CN115717034B - Water-resistant adhesive based on hydrogen bond condensate and hydrophobic group, and preparation method and application thereof - Google Patents
Water-resistant adhesive based on hydrogen bond condensate and hydrophobic group, and preparation method and application thereof Download PDFInfo
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- CN115717034B CN115717034B CN202211491754.2A CN202211491754A CN115717034B CN 115717034 B CN115717034 B CN 115717034B CN 202211491754 A CN202211491754 A CN 202211491754A CN 115717034 B CN115717034 B CN 115717034B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 74
- 239000000853 adhesive Substances 0.000 title claims abstract description 65
- 239000001257 hydrogen Substances 0.000 title claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 45
- 125000001165 hydrophobic group Chemical group 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 34
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 34
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 230000005855 radiation Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 20
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims description 13
- 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 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 30
- 238000001723 curing Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 230000001678 irradiating effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229920002125 Sokalan® Polymers 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 7
- 238000005345 coagulation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012267 brine Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- TUCIXUDAQRPDCG-UHFFFAOYSA-N benzene-1,2-diol Chemical group OC1=CC=CC=C1O.OC1=CC=CC=C1O TUCIXUDAQRPDCG-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 230000009881 electrostatic interaction Effects 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
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- 238000001727 in vivo Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 238000012722 thermally initiated polymerization Methods 0.000 description 1
Abstract
The application provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and a preparation method and application thereof, and relates to the field of materials. The raw materials of the water-resistant adhesive based on the hydrogen bond condensate and the hydrophobic group comprise polyvinylpyrrolidone, acrylic monomers, benzyl methacrylate monomers and an initiator. A method for preparing a water resistant adhesive based on hydrogen bond agglomerates and hydrophobic groups comprising: the raw materials are mixed to obtain a polymerization precursor, and then the polymerization precursor is subjected to ultraviolet radiation in-situ curing or heating reaction. The use of a water-resistant adhesive based on hydrogen bond aggregates and hydrophobic groups for underwater bonding. The water-resistant adhesive based on the hydrogen bond condensate and the hydrophobic group has excellent water resistance, salt water resistance, acid resistance and high humidity resistance.
Description
Technical Field
The application relates to the field of materials, in particular to a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and a preparation method and application thereof.
Background
The underwater adhesive plays an important role in daily life and industrial scenes, including wound dressing, underwater robots, water energy equipment, underwater repair, marine industry and the like. A wide variety of high strength adhesives have been developed for different substrates, however most conventional adhesives cannot be used directly under water or have poor water resistance. The problems that the adhesive and the interface form high strength, so that debonding is easy to occur after bonding, strength is weakened and the like are solved. In addition, the adhesive is required to have certain stability when directly used in water environment, especially underwater, and most of the traditional adhesives have low viscosity, are easy to diffuse and dissolve, and can not achieve the bonding effect and run off. Conventional methods generally use compounds with hydrophobic groups to achieve the effect of draining the hydration layer and water resistance, however these adhesives generally have difficulty achieving high strength adhesive properties on a variety of substrates such as glass, metal, and the like.
In recent years, a series of underwater adhesives based on catechol (catechol) groups have been developed, inspired by in vivo adhesion. Through the synergistic effect of phenolic hydroxyl and benzene ring, the series of adhesives show excellent adhesive property and water resistance on different base materials. However, these adhesives require complex precursor synthesis steps, which greatly increase the cost and difficulty of commercialization. Meanwhile, the adhesive has lower hardness after being swelled under water, and is not suitable for being used as a structural adhesive. On the other hand, aggregates (coacervate) are also widely used for underwater bonding. The agglomerates can also remain stable under water and achieve good bond strength through electrostatic interactions between the groups. However, most of the coagulation processes have different requirements for external conditions, such as pH, ionic bond strength, ion concentration, etc., thereby limiting the application scenarios of the aggregates.
Disclosure of Invention
The application aims to provide a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and a preparation method and application thereof, so as to solve the problems.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups is prepared from polyvinylpyrrolidone, acrylic monomer, benzyl methacrylate monomer and initiator.
Preferably, the acrylic monomer comprises acrylic acid and/or methacrylic acid.
Preferably, the benzyl methacrylate monomer comprises benzyl methacrylate and/or benzyl acrylate.
Preferably, the mass ratio of the benzyl methacrylate monomer to the acrylic monomer is (0.7-2.5): 1.
preferably, the initiator comprises a photoinitiator and a thermal initiator;
the photoinitiator comprises 2, 2-diethoxyacetophenone and/or 1-hydroxycyclohexyl phenyl ketone;
the thermal initiator comprises azobisisobutyronitrile and/or benzoyl peroxide.
Preferably, the mass of the photoinitiator or the thermal initiator is 0.7 to 2% of the total mass of the acrylic monomer and the benzyl methacrylate monomer, respectively.
Preferably, the molar ratio of the vinylpyrrolidone monomer in the polyvinylpyrrolidone to the acrylic monomer is 1:1.
the application also provides a preparation method of the water-resistant adhesive based on the hydrogen bond condensate and the hydrophobic group, which comprises the following steps:
the raw materials are mixed to obtain a polymerization precursor, and then the polymerization precursor is subjected to ultraviolet radiation in-situ curing or heating reaction.
Preferably, the ultraviolet radiation in-situ curing uses an ultraviolet light source with a power density of 30-50mW/cm 2 The ultraviolet radiation in-situ curing time is 5-60min, the heating reaction temperature is 65-80 ℃ and the time is 8-24h.
The application also provides an application of the water-resistant adhesive based on the hydrogen bond condensate and the hydrophobic group, which is used for underwater bonding.
Compared with the prior art, the beneficial effects of this application include:
the water-resistant adhesive based on the hydrogen bond condensate and the hydrophobic group provided by the application takes polyvinylpyrrolidone, acrylic acid monomer, benzyl methacrylate monomer and initiator as raw materials, obtains the condensation effect by utilizing the hydrogen bond action between the polyvinylpyrrolidone and the acrylic acid monomer, and obtains the hydrophilic-hydrophobic synergistic effect in a system by copolymerizing the benzyl methacrylate monomer serving as the hydrophobic monomer with the polyvinylpyrrolidone and the acrylic acid monomer; therefore, the adhesive can simultaneously absorb and discharge a hydration layer on a base material in underwater bonding, and can ensure water resistance while achieving high-strength bonding.
The water-resistant adhesive has a long-time water-resistant effect after curing is finished, and can meet the long-term use requirement; and the bonding process can be completely carried out under water without being limited by using conditions and environments, and comprises smearing precursors and photopolymerization, thereby enriching application scenes. Has excellent water resistance, brine resistance, acid resistance and high humidity resistance. Taking water resistance as an example, the sample can still keep the adhesive strength of 7MPa after soaking in water for 30 days.
The water-resistant adhesive based on the hydrogen bond condensate and the hydrophobic group has ultrahigh bonding strength on the surfaces of different substrates, including glass, ceramic, metal, polyvinyl chloride, organic glass and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a schematic illustration of the in situ coagulation and photocuring of acrylic, polyvinylpyrrolidone, benzyl methacrylate precursors and the internal forces of the adhesive body and the possible formation of adhesive with different substrates;
FIG. 2 is a comparison of the infrared spectra of the adhesive, polyvinylpyrrolidone, and benzyl acrylate-methacrylate copolymer obtained in example 1;
FIG. 3 is an infrared spectrum of the adhesive obtained in example 1 after 30 days of treatment in different environments;
figure 4 shows pictures of examples 4, 5 hanging weights in water and brine environments, respectively, over time.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
A water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups is prepared from polyvinylpyrrolidone, acrylic monomer, benzyl methacrylate monomer and photoinitiator.
Agglomeration may also occur between stronger hydrogen bond donors (e.g., acrylic acid, methacrylic acid, etc.) and stronger hydrogen bond acceptors (e.g., polyvinylpyrrolidone, etc.). Compared with the electrostatic coagulation process, the coagulation based on hydrogen bonding has remarkable advantages, such as low requirements on external environment, simple operation, low cost, suitability for mass production and the like. Taking polyacrylic acid and polyvinylpyrrolidone as examples, the strength of hydrogen bonding with water molecules in the aqueous solution is about-22.28 kJ/mol and-24.59 kJ/mol respectively, and the hydrogen bonding between the polyacrylic acid and polyvinylpyrrolidone is about-35.86 kJ/mol, so that the coagulation effect can be achieved by simply mixing the aqueous solutions. Meanwhile, in-situ condensation in the underwater polymerization process can lead the polymer to reach high bonding strength on the interface. In addition, it is possible to copolymerize with hydrophobic monomers (e.g., benzyl methacrylate, benzyl acrylate, etc.) during in situ coagulation to provide an in-system hydrophilic-hydrophobic synergy. On the one hand, the hydration layer on the base material can be absorbed and discharged simultaneously in underwater bonding, and on the other hand, the water resistance can be ensured while high-strength bonding is achieved. The application provides a preparation principle and a preparation method of an adhesive based on the synergistic effect of hydrogen bond condensate and hydrophobic groups, which provide a suitable solution for the scene of high-strength bonding and long-term water and acid resistant use under water, and the raw materials are simple, low in cost and easy to commercialize.
In fig. 1, a) represents in situ coagulation and photocuring of Acrylic Acid (AA), polyvinylpyrrolidone (PVP), benzyl methacrylate (BzMA) precursors; b) Indicating the possible interfacial forces of the adhesive with the different substrates and the non-covalent interactions formed within the adhesive.
In an alternative embodiment, the acrylic monomer comprises acrylic acid and/or methacrylic acid.
In an alternative embodiment, the benzyl methacrylate monomers include benzyl methacrylate and/or benzyl acrylate.
In an alternative embodiment, the mass ratio of the benzyl methacrylate monomer to the acrylic monomer is (0.7-2.5): 1.
the viscosity of the polymerization precursor can be changed by adjusting this mass ratio so that the precursor remains stable under water for a short period of time to complete photopolymerization.
Alternatively, the mass ratio of the benzyl methacrylate monomer to the acrylic monomer may be 0.7: 1. 1:1. 1.5: 1. 2: 1. 2.5:1 or (0.7-2.5): any value between 1.
In an alternative embodiment, the initiator comprises a photoinitiator and a thermal initiator;
the photoinitiator comprises 2, 2-diethoxyacetophenone and/or 1-hydroxycyclohexyl phenyl ketone;
the thermal initiator comprises azobisisobutyronitrile and/or benzoyl peroxide.
In an alternative embodiment, the photoinitiator is present in an amount of 0.7 to 2% by mass of the total mass of the acrylic monomer and the benzyl methacrylate monomer.
In an alternative embodiment, the polyvinylpyrrolidone has a molar ratio of vinylpyrrolidone monomer to acrylic monomer of 1:1.
the application also provides a preparation method of the water-resistant adhesive based on the hydrogen bond condensate and the hydrophobic group, which comprises the following steps:
the raw materials are mixed to obtain a polymerization precursor, and then the polymerization precursor is subjected to ultraviolet radiation in-situ curing or heating reaction.
In an alternative embodiment, the ultraviolet radiation in situ curing uses an ultraviolet light source having a power density of 30 to 50mW/cm 2 The ultraviolet radiation in-situ curing time is 5-60min, the heating reaction temperature is 65-80 ℃ and the time is 8-24h.
Alternatively, the ultraviolet radiation in situ curing may use an ultraviolet light source having a power density of 30mW/cm 2 、40mW/cm 2 、50mW/cm 2 Or 30-50mW/cm 2 The ultraviolet radiation in-situ curing time can be any value between 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min or 5-60min, the heating reaction temperature can be any value between 65 ℃ and 70 ℃, 75 ℃, 80 ℃ or 65-80 ℃ and the time can be any value between 8h, 12h, 16h, 20h, 24h or 8-24h.
The application also provides an application of the water-resistant adhesive based on the hydrogen bond condensate and the hydrophobic group, which is used for underwater bonding.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and the preparation method comprises the following steps:
uniformly mixing 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2, 2-diethoxyacetophenone, uniformly coating the precursor on a substrate in air at 50mW/cm 2 And irradiating the ultraviolet light source with power density for 30min to finish the curing.
FIG. 2 shows the adhesive and polyethylene obtained in example 1And (3) comparing infrared patterns of pyrrolidone and acrylic acid-benzyl methacrylate copolymer. The polyacrylic acid characteristic peak in the examples was found to be 1703cm -1 Move to 1720cm -1 The characteristic peak of polyvinylpyrrolidone is 1645cm -1 Move to 1630cm -1 Indicating strong hydrogen bonding between the two.
FIG. 3 is a comparison of infrared spectra of the adhesive obtained in example 1 after 30 days of treatment in different environments. The infrared characteristic peak shifts of PAA and PVP before and after treatment of example 1 both remained similar, indicating that the hydrogen bonding between PAA and PVP in the treated samples was not affected.
Example 2
The embodiment provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and the preparation method comprises the following steps:
uniformly mixing 1.2g of methacrylic acid, 1.54g of polyvinylpyrrolidone, 1.8g of benzyl methacrylate and 30mg of photoinitiator 2, 2-diethoxyacetophenone, uniformly coating the precursor on a substrate in air at 50mW/cm 2 And irradiating the ultraviolet light source with power density for 30min to finish the curing.
Example 3
The embodiment provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and the preparation method comprises the following steps:
1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl acrylate and 25mg of the photoinitiator 2, 2-diethoxyacetophenone are mixed homogeneously, the precursor is applied homogeneously to the substrate in air at 50mW/cm 2 And irradiating the ultraviolet light source with power density for 30min to finish the curing.
Example 4
The embodiment provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and the preparation method comprises the following steps:
uniformly mixing 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2, 2-diethoxyacetophenone, uniformly coating the precursor on a substrate in air at 50mW/cm 2 And irradiating the ultraviolet light source with power density for 30min to finish the curing. Will beThe resulting sample was immersed in water for 30 days.
Example 5
The embodiment provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and the preparation method comprises the following steps:
uniformly mixing 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2, 2-diethoxyacetophenone, uniformly coating the precursor on a substrate in air at 50mW/cm 2 And irradiating the ultraviolet light source with power density for 30min to finish the curing. The resulting sample was immersed in a 1mol/L aqueous sodium chloride solution for 30 days.
Fig. 4 is a photograph of example 4 and example 5, respectively, in water and 1M brine, with a 5kg weight suspended for two months. Indicating good water and salt water resistance (adhesive area of about 4 cm) 2 )。
Example 6
The embodiment provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and the preparation method comprises the following steps:
uniformly mixing 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2, 2-diethoxyacetophenone, uniformly coating the precursor on a substrate in air at 50mW/cm 2 And irradiating the ultraviolet light source with power density for 30min to finish the curing. The resulting sample was immersed in an aqueous hydrogen chloride solution having ph=1 for 30 days.
Example 7
The embodiment provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and the preparation method comprises the following steps:
uniformly mixing 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of photoinitiator 2, 2-diethoxyacetophenone, uniformly coating the precursor on a substrate in air at 50mW/cm 2 And irradiating the ultraviolet light source with power density for 30min to finish the curing. The resulting samples were kept in a humidity cabinet with 90% relative humidity for 30 days.
By adjusting the content of benzyl methacrylate in the adhesive component, the viscosity of the precursor can be changed, so that the precursor can be kept stable underwater for a short time, and the adhesive can be directly coated on the surface of a substrate underwater and polymerized, specifically:
example 8
The embodiment provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, and the preparation method comprises the following steps:
uniformly mixing 1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 0.7g of benzyl methacrylate and 17mg of photoinitiator 2, 2-diethoxyacetophenone, directly uniformly coating the precursor on an underwater substrate, and uniformly coating the precursor on the underwater substrate at the speed of 50mW/cm 2 And (3) irradiating the ultraviolet light source with the power density for 30min to finish curing in the water environment.
Comparative example 1
The glass substrates were bonded using a commercial 3M quick-setting adhesive (model CA 40H) and their lap shear strength was measured.
Comparative example 2
Uniformly mixing 2g of acrylic acid, 1.54g of polyvinylpyrrolidone and 25mg of photoinitiator 2, 2-diethoxyacetophenone, uniformly coating a precursor on a substrate in air at 50mW/cm 2 And irradiating the ultraviolet light source with power density for 30min to finish the curing.
The initial state of the adhesive property data was tested, and then the obtained samples were immersed in water for 7 days, respectively, to test the adhesive property.
Comparative example 3
Uniformly mixing 10wt% polyacrylic acid aqueous solution and 15wt% polyvinylpyrrolidone aqueous solution with the same mass, shaking, centrifuging at 7000rpm for 10min, obtaining white condensate, uniformly coating on a substrate in air, drying in air for 3 days until the condensate becomes transparent, and testing the adhesive property.
Comparative example 4
1g of acrylic acid, 1.5g of benzyl methacrylate and 25mg of the photoinitiator 2, 2-diethoxyacetophenone were mixed homogeneously, the precursor was applied homogeneously to the substrate in air at 50mW/cm 2 And irradiating the ultraviolet light source with power density for 30min to finish the curing. The resulting sample was immersed in water for 30 days.
The substrates used in the examples and comparative examples were glass, except as specified.
Table 1 compares the adhesive properties of the different formulations of examples 1-3 and comparative example 1.
Table 1 glass substrates of examples 1-3 and comparative example 1 overlap shear test performance comparison (non-foam water)
| Sample of | Shear strength (MPa) |
| Example 1 | 8.73±0.37 |
| Example 2 | 8.60±2.07 |
| Example 3 | 9.49±0.39 |
| Comparative example 1 | 2.00±0.40 |
Table 2 compares the adhesive properties of the different formulations of examples 4-7 and comparative examples 2-3.
Table 2 comparison of lap shear properties of glass substrates of examples 4-7 and comparative examples 2-3
| Sample of | Treatment conditions | Shear strength (MPa) |
| Example 4 | Water (30 days) | 7.00±0.12 |
| Example 5 | 1mol/L sodium chloride aqueous solution (30 days) | 8.04±0.85 |
| Example 6 | ph=1 aqueous hydrogen chloride (30 days) | 7.31±0.45 |
| Example 7 | 90% relative humidity (30 days) | 9.18±0.46 |
| Example 8 | Direct underwater application of precursor and underwater curing | 9.29±1.03 |
| Comparative example 2 | Water (7 days) | 1.55±0.26 |
| Comparative example 4 | Water (30 days) | 3.01±0.20 |
Table 3 compares the adhesive properties of the unfoamed water of comparative example 2 and comparative example 4.
Table 3 comparative example 2 and comparative example 4 glass substrate lap shear performance comparison
| Sample of | Treatment conditions | Shear strength (MPa) |
| Comparative example 2 | Unfoamed water | 11.75±0.40 |
| Comparative example 4 | Unfoamed water | 8.53±1.00 |
As is clear from a comparison of Table 3 and Table 2, when polyvinylpyrrolidone or benzyl methacrylate is absent, the initial shear strength is high, but the shear strength after soaking in water is greatly reduced, and thus the resulting composition is not suitable for use under water.
More importantly, the condensation caused by the super strong hydrogen bond action between polyacrylic acid and polyvinylpyrrolidone can be cooperated with hydrophobic groups, and the protection of internal hydrogen bonds ensures that the polyacrylic acid and polyvinylpyrrolidone keep low swelling in water for a long time, thus ensuring long-time water-resistant use. Whereas in comparative examples 2, 3, when the hydrophobic group is absent in the component or the hydrogen bond is condensed, the water resistance is remarkably lowered.
In addition, the adhesive can form non-covalent effect with the surfaces of different base materials, so that the adhesive has good bonding strength on different base materials.
Table 4 compares the adhesive properties of example 1 and example 8 on different substrates.
Table 4 lap shear properties of example 1 and example 8 at different substrates
In the above-described embodiments, the polymerization method is ultraviolet polymerization, and ultraviolet light is required to pass through the substrate to initiate polymerization. For the adhesion of opaque substrates, the above method is limited. The formulations of the present application solve this problem by thermally initiated polymerization to produce bond strength.
Specific: the other components of the adhesive are kept unchanged, a thermal initiator is used instead of the photoinitiator, and the precursor is polymerized by heating to a certain temperature. The thermal initiator can be azodiisobutyronitrile, benzoyl peroxide and the like, and the thermal curing time is unequal.
The specific scheme is as follows:
example 9
1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 50mg of azobisisobutyronitrile are uniformly mixed, placed in a round bottom bottle, deoxygenated by introducing nitrogen for 20min, gradually heated to 60 ℃ in the bottle for 30min, then uniformly coated on a substrate, and heated to 70 ℃ for 10h.
After the glass substrate is cured, the bonding strength of the glass substrate is 8.03+/-1.14 MPa, which is close to the photo-curing bonding effect, through lap shear experiments.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (8)
1. The water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups is characterized in that the raw materials of the adhesive comprise polyvinylpyrrolidone, acrylic acid monomers, benzyl methacrylate monomers and an initiator;
the acrylic monomer comprises acrylic acid and/or methacrylic acid;
the benzyl methacrylate monomer comprises benzyl methacrylate and/or benzyl acrylate.
2. The water-resistant adhesive based on hydrogen bond condensate and hydrophobic group as claimed in claim 1, wherein the mass ratio of the benzyl methacrylate monomer and the acrylic monomer is (0.7-2.5): 1.
3. the water resistant adhesive based on hydrogen bond aggregates and hydrophobic groups according to claim 1, wherein said initiator comprises a photoinitiator and a thermal initiator;
the photoinitiator comprises 2, 2-diethoxyacetophenone and/or 1-hydroxycyclohexyl phenyl ketone;
the thermal initiator comprises azobisisobutyronitrile and/or benzoyl peroxide.
4. A water-resistant adhesive based on hydrogen bond aggregates and hydrophobic groups according to claim 3, characterized in that the mass of the photoinitiator or the thermal initiator is each independently 0.7-2% of the total mass of the acrylic monomer and the benzyl methacrylate monomer.
5. The water-resistant adhesive based on hydrogen bond aggregates and hydrophobic groups according to any of claims 1 to 4, wherein the molar ratio of vinylpyrrolidone monomer to acrylic monomer in the polyvinylpyrrolidone is 1:1.
6. a method of preparing a water resistant adhesive based on hydrogen bond aggregates and hydrophobic groups as claimed in any one of claims 1 to 5, comprising:
the raw materials are mixed to obtain a polymerization precursor, and then the polymerization precursor is subjected to ultraviolet radiation in-situ curing or heating reaction.
7. The method for preparing a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups according to claim 6, wherein the ultraviolet radiation in-situ curing uses an ultraviolet light source with a power density of 30-50mW/cm 2 The ultraviolet radiation in-situ curing time is 5-60min, the heating reaction temperature is 65-80 ℃ and the time is 8-24h.
8. Use of a water-resistant adhesive based on hydrogen bond aggregates and hydrophobic groups according to any of claims 1-5, for underwater bonding.
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