CN103600530B - A kind of Elastic heat insulation encapsulant and preparation method thereof - Google Patents

A kind of Elastic heat insulation encapsulant and preparation method thereof Download PDF

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CN103600530B
CN103600530B CN201310573136.7A CN201310573136A CN103600530B CN 103600530 B CN103600530 B CN 103600530B CN 201310573136 A CN201310573136 A CN 201310573136A CN 103600530 B CN103600530 B CN 103600530B
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heat insulation
room temperature
fiber
silicone rubber
elastic heat
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CN103600530A (en
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宋寒
邹军锋
赵小玲
张昊
詹万初
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Aerospace Research Institute of Materials and Processing Technology
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Abstract

The invention provides a kind of Elastic heat insulation encapsulant and preparation method thereof.Described Elastic heat insulation encapsulant comprises fiber base framework and room temperature vulcanized silicone rubber, and described fiber base framework is made up of rigidity chopped fiber and flexible long fibre.Described method uses fibrous matrix as skeleton, and room temperature vulcanized silicone rubber is as bonding agent, through steps such as fiber base framework molding, compound, the sulfurations of silicon rubber bonder.The method of the present invention is simple, easy and simple to handle, environmental pollution is little.Described material can keep preferable low-density, high thermal insulation and elastic and processing performance by applied environment below 400 DEG C, the heat seal being applicable to such as high temperature applied environment uses, and has a good application prospect in the field such as aerospace industries, civilian industry.

Description

A kind of Elastic heat insulation encapsulant and preparation method thereof
Technical field
The present invention relates to high temperature heat-resistant encapsulant field, specifically, the present invention relates to a kind of high temperature heat-resistant sealing material Material and preparation method thereof.
Background technology
Aircraft with high speed get through the earth's atmosphere flight time, owing to it is to the compression of front air and with empty around The friction of gas, is transformed into the heat energy of air by some kinetic energy, makes aircraft face the thermal environment of sternness.At such environment Under, it is necessary to using the thermal protection system of excellent performance to protect aircraft, the most various sections and moving part need Seal for a long time under high temperature, be unusual the key link in whole thermal protection system, it is therefore desirable to possess temperature-resistance thermal-insulation performance Encapsulant, to stop heat internally to spread transmission.
At present, the material being used for heat-insulating and sealing both at home and abroad mainly has high-temperature resistant seal ring, high temperature resistant expansion ceramic, fluid sealant Deng, the condition of use mostly is less than 100 DEG C or is more than the environment of 800 DEG C, and the high temperature heat-resistant encapsulant master that the present invention relates to Will be for aircraft interior, temperature range at RT (room temperature, such as 25 DEG C)~the use environment of 400 DEG C.This material uses resistance to height Temperature fiber base framework is compound with high-temperature-resisting silicon rubber bonding agent to be made, and has temperature-resistance thermal-insulation functional, and density, elasticity are controlled Etc. advantage.Wherein fiber base framework is such as made up of such as inorfil, it is provided that temperature-resistance thermal-insulation and supporting role;Silicone rubber glues Connect agent and use the room temperature vulcanized silicone rubber that can use at 400 DEG C or higher temperature for a long time, it is provided that the resistance to gentle elasticity that strengthens is made With.
Summary of the invention
In order to solve one or more the problems referred to above, the invention provides a kind of Elastic heat insulation encapsulant and preparation side thereof Method.
It is an object of the invention to be achieved through the following technical solutions:
1, a kind of Elastic heat insulation encapsulant, wherein, described Elastic heat insulation encapsulant comprises fiber base framework and room Temperature vulcanizable silicone rubber, described fiber base framework is made up of rigidity chopped fiber and flexible long fibre.
2, according to the method described in technical scheme 1, wherein, described rigidity chopped fiber is to select the group of free llowing group of materials composition In the combination of one or more: quartz fibre, alumina fibre, mullite fiber and alumina silicate fibre;Described flexible long fibre The combination of one or more in the group that dimension forms for selecting free llowing group of materials: quartz fibre, basalt fibre, high silica are fine Dimension, glass fibre and alumina silicate fibre.
3, the Elastic heat insulation encapsulant as described in technical scheme 1 or 2, wherein, described rigidity chopped fiber a diameter of 3~ 15 μm, a length of 1~10mm;Long stapled a diameter of 1~10 μm of described flexibility, a length of 10~50cm.
4, the Elastic heat insulation encapsulant as according to any one of technical scheme 1 to 3, wherein, described rigidity chopped fiber with Flexible long stapled mass ratio is 1:(0.1~10).
5, the Elastic heat insulation encapsulant as according to any one of technical scheme 1~4, wherein, room temperature vulcanized silicone rubber selects Freely tolerate the silicone rubber of more than 400 DEG C.
6, the Elastic heat insulation encapsulant as according to any one of technical scheme 1~5, wherein, described room temperature vulcanization silicon rubber Glue selects free KH-CL-RTV silicone rubber and the group of PSN silicone rubber composition.
7, the Elastic heat insulation encapsulant as according to any one of technical scheme 1 to 6, wherein, described fiber base framework It is 1:(0.5~5 with the mass ratio of room temperature vulcanized silicone rubber).
8, the Elastic heat insulation encapsulant as according to any one of technical scheme 1 to 7, wherein, described Elastic heat insulation seals The compression ratio of material is 5~25%, and rebound degree is 50%~90%.
9, the Elastic heat insulation encapsulant as according to any one of technical scheme 1 to 8, wherein, described Elastic heat insulation seals Room temperature (25 DEG C) heat conductivity of material is 0.03~0.09W/m.K.
10, according to the Elastic heat insulation encapsulant according to any one of technical scheme 1 to 9, wherein, described Elastic heat insulation is close The density of closure material is 0.1~0.5g/cm3
11, a kind of method of Elastic heat insulation encapsulant prepared as according to any one of technical scheme 1~10, described side Method comprises the steps:
(1) it is mat by rigidity chopped fiber and flexible long fibre mixed-forming, then is plated in as having target thick through multilamellar The fiber base framework of degree;
(2) described fiber base framework is combined with described room temperature vulcanized silicone rubber, obtains fiber base framework-room temperature sulfur SiClx rubber composite;With
(3) described composite is vulcanized, obtain described Elastic heat insulation encapsulant.
12, the method as described in technical scheme 11, wherein, in the group of described Combined Mining choosing freely following method composition The combination of one or more: normal pressure dipping, vacuum impregnation and impregnating by pressure.
13, the method as described in technical scheme 11 or 12, wherein, is in mass in order to compound room temperature vulcanized silicone rubber Concentration room temperature vulcanized silicone rubber solution in the range of 5%~80%.
14, the method as according to any one of technical scheme 11 to 13, wherein, described being combined carries out one or many.
15, the Elastic heat insulation encapsulant prepared by the method according to any one of technical scheme 11 to 14.
The described Elastic heat insulation encapsulant of the present invention and method have the advantage that
(1) the Elastic heat insulation encapsulant resistance to elevated temperatures that prepared by the present invention is good, can below 400 DEG C life-time service;
(2) the Elastic heat insulation encapsulant heat conductivity that prepared by the present invention is relatively low, has preferable heat-proof quality, and room temperature is led Hot coefficient is 0.03~0.09W/m.K;
(3) the Elastic heat insulation encapsulant that prepared by the present invention has preferable elasticity, and elastic controlled, and compression ratio scope is 5~25%, rebound degree scope is 50%~90%;
(4) the Elastic heat insulation encapsulant density that prepared by the present invention is controlled, such as, can be controlled as 0.1~0.5g/cm3 Between;
(5) method of the present invention is simple, easy and simple to handle, environmental pollution is little;
(6) present invention may be used for preparing the component product of variously-shaped specification, aerospace industry and other high temperature, Need the environment of heat-insulating and sealing is with a wide range of applications.
Detailed description of the invention
The invention provides a kind of Elastic heat insulation encapsulant, described Elastic heat insulation encapsulant comprises fiber base framework Especially high-temperature fibre matrix skeleton, this skeleton can be made up of the fiber of variety classes different proportion so that fiber reinforcement There is different heat resistances and thermophysical property;Comprise the most high temperature resistant room temperature vulcanized silicone rubber of room temperature vulcanized silicone rubber. Additionally, present invention also offers a kind of method preparing described Elastic heat insulation encapsulant, described method is by adjusting room temperature sulfur The complex method of SiClx rubber, concentration and compounding times etc. make material can obtain different target mechanical properties and hot thing Rationality energy.
Specifically, the present invention provides a kind of Elastic heat insulation encapsulant, wherein, described Elastic heat insulation in first aspect Encapsulant comprises fiber base framework and room temperature vulcanized silicone rubber, and described fiber base framework is by rigidity chopped fiber and soft Property long fibre composition.
The fiber type of composition fiber base framework is not particularly limited by the present invention, and the fiber that premise is used needs energy Enough tolerance targets use ambient temperature.It is preferred, however, that, described rigidity chopped fiber is in the group selecting free llowing group of materials composition The combination of one or more: quartz fibre, alumina fibre, mullite fiber and alumina silicate fibre;Described flexible long fibre For select free llowing group of materials form group in the combination of one or more: quartz fibre, basalt fibre, high silica fiber, Glass fibre and alumina silicate fibre.It addition, described rigidity chopped fiber chemical composition long stapled with flexibility can be identical, such as may be used With simultaneously as quartz fibre;Described rigidity chopped fiber and the long stapled chemical composition of flexibility can also be different, the short fibre of such as rigidity Dimension can be quartz fibre, and flexible long fibre is basalt fiber.
For rigidity chopped fiber, its diameter is preferably 3~15 μm, such as, can be the arbitrary diameter in the range of this, example As being 3,4,5,6,7,8,9,10,11,12,13,14,15 μm, or anyon scope therebetween, such as 5~10 μm, 6 ~8 μm etc..Length is preferably 1~10mm, such as, can be 1,2,3,4,5,6,7,8,9 or 10mm, or anyon therebetween Scope, such as 2~8mm, 4~6mm etc..
For flexible long fibre, its diameter is preferably 1~10 μm, such as, can be 3,4,5,6,7,8,9 or 10 μm, or Person's anyon scope therebetween, such as 2~8 μm, 4~6 μm etc..Length is preferably 10~50cm, such as 10,15,20,25,30, 35,40,45 or 50cm, or anyon scope therebetween, such as, can be 15~45cm, 20~40cm etc..
The present inventor finds in the experimentation carried out by exploitation Elastic heat insulation encapsulant, is used alone rigidity short Fiber or be used alone flexible long fibre obtained material all cannot be made to ensure to have high thermal insulation, low-density and suitably Durothermic have higher elasticity simultaneously.It was found surprisingly that later, used rigidity chopped fiber and the long stapled combination of flexibility also Such problem can be solved in conjunction with suitable room temperature vulcanized silicone rubber binding agent, make resulting materials keep above-mentioned thermal insulation, close Spend, with durothermic, there is significantly higher (relative to being used alone rigidity chopped fiber or flexible long stapled situation is compared) simultaneously Elasticity.
Some preferred embodiment in, described rigidity chopped fiber and the long stapled mass ratio of flexibility be 1:(0.1~ 10), for example, 1:0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,2.0,3.0,4.0,5.0,6.0,7.0, 8.0,9.0 or 10.0.If the ratio of rigidity chopped fiber is excessive or flexible long stapled ratio is excessive, possibly cannot ensure with Shi Shixian target thermal insulation and elasticity.
For room temperature vulcanized silicone rubber, it primarily serves bonding agent in the present invention and provides the effect of elasticity, therefore exists Sometimes herein called silicon rubber bonder, silicone rubber or bonding agent.Room temperature vulcanized silicone rubber is had no particular limits by the present invention, But it allows for tolerating target and uses ambient temperature, such as 25 DEG C to 400 DEG C temperature the most higher.Room temperature vulcanization silicon rubber Glue can be commercially available prod, such as can be with KH-CL-RTV silicone rubber and/or PSN silicone rubber.
In some embodiments, the mass ratio of described fiber base framework and room temperature vulcanized silicone rubber is preferably 1: (0.5~5), for example, 1:0.5,0.6,0.7,0.8,0.9,1.0,2.0,3.0,4.0 or 5.0, this ratio is too high or too low can Can cannot realize thermal insulation and elastic balance.
The various performances of the described Elastic heat insulation encapsulant of the present invention can be long by regulation rigidity chopped fiber and flexibility The ratio of fiber, the consumption etc. of room temperature vulcanized silicone rubber are adjusted.Some preferred embodiment in, can be as required Described Elastic heat insulation encapsulant is prepared as compression ratio be 5~25% (can be such as 5,10,15,20 or 25% etc. or Anyon scope therebetween), rebound degree is the material of 50%~90% (can be such as 50,60,70,80 or 90%).It addition, Described Elastic heat insulation encapsulant can also be prepared as room temperature (25 DEG C) heat conductivity is 0.03~0.09W/m.K, such as 0.03,0.04,0.05,0.06,0.07,0.08 or 0.09W/m.K, or anyon scope therebetween.Alternatively, it is also possible to by institute Stating Elastic heat insulation encapsulant and being prepared as density is 0.1~0.5g/cm3, such as, can be 0.1,0.2,0.3,0.4 or 0.5g/ cm3
In a second aspect of the present invention, it is provided that a kind of method preparing Elastic heat insulation encapsulant as above, institute The method of stating may include steps of:
(1) it is mat by rigidity chopped fiber and flexible long fibre mixed-forming, then is plated in as having target thick through multilamellar The fiber base framework of degree;
(2) described fiber base framework is combined with described room temperature vulcanized silicone rubber, obtains fiber base framework-room temperature sulfur SiClx rubber composite;With
(3) described composite is vulcanized, obtain described Elastic heat insulation encapsulant.
In some embodiments, described being combined can be by using fiber base described in room temperature vulcanized silicone rubber solution impregnation Body skeleton is carried out, and dipping can use the combination of one or more in the group of choosing freely following method composition: normal pressure soaks Stain, vacuum impregnation and impregnating by pressure, it is preferred that from the point of view of impregnating speed and effect, vacuum impregnation is preferably used.Dipping is made The solution concentration in mass of room temperature vulcanized silicone rubber can be 5%~80%, can be such as 5,10,15,20, 25,30,35,40,45,50,55,60,65,70,75 or 80%, if concentration is too low, possibly larger amount of room temperature cannot be impregnated Sulphurated siliastic, so that the elasticity of finally obtained material is too low;If excessive concentration, may cannot be carried out sufficiently Dipping or dipping need the long time.It addition, the solvent preparing described solution is not particularly limited by the present invention, such as may be used Think hexamethylene etc..
It addition, described being combined can be carried out once, it is also possible to carry out several times.
The material of described method use and ratio thereof, as described in this specification first aspect, repeat no more again.
In a third aspect of the present invention, it is provided that the Elastic heat insulation encapsulant being worth by said method, this Elastic heat insulation The performance of encapsulant is for as described in first aspect present invention, again repeated no more.
It is further noted that, if not otherwise specified, any scope described in the present invention includes end value and end value Between any numerical value and and the anyon scope that constituted with any number between end value or end value.
Below in conjunction with embodiment, the invention will be further described.These embodiments are simply with regard to the side of being preferable to carry out of the present invention Formula is illustrated, and protection scope of the present invention is not read as pertaining only to these embodiments.
Various embodiments of the present invention relate to raw material and are market purchase.
Embodiment 1
Preparing Elastic heat insulation encapsulant of the present invention, wherein, fiber base framework is fine by rigidity chopped fiber quartz Dimension (diameter 5~8 μm, length 1~3mm) and flexible long fibre basalt fibre (diameter 1~3 μm, length 20~25cm) composition, Chopped fiber and long fibre mass ratio are 1:1.Bonding agent is silicone rubber KH-CL-RTV.
First rigidity chopped fiber and flexible long fibre are mixed and made into mat, then it is thick that 20 layers of such mat are made 25mm The fiber base framework of degree.The silicone rubber that concentration is 50% is glued by the mode then using vacuum impregnation (vacuum-0.09MPa) Connect agent (diluent is hexamethylene) and be combined 2h (hour), fiber base framework and silicon rubber bonder quality with fiber base framework Ratio is 1:0.67, through room temperature vulcanization 24h, can obtain Elastic heat insulation encapsulant.
Test sample performance: heatproof 400 DEG C (400 DEG C process 2h, and sample does not shrinks);Density 0.25g/cm3(GB/ T6343-2009);Room temperature heat conductivity 0.05W/m.K (GB/T10295-2008);Compression ratio 10%, rebound degree 75% (GB/ T7759-1996)。
Embodiment 2
Preparing Elastic heat insulation encapsulant of the present invention, wherein, fiber base framework is fine by rigidity chopped fiber quartz Dimension (diameter 5~8 μm, length 1~3mm) and flexible long fibre basalt fibre (diameter 1~3 μm, length 20~25cm) composition, Chopped fiber and long fibre mass ratio are 1:2.Bonding agent is silicone rubber KH-CL-RTV.
First rigidity chopped fiber and flexible long fibre are mixed and made into mat, then it is thick that 20 layers of such mat are made 25mm The fiber base framework of degree.The silicone rubber that concentration is 50% is glued by the mode then using vacuum impregnation (vacuum-0.09MPa) Connecing agent (diluent is hexamethylene) and be combined 2h with fiber base framework, fiber base framework and silicon rubber bonder mass ratio are 1: 0.67, through room temperature vulcanization 24h, obtain Elastic heat insulation encapsulant.
Test sample performance: heatproof 400 DEG C (400 DEG C process 2h, and sample does not shrinks);Density 0.25g/cm3(GB/ T6343-2009);Room temperature heat conductivity 0.054W/m.K (GB/T10295-2008);Compression ratio 10%, rebound degree 81% (GB/ T7759-1996)。
Embodiment 3~5
In addition to content listed in table 1, embodiment 3~5 uses to be implemented with the identical mode of embodiment 1 and 2.
Comparative example 1
Fiber base framework only uses rigidity chopped fiber quartz fibre (diameter 5~8 μm, length 1~3mm) to make.Bonding Agent is silicone rubber KH-CL-RTV.
First rigidity chopped fiber is made mat, then 20 layers of such mat are made the fibrous matrix bone of 25mm thickness Frame.Then (diluent is by silicon rubber bonder that concentration is 50% to use the mode of vacuum impregnation (vacuum-0.09MPa) Hexamethylene) it is combined 2h with fiber base framework, fiber reinforcement and silicon rubber bonder mass ratio are 1:0.67, through room temperature vulcanization 24h, obtains Elastic heat insulation encapsulant.
Test sample performance: heatproof 400 DEG C (400 DEG C process 2h, and sample does not shrinks);Density 0.25g/cm-3(GB/ T6343-2009);Room temperature heat conductivity 0.05W/m.K (GB/T10295-2008);Compression ratio 10%, rebound degree 5%, material base Originally cannot resilience (GB/T7759-1996).
Comparative example 2
Fiber base framework only uses flexible long fibre basalt fibre (diameter 1~3 μm, length 20~25cm) to make. Bonding agent is silicone rubber KH-CL-RTV.
First flexibility long fibre is made mat, then 20 layers of such mat are made the fiber base framework of 25mm.So By silicon rubber bonder that concentration is 50%, (diluent is hexamethylene to the mode of rear use vacuum impregnation (vacuum-0.09MPa) Alkane) it is combined 2h with fiber base framework, fiber reinforcement and silicon rubber bonder mass ratio are 1:0.67, through room temperature vulcanization 24h, Obtain Elastic heat insulation encapsulant.
Test sample performance: heatproof 400 DEG C (400 DEG C process 2h, and sample does not shrinks);Density 0.25g/cm3(GB/ T6343-2009);Room temperature heat conductivity 0.10W/m.K (GB/T10295-2008), heat-proof quality reduces;Compression ratio 10%, return Bullet rate 30% (GB/T7759-1996), material rebounds poor performance.
Comparative example 3
Fiber base framework is profound by rigidity chopped fiber quartz fibre (diameter 5~8 μm, length 1~3mm) and flexible long fibre Military rock fiber (diameter 1~3 μm, length 20~25cm) composition, chopped fiber and long fibre mass ratio are 1:1.Bonding agent is silicon rubber Glue KH-CL-RTV.
First rigidity chopped fiber and flexible long fibre are mixed and made into mat, then 20 layers of such mat are made 25mm's Fiber base framework.Concentration is the silicon rubber bonder of 50% by the mode then using vacuum impregnation (vacuum-0.09MPa) (diluent is hexamethylene) and fiber base framework are combined 2h, and fiber reinforcement and silicon rubber bonder mass ratio are 1:10, pass through Room temperature vulcanization 24h, obtains Elastic heat insulation encapsulant.
Test sample performance: heatproof 400 DEG C (400 DEG C process 2h, and sample does not shrinks);Density 0.6g/cm3(GB/T6343- 2009);Room temperature heat conductivity 0.2W/m.K (GB/T10295-2008), heat-proof quality reduces;Compression ratio 10%, rebound degree 90% (GB/T7759-1996)。
Comparative example 4
Fiber base framework be rigidity chopped fiber quartz fibre (diameter 5~8 μm, length 1~3mm) and flexible long fibre profound Military rock fiber (diameter 1~3 μm, length 20~25cm) composition, chopped fiber and long fibre mass ratio are 1:1.Bonding agent is silicon rubber Glue KH-CL-RTV.
First rigidity chopped fiber and flexible long fibre are mixed and made into mat, then it is thick that 20 layers of such mat are made 25mm The fiber base framework of degree.The silicone rubber that concentration is 50% is glued by the mode then using vacuum impregnation (vacuum-0.09MPa) Connecing agent (diluent is hexamethylene) and be combined 2h with fiber base framework, fiber reinforcement and silicon rubber bonder mass ratio are 1:0.1, Through room temperature vulcanization 24h, Elastic heat insulation encapsulant can be obtained.
Test sample performance: heatproof 400 DEG C (400 DEG C process 2h, and sample does not shrinks);Density 0.2g/cm3(GB/T6343- 2009);Room temperature heat conductivity 0.05W/m.K (GB/T10295-2008);Compression ratio 10%, rebound degree 10% (GB/T7759- 1996), material rebounds poor performance.
Embodiment 6~10
In addition to content listed in table 1, embodiment 6~10 uses to be implemented with the identical mode of embodiment 1 and 2.

Claims (11)

1. the method preparing Elastic heat insulation encapsulant, wherein said Elastic heat insulation encapsulant comprises fiber base framework And room temperature vulcanized silicone rubber, described fiber base framework is made up of rigidity chopped fiber and flexible long fibre, described method include as Lower step:
(1) it is mat by described rigidity chopped fiber and described flexible long fibre mixed-forming, then is plated in as having mesh through multilamellar The described fiber base framework of mark thickness;
(2) described fiber base framework is combined with described room temperature vulcanized silicone rubber, obtains fiber base framework-room temperature vulcanization silicon Rubber composite;With
(3) described composite is vulcanized, obtain described Elastic heat insulation encapsulant.
The most the method for claim 1, wherein it is that concentration exists in mass in order to compound described room temperature vulcanized silicone rubber Room temperature vulcanized silicone rubber solution in the range of 5%~80%.
Method the most according to claim 1, wherein, described rigidity chopped fiber is in the group selecting free llowing group of materials composition The combination of one or more: quartz fibre, alumina fibre, mullite fiber and alumina silicate fibre;Described flexible long fibre is Select the combination of one or more in the group that free llowing group of materials forms: quartz fibre, basalt fibre, high silica fiber, glass Glass fiber and alumina silicate fibre.
4. method as claimed any one in claims 1 to 3, wherein, a diameter of 3~15 μm of described rigidity chopped fiber are long Degree is 1~10mm;Long stapled a diameter of 1~10 μm of described flexibility, a length of 10~50cm.
5. method as claimed any one in claims 1 to 3, wherein, described rigidity chopped fiber and the long stapled quality of flexibility Ratio is 1: (0.1~10).
6. method as claimed any one in claims 1 to 3, wherein, described room temperature vulcanized silicone rubber selects free KH-CL-RTV Silicone rubber and the group of PSN silicone rubber composition.
7. method as claimed any one in claims 1 to 3, wherein, described fiber base framework and room temperature vulcanized silicone rubber Mass ratio be 1: (0.5~5).
8. as claimed any one in claims 1 to 3 method, wherein, the compression ratio of described Elastic heat insulation encapsulant be 5~ 25%, rebound degree is 50%~90%.
9. as claimed any one in claims 1 to 3 method, wherein, the room temperature heat conduction system of described Elastic heat insulation encapsulant Number is 0.03~0.09W/m.K.
10. method as claimed any one in claims 1 to 3, wherein, the density of described Elastic heat insulation encapsulant is 0.1 ~0.5g/cm3
The 11. Elastic heat insulation encapsulants prepared by the method according to any one of claim 1 to 10.
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