CN109439056B - Nonionic associative type water-based polyurethane thickener and preparation method thereof - Google Patents
Nonionic associative type water-based polyurethane thickener and preparation method thereof Download PDFInfo
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- CN109439056B CN109439056B CN201811132419.7A CN201811132419A CN109439056B CN 109439056 B CN109439056 B CN 109439056B CN 201811132419 A CN201811132419 A CN 201811132419A CN 109439056 B CN109439056 B CN 109439056B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
- C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
Abstract
The invention discloses a nonionic associative water-based polyurethane thickener and a preparation method thereof, wherein the preparation method comprises the following steps: (1) performing vacuum dehydration treatment on PEG; (2) mixing 250-500 parts of PEG and 18-25 parts of HDI at 60-70 ℃, adding a catalyst, and reacting at 105 +/-5 ℃ under the protection of inert gas; (3) adding 10-20 parts of GMO and 5-10 parts of C12 alcohol-C14 alcohol, adding a catalyst under the protection of inert gas at 105 +/-5 ℃, and heating to 110-120 ℃ for reaction; (4) cooling to 90-100 ℃, adding hydrogen peroxide and keeping reaction; (5) cooling, adding a solvent, stirring for 20-30min, adding water, and filtering to obtain the nonionic associative waterborne polyurethane thickening agent. Compared with foreign brands, the thickening agent prepared by the invention has the advantages of equivalent thickening effect, excellent water resistance and good storage stability.
Description
Technical Field
The invention relates to the field of coating additives, in particular to a nonionic associative water-based polyurethane thickener and a preparation method thereof.
Background
With the development of society, the environment faces severe examination, and the requirements of people on living environment are higher and higher, at present, the coating is mainly developed in the directions of high solid content, low VOC, powdering, water-based coating, photocuring and the like, wherein the powder coating has higher requirements on coating technology and paint film thickness, and has certain limitation in popularization and application, and the water-based coating is gradually accepted by people due to the fact that water is used as a dispersion medium, so that the water-based coating is environment-friendly and safe, is convenient to construct, and has high development speed. The aqueous thickener is an indispensable part in the formulation design of the aqueous paint, and the market demands the aqueous paint more and more.
Thickeners currently on the market are mainly classified into inorganic and organic types. The organic thickener contains alkali swelling associative thickener (ASE-60, TT-935, etc.), cellulose macromolecular thickener (hydroxyethyl cellulose, etc.) and nonionic associative aqueous polyurethane thickener. However, the nonionic aqueous polyurethane thickener in the domestic market is mainly made of foreign products, the cost of the nonionic aqueous polyurethane thickener is about 10 yuan/kg, the price reaches 60 yuan/kg in coating enterprises, and 8W and 12W of Romen Haas, 1290 series products of Bassfu, SN-612 series products of Japan company and the like exist in the market at present. Although corresponding nonionic associative aqueous polyurethane thickeners are available at home and only produced by a few manufacturers, the nonionic associative aqueous polyurethane thickeners produced by the manufacturers at home have the problems of yellow appearance, layering, low thickening efficiency and the like.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide the nonionic associative type aqueous polyurethane thickener and the preparation method thereof.
The technical scheme is as follows:
a preparation method of a nonionic associative water-based polyurethane thickener comprises the following steps:
(1) carrying out vacuum dehydration treatment on polyethylene glycol;
(2) mixing 250-500 parts of polyethylene glycol (PEG) and 18-25 parts of Hexamethylene Diisocyanate (HDI) in a reactor at 60-70 ℃, adding an organic tin catalyst, stirring under the protection of inert gas, heating to 105 +/-5 ℃, and then reacting for 2-3 h;
(3) adding 10-20 parts of Glycerol Monooleate (GMO) and 5-10 parts of C12 alcohol-C14 alcohol, keeping the temperature at 105 +/-5 ℃ under the protection of inert gas, reacting for 0.5-1 h, adding 1-2 parts of organic bismuth catalyst, heating to 110-120 ℃, keeping the temperature unchanged, and reacting for 3-4 h;
(4) cooling to 90-100 deg.C, adding 20-40 parts of hydrogen peroxide, and maintaining for 0.5-1.5 hr;
(5) cooling to below 70 ℃, adding 200-450 parts of dipropylene glycol monomethyl ether, stirring for 20-30min, then adding 200-400 parts of water, and filtering to obtain the nonionic associative waterborne polyurethane thickening agent.
The nonionic associative water-based polyurethane thickener is prepared by the steps of reacting polyethylene glycol with HDI to obtain polyurethane, introducing glycerol monooleate with hydrophobic groups into molecules by taking the HDI as a linking point, enabling the side chains to have the hydrophobic groups, and performing end capping on isocyanato in the molecular chains by using monohydroxy hydrophobic long-chain substances C12 alcohol-C14 alcohol to control the molecular weight, so that macromolecular chains with both ends of the molecular chains and the side chains being hydrophobic chains are obtained. At the initial stage of the reaction, reacting polyethylene glycol with HDI to obtain polyurethane, wherein HDI is used as a linking point, HDI is excessive, and isocyanate is remained in a synthesized molecular chain; then GMO is introduced into a molecular chain, an HDI chain segment is also used as a linking point, and the C12 alcohol-C14 alcohol is used for blocking the isocyanic acid radical, so that the C12 alcohol-C14 alcohol can control the molecular chain of the polyurethane on one hand, and the C12 alcohol-C14 alcohol alkyl chain segment can improve the hydrophobicity of the system on the other hand; adding hydrogen peroxide to carry out aftertreatment on the isocyanato, and finally adding water to emulsify to obtain the nonionic aqueous polyurethane thickener with excellent performance. In the design of the coating formula, a small amount of the thickening agent is only needed to be added to achieve good thickening efficiency, the thickening effect of the thickening agent mainly extends to the inside of latex particles through a hydrophobic chain end, and a hydrophilic chain segment of the polyethanol is remained in a water phase, so that the particles are connected in series, and the fluidity is reflected under the action of shearing force.
In one embodiment, the polyethylene glycol is PEG-6000, PEG-7000, PEG-8000 or PEG-10000. If the molecular weight of PEG is low, the molecular chain synthesized is short, and thickening efficiency is not as good as that of high molecular weight, but if the molecular weight is too high, the molecular weight of the synthesized chain is large, and the reaction is easy to gel and is not easy to control. Further, from the viewpoint of cost and performance, the preferred polyethylene glycol is PEG-6000.
In one embodiment, the polyethylene glycol vacuum dehydration treatment is: heating 550 parts of 250-80 ℃ polyethylene glycol to 70-80 ℃, adding 1-2 parts of antioxidant after the polyethylene glycol is completely dissolved, maintaining the temperature at 105 ℃ of 100-4 ℃, and vacuumizing for 3-4 hours. Because the polyethylene glycol contains impurity water, the later synthesis and the appearance of the emulsion are greatly influenced, the polyethylene glycol 6000 is firstly subjected to impurity removal, and the excessive water is removed by vacuumizing.
In one embodiment, the organotin catalyst is T-12 or tin octoate.
In one embodiment, the organobismuth catalyst is DY-20.
The nonionic associative aqueous polyurethane thickener prepared by the preparation method.
The invention has the beneficial effects that: the invention takes polyethylene glycol as a hydrophilic part and HDI as a linking point, glycerol monooleate with a hydrophobic group is introduced into molecules to lead a side chain to have the hydrophobic group, and the molecular chain is blocked by hydrophobic long-chain substances of monohydroxy to control the molecular weight, thereby obtaining a macromolecular chain with both ends of the molecular chain and the side chain being hydrophobic chains.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A nonionic associative aqueous polyurethane thickener is prepared by the following steps:
(1) heating 400 parts of polyethylene glycol (PEG-6000) to 70-80 ℃, adding 2 parts of antioxidant after the polyethylene glycol is completely dissolved, maintaining the temperature at 105 ℃, and vacuumizing for 3-4 hours;
(2) mixing 360 parts of purified polyethylene glycol (PEG-6000) and 26 parts of Hexamethylene Diisocyanate (HDI) in a four-neck flask at 60-70 ℃, adding 1.5g of organic tin catalyst T-12, replacing air in the four-neck flask by argon, stirring under the protection of inert gas argon, heating to 105 +/-5 ℃, and continuing to react for 2-3 hours;
(3) discharging gas in the four-neck flask, adding 18.5 parts of glycerol monooleate and 8.5 parts of C14 alcohol, keeping the temperature at 105 +/-5 ℃ under the protection of inert gas, reacting for 0.5-1 h, adding 1.5 parts of organic bismuth catalyst, heating to 110-120 ℃, keeping the temperature unchanged, and reacting for 3-4 h;
(4) cooling to 90-100 deg.C, adding 25 parts of hydrogen peroxide, and maintaining for 0.5-1.5 hr;
(5) and cooling to below 70 ℃, adding 324 parts of dipropylene glycol monomethyl ether, stirring for 20-30min, then adding 300 parts of water, and filtering to obtain the nonionic associative waterborne polyurethane thickening agent.
Example 2
A nonionic associative aqueous polyurethane thickener is prepared by the following steps:
(1) heating 550 parts of polyethylene glycol PEG-10000 to 70-80 ℃, adding 2 parts of antioxidant after the polyethylene glycol is completely dissolved, maintaining the temperature at 100 ℃ and 105 ℃, and vacuumizing for 3-4 hours;
(2) mixing 500 parts of purified polyethylene glycol (PEG-10000) and 22.3 parts of hexamethylene diisocyanate in a four-neck flask at 60-70 ℃, adding 2g of organic tin catalyst T-12, replacing air in the four-neck flask by argon, stirring under the protection of inert gas argon, heating to 105 +/-5 ℃, and continuing to react for 2-3 hours;
(3) discharging gas in the four-neck flask, adding 15.9 parts of glycerol monooleate and 7.3 parts of C14 alcohol, keeping the temperature at 105 +/-5 ℃ under the protection of inert gas, reacting for 0.5-1 h, adding 1.5 parts of organic bismuth catalyst, heating to 110-120 ℃, keeping the temperature unchanged, and reacting for 3-4 h;
(4) cooling to 90-100 deg.C, adding 30 parts of hydrogen peroxide, and maintaining for 0.5-1.5 hr;
(5) and (3) cooling to below 70 ℃, adding 420 parts of dipropylene glycol monomethyl ether, stirring for 20-30min, then adding 400 parts of water, and filtering to obtain the nonionic associative waterborne polyurethane thickening agent.
Example 3
A nonionic associative aqueous polyurethane thickener is prepared by the following steps:
(1) heating 300 parts of polyethylene glycol PEG-10000 to 70-80 ℃, adding 1 part of antioxidant after the polyethylene glycol is completely dissolved, maintaining the temperature at 100-105 ℃, and vacuumizing for 3-4 hours;
(2) mixing 250 parts of purified polyethylene glycol (PEG-6000) and 18.6 parts of hexamethylene diisocyanate in a four-neck flask at 60-70 ℃, adding 1g of organic tin catalyst T-12, replacing air in the four-neck flask by argon, stirring under the protection of inert gas argon, heating to 105 +/-5 ℃, and continuing to react for 2-3 hours;
(3) discharging gas in the four-neck flask, adding 13.3 parts of glycerol monooleate and 6 parts of C14 alcohol, keeping the temperature at 105 +/-5 ℃ under the protection of inert gas, reacting for 0.5-1 h, adding 1 part of organic bismuth catalyst, heating to 110-120 ℃, keeping the temperature unchanged, and reacting for 3-4 h;
(4) cooling to 90-100 deg.C, adding 20 parts of hydrogen peroxide, and maintaining for 0.5-1.5 hr;
(5) and (3) cooling to below 70 ℃, adding 200 parts of dipropylene glycol monomethyl ether, stirring for 20-30min, then adding 235 parts of water, and filtering to obtain the nonionic associative waterborne polyurethane thickening agent.
Example 4
A nonionic associative aqueous polyurethane thickener is prepared by the following steps:
(1) heating 500 parts of polyethylene glycol PEG-8000 to 70-80 ℃, adding 2 parts of antioxidant after the polyethylene glycol is completely dissolved, maintaining the temperature at 100-105 ℃, and vacuumizing for 3-4 hours;
(2) mixing 400 parts of purified polyethylene glycol (PEG-8000) and 22.3 parts of hexamethylene diisocyanate in a four-neck flask at the temperature of 60-70 ℃, adding 2g of organic tin catalyst T-12, replacing air in the four-neck flask by argon, stirring under the protection of inert gas argon, heating to 105 +/-5 ℃, and continuing to react for 2-3 hours;
(3) discharging gas in the four-neck flask, adding 15.9 parts of glycerol monooleate and 6.34 parts of C12 alcohol, keeping the temperature at 105 +/-5 ℃ under the protection of inert gas, reacting for 0.5-1 h, adding 2 parts of organic bismuth catalyst, heating to 110-120 ℃, keeping the temperature unchanged, and reacting for 3-4 h;
(4) cooling to 90-100 deg.C, adding 40 parts of hydrogen peroxide, and maintaining for 0.5-1.5 hr;
(5) and cooling to below 70 ℃, adding 370 parts of dipropylene glycol monomethyl ether, stirring for 20-30min, then adding 300 parts of water, and filtering to obtain the nonionic associative waterborne polyurethane thickening agent.
Comparative example 1
A thickener was prepared in substantially the same manner as in example 1 except that 9.06 parts of 1, 2-decanediol was used in step (3) in place of the glycerol monooleate in example 1.
Comparative example 2
A thickener was prepared in substantially the same manner as in example 1 except that 4.65 parts of trimethylolpropane was used in place of the glycerol monooleate in example 1 in step (3).
5g of each of the nonionic associative aqueous polyurethane thickeners prepared in examples 1 to 4 and the thickener prepared in comparative example 1 was added to 500g of a styrene-acrylic emulsion (Basff 296-DS), and the viscosity of the system was measured, and the measurement results are shown in Table 1.
TABLE 1
Selecting a formula of wood paint emulsion (Bayer 2695 hydroxyl dispersoid), adding the nonionic associative type waterborne polyurethane thickener synthesized in the experiment into the formula according to the amount of 0.5 percent, preparing a paint film on a glass plate, putting the paint film into a drying oven, baking for 8 hours at 50 ℃, taking out the paint film from the drying oven, cooling to room temperature, putting the glass plate into water, immersing the paint film into the water at the position below one third of the paint film, and observing the water resistance of the paint film. The test results are shown in Table 2.
TABLE 2
| Test items | 24h | 48h | 96h |
| Example 1 | No whitening and no bubbling | No whitening and no bubbling | No whitening and no bubbling |
| Example 2 | No whitening and no bubbling | No whitening and no bubbling | No whitening and no bubbling |
| Example 3 | No whitening and no bubbling | No whitening and no bubbling | No whitening and no bubbling |
| Example 4 | No whitening and no bubbling | No whitening and no bubbling | No whitening and no bubbling |
| Comparative example 1 | No whitening and no bubbling | No whitening and no bubbling | No bubbling of white |
| Comparative example 2 | No whitening and no bubbling | No whitening and no bubbling | No bubbling of white |
100g of the thickeners prepared in examples 1 to 4, comparative example 1 and comparative example 2 were placed in a 200mL reagent bottle, and the storage stability was judged by observing the appearance of the thickener. The results are shown in Table 3.
TABLE 3
The nonionic associative aqueous polyurethane thickener prepared in the embodiments 1 to 4 has a cost price of 9 yuan per kg, and has a significant price advantage compared with foreign products.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (4)
1. A preparation method of a nonionic associative water-based polyurethane thickener is characterized by comprising the following steps:
(1) carrying out vacuum dehydration treatment on polyethylene glycol;
(2) mixing 250-500 parts of polyethylene glycol and 18-25 parts of hexamethylene diisocyanate in a reactor at 60-70 ℃, adding an organic tin catalyst, stirring under the protection of inert gas, heating to 105 +/-5 ℃, and then reacting for 2-3 hours;
(3) adding 10-20 parts of glycerol monooleate and 5-10 parts of C12 alcohol-C14 alcohol, keeping the temperature at 105 +/-5 ℃ under the protection of inert gas, reacting for 0.5-1 h, adding 1-2 parts of organic bismuth catalyst, heating to 110-120 ℃, keeping the temperature unchanged, and reacting for 3-4 h;
(4) cooling to 90-100 deg.C, adding 20-40 parts of hydrogen peroxide, and maintaining for 0.5-1.5 hr;
(5) cooling to below 70 ℃, adding 200-450 parts of dipropylene glycol monomethyl ether, stirring for 20-30min, then adding 200-400 parts of water, and filtering to obtain the nonionic association type waterborne polyurethane thickening agent;
the polyethylene glycol is PEG-6000, PEG-7000, PEG-8000 or PEG-10000,
the polyethylene glycol vacuum dehydration treatment comprises the following steps: heating 550 parts of 250-80 ℃ polyethylene glycol to 70-80 ℃, adding 1-2 parts of antioxidant after the polyethylene glycol is completely dissolved, maintaining the temperature at 105 ℃ of 100-4 ℃, and vacuumizing for 3-4 hours.
2. The method according to claim 1, wherein the organotin catalyst is T-12 or tin octylate.
3. The process according to claim 1, wherein the organobismuth catalyst is DY-20.
4. The nonionic associative aqueous polyurethane thickener prepared by the process according to any one of claims 1 to 3.
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