CN110713572B - High-solid-content low-viscosity resin composition containing acrylic copolymer - Google Patents
High-solid-content low-viscosity resin composition containing acrylic copolymer Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Abstract
The present invention relates to a high solids, low viscosity resin composition comprising an acrylic copolymer, wherein the resin composition has a solids content of at least about 80 wt% based on the weight of the acrylic copolymer and a viscosity of 130000mpa.s or less as measured using a BROOKFIELD viscometer at 25 ℃, and the backbone of the acrylic copolymer has pendant poly (oxyalkylene) segments.
Description
Technical Field
The present invention relates to a resin composition having a high solid content and a low viscosity, and more particularly to a resin composition comprising an acrylic copolymer. The present invention also relates to a solvent-based coating composition comprising the resin composition.
Background
In recent years, with environmental concerns, environmental laws have been enacted in many countries and there is a demand for further reduction in the amount of VOCs that are allowed to be released into the air by coating compositions, particularly solvent-based coating compositions. For example, solvent-borne coating compositions with VOC levels in excess of 420g/L in China since 2015 and 2 months will be subject to additional consumer taxes, with tax rates as high as 4%, which will add significantly to the cost of the coating company. Thus, there is a rapidly increasing demand for high solids, low viscosity resin compositions for formulating solvent borne coating compositions having VOC levels not exceeding 420 g/L.
The prior art has disclosed two methods commonly used to prepare acrylic resin compositions of high solids and low viscosity, one method being the use of glycidyl compounds. For example, CN102702438 discloses the use of glycidyl versatate for the preparation of acrylic resins with high solids and low viscosity. However, the product thus obtained can only reach a solids content of about 70% and still contain relatively large amounts of organic solvents. Another approach is by the addition of hyperbranched modifiers. For example, CN103319666A discloses the use of hyperbranched modifiers for the preparation of aqueous acrylic resin dispersions. However, the product is suitable for use in aqueous coating systems and can only reach a solids content of 45%. The low VOC content requirement appears more difficult to achieve for solvent-based coating compositions than for water-based coating compositions.
In addition, a variety of commercial high solids, low viscosity acrylic resins have been disclosed, such as 854BA80 from Arkema, Setalux 1753 from Niupeisi resin, and A-870 from Bayer. However, these products still do not meet the needs of the coatings industry.
Thus, to meet the VOC content requirement of less than 420g/L, the coating industry still needs further improved acrylic resin compositions having high solids content, relatively low viscosity, and suitable for use in solvent-based coating compositions.
Disclosure of Invention
In one aspect, the present invention provides a resin composition comprising an acrylic copolymer, wherein the acrylic copolymer has pendant poly (oxyalkylene) segments in the backbone, and wherein the resin composition has a solids content of at least about 80 wt%, based on the weight of the acrylic copolymer, and a viscosity of 130000mpa.s or less at 25 ℃ as measured using a brookf ield viscometer.
In another aspect, the present invention relates to a method for preparing the above-mentioned acrylic copolymer-containing resin composition, the method comprising: copolymerizing a reaction mixture comprising as a first monomer an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment, an acrylic monomer different from the first monomer, and an additional ethylenically unsaturated monomer, in the presence of an organic solvent and a free radical initiator in an amount of no more than 20 wt% relative to the total weight of the resin composition, to form the resin composition.
In another aspect, the present invention relates to the use of ethylenically unsaturated monomers containing poly (oxyalkylene) segments for the preparation of a high solids, low viscosity resin composition according to the present invention.
In another aspect, the present invention relates to a solvent-based coating composition having a VOC emission of less than 420g/L comprising the resin composition of the present invention.
The inventors of the present invention have pioneered providing a resin composition comprising an acrylic copolymer, wherein the resin composition has a solids content of at least about 80 wt% based on the weight of the acrylic copolymer and a viscosity of 130000mpa.s or less at 25 ℃ as measured using a BROOKFIELD viscometer, and wherein the backbone of the acrylic copolymer has pendant poly (oxyalkylene) segments. Meanwhile, the resin composition according to the present invention comprises up to 20 wt% of an organic solvent, relative to the total weight of the resin composition.
The inventors of the present invention have surprisingly found that during the preparation of the resin composition of the present invention, by copolymerising the ethylenically unsaturated monomer containing the poly (oxyalkylene) segment with the acrylic monomer and additional ethylenically unsaturated monomer, to suspend the soft poly (oxyalkylene) segment in the backbone of the acrylic copolymer, the presence of the poly (oxyalkylene) segment can significantly reduce the viscosity of the resin composition while maintaining the solids content thereof, such that the resin composition can formulate solvent-based coating compositions having VOC emissions of no more than 420g/L without the need for additional diluents.
The inventors of the present invention further surprisingly found that high solids, low viscosity resin compositions according to the present invention can be formed by copolymerizing ethylenically unsaturated monomers containing poly (oxyalkylene) segments with acrylic monomers and additional ethylenically unsaturated monomers at very low organic solvent content, which was not foreseeable prior to the present invention.
The details of one or more embodiments of the invention are set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and from the claims.
Definition of
As used herein, unless otherwise indicated, "a," "an," "the," "at least one," and "one or more" are used interchangeably and are not used to describe a numerical word. Thus, for example, a coating composition that includes "an" additive can be interpreted to mean that "one or more" additives are included in the coating composition. The use of a singular form herein is intended to include the plural form as well, unless the context clearly indicates otherwise.
Where a composition is described as including or comprising a particular component, optional components not contemplated by the present invention are not contemplated as being excluded from the composition and it is contemplated that the composition may consist of or consist of the recited component or where a method is described as including or comprising a particular process step, optional process steps not contemplated by the present invention are not contemplated as being excluded from the method and it is contemplated that the method may consist of or consist of the recited process step.
The terms "comprise" and "comprise," and variations thereof, when appearing in the specification and claims, have no limiting meaning.
The term "high solids" when used in reference to a "resin composition" means that the resin composition has a solids content of at least 80 wt% or greater, wherein the solids content is calculated based on the resin components in the resin composition.
In the context of the present invention, the term "solvent-based coating composition" refers to a coating composition having a water content of less than 2g/L, preferably being substantially free, more preferably being substantially completely free, still more preferably being completely free of water, with an organic solvent as the dispersing medium.
The term "substantially free of" water, when used with respect to a "solvent-borne coating composition," means that the solvent-borne coating composition of the present invention comprises less than 1000 parts per million (ppm) of water; the term "essentially free of water" means that the solvent borne coating compositions of the present invention comprise less than 100ppm water; the term "essentially completely free of" water means that the solvent borne coating compositions of the present invention contain less than 5ppm water; the term "completely free" of water means that the solvent-borne coating compositions of the present invention contain less than 20 parts per billion (ppb) of water.
In the context of the present invention, the term "ethylenically unsaturated group" refers to a reactive carbon-carbon double bond unsaturated group having cis-or trans-configuration, but excluding aromatic unsaturated groups, carbon-carbon triple bonds, carbon-heteroatom unsaturated groups.
In the context of the present invention, the term "reactive mixture" means a mixture of monomers having reactivity, excluding solvents which do not participate in the reaction.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value may, as its lower or upper limit, be combined with any other point or individual value or with other lower or upper limits to form ranges not explicitly recited.
In the present invention, the numerical ranges defined by endpoints include all any number within the range, for example, a range of 1 to 5 encompasses the numbers 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. Moreover, the disclosed numerical ranges include all subranges within the broad range, e.g., a range of 1 to 5 includes subranges 1 to 4, 1.5 to 4.5, 1 to 2, etc.
The terms "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.
Detailed Description
According to a first aspect of the present invention, there is provided a resin composition comprising an acrylic copolymer, wherein the resin composition has a solids content of at least about 80 wt% based on the weight of the acrylic copolymer and a viscosity of 130000mpa.s or less at 25 ℃ as measured using a BROOKFIELD viscometer, and the acrylic copolymer has pendant poly (oxyalkylene) segments on the backbone.
The resin composition according to the present invention not only has a high solid content, but also has a very low viscosity, and thus can be used to formulate solvent-borne coating compositions without introducing excessive VOC. In one embodiment of the invention, the resin composition has a solids content of at least about 80 wt% based on the weight of the acrylic copolymer. The inventors have surprisingly found that the resin compositions of the present invention have a significantly lower viscosity while maintaining a high solids content. In one embodiment of the present invention, the resin composition has a viscosity of 60000mpa.s or less, more preferably 10000mpa.s or less, measured at 25 ℃ using a BROOKFIELD viscometer.
The resin composition according to the invention also comprises a relatively small amount of organic solvent, for example not more than 20% by weight of organic solvent, preferably not more than 18% by weight of organic solvent, relative to the total weight of the resin composition.
The resin composition with the characteristics does not need to add a large amount of solvent for dilution when used for preparing a solvent-based coating composition, even does not need to add the solvent as a diluent at all, and therefore, the resin composition can be prepared to form the solvent-based coating composition with the VOC emission of not more than 420 g/L.
In the resin composition according to the present invention, the acrylic copolymer has a pendant poly (oxyalkylene) segment on the backbone. In an embodiment of the invention, the poly (oxyalkylene) segments are present in an amount of 15 to 60 wt%, preferably 20 to 50 wt%, based on the weight of the acrylic copolymer. The poly (oxyalkylene) segments are pendant from the backbone of the acrylic copolymer so that a resin composition containing the acrylic copolymer can exhibit a significantly reduced viscosity while maintaining a high solids content.
According to the present invention, the poly (oxyalkylene) segments are selected from poly (oxyalkylene) segments of poly (oxyethylene) segments, poly (oxypropylene) segments, poly (oxybutylene) segments, poly (oxypentylene) segments, and any combination thereof. Preferably, the poly (oxyalkylene) segments are selected from the group consisting of poly (oxyethylene) segments, poly (oxypropylene) segments, and combinations thereof.
According to the invention, the poly (oxyalkylene) segments are derived from poly (oxyalkylene) -segment-containing ethylenically unsaturated monomers having the following formula I, also known as polyethers containing ethylenically unsaturated groups,
wherein A is
And R is1、R2And R3Independently of one another from-CH3H or
And R is1、R2And R3At most one of which is
Wherein X is- (CH)2)a-, -CO-or- (CH)2)a-CO-wherein a is 1 to 6; r4is-CH3Or H; b and c are independently of each other 0 to 500 and b and c are not simultaneously 0.
According to the invention, X is- (CH)2)aThe polyethers of the formula I above, in which X is-CO-or- (CH), are referred to as ether polyethers2)aThe polyethers of the above formula I of-CO-are referred to as ester polyethers.
In some embodiments, the ethylenically unsaturated group-containing polyether is an ether-type polyether. Examples of the ether type polyether according to the present invention include allyl polyether (e.g., allyl polyoxyethylene ether, allyl polyoxypropylene polyoxyethylene polyether), methallyl polyether, and the like, which are commercially available, such as HMP-523B, HMS-239B, HMS-233B, HMP-517B, and the like, from Royal of Zhejiang.
In some embodiments, the ethylenically unsaturated group-containing polyether is an ester-type polyether. Examples of the ester-type polyether according to the present invention include acryloxy polyoxyethylene ether, acryloxy polyoxypropylene ether, methacryloxy polyoxyethylene ether, methacryloxy polyoxypropylene ether, which are commercially available.
In some embodiments of the invention, the number average molecular weight of the ethylenically unsaturated group-containing polyether is between 100-10000, more preferably between 200-6000, and more preferably between 300-2000. The number average molecular weight can be measured using GPC.
According to the invention, the resin composition is made from components comprising:
15 to 60% by weight, relative to the total weight of the reaction mixture, of an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment (hereinafter referred to as "first monomer"),
35-60% by weight, relative to the total weight of the reaction mixture, of an acrylic monomer different from the first monomer,
5-30 wt% of additional ethylenically unsaturated monomer, relative to the total weight of the reaction mixture.
The inventors of the present invention have surprisingly found that the resin composition according to the present invention can be formed by: a first monomer, an acrylic monomer different from the first monomer, and an additional ethylenically unsaturated monomer are copolymerized in the presence of a free radical initiator and a very small amount of an organic solvent without gelation. Preferably, the organic solvent is present in an amount of 15 to 20 wt%, preferably 15 to 18 wt%, more preferably 15 to 17 wt%, relative to the total weight of the resin composition. A resin composition is thereby obtained not only having a high solids content but also having a significantly lower viscosity, for example, the resin composition having a solids content of at least about 80 wt% based on the weight of the acrylic copolymer and a viscosity of 130000mpa.s or less as measured at 25 ℃ using a BROOKFIELD viscometer.
In the preparation of the resin composition according to the present invention, the first monomer is necessary. As mentioned above, the inventors have surprisingly found that by introducing a first monomer, i.e. an ethylenically unsaturated monomer containing poly (oxyalkylene) segments, during the preparation of the resin composition, the viscosity of the resin composition can be significantly reduced while maintaining a high solids content thereof, such that the resin composition can formulate solvent-based coating compositions having VOC emissions of no more than 420g/L without the need for additional diluents.
The present invention therefore also relates to the use of the above-described ethylenically unsaturated monomers containing poly (oxyalkylene) segments for the preparation of a high solids, low viscosity resin composition comprising an acrylic copolymer according to the present invention.
Preferably, the components used to prepare the resin composition of the present invention comprise, relative to the total weight of the reaction mixture, from 15 to 55% by weight of ethylenically unsaturated monomers containing poly (oxyalkylene) segments, preferably from 20 to 50% by weight of ethylenically unsaturated monomers containing poly (oxyalkylene) segments, more preferably from 20 to 40% by weight of ethylenically unsaturated monomers containing poly (oxyalkylene) segments.
In the preparation of the resin composition according to the present invention, an acrylic monomer different from the first monomer may also be included. The presence of the monomer can be used to provide mechanical strength and film-forming properties to the resulting resin composition. In the embodiment of the present invention, as examples of the acrylic monomer, there may be used (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2- (acetoacetoxy) ethyl methacrylate, diacetone acrylamide, methylol (meth) acrylamide, acrylonitrile, allyl methacrylate, or a mixture thereof.
In some embodiments, the acrylic monomer may comprise at least one active hydrogen-containing monomer to provide the resulting final resin composition with active hydrogen functionality, such as those derived from hydroxyl, amine, and acid functionalities. Preferably, the active hydrogen-containing acrylic monomer is present in an amount of 5 to 20 wt%, preferably 10 to 15 wt%, based on the total weight of the reaction mixture. The presence of such active hydrogen-containing acrylic monomers ensures that the resulting acrylic copolymer-containing resin composition according to the present invention can be used to formulate two-component solvent borne coating compositions.
Preferably, the components used to prepare the resin composition of the present invention comprise an acrylic monomer present in an amount of at least 35 wt%, preferably in an amount of at least 40 wt%, more preferably in an amount of at least 45 wt%, most preferably in an amount of at least 50 wt%, relative to the total weight of the reaction mixture. More preferably, the acrylic monomer is present in an amount up to 60 wt%, more preferably in an amount up to 56 wt%, based on the total weight of the reaction mixture.
In the preparation of the resin composition according to the present invention, additional ethylenically unsaturated monomers may also be included. The monomer can be used to adjust the mechanical strength of the resulting resin composition. In an embodiment of the invention, the additional ethylenically unsaturated monomer is selected from styrene, vinyl toluene, vinyl acetate or mixtures thereof.
Preferably, the components used to prepare the resin composition of the present invention comprise an additional ethylenically unsaturated monomer present in an amount of from 15 to 30 wt%, relative to the total weight of the reaction mixture.
In the preparation of the resin composition according to the present invention, an organic solvent may be included to adjust the system viscosity. Suitable solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and the like; alcohols such as ethanol, isopropanol, n-butanol, t-butanol, and ethylhexanol, etc.; esters, such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. Other suitable solvents include ketones such as methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, and the like; glycols, such as propylene glycol and diethyl glycol; glycol ethers, such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether. Of course, various mixtures of solvents may be used. According to the present invention, the amount of organic solvent can be very low, for example, less than 20 wt%, less than 19 wt%, less than 18 wt%, less than 17 wt%, less than 15 wt%, without affecting the formation of the acrylic copolymer, wherein the amount is calculated with respect to the total weight of the resin composition, which was not conceivable prior to the present invention. As described in CN1201809, the amount of solvent used to reduce during the preparation of conventional resin compositions is practically limited, generally not less than 20% by weight of the total weight of the reaction mixture. If further solvent reduction is attempted, the resulting resin composition becomes too viscous, or even gelled, and therefore cannot be used in the formulation of coating compositions.
Accordingly, the present invention also relates to a process for preparing a resin composition comprising an acrylic copolymer according to the present invention, the process comprising: copolymerizing a reaction mixture comprising as a first monomer an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment, an acrylic monomer different from the first monomer, and an additional ethylenically unsaturated monomer in the presence of an organic solvent in an amount of not more than 20 wt%, relative to the total weight of the resin composition, and a free radical initiator to form the resin composition.
The appropriate conditions for the above reaction depend on various factors including the type of ethylenically unsaturated monomer and acrylic monomer containing the poly (oxyalkylene) segment, the presence or absence of solvent, and the type of initiator, among others, which can be determined empirically by those skilled in the art. Without wishing to be bound by any theory, the inventors provide the following explanation to enable the invention to be better understood.
In the acrylic copolymer-containing resin composition according to the present invention, an appropriate amount of poly (oxyalkylene) segments are suspended on the acrylic copolymer main chain, and due to the flexibility of the poly (oxyalkylene) segments, it is helpful to improve the molecular mobility of the acrylic copolymer, thereby achieving the purpose of significantly reducing the viscosity. In addition, the nonpolar side group pendant from the main chain weakens the interaction force between the molecular chains, further improving the solubility of the acrylic copolymer in a solvent, so that the preparation of the acrylic copolymer-containing resin composition according to the present invention can be carried out in the presence of a very small amount of an organic solvent without gelation or hardening.
Due to the high solids content and low viscosity, the acrylic copolymer-containing resin composition according to the present invention is suitable for formulating low VOC solvent-based coating compositions, for example, solvent-based coating compositions having VOC emissions of not more than 420g/L can be formulated.
Accordingly, another aspect of the present invention provides a solvent-based coating composition having a VOC emission of no more than 420g/L comprising the acrylic copolymer-containing resin composition disclosed herein and optionally additional additives. Specifically, the solvent-based coating composition comprises, relative to the total weight of the coating composition, (i)30 to 99.5 parts by weight of a resin composition comprising a polyether-modified polyester; (ii)0.5 to 70 parts by weight of optional additional additives.
According to the present invention, the content of the acrylic copolymer-containing resin composition described herein is in the range of 30 to 99.5 parts by weight, preferably in the range of 40 to 90 parts by weight, and more preferably in the range of 50 to 85 parts by weight, relative to the total weight of the solvent-based coating composition.
If desired, the coating compositions of the present invention may optionally include other additives that do not adversely affect the coating composition or the cured coating resulting therefrom. Suitable additives include, for example, those agents that improve the processability or manufacturability of the composition, enhance the aesthetics of the composition, or improve a particular functional property or characteristic (such as adhesion to a substrate) of the coating composition or cured composition resulting therefrom. Additives that may be included are solvents, carriers, additional polymers, pigments, metal powders or pastes, fillers, anti-migration aids, antimicrobials, extenders, lubricants, anti-foaming agents, biocides, plasticizers, thickeners, colorants, waxes, antioxidants, anti-corrosion agents, flow control agents, thixotropic agents, dispersants, UV stabilizers, or combinations thereof. The individual optional ingredients are present in an amount sufficient for their intended purpose, but preferably, such amount does not adversely affect the coating composition or the cured coating resulting therefrom. Examples of additional additives suitable for use in the coating composition include plasticizers, pigments, fillers, thickeners, defoamers, wetting agents, dispersants, solvents, or combinations thereof.
The content of the additional additive is in the range of 0.5 to 70 parts by weight, or more preferably in the range of 1 to 50 parts by weight, relative to the total weight of the solvent-based coating composition.
In addition to formulating the above solvent-based coating composition with a VOC emission of not more than 420g/L, the resin composition according to the present invention can also be used to formulate a two-component solvent-based coating composition. Thus, another aspect of the present invention includes a two-component solvent-based coating composition having a VOC emission of no more than 420g/L comprising a film-forming resin composition a) comprising the above-described acrylic copolymer-containing resin composition disclosed herein and optionally additional additives; and a crosslinking agent b).
Examples of suitable crosslinker components are polyisocyanates.
Suitable polyisocyanate crosslinking agents include aliphatic polyisocyanates, aromatic polyisocyanates, or any combination thereof. The term "aliphatic polyisocyanate" as used herein refers to a polyisocyanate compound in which the isocyanate groups are directly attached to an aliphatic chain or ring. The term "aromatic polyisocyanate" as used herein refers to a polyisocyanate compound in which the isocyanate groups are directly attached to the aromatic ring.
Suitable isocyanates for use in the present invention include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, butylene-1, 2-diisocyanate, butylene-1, 3-diisocyanate, ethylene diisocyanate; cycloaliphatic diisocyanates such as cyclohexylidene diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), 2, 4-trimethylhexamethyl diisocyanate, dimer acid diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate; and aromatic diisocyanates such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, chlorinated tolylene diisocyanate, m-phenylene diisocyanate chloride, o-phenylene diisocyanate, m-phenylene diisocyanate bromide, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthylene-1, 4-diisocyanate, naphthylene-1, 5-diisocyanate, naphthylene-2, 7-diisocyanate, 4 ', 4-biphenylene diisocyanate, 3' -dichloro-4, 4 '-biphenylene diisocyanate, 3' -dimethyl-4, 4 '-biphenylene diisocyanate, 3' -dimethoxy-4, 4 '-biphenylene diisocyanate, 2', 5,5 '-tetramethyl-4, 4' -biphenylene diisocyanate, 2-nitro-4, 4 '-biphenylene diisocyanate, 3' -diphenyl-4, 4 '-biphenylene diisocyanate, 4' -methylene-bis (phenyl isocyanate), 4 '-methylene-bis (2-tolyl isocyanate), 4' -isopropylene-bis (phenyl isocyanate), and fluorene diisocyanate; triisocyanates such as hexamethylene diisocyanate biuret, 4', 4 "-triphenylmethane triisocyanate and toluene-2, 4, 6-triisocyanate; isocyanurates, such as those based on hexamethylene diisocyanate or 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate; tetraisocyanates and mixtures thereof.
Particularly suitable isocyanates are polyfunctional aliphatic isocyanates based on Hexamethylene Diisocyanate (HDI). Some of the HDIs commercially available include
Or
Available from Rhone-Poulenc Inc. (organic chemistry division), Monmouth Junction, NJ, or
Or
Isocyanate, available from Bayer AG, Pittsburgh, Pa.
According to the present invention, the solvent-based coating composition may be applied by conventional coating methods known to those of ordinary skill in the art. The coating methods include dip coating, spin coating, spray coating, curtain coating, brush coating, roll coating, and other coating methods known in the art.
The low VOC solvent-based coating compositions can be applied to a variety of different substrates using conventional coating techniques. Examples of suitable substrates include wood, cement fiberboard, wood-plastic composites, tile, metal, plastic, glass, and fiberglass.
Test method
The following test methods were utilized in the examples below, unless otherwise indicated.
Solid content
The assay was performed according to GB/T1725-2007 standard.
Viscosity of the oil
The rheological properties of the non-Newtonian materials were determined according to ASTM D2196 (determination of the rheological properties of the non-Newtonian materials by means of a Brookfield viscometer).
Degree of gloss
This test measures the gloss of the cured coating. Gloss was evaluated according to ASTM D523.
Hardness of pencil
This test is used to measure the hardness of the cured coating. ASTM D3363 was used to evaluate pencil hardness. The data is reported as the pencil hardness that was tested successfully for the last time before the coating broke. Thus, for example, if the coating does not crack when tested with a 2H pencil, but cracks when tested with a 3H pencil, the coating is reported to have a pencil hardness of 2H.
Adhesion property
An adhesion test was performed to assess whether the coating adhered to the coated substrate. The adhesion test was performed according to ASTM D3359-test method B. Adhesion is generally classified on a scale of 0-5B, with 5B indicating optimal adhesion.
Examples
Hereinafter, the present disclosure will be described more specifically by examples. These examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention, as various modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art.
All parts, percentages, and ratios reported in the following examples are on a weight basis unless otherwise stated, and all reagents used in the examples are commercially available and can be used directly without further treatment.
Material
The materials used are listed in table 1 below.
Table 1: materials used and information relating thereto
Preparation of resin composition comprising acrylic copolymer
Resin compositions containing acrylic copolymers were prepared according to the ingredients shown in table 2 below. The method comprises the following specific steps:
(1) weighing the raw materials;
(2) part 3 was charged to the flask with a nitrogen purge, then heated to 140 ℃;
(3) keeping the reaction temperature of the flask at 140 ℃, and sequentially adding Part 1 and Part 2 into the reaction flask within 3-3.5 hours;
(4) after the monomer addition was complete, the mixture was held at 140 ℃ for 1 hour;
(5) part 4 was added to the reaction flask over 1 hour and then held at 140 ℃ for 2 hours;
(6) cooled to room temperature to obtain a resin composition containing an acrylic copolymer.
TABLE 2
The solid content and viscosity of the obtained resin composition were measured, and the results are shown in the following Table 3:
TABLE 3
| Examples of the invention | Solid content | Viscosity/mpa.s |
| Comparative resin | About 80 percent | Hard solids |
| Resin 1 | 81.87％ | 122000 |
| Resin 2 | 82.86％ | 54000 |
| Resin 3 | 81.75％ | 9600 |
From the above results, it can be seen that the incorporation of an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment in the preparation of an acrylic copolymer can form a high solids, low viscosity resin composition containing the acrylic copolymer having a solids content of at least about 80 wt% based on the weight of the acrylic copolymer and a viscosity of 130000mpa.s or less as measured at 25 ℃ using a BROOKFIELD viscometer. In contrast, the acrylic copolymers prepared with monomer mixtures that do not contain ethylenically unsaturated monomers having poly (oxyalkylene) segments are hard solids and cannot be used at all to formulate solvent-based coating compositions.
Preparation of low VOC solvent-based coating compositions
A low VOC solvent-based coating composition was prepared in the formulation of the following table 4, and a pigment, a filler, a thickener, a defoamer, a wetting dispersant and a solvent were added to the resin composition including the acrylic copolymer obtained above under stirring, thereby forming a solvent-based coating composition. Then, the solvent-based coating composition thus formed was applied to a bare steel plate with a film coater, thus obtaining a coating of 0.05mm (2. + -. 0.1mil) dry film thickness. The coating was cured at room temperature for two weeks and the measurements given in the table below were obtained
TABLE 4
From the above results, it can be seen that the acrylic copolymer-containing resin composition according to the present invention can be directly used to formulate a low VOC (VOC emission amount less than 420g/L) solvent-based coating composition, and that the coating layer formed therefrom has good coating properties.
While the invention has been described with reference to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the invention as disclosed herein.
Claims (23)
1. A resin composition comprising an acrylic copolymer, wherein the backbone of the acrylic copolymer has pendant poly (oxyalkylene) segments, and wherein the resin composition has a solids content of at least 80 wt% based on the weight of the acrylic copolymer and a viscosity of 130000mpa.s or less as measured at 25 ℃ using a BROOKFIELD viscometer, wherein the resin composition comprises up to 20 wt% of an organic solvent based on the total weight of the resin composition.
2. The resin composition of claim 1, wherein the resin composition has a solids content of at least 81 wt% based on the weight of the acrylic copolymer.
3. Resin composition according to claim 1, wherein the resin composition has a viscosity of 60000mpa.s or less, measured at 25 ℃ using a brookf ield viscometer.
4. The resin composition according to claim 1, wherein the resin composition has a viscosity of 10000mpa.s or less measured at 25 ℃ using a brookfiield viscometer.
5. The resin composition of claim 1, wherein the poly (oxyalkylene) segments are selected from poly (oxyethylene) segments, poly (oxypropylene) segments, poly (oxybutylene) segments, poly (oxypentylene) segments, and any combination thereof.
6. The resin composition of claim 1, wherein the poly (oxyalkylene) segments are selected from poly (oxyethylene) segments, poly (oxypropylene) segments, or combinations thereof.
7. The resin composition of claim 1, wherein the poly (oxyalkylene) segments are present in an amount of 15 to 60 wt%, based on the weight of the acrylic copolymer.
8. The resin composition of claim 1, wherein the poly (oxyalkylene) segments are present in an amount of 20 to 50 wt%, based on the weight of the acrylic copolymer.
9. Resin composition according to any one of claims 1 to 8, wherein the poly (oxyalkylene) segments are derived from poly (oxyalkylene) segment-containing ethylenically unsaturated monomers of the formula,
in the above-mentioned formula, the compound has the following structure,
a is
And R is1、R2And R3Independently of one another, from H, -CH3Or
And R is1、R2And R3At most one of which is
，
Wherein X is- (CH)2)a-, -CO-or- (CH)2)a-CO-wherein a is 1 to 6; r is4is-CH3Or H; b and c are independently of each other 0 to 500 and b and c are not simultaneously 0.
10. Resin composition according to any one of claims 1-8, wherein the resin composition comprises at most 15 wt% of organic solvent, based on the total weight of the resin composition.
11. A process for preparing a resin composition comprising an acrylic copolymer, wherein the backbone of the acrylic copolymer has pendant poly (oxyalkylene) segments, and wherein the resin composition has a solids content of at least 80 wt% based on the weight of the acrylic copolymer and a viscosity of 130000mpa.s or less as measured at 25 ℃ using a BROOKFIELD viscometer, the process comprising:
copolymerizing a reaction mixture comprising as a first monomer an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment, an acrylic monomer different from the first monomer, and an additional ethylenically unsaturated monomer in the presence of an organic solvent in an amount of not more than 20 wt%, relative to the total weight of the resin composition, and a free radical initiator, to form the resin composition;
wherein the number average molecular weight of the ethylenically unsaturated monomer containing a poly (oxyalkylene) segment is between 100-10000;
wherein the additional ethylenically unsaturated monomer is selected from styrene, vinyl toluene or mixtures thereof.
12. The method of claim 11, wherein the poly (oxyalkylene) segments are selected from poly (oxyethylene) segments, poly (oxypropylene) segments, poly (oxybutylene) segments, poly (oxypentylene) segments, and any combination thereof.
13. The method of claim 11, wherein the poly (oxyalkylene) segments are selected from poly (oxyethylene) segments, poly (oxypropylene) segments, or combinations thereof.
14. The method of claim 11 wherein the poly (oxyalkylene) -containing segment-containing ethylenically unsaturated monomer has the structure of formula I,
In the formula I above, the acid-base catalyst is,
a is
And R is1、R2And R3Independently of one another from-CH3H or
And R is1、R2And R3At most one of which is
，
Wherein X is- (CH)2)a-, -CO-or- (CH)2)a-CO-wherein a is 1 to 6; r4is-CH3Or H; b and c are independently of each other 0 to 500 and b and c are not simultaneously 0.
15. The method of claim 11 wherein the number average molecular weight of the ethylenically unsaturated monomer containing poly (oxyalkylene) segments is between 200 and 6000.
16. The method as claimed in claim 11 wherein the number average molecular weight of the ethylenically unsaturated monomer containing poly (oxyalkylene) segments is between 300-2000.
17. The method of any of claims 11-16, wherein the acrylic monomer different from the first monomer comprises (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2- (acetoacetoxy) ethyl methacrylate, diacetone acrylamide, methylol (meth) acrylamide, acrylonitrile, or a mixture thereof.
18. The process according to any one of claims 11 to 16, wherein the reaction mixture comprises, relative to the total weight of the reaction mixture,
15 to 60 weight percent of the first monomer;
35 to 60 weight percent of the acrylic monomer different from the first monomer; and
5 to 30 wt% of said additional ethylenically unsaturated monomer.
19. The method of any of claims 11-16, wherein the resin composition has a solids content of at least 81 wt% based on the weight of the acrylic copolymer.
20. The process of any of claims 11-16, wherein the resin composition has a viscosity of 60000mpa.s or less, measured at 25 ℃ using a BROOKFIELD viscometer.
21. The process according to any one of claims 11 to 16, wherein the resin composition has a viscosity of 10000mpa.s or less measured at 25 ℃ using a brookfiield viscometer.
22. The method of any of claims 11-16, wherein up to 15 wt% of an organic solvent is used, based on the total weight of the resin composition.
23. An organic solvent-based coating composition having a VOC emission of less than 420g/L comprising the resin composition of any one of claims 1 to 10 or the resin composition prepared by the method of any one of claims 11 to 22.
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| TW108123290A TWI747001B (en) | 2018-07-11 | 2019-07-02 | High-solid and low-viscosity resin composition containing acrylic copolymer and preparation method thereof |
| PCT/CN2019/094825 WO2020011108A1 (en) | 2018-07-11 | 2019-07-05 | High-solid content low-viscosity resin composition comprising acrylic copolymer |
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| CN102702438A (en) * | 2012-05-09 | 2012-10-03 | 中山大桥化工集团有限公司 | Quick-drying weather-resistant high-solid-content acrylic resin and preparation method thereof |
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| CN103819994A (en) * | 2014-01-27 | 2014-05-28 | 中科院广州化学有限公司 | UV (ultraviolet)-curable acrylate polymer water emulsion for coating polypropylene film |
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| US5475073A (en) * | 1994-11-18 | 1995-12-12 | Arco Chemical Technology, L.P. | Hydroxy-functional acrylate resins |
| JP2004331901A (en) * | 2003-05-12 | 2004-11-25 | Konishi Co Ltd | Vinyl acetate resin-based emulsion and method for producing the same |
| US20060025534A1 (en) * | 2004-07-30 | 2006-02-02 | Johnson Jeffery W | High solids coating composition based on thermal initiated free-radical polymerization |
| EP1863858A1 (en) * | 2005-03-18 | 2007-12-12 | Basf Aktiengesellschaft | Cationic polymers as thickeners for aqueous and alcoholic compositions |
| NZ553410A (en) * | 2006-03-02 | 2008-06-30 | Rohm & Haas | Scrub and stain-resistant copolymer coating composition |
| AU2010273513A1 (en) * | 2009-07-14 | 2012-02-02 | Basf Corporation | Low VOC solvent-borne printing inks |
| US9834698B2 (en) * | 2012-02-10 | 2017-12-05 | Arkema Inc. | Latex binders useful in zero or low VOC coating compositions |
| ES2947232T3 (en) * | 2012-02-10 | 2023-08-03 | Arkema Inc | Polymeric latex binders useful in zero or low VOC coating compositions |
| EP2639272A1 (en) * | 2012-03-13 | 2013-09-18 | Cytec Surface Specialties, S.A. | Active energy ray curable aqueous emulsions |
| CN104558431B (en) * | 2013-10-28 | 2018-05-18 | 广东华润涂料有限公司 | The dispersion of water-based latex and inorganic pigment granules comprising the water-based latex |
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| CN102702438A (en) * | 2012-05-09 | 2012-10-03 | 中山大桥化工集团有限公司 | Quick-drying weather-resistant high-solid-content acrylic resin and preparation method thereof |
| CN103319666A (en) * | 2013-06-18 | 2013-09-25 | 华南理工大学 | Hyperbranched modified hydroxy acrylic resin aqueous dispersion, and preparation method and application thereof |
| CN103819994A (en) * | 2014-01-27 | 2014-05-28 | 中科院广州化学有限公司 | UV (ultraviolet)-curable acrylate polymer water emulsion for coating polypropylene film |
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