CN114249994A - Coating material and coating layer - Google Patents
Coating material and coating layer Download PDFInfo
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- CN114249994A CN114249994A CN202011002684.0A CN202011002684A CN114249994A CN 114249994 A CN114249994 A CN 114249994A CN 202011002684 A CN202011002684 A CN 202011002684A CN 114249994 A CN114249994 A CN 114249994A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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Abstract
The invention provides a coating and a coating, wherein the coating comprises, by mass, 10-80 parts of a curing resin, 20-85 parts of a polymerization precursor, 1-5 parts of an initiator, 0.01-3 parts of a gem-dihalogenated cyclopropane derivative and 0.01-3 parts of a dicarboxylic acid salt, wherein the gem-dihalogenated cyclopropane derivative has a general formula:
when the coating is stressed, the gem-dihalogen cyclopropane derivative in the coating and the dicarboxylic acid salt are subjected to chemical crosslinking reaction, so that the elastic modulus of the coating after stress is larger than that of the coating before stress, the crosslinking degree of the coating is improved, and the strength and the service life of the coating in a stressed area are improved.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a coating and a coating.
Background
With the continuous improvement of the protection requirements of products, more and more protection means are applied to the protection of the products. The coating is used as a protective object coated on the surface of a protected or decorated object, can form a firmly attached continuous film on the surface of the protected object, and plays a good role in protecting the protected object.
However, when a coating formed by the conventional coating is stressed, the stress-concentrated part may be damaged by cracking, etc., so that the strength of the coating is deteriorated, and the normal use of the protected object is directly affected.
Disclosure of Invention
The invention provides a coating and a coating, which aim to solve the problem that the strength of the traditional coating is poor after being stressed.
In order to solve the problems, the invention adopts the following technical scheme:
in a first aspect, the invention provides a coating, which comprises the following components in parts by weight:
10-80 parts of curing resin, 20-85 parts of polymerization precursor, 1-5 parts of initiator, 0.01-3 parts of gem-dihalogenocyclopropane derivative and 0.01-3 parts of dicarboxylic acid salt, wherein the gem-dihalogenocyclopropane derivative has a general formula:
wherein, R1 and R2 are at least one of fluorine, chlorine, bromine and iodine, and R3 and R4 are ester groups containing unsaturated double bonds.
Optionally, the coating comprises, in parts by mass:
20-50 parts of curing resin, 35-75 parts of polymerization precursor, 1.5-3.5 parts of initiator, 0.5-2 parts of gem-dihalogenated cyclopropane derivative and 0.5-2 parts of dicarboxylic acid salt.
Optionally, each of R3 and R4 is independently at least one of a methacrylate group, an acrylate group, or a pentenoate group.
Optionally, the coating further comprises 0.01-2 parts by weight of a spiropyran derivative, wherein the spiropyran derivative has a general formula:
wherein R5 and R6 are ester groups containing an unsaturated double bond.
Optionally, the coating further comprises 0.5-1.5 parts of a spiropyran derivative by mass.
Optionally, the cured resin comprises at least one of a polyacrylate resin, an epoxy acrylate resin, a urethane acrylate resin, and an organosiloxane resin.
Optionally, the polymeric precursor includes at least one of a monofunctional acrylate, a multifunctional acrylate, and a polydimethylsiloxane prepolymer.
Optionally, the initiator comprises a photoinitiator and/or a thermal initiator, the photoinitiator comprising at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide;
the thermal initiator comprises at least one of azodiisobutyronitrile, potassium persulfate, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate and a platinum-containing initiator.
Optionally, the dicarboxylate comprises at least one of a sodium or potassium dicarboxylate salt.
Optionally, the coating further comprises 0.1-5 parts by mass of an auxiliary agent, and the auxiliary agent comprises at least one of a leveling agent, a defoaming agent and a polymerization inhibitor.
In a second aspect, the present invention provides a coating for surface protection of a product, comprising the coating of the first aspect.
The technical scheme adopted by the invention can achieve the following beneficial effects:
the invention provides a coating, which is characterized in that when the coating is stressed, the coating has a larger elastic modulus after being stressed than the coating before being stressed through a chemical crosslinking reaction between a derivative of gem-dihalogen cyclopropane in the coating and a dicarboxylic acid salt, so that the crosslinking degree of the coating is improved, and the strength and the service life of the coating in a stressed area are improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic diagram of a ring opening reaction of a derivative of a geminadihalocyclopropane in a coating provided in an example herein;
FIG. 2 is a flow chart of a method for preparing a coating according to an embodiment of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the specific embodiments of the present invention and the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It will be appreciated that the data so used may be interchanged under appropriate circumstances such that embodiments of the invention may be practiced other than those illustrated or described herein, and that the objects identified as "first," "second," etc. are generally a class of objects and do not limit the number of objects, e.g., a first object may be one or more. In addition, "and/or" in the specification and claims means at least one of connected objects, a character "/" generally means that a preceding and succeeding related objects are in an "or" relationship.
The technical solutions disclosed in the embodiments of the present invention are described in detail below with reference to the accompanying drawings.
The embodiment of the invention provides a coating which comprises the following components in parts by weight:
10-80 parts of curing resin, 20-85 parts of polymerization precursor, 1-5 parts of initiator, 0.01-3 parts of gem-dihalogenated cyclopropane derivative, 0.01-3 parts of dicarboxylic acid salt and 0.1-5 parts of assistant, wherein the gem-dihalogenated cyclopropane derivative has a general formula:
when the coating is stressed, the gem-dihalogen cyclopropane derivative in the coating and the dicarboxylic acid salt are subjected to chemical crosslinking reaction, so that the elastic modulus of the coating after stress is larger than that of the coating before stress, the crosslinking degree of the coating is improved, and the strength and the service life of the coating in a stressed area are improved.
In order to further improve the strength and the service life of the coating after being stressed, the coating preferably comprises 20-50 parts of curing resin, 35-75 parts of polymerization precursor, 1.5-3.5 parts of initiator, 0.5-2 parts of gem-dihalogen cyclopropane derivative, 0.5-2 parts of dicarboxylic acid salt and 1.5-4 parts of auxiliary agent in parts by mass.
Wherein, R1 and R2 are each independently at least one of fluorine, chlorine, bromine and iodine halogen atoms, and specifically, R1 and R2 may be both one kind of halogen atom and may be different kinds of halogen atoms. R3, R4 are unsaturated double bond containing ester groups including at least one of a methacrylate group, an acrylate group or a pentenoate group, and R3 and R4 may each independently be at least one of a methacrylate group, an acrylate group or a pentenoate group.
Specifically, when the coating is stressed, the gem-dihalo-cyclopropane derivative in the coating generates a ring opening reaction as shown in figure 1, the gem-dihalo-cyclopropane derivative is subjected to a ring opening reaction to form olefin, the olefin can generate nucleophilic substitution reaction with the dicarboxylate, so that a chemical crosslinking structure is formed, the crosslinking degree of the coating is improved, and the strength of the coating in a stressed area is improved. The strength includes the traditional mechanical strength and rigidity, so that the elastic modulus of the coating after being stressed is larger than that of the coating before being stressed, namely the coating can be automatically reinforced when being stressed, and the service life of the coating is prolonged. In addition, the stress applied to the coating material is consistent with the improvement degree of the strength of the stressed area of the coating material, that is, the higher the stress applied to the coating material is, the more obvious the crosslinking degree of the stressed area of the coating material is improved, and the higher the strength of the stressed area of the coating material is.
In a specific embodiment, both R1 and R2 in the gem-dihalogenated cyclopropane derivative are bromine and both R3 and R4 are acrylate groups, i.e. the gem-dihalogenated cyclopropane derivative is a diacrylate-based 1, 1-dibromocyclopropane of the formula:
the diacrylate-based 1, 1-dibromocyclopropane in the coating can generate a ring-opening reaction to form double bonds after being stressed, and the molecular formula of the ring-opened diacrylate-based 1, 1-dibromocyclopropane is as follows:
the molecular formula of the dicarboxylate is as follows:
[COO-R7-COO]M2
wherein R7 is- (CH2)n-, and n is an integer of 2 to 10, M is Na or K.
Olefin formed by the diacrylate-based 1, 1-dibromocyclopropane in the coating after being stressed and [ COO-R7-COO in the dicarboxylate]2-Nucleophilic substitution reaction occurs to form a cross-linked structure, and the cross-linking degree of the coating in a stressed area is highThe strength of the coating is improved.
Optionally, the coating further comprises 0.01-2 parts of spiropyran derivatives, preferably 0.5-1.5 parts by weight.
Specifically, the general formula of the spiropyran derivative is as follows:
wherein R5 and R6 are ester groups containing unsaturated double bonds, such as methacrylate groups, acrylate groups, or pentenoate groups. Due to the NO in the spiropyran derivatives2The paint can change color under UV illumination; and when the spiropyran derivative has at least two ester groups containing unsaturated double bonds, the coating can be discolored under the action of mechanical stress.
The coating can change color under the action of illumination or stress, when the coating is under the action of stress, the stress of the coating is consistent with the color change degree of the coating, namely, the larger the stress of the coating is, the higher the color change degree of a stressed area of the coating is, and the characteristic can be just combined with the characteristic that the structure of the coating is strengthened when the coating is stressed, so that a user can intuitively feel the strengthening degree of the structure strengthened part after the coating is stressed. For example, a higher degree of discoloration in the stressed area of the paint indicates a more pronounced increase in structural strength at this location.
In particular, in one aspect, the spiropyran derivative can change color under UV illumination, increasing the appearance diversity of the coating. On the other hand, the spiropyran derivative is copolymerized into the polymer chain of the polymerization precursor to form chemical bonds, when the coating is stressed, stress can be conducted to the spiropyran derivative molecules along the polymer chain of the polymerization precursor, so that the C-O bonds of the spiropyran derivative are broken, the spiropyran derivative molecules are isomerized, and an isomer with a purple color is generated, and the higher the stress on the coating is, the higher the isomerization degree of the spiropyran derivative is, and the higher the discoloration degree of the coating is.
In a specific embodiment, both R5 and R6 in the derivative of the spiropyran are acrylate groups, i.e. the derivative of the spiropyran is an acrylate spiropyran of the formula:
because the acrylate modified spiropyran contains NO2And the acrylic acid modified spiropyran copolymer coating has two acrylate groups, so that the coating can change color under UV illumination, and can be acted by stress, the stress can be transmitted to the acrylic acid modified spiropyran molecules along the macromolecular chain of the polymerization precursor, so that the C-O bond in the acrylic acid group of the acrylic acid modified spiropyran is broken, the acrylic acid modified spiropyran molecules are isomerized, and a purple isomer is generated.
Optionally, the cured resin comprises at least one of a polyacrylate resin, an epoxy acrylate resin, a urethane acrylate resin, and an organosiloxane resin.
Specifically, the curable resin is classified into a photo-curable resin and a thermosetting resin, and the photo-curable resin includes at least one of a polyacrylate resin, an epoxy acrylate resin, and a urethane acrylate resin;
the thermosetting resin includes at least one of polyacrylate resin, epoxy acrylate resin, urethane acrylate resin, and organosiloxane resin. The cured resin may combine with the gem-dihalogenated cyclopropane derivative and the dicarboxylate to form a uniform and dense coating, which improves toughness and adhesion of the coating. When the type of the curing resin is identical to the groups R3 and R4 derived from the gem-dihalo-cyclopropane derivative, for example, both of the acrylate esters are used, the force of polymerization between the curing resin and the gem-dihalo-cyclopropane derivative can be increased, and the structural strength of the coating can be improved.
Optionally, the polymeric precursor includes at least one of a monofunctional acrylate, a multifunctional acrylate, and a polydimethylsiloxane prepolymer.
Specifically, the monofunctional acrylate may further include at least one of monofunctional hydroxyethyl acrylate and monofunctional methacrylate, and the multifunctional acrylate may further include at least one of multifunctional hydroxyethyl acrylate and multifunctional methacrylate. The polymerization precursor can form a main carrier of the coating after polymerization, and the heat resistance, strength and service life of the coating can be ensured. When the type of the polymerization precursor is the same as the groups R3 and R4 derived from the gem-dihalogenocyclopropane derivative, for example, both of the acrylate esters are used, the force of polymerization between the polymerization precursor and the gem-dihalogenocyclopropane derivative can be increased, and the structural strength of the coating material can be improved.
Optionally, the initiator comprises a photoinitiator and/or a thermal initiator, the photoinitiator comprising at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide;
the thermal initiator comprises at least one of azodiisobutyronitrile, potassium persulfate, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate and a platinum-containing initiator.
Optionally, the auxiliary agent comprises at least one of a leveling agent, a defoaming agent and a polymerization inhibitor. Specifically, the polymerization inhibitor may be hydroquinone or p-hydroxyanisole.
Referring to fig. 2, an embodiment of the present invention further provides a preparation method of the coating, including:
s101, mixing and stirring a curing resin, a polymerization monomer, a gem-dihalogenated cyclopropane derivative and a dicarboxylic acid salt;
and S102, adding an initiator, and stirring to obtain the coating.
Specifically, the stirring time in step S101 is 0.5 to 2 hours, and the stirring time in step S102 is 10 to 30 minutes.
Alternatively, the addition of the derivative of the spiropyran may be included in the process in which the curable resin, the polymerizable monomer, the derivative of the geminadihalocyclopropane, and the dicarboxylic acid salt may be mixed at normal temperature. The addition of the spiropyran derivative can enable the coating to be discolored under the action of illumination or stress.
The embodiment of the invention also provides a coating which is used for protecting the surface of a product and comprises the paint.
In particular, the coating may be used for protection of vehicles, buildings, and the like.
The coating provided by the invention is formed by coating and curing the coating, curing the coated fluid coating comprises photo-curing and/or thermal curing, the photo-curing process can be used for curing the fluid coating by illuminating the fluid coating for 0.5-2 hours with the light intensity of 1000-.
After the coating provided by the embodiment of the invention is coated on the surface of a product, when the surface of the product is stressed, the strength of the coating in a stressed area is increased, so that the elastic modulus of the coating after being stressed is larger than that of the coating before being stressed, namely the coating can be automatically reinforced when being stressed, and the service life of the coating is prolonged.
The preparation of the coatings (containing spiropyran derivatives) is illustrated schematically by the following examples and comparative examples.
In the examples and comparative examples:
(1) the structural formula of the diacrylate spiropyran is as follows:
(2) the structural formula of the diacrylate-based 1, 1-dibromocyclopropane is as follows:
(3) the structural formula of the monoacrylate-based 1, 1-dibromocyclopropane is as follows:
(4) the structural formula of the monoacrylate-based spiropyran is as follows:
example 1 (Photocurable coating)
The components and weight percentages of the coating of this example are as follows:
20g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; diacrylate-based spiropyran 0.5 g; 0.5g of diacrylate-based 1, 1-dibromocyclopropane; 0.5g of adipic acid sodium salt; 1.5g of leveling agent; 0.5g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the coating comprises the following steps:
s101, mixing and uniformly stirring low-molecular-weight polybutylacrylate, the compound, diacrylate-based spiropyran, diacrylate-based 1, 1-dibromocyclopropane and sodium adipate at 25 ℃ for 1.5 hours;
s102, adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes to obtain the coating.
The coating obtained in this example was coated and cured by light irradiation to obtain a coating layer.
Example 2 (Photocurable coating)
The components and weight percentages of the coating of this example are as follows:
10g of low molecular weight polybutylacrylate; 20g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; diacrylate-based spiropyran 0.01 g; 0.01g of diacrylate-based 1, 1-dibromocyclopropane; 0.01g of adipic acid sodium salt; 0.1g of leveling agent; 0.1g of defoaming agent; 0.1g of polymerization inhibitor.
The preparation method of the coating comprises the following steps:
s101, mixing and uniformly stirring low-molecular-weight polybutylacrylate, the compound, diacrylate-based spiropyran, diacrylate-based 1, 1-dibromocyclopropane and sodium adipate at 25 ℃ for 1.5 hours;
s102, adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes to obtain the coating.
The coating obtained in this example was coated and cured by light irradiation to obtain a coating layer.
Example 3 (Photocurable coating)
The components and weight percentages of the coating of this example are as follows:
80g of low molecular weight polybutylacrylate; 85g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; diacrylate-based spiropyrans 2 g; 3g of diacrylate-based 1, 1-dibromocyclopropane; 3g of adipic acid sodium salt; 1.5g of leveling agent; 1.5g of defoaming agent; and 2g of polymerization inhibitor.
The preparation method of the coating comprises the following steps:
s101, mixing and uniformly stirring low-molecular-weight polybutylacrylate, the compound, diacrylate-based spiropyran, diacrylate-based 1, 1-dibromocyclopropane and sodium adipate at 25 ℃ for 1.5 hours;
s102, adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes to obtain the coating.
The coating obtained in this example was coated and cured by light irradiation to obtain a coating layer.
Example 4 (Photocurable coating)
The components and weight percentages of the coating of this example are as follows:
20g of low molecular weight polybutylacrylate; 35g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; diacrylate-based spiropyran 0.5 g; 0.5g of diacrylate-based 1, 1-dibromocyclopropane; 0.5g of adipic acid sodium salt; 0.5g of leveling agent; 0.5g of defoaming agent; 0.5g of polymerization inhibitor.
The preparation method of the coating comprises the following steps:
s101, mixing and uniformly stirring low-molecular-weight polybutylacrylate, the compound, diacrylate-based spiropyran, diacrylate-based 1, 1-dibromocyclopropane and sodium adipate at 25 ℃ for 1.5 hours;
s102, adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes to obtain the coating.
The coating obtained in this example was coated and cured by light irradiation to obtain a coating layer.
Example 5 (Photocurable coating)
The components and weight percentages of the coating of this example are as follows:
50g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide 3.5 g; 1.5g of diacrylate spiropyran; 2g of diacrylate-based 1, 1-dibromocyclopropane; 2g of adipic acid sodium salt; 1.5g of leveling agent; 1.5g of defoaming agent; 1g of polymerization inhibitor.
The preparation method of the coating comprises the following steps:
s101, mixing and uniformly stirring low-molecular-weight polybutylacrylate, the compound, diacrylate-based spiropyran, diacrylate-based 1, 1-dibromocyclopropane and sodium adipate at 25 ℃ for 1.5 hours;
s102, adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes to obtain the coating.
The coating obtained in this example was coated and cured by light irradiation to obtain a coating layer.
Example 6 (Photocurable coating)
The components and weight percentages of the coating of this example are as follows:
35g of low molecular weight polybutylacrylate; 55g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio is 3: 4: 3); 2.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; 1g of diacrylate spiropyran; 1g of diacrylate-based 1, 1-dibromocyclopropane; 1g of adipic acid sodium salt; 0.8g of leveling agent; 0.8g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the coating comprises the following steps:
s101, mixing and uniformly stirring low-molecular-weight polybutylacrylate, the compound, diacrylate-based spiropyran, diacrylate-based 1, 1-dibromocyclopropane and sodium adipate at 25 ℃ for 1.5 hours;
s102, adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes to obtain the coating.
The coating obtained in this example was coated and cured by light irradiation to obtain a coating layer.
Example 7 (Heat-curable coating)
The components and weight percentages of the coating of this example are as follows:
20g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of di-tert-butyl peroxide; diacrylate-based spiropyran 0.5 g; 0.5g of diacrylate-based 1, 1-dibromocyclopropane; 0.5g of adipic acid sodium salt; 1.5g of leveling agent; 0.5g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the coating comprises the following steps:
s101, mixing and uniformly stirring low-molecular-weight polybutylacrylate, the compound, diacrylate-based spiropyran, diacrylate-based 1, 1-dibromocyclopropane and sodium adipate at 25 ℃ for 1.5 hours;
s102, adding a flatting agent, an antifoaming agent, a polymerization inhibitor and di-tert-butyl peroxide, and stirring for 30 minutes to obtain a fluid coating;
the coating obtained in this example was coated and heat-cured to obtain a coating layer.
Example 8
The starting materials and preparation were the same as in example 1, except that the diacrylate-based spiropyran was not included.
Example 9
The starting materials and preparation were the same as in example 1, except that the diacrylate-based spiropyran was replaced with a conventional spiropyran.
Comparative example 1
The components and weight percentages of the paint of the comparative example are as follows:
20g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; monoacrylate-based spiropyrane 0.5 g; 0.5g of monoacrylate-based 1, 1-dibromocyclopropane; 0.5g of adipic acid sodium salt; 1.5g of leveling agent; 0.5g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the comparative example paint comprises the following steps:
mixing and stirring low molecular weight polybutyl acrylate, the compound, monoacrylate spiropyran, monoacrylate 1, 1-dibromocyclopropane and sodium adipate uniformly at 25 ℃ for 1.5 hours; adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes; the components are mixed according to a certain proportion, and then the paint can be obtained after sealing and storage.
And coating and light curing the coating obtained by the comparative example to obtain a coating.
Comparative example 2
The components and weight percentages of the paint of the comparative example are as follows:
20g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; 0.5g of monoacrylate-based 1, 1-dibromocyclopropane; 0.5g of adipic acid sodium salt; 1.5g of leveling agent; 0.5g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the comparative example paint comprises the following steps:
mixing and stirring the low molecular weight polybutyl acrylate, the compound, the monoacrylate-based 1, 1-dibromocyclopropane and the sodium adipate uniformly at 25 ℃ for 1.5 hours; adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes; the components are mixed according to a certain proportion, and then the paint can be obtained after sealing and storage.
And coating and light curing the coating obtained by the comparative example to obtain a coating.
Comparative example 3
The components and weight percentages of the paint of the comparative example are as follows:
20g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; diacrylate-based spiropyran 0.5 g; 0.5g of adipic acid sodium salt; 1.5g of leveling agent; 0.5g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the comparative example paint comprises the following steps:
mixing and stirring the low-molecular-weight polybutylacrylate, the compound, the diacrylate-based spiropyran and the sodium adipate uniformly at 25 ℃ for 1.5 hours; adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes; the components are mixed according to a certain proportion, and then the paint can be obtained after sealing and storage.
And coating and light curing the coating obtained by the comparative example to obtain a coating.
Comparative example 4
The components and weight percentages of the paint of the comparative example are as follows:
20g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; diacrylate-based spiropyran 0.5 g; 0.5g of diacrylate-based 1, 1-dibromocyclopropane; 1.5g of leveling agent; 0.5g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the comparative example paint comprises the following steps:
mixing and stirring low molecular weight polybutyl acrylate, the compound, diacrylate spiropyran and diacrylate 1, 1-dibromocyclopropane uniformly at 25 ℃ for 1.5 hours; adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes; the components are mixed according to a certain proportion, and then the paint can be obtained after sealing and storage.
And coating and light curing the coating obtained by the comparative example to obtain a coating.
Comparative example 5
The components and weight percentages of the paint of the comparative example are as follows:
20g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; diacrylate-based spiropyran 0.5 g; 1.5g of leveling agent; 0.5g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the comparative example paint comprises the following steps:
mixing and stirring the low molecular weight polybutyl acrylate, the compound and the diacrylate spiropyran uniformly at 25 ℃ for 1.5 hours; adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes; the components are mixed according to a certain proportion, and then the paint can be obtained after sealing and storage.
And coating and light curing the coating obtained by the comparative example to obtain a coating.
Comparative example 6
The components and weight percentages of the paint of the comparative example are as follows:
20g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; diacrylate-based spiropyran 0.5 g; 5g of diacrylate-based 1, 1-dibromocyclopropane; 0.5g of adipic acid sodium salt; 1.5g of leveling agent; 0.5g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the comparative example paint comprises the following steps:
mixing and stirring low molecular weight polybutyl acrylate, the compound, diacrylate spiropyran, diacrylate 1, 1-dibromocyclopropane and sodium adipate uniformly at 25 ℃ for 1.5 hours; adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes; the components are mixed according to a certain proportion, and then the paint can be obtained after sealing and storage.
And coating and light curing the coating obtained by the comparative example to obtain a coating.
Comparative example 7
The components and weight percentages of the paint of the comparative example are as follows:
20g of low molecular weight polybutylacrylate; 75g of a compound of hydroxyethyl acrylate, butyl acrylate and methacrylate (mass ratio of 3: 4: 3); 1.5g of bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide; diacrylate-based spiropyran 0.5 g; 0.5g of diacrylate-based 1, 1-dibromocyclopropane; 5g of adipic acid sodium salt; 1.5g of leveling agent; 0.5g of defoaming agent; 0.8g of polymerization inhibitor.
The preparation method of the comparative example paint comprises the following steps:
mixing and stirring low molecular weight polybutyl acrylate, the compound, diacrylate spiropyran and diacrylate 1, 1-dibromocyclopropane uniformly at 25 ℃ for 1.5 hours; adding a flatting agent, a defoaming agent, a polymerization inhibitor and bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, and stirring for 30 minutes; the components are mixed according to a certain proportion, and then the paint can be obtained after sealing and storage.
And coating and light curing the coating obtained by the comparative example to obtain a coating.
The experimental coating obtained in the example of the present invention and the comparative coating obtained in the comparative example were subjected to a light response test, a mechanical force response test, an elastic modulus test, and a crosslinking degree test, specifically as follows:
illumination response test
The test method comprises the following steps: the cured experimental and comparative coatings were each irradiated with a UV lamp for 1 minute and the color of the coating was observed.
Mechanical force response test
The same pressure was applied to the coated cured experimental and comparative coatings using an Instron (Instron) materials tester for 1 minute, followed by observing the color of the coating
Modulus of elasticity test
The same pressure was applied to the applied cured experimental and comparative coatings using an Instron material tester for 1 minute. The elastic modulus of the pressed part was measured and compared with that before pressing.
Degree of crosslinking test
And (3) respectively soaking the experimental coating and the comparative coating after being pressed for 3 days by using tetrahydrofuran as a solvent by adopting a Soxhlet extractor, drying after soaking, testing the quality after drying, comparing with the quality before drying, and calculating the crosslinking degree.
TABLE 1 test results
As can be seen from Table 1, the coating provided by the invention is coated and cured to obtain a coating, the crosslinking degree and the elastic modulus of the coating after mechanical stress are well improved, and the strength and the service life of the coating in a stressed area are improved. Compared with the examples, the derivatives of the geminal dihalogenated cyclopropane in the comparative examples 1-2 only contain ester groups with one unsaturated double bond, and the degree of crosslinking and the elastic modulus of the coating after being subjected to mechanical stress are unchanged; comparative examples 3 to 5 do not contain the gem-dihalocyclopropane derivatives and/or dicarboxylic acid salts of the invention, the degree of crosslinking and the elastic modulus of the coatings after mechanical stress are unchanged; the selection of the components in comparative examples 6 to 7 exceeds the scope of the present invention, the increase in the degree of crosslinking and the modulus of elasticity of the coating after mechanical stress is insignificant, and the strength and life of the coating in the stressed region cannot be improved well.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. The coating is characterized by comprising the following components in parts by mass:
10-80 parts of curing resin, 20-85 parts of polymerization precursor, 1-5 parts of initiator, 0.01-3 parts of gem-dihalogenocyclopropane derivative and 0.01-3 parts of dicarboxylic acid salt, wherein the gem-dihalogenocyclopropane derivative has a general formula:
wherein, R1 and R2 are at least one of fluorine, chlorine, bromine and iodine, and R3 and R4 are ester groups containing unsaturated double bonds.
2. The coating according to claim 1, comprising, in parts by mass:
20-50 parts of curing resin, 35-75 parts of polymerization precursor, 1.5-3.5 parts of initiator, 0.5-2 parts of gem-dihalogenated cyclopropane derivative and 0.5-2 parts of dicarboxylic acid salt.
3. The coating of claim 1, wherein each of R3 and R4 is independently at least one of a methacrylate group, an acrylate group, or a pentenoate group.
4. The coating of claim 1, further comprising 0.01-2 parts by weight of a spiropyran derivative having the formula:
wherein R5 and R6 are ester groups containing an unsaturated double bond.
5. The coating according to claim 4, comprising 0.5 to 1.5 parts by mass of the spiropyran derivative.
6. The coating of claim 1 or 2, wherein the cured resin comprises at least one of a polyacrylate resin, an epoxy acrylate resin, a urethane acrylate resin, and an organosiloxane resin.
7. The coating according to any one of claims 1 to 5, wherein the polymeric precursor comprises at least one of a monofunctional acrylate, a multifunctional acrylate and a polydimethylsiloxane prepolymer.
8. The coating according to any one of claims 1 to 5, wherein the initiator comprises a photoinitiator and/or a thermal initiator, the photoinitiator comprising at least one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide;
the thermal initiator comprises at least one of azodiisobutyronitrile, potassium persulfate, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate and a platinum-containing initiator.
9. The coating of any one of claims 1 to 5, wherein the dicarboxylate comprises at least one of a sodium salt of a dicarboxylic acid and a potassium salt of a dicarboxylic acid.
10. The coating according to claim 1, further comprising 0.1-5 parts by mass of an auxiliary agent, wherein the auxiliary agent comprises at least one of a leveling agent, a defoaming agent and a polymerization inhibitor.
11. A coating for surface protection of a product, comprising the coating of any one of claims 1-10.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112430306A (en) * | 2020-11-17 | 2021-03-02 | 南京工程学院 | Self-reinforcing photochromic material and preparation method thereof |
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| CN109679483A (en) * | 2018-12-10 | 2019-04-26 | 成都晨光博达橡塑有限公司 | A kind of UV photocureable coating of perfluoro-polyether modified additive and its preparation method and application |
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| US20040077882A1 (en) * | 2002-10-22 | 2004-04-22 | Norbert Moszner | Polymerizable bicyclic cyclopropane derivatives and their use for the preparation of dental materials |
| EP1983516A2 (en) * | 2007-04-19 | 2008-10-22 | FUJIFILM Corporation | Optical recording composition and holographic recording medium |
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