CN116376008A - A kind of coating additive and its preparation method and application - Google Patents
A kind of coating additive and its preparation method and application Download PDFInfo
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- CN116376008A CN116376008A CN202211732900.6A CN202211732900A CN116376008A CN 116376008 A CN116376008 A CN 116376008A CN 202211732900 A CN202211732900 A CN 202211732900A CN 116376008 A CN116376008 A CN 116376008A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/94—Oxygen atom, e.g. piperidine N-oxide
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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
- C09D7/65—Additives macromolecular
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
本发明涉及高分子技术领域，具体涉及一种涂料助剂及其制备方法和应用。所述涂料助剂由聚醚衍生物骨架和至少一种衍生于通式A的化合物；其中，Ra选自氢、‑烷基、‑亚烷基‑OH、‑O‑Rb、亚烷基‑O‑Rb、被一个或多个杂原子间隔的烷基、被一个或多个第一间隔基团单独或组合间隔的烷基、被一个或多个第一取代基取代的烷基、被一个或多个第一取代基取代杂烷基。本发明的涂料助剂可以有效改变涂料的润湿性能，具有高效的防老化性能，且制备方法更加简洁，低碳环保。The invention relates to the technical field of polymers, in particular to a coating additive and its preparation method and application. The coating additive is composed of a polyether derivative skeleton and at least one compound derived from the general formula A; wherein, R a is selected from hydrogen, -alkyl, -alkylene-OH, -O-R b , alkylene Group-O-R b , alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more first spacer groups alone or in combination, alkyl substituted by one or more first substituents , heteroalkyl substituted with one or more first substituents. The paint additive of the invention can effectively change the wetting performance of the paint, has high-efficiency anti-aging performance, and has a simpler preparation method, and is low-carbon and environment-friendly.
Description
Technical Field
The invention relates to the technical field of polymers, in particular to a coating auxiliary agent and a preparation method and application thereof.
Background
The paint is a continuous film which can be coated on the surface of an object to protect or decorate the object, and is usually mainly composed of resin, oil and emulsion, and pigment, filler, auxiliary agent and the like are added in the preparation process, and are required to be dissolved in an organic solvent or water to be prepared into viscous liquid.
The service life of the coating is different according to different products, the modified organic silicon resin emulsion adopted by the liquid marble texture product is taken as a base material, and the special coating technology is adopted to coat various color paints into colloidal aqueous color particles, so that the colloidal aqueous color particles are uniformly and stably dispersed in an aqueous solvent. The service life of the paint is about 15 years.
The film forming mechanism of the paint is divided into two types of physical film forming and chemical film forming. The physical film forming mechanism is a film forming form of a coating material, which is generally plastic, by evaporating or hot-melting a solvent in the coating material to obtain a dried coating film. The choice of solvent is particularly important in order to obtain a smooth and flat coating film, if the solvent evaporates too rapidly, the concentration is rapidly increased, the fluidity of the coating surface is reduced, and thus the coating surface is uneven, and in addition, the molecular morphology of the polymer is affected by the difference of the solvents, thereby affecting the microstructure of the coating film.
The chemical film forming is to coat soluble polymer with low molecular weight on the surface of the base material, and to crosslink or increase the molecular weight of the coating after heating to form tough film. For example: the drying oil and alkyd resin form a film through the action of oxygen, amino resin and hydroxyl-containing alkyd resin, polyester and acrylic resin form a film through the ether exchange reaction, and epoxy resin and polyamine cross-linking form a film and the like are formed by using a chemical reaction mode. The early paint is also called paint because vegetable oil is used as the main raw material in most cases. Synthetic resins have now replaced vegetable oils and are therefore known as coatings. The paint is not liquid, and the powder paint is a large class of paint varieties. The paint belongs to organic chemical polymer material, and the formed film belongs to polymer compound type. According to the classification of modern chemical products, the coating belongs to fine chemical products. Modern coatings are becoming a kind of multifunctional engineering materials gradually, and are an important industry in the chemical industry. The effects are mainly four points: protecting, decorating, masking defects and other special functions of the product, and improving the value of the product. Classifying the usage positions on a building: the paint is divided into an inner wall paint, an outer wall paint, a ground paint, a door and window paint and a ceiling paint. Classifying according to the use functions: can be divided into common paint and special functional building paint, such as fireproof paint, waterproof paint, mildew-proof paint, road marking paint, etc. The color effect is classified according to the use, such as metallic paint, natural color paint, also called solid color paint, transparent varnish, etc.
The existing coating product is easy to embrittle after long-term use, and can generate problems of cracking and yellowing or strength reduction when being coated on the surface of the product, or various surface defects such as cracks, pinholes, bubbles, scratches and the like are easy to generate in the coating process, so that the use value of the coating is influenced.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a coating auxiliary agent, and a preparation method and application thereof. The coating auxiliary agent can effectively change the wettability of the coating, has high-efficiency anti-aging performance, and has the advantages of simpler preparation method, low carbon and environmental protection.
The invention provides a coating auxiliary agent, which comprises a polyether derivative skeleton and at least one compound with a general formula A, wherein the compound is prepared by polymerization reaction;
the general formula A has the following structure:
a general formula A;
wherein R is a Selected from hydrogen, -alkyl, -alkylene-OH, -O-R b alkylene-O-R b An alkyl group interrupted by one or more heteroatoms, an alkyl group interrupted by one or more first spacer groups alone or in combination, an alkyl group substituted by one or more first substituents, a heteroalkyl group substituted by one or more first substituents.
The first spacer group is selected from a combination of one or more of the following groups: -C (=o) O-, amine, -OC (=o) O-, alkenyl, alkynyl, -C (=s) O-, amide groups, urea groups, arylene, heteroalkylene, heteroarylene;
The first substituent is selected from one or more of the following groups: hydrogen, hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkoxycarbonyl, heteroarylcarbonyl, heteroaryloxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, arylacyloxy, cycloalkyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-S, alkyl interrupted by one or more-C (=o) -S, alkyl interrupted by one or more-C (=s) O-S, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkylene interrupted by one or more alkyl interrupted by one or more heteroaryl groups;
p is
A degree of polymerization of the repeating units, p being 0 or 1; when p is 0, the repeating unit +.>
Is a single bond;
the o is
A degree of polymerization of the repeating units, o being an integer from 1 to 15 (e.g., o is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15);
in one example, the R b A combination of one or more selected from the following groups: alkyl, -cycloalkyl, -C (=o) R c A heterocycloalkyl group, an alkyl group interrupted by one or more heteroatoms, an alkyl group interrupted by one or more first spacer groups alone or in combination, an alkyl group substituted by one or more first substituents, a heteroalkyl group substituted by one or more first substituents, a cycloalkyl group substituted by one or more first substituents, -a phenyl group.
In one example, the R c A combination of one or more selected from the following groups: alkyl, cycloalkyl, phenyl, heterocycloalkyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more first spacer groups alone or in combination, alkyl substituted by one or more first substituents, heteroalkyl substituted by one or more first substituents, cycloalkyl substituted by one or more first substituents.
In one example, the o is
A degree of polymerization of the repeating units, o being an integer from 1 to 11, including but not limited to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11;
specifically, the general formula A includes the following structure:
where i is an integer from 1 to 18 (e.g., may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18).
In one example, the polyether derivative backbone is a compound comprising formula B;
the general formula B has the following structure:
a general formula B;
wherein,,
n 1 、n 2 ……n m an integer of 0 to 200 for the degree of polymerization of each repeating unit, (e.g., may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 50, 100, 150, or 200);
said n 1 +n 2 +……+n m ≥1；
When n is 1 、n 2 ……n m When one or more of them is 0, the repeating unit is a single bond;
m is an integer from 1 to 20 (e.g., may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20);
R 1 、R 2 、R 3 ……R m are identical or different substituents;
Rt 1 、Rt 2 are identical or different end-capping groups.
The R is 1 、R 2 、R 3 ……R m Independently selected from one or more of the following groups: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, phenyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups Group-interrupted alkyl, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by a combination of the above spacer groups, alkyl substituted by one or more second substituents, heteroalkyl substituted by one or more second substituents, cycloalkyl substituted by one or more second substituents, or-a benzene ring;
the second substituent is selected from the group consisting of one or more of the following: hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aralkoxy, heteroarylacyloxy, cycloalkyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more alkenyl groups, alkylene interrupted by one or more alkyl interrupted by one or more heteroaryl groups;
Preferably, the second substituent is selected from the group consisting of one or more of the following: hydroxy, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heterocycloalkyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkyloyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more-C (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more alkylene groups, alkyl interrupted by a combination of the above;
the Rt is 1 、Rt 2 Independently selected from one or more of the following: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, phenyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkylene groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by a combination of the above spacer groups, alkyl substituted by one or more third substituents, heteroalkyl substituted by one or more third substituents, cycloalkyl substituted by one or more third substituents;
The third substituent is selected from the group consisting of one or more of the following: hydroxyl, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aralkoxy, heteroarylacyloxy, cycloalkyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more-C (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more alkenyl groups, alkylene interrupted by one or more alkyl interrupted by one or more heteroaryl groups.
In one embodiment, one or more of the formulae B represents the same or different
And/or the number of the groups of groups,
representing a single bond.
Further, the general formula B is selected from the following structures:
in a second aspect the present invention provides a process for preparing a coating adjuvant according to the first aspect of the present invention, the process comprising polymerisation of a compound of formula A and a compound of formula B; optionally, the polymerization is carried out in the presence of a catalyst. Further, the polymerization reaction is carried out in a solvent selected from the group consisting of: one or more of tetrahydrofuran, 2-methyltetrahydrofuran, halogenated hydrocarbons, acetonitrile, propionitrile, butyronitrile, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, dimethyl sulfoxide, N-dimethylamide, diphenyl ether and water;
preferably, the halogenated hydrocarbon comprises: one or more of dichloromethane, dichloroethane or carbon tetrachloride;
preferably, the aromatic hydrocarbon comprises: one or more of benzene, toluene, xylene, chlorobenzene or dichlorotoluene;
preferably, the aliphatic hydrocarbon comprises: one or more of petroleum ether, n-hexane, n-heptane, cyclohexane and n-octane;
preferably, the alcohol comprises: one or more of methanol, ethanol, propanol, ethylene glycol, diethylene glycol, ethylene glycol methyl ether.
More preferably, the solvent is selected from one or more of water, toluene, benzene, chlorobenzene, xylene, cyclohexane, n-heptane or dichloromethane.
Particularly preferably, the solvent is selected from one or more of water, benzene, xylene or chlorobenzene.
Further, the catalyst is an alkaline catalyst;
preferably, the basic catalyst is selected from the group consisting of one or more of the following: k (K) 2 CO 3 、KOH、NaH、NaOMe、KO T Bu, rhodium complex, ruthenium complex, clay supported nickel bromide or ionic liquid;
more preferably, the molar ratio of the catalyst to the compound of formula a is (1:0.5) - (1:2), (e.g., the molar ratio may be 2:1, 1:1 or 1:2);
particularly preferably, the polymerization is a michael addition reaction;
particularly preferably, the reaction temperature of the polymerization reaction is 0 to 150 ℃ (including, but not limited to, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, or 150 ℃), preferably 0 to 80 ℃, more preferably 0 to 40 ℃.
In a third aspect the present invention provides a composition comprising a coating adjuvant according to the first aspect of the present invention and one or more organic substances that are sensitive to light, heat or oxidation; or, the coating adjuvant prepared by the method of the second aspect of the invention and one or more organic substances sensitive to light, heat or oxidation.
In one example, the amount of the coating aid may be 0.01 to 5wt% based on the weight of the standard formulation, i.e., the total weight of the composition.
In a fourth aspect, the present invention provides the use of a coating adjuvant according to the first aspect of the invention or a composition according to the third aspect of the invention in the preparation of a light stabilizer, in the preparation of a wetting agent and in the surface of an article.
Specifically, the product is an industrial product or a non-industrial product which needs to be coated with the coating;
preferably, the industrial product is a polymer material product.
Through the technical scheme, compared with the prior art, the invention has at least the following advantages:
(1) The hardness, gloss, impact test and solvent resistance test of the coating film surface added with the coating auxiliary agent are not weaker than those of the coating film surface added with the commercialized auxiliary agent, and meanwhile, the weather resistance of the coating film surface added with the coating auxiliary agent is obviously stronger than that of the commercialized auxiliary agent, so that the anti-aging performance of the coating can be obviously improved;
(2) The coating auxiliary agent can be prepared into a coating auxiliary agent with low alkalinity by selecting a raw material with a specific NOR-amine ether structure;
(3) The preparation method of the coating auxiliary agent is simpler, and is low-carbon and environment-friendly.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The inventors of the present invention found that by incorporating
And contain->
The raw materials of the (C) are reacted to generate the high molecular weight coating auxiliary agent. The novel coating auxiliary agent contains both hydrophilic ether-O-groups and lipophilic ester-C (=O) -O groups, and can effectively change the wettability of the coating by adding the novel coating auxiliary agent into the coating.
The inventor of the invention also introduces a piperidine group with anti-photoaging property, so that the coating auxiliary agent has high-efficiency anti-aging property; coating aids having low alkalinity can be prepared by selecting specific starting materials containing NOR amine ether structures.
The first aspect of the invention provides a coating auxiliary agent, which is prepared by polymerization reaction of a polyether derivative skeleton and at least one compound with a general formula A;
the general formula A has the following structure:
a general formula A;
wherein R is a Selected from hydrogen, -alkyl, -alkylene-OH, -O-R b alkylene-O-R b An alkyl group interrupted by one or more heteroatoms, an alkyl group interrupted by one or more first spacer groups alone or in combination, an alkyl group substituted by one or more first substituents, a heteroalkyl group substituted by one or more first substituents.
In one example, the first spacer group is selected from a combination of one or more of the following groups: -C (=o) O-, amine, -OC (=o) O-, alkenyl, alkynyl, -C (=s) O-, amide groups, urea groups, arylene, heteroalkylene, heteroarylene.
In one example, the first substituent is selected from the group consisting of hydrogen, hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkoxycarbon, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aralkoxy, heteroarylacyloxy, cycloalkyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-S, alkyl interrupted by one or more-C (=o) -S, alkyl interrupted by one or more-C (=s) O-S, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more aryl groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkylene groups, alkylene interrupted by one or more alkylene groups, interrupted by one or more alkylene groups.
In one example, p is
A degree of polymerization of the repeating units, p being 0 or 1;
the o is
The degree of polymerization of the repeating units, o being an integer from 1 to 15;
in one example, the R b A combination of one or more selected from the following groups: alkyl, -cycloalkyl, -C (=o) R c A heterocycloalkyl group, an alkyl group interrupted by one or more heteroatoms, an alkyl group interrupted by one or more first spacer groups alone or in combination, an alkyl group interrupted by one or more first substituentsSubstituted alkyl, heteroalkyl substituted with one or more first substituents, cycloalkyl substituted with one or more first substituents, -phenyl.
In one example, the R c Selected from the group consisting of alkyl, cycloalkyl, phenyl, heterocycloalkyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more first spacer groups, alkyl substituted by one or more first substituents, heteroalkyl substituted by one or more first substituents, cycloalkyl substituted by one or more first substituents, alone or in combination.
In one example, the o is
The degree of polymerization of the repeating units, o is an integer from 1 to 15, preferably an integer from 1 to 11 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11).
In one example, formula a includes the following structure:
where i is an integer from 1 to 18 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18).
In one example, the polyether derivative backbone comprises a compound of formula B;
the general formula B has the following structure:
and a general formula B.
In one example, n 1 、n 2 ……n m For the degree of polymerization of the individual repeating units, an integer of 0 to 200 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15. 16, 17, 18, 19, 20, 50, 100, 150 or 200);
in one example, the n 1 +n 2 +……+n m ≥1。
In one example, when n 1 、n 2 … … or n m When any one of them is 0, the repeating unit is a single bond.
In one example, m is an integer from 1-20 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20).
In one example, R 1 、R 2 、R 3 ……R m Are identical or different substituents;
in one example, rt 1 、Rt 2 Are identical or different end-capping groups.
In one example, R 1 、R 2 、R 3 ……R m Are the same substituents.
In one example, R 1 、R 2 、R 3 ……R m Are different substituents.
In one example, rt 1 、Rt 2 Are the same end capping groups.
In one example, rt 1 、Rt 2 Are different end capping groups.
In one example, rt 1 、Rt 2 May be any suitable end capping group.
In one example, rt 1 、Rt 2 May bear potentially reactive groups or be inert end capping groups.
In one example, rt 1 、Rt 2 Independently selected from one or more of the following groups: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, phenyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (=s) O-mA blocked alkyl group, an alkyl group interrupted by one or more amide groups, an alkyl group interrupted by one or more urea groups, an alkyl group interrupted by one or more arylene groups, an alkyl group interrupted by one or more heteroalkylene groups, an alkyl group interrupted by one or more heteroarylene groups, an alkyl group interrupted by a combination of the above spacer groups, an alkyl group substituted by one or more third substituents, a heteroalkyl group substituted by one or more third substituents, a cycloalkyl group substituted by one or more third substituents;
The third substituent is selected from the group consisting of one or more of the following: hydroxyl, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aralkoxy, heteroarylacyloxy, cycloalkyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more-C (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more alkenyl groups, alkylene interrupted by one or more alkyl interrupted by one or more heteroaryl groups.
In one example, rt 1 、Rt 2 The substituents in the selected groups are selected from the group consisting of: hydroxy, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heterocycloalkyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkylacyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonylAroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more-C (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more alkylene groups, alkyl interrupted by a combination of the above spacer groups.
In one example, rt 1 、Rt 2 Independently selected from hydrogen, C 1 -C 4 Is a hydrocarbon group.
In one example, R 1 、R 2 、R 3 ……R m Independently selected from one or more of the following groups: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, phenyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkylene groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by a combination of the above spacer groups, alkyl substituted by one or more second substituents, heteroalkyl substituted by one or more second substituents, cycloalkyl substituted by one or more second substituents, or a benzene ring;
The second substituent is selected from one or more of the following groups: hydroxyl, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aralkoxy, heteroarylacyloxy, cycloalkyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more-C (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more alkenyl groups, alkylene interrupted by one or more alkyl interrupted by one or more heteroaryl groups.
More specifically, the second substituent is selected from the group consisting of one or more of the following: hydroxyl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heterocycloalkyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkyloyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more-C (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more alkylene groups, alkyl interrupted by a combination of the above.
In one embodiment, in formula B- -represents one or more of the same or different
In one example, - - - - - - - - - - - - -, represents a single bond.
In one example, when m=4, the list
In one example, when m=5, it represents
In one embodiment, m is 1 and the formula B has the following structure:
B-1。
in one embodiment, the general formula B, where m is 2, has the following structure:
B-2。
in one example, the compound derived from formula B is selected from the following structures:
the inventors of the present invention have found that the coating adjuvant of the present invention has a wetting and light stabilizing effect in the coating.
In a second aspect the present invention provides a process for preparing a coating adjuvant according to the first aspect of the invention comprising the polymerisation of a compound of formula A and a compound of formula B.
Optionally, the polymerization is carried out in the presence of a catalyst.
The polymerization may or may not be carried out in a solvent. In one example, the polymerization reaction is performed in a solvent.
In one example, the solvent may be selected from one or more of tetrahydrofuran, 2-methyltetrahydrofuran, halogenated hydrocarbons (such as dichloromethane, dichloroethane, carbon tetrachloride, etc.), acetonitrile, propionitrile, butyronitrile, aromatic hydrocarbons (such as benzene, toluene, xylene, chlorobenzene, dichlorotoluene, etc.), aliphatic hydrocarbons (such as petroleum ether, N-hexane, N-heptane, cyclohexane, N-octane, etc.), alcohols (such as methanol, ethanol, propanol, ethylene glycol, diethylene glycol, ethylene glycol methyl ether), dimethyl sulfoxide, N-dimethylamide, diphenyl ether, water.
In one example, the solvent is selected from one or more of water, toluene, benzene, chlorobenzene, xylene, cyclohexane, n-heptane, and dichloromethane.
In one example, the solvent is an aromatic hydrocarbon solvent such as water, benzene, xylene, chlorobenzene, and the like.
The polymerization can be carried out with or without a catalyst.
In one example, the polymerization is conducted in the absence of a catalyst.
In one example, the polymerization is carried out in the presence of a catalyst.
In one example, the catalyst is a basic catalyst.
In one embodiment, the basic catalyst is selected from K 2 CO 3 、KOH、NaH、NaOMe、KO T Bu, rhodium complex, ruthenium complex, clay supported nickel bromide, ionic liquids, and the like.
Specifically, the molar ratio of catalyst to feedstock a is (1:0.5) - (1:2) (e.g., 1:0.5, 1:1, 1:1.5, 1:2).
In one example, the polymerization reaction is a Michael addition reaction.
Specifically, the reaction temperature of the polymerization reaction is 0 to 150 ℃ (e.g., 10 ℃, 20 ℃, 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃ or 150 ℃), preferably 0 to 80 ℃, more preferably 0 to 40 ℃.
In one example, the polymerization reaction is an atmospheric reaction.
In one example, the polymerization is carried out in a shielding gas, which may be a chemically inert gas such as argon, nitrogen.
The above materials may be used directly as commercially available products or may be prepared according to methods known in the art.
In a third aspect the present invention provides a composition comprising a coating adjuvant according to the first aspect of the present invention and one or more of the above organic substances which are sensitive to light, heat or oxidation; or the second aspect of the invention provides a coating adjuvant prepared by the method and one or more organic substances sensitive to light, heat or oxidation.
The amount of coating aid in the composition is dependent on the nature of the organic material, the end use and the additives, and the coating aid may be used in various proportions.
In one example, the amount of the coating aid in the composition may be 0.01 to 5wt% (e.g., 0.01%,0.05%,0.1%,0.15%,0.2%,0.25%,0.3%,0.35%,0.4%,0.45%,0.5%,1%,2%,3%,4%, 5%) by weight of the standard formulation. The standard formula weight is the total weight of the composition.
Preferably, the amount of the coating auxiliary is 0.05% -2% of the weight of the standard formula.
More preferably, the amount of the coating auxiliary is 0.05% -1% of the standard formula weight.
In one example, the organic material in the composition may be selected from one or more of polyurethane, polyamideimide, polyamide, polyimide, polyphenylene sulfide, polyethersulfone, polyetheretherketone, siloxane, polytetrafluoroethylene, hexafluoropropylene, 1-difluoroethylene, polytetrafluoroethylene, fluorinated ethylene propylene, or a perfluorinated hydrocarbon group.
In one example, the composition may further include one or more of antioxidants, UV absorbers, hindered amine light stabilizers, reinforcing agents, fillers, flame retardants, plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents, or blowing agents.
In one example, the antioxidant may be selected from: phenol and/or amine antioxidants, phosphites, thioesters, and the like, preferably, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, or antioxidant 168.
In one example, the UV absorber may be selected from: one or more of salicylate, benzoate, benzophenone, benzotriazole or triazine ultraviolet light absorbers.
In one example, the filler and reinforcing agent may be selected from: one or more of zinc oxide, aluminum oxide, titanium dioxide, iron oxide, chromium dioxide, silicon oxide, aluminum silicate, magnesium aluminum silicate, silicon carbide, titanium carbide, silicon oxide, titanium nitride, or boron nitride.
In one example, the filler and reinforcing agent are selected from: one or more of calcium carbonate, silicate, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flour or other natural or synthetic fibers.
In one example, the pigment may be selected from: cyan zeolite, channel black, carbon black, and the like.
In a fourth aspect, the present invention provides the use of a coating adjuvant according to the first aspect of the invention, or a composition according to the third aspect of the invention, in the preparation of a light stabilizer, in the preparation of a wetting agent and in the surface of an article.
Specifically, the product is an industrial product or a non-industrial product which needs to be coated with the coating;
preferably, the industrial product is a polymer material product.
In one example, the light stabilizer is used in the production, processing, and use of a coating article to delay or prevent the aging of the coating article, improve the service performance and service life of the coating article.
Further, the application fields of the coating product comprise different fields of road traffic, buildings, furniture, electric appliances and the like.
In one example, the polymeric material article may be a plastic, rubber, fiber, paint, adhesive, composite material, etc., and the polymeric material article may be used in the fields of automotive interior or exterior trim materials, floating devices, road traffic devices, agricultural products, electrical appliances, furniture, footwear, sanitary products, health care products, construction, etc.
The invention tests paint films according to the following criteria, wherein the hundred test is based on the scratch test of GB/T9286-1998 colored and clear paint films; the pencil hardness measuring method of the paint film is used for measuring the hardness of the paint film according to GB/T6739-2006 colored paint and varnish pencil method; wherein the gloss test hardness test method is based on the determination of 20 DEG, 60 DEG and 85 DEG specular gloss of paint films of GB/T9754 paint and varnish without metal pigments; wherein the impact test is according to GB/T48939-2013 furniture surface paint film impact resistance measurement method; wherein the solvent resistance test is determined according to GB/T23989-2009 "coating solvent resistance and wiping resistance determination method".
The term "alkyl" as used herein may be straight or branched chain alkyl, typically alkyl having from 1 to 22 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22) carbon atoms, i.e., C1-22 alkyl, such as C1-8 alkyl, C1-6 alkyl, C1-3 alkyl, examples of alkyl being methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-dodecyl, n-octadecyl. The same applies to alkoxy groups, typical alkoxy groups having 1 to 22 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22) carbon atoms, i.e. C1-22 alkoxy groups, e.g. C1-8 alkoxy groups, C1-6 alkoxy groups, C1-3 alkoxy groups, examples of alkoxy groups being methoxy, ethoxy, isopropoxy, propoxy, butoxy, hexyloxy, octyloxy, n-dodecyloxy, n-octadecyloxy groups. Preferred substituents thereof are halogen, aryl, hydroxy, cyano, nitro, alkoxy and alkylamino; preferred spacer groups thereof are oxygen, nitrogen, sulfur, arylene, heteroalkylene, -C (=o) -, or-C (=o) O-.
The term "alkylene" as used herein may be a straight or branched chain alkyl group, typical alkylene groups contain from 1 to 22 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22) carbon atoms, i.e., C1-22 alkylene groups, such as C1-18 alkylene, C1-12 alkylene, C1-8 alkylene, C1-6 alkylene, C1-3 alkylene, examples of alkylene groups such as methylene, ethylene, propylene, butylene, and the like.
The term "cycloalkyl" as used herein includes substituted cycloalkyl and unsaturated cycloalkyl, typical cycloalkyl groups containing 1 to 10 (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms, i.e. C1-10 cycloalkyl, e.g. C3-6 cycloalkyl, examples of cycloalkyl being cyclopentyl, cyclopropyl, cyclohexyl.
The term "aryl" as used herein, such as benzene ring and naphthalene ring type aryl, particularly benzene ring aryl. Aryl includes unsubstituted and substituted aryl, wherein the substituents may be alkyl, cyano, nitro, alkoxy, hydroxy, halogen, amino, alkylamino, aroyl, alkanoyl, arylsulfonyloxy, alkanoylamino or alkylsulfonylamino.
The term "heterocyclyl" as used herein includes heteroaryl and heteroalicyclic groups containing from 1 to 3 monocyclic and/or fused rings, from 3 to about 18 ring atoms. Examples of "heterocycloalkyl" are pyrrolidine, piperidine, morpholine, tetrahydrofuran, piperidone, piperazinone, imidazoline, imidazolidinone, 1,3, 5-triazinidinone or piperazine. Heterocycloalkyl includes unsubstituted as well as substituted forms of the foregoing groups, and the substituents may be alkyl, hydroxyalkyl, halogen, hydroxy, alkoxy, aroyl, alkanoyl, nitro, cyano, amino or alkylamino. Examples of heteroaryl groups are benzotriazole and 1,3, 5-triazine. Heteroaryl includes unsubstituted as well as substituted forms of the foregoing groups, and the substituents may be aryl, alkyl, arylamino, hydroxy, halogen, amino, alkenyl, nitro, cyano, or alkoxy. The heterocyclic group contains 1, 2 or 3 heteroatoms, which may be selected from: nitrogen, sulfur, oxygen, phosphorus, silicon, in particular oxygen, nitrogen.
The term "halogen" as used herein refers to bromine, chlorine, iodine or fluorine.
The term "heteroatom" as present in the present invention refers to N, O or S.
Various publications, patents, and published patent specifications cited herein are incorporated by reference in their entirety.
The polymerizable starting materials shown above are known in the art, are partially commercially available, or can be synthesized according to methods known in the art.
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Raw material 1-1:
raw materials 1-2:
in a 2000mL round bottom flask, 67.6g of raw material 1-1 is dissolved in 400mL of dimethylbenzene, 300mL of KOH solution (1 mol/L) is added, the temperature is heated to 40 ℃, 202g of raw material 1-2 is slowly added dropwise, stirring is continued for 4 hours, and 236.4g of target product P1-EX1 is obtained after complete reaction;
molecular weight of the target product P1-EX 1: 1081;
Viscosity (100 ℃ C.) of the target product P1-EX 1: 461cps.
Example 2
Raw material 2-1:
raw material 2-2:
in a 2L round bottom flask, 42.6g of raw material 2-1 is dissolved in 400mL of dimethylbenzene, 200mL of KOH solution (2 mol/L) is added, the temperature is controlled at 20 ℃, 267g of raw material 2-2 is slowly added dropwise, stirring is continued for 3 hours, and 276.41g of target product P1-EX2 is obtained after complete reaction;
molecular weight of the target product P1-EX 2: 1238.5;
viscosity (100 ℃ C.) of the target product P1-EX 2: 745cps.
Example 3
Raw material 3-1:
raw material 3-2:
in a 2L round bottom flask, 227.3g of raw material 3-1 is dissolved in 500mL of dimethylbenzene, 0.6mol of NaOMe is added, the temperature is controlled at 30 ℃, 332.35g of raw material 3-2 is slowly added dropwise, stirring is continued for 3h, and 521.3g of target product P1-EX3 is obtained after complete reaction;
molecular weight of the target products P1-EX 3: 2238.7
Viscosity (100 ℃ C.) of the target product P1-EX 3: 1045cps
Example 4
Raw material 4-1:
raw material 4-2:
in a 2L round bottom flask, 220.32g of raw material 4-1 is dissolved in 600mL of dimethylbenzene, 0.5mol of NaOMe is added, the temperature is controlled at 25 ℃, 385.8g of raw material 4-2 is slowly added dropwise, stirring is continued for 1.5h, and 573.59g of target product P1-EX4 is obtained after complete reaction;
molecular weight of target products P1-EX 4: 1859;
Viscosity (100 ℃ C.) of the target products P1 to EX 4: 1047cps.
Example 5
Raw material 5-1:
raw material 5-2:
in a 2L round bottom flask, 154.7g of raw material 5-1 is dissolved in 600mL of dimethylbenzene, 0.5mol of NaOMe is added, the temperature is controlled at 25 ℃, 103.5g of raw material 5-2 is slowly added dropwise, stirring is continued for 2 hours, and 203g of target product P1-EX5 is obtained after complete reaction;
molecular weight of the target product P1-EX 5: 2065;
viscosity of the target products P1 to EX 5: 1683cps (100 ℃ C.).
Example 6
Raw material 6-1:
raw material 6-2:
in a 2L round bottom flask, 213g of raw material 6-1 is dissolved in 500mL of dimethylbenzene, 0.5mol of NaOMe is added, the temperature is controlled at 30 ℃, 376g of raw material 6-2 is slowly added dropwise, stirring is continued for 2h, and 541g of target product P1-EX6 is obtained after complete reaction;
molecular weight of target products P1-EX 6: 2356;
viscosity of the target products P1 to EX 6: 1463cps (100deg.C).
Example 7
Raw material 7-1:
raw material 7-2:
in a 2L round bottom flask, 9.167g of raw material 7-1 is dissolved in 400mL of dimethylbenzene, 0.04mol of NaOMe is added, the temperature is controlled at 30 ℃, 446g of raw material 7-2 is slowly added dropwise, stirring is continued for 1h, and 426g of target product P1-EX7 is obtained through complete reaction;
molecular weight of target products P1-EX 7: 18238;
Viscosity of the target products P1 to EX 7: 1596cps (100 ℃).
Example 8
Raw material 8-1:
raw material 8-2:
in a 2L round bottom flask, 113g of raw material 8-1 is dissolved in 300mL of benzene, 0.4mol of NaOMe is added, the temperature is controlled at 30 ℃, 486g of raw material 8-2 is slowly added dropwise, stirring is continued for 1h, and 516g of target product P1-EX8 is obtained through complete reaction;
molecular weight of target products P1-EX 8: 2402;
viscosity of the target products P1 to EX 8: 682cps (100 ℃ C.).
Example 9
Raw material 9-1
Raw material 9-2:
in a 2L round bottom flask, 141.7g of raw material 9-1 is dissolved in 400mL of benzene, 0.5mol of NaOMe is added, the temperature is controlled at 30 ℃, 136g of raw material 9-2 is slowly added dropwise, stirring is continued for 1h, and 246g of target product P1-EX9 is obtained after complete reaction;
molecular weight of target products P1-EX 9: 1678.3;
viscosity of the target products P1 to EX 9: 1069cps (100deg.C).
Example 10
Raw material 10-1:
raw material 10-2:
in a 2L round bottom flask, 197.5g of raw material 10-1 is dissolved in 400mL of benzene, 0.5mol of NaOMe is added, the temperature is controlled at 30 ℃, 319.5g of raw material 10-2 is slowly added dropwise, stirring is continued for 1h, and 482g of target product P1-EX10 is obtained after complete reaction;
molecular weight of the target products P1-EX 10: 1033;
viscosity of the target products P1 to EX 10: 645cps (100 ℃).
Example 11
Raw material 11-1:
raw material 11-2:
in a 2L round bottom flask, 85g of raw material 11-1 is dissolved in 400mL of water, the temperature is controlled at 30 ℃, then 391g of raw material 11-2 is slowly added dropwise, stirring is continued for 2h, and 482g of target product P1-EX11 is obtained after complete reaction;
molecular weight of the target product P1-EX 11: 1702;
viscosity of the target products P1 to EX 11: 1036cps (100deg.C).
Example 12
Raw material 12-1:
raw material 12-2:
in a 2L round bottom flask, 241g of raw material 12-1 is dissolved in 500mL of water, the temperature is controlled at 30 ℃, 301g of raw material 12-2 is slowly added dropwise, stirring is continued for 3h, and 501g of target product P1-EX12 is obtained after complete reaction;
molecular weight of target products P1-EX 12: 1033;
viscosity of the target products P1-EX 12: 645cps (100 ℃).
Test example 1:
(1) Stable coating experiment (1-1) the basic formulation of the stable coating experiment is shown in Table 1.
Table 1 Standard formulation
The standard formulation consisted of:
example 1 was 99.7wt% of the standard formulation in Table 1, 0.3wt% of the coating auxiliary P1-EX1; example 2 is 99.7wt% of the standard formulation in Table 1, 0.3wt% of the coating auxiliary P1-EX2;
example 3 was 99.7wt% of the standard formulation in Table 1, 0.3wt% of the coating adjuvants P1-EX3;
example 4 was 99.7wt% of the standard formulation in Table 1, 0.3wt% of coating adjuvants P1-EX4;
Example 5 is 99.7wt% of the standard formulation in Table 1, 0.3wt% of the coating adjuvants P1-EX5;
example 6 was 99.7wt% of the standard formulation in Table 1, 0.3wt% of coating adjuvants P1-EX6;
example 7 is 99.7wt% of the standard formulation in Table 1, 0.3wt% of the coating adjuvants P1-EX7;
example 8 is 99.7wt% of the standard formulation in Table 1, 0.3wt% of coating adjuvants P1-EX8;
example 9 is 99.7wt% of the standard formulation in Table 1, 0.3wt% of coating adjuvants P1-EX9;
example 10 was 99.7wt% of the standard formulation in Table 1, 0.3wt% of coating adjuvants P1-EX10;
example 11 is 99.7wt% of the standard formulation in Table 1, 0.3wt% of the coating auxiliary P1-EX11;
example 12 is 99.7wt% of the standard formulation in Table 1, 0.3wt% of coating adjuvant P1-EX12;
the comparative example was 99.7wt% of the standard formulation in Table 1, 0.3wt% of a commercial wetting agent (Dow chemical wetting agent model: TERGITOL A-90).
(1-2) preparation of test samples:
preparing raw materials according to the basic formula of Table 1, adding water-based dispersion polyurethane, a dispersing agent, a leveling agent, a bactericide, a film forming additive, a coating additive, an additive, water and a half proportion of defoaming agent into a container which is stirred at a high speed, adding a thickening agent while stirring, adding nano silicon carbide after the thickening agent is completely dispersed, and stirring and dispersing at a high speed; rapidly transferring the dispersed liquid into a defoaming device, transferring the liquid into a low-speed stirring cylinder after the bubbles are basically eliminated, and regulating the PH value to 8 by using a PH regulator after the liquid is uniformly dispersed to obtain coating slurry, wherein the high-speed stirring speed is 1500r/min; the rate of low speed stirring was 450r/min.
Wherein the hundred test is based on the scratch test of GB/T9286-1998 color paint and varnish paint films; the pencil hardness measuring method of the paint film is used for measuring the hardness of the paint film according to GB/T6739-2006 colored paint and varnish pencil method; wherein the gloss test hardness test method is based on the determination of 20 DEG, 60 DEG and 85 DEG specular gloss of paint films of GB/T9754 paint and varnish without metal pigments; wherein the impact test is according to GB/T48939-2013 furniture surface paint film impact resistance measurement method; wherein the solvent resistance test is determined according to GB/T23989-2009 "coating solvent resistance and wiping resistance determination method".
When applied to coating, the detection results are shown in table 2:
table 2 results of physical property test of samples of examples 1 to 12 and comparative example
(2) Paint aging test
Based on the paint smear samples in the test samples (1-2) in the stable paint experiment (1), the samples were subjected to a xenon lamp aging test according to the standard GB/T16422.2-2014, and the test results of ΔE (low value is required) of the samples after the xenon lamp aging are shown in Table 3.
TABLE 3 Table 3
The experimental results in table 2 and table 3 show that the hardness, gloss, impact test and solvent resistance test of the film surface added with the coating auxiliary agent are equal to those of the film surface added with the commercial auxiliary agent, but the coating auxiliary agent has Hou Xingneng resistance higher than that of the commercial auxiliary agent, and has good ageing resistance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
The foregoing embodiments and methods described in this invention may vary based on the capabilities, experience, and preferences of those skilled in the art.
The listing of the steps of a method in a certain order in the present invention does not constitute any limitation on the order of the steps of the method.
Claims (12)
1. The coating auxiliary agent is characterized by being prepared by polymerization reaction of a polyether derivative skeleton and at least one compound with a general formula A;
the general formula A has the following structure:
a general formula A;
wherein R is a Selected from hydrogen, -alkyl, -alkylene-OH, -O-R b (iii) alkylene-O-R b An alkyl group interrupted by one or more heteroatoms, an alkyl group interrupted by one or more first spacer groups alone or in combination, an alkyl group substituted by one or more first substituents, a heteroalkyl group substituted by one or more first substituents;
The first spacer group is selected from a combination of one or more of the following groups: -C (=o) O-, amine, -OC (=o) O-, alkenyl, alkynyl, -C (=s) O-, amide groups, urea groups, arylene, heteroalkylene, heteroarylene;
the first substituent is selected from the group consisting of hydrogen, hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, alkoxycarbon, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aralkoxy, heteroarylacyloxy, cycloalkyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-S, alkyl interrupted by one or more-C (=s) O-S, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl, one or more alkylene interrupted by one or more heteroalkylene groups, one or more alkylene interrupted by one or more heteroaryl groups;
p is
A degree of polymerization of the repeating units, p being 0 or 1;
the o is
The degree of polymerization of the repeating units, o being an integer from 1 to 15;
the R is b A combination of one or more selected from the following groups: alkyl, -cycloalkyl, -C (=o) R c A heterocycloalkyl group, an alkyl group interrupted by one or more heteroatoms, an alkyl group interrupted by one or more first spacer groups alone or in combination, an alkyl group substituted by one or more first substituents, a heteroalkyl group substituted by one or more first substituents, a cycloalkyl group substituted by one or more first substituents, -a phenyl group;
the R is c A combination of one or more selected from the following groups: alkyl, cycloalkyl, phenyl, heterocycloalkyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more first spacer groups alone or in combination, alkyl substituted by one or more first substituents, heteroalkyl substituted by one or more first substituents, cycloalkyl substituted by one or more first substituents.
2. The coating aid of claim 1, wherein o is
And the polymerization degree of the repeating units, wherein o is an integer of 1-11.
3. The coating aid of claim 1, wherein the general formula a comprises the structure:
Wherein i is an integer of 1 to 18.
4. The coating adjuvant of claim 1, wherein the polyether derivative backbone comprises a compound of formula B;
the general formula B has the following structure:
a general formula B;
wherein,,
n 1 、n 2 ……n m the polymerization degree of each repeating unit is an integer of 0 to 200;
said n 1 +n 2 +……+n m ≥1；
m is an integer of 1 to 20;
R 1 、R 2 、R 3 ……R m are identical or different substituents;
Rt 1 、Rt 2 are identical or different end-capping groups;
the R is 1 、R 2 、R 3 ……R m Independently selected from one or more of the following groups: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, phenyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more heteroalkylene groups, alkyl interrupted by one or more heteroarylene groups, alkyl interrupted by a combination of the above spacer groups, alkyl substituted by one or more second substituents, heteroalkyl substituted by one or more second substituents, cycloalkyl substituted by one or more second substituents Or-a benzene ring;
the second substituent is selected from the group consisting of one or more of the following: hydroxy, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aralkoxy, heteroarylacyloxy, cycloalkyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more alkenyl groups, alkylene interrupted by one or more alkyl interrupted by one or more heteroaryl groups;
Preferably, the second substituent is selected from the group consisting of one or more of the following: hydroxy, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heterocycloalkyl, alkoxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, cycloalkyloyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more-C (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more alkylene groups, alkyl interrupted by a combination of the above;
the Rt is 1 、Rt 2 Independently selected from one or more of the following groups: hydrogen, alkyl, cycloalkyl, heterocycloalkyl, phenyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more amine groups, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkylene groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by a combination of the above spacer groups, alkyl substituted by one or more third substituents, heteroalkyl substituted by one or more third substituents, cycloalkyl substituted by one or more third substituents;
The third substituent is selected from the group consisting of one or more of the following: hydroxyl, halogen, aryl, cycloalkyl, hydroxyalkyl, alkoxy, thioalkoxy, nitro, cyano, amino, heteroaryl, heterocycloalkyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, heteroalkoxycarbonyl, alkoxythiocarbonyl, acyloxy, alkanoyloxy, aralkoxy, heteroarylacyloxy, cycloalkyloxy, heteroalkanoyloxy, alkanoyl, aminoacyl, alkylaminoacyl, alkylsulfonyl, aroyl, alkyl interrupted by one or more heteroatoms, alkyl interrupted by one or more-C (=o) O-, alkyl interrupted by one or more-OC (=o) O-, alkyl interrupted by one or more-C (=o) -O-, alkyl interrupted by one or more-C (=s) O-, alkyl interrupted by one or more amide groups, alkyl interrupted by one or more urea groups, alkyl interrupted by one or more arylene groups, alkyl interrupted by one or more alkenyl groups, alkyl interrupted by one or more alkynyl groups, alkyl interrupted by one or more alkenyl groups, alkylene interrupted by one or more alkyl interrupted by one or more heteroaryl groups.
5. The coating auxiliary according to claim 4, wherein in the formula B- -represents one or more of the same or different
And/or the number of the groups of groups,
-represents a single bond.
6. The coating adjuvant of claim 4 wherein the general formula B is selected from the following structures:
7. a process for preparing a coating adjuvant according to any one of claims 4 to 6, which comprises polymerizing a compound of formula a and a compound of formula B; optionally, the polymerization is carried out in the presence of a catalyst.
8. The process according to claim 7, wherein the polymerization is carried out in a solvent selected from the group consisting of: one or more of tetrahydrofuran, 2-methyltetrahydrofuran, halogenated hydrocarbons, acetonitrile, propionitrile, butyronitrile, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, dimethyl sulfoxide, N-dimethylamide, diphenyl ether and water;
preferably, the halogenated hydrocarbon comprises: one or more of dichloromethane, dichloroethane or carbon tetrachloride;
preferably, the aromatic hydrocarbon comprises: one or more of benzene, toluene, xylene, chlorobenzene or dichlorotoluene;
preferably, the aliphatic hydrocarbon comprises: one or more of petroleum ether, n-hexane, n-heptane, cyclohexane and n-octane;
Preferably, the alcohol comprises: one or more of methanol, ethanol, propanol, ethylene glycol, diethylene glycol, ethylene glycol methyl ether;
more preferably, the solvent is selected from one or more of water, toluene, benzene, chlorobenzene, xylene, cyclohexane, n-heptane or dichloromethane;
particularly preferably, the solvent is selected from one or more of water, benzene, xylene or chlorobenzene.
9. The method of claim 7, wherein the catalyst is a basic catalyst;
preferably, the basic catalyst is selected from the group consisting of one or more of the following: k (K) 2 CO 3 、KOH、NaH、NaOMe、KO T Bu, rhodium complex, ruthenium complex, clay supported nickel bromide or ionic liquid;
more preferably, the molar ratio of the catalyst to the compound of formula a is (1:0.5) - (1:2);
particularly preferably, the polymerization is a michael addition reaction;
particularly preferably, the reaction temperature of the polymerization reaction is from 0 to 150 ℃, preferably from 0 to 80 ℃, more preferably from 0 to 40 ℃.
10. A composition comprising the coating adjuvant of any one of claims 1 to 6 and one or more organic substances sensitive to light, heat or oxidation; or, a coating adjuvant prepared by the process of any one of claims 7-9 and one or more organic substances sensitive to light, heat or oxidation.
11. The composition of claim 10 wherein the amount of the coating aid may be 0.01-5wt% of the standard formulation weight, i.e. the total weight of the composition.
12. Use of a coating aid according to any one of claims 1 to 6 or a composition according to claim 10 or 11 for the preparation of light stabilizers, for the preparation of wetting agents and for the surface of articles.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4028288A1 (en) * | 1990-09-06 | 1992-03-12 | Huels Chemische Werke Ag | COLD-HARDENING, SOLVENT-FREE, DUROPLASTIC POLYURETHANE-POLYHANE MATERIALS |
| US5534618A (en) * | 1993-07-13 | 1996-07-09 | Ciba-Geigy Corporation | Polyethers containing hindered amines which can be cleaved off as stabilizers |
| CN1218071A (en) * | 1997-11-25 | 1999-06-02 | 通用电气公司 | Polycarbonate composition comprising hindered amine light stabilizer and polyether |
| TW555800B (en) * | 2000-11-03 | 2003-10-01 | Cytec Tech Corp | Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds |
| CN114195921A (en) * | 2021-12-13 | 2022-03-18 | 天集化工助剂（沧州）有限公司 | Polymeric steric hindrance amine and preparation method and application thereof |
| KR102388776B1 (en) * | 2021-08-03 | 2022-04-20 | 한국화학연구원 | Novel polyether polyol and aqueous dispersion assistant comprising the same, and aqueous coating composition comprising the same |
-
2022
- 2022-12-30 CN CN202211732900.6A patent/CN116376008B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4028288A1 (en) * | 1990-09-06 | 1992-03-12 | Huels Chemische Werke Ag | COLD-HARDENING, SOLVENT-FREE, DUROPLASTIC POLYURETHANE-POLYHANE MATERIALS |
| US5534618A (en) * | 1993-07-13 | 1996-07-09 | Ciba-Geigy Corporation | Polyethers containing hindered amines which can be cleaved off as stabilizers |
| CN1218071A (en) * | 1997-11-25 | 1999-06-02 | 通用电气公司 | Polycarbonate composition comprising hindered amine light stabilizer and polyether |
| TW555800B (en) * | 2000-11-03 | 2003-10-01 | Cytec Tech Corp | Polymeric articles containing hindered amine light stabilizers based on multi-functional carbonyl compounds |
| KR102388776B1 (en) * | 2021-08-03 | 2022-04-20 | 한국화학연구원 | Novel polyether polyol and aqueous dispersion assistant comprising the same, and aqueous coating composition comprising the same |
| CN114195921A (en) * | 2021-12-13 | 2022-03-18 | 天集化工助剂（沧州）有限公司 | Polymeric steric hindrance amine and preparation method and application thereof |
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