Waterproof membrane with high acoustic sensitivity and preparation method thereof

Abstract

The preparation method comprises the following steps: S1, in an inert atmosphere, adding hydroxyl-terminated polybutylene and toluene diisocynate into a reaction kettle, and generating a polyurethane prepolymer under the catalysis of dibutyltin dilaurate; s2, adding a chain extender into the polyurethane prepolymer to carry out chain extension reaction; s3, adding a waterproof functional body, methacryloyloxypropyl polyhedral oligomeric silsesquioxane and a silane coupling agent K560 into the polyurethane subjected to the chain extension reaction, uniformly mixing, and then forming a film, so as to obtain the high-waterproofness waterproof film. The waterproof film of the present invention has excellent acoustic sensitivity and waterproof performance.

Description

Technical Field

[0001] The invention relates to the technical field of waterproof membranes, and in particular to a high acoustic sensitivity waterproof membrane and a preparation method thereof. Background Art

[0002] In some underwater acoustic detection equipment, since it needs to work underwater for a long time, materials with excellent sound-transmitting and waterproof properties are needed to seal the equipment; in addition, during diving activities, the diving smart watches carried by divers require clear voice calls, which places high requirements on the sound-transmitting performance of the equipment's waterproof membrane.

[0003] Therefore, the object of the present invention is to develop a waterproof membrane with high acoustic sensitivity and high waterproof performance. Summary of the invention

[0004] Based on the technical problems existing in the background technology, the present invention proposes a high acoustic sensitivity waterproof membrane and a preparation method thereof, which has excellent acoustic sensitivity and waterproof performance.

[0005] The method for preparing the high acoustic sensitivity waterproof membrane proposed by the present invention comprises the following steps:

[0006] S1: Under an inert atmosphere, hydroxy-terminated polybutene and toluene diisocyanate are added into a reaction kettle, and a polyurethane prepolymer is generated under the catalysis of dibutyltin dilaurate;

[0007] S2: adding a chain extender to the polyurethane prepolymer to carry out a chain extension reaction;

[0008] S3: Add waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 to the polyurethane after chain extension reaction and mix them evenly, then form a film to obtain a highly waterproof film.

[0009] Preferably, the mass ratio of the hydroxy-terminated polybutene, toluene diisocyanate, catalyst and chain extender is 50:40-60:0.1-0.5:5-10; the temperature of the chain extension reaction is 50-70° C., and the time is 1-2 h.

[0010] Preferably, the preparation method of the chain extender is as follows: hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether are heated and stirred in a reaction kettle to obtain the chain extender.

[0011] Preferably, the mass ratio of hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether is 1:1-2:0.4-0.8; the heating and stirring temperature is 30-50° C., and the time is 1-5 h.

[0012] Preferably, the mass ratio of polyurethane, waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 is 100:15-25:5-10:0.1-0.5.

[0013] Preferably, the preparation method of the waterproof functional body is: dispersing perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, itaconate dimethacrylate glycidyl ester and potassium dihydrogen phosphate in deionized water, and then adding ammonium persulfate to carry out polymerization reaction to obtain the waterproof functional body.

[0014] Preferably, the mass ratio of perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, glycidyl itaconate dimethacrylate, potassium dihydrogen phosphate and ammonium persulfate is 20-40:20-40:20-60:0.5-1.5:1; the polymerization temperature is 70-90°C, and the time is 1-5h.

[0015] Preferably, the preparation method of itaconic acid dimethacrylate glycidyl ester is: heating itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate in a reactor to react to obtain itaconic acid dimethacrylate glycidyl ester.

[0016] Preferably, the mass ratio of itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate is 3-4:0.1-0.3:0.05-0.15:10; the heating reaction temperature is 105-115° C., and the time is 4-6 hours.

[0017] The high acoustic sensitivity waterproof membrane proposed by the present invention is prepared by the above method.

[0018] Beneficial technical effects of the present invention:

[0019] (1) The chain extender of the present invention is prepared by the reaction of hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether. The chain extender can regulate the porosity of polyurethane, thereby reducing the reflection and scattering of sound waves, improving the sound transmission performance, and making the prepared waterproof film have high acoustic sensitivity.

[0020] (2) The waterproof membrane of the present invention is made of polyurethane, a waterproof functional body, methacryloyloxypropyl cage-type polysilsesquioxane and a silane coupling agent K560, and has high acoustic sensitivity and excellent waterproof performance. When perfluorododecylethyl methacrylate and hexafluorobutyl methacrylate form a polymer with dimethacrylate glycidyl methacrylate, the fluorocarbon segments of the two will interweave to form a more compact and stable hydrophobic layer. At the same time, the polymer can also form a cross-linked network structure with polyurethane through methacryloyloxypropyl cage-type polysilsesquioxane and a coupling agent, thereby further improving the waterproof performance of the waterproof membrane. DETAILED DESCRIPTION

[0021] The present invention will be further explained below in conjunction with specific embodiments.

[0022] Example 1

[0023] The method for preparing the high acoustic sensitivity waterproof membrane proposed by the present invention comprises the following steps:

[0024] S1: Under an inert atmosphere, hydroxy-terminated polybutene and toluene diisocyanate are added into a reaction kettle, and a polyurethane prepolymer is generated under the catalysis of dibutyltin dilaurate;

[0025] S2: adding a chain extender to the polyurethane prepolymer to carry out a chain extension reaction;

[0026] S3: Add waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 to the polyurethane after chain extension reaction and mix them evenly, then form a film to obtain a highly waterproof film.

[0027] The mass ratio of hydroxy-terminated polybutene, toluene diisocyanate, catalyst and chain extender is 50:50:0.3:8; the temperature of the chain extension reaction is 60° C. and the time is 1.5 h.

[0028] The preparation method of the chain extender is as follows: hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether are heated and stirred in a reaction kettle to obtain the chain extender.

[0029] The mass ratio of hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether is 1:1.5:0.6; the heating and stirring temperature is 40°C and the time is 3h.

[0030] The mass ratio of polyurethane, waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 is 100:20:8:0.3.

[0031] The preparation method of the waterproof functional body is as follows: perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, itaconate dimethacrylate glycidyl ester and potassium dihydrogen phosphate are dispersed in deionized water, and then ammonium persulfate is added for polymerization reaction to obtain the waterproof functional body.

[0032] The mass ratio of perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, itaconate dimethacrylate glycidyl ester, potassium dihydrogen phosphate and ammonium persulfate is 30:30:40:1:1; the polymerization reaction temperature is 80°C and the time is 3h.

[0033] The preparation method of itaconic acid dimethacrylate glycidyl ester comprises the following steps: heating itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate in a reactor for reaction to obtain itaconic acid dimethacrylate glycidyl ester.

[0034] The mass ratio of itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate is 3.5:0.2:0.1:10; the heating reaction temperature is 110° C. and the time is 5 hours.

[0035] Example 2

[0036] The method for preparing the high acoustic sensitivity waterproof membrane proposed by the present invention comprises the following steps:

[0037] S1: Under an inert atmosphere, hydroxy-terminated polybutene and toluene diisocyanate are added into a reaction kettle, and a polyurethane prepolymer is generated under the catalysis of dibutyltin dilaurate;

[0038] S2: adding a chain extender to the polyurethane prepolymer to carry out a chain extension reaction;

[0039] S3: Add waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 to the polyurethane after chain extension reaction and mix them evenly, then form a film to obtain a highly waterproof film.

[0040] The mass ratio of terminal hydroxyl polybutene, toluene diisocyanate, catalyst and chain extender is 50:40:0.1:5; the temperature of chain extension reaction is 50°C and the time is 1 hour.

[0041] The preparation method of the chain extender is as follows: hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether are heated and stirred in a reaction kettle to obtain the chain extender.

[0042] The mass ratio of hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether is 1:1:0.4; the heating and stirring temperature is 30° C., and the time is 1 hour.

[0043] The mass ratio of polyurethane, waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 is 100:15:5:0.1.

[0044] The preparation method of the waterproof functional body is as follows: perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, itaconate dimethacrylate glycidyl ester and potassium dihydrogen phosphate are dispersed in deionized water, and then ammonium persulfate is added for polymerization reaction to obtain the waterproof functional body.

[0045] The mass ratio of perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, itaconate dimethacrylate glycidyl ester, potassium dihydrogen phosphate and ammonium persulfate is 20:20:20:0.5:1; the polymerization reaction temperature is 70°C and the time is 1 hour.

[0046] The preparation method of itaconic acid dimethacrylate glycidyl ester comprises the following steps: heating itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate in a reactor for reaction to obtain itaconic acid dimethacrylate glycidyl ester.

[0047] The mass ratio of itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate is 3:0.1:0.05:10; the heating reaction temperature is 105° C. and the time is 4 hours.

[0048] Example 3

[0049] The method for preparing the high acoustic sensitivity waterproof membrane proposed by the present invention comprises the following steps:

[0050] S1: Under an inert atmosphere, hydroxy-terminated polybutene and toluene diisocyanate are added into a reaction kettle, and a polyurethane prepolymer is generated under the catalysis of dibutyltin dilaurate;

[0051] S2: adding a chain extender to the polyurethane prepolymer to carry out a chain extension reaction;

[0052] S3: Add waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 to the polyurethane after chain extension reaction and mix them evenly, then form a film to obtain a highly waterproof film.

[0053] The mass ratio of hydroxy-terminated polybutene, toluene diisocyanate, catalyst and chain extender is 50:60:0.5:10; the temperature of the chain extension reaction is 70° C. and the time is 2 h.

[0054] The preparation method of the chain extender is as follows: hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether are heated and stirred in a reaction kettle to obtain the chain extender.

[0055] The mass ratio of hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether is 1:2:0.8; the heating and stirring temperature is 50° C., and the time is 5 hours.

[0056] The mass ratio of polyurethane, waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 is 100:25:10:0.5.

[0057] The preparation method of the waterproof functional body is as follows: perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, itaconate dimethacrylate glycidyl ester and potassium dihydrogen phosphate are dispersed in deionized water, and then ammonium persulfate is added for polymerization reaction to obtain the waterproof functional body.

[0058] The mass ratio of perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, itaconate dimethacrylate glycidyl ester, potassium dihydrogen phosphate and ammonium persulfate is 40:40:60:1.5:1; the polymerization reaction temperature is 90° C. and the time is 5 hours.

[0059] The preparation method of itaconic acid dimethacrylate glycidyl ester comprises the following steps: heating itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate in a reactor for reaction to obtain itaconic acid dimethacrylate glycidyl ester.

[0060] The mass ratio of itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate is 4:0.3:0.15:10; the heating reaction temperature is 115° C. and the time is 6 hours.

[0061] Comparative Example 1

[0062] The preparation method of the chain extender of the scheme is: heating and stirring hexamethylene diisocyanate and 1,6-hexanediol diglycidyl ether in a reaction kettle to prepare the chain extender.

[0063] The mass ratio of hexamethylene diisocyanate to 1,6-hexanediol diglycidyl ether is 2.5:0.6; the heating and stirring temperature is 40° C., and the time is 3 hours.

[0064] The remaining conditions are the same as those in Example 1.

[0065] Comparative Example 2

[0066] The preparation method of the chain extender of the scheme is: caprolactam and 1,6-hexanediol diglycidyl ether are heated and stirred in a reaction kettle to obtain the chain extender.

[0067] The mass ratio of caprolactam to 1,6-hexanediol diglycidyl ether is 2.5:0.6; the heating and stirring temperature is 40° C., and the time is 3 hours.

[0068] The remaining conditions are the same as those in Example 1.

[0069] Comparative Example 3

[0070] The preparation method of the waterproof functional body of the present scheme is: perfluorododecylethyl methacrylate, itaconic acid dimethacrylate glycidyl ester and potassium dihydrogen phosphate are dispersed in deionized water, and then ammonium persulfate is added to carry out polymerization reaction to obtain the waterproof functional body.

[0071] The mass ratio of perfluorododecylethyl methacrylate, itaconate dimethacrylate glycidyl ester, potassium dihydrogen phosphate and ammonium persulfate is 60:40:1:1; the polymerization temperature is 80°C and the time is 3h.

[0072] The remaining conditions are the same as those in Example 1.

[0073] Comparative Example 4

[0074] The preparation method of the waterproof functional body of the present scheme is: dispersing hexafluorobutyl methacrylate, dimethylglycidyl itaconate and potassium dihydrogen phosphate in deionized water, and then adding ammonium persulfate to carry out polymerization reaction to obtain the waterproof functional body.

[0075] The mass ratio of hexafluorobutyl methacrylate, glycidyl itaconate dimethacrylate, potassium dihydrogen phosphate and ammonium persulfate is 60:40:1:1; the polymerization temperature is 80°C and the time is 3h.

[0076] The remaining conditions are the same as those in Example 1.

[0077] The waterproof performance and sound transmission performance of Examples 1-3 and Comparative Examples 1-4 were tested, wherein the waterproof performance was tested by using a contact angle meter to measure the water static contact angle of the high acoustic sensitivity waterproof film; the sound transmission performance was tested by punching the material to be tested into a disc with a diameter of 5.0 mm, and then stacking the punched material to be tested and a circular double-sided tape with an outer diameter of 5.0 mm and an inner diameter of 1.7 mm concentrically, the thickness of the double-sided tape was 0.15 mm, and finally the double-sided tape was attached to a microphone test board with a sound outlet hole of 1 mm diameter and 0.8 mm depth, and the analog microphone was Knowles SPA1687LR5H. An artificial mouth was set 2 cm away from the microphone tooling. The analog microphone and the artificial mouth were both connected to an audio analyzer of the AudioPrecision x525 model. The audio test software provided by Audio Precision was used to make the artificial mouth emit a sound with a frequency of 500 Hz and a sound pressure level of 94 dB SPL. The response signals of the microphone end with and without the test components mounted on the surface of the microphone tooling are collected and subtracted, and finally the sound blocking value of the corresponding diaphragm at a certain Hz is obtained. The test results are shown in Table 1.

[0078] Table 1 Test results of waterproof performance and sound transmission performance of waterproof membrane

[0079] Group Water static contact angle (°) Sound blocking(dB) Example 1 167.3 1.5 Example 2 165.1 1.8 Example 3 165.9 1.7 Comparative Example 1 159.2 4.7 Comparative Example 2 157.5 4.3 Comparative Example 3 143.6 2.3 Comparative Example 4 141.7 2.5

[0080] It can be seen from the test results of Examples 1-3 that the waterproof film prepared by the present invention has excellent sound permeability and waterproof performance; it can be seen from the test results of Example 1 and Comparative Examples 1-2 that the chain extender of the present invention is prepared by the reaction of hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether, and the chain extender can regulate the porosity of polyurethane, thereby reducing the reflection and scattering of sound waves, improving the sound permeability, and making the prepared waterproof film have high acoustic sensitivity. It can be seen from the test results of Example 1 and Comparative Examples 3-4 that the waterproof membrane of the present invention is made of polyurethane, a waterproof functional body, methacryloyloxypropyl cage-type polysilsesquioxane and a silane coupling agent K560, and has high acoustic sensitivity while also having excellent waterproof performance; wherein when perfluorododecylethyl methacrylate and hexafluorobutyl methacrylate form a polymer with dimethacrylate glycidyl itaconate, the fluorocarbon segments of the two will interweave to form a tighter and more stable hydrophobic layer; at the same time, the polymer can also form a cross-linked network structure with polyurethane through methacryloyloxypropyl cage-type polysilsesquioxane and a coupling agent, thereby further improving the waterproof performance of the waterproof membrane.

Claims

1. A method for preparing a high acoustic sensitivity waterproof membrane, characterized in that: The steps are as follows: S1: Under an inert atmosphere, hydroxy-terminated polybutene and toluene diisocyanate are added into a reaction kettle, and a polyurethane prepolymer is generated under the catalysis of dibutyltin dilaurate; S2: adding a chain extender to the polyurethane prepolymer to carry out a chain extension reaction; S3: Add waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 to the polyurethane after chain extension reaction and mix them evenly, then form a film to obtain a highly waterproof film.

2. The method for preparing a high acoustic sensitivity waterproof membrane according to claim 1, characterized in that: The mass ratio of terminal hydroxyl polybutene, toluene diisocyanate, catalyst and chain extender is 50:40-60:0.1-0.5:5-10; the temperature of chain extension reaction is 50-70°C, and the time is 1-2h.

3. The method for preparing a high acoustic sensitivity waterproof membrane according to claim 1, characterized in that: The preparation method of the chain extender is as follows: hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether are heated and stirred in a reaction kettle to prepare the chain extender.

4. The method for preparing a high acoustic sensitivity waterproof membrane according to claim 3, characterized in that: The mass ratio of hexamethylene diisocyanate, caprolactam and 1,6-hexanediol diglycidyl ether is 1:1-2:0.4-0.8; the heating and stirring temperature is 30-50°C, and the time is 1-5h.

5. The method for preparing a high acoustic sensitivity waterproof membrane according to claim 1, characterized in that: The mass ratio of polyurethane, waterproof functional body, methacryloxypropyl cage-type polysilsesquioxane and silane coupling agent K560 is 100:15-25:5-10:0.1-0.

5.

6. The method for preparing a high acoustic sensitivity waterproof membrane according to claim 1, characterized in that: The preparation method of the waterproof functional body is as follows: perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, itaconate dimethacrylate glycidyl ester and potassium dihydrogen phosphate are dispersed in deionized water, and then ammonium persulfate is added for polymerization reaction to obtain the waterproof functional body.

7. The method for preparing a high acoustic sensitivity waterproof membrane according to claim 6, characterized in that: The mass ratio of perfluorododecylethyl methacrylate, hexafluorobutyl methacrylate, itaconate dimethacrylate glycidyl ester, potassium dihydrogen phosphate and ammonium persulfate is 20-40:20-40:20-60:0.5-1.5:1; the polymerization reaction temperature is 70-90°C and the time is 1-5h.

8. The method for preparing a high acoustic sensitivity waterproof membrane according to claim 6, characterized in that: The preparation method of itaconic acid dimethacrylate glycidyl ester comprises the following steps: heating itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate in a reactor for reaction to obtain itaconic acid dimethacrylate glycidyl ester.

9. The method for preparing a high acoustic sensitivity waterproof membrane according to claim 8, characterized in that: The mass ratio of itaconic acid, triphenylphosphine, p-hydroxyanisole and glycidyl methacrylate is 3-4:0.1-0.3:0.05-0.15:10; the heating reaction temperature is 105-115° C., and the time is 4-6 hours.

10. A high acoustic sensitivity waterproof membrane, characterized in that: The method is prepared by any one of claims 1 to 9.