CN113583559B - Self-repairing coating paint, preparation method thereof, coating, film and device - Google Patents
Self-repairing coating paint, preparation method thereof, coating, film and device Download PDFInfo
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- CN113583559B CN113583559B CN202110931110.XA CN202110931110A CN113583559B CN 113583559 B CN113583559 B CN 113583559B CN 202110931110 A CN202110931110 A CN 202110931110A CN 113583559 B CN113583559 B CN 113583559B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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Abstract
The invention discloses a self-repairing coating, which comprises the following components: nitrogen element monomer containing trivalent bond, carboxyl group-containing monomer and hydroxyl group-containing monomer. The invention also discloses a preparation method of the self-repairing coating, a film and a device. According to the invention, nitrogen elements containing triple bonds are introduced into a small amount of chemically crosslinked molecular structures, and quaternary ammonia of the nitrogen elements containing triple bonds is salinized through carboxyl of monomers containing carboxyl, so that the elongation at break of the coating is greatly improved under the condition of ensuring the self-repairing capability of the coating.
Description
Technical Field
The invention relates to a coating with high elongation at break and excellent self-repairing capability, and a preparation method and application thereof.
Background
In recent years, with the development of society and the progress of technology, new materials are more and more widely applied, thermoplastic polyurethane elastomers (TPU) and casting grade PVC are changed from military use to dual-purpose use for military and civilian use since the beginning of the last 80 th century, and mainly for civilian use, the variety brands of products are continuously increased, the production scale is gradually enlarged, and the thermoplastic polyurethane elastomers play an important role in various aspects of national economy departments and people's clothes and eating residences.
TPU and casting-grade PVC have the advantages of good flexibility, solvent resistance, wear resistance and the like, but the surfaces of the films have no self-repairing characteristic, and at present, many invisible car clothes and color-changing car clothes at home and abroad have self-repairing functions such as 3M car clothes, XPEL car clothes, Weigu car clothes and the like, the self-repairing coatings greatly improve the glossiness and the self-repairing capability of the protective film, and are continuously used in other more fields such as the surface protection of airplanes or ships, the protective film of the paint on the surface of wind blades and automobiles, then, in practical use, we find that in order to improve self-repairing capability, people often improve self-repairing capability by improving chemical crosslinking density, such as that in CN 110713781A, the Japanese crude chemical is mixed with some polyester polyol by introducing hydroxyl into acrylic resin, then, crosslinking the coating by using a substance with isocyanate groups to form a network structure so as to prepare a coating with excellent self-repairing function; songklanakarin J.Sci.Technol.33(2),201- & 207, Mar. -Apr.2011 mentions the use of UV initiation of certain acrylate oligomers to prepare coatings with excellent self-healing properties, in CN109354689A by Michael addition of aminopropyl bis-terminated polydimethylsiloxanes with acrylic acid; raising the temperature of the obtained oligomer, and initiating a polycondensation reaction of a system; crosslinking and curing to obtain the novel organosilicon elastomer, thereby preparing the chemically crosslinked self-repairing (self-healing) elastomer. The dow chemistry in CN102533207A achieves a self-healing function of the coating by crosslinking one or more polyols of natural oils with isocyanates. CN 207419113A Japanese Jienzhi initiates acrylic acid through photoinitiator, and fluorine-containing monomer to prepare a crosslinking self-repairing coating, the coating has the hydrophobic characteristic, the coating is coated on the tpu of Alutak Argotech in the embodiment of the patent, and the excellent self-repairing function is obtained. The NATOCO company in JP2002-026022 initiates functional acrylic monomers or oligomers with photoinitiators such as 184 to produce self-healing coatings with excellent gloss and can be used on a variety of plastic substrates. 3M in CN109765C adopts isocyanate to cure silicon-containing fluorine-containing polymer so as to prepare the coating with self-healing and scratch resistance, and the scheme of curing polycaprolactone polyol by adopting isocyanate in US8987352B1 realizes the self-healing function, and polycaprolactone has good elasticity.
Careful study found that the prior art achieves the effect of improving self-repairing capability by reacting to form new covalent bonds and increasing chemical crosslinking density, however, with the heavy use of TPU and casting-grade PVC protective films, one of the great advantages of TPU is that its elongation at break is typically 400% -600%. The elongation at break of the coating crosslinked by a large number of chemical bonds is generally low, no commercial self-repairing coating with the elongation at break exceeding 300% is found at present, the self-repairing coating is coated on TPU and casting-grade PVC which are soft and have extremely high elongation at break, and the low elongation at break of the self-repairing coating greatly limits the workability of the protective films. For example, in the process of constructing the protective film of the automobile, in order to make the protective film adhere to the automobile body more tightly, a constructor can pull the protective film with force, so that the deformation of the protective film is extremely large, especially at corners such as automobile doors, automobile engine covers and the like. Also in the construction of protective films for aircraft, similar situations occur in radar protection covers, helicopter rotors and the like, and the protective films are required to have an extremely large elongation.
However, the prior art coatings crosslinked by a large number of covalent bonds are subject to breakage during the construction of the protective film, thereby hindering the use of the constructor. In order to prevent the occurrence of the similar situation, protective film application personnel need to be trained to use the protective film with the coating layer well, which undoubtedly raises the requirements for the application personnel.
Therefore, there is a need to design self-healing coatings with high elongation at break.
Disclosure of Invention
All the known proposals at present improve the self-repairing capability of the coating by increasing the crosslinking density of covalent bonds of the coating, so that the coating is not flexible and cannot be extended along with the extension of a substrate such as a TPU film or a casting-grade PVC film due to the large increase of the crosslinking density, and the film pasting construction of the protective film is greatly limited.
The invention aims to introduce nitrogen elements containing triple bonds into the molecular structure of the original coating and form ionic bonds through quaternary ammonium salinization of carboxyl and nitrogen elements under the condition of ensuring the self-repairing capability and other capabilities of the self-repairing coating, and the ionic bonds still maintain excellent self-repairing capability under the condition of not reducing the flexibility of the coating and simultaneously improve the elongation at break of the coating.
The technical scheme of the invention is as follows:
a self-healing coating comprising: nitrogen element monomer containing trivalent bond, carboxyl group-containing monomer and hydroxyl group-containing monomer.
The invention firstly proposes that the ionic bond acting force is introduced on the basis of few covalent bond cross-links, so that the coating with good flexibility and excellent self-repairing function is obtained. The invention provides a method for introducing nitrogen elements containing triple bonds into a small amount of chemically crosslinked molecular structures, and quaternary ammonification of the nitrogen elements containing the triple bonds is realized through carboxyl of monomers containing carboxyl, so that the elongation at break of the prepared coating is greatly improved under the condition of ensuring the self-repairing capability of the coating.
Wherein, the nitrogen element monomer containing the trivalent bond is polymerized on the molecular chain by a polymerization mode, and the carboxyl is polymerized on the molecular chain by the monomer containing the carboxyl by a polymerization mode.
In some embodiments, the trivalent nitrogen-containing monomer is represented by formula (I):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Each independently is hydrogen, halogen, carboxyl, C 1-10 Alkyl (preferably C) 1-6 Alkyl, more preferably C 1-3 Alkyl group), C 2-10 Alkenyl radical, C 2-10 Alkynyl, NR 00 R 01 、-COR 00 、-SO 2 R 00 、-SOR 00 、-C(O)OR 00 、-OC(O)R 00 、-CONR 00 、-NR 00 COR 00 、NR 00 CONR 00 、SONR 00 、NR 00 SOR 00 、SO 2 NR 00 、NR 00 SO 2 R 00 、C 3-12 Cycloalkyl, 4-to 12-membered heterocyclyl, C 6-16 Aryl or 5 to 14 membered heteroaryl;
wherein R is 4 、R 5 Is not hydrogen;
L 1 、L 2 、L 3 each independently is a chemical bond, C 1-10 Alkylene radical, C 2-10 Alkenylene radical, C 2-10 Alkynylene, NR 00 R 01 Acyl, sulfonyl, sulfinyl, C (O) O, OC (O), CONR 00 、NR 00 CO、NR 00 CONR 00 、SONR 00 、NR 00 SO、SO 2 NR 00 、NR 00 SO 2 、C 3-12 Cycloalkyl, 4-to 12-membered heterocyclyl, C 6-16 Aryl or 5 to 14 membered heteroaryl;
or, R 4 、R 5 Together with the nitrogen atom to which they are attached, form a 3-8 membered heterocyclyl;
R 00 、R 01 each independently is hydrogen, C 1-3 Alkyl or amino (preferably hydrogen or methyl).
In some embodiments, the carboxyl-containing monomer is represented by formula (II):
wherein R is 1 、R 2 、R 3 Each independently is hydrogen, halogen, carboxyl, C 1-10 Alkyl (preferably C) 1-6 Alkyl, more preferably C 1-3 Alkyl group), C 2-10 Alkenyl radical, C 2-10 Alkynyl, NR 00 R 01 、-COR 00 、-SO 2 R 00 、-SOR 00 、-C(O)OR 00 、-OC(O)R 00 、-CONR 00 、-NR 00 COR 00 、NR 00 CONR 00 、SONR 00 、NR 00 SOR 00 、SO 2 NR 00 、NR 00 SO 2 R 00 、C 3-12 Cycloalkyl, 4-to 12-membered heterocyclyl, C 6-16 Aryl or 5 to 14 membered heteroaryl;
L 1 、L 2 、L 3 each independently is a chemical bond, C 1-10 Alkylene radical, C 2-10 Alkenylene radical, C 2-10 Alkynylene, NR 00 R 01 Acyl, sulfonyl, sulfinyl, C (O) O, OC (O), CONR 00 、NR 00 CO、NR 00 CONR 00 、SONR 00 、NR 00 SO、SO 2 NR 00 、NR 00 SO 2 、C 3-12 Cycloalkyl, 4-to 12-membered heterocyclyl, C 6-16 Aryl or 5 to 14 membered heteroaryl;
R 00 、R 01 each independently is hydrogen, C 1-3 Alkyl or amino (preferably hydrogen or methyl).
In some embodiments, R 1 、R 2 、R 3 Each independently hydrogen, methyl, ethyl, propyl or isopropyl (preferably hydrogen, methyl or ethyl); r 4 、R 5 Each independently is methyl or ethyl.
In some embodiments, L in formula (I) 1 、L 2 、L 3 Each independently is a bond, C (O) O, OC (O), C (O) NH, NHC (O), methylene, ethylene or propylene;
l in the formula (II) 1 、L 2 、L 3 Each independently a bond, methylene, ethylene or vinylene.
In some embodiments, the trivalent nitrogen-containing monomer is selected from: at least one of dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate or ethyleneurea ethoxy acrylate.
In some embodiments, the carboxyl-containing monomer is selected from: at least one of acrylic acid, methacrylic acid, 2-ethacrylic acid, 3-dimethylacrylic acid, or sorbic acid.
In some embodiments, the hydroxyl-containing monomer is selected from at least one of the group consisting of hydroxyl acrylates including, but not limited to, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, caprolactone-modified methacrylates.
In some embodiments, the coating further comprises an auxiliary agent, wherein the auxiliary agent is at least one of an initiator, a curing agent, a leveling agent and a solvent, and the initiator is at least one of an organic peroxide, an azo compound, a photoinitiator or a cationic initiator.
In some embodiments, the initiator is selected from: at least one of dibenzoyl peroxide, diisopropyl peroxydicarbonate (IPP), dicyclohexyl peroxydicarbonate (DCPD), Cumene Hydroperoxide (CHP), Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (AVBN), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ferrocenium hexafluorophosphate, or sulfonium hexafluoroantimonate.
In some embodiments, the curing agent is an isocyanate curing agent including, but not limited to, isophorone diisocyanate, IPDI dimer or polymer, Toluene Diisocyanate (TDI), TDI dimer or polymer, diphenylmethane diisocyanate (MDI), MDI dimer or polymer, dicyclohexylmethane-4, 4-diisocyanate (H) 12 MDI),H 12 MDI dimers or polymers, Hexamethylene Diisocyanate (HDI), HDI dimers or polymers, m-Xylylene Diisocyanate (XDI), XDI dimers or polymers, Hydrogenated Xylylene Diisocyanate (HXDI), HXDI dimers or polymers; HDI trimer curing agents are preferred.
Preferably, the hydroxyl to isocyanate molar ratio is from 0.95 to 1.05.
In some embodiments, the solvent includes, but is not limited to, acetone, ethyl acetate, DMF, butanone, tetrahydrofuran, xylene, toluene, dichloromethane, butyl acetate.
In some embodiments, other common monomers are included, including but not limited to at least one of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isooctyl methacrylate, isodecyl methacrylate, tridecyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl methacrylate, stearyl acrylate.
In some embodiments, the solvent mass fraction is 20% to 90%, the initiator mass fraction is 1% to 5%; the mass fraction of the nitrogen element monomer containing the trivalent bond is 1-10%; the mass fraction of the monomer containing carboxyl is 1-20%, the mass fraction of the monomer containing hydroxyl is 2-15%, and the mass fraction of other common monomers is 11-39%.
The invention also provides a preparation method of the self-repairing coating, which comprises the following steps:
(1) adding an initiator (such as Azobisisobutyronitrile (AIBN)) into a solvent under the protection of an inert atmosphere (such as a nitrogen atmosphere or an argon atmosphere), simultaneously adding a nitrogen element monomer containing a trivalent bond, a monomer containing a carboxyl group and a hydroxyl group-containing monomer, and reacting for 8-48 hours at a set temperature to prepare a resin containing the nitrogen element containing the trivalent bond and the carboxyl group;
(2) adding an auxiliary agent into the resin, wherein the auxiliary agent comprises at least one of a solvent (such as ethyl acetate), a flatting agent and a curing agent (such as an isocyanate curing agent), and preparing the self-repairing coating.
In the preparation method, in the step (1), the mass fraction of the solvent is 20-90%, and the mass fraction of the initiator is 1-5%; the mass fraction of the nitrogen element monomer containing the trivalent bond is 1-10%; 1-20% of monomer containing carboxyl, 2-15% of monomer containing hydroxyl and 11-39% of other common monomers;
in the step (2), the set temperature is 20-100 ℃. The setting is carried out according to different initiating temperatures of the initiator, and the reaction time is determined according to the reaction temperature and the type of the initiator.
The invention also provides a self-repairing coating which is formed by drying and aging any one of the self-repairing coatings or by drying and aging the coating prepared by the method.
The drying temperature of the self-repairing coating is 35-110 ℃, and the drying time is 2-10 minutes; the aging temperature is 10-60 deg.C, and the aging time is 1-7 days.
The invention also provides a film which comprises a substrate and the self-repairing coating, wherein the self-repairing coating is arranged on the surface of the substrate. The self-repairing coating is coated on one surface of the base material or coated on two surfaces of the base material.
The covering mode comprises: coating, spraying, dipping, etc., such as slot coating, dimpling, doctor blading, wire bars, etc., on the substrate.
The invention also provides a device, and the surface of the device is coated with the film. Such as automobiles, radars, airplanes, ships, boats, etc.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the self-repairing coating, the preparation method thereof, the coating and the film ensure high self-repairing capability by introducing nitrogen elements with triple bonds into the coating and quaternizing the nitrogen elements with quaternary ammonium through carboxyl, and simultaneously improve the elongation at break.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
Interpretation of terms
The definitions of specific functional groups and chemical terms are described in more detail below.
When a range of values is recited, it is intended to include each value and every subrange within the range. E.g. "C 1-6 Alkyl "includes C 1 、C 2 、C 3 、C 4 、C 5 、C 6 、C 1-6 、C 1-5 、C 1-4 、C 1-3 、C 1-2 、C 2-6 、C 2-5 、C 2-4 、C 2-3 、C 3-6 、C 3-5 、C 3-4 、C 4-6 、C 4-5 And C 5-6 An alkyl group.
"alkyl" refers to straight and branched chain saturated aliphatic hydrocarbon radicals, C 1-10 Alkyl is an alkyl group containing 1 to 10 carbon atoms, preferably C 1-8 Alkyl, more preferably C 1-5 Alkyl, more preferably C 1-3 An alkyl group. C 1-10 Non-limiting examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-ethyl-2-methylpropyl, 1, 2-trimethylpropyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2, 3-dimethylbutyl, n-heptyl, 2-methylhexyl, 2-methylpentyl, 1-dimethylpropyl, 1, 2-dimethylbutyl, 2-methylpentyl, 4-methylpentyl, 2, 3-dimethylbutyl, 2-heptenyl, 2-methylhexyl3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2, 3-dimethylpentyl, 2, 4-dimethylpentyl, 2-dimethylpentyl, 3-dimethylpentyl, 2-ethylpentyl, 3-ethylpentyl, n-octyl, 2, 3-dimethylhexyl, 2, 4-dimethylhexyl, 2, 5-dimethylhexyl, 2-dimethylhexyl, 3-dimethylhexyl, 4-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, n-nonyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2, 3-dimethylpentyl, 2, 4-dimethylhexyl, 2, 3-dimethylhexyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-dimethylhexyl, 2, 3-dimethylhexyl, 2-dimethylhexyl, 2, 3-dimethylhexyl, 2-dimethylhexyl, 2-ethylhexyl, 2-ethylhexyl, 2-ethyl-2-, 2, 2-diethylpentyl, n-decyl, 3-diethylhexyl, 2-diethylhexyl, and various branched isomers thereof.
"alkylene" means a divalent group formed by the removal of another hydrogen of the above-mentioned "alkyl" group, and may be substituted or unsubstituted. Preferably C 1-10 Alkylene, more preferably C 1-5 Alkylene, more preferably C 1-3 An alkylene group. Exemplary alkylene groups include, but are not limited to, methylene, ethylene, propylene, butylene, and the like.
“C 2-10 Alkenyl "refers to a straight or branched hydrocarbon group having 2 to 10 carbon atoms and at least one carbon-carbon double bond. In some embodiments, C 2-6 Alkenyl groups are preferred; in some embodiments, C 2-4 Alkenyl groups are preferred. C 2-10 Examples of alkenyl groups include: vinyl radical (C) 2 ) 1-propenyl (C) 3 ) 2-propenyl (C) 3 ) 1-butenyl (C) 4 ) 2-butenyl (C) 4 ) Butadienyl radical (C) 4 ) Pentenyl (C) 5 ) Pentadienyl (C) 5 ) Hexenyl (C) 6 ) Heptenyl (C) 7 ) Octenyl (C) 8 ) And so on. The term "C 2-10 Alkenyl "also includes heteroalkenyl groups in which one or more (e.g., 1, 2, 3, or 4) carbon atoms are replaced with a heteroatom (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus). The alkenyl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
"alkenylene" means a divalent group formed by removing another hydrogen from the above-mentioned "alkenyl" group, and may To be substituted or unsubstituted. Preferably C 2-10 Alkenylene, more preferably C 2-5 Alkenylene, more preferably C 2-3 An alkenylene group. Exemplary alkenylene groups include, but are not limited to, vinylene and the like.
“C 2-10 Alkynyl "refers to a straight or branched chain hydrocarbon group having 2 to 10 carbon atoms, at least one carbon-carbon triple bond. In some embodiments, C 2-6 Alkynyl groups are preferred; in some embodiments, C 2-4 Alkynyl groups are preferred. C 2-10 Examples of alkynyl groups include, but are not limited to: ethynyl (C) 2 ) 1-propynyl (C) 3 ) 2-propynyl (C) 3 ) 1-butynyl (C) 4 ) 2-butynyl (C) 4 ) Pentynyl group (C) 5 ) Hexynyl (C) 6 ) Heptynyl (C) 7 ) (C) octynyl group 8 ) And so on. The term "C 2-10 Alkynyl also includes heteroalkynyl in which one or more (e.g., 1, 2, 3, or 4) carbon atoms are replaced with a heteroatom (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus). An alkynyl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
"alkynylene" means a divalent group formed by the removal of another hydrogen from the above-mentioned "alkynyl" group, and may be substituted or unsubstituted. Preferably C 2-10 Alkynylene, further preferably C 2-5 Alkynylene, more preferably C 2-3 Alkynylene radical. Exemplary alkenylene groups include, but are not limited to, ethynylene and the like.
“C 3-12 Cycloalkyl "refers to a non-aromatic cyclic hydrocarbon group having 3 to 12 ring carbon atoms and zero heteroatoms. In some embodiments, C 3-7 Cycloalkyl and C 3-6 Cycloalkyl is particularly preferred, more preferably C 5-6 A cycloalkyl group. Cycloalkyl also includes ring systems in which the aforementioned cycloalkyl ring is fused to one or more aryl or heteroaryl groups, where the point of attachment is on the cycloalkyl ring, and in such cases the number of carbons continues to represent the number of carbons in the cycloalkyl system. Exemplary such cycloalkyl groups include, but are not limited to: cyclopropyl (C) 3 ) Cyclopropenyl group (C) 3 ) Cyclobutyl group (b), (c), (d) and aC 4 ) Cyclobutenyl radical (C) 4 ) Cyclopentyl (C) 5 ) Cyclopentenyl group (C) 5 ) Cyclohexyl (C) 6 ) Cyclohexenyl (C) 6 ) Cyclohexyldienyl (C) 6 ) Cycloheptyl (C) 7 ) Cycloheptenyl (C) 7 ) Cycloheptadienyl (C) 7 ) Cycloheptatrienyl (C) 7 ) And so on. The cycloalkyl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
"4-12 membered heterocyclyl" refers to a radical of a 3 to 12 membered non-aromatic ring system having ring carbon atoms and 1 to 5 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, sulfur, boron, phosphorus, and silicon. In heterocyclic groups containing one or more nitrogen atoms, the point of attachment may be carbon or a nitrogen atom, as valency permits. In some embodiments, a 4-12 membered heterocyclic group is preferred which is a 4 to 12 membered non-aromatic ring system having ring carbon atoms and 1 to 5 ring heteroatoms; in some embodiments, a 3-10 membered heterocyclic group is preferred which is a 3 to 10 membered non-aromatic ring system having ring carbon atoms and 1 to 5 ring heteroatoms; in some embodiments, a 3-7 membered heterocyclic group is preferred which is a 3 to 7 membered non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms; preferably a 3-6 membered heterocyclic group which is a 3 to 6 membered non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms; preferably a 4-8 membered heterocyclic group which is a 4 to 8 membered non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms; more preferred are 5-6 membered heterocyclic groups which are 5 to 6 membered non-aromatic ring systems having ring carbon atoms and 1 to 3 ring heteroatoms. Heterocyclyl also includes ring systems wherein the aforementioned heterocyclyl ring is fused to one or more cycloalkyl groups, wherein the point of attachment is on the cycloalkyl ring, or ring systems wherein the aforementioned heterocyclyl ring is fused to one or more aryl or heteroaryl groups, wherein the point of attachment is on the heterocyclyl ring; and in such cases the number of ring members continues to represent the number of ring members in the heterocyclyl ring system. Exemplary 3-membered heterocyclic groups containing one heteroatom include, but are not limited to: aziridinyl, oxacyclopropaneyl, thienylyl. Exemplary 4-membered heterocyclic groups containing one heteroatom include, but are not limited to: azetidins Alkyl, oxetanyl and thietanyl. Exemplary 5-membered heterocyclic groups containing one heteroatom include, but are not limited to: tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2, 5-dione. Exemplary 5-membered heterocyclic groups containing two heteroatoms include, but are not limited to: dioxolanyl, oxathiolanyl (oxathiolanyl), dithiolanyl (disulphuryl), and oxazolidin-2-one. Exemplary 5-membered heterocyclic groups containing three heteroatoms include, but are not limited to: triazolinyl, oxadiazolinyl and thiadiazolinyl. Exemplary 6-membered heterocyclic groups containing one heteroatom include, but are not limited to: piperidinyl, tetrahydropyranyl, dihydropyridinyl and thiacyclohexyl (thianyl). Exemplary 6-membered heterocyclic groups containing two heteroatoms include, but are not limited to: piperazinyl, morpholinyl, dithiinyl, dioxanyl. Exemplary 6-membered heterocyclic groups containing three heteroatoms include, but are not limited to: hexahydrotriazinyl (triazinanyl). Exemplary 7-membered heterocyclic groups containing one heteroatom include, but are not limited to: azepane, oxepanyl and thiepane. Exemplary with C 6 Aryl ring fused 5-membered heterocyclyl (also referred to herein as 5, 6-bicyclic heterocyclyl) includes, but is not limited to: indolinyl, isoindolinyl, dihydrobenzofuranyl, dihydrobenzothienyl, benzoxazolonyl, and the like. Exemplary with C 6 Aryl ring fused 6-membered heterocyclyl (also referred to herein as 6, 6-bicyclic heterocyclyl) includes, but is not limited to: tetrahydroquinolinyl, tetrahydroisoquinolinyl, and the like. The heterocyclyl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
“C 6-16 Aryl "refers to a group having a monocyclic or polycyclic (e.g., bicyclic) 4n +2 aromatic ring system (e.g., having 6 or 16 pi electrons shared in a cyclic arrangement) of 6 to 16 ring carbon atoms and zero heteroatoms. In some embodiments, an aryl group has six ring carbon atoms ("C) 6 Aryl "; for example, phenyl). In some embodiments, an aryl group has ten ring carbon atoms ("C) 10 Aryl ";e.g., naphthyl, e.g., 1-naphthyl and 2-naphthyl). Aryl also includes ring systems in which the aforementioned aryl ring is fused to one or more cycloalkyl or heterocyclyl groups, and the point of attachment is on the aryl ring, in which case the number of carbon atoms continues to represent the number of carbon atoms in the aryl ring system. The aryl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
"5-14 membered heteroaryl" refers to a group having a 5-14 membered monocyclic or bicyclic 4n +2 aromatic ring system (e.g., having 6, 10, or 14 pi electrons shared in a cyclic arrangement) with ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur. In heteroaryl groups containing one or more nitrogen atoms, the point of attachment may be a carbon or nitrogen atom, as valency permits. Heteroaryl bicyclic ring systems may include one or more heteroatoms in one or both rings. Heteroaryl also includes ring systems in which the aforementioned heteroaryl ring is fused to one or more cycloalkyl or heterocyclyl groups, and the point of attachment is on the heteroaryl ring, in which case the number of carbon atoms continues to represent the number of carbon atoms in the heteroaryl ring system. In some embodiments, 5-10 membered heteroaryl groups are preferred, which are 5-10 membered monocyclic or bicyclic 4n +2 aromatic ring systems having ring carbon atoms and 1-4 ring heteroatoms. In other embodiments, 5-6 membered heteroaryl groups are particularly preferred, which are 5-6 membered monocyclic or bicyclic 4n +2 aromatic ring systems having ring carbon atoms and 1-4 ring heteroatoms. Exemplary 5-membered heteroaryl groups containing one heteroatom include, but are not limited to: pyrrolyl, furanyl and thienyl. Exemplary 5-membered heteroaryl groups containing two heteroatoms include, but are not limited to: imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl and isothiazolyl. Exemplary 5-membered heteroaryl groups containing three heteroatoms include, but are not limited to: triazolyl, oxadiazolyl (e.g., 1,2, 4-oxadiazolyl), and thiadiazolyl. Exemplary 5-membered heteroaryl groups containing four heteroatoms include, but are not limited to: a tetrazolyl group. Exemplary 6-membered heteroaryl groups containing one heteroatom include, but are not limited to: a pyridyl group. Exemplary 6-membered heteroaryl groups containing two heteroatoms include, but are not limited to: pyridazinyl, pyrimidinyl and pyrazinyl. Exemplary 6-membered heteroaryl groups containing three or four heteroatoms include, but are not limited to: triazinyl and tetrazinyl. Exemplary 7-membered heteroaryl groups containing one heteroatom include, but are not limited to: azepinyl, oxacycloheptyl, and thiacycloheptyl trienyl groups. Exemplary 5, 6-bicyclic heteroaryls include, but are not limited to: indolyl, isoindolyl, indazolyl, benzotriazolyl, benzothienyl, isobenzothienyl, benzofuranyl, benzisothiafuranyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzooxadiazolyl, benzothiazolyl, benzisothiazolyl, benzothiadiazolyl, indezinyl, and purinyl. Exemplary 6, 6-bicyclic heteroaryls include, but are not limited to: naphthyridinyl, pteridinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, phthalazinyl and quinazolinyl. The heteroaryl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.
Alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, and the like, as defined herein, are optionally substituted groups.
Exemplary substituents on carbon atoms include, but are not limited to: halogen, -CN, -NO 2 、-N 3 、-SO 2 H、-SO 3 H、-OH、-OR aa 、-ON(R bb ) 2 、-N(R bb ) 2 、-N(R bb ) 3 + X - 、-N(OR cc )R bb 、-SH、-SR aa 、-SSR cc 、-C(＝O)R aa 、-CO 2 H、-CHO、-C(OR cc ) 2 、-CO 2 R aa 、-OC(＝O)R aa 、-OCO 2 R aa 、-C(＝O)N(R bb ) 2 、-OC(＝O)N(R bb ) 2 、-NR bb C(＝O)R aa 、-NR bb CO 2 R aa 、-NR bb C(＝O)N(R bb ) 2 、-C(＝NR bb )R aa 、-C(＝NR bb )OR aa 、-OC(＝NR bb )R aa 、-OC(＝NR bb )OR aa 、-C(＝NR bb )N(R bb ) 2 、-OC(＝NR bb )N(R bb ) 2 、-NR bb C(＝NR bb )N(R bb ) 2 、-C(＝O)NR bb SO 2 R aa 、-NR bb SO 2 R aa 、-SO 2 N(R bb ) 2 、-SO 2 R aa 、-SO 2 OR aa 、-OSO 2 R aa 、-S(＝O)R aa 、-OS(＝O)R aa 、-Si(R aa ) 3 、-OSi(R aa ) 3 、-C(＝S)N(R bb ) 2 、-C(＝O)SR aa 、-C(＝S)SR aa 、-SC(＝S)SR aa 、-SC(＝O)SR aa 、-OC(＝O)SR aa 、-SC(＝O)OR aa 、-SC(＝O)R aa 、-P(＝O) 2 R aa 、-OP(＝O) 2 R aa 、-P(＝O)(R aa ) 2 、-OP(＝O)(R aa ) 2 、-OP(＝O)(OR cc ) 2 、-P(＝O) 2 N(R bb ) 2 、-OP(＝O) 2 N(R bb ) 2 、-P(＝O)(NR bb ) 2 、-OP(＝O)(NR bb ) 2 、-NR bb P(＝O)(OR cc ) 2 、-NR bb P(＝O)(NR bb ) 2 、-P(R cc ) 2 、-P(R cc ) 3 、-OP(R cc ) 2 、-OP(R cc ) 3 、-B(R aa ) 2 、-B(OR cc ) 2 、-BR aa (OR cc ) Alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl is independently substituted with 0, 1, 2, 3, 4 or 5R dd Substituted by groups;
or two geminal hydrogens on a carbon atom are replaced by groups ═ O, ═ S, ═ NN (R) bb ) 2 、＝NNR bb C(＝O)R aa 、＝NNR bb C(＝O)OR aa 、＝NNR bb S(＝O) 2 R aa 、＝NR bb Or as NOR cc Substitution;
R aa each is independently selected from alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or two R aa The groups combine to form a heterocyclyl or heteroaryl ring wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5R dd Substituted by groups;
R bb each independently selected from: hydrogen, -OH, -OR aa 、-N(R cc ) 2 、-CN、-C(＝O)R aa 、-C(＝O)N(R cc ) 2 、-CO 2 R aa 、-SO 2 R aa 、-C(＝NR cc )OR aa 、-C(＝NR cc )N(R cc ) 2 、-SO 2 N(R cc ) 2 、-SO 2 R cc 、-SO 2 OR cc 、-SOR aa 、-C(＝S)N(R cc ) 2 、-C(＝O)SR cc 、-C(＝S)SR cc 、-P(＝O) 2 R aa 、-P(＝O)(R aa ) 2 、-P(＝O) 2 N(R cc ) 2 、-P(＝O)(NR cc ) 2 Alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or two R bb The groups combine to form a heterocyclyl or heteroaryl ring wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5R dd Substituted by groups;
R cc each is independently selected from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl, or two R cc The groups combine to form a heterocyclyl or heteroaryl ring wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5R dd Substituted by groups;
R dd each independently selected from: halogen, -CN, -NO 2 、-N 3 、-SO 2 H、-SO 3 H、-OH、-OR ee 、-ON(R ff ) 2 、-N(R ff ) 2 、-N(R ff ) 3 + X - 、-N(OR ee )R ff 、-SH、-SR ee 、-SSR ee 、-C(＝O)R ee 、-CO 2 H、-CO 2 R ee 、-OC(＝O)R ee 、-OCO 2 R ee 、-C(＝O)N(R ff ) 2 、-OC(＝O)N(R ff ) 2 、-NR ff C(＝O)R ee 、-NR ff CO 2 R ee 、-NR ff C(＝O)N(R ff ) 2 、-C(＝NR ff )OR ee 、-OC(＝NR ff )R ee 、-OC(＝NR ff )OR ee 、-C(＝NR ff )N(R ff ) 2 、-OC(＝NR ff )N(R ff ) 2 、-NR ff C(＝NR ff )N(R ff ) 2 、-NR ff SO 2 R ee 、-SO 2 N(R ff ) 2 、-SO 2 R ee 、-SO 2 OR ee 、-OSO 2 R ee 、-S(＝O)R ee 、-Si(R ee ) 3 、-OSi(R ee ) 3 、-C(＝S)N(R ff ) 2 、-C(＝O)SR ee 、-C(＝S)SR ee 、-SC(＝S)SR ee 、-P(＝O) 2 R ee 、-P(＝O)(R ee ) 2 、-OP(＝O)(R ee ) 2 、-OP(＝O)(OR ee ) 2 Alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl is independently substituted with 0, 1, 2, 3, 4 or 5R gg Substituted by radicals, or two geminal R dd Substituents may combine to form ═ O or ═ S;
R ee is independently selected from the group consisting of alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, and heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5R gg Substituted by groups;
R ff each is independently selected from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl, or two R ff The groups combine to form a heterocyclyl or heteroaryl ring wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5R gg Substituted by groups;
R gg is independently of each other: halogen, -CN, -NO 2 、-N 3 、-SO 2 H、-SO 3 H、-OH、-OC 1-6 Alkyl, -ON (C) 1-6 Alkyl radical) 2 、-N(C 1-6 Alkyl radical) 2 、-N(C 1-6 Alkyl radical) 3 + X - 、-NH(C 1-6 Alkyl radical) 2 + X - 、-NH 2 (C 1-6 Alkyl radical) + X - 、-NH 3 + X - 、-N(OC 1-6 Alkyl) (C 1-6 Alkyl), -N (OH) (C) 1-6 Alkyl), -NH (OH), -SH, -SC 1-6 Alkyl, -SS (C) 1-6 Alkyl), -C (═ O) (C) 1-6 Alkyl), -CO 2 H、-CO 2 (C 1-6 Alkyl), -OC (═ O) (C) 1-6 Alkyl), -OCO 2 (C 1-6 Alkyl), -C (═ O) NH 2 、-C(＝O)N(C 1-6 Alkyl radical) 2 、-OC(＝O)NH(C 1-6 Alkyl), -NHC (═ O) (C) 1-6 Alkyl), -N (C) 1-6 Alkyl) C (═ O) (C) 1-6 Alkyl), -NHCO 2 (C 1-6 Alkyl), -NHC (═ O) N (C) 1-6 Alkyl radical) 2 、-NHC(＝O)NH(C 1-6 Alkyl), -NHC (═ O) NH 2 、-C(＝NH)O(C 1-6 Alkyl), -OC (═ NH) (C) 1-6 Alkyl), -OC (═ NH) OC 1-6 Alkyl, -C (═ NH) N (C) 1-6 Alkyl radical) 2 、-C(＝NH)NH(C 1-6 Alkyl), -C (═ NH) NH 2 、-OC(＝NH)N(C 1-6 Alkyl radical) 2 、-OC(NH)NH(C 1-6 Alkyl), -OC (NH) NH 2 、-NHC(NH)N(C 1-6 Alkyl radical) 2 、-NHC(＝NH)NH 2 、-NHSO 2 (C 1-6 Alkyl), -SO 2 N(C 1-6 Alkyl radical) 2 、-SO 2 NH(C 1-6 Alkyl), -SO 2 NH 2 、-SO 2 C 1-6 Alkyl, -SO 2 OC 1-6 Alkyl, -OSO 2 C 1-6 Alkyl, -SOC 1-6 Alkyl, -Si (C) 1-6 Alkyl radical) 3 、-OSi(C 1-6 Alkyl radical) 3 、-C(＝S)N(C 1-6 Alkyl radical) 2 、C(＝S)NH(C 1-6 Alkyl), C (═ S) NH 2 、-C(＝O)S(C 1-6 Alkyl), -C (═ S) SC 1-6 Alkyl, -SC (═ S) SC 1-6 Alkyl, -P (═ O) 2 (C 1-6 Alkyl), -P (═ O) (C) 1-6 Alkyl radical) 2 、-OP(＝O)(C 1-6 Alkyl radical) 2 、-OP(＝O)(OC 1-6 Alkyl radical) 2 、C 1-6 Alkyl radical, C 1-6 Haloalkyl, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 3 -C 7 Cycloalkyl radical, C 6 -C 10 Aryl radical, C 3 -C 7 Heterocyclic group, C 5 -C 10 A heteroaryl group; or two geminal R gg Substituents may combine to form ═ O or ═ S; wherein, X - Are counter ions.
Exemplary substituents on the nitrogen atom include, but are not limited to: hydrogen, -OH, -OR aa 、-N(R cc ) 2 、-CN、-C(＝O)R aa 、-C(＝O)N(R cc ) 2 、-CO 2 R aa 、-SO 2 R aa 、-C(＝NR bb )R aa 、-C(＝NR cc )OR aa 、-C(＝NR cc )N(R cc ) 2 、-SO 2 N(R cc ) 2 、-SO 2 R cc 、-SO 2 OR cc 、-SOR aa 、-C(＝S)N(R cc ) 2 、-C(＝O)SR cc 、-C(＝S)SR cc 、-P(＝O) 2 R aa 、-P(＝O)(R aa ) 2 、-P(＝O) 2 N(R cc ) 2 、-P(＝O)(NR cc ) 2 Alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or toTwo R radicals attached to the nitrogen atom cc The groups combine to form a heterocyclyl or heteroaryl ring wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl is independently substituted with 0, 1, 2, 3, 4, or 5R dd Is substituted by radicals, and wherein R aa 、R bb 、R cc And R dd As described above.
Dimethylaminoethyl methacrylate (DMAEMA)
Dimethylaminopropyl methacrylamide (DMAPMA)
Dimethylaminoethyl acrylate:
propylenemethylamino ethyl ester (DEAM):
ethylene urea ethoxy methacrylate:
acrylic Acid (AA):
methacrylic acid (MAA):
2-ethacrylic acid (2-EAA);
3, 3-dimethylacrylic acid:
sorbic acid:
hydroxyethyl acrylate (HEA):
hydroxyethyl methacrylate (HEMA):
hydroxypropyl methacrylate:
and (3) testing and characterizing:
self-repair capability evaluation: the specimens were evaluated by vigorously brushing them 10 times at 25 ℃ with a brass brush (manufactured by Suzuwang Co., Ltd.) to thereby cause a marked scratch, and then leaving them at 60 ℃ for 5 minutes. Among them, the score of repairing more than 80% of scratches is excellent, and the score of repairing less than 50% of scratches is poor among the scores of repairing 50% -80%.
Gloss testing: gloss is the gloss value of a protective film coated with a self-healing coating, according to the test standard GBT 8807-1988.
Haze: the haze is the haze value of the protective film coated with the self-repairing coating stuck on the glass substrate, and the test is carried out according to the equipment and the procedure of GB/T2410.
Visible light transmittance: the visible light spectrum range is 380 nm-780 nm. Samples were prepared using glass as the substrate and tested according to the equipment and procedure of GB/T2680.
Elongation at break: coating cracks of the protective film containing the self-repairing coating under the stretching of a mechanical stretching machine are observed, a stress-strain curve is obtained under the constant-speed force application, the elongation at break value is calculated, and the test is carried out according to the method and the device of GB/T1040.1-2006 and GB/T1040.3-2006.
Stain resistance chooses for use morning light black oily marking pen (specifically be morning light double-jie pen black) as the pollutant, writes respectively on scribbling the protection film of selfreparing coating, washs with the cotton flannel that has the alcohol after one minute, notes the vestige condition, and the vestige condition divide into: none, small amount, large amount. The test method refers to a scrawling resistance test method in appendix A of the scrawling-preventing and pasting-resisting coating for the building JG/T304-2011.
In this context, a range of values from one value to another is a general expression avoiding any recitation of all values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the invention will be understood to cover all modifications and variations of this invention provided they come within the scope of the appended claims.
Ratios, proportions, parts, percentages herein are by weight and all temperatures are in degrees Celsius unless otherwise indicated.
EXAMPLE A preparation of self-healing coating
1) Adding an initiator such as Azobisisoheptonitrile (AVBN) into an organic solvent under the protection of nitrogen, and simultaneously adding a monomer containing nitrogen, a monomer containing carboxyl, a monomer containing hydroxyl and other common monomers, wherein the mass fraction of the organic solvent is 20-90%, and the mass fraction of the initiator is 1-5%; the mass fraction of the monomer containing nitrogen element is 1-10%; 1-20% of monomer containing carboxyl, 2-15% of monomer containing hydroxyl and 11-39% of other common monomers;
Specifically, the amounts of the organic solvent, the monomer containing nitrogen, the monomer containing carboxyl, the monomer containing hydroxyl and other common monomers are shown in table one;
(2) under the protection of nitrogen, continuously stirring, and reacting for 8-48 hours at a set temperature to prepare synthetic resin containing nitrogen elements with trivalent bonds and carboxyl; wherein the set temperature is 70 ℃ and the reaction time is 5 hours.
Synthetic resin
| Raw materials | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 |
| AVBN | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
| Ethyl acetate | 56.00 | 56.00 | 56.00 | 56.00 | 56.00 | 56.00 | 56.00 | 56.00 | 56.00 | 56.00 | 56.00 |
| Methacrylic acid methyl ester | 11.00 | 17.00 | 15.00 | 15.00 | 15.00 | 15.00 | 15.00 | 15.00 | 15.00 | 15.00 | 15.00 |
| Caprolactone-modified acrylic esters | 20.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 |
| Hydroxyethyl methacrylate | 5.50 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
| Methacrylic acid butyl ester | 2.00 | 8.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
| Methacrylic acid | 1.50 | 3.00 | 4.00 | 4.00 | 4.00 | ||||||
| Acrylic acid | 4.00 | 4.00 | 4.00 | ||||||||
| Dimethylacrylic acid | 4.00 | 4.00 | 4.00 | ||||||||
| DMAEMA | 5.00 | 5.00 | 5.00 | ||||||||
| DMAPMA | 5.00 | 5.00 | 5.00 | ||||||||
| DEAM | 5.00 | 5.00 | 5.00 | ||||||||
| Total amount of | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
Note: the addition amounts of the components in the table are mass percent
(3) And (3) adding a curing agent into the resin synthesized in the step (2) to prepare the self-repairing coating.
The molar contents of hydroxyl groups were calculated according to the formulations of examples and comparative examples, the number of moles of isocyanate groups was determined according to the molar content of hydroxyl groups and curing was carried out (molar ratio of hydroxyl group: isocyanate group: 0.95-1.05). Two curing agents were used in this example: HDI trimer curing agent and HXDI trimer curing agent, the HDI trimer curing agent is Desmodur N3600 of German Corseki group, and the HXDI trimer curing agent is TAKENATE D-120N of Japan Mitsui chemical company.
In the following tables, the amount of the synthetic resin added is 1, and the amount of the curing agent added is as shown in tables 1.1 and 1.2, and the unit in the tables is "%".
Wherein the synthetic resins used in comparative example 1A and comparative example 1B are all the synthetic resins prepared in comparative example 1; the synthetic resins used in comparative examples 2A and 2B were all the synthetic resins prepared in comparative example 2 of the table; the synthetic resins used in example 1A and comparative example 1B are all the synthetic resins prepared in example 1; the synthetic resins used in example 1A and example 1B are all the synthetic resins prepared in example 1; the synthetic resins used in example 2A and example 2B are all the synthetic resins prepared in example 2 of the table; the synthetic resins used in example 3A and example 3B are all the synthetic resins prepared in example 3 of the table; the synthetic resins used in example 4A and example 4B are all the synthetic resins prepared in example 4; the synthetic resins used in example 5A and example 5B are all the synthetic resins prepared in example 5; the synthetic resins used in example 6A and example 6B are all the synthetic resins prepared in example 6; the synthetic resins used in example 7A and example 7B were all the synthetic resins prepared in example 7; the synthetic resins used in example 8A and example 8B are all the synthetic resins prepared in example 8; the synthetic resins used in example 9A and example 9B are each the one prepared in example 9.
TABLE 1.1
| Starting materials | Comparative example 1A | Comparative example 1B | Comparative example 2A | Comparative example 2B | Example 1A | Example 1B | Example 2A | Example 2B | Example 3A | Example 3B | Example 4A | Example 4B |
| Synthetic resin addition | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| DesmodurN 3600 | 16.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | ||||||
| TAKENATED-120N | 8.00 | 5 | 5 | 5 | 5 | 5.00 | ||||||
| Ethyl acetate | 32.00 | 16.00 | 20.00 | 10 | 20.00 | 10 | 20.00 | 10 | 20.00 | 10 | 20.00 | 10.00 |
TABLE 1.2
| Raw materials | Example 5A | Example 5B | Example 6A | Example 6B | Example 7A | Example 7B | Example 8A | Example 8B | Example 9A | Example 9B |
| Synthetic resin addition | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
| DesmodurN 3600 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | |||||
| TAKENATED-120N | 5 | 5 | 5 | 5.00 | 5.00 | |||||
| Ethyl acetate | 20.00 | 10 | 20.00 | 10 | 20.00 | 10 | 20.00 | 10.00 | 20.00 | 10.00 |
Note: the addition amounts in the table are mass fractions
EXAMPLE two preparation of self-healing coatings
The self-repairing coating prepared in the first embodiment (tables 1.1 and 1.2) is coated on a tpu substrate of Argotech by a wire bar, the thickness of the coating is controlled to be 10-15 micrometers, the coating is dried at 90 ℃ for 2 minutes, and the coating is aged at 50 ℃ for 48 hours to obtain the self-repairing coating.
The self-healing coatings above were evaluated according to the test methods described above and the results are shown in tables 2.1 and 2.2.
TABLE 2.1
| Test items | Comparative example 1A | Comparative example 1B | Comparative example 2A | Comparative example 2B | Example 1A | Example 1B | Example 2A | Example 2B | Example 3A | Example 3B | Example 4A | Example 4B |
| Self-repair capability | Is excellent in | In | Difference (D) | Difference (D) | Is excellent in | In | Is excellent in | In | Is excellent in | In | Is excellent in | In |
| Elongation at Break (%) | 108.00 | 65.00 | 330.00 | 270.00 | 490.00 | 405.00 | 520.00 | 418.00 | 550.00 | 450.00 | 408.00 | 375.00 |
| Gloss of | 95.00 | 96.00 | 96.00 | 98.00 | 95.00 | 98.00 | 97.00 | 100.00 | 96.00 | 99.00 | 101.00 | 106.00 |
| Haze (%) | 1.20 | 0.10 | 1.10 | 0.10 | 0.30 | 0.10 | 0.20 | 0.10 | 0.20 | 0.10 | 0.50 | 0.10 |
| Light transmittance (%) | 90.20 | 91.00 | 91.20 | 91.8 | 91.20 | 91.4 | 90.10 | 90.9 | 90.90 | 91.5 | 91.40 | 91.70 |
| Stain resistance (mark) | Small amount of | Is free of | A large number of | Is free of | Small amount of | Is free of | Small amount of | Is free of | Small amount of | Is free of | Is free of | Is free of |
TABLE 2.2
| Test items | Example 5A | Example 5B | Example 6A | Example 6B | Example 7A | Example 7B | Example 8A | Example 8B | Example 9A | Example 9B |
| Self-repair capability | Is excellent in | Is excellent in | Is excellent in | Is excellent in | Is excellent in | In | Is excellent in | Is excellent in | Is excellent in | In |
| Elongation at Break (%) | 455.00 | 380.00 | 490.00 | 405.00 | 590.00 | 448.00 | 455.00 | 395.00 | 585.00 | 475.00 |
| Gloss of | 101.00 | 107.00 | 95.00 | 101.00 | 97.00 | 108.00 | 99.00 | 106.00 | 101.00 | 107.00 |
| Haze (%) | 0.40 | 0.20 | 0.20 | 0.10 | 0.30 | 0.10 | 0.20 | 0.10 | 0.30 | 0.10 |
| Light transmittance (%) | 91.40 | 91.6 | 91.50 | 91.5 | 91.50 | 91.7 | 91.70 | 91.7 | 91.40 | 91.70 |
| Stain resistance (mark) | Small amount of | Is free of | Small amount of | Is free of | Small amount of | Is free of | Is free of | Is free of | Small amount of | Is free of |
From the test results, the comparative example 1A has excellent self-repairing capability but has low elongation at break and cannot meet the requirement of the TPU protective film industry, and the comparative example 2A has improved elongation at break but has poor self-repairing capability and cannot meet the requirement of the TPU protective film industry.
It can be seen from examples 1A to 9B that when nitrogen having a triple bond is introduced and quaternized by a carboxyl group, the coating has good self-healing ability while maintaining high elongation at break.
In addition, the coating of the embodiment simultaneously reduces the haze, and the partial embodiment also improves the glossiness.
In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.
Claims (21)
1. Self-repairing coating paint, which is characterized by comprising: the monomer containing the nitrogen element with the trivalent bond, the monomer containing the carboxyl and the monomer containing the hydroxyl all contain unsaturated bonds;
the preparation method of the self-repairing coating comprises the following steps:
(1) adding an initiator into a solvent under the protection of inert atmosphere, simultaneously adding a nitrogen element monomer containing a trivalent bond, a monomer containing a carboxyl group and a monomer containing a hydroxyl group, and reacting for 8-48 hours at a set temperature to prepare synthetic resin containing the nitrogen element containing the trivalent bond and the carboxyl group;
(2) adding an auxiliary agent into the synthetic resin, wherein the auxiliary agent is an isocyanate curing agent, or an isocyanate curing agent and a solvent, or an isocyanate curing agent and a flatting agent, or an isocyanate curing agent, a solvent and a flatting agent, and preparing the self-repairing coating.
2. The self-healing coating of claim 1, wherein the trivalent nitrogen containing monomer is represented by formula (I):
wherein R is 1 、R 2 、R 3 Each independently is hydrogen, halogen, carboxyl, C 1-10 Alkyl radical, C 2-10 Alkenyl radical, C 2-10 Alkynyl, NR 00 R 01 、-COR 00 、-SO 2 R 00 、-SOR 00 、-C(O)OR 00 、-OC(O)R 00 、-CONR 00 、-NR 00 COR 00 、NR 00 CONR 00 、SONR 00 、NR 00 SOR 00 、SO 2 NR 00 、NR 00 SO 2 R 00 、C 3-12 Cycloalkyl, 4-to 12-membered heterocyclyl, C 6-16 Aryl or 5 to 14 membered heteroaryl;
R 4 、R 5 each independently is halogen, carboxyl, C 1-10 Alkyl radical, C 2-10 Alkenyl radical, C 2-10 Alkynyl, NR 00 R 01 、-COR 00 、-SO 2 R 00 、-SOR 00 、-C(O)OR 00 、-OC(O)R 00 、-CONR 00 、-NR 00 COR 00 、NR 00 CONR 00 、SONR 00 、NR 00 SOR 00 、SO 2 NR 00 、NR 00 SO 2 R 00 、C 3-12 Cycloalkyl, 4-to 12-membered heterocyclyl, C 6-16 Aryl or 5 to 14 membered heteroaryl; or, R 4 、R 5 Together with the nitrogen atom to which they are attached, form a 3-8 membered heterocyclyl;
L 1 、L 2 、L 3 each independently is a chemical bond, C 1-10 Alkylene radical, C 2-10 Alkenylene radical, C 2-10 Alkynylene, NR 00 R 01 Acyl, sulfonyl, sulfinyl, C (O) O, OC (O), CONR 00 、NR 00 CO、NR 00 CONR 00 、SONR 00 、NR 00 SO、SO 2 NR 00 、NR 00 SO 2 、C 3-12 Cycloalkyl, 4-to 12-membered heterocyclyl, C 6-16 Aryl or 5 to 14 membered heteroaryl;
wherein R is 00 、R 01 Each independently is hydrogen, C 1-3 Alkyl or amino.
3. The self-healing coating of claim 1, wherein the carboxyl-containing monomer is represented by formula (II):
wherein R is 1 、R 2 、R 3 Each independently is hydrogen, halogen, carboxyl, C 1-10 Alkyl radical, C 2-10 Alkenyl radical, C 2-10 Alkynyl, NR 00 R 01 、-COR 00 、-SO 2 R 00 、-SOR 00 、-C(O)OR 00 、-OC(O)R 00 、-CONR 00 、-NR 00 COR 00 、NR 00 CONR 00 、SONR 00 、NR 00 SOR 00 、SO 2 NR 00 、NR 00 SO 2 R 00 、C 3-12 Cycloalkyl, 4-to 12-membered heterocyclyl, C 6-16 Aryl or 5 to 14 membered heteroaryl;
L 1 、L 2 、L 3 each independently is a chemical bond, C 1-10 Alkylene radical, C 2-10 Alkenylene radical, C 2-10 Alkynylene, NR 00 R 01 Acyl, sulfonyl, sulfinyl, C (O) O, OC (O), CONR 00 、NR 00 CO、NR 00 CONR 00 、SONR 00 、NR 00 SO、SO 2 NR 00 、NR 00 SO 2 、C 3-12 Cycloalkyl, 4-to 12-membered heterocyclyl, C 6-16 Aryl or 5 to 14 membered heteroaryl;
R 00 、R 01 each independently is hydrogen, C 1-3 Alkyl or amino.
4. The self-healing coating of claim 2 or 3, wherein R is 1 、R 2 、R 3 Each independently is hydrogen, methyl, ethyl, propyl or isopropyl; said R is 4 、R 5 Each independently is methyl or ethyl.
5. The self-healing coating of claim 2 or claim 3, wherein L in formula (I) 1 、L 2 、L 3 Each independently is a bond, C (O) O, OC (O), C (O) NH, NHC (O), methylene, ethylene or propylene;
l in the formula (II) 1 、L 2 、L 3 Each independently a bond, methylene, ethylene or vinylene.
6. The self-healing coating of claim 1, wherein the trivalent nitrogen containing monomer is selected from the group consisting of: at least one of dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate or ethyleneurea ethoxy acrylate.
7. The self-healing coating of claim 1, wherein the carboxyl-containing monomer is selected from the group consisting of: at least one of acrylic acid, methacrylic acid, 2-ethacrylic acid, 3-dimethylacrylic acid, or sorbic acid.
8. The self-healing coating of claim 1, wherein the hydroxyl-containing monomer is selected from at least one of hydroxyl acrylates or caprolactone-modified methacrylates.
9. The self-healing coating of claim 8, wherein the hydroxyl-containing monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
10. The self-healing coating of claim 1, wherein the initiator is selected from at least one of an organic peroxide, an azo compound, a photoinitiator, or a cationic initiator.
11. The self-healing coating of claim 10, wherein the initiator is selected from the group consisting of: at least one of dibenzoyl peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide, azobisisobutyronitrile, azobisisoheptonitrile, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, arylcyclopentadienyl iron hexafluorophosphate or sulfonium hexafluoroantimonate.
12. The self-healing coating of claim 1, wherein the isocyanate curing agent includes, but is not limited to, isophorone diisocyanate, IPDI dimer or polymer, toluene diisocyanate, TDI dimer or polymer, diphenylmethane diisocyanate, MDI dimer or polymer, dicyclohexylmethane-4, 4-diisocyanate, H 12 MDI dimer or polymer, hexamethylene diisocyanate, HDI dimer or polymer, m-xylylene diisocyanate, XDI dimer or polymer, hydrogenated xylylene diisocyanate, HXDI dimer or polymer.
13. The self-healing coating of claim 12, wherein the isocyanate curing agent is an HDI trimer curing agent.
14. The self-healing coating of claim 1, wherein the solvent includes, but is not limited to, acetone, ethyl acetate, DMF, butanone, tetrahydrofuran, xylene, toluene, dichloromethane, butyl acetate.
15. The self-healing coating of claim 1, further comprising other common monomers including, but not limited to, at least one of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, isooctyl methacrylate, isodecyl methacrylate, tridecyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl methacrylate, and stearyl acrylate.
16. The method of making a self-healing coating of claim 1, comprising the steps of:
(1) adding an initiator into a solvent under the protection of inert atmosphere, simultaneously adding a nitrogen element monomer containing a trivalent bond, a monomer containing a carboxyl group and a monomer containing a hydroxyl group, and reacting for 8-48 hours at a set temperature to prepare synthetic resin containing the nitrogen element containing the trivalent bond and the carboxyl group;
(2) adding an auxiliary agent into the synthetic resin, wherein the auxiliary agent is an isocyanate curing agent, or an isocyanate curing agent and a solvent, or an isocyanate curing agent and a flatting agent, or an isocyanate curing agent, a solvent and a flatting agent, and preparing the self-repairing coating.
17. The method of claim 16,
in the step (2), the synthetic resin in the step (1) is added with the auxiliary agent and is heated, and the set temperature is 20-100 ℃ during heating.
18. A self-healing coating, characterized in that it is produced by drying and aging a self-healing coating according to any one of claims 1 to 15, or by drying and aging a coating produced by the method according to claim 16 or 17.
19. The self-healing coating of claim 18, wherein the coating is dried at a temperature of 35 to 110 ℃ for a time of 2 to 10 minutes; the aging temperature is 10-60 deg.C, and the aging time is 1-7 days.
20. A film comprising a substrate and the self-healing coating of claim 18 or 19 disposed on a surface of the substrate.
21. A device having a surface coated with a membrane according to claim 20.
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