CN116063843A - Sealing coating material for deep sea underwater acoustic transducer and preparation method thereof - Google Patents

Sealing coating material for deep sea underwater acoustic transducer and preparation method thereof Download PDF

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CN116063843A
CN116063843A CN202310364661.1A CN202310364661A CN116063843A CN 116063843 A CN116063843 A CN 116063843A CN 202310364661 A CN202310364661 A CN 202310364661A CN 116063843 A CN116063843 A CN 116063843A
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epoxy resin
polyurethane
prepolymer
reaction
curing agent
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CN116063843B (en
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高远
李珺杰
顾晓红
高峰
朱皓
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Haiying Enterprise Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks

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Abstract

The invention relates to the technical field of underwater sound transducers, in particular to a deep sea underwater sound transducer sealing coating material and a preparation method thereof, wherein the deep sea underwater sound transducer sealing coating material comprises polyurethane prepolymer, epoxy resin prepolymer and polyurethane curing agent in a mass ratio of 100:70:40-100:5:15 by constructing polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding; polyurethane prepolymer, the raw materials of which comprise isocyanate, polyol and catalyst; wherein the mass ratio of isocyanate to polyol is 1:1-10:1, and the dosage of the catalyst is 0.001% -0.1% of the total mass of the reaction system. The invention can reduce the free volume in the material, thereby improving the water blocking permeability of the material; the viscous modulus in the viscoelasticity of the material can be reduced, the intermolecular friction is reduced, and the acoustic energy loss is reduced, so that the sound transmission performance of the material is improved.

Description

Sealing coating material for deep sea underwater acoustic transducer and preparation method thereof
Technical Field
The invention relates to the technical field of underwater acoustic transducers, in particular to a sealing coating material for a deep sea underwater acoustic transducer and a preparation method thereof.
Background
The underwater sound transducer is an underwater working part of the sonar, and the functional components of the underwater sound transducer are sealed and coated by sound-transmitting sealing materials to be isolated from water. The acoustic sealing material for coating the underwater acoustic transducer is a high molecular polymer material and needs to have two important functions: sound transmission and water blocking sealing, wherein sound transmission means that sound waves pass through a material with low reflection and low attenuation; the water-blocking seal is to prevent moisture from penetrating into the interior of the transducer to cause the transducer to fail. The principle of attenuation and loss of sound waves in a polymer material is that, simply stated, the incidence of sound energy causes mutual movement between molecular chains of the polymer material, causing internal friction between the molecular chains, resulting in energy loss. The penetration of water molecules into the polymer is greatly related to the osmotic pressure difference between the inner and outer surfaces of the polymer.
But the deep sea environment is severe, the challenges to the underwater acoustic transducer are great, and especially the hydrostatic pressure in the deep sea is much greater than that in the shallow sea. The underwater sound transducer works underwater for a long time, so that the underwater sound transducer is an extension set with higher fault rate in a sonar system, and a large proportion of faults are related to the reduction of insulation performance. High hydrostatic pressure brings about higher osmotic pressure, so the rate of penetration of water molecules in the transducer seal cladding material at high water pressure may be much greater than shallow sea. In the face of high hydrostatic pressure in deep sea, water molecules penetrate through the sealing material more easily and enter the interior of the transducer, so that the electrical insulation of the transducer is reduced more rapidly than in shallow sea. Moreover, the cost and cost of the transducer operated in deep sea once the failure occurs is higher because of the difficulty in maintenance and replacement. In addition, according to theoretical analysis in the aspect of acoustic performance, under the action of strong hydrostatic pressure in deep sea, the intermolecular free space of the polymer material is compressed, intermolecular friction is increased, acoustic loss is increased, and the acoustic transmission performance is reduced compared with that of shallow sea. The water-sound transducer packaging material widely used in China at present, namely polyether polyurethane (JA-2S) has higher water permeability coefficient (1 multiplied by 10) -12 g·cm/cm 2 S.pa), the average acoustic insertion loss in the high frequency range is 270dB/m (350-700 Hz), and the reliable packaging requirement of the transducer working in the deep sea cannot be met in terms of sound transmission and water blocking permeability. Therefore, for the sealing coating material of the deep sea transducer, the improvement of the sound transmission performance and the water blocking permeability is an industry 'pain point' which needs to be solved.
CN111518253a discloses a preparation method of solid filling material for underwater cable, which uses polyolefin polyol with low water permeability, such as hydroxyl-terminated polybutadiene, as component of synthetic polyurethane, and graft-copolymerizing with epoxy resin with low water permeability to reduce water permeability of the material, and achieve better heat resistance, aging resistance, impact resistance and bending resistance; the diluent is added to play a role in adjusting the viscosity and density of the solid filler, different catalysts are selected and the proportion of the catalysts is adjusted, and the initial viscosity of the material is adjusted, so that different process requirements of filling the underwater cable can be met. The material has better comprehensive performance as a solid filling material of the underwater cable, but is not applicable to the application scene of cladding and sealing of the deepwater underwater acoustic transducer. Firstly, the deepwater underwater acoustic transducer cladding sealing material needs to be poured and then solidified and molded, the initial viscosity of the material is required to be low, the initial viscosity of polyolefin polyol is very high, and the method of selecting different catalysts and adjusting the proportion of the catalysts in CN111518253A can only adjust the solidification reaction rate of the material, namely can only adjust the rising rate of the initial viscosity and can not reduce the initial viscosity of the material; the method of reducing the viscosity of the material by adding ester plasticizer, paraffin base and cycloalkyl white oil, solvent oil, silicone oil and other diluents as described in CN111518253a cannot be used for coating sealing materials of deepwater underwater acoustic transducers, because of two points: 1. the ester plasticizer, the paraffin base, the naphthenic base white oil, the solvent oil, the silicone oil and other diluents do not participate in the reaction, are present in a material system in a physical blending mode, can be slowly separated out along with time, particularly can be separated out at a higher speed under the environment of deep water and high osmotic pressure, and the separation of the diluents can cause micro holes in the material, thereby being beneficial to the permeation of water molecules in the material; 2. the existence of the diluent can reduce the mechanical property and sound transmission property, especially the sound transmission property of the material, and the diluent is added to enable the molecules to slide relatively more easily, so that the intermolecular internal consumption is increased, the acoustic energy loss is increased, and the sound transmission property is reduced. Secondly, in the graft copolymerization reaction of polyurethane and epoxy resin in CN111518253a, a ring-opening curing agent of epoxy resin is not added, but epoxy resin monomer E51 is allowed to react directly with polyurethane, specifically, NCO groups in polyurethane react with secondary hydroxyl groups of epoxy resin monomer. There are two problems here: 1. the reactivity of NCO groups and secondary hydroxyl groups is weak, and the grafting efficiency is poor; 2. the epoxy resin monomer does not undergo a crosslinking reaction, and cannot form an interpenetrating network structure with a crosslinked network of polyurethane.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a deep sea underwater acoustic transducer sealing coating material and a preparation method thereof, and the realization mode of the invention is realized by constructing a polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding: 1. the free volume in the material is reduced, so that the water blocking permeability of the material is improved; 2. the viscous modulus in the viscoelasticity of the material is reduced, the intermolecular friction is reduced, and the acoustic energy loss is reduced, so that the sound transmission performance of the material is improved. Meanwhile, the material has lower initial viscosity so as to adapt to the process requirement of the filling molding of the sealing coating material of the underwater acoustic transducer.
The invention is realized by the following technical scheme:
a sealing cladding material for a deep sea underwater acoustic transducer is prepared by constructing a polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding, wherein the raw materials comprise polyurethane prepolymer, epoxy resin prepolymer and polyurethane curing agent in a mass ratio of 100:70:40-100:5:15;
the polyurethane prepolymer comprises isocyanate, polyalcohol and catalyst as raw materials; wherein the mass ratio of isocyanate to polyol is 1:1-10:1, and the dosage of the catalyst is 0.001% -0.1% of the total mass of the reaction system;
the epoxy resin prepolymer comprises the raw materials of an epoxy resin monomer and an epoxy resin curing agent in a mass ratio of 100:5-100:10.
Preferably, the polyurethane curing agent is one or more of diamine curing agent and dihydric alcohol curing agent.
Preferably, the isocyanate is a mixture of dimer diisocyanate and one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate, and the mass ratio of the dimer diisocyanate to other isocyanate mixtures is 100:100-100:0.
Preferably, the polyol is a mixture of polyolefin polyol and polyether polyol, and the mass ratio of the polyolefin polyol to the polyether polyol is 100:100-100:0.
Preferably, the polyolefin polyol is an epoxidized hydroxyl terminated polybutadiene.
Preferably, the catalyst is one or more of an organotin catalyst, an organobismuth catalyst and an organoiron catalyst.
Preferably, the epoxy resin monomer is a low viscosity epoxy resin having a viscosity of less than 1000 mPas (25 ℃).
Preferably, the epoxy resin curing agent is an imidazole curing agent.
The invention also provides a preparation method of the sealing coating material for the deep sea underwater acoustic transducer, which comprises the following steps:
1) Preparation of polyurethane prepolymer:
the isocyanate, the polyol and the catalyst are subjected to polymerization reaction under the protection of inert gas, and the reaction is stopped after a certain time of reaction, so as to obtain polyurethane prepolymer;
2) Preparation of epoxy resin prepolymer:
performing polymerization reaction on the epoxy resin monomer and the epoxy resin curing agent, and stopping the reaction when the viscosity of the reaction system reaches a certain value to obtain an epoxy resin prepolymer;
3) Preparation of a polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding:
and uniformly mixing the polyurethane prepolymer, the epoxy resin prepolymer and the polyurethane curing agent, pouring into a mold for curing reaction, and curing to obtain the polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding.
Preferably, the polymerization reaction temperature in the step 1) is 40-120 ℃ and the reaction time is 1-10 h; the viscosity in the step 2) is 500-8000 cps (25 ℃); the curing reaction temperature in the step 3) is 50-130 ℃ and the reaction time is 3-24 hours.
The design principle of the invention is as follows: the water permeability and sound permeability of the polymer material are related to the microstructure of the material, and related mechanisms are all supported by a relatively mature theory. First is the water permeation mechanism of the polymeric material: the permeation process of water molecules in the polymer is controlled by diffusion and adsorption, the diffusion of water molecules in the polymer is mainly related to free volume, the adsorption of water molecules on the surface of the polymer is mainly related to hydrophilic groups in the polymer, the free volume is micropores in a molecular structure, the diffusion resistance of water molecules in the polymer is greatly reduced due to the existence of the micropores, and the larger the free volume in the polymer material is, the larger the water molecule permeation capacity is. The second is the sound transmission mechanism of the polymer material: the sound transmission performance of the polymer material is directly related to the viscoelasticity of the material, the molecular chains of the polymer are long and easy to curl and tangle, when sound energy enters the polymer, the sound energy applies work to the polymer, the curled molecular chains stretch to store a part of the sound energy, the stored sound energy is released again through the re-curling of the molecular chains, and the energy is
Figure SMS_1
Wherein->
Figure SMS_2
Is the elastic modulus of the material, and the other part of energy is converted into heat energy to be dissipated by overcoming the internal friction between molecular chain segments generated during the curling-stretching movement of the molecular chain, and the part of the dissipated energy is the loss of sound energy, and the part of energy is>
Figure SMS_3
Wherein->
Figure SMS_4
The viscous modulus of the material is that the more intense the friction is in the molecular chain segments, the more energy is dissipated, and the poorer the sound transmission performance of the material is. Therefore, the free volume in the polymer material is reduced, and the water-blocking permeability and sound-transmitting performance of the material can be improved by reducing the intermolecular friction.
The interpenetrating polymer network structure polymer is a unique structure that two or more than two crosslinked polymers are mutually interpenetrated among polymer networks at molecular chain scale to form a plurality of mutually interweaved polymer networks. The structure can inhibit the formation of free volume in the polymer material, and simultaneously, the interpenetrating network structure which is mutually interwoven and pulled can limit the movement degree of molecular chains and reduce the inter-molecular friction. Interpenetrating network polymers are classified into two types, physical entanglement and chemical grafting, according to the kind of network interlacing entanglement. The physical entanglement interpenetrating network material does not form chemical bonds such as covalent bonds among several polymer networks, and the polymer networks are forced to mutually contain by mutually interpenetration and interweaving on the physical structure. The chemical grafting interpenetrating network polymer is formed by chemical bonding between different polymer networks, the interpenetrating and intertwining degree between the polymer networks is larger, the interlocking degree between the polymer networks is larger, the free volume in the polymer material can be reduced to a larger degree, and the intermolecular friction is reduced, so that the water-blocking permeation and sound-transmitting performance of the material is improved. However, the improvement of the water-blocking permeation and sound-transmitting performance of the material by chemical grafting of interpenetrating network polymer also has technical difficulties. The chemical grafting interpenetrating network polymer in the traditional sense cannot control the chemical bonding degree between polymer networks, the free volume in the polymer material is reduced if the chemical bonding quantity is small, the degree of intermolecular friction is low, the interlocking degree between polymer networks is too high if the chemical bonding quantity is too large, the elastic modulus of the material is reduced, and the sound transmission performance of the material is affected. According to the deep sea underwater sound transducer sealing coating material and the preparation method thereof, the polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding is constructed, so that the chemical bonding degree between interpenetrating networks can be controllably regulated, and the optimal solution for improving the water blocking permeability and the sound transmission performance of the material is realized. The specific technical path is as follows: the polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding is obtained by adding a polyurethane prepolymer and an epoxy resin prepolymer into a reaction system, respectively carrying out polymerization reaction and simultaneously carrying out chemical grafting reaction, wherein the mass ratio of the polyurethane prepolymer to the epoxy resin prepolymer is 100:70-100:5; the polyurethane prepolymer is prepared by polymerizing isocyanate and polyol under the catalysis of a catalyst, and the feeding ratio of the isocyanate to the polyol is such that the NCO: OH in the system is 1:1-10:1 before the reaction starts; the epoxy resin prepolymer is obtained by the polymerization reaction of an epoxy resin monomer under the action of an epoxy resin curing agent. The controllable chemical bonding in the polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding is that when the prepolymerization reaction of polyurethane and epoxy resin is carried out, the purpose of controlling the number of epoxy groups participating in the interpenetrating network chemical grafting reaction is achieved by controlling the viscosity of the epoxy resin prepolymer to control the prepolymerization reaction degree and adjusting the means of epoxy hydroxyl-terminated polybutadiene addition amount in the polyurethane prepolymer synthesis reaction, and finally the control of the chemical bonding degree between two polymer networks is realized. The chemical grafting reaction is that the epoxy groups in the epoxy resin prepolymer and the epoxy groups in the polyurethane prepolymer are subjected to ring opening reaction under the action of an epoxy resin curing agent. The epoxy groups in the polyurethane prepolymer are derived from the starting epoxidized hydroxyl terminated polybutadiene.
The invention has the following beneficial effects:
(1) By constructing the polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding, the free volume of the material is reduced, the intermolecular friction is inhibited, the interlocking degree between polymer networks is not too high, and the elastic modulus of the material is reduced
Figure SMS_5
The water-blocking permeation and sound-transmitting performance of the material is improved to the greatest extent. Underwater sound transducer bag commonly used in ChinaThe water permeability coefficient of the coating material JA-2S is 1 multiplied by 10 -12 g·cm/cm 2 S.pa, the water permeability coefficient of the sealing and coating material of the deep sea underwater acoustic transducer is 3.6X10 -14 g·cm/cm 2 S.pa, the water permeability coefficient was reduced by 96% as compared with JA-2S. The average acoustic loss of JA-2S in the range of 300-800 kHz is 272dB/m, and the average acoustic loss of the deep sea underwater acoustic transducer sealing coating material in the range of 300-800 kHz is 112dB/m, so that the acoustic transmission performance of the deep sea underwater acoustic transducer sealing coating material is improved by 59% compared with that of JA-2S.
(2) The dimer diisocyanate selected by the invention has the characteristics of better flexibility, adhesiveness and low viscosity than other aliphatic isocyanates due to the long chain structure, so that the viscosity of the polyurethane prepolymer can be reduced by mixing the dimer diisocyanate with other isocyanates. In addition, NCO groups in the dimeric diisocyanate react with active hydrogen slowly, so that the deep-sea underwater sound transducer sealing and coating material has longer operation time and longer application period, and brings convenience to process operation.
(3) The epoxidized hydroxyl-terminated polybutadiene selected by the invention has a long-chain nonpolar molecular configuration, high electrical insulation and low dielectric constant, and the selected dimer diisocyanate also has higher insulation performance due to the unique molecular configuration, so that the sealing and coating material of the deep sea underwater acoustic transducer prepared based on the two raw materials has very excellent electrical insulation performance. The volume resistivity of the sealing coating material of the deep sea underwater acoustic transducer is 1.4 multiplied by 10 13 [ omega ] cm, volume resistivity of JA-2S of 10 11 ~10 12 And the volume resistivity is improved by 1-2 orders of magnitude compared with JA-2S.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a photograph showing a JA-2S coated 2A-12 aluminum alloy material subjected to a 70 ℃ soaking test in artificial seawater, wherein 1- (1), 1- (2), 1- (3) and 1- (4) are taken on the 1 st day, 26 th day, 41 th day and 60 th day of the test respectively.
FIG. 2 is a photograph showing the immersion test of the material coated 2A-12 aluminum alloy material prepared in example 1 in artificial seawater at 70 ℃, wherein 2- (1), 2- (2), 2- (3), 2- (4) are taken on the 1 st day, 39 th day, 64 th day and 88 th day of the test, respectively.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
(1) Preparation of polyurethane prepolymers
75g of dimer diisocyanate (DDI, the molecular structure of which has an NCO group content of 14% -15%, the molecular weight of which is 586, and which is purchased from dawn chemical industry institute), 16g of diphenylmethane diisocyanate (mdi-50), 124g of epoxidized hydroxyl terminated polybutadiene (EHTPB, the hydroxyl functionality of which is 0.8-0.85, the molecular weight of which is 2900, which is purchased from gram Lei Weili chemical industry Co., ltd.), 14g of polyether polyol (the molecular weight of which is 1000, the functionality of which is 2, which is purchased from Dow chemical industry), 10mg of bismuth neodecanoate, and stirring and reacting for 8 hours at 80 ℃ under the protection of nitrogen atmosphere, and stopping the reaction to obtain the polyurethane prepolymer.
(2) Preparation of epoxy resin prepolymer
80g of low-viscosity epoxy resin EPON815C and 3g of 2-ethyl-4-methylimidazole are weighed and reacted for 2.5 hours at 60 ℃, and when the viscosity is 1700cps (25 ℃), the reaction is stopped to obtain the epoxy resin prepolymer.
(3) Preparation of polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding
100g of polyurethane prepolymer, 25g of epoxy resin prepolymer, 5g of E300 curing agent and 5.6g of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are weighed, uniformly stirred, defoamed in vacuum for 5min, poured into a mold for curing reaction, and reacted for 12h at 80 ℃ to obtain the polyurethane-epoxy resin interpenetrating network structure polymer material with controllable chemical bonding.
Example 2:
(1) Preparation of polyurethane prepolymers
42g of dimer diisocyanate (DDI, the molecular structure of which has an NCO group content of 14% -15%, the molecular weight of which is 586, purchased from dawn chemical industry institute), 29.8g of diphenylmethane diisocyanate (mdi-50), 124g of epoxidized hydroxyl terminated polybutadiene (EHTPB, hydroxyl functionality of 0.8-0.85, molecular weight of 2900, purchased from gram Lei Weili chemical Co., ltd.), 14g of polyether polyol (molecular weight of 1000, functionality of 2, purchased from Dow chemical industry), 12mg of iron acetylacetonate, and stirring at 70 ℃ for reaction for 12 hours under the protection of nitrogen atmosphere, and stopping the reaction to obtain the polyurethane prepolymer.
(2) Preparation of epoxy resin prepolymer
80g of low-viscosity epoxy resin EPON815C and 3g of 2-ethyl-4-methylimidazole are weighed and reacted for 2.5 hours at 60 ℃, and when the viscosity is 1700cps (25 ℃), the reaction is stopped to obtain the epoxy resin prepolymer.
(3) Preparation of polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding
100g of polyurethane prepolymer, 25g of epoxy resin prepolymer, 5g of E300 curing agent and 5.6g of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are weighed, uniformly stirred, defoamed in vacuum for 5min, poured into a mold for curing reaction, and reacted for 12h at 80 ℃ to obtain the polyurethane-epoxy resin interpenetrating network structure polymer material with controllable chemical bonding.
Example 3:
(1) Preparation of polyurethane prepolymers
Weighing 75g of dimeric diisocyanate (DDI, wherein the NCO group content in the molecular structure is 14% -15%, the molecular weight is 586, the preparation is purchased from dawn chemical industry institute), 16g of diphenylmethane diisocyanate (mdi-50), 75g of epoxidized hydroxyl terminated polybutadiene (EHTPB, the hydroxyl functionality is 0.8-0.85, the molecular weight is 2900, the preparation is purchased from gram Lei Weili chemical industry Co., ltd.), 30g of polyether polyol (the molecular weight is 1000, the functionality is 2, the preparation is purchased from the Dow chemical industry), 10mg of bismuth neodecanoate, stirring and reacting for 3 hours at 100 ℃ under the protection of nitrogen atmosphere, and stopping the reaction to obtain the polyurethane prepolymer.
(2) Preparation of epoxy resin prepolymer
80g of low-viscosity epoxy resin EPON815C and 3g of 2-ethyl-4-methylimidazole are weighed and reacted for 2.5 hours at 60 ℃, and when the viscosity is 1700cps (25 ℃), the reaction is stopped to obtain the epoxy resin prepolymer.
(3) Preparation of polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding
100g of polyurethane prepolymer, 25g of epoxy resin prepolymer, 5g of E300 curing agent and 5.6g of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are weighed, uniformly stirred, defoamed in vacuum for 5min, poured into a mold for curing reaction, and reacted for 12h at 80 ℃ to obtain the polyurethane-epoxy resin interpenetrating network structure polymer material with controllable chemical bonding.
Example 4:
(1) Preparation of polyurethane prepolymers
75g of dimer diisocyanate (DDI, the molecular structure of which has an NCO group content of 14% -15%, the molecular weight of which is 586, and which is purchased from dawn chemical industry institute), 16g of diphenylmethane diisocyanate (mdi-50), 124g of epoxidized hydroxyl terminated polybutadiene (EHTPB, the hydroxyl functionality of which is 0.8-0.85, the molecular weight of which is 2900, which is purchased from gram Lei Weili chemical industry Co., ltd.), 14g of polyether polyol (the molecular weight of which is 1000, the functionality of which is 2, which is purchased from Dow chemical industry), 10mg of bismuth neodecanoate, and stirring and reacting for 8 hours at 80 ℃ under the protection of nitrogen atmosphere, and stopping the reaction to obtain the polyurethane prepolymer.
(2) Preparation of epoxy resin prepolymer
80g of low viscosity epoxy resin EPON815C,3g of 2-ethyl-4-methylimidazole is weighed and reacted for 2 hours at 80 ℃, and when the viscosity of the epoxy resin EPON815C is 4300cps (25 ℃), the reaction is stopped to obtain the epoxy resin prepolymer.
(3) Preparation of polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding
100g of polyurethane prepolymer, 25g of epoxy resin prepolymer, 5g of E300 curing agent and 5.6g of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are weighed, uniformly stirred, defoamed in vacuum for 5min, poured into a mold for curing reaction, and reacted for 5h at 100 ℃ to obtain the polyurethane-epoxy resin interpenetrating network structure polymer material with controllable chemical bonding.
Example 5:
(1) Preparation of polyurethane prepolymers
75g of dimeric diisocyanate (DDI, the NCO group content in the molecular structure of which is 14% -15%, the molecular weight is 586, the preparation is purchased from dawn chemical industry institute), 16g of diphenylmethane diisocyanate (mdi-50), 124g of epoxidized hydroxyl terminated polybutadiene (EHTPB, the hydroxyl functionality of which is 0.8-0.85, the molecular weight is 2900, the preparation is purchased from gram Lei Weili chemical industry Co., ltd.), 14g of polyether polyol (the molecular weight of which is 1000, the functionality of which is 2, the preparation is purchased from the Dow chemical industry), 12mg of ferric acetylacetonate, and the preparation is stirred and reacted for 8 hours at 80 ℃ under the protection of nitrogen atmosphere, and the reaction is stopped to obtain the polyurethane prepolymer.
(2) Preparation of epoxy resin prepolymer
80g of low-viscosity epoxy resin EPON815C and 3g of 2-ethyl-4-methylimidazole are weighed and reacted for 2.5 hours at 60 ℃, and when the viscosity is 1700cps (25 ℃), the reaction is stopped to obtain the epoxy resin prepolymer.
(3) Preparation of polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding
100g of polyurethane prepolymer, 15g of epoxy resin prepolymer, 5g of E300 curing agent and 5.6g of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are weighed, uniformly stirred, defoamed in vacuum for 5min, poured into a mold for curing reaction, and reacted for 12h at 80 ℃ to obtain the polyurethane-epoxy resin interpenetrating network structure polymer material with controllable chemical bonding.
Example 6:
(1) Preparation of polyurethane prepolymers
42g of dimer diisocyanate (DDI, the NCO group content in the molecular structure of which is selected to be 14% -15%, the molecular weight of which is 586, purchased from dawn chemical industry institute), 29.8g of diphenylmethane diisocyanate (mdi-50), 90g of epoxidized hydroxyl terminated polybutadiene (EHTPB, hydroxyl functionality of which is 0.8-0.85, molecular weight of which is 2900, purchased from gram Lei Weili chemical company, inc.), 25g of polyether polyol (molecular weight of which is 1000, functionality of which is 2, purchased from the Dow chemical industry), 6mg of ferric acetylacetonate, and stirring at 90 ℃ for 6 hours under the protection of nitrogen atmosphere, and stopping the reaction to obtain the polyurethane prepolymer.
(2) Preparation of epoxy resin prepolymer
80g of low-viscosity epoxy resin EPON815C and 3g of 2-ethyl-4-methylimidazole are weighed and reacted for 2.5 hours at 60 ℃, and when the viscosity is 1700cps (25 ℃), the reaction is stopped to obtain the epoxy resin prepolymer.
(3) Preparation of polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding
100g of polyurethane prepolymer, 25g of epoxy resin prepolymer, 6.5g of E300 curing agent and 3.9g of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are weighed, uniformly stirred, vacuum defoamed for 5min, poured into a mold for curing reaction, and reacted at 90 ℃ for 8h to obtain the polyurethane-epoxy resin interpenetrating network structure polymer material with controllable chemical bonding.
Comparative example 1:
the difference between this comparative example and example 1 is that the isocyanate in this comparative example does not contain a dimer diisocyanate.
(1) Preparation of polyurethane prepolymers
47.3g of diphenylmethane diisocyanate (mdi-50), 124g of epoxidized hydroxyl terminated polybutadiene (EHTPB, hydroxyl functionality 0.8-0.85, molecular weight 2900, available from g Lei Weili chemical Co., ltd.), 14g of polyether polyol (molecular weight 1000, functionality 2, available from Dow chemical), 10mg of bismuth neodecanoate, and stirring and reacting for 8 hours at 80 ℃ under the protection of nitrogen atmosphere, and stopping the reaction to obtain the polyurethane prepolymer.
(2) Preparation of epoxy resin prepolymer
80g of low-viscosity epoxy resin EPON815C and 3g of 2-ethyl-4-methylimidazole are weighed and reacted for 2.5 hours at 60 ℃, and when the viscosity is 1700cps (25 ℃), the reaction is stopped to obtain the epoxy resin prepolymer.
(3) Preparation of polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding
100g of polyurethane prepolymer, 25g of epoxy resin prepolymer, 5g of E300 curing agent and 5.6g of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are weighed, uniformly stirred, defoamed in vacuum for 5min, poured into a mold for curing reaction, and reacted for 12h at 80 ℃ to obtain the polyurethane-epoxy resin interpenetrating network structure polymer material with controllable chemical bonding.
Comparative example 2:
the difference between this comparative example and example 1 is that the polyol in this comparative example does not contain epoxidized hydroxyl terminated polybutadiene.
(1) Preparation of polyurethane prepolymers
75g of dimeric diisocyanate (DDI, the NCO group content in the molecular structure of which is 14% -15%, the molecular weight is 586, the polyurethane prepolymer is obtained by stirring and reacting 16g of diphenylmethane diisocyanate (mdi-50), 55g of polyether polyol (the molecular weight is 1000, the functionality is 2, the polyurethane prepolymer is obtained by the Dow chemical industry) and 10mg of bismuth neodecanoate for 8 hours under the protection of nitrogen atmosphere at 80 ℃ and stopping the reaction.
(2) Preparation of epoxy resin prepolymer
80g of low-viscosity epoxy resin EPON815C and 3g of 2-ethyl-4-methylimidazole are weighed and reacted for 2.5 hours at 60 ℃, and when the viscosity is 1700cps (25 ℃), the reaction is stopped to obtain the epoxy resin prepolymer.
(3) Preparation of polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding
100g of polyurethane prepolymer, 25g of epoxy resin prepolymer, 5g of E300 curing agent and 5.6g of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are weighed, uniformly stirred, defoamed in vacuum for 5min, poured into a mold for curing reaction, and reacted for 12h at 80 ℃ to obtain the polyurethane-epoxy resin interpenetrating network structure polymer material with controllable chemical bonding.
Comparative example 3:
the difference between this comparative example and example 1 is that the epoxy resin in this comparative example is not the low viscosity epoxy resin EPON815C but the ordinary epoxy resin E51.
(1) Preparation of polyurethane prepolymers
75g of dimer diisocyanate (DDI, the molecular structure of which has an NCO group content of 14% -15%, the molecular weight of which is 586, and which is purchased from dawn chemical industry institute), 16g of diphenylmethane diisocyanate (mdi-50), 124g of epoxidized hydroxyl terminated polybutadiene (EHTPB, the hydroxyl functionality of which is 0.8-0.85, the molecular weight of which is 2900, which is purchased from gram Lei Weili chemical industry Co., ltd.), 14g of polyether polyol (the molecular weight of which is 1000, the functionality of which is 2, which is purchased from Dow chemical industry), 10mg of bismuth neodecanoate, and stirring and reacting for 8 hours at 80 ℃ under the protection of nitrogen atmosphere, and stopping the reaction to obtain the polyurethane prepolymer.
(2) Preparation of epoxy resin prepolymer
80g of epoxy resin E51 and 3g of 2-ethyl-4-methylimidazole are weighed and reacted for 2.5 hours at 60 ℃, and when the viscosity of the epoxy resin E51 is 18000cps (25 ℃), the reaction is stopped to obtain an epoxy resin prepolymer.
(3) Preparation of polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding
100g of polyurethane prepolymer, 25g of epoxy resin prepolymer, 5g of E300 curing agent and 5.6g of 3-hydroxyethyl oxyethyl-1-hydroxyethyl benzene diether are weighed, uniformly stirred, defoamed in vacuum for 5min, poured into a mold for curing reaction, and reacted for 12h at 80 ℃ to obtain the polyurethane-epoxy resin interpenetrating network structure polymer material with controllable chemical bonding.
Test example 1:
test examples 1 to 6 and comparative examples 1 to 3 were tested for water permeability of 9 samples in total, and the test method was referred to the standard GB/T1037 test method for Water vapor permeability of Plastic films and sheets-cup method, at a test temperature of 38℃and a relative humidity of 90% and a water vapor permeation area of 33cm 2 The test parameters were measured with a sample thickness of 2mm, and the results are shown in Table 1.
Table 1 water permeability coefficients for examples and comparative examples.
Figure SMS_6
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From the test results of table 1, comparing example 1 with example 3, example 4 and comparative example 2, it is known that the amount of epoxidized hydroxyl terminated polybutadiene and the viscosity of the epoxy resin prepolymer in example 1 can be such that the amount of chemical bonding between interpenetrating networks is improved to a good degree, thereby obtaining a very low water permeability coefficient result, while the decrease of epoxy groups in the reaction system can reduce the amount of chemical bonding between interpenetrating networks, resulting in an increase in water permeability coefficient, which is greatly increased when there is almost no chemical bonding of epoxy groups between interpenetrating networks (comparative example 2). Comparing example 1 with example 2 shows that the increased content of the dimeric diisocyanate reduces the water permeability coefficient because the dimeric diisocyanate is a long chain hydrophobic structure.
Test example 2:
the average acoustic loss of 9 samples of examples 1-6 and comparative examples 1-3 at 300 kHz-800 kHz was measured, and the test method was referred to the standard GB/T18022-2000 1MHz-10MHz measuring method for longitudinal wave sound velocity and attenuation coefficient of rubber and plastic, and the results are shown in Table 2.
Table 2 the specific measured values of the average sound attenuation coefficient of 300khz to 800khz for the examples and comparative examples are: the average sound attenuation coefficient of 300kHz to 800kHz is the average value of the sound attenuation coefficients under the condition of 11 test frequencies, wherein the sound attenuation coefficients are 11 test frequencies such as 300kHz,350kHz,400kHz,450kHz,500kHz,550kHz,600kHz,650kHz,700kHz,750kHz,800kHz and the like.
Figure SMS_7
The data in table 2 shows that the sound transmission performance also has a direct relationship with the number of chemical bonds between the interpenetrating networks, with the most number of chemical bonds between the interpenetrating networks having the least acoustic attenuation coefficient as in example 1 and the least number of chemical bonds between the interpenetrating networks having the most acoustic attenuation coefficient as in comparative example 2.
Test example 3:
test examples 1 to 6 and comparative examples 1 to 3 were tested under the conditions of the test parameters of the viscosity meter model NDJ-5S, the rotor model 3 and the rotation speed of 12 rpm by referring to the standard GB/T2794-2013 measurement of adhesive viscosity-single cylinder rotational viscometer, by the viscosity of the perfusate before the solidification reaction after the vacuum defoamation in the preparation step (3), and the results are shown in table 3.
Table 3 viscosity of the perfusate of examples and comparative examples
Figure SMS_8
Analysis of the results in Table 3, comparing comparative example 3 with other test subjects, can be seen that the use of low viscosity epoxy resins significantly reduced the viscosity of the potting compound. Comparing examples 1, 2 and comparative example 1, it was found that the higher the proportion of dimer acid diisocyanate in the raw material, the lower the viscosity of the potting compound. The viscosity of comparative example 2 was the lowest because the higher viscosity epoxidized hydroxyl terminated polybutadiene was not used in the feed.
In FIG. 1, the JA-2S coated 2A-12 aluminum alloy material is subjected to a 70 ℃ soaking test in artificial seawater, so that the blackening phenomenon of the aluminum alloy surface corrosion occurs on the 26 th day due to the large water permeability coefficient of the JA-2S material, and the subsequent surface corrosion blackening continues to expand and spread, which is quite obvious on the 60 th day. FIG. 2 example 1 preparation of material coated 2A-12 aluminum alloy material in a photograph of a 70 ℃ immersion test in artificial seawater, the aluminum alloy surface did not appear to corrode or blacken until the 88 th day of photographing.
In summary, example 1 has the most excellent combination property, and the water permeability coefficient and the sound permeability are better than those of the underwater acoustic polyurethane JA-2S used at home at present. The viscosity of the filling material can also meet the filling molding requirement of the sealing coating material of the underwater acoustic transducer, and the problem of insufficient reliability of the sealing coating material when the current deep-sea acoustic equipment works underwater for a long time can be solved.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (7)

1. The sealing and cladding material for the deep sea underwater acoustic transducer is characterized by comprising polyurethane prepolymer, epoxy resin prepolymer and polyurethane curing agent in a mass ratio of 100:70:40-100:5:15 by constructing polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding;
the polyurethane prepolymer comprises isocyanate, polyalcohol and catalyst as raw materials; wherein the mass ratio of isocyanate to polyol is 1:1-10:1, and the dosage of the catalyst is 0.001% -0.1% of the total mass of the reaction system;
the polyol is a mixture of polyolefin polyol and polyether polyol, and the mass ratio of the polyolefin polyol to the polyether polyol is 100:100-100:0; the polyolefin polyol is epoxidized hydroxyl terminated polybutadiene;
the epoxy resin prepolymer comprises the raw materials of an epoxy resin monomer and an epoxy resin curing agent in a mass ratio of 100:5-100:10; the epoxy resin monomer is low-viscosity epoxy resin, and the viscosity is less than 1000 mPa.s.
2. The deep sea acoustic transducer seal coat material of claim 1, wherein the polyurethane curing agent is one or more of a diamine curing agent and a glycol curing agent.
3. The sealing and cladding material for deep sea underwater sound transducer according to claim 1, wherein the isocyanate is a mixture of dimer diisocyanate and one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate, and the mass ratio of the dimer diisocyanate to the other isocyanate mixture is 100:100-100:0.
4. The sealing and coating material for the deep sea underwater sound transducer according to claim 1, wherein the catalyst is one or more of an organotin-based catalyst, an organobismuth-based catalyst and an organoiron-based catalyst.
5. The deep sea underwater sound transducer sealing and cladding material of claim 1, wherein the epoxy resin curing agent is an imidazole curing agent.
6. A method for preparing a sealing and cladding material for a deep sea underwater acoustic transducer according to any one of claims 1 to 5, comprising the steps of:
1) Preparation of polyurethane prepolymer:
the isocyanate, the polyol and the catalyst are subjected to polymerization reaction under the protection of inert gas, and the reaction is stopped after a certain time of reaction, so as to obtain polyurethane prepolymer;
2) Preparation of epoxy resin prepolymer:
performing polymerization reaction on the epoxy resin monomer and the epoxy resin curing agent, and stopping the reaction when the viscosity of the reaction system reaches a certain value to obtain an epoxy resin prepolymer;
3) Preparation of a polyurethane-epoxy interpenetrating network structure polymer with controllable chemical bonding:
and uniformly mixing the polyurethane prepolymer, the epoxy resin prepolymer and the polyurethane curing agent, pouring into a mold for curing reaction, and curing to obtain the polyurethane-epoxy resin interpenetrating network structure polymer with controllable chemical bonding.
7. The method for preparing the sealing and cladding material for the deep sea underwater acoustic transducer according to claim 6, wherein the polymerization reaction temperature in the step 1) is 40-120 ℃ and the reaction time is 1-10 h; the viscosity in the step 2) is 500-8000 cps; the curing reaction temperature in the step 3) is 50-130 ℃ and the reaction time is 3-24 hours.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104530366A (en) * 2014-12-18 2015-04-22 黎明化工研究设计院有限责任公司 Polyurethane sealing material and preparation method thereof
CN110698625A (en) * 2019-09-17 2020-01-17 南京聚发新材料有限公司 Preparation method of viscoelastic microporous elastomer
CN111484727A (en) * 2020-03-13 2020-08-04 中山大学 Wide-pH-range underwater self-repairing topological interlocking network and preparation method and application thereof
CN111518253A (en) * 2020-04-10 2020-08-11 李春梅 Underwater cable solid filling material, preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104530366A (en) * 2014-12-18 2015-04-22 黎明化工研究设计院有限责任公司 Polyurethane sealing material and preparation method thereof
CN110698625A (en) * 2019-09-17 2020-01-17 南京聚发新材料有限公司 Preparation method of viscoelastic microporous elastomer
CN111484727A (en) * 2020-03-13 2020-08-04 中山大学 Wide-pH-range underwater self-repairing topological interlocking network and preparation method and application thereof
CN111518253A (en) * 2020-04-10 2020-08-11 李春梅 Underwater cable solid filling material, preparation method and application

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