CN115340656B - Modified isocyanate with water dispersion and protection functions and preparation method thereof - Google Patents
Modified isocyanate with water dispersion and protection functions and preparation method thereof Download PDFInfo
- Publication number
- CN115340656B CN115340656B CN202211008656.9A CN202211008656A CN115340656B CN 115340656 B CN115340656 B CN 115340656B CN 202211008656 A CN202211008656 A CN 202211008656A CN 115340656 B CN115340656 B CN 115340656B
- Authority
- CN
- China
- Prior art keywords
- isocyanate
- water dispersion
- modified isocyanate
- protection functions
- salicylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
- C08G65/3326—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic aromatic
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to modified isocyanate with water dispersion and protection functions and a preparation method thereof. The preparation method of the modified isocyanate with the water dispersion and protection functions comprises the following steps: according to the mass percentage, 68-82% of isocyanate, 8-10% of organic solvent and 10-22% of amphiphilic molecular chain compound are reacted for 4-8 hours at the temperature of 80-90 ℃ to obtain the modified polyurethane resin; wherein the amphiphilic molecular chain compound is polyethylene glycol monomethyl ether-salicylic acid compound. The isocyanate and the amphiphilic molecular chain are used as the main agents, and the prepared modified isocyanate has a self-emulsifying function, so that the dispersibility of the isocyanate in a water environment can be improved; meanwhile, the isocyanate has a protection function, can improve the stability of the isocyanate when the isocyanate contains active hydrogen (water), prolongs the application period of the isocyanate in water environment, and greatly expands the application range of the isocyanate.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to modified isocyanate with water dispersion and protection functions and a preparation method thereof.
Background
Isocyanate has a series of advantages of good cementing property, quick crosslinking and curing at room temperature and high temperature, high stability of related products, excellent water resistance, chemical corrosion resistance and the like, and is widely applied to the fields of paint, adhesives, medicines, agriculture, composite materials and the like. However, isocyanate has a relatively high chemical activity, and is poor in stability in water and poor in water dispersibility, so that its application in the above fields is greatly limited.
In the prior art, isocyanate and polyethylene glycol monomethyl ether are generally adopted to react to improve the hydrophilicity of the isocyanate, so that the dispersibility of the isocyanate in water is improved. However, although the hydrophilicity of the isocyanate prepared by the prior method is improved, the side reaction of the active groups in the isocyanate and water is also aggravated along with the improvement of the water dispersion degree, so that the isocyanate active groups are consumed, and the activity of the isocyanate is reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for producing a modified isocyanate having both water dispersibility and protection functions, which can improve the water dispersibility of isocyanate, and can effectively protect isocyanate-reactive groups to improve the stability of isocyanate in water.
The invention also aims to provide a modified isocyanate with water dispersion and protection functions, which has excellent water dispersion and stability.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of modified isocyanate with water dispersion and protection functions comprises the following steps: according to the mass percentage, 68-82% of isocyanate, 8-10% of organic solvent and 10-22% of amphiphilic molecular chain compound are reacted for 4-8 hours at the temperature of 80-90 ℃ to obtain the modified polyurethane resin; wherein the amphiphilic molecular chain compound is polyethylene glycol monomethyl ether-salicylic acid compound.
According to the invention, isocyanate, an organic solvent and an amphiphilic molecular chain compound (polyethylene glycol monomethyl ether-salicylic acid compound) are subjected to a blending reaction at a certain temperature, so that the modified isocyanate with water dispersion and protection functions can be obtained. In the modified isocyanate, an isocyanate group is positioned in the center part, salicylic acid is directly grafted, and then the salicylic acid is connected with polyethylene glycol monomethyl ether. The salicylic acid group can effectively prevent water from approaching the isocyanate at the central part, plays an effective protective role, increases the stability of the isocyanate in water, and the polyethylene glycol monomethyl ether at the outer layer has good hydrophilicity and can effectively improve the water solubility of the isocyanate, so that the isocyanate prepared by the invention has excellent dispersion and stability in water, and greatly meets the application requirements of the isocyanate in water environment.
The isocyanate may be of the type commonly known in the art. Preferably, the isocyanate is one or more of polymethylene polyphenyl polyisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
The kind of the organic solvent is not particularly limited, and the organic solvent is only required to be capable of dissolving and adjusting the viscosity of the corresponding isocyanate and not contain active hydrogen for reacting with the isocyanate. Preferably, the organic solvent is one or more of dichloromethane, chloroform, toluene, dichloroethane, ethyl acetate and butyl acetate, and more preferably dichloromethane.
Preferably, the preparation process of the polyethylene glycol monomethyl ether-salicylic acid compound comprises the following steps:
(1) Dissolving salicylic acid in N, N-dimethylformamide, cooling to-10 ℃ to 10 ℃, dropwise adding an acyl chloride reagent while stirring, and reacting for 0.5-1.5 h at 50-60 ℃;
(2) Adding polyethylene glycol monomethyl ether into the system after the reaction in the step (1), continuously reacting for 1.5-2.5 h under the protection of nitrogen, and then purifying to obtain the product.
The polyethylene glycol monomethyl ether-salicylic acid compound prepared by the method is an amphiphilic molecular chain compound. The amphiphilic molecular weight compound is prepared by reacting hydroxyl groups of polyethylene glycol monomethyl ether (MPEG) with carboxyl groups of Salicylic Acid (SA) to form a desired amphiphilic molecular chain structure. The salicylic acid end is a hydrophobic end, and the polyethylene glycol monomethyl ether end is a hydrophilic end, so that side reactions can be effectively avoided through the reaction process, the salicylic acid at the hydrophobic end is enabled to retain active hydroxyl groups, and the salicylic acid can be subsequently reacted with isocyanate to be effectively grafted onto the isocyanate; at the same time, through the reaction process, active hydroxyl groups in the hydrophilic end polyethylene glycol monomethyl ether are consumed, so that active groups capable of reacting with isocyanate are lost, and the structural stability of the modified isocyanate is further improved.
The salicylic acid and the polyethylene glycol monomethyl ether are provided with more than one active group, so that the side reaction is numerous, the residual of byproducts is reduced, and the reaction efficiency is improved, so that the required product of the reaction between the hydroxyl of the polyethylene glycol monomethyl ether (MPEG) and the carboxyl of the Salicylic Acid (SA) is obtained.
In order to ensure the modification effect of the amphiphilic molecular chain on the water dispersibility and the water stability of isocyanate, as a further preferable scheme, the molecular weight of the polyethylene glycol monomethyl ether is 750-1000.
In order to improve the conversion effect of the products of the reaction in each step, preferably, the mol ratio of salicylic acid, acyl chloridizing reagent and polyethylene glycol monomethyl ether is 1: (1-1.2): (1-1.2).
Preferably, the purification is specifically: and extracting and purifying the product by using dichloromethane as a solvent and adopting a solvent extraction method.
The modified isocyanate with the water dispersion and protection functions is prepared by adopting the preparation method.
The invention has the beneficial effects that:
according to the preparation method of the modified isocyanate with the water dispersion and protection functions, the isocyanate and the amphiphilic molecular chain are used as main agents, and the prepared isocyanate has a self-emulsifying function and can improve the dispersibility of the isocyanate in a water environment; meanwhile, the isocyanate has a protection function, can improve the stability of the isocyanate when the isocyanate contains active hydrogen (water), and prolongs the applicable period of the isocyanate in water environment.
The modified isocyanate with the water dispersion and protection functions can be dispersed and emulsified in water environment without an additional emulsifier, and the self-emulsifying water dispersion isocyanate improves the hydrophilicity through polar molecular chains, so that the modified isocyanate is not influenced by ions, and the stability of isocyanate dispersion liquid or emulsion can be improved.
The modified isocyanate with the water dispersion and protection functions has higher activity, and experiments show that the active-NCO group still has higher active group content after being stored in water for 8 hours, and has the advantages of convenient use, transportation and storage, and the like.
Drawings
FIG. 1 is a Fourier infrared spectrum of a modified isocyanate with water dispersion and protection functions prepared in example 1 of the present invention;
FIG. 2 is a graph showing the particle size and distribution of the emulsion prepared in example 1 according to the present invention for the modified isocyanate having both water dispersion and protection functions;
FIG. 3 is a physical diagram of the emulsion prepared in example 1 according to the invention corresponding to the modified isocyanate with both water dispersion and protection functions in different time periods;
FIG. 4 shows the isocyanate reactive content of the modified isocyanate-reactive emulsion prepared in example 1 according to the present invention with both water dispersion and protection over different time periods.
Detailed Description
The technical scheme of the present invention is further described below with reference to the specific embodiments, but the present invention is not limited thereto. In the following examples, the reagents involved, unless otherwise specified, are all commercially available conventional reagents; the test methods are conventional, unless otherwise specified. In the following examples, polymethylene polyphenyl polyisocyanates were used having an active group-NCO content of 30%; the content of active group-NCO in the isophorone diisocyanate raw material is 37%; in the following examples, polyethylene glycol monomethyl ether was used as MPEG-750 and MPEG-1000 having molecular weights of 750 and 1000, respectively.
Example 1
The modified isocyanate with the water dispersion and protection functions is prepared by a method comprising the following steps:
adding 82% of isocyanate and 8% of organic solvent into a dry reaction kettle, heating in an oil bath at constant temperature, then dripping 10% of amphiphilic molecular chain compound into the reaction kettle, heating the oil bath to 85 ℃, and finishing the reaction after 4 hours to obtain the modified polyurethane foam.
Wherein the isocyanate is polymethylene polyphenyl polyisocyanate (PAPI); the organic solvent is methylene dichloride; the amphiphilic molecular chain compound is polyethylene glycol monomethyl ether 750-salicylic acid compound (marked as MPEG-SA).
The specific preparation method of the amphiphilic molecular chain compound MPEG-SA in the embodiment is as follows:
adding salicylic acid and N, N-dimethylformamide into a dried reaction kettle, dissolving, putting into an ice-water bath, dropwise adding thionyl chloride (the molar ratio of salicylic acid to thionyl chloride is 1:1.1) while stirring, finishing the addition within 30min, and raising the temperature of the water bath to 55 ℃ to perform acyl chlorination reaction for 1h; after the acyl chlorination reaction, dropwise adding MPEG-750 (salicylic acid, MPEG-750 mol ratio 1:1.1) into a reaction kettle, and continuing to react for 2h under the protection of nitrogen; and extracting and purifying the product by using methylene dichloride to obtain the MPEG-SA.
Example 2
The modified isocyanate with the water dispersion and protection functions is prepared by a method comprising the following steps:
adding 76% of isocyanate and 10% of organic solvent into a dry reaction kettle, heating in an oil bath at constant temperature, then dripping 14% of amphiphilic molecular chain compound into the reaction kettle, heating the oil bath to 85 ℃, and finishing the reaction after 4 hours to obtain the modified polyurethane foam.
Wherein the isocyanate is polymethylene polyphenyl polyisocyanate (PAPI); the organic solvent is methylene dichloride; the amphiphilic molecular chain compound is polyethylene glycol monomethyl ether 750-salicylic acid compound (marked as MPEG-SA).
The specific preparation method of the amphiphilic molecular chain compound MPEG-SA comprises the following steps:
adding salicylic acid and N, N-dimethylformamide into a dried reaction kettle, dissolving, putting into an ice-water bath, dropwise adding thionyl chloride (the molar ratio of salicylic acid to thionyl chloride is 1:1.1) while stirring, finishing the addition within 30min, and raising the temperature of the water bath to 55 ℃ to perform acyl chlorination reaction for 1h; after the acyl chlorination reaction, dropwise adding MPEG-750 (salicylic acid, MPEG-750 mol ratio 1:1.1) into a reaction kettle, and continuing to react for 2h under the protection of nitrogen; and extracting and purifying the product by using methylene dichloride to obtain the MPEG-SA.
Example 3
The modified isocyanate with the water dispersion and protection functions is prepared by a method comprising the following steps:
adding 76% of isocyanate and 10% of organic solvent into a dry reaction kettle, heating in an oil bath at constant temperature, then dripping 14% of amphiphilic molecular chain compound into the reaction kettle, heating the oil bath to 85 ℃, and finishing the reaction after 8 hours to obtain the modified polyurethane foam.
Wherein the isocyanate is isophorone diisocyanate (IPDI); the organic solvent is methylene dichloride; the amphiphilic molecular chain compound is polyethylene glycol monomethyl ether 750-salicylic acid (marked as MPEG-SA).
The specific preparation method of the amphiphilic molecular chain compound MPEG-SA in the embodiment is as follows:
adding salicylic acid and N, N-dimethylformamide into a dried reaction kettle, dissolving, putting into an ice-water bath, dropwise adding thionyl chloride (the molar ratio of salicylic acid to thionyl chloride is 1:1.1) while stirring, finishing the addition within 30min, and raising the temperature of the water bath to 55 ℃ to perform acyl chlorination reaction for 1h; after the acyl chlorination reaction, dropwise adding MPEG-750 (salicylic acid, MPEG-750 mol ratio 1:1.1) into a reaction kettle, and continuing to react for 2h under the protection of nitrogen; and extracting and purifying the product by using methylene dichloride to obtain the MPEG-SA.
Example 4
The modified isocyanate with the water dispersion and protection functions is prepared by a method comprising the following steps:
adding 68% of isocyanate and 10% of organic solvent into a dry reaction kettle, heating in an oil bath at constant temperature, then dripping 22% of amphiphilic molecular chain compound into the reaction kettle, heating the oil bath to 85 ℃, and finishing the reaction after 8 hours to obtain the modified polyurethane foam.
Wherein the isocyanate is isophorone diisocyanate (IPDI); the organic solvent is methylene dichloride; the amphiphilic molecular chain compound is polyethylene glycol monomethyl ether 1000-salicylic acid compound (marked as MPEG-SA).
The specific preparation method of the amphiphilic molecular chain compound MPEG-SA in the embodiment is as follows:
adding salicylic acid and N, N-dimethylformamide into a dried reaction kettle, dissolving, putting into an ice-water bath, dropwise adding thionyl chloride (the molar ratio of salicylic acid to thionyl chloride is 1:1.1) while stirring, finishing the addition within 30min, and raising the temperature of the water bath to 55 ℃ to perform acyl chlorination reaction for 1h; after the acyl chlorination reaction, dropwise adding MPEG-1000 (salicylic acid, MPEG-1000 mol ratio 1:1.1) into a reaction kettle, and continuing to react for 2h under the protection of nitrogen; and extracting and purifying the product by using methylene dichloride to obtain the MPEG-SA.
Comparative example 1
The preparation method of the modified isocyanate adopted by the comparative example comprises the following steps: adding 82% of isocyanate and 8% of organic solvent into a dry reaction kettle, heating in an oil bath at constant temperature, then dripping 10% of polyethylene glycol monomethyl ether 750 into the reaction kettle, heating the oil bath to 85 ℃, and finishing the reaction after 4 hours to obtain the modified polyethylene glycol monomethyl ether.
Comparative example 2
The modified isocyanate of this comparative example was prepared in substantially the same manner as in example 1, except that: the amphiphilic molecular chain compound is prepared by adopting tartaric acid to replace salicylic acid.
Comparative example 3
The modified isocyanate of this comparative example was prepared in substantially the same manner as in example 1, except that: the amphiphilic molecular chain compound is prepared by adopting malic acid to replace salicylic acid.
Comparative example 4
The modified isocyanate of this comparative example was prepared in substantially the same manner as in example 1, except that: the amphiphilic molecular chain compound is prepared by adopting thioglycollic acid to replace salicylic acid.
Comparative example 5
The modified isocyanate of this comparative example was prepared in substantially the same manner as in example 1, except that: the amphiphilic molecular chain compound is prepared by adopting tyrosine to replace salicylic acid.
Test example 1
The following test examples characterize and test the structural and appearance stability of the modified isocyanate with both water dispersion and protection functions prepared in example 1 of the present invention.
The result of fourier infrared spectrum test on the MPEG-SA referred to in example 1 of the present invention is shown in fig. 1.
As can be seen from FIG. 1, 3236cm of the infrared spectrum of Salicylic Acid (SA) -1 The vicinity is a characteristic peak of-OH, and 1210cm -1 Is characterized by a characteristic peak of phenolic hydroxyl; the characteristic absorption peak of carboxyl (Ph-COOH) connected with benzene ring (Ph) moves to low wave number under the influence of benzene ring conjugation and hydrogen bond, and is 1656cm -1 The occurrence of the site; 1298cm -1 Characterized by absorption peaks of carboxylic acid or carboxylic ester (Ph-COO-) connected with aromatic; 758cm -1 Is characterized by adjacent disubstituted (carboxyl and hydroxyl) benzene ring characteristic peaks. 3453cm in the infrared spectrum of polyethylene glycol monomethyl ether (MPEG) -1 The characteristic peak of the alcohol hydroxyl (R-OH) is nearby; 2850cm -1 、1106cm -1 Is respectively-CH in molecular chain 2 -/CH 3 -O-characteristic absorption peak. No 3453cm was found in the infrared spectrum of MPEG-SA -1 Near the R-OH characteristic peak and 1656cm -1 The characteristic peak of Ph-COOH at 1210cm -1 Characteristic peak of phenolic hydroxyl Ph-OH at 2850cm -1 、1106cm -1 at-CH 2 Characteristic absorption peak of-O-, 1298cm -1 The Ph-COO-characteristic absorption peak and 758cm -1 The characteristic peak average of adjacent disubstituted benzene rings is reserved; in addition, 1729cm of -1 Characteristic absorption peak of ester bond (Ph-COOR) connected with aromatic ring and 1676cm -1 The carbonyl bond (Ph-CO-) connected with the aromatic ring is characterized as an absorption peak. Thus, the synthesized MPEG-SA molecule of the invention has no R-OH and Ph-COOH, and has newly generated Ph-COOR, which indicates that SA and MPEG have esterification reaction, and the required amphiphilic molecular chain compound is obtained.
The emulsion prepared from the modified isocyanate obtained in example 1 of the present invention was further tested for particle size and appearance stability. During testing, mixing the modified isocyanate with water according to the mass ratio of 1:9, and uniformly mixing to obtain the modified isocyanate emulsion. Particle size testing process: 1mL of the emulsion was diluted 100 times, and the particle size and distribution thereof were measured by a laser particle sizer. Emulsion appearance stability test is to emulsify modified isocyanate to prepare emulsion, then take pictures every one hour and compare emulsion stability. The results are shown in FIGS. 2 and 3.
As can be seen from FIG. 2, the emulsion droplet size of the modified isocyanate emulsion prepared by the invention is about 50 μm, the particle size distribution is parabolic, and the distribution is relatively narrow, which shows that the modified isocyanate can be uniformly dispersed in water.
As can be seen from FIG. 3, the modified isocyanate prepared by the invention has uniform milky color after water dispersion and emulsification, and has good appearance stability without obvious delamination phenomenon after long-term standing.
Test example 2
The modified isocyanates of inventive example 1 and comparative example 1 were tested for water stability and the results are shown in fig. 4 and table 1. The stability test process is as follows: the modified isocyanate sample was subjected to the method of test example 1 to obtain an emulsion, and then the prepared emulsion was uniformly sampled (about 2 g) every 1 hour, and the active group (-NCO) content (calculated as isocyanate) in the modified isocyanate sample was tested by using di-n-butylamine chemical analysis titration method.
TABLE 1 stability test results for modified isocyanates
As can be seen from FIG. 1 and Table 1, the modified isocyanate prepared by the method of the invention has the active-NCO group content still kept about 61.4% of the initial content after the emulsion is placed for 8 hours, while the active group loss is fast and the active ingredient content can be kept only 13.8% of the active ingredient content. Therefore, the modified isocyanate prepared by the preparation method can effectively reduce the influence of water on isocyanate active ingredients and improve the stability of the modified isocyanate in water environment.
Further, the modified isocyanates obtained in examples 1 to 4 of the present invention and comparative examples 1 to 5 were subjected to comparative tests for water dispersion and water stability, and the results are shown in Table 2. The water dispersibility testing process comprises the following steps: the modified isocyanate thus prepared was mixed with 9 times of water by mass (shaking up for 1 minute), and then left for 6 hours, and then the emulsion was observed for delamination. The stability test process is as follows: the modified isocyanate is emulsified to prepare emulsion, the prepared emulsion is placed for 6 hours and then is uniformly sampled (about 2 g), and the active group (-NCO) content (calculated by isocyanate) of the modified isocyanate is tested by adopting a di-n-butylamine chemical analysis titration method.
TABLE 2 Dispersion Properties and stability of different modified isocyanate materials
| Numbering device | Water dispersion | Active group content, percent |
| Example 1 | Not layered | 16.68 |
| Example 2 | Not layered | 13.68 |
| Example 3 | Not layered | 23.31 |
| Example 4 | Not layered | 19.20 |
| Comparative example 1 | Not layered | 4.09 |
| Comparative example 2 | Obvious delamination | Delamination, failure to measure |
| Comparative example 3 | Obvious delamination | Delamination, failure to measure |
| Comparative example 4 | Obvious delamination | Delamination, failure to measure |
| Comparative example 5 | Slightly layered | Delamination, failure to measure |
As can be seen from table 2, the use of multifunctional hydroxy acids (tartaric acid, malic acid) or thiol-and amino-containing acids (thioglycollic acid, tyrosine) instead of salicylic acid does not allow for the efficient preparation of amphiphilic molecular chains that exhibit good water dispersibility and water stability, and therefore, it is not possible to successfully prepare uniform modified isocyanate emulsions, and to accurately determine the active group content due to the layering of the emulsions and the inability to sample uniformity. Therefore, the invention has special requirements on the hydroxy acid, the molecule of the hydroxy acid needs to contain one carboxyl group and one hydroxyl group, and the special structure limitation is needed, so that the chain extension reaction such as esterification or amidation among molecules is not easy to occur in the process of preparing the amphiphilic molecular chain.
In conclusion, the modified isocyanate prepared by the invention has the advantages of high active group content after the active-NCO groups are stored in water for 8 hours while realizing uniform dispersion, good stability, no smell basically, convenient use, transportation and storage, and the like.
Claims (8)
1. The preparation method of the modified isocyanate with the functions of water dispersion and protection is characterized by comprising the following steps: according to the mass percentage, 68-82% of isocyanate, 8-10% of organic solvent and 10-22% of amphiphilic molecular chain compound are reacted for 4-8 hours at the temperature of 80-90 ℃ to obtain the modified polyurethane resin;
wherein the amphiphilic molecular chain compound is polyethylene glycol monomethyl ether-salicylic acid compound; the polyethylene glycol monomethyl ether-salicylic acid compound is prepared by esterification reaction of polyethylene glycol monomethyl ether and salicylic acid.
2. The method for preparing a modified isocyanate with both water dispersion and protection functions according to claim 1, wherein the isocyanate is one or more of polymethylene polyphenyl polyisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
3. The method for preparing modified isocyanate with water dispersion and protection functions according to claim 1, wherein the organic solvent is one or more of dichloromethane, chloroform, toluene, dichloroethane, ethyl acetate and butyl acetate.
4. The method for preparing the modified isocyanate with the water dispersion and protection functions according to claim 1, wherein the preparation process of the polyethylene glycol monomethyl ether-salicylic acid compound comprises the following steps:
(1) Dissolving salicylic acid in N, N-dimethylformamide, cooling to-10 ℃ to 10 ℃, dropwise adding an acyl chloride reagent while stirring, and reacting for 0.5-1.5 h at 50-60 ℃;
(2) Adding polyethylene glycol monomethyl ether into the system after the reaction in the step (1), continuing to react for 1.5-2.5 h under the protection of nitrogen, and then purifying to obtain the product.
5. The method for preparing modified isocyanate with water dispersion and protection functions according to claim 4, wherein the acyl chloride reagent is one or more of thionyl chloride, phosphorus trichloride and phosphorus pentachloride.
6. The method for preparing modified isocyanate with water dispersion and protection functions according to claim 4, wherein the molecular weight of polyethylene glycol monomethyl ether is 750-1000.
7. The method for preparing the modified isocyanate with water dispersion and protection functions according to any one of claims 4 to 6, wherein the molar ratio of salicylic acid, acyl chloride reagent and polyethylene glycol monomethyl ether is 1: (1 to 1.2): (1-1.2).
8. The modified isocyanate with the water dispersion and protection functions is characterized in that the modified isocyanate with the water dispersion and protection functions is prepared by the preparation method of the modified isocyanate with the water dispersion and protection functions according to any one of claims 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211008656.9A CN115340656B (en) | 2022-08-22 | 2022-08-22 | Modified isocyanate with water dispersion and protection functions and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211008656.9A CN115340656B (en) | 2022-08-22 | 2022-08-22 | Modified isocyanate with water dispersion and protection functions and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115340656A CN115340656A (en) | 2022-11-15 |
| CN115340656B true CN115340656B (en) | 2023-07-07 |
Family
ID=83953045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211008656.9A Active CN115340656B (en) | 2022-08-22 | 2022-08-22 | Modified isocyanate with water dispersion and protection functions and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115340656B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4226243A1 (en) * | 1992-08-08 | 1994-02-10 | Herberts Gmbh | Water-thinnable coating agent based on polyol and polyisocyanate, process for its preparation and its use |
| JP2012077255A (en) * | 2010-10-06 | 2012-04-19 | Mitsui Chemicals Inc | Aqueous polyurethane resin, hydrophilic resin and film |
| CN107849349A (en) * | 2015-08-31 | 2018-03-27 | 富士胶片株式会社 | Water dispersion and its manufacture method and image forming method |
| WO2018056408A1 (en) * | 2016-09-23 | 2018-03-29 | 旭化成株式会社 | Polyisocyanate composition, block polyisocyanate composition, coating composition, aqueous coating composition, and coating base material |
| CN108602931A (en) * | 2016-02-05 | 2018-09-28 | 富士胶片株式会社 | Water dispersion and its manufacturing method and image forming method |
| CN108623813A (en) * | 2018-03-30 | 2018-10-09 | 佛山市巴盛诺新材料科技有限公司 | Fatty poly-ester carbonate-g- polyethylene glycol amphiphilic graft polymers and preparation method thereof |
| CN109843953A (en) * | 2016-10-14 | 2019-06-04 | 旭化成株式会社 | Isocyanate composition, the aqueous dispersion of isocyanate composition and its manufacturing method, coating composition and film |
| EP3599255A1 (en) * | 2018-07-23 | 2020-01-29 | Covestro Deutschland AG | Ionically hydrophilized polyisocyanates with improved drying |
| JP2020019877A (en) * | 2018-07-31 | 2020-02-06 | 旭化成株式会社 | Water-dispersed blocked polyisocyanate composition, water dispersion, aqueous coating composition, and coating substrate |
-
2022
- 2022-08-22 CN CN202211008656.9A patent/CN115340656B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4226243A1 (en) * | 1992-08-08 | 1994-02-10 | Herberts Gmbh | Water-thinnable coating agent based on polyol and polyisocyanate, process for its preparation and its use |
| JP2012077255A (en) * | 2010-10-06 | 2012-04-19 | Mitsui Chemicals Inc | Aqueous polyurethane resin, hydrophilic resin and film |
| CN107849349A (en) * | 2015-08-31 | 2018-03-27 | 富士胶片株式会社 | Water dispersion and its manufacture method and image forming method |
| CN108602931A (en) * | 2016-02-05 | 2018-09-28 | 富士胶片株式会社 | Water dispersion and its manufacturing method and image forming method |
| WO2018056408A1 (en) * | 2016-09-23 | 2018-03-29 | 旭化成株式会社 | Polyisocyanate composition, block polyisocyanate composition, coating composition, aqueous coating composition, and coating base material |
| CN109843953A (en) * | 2016-10-14 | 2019-06-04 | 旭化成株式会社 | Isocyanate composition, the aqueous dispersion of isocyanate composition and its manufacturing method, coating composition and film |
| CN108623813A (en) * | 2018-03-30 | 2018-10-09 | 佛山市巴盛诺新材料科技有限公司 | Fatty poly-ester carbonate-g- polyethylene glycol amphiphilic graft polymers and preparation method thereof |
| EP3599255A1 (en) * | 2018-07-23 | 2020-01-29 | Covestro Deutschland AG | Ionically hydrophilized polyisocyanates with improved drying |
| JP2020019877A (en) * | 2018-07-31 | 2020-02-06 | 旭化成株式会社 | Water-dispersed blocked polyisocyanate composition, water dispersion, aqueous coating composition, and coating substrate |
Non-Patent Citations (3)
| Title |
|---|
| Reaction between isocyanides and salicylic acid or 3-hydroxy-2-naphthoic acid to produce benzo or naphtho-fused 2-(alkylamino)-1,3-dioxin-4-one derivatives;Anary-Abbasinejad等;journal of chemical research(第2期);95-96 * |
| Ring-opening polymerization-induced self-assembly (ROPISA) of salicylic acid o-carboxyanhydride;Shi, Qianqian等;Chemical Communications;第57卷(第86期);11390-11393 * |
| 偶合接枝聚乙二醇单甲醚实现聚砜膜材亲水性改性;杜瑞奎;高保娇;安富强;李延斌;;过程工程学报(05);第857-862页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115340656A (en) | 2022-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1134246B1 (en) | Polyisocyanate | |
| CN101235130B (en) | Cation water polyurethane emulsion and preparation method thereof | |
| CN101235195B (en) | Cation water polyurethane/acrylic ester composite emulsion and preparation method thereof | |
| Coogan | Post-crosslinking of water-borne urethanes | |
| CN107586510B (en) | Preparation method of corrosion-resistant polyurethane modified epoxy resin emulsion | |
| CN101307130B (en) | Anion water-soluble polyurethane disperse system for finishing leather and method for preparing same | |
| EP0802210B1 (en) | Aqueous or waterborne blocked polyisocyanates for the preparation of aqueous 1-component-PUR-clearcoat with reduced thermoyellowing | |
| CN102702471A (en) | Method for preparing solvent-free aqueous polyurethane dispersion | |
| EP0272566B1 (en) | Aqueous polyurethane adhesive dispersions | |
| DE102006052240A1 (en) | Solutions of blocked polyimides or polyamide-imides | |
| CN109734871B (en) | Preparation method of polyurethane emulsion with low water absorption and high solid content | |
| CN108264621B (en) | Heterogeneous chain extension synthesis method for waterborne polyurethane | |
| CN107840937A (en) | Solvent-free aqueous polyurethane dispersion of extrusion molding and its preparation method and application | |
| CN113980571B (en) | Waterborne polyurethane waterproof coating and preparation method and application thereof | |
| CN106349906A (en) | Waterborne epoxy emulsion and preparation method thereof | |
| CN110295503A (en) | A kind of preparation method of waterborne polyurethane synthetic leather | |
| CN102516920A (en) | Aqueous polyurethane adhesive and preparation method thereof | |
| CN107227017B (en) | Normal-temperature synthetic environment-friendly polyurethane grouting plugging agent and preparation method thereof | |
| CN102432800A (en) | Water-oil dual-purpose dispersion agent as well as preparation method and application thereof | |
| CN105646838B (en) | A kind of preparation method of newtrex based polyurethanes performed polymer | |
| CN107903376A (en) | Solvent-free aqueous polyurethane dispersion of continous way and its preparation method and application | |
| CN102181032A (en) | Reactive hyperbranched waterborne polyurethane film and preparation method thereof | |
| CN115340656B (en) | Modified isocyanate with water dispersion and protection functions and preparation method thereof | |
| CN104974313A (en) | Preparation method of waterborne polyurethane based on glycidyl methacrylate | |
| EP1674492A1 (en) | Polyol composition and isocyanate prepolymer for one-component polyurethane foam compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |