CN115960297A - Preparation method and application of solvent-free polyacrylic acid aqueous dispersion - Google Patents
Preparation method and application of solvent-free polyacrylic acid aqueous dispersion Download PDFInfo
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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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Abstract
The invention discloses a method for preparing solvent-free polyacrylic acid aqueous dispersion containing hydroxyl functional groups, which comprises the following steps: polymerizing one or more monomers in the presence of reactive oligomer by initiator to obtain polyacrylic copolymer, adding neutralizer for neutralization, and dispersing in water. The reactive oligomer used in the invention only exists as a diluent in the preparation process of the polyacrylic acid aqueous dispersion, does not participate in any reaction, and can react with a curing agent when matched with the curing agent for use. The invention thus enables a solvent-free preparation process of polyacrylic dispersions (oligomers as reaction medium instead of organic solvents) without affecting the properties of the polyacrylic dispersions in the coating.
Description
Technical Field
The invention belongs to the field of coatings, and relates to a preparation method of a solvent-free polyacrylic acid aqueous dispersion containing a hydroxyl functional group, the obtained polyacrylic acid aqueous dispersion and application thereof.
Background
One of the most commonly used resins for the preparation of waterborne coatings is an aqueous dispersion of hydroxyl-containing polyacrylic acid. In the preparation of the hydroxyl group-containing polyacrylic acid aqueous dispersion, it is usually necessary to prepare a hydroxyl group-containing polypropylene resin first. Specifically, such a preparation process generally includes providing a certain amount of organic solvent (such as propylene glycol butyl ether, etc.), adding into a reaction kettle, stirring and heating to a desired temperature, adding a mixed solution of acrylic monomers and a part of initiator, and finally adding organic amine for neutralization. Due to the synthesis and dispersion processes required, and to reduce viscosity, these systems require the addition of certain organic solvents, which generate VOCs that are harmful to the environment and human body.
In addition, in the subsequent process of removing the organic solvent in the dispersion, the solvent may be removed by distillation under reduced pressure by heating. Although this allows the solvent to be recovered to some extent, much energy is consumed, and the recovered solvent component is complicated and cannot be reused.
For example, U.S. Pat. No. 5,5750613 discloses a process which makes it possible to use polyethers containing hydroxyl functions in the polymerization in place of, in whole or in part, organic solvents. During subsequent crosslinking, the hydroxyl functional polyether can react with the blocked isocyanate curing agent to form urethane, which is not effective in reducing VOC. And hydroxyl-containing polyethers as diluents tend to produce products of poor stability.
For another example, chinese patent application publication No. CN1898280A discloses a method for preparing copolymer dispersions, in which lactone and polyol with small molecular weight are combined as reactive diluents to obtain aqueous copolymer dispersions based on hydroxy-functional copolymers with low solvent content. In this method, a small amount of other organic solvents is used as needed, and zero solvent cannot be realized.
As another example, chinese patent application publication No. CN1914237A discloses aqueous copolymer dispersions based on hydroxy-functional copolymers with low solvent content and giving the films thereof a high level of stability. The process uses a compound of formula I as a reaction medium, with a small amount of additional organic solvent. The compounds of formula I have a hydroxyl function and a tertiary carbon group, n ranges from 1 to 4, i.e. it has 1 to 4 hydroxyl groups. In the process of preparing the polyacrylic acid copolymer, the compound exists as a diluent, and tertiary carbon groups can play a role in viscosity reduction and can participate in reaction when being matched with a curing agent for use. When n is 1 in formula I, it can only participate in the reaction and does not form crosslinks, which can affect the properties of the final paint film. In this method, when a component having both a hydroxyl functional group and a tertiary carbon group is used as a diluent, an additional organic solvent is used as needed, and zero solvent cannot be realized.
For example, chinese patent application publication No. CN103998472A discloses that glycidyl ester of aliphatic carboxylic acid is introduced as a reactive diluent into a reaction system, and simultaneously an epoxy group reacts with a carboxyl group-containing monomer to intervene in a polymer chain in the course of radical polymerization. However, as the reaction proceeds, the content of the glycidyl ester of the free aliphatic carboxylic acid gradually decreases and the diluent effect gradually decreases.
There are also methods in the prior art that use a reduction in the molecular weight of a hydroxyl-containing polyacrylic resin to increase the solids content of the resin, thereby achieving an effect approaching that of a solvent-free system. While methods of reducing the molecular weight include increasing the amount of initiator, using chain transfer agents, or increasing the reaction temperature. Taking the method of increasing the reaction temperature as an example, the highest reaction temperature is usually determined by the boiling point of the organic solvent, and although the method can be applied under pressure, the method has higher requirements on hardware and further increases the cost.
In view of the above, there is a need in the art to develop hydroxyl-containing polyacrylic acid dispersions that avoid the use of organic solvents in the preparation process, while not interfering with the use of the resin in coatings.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a method for preparing a solvent-free polyacrylic acid aqueous dispersion containing hydroxyl functional groups and application thereof.
In a first aspect the present invention provides a process for preparing a solvent-free aqueous dispersion of a polyacrylic acid containing hydroxyl functional groups comprising the steps of: initiating polymerization of a monomer or a mixture of a plurality of monomers a by an initiator c in the presence of a reactive oligomer b to obtain a polyacrylic copolymer A, adding a neutralizing agent d for neutralization, and dispersing in water;
wherein monomer mixture a comprises one or more of:
a1 non-hydroxyl acrylate, non-hydroxyl methacrylate, and/or non-hydroxyl vinyl aromatic hydrocarbon,
a2 acrylate containing hydroxyl functional groups, methacrylate containing hydroxyl functional groups and/or vinyl monomers,
a3 ionic and/or potentially ionic monomers which can be polymerized free-radically;
wherein the reactive oligomer b comprises one or more of the following characteristics:
(1) The reactive oligomer b does not include a radical polymerizable unsaturated bond;
(2) The reactive oligomer b is capable of reacting with a curing agent.
In a preferred embodiment, component a1 is selected from one or more of acrylates or methacrylates wherein the alcohol residue moiety has from 1 to 18 carbon atoms; preferably, the alcohol residue moiety is selected from one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, octyl, dimethylaminoethyl, cyclohexyl, glycidyl, lauryl, dodecyl, ethylene glycol dimethyl or isobornyl.
In a preferred embodiment, component a1 comprises a vinyl aromatic hydrocarbon; preferably comprising styrene.
In a preferred embodiment, component a2 is a hydroxyl functional vinyl monomer; preferably alkyl esters of unsaturated carboxylic acids; more preferably one or more selected from hydroxyalkyl acrylates and/or hydroxyalkyl methacrylates.
In a preferred embodiment, component a2 comprises one or more of the reaction product of an epoxy-containing alkyl group and acrylic acid and/or the reaction product of an epoxy-containing alkyl group and methacrylic acid.
In a preferred embodiment, component a2 comprises the product of the reaction of glycidyl versatate with acrylic acid, which product has the general formula II, wherein R is 1 Group and R 2 The total number of carbon atoms in the group is 7:
specifically, the glycidyl versatate is selected from glycidyl versatate provided by Meiji corporation of America with the product model number of Cardura E10P.
In a preferred embodiment, component a2 comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate; preferably comprising one or both of hydroxyethyl methacrylate or hydroxypropyl methacrylate.
In a preferred embodiment, component a3 is an ionic and/or potentially ionic monomer which is free radically polymerizable; preferably a3 is a vinyl monomer containing a carboxylic acid group; preferably, the vinyl monomer containing carboxylic acid group is selected from vinyl monomers containing acrylic acid, methacrylic acid or dibasic acid, preferably the dibasic acid is selected from one or more of itaconic acid, fumaric acid or maleic acid, more preferably the vinyl monomer containing carboxylic acid group is selected from vinyl monomers containing acrylic acid or methacrylic acid.
In a preferred embodiment, component a3 is a vinyl monomer containing a phosphate group, preferably 2-hydroxyethyl methacrylate phosphate.
In a preferred embodiment, the proportions by weight of components a1 to a3 are in the range from 55 to 90 parts by weight of a1, from 10 to 40 parts by weight of a2 and from 0.5 to 5 parts by weight of a3, based on 100 parts by weight of the sum of a1, a2 and a 3.
In a preferred embodiment, the reactive oligomer b contains a group capable of reacting with a curing agent, the group including a hydroxyl group, an amino group, a carboxyl group and/or an amide group; preferably, the group is hydroxyl; more preferably, it is low, and the hydroxyl group content is not less than 1.5mol on average per 1mol of the reactive oligomer b; more preferably 2mol of hydroxyl groups per 1mol of the reactive oligomer b.
The use of monohydroxy groups b makes it possible to prepare aqueous dispersions of polyacrylic acids which are advantageous for reducing the viscosity of the product, but such aqueous dispersions, when subsequently cured by reaction with a curing agent, give rise to a large amount of oligomers which affect the final properties of the paint film. Therefore, it is preferable that the hydroxyl group is contained in an amount of not less than 1.5mol per 1mol of the reactive oligomer b on the average in consideration of the production convenience and the application properties of the product.
In a preferred embodiment, the molecular weight of the reactive oligomer b is in the range of 200 to 1000g/mol; preferably from 200 to 600g/mol.
In a preferred embodiment, the reactive oligomer b is a reaction product of an aliphatic glycidyl ester b1 and a carboxylic acid b 2.
In a preferred embodiment, the aliphatic glycidyl ester b1 is selected from glycidyl esters of alkane carboxylic acids, preferably glycidyl versatate, e.g. Cardura E10P.
In a preferred embodiment, the number of carboxyl groups of the carboxylic acid b2 is 2 or more, preferably the polycarboxylic acid b2 is an aliphatic carboxylic acid having a number of carboxyl groups of 2, more preferably adipic acid, pimelic acid, suberic acid or a combination thereof.
In a preferred embodiment, the reactive oligomer b is the reaction product of Cardura E10P and adipic acid.
In a preferred embodiment, the mass of the reactive oligomer b is 5 to 40%, preferably 10 to 30%, more preferably 15 to 25% of the sum of the masses of the components a1 to a 3.
In a preferred embodiment, the polymerization of the monomer mixture a or monomer mixtures a is initiated in the process by means of an initiator at a reaction temperature in the range from 50 to 200 ℃ and preferably from 100 to 150 ℃.
In a preferred embodiment, the initiator c is an organic peroxide and/or an azo compound, preferably di-tert-butyl peroxide and/or Azobisisobutyronitrile (AIBN), more preferably di-tert-butyl peroxide. The amount of initiator added can be calculated from the molecular weight set.
In a preferred embodiment, the monomers a1 to a3 are polymerized in two stages in the presence of the reactive oligomer b, and the temperature is maintained for 0.5 to 1 hour after each stage of polymerization. Preferably, the proportion of hydrophilic monomer in the second stage is higher than the proportion of hydrophilic monomer in the first stage.
In a preferred embodiment, the neutralizing agent d is an organic amine, preferably triethylamine, N-dimethylethanolamine, triethanolamine, ethyldiisopropylamine, N-dimethylisopropanolamine, N-methyldiethanolamine and/or diethylethanolamine, more preferably N, N-dimethylethanolamine and/or triethanolamine. The neutralizing agent may cause the polyacrylic acid copolymer to change from an acid to a salt form prior to emulsification.
In a preferred embodiment, the neutralizing agent is added in a molar ratio such that the theoretical degree of neutralization is 50 to 150%, preferably 80 to 120%. The theoretical degree of neutralization refers to the ratio of added basic groups to acidic groups in the polyacrylic acid copolymer. The pH of the neutralized and emulsified aqueous polyacrylic acid dispersion is in the range of 6 to 10, preferably 6.5 to 8.5.
In a preferred embodiment, the non-volatile content of the aqueous polyacrylic acid dispersion is in the range of 30 to 70% by mass, preferably 40 to 60% by mass; the organic solvent content is zero.
The second aspect of the present invention provides an aqueous polyacrylic acid dispersion obtained by the above method.
The third aspect of the present invention also provides an aqueous coating composition comprising:
(1) One or more aqueous polyacrylic acid dispersions obtained by the production method of the first aspect of the present invention; and
(2) At least one curing agent capable of reacting with hydroxyl groups.
In a preferred embodiment, the curing agent suitable for reacting with hydroxyl groups comprises a non-blocked polyisocyanate curing agent, a blocked polyisocyanate curing agent and/or an amine-based curing agent. Non-blocked polyisocyanate curing agents and/or blocked polyisocyanate curing agents are preferred. The polyisocyanate curing agent has two or more-NCO groups, and a hydrophilically modified polyisocyanate curing agent may be used.
The polyacrylic acid aqueous dispersion containing the hydroxyl functional group can be matched with a curing agent to be applied to aqueous coatings. One-component or two-component coatings can be prepared depending on whether the curing agent is a latent curing agent. The two-component coating materials for the purposes of the present invention, whose binder part and curing agent are stored separately, are mixed homogeneously during use, preferably by means of heat, to promote the crosslinking reaction, while the oligomer component also participates in the reaction.
In a preferred embodiment, the aqueous coating composition of the present invention comprising an aqueous dispersion of a hydroxy-functional polyacrylic acid can be applied to the surface of a metal, mineral or wood material, and can be used as a pigmented or clear top coat, a clear coat or a high gloss coating.
In a preferred embodiment, the curing temperature of the aqueous coating composition of the invention is in the range of 0 to 140 ℃, preferably 15 to 100 ℃.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
1. in the preparation process of the polyacrylic acid aqueous dispersion, the reactive oligomer is used for replacing an organic solvent to obtain a solvent-free polyacrylic acid aqueous dispersion;
2. the reactive oligomer used in the invention only exists as a diluent in the preparation process of the polyacrylic acid aqueous dispersion, can not be polymerized by free radicals, and then participates in the reaction when being matched with a curing agent for use. Therefore, the invention realizes the solvent-free preparation process of the polyacrylic acid dispersoid, namely, oligomer is used as a reaction medium to replace an organic solvent, and the performance of the polyacrylic acid dispersoid in the coating is not influenced;
3. since the deliberately introduced volatile organic solvent content of the aqueous polyacrylic acid dispersion containing a hydroxyl functional group of the present invention is 0, the VOC content of the aqueous coating composition can be greatly reduced with little effect on the constructors.
It should be noted that: in the present invention, the VOC content actually measured is not always 0, because a small amount of residual solvent is carried into the raw material due to the raw material preparation process, or a small amount of volatile organic compounds is generated by the reaction of the raw material under the production conditions, and neither of these is considered as a volatile organic solvent intentionally introduced.
Drawings
FIG. 1 is a graph of the change in viscosity over 6 hours for a coating based on an aqueous dispersion of polyacrylic acid according to the invention.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. However, the present invention should be understood not to be limited to such an embodiment described below, and the technical idea of the present invention may be implemented in combination with other known techniques or other techniques having the same functions as those of the known techniques.
In the following description of the embodiments, for purposes of clearly illustrating the structure and operation of the present invention, directional terms are used, but the terms "front", "rear", "left", "right", "outer", "inner", "outward", "inward", "axial", "radial", and the like are to be construed as words of convenience and are not to be construed as limiting terms.
Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not intended to limit the temporal order, quantity, or importance, but are not intended to indicate or imply relative importance or implicitly indicate the number of technical features indicated, but merely to distinguish one technical feature from another technical feature in the present disclosure. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically stated otherwise. Similarly, the appearances of the phrases "a" or "an" in various places herein are not intended to be limiting, but rather to describe various features not expressly shown or described in connection with the above description. Similarly, unless a specific number is used to modify a noun, it is intended that the specification be read as including both the singular and the plural, as well as the singular and plural of the present technical features. Similarly, modifiers similar to "about", "approximately" or "approximately" that occur before a numerical term herein typically include the same number, and their specific meaning should be read in conjunction with the context.
It should be understood that in the present application, "at least one" means one or more, "a plurality" means two or more. "and/or" is used to describe the association relationship of the associated object, and indicates that there may be three relationships, for example, "a and/or B" may indicate: only A, only B and both A and B are present, wherein A and B may be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single item(s) or plural items. For example, at least one (one) of a, b, or c, may represent: a, b, c, "a and b", "a and c", "b and c", or "a and b and c", wherein a, b, c may be single or plural.
Unless clearly indicated to the contrary, each aspect or embodiment defined herein may be combined with any other aspect or embodiments. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature indicated as being preferred or advantageous.
Description of terms and test methods and conditions
In the following examples, all percentages are by weight unless otherwise indicated.
Measurement of resin viscosity was measured at 25 ℃ using a Brookfield viscometer.
Measurement of coating viscosity was measured at 25 ℃ using a stormer viscometer.
Acid value test method: ISO 2114-2000.
Non-volatile content test conditions: 1g of sample was dried at 120 ℃ for 1 hour.
The product obtained by reacting the glycidyl versatate with acrylic acid used in examples 4 and 5 is commercially available from Shibatan and Jinjia New materials science and technology Co., ltd., under the name ACE. It can also be obtained by reacting Cardura E10P with acrylic acid as described below.
Example 1: preparation of reactive oligomer b-1
1548g of aliphatic glycidyl ester b 1-Cardura E10P (glycidyl Tertiary carbonate, from Mayer company, USA) and 452g of polycarboxylic acid b 2-adipic acid were added to a 3L reaction vessel, and the temperature was raised to 140 ℃ with stirring, at which point a substantial exotherm occurred in the reaction, ensuring a temperature of no more than 160 ℃. And (3) keeping the temperature at 140 ℃ for 2h, detecting the acid value per hour, finishing the reaction when the acid value is less than 1mg KOH/g, and cooling and discharging to obtain the light yellow resin.
Example 2: preparation of reactive oligomer b-2
634.9g of aliphatic glycidyl ester b 1-Cardura E10P (glycidyl versatate, from Mayer company, USA) and 365.1g of carboxylic acid b 2-isooctanoic acid were added to a 3L reaction vessel, and the temperature was raised to 140 ℃ with stirring, at which point a large exotherm occurred in the reaction, ensuring a temperature of no more than 160 ℃. And (3) keeping the temperature at 140 ℃ for 2h, detecting the acid value per hour, finishing the reaction when the acid value is less than 1mg KOH/g, and cooling and discharging to obtain the light yellow resin.
Example 3: preparation of solvent-free aqueous polyacrylic acid Dispersion 1 containing hydroxyl functional groups
195.58g of the reactive oligomer b-1 obtained in example 1 was charged into a 3L reaction vessel, the temperature was raised to 145 ℃ and 117.3g of the component a1 methyl methacrylate, 128.7g of the component a2 hydroxyethyl methacrylate, 189.3g of the component a1 n-butyl acrylate, component a1 164.7g of styrene, and 33.3g of the initiator c di-tert-butyl peroxide (DTBP) were mixed in advance and added dropwise at a constant rate over 4 hours at 145 ℃ with the reaction temperature being controlled to 145. + -. 3 ℃ due to the exothermic reaction. After the dropwise addition, the temperature is kept for 30min.
Then, 43.35g of component a1 methyl methacrylate, 61.2g of component a2 hydroxyethyl methacrylate, 34g of component a1 n-butyl acrylate, 27.15g of component a3 acrylic acid and 6.53g of initiator c di-tert-butyl peroxide are mixed uniformly, and then the uniform dropping is finished within 1h, and the temperature is kept for 1h.
Then the temperature is reduced to 100 ℃, and 56.65g of neutralizing agent d triethanolamine is added for heat preservation for 30min. Then 1040g of water were added over 30min and the temperature was kept at 80 ℃ for 1.5h. Finally, the temperature is reduced to 45 ℃ for discharging.
The basic parameters of this aqueous polyacrylic acid dispersion 1 are shown in table 1 below.
TABLE 1
| Test item | Numerical value |
| Acid value (solid) | 26.6mgKOH/g |
| Content of non-volatile component | 45.8％ |
| Viscosity (S64 60rpm,25 ℃ C.) | 2440cps |
| pH | 7.4 |
Example 4: preparation of solvent-free aqueous polyacrylic acid Dispersion 2 containing hydroxyl functional groups
182g of the reactive oligomer b-1 in example 1 is added into a 3L reaction vessel, the temperature is raised and heated to 145 ℃, 368.5g of component a1 methyl methacrylate, 177g of component a2 hydroxyethyl methacrylate, 236.6g of component a1 isooctyl acrylate, 20.1g of the product of the reaction of component a2 glycidyl versatate and acrylic acid and 16.6g of initiator c di-tert-butyl peroxide (DTBP) are mixed uniformly in advance, and the mixture is dripped at a constant speed within 4h at 145 ℃, and the reaction temperature needs to be controlled at 145 +/-3 ℃ due to reaction heat release. After the dropwise addition, the temperature is kept for 30min.
Then, 92.8g of component a1 methyl methacrylate, 73.4g of component a2 hydroxyethyl methacrylate, 26.04g of component a3 acrylic acid and 3.3g of initiator c di-tert-butyl peroxide are uniformly mixed, and then dropwise addition is carried out at a constant speed within 1 hour, and heat preservation is carried out for 1 hour.
Then the temperature is reduced to 100 ℃, and 50.5g of neutralizing agent d triethanolamine is added for heat preservation for 30min. 1454.1g of water dispersion are then added over 30min and the temperature is kept at 80 ℃ for 1.5h. Finally, cooling to 45 ℃ and discharging.
The basic parameters of this aqueous polyacrylic acid dispersion 2 are shown in Table 2 below.
TABLE 2
| Test item | Numerical value |
| Acid value (solid) | 21.5mgKOH/g |
| Non-volatile content | 43.6％ |
| Viscosity (S64 60rpm,25 ℃ C.) | 332cps |
| pH | 7.19 |
Example 5: preparation of solvent-free aqueous polyacrylic acid Dispersion 3 containing hydroxyl functional groups
A3L reaction vessel was charged with 91.2g of the reactive oligomer b-1 of example 1 and 245.6g of the reactive oligomer b-245 of example 2 (the mixture of b-1 and b-2 contained 1.55mol of hydroxyl groups per 1mol on average), the temperature was raised and the mixture was heated to 145 ℃ to mix 248.9g of component a1 methyl methacrylate, 125.3g of component a2 hydroxyethyl methacrylate, 157.5g of component a1 ethylhexyl acrylate, 70.08g of the product of the reaction of component a2 glycidyl versatate with acrylic acid and 24.9g of initiator c di-tert-butyl peroxide (DTBP) uniformly, and the mixture was added dropwise at a constant rate over 2 hours at 145 ℃ while controlling the reaction temperature to 145. + -. 3 ℃ due to exothermic reaction. After the dropwise addition, the temperature is kept for 30min.
Then, 69.6g of component a1 methyl methacrylate, 55.05g of component a2 hydroxyethyl methacrylate, 19.53g of component a3 acrylic acid and 4.96g of initiator c di-tert-butyl peroxide are mixed uniformly, dropwise added at a constant speed within 1 hour, and the temperature is kept for 1 hour.
Then the temperature is reduced to 100 ℃, and 37.85g of neutralizer d triethanolamine is added for heat preservation for 30min. 765g of water dispersion were then added over 30min and the temperature was maintained at 80 ℃ for 1.5h. Finally, the temperature is reduced to 45 ℃ for discharging.
The basic parameters of the aqueous polyacrylic acid dispersion are shown in Table 3 below.
TABLE 3
| Test item | Numerical value |
| Acid value (solid) | 21.7mgKOH/g |
| Non-volatile content | 43.2％ |
| Viscosity (S64 60rpm,25 ℃ C.) | 2690cps |
| pH | 7.17 |
EXAMPLE 6 period of activation
To determine the pot life, the aqueous polyacrylic acid dispersion from example 4 was formulated as a coating and reacted
268 curative combinations (water dispersible isocyanate curative based on hexamethylene diisocyanate, vanhua) viscosity change over 6h was measured according to-OH: -NCO 1.1 combinations and is shown in FIG. 1 below.
As can be seen from the figure, the aqueous polyacrylic acid dispersion of the present invention exhibits a long pot life with a viscosity change of less than 10KU within 6 hours. The invention realizes that no organic solvent is needed to be added in the preparation process of the polyacrylic acid dispersoid, and simultaneously, the performance of the polyacrylic acid dispersoid in the coating is not influenced.
The embodiments described in the specification are only preferred embodiments of the present invention, and the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the present invention. Technical solutions that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments according to the concept of the present invention should be within the scope of the present invention.
Claims (19)
1. A method of preparing a solvent-free aqueous dispersion of a hydroxy-functional polyacrylic acid comprising the steps of: initiating polymerization of a monomer or a mixture of a plurality of monomers a by an initiator c in the presence of a reactive oligomer b to obtain a polyacrylic copolymer A, adding a neutralizer d for neutralization, and dispersing in water;
wherein monomer mixture a comprises one or more of:
a1 a non-hydroxyl acrylate, non-hydroxyl methacrylate, and/or non-hydroxyl vinyl aromatic hydrocarbon,
a2 acrylates containing hydroxyl functional groups, methacrylates containing hydroxyl functional groups and/or vinyl monomers containing hydroxyl functional groups,
a3 ionic and/or potentially ionic monomers which can be polymerized free-radically;
wherein the reactive oligomer b comprises one or more of the following characteristics:
(1) The reactive oligomer b does not include a radically polymerizable unsaturated bond;
(2) The reactive oligomer b is capable of reacting with a curing agent.
2. The method of claim 1 wherein component a1 is selected from one or more of acrylates or methacrylates wherein the alcohol residue moiety has from 1 to 18 carbon atoms; preferably, the alcohol residue moiety is selected from one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, octyl, dimethylaminoethyl, cyclohexyl, glycidyl, lauryl, dodecyl, ethylene glycol dimethyl or isobornyl.
3. The process according to any one of claims 1 to 2, wherein component a1 comprises styrene.
4. A process according to any one of claims 1 to 3, wherein component a2 is a hydroxyl-functional vinyl monomer; preferably alkyl esters of unsaturated carboxylic acids, more preferably one or more selected from hydroxyalkyl acrylates and/or hydroxyalkyl methacrylates.
5. The process of claim 1, wherein component a2 comprises one or more of a reaction product of an epoxy-containing alkyl group and acrylic acid and/or a reaction product of an epoxy-containing alkyl group and methacrylic acid; preferably, component a2 comprises the product of the reaction of glycidyl versatate with acrylic acid, which product has the general formula I, wherein R is 1 Group and R 2 The total number of carbon atoms in the group is 7:
6. the method of claim 4, wherein component a2 comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, or hydroxypropyl methacrylate; preferably comprising one or both of hydroxyethyl methacrylate or hydroxypropyl methacrylate.
7. The process of any one of claims 1 to 6, wherein component a3 is a vinyl monomer containing carboxylic acid groups; preferably the carboxylic acid group containing vinyl monomer is selected from acrylic acid, methacrylic acid or a diacid containing vinyl monomer; preferred dibasic acids are selected from one or more of itaconic acid, fumaric acid or maleic acid; more preferably, the carboxylic acid group-containing vinyl monomer is selected from one or both of acrylic acid or methacrylic acid.
8. The method of any one of claims 1-7, wherein component a3 comprises a vinyl monomer containing a phosphate group; preferably, 2-hydroxyethyl methacrylate phosphate is included.
9. The process according to any one of claims 1 to 8, wherein the proportions by weight of components a1 to a3 are in the range: 55-90 parts of a1, 10-40 parts of a2, 0.5-5 parts of a3 and 100 parts of the sum of a1, a2 and a 3.
10. The method according to any one of claims 1 to 9, wherein the reactive oligomer b contains groups which can react with the curing agent, the groups comprising hydroxyl, amino, carboxyl and/or amide groups; preferably the group is hydroxyl; more preferably not less than 1.5mol of hydroxyl groups per 1mol of the reactive oligomer b on average; more preferably 2mol of hydroxyl groups per 1mol of the reactive oligomer b.
11. The process according to any of claims 1 to 9, wherein the reactive oligomer b has a molecular weight in the range of 200 to 1000g/mol, preferably 200 to 600g/mol.
12. The method according to any one of claims 1 to 11, wherein the reactive oligomer b is a reaction product of an aliphatic glycidyl ester b1 and a carboxylic acid b 2; preferably, the number of carboxyl groups of the carboxylic acid b2 is 2 or more; more preferably, the carboxylic acid b2 is an aliphatic carboxylic acid having a carboxyl number of 2, still more preferably adipic acid, pimelic acid, suberic acid or a combination thereof.
13. The process according to any of claims 1 to 12, wherein the mass of the reactive oligomer b is 5 to 40%, preferably 10 to 30%, more preferably 15 to 25% of the sum of the masses of the components a1 to a 3.
14. The process according to any one of claims 1 to 13, wherein the polymerization of the monomer or monomer mixture a is initiated by means of an initiator at a temperature in the range from 50 to 200 ℃, preferably from 100 to 150 ℃.
15. The process according to any one of claims 1 to 14, wherein the initiator c is an organic peroxide and/or an azo compound, preferably di-tert-butyl peroxide and/or Azobisisobutyronitrile (AIBN), more preferably di-tert-butyl peroxide.
16. The process according to any one of claims 1 to 15, wherein the monomers a1 to a3 are polymerized in two stages in the presence of the reactive oligomer b; preferably, the proportion of hydrophilic monomer in the second stage is higher than the proportion of hydrophilic monomer in the first stage.
17. Process according to any of claims 1 to 16, characterized in that the neutralizing agent d is an organic amine, preferably one or more selected from triethylamine, N-dimethylethanolamine, triethanolamine, ethyldiisopropylamine, N-dimethylisopropanolamine, N-methyldiethanolamine and/or diethylethanolamine, more preferably one or two selected from N, N-dimethylethanolamine and/or triethanolamine.
18. An aqueous polyacrylic acid dispersion obtainable by the process according to any one of claims 1 to 17, wherein the aqueous polyacrylic acid dispersion has a non-volatile content in the range of 30 to 70%, a volatile organic solvent content of 0, a pH in the range of 6 to 10, preferably wherein the aqueous polyacrylic acid dispersion a has a non-volatile content in the range of 40 to 60%, and a pH in the range of 6.5 to 8.5.
19. An aqueous coating composition comprising:
1) One or more aqueous polyacrylic acid dispersions obtainable by the process according to any one of claims 1 to 18; and
2) At least one curing agent capable of reacting with hydroxyl groups.
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| CN202111181638.6A CN115960297A (en) | 2021-10-11 | 2021-10-11 | Preparation method and application of solvent-free polyacrylic acid aqueous dispersion |
| PCT/CN2021/137107 WO2023060738A1 (en) | 2021-10-11 | 2021-12-10 | Preparation method for and application of solvent-free aqueous polyacrylic acid dispersion |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE4331061A1 (en) * | 1993-09-13 | 1995-03-16 | Hoechst Ag | Solvent-free, aqueous synthetic resin dispersion |
| AT405518B (en) * | 1997-08-07 | 1999-09-27 | Vianova Kunstharz Ag | NEW ACRYLATE POLYMERISATES, THE BASIS OF WHICH ARE POLYESTER RESINS OR POLYESTER OLIGOMERS, THEIR PRODUCTION AND USE IN COATING AGENTS |
| DE19914899A1 (en) * | 1999-04-01 | 2000-10-05 | Basf Coatings Ag | Three-component, polyurethane-based coating material, e.g. for painting cars, contains a special hydrophobic polyester in the isocyanate-reactive binder component and/or the third, water-containing component |
| DE102004054500A1 (en) * | 2004-11-11 | 2006-05-18 | Bayer Materialscience Ag | Polyester-polyacrylate dispersions with reactive diluents based on hydroxy-functional esters |
| DE102006049764A1 (en) * | 2006-10-21 | 2008-04-24 | Bayer Materialscience Ag | UV-curable polyurethane dispersions |
| DE102007010614A1 (en) * | 2007-03-02 | 2008-09-04 | Bayer Materialscience Ag | Aqueous copolymer-dispersion, useful e.g. to prepare ground coat, comprises a polyester portion, made from a compound comprising e.g. polyol and a polyacrylate portion, obtained from monomer comprising e.g. (meth)acrylic acid ester |
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