WO2020011108A1 - 一种包含丙烯酸类共聚物的高固低粘的树脂组合物 - Google Patents

一种包含丙烯酸类共聚物的高固低粘的树脂组合物 Download PDF

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WO2020011108A1
WO2020011108A1 PCT/CN2019/094825 CN2019094825W WO2020011108A1 WO 2020011108 A1 WO2020011108 A1 WO 2020011108A1 CN 2019094825 W CN2019094825 W CN 2019094825W WO 2020011108 A1 WO2020011108 A1 WO 2020011108A1
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resin composition
poly
weight
fragment
oxyalkylene
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PCT/CN2019/094825
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English (en)
French (fr)
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开卫华
张平
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广东华润涂料有限公司
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Publication of WO2020011108A1 publication Critical patent/WO2020011108A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates

Definitions

  • the invention relates to a resin composition with high solids and low viscosity, and in particular to a resin composition containing an acrylic copolymer.
  • the present invention also relates to a solvent-based coating composition comprising the resin composition.
  • CN102702438 discloses the use of glycidyl tert-carbonate to prepare high solids and low viscosity acrylic resins.
  • the product thus obtained can only reach a solids content of about 70% and still contain a relatively large amount of organic solvents.
  • Another method is by adding hyperbranched modifiers.
  • CN103319666A discloses the use of hyperbranched modifiers to prepare aqueous dispersions of acrylic resins.
  • this product is suitable for water-based coating systems and can only achieve a solids content of 45%. Compared to water-based coating compositions, low VOC content requirements appear more difficult to achieve with solvent-based coating compositions.
  • the coating industry still needs to further improve the acrylic resin composition with high solid content, relatively low viscosity, and suitable for solvent-based coating composition.
  • the present invention provides a resin composition
  • a resin composition comprising an acrylic copolymer, wherein the acrylic copolymer has a hanging poly (oxyalkylene) segment on a main chain thereof, and wherein the resin composition It has a solid content of at least about 80% by weight based on the weight of the acrylic copolymer and a viscosity of 130,000 mPa.s or lower measured at 25 ° C using a BROOKFIELD viscometer.
  • the present invention relates to a method for preparing the above-mentioned acrylic copolymer-containing resin composition, the method comprising: using an organic solvent in an amount of not more than 20% by weight relative to the total weight of the resin composition and free In the presence of a radical initiator, an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment as a first monomer, an acrylic monomer different from the first monomer, and an additional ethylenic The reaction mixture of unsaturated monomers is copolymerized to form the resin composition.
  • the present invention relates to the use of an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment for the preparation of a high-solid low-viscosity resin composition according to the present invention.
  • the present invention relates to a solvent-based coating composition having a VOC emission amount of less than 420 g / L, which includes the resin composition of the present invention.
  • the inventors of the present invention pioneeredly provided a resin composition including an acrylic copolymer, wherein the resin composition has a solid content of at least about 80% by weight based on the weight of the acrylic copolymer and at 25 ° C A viscosity of 130,000 mPa.s or lower is measured using a BROOKFIELD viscometer, and wherein the main chain of the acrylic copolymer has a hanging poly (oxyalkylene) segment.
  • the resin composition according to the present invention contains up to 20% by weight of an organic solvent with respect to the total weight of the resin composition.
  • the inventors of the present invention have surprisingly discovered that during the preparation of the resin composition of the present invention, the ethylenically unsaturated monomers and acrylic monomers and additional ethylenically unsaturated monomers containing poly (oxyalkylene) fragments
  • the copolymerization of the monomers allows the soft poly (oxyalkylene) segment to hang on the backbone of the acrylic copolymer.
  • the presence of the poly (oxyalkylene) segment can significantly reduce the solid content of the resin composition while significantly reducing Its viscosity enables the resin composition to be formulated into a solvent-based coating composition with a VOC emission of not more than 420 g / L without the need for additional diluents.
  • the inventors of the present invention have further surprisingly found that the high-solid, low-viscosity resin composition according to the present invention can be obtained by combining an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment with It was formed by copolymerization of an acrylic monomer and an additional ethylenically unsaturated monomer, which was difficult to predict before the present invention.
  • composition is described as including or including specific components, it is not expected that optional components not involved in the present invention are not excluded in the composition, and it is expected that the composition may consist of or consist of the components involved, or Where a method is described as including or including a particular process step, it is expected that the method does not exclude optional process steps that are not involved in the present invention, and it is expected that the method may consist of or consist of the process steps involved.
  • the term “high solid content” means that the solid content of the resin composition is at least 80% by weight or more, wherein the solid content is calculated based on the resin component in the resin composition.
  • solvent-based coating composition means that the organic solvent is used as an organic solvent as a water content of less than 2 g / L, preferably substantially free, more preferably substantially free, and still more preferably completely free of water. Coating composition for a dispersion medium.
  • substantially free of water when used in reference to a "solvent-based coating composition” means that the solvent-based coating composition of the present invention contains 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 contains less than 100 ppm water; the term” substantially completely free “water means that the solvent-based coating composition of the present invention contains less than 5 ppm water; the term” completely free “water It means that the solvent-based coating composition of the present invention contains less than 20 parts per billion (ppb) water.
  • ppm parts per million
  • ethylenically unsaturated group means a reactive carbon-carbon double bond unsaturated group having a cis- or trans-configuration, but does not include aromatic unsaturated groups Groups, carbon-carbon triple bonds, carbon-heteroatom unsaturated groups.
  • reactive mixture refers to a mixture composed of monomers having reactivity, excluding solvents that do not participate in the reaction.
  • any lower limit may be combined with any upper limit to form an unclearly stated range; and any lower limit may be combined with other lower limits to form an unclearly stated range, and likewise any arbitrary upper limit may be combined with any other upper limit to form an unclearly stated range.
  • every point or single value between the endpoints of the range is included in the range. Therefore, each point or single numerical value can be used as its own lower limit or upper limit in combination with any other point or single numerical value or in combination with other lower limits or upper limits to form a range that is not explicitly recorded.
  • the range of values defined by the endpoints includes all values within the range, for example, the range of 1 to 5 covers the values 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, and so on.
  • the disclosed numerical range includes all subset ranges within the wider range.
  • the range from 1 to 5 includes the sub-ranges 1 to 4, 1.5 to 4.5, 1 to 2, and so on.
  • the present invention provides a resin composition including an acrylic copolymer, wherein the resin composition has a solid content of at least about 80% by weight based on the weight of the acrylic copolymer, and A viscosity of 130,000 mPa.s or lower was measured with a BROOKFIELD viscometer at 25 ° C, and the acrylic copolymer had a hanging poly (oxyalkylene) segment on the main chain.
  • 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 a solvent-based coating composition without introducing excessive VOC.
  • the resin composition has a solid content of at least about 80% by weight based on the weight of the acrylic copolymer.
  • the inventors have surprisingly found that the resin composition of the present invention has a significantly lower viscosity while maintaining a high solids content.
  • the resin composition has a viscosity of 60,000 mPa.s or lower measured at 25 ° C using a BROOKFIELD viscometer, and more preferably a viscosity of 10,000 mPa.s or lower.
  • the resin composition according to the present invention further contains a relatively small amount of an organic solvent, for example, containing not more than 20% by weight of the organic solvent, preferably not more than 18% by weight of the organic solvent with respect to the total weight of the resin composition.
  • the resin composition having the above characteristics does not need to add a large amount of solvent for dilution when it is used to formulate a solvent-based coating composition, and does not even need to add a solvent as a diluent at all, so it can be formulated to form a VOC emission amount not exceeding 420g / L Solvent-based coating composition.
  • the acrylic copolymer has a hanging poly (oxyalkylene) segment on the backbone.
  • the poly (oxyalkylene) segment is present in an amount of 15-60 wt%, preferably in an amount of 20-50 wt% based on the weight of the acrylic copolymer.
  • the poly (oxyalkylene) segment is suspended on the backbone of the acrylic copolymer so that the resin composition containing the acrylic copolymer can show a significantly reduced viscosity while maintaining a high solid content.
  • the poly (oxyalkylene) is selected from a poly (oxyethylene) fragment, a poly (oxypropylene) fragment, a poly (oxybutylene) fragment, a poly (oxypentyl) fragment, and Any combination of poly (oxyalkylene) fragments.
  • the poly (oxyalkylene) fragment is selected from the group consisting of a poly (oxyethylene) fragment, a poly (oxypropylene) fragment, and a combination thereof.
  • the poly (oxyalkylene) segment is derived from an ethylenically unsaturated monomer having a poly (oxyalkylene) segment containing the following formula I, also known as an ethylenically unsaturated group-containing Polyether,
  • R 1 , R 2 and R 3 are independently selected from-CH 3 , H or And at most one of R 1 , R 2 and R 3 is
  • X is - (CH 2) a -, - CO- or - (CH 2) a -CO-, wherein a is 1-6; R 4 is -CH 3 or H; b and c are each independently 0 to 500 and b and c are not 0 at the same time.
  • the (CH 2) a -CO- is - according to the invention, wherein X is - (CH 2) a - is shown in formula I is referred to as polyether ether polyether, wherein X is -CO- or
  • the polyether represented by Formula I is called an ester-type polyether.
  • the ethylenically unsaturated group-containing polyether is an ether-type polyether.
  • the ether-type polyether according to the present invention include allyl polyether (for example, allyl polyoxyethylene ether, allyl polyoxypropylene polyoxyethylene polyether), methallyl polyether, and the like, all of which are It is commercially available, such as HMP-523B, HMS-239B, HMS-233B, HMP-517B, etc. from Real Madrid, Zhejiang.
  • the ethylenically unsaturated group-containing polyether is an ester-type polyether.
  • ester-type polyether examples include acryloxy polyoxyethylene ether, acryloxy polyoxypropylene ether, methacryloxy polyoxyethylene ether, methacryloxy polyoxypropylene ether These are all commercially available.
  • the number-average molecular weight of the ethylenically unsaturated group-containing polyether is between 100 and 10,000, more preferably between 200 and 6000, and even more preferably between 300 and 2000. .
  • the number average molecular weight can be measured using GPC.
  • the resin composition is made of the following components:
  • first monomer an ethylenically unsaturated monomer (hereinafter referred to as a "first monomer”) containing a poly (oxyalkylene) segment relative to the total weight of the reaction mixture
  • the resin composition according to the present invention can be formed by making a first monomer different from the first monomer in the presence of a radical initiator and a very small amount of an organic solvent.
  • the acrylic monomer and the additional ethylenically unsaturated monomer were copolymerized without gelation.
  • the organic solvent is present in an amount of 15-20% by weight, preferably 15-18% by weight, and more preferably 15-17% by weight relative to the total weight of the resin composition.
  • the resin composition thus obtained has not only a high solids content but also a significantly lower viscosity, for example the resin composition has a solids content of at least about 80% by weight based on the weight of the acrylic copolymer and utilizes BROOKFIELD viscosity at 25 ° C The meter measures a viscosity of 130000 mPa.s or lower.
  • a first monomer is necessary.
  • a first monomer that is, an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment
  • the high solid content and the significant reduction of its viscosity allow the resin composition to be formulated into a solvent-based coating composition with a VOC emission of not more than 420 g / L without the need for an additional thinner.
  • the present invention also relates to the use of the aforementioned ethylenically unsaturated monomer containing a poly (oxyalkylene) segment for preparing a high-solid low-viscosity resin composition containing an acrylic copolymer according to the present invention.
  • the components used to prepare the resin composition of the present invention comprise, based on the total weight of the reaction mixture, 15 to 55% by weight of an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment, preferably 20-50 wt% of ethylenically unsaturated monomers containing poly (oxyalkylene) fragments, and more preferably 20-40 wt% of ethylenically unsaturated monomers containing poly (oxyalkylene) fragments.
  • an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment preferably 20-50 wt% of ethylenically unsaturated monomers containing poly (oxyalkylene) fragments, and more preferably 20-40 wt% of ethylenically unsaturated monomers containing poly (oxyalkylene) fragments.
  • an acrylic monomer different from the first monomer may be further included.
  • the presence of this monomer can be used to provide the mechanical strength and film-forming properties of the resulting resin composition.
  • the acrylic monomer (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (formyl) Methyl) 2-ethylhexyl acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2- (acetoacetoxy) ethyl methacrylate, Diacetone acrylamide, hydroxymethyl (meth) acrylamide, acrylonitrile, allyl methacrylate, or mixtures thereof.
  • the acrylic monomer may include at least one active hydrogen-containing monomer so that the final resin composition obtained has active hydrogen functionality, such as those derived from hydroxyl, amine, and acid functionality .
  • the active hydrogen-containing acrylic monomer is present in an amount of 5-20 wt%, preferably in an amount of 10-15 wt%, based on the total weight of the reaction mixture. The presence of such an active hydrogen-containing acrylic monomer ensures that the obtained acrylic resin-containing resin composition according to the present invention can be used to formulate a two-component solvent-based coating composition.
  • the components used to prepare the resin composition of the present invention comprise, in an amount of at least 35% by weight relative to the total weight of the reaction mixture, preferably in an amount of at least 40% by weight, more preferably in an amount of at least 45% by weight
  • the acrylic monomer is present in an amount of at least 50% by weight. More preferably, the acrylic monomer is present in an amount of up to 60% by weight, and more preferably in an amount of up to 56% by weight, based on the total weight of the reaction mixture.
  • an additional ethylenically unsaturated monomer may be further included. This monomer can be used to adjust the mechanical strength of the obtained resin composition.
  • the additional ethylenically unsaturated monomer is selected from styrene, vinyl toluene, vinyl acetate or a mixture thereof.
  • the components used to prepare the resin composition of the present invention comprise additional ethylenically unsaturated monomers present in an amount of 15-30% by weight relative to the total weight of the reaction mixture.
  • an organic solvent may be included to adjust the system viscosity.
  • Suitable solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; alcohols such as ethanol, isopropanol, n-butanol, tert-butanol, and ethylhexanol; and esters such as ethyl acetate, propyl acetate, and butyl acetate Esters, isobutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like.
  • solvents include ketones, such as methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, etc .; glycols such as propylene glycol and diethyl glycol; glycol ethers such as propylene glycol monomethyl ether , Ethylene glycol monomethyl ether.
  • ketones such as methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, etc .
  • glycols such as propylene glycol and diethyl glycol
  • glycol ethers such as propylene glycol monomethyl ether , Ethylene glycol monomethyl ether.
  • various mixtures of solvents can be used.
  • the amount of the organic solvent can be very low, for example, less than 20% by weight, less than 19% by weight, less than 18% by weight, less than 17% by weight, and less than 15% by weight, without affecting the formation of the acrylic copolymer, Wherein the amount is calculated relative to the total weight of the resin composition, which was unimaginable before the present invention.
  • the reduction in the amount of solvent used during the preparation of a conventional resin composition is actually limited, usually not less than 20% by weight of the total weight of the reaction mixture. If an attempt is made to lower the solvent, the obtained resin composition becomes too viscous or even gelled, and thus cannot be used for the formulation of a coating composition.
  • the present invention also relates to a method for preparing a resin composition containing an acrylic copolymer according to the present invention, the method comprising: an amount of not more than 20% by weight relative to the total weight of the resin composition In the presence of an organic solvent and a radical initiator, an ethylenically unsaturated monomer containing a poly (oxyalkylene) segment as a first monomer, an acrylic monomer different from the first monomer, and The reaction mixture of the additional ethylenically unsaturated monomer is copolymerized to form the resin composition.
  • an appropriate amount of poly (oxyalkylene) segment is suspended on the acrylic copolymer main chain. Due to the flexibility of the poly (oxyalkylene) segment, there is Helps improve the molecular mobility of acrylic copolymers, thereby achieving the purpose of significantly reducing viscosity. In addition, the non-polar side groups suspended on the main chain weaken the interaction between the molecular chains, further improving the solubility of the acrylic copolymer in a solvent, thereby enabling the acrylic copolymer-containing resin combination according to the present invention.
  • the preparation can be carried out in the presence of very small amounts of organic solvents without gelling or hardening.
  • the resin composition containing an acrylic copolymer according to the present invention is suitable for formulating a solvent-based coating composition having a low VOC, for example, a solvent-based coating composition having a VOC emission amount not exceeding 420 g / L Thing.
  • another aspect of the present invention provides a solvent-based coating composition having a VOC emission amount not exceeding 420 g / L, which includes the acrylic copolymer-containing resin composition disclosed herein and optional additional additives.
  • the solvent-based coating composition includes (i) 30 to 99.5 parts by weight of a resin composition including a polyether-modified polyester with respect to the total weight of the coating composition; (ii) 0.5 to 70 parts by weight of optional additional additives.
  • the content of the acrylic copolymer-containing resin composition described herein is in the range of 30 to 99.5 parts by weight, and preferably in the range of 40 to 90 parts by weight relative to the total weight of the solvent-based coating composition. Within the range of 50 to 85 parts by weight.
  • the coating composition of the present invention may optionally include other additives that do not adversely affect the coating composition or the cured coating obtained therefrom.
  • Suitable additives include, for example, improving the processability or manufacturing performance of the composition, enhancing the aesthetics of the composition, or improving specific functional properties or characteristics of the coating composition or the cured composition derived therefrom, such as adhesion to a substrate ) Those reagents.
  • Additives that can be included are solvents, carriers, additional polymers, pigments, metal powders or pastes, fillers, anti-migration aids, antibacterial agents, extenders, lubricants, defoamers, biocides, plasticizers Agents, thickeners, colorants, waxes, antioxidants, corrosion inhibitors, flow control agents, thixotropic agents, dispersants, UV stabilizers, or combinations thereof.
  • plasticizers Agents, thickeners, colorants, waxes, antioxidants, corrosion inhibitors, flow control agents, thixotropic agents, dispersants, UV stabilizers, or combinations thereof The content of each optional ingredient is sufficient to achieve its intended purpose, but preferably such content does not adversely affect the coating composition or the cured coating obtained therefrom.
  • additional additives suitable for the coating composition include plasticizers, pigments, fillers, thickeners, defoamers, wetting agents, dispersants, solvents, or combinations thereof.
  • the content of the additional additive is within a range of 0.5 to 70 parts by weight, or more preferably within a range of 1 to 50 parts by weight, with respect to the total weight of the solvent-based coating composition.
  • the resin composition according to the present invention can also be used to formulate a two-component solvent-based coating composition. Therefore, another aspect of the present invention includes a two-component solvent-based coating composition having a VOC emission amount not exceeding 420 g / L, which comprises a film-forming resin composition a), which includes the above-mentioned The disclosed resin composition comprising an acrylic copolymer and optional additional additives; and a crosslinking agent b).
  • Suitable crosslinker component is a polyisocyanate.
  • Suitable polyisocyanate crosslinking agents include aliphatic polyisocyanates, aromatic polyisocyanates, or any combination thereof.
  • aliphatic polyisocyanate refers to a polyisocyanate compound in which an isocyanate group is directly attached to an aliphatic chain or ring.
  • aromatic polyisocyanate refers to a polyisocyanate compound in which an isocyanate group is directly attached to an 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, ten Methylene diisocyanate, butylene-1,2-diisocyanate, butylene-1,3-diisocyanate, ethylene diisocyanate; cycloaliphatic diisocyanates, such as cyclohexylene diisocyanate, 4,4′- Methylene bis (cyclohexyl isocyanate), 2,2,4-trimethylhexamethyl diisocyanate, dimer acid diisocyanate, 3-isocyanatomethyl-3,5,5-trimethyl Cyclohexyl isocyanate; and aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate
  • Particularly suitable isocyanates are polyfunctional aliphatic isocyanates based on hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • Some commercially available HDI include HDT or HDT LV, purchased from Rhone-Poulenc Inc. (organic chemical branch), Monmouth Junction, NJ, or N-3300 or N-3390 isocyanate, commercially available from Bayer AG, Pittsburgh, PA.
  • the solvent-based coating composition may be applied by a conventional coating method known to those skilled 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.
  • Low-VOC solvent-based coating compositions can be applied to a variety of different substrates using conventional coating techniques.
  • suitable substrates include wood, cement, cement fiberboard, wood-plastic composites, tiles, metal, plastic, glass, and fiberglass.
  • 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 of the last successful test before the coating broke. So, for example, if the coating does not crack when tested with a 2H pencil, but breaks when tested with a 3H pencil, the coating is reported to have a pencil hardness of 2H.
  • 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 usually classified on a scale of 0-5B, with 5B representing the best adhesion.
  • HSA Hydroxyethyl acrylate
  • TBPB Tert-butyl peroxybenzoate
  • PMA Propylene glycol monomethyl ether acetate
  • a resin composition containing an acrylic copolymer was prepared according to the ingredients shown in Table 2 below. The specific steps are:
  • reaction temperature of the flask is maintained at 140 ° C, and Part 1 and Part 2 are sequentially added to the reaction flask within a period of 3-3.5 hours;
  • the introduction of ethylenically unsaturated monomers containing poly (oxyalkylene) fragments can form high-solid, low-viscosity resin compositions containing acrylic copolymers.
  • the resin composition has a solid content of at least about 80% by weight based on the weight of the acrylic copolymer and a viscosity of 130,000 mPa.s or lower measured at 25 ° C using a BROOKFIELD viscometer.
  • acrylic copolymers prepared from monomer mixtures containing no ethylenically unsaturated monomers with poly (oxyalkylene) fragments are hard solids and cannot be used to formulate solvent-based coating compositions at all.
  • a low VOC solvent-based coating composition according to the following Table 4, the pigments, fillers, thickeners, defoamers, wetting and dispersing agents, and solvents were added to the acrylic copolymer-containing copolymer obtained according to the above while stirring.
  • the resin composition forms a solvent-based coating composition.
  • the solvent-based coating composition thus formed was applied on a bare steel plate with a coating film applicator, so as to obtain a coating layer having a dry film thickness of 0.05 mm (2 ⁇ 0.1 mil).
  • the coating was cured for two weeks at room temperature and then the measurements given in the table below were obtained
  • the resin composition containing an acrylic copolymer according to the present invention can be directly used to formulate a solvent-based coating composition having a low VOC (VOC emission amount below 420 g / L), and the coating formed therefrom The layer has good coating properties.

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Abstract

本发明涉及一种包含丙烯酸类共聚物的高固低粘的树脂组合物，其中，所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少约80wt％的固含量以及在25℃下利用BROOKFIELD粘度计测量130000mPa.s或更低的粘度，并且所述丙烯酸类共聚物的主链具有悬挂的聚(氧亚烷基)片段。

Description

一种包含丙烯酸类共聚物的高固低粘的树脂组合物
相关申请的交叉引用
本申请要求2018年7月11日提交的中国专利申请201810759658.9的权益，所述申请通过引用整体并入本文。
技术领域
本发明涉及一种高固低粘的树脂组合物，具体涉及一种包含丙烯酸类共聚物的树脂组合物。本发明还涉及包含所述树脂组合物的溶剂基涂料组合物。
背景技术
近年来，随着人们对环境的关注，很多国家已制定了环境法律，并要求进一步降低允许涂料组合物，特别是溶剂型涂料组合物，向空气中释放的VOC量。例如，在中国自2015年2月起，VOC含量超过420g/L的溶剂型涂料组合物将被征收额外消费税，税率高达4％，这将大大增加了涂料公司的成本。因此，对于用于配制VOC含量不超过420g/L的溶剂型涂料组合物的高固低粘树脂组合物的需求急剧增加。
现有技术已经公开了两种常用于制备高固低粘的丙烯酸类树脂组合物的方法，一种方法是使用缩水甘油基化合物。例如CN102702438公开了使用叔碳酸缩水甘油酯来制备高固低粘的丙烯酸树脂。然而，由此得到的产品仅仅可以达到约70％的固含量，而且仍然含有较大量的有机溶剂。另一种方法是通过添加超支化改性剂。例如CN103319666A公开了使用超支化改性剂制备丙烯酸树脂水性分散体。然而，该产品适用于水性涂料体系，仅仅可以达到45％的固含量。与水基涂料组合物相比，低VOC含量要求对于溶剂基涂料组合物显得更难以实现。
此外，业已公开了多种高固低粘的丙烯酸类树脂的商品，例如来自Arkema的854BA80、来自Niupeisi树脂的Setalux 1753以及来自Bayer的 A-870。但是，这些产品仍不能满足涂料工业的需求。
因此，为了满足低于420g/L的VOC含量要求，涂料工业仍需要进一步改进的固含量高、粘度相对较低且适用于溶剂基涂料组合物的丙烯酸类树脂组合物。
发明内容
一方面，本发明提供了一种包含丙烯酸类共聚物的树脂组合物，其中，所述丙烯酸类共聚物的主链上具有悬挂的聚(氧亚烷基)片段，并且其中所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少约80wt％的固含量以及在25℃下利用BROOKFIELD粘度计测量130000mPa.s或更低的粘度。
另一方面，本发明涉及用于制备上述包含丙烯酸类共聚物的树脂组合物的方法，所述方法包括：在相对于所述树脂组合物的总重，用量不超过20wt％的有机溶剂和自由基引发剂的存在下，使包含作为第一单体的含有聚(氧亚烷基)片段的烯属不饱和单体、不同于所述第一单体的丙烯酸类单体和附加的烯属不饱和单体的反应混合物进行共聚，从而形成所述树脂组合物。
另一方面，本发明涉及含有聚(氧亚烷基)片段的烯属不饱和单体用于制备根据本发明的高固低粘树脂组合物的用途。
另一方面，本发明涉及一种VOC排放量低于420g/L的溶剂基涂料组合物，其包含本发明的树脂组合物。
本发明的发明人开创性地提供了一种包含丙烯酸类共聚物的树脂组合物，其中，所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少约80wt％的固含量以及在25℃下利用BROOKFIELD粘度计测量130000mPa.s或更低的粘度，并且其中所述丙烯酸类共聚物的主链具有悬挂的聚(氧亚烷基)片段。与此同时，根据本发明的树脂组合物包含，相对于所述树脂组合物的总重，至多20wt％的有机溶剂。
本发明的发明人惊讶地发现，在本发明的树脂组合物的制备过程中，通过含有聚(氧亚烷基)片段的烯属不饱和单体与丙烯酸类单体和附加的烯属不饱和单体的共聚，使柔软的聚(氧亚烷基)片段悬挂在丙烯酸类共聚物的骨架上，该聚(氧亚烷基)片段的存在可以在保持树脂组合物的固含量的同时显 著降低其粘度，使得该树脂组合物可以配制VOC排放量不超过420g/L的溶剂基涂料组合物，而不需要额外的稀释剂。
本发明的发明人进一步惊讶地发现，根据本发明的高固低粘树脂组合物可以在有机溶剂含量非常低的情况下通过使含有聚(氧亚烷基)片段的烯属不饱和单体与丙烯酸类单体和附加的烯属不饱和单体的共聚来形成，这在本发明之前是难以预见的。
本发明的一个或多个实施方案的细节在以下的说明书中阐明。根据说明书和权利要求，本发明其它特征、目的和优点将变得清楚。
定义
在本文中使用时，除非另有说明，“一种”、“这种”、“至少一种”和“一种或多种”以及不使用数量词的情形可互换使用。因此，例如包含“一种”添加剂的涂料组合物可以被解释为表示该涂料组合物中包含“一种或多种”添加剂。除本文中另有说明外，本文中单数形式的使用还意在包括复数形式。
在组合物被描述为包括或包含特定组分的情况下，预计该组合物中并不排除本发明未涉及的可选组分，并且预计该组合物可由所涉及的组分构成或组成，或者在方法被描述为包括或包含特定工艺步骤的情况下，预计该方法中并不排除本发明未涉及的可选工艺步骤，并且预计该方法可由所涉及的工艺步骤构成或组成。
当出现在本说明书和权利要求中时，术语“包含”和“包括”及其变体不具有限制性含义。
在涉及“树脂组合物”使用时，术语“高固含量”是指该树脂组合物的固含量为至少80wt％或更高，其中所述固含量是基于树脂组合物中的树脂组分计算。
在本发明的上下文中，术语“溶剂基涂料组合物”是指水含量小于2g/L，优选基本上不含，更优选基本上完全不含，还要更优选完全不含水的以有机溶剂作为分散介质的涂料组合物。
当针对“溶剂型涂料组合物”使用时，术语“基本上不含”水是指，本发 明的溶剂型涂料组合物包含小于1000份每百万(ppm)的水；术语“本质上不含”水是指，本发明的溶剂型涂料组合物包含小于100ppm水；术语“本质上完全不含”水是指，本发明的溶剂型涂料组合物包含小于5ppm水；术语“完全不含”水是指，本发明的溶剂型涂料组合物包含小于20份每十亿(ppb)水。
在本发明的上下文中，术语“烯属不饱和基团”是指，具有顺式-或反式-构型的反应性碳-碳双键不饱和基团，但不包括芳族不饱和基团、碳-碳三键、碳-杂原子不饱和基团。
在本发明的上下文中，术语“反应性混合物”是指，由具有反应性的单体构成的混合物，不包括未参与反应的溶剂。
为了简便，本文仅明确地公开了一些数值范围。然而，任意下限可以与任何上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，尽管未明确记载，但是范围端点间的每个点或单个数值都包含在该范围内。因而，每个点或单个数值可以作为自身的下限或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
在本发明中，通过端点限定的数值范围包括该范围内的所有任何数值，例如1到5的范围涵盖了数值1、1.5、2、2.75、3、3.80、4、5等。而且，公开的数值范围包括在该较宽范围内的所有子集范围，例如1到5的范围包括了子范围1到4、1.5到4.5、1到2等。
术语“优选的”和“优选地”是指在某些情况下可提供某些益处的本发明实施方案。然而，在相同或其他情况下，其他实施方案也可能是优选的。另外，一个或多个优选的实施方案的叙述不意味着其他实施方案是不可用的，并且不旨在将其他实施方案排除在本发明范围外。
具体实施方式
根据本发明的第一方面，本发明提供了一种包含丙烯酸类共聚物的树脂组合物，其中，所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少约80wt％的固含量以及在25℃下利用BROOKFIELD粘度计测量130000mPa.s或更低的粘度，并且所述丙烯酸类共聚物的主链上具有悬挂的聚(氧亚烷基) 片段。
根据本发明的树脂组合物不仅具有高固含量，而且具有非常低的粘度，因而可被用于配制溶剂型涂料组合物，而不会引入过量的VOC。在本发明的一个实施方式中，所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少约80wt％的固含量。发明人惊讶地发现，本发明的树脂组合物在保持高固含量的同时具有显著更低的粘度。在本发明的一个实施方式中，所述树脂组合物具有在25℃下利用BROOKFIELD粘度计测量60000mPa.s或更低的粘度，更优选10000mPa.s或更低的粘度。
根据本发明的树脂组合物还包含相当少量的有机溶剂，例如包含，相对于所述树脂组合物的总重，不超过20重量％的有机溶剂，优选不超过18重量％的有机溶剂。
具有上述特性的树脂组合物在被用于配制溶剂型涂料组合物时不需要添加大量的溶剂进行稀释，甚至根本不需要添加溶剂作为稀释剂，因此可以配制形成VOC排放量不超过420g/L的溶剂型涂料组合物。
在根据本发明的树脂组合物中，丙烯酸类共聚物的骨架上具有悬挂的聚(氧亚烷基)片段。在本发明的实施方式中，基于所述丙烯酸类共聚物的重量，所述聚(氧亚烷基)片段以15-60wt％的量存在，优选以20-50wt％的量存在。聚(氧亚烷基)片段悬挂在丙烯酸类共聚物的骨架上使得含有该丙烯酸类共聚物的树脂组合物可以在保持高固含量的同时显示显著降低的粘度。
根据本发明，所述聚(氧亚烷基)选自聚(氧亚乙基)片段、聚(氧亚丙基)片段、聚(氧亚丁基)片段、聚(氧亚戊基)片段及其任意组合的聚(氧亚烷基)片段。优选地，聚(氧亚烷基)片段选自由聚(氧亚乙基)片段、聚(氧亚丙基)片段及其组合组成的组。
根据本发明，所述聚(氧亚烷基)片段衍生自具有下式I的含有聚(氧亚烷基)片段的烯属不饱和单体，也被称为含烯属不饱和基团的聚醚，
Figure PCTCN2019094825-appb-000001
其中A为
Figure PCTCN2019094825-appb-000002
并且R 1、R 2和R 3相互独立地选自- CH 3、H或
Figure PCTCN2019094825-appb-000003
且R 1、R 2和R 3中的至多一个为
Figure PCTCN2019094825-appb-000004
其中X为-(CH 2) a-、-CO-或-(CH 2) a-CO-，其中a为1-6；R 4为-CH 3或H；b和c相互独立地为0至500且b和c不同时为0。
根据本发明，其中的X为-(CH 2) a-的上式I所示聚醚被称为醚型聚醚，其中的X为-CO-或-(CH 2) a-CO-的上式I所示聚醚被称为酯型聚醚。
在一些实施方式中，所述含烯属不饱和基团的聚醚为醚型聚醚。根据本发明的醚型聚醚的实例包括烯丙基聚醚(例如烯丙基聚氧乙烯醚、烯丙基聚氧丙烯聚氧乙烯聚醚)、甲基烯丙基聚醚等，这些都是可商购的，例如来自浙江皇马的HMP-523B、HMS-239B、HMS-233B、HMP-517B等。
在一些实施方式中，所述含烯属不饱和基团的聚醚为酯型聚醚。根据本发明的酯型聚醚的实例包括丙烯酰氧基聚氧乙烯醚、丙烯酰氧基聚氧丙烯醚、甲基丙烯酰氧基聚氧乙烯醚、甲基丙烯酰氧基聚氧丙烯醚，这些都是可商购的。
在本发明的一些实施方式中，所述含烯属不饱和基团的聚醚的数均分子量在100-10000之间，更优选地在200-6000之间，更优选在300-2000之间。所述数均分子量可以使用GPC来测定。
根据本发明，所述树脂组合物是由包含如下的组分制成的：
相对于反应混合物的总重，15-60wt％的含有聚(氧亚烷基)片段的烯属不饱和单体(此后称为“第一单体”)，
相对于反应混合物的总重，35-60wt％的不同于第一单体的丙烯酸类单体，
相对于反应混合物的总重，5-30wt％的附加的烯属不饱和单体。
本发明的发明人惊讶地发现，根据本发明的树脂组合物可以通过如下形成：在自由基引发剂和非常少量的有机溶剂的存在下使第一单体、不同于所述第一单体的丙烯酸类单体和附加的烯属不饱和单体进行共聚合而没有发生凝胶。优选地，所述有机溶剂以相对于所述树脂组合物的总重，15-20wt％、 优选15-18wt％、更优选15-17wt％的量存在。由此获得树脂组合物不仅具有高固含量而且具有显著更低的粘度，例如所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少约80wt％的固含量以及在25℃下利用BROOKFIELD粘度计测量130000mPa.s或更低的粘度。
在根据本发明的树脂组合物的制备中，第一单体是必需的。如上所述，发明人惊讶地发现，在树脂组合物的制备过程中通过引入第一单体，即含有聚(氧亚烷基)片段的烯属不饱和单体，可以在保持树脂组合物的高固含量的同时显著降低其粘度，使得该树脂组合物可以配制VOC排放量不超过420g/L的溶剂基涂料组合物，而不需要额外的稀释剂。
因此，本发明还涉及上述含有聚(氧亚烷基)片段的烯属不饱和单体用于制备根据本发明的包含丙烯酸类共聚物的高固低粘树脂组合物的用途。
优选地，用于制备本发明的树脂组合物的组分包含，相对于所述反应混合物的总重，15-55wt％的含有聚(氧亚烷基)片段的烯属不饱和单体，优选20-50wt％的含有聚(氧亚烷基)片段的烯属不饱和单体，更优选20-40wt％的含有聚(氧亚烷基)片段的烯属不饱和单体。
在根据本发明的树脂组合物的制备中，还可以包括不同于第一单体的丙烯酸类单体。该单体的存在可被用于提供所得树脂组合物的机械强度和成膜性能。在本发明的实施方式中，作为丙烯酸类单体的实例，可以使用(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丁酯、(甲基)丙烯酸羟丙酯、甲基丙烯酸2-(乙酰乙酰氧)乙酯、二丙酮丙烯酰胺、羟甲基(甲基)丙烯酰胺、丙烯腈、甲基丙烯酸烯丙基酯或其混合物。
在一些实施方式中，丙烯酸类单体可以包含至少一种含活性氢的单体，以使所获得的最终树脂组合物具有活性氢官能度，例如来自羟基、胺和酸官能度的那些官能度。优选地，基于反应混合物的总重量，所述含活性氢的丙烯酸类单体以5-20wt％的量存在，优选以10-15wt％的量存在。这种含活性氢的丙烯酸类单体的存在，确保了所得到的根据本发明的包含丙烯酸类共聚物的树脂组合物可被用于配制双组分溶剂型涂料组合物。
优选地，用于制备本发明的树脂组合物的组分包含，相对于反应混合物 的总重量，以至少35wt％的量存在，优选以至少40wt％的量，更优选以至少45wt％的量存在，最优选以至少50wt％的量存在的丙烯酸类单体。更优选地，基于反应混合物的总重量，所述丙烯酸类单体以至多60wt％的量存在，更优选以至多56wt％的量存在。
在根据本发明的树脂组合物的制备中，还可以包括附加的烯属不饱和单体。该单体可被用于调节所得树脂组合物的机械强度。在本发明的实施方式中，所述附加的烯属不饱和单体选自苯乙烯、乙烯基甲苯、乙酸乙烯酯或其混合物。
优选地，用于制备本发明的树脂组合物的组分包含，相对于反应混合物的总重量，以15-30wt％的量存在的附加的烯属不饱和单体。
在根据本发明的树脂组合物的制备中，可以包含有机溶剂以调节体系粘度。合适的溶剂包括芳烃，如苯、甲苯和二甲苯等；醇，如乙醇、异丙醇、正丁醇、叔丁醇和乙基己醇等；酯，如乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸异丁酯、乙二醇单甲基醚乙酸酯、乙二醇单乙基醚乙酸酯、丙二醇单甲基醚乙酸酯等。其它适用的溶剂包括酮，如甲基乙基酮、甲基戊基酮、甲基异丁基酮等；二醇，如丙二醇和二乙基二醇；二醇醚，如丙二醇单甲基醚、乙二醇单甲基醚。当然，可以使用溶剂的各种混合物。根据本发明，有机溶剂的量可以非常低，例如低于20wt％、低于19wt％、低于18wt％、低于17wt％、低于15wt％，而并不会影响丙烯酸类共聚物的形成，其中该用量是相对于树脂组合物的总重计算的，这在本发明之前是难以想象的。如CN1201809所记载的，在常规树脂组合物的制备期间降低使用的溶剂量实际上是有限的，通常不低于反应混合物总重量的20wt％。若试图再降低溶剂，则所得树脂组合物变得过粘，甚至凝胶，从而无法用于涂料组合物的配制。
因此，本发明还涉及一种用于制备根据本发明的包含丙烯酸类共聚物的树脂组合物的方法，所述方法包括：在相对于所述树脂组合物的总重，用量不超过20wt％的有机溶剂和自由基引发剂的存在下，使包含作为第一单体的含有聚(氧亚烷基)片段的烯属不饱和单体、不同于所述第一单体的丙烯酸类单体和附加的烯属不饱和单体的反应混合物进行共聚，从而形成所述树脂组合物。
上述反应的适当条件取决于各种因素，包括含有聚(氧亚烷基)片段的烯属不饱和单体和丙烯酸类单体的类型、溶剂存在与否、以及引发剂的类型等等，这些可由本领域技术人员以经验确定。并不希望束缚于任何理论，发明人提供如下解释，以使本发明能够被更好地理解。
在根据本发明的包含丙烯酸类共聚物的树脂组合物中，丙烯酸类共聚物主链上悬挂有适量的聚(氧亚烷基)片段，由于聚(氧亚烷基)片段的柔韧性，有助于提高丙烯酸类共聚物的分子活动性，从而达到显著降低粘度的目的。此外，悬挂在主链上的非极性侧基弱化了分子链间的作用力，进一步提高了丙烯酸类共聚物在溶剂中的溶解性，从而使得根据本发明的含有丙烯酸类共聚物的树脂组合物的制备可以在非常少量的有机溶剂的存在下进行，而不会发生凝胶或硬化。
由于具有高固含量和低粘度，根据本发明的包含丙烯酸类共聚物的树脂组合物适用于配制低VOC的溶剂基涂料组合物，例如可以配制VOC排放量不超过420g/L的溶剂基涂料组合物。
因此，本发明的另一方面提供了一种VOC排放量不超过420g/L的溶剂基涂料组合物，其包含本文所公开的包含丙烯酸类共聚物的树脂组合物和可选的附加添加剂。具体地，所述溶剂基涂料组合物，包含，相对于所述涂料组合物的总重，(i)30至99.5重量份包含聚醚改性的聚酯的树脂组合物；(ii)0.5至70重量份的可选的附加添加剂。
根据本发明，本文所述的包含丙烯酸类共聚物的树脂组合物的含量，相对于溶剂基涂料组合物的总重，在30至99.5重量份的范围内，优选在40至90重量份的范围内，更优选在50至85重量份的范围内。
如果需要，本发明的涂料组合物可选包含其他添加剂，这些添加剂不会不利地影响涂料组合物或由其得到的固化涂层。适当的添加剂包括例如会改善组合物的加工性能或制造性能、增强组合物的美感、或改善涂料组合物或由其得到的固化组合物的特定功能性质或特性(诸如对基材的粘附性)的那些试剂。可以包含的添加剂是溶剂、载剂、附加聚合物、颜料、金属粉末或膏体、填料、抗迁移助剂、抗菌剂、增量剂、润滑剂、消泡剂、生物杀灭剂、增塑剂、增稠剂、着色剂、蜡、抗氧化剂、防腐蚀剂、流动控制剂、触变剂、 分散剂、UV稳定剂、或其组合。各个可选成分的含量足以起到其意欲达到的目的，但优选地，这样的含量不会不利地影响涂料组合物或由其得到的固化涂层。适用于该涂料组合物的附加添加剂的实例包括增塑剂、颜料、填料、增稠剂、消泡剂、润湿剂、分散剂、溶剂或其组合。
附加添加剂的含量，相对于溶剂基涂料组合物的总重，在0.5至70重量份的范围内，或者更优选在1至50重量份的范围内。
除了配制以上VOC排放量不超过420g/L的溶剂基涂料组合物以外，根据本发明的树脂组合物还可用于配制双组份的溶剂基涂料组合物。因此，本发明另一方面包括一种双组份的VOC排放量不超过420g/L的溶剂基涂料组合物，其包含成膜树脂组合物a)，所述成膜树脂组合物包含上述本文所公开的包含丙烯酸类共聚物的树脂组合物和可选的附加添加剂；和交联剂b)。
合适的交联剂组分的例子为多异氰酸酯。
适当的多异氰酸酯交联剂包括脂族多异氰酸酯、芳族多异氰酸酯或其任意组合。本文使用的术语“脂族多异氰酸酯”指异氰酸酯基直接连接到脂族链或环上的多异氰酸酯化合物。本文使用的术语“芳族多异氰酸酯”指异氰酸酯基直接连接到芳族环上的多异氰酸酯化合物。
用于本发明的合适的异氰酸酯包括脂族二异氰酸酯，如三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、八亚甲基二异氰酸酯、十亚甲基二异氰酸酯、亚丁基-1,2-二异氰酸酯、亚丁基-1,3-二异氰酸酯、亚乙基二异氰酸酯；环脂族二异氰酸酯，如环亚己基二异氰酸酯、4,4′-亚甲基双(环己基异氰酸酯)、2,2,4-三甲基六甲基二异氰酸酯、二聚体酸二异氰酸酯、3-异氰酸根合甲基-3,5,5-三甲基环己基异氰酸酯；和芳族二异氰酸酯，如2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、氯化甲苯二异氰酸酯、间亚苯基二异氰酸酯、氯化间亚苯基二异氰酸酯、邻亚苯基二异氰酸酯、溴化间-亚苯基二异氰酸酯、间亚二甲苯基二异氰酸酯、对亚二甲苯基二异氰酸酯、亚萘基-1,4-二异氰酸酯、亚萘基-1,5-二异氰酸酯、亚萘基-2,7-二异氰酸酯、4′,4-亚联苯基二异氰酸酯、3,3′-二氯-4,4′-亚联苯基二异氰酸酯、3,3′-二甲基-4,4′-亚联苯基二异氰酸酯、3,3′-二甲氧基-4,4′-亚联苯基 二异氰酸酯、2,2′,5,5′-四甲基-4,4′-亚联苯基二异氰酸酯、2-硝基-4,4′-亚联苯基二异氰酸酯、3,3′-二苯基-4,4′-亚联苯基二异氰酸酯、4,4′-亚甲基-双(苯基异氰酸酯)、4,4′-亚甲基-双(2-甲苯基异氰酸酯)、4,4′-异亚丙基-双(苯基异氰酸酯)和芴二异氰酸酯；三异氰酸酯，如六亚甲基二异氰酸酯缩二脲、4,4′,4″-三苯基甲烷三异氰酸酯和甲苯-2,4,6-三异氰酸酯；异氰脲酸酯，如那些基于六亚甲基二异氰酸酯或3-异氰酸根合甲基-3,5,5-三甲基环己基异氰酸酯的异氰脲酸酯；四异氰酸酯及其混合物。
特别适用的异氰酸酯是基于六亚甲基二异氰酸酯(HDI)的多官能脂族异氰酸酯。一些市购HDI包括
Figure PCTCN2019094825-appb-000005
HDT或
Figure PCTCN2019094825-appb-000006
HDT LV，购自Rhone-Poulenc Inc.(有机化学分公司)，Monmouth Junction，NJ，或
Figure PCTCN2019094825-appb-000007
N-3300或
Figure PCTCN2019094825-appb-000008
N-3390异氰酸酯，购自Bayer AG，Pittsburgh，PA。
根据本发明，所述溶剂基涂料组合物可以通过本领域普通技术人员已知的常规涂覆方法进行涂布。所述涂覆方法包括浸涂、旋涂、喷涂、帘涂、刷涂、辊涂以及本领域已知的其他涂覆方法。
可以利用常规涂覆技术将低VOC的溶剂基涂料组合物涂覆到各种不同基材上。适当基材的实例包括木材、水泥、水泥纤维板、木材-塑料复合物、瓦片、金属、塑料、玻璃和纤维玻璃。
测试方法
除非另外指出，以下实施例中利用下述测试方法。
固含量
根据GB/T1725-2007标准进行测定。
粘度
按照ASTMD 2196测定(通过旋转(Brookfield)粘度计测定非牛顿材料的流变性能)。
光泽度
该测试测量固化涂层的光泽度。根据ASTM D523来评估光泽。
铅笔硬度
该测试用于测量固化涂层的硬度。使用ASTM D3363来评估铅笔硬度。数据被报告为在涂层破裂前最后一次成功进行测试的铅笔硬度。因此，例如，如果用2H铅笔测试时，涂层不破裂，但用3H铅笔进行测试时破裂，则涂层被报告为具有2H的铅笔硬度。
粘附性
进行粘附性测试以评估涂层是否粘附到经涂布的基材上。该粘附性测试根据ASTM D 3359-测试方法B进行。粘附性通常被分为0-5B的等级，其中5B表示最优的粘附性。
实施例
下面，通过实施例更具体地描述本发明公开的内容。这些实施例仅仅用于阐述性说明，并且不能解释为限制本发明的保护范围，因为在本发明公开内容的范围内进行各种修正和变化对本领域技术人员来说是明显的。
除非另有声明，以下实施例中所报道的所有份、百分比和比值都是基于重量计，而且实施例中使用的所有试剂都可商购并且可直接使用而无需进一步处理。
材料
所使用的材料列于下表1中。
表1：所使用的材料及相关信息
组分 供应商 简要描述
丙烯酸(AA) Aladdin CAS：79-10-7
甲基丙烯酸甲酯(MMA) Aladdin CAS：80-62-6
苯乙烯(ST) Aladdin CAS：100-42-5
丙烯酸丁酯(BA) Aladdin CAS：141-32-2
甲基丙烯酸正丁酯(n-BMA) Alfa Aesar CAS：97-88-1
丙烯酸羟乙酯(HEA) Aladdin CAS：818-61-1
过氧化苯甲酸叔丁酯(TBPB) Alfa Aesar CAS：614-45-9
HMS-523B 浙江皇马 含有聚(氧亚丙基)片段的烯属不饱和单体
丙二醇单甲基醚乙酸酯(PMA) 天津希恩思 CAS：84540-57-8
二甲苯 Aladdin CAS：1330-20-7
包含丙烯酸类共聚物的树脂组合物的制备
按下表2所示的成分来制备包含丙烯酸类共聚物的树脂组合物。具体步骤为：
(1)称取各原料；
(2)在用氮气吹扫下将Part 3装入烧瓶，然后加热至140℃；
(3)将烧瓶的反应温度保持在140℃，并在3-3.5小时的时间内依次将Part 1和Part 2加入反应烧瓶中；
(4)单体加料结束后，在140℃下保持1小时；
(5)将Part 4在1小时内加入反应烧瓶中，然后在140℃下保持2小时；
(6)冷却至室温，得到包含丙烯酸类共聚物的树脂组合物。
表2
Figure PCTCN2019094825-appb-000009
测定所得树脂组合物的固含量和粘度，结果如下表3所示：
表3
实例 固含量 粘度/mpa ·s
对比树脂 约80％ 硬固体
树脂1 81.87％ 122000
树脂2 82.86％ 54000
树脂3 81.75％ 9600
从上述结果可以看出，在丙烯酸类共聚物的制备中，引入含有聚(氧亚烷基)片段的烯属不饱和单体可以形成含有丙烯酸类共聚物的高固低粘树脂组合物，该树脂组合物具有基于所述丙烯酸类共聚物的重量至少约80wt％的固含量以及在25℃下利用BROOKFIELD粘度计测量130000mPa.s或更低的粘度。与之相比，采用不含具有聚(氧亚烷基)片段的烯属不饱和单体的单体混合物制备得到的丙烯酸类共聚物是硬固体，根本不能用于配制溶剂基涂料组合物。
低VOC的溶剂基涂料组合物的制备
按照下面表4的配比来制备低VOC溶剂基涂料组合物，在搅拌下将颜料、填料、增稠剂、消泡剂、润湿分散剂和溶剂加入根据上面得到的包含丙烯酸类共聚物的树脂组合物中，从而形成溶剂基涂料组合物。然后，将由此形成的溶剂基涂料组合物用涂膜涂布器施于裸钢板上，如此得到0.05mm(2±0.1mil)干膜厚度的涂层。将该涂层在室温下固化两周，然后获得下表中给出的测量值
表4
Figure PCTCN2019094825-appb-000010
Figure PCTCN2019094825-appb-000011
从上述结果可以看出，根据本发明的包含丙烯酸类共聚物的树脂组合物可以直接用于配制低VOC(VOC排放量低于420g/L)的溶剂基涂料组合物，而且由其形成的涂层具有良好的涂层性质。
尽管本发明参照大量实施方式和实施例进行描述，但是本领域普通技术人员根据本发明公开的内容能够认识到可以设计其它实施方式，这并未脱离本发明的保护范围和精神。

Claims (19)

  1. 一种包含丙烯酸类共聚物的树脂组合物，其中，所述丙烯酸类共聚物的主链具有悬挂的聚(氧亚烷基)片段，并且其中所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少80wt％的固含量和在25℃下利用BROOKFIELD粘度计测量130000mPa.s或更低的粘度。
  2. 如权利要求1所述的树脂组合物，其中，所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少81wt％的固含量。
  3. 如权利要求1所述的树脂组合物，其中，所述树脂组合物具有在25℃下利用BROOKFIELD粘度计测量60000mPa.s或更低的粘度，优选10000mPa.s或更低的粘度。
  4. 如权利要求1所述的树脂组合物，其中，所述聚(氧亚烷基)片段选自聚(氧亚乙基)片段、聚(氧亚丙基)片段、聚(氧亚丁基)片段、聚(氧亚戊基)片段及其任意组合，优选选自聚(氧亚乙基)片段、聚(氧亚丙基)片段或其组合。
  5. 如权利要求1所述的树脂组合物，其中，基于所述丙烯酸类共聚物的重量，所述聚(氧亚烷基)片段以15-60wt％的量存在，优选以20-50wt％的量存在。
  6. 如权利要求1-5中任意一项所述的树脂组合物，其中，所述聚(氧亚烷基)片段衍生自下式的含聚(氧亚烷基)片段的烯属不饱和单体，
    Figure PCTCN2019094825-appb-100001
    上式中，
    A为
    Figure PCTCN2019094825-appb-100002
    并且R 1、R 2和R 3相互独立地选自H、-CH 3或
    Figure PCTCN2019094825-appb-100003
    且R 1、R 2和R 3中的至多一个为
    Figure PCTCN2019094825-appb-100004
    其中X为-(CH 2) a-、-CO-或-(CH 2) a-CO-，其中a为1-6；R 4为-CH 3或H；b和c相互独立地为0至500且b和c不同时为0。
  7. 如权利要求1-5中任意一项所述的树脂组合物，其中，所述树脂组合物包含基于所述树脂组合物的总重至多20wt％的溶剂。
  8. 如权利要求1-5中任意一项所述的树脂组合物，其中，所述树脂组合物包含基于所述树脂组合物的总重至多15wt％的溶剂。
  9. 一种用于制备包含丙烯酸类共聚物的树脂组合物的方法，其中所述丙烯酸类共聚物的骨架具有悬挂的聚(氧亚烷基)片段，并且其中所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少80wt％的固含量以及在25℃下利用BROOKFIELD粘度计测量130000mPa.s或更低的粘度，所述方法包括：
    在相对于所述树脂组合物的总重，用量不超过20wt％的溶剂和自由基引发剂的存在下，使包含作为第一单体的含有聚(氧亚烷基)片段的烯属不饱和单体、不同于所述第一单体的丙烯酸类单体和附加的烯属不饱和单体的反应混合物进行共聚，从而形成所述树脂组合物。
  10. 如权利要求9所述的方法，其中，所述聚(氧亚烷基)片段选自聚(氧亚乙基)片段、聚(氧亚丙基)片段、聚(氧亚丁基)片段、聚(氧亚戊基)片段及其任意组合，优选选自聚(氧亚乙基)片段、聚(氧亚丙基)片段或其组合。
  11. 如权利要求9所述的方法，其中，所述含聚(氧亚烷基)片段的烯属不饱和单体具有下式I所示的结构，
    Figure PCTCN2019094825-appb-100005
    上式(I)中，
    A为
    Figure PCTCN2019094825-appb-100006
    并且R 1、R 2和R 3相互独立地选自-CH 3、H或
    Figure PCTCN2019094825-appb-100007
    且R 1、R 2和R 3中的至多一个为
    Figure PCTCN2019094825-appb-100008
    其中X为-(CH 2) a-、-CO-或-(CH 2) a-CO-，其中a为1-6；R 4为-CH 3或H；b和c相互独立地为0至500且b和c不同时为0。
  12. 如权利要求9所述的方法，其中，所述含有聚(氧亚烷基)片段的烯属不饱和单体的数均分子量在100-10000之间，优选地在200-6000之间，更优选在300-2000之间。
  13. 如权利要求9-12中任意一项所述的方法，其中，所述不同于第一单体的丙烯酸类单体包括(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丁酯、(甲基)丙烯酸羟丙酯、甲基丙烯酸2-(乙酰乙酰氧)乙酯、二丙酮丙烯酰胺、羟甲基(甲基)丙烯酰胺、丙烯腈、或其混合物。
  14. 如权利要求9-12中任意一项所述的方法，其中，所述附加的烯属不饱和单体选自苯乙烯、乙烯基甲苯或其混合物。
  15. 如权利要求9-12中任意一项所述的方法，其中，所述反应混合物包含，相对于所述反应混合物的总重量，
    15-60wt％的所述第一单体；
    35-60wt％的所述不同于第一单体的丙烯酸类单体；和
    5-30wt％的所述附加的烯属不饱和单体。
  16. 如权利要求9-12中任意一项所述的方法，其中，所述树脂组合物具有基于所述丙烯酸类共聚物的重量至少81wt％的固含量。
  17. 如权利要求9-12中任意一项所述的方法，其中，所述树脂组合物具有在25℃下利用BROOKFIELD粘度计测量60000mPa.s或更低的粘度，优选具有10000mPa.s或更低的粘度。
  18. 如权利要求9所述的方法，其中，基于所述的树脂组合物的总重，使用至多15wt％的溶剂。
  19. 一种VOC排放量低于420g/L的溶剂基涂料组合物，其包含权利要求1至8中任意一项所述的树脂组合物或权利要求9至18中任意一项所述的方法制备得到的树脂组合物。
PCT/CN2019/094825 2018-07-11 2019-07-05 一种包含丙烯酸类共聚物的高固低粘的树脂组合物 WO2020011108A1 (zh)

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