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CN114605463A - Preparation method and use mode of polyurethane hydrophilic modifier - Google Patents

Preparation method and use mode of polyurethane hydrophilic modifier Download PDF

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Publication number
CN114605463A
CN114605463A CN202111499982.XA CN202111499982A CN114605463A CN 114605463 A CN114605463 A CN 114605463A CN 202111499982 A CN202111499982 A CN 202111499982A CN 114605463 A CN114605463 A CN 114605463A
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modifier
polyurethane
water dispersible
solvent medium
polyisocyanate
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谭卉文
余军
张政
曾逸
谢武挺
胡建新
陈阳
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Guangzhou Yele New Material Technology Co ltd
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Guangzhou Yele New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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    • 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
    • C08G18/83—Chemically modified polymers
    • C08G18/837—Chemically modified polymers by silicon containing compounds
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers

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  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides a preparation method and a use mode of a polyurethane hydrophilic modifier, which comprises the following steps: (1) under the condition of constant temperature, adding a heterocyclic sulfur-containing compound into a solvent medium, uniformly mixing, and then dropwise adding aminosilane; (2) heating to 65-75 ℃, keeping constant temperature, and performing reflux reaction to obtain a mixed solution; (3) and compressing and filtering the mixed solution, washing filter residues by using the same solvent medium to obtain a white solid, and drying to obtain the modifier. The prepared modifier can be used in a two-component water dispersible polyisocyanate and a two-component water dispersible polyurethane dispersoid to improve the water dispersible capability and the self stability of the two-component water dispersible polyisocyanate and the two-component water dispersible polyurethane dispersoid and improve the compatibility between the two-component water dispersible polyisocyanate and the water-based hydroxyl resin, can be applied to the field of coatings, can reduce the surface energy between the coating and a substrate interface, improves the adhesive force, the high temperature resistance, the weather resistance, the chemical resistance and the physiological inertia of the coating, and forms a coating film with high fullness and high gloss.

Description

Preparation method and use mode of polyurethane hydrophilic modifier
Technical Field
The invention relates to the technical field of C07F7/18, in particular to a preparation method and a use mode of a polyurethane hydrophilic modifier.
Background
With the increasing strictness of environmental regulations and the increasing awareness of people on environmental protection, the waterborne polyurethane containing no or little organic solvent and mild application conditions is receiving more and more attention.
The aqueous polyurethane material is mainly divided into two types of double components and single component, the single component aqueous polyurethane is a dispersoid which is redispersed in water after isocyanate monomer reacts with polyalcohol and hydrophilic modifier, generally has low relative molecular mass or low crosslinking, and has less groups which can generate chemical reaction in the process of drying and film forming, so the comprehensive performance of a coating film generally has the defects of adhesive force, tolerance and physical performance; the single-component waterborne polyurethane is widely used because the construction convenience and the cost are lower than those of two components.
The two-component waterborne polyurethane material comprises a waterborne hydroxyl resin component and a water dispersible isocyanate component, wherein the water dispersible isocyanate component is usually prepared by carrying out hydrophilic modification on polyisocyanate so that the polyisocyanate can be dispersed in a water phase, so that the waterborne hydroxyl resin material has good compatibility with the waterborne hydroxyl resin component and can be mixed and matched for use. However, the hydrophilic groups exist in the molecular chain of the isocyanate component, so that the chemical resistance and water resistance of the coating film are poor, and the heat resistance, adhesion on a special substrate and other properties of the coating film are required to be improved. In order to enlarge the application range of the waterborne polyurethane material, a great deal of research is carried out on the modification of the isocyanate main chain by properly adding the modifier from the angle of isocyanate molecular design, so that the comprehensive performance of the waterborne polyurethane coating film is improved; however, as for the research reported at present, the influence of the introduced hydrophilic molecular chain on the resistance is not fundamentally solved, and most of the water resistance and chemical resistance of the water-based polyurethane coating film are poor.
Chinese patent CN109679056B discloses a preparation method of self-crosslinking polyurethane aqueous dispersion, which comprises the steps of mixing the prepared isocyanate-terminated prepolymer, aminosiloxane, sulfamic acid or ethanolamine and the like, and carrying out chain extension reaction at 20-60 ℃ to obtain the polyurethane aqueous dispersion. In the patent, amino siloxane, sulfamic acid or ethanolamine is used as a chain extender and is respectively introduced into a polyurethane chain segment, and the adhesion of the polyurethane dispersion on the surface of a base material is further improved by improving the density of self-crosslinking groups of the polyurethane dispersion.
Chinese patent CN111116865A discloses a polyisocyanate curing agent, which is prepared by mixing sultone, a silane coupling agent and polyisocyanate and reacting together. However, the polyisocyanate curing agent prepared according to this patent cannot control side reactions well, and generates a large amount of by-products, which directly reduces the use effect of the polyisocyanate curing agent.
Based on the polyurethane hydrophilic modifier, the invention provides a polyurethane hydrophilic modifier, and a preparation method and a use method thereof.
Disclosure of Invention
The invention provides a preparation method of a polyurethane hydrophilic modifier, which comprises the following steps:
(1) adding a heterocyclic sulfur-containing compound into a solvent medium at a constant temperature of 60-65 ℃, uniformly mixing, and then dropwise adding aminosilane;
(2) heating to 65-75 ℃, keeping constant temperature, and performing reflux reaction to obtain a mixed solution;
(3) and compressing and filtering the mixed solution, washing filter residues by using the same solvent medium to obtain a white solid, and drying to obtain the modifier.
In a preferred embodiment, the heterocyclic sulfur-containing compound and the aminosilane are present in a mass ratio of 1: (1.1-2). More preferably, the mass ratio of the heterocyclic sulfur-containing compound to the aminosilane is 1: (1.3-1.8).
In a preferred embodiment, the aminosilane is selected from at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane, and the like.
In a preferred embodiment, the heterocyclic sulfur-containing compound has the following structural formula:
Figure BDA0003402335940000021
wherein R1 and R2 are the same and are selected from any one of H, O; and R3 is selected from-CH3Any one of H and OH, R4 is selected from-CH3Any one of H and OH, R5 is selected from-CH3Any one of H and-OH.
In a preferred embodiment, the heterocyclic sulfur-containing compound is at least one selected from the group consisting of 1, 3-propane sultone, 1, 4-butane sultone, 2, 4-butane sultone, 5-methyloxathiolane 2, 2-dioxide, and 4-methyloxathiolane 2, 2-dioxide.
In a preferred embodiment, the heterocyclic sulfur-containing compound is 1, 3-propane sultone or 1, 4-butane sultone.
In a preferred embodiment, the aminosilane is aminopropyltrimethoxysilane or aminopropyltriethoxysilane.
In a preferred embodiment, the solvent medium I and the solvent medium II are the same solvent medium.
In a preferred embodiment, the solvent medium is selected from at least one of acetone, butanone, toluene, ethyl acetate, butyl acetate, cyclohexanone, and the like.
In a preferred embodiment, the dropping time of the aminosilane dropwise added in the step (1) is 40 to 50 min.
In a preferred embodiment, in the step (2), the constant temperature is 70-72 ℃.
In a preferred embodiment, in the step (2), the time for the reflux reaction is 3 hours.
The applicant finds that in the experimental process, the modifier prepared by mixing and reacting aminosilane and heterocyclic sulfur-containing compound effectively introduces an organosilicon chain segment and a hydrophilic sulfonic acid group into isocyanate or a polyurethane chain segment in the process of modifying isocyanate, so that the water dispersion performance of isocyanate and polyurethane dispersoid is improved, the stability of the isocyanate and polyurethane dispersoid is promoted, the compatibility with water-based hydroxyl resin is improved, the surface energy between a coating and a substrate interface can be reduced when the modifier is applied to the field of coatings, the adhesive force and the high-temperature resistance between the coating and the substrate are improved by improving the intermolecular force between the coating and the substrate surface, and a coating film with high fullness and high gloss is formed.
The second aspect of the invention provides a use mode of the prepared polyurethane hydrophilic modifier, and the polyurethane hydrophilic modifier is added into the two-component water-dispersible polyisocyanate and/or the aqueous polyurethane dispersion for use.
In a preferred embodiment, the two-component water dispersible polyisocyanate is used in the following manner: under the condition of constant temperature, the polyisocyanate and the hydrophilic modifier are mixed according to the molar ratio (20-80): 1, adding the mixture into a reaction vessel, adding an amino catalytic neutralizer, and heating for reaction until the solution becomes completely clear to obtain the water dispersible polyisocyanate.
In a preferred embodiment, the molar ratio of the polyisocyanate to the hydrophilic modifier is 50: 1.
In a preferred embodiment, the amine-based catalytic neutralizing agent is selected from at least one of N, N-dimethylbutylamine, dimethylcyclohexylamine, triethylamine, triethylenediamine, N-methylmorpholine.
In a preferred embodiment, the temperature of the constant temperature condition is 80 to 100 ℃, and more preferably, the temperature of the constant temperature condition is 80 ℃.
In a preferred embodiment, the temperature of the temperature-raising reaction is 100 ℃, and the time of the temperature-raising reaction is 5 hours.
In a preferred embodiment, the mode of use of the addition to the aqueous polyurethane dispersion is as follows: adding polyether glycol, isocyanate and an organic tin catalyst into a reaction vessel, reacting at 70-75 ℃, dissolving butanediol and a hydrophilic modifier, adding into the reaction vessel, stirring uniformly, adding an amino catalytic neutralizer, heating for reaction, and adding water for dispersion to obtain the aqueous polyurethane dispersion.
In a preferred embodiment, the ratio of the molar amount of isocyanate groups in the isocyanate to the molar amount of hydroxyl groups in the polyether polyol is (2-3): 1.
in a preferred embodiment, the molar ratio of butanediol to hydrophilic modifier is 10: 9.
In a preferred embodiment, the ratio of the molar amount of isocyanate groups in the isocyanate to the molar amount of hydrophilic modifier is 100: (9-15).
In a preferred embodiment, the specific process of the temperature-rising reaction is as follows: heating to 85 ℃, reacting for 2 hours under the condition of heat preservation, and cooling to 50 ℃.
In a preferred embodiment, the solids content of the aqueous polyurethane dispersion is from 30 to 38%, preferably 35%.
In the present application, the specific kind of the isocyanate is not particularly limited, and may be any one or more selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.
In the present application, the specific type of polyisocyanate is not particularly limited, and may be any one or more selected from isocyanurate polyisocyanates, biuret polyisocyanates, carbodiimide polyisocyanates, uretonimine polyisocyanates, uretdione polyisocyanates, allophanate polyisocyanates, urethane polyisocyanates, iminooxadiazinedione polyisocyanates based on isocyanate monomers such as hexamethylene diisocyanate, isophorone diisocyanate, or toluene diisocyanate.
In the present application, the isocyanurate polyisocyanates are exemplified by the types Coxikon N3300, Pasteur HI100, Vanhua HT 100.
In a preferred embodiment, the preparation method comprises the following steps:
(1) under the condition of constant temperature of 60 ℃, 60-70g of heterocyclic sulfur-containing compound is added into 500g of butanone, after uniform mixing, 90-115g of aminopropyl trimethoxy silane is added dropwise for 50 min;
(2) heating to 72 ℃, keeping the constant temperature, and performing reflux reaction for 3 hours to obtain a mixed solution;
(3) and compressing and filtering the mixed solution, washing filter residues with butanone to obtain a white solid, and drying to obtain the modifier.
Compared with the prior art, the invention has the following beneficial effects:
1. the hydrophilic modifier prepared by the invention is obtained by adopting silane and sultone to react in a proper solvent medium by a dropping method and then treating, and has higher purity and less impurity content. Compared with the method of directly mixing silane, sultone and isocyanate for reaction, the hydrophilic modifier prepared by the invention is mixed with isocyanate, has smaller addition amount, convenient use and wide application, and can also be used in single-component aqueous polyurethane dispersoid.
2. According to the modifier prepared by the invention, after isocyanate is modified, an organic silicon chain segment and a hydrophilic sulfonic acid group are effectively introduced, the water dispersing capacity of the isocyanate is improved, the self stabilizing capacity of the isocyanate and a polyurethane dispersion is promoted, the compatibility between the isocyanate and a water-based hydroxyl resin can be improved, the modifier is applied to the field of coatings, the surface energy between the coating and a substrate interface can be reduced, the adhesive force, the high temperature resistance, the weather resistance, the chemical resistance and the physiological inertia of the coating are improved, and a coating film with high fullness and high gloss is formed.
Detailed Description
Example 1
The embodiment provides a preparation method of a polyurethane hydrophilic modifier, which comprises the following steps:
(1) under the condition of constant temperature of 60 ℃, 68g of 1, 4-butanesultone is added into 500g of butanone, after uniform mixing, 90g of aminopropyltrimethoxysilane is dropwise added, and the dropwise addition is completed within 50 min;
(2) heating to 72 ℃, keeping the constant temperature, and performing reflux reaction for 3 hours to obtain a mixed solution;
(3) and compressing and filtering the mixed solution, washing filter residues with butanone to obtain a white solid, and drying to obtain the modifier.
Example 2
The embodiment provides a preparation method of a polyurethane hydrophilic modifier, which comprises the following steps:
(1) under the condition of constant temperature of 60 ℃, 68g of 1, 4-butyl sultone is added into 500g of cyclohexanone, after uniform mixing, 111g of aminopropyltriethoxysilane is added dropwise, and the dropwise addition is completed within 45 min;
(2) heating to 72 ℃, keeping the constant temperature, and performing reflux reaction for 3 hours to obtain a mixed solution;
(3) and compressing and filtering the mixed solution, washing filter residues with butanone to obtain a white solid, and drying to obtain the modifier.
Example 3
The embodiment provides a preparation method of a polyurethane hydrophilic modifier, which comprises the following steps:
(1) under the condition of constant temperature of 60 ℃, adding 61g of 1, 3-propane sultone into 500g of butanone, uniformly mixing, dropwise adding 90g of aminopropyl trimethoxy silane, and completing dropwise adding within 50 min;
(2) heating to 72 ℃, keeping the constant temperature, and performing reflux reaction for 3 hours to obtain a mixed solution;
(3) and compressing and filtering the mixed solution, washing filter residues with butanone to obtain a white solid, and drying to obtain the modifier.
Example 4
The embodiment provides a preparation method and a use method of a polyurethane hydrophilic modifier, the preparation method of the polyurethane hydrophilic modifier is the same as that of embodiment 1, and the use method of the polyurethane hydrophilic modifier in water dispersible polyisocyanate is as follows:
(1) adding isocyanurate polyisocyanate and a hydrophilic modifier into a three-neck flask, uniformly stirring, and heating to 80 ℃;
(2) adding 0.02mol of N, N-dimethylbutylamine, mixing, heating to 100 ℃, and reacting for 5 hours until the solution becomes completely clear to obtain the water-dispersible polyisocyanate.
Wherein the molar ratio of isocyanate group to hydrophilic modifier in the isocyanurate polyisocyanate is 50:1, and the molar amount of the hydrophilic modifier is 0.02 mol.
The isocyanurate polyisocyanate is purchased from kossi N3300.
Example 5
This example proposes a preparation method and a use method of a polyurethane hydrophilic modifier, the preparation method of the polyurethane hydrophilic modifier is the same as that of example 1, the polyurethane hydrophilic modifier is used in an aqueous polyurethane dispersion, and the use method specifically is as follows:
(1) putting polyether glycol into a three-neck flask, heating to 85 ℃, carrying out vacuum dehydration, cooling to 70 ℃, adding isophorone diisocyanate and a T12 organic tin catalyst, and keeping the temperature at 70 ℃ for 1.5 h;
(2) dissolving 1, 4-butanediol and a hydrophilic modifier in 140g of acetone, adding the mixture, stirring the mixture uniformly, adding N, N-dimethylbutylamine, heating the mixture to 85 ℃, and keeping the temperature for 2 hours;
(3) cooling to 50 ℃, transferring to a dispersion machine, slowly adding 650g of water for dispersing for 15min, gradually dropwise adding 300g of aqueous solution containing 0.18mol of ethylenediamine, and uniformly dispersing;
(4) acetone was removed in a slight vacuum to give an aqueous polyurethane dispersion having a solids content of 35%.
The polyether polyol is purchased from Lanxingdong, and has the model of N220, the added polyether polyol is 0.35mol based on the molar amount of hydroxyl, the added isophorone diisocyanate is 1mol based on the molar amount of isocyanic acid radical, and the added amount of T12 organic tin catalyst is 0.2 g.
Wherein the adding amount of the 1, 4-butanediol is 0.2mol based on the molar amount of the hydroxyl, the adding amount of the hydrophilic modifier is 0.09mol, and the adding amount of the N, N-dimethylbutylamine is 0.09 mol.
Comparative example 1
The embodiment provides a preparation method and a use mode of a polyurethane hydrophilic modifier, wherein the polyurethane hydrophilic modifier is 3- (cyclohexylamine) -1-propanesulfonic acid, and is used in water dispersible polyisocyanate, and the preparation method specifically comprises the following steps:
(1) adding isocyanurate polyisocyanate and 3- (cyclohexylamine) -1-propanesulfonic acid into a three-neck flask, uniformly stirring, and heating to 80 ℃;
(2) adding 0.02mol of N, N-dimethylbutylamine, mixing, heating to 100 ℃, and reacting for 5 hours until the solution becomes completely clear to obtain the water-dispersible polyisocyanate.
Wherein the molar ratio of the isocyanic acid radical to the 3- (cyclohexylamine) -1-propanesulfonic acid in the isocyanurate polyisocyanate is 50:1, and the molar quantity of the 3- (cyclohexylamine) -1-propanesulfonic acid is 0.02 mol.
The isocyanurate polyisocyanate is purchased from kossi N3300.
Comparative example 2
The embodiment provides a preparation method and a use mode of a polyurethane hydrophilic modifier, and the preparation method comprises the following specific steps: adding 1g of 1, 4-butyl sultone into a reactor in nitrogen atmosphere, adding 1g of silane coupling agent KH540 at 60 ℃ while stirring, continuously stirring for reaction for 10min, adding 98g of polyisocyanate, heating to 100 ℃, adding N, N-dimethylbutylamine for neutralization, and keeping 100 ℃ for reaction to obtain a product A.
The content of isocyanate in the product A is 21-22 wt%.
The polyisocyanate is a Pasteur HDI trimer with the model of HI 100.
Comparative example 3
This example proposes a way of using a polyurethane hydrophilic modifier, and the specific raw materials and the steps used are the same as those in example 5, except that the polyurethane hydrophilic modifier is dimethylolpropionic acid.
Performance testing
1. The water-dispersible polyisocyanates obtained in example 4, comparative example 1 and comparative example 2 were subjected to tests for NCO content, viscosity, emulsified particle size in water, appearance, and storage stability at 50 ℃ and the data are shown in Table 1. The NCO content was determined with reference to GB/T12009.4-2016. The viscosity was measured with a viscometer. The emulsified particle size in water is detected by a light scattering instrument.
TABLE 1
Figure BDA0003402335940000081
2. The water-dispersible polyisocyanate prepared in example 4, comparative example 1 and comparative example 2 and the water-based hydroxypropyl dispersion with the hydroxyl content of 3.9 wt% (purchased from Guangdong Rele New Material manufacturing Co., Ltd., model YL-MY7139) are respectively mixed uniformly, coated on the surface of a carbon steel material, and after the coating film is naturally cured, the gloss, the water resistance, the boiling resistance, the butanone resistance and the hardness of the coating film are tested. Data results are recorded in table 2.
Coating film gloss: and the paint film glossiness test is carried out according to GB/T9754.
Water resistance: and (3) immersing the carbon steel with the surface coated with the coating film in normal-temperature water for 240 hours, and observing the surface performance of the coating film.
Boiling resistance: and (3) immersing the carbon steel with the surface coated with the coating film in water at 95 ℃ for 2h, and observing the surface performance of the coating film.
Butanone resistance: the carbon steel material with the coating film on the surface is wiped back and forth 100 times by butanone solution, and the surface performance of the coating film is observed.
TABLE 2
Example 4 Comparative example 1 Comparative example 2
Gloss/° of coating film 85°/93° 84°/93° 75°/85°
Water-resistant No abnormality High foaming No abnormality
Resistant poaching No abnormality Shedding of blisters Leukogenic microvesicles
Butanone-resistant wiping No abnormality The paint film is soft and can not be recovered The paint film can be softened and restored
Hardness of 2H 2H 2H
3. The aqueous polyurethane dispersions prepared in example 5 and comparative example 3 were subjected to the tests of appearance, viscosity, and particle size in water emulsion, and the data are shown in table 3. The viscosity was measured with a viscometer. The emulsified particle size in water is detected by a light scattering instrument.
TABLE 3
Example 5 Comparative example 3
Appearance of the product Milky white blue light Milky white blue light
Viscosity/mpa.s 25 deg.C 150 460
Particle size of emulsion in water 120nm 95nm
4. The aqueous polyurethane dispersions prepared in example 5 and comparative example 3 were applied to the surface of a carbon steel material, and after the coating film was naturally cured, the appearance, gloss, adhesion, water resistance, boiling resistance, butanone resistance, and hardness of the coating film were tested. Data results are recorded in table 4. The tests of the coating film on the gloss, water resistance, boiling resistance, butanone resistance and hardness are the same as those of the water dispersible polyisocyanate coating film. The test modes of the gloss, water resistance, boiling resistance and butanone resistance of the coating film are the same as those in Table 2. The adhesion test is carried out with reference to GB/T9286-88; hardness was tested with reference to GB/T6739-2006.
TABLE 4
Example 5 Comparative example 3
Appearance of the product Water white transparent Water white transparent
Gloss/degree of coating film 81°/91° 82°/90°
Adhesion force Level 0 Stage 2
Water-resistant No abnormality High foaming
Resistant poaching Can recover from slight whitish Shedding of blisters
Butanone-resistant wiping Can recover from slight whitish The paint film is soft and can not be recovered
Hardness of HB HB

Claims (10)

1. A preparation method of a polyurethane hydrophilic modifier is characterized by comprising the following steps:
(1) adding a heterocyclic sulfur-containing compound into a solvent medium I at a constant temperature of 60-65 ℃, uniformly mixing, and dropwise adding aminosilane;
(2) heating to 65-75 ℃, keeping constant temperature, and performing reflux reaction to obtain a mixed solution;
(3) and compressing and filtering the mixed solution, washing the filter residue by using a solvent medium II to obtain a white solid, and drying to obtain the modifier.
2. The method according to claim 1, wherein the heterocyclic sulfur compound and the aminosilane are present in a mass ratio of 1: (1.1-2).
3. The method according to claim 1, wherein the solvent medium I and the solvent medium II are the same solvent medium.
4. The method according to any one of claims 1 to 3, wherein the aminosilane is at least one selected from the group consisting of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- β (aminoethyl) - γ -aminopropyltriethoxysilane, N- β (aminoethyl) - γ -aminopropylmethyldiethoxysilane and the like.
5. The process according to any one of claims 1 to 3, wherein the heterocyclic sulfur-containing compound has the following structural formula:
Figure FDA0003402335930000011
wherein R1 and R2 are the same and are selected from any one of H, O; and R3 is selected from-CH3Any one of H and OH, R4 is selected from-CH3Any one of H and OH, R5 is selected from-CH3Any one of H and-OH.
6. The method according to claim 3, wherein the solvent medium is at least one selected from acetone, methyl ethyl ketone, toluene, ethyl acetate, butyl acetate, cyclohexanone, and the like.
7. The method according to claim 3, wherein the constant temperature in the step (2) is 70 to 72 ℃.
8. Use of the hydrophilic polyurethane modifier obtained by the process according to any one of claims 1 to 7, wherein the hydrophilic polyurethane modifier is used by adding to a two-component aqueous dispersion of polyisocyanate and/or aqueous polyurethane dispersion.
9. The use according to claim 8, wherein the two-component water dispersible polyisocyanate is used as follows: under the condition of constant temperature, the polyisocyanate and the hydrophilic modifier are mixed according to the molar ratio (20-80): 1, adding the mixture into a reaction vessel, adding an amino catalytic neutralizer, and heating for reaction until the solution becomes completely clear to obtain the water dispersible polyisocyanate.
10. The use according to claim 8, wherein the aqueous polyurethane dispersion is used in the following manner: adding polyether glycol, isocyanate and an organic tin catalyst into a reaction vessel, reacting at 70-75 ℃, dissolving butanediol and a hydrophilic modifier, adding into the reaction vessel, stirring uniformly, adding an amino catalytic neutralizer, heating for reaction, and adding water for dispersion to obtain the aqueous polyurethane dispersion.
CN202111499982.XA 2021-12-09 2021-12-09 Preparation method and use mode of polyurethane hydrophilic modifier Pending CN114605463A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101696262A (en) * 2009-10-23 2010-04-21 华南理工大学 Preparation method and application of modified polyurethane aqueous dispersions of polyisocyanate curing agents
CN104387890A (en) * 2014-11-28 2015-03-04 苏州伊埃夫化学材料科技有限公司 Modified polyurethane coating and preparation method thereof
JP2021017470A (en) * 2019-07-18 2021-02-15 東ソー株式会社 Self-emulsifiable polyisocyanate composition and coating composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101696262A (en) * 2009-10-23 2010-04-21 华南理工大学 Preparation method and application of modified polyurethane aqueous dispersions of polyisocyanate curing agents
CN104387890A (en) * 2014-11-28 2015-03-04 苏州伊埃夫化学材料科技有限公司 Modified polyurethane coating and preparation method thereof
JP2021017470A (en) * 2019-07-18 2021-02-15 東ソー株式会社 Self-emulsifiable polyisocyanate composition and coating composition

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