CN112358575A - Environment-friendly polyurethane-acrylate hybrid emulsion and preparation method thereof - Google Patents
Environment-friendly polyurethane-acrylate hybrid emulsion and preparation method thereof Download PDFInfo
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Abstract
The present application relates toAn environment-friendly polyurethane-acrylate hybrid emulsion and a preparation method thereof comprise the following steps: a. synthesis of a polyurethane prepolymer: reacting hydroxyl-terminated polybutadiene, hexamethylene diisocyanate, castor oil, hydroxyl-terminated polyethylene glycol and dibutyltin dilaurate to obtain a polyolefin type polyurethane prepolymer; b. synthesis of a blending pre-emulsion: mixing polyolefin type polyurethane prepolymer, acrylate functional monomer, acrylate crosslinking monomer and acrylate monomer, adding water for high-speed emulsification, and adding a chain extender for reaction; c. polyurethane-acrylate hybrid emulsion polymerization: mixing water, initiator and NaHCO3And uniformly mixing, and then dropwise adding the blending pre-emulsion to perform polymerization reaction to obtain the polyurethane-acrylate hybrid emulsion, wherein the polyurethane-acrylate hybrid emulsion is green and environment-friendly and has high adhesive force, film forming speed, ageing resistance and strength.
Description
Technical Field
The application relates to the technical field of adhesives, in particular to an environment-friendly polyurethane-acrylate hybrid emulsion and a preparation method thereof.
Background
With the technological progress and the rapid development of national economy, the environmental protection consciousness of people is continuously enhanced, environmental protection laws and regulations are increasingly strict, and at present, water-soluble polymer products with low VOC content and environmental friendliness are more used for replacing solvent-based adhesives and are used for bonding between films and paper.
The polyurethane is a polyurethane, belongs to a high molecular compound, has the advantages of difficult combustion, low cost, environmental protection and the like, and is a representative waterborne polymer product. Acrylic ester has good hydrophobicity and can be self-polymerized or copolymerized with other monomers, so polyurethane and acrylic ester are usually mixed, and an emulsifier is added to prepare polyurethane acrylic hybrid emulsion (PUA) serving as a composite adhesive for bonding between a film and paper.
However, the compatibility between the polyurethane and the acrylic acid is poor, so that the two components are difficult to exert respective advantages, and the existence of the emulsifier causes the defects of the polyurethane acrylic acid hybrid emulsion (PUA) in the aspects of adhesive force, film forming speed and the like.
Disclosure of Invention
The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion is provided, so that the prepared polyurethane-acrylate hybrid emulsion has high adhesive force, is easy to form a film and is environment-friendly.
The second purpose of the application is to provide the polyurethane-acrylate hybrid emulsion prepared by the method.
The above object of the present application is achieved by the following technical solutions:
a preparation method of an environment-friendly polyurethane-acrylate hybrid emulsion comprises the following steps:
a. synthesis of a polyurethane prepolymer:
a 1: respectively drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at the temperature of 75-85 ℃ for 2-3 h;
a 2: mixing the dried hydroxyl-terminated polybutadiene, castor oil, hydroxyl-terminated polyethylene glycol, hexamethylene diisocyanate and catalytic amount of dibutyltin dilaurate, heating to 70-90 ℃ under the protection of nitrogen, and reacting for 2-3 hours to obtain the polyolefin polyurethane prepolymer, wherein the weight ratio of the hexamethylene diisocyanate to the hydroxyl-terminated polybutadiene to the hydroxyl-terminated polyethylene glycol to the castor oil is (8.5-9.5): (4.5-5.5): (1.52-1.60): 1;
b. synthesis of polyurethane and acrylate monomer blending pre-emulsion:
b 1: mixing polyolefin type polyurethane prepolymer, 3-5 parts by weight of hydroxyethyl acrylate, 15-25 parts by weight of hydroxypropyl acrylate, 10-20 parts by weight of methyl methacrylate, 12-16 parts by weight of butyl acrylate, 8-10 parts by weight of isooctyl acrylate and 0.5-0.54 part by weight of hexanediol di (meth) acrylate, and stirring for 30-35 min;
b 2: and b, mixing the product obtained in the step b1 with water at a rotating speed of 1200-1250 r/min, emulsifying at a high speed for 30-60 min, mixing with a chain extender, and reacting for 60min to obtain a polyurethane and acrylate monomer blending pre-emulsion, wherein the weight ratio of the product obtained in the step b1, water and the chain extender is 50: (25-40): (0.2 to 0.3);
c. polyurethane-acrylate hybrid emulsion polymerization:
15 to 25 weight portions of water, 0.025 to 0.035 weight portion of initiator and 0.015 to 0.025 weight portion of NaHCO3Uniformly mixing to obtain a mixed solution, heating to 80-84 ℃, dropwise adding the polyurethane and acrylate monomer blending pre-emulsion for 2.0-2.5 h, reacting for 0.8-1.2 h after dropwise adding, then cooling to 40-50 ℃, adjusting the pH value to 7-9, stirring for 25-30 min, filtering, and discharging to obtain the polyurethane-acrylate hybrid emulsion.
By adopting the technical scheme, molecular chains between polyurethane and acrylate are crosslinked through chemical reaction to form a mutually-penetrated network structure, and the compatibility, adhesive force and strength of the polyurethane-acrylate hybrid emulsion can be greatly improved through the network structure; and migration phase-splitting behavior of molecular chains is limited through chemical copolymerization, and compatibility of the molecular chains and the molecular chains is improved, so that the adhesive force and film forming speed of the polyurethane-acrylate hybrid emulsion are further improved.
Meanwhile, the emulsifiable polyolefin type polyurethane prepolymer is prepared from hydroxyl-terminated polybutadiene, hexamethylene diisocyanate, hydroxyl-terminated polyethylene glycol, castor oil and catalytic amount of dibutyltin dilaurate, and the hydroxyl-terminated polybutadiene has high adhesive force to a plurality of plastic substrates, so that the polyolefin type polyurethane prepolymer has high adhesive force, and the adhesive force of the polyurethane-acrylate hybrid emulsion is improved; in addition, due to the introduction of the hydroxyl-terminated polyvinyl alcohol and the castor oil, the polyolefin type polyurethane prepolymer contains a hydrophilic PEG chain segment, so that the polyolefin type polyurethane prepolymer has surface activity, an emulsifier is not required to be added in the process of blending the polyolefin type polyurethane prepolymer and the acrylate monomer pre-emulsion, a soap-free polyurethane-acrylate hybrid emulsion is directly obtained, the influence caused by the emulsifier is eliminated, and the performances of the polyurethane-acrylate hybrid emulsion in the aspects of adhesive force, film forming speed and the like are improved.
In the step b, the polyolefin polyurethane emulsion is mixed with acrylate functional monomers (hydroxyethyl acrylate and hydroxypropyl acrylate), an acrylate crosslinking monomer (hexanediol di (methyl) acrylate) and acrylate monomers (methyl methacrylate, butyl acrylate and isooctyl acrylate) according to a specific proportion, the acrylate functional monomers have a polyhydroxy structure, reaction sites are increased, so that grafting or crosslinking positions between the polyolefin polyurethane emulsion and the acrylate monomers are more, a hybridization net structure is tighter, grafting or mutual penetration occurs between an acrylate core and a polyolefin polyurethane shell in the polymerization process, the shape compatibility between two polymers is obviously improved, the viscosity of the polyolefin polyurethane is reduced by the acrylate monomers, and polymerization is carried out under specific reaction conditions in the step c, the polymerization reaction rate is kept unchanged, so that the preparation process is always carried out stably, the polyurethane-acrylate hybrid emulsion is always kept high in stability in the reaction process, the possibility of transient phenomenon in the conventional continuous emulsion polymerization process is reduced, and the prepared polyurethane-acrylate hybrid emulsion has high adhesive force and film forming speed.
According to the method, the polymerization temperature in the step c is strictly controlled, so that the polyurethane-acrylate hybrid emulsion keeps high stability, the particle size is reduced, if the polymerization temperature is too high, the thermal motion among emulsion particles in the system is intensified, the emulsion particles are collided and coalesced, the particle size of the polyurethane-acrylate hybrid emulsion is increased, and the stability of the polyurethane-acrylate hybrid emulsion is reduced.
According to the preparation method, the adding proportion of each component is controlled, and the specific components are selected, so that the polyurethane-acrylate hybrid emulsion prepared by the preparation method has low VOC content, has high adhesive force, film forming speed and strength, and is green and environment-friendly.
Preferably, the initiator comprises ammonium persulfate and/or sodium persulfate.
By adopting the technical scheme, one of ammonium persulfate and sodium persulfate or two components are mixed and matched in any proportion for use, and the mixture is added into the step c according to a specific proportion and is used as an initiator of copolymerization reaction, so that the polymerization reaction can be smoothly carried out, and the adhesive force and the film forming speed of the polyurethane-acrylate hybrid emulsion are improved.
Preferably, the chain extender is 1, 4-butanediol and/or sorbitol.
By adopting the technical scheme, when the hydroxyl-terminated polybutadiene and the hexamethylene diisocyanate are subjected to polymerization reaction, the hydroxyl-terminated polybutadiene is used as a soft segment of the hexamethylene diisocyanate, one of 1, 4-butanediol and sorbitol or two components are mixed and matched in any proportion to be used as a chain extender, and the polymerization reaction is carried out according to specific reaction conditions, so that the contact angle of the polyolefin polyurethane is increased, the hydrophobicity is enhanced, the waterproof capability is improved, the mechanical property is improved, the polyolefin polyurethane has higher ageing resistance, and the service life of the polyurethane emulsion is prolonged.
Preferably, the castor oil is further preferably modified castor oil obtained by modification treatment using maleic anhydride as a modifier.
Preferably, the modified castor oil is prepared by the following method:
at the temperature of 118-122 ℃, the weight ratio is (2.5-3.5): 1, mixing and stirring maleic anhydride and castor oil, reacting for 4-4.5 hours until the acid value is lower than 145mgKOH/g, and stopping the reaction to obtain the modified castor oil.
By adopting the technical scheme, the castor oil is natural oil and has more active groups, the main chemical structure is ricinoleic acid triglyceride, and can provide active grafting points for polymerization of polyurethane and acrylate to form a cross-linked network structure, so that the adhesive force, the film forming speed and the strength of the polyurethane-acrylate hybrid emulsion are improved, but the cross-linking degree of the castor oil and other components is lower, therefore, the castor oil is modified by adopting maleic anhydride with a specific proportion according to specific reaction conditions, and double bonds are introduced, so that the cross-linking degree between the modified castor oil and each component is higher, and the adhesive force, the film forming speed and the strength of the polyurethane-acrylate hybrid emulsion are further improved.
The second purpose of the application is to provide the polyurethane-acrylate hybrid emulsion prepared by the method.
By adopting the technical scheme, the polyurethane-acrylate hybrid emulsion prepared by the method is soap-free hybrid emulsion, has high adhesive force, film forming speed and strength, has low VOC content, and is green and environment-friendly.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the preparation method, the polyurethane emulsion and the acrylate emulsion are chemically copolymerized, so that molecules in the prepared polyurethane-acrylate hybrid emulsion form a mutually-penetrated network structure, and the adhesive force, film forming speed and strength of the polyurethane-acrylate hybrid emulsion are improved;
2. according to the preparation method, the polyolefin type polyurethane emulsion capable of emulsifying is adopted, so that the influence caused by the emulsifier is eliminated, the prepared polyurethane-acrylate hybrid emulsion is a soap-free hybrid emulsion, the hydrophobicity and the ageing resistance of the polyurethane-acrylate hybrid emulsion are improved, and the service life of the polyurethane-acrylate hybrid emulsion is prolonged;
3. the polyurethane-acrylate hybrid emulsion prepared by the preparation method has low VOC content and is green and environment-friendly.
Detailed Description
The present application will be described in further detail with reference to examples.
Hydroxyethyl acrylate was purchased from Jinan Yuanxiang chemical Co., Ltd;
hydroxypropyl acrylate was purchased from Jiangsu Sanmu group, Inc.;
hexanediol di (meth) acrylate was purchased from Hebei Hengjing Chemicals, Inc.;
castor oil was purchased from southern jia chemical technology ltd, guangzhou (hydroxyl number =163 mgKOH/g);
dibutyltin dilaurate was purchased from Shandong-Chi-An chemical Co., Ltd.
Example 1
A preparation method of an environment-friendly polyurethane-acrylate hybrid emulsion comprises the following steps:
a. synthesis of a polyurethane prepolymer:
a 1: respectively drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at the temperature of 75 ℃ for 2 h;
a 2: mixing 45g of dried hydroxyl-terminated polybutadiene, 10g of castor oil, 15.2g of hydroxyl-terminated polyethylene glycol, 85g of hexamethylene diisocyanate and catalytic amount of dibutyltin dilaurate, heating to 70 ℃ under the protection of nitrogen, and reacting for 2 hours to obtain polyolefin type polyurethane prepolymer;
b. synthesis of polyurethane and acrylate monomer blending pre-emulsion:
b 1: mixing polyolefin type polyurethane prepolymer, 3g hydroxyethyl acrylate, 25g hydroxypropyl acrylate, 10g methyl methacrylate, 16g butyl acrylate, 8g isooctyl acrylate and 0.54g hexanediol diacrylate, and stirring for 30 min;
b 2: mixing 50g of the product obtained in the step b1 with 25g of water at the rotating speed of 1200r/min, emulsifying at a high speed for 30min, mixing with 0.2g of chain extender (0.1 g of 1, 4-butanediol and 0.1g of sorbitol), and reacting for 60min to obtain a polyurethane and acrylate monomer blending pre-emulsion;
c. polyurethane-acrylate hybrid emulsion polymerization:
15g of water, 0.035g of initiator (sodium persulfate), 0.015g of NaHCO3Uniformly mixing to obtain a mixed solution, then dropwise adding the polyurethane and acrylate monomer blended pre-emulsion at the temperature of 80 ℃, dropwise adding for 2.0h, reacting for 0.8h after dropwise adding, then cooling to 40 ℃, adjusting the pH value to 7, stirring for 25min, filtering, and discharging to obtain the polyurethane-acrylate hybrid emulsion.
Example 2
A preparation method of an environment-friendly polyurethane-acrylate hybrid emulsion comprises the following steps:
a. synthesis of a polyurethane prepolymer:
a 1: respectively drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at the temperature of 80 ℃ for 2.5 h;
a 2: mixing dried 50g of hydroxyl-terminated polybutadiene, 10g of castor oil, 15.6g of hydroxyl-terminated polyethylene glycol, 90g of hexamethylene diisocyanate and catalytic amount of dibutyltin dilaurate, heating to 80 ℃ under the protection of nitrogen, and reacting for 2.5 hours to obtain a polyolefin type polyurethane prepolymer;
b. synthesis of polyurethane and acrylate monomer blending pre-emulsion:
b 1: mixing polyolefin type polyurethane prepolymer, 4g hydroxyethyl acrylate, 20g hydroxypropyl acrylate, 15g methyl methacrylate, 14g butyl acrylate, 9g isooctyl acrylate, and 0.52g hexanediol diacrylate, and stirring for 32.5 min;
b 2: mixing 50g of the product obtained in the step b1 with 32.5g of water at a rotating speed of 1225r/min, emulsifying at a high speed for 45min, mixing with 0.25g of a chain extender (sorbitol), and reacting for 60min to obtain a polyurethane and acrylate monomer blending pre-emulsion;
c. polyurethane-acrylate hybrid emulsion polymerization:
20g of water, 0.030g of initiator (ammonium persulfate 0.01g, sodium persulfate 0.02 g), 0.020g of NaHCO3Uniformly mixing to obtain a mixed solution, then dropwise adding the polyurethane and acrylate monomer blended pre-emulsion at the temperature of 82 ℃, dropwise adding for 2.25h, reacting for 1.0h after dropwise adding, then cooling to 45 ℃, adjusting the pH value to 8, stirring for 27.5min, filtering, and discharging to obtain the polyurethane-acrylate hybrid emulsion.
Example 3
A preparation method of an environment-friendly polyurethane-acrylate hybrid emulsion comprises the following steps:
a. synthesis of a polyurethane prepolymer:
a 1: respectively drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at the temperature of 85 ℃ for 3 hours;
a 2: mixing 55g of dried hydroxyl-terminated polybutadiene, 10g of castor oil, 16g of hydroxyl-terminated polyethylene glycol, 95g of hexamethylene diisocyanate and a catalytic amount of dibutyltin dilaurate, heating to 90 ℃ under the protection of nitrogen, and reacting for 3 hours to obtain a polyolefin type polyurethane prepolymer;
b. synthesis of polyurethane and acrylate monomer blending pre-emulsion:
b 1: mixing polyolefin type polyurethane prepolymer, 5g hydroxyethyl acrylate, 15g hydroxypropyl acrylate, 20g methyl methacrylate, 12g butyl acrylate, 10g isooctyl acrylate and 0.50g hexanediol dimethacrylate, and stirring for 35 min;
b 2: mixing 50g of the product obtained in the step b1 with 40g of water at the rotating speed of 1250r/min, emulsifying at a high speed for 60min, mixing with 0.3g of chain extender (1, 4-butanediol), and reacting for 60min to obtain polyurethane and acrylate monomer blending pre-emulsion;
c. polyurethane-acrylate hybrid emulsion polymerization:
25g of water, 0.025g of initiator (ammonium persulfate), 0.025g of NaHCO3Mixing to obtain a mixtureAnd then dropwise adding the polyurethane and acrylate monomer blended pre-emulsion at the temperature of 84 ℃, dropwise adding for 2.5h, reacting for 1.2h after dropwise adding, then cooling to 50 ℃, adjusting the pH value to 9, stirring for 30min, filtering, discharging, and obtaining the polyurethane-acrylate hybrid emulsion.
Example 4
The difference between the preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion and the embodiment 2 is that: the castor oil is modified by the following method:
at the temperature of 118 ℃, 25g of maleic anhydride and 10g of castor oil are mixed and stirred for reaction for 4 hours until the acid value is lower than 145mgKOH/g, and the reaction is stopped to obtain the modified castor oil.
Example 5
The difference between the preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion and the embodiment 2 is that: the castor oil is modified by the following method:
at the temperature of 122 ℃, 35g of maleic anhydride and 10g of castor oil are mixed and stirred for reaction for 4.5 hours until the acid value is lower than 145mgKOH/g, and the reaction is stopped to obtain the modified castor oil.
Comparative example 1
The difference from example 2 is that: and a, during the synthesis of the polyurethane prepolymer in the step a, hydroxyl-terminated polybutadiene and castor oil are not added, so that a common polyurethane prepolymer is obtained, and the rest is the same.
Comparative example 2
The difference from example 2 is that: the same applies to the rest without the addition of castor oil.
Performance testing
The polyurethane-acrylate hybrid emulsions prepared in examples 1 to 5 and comparative examples 1 to 2 were tested for adhesion, film forming speed, elongation at break, and dynamic shear strength, and the test results are shown in table 1:
and (3) testing the adhesive force: according to GB/T2791-1995, the polyurethane-acrylate hybrid emulsions prepared in examples 1-5 and comparative examples 1-2 are respectively coated on PP plastic plates, the specification of each PP plastic plate is 100mm multiplied by 30mm, the weight of the polyurethane-acrylate hybrid emulsion coated on the PP plastic plate is 150g per square meter, and after the PP plastic plates are naturally dried for 24 hours, the peel strength (N/m) of the polyurethane-acrylate hybrid emulsion is tested;
testing the film forming speed: respectively coating the polyurethane-acrylate hybrid emulsions prepared in the examples 1-5 and the comparative examples 1-2 on PP plastic plates, wherein the specification of each PP plastic plate is 100mm multiplied by 30mm, the weight of the polyurethane-acrylate hybrid emulsion coated on the PP plastic plate is 150g per square meter, and recording the curing time (min) of the internal complete curing;
elongation at break test: according to GB/T20028-;
and (3) testing the dynamic shear strength: the dynamic shear strength (N/cm) of the polyurethane-acrylate hybrid emulsion prepared in the examples 1-5 and the comparative examples 1-2 was tested according to the test method for the dynamic shear strength of adhesive tape of GB/T33332-.
Table 1 table of performance test results
| Item | Peel strength (N/m) | Curing time (min) | Elongation at Break (%) | Dynamic shear Strength (N/cm) |
| Example 1 | 305.6 | 80 | 252.5 | 10.5 |
| Example 2 | 307.5 | 65 | 253.1 | 11.2 |
| Example 3 | 306.2 | 76 | 252.7 | 10.7 |
| Example 4 | 317.5 | 55 | 263.6 | 11.5 |
| Example 5 | 316.8 | 56 | 262.9 | 11.7 |
| Comparative example 1 | 217.5 | 135 | 178.2 | 5.6 |
| Comparative example 2 | 232.5 | 120 | 189.6 | 6.2 |
As can be seen from Table 1, the polyurethane-acrylate hybrid emulsion prepared according to the embodiments 1-5 of the present application has high adhesive force, high film forming speed and high dynamic shear strength, and the content of VOC in the polyurethane-acrylate hybrid emulsion prepared according to the present application is lower than 20g/L, so that the polyurethane-acrylate hybrid emulsion is green and environment-friendly.
Comparing the data of examples 1-3 with the data of comparative example 1, it can be seen that the peel strength, elongation at break and dynamic shear strength of examples 1-3 are significantly higher than those of comparative example 1, and the curing time of examples 1-3 is shorter than that of comparative example 1, which indicates that the polyurethane-acrylate hybrid emulsion prepared by using the polyolefin type polyurethane prepolymer has higher adhesive force, film forming speed, anti-aging capability and strength.
Comparing the data of the examples 4-5 with the data of the example 2, it can be seen that the peel strength, the elongation at break and the dynamic shear strength of the examples 4-5 are higher than those of the example 2, and the curing time of the examples 4-5 is shorter than that of the example 2, which shows that the modified castor oil and the components are more highly crosslinked by modifying the castor oil with maleic anhydride, so that the adhesive force, the film forming speed, the anti-aging capability and the strength of the polyurethane-acrylate hybrid emulsion are improved.
Comparing the data of example 2 with the data of comparative example 2, it can be seen that the peel strength, elongation at break and dynamic shear strength of example 2 are significantly higher than those of comparative example 2, and the curing time of example 2 is shorter than that of comparative example 2, which indicates that the castor oil and the hydroxyl-terminated polyethylene glycol can exert a synergistic effect to significantly improve the adhesion, film forming speed and dynamic shear strength of the polyurethane-acrylate hybrid emulsion.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (6)
1. A preparation method of environment-friendly polyurethane-acrylate hybrid emulsion is characterized by comprising the following steps: the method comprises the following steps:
a. synthesis of a polyurethane prepolymer:
a 1: respectively drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at the temperature of 75-85 ℃ for 2-3 h;
a 2: mixing the dried hydroxyl-terminated polybutadiene, castor oil, hydroxyl-terminated polyethylene glycol, hexamethylene diisocyanate and catalytic amount of dibutyltin dilaurate, heating to 70-90 ℃ under the protection of nitrogen, and reacting for 2-3 hours to obtain the polyolefin polyurethane prepolymer, wherein the weight ratio of the hexamethylene diisocyanate to the hydroxyl-terminated polybutadiene to the hydroxyl-terminated polyethylene glycol to the castor oil is (8.5-9.5): (4.5-5.5): (1.52-1.60): 1;
b. synthesis of polyurethane and acrylate monomer blending pre-emulsion:
b 1: mixing polyolefin type polyurethane prepolymer, 3-5 parts by weight of hydroxyethyl acrylate, 15-25 parts by weight of hydroxypropyl acrylate, 10-20 parts by weight of methyl methacrylate, 12-16 parts by weight of butyl acrylate, 8-10 parts by weight of isooctyl acrylate and 0.5-0.54 part by weight of hexanediol di (meth) acrylate, and stirring for 30-35 min;
b 2: and b, mixing the product obtained in the step b1 with water at a rotating speed of 1200-1250 r/min, emulsifying at a high speed for 30-60 min, mixing with a chain extender, and reacting for 60min to obtain a polyurethane and acrylate monomer blending pre-emulsion, wherein the weight ratio of the product obtained in the step b1, water and the chain extender is 50: (25-40): (0.2 to 0.3);
c. polyurethane-acrylate hybrid emulsion polymerization:
15 to 25 weight portions of water, 0.025 to 0.035 weight portion of initiator and 0.015 to 0.025 weight portion of NaHCO3Uniformly mixing to obtain a mixed solution, heating to 80-84 ℃, dropwise adding the polyurethane and acrylate monomer blending pre-emulsion for 2.0-2.5 h, reacting for 0.8-1.2 h after dropwise adding, then cooling to 40-50 ℃, adjusting the pH value to 7-9, stirring for 25-30 min, filtering, and discharging to obtain the polyurethane-acrylate hybrid emulsion.
2. The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion according to claim 1, wherein the preparation method comprises the following steps: the initiator comprises ammonium persulfate and/or sodium persulfate.
3. The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion according to claim 1, wherein the preparation method comprises the following steps: the chain extender is 1, 4-butanediol and/or sorbitol.
4. The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion according to claim 1, wherein the preparation method comprises the following steps: the castor oil is further preferably modified castor oil obtained by modifying with maleic anhydride as a modifier.
5. The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion according to claim 4, wherein the preparation method comprises the following steps: the modified castor oil is prepared by the following method:
at the temperature of 118-122 ℃, the weight ratio is (2.5-3.5): 1, mixing and stirring maleic anhydride and castor oil, reacting for 4-4.5 hours until the acid value is lower than 145mgKOH/g, and stopping the reaction to obtain the modified castor oil.
6. The polyurethane-acrylate hybrid emulsion prepared by the preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion according to any one of claims 1 to 5.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650780A (en) * | 2015-02-06 | 2015-05-27 | 翰博高新材料(合肥)股份有限公司 | Adhesive for optical thin film |
| CN105601828A (en) * | 2015-12-19 | 2016-05-25 | 高明志 | Castor-oil-based polyurethane-acrylate emulsion preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650780A (en) * | 2015-02-06 | 2015-05-27 | 翰博高新材料(合肥)股份有限公司 | Adhesive for optical thin film |
| CN105601828A (en) * | 2015-12-19 | 2016-05-25 | 高明志 | Castor-oil-based polyurethane-acrylate emulsion preparation method |
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| PRITISHREE NAYAK: "Polymers from renewable resources.IX.Interpenetrating polymer networks based on castor oil polyurethane poly(hydroxyethyl methacrylate):synthesis, chemical , thermal, and mechanial properties", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
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