CN115558060A - Polyurethane acrylate adhesive and preparation method thereof - Google Patents
Polyurethane acrylate adhesive and preparation method thereof Download PDFInfo
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- CN115558060A CN115558060A CN202211164181.2A CN202211164181A CN115558060A CN 115558060 A CN115558060 A CN 115558060A CN 202211164181 A CN202211164181 A CN 202211164181A CN 115558060 A CN115558060 A CN 115558060A
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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Abstract
The invention belongs to the field of adhesives, and particularly relates to a polyurethane acrylate adhesive and a preparation method thereof, wherein the adhesive takes polyurethane as a main chain and grafts copolymerization modified acrylate, and the adhesive contains a hydrophilic monomer DMPA, a functional monomer HEMA and a modified organosilicon unit, and the modified organosilicon unit is formed by introducing a silicon side chain on a carbon chain to form a graft, block or interpenetrating network system; and provides a specific preparation method. The invention solves the defects of the existing polyurethane adhesive and acrylate adhesive, modifies the acrylate emulsion polymer by utilizing the excellent performance of the waterborne polyurethane, and the obtained emulsion has excellent printing performance, thereby not only effectively reducing the production cost of the adhesive, but also simultaneously combining the performances of the two adhesives, and having great value for the research of the adhesives.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a polyurethane acrylate adhesive and a preparation method thereof.
Background
Pigment printing is a process of imparting color and texture to fibers by adhering pigment particles, which have no affinity or reactivity with the fibers, to the fiber surfaces with a binder. At present, the pigment printing adhesives commonly used in China are various, including: polyacrylate type adhesives, polyurethane type adhesives, butadiene type adhesives, vinyl acetate type adhesives, and the like. The waterborne polyurethane has good flexibility and low temperature resistance. Strong adhesion and the like, but the water-based polyurethane adhesive is slow to dry and poor in wettability in the using process. If the coating is suddenly dried by heating while moisture remains in the coating during use, the resultant film has poor crosslinkability. When the waterborne polyurethane is used for the fabric, the fabric can be endowed with excellent wear resistance, rebound resilience, antistatic property, washing resistance, plumpness, smoothness, moisture permeability and the like, but the fabric has hard hand feeling, and the cost of the waterborne polyurethane as the adhesive is higher. The acrylate adhesive has received great attention due to its many advantages, such as high adhesion, fast curing speed, wide adaptability, excellent mechanical properties and no selectivity to the adhesion object, but many defects are also revealed, such as sticky adhesive film, poor water resistance and temperature resistance, poor moisture permeability and air permeability, poor low temperature film forming property, poor anti-tack property at high temperature, and relatively low elongation.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a polyurethane acrylate adhesive, which overcomes the defects of the existing polyurethane adhesive and acrylate adhesive, utilizes the excellent performance of waterborne polyurethane to modify an acrylate emulsion polymer, and the obtained emulsion has excellent printing performance, thereby not only effectively reducing the production cost of the adhesive, but also simultaneously combining the performances of the two adhesives, and having great value for the research of the adhesives.
In order to realize the technical purpose, the technical scheme of the invention is as follows:
the adhesive takes polyurethane as a main chain and is grafted with copolymerized modified acrylate, and the adhesive contains a hydrophilic monomer DMPA, a functional monomer HEMA and a modified organosilicon unit.
The modified organosilicon unit is formed by introducing a silicon side chain on a carbon chain to form a grafting, block or interpenetrating network system.
The polyurethane is a vinyl-terminated polyurethane emulsion containing double bonds.
The acrylic ester takes MMA and AN as hard monomers, butyl acrylate and ethyl acrylate as soft monomers, and hydroxyethyl acrylate as functional monomers. The mass ratio of the hard monomer to the soft monomer is 1:1
The polyurethane main chain is formed by polymerizing polyol, isocyanate compound, DMPA and functional monomer HEMA. The molar ratio of the isocyanate-based compound to the polyol is 4:1-1.2.
The polyol is formed by combining castor oil and polytetrahydrofuran, and the castor oil accounts for 10% of the mass of the polyol.
The reactive functional groups of the isocyanate are hydroxyl groups, primary amino groups, and combinations thereof.
The organic silicon unit is formed by modifying an end vinyl chain extension by organic silicon, hydrazine hydrate and diethylenetriamine.
The preparation of the adhesive comprises the following steps:
step 1, synthesis of polyurethane emulsion: a1, reacting PTMG, TMP, NPG, castor oil and I PDI in a three-neck flask at 80 ℃ to form a prepolymer, and cooling to 70 ℃ after reaching the reaction end point; a2, adding a hydrophilic chain extender DMPA, a solvent NMP and a small amount of a catalyst DBTDL, carrying out heat preservation reaction at 70 ℃ until the molar fraction of isocyanato reaches the calculated theoretical value, and adding an acrylic acid functional monomer HEMA; a3, after the reaction is completed, replacing a part of solvent MEK with a small amount of butyl acrylate to reduce the viscosity of the polyurethane prepolymer, and cooling to 40 ℃; a4, adding TEA (ethylene-vinyl acetate) with the same mole as DMPA (dimethyl formamide) as a salt forming agent for salt forming reaction, and reacting for 5min to synthesize a prepolymer of the vinyl-terminated polyurethane containing double bonds in a molecular chain; a5, adding gel water and adjusting the stirring speed, dispersing the prepolymer into distilled water under high-speed stirring, then slowly adding an organosilicon/hydrazine hydrate/Diethylenetriamine (DETA) composite chain extender, and stirring at a low speed for 1-2h to obtain a vinyl-terminated polyurethane emulsion for modification; wherein the addition amount of HEMA is 3 percent of the whole solid content state;
step 2, synthesis of polyurethane graft copolymerization modified acrylic acid copolymer emulsion: b1, placing methyl methacrylate, acrylonitrile, butyl acrylate, ethyl acrylate and a modified vinyl-terminated polyurethane emulsion into a three-neck flask, and emulsifying for about 40min under the condition of introducing N2, so that on one hand, PU can fully wrap monomers, on the other hand, oxygen with polymerization inhibition in the three-neck flask and reaction liquid is discharged, and on the other hand, an emulsifier can be fully dissolved in the reaction liquid and can uniformly mix various acrylic monomers; and slowly heating to 65 ℃, dropwise adding an initiator into the three-neck flask, finishing dropping within 1.5h, heating to 75 ℃, and carrying out heat preservation reaction for 2h to obtain the PUA raw emulsion, namely the polyurethane acrylate adhesive.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the defects of the existing acrylate adhesive and polyurethane adhesive, and provides modified acrylate which takes polyurethane as a main chain and is grafted and copolymerized, and the modified acrylate contains a hydrophilic monomer DMPA, a functional monomer HEMA and a modified organic silicon unit. Wherein, the organosilicon introduces a silicon side chain on a carbon chain to form a grafting, block or interpenetrating network system.
2. According to the invention, the acrylate emulsion polymer is modified by using the excellent performance of the waterborne polyurethane, the obtained emulsion has excellent printing performance, the production cost of the adhesive is effectively reduced, the performances of the two adhesives can be combined, and the research on the adhesive has great value.
3. The adhesive provided by the invention improves the name of the hot question, and the compatibility of the particles is improved.
Drawings
FIG. 1 is a transmission electron micrograph of a PUA protoemulsion of example 1 and a stamp electron micrograph thereof.
Detailed Description
With reference to fig. 1, a specific embodiment of the present invention is described in detail, but the present invention is not limited in any way by the claims.
Example 1
Pretreated isophorone diisocyanate (IPDI), polytetrahydrofuran diol (PTMG), neopentyl glycol (NPG) and Trimethylolpropane (TMP) are mixed according to the mass ratio of 11:4:7:2 into a three-neck flask, then 10 percent of castor oil and 2 thousandth of catalyst dibutyl tin dilaurate (DBTDL) are added, and the temperature is slowly raised to 80 ℃. After reaching the end point, the temperature was reduced to 70 ℃. Then, 1.2g of a hydrophilic chain extender dimethylolpropionic acid (DMPA), 0.6g of a solvent N-methylpyrrolidone (NMP) and 0.6g of hydroxyethyl methacrylate (HEMA) were added to the flask, and after the reaction was carried out at 70 ℃ with heat preservation until the molar fraction of isocyanate groups reached the calculated theoretical value, 0.15g of Methyl Ethyl Ketone (MEK) was added to lower the viscosity of the polyurethane prepolymer and the temperature was lowered to 40 ℃. Triethylamine (TEA) was added in equimolar amounts to DMPA as a salt forming agent for the salt formation reaction. 100g of distilled water was added and the stirring speed was adjusted, and the resulting prepolymer having hydrophilic polyurethane was dispersed in distilled water under stirring at 1000 r/min. And adjusting the stirring speed, slowly adding 3g of organosilicon/hydrazine hydrate/Diethylenetriamine (DETA) composite chain extender, and stirring for 1 to 2 hours at 100r/min to obtain the modified vinyl-terminated polyurethane emulsion. 8g of methyl methacrylate, 2g of acrylonitrile and 2g of butyl acrylate are taken. Ethyl acrylate and 10g of modified vinyl-terminated PU prepared by an in-situ emulsion polymerization method were placed in a three-neck flask and emulsified for about 40min under N2. Then slowly heating to 65 ℃, dropwise adding 0.6 percent of initiator AIBN into the three-neck flask, finishing dropping within 1.5h, heating to 75 ℃, and carrying out heat preservation reaction for 2h to prepare the copolymerized PUA original emulsion. The transmission electron microscope image and the printing electron microscope image of the product are shown in figure 1.
Example 2
PTMG, TMP, NPG, castor oil and IPDI are reacted in a three-neck flask at 80 ℃ to form a prepolymer as in example 1. After the reaction end point is reached, the temperature is reduced to 70 ℃. Adding 0.12g of hydrophilic chain extender DMPA, 0.6g of solvent NMP, a calculated amount of HEMA and a small amount of catalyst DBTDL, keeping the temperature at 70 ℃ for reaction until the molar fraction of the isocyanic acid radical reaches the calculated theoretical value, adding 0.15g of MEK to reduce the viscosity of the prepolymer, and cooling to 40 ℃. Adding TEA with the same mol as DMPA to be used as a salt forming agent for salt forming reaction, and reacting for 5min to synthesize the prepolymer of the vinyl-terminated polyurethane containing double bonds in the molecular chain. 100g of distilled water was added and the stirring speed was adjusted, and the resulting prepolymer having hydrophilic polyurethane was dispersed in distilled water with stirring at 1000 r/min. And adjusting the stirring speed, slowly adding 3g of organosilicon/hydrazine hydrate/Diethylenetriamine (DETA) composite chain extender, and stirring for 1 to 2 hours at 100r/min to obtain the modified vinyl-terminated polyurethane emulsion. 8g of methyl methacrylate, 2g of acrylonitrile and 2g of butyl acrylate are taken. Ethyl acrylate and 10g of modified vinyl-terminated PU prepared by an in-situ emulsion polymerization method were placed in a three-neck flask and emulsified for about 40min under N2. Then slowly heating to 65 ℃, dropwise adding 0.6 percent of initiator AIBN into the three-neck flask, finishing dropping within 1.5h, heating to 75 ℃, and carrying out heat preservation reaction for 2h to prepare the copolymerized PUA original emulsion.
Example 3
PTMG, TMP, NPG, castor oil and IPDI are firstly reacted in a three-neck flask at 80 ℃ to form a prepolymer. And after the reaction end point is reached, cooling to 70 ℃. Then adding 1.2g of hydrophilic chain extender DMPA, 0.6g of solvent NMP and a small amount of catalyst DBTDL, carrying out heat preservation reaction at 70 ℃ until the molar fraction of the isocyanic acid radical reaches the calculated theoretical value, and adding 0.6g of acrylic acid functional monomer HEMA. After the reaction is finished, a small amount of butyl acrylate is used for replacing part of MEK solvent to reduce the viscosity of the polyurethane prepolymer, and the temperature is reduced to 40 ℃. Adding TEA with the same mol as DMPA to be used as a salt forming agent for salt forming reaction, and reacting for 5min to synthesize the prepolymer of the vinyl-terminated polyurethane containing double bonds in the molecular chain. 100g of distilled water was added and the stirring speed was increased, and the resulting prepolymer having hydrophilic polyurethane was dispersed in distilled water with stirring at 1000 r/min. And (3) regulating the stirring speed, slowly adding 3g of organosilicon/hydrazine hydrate/Diethylenetriamine (DETA) composite chain extender, and stirring at a low speed for 1 to 2 hours to obtain the modified vinyl-terminated polyurethane emulsion. 8g of methyl methacrylate, 2g of propylene and 2g of butyl acrylate were taken. Placing ethyl acrylate and a certain amount of modified vinyl-terminated PU prepared by an in-situ emulsion polymerization method into a three-neck flask, and emulsifying for about 40min under the condition of introducing N2. Then slowly heating to 65 ℃, dropwise adding 0.6 percent of initiator AIBN into the three-neck flask, finishing dropping within 1.5h, heating to 75 ℃, and carrying out heat preservation reaction for 2h to prepare the copolymerized PUA original emulsion.
Comparative example
First, 4g of PTMG, 2g of TMP and 7g of NPG are reacted in a three-neck flask at 80 ℃ to form a prepolymer. And after the reaction end point is reached, cooling to 70 ℃. Then, 1.2g of dimethylolpropionic acid (DMPA), a hydrophilic chain extender, 0.6g of N-methylpyrrolidone (NMP), and 0.6g of hydroxyethyl methacrylate (HEMA) were added to the flask, and after the reaction was carried out at 70 ℃ with maintaining the temperature until the molar fraction of isocyanate groups reached the theoretical value calculated, 0.15g of Methyl Ethyl Ketone (MEK) was added to lower the viscosity of the polyurethane prepolymer, and the temperature was lowered to 40 ℃. Triethylamine (TEA) was added in equimolar amounts to DMPA as a salt forming agent for the salt formation reaction. 100g of distilled water was added and the stirring speed was adjusted, and the resulting prepolymer having hydrophilic polyurethane was dispersed in distilled water under stirring at 1000 r/min. 8g of methyl methacrylate, 2g of acrylonitrile and 2g of butyl acrylate were mixed. Placing ethyl acrylate and a certain amount of vinyl-PU prepared by an in-situ emulsion polymerization method into a three-neck flask, and emulsifying for about 40min under the condition of introducing N2. Then slowly heating to 65 ℃, dropwise adding 0.6 percent of initiator AIBN into the three-neck flask, finishing dropping within 1.5h, heating to 75 ℃, and carrying out heat preservation reaction for 2h to prepare the copolymerized PUA original emulsion.
The products of examples 1-3 and comparative example 1 were tested for performance as follows:
the table shows that the waterborne polyurethane modified acrylate copolymer improves the compatibility of the two components, gives full play to the advantages of the two components and improves the comprehensive performance of the two components. The synthesized emulsion has graft copolymerization, the particle size is slightly coarser than that of PU, but the distribution is narrow, the heat stability of PUA is greatly improved, and the compatibility of the particles is very good.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (10)
1. A urethane acrylate adhesive characterized by: the adhesive takes polyurethane as a main chain and grafts copolymerization modified acrylate, and the adhesive contains a hydrophilic monomer DMPA, a functional monomer HEMA and a modified organosilicon unit.
2. The urethane acrylate adhesive according to claim 1, characterized in that: the modified organosilicon unit is formed by introducing a silicon side chain on a carbon chain to form a grafting, block or interpenetrating network system.
3. The urethane acrylate adhesive according to claim 1, characterized in that: the polyurethane is a vinyl-terminated polyurethane emulsion containing double bonds.
4. The urethane acrylate adhesive according to claim 1, characterized in that: the acrylic ester takes MMA and AN as hard monomers, butyl acrylate and ethyl acrylate as soft monomers, and hydroxyethyl acrylate as functional monomers.
5. The urethane acrylate adhesive according to claim 4, characterized in that: the mass ratio of the hard monomer to the soft monomer is 1:1.
6. The urethane acrylate adhesive according to claim 1, characterized in that: the polyurethane main chain is formed by polymerizing polyol, isocyanate group compound, DMPA and functional monomer HEMA, and the molar ratio of the isocyanate group compound to the polyol is 4:1-1.2.
7. The urethane acrylate adhesive according to claim 6, wherein: the polyol is formed by combining castor oil and polytetrahydrofuran, and the castor oil accounts for 10% of the mass of the polyol.
8. The urethane acrylate adhesive according to claim 6, wherein: the reactive functional groups of the isocyanate are hydroxyl groups, primary amino groups, and combinations thereof.
9. The urethane acrylate adhesive according to claim 1, characterized in that: the organic silicon unit is formed by modifying an end vinyl chain extension by organic silicon, hydrazine hydrate and diethylenetriamine.
10. The urethane acrylate adhesive according to claim 1, characterized in that: the preparation of the adhesive comprises the following steps:
step 1, synthesis of polyurethane emulsion: a1, reacting PTMG, TMP, NPG, castor oil and IPDI in a three-neck flask at 80 ℃ to form a prepolymer, and cooling to 70 ℃ after reaching the reaction end point; a2, adding a hydrophilic chain extender DMPA, a solvent NMP and a small amount of a catalyst DBTDL, carrying out heat preservation reaction at 70 ℃ until the molar fraction of isocyanato reaches the calculated theoretical value, and adding an acrylic acid functional monomer HEMA; a3, after the reaction is completed, replacing a part of solvent MEK with a small amount of butyl acrylate to reduce the viscosity of the polyurethane prepolymer, and cooling to 40 ℃; a4, adding TEA (ethylene-vinyl acetate) with the same mole as DMPA (dimethyl formamide) as a salt forming agent for salt forming reaction, and reacting for 5min to synthesize a prepolymer of the vinyl-terminated polyurethane containing double bonds in a molecular chain; a5, adding gel water and adjusting the stirring speed, dispersing the prepolymer into distilled water under high-speed stirring, then slowly adding an organosilicon/hydrazine hydrate/Diethylenetriamine (DETA) composite chain extender, and stirring at a low speed for 1-2h to obtain a vinyl-terminated polyurethane emulsion for modification; wherein the addition amount of HEMA is 3 percent of the whole solid content state;
step 2, synthesis of polyurethane graft copolymerization modified acrylic acid copolymer emulsion: b1, placing methyl methacrylate, acrylonitrile, butyl acrylate, ethyl acrylate and a modified vinyl-terminated polyurethane emulsion into a three-neck flask, and emulsifying for about 40min under the condition of introducing N2, so that on one hand, PU can fully wrap monomers, on the other hand, oxygen with polymerization inhibition in the three-neck flask and reaction liquid is discharged, and on the other hand, an emulsifier can be fully dissolved in the reaction liquid and can uniformly mix various acrylic monomers; and slowly heating to 65 ℃, dropwise adding an initiator into the three-neck flask, finishing dropping within 1.5h, heating to 75 ℃, and carrying out heat preservation reaction for 2h to obtain a PUA (polyurethane acrylic ester) raw emulsion, namely the polyurethane acrylate adhesive.
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