CN112608440A - Self-extinction waterborne polyurethane and preparation method thereof - Google Patents
Self-extinction waterborne polyurethane and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Abstract
The invention relates to self-extinction waterborne polyurethane and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing diisocyanate and polyether polyol and carrying out addition reaction; (2) adding a diluent and a hydrophilic chain extender into the addition reaction product, and continuously reacting for 1-2h at 55-65 ℃; (3) after the reaction in the step (2) is finished, adding a catalyst, and heating to 85-90 ℃ for reaction for 1-2 h; (4) after the reaction in the step (3) is finished, cooling, and adding triethylamine to form salt to obtain a prepolymer; (5) adding the salified prepolymer in the step (4) into a sulfonate mixed solution, stirring, and forming an emulsion under the emulsification action; (6) and (3) adding polyether ammonia dropwise into the emulsion to carry out chain extension to obtain the self-extinction waterborne polyurethane resin. The self-extinction waterborne polyurethane provided by the invention can achieve a matte effect after resin curing without adding extinction powder, and has the advantages of attractive appearance, high tensile strength, good flexibility and good market application prospect.
Description
Technical Field
The invention relates to a polyurethane preparation technology, in particular to self-extinction waterborne polyurethane and a preparation method thereof.
Background
The polyurethane is widely applied to industry and life, wherein the waterborne polyurethane takes water as a dispersion medium, has the advantages of no toxicity, no flammability, low Volatile Organic Compounds (VOC), environmental protection and the like, meets the requirements of people on human health and environmental protection, and is widely applied to the fields of coatings, adhesives, rubber, foamed plastics and the like.
Waterborne polyurethanes vary in gloss, use and range: the high gloss is suitable for the surface decoration of outdoor buildings because the surface color is bright; the soft color usually gives people a feeling of elegance, comfort and peaceful, and is widely applied to surface coating of indoor instruments, furniture and the like; low gloss finishes useful on synthetic leather surfaces.
In order to obtain better glossiness of the aqueous polyurethane, a flatting agent or a flatting powder is usually added to achieve the purpose of flatting. A common matting agent is silica. However, when the matting agent is added, the system stability is lowered due to precipitation of the matting agent. In addition, the dust pollution in the production is serious, and is particularly unfavorable for the health of production personnel, so that the preparation of the waterborne polyurethane without adding the flatting agent is more and more paid more attention by people in recent years.
The self-matting resin can generate the effect of low gloss without adding any matting agent and matting powder.
Patent application CN 110951039A discloses an environment-friendly self-matting waterborne polyurethane, a preparation method and an application thereof, wherein the preparation method comprises the following steps: firstly, preparing a polyurethane prepolymer: respectively adding the oligomer polymeric dihydric alcohol, the small molecular trihydric alcohol compound and the terminal hydroxyl-terminated organic silicone oil which are all dehydrated into a reaction vessel, and then adding aliphatic diisocyanate and a catalyst to react to obtain a prepolymer; adding a carboxylic acid type hydrophilic chain extender, and then adding a neutralizer to perform a neutralization reaction; and carrying out first emulsification chain extension on the amine sulfonate hydrophilic chain extender and deionized water, and then adding the active hydrogen-containing micromolecule chain extender to carry out second post-chain extension. Although no matting agents such as silicon dioxide and the like are introduced into the product, organic silicone oil is adopted to participate in the reaction, and the organic silicone oil is also a matting material per se, and the problem of matting of polyurethane per se is not solved.
Disclosure of Invention
The invention aims to overcome the technical difficulty that the existing waterborne polyurethane has a delustering effect, and provides self-delustering waterborne polyurethane and a preparation method thereof.
In the invention, the molar ratio of the total content of hydroxyl in the polyether polyol and the chain extender to the total content of isocyanate in the diisocyanate is (0.75-0.90): 1; the molar ratio of the chain extender to the diisocyanate is (0.5-1): 1, and the chain extender comprises a hydrophilic chain extender, a sulfonate chain extender and polyether ammonia.
The specific scheme is as follows:
a preparation method of self-extinction waterborne polyurethane comprises the following steps:
(1) mixing diisocyanate and polyether polyol and carrying out addition reaction, wherein the molar ratio of the diisocyanate to the polyether polyol is (2-4) to 1, so as to obtain an isocyanate-terminated addition reaction product;
(2) adding a diluent and a hydrophilic chain extender into the addition reaction product, and continuously reacting for 1-2h at 55-65 ℃;
(3) after the reaction in the step (2) is finished, adding a catalyst, and heating to 85-90 ℃ for reaction for 1-2 h;
(4) after the reaction in the step (3) is finished, cooling to normal temperature, and adding triethylamine to form salt to obtain a prepolymer;
(5) emulsifying the prepolymer, namely preparing a mixed solution of a sulfonate chain extender A95 and distilled water in advance, adding the prepolymer subjected to salt formation in the step (4) into the mixed solution, stirring, and forming an emulsion under the emulsification action;
(6) and after the emulsification is finished, adding polyether ammonia dropwise for chain extension to obtain the self-extinction waterborne polyurethane resin.
Further, in the step (1), the reaction temperature of the addition reaction is 85-88 ℃;
optionally, in the step (1), the diisocyanate is selected from at least one of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, norbornane diisocyanate, 1, 4 cyclohexane diisocyanate or tetramethylxylylene diisocyanate;
optionally, in step (1), the polyether polyol is selected from polytetrahydrofuran polyol or polyoxypropylene ether polyol.
Further, in the step (2), the diluent is selected from at least one of DMAC, DMF, NMP or acetone;
optionally, in the step (2), the hydrophilic chain extender is at least one selected from DMPA, DMBA and polyethylene glycol, and the hydrophilic chain extender is a solution with a mass fraction of 3% to 6%.
Further, in the step (3), the catalyst is selected from at least one of organic bismuth, organic silver, organic zirconium, organic mercury, organic tin or organic zinc.
Further, in the step (4), the addition amount of triethylamine is 95-99% of the molar mass of the hydrophilic chain extender;
optionally, cooling to normal temperature after the reaction in the step (3) is finished, so that side reaction caused by catalysis of the isocyanate group by triethylamine as a catalyst is reduced; after triethylamine is added, the triethylamine reacts with carboxyl in molecules to form salt, and therefore the prepolymer with hydrophilicity is obtained.
Further, in the step (5), the addition amount of the sulfonate chain extender A95 is 2-5% of the mass of a hard segment, wherein the hard segment refers to all components except polyether polyol in the raw materials.
Further, in the step (6), the polyether amine is selected from D230 of Henschel.
The invention also discloses the self-extinction waterborne polyurethane which is prepared by the preparation method of the self-extinction waterborne polyurethane, and the appearance of the self-extinction waterborne polyurethane is milky white or bluish semitransparent.
The invention also protects the application of the self-extinction waterborne polyurethane in surface treatment.
The invention also protects a polyurethane film which comprises the self-extinction waterborne polyurethane, wherein the tensile strength of the polyurethane film is 10-16MPa, the elongation at break is 140-220%, and the glossiness is 50-60 ℃.
Has the advantages that:
in the invention, diisocyanate and polyether polyol are mixed and subjected to addition reaction, and the obtained addition product is diluted by a diluent and subjected to hydrophilic chain extension reaction, thereby laying a foundation for the main structure of the product.
After triethylamine is added, triethylamine reacts with carboxyl in target molecules to form salt with hydrophilicity, the part of carboxyl is mainly derived from a hydrophilic chain extender, and the carboxyl is combined to target object molecules in a molecular chain extension reaction, so that the prepolymer has hydrophilicity. Subsequently, the sulfonate chain extender mainly reacts with isocyanate-based NCO for chain extension, and the two reactions are exothermic reactions, so that the temperature of the system can be increased violently by adding the triethylamine and the sulfonate chain extender together, the reaction speed is not controlled favorably, and the system has more byproducts, high viscosity and difficult emulsification. More importantly, compared with the prepolymer without the hydrophilic effect, the hydrophilic prepolymer can be uniformly mixed with hydrophilic sulfonate, particles with controllable particle size can be formed, the emulsifying effect is achieved, a rough surface is formed after the emulsion is cured, and therefore light scattering is increased, reflection is reduced, and the extinction effect of polyurethane is achieved.
Furthermore, after diisocyanate reacts with polyether polyol, polyether ammonia is combined for chain extension, so that the problems of high hardness and poor flexibility of polyurethane can be effectively solved, and the application requirements of related products are met.
In a word, the self-extinction waterborne polyurethane provided by the invention can achieve the matte effect after the resin is cured under the condition that no extinction powder is added. Different from the traditional resin synthesis process, the emulsion with different particle sizes is obtained, and a rough surface is formed after solidification, so that the light scattering is increased, the reflection is reduced, and the matte effect is achieved. Meanwhile, the resin has good glossiness, attractive appearance, high tensile strength, good flexibility and good market application prospect.
The invention can reduce the use of the matting powder and reduce the pollution of dust, and is particularly beneficial to the health of production personnel.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
In the following examples, the organobismuth catalyst is provided by Vanderue or leading Chemicals USA, and the product model is: 8118. 8330R, 8106 and 8108. The organozinc catalyst is provided by leading chemical companies in the United states, specifically zinc isooctanoate. The organic silver catalyst was provided by Korea seiko, and specifically was a complex of silver ions, model 100 Ag-18. The polyether amine is selected from Henschel D230.
Example 1
This example is provided to illustrate a self-matting waterborne polyurethane resin and a method for preparing the same according to the present invention.
Weighing the raw materials in parts by weight as follows:
IPDI: 36.11 parts by weight;
polytetrahydrofuran polyol PTMEG, number average molecular weight 2000: 100 parts by weight;
2, 2-dimethylolpropionic acid DMPA: 4.82 parts by weight;
DMAC: 30 parts by weight;
organic bismuth catalyst (model 8118): 0.15 part by weight;
distilled water: 312.22 parts by weight;
triethylamine: 3.35 parts by weight;
sulfonate chain extender a 95: 1.16 parts by weight;
polyether ammonia D230: 4.6 parts by weight;
wherein the molar ratio of the total content of hydroxyl groups in the polytetrahydrofuran polyol, hydroxyl groups of 2, 2-dimethylolpropionic acid, amine groups in D230 and amine groups in the sulfonate A95 to the total content of isocyanate groups in the IPDI is 0.75: 1.
The preparation process comprises the following steps:
(a) according to the proportion of the formula design, PTMEG2000 and DMPA are subjected to reduced pressure distillation dehydration at the high temperature of 120 ℃ until the moisture content in the raw materials is lower than 0.05 wt%.
(b) Uniformly mixing the dehydrated PTMEG2000 and IPDI in a nitrogen-filled reaction kettle, gradually raising the temperature in the reaction kettle, controlling the temperature in the reaction kettle within 85-88 ℃, and reacting for 2H to obtain an isocyanate-terminated reaction product;
(c) adding DMAC and DMPA into the addition reaction product of the step (b) and continuously reacting for 2 hours at the temperature of 60-65 ℃;
(d) 8118 catalyst is added after the reaction of (c) is finished, and the reaction is kept at 85-90 ℃ for 2 h;
(e) after the reaction is finished, (d) cooling to normal temperature, and adding triethylamine to form salt;
(f) emulsifying the prepolymer, preparing a mixed solution of a sulfonate chain extender A95 and distilled water in advance, slowly adding the salified prepolymer of the step (e) into the mixed solution, and stirring at a high speed until the rotating speed reaches 1000 r/min;
(g) after the emulsification is finished, regulating the rotating speed to be below 500r/min, and slowly dripping polyether ammonia for chain extension to obtain the self-extinction waterborne polyurethane resin.
Example 2
This example is provided to illustrate a self-matting waterborne polyurethane resin and a method for preparing the same according to the present invention.
Weighing the raw materials in parts by weight as follows:
h12 MDI: 48.85 parts by weight;
polytetrahydrofuran polyol PTMEG1000, number average molecular weight 1000: 100 parts by weight;
2, 2-dimethylolpropionic acid DMPA: 7.54 parts by weight;
NMP: 36 parts by weight;
organic bismuth catalyst (type 8330R): 0.15 part by weight;
distilled water: 204.63 parts by weight;
triethylamine: 5.4 parts by weight;
sulfonate chain extender a 95: 1.4 parts by weight;
polyether ammonia: 9.75 parts by weight;
wherein the molar ratio of the total content of hydroxyl groups in the polytetrahydrofuran polyol, hydroxyl groups of DMPA, amine groups in D230 and amine groups in the sulfonate A95 to the total content of isocyanate groups in H12MDI is 0.85: 1.
The preparation process comprises the following steps:
(a) according to the proportion of the formula design, PTMEG and DMPA are subjected to reduced pressure distillation dehydration at the high temperature of 120 ℃ until the moisture content in the raw materials is lower than 0.05 wt%.
(b) Uniformly mixing the dehydrated PTMEG and H12MDI in a reaction kettle filled with nitrogen, gradually raising the temperature in the reaction kettle, controlling the temperature in the reaction kettle within 85-90 ℃, and reacting for 2H to obtain an isocyanate-terminated reaction product;
(c) adding NMP and DMPA into the addition reaction product of the step (b) and continuously reacting for 2 hours at the temperature of 60-65 ℃;
(d) adding 8330R catalyst after the reaction of (c) is finished, and keeping the temperature of 85-90 ℃ for reaction for 2 h;
(e) after the reaction is finished, (d) cooling to normal temperature, and adding triethylamine to form salt;
(f) emulsifying the prepolymer, preparing a mixed solution of a sulfonate chain extender A95 and distilled water in advance, slowly adding the salified prepolymer of the step (e) into the mixed solution, and stirring at a high speed until the rotating speed reaches 1100 r/min;
(g) after the emulsification is finished, regulating the rotating speed to 400r/min, and slowly dripping polyether ammonia for chain extension to obtain the self-extinction waterborne polyurethane resin.
Example 3
This example is provided to illustrate a self-matting waterborne polyurethane resin and a method for preparing the same according to the present invention.
Weighing the raw materials in parts by weight as follows:
h12 MDI: 48.85 parts by weight;
polyoxypropylene ether polyol, number average molecular weight 2000: 100 parts by weight;
2, 2-dimethylolpropionic acid: 7.54 parts by weight;
NMP: 36 parts by weight;
organic bismuth catalyst (type 8330R): 0.15 part by weight;
distilled water: 183.49 parts by weight;
triethylamine: 5.4 parts by weight;
sulfonate chain extender a 95: 1.4 parts by weight;
polyether ammonia: 2.62 parts by weight;
wherein the molar ratio of the total content of hydroxyl groups in the polyoxypropylene ether polyol, hydroxyl groups of DMPA, amine groups in D230 and amine groups of the sulfonate A95 to the total content of isocyanate groups in H12MDI is 0.85: 1.
The preparation process comprises the following steps:
(a) according to the proportion of the formula design, PTMEG2000 and DMPA are subjected to reduced pressure distillation dehydration at the high temperature of 120 ℃ until the moisture content in the raw materials is lower than 0.05 wt%.
(b) Uniformly mixing the dehydrated PTMEG2000 and IPDI in a nitrogen-filled reaction kettle, gradually raising the temperature in the reaction kettle, controlling the temperature in the reaction kettle within 85-90 ℃, and reacting for 2H to obtain an isocyanate-terminated reaction product;
(c) adding NMP and DMPA into the addition reaction product of the step (b) and continuously reacting for 2 hours at the temperature of 60-65 ℃;
(d) adding 8330R catalyst after the reaction of (c) is finished, and keeping the temperature of 85-90 ℃ for reaction for 2 h;
(e) after the reaction is finished, (d) cooling to normal temperature, and adding triethylamine to form salt;
(f) emulsifying the prepolymer, preparing a mixed solution of a sulfonate chain extender A95 and distilled water in advance, slowly adding the salified prepolymer of the step (e) into the mixed solution, and stirring at a high speed until the rotating speed reaches 1100 r/min;
(g) after the emulsification is finished, regulating the rotating speed to 400r/min, and slowly dripping polyether ammonia for chain extension to obtain the self-extinction waterborne polyurethane resin.
Comparative example 1
On the basis of example 2, polytetrahydrofuran polyol PTMEG is replaced by polycaprolactone polyol, the number average molecular weight of the polycaprolactone polyol is 1000, the using amount is 100 parts by weight, and the other raw materials and the preparation method are the same.
Comparative example 2
On the basis of example 2, the polyether ammonia was replaced with ethylenediamine in an amount of 9.75 parts by weight, and the other raw materials and the preparation method were the same.
Comparative example 3
The raw materials were the same as in example 1, and the preparation procedure was as follows:
(a) according to the proportion of the formula design, PTMEG2000 and DMPA are subjected to reduced pressure distillation dehydration at the high temperature of 120 ℃ until the moisture content in the raw materials is lower than 0.05 wt%.
(b) Uniformly mixing the dehydrated PTMEG2000 and IPDI in a nitrogen-filled reaction kettle, gradually raising the temperature in the reaction kettle, controlling the temperature in the reaction kettle within 85-88 ℃, and reacting for 2H to obtain an isocyanate-terminated reaction product;
(c) adding DMAC and DMPA into the addition reaction product of the step (b) and continuously reacting for 2 hours at the temperature of 60-65 ℃;
(d) 8118 catalyst is added after the reaction of (c) is finished, and the reaction is kept at 85-90 ℃ for 2 h;
(e) cooling the reaction product obtained in the step (d) to normal temperature after the reaction is finished, adding triethylamine and a mixed solution of a sulfonate chain extender A95 and distilled water which are prepared in advance, and stirring at a high speed until the rotating speed reaches 1000r/min to obtain an emulsified prepolymer;
(f) after the emulsification is finished, regulating the rotating speed to be below 500r/min, and slowly dripping polyether ammonia for chain extension to obtain the self-extinction waterborne polyurethane resin.
And (3) carrying out performance detection on the prepared sample, wherein the tensile strength, the elongation at break, the glossiness and the flexibility are detected after the sample is cured, the curing process is to pour the waterborne polyurethane on a polytetrafluoroethylene plate to form an emulsion with the area of 3cm multiplied by 3cm, the emulsion is dried to form a film at room temperature, and then the film plate is placed in a vacuum drying oven and dried for 24 hours at the temperature of 60 ℃ to obtain the dry self-extinction adhesive film. The results of the various property measurements are shown in Table 1.
Table 1 product performance test results table
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of self-extinction waterborne polyurethane is characterized in that: the method comprises the following steps:
(1) mixing diisocyanate and polyether polyol and carrying out addition reaction, wherein the molar ratio of the diisocyanate to the polyether polyol is (2-4) to 1, so as to obtain an isocyanate-terminated addition reaction product;
(2) adding a diluent and a hydrophilic chain extender into the addition reaction product, and continuously reacting for 1-2h at 55-65 ℃;
(3) after the reaction in the step (2) is finished, adding a catalyst, and heating to 85-90 ℃ for reaction for 1-2 h;
(4) after the reaction in the step (3) is finished, cooling to normal temperature, and adding triethylamine to form salt to obtain a prepolymer;
(5) emulsifying the prepolymer, namely preparing a mixed solution of a sulfonate chain extender A95 and distilled water in advance, adding the prepolymer subjected to salt formation in the step (4) into the mixed solution, stirring, and forming an emulsion under the emulsification action;
(6) and after the emulsification is finished, adding polyether ammonia dropwise for chain extension to obtain the self-extinction waterborne polyurethane resin.
2. The method for preparing self-matting aqueous polyurethane according to claim 1, characterized in that: in the step (1), the reaction temperature of the addition reaction is 85-88 ℃;
optionally, in the step (1), the diisocyanate is selected from at least one of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, norbornane diisocyanate, 1, 4 cyclohexane diisocyanate or tetramethylxylylene diisocyanate;
optionally, in step (1), the polyether polyol is selected from polytetrahydrofuran polyol or polyoxypropylene ether polyol.
3. The method for preparing self-matting aqueous polyurethane according to claim 1, characterized in that: in the step (2), the diluent is at least one selected from DMAC, DMF, NMP or acetone;
optionally, in the step (2), the hydrophilic chain extender is at least one selected from DMPA, DMBA and polyethylene glycol, and the hydrophilic chain extender is a solution with a mass fraction of 3% to 6%.
4. The method for preparing self-matting aqueous polyurethane according to claim 1, characterized in that: in the step (3), the catalyst is selected from at least one of organic bismuth, organic silver, organic zirconium, organic mercury, organic tin or organic zinc.
5. The method for preparing self-matting aqueous polyurethane according to claim 1, characterized in that: in the step (4), the addition amount of triethylamine is 95-99% of the molar mass of the hydrophilic chain extender;
optionally, cooling to normal temperature after the reaction in the step (3) is finished, so that side reaction caused by catalysis of the isocyanate group by triethylamine as a catalyst is reduced; after triethylamine is added, the triethylamine reacts with carboxyl in molecules to form salt, and therefore the prepolymer with hydrophilicity is obtained.
6. The method for preparing self-matting aqueous polyurethane according to claim 1, characterized in that: in the step (5), the addition amount of the sulfonate chain extender A95 is 2-5% of the mass of a hard segment, wherein the hard segment refers to all components except polyether polyol in the raw material.
7. The method for producing the self-matting aqueous polyurethane according to any one of claims 1 to 6, characterized in that: in the step (6), the polyether amine is selected from D230 of Henscman.
8. A self-matting waterborne polyurethane prepared by the method for preparing the self-matting waterborne polyurethane as claimed in any one of claims 1 to 7, wherein the method comprises the following steps: the self-extinction waterborne polyurethane is milky white or bluish translucent in appearance.
9. Use of the self-matting aqueous polyurethane according to claim 8 for surface treatment of a surface.
10. A polyurethane film comprising the self-matting aqueous polyurethane according to claim 8, characterized in that: the tensile strength of the polyurethane film is 10-16MPa, or the elongation at break is 140-220%, or the glossiness is 50-60 degrees.
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| CN114736349A (en) * | 2022-03-09 | 2022-07-12 | 华南理工大学 | Self-extinction waterborne polyurethane and preparation method and application thereof |
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| CN111138614A (en) * | 2019-12-19 | 2020-05-12 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane emulsion for low-modulus high-strength ultrathin polyurethane condom and preparation method thereof |
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| CN114736349A (en) * | 2022-03-09 | 2022-07-12 | 华南理工大学 | Self-extinction waterborne polyurethane and preparation method and application thereof |
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