CN113025266A - Intrinsic flame-retardant heat-insulation organic silicon foaming adhesive and preparation method thereof - Google Patents
Intrinsic flame-retardant heat-insulation organic silicon foaming adhesive and preparation method thereof Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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Abstract
The invention discloses an intrinsic flame-retardant heat-insulation organic silicon foaming adhesive and a preparation method thereof. The organic silicon foaming glue is prepared from raw materials comprising active polysiloxane, hydroxyl-containing substances and a catalyst; based on 100 parts by weight of active polysiloxane, 1-50 parts by weight of hydroxyl-containing substance and 0.05-5 parts by weight of catalyst. The preparation method comprises the following steps: firstly, respectively mixing the component A and the component B according to the using amount of each component, and then mixing the component A and the component B to prepare the intrinsic flame-retardant heat-insulation organic silicon foaming adhesive; the foaming temperature is 30-70 ℃; the foaming time is 1-30 min. According to the invention, a foaming agent, a flame retardant and a high-temperature-resistant filler are not required to be added, the prepared organic silicon foaming adhesive has more silica-silica structures, is excellent in thermal stability, low in thermal weight loss, free of halogen, difficult to burn in air, free of toxic gas release, rapid, light, environment-friendly, non-combustible and the like, and has wide application prospects in the fields of aviation, aerospace, electronics and the like.
Description
Technical Field
The invention relates to the field of flame-retardant heat-insulating materials, in particular to an intrinsic flame-retardant heat-insulating organic silicon foaming adhesive and a preparation method thereof.
Background
The foaming adhesive is a filling material widely applied to various fields of buildings, industries and the like, is used for filling gaps and has the effects of heat insulation and sound insulation, the heat insulation foaming adhesive is necessary to have flame retardance and high temperature resistance, most of the foaming adhesives are polyurethanes at present, the material is inflammable and generates a large amount of molten drops, the flame propagation speed is high and difficult to control, the famous great red door fire disaster in Beijing is a malignant accident caused by electric welding spark ignition in a construction site by using the polyurethane foaming adhesive, and the accident can be avoided if the foaming adhesive with the flame retardant function is used.
Silicone foam is a novel multifunctional material that integrates the properties of silicone and foam into one. The polysiloxane-modified polyurethane foam material not only keeps the excellent characteristics of no toxicity, environmental protection, high and low temperature resistance, insulation, strong weather resistance and the like of polysiloxane, but also has the characteristics of light weight, sound absorption, shock resistance and the like of foam materials, can be used as high-performance materials for damping, vibration reduction, sound insulation, heat insulation and the like, and is widely applied to the fields of national defense, aerospace, transportation, electronic industry, buildings and the like.
The preparation method of the organic silicon foaming adhesive generally comprises a physical foaming method and a chemical foaming method, wherein the chemical foaming method can be generally divided into two methods according to different reaction mechanisms, one method is that a silicon-hydrogen condensation reaction is utilized, and gas is released through the reaction between organic silicon compounds, specifically, for example, hydrogen is generated by alkane containing hydroxyl or Si-OH of hydroxyl-terminated silicone oil and hydrogen-containing silicone oil Si-H under the catalysis of a catalyst, so that the foam material can be prepared. The method is also one of the methods for preparing the organic silicon foaming adhesive which is used more at home and abroad at present. Chinese patent CN105860537A discloses a high flame-retardant organic silicon sponge material and a preparation method thereof, CN107603229A discloses a heat-resistant organic silicon foam material and a preparation method thereof, and CN104774473A discloses a room-temperature vulcanized phenyl silicone rubber foam material and a preparation method thereof, wherein the patents adopt organic silicon foams prepared by a method of generating gas by silicon-hydrogen condensation. Another is to use a chemical blowing agent which can undergo a thermal decomposition reaction. Chinese patent CN107236304A discloses a porcelainized flame-retardant silicone rubber foam material prepared by using an external foaming agent such as nitroso compound, N, N-dinitrosopentamethylenetetramine and the like.
The foam materials such as the organic silicon foaming glue and the like are widely used, so that the requirements on safety and environmental performance of the foam materials are better, and the preparation route of the foam materials is required to be environment-friendly, green, fireproof and flame-retardant. However, most of the prepared silicone foaming rubbers are silicone rubber foams, the materials are soft, and the flame retardant property is endowed by adding a flame retardant or introducing halogen.
U.S. Pat. No. 3,795,705 discloses a method of adding platinum-containing complexes to improve the flame retardant properties of silicone foams, but the effect is poor. Chinese patent CN1339044A discloses a method for improving the flame retardant property of organosilicon foam by adding wollastonite and other inorganic minerals, and although the method improves the flame retardant property to a certain extent, the mechanical property of the foam is greatly reduced by a large amount of inorganic fillers, and the service performance of the foam is influenced. The Chinese patent CN107141806A introduces halogen through modifying silicone oil, and the method can improve the flame retardant property to a certain extent, but releases toxic gas when burning. In general, most of the prior organosilicon foams have no flame retardance and need additional flame retardant, but the cellular structure is greatly influenced, so that the comprehensive performance of the organosilicon foams is reduced.
Therefore, the flame-retardant heat-insulation organic silicon foaming adhesive needs to be developed, a flame retardant and a filler do not need to be additionally added, and the flame-retardant heat-insulation organic silicon foaming adhesive has a better application prospect in the fields of plugging, sealing, filling and the like.
Disclosure of Invention
The invention provides a flame-retardant heat-insulation organic silicon foaming adhesive and a preparation method thereof, aiming at solving the technical problem that the organic silicon foaming adhesive can have good flame-retardant performance without adding a flame retardant and a filler additionally.
The invention takes active polysiloxane as a substrate, adds a certain amount of hydroxyl-containing substances, and utilizes the gas generated by the reaction to foam on site under the catalysis of a certain amount of catalyst so as to prepare the organosilicon foam material. And the density and the pore structure of the foaming adhesive can be adjusted by changing the active groups of the active polysiloxane, the content of the active groups and the types of hydroxyl-containing substances. The preparation route of the invention is environment-friendly and simple, the foaming is carried out at normal temperature, the foaming speed is high, the foaming can be carried out on site in construction, the raw materials are easy to obtain and have low price, no flame retardant or other fillers are added, the prepared organic silicon foaming adhesive has more silicon-oxygen-silicon structures, excellent thermal stability, low thermal weight loss, no halogen, flame retardancy in air and no release of toxic gases. The elasticity and the flame retardance can be adjusted.
The invention aims to provide an intrinsic flame-retardant heat-insulation organic silicon foaming adhesive.
The organic silicon foaming adhesive is prepared from the following raw materials:
a component A and a component B;
the component A comprises active polysiloxane, and the component B comprises hydroxyl-containing substances and a catalyst;
based on 100 parts by weight of active polysiloxane:
1-50 parts by weight of hydroxyl-containing substances; preferably 10 to 35 parts by weight;
0.05-5 parts by weight of a catalyst; preferably 0.2 to 4 parts by weight.
In a preferred embodiment of the present invention,
the structure of the component A is as follows:
R1one or more of methyl, ethyl, isopropyl, butyl, octyl, phenyl, epoxy, vinyl, allyl, ketoximino and Cl;
R2is one or more of hydrogen, hydroxyl, methoxy, ethoxy, butoxy, epoxy, vinyl, allyl, ketoximino and Cl;
R3、R4each independently selected from one of methyl, ethyl, isopropyl, butyl, octyl, phenyl, hydrogen, hydroxyl, methoxyl, ethoxyl, epoxy, vinyl, allyl, ketoximino and Cl;
1. ltoreq. n.ltoreq.2000, preferably 20. ltoreq. n.ltoreq.1500.
In a preferred embodiment of the present invention,
r in the A component2The content of the group is in the range of 0.1 to 1.55mol/100g, preferably 0.5 to 1.55mol/100 g.
In a preferred embodiment of the present invention,
r in the A component2The molar ratio of the group to the hydroxyl in the component B is 1: 0.1-1: 2, preferably 1: 0.1-1: 1.
In a preferred embodiment of the present invention,
the active polysiloxane is at least one of methyl hydrogen-containing silicone oil, methyl phenyl hydrogen-containing silicone oil, ethyl hydrogen-containing silicone oil, methyl ethoxy silicone oil, vinyl hydrogen-containing silicone oil, methyl methoxy hydrogen-containing silicone oil, epoxy methyl silicone oil, methoxy methyl silicone oil and vinyl methyl silicone oil; and/or the presence of a gas in the gas,
the hydroxyl-containing substance is C1-11At least one of monohydric alcohol, substance containing phenolic hydroxyl group, substance containing silicon hydroxyl group, and substance containing hydroxy hydrocarbon silicon oil.
In a preferred embodiment of the present invention,
the hydroxyl-containing substance is at least one of methanol, ethanol, phenol, diphenyl silanediol and hydroxyl-terminated polysiloxane.
In a preferred embodiment of the present invention,
the catalyst is at least one of alkali metal hydroxide, platinum-containing complex, strong inorganic acid, organic base, boron-containing substance and organic tin.
In a preferred embodiment of the present invention,
the catalyst is at least one of sodium hydroxide, tetramethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide and chloroplatinic acid.
The invention also aims to provide a preparation method of the intrinsic flame-retardant heat-insulation organic silicon foaming adhesive, which comprises the following steps:
the component A and the component B are mixed according to the using amount of each component, and then the component A and the component B are mixed to prepare the flame-retardant heat-insulation organic silicon foaming adhesive.
The foaming temperature is 30-70 ℃; the foaming time is 1-30 min.
The invention can adopt the following technical scheme:
the invention discloses an intrinsic flame-retardant heat-insulation organic silicon foaming adhesive, which comprises the following components in parts by weight:
the composition comprises a component A and a component B, wherein the component A comprises the following components in parts by mass:
100 parts of active polysiloxane;
the component B is characterized by comprising the following components in parts by mass:
1-50 parts of hydroxyl-containing substances, preferably 10-35 parts;
0.05-5 parts of catalyst, preferably 0.2-4 parts.
In the flame-retardant heat-insulation organic silicon foaming adhesive, the structure of the active polysiloxane is as follows:
R1one or more of methyl, ethyl, isopropyl, butyl, octyl, phenyl, epoxy, vinyl, allyl, ketoximino and Cl;
R2is one or more of hydrogen, hydroxyl, methoxy, ethoxy, butoxy, epoxy, vinyl, allyl, ketoximino and Cl;
R3、R4each independently selected from one of methyl, ethyl, isopropyl, butyl, octyl, phenyl, hydrogen, hydroxyl, methoxyl, ethoxyl, epoxy, vinyl, allyl, ketoximino and Cl;
1. ltoreq. n.ltoreq.2000, preferably 20. ltoreq. n.ltoreq.1500.
R in the A component2The content of the group is in the range of 0.1 to 1.55mol/100g, preferably 0.5 to 1.55mol/100 g.
R in the A component2The molar ratio of the group to the hydroxyl in the component B is 1: 0.1-1: 2, preferably 1: 0.1-1: 1.
The active polysiloxane is at least one of methyl hydrogen-containing silicone oil, methyl phenyl hydrogen-containing silicone oil, ethyl hydrogen-containing silicone oil, methyl ethoxy silicone oil, vinyl hydrogen-containing silicone oil, methyl methoxy hydrogen-containing silicone oil, epoxy methyl silicone oil, methoxy methyl silicone oil and vinyl methyl silicone oil, and preferably at least one of methyl hydrogen-containing silicone oil, phenyl hydrogen-containing silicone oil, methyl phenyl hydrogen-containing silicone oil and methoxy methyl silicone oil;
the hydroxyl-containing substance in the component B is C1-11At least one of monohydric alcohol (methanol, ethanol, n-propanol, n-butanol, etc.), substance containing phenolic hydroxyl group (such as phenol, hydroquinone, p-hydroxybenzaldehyde, etc.), substance containing silicon hydroxyl group (diphenyl silanediol, hydroxyl terminated polysiloxane, etc.), and hydroxy hydrocarbon silicone oil, preferably at least one of methanol, ethanol, phenol, diphenyl silanediol, hydroxyl terminated polysiloxane;
the catalyst in the component B comprises at least one of alkali metal hydroxide, quaternary ammonium base, platinum-containing complex, strong inorganic acid, organic base, boron-containing substance and organic tin, preferably at least one of sodium hydroxide, tetramethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide and chloroplatinic acid.
The preparation method of the intrinsic flame-retardant heat-insulation organic silicon foaming adhesive comprises the following steps:
and (3) fully mixing the active polysiloxane in the component A, the hydroxyl substance in the component B and a reaction catalyst, and carrying out in-situ foaming at a proper temperature and time according to the filled part to obtain the required material.
The foaming agent can be foamed at room temperature, the foaming is better at 30-70 ℃, the higher the temperature is, the higher the foaming speed is, and the foaming time can be adjusted by controlling the foaming temperature and the concentration of the catalyst according to the actual application condition.
The method comprises the following specific steps:
(1) preparation of raw materials:
the raw material consists of A, B two components; the component A is one or more of polysiloxane with reactive groups, and the component B is a mixture of hydroxyl-containing substances with reactive groups and a reaction catalyst.
(2) Mixing of raw materials
Mixing the component A and the component B, and rapidly stirring; or A, B can be respectively loaded into the two-component glue gun, the glue gun rod is pushed out by force, and A, B two components are mixed at the head of the glue gun.
A component R2The mole ratio of the group to the hydroxyl in the component B has larger influence on the foaming effect, and when the mole ratio is close to 1 or less than 1, the foaming effect is better, mainly because the hydroxyl substance reacts with the active polysiloxane to generate new polysiloxane, and the excessive active polysiloxane reacts with the newly generated polysiloxane to foam to finally obtain the foaming adhesive.
(3) Foaming:
filling the mixed materials into a space to be filled, and foaming at normal temperature; or placing into a mold, and placing into an oven at 30-70 deg.C for foaming.
In the invention, the two-component substance is adopted for in-situ foaming, the method is simple and easy to implement, and the reaction mechanism is favorable for forming a material with a more compact structure to obtain the organic silicon foaming adhesive with flame retardance, good heat insulation performance, high temperature resistance and low weight loss rate.
The invention has the beneficial effects that:
the invention does not add flame retardant, the reaction between the raw materials of organic silicon generates a large amount of silicon-oxygen-silicon structures, the thermal stability is quite good because the silicon-oxygen bond energy is as high as 1014.2kJ/mol, as shown in figure 2, the solid29The Si-NMR spectrogram shows that the prepared organic silicon foam mainly contains a T structural unit, and the organic silicon foam prepared by the invention has high crosslinking density and more silicon-oxygen-silicon structures than common organic silicon foaming materials, so the organic silicon foam has better flame retardant property.
The invention creates the elastic high-temperature-resistant intrinsic flame-retardant foam, the two components can be mixed to foam, the foam can be foamed in situ, and the prepared foaming agent has good flame-retardant effect without adding a flame retardant. The method is simple and easy to implement, low in raw material cost, rapid in reaction, capable of foaming in situ, free of foaming agent, flame retardant and high-temperature resistant filler, capable of foaming on site instantly, suitable for various occasions, safe and environment-friendly, and free of toxic gas after being heated. The composite material has wide application prospect in military fields such as aerospace and the like, new energy battery packs, civil buildings and various occasions where high-temperature resistance, heat insulation and flame retardance are needed for sealing and filling.
Compared with the prior art, the invention has the following beneficial effects:
(1) the system is energy-saving and environment-friendly, the raw materials are cheap and easy to obtain, an organic solvent is not required to be added, the preparation process is simple and convenient, and complex equipment and severe experimental conditions are not required;
(2) the intrinsic flame-retardant heat-insulation organic silicon foaming adhesive disclosed by the invention has more silica-silica structures, does not need to add a flame retardant, has the advantages of rapidness, light weight, no halogen, environmental friendliness, non-combustibility and the like, and has wide application prospects in the fields of aviation, aerospace, electronics and the like, such as high-temperature-resistant heat-insulation plugging of the periphery of an engine, wire tube plugging in building flame-retardant requirements, heat insulation of battery components in a new energy automobile and the like.
Drawings
FIG. 1 is a graph showing the thermal weight loss of silicone rubber foam prepared in example 1 in an air atmosphere;
FIG. 2 shows the preparation of silicone rubber foam in example 329Si-NMR spectrum.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.
The raw materials used in the examples are all conventional commercially available raw materials.
The parts described in the examples are parts by weight.
Example 1
The flame-retardant heat-insulation organic silicon foaming adhesive comprises a component A and a component B, wherein the component A mainly comprises the following components in parts by weight: 100 parts of methyl hydrogen-containing silicone oil with the polymerization degree n of 50-60 and the content of silicon hydrogen functional groups of 1mol/100 g; the component B mainly comprises the following components in parts by weight: 10 parts of diphenyl silanediol and 0.5 part of chloroplatinic acid catalyst; the molar ratio of the silicon-hydrogen functional groups of the polysiloxane of the component A to the hydroxyl groups in the component B is 1: 0.1.
The preparation method of the flame-retardant heat-insulation organic silicon foaming adhesive comprises the following steps:
(1) weighing methyl hydrogen-containing silicone oil according to a formula;
(2) weighing diphenyl silanediol and chloroplatinic acid according to the formula, and fully stirring to uniformly mix the diphenyl silanediol and the chloroplatinic acid;
(3) adding a mixture of diphenyl silanediol and chloroplatinic acid into methyl hydrogen-containing silicone oil, stirring while adding until gas comes out of the system, stopping stirring, reacting quickly after 50 ℃ for about 1min, and generating white solid foam to obtain the flame-retardant heat-insulating organic silicon foaming adhesive.
The prepared organic silicon foaming adhesive is subjected to flame retardance, thermal weight loss and heat insulation tests, and the flame retardance grade reaches the V-0 standard through a UL-94 vertical combustion test and a limit oxygen index test, the limit oxygen index is 31, and the organic silicon foaming adhesive is non-combustible at room temperature and has no smoldering phenomenon; through TGA, the thermal weight loss test is carried out on the alloy, the weight loss of the alloy at 1000 ℃ is only about 23 wt%, and the high temperature resistance is excellent; the thermal conductivity of the material is measured by a thermal conductivity meter to be about 0.09W (mk)-1。
Example 2
The flame-retardant heat-insulation organic silicon foaming adhesive comprises a component A and a component B, wherein the component A mainly comprises the following components in parts by weight: 100 parts of methyl phenyl hydrogen-containing silicone oil with the polymerization degree n of 100-120 and the content of silicon hydrogen functional groups of 0.5mol/100 g; the component B mainly comprises the following components in parts by weight: 15 parts of phenol and 0.2 part of benzyl trimethyl ammonium hydroxide catalyst; the molar ratio of the silicon-hydrogen functional groups of the polysiloxane of the component A to the hydroxyl groups in the component B is 1: 0.3.
The preparation method of the flame-retardant heat-insulation organic silicon foaming adhesive comprises the following steps:
(1) weighing methyl phenyl hydrogen-containing silicone oil according to a formula;
(2) weighing phenol and benzyl trimethyl ammonium hydroxide according to a formula, and fully stirring to uniformly mix the phenol and the benzyl trimethyl ammonium hydroxide;
(3) adding the mixture of phenol and benzyl trimethyl ammonium hydroxide into methyl phenyl hydrogen-containing silicone oil, stirring while adding until gas comes out of the system, stopping stirring, reacting at 40 deg.C for about 5min, and allowing the system to react rapidly to obtain white solid foam to obtain the final product
The prepared foam material is subjected to flame retardance, thermal weight loss and heat insulation tests, and the flame retardance grade reaches the V-0 standard through a UL-94 vertical combustion test and a limit oxygen index test, the limit oxygen index is 29, and the foam material is non-combustible at room temperature and has no smoldering phenomenon; through TGA, the thermal weight loss test is carried out on the alloy, the weight loss of the alloy at 1000 ℃ is only about 20 wt%, and the high temperature resistance is excellent; the thermal conductivity of the material is measured by a thermal conductivity meter to be about 0.15W (mk)-1。
Example 3
The flame-retardant heat-insulation organic silicon foaming adhesive comprises a component A and a component B, wherein the component A mainly comprises the following components in parts by weight: the polymerization degree n is 500-550, and the content of silicon hydrogen functional groups is 1.5mol per 100g of methyl hydrogen-containing silicone oil 100 parts; the component B mainly comprises the following components in parts by weight: 35 parts of ethanol and 0.5 part of tetramethyl ammonium hydroxide catalyst; the molar ratio of the silicon-hydrogen functional groups of the polysiloxane of the component A to the hydroxyl groups in the component B is 1: 0.5.
The preparation method of the flame-retardant heat-insulation organic silicon foaming adhesive comprises the following steps:
(1) weighing methyl hydrogen-containing silicone oil according to a formula;
(2) weighing ethanol and tetramethylammonium hydroxide according to the formula, and fully stirring to uniformly mix;
(3) and adding a mixture of ethanol and tetramethylammonium hydroxide into methyl hydrogen-containing silicone oil, stirring while adding until gas is blown out of the system, stopping stirring, quickly reacting the system after about 7min at 45 ℃, and generating white solid foam to obtain the flame-retardant heat-insulating organic silicon foaming adhesive.
The prepared foam material is subjected to flame retardance, thermal weight loss and heat insulation tests, and the flame retardance grade reaches the V-0 standard through a UL-94 vertical combustion test and a limit oxygen index test, the limit oxygen index is 30, and the foam material is non-combustible at room temperature and has no smoldering phenomenon; the thermal weight loss test is carried out on the composite material by TGA, the weight loss is only about 18 wt.% at 1000 ℃, and the composite material has high temperature resistanceThe performance is excellent; the thermal conductivity of the material is measured by a thermal conductivity meter to be about 0.13W (mk)-1。
Example 4
The flame-retardant heat-insulation organic silicon foaming adhesive comprises a component A and a component B, wherein the component A mainly comprises the following components in parts by weight: degree of polymerization n is 1000 to 1100, R2The content of the methoxyl functional group is 0.8mol per 100g of methyl methoxyl silicone oil 100 parts; the component B mainly comprises the following components in parts by weight: 25 parts of methanol and 2 parts of sodium hydroxide catalyst; r of component A polysiloxane2The molar ratio of the methoxy functional group to the hydroxyl in the component B is 1:1.
The preparation method of the flame-retardant heat-insulation organic silicon foaming adhesive comprises the following steps:
(1) weighing methyl methoxy silicone oil according to a formula;
(2) weighing methanol and sodium hydroxide catalyst according to a formula, and fully stirring to uniformly mix the methanol and the sodium hydroxide catalyst;
(3) adding a mixture of methanol and sodium hydroxide into methyl methoxy silicone oil, stirring while adding until gas is blown out of the system, stopping stirring, and after about 4min at 60 ℃, quickly reacting the system to generate white solid foam to obtain the flame-retardant heat-insulation organic silicon foaming adhesive.
The prepared foam material is subjected to flame retardance, thermal weight loss and heat insulation tests, and the flame retardance grade reaches the V-0 standard through a UL-94 vertical combustion test and a limit oxygen index test, the limit oxygen index is 29, and the foam material is non-combustible at room temperature and has no smoldering phenomenon; through TGA, the thermal weight loss test is carried out on the alloy, the weight loss of the alloy is only about 25 wt% at 1000 ℃, and the high temperature resistance is excellent; the thermal conductivity of the material is measured by a thermal conductivity meter to be about 0.16W (mk)-1。
Example 5
The flame-retardant heat-insulation organic silicon foaming adhesive comprises a component A and a component B, wherein the component A mainly comprises the following components in parts by weight: the polymerization degree n is 1400-1500, R 2100 parts of methyl phenyl methoxy silicone oil with the content of the methoxy functional group of 0.3mol/100 g; the component B mainly comprises the following components in parts by weight:25 parts of ethanol and 4 parts of sodium hydroxide catalyst; r of component A polysiloxane2The molar ratio of the methoxy functional group to the hydroxyl in the component B is 1: 1.8.
The preparation method of the intrinsic flame-retardant organic silicon heat-insulation foaming adhesive comprises the following steps:
(1) weighing methyl phenyl methoxy silicone oil according to a formula;
(2) weighing ethanol and sodium hydroxide catalyst according to the formula, and fully stirring to uniformly mix the ethanol and the sodium hydroxide catalyst;
(3) adding a mixture of ethanol and sodium hydroxide into methyl phenyl methoxy silicone oil, stirring while adding until gas is blown out of the system, stopping stirring, quickly reacting the system after about 5min at 60 ℃, and generating white solid foam to obtain the flame-retardant heat-insulation organic silicon foaming adhesive.
The prepared foaming adhesive is subjected to flame retardance, thermal weight loss and heat insulation tests, and the flame retardance grade reaches the V-0 standard through a UL-94 vertical combustion test and a limit oxygen index test, the limit oxygen index is 31, the foaming adhesive is non-combustible at room temperature, and the smoldering phenomenon does not occur; through TGA, the thermal weight loss test is carried out on the alloy, the weight loss of the alloy at 1000 ℃ is only about 22 wt%, and the high temperature resistance is excellent; the thermal conductivity of the material is measured by a thermal conductivity meter to be about 0.19W (mk)-1。
Claims (10)
1. An intrinsic flame-retardant heat-insulation organic silicon foaming adhesive is characterized in that:
the organic silicon foaming adhesive is prepared from the following raw materials:
a component A and a component B;
the component A comprises active polysiloxane, and the component B comprises hydroxyl-containing substances and a catalyst;
based on 100 parts by weight of active polysiloxane:
1-50 parts by weight of hydroxyl-containing substances;
0.05-5 parts by weight of a catalyst.
2. The intrinsic flame-retardant heat-insulating silicone foam adhesive according to claim 1, characterized in that:
based on 100 parts by weight of active polysiloxane:
10-35 parts by weight of a hydroxyl-containing substance;
0.2-4 parts by weight of a catalyst.
3. The intrinsic flame-retardant heat-insulating silicone foam adhesive according to claim 1, characterized in that:
the structure of the component A is as follows:
R1one or more of methyl, ethyl, isopropyl, butyl, octyl, phenyl, epoxy, vinyl, allyl, ketoximino and Cl;
R2is one or more of hydrogen, hydroxyl, methoxy, ethoxy, butoxy, epoxy, vinyl, allyl, ketoximino and Cl;
R3、R4each independently selected from one of methyl, ethyl, isopropyl, butyl, octyl, phenyl, hydrogen, hydroxyl, methoxyl, ethoxyl, epoxy, vinyl, allyl, ketoximino and Cl;
1. ltoreq. n.ltoreq.2000, preferably 20. ltoreq. n.ltoreq.1500.
4. The intrinsic flame-retardant heat-insulating silicone foam adhesive according to claim 3, characterized in that:
r in the A component2The content of the group is in the range of 0.1 to 1.55mol/100g, preferably 0.5 to 1.55mol/100 g.
5. The intrinsic flame-retardant heat-insulating silicone foam adhesive according to claim 4, characterized in that:
r in the A component2The molar ratio of the group to the hydroxyl in the component B is 1: 0.1-1: 2, preferably 1: 0.1-1: 1.
6. The intrinsic flame-retardant heat-insulating silicone foam adhesive according to claim 1, characterized in that:
the active polysiloxane is at least one of methyl hydrogen-containing silicone oil, methyl phenyl hydrogen-containing silicone oil, ethyl hydrogen-containing silicone oil, methyl ethoxy silicone oil, vinyl hydrogen-containing silicone oil, methyl methoxy hydrogen-containing silicone oil, epoxy methyl silicone oil, methoxy methyl silicone oil and vinyl methyl silicone oil; and/or the presence of a gas in the gas,
the hydroxyl-containing substance is C1-11At least one of monohydric alcohol, substance containing phenolic hydroxyl group, substance containing silicon hydroxyl group, and substance containing hydroxy hydrocarbon silicon oil.
7. The intrinsic flame-retardant heat-insulating silicone foam adhesive according to claim 6, characterized in that:
the hydroxyl-containing substance is at least one of methanol, ethanol, phenol, diphenyl silanediol and hydroxyl-terminated polysiloxane.
8. The intrinsic flame-retardant heat-insulating silicone foam adhesive according to claim 1, characterized in that:
the catalyst is at least one of alkali metal hydroxide, platinum-containing complex, strong inorganic acid, organic base, boron-containing substance and organic tin.
9. The intrinsic flame-retardant heat-insulating silicone foam adhesive according to claim 8, characterized in that:
the catalyst is at least one of sodium hydroxide, tetramethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide and chloroplatinic acid.
10. The preparation method of the intrinsic flame-retardant heat-insulating organic silicon foaming adhesive as claimed in any one of claims 1 to 9, characterized by comprising the following steps:
firstly, respectively mixing the component A and the component B according to the using amount of each component, and then mixing the component A and the component B to prepare the intrinsic flame-retardant heat-insulation organic silicon foaming adhesive;
the foaming temperature is 30-70 ℃; the foaming time is 1-30 min.
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| US3923705A (en) * | 1974-10-30 | 1975-12-02 | Dow Corning | Method of preparing fire retardant siloxane foams and foams prepared therefrom |
| EP2090294A1 (en) * | 2008-02-12 | 2009-08-19 | Coty Deutschland GmbH | Two-part cosmetic product with swelling effect to biological surfaces |
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