, and the vinyl content of 0.45mol%.
The hydroxyl silicone oil is purchased from Jinan Ruiyuan chemical Co., ltd, and the hydroxyl content is 9mol%.
The polymethylhydrosiloxane is purchased from Hubei Kovesudade chemical Co., ltd, and the viscosity of the polymethylhydrosiloxane at 25 ℃ is 15-40mm 2 S, hydrogen content > 1.58mol%.
The filler comprises the mixture of precipitated white carbon black, calcium carbonate and zinc oxide whiskers, and the weight ratio of the filler to the filler is 1:1.8:0.5.
the precipitated white carbon black is purchased from New materials Co., ltd of Shandong Siricco, and the particle size is 1250 meshes.
The calcium carbonate is purchased from Xin Chang chemical industry, llc of Wuhan city, and has a particle size of 1250 meshes.
The particle size of the zinc oxide whisker is 0.5-5 mu m, and the zinc oxide whisker is purchased from Changzhou company of novel carbon material of Onsan.
The inhibitor is ethynyl cyclohexanol.
The foaming agent is azodicarbonamide.
The foaming auxiliary agent is urea.
The ultraviolet absorbent comprises UV235 and UV531, and the weight ratio is 1:1.
the antioxidant is 1010.
The flame retardant is aluminum hydroxide, is purchased from Jinan Supper-Italian chemical industry Co., ltd, and has a grain size of 1250 meshes.
Another aspect of this embodiment provides an application of a high elasticity silica gel foam for environmental sealing, LED lamp moisture and dust sealing, precision instrument gasket, automobile engine and electronic component sealing, high temperature equipment sealing.
Example 4
This example provides a highly elastic silicone foam in the same manner as example 1 except that the filler does not contain zinc oxide whiskers.
Example 5
This example provides a highly elastic silicone foam in a manner similar to example 1 except that the filler does not contain precipitated silica.
The raw material formulas provided in examples 1 to 5 were prepared into silica gel foams according to the following preparation methods, which specifically included the following steps: adding vinyl silicone oil, hydroxyl silicone oil, polymethylhydrosiloxane, a catalyst, a filler, an inhibitor, a foaming aid and a functional material into a reaction kettle, stirring at the room temperature at the speed of 50rpm for 2.5h, then adding a foaming agent and the foaming aid, fully and uniformly mixing, then uniformly paving on the surface of the PET fluoroplastic release film, and placing in a drying oven at 130 ℃ for foaming to obtain the PET fluoroplastic release film.
Performance testing
1. The silica gel foams prepared in example 1 were subjected to performance tests and the results are shown in Table 1.
TABLE 1
| Test items | Data of | Test method |
| Tensile Strength (kPa) | 60 | ASTM D 412 |
| Elongation (%) | 60 | ASTM D 412 |
| Flame retardancy | V-0 | UL 94 |
| Smoke diffusion index (Ls) | 20 | ASTM E 162 |
| Toxic gas emission rating | By passing | SMP-800C |
2. Compression set
The silicone foams provided in examples 1 to 5 were subjected to compression set testing at 70 ℃ in accordance with ASTM D1056, and the results are shown in Table 1.
TABLE 1
| Numbering | Compression set (%) |
| Example 1 | 0.92 |
| Example 2 | 0.95 |
| Example 3 | 0.98 |
| Example 4 | 1.20 |
| Example 5 | 1.53 |
Claims (10)
1. The high-elasticity silica gel foam is characterized by comprising the following raw materials in parts by weight:
2. the highly elastic silicone foam according to claim 1, wherein said vinyl silicone oil has a viscosity of 4000-6000cst at 25 ℃ and a vinyl content of 0.35-0.6mol%.
3. The highly elastic silicone foam according to claim 1, wherein the hydroxyl silicone oil has a hydroxyl group content of 6 to 12mol%.
4. The high-elasticity silicone foam according to claim 1, wherein the viscosity of the polymethylhydrosiloxane is 10-50mm at 25 ℃ 2 S, hydrogen content > 1.2mol%.
5. A highly elastic silica gel foam according to any one of claims 1 to 4, wherein said filler comprises one or more of white carbon black, calcium carbonate, talc, montmorillonite, mica powder, attapulgite.
6. The high elasticity silica gel foam according to claim 5, wherein the white carbon black comprises precipitated white carbon black and fumed white carbon black in a weight ratio of 1: (0.6-1).
7. The highly elastic silicone foam according to claim 1, wherein said inhibitor comprises ethynylcyclohexanol.
8. The high elasticity silicone foam according to claim 1, wherein the raw material further comprises 10-15 parts of a functional material.
9. The high resilience silicone foam of claim 8, wherein the functional material comprises one or more of an ultraviolet absorber, an antioxidant, and a flame retardant.
10. Use of a highly elastic silicone foam according to any one of claims 1 to 9 for environmental sealing, moisture and dust sealing of LED lamps, gaskets for precision instruments, sealing of automotive engines and electronic components, sealing of high temperature equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111018498.0A CN115246992A (en) | 2021-09-01 | 2021-09-01 | High-elasticity silica gel foam and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111018498.0A CN115246992A (en) | 2021-09-01 | 2021-09-01 | High-elasticity silica gel foam and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN115246992A true CN115246992A (en) | 2022-10-28 |
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