A silica-based sound-absorbing material, preparation method thereof and application thereof

Abstract

The present invention belongs to the field of sound-absorbing materials, and specifically relates to a silica-based sound-absorbing material, a preparation method and its application. The sound-absorbing material includes: 65-80 parts of foamed polyurethane resin, 1-10 parts of halloysite nanotube composite modified silica, and 0.1-3 parts of dispersant; the halloysite nanotube composite modified silica is a condensation reaction product of amino-modified halloysite nanotubes and carboxyl-modified silica. The sound-absorbing material prepared by adding the halloysite nanotube composite modified silica of the present invention to the polyurethane foam material can significantly improve the sound-absorbing performance, compressive strength and tensile strength of the sound-absorbing material, so that the sound-absorbing material can balance high mechanical strength and high sound-absorbing performance. The multi-layer composite sound-absorbing panel composed of the sound-absorbing material of the present invention has excellent sound-absorbing performance.

Description

Technical Field

[0001] The present invention belongs to the field of sound-absorbing materials, and particularly relates to a silica-based sound-absorbing material, a preparation method thereof, and an application thereof. Background Art

[0002] With the progress of society, special-shaped buildings, with their unique forms and visual impacts, have become a highly regarded innovative form. Buildings with their streamlined curved spaces, irregular shapes, and personalized designs have broken the framework of traditional buildings, bringing endless vitality and imagination to the spatial landscape. However, the curved spaces of special-shaped buildings require good sound-absorbing performance. The complex structures such as curved ceilings and walls not only increase the processing difficulty of sound-absorbing materials but also pose higher requirements for material installation.

[0003] To achieve a unique spatial effect, special-shaped buildings often need to use materials with good plasticity and processability. For example, foamed resin is molded in a mold, or is machined into the required shape after molding, or is filled in building walls and roof frames for foaming. Although the problem of material molding is solved, the sound-absorbing performance and mechanical strength still need to be further improved. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a silica-based sound-absorbing material, a preparation method thereof, and an application thereof, which improve the sound-absorbing performance and mechanical strength.

[0005] The present invention provides a silica-based sound-absorbing material, comprising the following raw materials in parts by weight:

[0006] 65 - 80 parts of foamed polyurethane resin, 1 - 10 parts of halloysite nanotube composite modified silica, 0.1 - 3 parts of dispersant;

[0007] The halloysite nanotube composite modified silica (abbreviated as HNTs-SiO2) is a condensation reaction product of amino-modified halloysite nanotubes (amino-HNTs) and carboxyl-modified silica.

[0008] Optionally, the halloysite nanotube composite modified silica comprises the following raw materials in parts by weight:

[0009] 20 - 35 parts of amino-HNTs, 5 - 15 parts of carboxyl-modified silica, 0.1 - 5 parts of amide condensing agent; wherein, the mass ratio of carboxyl-modified silica to amino-HNTs is 1:1.6 - 3.

[0010] Optionally, the amide condensing agent is one or more of HATU, HBTU, and HCTU.

[0011] Optionally, the preparation method of the amino-HNTs comprises the following steps:

[0012] Mix halloysite nanotubes with an organic solvent, activate by ultrasonic treatment, then dropwise add a silane coupling agent under heating and stirring, cool, filter by suction, wash, and dry to obtain amino-HNTs.

[0013] Optionally, the mass ratio of the halloysite nanotubes to the silane coupling agent is 1:0.2 - 2.

[0014] Optionally, the silane coupling agent is KH550 silane coupling agent or KH560 silane coupling agent.

[0015] Optionally, the foamed polyurethane resin comprises components in the following mass ratio:

[0016] The mass ratio of polyester polyol, polyisocyanate, foaming agent, catalyst, and chain extender is 95 - 105:80 - 100:30 - 45:1 - 5:0.5 - 2.

[0017] The organic solvent is at least one of methanol, ethanol, ethylene glycol, n-propanol, n-butanol, dichloromethane, toluene, and dimethyl sulfoxide.

[0018] The polyester polyol is at least one of polycaprolactone polyol, adipic acid polyester polyol, and polycarbonate diol.

[0019] The polyisocyanate is at least one of 1,6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane - 4,4'-diisocyanate, and trimethylhexane diisocyanate.

[0020] The dispersant is sodium dodecylbenzenesulfonate.

[0021] The catalyst is any one of triethylenediamine (TEDA), dimethylcyclohexylamine (DMCHA), N,N-dimethylethanolamine (DMEA), and dimethyltin diolate (DMT).

[0022] The chain extender is at least one of 1,4-butanediol (BDO), 1,6-hexanediol, diethylene glycol (DEG), ethylenediamine (DA), N,N-dihydroxy(diisopropyl)aniline (HPA), and 3,5-diethyltoluenediamine (DETDA).

[0023] The foaming agent is dimethyl ether or water.

[0024] The present invention provides a preparation method of a silica-based sound-absorbing material, comprising the following steps:

[0025] Mix the foamed polyurethane resin, HNTs-SiO2, and dispersant evenly by heating and stirring, and carry out foaming molding to obtain the silica-based sound-absorbing material.

[0026] The present invention provides a multi-layer composite sound-absorbing panel, including at least one layer of the sound-absorbing material.

[0027] The beneficial effects of the present invention are that the sound-absorbing material prepared by adding the provided HNTs-SiO2 to the polyurethane foam material can significantly improve the sound-absorbing performance, compressive strength and tensile strength of the sound-absorbing material, enabling the sound-absorbing material to have both high mechanical strength and high sound-absorbing performance. And by controlling the mass ratio of carboxyl-modified silica to amino-HNTs to be 1:1.6 - 3 in the preparation of amino-HNTs, a sound-absorbing material with more excellent sound-absorbing performance can be obtained. Description of the Drawings

[0028] Figure 1 It is the infrared spectrum diagram of halloysite nanotubes and amino-HNTs in Example 1;

[0029] Figure 2 It is the thermogravimetric curve of amino-HNTs and HNTs-SiO2 in Example 1. Detailed Embodiments

[0030] Example 1

[0031] Preparation of amino-HNTs:

[0032] By weight, 10 parts of halloysite nanotubes are mixed with ethanol and ultrasonically treated for 1 h. The mixed solution is heated under reflux, and then 5 parts of KH550 silane coupling agent are added dropwise under mechanical stirring, and the reaction is continuously heated and stirred for 12 h. It is cooled to room temperature, filtered by suction and washed with ethanol 3 times, and then dried in a vacuum at 50 °C for 6 h to obtain amino-HNTs.

[0033] As Figure 1 shown, the infrared characteristic absorption peaks of amino-HNTs can be seen. An N-H stretching vibration peak appears at 3312 cm -1 ⁻¹, an N-H bending vibration peak appears at 1646 cm -1 ⁻¹, and a C-H stretching vibration peak appears at 2931 cm -1 ⁻¹, which is the characteristic peak of KH550, indicating that the KH550 silane coupling agent has been grafted onto the surface of the halloysite nanotubes, and the halloysite nanotubes have been successfully amino-functionalized.

[0034] Preparation of HNTs-SiO2:

[0035] According to parts by weight, 25 parts of the obtained amino-HNTs are mixed with dimethyl sulfoxide to obtain a first mixed solution. 10 parts of carboxyl-modified silica, 3 parts of HATU, and dimethyl sulfoxide are mixed to obtain a second mixed solution. Then, the second mixed solution is added dropwise to the first mixed solution, and the mixture is continuously stirred and reacted for 6 h under ultrasonic conditions and heating at 80 °C. After cooling to room temperature, it is filtered and washed twice with water first, and then washed three times with ethanol, and then dried in vacuo at 50 °C for 6 h to obtain HNTs-SiO2.

[0036] As Figure 2 shown (wherein the thermogravimetric curves of amino-HNTs, the mixed material of amino-HNTs and carboxyl-modified silica according to the feeding ratio, and HNTs-SiO2 are respectively shown), the thermogravimetric rate of amino-HNTs is less than that of the mixed material of amino-HNTs and carboxyl-modified silica according to the feeding ratio, because the thermogravimetric rate of carboxyl-modified silica is relatively large and two obvious turning points appear, while the thermogravimetric rate of HNTs-SiO2 is between the other two and also two obvious turning points appear. This is because the condensation of amino and carboxyl results in water loss, which reduces the thermogravimetric rate. Thus, it can be known that the condensation of amino-HNTs and carboxyl-modified silica is successful.

[0037] Preparation of the sound-absorbing material based on silica:

[0038] According to parts by weight;

[0039] S1. 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 part of chain extender BDO are stirred and mixed evenly in a container;

[0040] S2. 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, 1 part of the obtained HNTs-SiO2, and 1 part of sodium dodecylbenzenesulfonate are stirred and mixed evenly in a container;

[0041] The mixtures of S1 and S2 are fully mixed together, and then foamed and molded in a corresponding mold to obtain the sound-absorbing material based on silica.

[0042] Example 2

[0043] Preparation of the sound-absorbing material based on silica:

[0044] According to parts by weight;

[0045] S1. 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 part of chain extender BDO are stirred and mixed evenly in a container;

[0046] S2. 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, 5 parts of the obtained HNTs-SiO2, and 1 part of sodium dodecylbenzenesulfonate are stirred and mixed evenly in a container;

[0047] Mix the mixture of S1 and S2 thoroughly, and then carry out foaming molding in the corresponding mold to obtain the silica-based sound-absorbing material.

[0048] Example 3

[0049] Preparation of silica-based sound-absorbing material:

[0050] By weight;

[0051] S1: Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether as foaming agent, 1 part of catalyst TEDA, and 0.3 part of chain extender BDO evenly in a container;

[0052] S2: Stir and mix 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether as foaming agent, 10 parts of the obtained HNTs-SiO2, and 1 part of dispersant sodium dodecylbenzenesulfonate evenly in a container;

[0053] Mix the mixture of S1 and S2 thoroughly, and then carry out foaming molding in the corresponding mold to obtain the silica-based sound-absorbing material.

[0054] Example 4

[0055] Preparation of silica-based sound-absorbing material:

[0056] By weight;

[0057] S1: Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 part of chain extender BDO evenly in a container;

[0058] S2: Stir and mix 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, 12 parts of the obtained HNTs-SiO2, and 1 part of sodium dodecylbenzenesulfonate evenly in a container;

[0059] Mix the mixture of S1 and S2 thoroughly, and then carry out foaming molding in the corresponding mold to obtain the silica-based sound-absorbing material.

[0060] Example 5

[0061] Preparation of HNTs-SiO2:

[0062] By weight parts, mix 16 parts of the obtained amino-HNTs with dimethyl sulfoxide to obtain a first mixed solution. Mix 10 parts of carboxyl-modified silica, 3 parts of HATU with dimethyl sulfoxide to obtain a second mixed solution. Then, add the second mixed solution dropwise to the first mixed solution, and continuously stir and react for 6 h under ultrasonic conditions and heating at 80 °C. Cool to room temperature, perform suction filtration, wash twice with water first, and then wash three times with ethanol, and dry in vacuum at 50 °C for 6 h to obtain HNTs-SiO2.

[0063] Preparation of silica-based sound-absorbing material:

[0064] By weight parts;

[0065] S1. Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 part of chain extender BDO evenly in a container;

[0066] S2. Stir and mix 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, 5 parts of the obtained HNTs-SiO2, and 1 part of sodium dodecylbenzenesulfonate evenly in a container;

[0067] Fully mix the mixtures of S1 and S2 together, and then perform foaming molding in a corresponding mold to obtain a silica-based sound-absorbing material.

[0068] Comparative Example 1

[0069] Preparation of silica-based sound-absorbing material:

[0070] By weight parts;

[0071] S1. Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 part of chain extender BDO evenly in a container;

[0072] S2. Stir and mix 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, 5 parts of carboxyl-modified silica, and 1 part of sodium dodecylbenzenesulfonate evenly in a container;

[0073] Fully mix the mixtures of S1 and S2 together, and then perform foaming molding in a corresponding mold to obtain a silica-based sound-absorbing material.

[0074] Comparative Example 2

[0075] Preparation of silica-based sound-absorbing material:

[0076] By weight parts;

[0077] S1. Stir and mix 32 parts of polycaprolactone polyol, 5 parts of foaming agent dimethyl ether, 1 part of catalyst TEDA, and 0.3 part of chain extender BDO evenly in a container;

[0078] S2, 28 parts of 1,6 - hexamethylene diisocyanate, 5 parts of dimethyl ether, 3.5 parts of halloysite nanotubes obtained in Example 1, 1.5 parts of carboxyl - modified silica, and 1 part of sodium dodecylbenzenesulfonate were stirred and mixed evenly in a container;

[0079] The mixtures of S1 and S2 were fully mixed together, and then foamed and molded in the corresponding mold to obtain the silica - based sound - absorbing material.

[0080] Comparative Example 3

[0081] By weight, 25 parts of amino - modified carbon nanotubes were mixed with dimethyl sulfoxide to obtain Mixture 1. 10 parts of carboxyl - modified silica, 3 parts of HATU, and dimethyl sulfoxide were mixed to obtain Mixture 2. Then, Mixture 2 was added dropwise to Mixture 1, and the mixture was continuously stirred and reacted under ultrasonic and heating conditions at 80 °C for 6 h. After cooling to room temperature, it was filtered, washed twice with water first, then washed three times with ethanol, and vacuum - dried at 50 °C for 6 h to obtain carbon nanotube - composite - modified silica.

[0082] Preparation of the silica - based sound - absorbing material:

[0083] By weight;

[0084] S1, 32 parts of polycaprolactone polyol, 5 parts of foaming agent dimethyl ether, 1 part of catalyst TEDA, and 0.3 part of chain extender BDO were stirred and mixed evenly in a container;

[0085] S2, 28 parts of 1,6 - hexamethylene diisocyanate, 5 parts of dimethyl ether, 5 parts of carbon nanotube - composite - modified silica obtained in Comparative Example 3, and 1 part of sodium dodecylbenzenesulfonate were stirred and mixed evenly in a container;

[0086] The mixtures of S1 and S2 were fully mixed together, and then foamed and molded in the corresponding mold to obtain the silica - based sound - absorbing material.

[0087] Comparative Example 4

[0088] Preparation of HNTs - SiO2:

[0089] By weight, 30 parts of the above - obtained amino - HNTs were mixed with dimethyl sulfoxide to obtain Mixture 1. 10 parts of carboxyl - modified silica, 3 parts of HATU, and dimethyl sulfoxide were mixed to obtain Mixture 2. Then, Mixture 2 was added dropwise to Mixture 1, and the mixture was continuously stirred and reacted under ultrasonic and heating conditions at 80 °C for 6 h. After cooling to room temperature, it was filtered, washed twice with water first, then washed three times with ethanol, and vacuum - dried at 50 °C for 6 h to obtain HNTs - SiO2.

[0090] Preparation of the silica - based sound - absorbing material:

[0091] According to weight parts;

[0092] S1. Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether as a blowing agent, 1 part of TEDA as a catalyst, and 0.3 parts of BDO as a chain extender in a container;

[0093] S2, 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, 5 parts of HNTs-SiO2 obtained in Comparative Example 4, and 1 part of sodium dodecylbenzene sulfonate were stirred and mixed in a container;

[0094] The mixture of S1 and S2 is fully mixed together, and then foamed and molded in a corresponding mold to obtain a sound absorbing material based on silica.

[0095] The sources of the above raw materials are as follows:

[0096] The halloysite nanotubes were XFI50 from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd., with a length of 1-12 μm and an outer diameter of 50-150 nm;

[0097] The carboxyl-modified silica was JK-04-005-50 from Nanjing Jike Biotechnology Co., Ltd., with an average particle size of 50 nm;

[0098] The amino-modified carbon nanotubes were BM11623 from Beijing Zhongke Yannuo New Materials Technology Co., Ltd.;

[0099] The polycaprolactone polyol was PA93506 from Guangdong Wengjiang Chemical Reagent Co., Ltd.;

[0100] The polycarbonate diol was PB063493 from Guangdong Wengjiang Chemical Reagent Co., Ltd.;

[0101] 1,6-hexamethylene diisocyanate is H811014 from Shanghai MacLean Biochemical Technology Co., Ltd.;

[0102] Toluene diisocyanate was WB07215 from Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0103] The sound absorbing materials prepared in the above embodiments and comparative examples were subjected to performance tests. The compressive strength was tested according to the reference standard GB / T8813-2008, the tensile strength was tested according to the reference standard GB / T9641-1988, and the average sound absorption coefficient at 200-3000 Hz was measured according to the GB / T 20247-2006 standard. The test results are shown in Table 1.

[0104] Table 1

[0105]

[0106] As can be seen from Table 1, compared with the comparative examples through the examples, the sound-absorbing material prepared by adding HNTs-SiO2 provided by the present invention to the polyurethane foam material can significantly improve the sound-absorbing performance, compressive strength and tensile strength of the sound-absorbing material, so that the sound-absorbing material can take into account high mechanical strength and high sound-absorbing performance.

[0107] As can be seen from Examples 1-4, after the addition amount of HNTs-SiO2 reaches 14%, although the compressive strength and tensile strength of the sound-absorbing material are increasing, the sound-absorbing performance decreases significantly instead. The reason is that excessive HNTs-SiO2 will affect the pore uniformity and size inside the sound-absorbing material, and have a negative impact on the sound absorption coefficient.

[0108] By comparing Example 5 and Comparative Example 4 with Example 3, it can be seen that when the mass ratio of amino-HNTs to carboxyl-modified silica is 1.6 times and 3 times, the prepared HNTs-SiO2 has a significant decrease in the influence on the sound-absorbing performance of the sound-absorbing material; therefore, preferably, the mass ratio of carboxyl-modified silica to amino-HNTs is controlled to be 1:1.6 - 3 in the preparation of amino-HNTs.

[0109] Those of ordinary skill in the art should understand that: the discussion of any of the above embodiments is only exemplary and is not intended to imply that the scope of protection of this application is limited to these examples; under the concept of this application, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of one or more embodiments of this application as described above, which are not provided in detail for the sake of brevity.

[0110] One or more embodiments of this application are intended to cover all such substitutions, modifications and variations that fall within the broad scope of this application. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of one or more embodiments of this application shall be included within the scope of protection of this application.

Claims

1. A silica-based sound-absorbing material, characterized in that, It comprises the following raw materials in parts by weight: 65 - 80 parts of foamed polyurethane resin, 1 - 12 parts of halloysite nanotube composite modified silica, 0.1 - 3 parts of dispersant; The halloysite nanotube composite modified silica is a condensation reaction product of amino modified halloysite nanotubes and carboxyl modified silica; The halloysite nanotube composite modified silica comprises the following raw materials in parts by weight: 20 - 35 parts of amino modified halloysite nanotubes, 5 - 15 parts of carboxyl modified silica, 0.1 - 5 parts of amide condensing agent, wherein the mass ratio of carboxyl modified silica to amino modified halloysite nanotubes is 1:1.6 - 3.

2. The silica-based sound-absorbing material according to claim 1, characterized in that, It comprises the following raw materials in parts by weight: 70 - 75 parts of the foamed polyurethane resin, 5 - 10 parts of halloysite nanotube composite modified silica, 0.5 - 1 part of dispersant.

3. The silica-based sound-absorbing material according to claim 1, wherein The amide condensing agent is one or more of HATU, HBTU, and HCTU.

4. The silica-based sound-absorbing material according to claim 1, characterized in that, The preparation method of the amino modified halloysite nanotubes comprises the following steps: Mix halloysite nanotubes with an organic solvent, after ultrasonic activation, dropwise add a silane coupling agent under heating and stirring to react, cool, filter by suction, wash, and dry to obtain amino modified halloysite nanotubes.

5. The silica-based sound-absorbing material according to claim 4, wherein, The mass ratio of the halloysite nanotubes to the silane coupling agent is 1:0.2 - 2.

6. The silica-based sound-absorbing material according to claim 4, wherein, The silane coupling agent is KH550 silane coupling agent or KH560 silane coupling agent.

7. The silica-based sound-absorbing material according to any one of claims 1-6, characterized in that, The foamed polyurethane resin comprises components with the following mass ratio: The mass ratio of polyester polyol, polyisocyanate, foaming agent, catalyst, and chain extender is 95 - 105:80 - 100:30 - 45:1 - 5:0.5 - 2.

8. A method for preparing the silica-based sound-absorbing material according to any one of claims 1-7, characterized in that, It comprises the following steps: Heat and stir the foamed polyurethane resin, halloysite nanotube composite modified silica, and dispersant to mix evenly, and carry out foaming molding to obtain a silica-based sound absorption material.

9. A multi-layer composite sound-absorbing panel, characterized in that, It comprises at least one layer of the sound absorption material according to any one of claims 1 - 7.

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