CN115651592B - Adhesive capable of being used underwater and preparation method thereof - Google Patents
Adhesive capable of being used underwater and preparation method thereof Download PDFInfo
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- CN115651592B CN115651592B CN202211406625.9A CN202211406625A CN115651592B CN 115651592 B CN115651592 B CN 115651592B CN 202211406625 A CN202211406625 A CN 202211406625A CN 115651592 B CN115651592 B CN 115651592B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 58
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 66
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 45
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 29
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 22
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 20
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 20
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 17
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000005457 ice water Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 4
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- 239000000758 substrate Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 229920002379 silicone rubber Polymers 0.000 abstract 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 12
- 229960003638 dopamine Drugs 0.000 description 6
- 239000013535 sea water Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 241000237536 Mytilus edulis Species 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 235000020638 mussel Nutrition 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 241000238586 Cirripedia Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an adhesive capable of being used underwater and a preparation method thereof, wherein the adhesive is prepared from the following raw materials in parts by weight: 10 parts of diaminopropyl-terminated polydimethylsiloxane, 4.5 parts of isophorone diisocyanate, 0.5-0.7 part of 1, 4-butanediol, 0.30 part of UD powder, 0.08-0.3 part of dopamine hydrochloride, 0.04-0.2 part of triethylamine, 0.031-0.033 part of dibutyltin dilaurate and 25-35 parts of N, N-dimethylformamide. The invention is inspired by the fact that catechol groups can be adhered to a substrate material underwater, an organic silicon rubber network containing a multi-hydrogen bond supermolecular structure and a catechol unit structure is constructed, and the organic silicon rubber network has the advantages of good underwater adhesion performance, small underwater use pollution and convenience in use.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to an adhesive capable of being used underwater and a preparation method thereof.
Background
An adhesive is a material that tightly adheres two or more, homogenous or heterogeneous objects together and has an important role in construction, aerospace, transportation and daily life. Currently mainstream adhesives also require that the bonding surfaces be kept dry during use to achieve the desired level of adhesion.
The organic silicon material is a high polymer material with excellent mechanical property, hydrophobic property and biocompatibility, and is widely used in the industries of rubber materials, food contact materials, adhesive materials and the like. Because of the intrinsic hydrophobic properties of the material, organosiloxane is selected as the main raw material of the adhesive.
Dopamine structural units (catechol units) have been shown to be widely present in marine organisms such as mussels, barnacles, sarburg worms, etc., where dopamine content in mussel byssus proteins (mfp-3, mfp-5) is up to 21% -27%, a structural unit with wet adhesion properties.
Therefore, a new molecular structure is designed by utilizing the dopamine structural unit, the problem of limiting the application scene of the adhesive is solved, and the method has important significance.
Disclosure of Invention
The invention aims to provide an adhesive capable of being used underwater and a preparation method thereof. The adhesive material contains supermolecule groups with multiple hydrogen bonds and dopamine groups, and the synergistic enhancement of the supermolecule groups and the dopamine groups ensures that the adhesive has strong shearing adhesion performance on a substrate in a wet environment.
In order to achieve the above object, the technical scheme of the present invention is as follows:
an adhesive capable of being used underwater is prepared from the following raw materials in parts by weight: 10 parts of diaminopropyl-terminated polydimethylsiloxane, 4.5 parts of isophorone diisocyanate, 0.5-0.7 part of 1, 4-butanediol, 0.30 part of UD powder, 0.08-0.3 part of dopamine hydrochloride, 0.04-0.2 part of triethylamine, 0.031-0.033 part of dibutyltin dilaurate and 25-35 parts of N, N-dimethylformamide.
Furthermore, the adhesive capable of being used underwater is prepared from the following raw materials in parts by weight: 10 parts of bisaminopropyl end-capped polydimethylsiloxane (Mw=1000 g/mol), 4.5 parts of isophorone diisocyanate, 0.65 part of 1, 4-butanediol, 0.30 part of UD powder, 0.08 part of dopamine hydrochloride, 0.08 part of triethylamine, 0.032 part of dibutyltin dilaurate and 30 parts of N, N-dimethylformamide.
Further, the UD powder is prepared from the following raw materials in parts by weight: 10 parts of UPy-NCO powder, 12 parts of 2-amino-2-methyl-1, 3-propanediol and 100 parts of anhydrous chloroform; the preparation method comprises the following steps: (1) Mixing UPy-NCO powder with 2-amino-2-methyl-1, 3-propanediol, adding anhydrous chloroform, and adding N at 60deg.C 2 Reacting for 6.5-7.5 hours under the atmosphere; (2) After suction filtration, a white solid was obtained, which was washed with warm water and filtered, and dried in an oven for 24 hours to obtain UD powder.
Wherein the UPy-NCO powder is prepared from the following raw materials in parts by weight: 10 parts of 2-amino-6-methyl-4-pyrimidinol, 60 parts of hexamethylene diisocyanate and 7 parts of pyridine. The preparation method comprises the following steps: (1) Adding 2-amino-6-methyl-4-pyrimidinol, hexamethylene diisocyanate and pyridine into a three-neck flask, uniformly mixing, and purging with nitrogen for 30-35 minutes; (2) N at 90 DEG C 2 Stirring and reacting for 9.5-10.5 h under the atmosphere; (3) After the reaction is finished, unreacted raw materials are removed by suction filtration, and the product is washed to be white by n-hexane and acetone in batches; (4) The white product was dried by vacuum for 24h to give UPy powder.
The preparation method of the underwater adhesive comprises the following steps:
(1) Adding the diaminopropyl-terminated polydimethylsiloxane into a three-neck flask, heating to 115-125 ℃, continuously heating for 2-2.1 h, vacuumizing for 30s every 10min, cooling to 80 ℃ after 2-2.1 h, and introducing N into the system 2 ；
(2) Dividing N, N-dimethylformamide into 6 parts, and respectively dissolving isophorone diisocyanate, UD powder, dibutyl tin dilaurate, 1, 4-butanediol, dopamine hydrochloride and triethylamine in the N, N-dimethylformamide and performing ultrasonic treatment to respectively obtain isophorone diisocyanate solution, UD solution, dibutyl tin dilaurate solution, 1, 4-butanediol solution, dopamine hydrochloride solution and triethylamine solution;
(3) Adding the isophorone diisocyanate solution into the three-neck flask in the step (1), and reacting for 2-3 hours; adding UD solution and dibutyl tin dilaurate solution, and continuing to react for 2-3 hours; finally, adding 1, 4-butanediol solution, continuing to react for 2-3 hours, cooling to room temperature, and then moving the reaction device into an ice water bath;
(4) Adding dopamine hydrochloride solution into the reaction device under the condition of starting magnetic stirring in an ice-water bath, stirring for 10min, adding triethylamine solution, and reacting for 24h in a dark place;
(5) After the reaction is finished, the obtained product is dissolved by chloroform and then is washed by distilled water, then the obtained chloroform phase is poured into a polytetrafluoroethylene mould, and after the solvent is volatilized, the product is dissolved in absolute ethyl alcohol according to the mass ratio of 1:1, so that the adhesive capable of being used under water is obtained.
Please verify that the content of the guaranteed and absolute ethyl alcohol is 10-20 parts
The invention adopts the technical proposal, designs and synthesizes the dopamine-terminated organosilicon polymer material according to the principle of marine organism wet adhesion, introduces dopamine groups into the adhesive to improve the underwater adhesion performance of the material, and further improves the underwater adhesion strength of the adhesive under the condition of cooperating with multi-hydrogen bond supermolecular structural units,
the invention solves the problem of the restriction of the use scene of the existing adhesive, and the synthesized adhesive has strong shearing adhesion performance to the base material because of the introduction of the multi-hydrogen bond supermolecule unit. The molecular structure of the invention is novel in design, and the prepared adhesive has the advantages of good underwater adhesion performance, small underwater use pollution and convenient use.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of an adhesive that can be used underwater.
FIG. 2 shows NMR-on-water usable adhesive 1 H spectrum (solvent CDCL) 3 ）。
FIG. 3 shows NMR-on-water usable adhesive 1 H spectrum (solvent DMSO-D) 6 ）。
FIG. 4 is FT-IR spectrum of an adhesive which can be used underwater.
FIG. 5 is a GPC spectrum of an adhesive that can be used underwater.
FIG. 6 is a schematic illustration of the use of an adhesive that may be used underwater.
FIG. 7 shows the lap shear strength (distilled water environment) of the adhesive prepared in examples 1-3 to stainless steel substrates over 72 hours.
FIG. 8 shows the lap shear strength of the adhesive prepared in example 2 against a stainless steel substrate after various times in a distilled water environment (distilled water environment).
FIG. 9 shows the lap shear strength (artificial seawater environment) of the adhesive prepared in example 2 after one week of adhesion to various substrates in an artificial seawater environment.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The parts are given below in parts by weight.
Example 1
The preparation method of the adhesive capable of being used underwater comprises the following steps:
preparation of UPy-NCO powder: (1) 10 parts of 2-amino-6-methyl-4-pyrimidinol, 60 parts of hexamethylene diisocyanate and 7 parts of pyridine are added into a 250ml three-neck flask, uniformly mixed and purged with nitrogen for 30 minutes; (2) N at 90 ℃ after the step (1) is finished 2 Stirring and reacting for 10h under the atmosphere; (3) After the reaction is finished, unreacted raw materials are removed by suction filtration, and the product is washed to be white by 300 parts of normal hexane and 300 parts of acetone in batches; (4) The white product was dried by vacuum for 24h to give UPy powder.
Preparation of UD powder: (1) 10 parts of UPy-NCO powder and 12 parts of 2-amino-2-methyl-1, 3-propanediol are mixed uniformly, 100 parts of anhydrous chloroform are added, and N is added at 60 DEG C 2 Reaction 7 h under atmosphere; (2) After suction filtration, a white solid was obtained, which was washed with warm water and filtered, and dried in an oven for 24 hours to obtain UD powder.
Preparing an adhesive:
(1) 10 parts of a diaminopropyl-terminated polydimethylsiloxane having mw=1000 g/mol were introduced into a three-necked flask and heated to 110℃for 2h, during which a vacuum was drawn for 30s every 10min, after 2h, the temperature was reduced to 80℃and N was introduced into the system 2 ；
(2) Dividing N, N-dimethylformamide (total 30 parts) into 6 parts, and then respectively dissolving 4.5 parts of isophorone diisocyanate, 0.3 part of UD powder, 0.032 part of dibutyltin dilaurate, 0.65 part of 1, 4-butanediol, 0.08 part of dopamine hydrochloride and 0.04 part of triethylamine in the N, N-dimethylformamide, and performing ultrasonic treatment to respectively obtain isophorone diisocyanate solution, UD solution, dibutyltin dilaurate solution, 1, 4-butanediol solution, dopamine hydrochloride solution and triethylamine solution;
(3) Adding the isophorone diisocyanate solution into the three-neck flask in the step (1), and reacting for 2.5 hours; adding UD solution and dibutyl tin dilaurate solution, and continuing to react for 2.5h; finally adding 1, 4-butanediol solution, continuously reacting for 2.5 hours, cooling to room temperature, and then moving the reaction device into an ice water bath;
(4) Adding dopamine hydrochloride solution into the device under the condition of starting magnetic stirring in an ice-water bath, stirring for 10min, adding triethylamine solution, and reacting for 24h in a dark place;
(5) After the reaction is finished, the obtained product is dissolved by 50 parts of chloroform and then is washed by 150 parts of distilled water, then the obtained chloroform phase is poured into a polytetrafluoroethylene mould to volatilize the solvent, and then the product is dissolved in absolute ethyl alcohol according to the mass ratio of 1:1, so that the adhesive capable of being used under water is obtained.
Example 2
The preparation method of the adhesive capable of being used underwater comprises the following steps:
in this example, 0.63 part of 1, 4-butanediol, 0.16 part of dopamine hydrochloride and 0.08 part of triethylamine were used, and the rest of the procedure was as in example 1.
Example 3
The preparation method of the adhesive capable of being used underwater comprises the following steps:
in this example, 0.59 part of 1, 4-butanediol, 0.30 part of dopamine hydrochloride and 0.16 part of triethylamine were used, and the rest of the procedure was as in example 1.
Example 4
The preparation method of the adhesive capable of being used underwater comprises the following steps:
preparation of UPy-NCO powder: same as in example 1
Preparation of UD powder: same as in example 1
Preparing an adhesive:
(1) 10 parts of a diaminopropyl-terminated polydimethylsiloxane having mw=1000 g/mol were introduced into a three-necked flask and heated to 115℃for 2 hours, during which a vacuum was drawn for 30s every 10min, after 2 hours, the temperature was reduced to 80℃and N was introduced into the system 2 ；
(2) Dividing N, N-dimethylformamide (total 25 parts) into 6 parts, and then respectively dissolving 4.5 parts of isophorone diisocyanate, 0.3 part of UD powder, 0.031 part of dibutyltin dilaurate, 0.5 part of 1, 4-butanediol, 0.2 part of dopamine hydrochloride and 0.2 part of triethylamine in the N, N-dimethylformamide, and performing ultrasonic treatment to respectively obtain isophorone diisocyanate solution, UD solution, dibutyltin dilaurate solution, 1, 4-butanediol solution, dopamine hydrochloride solution and triethylamine solution;
(3) Adding the isophorone diisocyanate solution into the three-neck flask in the step (1), and reacting for 3 hours; adding UD solution and dibutyl tin dilaurate solution, and continuing to react for 3 hours; finally adding 1, 4-butanediol solution, continuously reacting for 3 hours, cooling to room temperature, and then moving the reaction device into an ice water bath;
(4) Adding dopamine hydrochloride solution into the device under the condition of starting magnetic stirring in an ice-water bath, stirring for 10min, adding triethylamine solution, and reacting for 24h in a dark place;
(5) After the reaction is finished, the obtained product is dissolved by 45 parts of chloroform and then is washed by 140 parts of distilled water, then the obtained chloroform phase is poured into a polytetrafluoroethylene mould to volatilize the solvent, and then the product is dissolved in absolute ethyl alcohol according to the mass ratio of 1:1, so that the adhesive capable of being used under water is obtained.
Example 5
The preparation method of the adhesive capable of being used underwater comprises the following steps:
preparation of UPy-NCO powder: same as in example 1
Preparation of UD powder: same as in example 1
Preparing an adhesive:
(1) 10 parts of a diaminopropyl-terminated polydimethylsiloxane having mw=1000 g/mol were introduced into a three-necked flask and heated to 125℃for 2h, during which a vacuum was drawn for 30s every 10min, after 2h, the temperature was reduced to 80℃and N was introduced into the system 2 ；
(2) Dividing N, N-dimethylformamide (total 35 parts) into 6 parts, and then respectively dissolving 4.5 parts of isophorone diisocyanate, 0.3 part of UD powder, 0.033 part of dibutyltin dilaurate, 0.7 part of 1, 4-butanediol, 0.25 part of dopamine hydrochloride and 0.1 part of triethylamine in the N, N-dimethylformamide, and performing ultrasonic treatment to respectively obtain isophorone diisocyanate solution, UD solution, dibutyltin dilaurate solution, 1, 4-butanediol solution, dopamine hydrochloride solution and triethylamine solution;
(3) Adding the isophorone diisocyanate solution into the three-neck flask in the step (1), and reacting for 2.5 hours; adding UD solution and dibutyl tin dilaurate solution, and continuing to react for 2.5h; finally adding 1, 4-butanediol solution, continuously reacting for 2.5 hours, cooling to room temperature, and then moving the reaction device into an ice water bath;
(4) Adding dopamine hydrochloride solution into the device under the condition of starting magnetic stirring in an ice-water bath, stirring for 10min, adding triethylamine solution, and reacting for 24h in a dark place;
(5) After the reaction is finished, the obtained product is dissolved by 55 parts of chloroform and then is washed by 160 parts of distilled water, then the obtained chloroform phase is poured into a polytetrafluoroethylene mould to volatilize the solvent, and then the product is dissolved in absolute ethyl alcohol according to the mass ratio of 1:1, so that the adhesive capable of being used under water is obtained.
To demonstrate successful synthesis of the target molecular structure, NMR was used 1 H. The test means of FT-IR and GPC are verified, see FIGS. 2 to 5.
To demonstrate the excellent underwater adhesion properties of the underwater usable adhesives of the present invention, the products of examples 1-3 were tested and a schematic sample preparation is shown in FIG. 6. The adhesion strength (MPa) is represented by the magnitude of the lap shear strength (Lap shear strength), see fig. 7 to 9.
As shown in fig. 6, the adhesive of examples 1 to 3 was directly injected to the surface of the substrate to be glued using a syringe in an underwater environment, the two substrates were fixed using a dovetail clamp after being pressed for 5 seconds in contact, the sample was left in a water environment, and the sample was taken out to complete the test rapidly when it was to be tested.
FIG. 7 is a graph of the trend of change in lap shear strength of the adhesives of examples 1-3 to stainless steel substrates in distilled water environments, with increasing time, and the adhesive of example 2 exhibited the best adhesion performance after 72 hours. The adhesive of example 2 was selected as a test object to continue the test of the adhesion effect to the stainless steel substrate, and as shown in fig. 8, the adhesion strength of the adhesive of example 2 to the stainless steel substrate was increased with time, the adhesion strength reached the maximum (7 MPa) after two weeks, and the adhesion strength was maintained at 6MPa or more after one month.
FIG. 9 is a graph showing the effect of the adhesive of example 2 on various substrates in an artificial seawater water environment after one week, wherein the adhesion strength of the underwater usable adhesive of the present invention to the substrates was 1MPa or more even in the artificial seawater water environment.
In conclusion, the adhesive capable of being used underwater provided by the invention has excellent underwater adhesion performance and shows good substrate adhesion effect in a simulated seawater environment.
Claims (3)
1. The preparation method of the adhesive capable of being used underwater is characterized in that the adhesive is prepared from the following raw materials in parts by weight:
10 parts of bisaminopropyl end-capped polydimethylsiloxane;
4.5 parts of isophorone diisocyanate;
0.5-0.7 parts of 1, 4-butanediol;
0.30 parts of UD powder;
0.08-0.3 parts of dopamine hydrochloride;
0.04-0.2 parts of triethylamine;
0.031-0.033 parts of dibutyltin dilaurate;
25-35 parts of N, N-dimethylformamide;
the UD powder is prepared by a) adding 10 parts by weight of 2-amino-6-methyl-4-pyrimidinol, 60 parts by weight of hexamethylene diisocyanate and 7 parts by weight of pyridine into a three-neck flask, uniformly mixing, purging for 30-35 minutes by using nitrogen, and then N at 90 DEG C 2 Stirring and reacting for 9.5-10.5 hours under the atmosphere, filtering out unreacted raw materials after the reaction is finished, washing the product to be white by n-hexane and acetone in batches, and finally drying the product to obtain UPy-NCO powder; b) Uniformly mixing 10 parts by weight of UPy-NCO powder with 12 parts by weight of 2-amino-2-methyl-1, 3-propanediol, adding 100 parts by weight of anhydrous chloroform, and N at 60 DEG C 2 Reacting for 6.5-7.5 hours under the atmosphere, filtering to obtain white solid, washing, filtering and drying to obtain UD powder;
the preparation method comprises the following steps:
(1) Adding the diaminopropyl-terminated polydimethylsiloxane into a three-neck flask, heating to 115-125 ℃, keeping the temperature for 2-2.1 h, cooling to 80 ℃ and introducing N into the system 2 ；
(2) Dividing N, N-dimethylformamide into 6 parts, and respectively dissolving isophorone diisocyanate, UD powder, dibutyl tin dilaurate, 1, 4-butanediol, dopamine hydrochloride and triethylamine in the N, N-dimethylformamide and performing ultrasonic treatment to respectively obtain isophorone diisocyanate solution, UD solution, dibutyl tin dilaurate solution, 1, 4-butanediol solution, dopamine hydrochloride solution and triethylamine solution;
(3) Adding the isophorone diisocyanate solution into the three-neck flask in the step (1), and reacting for 2-3 hours; adding UD solution and dibutyl tin dilaurate solution, and continuing to react for 2-3 hours; finally, adding 1, 4-butanediol solution, continuing to react for 2-3 hours, cooling to room temperature, and then moving the reaction device into an ice water bath;
(4) Adding dopamine hydrochloride solution into a reaction device under the condition of starting magnetic stirring in an ice-water bath, stirring, adding triethylamine solution, and carrying out light-shielding reaction for at least 24 hours;
(5) After the reaction is finished, the obtained product is dissolved by chloroform and then is washed by distilled water, then the obtained chloroform phase is poured into a polytetrafluoroethylene mould, and after the solvent is volatilized, the product is dissolved in absolute ethyl alcohol according to the mass ratio of 1:1, so that the adhesive capable of being used under water is obtained.
2. The method for preparing the underwater usable adhesive according to claim 1, wherein the adhesive is prepared from the following raw materials in parts by weight:
10 parts of bisaminopropyl end-capped polydimethylsiloxane;
4.5 parts of isophorone diisocyanate;
0.63 part of 1, 4-butanediol;
0.30 parts of UD powder;
0.08 part of dopamine hydrochloride;
0.08 part of triethylamine;
0.032 parts of dibutyltin dilaurate;
30 parts of N, N-dimethylformamide.
3. The method for preparing an underwater usable adhesive according to claim 1, wherein in the step (1), the double aminopropyl terminated polydimethylsiloxane is added into a three-neck flask and heated to 115-125 ℃, and the temperature is kept for 2-2.1 h, and vacuum is pumped for 30s every 10 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211406625.9A CN115651592B (en) | 2022-11-10 | 2022-11-10 | Adhesive capable of being used underwater and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211406625.9A CN115651592B (en) | 2022-11-10 | 2022-11-10 | Adhesive capable of being used underwater and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN115651592A CN115651592A (en) | 2023-01-31 |
| CN115651592B true CN115651592B (en) | 2024-01-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479616A (en) * | 2014-12-17 | 2015-04-01 | 广东菲安妮皮具股份有限公司 | Adhesive with strong adhesion performance and preparation method thereof |
| CN113698571A (en) * | 2020-05-22 | 2021-11-26 | 万华化学集团股份有限公司 | Polyurethane emulsion and preparation and application thereof |
| CN114774075A (en) * | 2022-05-23 | 2022-07-22 | 福建师范大学 | Preparation method of organic silicon adhesive with strong joint strength |
| CN115011233A (en) * | 2022-05-19 | 2022-09-06 | 广州大学 | Hydrogel coating capable of being adhered underwater, and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479616A (en) * | 2014-12-17 | 2015-04-01 | 广东菲安妮皮具股份有限公司 | Adhesive with strong adhesion performance and preparation method thereof |
| CN113698571A (en) * | 2020-05-22 | 2021-11-26 | 万华化学集团股份有限公司 | Polyurethane emulsion and preparation and application thereof |
| CN115011233A (en) * | 2022-05-19 | 2022-09-06 | 广州大学 | Hydrogel coating capable of being adhered underwater, and preparation method and application thereof |
| CN114774075A (en) * | 2022-05-23 | 2022-07-22 | 福建师范大学 | Preparation method of organic silicon adhesive with strong joint strength |
Non-Patent Citations (1)
| Title |
|---|
| 贻贝仿生聚氨酯的合成与性能研究;孙培育;中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑(第07期);B016-50 * |
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