CN113999390A - Polyurea modified polyamide aqueous rheological additive and preparation method thereof - Google Patents
Polyurea modified polyamide aqueous rheological additive and preparation method thereof Download PDFInfo
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- CN113999390A CN113999390A CN202111273542.2A CN202111273542A CN113999390A CN 113999390 A CN113999390 A CN 113999390A CN 202111273542 A CN202111273542 A CN 202111273542A CN 113999390 A CN113999390 A CN 113999390A
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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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
- C09D7/45—Anti-settling agents
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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
- C09D7/47—Levelling agents
Abstract
The invention relates to the field of aqueous rheological additives, in particular to a polyurea modified polyamide aqueous rheological additive and a preparation method thereof, wherein the polyurea modified polyamide aqueous rheological additive comprises the following raw materials in parts by weight: 1-30 parts of diamine, 50-100 parts of dibasic acid, 1-10 parts of binary polyisocyanate, 1-30 parts of a neutralizing agent, 78-200 parts of a solvent A50 and 50-50 parts of a solvent B10. The aqueous rheological additive solves the problems of insufficient thixotropy, poor solvent tolerance, easy thickening, poor dispersion in resin and insufficient anti-settling property on pigment and anti-sagging property of a paint film of the conventional polyamide aqueous rheological additive by virtue of the strong hydrogen bond characteristic of a polyurea structure, can solve the problem that multiple rheological additives are required to be mutually coordinated to solve the anti-settling and anti-sagging problems by singly using the aqueous rheological additive, is more convenient and effective to use, does not need to be tested by multiple matching tests to judge whether the aqueous rheological additive is effective or not as the conventional rheological additive, and can not cause paint film extinction.
Description
Technical Field
The invention relates to the field of aqueous rheological additives, in particular to a polyurea modified polyamide aqueous rheological additive and a preparation method thereof.
Background
The development of water-based coatings is also rapid with the gradual increase of the water-based trend in the global coating field, but the sedimentation phenomenon of the water-based coatings is an important problem often encountered in the production and use processes of the coatings. The rheological properties of the coating are also an important factor that must be considered during the various stages of its production and use. With the research and development of special functional coatings, the requirements on the performance of the coatings are higher and higher. The anti-settling agent is added into the paint, namely a loose network thixotropic structure is introduced into the paint, so that pigment and filler particles can be suspended without caking, the pigment is prevented from settling, the performance of the paint is improved, and excellent leveling property is kept.
In the prior art, for example, silica, modified bentonite, polyurethane thickeners and aqueous polyamide waxes are commonly used in aqueous coating materials in order to control the rheology of liquid systems. In the field of polyamides and polyamide waxes, there are numerous patents, such as DE 69523221, EP 0239419, US 5510452l, etc. Also combinations of modified bentonites with polyamides are used as described in EP 0509202 and DE 69704691. The above techniques are usually powders or slurries, which however have to be converted into semifinished products by means of solvents and the application of shear forces or introduced into liquid coating systems by means of special temperature control. Unless the desired temperature is difficult to control, the process is complicated and the resulting finished coating system, once the temperature is too high or too low, can produce particles resulting in coating product defects. Thus, the resultant clear coatings are dull and opaque, and these coatings cannot be used in aqueous systems and have a limited range of applications.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a polyurea modified polyamide aqueous rheological additive, the polyurea modified polyamide aqueous rheological additive solves the problem of insufficient thixotropy of the conventional polyamide aqueous rheological additive by means of the strong hydrogen bond characteristic of a polyurea structure, poor solvent resistance, easy coarsening or poor dispersion in resin, insufficient anti-settling property on pigment and anti-sagging property of paint film, meanwhile, the single use of the aqueous rheological additive can solve the problem that a plurality of rheological additives are needed to be mutually coordinated to solve the anti-sinking and anti-sagging problems in the past, the use is more convenient and effective, and the test of multiple matching tests to judge whether the aqueous rheological additive is effective as the conventional rheological additive is not needed, the rheological additive can not cause paint film extinction, has excellent compatibility, and can obtain paint films with good leveling property, high gloss and plump paint films.
The invention aims to provide a preparation method of a polyurea modified polyamide aqueous rheological additive, which is simple and efficient, convenient to operate and control, high in quality of produced products, low in cost, beneficial to industrial production and capable of effectively overcoming the defects of the conventional rheological additive.
The purpose of the invention is realized by the following technical scheme: the polyurea modified polyamide aqueous rheological additive comprises the following raw materials in parts by weight: 1-30 parts of diamine, 50-100 parts of dibasic acid, 1-10 parts of binary polyisocyanate, 1-30 parts of a neutralizing agent, 78-200 parts of a solvent A50 and 50-50 parts of a solvent B10.
More preferably, the feed comprises the following raw materials in parts by weight: 10-25 parts of diamine, 70-100 parts of dibasic acid, 5-10 parts of binary polyisocyanate, 1-10 parts of neutralizing agent, 50-150 parts of solvent A and 20-50 parts of solvent B.
The polyurea modified polyamide aqueous rheological additive solves the problems of insufficient thixotropy, poor solvent tolerance, poor coarseness or poor dispersion in resin, and insufficient anti-settling property and paint film anti-sagging property of a conventional polyamide aqueous rheological additive by means of the strong hydrogen bond characteristic of a polyurea structure, and simultaneously can solve the problem that multiple rheological additives are required to be mutually coordinated to solve the anti-settling and anti-sagging problems by independently using the aqueous rheological additive, is more convenient and effective to use, does not need to be tested by multiple matching tests to judge whether the aqueous rheological additive is effective or not like the conventional rheological additive, does not cause paint film extinction and has excellent compatibility, and can obtain a paint film with good leveling property, high gloss and full paint film. The diamine molecular chain structure adopted is regular, intermolecular hydrogen bonds with amido bonds are formed, the crystallization capacity is high, and the diamine molecular chain structure is very suitable for being used as crystal nucleus to induce the regular arrangement of the aqueous polyamide molecular chain and improve the crystallization capacity of the polyurea modified polyamide aqueous rheological additive.
Preferably, the diamine is at least one of decamethylene diamine, hexamethylene diamine, ethylene diamine, diethylene triamine, propylene diamine, heptamethylene diamine, octamethylene diamine, nonane diamine, p-phenylene diamine, o-phenylene diamine, m-phenylene diamine, polyoxyethylene diamine, butylene diamine, and pentylene diamine; more preferably, the diamine is a mixture of decamethylenediamine, ethylenediamine, polyoxyethylenediamine, and pentanediamine in a weight ratio of 0.8-1.2:0.2-0.6:0.6-1.0: 0.4-0.8.
According to the invention, the variety of the diamine and the weight ratio of different diamines are reasonably selected to improve the low-temperature activation performance of the product, so that the prepared polyurea modified polyamide aqueous rheological additive can play excellent anti-settling and anti-sagging roles at normal temperature, has excellent compatibility, and can obtain a paint film with good leveling property, high gloss and plump paint film.
Preferably, the dibasic acid is at least one of adipic acid, terephthalic acid, isophthalic acid, azelaic acid, sebacic acid, glutaric acid, succinic acid, dimer acid and DMPA; more preferably, the dibasic acid is a mixture of adipic acid, terephthalic acid, succinic acid, dimer acid and DMPA in a weight ratio of 0.4-0.8:0.8-1.2:0.6-1.0: 0.4-0.8.
According to the invention, through reasonably selecting the variety of the dibasic acid and the weight ratio of different dibasic acids, the advantages of each specific dibasic acid are cooperated, so that the acidification effect of the mixed dibasic acid is further promoted.
Preferably, the binary polyisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate; more preferably, the diisocyanate is a mixture of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate in a weight ratio of 0.4-0.8:0.6-1.0:0.4-0.8: 0.8-1.2.
The polyurea modified polyamide aqueous rheological additive prepared by polymerizing the binary polyisocyanate and other raw materials has high bonding strength and impact toughness and a full paint film.
Preferably, the solvent a is water.
Preferably, the solvent B is DMF and/or NMP.
Preferably, the neutralizing agent is at least one of potassium hydroxide, sodium hydroxide, AMP-95, ethanolamine, diethanolamine, triethanolamine, triethylamine and dimethylethanolamine. In the present invention, the diamine is neutralized by using the above-mentioned neutralizing agent after the reaction with the dibasic acid.
The invention also provides a preparation method of the polyurea modified polyamide aqueous rheological additive, which comprises the following steps:
1) adding a solvent B and diamine into a reaction kettle with a reflux condenser pipe, a distillation pipe, a constant-pressure dropping funnel, a mechanical stirrer, a thermometer and a cooling and heating system according to parts by weight, starting the cooling system and the stirrer of the reaction kettle, controlling the stirring speed to be 100 plus one (1000) RPM, slowly dropping the diisocyanate into the reaction kettle by using the constant-pressure dropping funnel, controlling the material temperature in the reaction kettle to be not higher than 50 ℃, and continuously keeping the reaction for 15-30min after the dropping is finished to obtain a binary prepolymer terminated by amino groups for later use;
2) adding dibasic acid into the binary prepolymer obtained in the step 1), closing a cooling system, starting a heating system, heating to 130-160 ℃, stopping heating after reaction and distillation of amide-generating reaction water, cooling to 90-100 ℃, adding a neutralizing agent, adding a solvent A at the temperature of 90-100 ℃ after neutralization, uniformly stirring, discharging to a packing material, and cooling to normal temperature to obtain the urea modified polyamide aqueous rheological additive.
The polyurea modified polyamide aqueous rheological additive is prepared by the method, and the polyurea modified polyamide aqueous rheological additive prepared by the method solves the problems of insufficient thixotropy, poor solvent tolerance, easy thickening, poor dispersion in resin, insufficient anti-sinking property of pigment and insufficient anti-sagging property of paint film by generating the strong hydrogen bond characteristic of a polyurea structure; meanwhile, through the regulation and control of the polymerization reaction process, the volatilization loss of the low-boiling-point raw material is avoided, and the reaction conversion rate of the diamine and the dibasic acid is improved.
The invention has the beneficial effects that:
(1) the strong hydrogen bond characteristic of the polyurea structure of the additive solves the problems of insufficient thixotropy, poor solvent tolerance, easy thickening, poor dispersion in resin, insufficient anti-settling property on pigment and insufficient anti-sagging property of paint film of the conventional polyamide aqueous rheological additive.
(2) The single use of the aqueous rheological additive can solve the problem that multiple rheological additives are needed to be mutually coordinated to solve the anti-sinking and anti-sagging problems in the prior art, the use is more convenient and effective, and the test of multiple matching tests to judge whether the rheological additive is effective as the conventional rheological additive is not needed.
(3) The rheological additive provided by the invention can not cause paint film extinction, has excellent compatibility, and can obtain a paint film with good leveling property, high gloss and plump paint film.
(4) The preparation method of the polyurea modified polyamide aqueous rheological additive is simple and efficient, is convenient to operate and control, has high quality of produced products and low cost, is beneficial to industrial production, and can effectively overcome the defects of the conventional rheological additive.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The polyurea modified polyamide aqueous rheological additive comprises the following raw materials in parts by weight: 1 part of diamine, 50 parts of dibasic acid, 1 part of binary polyisocyanate, 1 part of neutralizer, 50 parts of solvent A and 10 parts of solvent B.
The diamine is a mixture of decamethylenediamine, ethylenediamine, polyoxyethylene diamine and pentanediamine according to the weight ratio of 0.8:0.2:0.6: 0.4.
The dibasic acid is a mixture of adipic acid, terephthalic acid, succinic acid, dimer acid and DMPA in a weight ratio of 0.4:0.8:0.6: 0.4.
The binary polyisocyanate is a mixture of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate in a weight ratio of 0.4:0.6:0.4: 0.8.
The solvent A is water; and the solvent B is DMF. The neutralizing agent is potassium hydroxide.
The preparation method of the polyurea modified polyamide aqueous rheological additive is prepared by the following steps:
1) adding a solvent B and diamine into a reaction kettle with a reflux condenser pipe, a distillation pipe, a constant-pressure dropping funnel, a mechanical stirrer, a thermometer and a cooling and heating system according to parts by weight, starting the cooling system and the stirrer of the reaction kettle, controlling the stirring speed to be 100RPM, slowly dropping diisocyanate by using the constant-pressure dropping funnel, controlling the material temperature in the reaction kettle to be 30 ℃, and continuously keeping the reaction for 15min after the dropping is finished to obtain a binary prepolymer terminated by amino groups for later use;
2) adding dibasic acid into the binary prepolymer obtained in the step 1), closing a cooling system, starting a heating system, heating to 130 ℃, stopping heating after reaction and distillation of amide-generating reaction water, cooling to 90 ℃, adding a neutralizer, adding a solvent A at the temperature of 90 ℃ after neutralization, uniformly stirring, discharging to a package, and cooling to normal temperature to obtain the urea modified polyamide aqueous rheological aid.
Example 2
The polyurea modified polyamide aqueous rheological additive comprises the following raw materials in parts by weight: 10 parts of diamine, 60 parts of dibasic acid, 3 parts of binary polyisocyanate, 10 parts of neutralizing agent, 100 parts of solvent A and 20 parts of solvent B.
The diamine is a mixture of decamethylenediamine, ethylenediamine, polyoxyethylenediamine and pentanediamine according to the weight ratio of 0.9:0.3:0.7: 0.5.
The dibasic acid is a mixture of adipic acid, terephthalic acid, succinic acid, dimer acid and DMPA according to a weight ratio of 0.5:0.9:0.7: 0.5.
The binary polyisocyanate is a mixture of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate in a weight ratio of 0.5:0.7:0.5: 0.9.
The solvent A is water; the solvent B is NMP. The neutralizing agent is AMP-95.
The preparation method of the polyurea modified polyamide aqueous rheological additive is prepared by the following steps:
1) adding a solvent B and diamine into a reaction kettle with a reflux condenser pipe, a distillation pipe, a constant-pressure dropping funnel, a mechanical stirrer, a thermometer and a cooling and heating system according to parts by weight, starting the cooling system and the stirrer of the reaction kettle, controlling the stirring speed to be 300RPM, slowly dropping diisocyanate by using the constant-pressure dropping funnel, controlling the material temperature in the reaction kettle to be 35 ℃, and continuously keeping the reaction for 18min after the dropping is finished to obtain a binary prepolymer terminated by amino groups for later use;
2) adding dibasic acid into the binary prepolymer obtained in the step 1), closing a cooling system, starting a heating system, heating to 138 ℃, stopping heating after reaction and distillation of amide-generating reaction water, cooling to 93 ℃, adding a neutralizer, adding a solvent A at the temperature of 93 ℃ after neutralization, uniformly stirring, discharging to a package, and cooling to normal temperature to obtain the urea modified polyamide aqueous rheological aid.
Example 3
The polyurea modified polyamide aqueous rheological additive comprises the following raw materials in parts by weight: 15 parts of diamine, 70 parts of dibasic acid, 5 parts of binary polyisocyanate, 20 parts of a neutralizing agent, 150 parts of a solvent A and 30 parts of a solvent B.
The diamine is a mixture of decamethylenediamine, ethylenediamine, polyoxyethylene diamine and pentanediamine according to the weight ratio of 1.0:0.4:0.8: 0.6.
The dibasic acid is a mixture of adipic acid, terephthalic acid, succinic acid, dimer acid and DMPA according to a weight ratio of 0.6:1.0:0.8: 0.6.
The binary polyisocyanate is a mixture of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate in a weight ratio of 0.6:0.8:0.6: 1.0.
The solvent A is water; the solvent B is a mixture of DMF and NMP in a weight ratio of 0.6: 0.8.
The neutralizing agent is diethanolamine.
The preparation method of the polyurea modified polyamide aqueous rheological additive is prepared by the following steps:
1) adding a solvent B and diamine into a reaction kettle with a reflux condenser pipe, a distillation pipe, a constant-pressure dropping funnel, a mechanical stirrer, a thermometer and a cooling and heating system according to parts by weight, starting the cooling system and the stirrer of the reaction kettle, controlling the stirring speed to be 500RPM, slowly dropping diisocyanate by using the constant-pressure dropping funnel, controlling the material temperature in the reaction kettle to be 40 ℃, and continuously keeping the reaction for 23min after the dropping is finished to obtain a binary prepolymer terminated by amino groups for later use;
2) adding dibasic acid into the binary prepolymer obtained in the step 1), closing a cooling system, starting a heating system, heating to 145 ℃, stopping heating after reaction and distillation of amide-generating reaction water, cooling to 95 ℃, adding a neutralizer, adding a solvent A at the temperature of 95 ℃ after neutralization, uniformly stirring, discharging to a package, and cooling to normal temperature to obtain the urea modified polyamide aqueous rheological aid.
Example 4
The polyurea modified polyamide aqueous rheological additive comprises the following raw materials in parts by weight: 25 parts of diamine, 80 parts of dibasic acid, 8 parts of binary polyisocyanate, 25 parts of neutralizing agent, 170 parts of solvent A and 410 parts of solvent B.
The diamine is a mixture of decamethylenediamine, ethylenediamine, polyoxyethylene diamine and pentanediamine according to the weight ratio of 1.1:0.5:0.9: 0.7.
The dibasic acid is a mixture of adipic acid, terephthalic acid, succinic acid, dimer acid and DMPA according to a weight ratio of 0.7:1.1:0.9: 0.7.
The binary polyisocyanate is a mixture of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate in a weight ratio of 0.7:0.9:0.7: 1.1.
The solvent A is water; the solvent B is a mixture of DMF and NMP in a weight ratio of 0.7: 0.8.
The neutralizing agent is triethylamine.
The preparation method of the polyurea modified polyamide aqueous rheological additive is prepared by the following steps:
1) adding a solvent B and diamine into a reaction kettle with a reflux condenser pipe, a distillation pipe, a constant-pressure dropping funnel, a mechanical stirrer, a thermometer and a cooling and heating system according to parts by weight, starting the cooling system and the stirrer of the reaction kettle, controlling the stirring speed to be 800RPM, slowly dropping diisocyanate by using the constant-pressure dropping funnel, controlling the material temperature in the reaction kettle to be 45 ℃, and continuously keeping the reaction for 26min after the dropping is finished to obtain a binary prepolymer terminated by amino groups for later use;
2) adding dibasic acid into the binary prepolymer obtained in the step 1), closing a cooling system, starting a heating system, heating to 152 ℃, stopping heating after reaction and distillation of amide-generating reaction water, cooling to 98 ℃, adding a neutralizer, adding a solvent A at the temperature of 98 ℃ after neutralization, uniformly stirring, discharging to a package, and cooling to normal temperature to obtain the urea modified polyamide aqueous rheological aid.
Example 5
The polyurea modified polyamide aqueous rheological additive comprises the following raw materials in parts by weight: 30 parts of diamine, 100 parts of dibasic acid, 10 parts of binary polyisocyanate, 30 parts of a neutralizing agent, 200 parts of a solvent A and 50 parts of a solvent B.
The diamine is a mixture of decamethylenediamine, ethylenediamine, polyoxyethylene diamine and pentanediamine according to the weight ratio of 1.2:0.6:1.0: 0.8.
The dibasic acid is a mixture of adipic acid, terephthalic acid, succinic acid, dimer acid and DMPA according to the weight ratio of 0.8:1.2:1.0: 0.8.
The binary polyisocyanate is a mixture of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate in a weight ratio of 0.8:1.0:0.8: 1.2.
The solvent A is water; the solvent B is DMFP.
The neutralizing agent is a mixture of potassium hydroxide, triethylamine and dimethylethanolamine in a weight ratio of 0.8:1.0: 1.2.
The preparation method of the polyurea modified polyamide aqueous rheological additive is prepared by the following steps:
1) adding a solvent B and diamine into a reaction kettle with a reflux condenser pipe, a distillation pipe, a constant-pressure dropping funnel, a mechanical stirrer, a thermometer and a cooling and heating system according to parts by weight, starting the cooling system and the stirrer of the reaction kettle, controlling the stirring speed to be 1000RPM, slowly dropping diisocyanate by using the constant-pressure dropping funnel, controlling the material temperature in the reaction kettle to be not higher than 50 ℃, and continuously keeping the reaction for 30min after dropping is finished to obtain a binary prepolymer terminated by amino groups for later use;
2) adding dibasic acid into the binary prepolymer obtained in the step 1), closing a cooling system, starting a heating system, heating to 160 ℃, stopping heating after reaction and distillation of amide-generating reaction water, cooling to 100 ℃, adding a neutralizer, adding a solvent A at the temperature of 100 ℃ after neutralization, uniformly stirring, discharging to a package, and cooling to normal temperature to obtain the urea modified polyamide aqueous rheological aid.
Comparative example 1
This comparative example differs from example 3 above in that: in this comparative example, hexamethylene diisocyanate was used in place of the mixed binary polyisocyanate composed of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate in a weight ratio of 0.6:0.8:0.6:1.0, and the rest of this comparative example was the same as example 3 and will not be described again.
The polyurea modified polyamide aqueous rheological additives prepared in examples 1, 3 and 5 and comparative example 1 and the commercial products were subjected to performance tests, and the test results are shown in the following table 1:
the sag resistance was tested according to (GB/T9264-; gloss was measured using an OU4200 gloss tester.
TABLE 1
| Item | TI value | Sag resistance | Gloss (/ °) |
| Example 1 | 1.25 | 200 | 95 |
| Example 3 | 1.50 | 275 | 91 |
| Example 5 | 1.51 | 276 | 93 |
| Comparative example 1 | 1.20 | 183 | 92 |
| Commercially available product | 1.18 | 175 | 91 |
From the comparison of example 1, example 3 and example 5, it can be seen that the polyurea modified polyamide aqueous rheological additive prepared by the invention has very good thixotropic index TI, sagging resistance and film-forming glossiness.
As can be seen from the comparison among examples 1, 3 and 5, comparative example 1 and the commercial products, the polyurea modified polyamide aqueous rheological additive prepared by adding the mixed binary polyisocyanate consisting of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate in the weight ratio of 0.6:0.8:0.6:1.0 has good thixotropic index TI, sag resistance and film-forming gloss, and has wide market prospect and application value.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (9)
1. The polyurea modified polyamide aqueous rheological additive is characterized in that: the feed comprises the following raw materials in parts by weight: 1-30 parts of diamine, 50-100 parts of dibasic acid, 1-10 parts of binary polyisocyanate, 1-30 parts of a neutralizing agent, 78-200 parts of a solvent A50 and 50-50 parts of a solvent B10.
2. The aqueous rheological additive for polyurea-modified polyamides of claim 1, wherein: the feed comprises the following raw materials in parts by weight: 10-25 parts of diamine, 70-100 parts of dibasic acid, 5-10 parts of binary polyisocyanate, 1-10 parts of neutralizing agent, 50-150 parts of solvent A and 20-50 parts of solvent B.
3. The aqueous rheological additive for polyurea-modified polyamides of claim 1, wherein: the diamine is at least one of decamethylene diamine, hexamethylene diamine, ethylene diamine, diethylene triamine, propane diamine, heptamethylene diamine, octamethylene diamine, nonane diamine, p-phenylene diamine, o-phenylene diamine, m-phenylene diamine, polyoxyethylene diamine, butanediamine and penta diamine.
4. The aqueous rheological additive for polyurea-modified polyamides of claim 1, wherein: the dibasic acid is at least one of adipic acid, terephthalic acid, isophthalic acid, azelaic acid, sebacic acid, glutaric acid, succinic acid, dimer acid and DMPA.
5. The aqueous rheological additive for polyurea-modified polyamides of claim 1, wherein: the binary polyisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.
6. The aqueous rheological additive for polyurea-modified polyamides of claim 1, wherein: the solvent A is water.
7. The aqueous rheological additive for polyurea-modified polyamides of claim 1, wherein: the solvent B is DMF and/or NMP.
8. The aqueous rheological additive for polyurea-modified polyamides of claim 1, wherein: the neutralizing agent is at least one of potassium hydroxide, sodium hydroxide, AMP-95, ethanolamine, diethanolamine, triethanolamine, triethylamine and dimethylethanolamine.
9. A method for preparing the polyurea modified polyamide aqueous rheological aid according to any one of claims 1 to 8, wherein the method comprises the following steps: the preparation method comprises the following steps:
1) adding a solvent B and diamine into a reaction kettle with a reflux condenser pipe, a distillation pipe, a constant-pressure dropping funnel, a mechanical stirrer, a thermometer and a cooling and heating system according to parts by weight, starting the cooling system and the stirrer of the reaction kettle, controlling the stirring speed to be 100 plus one (1000) RPM, slowly dropping the diisocyanate into the reaction kettle by using the constant-pressure dropping funnel, controlling the material temperature in the reaction kettle to be not higher than 50 ℃, and continuously keeping the reaction for 15-30min after the dropping is finished to obtain a binary prepolymer terminated by amino groups for later use;
2) adding dibasic acid into the binary prepolymer obtained in the step 1), closing a cooling system, starting a heating system, heating to 130-160 ℃, stopping heating after reaction and distillation of amide-generating reaction water, cooling to 90-100 ℃, adding a neutralizing agent, adding a solvent A at the temperature of 90-100 ℃ after neutralization, uniformly stirring, discharging to a packing material, and cooling to normal temperature to obtain the urea modified polyamide aqueous rheological additive.
Priority Applications (1)
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| JP2003183583A (en) * | 2001-12-13 | 2003-07-03 | Kusumoto Kasei Kk | Antisag agent for nonaqueous coating material |
| JP2010242099A (en) * | 1998-02-13 | 2010-10-28 | Elementis Specialties Inc | Liquid rheological additive containing active hydrogen moiety for non-aqueous system and non-aqueous composition system containing the liquid rheological additive |
| CN106795260A (en) * | 2014-08-11 | 2017-05-31 | 路博润先进材料公司 | For industry and the aqueous copolymer coating composition of structure application |
| CN107629538A (en) * | 2016-07-15 | 2018-01-26 | 德谦（上海）化学有限公司 | New non-ionic type polyamide rheology modifier for water paint |
| CN108070066A (en) * | 2017-12-29 | 2018-05-25 | 陈鹏 | A kind of coating and printing ink anti-settling agent and preparation method thereof |
| US20190390011A1 (en) * | 2017-01-30 | 2019-12-26 | Byk-Chemie Gmbh | Urea-group- and/or urethane-group-containing amides as and in rheology control agents, their preparation and their use |
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| JP2010242099A (en) * | 1998-02-13 | 2010-10-28 | Elementis Specialties Inc | Liquid rheological additive containing active hydrogen moiety for non-aqueous system and non-aqueous composition system containing the liquid rheological additive |
| JP2003183583A (en) * | 2001-12-13 | 2003-07-03 | Kusumoto Kasei Kk | Antisag agent for nonaqueous coating material |
| CN106795260A (en) * | 2014-08-11 | 2017-05-31 | 路博润先进材料公司 | For industry and the aqueous copolymer coating composition of structure application |
| CN107629538A (en) * | 2016-07-15 | 2018-01-26 | 德谦（上海）化学有限公司 | New non-ionic type polyamide rheology modifier for water paint |
| US20190390011A1 (en) * | 2017-01-30 | 2019-12-26 | Byk-Chemie Gmbh | Urea-group- and/or urethane-group-containing amides as and in rheology control agents, their preparation and their use |
| CN108070066A (en) * | 2017-12-29 | 2018-05-25 | 陈鹏 | A kind of coating and printing ink anti-settling agent and preparation method thereof |
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