CN110724247A - Preparation method of cationic photocuring waterborne polyurethane emulsifier - Google Patents
Preparation method of cationic photocuring waterborne polyurethane emulsifier Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- 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
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
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- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- 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
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/65—Additives macromolecular
Abstract
The invention discloses a preparation method of a cationic photo-curing polyurethane emulsifier, which comprises the steps of firstly using dihydric alcohol as A2Monomers with trifunctional hydroxy monomers as B3Monomers or tetrafunctional hydroxy monomers as B4Monomer, dihydroxyamine as C2Monomers, diisocyanates as D2Preparing isocyanate end group prepolymer by monomer reaction, adopting' A2+B3+C2+D2”，“A2+B4+C2+D2"or" A2+C2+D2The isocyanate-terminated resin is prepared by the reaction principle, the hydroxyl acrylate monomer is utilized for blocking, and the neutralization agent is used for neutralizing to prepare the photo-curing polyurethane emulsifier. The cationic light-cured polyurethane emulsifier prepared by the invention has good emulsification effect, can emulsify commercial resin to prepare stable light-cured water-based emulsion, has wide selectable resin variety, adjustable performance, environmental protection and economy, and can be widely applied to leather, textile, coating, papermaking and other industries.
Description
Technical Field
The invention relates to a preparation method of a cationic photocuring waterborne polyurethane emulsifier, which utilizes' A2+B3+C2+D2”，“A2+B4+C2+D2"or" A2+C2+D2And then preparing the light-curable waterborne polyurethane emulsifier by utilizing a hydroxyl acrylate monomer end-capping reaction principle, belonging to a cross system of water-based curing and light-curing.
Background
UV ultraviolet curing has been rapidly developed in China from the last 80 th century because of its advantages of environmental protection, energy saving, low VOC emission, small volume, wide application range, etc. However, the viscosity of most of the photocuring prepolymers is high during spraying, so that it is not possible to use the prepolymers or reactive diluent monomers or even organic solvents must be added to adjust the viscosity of the system. However, these reactive diluent monomers and solvents not only have strong pungent odor but also are flammable, and also have strong irritation to parts of human organs and skin, and may cause damage to human body and environment during use. Therefore, the development of new solvent-free photo-curable sprayable coatings is receiving attention from researchers, and the combination of the advantages of the water-based coating and the photo-curable coating becomes a research hotspot.
Among the aqueous polyurethanes, anionic aqueous polyurethanes are most widely used due to their excellent properties of abrasion resistance, folding resistance, solvent resistance and low temperature resistance, and mainly introduce anionic groups into polyurethane segments so that they have sufficient hydrophilicity and are dispersed in aqueous solutions to form stable emulsions. However, the introduction of anionic groups into the segments has limitations when applied to leather, textile, paper and other industries. Mainly because such articles are usually treated with anionic retanning agents prior to finishing, and also carry a large number of-OH, -COOH, etc. groups themselves, which affect the performance of the product.
The cationic waterborne polyurethane can be widely applied to industries such as leather, textile, coating, papermaking and the like because the chain segment of the cationic waterborne polyurethane has cations. The related reports are as follows: patent CN 1749291 a: the emulsion is prepared by diisocyanate, flame-retardant polyol, non-flame-retardant polyol, compound which can form hydrophilic group and has active hydrogen, neutralizer, micromolecular chain extender and the like. Patent CN 101565494 utilizes oligomer diol, diisocyanate, cationic hydrophilic chain extender, etc. to prepare cationic polyurethane emulsion. Patent CN 105693988A utilizes hydroxylated tung oil containing three conjugated double bonds, N-methyldiethylamine, 4' -er cyclohexylmethane diisocyanate and other polyols to prepare cationic polyurethane emulsion. Patent CN 103497307A uses polyether diol, linear body of alkyl terminated polysiloxane and diisocyanate to prepare cationic polyurethane emulsion. However, the current relevant reports are all self-emulsifying cationic polyurethane emulsion, and there are only reports of external emulsifying type cationic polyurethane. And the cationic polyurethane emulsifier can emulsify other oil-based polyurethane, and has wider application prospect.
Disclosure of Invention
Aiming at the defects of the anionic waterborne polyurethane, the invention solves the technical problem of preparing the cationic photo-curing polyurethane emulsifier by combining the existing synthesis and emulsification processes of the anionic waterborne polyurethane. The light-cured water-based emulsion has a good emulsification effect, can emulsify commercial resin to prepare stable light-cured water-based emulsion, and has the advantages of wide selectable resin variety, adjustable performance, environmental protection and economy.
The invention relates to a preparation method of a cationic photocuring waterborne polyurethane emulsifier, which comprises the steps of firstly using dihydric alcohol as A2Monomers with trifunctional hydroxy monomers as B3Monomers or tetrafunctional hydroxy monomers as B4Monomer, dihydroxyamine as C2Monomers, diisocyanates as D2Preparing isocyanate end group prepolymer by monomer reaction, adopting' A2+B3+C2+D2”，“A2+B4+C2+D2"or" A2+C2+D2"preparation of isocyanate-terminated resin by reaction principle, utilizing hydroxyl groupAnd (3) end-capping the acrylate monomer, and neutralizing with a neutralizer to obtain the photocuring polyurethane emulsifier.
The method comprises the following steps:
(1) step one, mixing 0-10 parts of trifunctional hydroxyl monomer or tetrafunctional hydroxyl monomer, 40-60 parts of dihydric alcohol, 10-20 parts of dihydroxyamine, 0.01-0.05 part of catalyst and 10-20 parts of acetone, stirring for 20-40 min at the temperature of 30-60 ℃, slowly adding 50-80 parts of diisocyanate, and stirring and reacting for 1-3h at the temperature of 40-80 ℃ to obtain the isocyanate-terminated prepolymer.
(2) And step two, uniformly mixing 0.01-0.05 part of catalyst and acetone, slowly adding the mixture into the product obtained in the step one, stirring and reacting for 1-3 hours at the temperature of 40-80 ℃, and further reacting and chain extending.
(3) And step three, uniformly mixing 20-35 parts of hydroxyl acrylate monomer, 0.01-0.2 part of catalyst and 0.05-0.1 part of polymerization inhibitor, slowly adding the mixture into the product obtained in the step three, and stirring and reacting for 4-8 hours at the temperature of 60-80 ℃.
(4) And step four, adding 5-20 parts of neutralizing agent into the product obtained in the step three for neutralization, and stirring and reacting at the temperature of 50-70 ℃ for 20-60 min to obtain the photocuring polyurethane emulsifier.
The dihydric alcohol is one or a mixture of two of polyethylene glycol, polylactide dihydric alcohol, polypropylene glycol, polytetrahydrofuran dihydric alcohol, polycaprolactone dihydric alcohol, polycarbonate dihydric alcohol, polyhexamethylene glycol terephthalate, polyhexamethylene glycol adipate, 1, 4-butanediol and octanethylene glycol.
The dihydroxyamine is one or a mixture of N-methyldiethanolamine and diethylenetriamine.
The catalyst is one or a mixture of two of stannous octoate, dibutyl tin dilaurate and organic bismuth.
The diisocyanate is one of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate.
The trifunctional hydroxyl monomer is one of trihydroxypropane, trimethylolethane and glycerol.
The tetrafunctional hydroxyl monomer is one of pentaerythritol and bis (trimethylolpropane).
The hydroxyl acrylate monomer is one or a mixture of two of hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, pentaerythritol triacrylate and pentaerythritol diacrylate.
The polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone.
The neutralizer is one or a mixture of two of glacial acetic acid, formic acid and epoxy chloropropane.
The invention has the advantages of
(1) The prepared cationic photo-curing polyurethane emulsifier has good emulsifying effect.
(2) The method can emulsify commercial light-cured resin to prepare stable light-cured water-based emulsion, and has the advantages of wide range of selectable resin, adjustable performance, environmental protection and economy.
(3) When the emulsion is prepared, only water needs to be added for dispersion, and any diluting solvent is not needed.
(4) Compared with the same type of anionic waterborne photo-curing polyurethane coating, the coating has the characteristics of high hardness and good water resistance.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the present invention is not limited thereto.
Example 1
20.64g of N-methyldiethanolamine, 1.30g of pentaerythritol and 57.17g of polyethylene glycol are stirred at 45 ℃ until the pentaerythritol is completely dissolved, and 63.54g of isophorone diisocyanate and 15mL of acetone are slowly added dropwise. The reaction is carried out for 1h, and then the temperature is increased to 65 ℃ for 0.5 h.
And (3) uniformly mixing 0.5g of catalyst and 4ml of acetone, slowly adding the mixture into the product obtained in the step one, stirring and reacting at 70 ℃ for 1h, and heating to 70 ℃ to react for 0.5h to obtain the isocyanate-terminated resin.
8.85g of hydroxyethyl acrylate, 0.117g of hydroquinone, 1g of catalyst and 15ml of acetone are mixed uniformly, slowly added into the product obtained in the previous step, and stirred and reacted for 8 hours at 70 ℃.
And (3) cooling to 50 ℃, slowly adding 12.36g of glacial acetic acid into the product obtained in the last step, and reacting for 1h to obtain the photocuring polyurethane emulsifier.
Taking 20g of light-cured polyurethane emulsifier and 80g of commercial hexa-functional polyurethane according to the weight percentage, heating to 50 ℃, stirring for 15min, adding 100g of deionized water, increasing the rotating speed to 2500 rpm, and shearing at high speed for 20min to obtain the light-cured dispersoid which is milky white, contains 49.69% of solid, and is stable after being stored for 15 days at 60 ℃.
20g of the photo-curing dispersion prepared in the embodiment is taken, 0.12g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (Irgacure-1173) is added to be uniformly mixed, the mixture is coated on an ABS substrate, the ABS substrate is dried in an oven at 60 ℃ for 15min, a UV Best-120 UV curing machine of the blue and eye lamp company is used for curing for 15 seconds to obtain a cured film, the adhesive force is 0 grade, the hardness is 3H, the glossiness is 90.2, the coating is tested to be unchanged for 2H by a 5% NaOH solution, and the coating is tested to be 10% H2SO4The solution test showed no change for 2h, and the 75% ethanol solution test showed no change for 8h.
The branched cationic photocuring waterborne polyurethane emulsifier prepared by the embodiment has good emulsifying effect, and a stable photocuring dispersion can be prepared by only needing a small amount of emulsifier.
Example 2
46.04g of N-methyldiethanolamine, 2.55g of trimethylolethane and 127.51g of polyethylene glycol are stirred at 45 ℃ until the trimethylolethane is completely dissolved, and 113.37g of isophorone diisocyanate and 25mL of acetone are slowly added dropwise. The reaction is carried out for 1h, and then the temperature is increased to 60 ℃ for reaction for 0.5 h.
And (3) uniformly mixing 0.0175g of organic bismuth and 4ml of acetone, slowly adding the mixture into the product obtained in the step one, stirring and reacting at 60 ℃ for 1h, and heating to 70 ℃ for reacting for 0.5h to obtain the isocyanate-terminated resin.
24.43g of pentaerythritol triacrylate, 15.56g of hydroxyethyl acrylate, 0.273g of p-hydroxyanisole, 0.0175g of catalyst and 16ml of acetone are mixed uniformly, slowly added into the product obtained in the previous step, and stirred and reacted at 70 ℃ for 8 hours.
And (3) cooling to 50 ℃, slowly adding 27.56g of glacial acetic acid into the product obtained in the last step, and reacting for 1h to obtain the photocuring polyurethane emulsifier.
1. Taking 28g of light-cured polyurethane emulsifier and 72g of commercial hexa-functional polyurethane according to the weight percentage, heating to 50 ℃, stirring for 15min, adding 100g of deionized water, increasing the rotating speed to 2500 rpm, and shearing at high speed for 20min to obtain the light-cured dispersion which is milky white, contains 52.30% of solid, has the viscosity of 240mPa & s, and is stable when being stored for 30 days at 60 ℃.
20g of the photo-curing dispersion prepared in the embodiment is taken, 0.314g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (Irgacure-1173) is added to be uniformly mixed, the mixture is coated on an ABS substrate, the ABS substrate is dried in an oven at 60 ℃ for 15min, a UV Best-120 UV curing machine of the blue-eye lamp company is used for curing for 15 seconds to obtain a cured film, the adhesive force is 0 grade, the hardness is 5H, the glossiness is 90.5, the coating is boiled in water at 80 ℃ for 48 hours, and the flexibility is unchanged, the coating is not changed>7cm, 5% NaOH solution test 2H coating no change, 10% H2SO4The solution test showed no change in the coating for 2h, the 75% ethanol solution test showed no change in the coating for 8h, and the acetone swabs 200 times.
2. Taking 30g of light-cured polyurethane emulsifier and 70g of commercial difunctional polyurethane according to the weight percentage, heating to 50 ℃, stirring for 15min, adding 100g of deionized water, increasing the rotating speed to 2500 rpm, and shearing for 20min at high speed to obtain the light-cured dispersion which is milky white, has the solid content of 51.50 percent, has the viscosity of 267mPa & s, and is stable after being stored for 20 days at 60 ℃.
20g of the photo-curing dispersion prepared in the embodiment is taken, 0.306g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (Irgacure-1173) is added to be uniformly mixed, the mixture is coated on an ABS substrate, the ABS substrate is dried in an oven at 60 ℃ for 15min, a UV Best-120 UV curing machine of the blue-eye lamp company is used for curing for 15 seconds to obtain a cured film, the adhesive force is 0 grade, the hardness is 2H, the glossiness is 92.3, the coating is boiled in water at 80 ℃ for 48 hours, and the flexibility is unchanged, the coating is not changed>7cm, 5% NaOH solution test 2H coating no change, 10% H2SO4The solution test showed no change in the coating for 2h, the 75% ethanol solution test showed no change in the coating for 8h, and the acetone swabs 200 times. This example systemThe prepared branched cationic photocuring waterborne polyurethane emulsifier can emulsify different types of commercial polyurethane, has adjustable performance and can be used for preparing high-hardness photocuring dispersions.
Example 3
19.27g N-methyldiethanolamine and 53.38g polyethylene glycol were pre-stirred at 45 ℃ for 0.5h, and 46.48g toluene diisocyanate and 15mL acetone were slowly added dropwise. The reaction is carried out for 1h, and then the temperature is increased to 65 ℃ for 0.5 h.
And (3) uniformly mixing 0.0075g of organic bismuth and 4ml of acetone, slowly adding the mixture into the product obtained in the step one, stirring and reacting at 60 ℃ for 1h, and heating to 70 ℃ for reacting for 0.5h to obtain the isocyanate-terminated linear resin.
8.68g of hydroxyethyl acrylate, 0.09g of p-hydroxyanisole, 0.0075g of organic bismuth and 15ml of acetone are uniformly mixed, slowly added into the product obtained in the previous step, and stirred and reacted for 8 hours at 70 ℃.
And (3) cooling to 50 ℃, slowly adding 9.614g of glacial acetic acid into the product obtained in the last step, and reacting for 1h to obtain the linear-chain photo-curing polyurethane emulsifier.
Taking 50g of linear photo-curing polyurethane emulsifier and 50g of commercial hexa-functional polyurethane according to the weight percentage, heating to 50 ℃, stirring for 15min, adding 66.67g of deionized water, increasing the rotating speed to 2500 rpm, and shearing at high speed for 20min to obtain the photo-curing dispersion which is milk white, contains 62.98% of solid and has the viscosity of 545mPa & s, and is stable when being stored for 15 days at 50 ℃.
20g of the photo-curing dispersion prepared in the embodiment is taken, 0.372g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (Irgacure-1173) is added to be uniformly mixed, the mixture is coated on an ABS substrate, the ABS substrate is dried in an oven at 60 ℃ for 15min, a UV Best-120 UV curing machine of the blue and spatially lamp company is used for curing for 15 seconds to obtain a cured film, the adhesive force is 1 grade, the hardness is 3H, the coating does not change after 2 hours of testing by a 5% NaOH solution, and the coating is 10% H2SO4The solution test showed no change in the coating for 2h, the 75% ethanol solution test showed no change in the coating for 8h, and the acetone swabs 200 times.
The linear cationic photocuring waterborne polyurethane emulsifier prepared in the example can be used for preparing high-solid photocuring dispersions.
Example 4
16.95g of 16.95g N-methyldiethanolamine and 0.94g of trimethylolethane and 46.95g of polyethylene glycol are stirred beforehand at 45 ℃ until the trimethylolethane is completely dissolved, and 52.18g of isophorone diisocyanate and 15mL of acetone are slowly added dropwise. The reaction is carried out for 1h, and then the temperature is increased to 60 ℃ for reaction for 0.5 h.
And (3) uniformly mixing 1.375g of dibutyltin dilaurate with 4ml of acetone, slowly adding the mixture into the product obtained in the first step, stirring and reacting at 60 ℃ for 1h, and heating to 70 ℃ for reacting for 0.5h to obtain the isocyanate-terminated resin.
32.98g of pentaerythritol triacrylate, 0.28g of p-hydroxyanisole, 2.75g of catalyst and 16ml of acetone are mixed uniformly, slowly added into the product obtained in the previous step, and stirred at 70 ℃ for reaction for 8 hours.
And (3) cooling to 50 ℃, slowly adding 21.66g of glacial acetic acid into the product obtained in the last step, and reacting for 1h to obtain the photocuring polyurethane emulsifier.
1. Taking 25g of light-cured polyurethane emulsifier and 75g of commercial hexa-functional polyurethane according to the weight percentage, heating to 50 ℃, stirring for 15min, adding 92g of deionized water, increasing the rotating speed to 2500 rpm, and shearing for 20min at high speed to obtain the light-cured dispersion which is milky white, has the solid content of 52.91 percent and the viscosity of 278mPa & s, and is stable when being stored for 25 days at 60 ℃.
20g of the photo-curing dispersion prepared in the embodiment is taken, 0.31g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (Irgacure-1173) is added to be uniformly mixed, the mixture is coated on an ABS substrate, the ABS substrate is dried in an oven at 60 ℃ for 15min, a UV Best-120 UV curing machine of the blue-eye lamp company is used for curing for 15 seconds to obtain a cured film, the adhesive force is 0 grade, the hardness is 5H, the glossiness is 91.7, the coating is not changed after being boiled in water at 80 ℃ for 48 hours, the coating is not changed after being tested for 2 hours by a 5% NaOH solution, and the coating is not changed after being tested for 10% H2SO4The solution test showed no change in the coating for 2h, the 75% ethanol solution test showed no change in the coating for 8h, and the acetone swabs 200 times.
2. Taking 30g of light-cured polyurethane emulsifier and 70g of commercial hexa-functional polyurethane according to the weight percentage, heating to 50 ℃, stirring for 15min, adding 90g of deionized water, increasing the rotating speed to 2500 rpm, and shearing for 20min at high speed to obtain the light-cured dispersion which is milky white, contains 54.96% of solid, has the viscosity of 532mPa & s, and is stable when being stored for 90 days at 60 ℃.
20g of the photo-curing dispersion prepared in the embodiment is taken, 0.31g of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (Irgacure-1173) is added to be uniformly mixed, the mixture is coated on an ABS substrate, the ABS substrate is dried in an oven at 60 ℃ for 15min, a UV Best-120 UV curing machine of the blue-eye lamp company is used for curing for 15 seconds to obtain a cured film, the adhesive force is 0 grade, the hardness is 4H, the glossiness is 90.2, the coating is not changed after being boiled in water at 80 ℃ for 48 hours, the coating is not changed after being tested for 2 hours by a 5% NaOH solution, and the coating is not changed after being tested for 10% H2SO4Solution test 2h no change in coating, 75% ethanol solution test 8h no change in coating acetone wipe 200 times no change in coating.
The branched cationic photocuring waterborne polyurethane emulsifier prepared by the embodiment can adjust the performances of the emulsion and the coating by adjusting the ratio of the photocuring polyurethane emulsifier to the commercialized polyurethane.
Claims (10)
1. A preparation method of a cationic photocuring waterborne polyurethane emulsifier is characterized in that dihydric alcohol is firstly used as A2Monomers with trifunctional hydroxy monomers as B3Monomers or tetrafunctional hydroxy monomers as B4Monomer, dihydroxyamine as C2Monomers, diisocyanates as D2Preparing isocyanate end group prepolymer by monomer reaction, adopting A2、B3、C2、D2A mixed reaction, or A2、B4、C2、D2A mixed reaction, or A2、C2、D2The isocyanate-terminated resin is prepared by mixing reaction, the hydroxyl acrylate monomer is utilized for blocking, and hydrophilic ammonium ions are formed under the action of acid or alkylating reagent, so that the photo-curing polyurethane emulsifier is prepared.
2. The method of claim 1, comprising the steps of:
(1) mixing 0-10 parts of trifunctional hydroxyl monomer or tetrafunctional hydroxyl monomer, 40-60 parts of dihydric alcohol, 10-20 parts of dihydroxyamine, 0.01-0.05 part of catalyst and 10-20 parts of acetone, stirring at 30-60 ℃ for 20-40 min, slowly adding 50-80 parts of diisocyanate, and stirring at 40-80 ℃ for reaction for 1-3h to obtain an isocyanate end group prepolymer;
(2) step two, uniformly mixing 0.01-0.05 part of catalyst and acetone, slowly adding the mixture into the product obtained in the step one, stirring and reacting for 1-3 hours at the temperature of 40-80 ℃, and further reacting and chain extending;
(3) step three, uniformly mixing 20-35 parts of hydroxyl acrylate monomer, 0.01-0.2 part of catalyst and 0.05-0.1 part of polymerization inhibitor, slowly adding the mixture into the product obtained in the step three, and stirring and reacting for 4-8 hours at the temperature of 60-80 ℃;
(4) and step four, adding 5-20 parts of neutralizing agent into the product obtained in the step three for neutralization, and stirring and reacting at the temperature of 50-70 ℃ for 20-60 min to obtain the photocuring polyurethane emulsifier.
3. The method for preparing the cationic photo-curable aqueous polyurethane emulsifier according to claim 2, wherein the diol is one or a mixture of two of polyethylene glycol, polylactide diol, polypropylene glycol, polytetrahydrofuran diol, polycaprolactone diol, polycarbonate diol, polyhexamethylene terephthalate, polyhexamethylene adipate, 1, 4-butanediol, and octapentanediol.
4. The cationic photo-curable aqueous polyurethane emulsifier according to claim 2, wherein the dihydroxyamine is one or a mixture of N-methyldiethanolamine and diethylenetriamine.
5. The cationic photo-curable aqueous polyurethane emulsifier of claim 2, wherein the catalyst is one or a mixture of stannous octoate, dibutyl tin dilaurate and organic bismuth.
6. The method for preparing the cationic photocurable aqueous polyurethane emulsifier according to claim 2, wherein the diisocyanate is one of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate.
7. The method for preparing the cationic photo-curing waterborne polyurethane emulsifier according to claim 2, wherein the tri-functional hydroxyl monomer is one of trihydroxypropane, trimethylolethane and glycerol.
8. The method for preparing a cationic photo-curable aqueous polyurethane emulsifier according to claim 2, wherein the tetra-functional hydroxyl monomer is one of pentaerythritol and di (trimethylolpropane).
9. The method for preparing the cationic photo-curable aqueous polyurethane emulsifier according to claim 2, wherein the hydroxy acrylate monomer is one or a mixture of two of hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, pentaerythritol triacrylate and pentaerythritol diacrylate.
10. The method for preparing the cationic photo-curing waterborne polyurethane emulsifier according to claim 2, wherein the polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone, and the neutralizer is one of glacial acetic acid, formic acid and epichlorohydrin or a mixture of two of the glacial acetic acid, the formic acid and the epichlorohydrin.
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