阅读说明：本技术 一种含有气凝胶的隔热硅橡胶泡沫材料及其制备方法 (Aerogel-containing heat-insulating silicone rubber foam material and preparation method thereof ) 是由 张昌录 于 2019-08-23 设计创作，主要内容包括：本发明涉及硅橡胶泡沫材料领域,具体涉及到一种含有气凝胶的隔热硅橡胶泡沫材料及其制备方法。所述含有气凝胶的隔热硅橡胶泡沫材料其制备原料,按重量计,包括硅橡胶生胶98-102、气凝胶14-16、低热导率隔热填料14-16、空心微珠8-12、阻燃剂8-16、改性水滑石2-4、硅烷偶联剂KH-550 1-3、交联剂2-4、发泡剂4-10、发泡助剂1-3、脱模剂0.1-0.5、硫化剂3-7。本发明制得的含有气凝胶的隔热硅橡胶泡沫材料,具有良好的隔热性能、阻燃效果、力学性能和持久稳定的抗静电性和耐紫外性能,能够满足国防军工、航空航天等领域对该材料的特殊需求。(The invention relates to the field of silicon rubber foam materials, in particular to a heat-insulating silicon rubber foam material containing aerogel and a preparation method thereof. The aerogel-containing heat-insulating silicon rubber foam material comprises, by weight, 98-102 parts of raw silicon rubber, 14-16 parts of aerogel, 14-16 parts of low-thermal-conductivity heat-insulating filler, 8-12 parts of hollow microspheres, 8-16 parts of flame retardant, 2-4 parts of modified hydrotalcite, 1-5501-3 parts of silane coupling agent, 2-4 parts of cross-linking agent, 4-10 parts of foaming agent, 1-3 parts of foaming auxiliary agent, 0.1-0.5 part of release agent and 3-7 parts of vulcanizing agent. The aerogel-containing heat-insulating silicone rubber foam material prepared by the invention has good heat-insulating property, flame-retardant effect, mechanical property and lasting and stable antistatic property and ultraviolet resistance, and can meet the special requirements of the material in the fields of national defense and military industry, aerospace and the like.)

1. The aerogel-containing heat-insulating silicon rubber foam material is characterized by comprising, by weight, 98-102 parts of raw silicon rubber, 14-16 parts of aerogel, 14-16 parts of low-thermal-conductivity heat-insulating filler, 8-12 parts of hollow microspheres, 8-16 parts of flame retardant, 2-4 parts of modified hydrotalcite, 1-5501 parts of silane coupling agent KH, 2-4 parts of crosslinking agent, 4-10 parts of foaming agent, 1-3 parts of foaming auxiliary agent, 0.1-0.5 part of mold release agent and 3-7 parts of vulcanizing agent.

2. The aerogel containing, insulating, silicone rubber foam of claim 1, wherein said raw silicone rubber is methyl vinyl silicone rubber.

3. the aerogel containing, insulating, silicone rubber foam material as claimed in claim 1, wherein said aerogel is a silica aerogel; the low-thermal-conductivity heat-insulating filler is potassium hexatitanate whisker; the hollow microspheres are hollow glass microspheres.

4. The aerogel-containing, insulating, silicone rubber foam material as claimed in claim 1, wherein the mass ratio of the flame retardant to the modified hydrotalcite is (2-6): 1.

5. The aerogel containing, insulating, silicone rubber foam of claim 1, wherein said flame retardant is a combination of bis (2,6, 7-trioxa-1-phosphabicyclo [2.2.2] octane-1-oxo-4-methylene) acid phosphate melamine and melamine polyphosphate.

6. The aerogel-containing, insulating, silicone rubber foam of claim 5, wherein said melamine bis (2,6, 7-trioxa-1-1 phosphabicyclo [2.2.2] octane-1-oxo-4-methylene) acid phosphate and melamine polyphosphate are present in a mass ratio of (1-5): 1.

7. the aerogel-containing insulating silicone rubber foam material of claim 1, wherein the modified hydrotalcite is prepared from sodium metasilicate nonahydrate, hydrotalcite, sodium dodecyl sulfate, and phosphate ester salt.

8. The aerogel containing insulating silicone rubber foam of claim 7, wherein the phosphate salt is a monoalkyl ether phosphate triethanolamine salt.

9. The aerogel containing, insulating, silicone rubber foam of claim 1, wherein the cross-linking agent is hydrogen-containing silicone oil; the foaming agent is azodicarbonamide; the foaming auxiliary agent is zinc oxide; the release agent is zinc stearate; the vulcanizing agent is benzoyl peroxide.

10. A method for preparing an aerogel containing insulating silicone rubber foam material according to any one of claims 1 to 9, comprising the steps of: mixing and aging raw silicon rubber, aerogel, low-thermal-conductivity heat-insulating filler, hollow microspheres, a flame retardant, modified hydrotalcite and a silane coupling agent KH-550; and then placing the mixture in a vacuum drying oven with the temperature of 100-120 ℃ for heat treatment for 2-3h, cooling to room temperature, then remilling the mixture, adding a foaming agent, a blowing aid, a release agent and a vulcanizing agent, continuing mixing for 10-15min, foaming and vulcanizing to obtain a semi-finished product, carrying out heat treatment on the semi-finished product, and cooling to room temperature to obtain the aerogel-containing heat-insulating silicon rubber foam material.

Technical Field

The invention belongs to the field of silicon rubber foam materials, and particularly relates to a heat-insulating silicon rubber foam material containing aerogel and a preparation method thereof.

background

The silicone rubber is a kind of semi-organic semi-inorganic polymer, its main chain is formed by Si-O-Si bonds alternatively connected, and the side chain is connected with organic group. Silicone rubber has many unique properties, including good dielectric properties, chemical resistance, uv resistance and mechanical stability, due to the specific skeletal structure. The silicon rubber foam material is a porous material obtained by foaming silicon rubber, has the characteristics of sound insulation, heat insulation, high elasticity, low density and the like of common organic foam materials, has the advantages of high and low temperature resistance, radiation resistance, chemical stability and the like of the silicon rubber, is an ideal cushion layer, sealing, insulating, vibration damping, sound insulation and heat insulation material, and has important application in national defense and military industry and aerospace weaponry.

With the development of production and society, the requirements on certain special properties of silicone rubber foam materials are higher and higher, for example, in the field of aerospace, the silicone rubber foam materials are required to have good mechanical properties while having lower density. However, the existing silicone rubber foam material has the problems of poor heat resistance, easy softening at high temperature, poor flame retardant effect, poor antistatic, ultraviolet resistance and mechanical properties and the like, and influences the service performance of the silicone rubber foam.

Disclosure of Invention

In order to solve the problems, the first aspect of the invention provides an aerogel-containing heat-insulating silicone rubber foam material, and the aerogel-containing heat-insulating silicone rubber foam material comprises, by weight, 98-102 parts of raw silicone rubber, 14-16 parts of aerogel, 14-16 parts of low-thermal-conductivity heat-insulating filler, 8-12 parts of hollow microspheres, 8-16 parts of a flame retardant, 2-4 parts of modified hydrotalcite, 1-5501-3 parts of a silane coupling agent, 2-4 parts of a cross-linking agent, 4-10 parts of a foaming agent, 1-3 parts of a foaming auxiliary agent, 0.1-0.5 part of a mold release agent and 3-7 parts of a vulcanizing agent.

As a preferable technical scheme, the raw silicone rubber is methyl vinyl silicone rubber.

As a preferable technical scheme, the methyl vinyl silicone rubber has the vinyl content of 0.19-0.24% and the molecular weight of 45-70 ten thousand.

As a preferred technical solution, the aerogel is silica aerogel.

As a preferable technical solution, the low thermal conductivity heat insulating filler is potassium hexatitanate whisker.

As a preferable technical scheme, the hollow microspheres are hollow glass microspheres.

As a preferable technical scheme, the diameter of the hollow glass bead is 10-30 μm.

As a preferable technical scheme, the mass ratio of the flame retardant to the modified hydrotalcite is (2-6): 1.

As a preferred technical scheme, the flame retardant is a composition of bis (2,6, 7-trioxa-1-1 phosphabicyclo [2.2.2] octane-1-oxygen-4-methylene) acid phosphate ester melamine and polyphosphoric acid melamine.

As a preferable technical scheme, the mass ratio of the bis (2,6, 7-trioxa-1-1 phosphabicyclo [2.2.2] octane-1-oxygen-4-methylene) acid phosphate melamine to the melamine polyphosphate is (1-5): 1.

As a preferable technical scheme, the raw materials for preparing the modified hydrotalcite comprise sodium metasilicate nonahydrate, hydrotalcite, sodium dodecyl sulfate and phosphate ester salt.

As a preferable technical scheme, the phosphate ester salt is monoalkyl ether phosphate triethanolamine salt.

as a preferred technical scheme, the preparation method of the modified hydrotalcite comprises the following steps:

(1) dissolving sodium metasilicate nonahydrate into deionized water to prepare 0.08-0.12mol/L sodium metasilicate solution;

(2) Weighing 9-12g of hydrotalcite, placing the hydrotalcite in a three-neck flask, pouring the prepared 0.08-0.12mol/L sodium metasilicate solution, and adding 0.8-1.2mol/L HNO₃Adjusting pH of the solution to 10-11, stirring at 70-80 deg.C in oil bath for 15-25h, centrifuging the reaction solution after reaction, repeatedly washing with anhydrous ethanol until pH of the washing solution is 7-8, drying the precipitate in air drying oven at 80-86 deg.C for 22-26h to obtain modified waterA precursor of talc;

(3) Adding the modified hydrotalcite precursor obtained in the step (2) into a sodium dodecyl sulfate solution with the concentration of 0.16-0.20mol/L, wherein each gram of hydrotalcite corresponds to 1-4mL of sodium dodecyl sulfate, stirring the mixture in a water bath at the temperature of 70-80 ℃ for 1-4h, then adding a monoalkyl ether phosphate triethanolamine salt solution with the concentration of 0.1-0.3mol/L, each gram of hydrotalcite corresponds to 4-6mL of the monoalkyl ether phosphate triethanolamine salt solution, stirring the mixture in a water bath at the temperature of 75-85 ℃ for reaction for 5-8h, filtering, washing and draining the product, drying the product at the temperature of 90-110 ℃, and activating the product at the temperature of 110-; to obtain the modified hydrotalcite.

As a preferred technical scheme, the cross-linking agent is hydrogen-containing silicone oil; the foaming agent is azodicarbonamide; the foaming auxiliary agent is zinc oxide; the release agent is zinc stearate; the vulcanizing agent is benzoyl peroxide.

The second aspect of the present invention provides a method for preparing an aerogel-containing insulating silicone rubber foam material as described above, comprising the steps of: mixing and aging raw silicon rubber, aerogel, low-thermal-conductivity heat-insulating filler, hollow microspheres, a flame retardant, modified hydrotalcite and a silane coupling agent KH-550; and then placing the mixture in a vacuum drying oven with the temperature of 100-120 ℃ for heat treatment for 2-3h, cooling to room temperature, then remilling the mixture, adding a foaming agent, a blowing aid, a release agent and a vulcanizing agent, continuing mixing for 10-15min, foaming and vulcanizing to obtain a semi-finished product, carrying out heat treatment on the semi-finished product, and cooling to room temperature to obtain the aerogel-containing heat-insulating silicon rubber foam material.

Has the advantages that: the invention provides an aerogel-containing heat-insulating silicon rubber foam material. The silicone rubber foam material is prepared by adding the mixture of the low-thermal-conductivity heat-insulating filler, the hollow microspheres, the flame retardant and the modified hydrotalcite into raw rubber. The rubber foam material has low heat conductivity coefficient resistance, good heat insulation performance, flame retardant effect, mechanical property, ultraviolet resistance and lasting and stable antistatic property; meanwhile, silicon rubber is reinforced by adopting the silicon dioxide aerogel, so that the dispersity and compatibility between the inorganic filler and the silicon rubber are improved, and the structurization phenomenon is avoided. Therefore, the high-performance silicon rubber foam material with high strength, high wear resistance, low heat conductivity coefficient, temperature resistance, aging resistance, flame retardance and static resistance can be obtained by combining the raw materials. Can meet the special requirements of the material in the fields of national defense, military industry, aerospace and the like.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "including". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase will render the claim closed except for the materials described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

Aiming at the technical problems, the first aspect of the invention provides an aerogel-containing heat-insulating silicone rubber foam material, which comprises, by weight, 98-102 parts of raw silicone rubber, 14-16 parts of aerogel, 14-16 parts of low-thermal-conductivity heat-insulating filler, 8-12 parts of cenospheres, 8-16 parts of flame retardant, 2-4 parts of modified hydrotalcite, 1-5501-3 parts of silane coupling agent KH, 2-4 parts of cross-linking agent, 4-10 parts of foaming agent, 1-3 parts of foaming auxiliary agent, 0.1-0.5 part of release agent and 3-7 parts of vulcanizing agent.

[ Silicone Green rubber ]

In one embodiment, the raw silicone rubber is a methyl vinyl silicone rubber.

In a preferred embodiment, the raw silicone rubber is methyl vinyl silicone rubber, the vinyl content of the raw silicone rubber is 0.19-0.24%, and the molecular weight of the raw silicone rubber is 45-70 ten thousand.

The methyl vinyl silicone rubber is prepared by copolymerizing dimethyl siloxane and a small amount of vinyl siloxane, and the vinyl content is generally 0.1-0.3 percent (mole fraction). The content of methylvinylsiloxane units has a great influence on the vulcanization and the heat resistance of the vulcanizate, with an excessively low content of methylvinylsiloxane units having insignificant effects and an excessively high content of up to 0.5% (mole fraction) of methylvinylsiloxane units reducing the heat resistance of the vulcanizate.