CN110713592A - High-solid low-viscosity resin composition containing polyether modified polyester - Google Patents
High-solid low-viscosity resin composition containing polyether modified polyester Download PDFInfo
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- CN110713592A CN110713592A CN201810759016.9A CN201810759016A CN110713592A CN 110713592 A CN110713592 A CN 110713592A CN 201810759016 A CN201810759016 A CN 201810759016A CN 110713592 A CN110713592 A CN 110713592A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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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
- C09D7/20—Diluents or solvents
Abstract
The present invention relates to a high solids, low viscosity resin composition comprising a polyether modified polyester, wherein the resin composition has a solids content of at least about 75 wt% based on the weight of the polyether modified polyester and a viscosity of 6000mpa.s or less at 25 ℃ as measured using a BROOKFIELD viscometer, and the polyether modified polyester bears poly (oxyalkylene) segments.
Description
Technical Field
The invention relates to a resin composition with high solid content and low viscosity, in particular to a resin composition with high solid content and low viscosity, which comprises polyether modified polyester. 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-based coating compositions having VOC levels in excess of 420g/L in China since 2 months 2015 would be subject to additional royalties of up to 4%, which would 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 based coating compositions having a VOC content of no more than 420 g/L.
To meet the above requirements, it has been disclosed to reduce the resin viscosity by introducing hyperbranched structures in polyester resins to obtain high solids low viscosity resin compositions suitable for solvent based coating compositions, as disclosed in CN 106700047. The application of the resin composition can obviously reduce the using amount of the diluent in the coating preparation and reduce the emission of VOC. However, this method has problems in that the process is difficult to control and the resin is liable to gel during the preparation process. In addition to this, by reducing the molecular weight of the polymer and the amount of solvent used during the preparation of the resin composition, it is another direction to reduce VOC emissions of the resulting solvent-based coating composition. However, the space for reducing the amount of solvent during the preparation of conventional resin compositions is practically limited, and usually not less than 20% by weight based on the total weight of the resin composition. If an attempt is made to lower the solvent again, the resulting resin composition becomes too viscous, or even gel, to be useful in the formulation of coating compositions.
Thus, to meet the VOC content requirement of less than 420g/L, the coating industry still needs further improved polyester 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 a polyether modified polyester, wherein the polyether modified polyester has poly (oxyalkylene) segments, and wherein the resin composition has a solids content of at least about 75 wt% based on the weight of the polyether modified polyester and a viscosity of 6000mpa.s or less at 25 ℃ as measured using a BROOKFIELD viscometer. Preferably, the resin composition comprises, relative to the total weight of the resin composition, not more than 9 wt.%, preferably not more than 8 wt.% of an organic solvent.
In another aspect, the present invention provides a method for preparing a resin composition comprising a polyether modified polyester according to the present invention, the method comprising: the polyether polyol and optionally other polyols other than the polyether polyol are subjected to an esterification reaction with a polybasic acid or anhydride and optionally a monofunctional acid in the presence of an organic solvent in an amount of not more than 9% by weight relative to the total weight of the resin composition, thereby forming the polyether-modified polyester-containing resin composition.
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.
In another aspect, the present invention relates to the use of a polyether polyol for the preparation of a high solids low viscosity resin composition according to the present invention.
The inventors of the present invention have pioneering provided a resin composition comprising a polyether modified polyester having a solids content of at least about 75 wt% based on the weight of the polyether modified polyester and a viscosity of 6000mpa.s or less at 25 ℃ as measured using a BROOKFIELD viscometer, wherein the polyether modified polyester bears poly (oxyalkylene) segments. Meanwhile, the resin composition according to the present invention comprises, relative to the total weight of the resin composition, not more than 9 wt% of organic solvent, preferably not more than 8 wt% of organic solvent, and even as low as 5 wt% of organic solvent.
The inventors of the present invention have surprisingly found that the introduction of a polyether polyol having a poly (oxyalkylene) segment during the preparation of the resin composition of the present invention, 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 the high solids, low viscosity resin composition according to the present invention can be formed by esterifying a polyether polyol and optionally a further polyol different from said polyether polyol with a polycarboxylic acid and optionally a monofunctional acid at very low organic solvent content, which was not foreseen 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 herein, as well as where no numerical word is used. Thus, for example, a coating composition comprising "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 about 75 wt% or greater, preferably 80 wt% or greater, wherein the solids content is based on the resin components of 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-based coating composition," means that the solvent-based 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-based coating composition of the present invention comprises less than 100ppm water; the term "essentially completely free of" water means that the solvent-based coating composition of the present invention comprises less than 5ppm water; the term "completely free of water means that the solvent-based coating composition of the present invention contains less than 20 parts per billion (ppb) of water.
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 can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
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, and the like. Moreover, the disclosed numerical ranges include all subranges within the broad range, for example, 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 be preferred, under the same or other circumstances. In addition, 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 a polyether modified polyester, wherein the resin composition has a solids content of at least about 75 wt% based on the weight of the polyether modified polyester and a viscosity of 6000mpa.s or less at 25 ℃ as measured using a BROOKFIELD viscometer, and the polyether modified polyester bears poly (oxyalkylene) segments.
The resin composition according to the present invention not only has a high solids content, but also has a very low viscosity, and thus can be used to formulate solvent-based coating compositions without introducing excessive amounts of VOCs. 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 polyether modified polyester. In a more preferred embodiment of the present invention, the resin composition has a solids content of about 83 wt% or more based on the weight of the polyether modified polyester. The inventors of the present invention have surprisingly found that the resin composition of the present invention has a significantly lower viscosity while maintaining a high solids content. In one embodiment of the present invention, the resin composition has a viscosity of 5000mpa.s or less, preferably 4000mpa.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 9% by weight, preferably not more than 8% by weight, of organic solvent, relative to the total weight of the resin composition.
The resin composition having the above characteristics does not require addition of a large amount of solvent for dilution when used for formulating a solvent-based coating composition, or even does not require addition of a solvent as a diluent at all, and therefore can be formulated to form a solvent-based coating composition having a VOC emission of not more than 420 g/L.
In the resin composition according to the present invention, the polyether modified polyester has a poly (oxyalkylene) segment. In an embodiment of the invention, the polyether modified polyester comprises from 30% to 70%, preferably from 40% to 65%, more preferably from 45% to 60% by weight of poly (oxyalkylene) segments, based on the weight of the polyether modified polyester. The presence of poly (oxyalkylene) segments in the polyether modified polyester allows resin compositions containing the polyether modified polyester to exhibit significantly reduced viscosity while maintaining high solids content.
According to the present invention, the poly (oxyalkylene) segments are selected from the group consisting 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 a polyether polyol. The polyether polyol comprises polyether diol, polyether triol, polyether tetraol and the like. In one embodiment of the present invention, the number average molecular weight of the polyether polyol is in the range of 200-. The number average molecular weight can be measured using GPC.
In the resin composition according to the present invention, the polyether-modified polyester may have a number average molecular weight (M) in the range of 2000-8000g/mol, more preferably in the range of 2100-6000g/mol, even more preferably in the range of 2200-4000g/moln) (ii) a And a weight average molecular weight (M) in the range of 4000-16000g/mol, preferably in the range of 4200-10000g/mol, more preferably in the range of 5000-9000g/molw). The number average molecular weight and the weight average molecular weight can be measured using GPC. Preferably, the Polydispersity (PD) of the polyether modified polyester is less than 2.65, more preferably less than 2.60, even more preferably less than 2.55, most preferably less than 2.50. The polydispersity is a parameter that characterizes the degree of molecular weight dispersion, and a smaller PD means a narrow molecular weight distribution, which contributes to obtaining a resin with a high solid content.
In the resin composition according to the present invention, the polyether modified polyester may have a glass transition temperature in the range of-20 ℃ to 10 ℃, preferably in the range of-17 ℃ to 5 ℃, more preferably in the range of-16 ℃ to 0 ℃. The glass transition temperature can be measured by Differential Scanning Calorimetry (DSC) according to ISO 11357 at a heating rate of 5 ℃/min. The present inventors have surprisingly found that by incorporating an appropriate amount of poly (oxyalkylene) segments in the polyester backbone via polyether modification, polyester resins having lower glass transition temperatures are obtained.
According to the present invention, the resin composition is made of components comprising: 30-65 wt% of a polyether polyol, relative to the total weight of the resin composition; 0-25 wt.%, relative to the total weight of the resin composition, of a further polyol different from polyether polyol; 15-30 wt% of a polybasic acid or anhydride, relative to the total weight of the resin composition; and 0 to 10 wt%, preferably 5 to 10 wt%, of a monofunctional acid, relative to the total weight of the resin composition.
The inventors of the present invention have surprisingly found that the resin composition according to the present invention can be formed by: the polyether polyol and optionally other polyols other than polyether polyol are condensation polymerized with a polybasic acid, a monofunctional acid in the presence of a very small amount of an organic solvent without gelling. Preferably, the organic solvent is present in an amount of 2 to 9 wt%, preferably 2 to 8 wt%, more preferably 2 to 5 wt%, relative to the total weight of the resin composition. Resin compositions are thereby obtained which not only have a high solids content but also have a significantly lower viscosity, for example, the resin composition has a solids content of at least about 75 wt% based on the weight of the polyether modified polyester and a viscosity of 6000mpa.s or less as measured at 25 ℃ using a BROOKFIELD viscometer.
According to the present invention, the polyether polyol may have a structure represented by the following formula:
wherein a and b are independently of each other 0 to 500 and a and b are not simultaneously 0; c is an integer from 1 to 6;is a backbone derived from a polyol selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, neopentyl glycol, dipentaerythritol, and combinations thereof. The above polyether polyols may be synthetic, such as may be obtained by grafting polyoxyethylene, polyoxypropylene, a copolymer of polyoxyethylene and polyoxypropylene, or combinations thereof, onto the above polyols, or may be commercially available, such as the polyether polyol HMP-547B available from royal horse, zhejiang. The skilled person can select as desired.
In the preparation of the resin composition according to the present invention, polyether polyol is necessary. As described above, the inventors of the present invention have surprisingly found that the viscosity of a resin composition can be significantly reduced while maintaining the solids content of the resin composition by introducing a polyether polyol containing poly (oxyalkylene) segments during the preparation of the resin composition, so 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 polyether polyols for the preparation of a high solids low viscosity resin composition comprising a polyether modified polyester according to the present invention.
Preferably, the components used for preparing the resin composition of the present invention comprise, relative to the total weight of the resin composition, 30-65 wt% of polyether polyol, preferably 40-65 wt% of polyether polyol.
According to the present invention, the other polyol than the polyether polyol is an optional component, and the presence of this component makes it possible to form a polyester resin having a branched structure, thereby making it possible to further reduce the viscosity and improve the solid content of the resin composition according to the present invention. In an embodiment according to the invention, the other polyol than the polyether polyol comprises one or more of trimethylolpropane, pentaerythritol, neopentyl glycol, diethylene glycol, 1, 4-butanediol, ethylbutylpropanediol, 2, 4-diethyl-1, 5-pentanediol, ditrimethylolpropane, dipentaerythritol, preferably trimethylolpropane.
Preferably, the components used for preparing the resin composition of the present invention comprise, relative to the total weight of the resin composition, from 0 to 25% by weight of other polyols different from polyether polyols, preferably from 10 to 25% by weight of other polyols different from polyether polyols.
According to the invention, the polybasic acid or anhydride comprises one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic anhydride, terephthalic anhydride, maleic anhydride, fumaric anhydride, trimellitic anhydride, preferably phthalic anhydride. The polyacid or anhydride is present in an amount of 15 to 30 wt.%, relative to the total weight of the resin composition.
According to the present invention, the monofunctional acid is an optional component, and the presence of this component serves to adjust the drying properties of the resulting resin composition. In one embodiment according to the present invention, the monofunctional acid comprises one or more of caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, preferably lauric acid. The monofunctional acid is present in an amount of 0 to 10 wt%, preferably 5 to 10 wt%, relative to the total weight of the resin composition.
In the preparation of the resin composition according to the present invention, an organic solvent may be included to adjust the viscosity of the system. The organic solvent comprises any one or more of xylene, toluene or cyclohexane, preferably xylene. According to the present invention, the amount of organic solvent can be very low, e.g. below 10 wt%, below 9 wt%, below 8 wt%, below 7 wt%, below 6 wt%, even below 5 wt%, calculated with respect to the total weight of the resin composition, without affecting the formation of the polyester resin, 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 in practice limited, generally not less than 20% by weight of the total weight of the resin composition. If an attempt is made to lower the solvent again, the resulting resin composition becomes too viscous, or even gel, to be useful in the formulation of coating compositions.
Accordingly, the present invention also relates to a process for preparing a resin composition comprising a polyether modified polyester according to the present invention, the process comprising: the polyether polyol and optionally other polyols other than the polyether polyol are subjected to an esterification reaction with a polybasic acid or anhydride and optionally a monofunctional acid in the presence of an organic solvent in an amount of not more than 9% by weight relative to the total weight of the resin composition, thereby forming the polyether-modified polyester-containing resin composition.
In a particular embodiment of the present invention, the resin composition comprising a polyether modified polyester according to the present invention is prepared in the presence of 2 to 9 wt% of xylene with respect to the total weight of the resin composition, from the following components: 30-65 wt% of HMP-547B, relative to the total weight of the resin composition; 10-25 wt% of trimethylolpropane, relative to the total weight of the resin composition; 15-30 wt% phthalic anhydride, relative to the total weight of the resin composition; and 0-10 wt% of lauric acid, relative to the total weight of the resin composition.
Preferably, the resin composition comprising the polyether modified polyester has a solids content of at least about 80 wt%, more preferably at least about 83 wt%, based on the weight of the polyether modified polyester. Preferably, the resin composition comprising the polyether modified polyester has a viscosity of 5000mpa.s or less, more preferably 4000mpa.s or less, measured at 25 ℃ using a BROOKFIELD viscometer.
Without wishing to be bound by any theory, the inventors provide the following explanation to enable the invention to be better understood.
According to the present invention, a poly (oxyalkylene) segment is introduced into the molecular skeleton of the polyether modified polyester contained in the resin composition in an appropriate amount, and the poly (oxyalkylene) segment has excellent flexibility and contributes to improvement of molecular mobility of the polyester, so that the purpose of significantly reducing the viscosity of the resin composition can be achieved. Further, a polyester resin composition having further improved properties can be obtained by appropriately combining the polyether polyol with the other polyol than the polyether polyol. For example, trimethylolpropane has 3 primary hydroxyl groups, which not only has high reactivity, but also contributes to the formation of branched chains, and the presence of branched chains is beneficial to reducing the polarity of the polyester, improving the solubility of the polyester in a solvent, and making it possible to prepare a resin with high solid content without requiring an excessive amount of organic solvent.
Due to the high solids content and low viscosity, the resin composition comprising the polyether-modified polyester according to the present invention is suitable for formulating low VOC solvent-based coating compositions, for example, solvent-based coating compositions having a VOC emission 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 polyether modified polyester resin composition disclosed herein and optional 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 resin composition comprising polyether modified polyester 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, more preferably in the range of 50 to 85 parts by weight, relative to the total weight of the solvent-based coating composition.
According to the present invention, the solvent-based coating composition may further comprise one or more additional additives. Examples of additional additives suitable for use in the coating composition include crosslinking agents, surfactants, dispersants, wax adjuvants, defoamers, rheology modifiers, colorants (including pigments and dyes), fillers, heat stabilizers, flow/leveling agents, matting agents, settling inhibitors, light stabilizers, biological agents, plasticizers, solvents, and combinations thereof.
In one embodiment, the low VOC solvent-based coating composition comprises a crosslinking agent, a dispersant, a matting agent, a leveling agent, a defoaming agent and a solvent as additional additives, as long as the VOC emission amount of the composition does not exceed 420 g/L.
Examples of suitable crosslinker components are amino resins and polyisocyanates. Polyisocyanates are preferred.
The amino resin is obtained by reacting formaldehyde with an amine or amide. The most commonly used amines or amides are melamine, urea or benzoguanamine. However, amino resins prepared from other amines and amides, such as aldehyde condensates or the alkyl and aryl disubstituted derivatives of diazines, triazoles, guanidines, guanamines and these compounds, including alkyl and aryl substituted ureas and alkyl and aryl substituted melamines and benzoguanamines, may also be used. Some examples of these compounds are N, N-dimethylurea, ethylenediurea, N-phenylurea, formylguanamine, acetoguanamine, 6-methyl-2, 4-diamino-1, 3, 5-triazine, 3, 5-diaminotriazole, triaminopyrimidine, 2, 6-triethyltriamine-1, 3, 5-triazine, and mixtures thereof.
Although the aldehyde used to prepare the amino resin is typically formaldehyde, other aldehydes such as acetaldehyde, crotonaldehyde, benzaldehyde, and furfural may also be used. The amino resin preferably contains methylol or similar hydroxyalkyl groups, preferably at least some up to substantially all of the hydroxyalkyl groups are etherified by reaction with an alcohol to assist in providing an organic solvent soluble resin. Any monohydric alcohol may be used for this purpose, examples of such alcohols include methanol, ethanol, butanol and hexanol.
Preferred amino resins include melamine, urea-or benzoguanamine-formaldehyde condensates etherified with alcohols containing 1 to 4 carbon atoms, such as methanol, ethanol, butanol, or mixtures thereof.
When amino resin-containing crosslinkers are utilized as crosslinkers, the coating of the solvent-based coating composition is typically cured at a temperature of 200 ℃ to 300 ℃ for 15 to 20 minutes.
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 polyisocyanates are polyfunctional aliphatic isocyanates based on Hexamethylene Diisocyanate (HDI). Some of the HDIs commercially available include
HDT or
HDT LV, available from Rhone-Poulenc Inc. (division of organic chemistry), Monmouth Junction, NJ, or
N-3300 or
N-3390 isocyanate from Bayer AG, Pittsburgh, Pa.
One advantage of using a polyisocyanate component in the solvent-based coating composition of the present invention is that the coating can be cured at room temperature.
As an example of the dispersant, BYK 103 available from BYK corporation can be used. As an example of the matting agent, GRACE 7000 available from the American lace company can be used. As an example of the leveling agent, BYK358 available from BYK corporation can be used. As an example of the antifoaming agent, BYK-071 available from BYK company can be used. As examples of solvents, xylene, propylene glycol monomethyl ether acetate, butyl acetate, and other solvents suitable for coating compositions, or any combination thereof, may be used.
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.
According to the present invention, the solvent-based coating composition may be applied by a conventional coating method 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 following examples 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).
Molecular weight
"GPC molecular weight" refers to a molecular weight determined by Gel Permeation Chromatography (GPC) using a differential refractometer as a detector. A set of 3 GPC columns loaded with styrene/divinylbenzene beads having a bead pore size of 100 to 10,000 angstroms was used during the analysis. The solvent used was Tetrahydrofuran (THF), which flowed through the GPC column at a rate of 1.0 ml/min. The column temperature was maintained at 40 ℃.
Hardness of pencil
This test is used to measure the hardness of the cured coating. Pencil hardness was evaluated using ASTM D3363. 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 d 3359-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 polyether-modified polyester
The resin compositions containing polyether modified polyesters were prepared in the amounts of the components shown in Table 2 below. The method comprises the following specific steps:
(1) weighing the raw materials;
(2) TMP, HMP-547B, phthalic anhydride, lauric acid and half volume of xylene were added to the reaction vessel in order and heating was started;
(3) after the raw materials are completely melted, introducing nitrogen to remove oxygen for 10 minutes, starting stirring, heating to 180-210 ℃, and carrying out esterification for 5-6 hours;
(4) and cooling to 150 ℃, gradually adding the rest dimethylbenzene, and stirring for 15-20min to obtain the resin composition containing the polyether modified polyester.
TABLE 2
| Composition (I) | Comparative resin/g | Resin 1/g | Resin 2/g |
| TMP | 470 | 226 | 117 |
| HMP-547B | 0 | 420 | 616 |
| Phthalic anhydride | 367 | 233 | 167 |
| Lauric acid | 114 | 73 | 52 |
| Xylene | 48 | 48 | 48 |
| Total of | 999 | 1000 | 1000 |
The solid content and viscosity of the obtained resin composition, and the weight average molecular weight, number average molecular weight, dispersion coefficient and glass transition temperature of the polymer resin were measured, and the results are shown below:
TABLE 3
| Examples of the invention | Solid content | Viscosity/mpa.s | Mn | Mw | PD | Tg/℃ |
| Comparative resin | 83.3％ | 384000 | 2051 | 5518 | 2.69 | 21.3 |
| Resin 1 | 83.7％ | 4579 | 2249 | 5739 | 2.55 | -15.3 |
| Resin 2 | 84.4％ | 2971 | 3216 | 7492 | 2.33 | -4.3 |
From the above results, it can be seen that in the preparation of polyester resins, a high solids, low viscosity resin composition containing a polyether modified polyester having a solids content of at least about 75% by weight based on the weight of the polyether modified polyester and a viscosity of 6000mPa.s or less as measured at 25 ℃ using a BrookFIELD viscometer can be formed by incorporating an appropriate amount of poly (oxyalkylene) segments in the polyester backbone. Furthermore, the resin composition according to the invention comprises a very small amount of organic solvent, for example as low as 5 wt%.
Preparation of low VOC solvent-based coating compositions
Solvent-based coating compositions were prepared according to the formulation of table 4 below, and a dispersant, a drier, a leveling agent, a defoaming agent and polyisocyanate were added to the polyester composition obtained above under stirring, thereby forming solvent-based coating compositions.
The solvent-based coating composition thus formed was applied to a bare steel plate with a film coater, thus obtaining a coating layer of 0.05mm (2. + -. 0.1mil) dry film thickness. The coating was cured at room temperature for two weeks and then the coating properties given in Table 4 below were obtained
TABLE 4
From the above results, it can be seen that the resin composition comprising polyether modified polyester according to the present invention can be directly used to formulate a low VOC (VOC emission less than 420g/L) solvent based coating composition, and that the coating layer formed therefrom has comparable or better coating properties than the coating layer formed from the conventional solvent based coating composition.
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 (22)
1. A resin composition comprising a polyether modified polyester, wherein the polyether modified polyester has poly (oxyalkylene) segments, and wherein the resin composition has a solids content of at least about 75 wt% based on the weight of the polyether modified polyester and a viscosity of 6000mpa.s or less at 25 ℃ as measured using a BROOKFIELD viscometer.
2. The resin composition of claim 1, wherein the resin composition has a solids content of at least about 80 wt% based on the weight of the polyether modified polyester.
3. The resin composition of claim 1, wherein the resin composition has a solids content of at least about 83 wt% based on the weight of the polyether modified polyester.
4. Resin composition according to claim 1, wherein the resin composition has a viscosity of 5000mpa.s or less, preferably 4000mpa.s or less, measured at 25 ℃ using a BROOKFIELD viscometer.
5. The resin composition according to claim 1, wherein the resin composition comprises not more than 9% by weight of an organic solvent, preferably not more than 8% by weight of an organic solvent, relative to the total weight of the resin composition.
6. The resin composition according to claim 1, wherein the polyether modified polyester comprises from 30% to 70% by weight, preferably from 40% to 65% by weight of poly (oxyalkylene) segments, based on the weight of the polyether modified polyester.
7. The resin composition of claim 6, wherein the polyether modified polyester has poly (oxyalkylene) segments selected from poly (oxyethylene) segments, poly (oxypropylene) segments, poly (oxybutylene) segments, poly (oxypentylene) segments, and any combination thereof.
8. Resin composition according to any one of claims 1-7, wherein the poly (oxyalkylene) segments are derived from a polyether polyol.
9. The resin composition according to any one of claims 1 to 7, wherein the polyether-modified polyester has a number average molecular weight in the range of 2000-8000g/mol and a weight average molecular weight in the range of 4000-16000 g/mol.
10. The resin composition according to any one of claims 1 to 7, wherein the glass transition temperature of the polyether modified polyester is in the range of-20 ℃ to 10 ℃.
11. The resin composition according to any one of claims 1 to 7, wherein the resin composition is prepared from components comprising:
30-65 wt.%, relative to the total weight of the resin composition, of a polyether polyol,
0-25 wt.%, relative to the total weight of the resin composition, of a further polyol different from polyether polyol,
15-30 wt% of a polybasic acid or anhydride, relative to the total weight of the resin composition, and
0 to 10 wt%, preferably 5 to 10 wt%, of a monofunctional acid with respect to the total weight of the resin composition.
12. A process for preparing a resin composition comprising a polyether modified polyester, wherein the polyether modified polyester has poly (oxyalkylene) segments, and wherein the resin composition has a solids content of at least about 75 wt% based on the weight of the polyether modified polyester and a viscosity of 6000mpa.s or less at 25 ℃ as measured using a BROOKFIELD viscometer, the process comprising:
the polyether polyol and optionally other polyols other than the polyether polyol are subjected to an esterification reaction with a polybasic acid or anhydride and optionally a monofunctional acid in the presence of an organic solvent in an amount of not more than 9% by weight relative to the total weight of the resin composition, thereby forming the polyether-modified polyester-containing resin composition.
13. The method of claim 12, wherein the polyether polyol comprises poly (oxyalkylene) segments selected from the group consisting of poly (oxyethylene) segments, poly (oxypropylene) segments, poly (oxybutylene) segments, poly (oxypentylene) segments, and any combination thereof.
14. The method of claim 13, wherein the polyether polyol has the structure shown by the formula:
wherein a and b are independently of each other 0 to 500 and a and b are not simultaneously 0; c isAn integer of 1 to 6;
is a backbone derived from a polyol selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, neopentyl glycol, dipentaerythritol, and combinations thereof.
15. The process as claimed in claim 14, wherein the polyether polyol has a number average molecular weight in the range of 200-5000g/mol, preferably in the range of 300-3000g/mol, more preferably in the range of 400-2000 g/mol.
16. The method of claim 12, wherein the resin composition is made from components comprising:
30-65 wt.%, relative to the total weight of the resin composition, of a polyether polyol,
0-25 wt.%, relative to the total weight of the resin composition, of a further polyol different from polyether polyol,
15-30 wt% of a polybasic acid or anhydride, relative to the total weight of the resin composition, and
0 to 10 wt%, preferably 5 to 10 wt%, of a monofunctional acid with respect to the total weight of the resin composition.
17. A process according to claim 16, wherein the other polyol than polyether polyol comprises one or more of trimethylolpropane, pentaerythritol, neopentyl glycol, diethylene glycol, 1, 4-butanediol, ethylbutylpropanediol, 2, 4-diethyl-1, 5-pentanediol, ditrimethylolpropane, dipentaerythritol.
18. The method of claim 16, wherein the monofunctional acid comprises one or more of caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid.
19. The process of claim 16, wherein the polyacid or anhydride comprises one or more of adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid and anhydride, isophthalic acid and anhydride, terephthalic acid and anhydride, maleic anhydride, fumaric anhydride, trimellitic anhydride.
20. The method of claim 12, wherein the organic solvent comprises any one or more of xylene, toluene, or cyclohexane.
21. A solvent-based coating composition having a VOC emission of less than 420g/L comprising the resin composition of any one of claims 1 to 11 or the resin composition prepared by the method of any one of claims 12 to 20.
22. Use of a polyether polyol as defined in any of claims 13-15 for the preparation of a high solids, low viscosity resin composition, wherein the resin composition comprises a polyether modified polyester, and wherein the resin composition has a solids content of at least about 75 wt% based on the weight of the polyether modified polyester and a viscosity of 6000mpa.s or less measured at 25 ℃ using a BROOKFIELD viscometer.
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| CN201810759016.9A CN110713592A (en) | 2018-07-11 | 2018-07-11 | High-solid low-viscosity resin composition containing polyether modified polyester |
| TW108123289A TWI718579B (en) | 2018-07-11 | 2019-07-02 | High-solid low-viscosity resin composition containing polyether modified polyester and preparation method thereof |
| PCT/CN2019/094819 WO2020011107A1 (en) | 2018-07-11 | 2019-07-05 | High-solid low-viscosity resin composition comprising polyether-modified polyester |
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| TW202006008A (en) | 2020-02-01 |
| WO2020011107A1 (en) | 2020-01-16 |
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