CN118496704A - Preparation method, product and application of high-thixotropic aqueous polyamide wax - Google Patents
Preparation method, product and application of high-thixotropic aqueous polyamide wax Download PDFInfo
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- CN118496704A CN118496704A CN202410518498.4A CN202410518498A CN118496704A CN 118496704 A CN118496704 A CN 118496704A CN 202410518498 A CN202410518498 A CN 202410518498A CN 118496704 A CN118496704 A CN 118496704A
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 87
- 229920002647 polyamide Polymers 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 55
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000000539 dimer Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000004480 active ingredient Substances 0.000 claims description 12
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 12
- 239000006184 cosolvent Substances 0.000 claims description 11
- 150000004985 diamines Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 150000003384 small molecules Chemical class 0.000 claims description 7
- 238000000518 rheometry Methods 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- -1 aliphatic amines Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 15
- 238000007665 sagging Methods 0.000 abstract description 6
- 239000001993 wax Substances 0.000 description 103
- 230000000052 comparative effect Effects 0.000 description 22
- 239000011259 mixed solution Substances 0.000 description 20
- 239000007795 chemical reaction product Substances 0.000 description 12
- 238000009413 insulation Methods 0.000 description 12
- 239000003973 paint Substances 0.000 description 11
- 238000005338 heat storage Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 230000007246 mechanism Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000000110 cooling liquid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention relates to a preparation and application of a high thixotropic aqueous polyamide wax, which comprises the following preparation steps: and (3) preparing the aqueous polyamide wax resin in the step (1) and preparing the high thixotropic aqueous wax slurry in the step (2). Aiming at the problem that the dispersibility and the thixotropy of the aqueous polyamide wax are difficult to be compatible under the background of the prior art, the invention provides the novel aqueous polyamide wax which is easy to disperse and has high thixotropy, namely the aqueous wax has excellent dispersion performance and excellent thixotropic performance. The water-based polyamide wax with easy dispersion and high thixotropic property can be widely applied to various water-based coatings and provides anti-sinking and anti-sagging performances for the system.
Description
Technical Field
The invention relates to a high thixotropic aqueous polyamide wax; belongs to the technical field of paint rheological auxiliary agents.
Background
The aqueous polyamide wax is a thickening rheological aid for the water-based paint, can better balance the sagging resistance and the leveling property of a coating film, and endows the water-based paint system with higher thixotropic property.
Commercial grade aqueous polyamide waxes often have contradictory dispersing and thixotropic properties during actual use. The solid content of the aqueous polyamide wax with good dispersion performance is about 10% or lower, and the aqueous polyamide wax only has slight thickening and sagging resistance in a system, so that the application scene of the aqueous polyamide wax is limited; however, the aqueous polyamide wax with poor dispersion performance has a solid content of about 20% or more, such as the high solid content aqueous wax mentioned in publication No. CN114163864A, and this type of aqueous wax shows a good thickening and sagging-resistant thixotropic effect, but the wax is difficult to disperse, and usually needs to be diluted to prepare 20-30% of pregelatinized before the wax is added into the system, so that the process difficulty is increased and the due effect is reduced. Therefore, there are few products available in commercial polyamide waxes that combine both dispersing and thixotropic properties.
The invention patent application with publication number (CN 109735160A, publication day: 2019.5.10) discloses a preparation method of an easily dispersible aqueous polyamide wax, wherein the preparation method is to add an additional active ingredient B (namely a surfactant) to improve the dispersibility of the aqueous polyamide wax. In addition, U.S. Pat. No. (US 20120125235A, publication day: 2012.5.24) also mentions a method for preparing an aqueous wax, according to which we can increase the dispersion property of an aqueous polyamide wax by increasing the acid value of an aqueous wax resin, but it has been found in practice that an aqueous polyamide wax having an excessively high acid value is relatively weak in thixotropic property, and therefore, a simple method for increasing the acid value of an aqueous wax resin cannot solve the contradiction between the dispersion property and thixotropic property of an aqueous polyamide wax.
Disclosure of Invention
Aiming at the problem that the dispersibility and the thixotropy of the commercial-grade aqueous polyamide wax are difficult to be compatible, the invention provides a novel aqueous polyamide wax which is easy to disperse and has high thixotropy, namely the aqueous wax has excellent dispersion performance and excellent thixotropic performance. The water-based polyamide wax with easy dispersion and high thixotropic property can be widely applied to various water-based coatings and provides anti-sinking and anti-sagging performances for the system.
The technical scheme for solving the problems is as follows:
a high thixotropic aqueous polyamide wax prepared by the steps of:
Preparation of aqueous Polyamide wax resin in step (1)
S11, adding mixed acid of dimer acid and small-molecule dibasic acid and organic diamine into a reaction device with a stirrer, a temperature control system, a condenser tube, a dripping tank and a constant-temperature oil bath pot;
s12, slowly heating to 130-170 ℃, and keeping until all materials are completely melted;
S13, carrying out constant-temperature reaction until the acid value reaches the specified value, and pouring out for later use;
Preparation of high thixotropic aqueous wax slurry in step (2)
S21, adding a certain amount of synthesized aqueous wax resin, organic cosolvent and organic amine into a reaction device with a stirrer, a temperature control system, a condenser pipe and a constant-temperature oil bath pot;
S22, heating to 100-120 ℃, and then slowly stirring and dispersing uniformly;
S23, heating deionized water with a certain mass to 80-90 ℃, placing the deionized water under a dispersing machine for stirring and dispersing, slowly adding the dissolved active ingredients into hot deionized water under the stirring condition, and then continuing stirring and dispersing;
s24, adding a surfactant when the temperature is reduced to 50-60 ℃, and then continuously stirring and dispersing;
s25, finally cooling to room temperature, and stopping stirring to obtain the corresponding aqueous polyamide wax paste.
Preferably, in order to improve the dispersion performance of the aqueous wax, the above patent either adds an additional auxiliary agent or improves the acid value of the aqueous resin, but practice proves that the contradiction between the dispersion performance and thixotropic performance of the aqueous polyamide wax cannot be effectively solved by the two ideas. The method adopted by the invention is to modify the water-based wax resin by a synthetic means so as to improve the hydrophilic performance of the water-based wax resin, and in addition, the thixotropic performance of the water-based wax resin is considered. The general aqueous wax resin has the following structure:
A-B-A-……B-A
Wherein A represents a dibasic acid and B represents a diamine. The size of the acid number can be adjusted by the molecular weight. The most commonly used diacids and diamines are dimer acids and hexamethylenediamine, wherein if they are divided according to a hydrophilic-hydrophobic segment, the amide groups between A and B are polar groups, the carboxylic acid groups at the chain ends are also polar groups, these two groups belonging to a hydrophilic segment, the methylene carbon chain (consisting of 34 CH 2s in dimer acids) linking the two groups of amide groups clearly constituting the hydrophobic segment, in contrast to the hydrophilic segment which corresponds approximately to the length of a methylene chain of only 10 CH2 s. Obviously, too long hydrophobic segment in the molecular chain of the water-based wax is a main reason for poor hydrophilicity and poor dispersion performance of the water-based wax. In order to solve the problem, a small amount of small molecular dibasic acid such as adipic acid, suberic acid, sebacic acid and the like is introduced during synthesis, and amide groups formed by the small molecular dibasic acid can remarkably improve the proportion of hydrophilic chain segments, so that the hydrophilic performance and the dispersion performance of the water-based wax are improved; in addition, the number of amide groups in a molecular chain is also greatly increased, more amide groups can participate in the construction of hydrogen bonds in a coating system, and the thickening, sagging resistance and other thixotropic properties of the aqueous polyamide wax are additionally improved. It should be noted that the reactivity of these small-molecule dibasic acids is far greater than that of large-molecule dibasic acids such as dimer acid, and therefore, the addition amount of the small-molecule dibasic acid must be strictly controlled. If the amount of small molecule diacid is too large, a water insoluble polyamide resin is formed, rendering it unsuitable for use in preparing an aqueous polyamide wax.
As the preferable choice of the technical proposal, the aqueous polyamide wax resin is prepared by mixing dibasic acid and diamine through polycondensation; wherein the macromolecular diacid in the mixed diacid is dimer acid, and the micromolecular diacid is one or more of adipic acid, glutaric acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid; the diamine is one or more of C2-C36 diamine fatty amine. Wherein, the mol ratio of the dimer acid to the small molecule dibasic acid is 2:1-10:1, more preferably 3:1-8:1, and most preferably 4:1-6:1.
Preferably, in the step (2), a coalescing aid is added, namely 2-ethylhexanoic acid-3-alkoxy-2-hydroxypropyl ester, wherein the coalescing aid is an organic solvent and is widely used for film formation of water-based paint, the coalescing aid improves viscosity through particle swelling and solvation, and the coalescing aid has better effect in a solvent with higher hydrophilicity.
Preferably, the aqueous polyamide wax comprises the following components in parts by mass: 15.0-25.0 parts of aqueous polyamide wax resin, 2.0-7.0 parts of surfactant, 1.0-5.0 parts of organic amine, 5.0-15.0 parts of organic cosolvent, 1.0-5.0 parts of coalescing aid and 100 parts of deionized water.
The invention has the advantages that the water-based wax resin is modified, the hydrophilic performance is improved, and the due thixotropic property is also considered; in addition, the boiling point of the coalescing aid 2-ethylhexanoic acid-3-alkoxy-2-hydroxypropyl is 270-283 ℃, and meets the requirements of national environmental protection regulations on VOCs; compared with the traditional coalescing aid, the product has low volatility, does not belong to VOC, is safe and environment-friendly, has better performance than the commonly used coalescing aid of Texanol (2, 4-trimethyl-1, 3-pentanediol monoisobutyrate) in the market, and has obvious advantages.
As a preferable mode of the above technical scheme, the acid value of the aqueous polyamide wax resin is 70-120mgKOH/g.
As a preferable mode of the above technical scheme, the surfactant is a nonionic surfactant with HLB value of 10.0-14.0, and the hydrophilic group of the surfactant is mainly composed of oxygen-containing groups.
As a preferable mode of the above technical scheme, the oxygen-containing group is an ether group or a hydroxyl group.
Preferably, the organic amine is one or more selected from fatty amine, alcohol amine, amide and aromatic amine.
Preferably, the organic solvent is selected from one or more of propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether and dipropylene glycol butyl ether.
In summary, the invention has the following beneficial effects:
1. The novel aqueous polyamide wax provided by the invention has high solid content, can simultaneously consider the dispersion performance and the thixotropic performance, and has excellent thixotropic performance while maintaining good dispersion performance;
2. Compared with commercial-grade aqueous polyamide wax in the market, the high-thixotropic aqueous polyamide wax provided by the invention has excellent dispersion performance under higher solid content conditions, such as 25% solid content, can be directly added into a system without preparing pregelatinization, and has excellent thixotropic performance;
3. the high thixotropic aqueous polyamide wax provided by the invention has high thixotropic property and excellent heat storage stability.
Drawings
FIG. 1 is a graph showing the relationship between shear rate and viscosity for example 1 of the present invention;
FIG. 2 is a graph showing the relationship between time and viscosity in example 2 of the present invention;
FIG. 3 is a graph showing the relationship between shear rate and viscosity for example 3 of the present invention;
FIG. 4 is a schematic front view of a dispersing machine for preparing aqueous polyamide wax according to example 6 of the present invention;
FIG. 5 is a schematic diagram showing a dispersing machine for preparing an aqueous polyamide wax according to example 6 of the present invention.
Detailed Description
The following specific examples are intended to be illustrative of the invention and are not intended to be limiting, as modifications of the invention will be apparent to those skilled in the art upon reading the specification without inventive contribution thereto, and are intended to be protected by the patent law within the scope of the appended claims.
The preparation and use of such readily dispersible, highly thixotropic aqueous polyamide wax adjuvants are described below in connection with specific examples.
Example 1
Step (1) Synthesis of aqueous Polyamide wax resin A1
In a 1000ml four-necked flask, 1mol of dimer acid and 0.26mol of adipic acid are firstly added, 0.69 mol mol of hexamethylenediamine is correspondingly added, an oil bath pot, a stirrer, a temperature controller and a spherical condenser are arranged, the temperature is raised to 160 ℃ while stirring, the reaction is carried out at constant temperature, and when the acid value of a reaction product is reduced to 95mgKOH/g, the reaction is stopped, and the reaction product is poured out for standby. The aqueous wax resin having an acid value of 95 was designated as aqueous wax resin A1.
Preparation of high thixotropic aqueous Polyamide wax A2 in step (2)
Adding 40g of water-based wax resin A1, then adding 18g of propylene glycol monomethyl ether as an organic cosolvent into a 500mL four-necked flask, installing an oil bath pot, a stirrer, a temperature controller and a spherical condenser pipe, heating to 120 ℃ and keeping the temperature for 0.5h for stirring and dissolving, adding 5g of N, N-diethyl ethanolamine after the components are dissolved, and then reducing the temperature to 90-100 ℃; meanwhile, 131g of deionized water is heated to 90 ℃ and placed under a dispersing machine to be stirred and dispersed, then the mixed solution is slowly added into hot deionized water under the stirring condition, the stirring speed is controlled at 1000rmp, the temperature of the mixed solution is slowly reduced to 60 ℃, 6gAEO-9 polyoxyethylene ether is added, then the mixed solution is continuously stirred and cooled to room temperature, and the mixed solution is poured into a transparent plastic tank, so that the aqueous polyamide wax paste with 20% of active ingredients is obtained.
The results are shown in FIG. 1, wherein red is the control, black is comparative example 1, and green is example 1.
Comparative example 1
Commercial grade aqueous polyamide wax, active ingredient content: 20%, acid value: 12.5.
Example 2
Step (1) Synthesis of aqueous Polyamide wax resin B1
In a 1000ml four-necked flask, 1mol of dimer acid and 0.15mol of suberic acid are firstly added, 0.55 mol of decanediamine is correspondingly added, an oil bath pot, a stirrer, a temperature controller and a spherical condenser are arranged, the temperature is raised to 150 ℃ while stirring, the reaction is carried out at constant temperature, and when the acid value of a reaction product is reduced to 100mgKOH/g, the reaction is stopped, and the reaction product is poured out for standby. The aqueous wax resin having an acid value of 100 was designated as aqueous wax resin B1.
Preparation of high thixotropic aqueous polyamide wax B2 in step (2)
Adding 30g of water-based wax resin B1, adding 14g of propylene glycol monomethyl ether as an organic cosolvent into a 500mL four-necked flask, installing an oil bath pot, a stirrer, a temperature controller and a spherical condenser pipe, heating to 120 ℃ and keeping the temperature for 0.5h for stirring and dissolving, adding 4g of N, N-diethyl ethanolamine after the components are dissolved, and then cooling to 90-100 ℃; simultaneously, 148g of deionized water is heated to 90 ℃ and is placed under a dispersing machine to be stirred and dispersed, then the mixed solution is slowly added into hot deionized water under the stirring condition, the stirring speed is controlled at 1000rmp, the temperature of the mixed solution is slowly reduced to 60 ℃, 4g of laurinol polyoxyethylene ether is added, then the mixture is continuously stirred and cooled to room temperature, and the mixture is poured into a transparent plastic tank, so that the aqueous polyamide wax paste with the active ingredient of 15% is obtained.
The results are shown in FIG. 2, where orange is the control, blue is comparative example 2, and red is example 2.
Comparative example 2
Commercial grade aqueous polyamide wax, active ingredient content: 15%, acid value: 12.5.
Example 3
Step (1) Synthesis of aqueous Polyamide wax resin C1
In a 1000ml four-necked flask, 1mol of dimer acid and 0.32mol of sebacic acid are firstly added, 0.79 mol mol of ethylenediamine is correspondingly added, an oil bath pot, a stirrer, a temperature controller and a spherical condenser are arranged, the temperature is raised to 140 ℃ while stirring, the reaction is carried out at constant temperature, and when the acid value of a reaction product is reduced to 90mgKOH/g, the reaction is stopped, and the reaction product is poured out for standby. The aqueous wax resin having an acid value of 90 was designated as aqueous wax resin C1.
Preparation of step (2) high thixotropic aqueous polyamide wax C2
Adding 45g of water-based wax resin C1, then adding 20g of propylene glycol monomethyl ether as an organic cosolvent into a 500mL four-necked flask, installing an oil bath pot, a stirrer, a temperature controller and a spherical condenser pipe, heating to 120 ℃ and keeping the temperature for 0.5h for stirring and dissolving, adding 6g of N, N-diethyl ethanolamine after the components are dissolved, and then cooling to 90-100 ℃; meanwhile, 121g of deionized water is heated to 90 ℃ and placed under a dispersing machine to be stirred and dispersed, then the mixed solution is slowly added into hot deionized water under the stirring condition, the stirring speed is controlled at 1000rmp, the temperature of the mixed solution is slowly reduced to 60 ℃, 8g of AOE-9 polyoxyethylene ether is added, then the mixed solution is continuously stirred and cooled to room temperature, and the mixed solution is poured into a transparent plastic tank, so that the aqueous polyamide wax paste with the active ingredient of 22.5% is obtained.
The results are shown in FIG. 3, wherein red is the control, black is comparative example 3, and green is example 3.
Comparative example 3
Commercial grade aqueous polyamide wax, active ingredient content: 22.5% and an acid value of 20.
The table for example 1 and comparative example 1 is as follows:
the tables for example 2 and comparative example 2 are as follows:
example 3 and comparative example 3 are referred to as follows:
Example 4
Step (1) Synthesis of aqueous Polyamide wax resin D1
In a 1000ml four-necked flask, 1mol of dimer acid and 0.5mol of suberic acid are firstly added, 0.83 mol mol of decanediamine is correspondingly added, an oil bath pot, a stirrer, a temperature controller and a spherical condenser are arranged, the temperature is raised to 130 ℃ while stirring, the reaction is carried out at constant temperature, and when the acid value of a reaction product is reduced to 100mgKOH/g, the reaction is stopped, and the reaction product is poured out for standby. The aqueous wax resin having an acid value of 100 was designated as aqueous wax resin D1.
Preparation of step (2) high thixotropic aqueous polyamide wax D2
Adding 50g of water-based wax resin E1, adding 30g of propylene glycol monomethyl ether as an organic cosolvent into a 500mL four-necked flask, installing an oil bath pot, a stirrer, a temperature controller and a spherical condenser pipe, heating to 110 ℃ and keeping the temperature for 0.5h for stirring and dissolving, adding 10g of N, N-diethyl ethanolamine after the components are dissolved, and then cooling to 90-100 ℃; at the same time, 100g of deionized water is heated to 90 ℃ and placed under a dispersing machine to be stirred and dispersed, then the mixed solution is slowly added into hot deionized water under the stirring condition, the stirring speed is controlled at 1000rmp, the temperature of the mixed solution is slowly reduced to 60 ℃, 10g of AOE-9 polyoxyethylene ether is added, then the mixed solution is continuously stirred and cooled to room temperature, and the mixed solution is poured into a transparent plastic tank, thus obtaining the aqueous polyamide wax paste with the active ingredient of 22.5%.
Example 5
Step (1) Synthesis of aqueous Polyamide wax resin E1
In a 1000ml four-necked flask, 1mol of dimer acid and 0.1mol of suberic acid are firstly added, 0.42 mol of decanediamine is correspondingly added, an oil bath pot, a stirrer, a temperature controller and a spherical condenser are arranged, the temperature is raised to 170 ℃ while stirring, the reaction is carried out at constant temperature, and when the acid value of a reaction product is reduced to 110mgKOH/g, the reaction is stopped, and the reaction product is poured out for standby. The aqueous wax resin having an acid value of 100 was designated as aqueous wax resin E1.
Preparation of step (2) high thixotropic aqueous polyamide wax E2
Adding 42g of water-based wax resin E1, adding 10g of propylene glycol monomethyl ether as an organic cosolvent into a 500mL four-necked flask, installing an oil bath pot, a stirrer, a temperature controller and a spherical condenser pipe, heating to 110 ℃ and keeping the temperature for 0.5h for stirring and dissolving, adding 2g of N, N-diethyl ethanolamine after the components are dissolved, and then cooling to 90-100 ℃; at the same time, 142g of deionized water is heated to 90 ℃ and placed under a dispersing machine to be stirred and dispersed, then the mixed solution is slowly added into hot deionized water under the stirring condition, the stirring speed is controlled at 1000rmp, the temperature of the mixed solution is slowly reduced to 60 ℃, 4g of AOE-9 polyoxyethylene ether is added, then the mixed solution is continuously stirred and cooled to room temperature, and the mixed solution is poured into a transparent plastic tank, thus obtaining the aqueous polyamide wax paste with the active ingredient of 22.5%.
Example 6
Step (1) Synthesis of aqueous Polyamide wax resin C1
In a 1000ml four-necked flask, 1mol of dimer acid and 0.32mol of sebacic acid are firstly added, 0.79 mol mol of ethylenediamine is correspondingly added, an oil bath pot, a stirrer, a temperature controller and a spherical condenser are arranged, the temperature is raised to 140 ℃ while stirring, the reaction is carried out at constant temperature, and when the acid value of a reaction product is reduced to 90mgKOH/g, the reaction is stopped, and the reaction product is poured out for standby. The aqueous wax resin having an acid value of 90 was designated as aqueous wax resin C1.
Preparation of step (2) high thixotropic aqueous polyamide wax C2
Adding 45g of water-based wax resin C1, then adding 20g of propylene glycol monomethyl ether as an organic cosolvent into a 500mL four-necked flask, installing an oil bath pot, a stirrer, a temperature controller and a spherical condenser pipe, heating to 120 ℃ and keeping the temperature for 0.5h for stirring and dissolving, adding 6g of N, N-diethyl ethanolamine after the components are dissolved, and then cooling to 90-100 ℃; meanwhile, heating 116g of deionized water to 90 ℃, placing under a dispersing machine for stirring and dispersing, then slowly adding the mixed solution into hot deionized water under the stirring condition, controlling the stirring speed to be 1000rmp, slowly reducing the temperature of the mixed solution to 60 ℃, adding 8g of AOE-9 polyoxyethylene ether, continuously stirring and cooling to room temperature, and pouring into a transparent plastic tank to obtain the aqueous polyamide wax paste with the effective active ingredient of 22.5%;
preferably, in step (2) 5g of coalescing aid is also added as 3-alkoxy-2-hydroxypropyl 2-ethylhexanoate.
As a preferred mode, the dispersing machine for preparing the aqueous wax resin is further used for preparing the aqueous polyamide wax, please refer to fig. 4-5, and the dispersing machine comprises an insulation box 1, wherein a stirring tank 2 is arranged on the insulation box 1, a liquid inlet pipe 3 and an air inlet pipe 4 are arranged on one side of the insulation box 1, a liquid outlet pipe 5 is arranged on the insulation box 1, an annular pipe 6 is arranged in the insulation box 1, an air guide pipe 7 is arranged on one side of the insulation box 1, the air guide pipe 7 is communicated with the annular pipe 6, a first thread groove is formed in the top end of the stirring tank 2, a first thread ring 8 is arranged on the first thread groove, a top cover 9 is arranged on the first thread ring 8, and a stirring mechanism is arranged on the top cover 9, The top end of the connecting pipe 11 is provided with a second thread groove, the second thread groove is provided with a second thread ring 13, the air duct 7 is bent and extends to the upper part of the top cover 9, a flange is arranged between the air duct 7 and the second thread ring 13, the heat insulation box 1 is provided with a filtering mechanism, the bottom end of the stirring tank 2 is provided with a discharge mechanism, in the embodiment, the liquid inlet pipe 3 is connected into a pipeline of liquid supply equipment, the liquid outlet pipe 5 is connected into a pipeline of liquid return equipment, cooling liquid enters the heat insulation box 1 through the liquid inlet pipe 3 and then flows into the liquid return equipment through the liquid outlet pipe 5, the cooling liquid is recycled, Then the water-based polyamide wax particle materials are fed into the stirring tank through the feeding pipe 10, then the stirring mechanism is used for stirring and scattering the water-based polyamide wax particle materials, then the scattered water-based polyamide wax particle materials are discharged through the discharging mechanism, the subsequent operation is convenient, the temperature around the stirring tank 2 is in a lower state through the cooling effect of cooling liquid on the stirring tank 2 in the scattering process, meanwhile, the air is connected into a pipeline of an air supply device through the air inlet pipe 4, the air is influenced by the cooling liquid in the heat insulation box 1 in the annular pipe 6, the air is stably reduced and then enters the stirring tank 2 through the air guide pipe 7, so that the water-based polyamide wax particle materials are uniformly cooled, When the inner wall of the stirring tank 2 needs to be cleaned, the parts on the flange between the air duct 7 and the second threaded ring 13 are removed, then the second threaded ring 13 is rotated, the second threaded ring 13 moves downwards in the second threaded groove in a rotating way, the second threaded ring 13 leaves the air duct 7, then the first threaded ring 8 is rotated, so that the top cover 9 leaves the first threaded groove, when the first threaded ring 8 drives the top cover 9 to move upwards in a rotating way, the second threaded ring 13 is effectively prevented from colliding with the air duct 7 through the previous step of downwards rotating in the second threaded groove, then the top cover 9 is removed, Thereby be convenient for clear up agitator tank 2 inner wall, the clearance is accomplished the back, with top cap 9 through first screwed ring 8 and first thread groove threaded connection, can make top cap 9 assembly in the top of agitator tank 2, then with second screwed ring 13 and air duct 7 alignment, rotatory second screwed ring 13 this moment, thereby make second screwed ring 13 pass through the flange and air duct 7 alignment, then use the part to pass through the flange with second screwed ring 13 and air duct 7 is fixed, thereby under the circumstances such as the rocking that can guarantee the rabbling mechanism during operation to produce, first screwed ring 8 and second screwed ring 13 receive the restriction of flange can not appear not hard up condition, guarantee structural stability.
In this scheme, filtering mechanism includes filter vat and fixed box 14, the filter vat is seted up the top of insulation can 1, the filter vat intercommunication inlet tube 3 and intake pipe 4, be equipped with filter 15 on the filter vat, filter 15 with inlet tube 3 and be equipped with the filter screen layer between the intake pipe 4, the fixed box 14 is installed one side of insulation can 1, the one end of fixed box 14 with the fixed orifices has been seted up between the filter vat, be equipped with fixed column 16 on the fixed orifices, the fixed vat has been seted up to one side of filter 15, fixed column 16 supports on the fixed vat, can effectively filter cooling medium and air through the filter screen layer between filter 15 and inlet tube 3 and the intake pipe 4, reduces impurity, guarantees the circulation of liquid inside insulation can 1, guarantees the circulation of air in air duct 7 and annular duct 6, when needs clearance or change filter screen layer, leaves the fixed vat through pulling fixed column 16, thereby will filter screen 15 from the fixed slot is removed to take down the filter screen layer or take down the fixed column 16, so that the fixed column 16 is convenient for remove in the fixed slot 15 or take down the filter screen, the fixed column is convenient to be equipped with the filter vat after the filter vat is removed or takes down the filter screen 15, the fixed column is convenient for be removed in the fixed column 15 after the filter vat is removed or is changed, the filter vat is convenient for be removed.
In this scheme, rabbling mechanism includes agitator motor 17 and (mixing) shaft 18, agitator motor 17 installs the top of top cap 9, (mixing) shaft 18 is located the inside of agitator tank 2, agitator motor 17's output is connected (mixing) shaft 18, be equipped with stirring leaf 19 on the (mixing) shaft 18, rotatory (mixing) shaft 18 through the output of control agitator motor 17, stirring leaf 19 rotation is driven to (mixing) shaft 18, and stirring leaf 19 can stir polyamide wax granule of breaking up.
In this scheme, the discharging mechanism includes row material pipe 20, row material pipe 20 installs the bottom of agitator tank 2, be equipped with the valve on the row material pipe 20, through the switching valve, the material that breaks up in the agitator tank 2 of can being convenient for is discharged.
In this scheme, all be equipped with the sealing washer on first screwed ring 8 and the second screwed ring 13, can improve the leakproofness between first screwed ring 8 and the first screw groove and between second screwed ring 13 and the second screw groove through the sealing washer.
In this scheme, one end of the fixing post 16 is provided with an elastic sleeve, the elastic effect of the elastic sleeve can enable one end of the fixing post 16 to be inserted into the fixing groove more stably,
In this scheme, agitator motor 17 is servo motor, and servo motor has the characteristics that the rotation precision is high to can improve agitator motor 17's rotation precision.
In the scheme, the valve is an electric valve, and the electric valve has the advantage of being convenient to operate and use, so that the valve can be conveniently opened and closed.
It can be derived that:
The aqueous polyamide wax rheology aids of the above example one and comparative example one were tested for performance, aqueous acrylic white paints were formulated according to the formulations shown in table 1 and then tested for shear thinning profile, i.e. viscosity decreasing with increasing shear rate, using a rheometer. A low shear viscosity means good storage properties and a low shear viscosity means good workability. The greater the difference between the low and high shear viscosities, the better the thixotropic and rheological properties of the sample. As can be seen from fig. 1, the low shear viscosity of example one is highest, while the high shear viscosity is consistent with the other two samples, meaning that the thixotropic properties of example one are best. Because no rheology additive was added, the control group had the lowest low shear viscosity and the worst thixotropic properties. The thixotropic properties of comparative example one were centered. Table 2 shows the sag resistance of three groups of aqueous acrylic white paint before and after heat storage for one week at 50 ℃, the sag resistance of the first example is 225 microns before heat storage, which is higher than that of the first comparative example, and after heat storage, the sag resistance of the first example is unchanged, and the sag resistance of the first comparative example and the comparative group is slightly reduced.
Performance tests were performed on the aqueous polyamide wax rheology aids of examples two and comparative example two above to formulate aqueous epoxy paints according to the formulations shown in table 3. The viscosity recovery curve was then tested with a rheometer using a three-stage procedure. The first and third sections employ low shear and the second section employs high shear. The first section simulates the viscosity during storage, the second section simulates the viscosity during construction, and the third section simulates viscosity recovery after construction. As can be seen from fig. 2, the second example has a high first stage viscosity, a low second stage viscosity, and a fast recovery of the third stage viscosity, compared with the control group and the second comparative example, which demonstrates that the highly thixotropic aqueous polyamide wax prepared by the method of the present invention has a better thixotropic effect in an aqueous epoxy system. Table 4 shows the sag resistance comparisons of three groups of waterborne epoxy paints before and after heat storage for one week at 50 ℃, wherein before heat storage, the sag resistance of the second antibody of the example is 375 microns, which is 325 microns higher than that of the second epoxy paint of the comparative example, and which is 200 microns higher than that of the control group; after heat storage, the sag resistance of the second example remained unchanged, and both the control group and the second comparative example were reduced to some extent.
Performance tests were performed on the aqueous polyamide wax rheology aids of the third and comparative examples described above, to prepare aqueous aluminum powder paints according to the formulations shown in table 5, and then to test the shear thinning profile, i.e., the decrease in viscosity with increasing shear rate, with a rheometer. A low shear viscosity means good storage properties and a low shear viscosity means good workability. The greater the difference in low and high shear viscosities, the better the thixotropic and rheological properties of the sample. As can be seen from fig. 3, the low shear viscosity of example three is highest, while the high shear viscosity is consistent with the other two samples, meaning that the thixotropic properties of example three are best. Because no rheology additive was added, the control group had the lowest low shear viscosity and the worst thixotropic properties. The thixotropic properties of comparative example three were centered. Table 6 shows the sag resistance comparisons of three groups of aqueous aluminum paint before and after heat storage at 50 ℃ for one week, the sag resistance of the example three is 450 microns before heat storage, the sag resistance of the comparative example three is 300 microns, the sag resistance of the comparative group is 225 microns, and the sag resistance is equal to that before heat storage.
The molar ratio of the macromolecular dimer acid to the small diacid in examples 4 and 5 is not in the preferred ratio, and no coalescing aid is added, so that the performance of the process is far worse than that of examples 1-3.
Example 6 gave the best results, with both good dispersibility and thixotropic properties, and the greatest difference in low-shear viscosity and high-shear viscosity, meaning that it has both high thixotropic and rheological properties.
Claims (10)
1. A preparation method of a high thixotropic aqueous polyamide wax, which is characterized by comprising the following steps:
Preparation of aqueous Polyamide wax resin in step (1)
S11, adding mixed acid of dimer acid and small-molecule dibasic acid and organic diamine into a stirring and heating reaction device;
s12, slowly heating to 130-170 ℃, and keeping until all materials are completely melted;
S13, carrying out constant-temperature reaction until the acid value reaches the specified value, and pouring out for later use;
Preparation of high thixotropic aqueous wax slurry in step (2)
S21, adding a certain amount of synthesized aqueous wax resin, organic cosolvent and organic amine into a stirring and heating reaction device;
S22, heating to 100-120 ℃, and then slowly stirring and dispersing uniformly;
S23, heating deionized water with a certain mass to 80-90 ℃, placing the deionized water under a dispersing machine for stirring and dispersing, slowly adding the dissolved active ingredients into hot deionized water under the stirring condition, and then continuing stirring and dispersing;
s24, adding a surfactant when the temperature is reduced to 50-60 ℃, and then continuously stirring and dispersing;
s25, finally cooling to room temperature, and stopping stirring to obtain the corresponding aqueous polyamide wax paste.
2. The method for preparing the high thixotropic aqueous polyamide wax according to claim 1, wherein the method comprises the following steps:
The preparation of the aqueous polyamide wax resin in the step (1) is prepared by polycondensation of mixed dibasic acid and diamine, wherein the macromolecular dibasic acid in the mixed dibasic acid is dimer acid, and the micromolecular dibasic acid is one or more of adipic acid, glutaric acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid; the diamine is one or more of C2-C36 diamine fatty amine.
3. The preparation of the aqueous polyamide wax resin according to claim 2, wherein the molar ratio of the dimer acid to the small-molecule diacid in the step (1) is 2:1-10:1, and the acid value of the aqueous polyamide wax resin in the step (1) is 70-120 mgKOH/g.
4. The method for preparing a high thixotropic aqueous polyamide wax according to claim 1, wherein 1.0-5.0 parts of a coalescing aid is added in step S21, and the coalescing aid is 2-ethylhexanoic acid-3-alkoxy-2-hydroxypropyl ester.
5. The method for preparing the high thixotropic aqueous polyamide wax according to claim 1, wherein the method comprises the following steps:
The preparation raw materials of the high thixotropic aqueous wax slurry comprise the following components in parts by mass: 15.0 to 25.0 parts of aqueous polyamide wax resin, 2.0 to 7.0 parts of surfactant, 1.0 to 5.0 parts of organic amine, 5.0 to 15.0 parts of organic cosolvent and deionized water which are supplemented to 100 parts.
6. The method for preparing a highly thixotropic aqueous polyamide wax according to claim 5, wherein the surfactant is a nonionic surfactant having an HLB value of 10.0 to 14.0, and the hydrophilic group of the nonionic surfactant is mainly composed of an oxygen-containing group.
7. The method for preparing a highly thixotropic aqueous polyamide wax according to claim 5, wherein the oxygen-containing group as a hydrophilic group is an ether group or a hydroxyl group.
8. The method for preparing a highly thixotropic aqueous polyamide wax according to claim 5, wherein the organic amine is one or more selected from the group consisting of aliphatic amines, alcohol amines, amides and aromatic amines.
9. The method for preparing a highly thixotropic aqueous polyamide wax according to claim 5, wherein the organic cosolvent is one or more selected from propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether and dipropylene glycol butyl ether.
10. A highly thixotropic aqueous polyamide wax, characterized in that it is produced according to a process for the preparation of a highly thixotropic aqueous polyamide wax according to any one of claims 1 to 9 and is used in the field of coating rheology auxiliaries.
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