CN116549840B - Processing technology for auditory vagus nerve electrode - Google Patents
Processing technology for auditory vagus nerve electrode Download PDFInfo
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- CN116549840B CN116549840B CN202310829040.6A CN202310829040A CN116549840B CN 116549840 B CN116549840 B CN 116549840B CN 202310829040 A CN202310829040 A CN 202310829040A CN 116549840 B CN116549840 B CN 116549840B
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- 210000001186 vagus nerve Anatomy 0.000 title claims abstract description 39
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 238000012545 processing Methods 0.000 title claims abstract description 17
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000004945 silicone rubber Substances 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 37
- 239000011231 conductive filler Substances 0.000 claims abstract description 17
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical group NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 14
- 229960003151 mercaptamine Drugs 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
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- -1 pentane sultone Chemical class 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
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- 239000007822 coupling agent Substances 0.000 claims description 4
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical group C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
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- 238000012986 modification Methods 0.000 claims description 4
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- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 3
- QYMUDOWMRHNHHP-UHFFFAOYSA-N n-[4-(dimethylamino)butyl]prop-2-enamide Chemical compound CN(C)CCCCNC(=O)C=C QYMUDOWMRHNHHP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- YJZYDJLNWSMVKJ-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]but-2-enamide Chemical compound CC=CC(=O)NCCCN(C)C YJZYDJLNWSMVKJ-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 230000000638 stimulation Effects 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 21
- 230000000694 effects Effects 0.000 description 9
- 230000001515 vagal effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 4
- 238000001467 acupuncture Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 210000005036 nerve Anatomy 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 208000003098 Ganglion Cysts Diseases 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 208000013738 Sleep Initiation and Maintenance disease Diseases 0.000 description 1
- 208000005400 Synovial Cyst Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QZLJNVMRJXHARQ-UHFFFAOYSA-N [Zr].[Cr].[Cu] Chemical compound [Zr].[Cr].[Cu] QZLJNVMRJXHARQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- BZWQNMUGNDAMBX-UHFFFAOYSA-N butyl butane-1-sulfonate Chemical group CCCCOS(=O)(=O)CCCC BZWQNMUGNDAMBX-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 description 1
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 210000000613 ear canal Anatomy 0.000 description 1
- 210000000959 ear middle Anatomy 0.000 description 1
- 206010015037 epilepsy Diseases 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 206010022437 insomnia Diseases 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 230000003238 somatosensory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000008053 sultones Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/02—Details
- A61N1/04—Electrodes
- A61N1/05—Electrodes for implantation or insertion into the body, e.g. heart electrode
- A61N1/0526—Head electrodes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
- A61N1/00—Electrotherapy; Circuits therefor
- A61N1/18—Applying electric currents by contact electrodes
- A61N1/32—Applying electric currents by contact electrodes alternating or intermittent currents
- A61N1/36—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
- A61N1/36036—Applying electric currents by contact electrodes alternating or intermittent currents for stimulation of the outer, middle or inner ear
Landscapes
- Health & Medical Sciences (AREA)
- Radiology & Medical Imaging (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Cardiology (AREA)
- Otolaryngology (AREA)
- Electrotherapy Devices (AREA)
Abstract
The application discloses a processing technology for an ear vagus nerve electrode, which comprises an earplug electrode and an auricle electrode and comprises the following steps: modifying the surface of the metal electrode body by using a sulfhydryl silane coupling agent to obtain a modified electrode body; and injecting conductive silicone rubber on the surface of the modified electrode body, and forming to obtain the ear vagus nerve electrode, wherein the conductive silicone rubber comprises the following components: 30-50 parts of double bond terminated silicon rubber, 10-20 parts of functional auxiliary agents, 1-3 parts of conductive fillers and 1-3 parts of vulcanizing agents. The ear vagus nerve electrode prepared by the processing technology has excellent deformation resistance, and the silicon rubber on the surface of the electrode has stronger binding force with the electrode body, so that the phenomenon that the electric stimulation intensity is reduced due to oxidation of the surface of the electrode can be effectively prevented.
Description
Technical Field
The application relates to a processing technology for an ear vagus nerve electrode, and belongs to the technical field of ear vagus nerve electrode processing.
Background
Clinical verification shows that the nerve electric stimulation therapy combining the electronic technology and the traditional acupuncture and moxibustion meridian theory has curative effect on nerve dysfunction diseases. The vagus nerve innervates the sensory and motor and gland secretion of the vast majority of organs and hearts of the respiratory system and the digestive system, carries out electric stimulation on the vagus nerve, and has good auxiliary treatment effects on epilepsy, diabetes, insomnia, depression and the like. The auricle branch in the cervical branch of the vagus nerve contains general somatosensory fibers which are emitted from the upper ganglion and are distributed outside behind the auricle and on the skin of the external auditory canal, as described in the prior art CN105056384A, the auricle opening and the auricle part are ear acupuncture points of the vagus nerve, and the vagus nerve endings are rich, so that the effect of nerve electric stimulation treatment can be achieved by carrying out electric stimulation on the auricle opening and the auricle part acupuncture points.
The existing auditory vagus nerve electrode is mostly directly coated with conductive silicone rubber on the surface of a metal electrode, however, different users have differences in size and even shape of auditory meatus, when the auditory vagus nerve electrode is used, if the auditory vagus nerve electrode is not attached to the auditory meatus, the user can adjust the angle of the auditory electrode at any time according to personal comfort level when the auditory vagus nerve electrode is used, after the auditory vagus nerve electrode is used for a period of time, the user can adjust the silicone rubber on the surface of the electrode for many times to age and deform, in addition, gaps are easily formed after the silicone rubber is separated from the surface of the electrode, oxidation of the surface of the electrode is caused, the phenomenon that the electric stimulation intensity is weakened or even no electric stimulation output occurs, and the user experience is affected.
Disclosure of Invention
In order to solve the problems, the processing technology for the auditory vagus nerve electrode is provided, the auditory vagus nerve electrode prepared by the processing technology has excellent rebound capability, and the silicon rubber on the surface of the electrode has strong binding force with the electrode body, so that the phenomenon that the electric stimulation intensity is reduced due to oxidation of the surface of the electrode can be effectively prevented.
According to one aspect of the present application, there is provided a process for an ear vagus electrode comprising an earplug electrode and an auricle electrode, comprising the steps of:
modifying the surface of the metal electrode body by using a sulfhydryl silane coupling agent to obtain a modified electrode body;
and injecting conductive silicone rubber on the surface of the modified electrode body, and forming to obtain the ear vagus nerve electrode, wherein the conductive silicone rubber comprises the following components:
30-50 parts of double bond terminated silicon rubber, 10-20 parts of functional auxiliary agents, 1-3 parts of conductive fillers, 1-3 parts of vulcanizing agents and 1-3 parts of initiators;
the structural formula of the functional auxiliary agent is as follows:，
wherein R is 1 Selected from ethenyl or propenyl, R 2 、R 3 And R is 4 Independently selected from one of C1-C3 alkyl groups containing straight or branched chains, R 5 Selected from one of C3-C6 alkyl groups containing a straight chain or branched chain.
The application uses the sulfhydryl silane coupling agent to modify the surface of the metal electrode, firstly, the sulfhydryl in the sulfhydryl silane coupling agent can generate stronger bonding action with the surface of the metal so as to form a self-assembled film on the surface of the metal, secondly, the sulfhydryl silane coupling agent usually exists in a hydrolysis form in solution, and the hydrolyzed Si-OH group can generate a shrink reaction with the Me-OH group (Me represents the metal) on the surface of the metal so as to form a covalent bond and be adsorbed on the surface of the metal, thereby forming grafting on the surface of the metal electrode, and having good corrosion inhibition effect.
In addition, functional auxiliary agents are added into the conductive silicon rubber, the functional auxiliary agents contain double bonds and can be crosslinked with the silicon rubber blocked by the double bonds, so that the functional auxiliary agents and the silicon rubber form a crosslinked network, the mechanical property of the electric silicon rubber is improved, the conductivity of the silicon rubber can be improved by sulfonate groups contained in the functional auxiliary agents, and the mutual exclusion among sulfonate groups is beneficial to the dispersion of the functional auxiliary agents in a silicon rubber substrate; the amide group has good polarity, so that the mechanical property and stability of the conductive silicon rubber can be improved, and wider application conditions of the ear electrode are ensured; in addition, an acid-base pair effect may be formed between the sulfonate and the tertiary amine groups, which may enhance the electron conduction capability in the crosslinked network.
The prepared conductive silicon rubber is injection-molded on the surface of a metal electrode modified by a sulfhydryl silane coupling agent, silane molecules in the silicon rubber can be subjected to polycondensation reaction with silane molecules on the surface of the metal electrode to form a three-dimensional network structure of Si-O-Si on the surface of the metal, and sulfhydryl groups on the surface of the metal can be subjected to reaction with double bonds in the conductive silicon rubber to form dynamic chemical bonds, so that the bonding force between the conductive silicon rubber and the metal electrode body is greatly enhanced, the stripping resistance between the conductive silicon rubber and the metal electrode body is improved, the oxidation phenomenon on the surface of the metal electrode caused by stripping between the conductive silicon rubber and the metal electrode body is avoided, and the ear electrode can still maintain excellent conductivity after being deformed or used for multiple times.
It is to be understood that the metal electrode body in the present application may be a copper electrode, a chromium electrode, a zinc electrode, or the like, or may be an alloy electrode such as chromium copper, zirconium copper, chromium zirconium copper, or the like, and is preferably a copper electrode.
Optionally, the functional auxiliary agent is prepared by reacting a monomer A and a monomer B, wherein the monomer A is at least one of dimethylaminopropyl acrylamide, dimethylaminopropyl butenamide and dimethylaminobutyl acrylamide;
the monomer B is at least one selected from propane sultone, butane sultone, pentane sultone and hexane sultone.
The tertiary amine in the monomer A and the sultone group in the monomer B react to obtain sulfonate, the alkyl groups in the monomer A and the monomer B can increase the movement capacity of the functional auxiliary, facilitate the extension of a molecular chain, enhance the deformation resistance of the conductive silicone rubber, and in addition, the existence of the alkyl groups can improve the crosslinking property and compatibility between the functional auxiliary and the silicone rubber base material (namely double-bond capped silicone rubber), so that the functional auxiliary is uniformly dispersed in a crosslinking network, and a single bond in the alkyl can rotate freely, thereby ensuring the excellent rebound performance of the conductive silicone rubber.
Alternatively, the molar ratio will be 1: the monomer A and the monomer B of (1-1.1) are dissolved in a first solution, and the functional auxiliary agent is obtained after stirring reaction for 2-4 hours at 50-130 ℃, wherein the first solution is selected from ethanol, isopropanol or acetone.
Preferably, the molar ratio is 1:1 and the monomer A and the monomer B are dissolved in a first solution, and are obtained after stirring reaction for 3 hours at 90 ℃, wherein the first solution is isopropanol.
Optionally, the conductive filler is graphene oxide modified by mercaptoethylamine.
The surface of the graphene oxide is modified with the mercaptoethylamine, so that the mercaptoethylamine and double bonds in the silicon rubber substrate can form dynamic chemical bonds, the graphene oxide can be used as a crosslinking point to directly participate in the construction of the dynamic chemical bonds, and the mechanical properties such as rebound resilience of the conductive silicon rubber are improved; secondly, the surface of the graphene oxide can be provided with amino groups, so that the compatibility with the functional auxiliary agent is improved, the graphene oxide can be uniformly dispersed along a cross-linked network of the functional auxiliary agent, and the conductivity of the electric silicon rubber is improved.
Optionally, dispersing graphene oxide in a second solution containing mercaptoethylamine, aminating for 12-18 hours at 100-120 ℃, and centrifugally drying to obtain the conductive filler;
wherein the weight ratio of graphene oxide to mercaptoethylamine is 1:0.3-0.5, and the second solution is selected from methanol or ethanol.
Optionally, the surface modification of the metal electrode body comprises the following steps: and (3) cleaning, polishing and drying the metal electrode, putting the metal electrode into a third solution containing a sulfhydryl silane coupling agent, wherein the mass concentration of the third solution is 5-15wt%, soaking for 4-12h, and drying for 2-4h at 80-100 ℃ to obtain the modified electrode body.
Optionally, the mercaptosilane coupling agent is at least one selected from mercaptopropyl trimethoxy silane, mercaptopropyl triethoxy silane and mercaptopropyl methyl dimethoxy silane.
Optionally, the step of synthesizing the conductive silicone rubber includes: and (3) carrying out primary mixing on the double-bond terminated silicon rubber and the functional auxiliary agent, and then adding the conductive filler, the vulcanizing agent and the initiator for secondary mixing to obtain the conductive silicon rubber, wherein the primary mixing temperature is 40-50 ℃, the time is 5-15min, the secondary mixing temperature is 130-150 ℃, and the time is 5-10min. Firstly, the functional auxiliary agent and the silicon rubber base material are mixed in one step, so that the mixing uniformity between the functional auxiliary agent and the silicon rubber base material is improved, the functional auxiliary agent is uniformly dispersed in the silicon rubber base material, the conductive filler is added for two-step mixing on the basis of uniform dispersion of the functional auxiliary agent, and the groups contained on the functional auxiliary agent can improve the dispersion uniformity of the conductive filler, so that the silicon rubber base material, the functional auxiliary agent and the conductive filler are mutually crosslinked to form a uniform three-dimensional crosslinked network, and the electrical property and the mechanical property of the mixed conductive silicon rubber are ensured.
Optionally, the working temperature of the injection molding is 70-140 ℃.
Optionally, the double bond terminated silicone rubber is selected from methyl vinyl silicone rubber and/or methyl vinyl phenyl silicone rubber;
the vulcanizing agent is at least one selected from 2, 4-toluene diisocyanate, 1, 4-di-tert-butyl peroxyisopropyl benzene, dicumyl peroxide and tert-butyl perbenzoate;
the initiator is at least one selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, ammonium persulfate and sodium persulfate, preferably azobisisobutyronitrile.
Preferably, the vulcanizing agent is 2, 4-toluene diisocyanate, which is more suitable for bonding of conductive silicone rubber to metal surfaces.
The beneficial effects of the application include, but are not limited to:
1. according to the processing technology for the auditory vagus nerve electrode, the surface of the metal electrode is modified by using the sulfhydryl silane coupling agent, firstly, sulfhydryl groups in the sulfhydryl silane coupling agent can have a strong bonding effect with the surface of the metal, so that a self-assembled film can be formed on the surface of the metal, secondly, the sulfhydryl silane coupling agent usually exists in a hydrolysis form in a solution, and the hydrolyzed Si-OH groups can be subjected to a shrinkage reaction with Me-OH groups (Me represents metal) on the surface of the metal to form covalent bonds so as to be adsorbed on the surface of the metal, so that grafting is formed on the surface of the metal electrode, and a good corrosion inhibition effect can be achieved.
2. According to the processing technology for the auditory vagus nerve electrode, the functional auxiliary agent is added into the conductive silicone rubber, the functional auxiliary agent contains double bonds and can be crosslinked with the silicone rubber terminated by the double bonds, so that the functional auxiliary agent and the silicone rubber form a crosslinked network, the dispersibility of the functional auxiliary agent in the silicone rubber is improved, the conductivity of the silicone rubber can be increased by sulfonate groups contained in the functional auxiliary agent, and the mutual exclusion effect among sulfonate groups is beneficial to the dispersion of the functional auxiliary agent in a silicone rubber substrate; the amide group has good polarity, so that the mechanical property and stability of the conductive silicon rubber can be improved, and wider application conditions of the ear electrode are ensured; in addition, an acid-base pair effect may be formed between the sulfonate and the tertiary amine groups, which may enhance the electron conduction capability in the crosslinked network.
3. According to the processing technology for the auditory vagus nerve electrode, the prepared conductive silicone rubber is injection molded on the surface of the metal electrode modified by the sulfhydryl silane coupling agent, silane molecules in the silicone rubber can be subjected to polycondensation reaction with silane molecules on the surface of the metal electrode to form a three-dimensional network structure of Si-O-Si on the surface of the metal, and sulfhydryl groups on the surface of the metal can be subjected to reaction with double bonds in the conductive silicone rubber to form dynamic chemical bonds, so that the binding force between the conductive silicone rubber and the metal electrode body is greatly enhanced, the stripping resistance between the conductive silicone rubber and the metal electrode body is improved, the oxidation phenomenon on the surface of the metal electrode caused by stripping between the conductive silicone rubber and the ear electrode can still maintain excellent conductive performance after being deformed or used for multiple times.
4. According to the processing technology for the auditory vagus nerve electrode, the mercaptoethylamine is modified on the surface of the graphene oxide, so that the mercaptoethylamine and double bonds in the silicone rubber substrate can form dynamic chemical bonds, the graphene oxide can be used as a crosslinking point to directly participate in the construction of the dynamic chemical bonds, and mechanical properties such as rebound resilience of conductive silicone rubber are improved; secondly, the surface of the graphene oxide can be provided with amino groups, so that the compatibility with the functional auxiliary agent is improved, the graphene oxide can be uniformly dispersed along a cross-linked network of the functional auxiliary agent, and the conductivity of the electric silicon rubber is improved.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The middle ear vagus nerve electrode is a component part in the ear vagus nerve stimulator, wherein the ear vagus nerve stimulator is of a common structure on the market, and specifically, the ear vagus nerve stimulator comprises a host machine used for sending out an electric stimulation signal and an ear electrode used for electrically stimulating an ear acupoint of a human body, the host machine and the ear electrode can be connected through an electric wire, and can also be connected in a wireless mode, so long as the ear electrode can receive the stimulation signal sent by the host machine. Wherein the ear electrode comprises an earplug electrode and an auricle electrode for stimulating different positions of the ear.
The processing technology of the pair ear vagus nerve electrode in the embodiment is the processing technology of the pair ear plug electrode and the auricle electrode.
The processing technology of the ear vagus nerve electrode 1# comprises the following steps:
dissolving dimethylaminopropyl acrylamide in isopropanol, heating to 90 ℃ under nitrogen atmosphere, then dropwise adding butanesulfonic acid lactone, wherein the molar ratio of the dimethylaminopropyl acrylamide to the butanesulfonic acid lactone is 1:1, and stirring and reacting for 3 hours to obtain a functional auxiliary agent 1#;
dispersing graphene oxide in an ethanol solution containing mercaptoethylamine, stirring and aminating for 15 hours at 110 ℃, and centrifugally washing and drying to obtain a conductive filler 1#, wherein the weight ratio of the graphene oxide to the mercaptoethylamine is 1:0.4;
mixing 40 parts of methyl vinyl silicone rubber and 15 parts of functional auxiliary agent 1# at 45 ℃ for 10min, and then adding 2 parts of conductive filler 1#, 2 parts of 2, 4-toluene diisocyanate and 2 parts of azobisisobutyronitrile, mixing for 7min at 140 ℃ to obtain conductive silicone rubber 1#;
adding 10g of mercaptopropyl trimethoxysilane into 100g of ethanol solution, stirring for 6h to obtain a third solution with the mass concentration of 10wt%, cleaning the surface of a copper electrode, polishing with sand paper, cleaning, drying, soaking in the third solution for 8h, and drying at 90 ℃ for 3h to obtain a modified electrode body 1#;
and (3) injection molding conductive silicon rubber No. 1 on the surface of the modified electrode body No. 1, wherein the injection molding temperature is 120 ℃, and the auditory vagus nerve electrode No. 1 is obtained.
Example 2 was different from example 1 in that dimethylaminopropyl acrylamide was replaced with dimethylaminobutyl acrylamide and butylsultone was replaced with caprolactone in example 2, and the remaining steps were the same as in example 1, to obtain the auditory vagal electrode # 2.
Example 3 differs from example 1 in that 10 parts of functional auxiliary agent was added in example 3, and the remaining steps were the same as in example 1, to obtain an ear vagus nerve electrode 3#.
Example 4 differs from example 1 in that 1 part of conductive filler was added in example 4, and the remaining steps were the same as in example 1, to obtain an ear vagus nerve electrode # 4.
Example 5 differs from example 1 in that mercaptopropyl methyl dimethoxy silane was used in place of mercaptopropyl trimethoxy silane in example 5, and the remaining steps were the same as in example 1 to obtain the auditory vagal electrode 5#.
Example 6 is different from example 1 in that the conductive filler added in example 6 is graphene oxide not modified with mercaptoethylamine, and the remaining steps are the same as in example 1, to obtain the auditory vagal electrode 6#.
Example 7 differs from example 1 in that mercaptoethane was used in place of mercaptoethylamine in example 7, and the remaining steps were the same as in example 1 to obtain the auditory vagal electrode # 7.
Comparative example 1 differs from example 1 in that dimethylacrylamide was used in place of dimethylaminopropyl acrylamide in comparative example 1, and the remaining steps were the same as in example 1 to obtain an auditory vagal electrode d1#.
Comparative example 2 auditory vagus nerve electrode d2#
Comparative example 2 differs from example 1 in that in comparative example 2, butyrolactone was directly used as a functional auxiliary agent, and the remaining steps were the same as in example 1, to obtain an ear vagal electrode d2#.
Comparative example 3 is different from example 1 in that the electrode body in comparative example 3 is a copper electrode not modified with a mercaptosilane coupling agent, and the remaining steps are the same as in example 1, to obtain an auditory vagal electrode d3#.
Comparative example 4 differs from example 1 in that no conductive filler was added in comparative example 4, and the remaining steps were the same as in example 1, to obtain an ear vagus electrode d4#.
Comparative example 5 differs from example 1 in that 30 parts of a functional auxiliary agent was added to comparative example 5, and the remaining steps were the same as example 1, to obtain an ear vagus nerve electrode d5#.
Comparative example 6 ear vagus nerve electrode D6#
Comparative example 6 differs from example 1 in that methyl vinyl silicone rubber was replaced with methyl silicone rubber in comparative example 6, and the remaining procedure was the same as in example 1, to obtain an ear vagus nerve electrode d6#.
The conductive silicone rubbers obtained in examples 1 to 7 and comparative examples 1 to 6 were subjected to performance tests, respectively, according to the test methods in the national standard, for elongation at break, tensile strength, rebound value, tear strength, shore A hardness, volume resistivity, and in addition, the test methods in the national standard were used for peel strength of the vagus nerve electrodes 1 to 7# and D1 to D6# and the results are shown in Table 1.
TABLE 1
| Numbering device | Elongation at break (%) | Tensile Strength (MPa) | Rebound value (%) | Tear strength (MPa) | Shore A hardness | Volume resistivity (Ω cm) | Peel strength (kN/m) |
| Example 1 | 656 | 8.9 | 68 | 41 | 50 | 24 | 19 |
| Example 2 | 649 | 8.9 | 66 | 42 | 48 | 23.7 | 18.8 |
| Example 3 | 621 | 7.2 | 58.1 | 38 | 55 | 28 | 16.2 |
| Example 4 | 650 | 8.5 | 62.3 | 39 | 48 | 32 | 18.2 |
| Example 5 | 656 | 8.9 | 68 | 41 | 50 | 24 | 19.1 |
| Example 6 | 628 | 6.9 | 60.1 | 36 | 57 | 29.4 | 16.1 |
| Example 7 | 632 | 7.5 | 59.2 | 38 | 56 | 27 | 17.3 |
| Comparative example D1 | 613 | 5.4 | 48.4 | 32 | 59 | 26.7 | 17.5 |
| Comparative example D2 | 635 | 7.3 | 62.3 | 37.9 | 54.2 | 37.4 | 16.9 |
| Comparative example D3 | 656 | 8.9 | 68 | 41 | 50 | 24 | 10.3 |
| Comparative example D4 | 617 | 6.1 | 56.9 | 34 | 58 | 43.9 | 15.2 |
| Comparative example D5 | 643 | 7.8 | 61.4 | 33.5 | 57.3 | 23.9 | 17.2 |
| Comparative example D6 | 602 | 5.2 | 51.3 | 32.2 | 54.7 | 25.2 | 16.3 |
According to the data obtained in the test example, the silicon rubber prepared by the application has better elongation at break, tensile strength, rebound value, tearing strength, shore A hardness and volume resistivity, and has large peel strength after being combined with the surface of the metal electrode modified by the mercaptosilane coupling agent, and sufficient adhesive force is provided between the metal electrode and the metal electrode, so that the influence of oxidation on the electric stimulation strength of the surface of the metal electrode can be effectively avoided.
The above description is only an example of the present application, and the scope of the present application is not limited to the specific examples, but is defined by the claims of the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A process for an ear vagus electrode comprising an earplug electrode and an auricle electrode, comprising the steps of:
modifying the surface of the metal electrode body by using a sulfhydryl silane coupling agent to obtain a modified electrode body;
and injecting conductive silicone rubber on the surface of the modified electrode body, and forming to obtain the ear vagus nerve electrode, wherein the conductive silicone rubber comprises the following components:
30-50 parts of double bond terminated silicon rubber, 10-20 parts of functional auxiliary agents, 1-3 parts of conductive fillers, 1-3 parts of vulcanizing agents and 1-3 parts of initiators;
the structural formula of the functional auxiliary agent is as follows:，
wherein R is 1 Selected from ethenyl or propenyl, R 2 、R 3 And R is 4 Independently selected from one of C1-C3 alkyl groups containing straight or branched chains, R 5 Selected from one of C3-C6 alkyl groups containing a straight chain or branched chain.
2. The processing technology according to claim 1, wherein the functional auxiliary agent is prepared by reacting a monomer A and a monomer B, and the monomer A is at least one selected from dimethylaminopropyl acrylamide, dimethylaminopropyl butenamide and dimethylaminobutyl acrylamide;
the monomer B is at least one selected from propane sultone, butane sultone, pentane sultone and hexane sultone.
3. The process according to claim 2, wherein the molar ratio is 1: the monomer A and the monomer B of (1-1.1) are dissolved in a first solution, and the functional auxiliary agent is obtained after stirring reaction for 2-4 hours at 50-130 ℃, wherein the first solution is selected from ethanol, isopropanol or acetone.
4. The processing technology according to claim 1, wherein the conductive filler is graphene oxide modified with mercaptoethylamine.
5. The process according to claim 4, wherein graphene oxide is dispersed in a second solution containing mercaptoethylamine, aminated for 12-18 hours at 100-120 ℃, and centrifugally dried to obtain the conductive filler;
wherein the weight ratio of graphene oxide to mercaptoethylamine is 1:0.3-0.5, and the second solution is selected from methanol or ethanol.
6. The process according to claim 1, wherein the surface modification of the metal electrode body comprises the steps of: and (3) cleaning, polishing and drying the metal electrode, putting the metal electrode into a third solution containing a sulfhydryl silane coupling agent, wherein the mass concentration of the third solution is 5-15wt%, soaking for 4-12h, and drying for 2-4h at 80-100 ℃ to obtain a modified electrode body, and the third solution is selected from methanol, ethanol or isopropanol.
7. The process according to claim 6, wherein the mercaptosilane coupling agent is at least one selected from mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane, mercaptopropyl methyldimethoxysilane.
8. The process according to any one of claims 1 to 7, wherein the step of synthesizing the conductive silicone rubber comprises: and (3) carrying out primary mixing on the double-bond terminated silicon rubber and the functional auxiliary agent, and then adding the conductive filler, the vulcanizing agent and the initiator for secondary mixing to obtain the conductive silicon rubber, wherein the primary mixing temperature is 40-50 ℃, the time is 5-15min, the secondary mixing temperature is 130-150 ℃, and the time is 5-10min.
9. The process according to any one of claims 1 to 7, wherein the injection molding has a working temperature of 70 to 140 ℃.
10. The process according to any one of claims 1 to 7, wherein the double bond terminated silicone rubber is selected from methyl vinyl silicone rubber and/or methyl vinyl phenyl silicone rubber;
the vulcanizing agent is at least one selected from 2, 4-toluene diisocyanate, 1, 4-di-tert-butyl peroxyisopropyl benzene, dicumyl peroxide and tert-butyl perbenzoate;
the initiator is at least one selected from azodiisobutyronitrile, azodiisoheptonitrile, ammonium persulfate and sodium persulfate.
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