CN115717034A - 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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- CN115717034A CN115717034A CN202211491754.2A CN202211491754A CN115717034A CN 115717034 A CN115717034 A CN 115717034A CN 202211491754 A CN202211491754 A CN 202211491754A CN 115717034 A CN115717034 A CN 115717034A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 72
- 239000000853 adhesive Substances 0.000 title claims abstract description 69
- 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 19
- 239000000178 monomer Substances 0.000 claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 36
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 36
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 36
- 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 35
- 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
- 239000002994 raw material Substances 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
- 238000002156 mixing Methods 0.000 claims abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 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
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 description 29
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- 230000000052 comparative effect Effects 0.000 description 19
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- 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
- 238000005054 agglomeration Methods 0.000 description 2
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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Abstract
The application provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, 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 preparation method of a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups comprises the following steps: mixing the raw materials to obtain a polymerization precursor, and then carrying out ultraviolet radiation in-situ curing or heating reaction on the polymerization precursor. Application of a water-resistant adhesive based on hydrogen bond condensate 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 dressings, underwater robots, water-borne energy equipment, underwater repair, marine industry and the like. Various high strength adhesives have been developed for different substrates, however most conventional adhesives cannot be used directly under water or have poor water resistance. This is because a hydrated layer is formed on the surface of the underwater base material, and thus the adhesive and the interface are prevented from having a high strength function, and problems such as debonding and strength reduction are likely to occur after bonding. In addition, the adhesive is required to have certain stability when being directly used in water environment, particularly underwater, and most of the traditional adhesives have low viscosity, are easy to diffuse and dissolve and are lost when the bonding effect cannot be achieved. The traditional method is that compounds with hydrophobic groups are used to achieve the effects of draining a laminated layer and resisting water, however, the adhesives generally have difficulty in achieving high-strength adhesive performance on various substrates such as glass, metal and the like.
In recent years, inspired by in vivo adhesion, a series of underwater adhesives based on catechol (cathhol) groups were developed. Through the synergistic action of phenolic hydroxyl and benzene ring, the series of adhesives show excellent bonding performance and water resistance on different substrates. However, these adhesives require complex precursor synthesis steps, which greatly increase cost and commercialization difficulties. Meanwhile, the hardness of the adhesive is low after the adhesive swells underwater, and the adhesive is not suitable for being used as a structural adhesive. On the other hand, coacervates (cocarvates) are also widely used for underwater bonding. The condensate can be kept stable under water and good bonding strength can be achieved through electrostatic interaction between the groups. However, most agglomeration processes have different requirements for external conditions, such as pH, ionic bond strength, ionic concentration, etc., thereby limiting the application scenarios of the agglomerates.
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 purpose, the following technical scheme is adopted in the application:
a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups comprises raw materials of polyvinylpyrrolidone, acrylic monomers, benzyl methacrylate monomers and an initiator.
Preferably, the acrylic monomer comprises acrylic acid and/or methacrylic acid.
Preferably, the benzyl methacrylate monomers include 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 each independently 0.7 to 2% of the total mass of the acrylic monomer and the benzyl methacrylate monomer.
Preferably, the molar ratio of the vinylpyrrolidone monomer to the acrylic monomer in the polyvinylpyrrolidone 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:
mixing the raw materials to obtain a polymerization precursor, and then carrying out ultraviolet radiation in-situ curing or heating reaction on the polymerization precursor.
Preferably, the power density of the ultraviolet light source used for the in-situ curing of the ultraviolet radiation is 30-50mW/cm 2 The time of the ultraviolet radiation in-situ curing is 5-60min, and the temperature of the heating reaction isThe 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, and the water-resistant adhesive is used for underwater bonding.
Compared with the prior art, the beneficial effect of this application includes:
the application provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups, which takes polyvinylpyrrolidone, acrylic monomers, benzyl methacrylate monomers and an initiator as raw materials, obtains a condensation effect by utilizing the hydrogen bond action between the polyvinylpyrrolidone and the acrylic monomers, and obtains a hydrophilic-hydrophobic synergistic effect in a system by taking the benzyl methacrylate monomers as hydrophobic monomers and copolymerizing the benzyl methacrylate monomers with the polyvinylpyrrolidone and the acrylic monomers; therefore, the adhesive can simultaneously absorb and discharge the hydration layer on the 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 the curing is finished, and can meet the requirement of long-term use; the adhesive is not limited by using conditions and environment, the bonding process can be completely carried out underwater, and comprises the steps of coating a precursor and photopolymerization, so that the application scene is enriched. Has excellent water resistance, salt water resistance, acid resistance and high humidity resistance. Taking water resistance as an example, the sample can still maintain the bonding strength of 7MPa after being soaked in water for 30 days.
The application provides a water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups has ultrahigh bonding strength to different substrate surfaces, and comprises glass, ceramics, metal, polyvinyl chloride, organic glass and the like.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a schematic diagram of the in-situ condensation and photocuring of acrylic acid, polyvinylpyrrolidone, benzyl methacrylate precursor and the internal forces of the adhesive body and the possible forces of the adhesive with different substrates;
FIG. 2 is an infrared spectrum comparison of the adhesive, polyvinylpyrrolidone and acrylic acid-benzyl methacrylate copolymer obtained in example 1;
FIG. 3 is an IR spectrum of the adhesive obtained in example 1 and its 30 days after treatment in different environments;
fig. 4 shows pictures of examples 4, 5 hanging weights in water and salt water environments for a long time, respectively.
Detailed Description
The terms as used herein:
"by 8230; \ 8230; preparation" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, 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, process, method, article, or apparatus.
The conjunction "consisting of 823070, 8230composition" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of 8230' \8230"; composition "appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range 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 a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent an arbitrary unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: 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 unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A water-resistant adhesive based on hydrogen bond condensate and hydrophobic groups comprises raw materials of polyvinylpyrrolidone, acrylic monomers, benzyl methacrylate monomers and a photoinitiator.
Agglomeration can 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 requirement on external environment, simple operation, low cost, suitability for large-scale production and the like. Taking polyacrylic acid and polyvinylpyrrolidone as examples, the hydrogen bonding strength of the polyacrylic acid and the polyvinylpyrrolidone with water molecules in aqueous solution is about-22.28 kJ/mol and-24.59 kJ/mol respectively, and the hydrogen bonding strength between the polyacrylic acid and the polyvinylpyrrolidone is about-35.86 kJ/mol, so that the coagulation effect can be achieved by simply mixing the aqueous solution. Meanwhile, in-situ condensation in the underwater polymerization process can enable the polymer to achieve high bonding strength on an interface. In addition, the polymer can be copolymerized with hydrophobic monomers (such as benzyl methacrylate, benzyl acrylate and the like) in an in-situ coagulation process, so that hydrophilic and hydrophobic synergistic effects are realized in the system. In underwater bonding, on one hand, the bonding layer on the base material can be absorbed and discharged at the same time, and on the other hand, the high-strength bonding can be achieved while the water resistance is ensured. The application provides a preparation principle and a preparation method of an adhesive based on synergistic effect of hydrogen bond condensate and hydrophobic groups, provides a suitable solution for scenes in which high-strength bonding and long-term water and acid resistance use need to be completed underwater, and has the advantages of simple and cheap raw materials and easy commercialization.
In fig. 1, a) represents the in situ condensation and photocuring of Acrylic Acid (AA), polyvinylpyrrolidone (PVP), benzyl methacrylate (BzMA) precursors; b) Indicating the interfacial forces that the adhesive may form with different substrates and the non-covalent interactions that form within the adhesive.
In an alternative embodiment, the acrylic monomer comprises acrylic acid and/or methacrylic acid.
In an alternative embodiment, the benzyl methacrylate-based monomer comprises benzyl methacrylate and/or benzyl acrylate.
In an alternative embodiment, the mass ratio of the benzyl methacrylate-based monomer to the acrylic monomer is (0.7-2.5): 1.
by adjusting this mass ratio, the viscosity of the polymerized precursor can be changed so that the precursor is kept stable under water for a short time to complete photopolymerization.
Optionally, 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): 1, or any value between.
In an alternative embodiment, the initiator includes 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 mass of the photoinitiator is 0.7 to 2% 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:
mixing the raw materials to obtain a polymerization precursor, and then carrying out ultraviolet radiation in-situ curing or heating reaction on the polymerization precursor.
In an alternative embodiment, the UV radiation in-situ curing uses a UV light source with a power density of 30-50mW/cm 2 The time of the ultraviolet radiation in-situ curing is 5-60min, the temperature of the heating reaction is 65-80 ℃, and the time is 8-24h.
Optionally, the power density of the ultraviolet light source used for the in-situ curing of the ultraviolet radiation can be 30mW/cm 2 、40mW/cm 2 、50mW/cm 2 Or 30-50mW/cm 2 The time for the ultraviolet radiation in-situ curing can be any value between 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min or 5-60min, the temperature for the heating reaction can be any value between 65 ℃, 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, and the water-resistant adhesive is used for underwater bonding.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
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:
1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of the photoinitiator 2, 2-diethoxyacetophenone were mixed homogeneously, the precursor was spread homogeneously on the substrate in air at 50mW/cm 2 And (3) irradiating for 30min by using an ultraviolet light source with power density to finish curing.
FIG. 2 is an infrared spectrum comparison of the adhesive obtained in example 1, polyvinylpyrrolidone, and acrylic acid-benzyl methacrylate copolymer. The polyacrylic acid characteristic peak in the examples is represented by 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 the IR spectra of the adhesive of example 1 and its 30 days post-treatment in different environments. The results of example 1, in which the infrared characteristic peak shifts of PAA and PVP before and after treatment are both kept similar, indicate that the hydrogen bonding effect between PAA and PVP in the treated sample is 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 specific steps:
1.2g of methacrylic acid, 1.54g of polyvinylpyrrolidone, 1.8g of benzyl methacrylate and 30mg of photoinitiator 2, 2-diethoxyacetophenone were mixed well and the precursor was spread evenly on a substrate in air at 50mW/cm 2 And (3) irradiating for 30min by using an ultraviolet light source with power density to finish 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 specific steps:
1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl acrylate and 25mg of the photoinitiator 2, 2-diethoxyacetophenone were mixed homogeneously, the precursor was spread homogeneously on the substrate in air at 50mW/cm 2 Power density ultraviolet source illuminationThe curing is completed after 30min of shooting.
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:
1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of the photoinitiator 2, 2-diethoxyacetophenone were mixed in a uniform manner, and the precursor was applied uniformly to the substrate in air at 50mW/cm 2 And (3) irradiating for 30min by using an ultraviolet light source with power density to finish curing. The resulting sample was soaked 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 specific steps:
1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of the photoinitiator 2, 2-diethoxyacetophenone were mixed homogeneously, the precursor was spread homogeneously on the substrate in air at 50mW/cm 2 And (3) irradiating for 30min by using an ultraviolet light source with power density to finish curing. The obtained sample was soaked in a 1mol/L aqueous solution of sodium chloride and kept for 30 days.
FIG. 4 is a photograph of example 4 and example 5, respectively, hanging a 5kg weight in water and 1M saline for two months. Show good water-resistant and salt water-resistant bonding performance (the bonding area is 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 specific steps:
1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of the photoinitiator 2, 2-diethoxyacetophenone were mixed in a uniform manner, and the precursor was applied uniformly to the substrate in air at 50mW/cm 2 And (3) irradiating for 30min by using an ultraviolet light source with power density to finish curing. The obtained sample was soaked in an aqueous hydrogen chloride solution of 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 specific steps:
1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 1.5g of benzyl methacrylate and 25mg of the photoinitiator 2, 2-diethoxyacetophenone were mixed homogeneously, the precursor was spread homogeneously on the substrate in air at 50mW/cm 2 And (3) irradiating for 30min by using an ultraviolet light source with power density to finish curing. The resulting sample was placed in a humidity cabinet at 90% relative humidity for 30 days.
The viscosity of the precursor can be changed by adjusting the content of benzyl methacrylate in the adhesive component, 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 base material underwater and can complete polymerization, 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 specific steps:
1g of acrylic acid, 1.54g of polyvinylpyrrolidone, 0.7g of benzyl methacrylate and 17mg of the photoinitiator 2, 2-diethoxyacetophenone were mixed uniformly and the precursor was applied directly and uniformly to an underwater substrate at 50mW/cm 2 And (3) irradiating the mixture for 30min by using an ultraviolet light source with power density to finish curing in a water environment.
Comparative example 1
The lap shear strength was measured using commercial 3M quick-drying glue (model CA 40H) to bond the glass substrates.
Comparative example 2
2g of acrylic acid, 1.54g of polyvinylpyrrolidone and 25mg of photoinitiator 2, 2-diethoxyacetophenone were mixed uniformly, and the precursor was coated on a substrate uniformly in air at 50mW/cm 2 And (3) irradiating for 30min by using an ultraviolet light source with power density to finish curing.
The adhesion property data of the initial state thereof was measured, and then the obtained samples were respectively soaked in water for 7 days to measure the adhesion property thereof.
Comparative example 3
Mixing 10wt% polyacrylic acid water solution and 15wt% polyvinylpyrrolidone water solution with the same mass, shaking, centrifuging at 7000rpm for 10min to obtain white aggregate, uniformly coating on the substrate in air, drying in air for 3 days until the aggregate becomes transparent, and testing its bonding performance.
Comparative example 4
1g of acrylic acid, 1.5g of benzyl methacrylate and 25mg of the photoinitiator 2, 2-diethoxyacetophenone were mixed in a uniform manner, and the precursor was applied uniformly to the substrate in air at 50mW/cm 2 And (3) irradiating for 30min by using an ultraviolet light source with power density to finish curing. The obtained sample was soaked in water for 30 days.
The substrates used in the examples and comparative tests were glass, except as otherwise indicated.
Table 1 compares the adhesive properties of the different formulations of examples 1-3 and comparative example 1.
TABLE 1 comparison of lap shear test performance of glass substrates (without water soak) for examples 1-3 and comparative example 1
| Sample(s) | 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 examples 4-7 and comparative examples 2-3 glass substrates
| Sample (I) | Conditions of treatment | Shear strength (MPa) |
| Example 4 | Water (30 days) | 7.00±0.12 |
| Example 5 | 1mol/L aqueous sodium chloride solution (30 days) | 8.04±0.85 |
| Example 6 | pH =1 aqueous hydrogen chloride solution (30 days) | 7.31±0.45 |
| Example 7 | 90% relative humidity (30 days) | 9.18±0.46 |
| Example 8 | Direct underwater precursor application and underwater cure | 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 non-soaked water of comparative example 2 and comparative example 4.
TABLE 3 comparative example 2 and comparative example 4 comparison of lap shear properties of glass substrates
| Sample (I) | Conditions of treatment | Shear strength (MPa) |
| Comparative example 2 | Non-soaking water | 11.75±0.40 |
| Comparative example 4 | Not soaking in water | 8.53±1.00 |
As can be seen from a comparison of tables 3 and 2, in the absence of polyvinylpyrrolidone or benzyl methacrylate, although the initial shear strength was high, the shear strength after soaking in water was greatly reduced, and thus it was not suitable for underwater use.
More importantly, the coagulation brought by the super-strong hydrogen bond action between polyacrylic acid and polyvinylpyrrolidone can cooperate with hydrophobic groups, and the protection of internal hydrogen bonds ensures that the polyacrylic acid and polyvinylpyrrolidone can keep low swelling in water for a long time, thereby ensuring long-time water-resistant use. Whereas in comparative examples 2 and 3, the water resistance was significantly reduced when hydrophobic groups or hydrogen bonds in the components were condensed.
In addition, the adhesive can form a non-covalent action with the surfaces of different substrates, so that the adhesive shows good bonding strength on the different substrates.
Table 4 compares the adhesion performance of example 1 and example 8 on different substrates.
Table 4 lap shear performance of example 1 and example 8 on different substrates
In the above-described embodiments, the polymerization method is ultraviolet polymerization, and ultraviolet rays are required to penetrate through the base material to initiate polymerization. For the bonding of opaque substrates, the above method is limited. The formulations of the present application may address this problem by creating adhesive strength through thermally initiated polymerization.
Specifically, the method comprises the following steps: the other components of the adhesive are kept unchanged, a thermal initiator is used instead of a 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 different.
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 mixed uniformly, placed in a round-bottomed bottle and deoxygenated by introducing nitrogen for 20min, gradually heated in the bottle to 60 ℃ for 30min, then the precursor is uniformly coated on a substrate and heated to 70 ℃ for 10h.
In the above examples, after the curing is completed on the glass substrate, the bonding strength measured by the lap shear test is 8.03 ± 1.14MPa, which is close to the photo-curing bonding effect.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions 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 solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, 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 (10)
1. The water-resistant adhesive is characterized in that raw materials comprise polyvinylpyrrolidone, acrylic monomers, benzyl methacrylate monomers and an initiator.
2. A water resistant adhesive based on hydrogen bond condensates and hydrophobic groups as claimed in claim 1 characterised in that said acrylic monomer includes acrylic acid and/or methacrylic acid.
3. The water resistant adhesive based on hydrogen bond agglomerates and hydrophobic groups of claim 1 wherein said benzyl methacrylate monomers comprise benzyl methacrylate and/or benzyl acrylate.
4. The water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups as claimed in claim 1, characterized in that the mass ratio of the benzyl methacrylate monomer to the acrylic monomer is (0.7-2.5): 1.
5. the water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups of claim 1, characterized in that 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.
6. A water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups as claimed in claim 5, characterized in that the mass of said photoinitiator or said thermal initiator is each independently 0.7-2% of the total mass of said acrylic monomer and said benzyl methacrylate monomer.
7. The water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups of any one of claims 1 to 6, characterized in that the molar ratio of vinylpyrrolidone monomer to acrylic monomer in the polyvinylpyrrolidone is 1:1.
8. a method of preparing a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups as claimed in any one of claims 1 to 7, which comprises:
mixing the raw materials to obtain a polymerization precursor, and then carrying out ultraviolet radiation in-situ curing or heating reaction on the polymerization precursor.
9. The method of claim 8, wherein the UV radiation cures in situ using a UV light source having workThe specific density is 30-50mW/cm 2 The time of the ultraviolet radiation in-situ curing is 5-60min, the temperature of the heating reaction is 65-80 ℃, and the time is 8-24h.
10. Use of a water-resistant adhesive based on hydrogen bond condensates and hydrophobic groups as defined in any one of claims 1 to 7 for underwater bonding.
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