Silica-based sound absorption material, preparation method and application thereof

Abstract

The invention belongs to the field of sound absorption materials, and particularly relates to a sound absorption material based on silicon dioxide, a preparation method and application of the sound absorption material, and the sound absorption material comprises 65-80 parts of foamed polyurethane resin, 1-10 parts of halloysite nanotube composite modified silicon dioxide and 0.1-3 parts of a dispersing agent; the halloysite nanotube composite modified silicon dioxide is a condensation reaction product of amino modified halloysite nanotubes and carboxyl modified silicon dioxide, the halloysite nanotube composite modified silicon dioxide is added into a polyurethane foam material to prepare a sound absorption material, and the sound absorption performance, the compression strength and the tensile strength of the sound absorption material can be obviously improved; the sound absorption material can give consideration to both high mechanical strength and high sound absorption performance, and the multi-layer composite sound absorption board composed of the sound absorption material is excellent in sound absorption performance.

Description

Technical Field

[0001] The invention belongs to the field of sound absorbing materials, and in particular relates to a silicon dioxide-based sound absorbing material, a preparation method and application thereof. Background Art

[0002] With the progress of society, special-shaped buildings have become a highly anticipated form of innovation with their unique form and visual impact. With their streamlined curved space, irregular shape and personalized design, the building breaks the framework of traditional architecture and brings endless vitality and imagination to the spatial landscape. However, the curved space of special-shaped buildings requires good sound absorption performance. The complex structures of curved ceilings, walls, etc. not only increase the difficulty of processing sound-absorbing materials, but also put forward higher requirements for material installation.

[0003] In order to achieve a unique spatial effect, special-shaped buildings often need to use materials with good plasticity and processability, such as foaming resin in a mold, or cutting into the required shape after molding, or filling the building wall and roof frame for foaming. Although the problem of material molding has been solved, the sound absorption performance and mechanical strength need to be further improved. Summary of the invention

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

[0005] The present invention provides a silicon dioxide-based sound-absorbing material, comprising the following raw materials in parts by weight: 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 (HNTs-SiO 2 ) is the condensation reaction product of amino-modified halloysite nanotubes (amino-HNTs) and carboxyl-modified silica.

[0006] Optionally, the halloysite nanotube composite modified silica comprises the following raw materials in parts by weight: 20-35 parts of amino-HNTs, 5-15 parts of carboxyl-modified silica, and 0.1-5 parts of amide condensation agent; wherein the mass ratio of carboxyl-modified silica to amino-HNTs is 1:1.6-3.

[0007] Optionally, the amide condensation agent is one or more of HATU, HBTU, and HCTU.

[0008] Optionally, the preparation method of amino-HNTs comprises the following steps: The halloysite nanotubes are mixed with an organic solvent, and after ultrasonic activation, a silane coupling agent is added dropwise under heating and stirring to react, and then cooled, filtered, washed, and dried to obtain amino-HNTs.

[0009] Optionally, the mass ratio of the halloysite nanotubes to the silane coupling agent is 1:0.2-2.

[0010] Optionally, the silane coupling agent is KH550 silane coupling agent or KH560 silane coupling agent.

[0011] Optionally, the foamed polyurethane resin comprises components in the following mass ratios: The mass ratio of polyester polyol, polyisocyanate, blowing agent, catalyst and chain extender is 95~105:80~100:30~45:1~5:0.5~2.

[0012] The organic solvent is at least one of methanol, ethanol, ethylene glycol, n-propanol, n-butanol, dichloromethane, toluene and dimethyl sulfoxide.

[0013] The polyester polyol is at least one of polycaprolactone polyol, adipic acid polyester polyol and polycarbonate diol.

[0014] The polyisocyanate is at least one of hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4,4′-diisocyanate, and trimethylhexane diisocyanate.

[0015] The dispersant is sodium dodecylbenzene sulfonate.

[0016] The catalyst is any one of triethylenediamine (TEDA), dimethylcyclohexylamine (DMCHA), N,N-dimethylethanolamine (DMEA), and dimethyltin glycolate (DMT).

[0017] 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).

[0018] The blowing agent is dimethyl ether or water.

[0019] The present invention provides a method for preparing a sound absorbing material based on silicon dioxide, comprising the following steps: The foamed polyurethane resin, HNTs-SiO 2 , the dispersant is heated and stirred to mix evenly, and foaming is performed to obtain a sound-absorbing material based on silica.

[0020] The invention provides a multi-layer composite sound absorbing board, comprising at least one layer of the sound absorbing material.

[0021] The beneficial effect of the present invention is that the HNTs-SiO 2 The sound-absorbing material prepared by adding it to the polyurethane foam material can significantly improve the sound absorption performance, compression strength and tensile strength of the sound-absorbing material, so that the sound-absorbing material can have both high mechanical strength and high sound absorption performance. In addition, in the preparation of amino-HNTs, the mass ratio of carboxyl-modified silica to amino-HNTs is controlled to be 1:1.6~3, which can obtain a sound-absorbing material with better sound absorption performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the infrared spectrum of halloysite nanotubes and amino-HNTs in Example 1; Figure 2 Example 1: amino-HNTs and HNTs-SiO 2 Thermogravimetric curve of . DETAILED DESCRIPTION

[0023] Example 1 Preparation of amino-HNTs: According to weight, 10 parts of halloysite nanotubes were mixed with ethanol, ultrasonicated for 1 hour, and the mixture was heated to reflux. Then, 5 parts of KH550 silane coupling agent were added dropwise under mechanical stirring, and the reaction was continued by heating and stirring for 12 hours. The mixture was cooled to room temperature, filtered and washed with ethanol for 3 times, and dried in a vacuum at 50°C for 6 hours to obtain amino-HNTs.

[0024] like Figure 1 As shown in the figure, the characteristic infrared absorption peak of amino-HNTs is visible at 3312 cm -1 The NH contraction vibration peak appears at 1646 cm -1 The NH bending vibration peak appears at 2931cm -1 A CH contraction vibration peak appears at , 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 amination modification of the halloysite nanotubes is successful.

[0025] HNTs-SiO 2 Preparation: According to weight parts, 25 parts of the amino-HNTs obtained above were mixed with dimethyl sulfoxide to obtain a mixed solution 1, 10 parts of carboxyl-modified silica and 3 parts of HATU were mixed with dimethyl sulfoxide to obtain a mixed solution 2, and then the mixed solution 2 was added dropwise to the mixed solution 1, and the mixture was stirred and reacted for 6 hours under ultrasonic and 80°C heating conditions, cooled to room temperature, filtered and washed with water twice, then washed with ethanol three times, and dried in vacuum at 50°C for 6 hours to obtain HNTs-SiO 2 .

[0026] like Figure 2As shown in the figure (Amino-HNTs, amino-HNTs and carboxyl-modified silica are mixed according to the feed ratio, HNTs-SiO 2 The thermal weight loss curve of amino-HNTs is smaller than that of the mixture of amino-HNTs and carboxyl-modified silica according to the feed ratio. This is because the thermal weight loss rate of carboxyl-modified silica is larger and has two obvious turning points, while HNTs-SiO 2 The thermal weight loss rate of is between the other two, and there are also two obvious turning points. This is because the amino group and the carboxyl group condense to lose water, which reduces the thermal weight loss rate. It can be seen that the condensation of amino-HNTs and carboxyl-modified silica is successful.

[0027] Preparation of sound absorbing materials based on silica: According to weight parts; S1. Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 parts of chain extender BDO in a container; S2, 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, the HNTs-SiO 2 1 part of 1,1 part of sodium dodecylbenzenesulfonate are stirred and mixed evenly in a container; 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.

[0028] Example 2 Preparation of sound absorbing materials based on silica: According to weight parts; S1. Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 parts of chain extender BDO in a container; S2, 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, the HNTs-SiO 2 5 parts of propylene glycol and 1 part of sodium dodecylbenzene sulfonate are stirred and mixed evenly in a container; 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.

[0029] Example 3 Preparation of sound absorbing materials based on silica: According to weight parts; S1, 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 are stirred and mixed uniformly in a container; S2, 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether as a blowing agent, and the HNTs-SiO2 10 parts of 1,10 parts of sodium dodecylbenzene sulfonate, a dispersant, are stirred and mixed in a container; 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.

[0030] Example 4 Preparation of sound absorbing materials based on silica: According to weight parts; S1. Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 parts of chain extender BDO in a container; S2, 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, the HNTs-SiO 2 12 parts of 1,1 part of sodium dodecylbenzenesulfonate are stirred and mixed in a container; 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.

[0031] Example 5 HNTs-SiO 2 Preparation: According to weight parts, 16 parts of the amino-HNTs obtained above were mixed with dimethyl sulfoxide to obtain a mixed solution 1, 10 parts of carboxyl-modified silica and 3 parts of HATU were mixed with dimethyl sulfoxide to obtain a mixed solution 2, and then the mixed solution 2 was added dropwise to the mixed solution 1, and the mixture was stirred and reacted for 6 hours under ultrasonic and 80°C heating conditions, cooled to room temperature, filtered and washed with water twice, then washed with ethanol three times, and dried under vacuum at 50°C for 6 hours to obtain HNTs-SiO 2 .

[0032] Preparation of sound absorbing materials based on silica: According to weight parts; S1. Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 parts of chain extender BDO in a container; S2, 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, the HNTs-SiO 2 5 parts of propylene glycol and 1 part of sodium dodecylbenzene sulfonate are stirred and mixed evenly in a container; 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.

[0033] Comparative Example 1 Preparation of sound absorbing materials based on silica: According to weight parts; S1. Stir and mix 32 parts of polycaprolactone polyol, 5 parts of dimethyl ether, 1 part of catalyst TEDA, and 0.3 parts of chain extender BDO in a container; S2, 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, 5 parts of carboxyl-modified silica, and 1 part of sodium dodecylbenzene sulfonate were stirred and mixed in a container; 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.

[0034] Comparative Example 2 Preparation of sound absorbing materials based on silica: According to weight parts; S1, 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 are stirred and mixed uniformly in a container; 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 dodecylbenzene sulfonate were stirred and mixed in a container; 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.

[0035] Comparative Example 3 According to weight parts, 25 parts of amino-modified carbon nanotubes were mixed with dimethyl sulfoxide to obtain mixed solution 1, 10 parts of carboxyl-modified silica and 3 parts of HATU were mixed with dimethyl sulfoxide to obtain mixed solution 2, and then mixed solution 2 was added dropwise to mixed solution 1, and the reaction was continuously stirred for 6 hours under ultrasonic and 80°C heating conditions, cooled to room temperature, filtered and washed twice with water, then washed three times with ethanol, and vacuum dried at 50°C for 6 hours to obtain carbon nanotube composite modified silica.

[0036] Preparation of sound absorbing materials based on silica: According to weight parts; S1, 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 are stirred and mixed uniformly in a container; S2, 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, 5 parts of the carbon nanotube composite modified silica obtained in Comparative Example 3, and 1 part of sodium dodecylbenzene sulfonate were stirred and mixed in a container; 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.

[0037] Comparative Example 4 HNTs-SiO 2Preparation: According to weight parts, 30 parts of the amino-HNTs obtained above were mixed with dimethyl sulfoxide to obtain a mixed solution 1, 10 parts of carboxyl-modified silica and 3 parts of HATU were mixed with dimethyl sulfoxide to obtain a mixed solution 2, and then the mixed solution 2 was added dropwise to the mixed solution 1, and the mixture was stirred and reacted for 6 hours under ultrasonic and 80°C heating conditions, cooled to room temperature, filtered and washed with water twice, then washed with ethanol three times, and dried in vacuum at 50°C for 6 hours to obtain HNTs-SiO 2 .

[0038] Preparation of sound absorbing materials based on silica: According to weight parts; S1, 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 are stirred and mixed uniformly in a container; S2, 28 parts of 1,6-hexamethylene diisocyanate, 5 parts of dimethyl ether, and HNTs-SiO obtained in Comparative Example 4 2 5 parts of propylene glycol and 1 part of sodium dodecylbenzene sulfonate are stirred and mixed evenly in a container; 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.

[0039] The sources of the above raw materials are as follows: 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; The carboxyl-modified silica was JK-04-005-50 from Nanjing Jike Biotechnology Co., Ltd., with an average particle size of 50 nm; The amino-modified carbon nanotubes were BM11623 from Beijing Zhongke Yannuo New Materials Technology Co., Ltd.; The polycaprolactone polyol was PA93506 from Guangdong Wengjiang Chemical Reagent Co., Ltd.; The polycarbonate diol was PB063493 from Guangdong Wengjiang Chemical Reagent Co., Ltd.; 1,6-hexamethylene diisocyanate is H811014 from Shanghai MacLean Biochemical Technology Co., Ltd.; Toluene diisocyanate was WB07215 from Guangdong Wengjiang Chemical Reagent Co., Ltd.

[0040] 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.

[0041] Table 1

[0042] It can be seen from Table 1 that, by comparing the examples with the comparative examples, the HNTs-SiO 2 The sound-absorbing material prepared by adding the sound-absorbing material to the polyurethane foam material can significantly improve the sound absorption performance, compression strength and tensile strength of the sound-absorbing material, so that the sound-absorbing material can have both high mechanical strength and high sound absorption performance.

[0043] It can be seen from Examples 1-4 that HNTs-SiO 2 When the addition amount reaches 14%, the compressive strength and tensile strength of the sound-absorbing material are improved, but the sound absorption performance is significantly reduced. The reason is that the excessive HNTs-SiO 2 It will affect the uniformity and size of the pores inside the sound-absorbing material, and have a negative impact on the sound absorption coefficient.

[0044] 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-SiO 2 , the effect on the sound absorption performance of the sound absorbing material is significantly reduced; therefore, preferably, in the preparation of amino-HNTs, the mass ratio of carboxyl-modified silica to amino-HNTs is controlled to be 1:1.6~3.

[0045] A person skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of protection of the present application is limited to these examples. In line with the concept of the present application, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of different aspects of one or more embodiments of the present application as described above, which are not provided in detail for the sake of simplicity.

[0046] One or more embodiments of the present application are intended to cover all such substitutions, modifications and variations that fall within the broad scope of the present application. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of one or more embodiments of the present application should be included in the protection scope of the present application.

Claims

1. A sound absorbing material based on silicon dioxide, characterized in that: The invention 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, 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.

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

3. The silicon dioxide-based sound absorbing material according to claim 1, characterized in that 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, and 0.1-5 parts of an amide condensation agent, wherein the mass ratio of carboxyl-modified silica to amino-modified halloysite nanotubes is 1:1.6-3.

4. The silicon dioxide-based sound absorbing material according to claim 3, characterized in that The amide condensation agent is one or more of HATU, HBTU and HCTU.

5. The silicon dioxide-based sound absorbing material according to claim 1, characterized in that The preparation method of the amino-modified halloysite nanotubes comprises the following steps: The halloysite nanotubes are mixed with an organic solvent, and after ultrasonic activation, a silane coupling agent is added dropwise under heating and stirring to react, and then cooled, filtered, washed, and dried to obtain amino-modified halloysite nanotubes.

6. The silicon dioxide-based sound absorbing material according to claim 5, characterized in that The mass ratio of the halloysite nanotubes to the silane coupling agent is 1:0.2-2.

7. The silicon dioxide-based sound absorbing material according to claim 5, characterized in that The silane coupling agent is KH550 silane coupling agent or KH560 silane coupling agent.

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

9. A method for preparing a silicon dioxide-based sound-absorbing material according to any one of claims 1 to 8, characterized in that: The following steps are involved: The foamed polyurethane resin, the halloysite nanotube composite modified silica and the dispersant are heated and stirred to be uniformly mixed, and foaming molding is performed to obtain the silica-based sound absorbing material.

10. A multi-layer composite sound absorbing board, characterized in that: The method comprises at least one layer of the sound absorbing material according to any one of claims 1 to 8.

Images