CN117362588A - Controllably crosslinked waterborne polyurethane and synthetic method thereof - Google Patents

Controllably crosslinked waterborne polyurethane and synthetic method thereof Download PDF

Info

Publication number
CN117362588A
CN117362588A CN202311439898.8A CN202311439898A CN117362588A CN 117362588 A CN117362588 A CN 117362588A CN 202311439898 A CN202311439898 A CN 202311439898A CN 117362588 A CN117362588 A CN 117362588A
Authority
CN
China
Prior art keywords
diisocyanate
polyurethane
reaction
amount
acrylamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202311439898.8A
Other languages
Chinese (zh)
Inventor
张望清
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Borui Technology Co ltd
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202311439898.8A priority Critical patent/CN117362588A/en
Publication of CN117362588A publication Critical patent/CN117362588A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides controllable cross-linked waterborne polyurethane and a synthesis method thereof, and relates to the technical field of waterborne polyurethane synthesis. The polyurethane prepolymer of the invention contains isocyanate and acrylate groups (or acrylamide groups) at the same time, and the introduction of the acrylate groups (or acrylamide groups) has the following two beneficial effects: (1) The introduction of the acrylic ester group (or the acrylamide group) can reduce or avoid using a cross-linking agent such as triol and the like, thereby reducing the viscosity of the polyurethane prepolymer, reducing or avoiding using a diluent such as acetone and the like, and creating conditions for synthesizing the cross-linked waterborne polyurethane by an acetone-free method; (2) The introduction of the acrylic ester group (or the acrylamide group) respectively completes chain extension and crosslinking reaction through the addition reaction of the amine chain extender and isocyanate and the Michael addition reaction of the primary amine group in the amine chain extender and acrylic ester, so as to form the controllable crosslinked waterborne polyurethane, and improve the performance of the polyurethane.

Description

Controllably crosslinked waterborne polyurethane and synthetic method thereof
Technical Field
The invention relates to the technical field of waterborne polyurethane synthesis, in particular to a controllable crosslinked waterborne polyurethane and a synthesis method thereof.
Background
The aqueous polyurethane dispersoid or emulsion is commonly called aqueous polyurethane, is a high polymer material taking water as a dispersion medium, and has wide application in the industries of paint, printing ink, textile, leather, adhesive and the like. At present, one main production method of the waterborne polyurethane is to introduce hydrophilic groups such as carboxyl groups, tertiary amino groups or oligo (poly) glycol chain segments into polyurethane prepolymer containing isocyanate end groups, add proper amount of ketone to adjust the viscosity of the polyurethane prepolymer, then disperse the polyurethane prepolymer into water, then add chain extender containing amino groups to carry out chain extension of the polyurethane prepolymer, and finally decompress and distill to remove ketone to form anionic, cationic or nonionic waterborne polyurethane.
The water resistance of aqueous polyurethane is inferior to that of solution polyurethane. The common method for improving the water resistance of the waterborne polyurethane is to introduce multifunctional triol into the prepolymer or add trifunctional or multifunctional amine chain extender into the waterborne dispersion of the polyurethane prepolymer to synthesize the crosslinked waterborne polyurethane. The introduction of multifunctional triols into the prepolymer generally increases the viscosity of the polyurethane prepolymer, which causes inconvenience to production; the addition of trifunctional or multifunctional amine chain extenders to the aqueous dispersion of polyurethane prepolymers may result in increased particle size or decreased stability of the aqueous polyurethane.
Disclosure of Invention
The invention aims to provide the controllable cross-linked aqueous polyurethane and the synthesis method thereof, and the aqueous polyurethane synthesized by the method can reduce or avoid using the cross-linking agents such as triol and the like, so that the viscosity of polyurethane prepolymer is reduced, the use of the diluents such as acetone and the like is reduced or avoided, and conditions are created for synthesizing the cross-linked aqueous polyurethane by an acetone-free method, and the aqueous polyurethane has good stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a synthesis method of controllably crosslinked waterborne polyurethane, which comprises the following steps:
mixing polyether glycol, polyester glycol, dimethylol carboxylic acid, diisocyanate and an organic metal catalyst, performing a first prepolymerization reaction, adding acetone or not adding acetone into the obtained first prepolymerization reaction system, continuously performing a second prepolymerization reaction, adding hydroxy acrylic ester or hydroxy acrylamide and a polymerization inhibitor into the obtained second prepolymerization reaction system, and performing an addition polymerization reaction to obtain a polyurethane prepolymer;
adding a neutralizing agent into the polyurethane prepolymer for neutralization reaction, dispersing the neutralized polyurethane prepolymer into water, adding an aqueous solution of an amine chain extender containing primary amine groups into the obtained dispersion system, and simultaneously carrying out chain extension and crosslinking reaction.
Preferably, the molecular weight of the polyether glycol and the polyester glycol is 1000-2000 Da; the ratio of the total amount of hydroxyl groups in the polyether glycol and the polyester glycol to the amount of isocyanate groups in the diisocyanate is (0.1 to 0.3): 1, a step of;
the dimethylol carboxylic acid comprises dimethylol propionic acid and/or dimethylol butyric acid; the ratio of the amount of the hydroxyl group-containing substance in the dimethylol carboxylic acid to the amount of the isocyanate group-containing substance in the diisocyanate is (0.1 to 0.3): 1, a step of;
the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, ethylbenzene diisocyanate, methylcyclohexane diisocyanate and trimethylhexane diisocyanate;
the organic metal catalyst is an organic metal tin catalyst or an organic metal bismuth catalyst; the mass of the organic metal catalyst is 0.001-0.1% of the mass of diisocyanate.
Preferably, the temperature of the first prepolymerization reaction is 75-85 ℃ and the time is 1-4 hours;
the temperature of the second prepolymerization reaction is 75-85 ℃ and the time is 1-4 hours.
Preferably, the hydroxy acrylate comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, glycerol 1, 3-diglycerol alkyd diacrylate and glycerol diacrylate; the hydroxy acrylamide comprises one or more of N-hydroxyethyl acrylamide, N- (3-hydroxypropyl) acrylamide and N- (4-hydroxybutyl) acrylamide; the ratio of the amount of hydroxyl groups in the hydroxyacrylate or hydroxyacrylamide to the amount of isocyanate groups in the diisocyanate is (0.1-0.3): 1;
the polymerization inhibitor is one or more of hydroquinone, tert-butyl catechol and p-hydroxyanisole; the mass of the polymerization inhibitor is 0.1-1.5% of that of the hydroxy acrylic ester or hydroxy acrylamide.
Preferably, the temperature of the addition polymerization reaction is 75-85 ℃ and the time is 2-4 hours.
Preferably, the neutralizing agent is an amine compound; the amount of the neutralizing agent is 50-100% of the amount of the dimethylol carboxylic acid.
Preferably, the amine compound comprises triethylamine and/or triethanolamine.
Preferably, the amine chain extender containing primary amine groups comprises one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methylpentylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine and ethylenediamine sodium ethanesulfonate; the ratio of the amount of the primary amino group in the amine chain extender containing a primary amino group to the amount of the substance of the isocyanate group in the diisocyanate is (0.2 to 0.4): 1.
Preferably, the temperature of the chain extension and crosslinking reaction is room temperature and the time is 0.5-2 hours.
The invention provides the controllably crosslinked waterborne polyurethane synthesized by the synthesis method.
The invention provides a method for synthesizing controllable cross-linked waterborne polyurethane, which comprises the following two beneficial effects that isocyanate and acrylate groups (or acrylamide groups) are simultaneously contained in a prepolymer, and the introduction of the acrylate groups (or acrylamide groups) has the following two aspects: (1) The introduction of the acrylic ester group (or the acrylamide group) can reduce or avoid using a cross-linking agent such as triol, thereby reducing the viscosity of the polyurethane prepolymer, reducing or avoiding using a diluent such as acetone, and creating conditions for synthesizing the cross-linked waterborne polyurethane by an acetone-free method. (2) The introduction of the acrylic ester group (or the acrylamide group) respectively completes chain extension and crosslinking reaction through the addition reaction of the amine chain extender and isocyanate and the Michael addition reaction of the primary amine group in the amine chain extender and acrylic ester, so as to form the controllable crosslinked waterborne polyurethane, and improve the performance of the polyurethane.
In particular, isocyanate groups have a feature of reacting with water or amines to form urea. Unlike the characteristic of isocyanate groups being reactive with water and amines, acrylate or acrylamide groups are generally not reactive with water but are capable of undergoing michael addition reactions with primary amines, which are very fast. Therefore, if acrylate or acrylamide groups are introduced into the polyurethane prepolymer by the reaction of hydroxyacrylate and isocyanate, the crosslinking reaction does not occur even under the condition that a plurality of acrylate or acrylamide groups exist in the molecular chain of the polyurethane prepolymer, so that the viscosity of the prepolymer can be kept low, the consumption of the diluent can be reduced, and the prepolymer can be rapidly dispersed in water. When the amine chain extender is added into the prepolymer, primary amine and secondary amine groups of the amine chain extender can be subjected to addition reaction with isocyanate, and only primary amine groups in the amine chain extender can be subjected to Michael addition reaction with acrylic ester, so that chain extension and crosslinking reaction of the polyurethane prepolymer are completed, and the controllably crosslinked waterborne polyurethane is formed. The method for synthesizing the crosslinked aqueous polyurethane can keep low prepolymer viscosity, so that the solvent-free method for producing the aqueous polyurethane (i.e. acetone is not added) can be realized. In addition, due to the cross-linked structure of the polyurethane, the water-based polyurethane can keep better water resistance and solvent resistance, and has good application prospect in the aspects of paint, ink and leather.
Detailed Description
The invention provides a synthesis method of controllably crosslinked waterborne polyurethane, which comprises the following steps: mixing polyether glycol, polyester glycol, dimethylol carboxylic acid, diisocyanate and an organic metal catalyst, performing a first prepolymerization reaction, adding acetone or not adding acetone into the obtained first prepolymerization reaction system, continuously performing a second prepolymerization reaction, adding hydroxy acrylic ester or hydroxy acrylamide and a polymerization inhibitor into the obtained second prepolymerization reaction system, and performing an addition polymerization reaction to obtain a polyurethane prepolymer;
adding a neutralizing agent into the polyurethane prepolymer for neutralization reaction, dispersing the neutralized polyurethane prepolymer into water, adding an aqueous solution of an amine chain extender containing primary amine groups into the obtained dispersion system, and simultaneously carrying out chain extension and crosslinking reaction.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
Polyether glycol, polyester glycol, dimethylol carboxylic acid, diisocyanate and organic metal catalyst are mixed for a first prepolymerization reaction.
The invention has no special requirements on the types of the polyether glycol and the polyester glycol, and the polyether glycol and the polyester glycol which are well known in the field can be used. In the invention, the molecular weight of the polyether glycol and the polyester glycol is preferably 1000-2000 Da; the ratio of the total amount of hydroxyl groups in the polyether diol and the polyester diol to the amount of isocyanate groups in the diisocyanate is preferably (0.1 to 0.3): 1, more preferably (0.15 to 0.25): 1, more preferably 0.2:1.
In the present invention, the dimethylol carboxylic acid preferably includes dimethylol propionic acid and/or dimethylol butyric acid; the ratio of the amount of the substance of hydroxyl group in the dimethylol carboxylic acid to the amount of the substance of isocyanate group in the diisocyanate is preferably (0.1 to 0.3): 1, more preferably (0.15 to 0.25): 1, more preferably 0.2:1.
In the present invention, the diisocyanate is preferably one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, ethylbenzene diisocyanate, methylcyclohexane diisocyanate, and trimethylhexane diisocyanate.
In the present invention, the organometallic catalyst is preferably an organometallic tin catalyst or an organometallic bismuth catalyst; the mass of the organometallic catalyst is preferably 0.001 to 0.1%, more preferably 0.01 to 0.09%, and even more preferably 0.02 to 0.07% of the mass of the diisocyanate.
In the present invention, the temperature of the first prepolymerization is preferably 75 to 85 ℃, more preferably 78 to 82 ℃; the time of the first prepolymerization is preferably 1 to 4 hours, more preferably 2 to 3 hours.
In the invention, after the first prepolymerization reaction is completed, acetone or no acetone is added into the obtained first prepolymerization reaction system, and the second prepolymerization reaction is continued. The person skilled in the art preferably selects the addition of acetone or the absence of acetone according to the circumstances. In the invention, acetone is added for the purpose of reducing the viscosity to a proper range and ensuring that the subsequent reaction is carried out smoothly.
In the present invention, the temperature of the second prepolymerization is preferably 75 to 85 ℃, more preferably 78 to 82 ℃; the time of the second prepolymerization is preferably 1 to 4 hours, more preferably 2 to 3 hours.
In the invention, after the second prepolymerization reaction is completed, hydroxy acrylic ester or hydroxy acrylamide and a polymerization inhibitor are added into the obtained second prepolymerization reaction system to carry out addition polymerization reaction, thus obtaining polyurethane prepolymer.
In the present invention, the hydroxyacrylate preferably includes one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, glycerol 1, 3-diglycerol alkyd diacrylate and glycerol diacrylate; the hydroxyacrylamide preferably comprises one or more of N-hydroxyethyl acrylamide, N- (3-hydroxypropyl) acrylamide and N- (4-hydroxybutyl) acrylamide; the ratio of the amount of hydroxyl groups in the hydroxyacrylate or hydroxyacrylamide to the amount of isocyanate groups in the diisocyanate is preferably (0.1 to 0.3): 1, more preferably (0.15 to 0.25): 1, more preferably 0.2:1.
In the present invention, the polymerization inhibitor is preferably one or more of hydroquinone, tert-butylcatechol and p-hydroxyanisole; the mass of the polymerization inhibitor is preferably 0.1 to 1.5%, more preferably 0.3 to 1.2%, and even more preferably 0.5 to 1.0% of the mass of the hydroxyacrylate or hydroxyacrylamide.
In the present invention, the temperature of the addition polymerization reaction is preferably 75 to 85 ℃, more preferably 78 to 82 ℃; the polymerization time is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours.
After completion of the addition polymerization, the present invention is preferably cooled to room temperature to obtain a polyurethane prepolymer.
After the polyurethane prepolymer is obtained, a neutralizing agent is added into the polyurethane prepolymer to carry out a neutralization reaction.
In the present invention, the neutralizing agent is preferably an amine compound; the amine compound preferably comprises triethylamine and/or triethanolamine. In the present invention, the amount of the neutralizing agent is preferably 50 to 100%, more preferably 60 to 90%, and still more preferably 70 to 80% of the amount of the dimethylol carboxylic acid. In the present invention, the neutralization reaction is preferably carried out under stirring, and the stirring time is preferably 1 to 10 minutes.
After the neutralization reaction is completed, the polyurethane prepolymer after neutralization is dispersed into water to obtain a dispersion system.
In the present invention, the water is preferably used in an amount such that the solid content of the aqueous polyurethane is 30 to 40%. In the present invention, the temperature of the water is preferably 2 to 10 ℃. In the present invention, the dispersion is preferably performed under stirring for a period of 1 to 5 minutes.
After the dispersion system is obtained, the invention adds an amine chain extender aqueous solution containing primary amine groups into the obtained dispersion system, and simultaneously carries out chain extension and crosslinking reaction.
In the present invention, the amine chain extender containing a primary amine group preferably includes one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methylpentylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine and ethylenediamine sodium ethanesulfonate; the ratio of the amount of primary amino groups in the amine chain extender containing primary amino groups to the amount of isocyanate groups in the diisocyanate is preferably (0.2 to 0.4): 1, more preferably (0.25 to 0.35): 1, more preferably 0.3:1. In the present invention, the mass concentration of the aqueous amine chain extender solution containing a primary amine group is preferably 50%.
In the invention, the aqueous solution of the amine chain extender containing the primary amine group is preferably added under stirring, and the adding mode is preferably dropwise adding; the time for the dropping is preferably 1 to 5 minutes.
In the present invention, the temperature of the chain extension and crosslinking reaction is preferably room temperature, and the time is preferably 0.5 to 2 hours, more preferably 1 to 1.5 hours. In the invention, the introduction of the acrylic ester group (or the acrylamide group) respectively completes chain extension and crosslinking reaction through the addition reaction of the amine chain extender and isocyanate and the Michael addition reaction of the primary amine group in the amine chain extender and acrylic ester, so as to form the controllably crosslinked waterborne polyurethane.
In the invention, when acetone is added into the prepolymer, acetone is removed after the chain extension and crosslinking reaction is completed, and the controllably crosslinked aqueous polyurethane is obtained.
The method for removing the acetone is not particularly required, and the method for removing the acetone is well known in the art, such as distillation.
The invention provides the controllably crosslinked waterborne polyurethane synthesized by the synthesis method. The method for synthesizing the crosslinked aqueous polyurethane can keep low prepolymer viscosity, so that the solvent-free method for producing the aqueous polyurethane (i.e. acetone is not added) can be realized. In addition, due to the cross-linked structure of the polyurethane, the water-based polyurethane can keep better water resistance and solvent resistance, and has good application prospect in the aspects of paint, ink and leather.
The controllably crosslinked aqueous polyurethane and the method of synthesizing the same provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
4000 g of dry polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong Da), 200 g of polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da) and 134 g of dimethylolpropionic acid, 1112 g of isophorone diisocyanate and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 1.5 hours, 600 g of acetone is added, the reaction is continued for 2 hours, 116 g of hydroxyethyl acrylate, 298 g of pentaerythritol triacrylate and 0.5 g of p-hydroxyanisole are added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
To the polyurethane prepolymer, 80 g of triethylamine was added, followed by stirring for 5 minutes, 10760 g of pure water at 2 to 10℃and stirring at high speed for 3 minutes, while stirring, 240 g of an aqueous solution of ethylenediamine with a mass concentration of 50% was added dropwise over 2 minutes, stirring was carried out for 1 hour, and acetone was removed under reduced pressure to obtain an aqueous crosslinked polyurethane dispersion.
Example 2
4000 g of dry polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong Da), 200 g of polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da) and 871 g of toluene diisocyanate, 134 g of dimethylolpropionic acid and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 1.5 hours, 600 g of acetone is added, the reaction is continued for 2 hours, 116 g of hydroxyethyl acrylate, 298 g of pentaerythritol triacrylate and 0.5 g of p-hydroxyanisole are added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
To the polyurethane prepolymer, 80 g of triethylamine was added, followed by stirring for 5 minutes, 10315 g of pure water at 2 to 10℃was added, followed by stirring at high speed for 3 minutes, and under stirring, 240 g of an aqueous solution of ethylenediamine having a mass concentration of 50% was added dropwise over 2 minutes, followed by stirring for 1 hour, followed by removal of acetone under reduced pressure to obtain an aqueous crosslinked polyurethane dispersion.
Example 3
Dried polyester diol (PE-5566, molecular weight 2000Da, hua Fengji group) 2000 g, polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong Da) 2000 g, polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da) 200 g, isophorone diisocyanate 1112 g, dimethylol propionic acid 134 g and bismuth catalyst (MC-710, beijing Bai Yuan chemical) 0.50 g are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for 1.5 hours, acetone 600 g is added, the reaction is continued for 2 hours, hydroxyethyl acrylate 116 g, pentaerythritol triacrylate 298 g and p-hydroxyanisole 0.5 g are added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining polyurethane prepolymer.
To the polyurethane prepolymer, 80 g of triethylamine was added, followed by stirring for 5 minutes, 10760 g of pure water at 2 to 10℃and stirring at high speed for 3 minutes, while stirring, 240 g of an aqueous solution of ethylenediamine with a mass concentration of 50% was added dropwise over 2 minutes, stirring was carried out for 1 hour, and acetone was removed under reduced pressure to obtain an aqueous crosslinked polyurethane dispersion.
Example 4
Dried polycarbonate diol (AS-302, molecular weight 2000Da, asahi formation) 2000 g, polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong Da) 2000 g, polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da) 200 g, isophorone diisocyanate 1112 g, dimethylol propionic acid 134 g and 0.50 g dibutyl tin dilaurate were added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction 1.5 hours, acetone 600 g was added, the reaction was continued for 2 hours, hydroxyethyl acrylate 116 g, pentaerythritol triacrylate 298 g and 0.5 g p-hydroxyanisole were added, the reaction was continued for 3 hours, and the temperature was lowered to room temperature to obtain a polyurethane prepolymer.
To the polyurethane prepolymer, 80 g of triethylamine was added, followed by stirring for 5 minutes, 10760 g of pure water at 2 to 10℃and stirring at high speed for 3 minutes, while stirring, 240 g of an aqueous solution of ethylenediamine with a mass concentration of 50% was added dropwise over 2 minutes, stirring was carried out for 1 hour, and acetone was removed under reduced pressure to obtain an aqueous crosslinked polyurethane dispersion.
Example 5
4000 g of dry polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong Da), 200 g of polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da) and 1112 g of isophorone diisocyanate, 134 g of dimethylol propionic acid and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical industry) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 1.5 hours, 600 g of acetone is added, the reaction is continued for 2 hours, 232 g of hydroxyethyl acrylate and 0.5 g of p-hydroxyanisole are added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
80 g of triethylamine is added into the polyurethane prepolymer, stirring is carried out for 5 minutes, 10645 g of pure water at 2-10 ℃ is added, high-speed stirring is carried out for 3 minutes, under the stirring condition, 240 g of ethylenediamine water solution with the mass concentration of 50% is added dropwise in 2 minutes, stirring is carried out for 1 hour, acetone is removed under reduced pressure, and the aqueous cross-linked polyurethane dispersion is obtained.
Example 6
4000 g of dry polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong Da), 200 g of polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da) and 1112 g of isophorone diisocyanate, 134 g of dimethylol propionic acid and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical industry) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 3.5 hours, 232 g of hydroxyethyl acrylate and 0.5 g of p-hydroxyanisole are added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
To the above polyurethane prepolymer, 80 g of triethylamine was added, stirred for 5 minutes, 10645 g of pure water at 2 to 10℃was added, stirred at high speed for 4 minutes, and under stirring, 240 g of an aqueous solution of ethylenediamine with a mass concentration of 50% was added dropwise over 2 minutes, and stirred for 1 hour to obtain an aqueous crosslinked polyurethane dispersion.
Example 7
4000 g of dry polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong Da), 200 g of polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da) and 1112 g of isophorone diisocyanate, 134 g of dimethylol propionic acid and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical industry) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 3.5 hours, 232 g of hydroxyethyl acrylate and 0.5 g of p-hydroxyanisole are added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
80 g of triethylamine is added into the polyurethane prepolymer, the mixture is stirred for 5 minutes, 10720 g of pure water at a temperature of 2-10 ℃ is added, the mixture is stirred at a high speed for 4 minutes, and under the stirring condition, 352 g of 1, 4-butanediamine aqueous solution with a mass concentration of 50% is dropwise added within 2 minutes, and the mixture is stirred for 1 hour, so that the water-based crosslinked polyurethane is obtained.
Comparative example 1
4000 g of dry polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong Da), 200 g of polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da), 134 g of dimethylolpropionic acid, 1112 g of isophorone diisocyanate and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 1.5 hours, 600 g of acetone is added, the reaction is continued for 3 hours, and the temperature is reduced to room temperature, thus obtaining the polyurethane prepolymer.
80 g of triethylamine is added into the polyurethane prepolymer, stirring is carried out for 5 minutes, 10210 g of pure water with the temperature of 2-10 ℃ is added, high-speed stirring is carried out for 3 minutes, under the stirring condition, 228 g of ethylenediamine water solution with the mass concentration of 50% is dropwise added in 2 minutes, stirring is carried out for 1 hour, acetone is removed under reduced pressure, and thus the waterborne polyurethane is obtained.
Comparative example 2
4000 g of dry polypropylene glycol (DL 2000, molecular weight 2000Da, blue star Dong Da), 200 g of polyethylene glycol (PEG 2000, molecular weight 2000Da, shanghai Dong Da), 134 g of dimethylolpropionic acid, 1112 g of isophorone diisocyanate and 0.50 g of bismuth catalyst (MC-710, beijing Bai Yuan chemical industry) are added into a reaction kettle, stirred uniformly, heated to 75 ℃ for reaction for 4.5 hours, and cooled to room temperature to obtain a polyurethane prepolymer.
To the polyurethane prepolymer, 80 g of triethylamine was added, followed by stirring for 5 minutes, 10210 g of pure water at 2 to 10℃was added, followed by stirring at high speed for 5 minutes, and under stirring, 228 g of an aqueous solution of ethylenediamine with a mass concentration of 50% was added dropwise over 2 minutes, followed by stirring for 1 hour, to obtain an aqueous polyurethane.
Aqueous polyurethane parameters and results analysis
The basic parameters of the aqueous polyurethanes prepared in examples 1 to 7 and comparative examples 1 to 2 are shown in Table 1.
Among them, the polyester diol and the polyether diol used in examples 1 to 4 are different, and the diisocyanate is also different, but the viscosity of the polyurethane prepolymer is adjusted by the acetone method. Example 5 and example 6 are identical for all materials except that example 5 uses acetone to adjust the prepolymer viscosity and example 6 does not add acetone to adjust the viscosity. Example 7 viscosity was adjusted without the addition of acetone. Comparative examples 1 and 2 were not blocked with hydroxyacrylate, comparative example 1 was used to adjust the viscosity of polyurethane prepolymer using acetone, and comparative example 2 was not used to adjust the viscosity with acetone.
Wherein, appearance, solid content, viscosity, freeze thawing stability and centrifugal stability are tested with reference to GB/T11175-2002; viscosity testing instrument: brookfield viscometer DV1, method of measurement: direct testing at 25 ℃. Volatile organics: the test was performed with reference to GB/T23986-2009. Freeze thawing stability: taking 50mL of aqueous polyurethane, putting in a low-temperature box at-5+/-2 ℃, taking out after 18 hours, standing for 6 hours at the temperature of 23+/-2 ℃, and repeatedly operating to observe whether sediment exists or not. Centrifugal stability: 30mL of aqueous polyurethane is taken in a centrifuge, and the centrifugal stability of the aqueous polyurethane is tested under the conditions of 3000r/min and 30 min.
Table 1 waterborne polyurethane parameters
The results in Table 1 show that the aqueous polyurethanes prepared in examples 1 to 7 and comparative example 1 are all water-white and have good stability. The emulsion of comparative example 2 was white in color, indicating that the emulsion had a larger particle size and slightly less stability. This demonstrates that by the acetone method, both in examples and comparative examples, aqueous polyurethanes with good stability can be obtained, but the removal of the acetone (0.1%) is difficult with a small amount, and the aqueous polyurethane has a slight acetone taste. By the acetone-free method, examples 6 to 7 can give stable aqueous polyurethanes, whereas the aqueous polyurethane obtained in comparative example 2 is slightly inferior in stability. This shows that the use of the examples provides a method for synthesizing aqueous polyurethane without acetone.
Aqueous polyurethane dry film parameters and results analysis
The basic parameters of the aqueous polyurethane dry films prepared in examples 1 to 7 and comparative examples 1 to 2 are shown in Table 2. Wherein, 100% modulus: placing a certain amount of aqueous polyurethane in a polytetrafluoroethylene mould, placing for 1-2 days, naturally drying, then drying the polyurethane film in a vacuum drying oven at 25 ℃ for 2 days, measuring 100% modulus, elongation at break and glossiness of the polyurethane film, wherein the 100% tensile modulus (the proportionality constant of stress to strain ratio when the polyurethane film is stretched to 100% of the original length) of the polyurethane film is measured by a tensile testing machine (Shanghai Songton, WDW-5), and the glossiness using and microscopic three-component glossiness meter (CS-380) are respectively tested at an incident angle of 60; alcohol resistance test conditions: 339 type rubber alcohol friction resistance tester, solvent is 75% ethanol water solution, and weight 200 g.
Table 2 performance parameters of waterborne polyurethane Dry films
The results in Table 2 show that the dry films prepared in examples 1-7 and comparative examples 1-2 are clear and have similar gloss. The dry film of the embodiment has a cross-linked structure, so that the 100% modulus is improved, the elongation at break is reduced, and the alcohol resistance is obviously improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The synthesis method of the controllably crosslinked waterborne polyurethane is characterized by comprising the following steps of:
mixing polyether glycol, polyester glycol, dimethylol carboxylic acid, diisocyanate and an organic metal catalyst, performing a first prepolymerization reaction, adding acetone or not adding acetone into the obtained first prepolymerization reaction system, continuously performing a second prepolymerization reaction, adding hydroxy acrylic ester or hydroxy acrylamide and a polymerization inhibitor into the obtained second prepolymerization reaction system, and performing an addition polymerization reaction to obtain a polyurethane prepolymer;
adding a neutralizing agent into the polyurethane prepolymer for neutralization reaction, dispersing the neutralized polyurethane prepolymer into water, adding an aqueous solution of an amine chain extender containing primary amine groups into the obtained dispersion system, and simultaneously carrying out chain extension and crosslinking reaction.
2. The method of claim 1, wherein the polyether glycol and the polyester glycol each have a molecular weight of 1000 to 2000Da; the ratio of the total amount of hydroxyl groups in the polyether glycol and the polyester glycol to the amount of isocyanate groups in the diisocyanate is (0.1 to 0.3): 1, a step of;
the dimethylol carboxylic acid comprises dimethylol propionic acid and/or dimethylol butyric acid; the ratio of the amount of the hydroxyl group-containing substance in the dimethylol carboxylic acid to the amount of the isocyanate group-containing substance in the diisocyanate is (0.1 to 0.3): 1, a step of;
the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, ethylbenzene diisocyanate, methylcyclohexane diisocyanate and trimethylhexane diisocyanate;
the organic metal catalyst is an organic metal tin catalyst or an organic metal bismuth catalyst; the mass of the organic metal catalyst is 0.001-0.1% of the mass of diisocyanate.
3. The synthetic method according to claim 1 or 2, wherein the temperature of the first prepolymerization is 75 to 85 ℃ for 1 to 4 hours;
the temperature of the second prepolymerization reaction is 75-85 ℃ and the time is 1-4 hours.
4. The method of synthesis according to claim 1, wherein the hydroxy acrylate comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, glycerol 1, 3-diglycerol alkyd diacrylate and glycerol diacrylate; the hydroxy acrylamide comprises one or more of N-hydroxyethyl acrylamide, N- (3-hydroxypropyl) acrylamide and N- (4-hydroxybutyl) acrylamide; the ratio of the amount of hydroxyl groups in the hydroxyacrylate or hydroxyacrylamide to the amount of isocyanate groups in the diisocyanate is (0.1-0.3): 1;
the polymerization inhibitor is one or more of hydroquinone, tert-butyl catechol and p-hydroxyanisole; the mass of the polymerization inhibitor is 0.1-1.5% of that of the hydroxy acrylic ester or hydroxy acrylamide.
5. The synthetic method according to claim 1 or 4, wherein the temperature of the addition polymerization reaction is 75 to 85 ℃ for 2 to 4 hours.
6. The synthetic method of claim 1, wherein the neutralizing agent is an amine compound; the amount of the neutralizing agent is 50-100% of the amount of the dimethylol carboxylic acid.
7. The method of synthesis according to claim 6, wherein the amine compounds comprise triethylamine and/or triethanolamine.
8. The method of synthesis according to claim 1, wherein the amine chain extender containing primary amine groups comprises one or more of ethylenediamine, propylenediamine, butylenediamine, 2-methylpentanediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine and sodium ethylenediamine ethanesulfonate; the ratio of the amount of the primary amino group in the amine chain extender containing a primary amino group to the amount of the substance of the isocyanate group in the diisocyanate is (0.2 to 0.4): 1.
9. The method according to claim 1 or 8, wherein the chain extension and crosslinking reaction is carried out at room temperature for 0.5 to 2 hours.
10. A controllably crosslinked aqueous polyurethane synthesized by the synthesis method of any one of claims 1 to 9.
CN202311439898.8A 2023-11-01 2023-11-01 Controllably crosslinked waterborne polyurethane and synthetic method thereof Pending CN117362588A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311439898.8A CN117362588A (en) 2023-11-01 2023-11-01 Controllably crosslinked waterborne polyurethane and synthetic method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311439898.8A CN117362588A (en) 2023-11-01 2023-11-01 Controllably crosslinked waterborne polyurethane and synthetic method thereof

Publications (1)

Publication Number Publication Date
CN117362588A true CN117362588A (en) 2024-01-09

Family

ID=89396376

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311439898.8A Pending CN117362588A (en) 2023-11-01 2023-11-01 Controllably crosslinked waterborne polyurethane and synthetic method thereof

Country Status (1)

Country Link
CN (1) CN117362588A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117757415A (en) * 2024-02-22 2024-03-26 上海蒂姆新材料科技有限公司 water-based polyurethane adhesive for automobile cladding and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117757415A (en) * 2024-02-22 2024-03-26 上海蒂姆新材料科技有限公司 water-based polyurethane adhesive for automobile cladding and preparation method and application thereof
CN117757415B (en) * 2024-02-22 2024-05-28 上海蒂姆新材料科技有限公司 Water-based polyurethane adhesive for automobile cladding and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN111793188B (en) Hydroxyl-containing self-extinction waterborne polyurethane and self-extinction coating composed of same
CN112048051B (en) Polyurethane acrylate resin and preparation method thereof
CN117362588A (en) Controllably crosslinked waterborne polyurethane and synthetic method thereof
CN111333808A (en) Preparation method of solvent-free waterborne polyurethane
CN107254251A (en) A kind of aqueous UV urethane acrylate dispersoids with self-initiating function and preparation method thereof
CN107903372A (en) A kind of UV photocurings flexibility ultra-branched polyurethane acrylate resin and preparation method and application
CN108264621B (en) Heterogeneous chain extension synthesis method for waterborne polyurethane
CN109880060B (en) Dendritic waterborne polyurethane-based high-molecular dye and preparation method thereof
CN106700021A (en) Chitosan modified cationic waterborne polyurethane resin and preparation method and application thereof
WO2022001690A1 (en) Polyurethane resin for terylene figured sea-island superfine fiber, and preparation method therefor
CN101096475A (en) Preparation method of polyurethane thickening agent
CN105669940B (en) Colored chain extender, copoly type colorful polyurethane emulsion and colour polyurethane-acrylate copolymer emulsion and preparation method thereof
CN107325246B (en) Modified polyurethane oligomer, preparation method thereof and application thereof in photocuring digital ink-jet printing
CN110606928B (en) Synthetic method of carbazole-based fluorescent waterborne polyurethane
CN113121773A (en) Sulfonic acid type solvent-free aqueous polyurethane resin and preparation method thereof
CN109337034A (en) A kind of polyaminoester emulsion and its synthetic method of composite multiple cross-linking system
CN110358046A (en) A kind of heatproof transfer coatings aqueous polyurethane emulsion of good film-forming property and preparation method thereof
CN114933690A (en) Method for preparing stain-resistant ultraviolet curing resin by utilizing core-shell structure
CN114133851A (en) Organosilicon modified hydroxyl polyacrylate dispersion and preparation method and application thereof
CN117430534A (en) Sulfamate chain extender, preparation method and application thereof, and preparation method of waterborne polyurethane
CN114213622A (en) Preparation method of modified urethane acrylate photocureable resin
CN110669196A (en) Waterborne polyurethane and method for preparing transfer agent by using same and application of waterborne polyurethane
CN113501927A (en) Colored waterborne polyurethane and preparation method thereof
CN117510772A (en) Comb-shaped water-based polyurethane with temperature-sensitive effect, preparation method and application thereof, water-based ink and preparation method thereof
CN117304444B (en) Water-based polyurethane and preparation method thereof, and water-based scratch-off ink and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20240119

Address after: 518101 Tea Tree Commercial Building B, Building 407, Sanwei Inner Ring Road, Sanwei Community, Hangcheng Street, Bao'an District, Shenzhen City, Guangdong Province

Applicant after: Shenzhen Borui Technology Co.,Ltd.

Address before: 300071 Weijin Road, Nankai District, Tianjin Nankai University North Village 12-2-304

Applicant before: Zhang Wangqing