CN112358575B - 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 application relates to an environment-friendly polyurethane-acrylic ester hybrid emulsion and a preparation method thereof, comprising the following steps: a. synthesis of polyurethane prepolymer: hydroxyl-terminated polybutadiene, hexamethylene diisocyanate, castor oil, hydroxyl-terminated polyethylene glycol and dibutyltin dilaurate are reacted to obtain a polyolefin polyurethane prepolymer; b. synthesis of blending pre-emulsion: mixing a polyolefin polyurethane prepolymer, an acrylic ester functional monomer, an acrylic ester crosslinking monomer and an acrylic ester monomer, adding water for high-speed emulsification, and then adding a chain extender for reaction; c. polyurethane-acrylate hybrid emulsion polymerization: water, initiator and NaHCO 3 And (3) 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 environment-friendly and has higher 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 technological progress and high-speed development of national economy, environmental protection consciousness of people is continuously enhanced, environmental protection laws and regulations are also becoming severe, and currently, water-soluble polymer products with low VOC content and environmental friendliness are used for replacing solvent type adhesives for bonding between films and papers.
Polyurethane is named polyurethane, belongs to a high molecular compound, has the advantages of difficult combustion, low cost, environmental protection and the like, and is a representative water-based polymer product. The acrylic ester has better hydrophobicity and can be self-polymerized or copolymerized with other monomers, so polyurethane and acrylic ester are generally 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 polyurethane and acrylic acid have the problem of poor compatibility, so that the two components are difficult to exert their advantages, and the polyurethane acrylic acid hybrid emulsion (PUA) has defects in the aspects of adhesive force, film forming speed and the like due to the existence of an emulsifier.
Disclosure of Invention
The application aims to provide a preparation method of an environment-friendly polyurethane-acrylate hybrid emulsion, so that the prepared polyurethane-acrylate hybrid emulsion has the advantages of high adhesive force, easiness in film formation and environment friendliness.
The application also provides the polyurethane-acrylate hybrid emulsion prepared by the method.
The first object of the present application is achieved by the following technical solutions:
the preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion comprises the following steps:
a. synthesis of polyurethane prepolymer:
a1: respectively drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at the temperature of 75-85 ℃ for 2-3 hours;
a2: mixing 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 a 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 to 5.5): (1.52-1.60): 1, a step of;
b. synthesis of polyurethane and acrylate monomer blending pre-emulsion:
b1: mixing polyolefin 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;
b2: mixing the obtained product in the step b1 with water at a high speed for emulsification for 30-60 min at a rotating speed of 1200-1250r/min, mixing with a chain extender, and reacting for 60min to obtain polyurethane and acrylate monomer blending pre-emulsion, wherein the weight ratio of the obtained product in the step b1 to the water to the chain extender is 50: (25-40): (0.2 to 0.3);
c. polyurethane-acrylate hybrid emulsion polymerization:
15 to 25 parts by weight of water, 0.025 to 0.035 parts by weight of an initiator, 0.015 to 0.025 parts by weight of NaHCO 3 Uniformly mixing to obtain a mixed solution, heating to 80-84 ℃, dropwise adding polyurethane and acrylate monomer blending pre-emulsion, dropwise adding for 2.0-2.5 h, reacting for 0.8-1.2 h after the dropwise adding is finished, 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, the polyurethane-acrylate hybrid emulsion prepared by the chemical copolymerization method has the advantages that the molecular chains between polyurethane and acrylate are crosslinked through chemical reaction, an interpenetrating network structure is formed, and the compatibility, the adhesive force and the strength of the polyurethane-acrylate hybrid emulsion can be greatly improved by the network structure; and the migration phase-splitting behavior of the molecular chain is limited by chemical copolymerization, so that the compatibility of the molecular chain and the polyurethane-acrylate hybrid emulsion is improved, and the adhesive force and the film forming speed of the polyurethane-acrylate hybrid emulsion are further improved.
Meanwhile, the application adopts hydroxyl-terminated polybutadiene, hexamethylene diisocyanate, hydroxyl-terminated polyethylene glycol, castor oil and catalytic amount of dibutyl tin dilaurate to prepare the emulsifiable polyolefin polyurethane prepolymer, and the hydroxyl-terminated polybutadiene has higher adhesive force to a plurality of plastic substrates, so that the polyolefin polyurethane prepolymer has higher adhesive force, thereby improving the adhesive force of polyurethane-acrylic ester hybrid emulsion; in addition, due to the introduction of hydroxyl-terminated polyvinyl alcohol and castor oil, the polyolefin polyurethane prepolymer contains a hydrophilic PEG chain segment, so that the polyolefin polyurethane prepolymer has surface activity, and therefore, an emulsifier is not required to be added in the process of blending the polyolefin polyurethane prepolymer and the acrylic ester monomer into the pre-emulsion, the soap-free polyurethane-acrylic ester hybrid emulsion is directly obtained, the influence of the emulsifier is eliminated, and the performances of the polyurethane-acrylic ester hybrid emulsion in the aspects of adhesive force, film forming speed and the like are improved.
According to the application, in the step b, polyolefin polyurethane emulsion is mixed with acrylate functional monomers (hydroxyethyl acrylate, hydroxypropyl acrylate), acrylate crosslinking monomers (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 network structure is more compact, grafting or interpenetration occurs between an acrylate core and a polyolefin polyurethane shell in the polymerization process, the compatibility between the two polymers is obviously improved, the viscosity of the polyolefin polyurethane is reduced by the acrylate monomers, the polymerization is carried out under specific reaction conditions in the step c, the polymerization reaction rate is kept unchanged, the preparation process is always and stably carried out, the polyurethane-acrylate hybrid emulsion is always kept to be higher in stability in the reaction process, the possibility of transient phenomena in the conventional continuous emulsion polymerization process is reduced, and the prepared polyurethane-acrylate hybrid emulsion has higher adhesive force and film forming speed.
According to the application, the polymerization temperature in the step c is strictly controlled, so that the polyurethane-acrylic ester hybrid emulsion keeps higher stability, meanwhile, the particle size is reduced, if the polymerization temperature is too high, the thermal movement among emulsion particles in a system is aggravated, so that the emulsion is collided to generate coalescence, the particle size of the polyurethane-acrylic ester hybrid emulsion is increased, and the stability of the polyurethane-acrylic ester hybrid emulsion is reduced.
The application controls the adding proportion of each component in the preparation method, and selects specific components, so that the polyurethane-acrylic ester hybrid emulsion prepared by the application has lower VOC content, higher adhesive force, film forming speed and strength, and is 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 the mixture of the two components in any proportion is selected for use, and the mixture is added into the step c according to a specific proportion to serve as an initiator of copolymerization, so that the polymerization can be smoothly and stably 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 hydroxyl-terminated polybutadiene and hexamethylene diisocyanate are subjected to polymerization reaction, the hydroxyl-terminated polybutadiene is used as a soft segment of the hexamethylene diisocyanate, one or two components of 1, 4-butanediol and sorbitol are mixed and matched according to any proportion to be used as a chain extender, and polymerization reaction is carried out according to specific reaction conditions, so that the contact angle of 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 polyurethane emulsion is prolonged.
Preferably, the castor oil is further preferably modified castor oil obtained by modifying the castor oil with 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): and (1) mixing and stirring maleic anhydride and castor oil, and reacting for 4-4.5 h until the acid value is lower than 145mgKOH/g, and stopping the reaction to obtain the modified castor oil.
Through adopting the technical scheme, the castor oil is natural grease, has more active groups, has the main chemical structure of ricinoleic acid triglyceride, can provide active grafting points for polymerization of polyurethane and acrylic ester to form a cross-linked network structure, improves the adhesive force, film forming speed and strength of polyurethane-acrylic ester hybrid emulsion, but has lower cross-linking degree of the castor oil and other components, so that the castor oil is modified according to specific reaction conditions by adopting maleic anhydride with specific proportion, double bonds are introduced, and the cross-linking degree between the modified castor oil and each component is higher, thereby further improving the adhesive force, film forming speed and strength of the polyurethane-acrylic ester hybrid emulsion.
The application also provides the polyurethane-acrylate hybrid emulsion prepared by the method.
By adopting the technical scheme, the polyurethane-acrylate hybrid emulsion prepared by the application is soap-free hybrid emulsion, has higher adhesive force, film forming speed and strength, has lower VOC content, and is 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 acrylic ester emulsion are subjected to chemical copolymerization, so that molecules in the prepared polyurethane-acrylic ester hybrid emulsion form an interpenetrating network structure, and the adhesive force, the film forming speed and the strength of the polyurethane-acrylic ester hybrid emulsion are improved;
2. in the preparation method, the emulsifiable polyolefin polyurethane emulsion is adopted, so that the influence caused by an emulsifier is eliminated, the prepared polyurethane-acrylic ester hybrid emulsion is soap-free hybrid emulsion, the hydrophobicity and ageing resistance of the polyurethane-acrylic ester hybrid emulsion are improved, and the service life of the polyurethane-acrylic ester hybrid emulsion is prolonged;
3. the polyurethane-acrylate hybrid emulsion prepared by the preparation method disclosed by the application has low VOC content and is environment-friendly.
Detailed Description
The present application will be described in further detail with reference to examples.
Hydroxyethyl acrylate was purchased from atanan Yuanxiang chemical Co., ltd;
hydroxypropyl acrylate was purchased from Jiangsu Sanmu group Co., ltd;
hexanediol di (meth) acrylate was purchased from Hubei Heng Jing Rui chemical Co., ltd;
castor oil was purchased from south america chemical technology limited (hydroxyl value=163 mgKOH/g);
dibutyl tin dilaurate was purchased from Shandonghui chemical Co.
Example 1
The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion comprises the following steps:
a. synthesis of polyurethane prepolymer:
a1: drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at 75 ℃ for 2 hours respectively;
a2: mixing 45g of dried hydroxyl-terminated polybutadiene, 10g of castor oil, 15.2g of hydroxyl-terminated polyethylene glycol, 85g of hexamethylene diisocyanate and a catalytic amount of dibutyltin dilaurate, heating to 70 ℃ under the protection of nitrogen, and reacting for 2 hours to obtain a polyolefin type polyurethane prepolymer;
b. synthesis of polyurethane and acrylate monomer blending pre-emulsion:
b1: mixing polyolefin type polyurethane prepolymer, 3g of hydroxyethyl acrylate, 25g of hydroxypropyl acrylate, 10g of methyl methacrylate, 16g of butyl acrylate, 8g of isooctyl acrylate and 0.54g of hexanediol diacrylate, and stirring for 30min;
b2: mixing 50g of the obtained product in the step b1 with 25g of water at a high speed for emulsification for 30min at a rotation speed of 1200r/min, mixing with 0.2g of a 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 NaHCO 3 Uniformly mixing to obtain a mixed solution, then dropwise adding polyurethane and acrylate monomer blending pre-emulsion at the temperature of 80 ℃, dropwise adding for 2.0h, reacting for 0.8h after the dropwise adding is finished, cooling to 40 ℃, regulating the pH value to 7,stirring for 25min, filtering, discharging to obtain polyurethane-acrylate hybrid emulsion.
Example 2
The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion comprises the following steps:
a. synthesis of polyurethane prepolymer:
a1: drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at 80 ℃ for 2.5h respectively;
a2: mixing 50g of dried hydroxyl-terminated polybutadiene, 10g of castor oil, 15.6g of hydroxyl-terminated polyethylene glycol, 90g of hexamethylene diisocyanate and a catalytic amount of dibutyltin dilaurate, heating to 80 ℃ under the protection of nitrogen, and reacting for 2.5h to obtain a polyolefin type polyurethane prepolymer;
b. synthesis of polyurethane and acrylate monomer blending pre-emulsion:
b1: mixing polyolefin type polyurethane prepolymer, 4g of hydroxyethyl acrylate, 20g of hydroxypropyl acrylate, 15g of methyl methacrylate, 14g of butyl acrylate, 9g of isooctyl acrylate and 0.52g of hexanediol diacrylate, and stirring for 32.5min;
b2: mixing 50g of the obtained product in the step b1 with 32.5g of water at a speed of 1225r/min, emulsifying for 45min at a high speed, mixing with 0.25g of chain extender (sorbitol), and reacting for 60min to obtain 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) and 0.020g of NaHCO 3 Uniformly mixing to obtain a mixed solution, then dropwise adding polyurethane and acrylate monomer blending pre-emulsion at the temperature of 82 ℃, dropwise adding for 2.25h, reacting for 1.0h after the dropwise adding is finished, 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
The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion comprises the following steps:
a. synthesis of polyurethane prepolymer:
a1: drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at 85 ℃ for 3h respectively;
a2: 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:
b1: mixing polyolefin type polyurethane prepolymer, 5g of hydroxyethyl acrylate, 15g of hydroxypropyl acrylate, 20g of methyl methacrylate, 12g of butyl acrylate, 10g of isooctyl acrylate and 0.50g of hexanediol dimethacrylate, and stirring for 35min;
b2: mixing 50g of the obtained product in the step b1 with 40g of water at a high speed for emulsification for 60min at a rotating speed of 1250r/min, 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 NaHCO 3 Uniformly mixing to obtain a mixed solution, then dropwise adding polyurethane and acrylate monomer blending pre-emulsion at the temperature of 84 ℃, dropwise adding for 2.5h, reacting for 1.2h after the dropwise adding is finished, cooling to 50 ℃, adjusting the pH value to 9, stirring for 30min, filtering, and discharging to obtain the polyurethane-acrylate hybrid emulsion.
Example 4
The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion is different from that of the embodiment 2 in that: the castor oil is modified by the following method:
25g of maleic anhydride and 10g of castor oil are mixed and stirred at a temperature of 118 ℃ and reacted 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 preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion is different from that of the embodiment 2 in that: the castor oil is modified by the following method:
35g of maleic anhydride and 10g of castor oil are mixed and stirred at the temperature of 122 ℃ and reacted 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: in the synthesis of the polyurethane prepolymer in the step a, hydroxyl-terminated polybutadiene and castor oil are not added to obtain the common polyurethane prepolymer, and the rest are the same.
Comparative example 2
The difference from example 2 is that: castor oil was not added and the remainder were identical.
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:
adhesion test: according to GB/T2791-1995, respectively coating the polyurethane-acrylate hybrid emulsion prepared in examples 1-5 and comparative examples 1-2 on PP plastic plates, wherein the specification of each PP plastic plate is 100mm multiplied by 30mm, the coating weight of the polyurethane-acrylate hybrid emulsion on the PP plastic plate is 150g per square meter, and after naturally drying for 24 hours, testing the peel strength (N/m) of the polyurethane-acrylate hybrid emulsion;
film forming speed test: coating the polyurethane-acrylate hybrid emulsion prepared in the examples 1-5 and the comparative examples 1-2 on PP plastic plates respectively, wherein the specification of each PP plastic plate is 100mm multiplied by 30mm, the coating weight of the polyurethane-acrylate hybrid emulsion on the PP plastic plate is 150g per square meter, and recording the curing time (min) of internal complete curing;
elongation at break test: according to GB/T20028-2005, after the polyurethane-acrylate hybrid emulsion prepared in examples 1-5 and comparative examples 1-2 is cured (120 ℃ for 1 h), cutting the emulsion into strips, and testing the elongation at break (%) of the strips;
dynamic shear strength test: the dynamic shear strength (N/cm) of the polyurethane-acrylate hybrid emulsions prepared in examples 1-5 and comparative examples 1-2 was tested according to GB/T33332-2016 "test method for adhesive dynamic shear strength".
Table 1 results of performance test table
| Project | 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 application has higher adhesive force, film forming speed and dynamic shear strength, and the content of VOC (volatile organic compound) in the polyurethane-acrylate hybrid emulsion prepared by the application is lower than 20g/L, thus being environment-friendly.
Comparing the data of examples 1-3 with 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 less than that of comparative example 1, indicating that the polyurethane-acrylate hybrid emulsion prepared from the polyolefin-based polyurethane prepolymer has higher adhesion, film forming speed, aging resistance and strength.
Comparing the data of examples 4-5 with example 2, it can be seen that the peel strength, elongation at break and dynamic shear strength of examples 4-5 are higher than those of example 2, and the curing time of examples 4-5 is shorter than that of example 2, which means that the modified castor oil is modified by using maleic anhydride, so that the crosslinking degree between the modified castor oil and each component is higher, and the adhesive force, film forming speed, aging resistance and strength of the polyurethane-acrylate hybrid emulsion are improved.
Comparing the data of example 2 with 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 less than that of comparative example 2, which demonstrates that castor oil can exert a synergistic effect with hydroxyl-terminated polyethylene glycol, and significantly improve the adhesion, film forming speed and dynamic shear strength of polyurethane-acrylate hybrid emulsion.
The embodiments of the present application are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in this way, therefore: all equivalent changes in structure, shape and principle of the application should be covered in the scope of protection of the application.
Claims (6)
1. The preparation method of the environment-friendly polyurethane-acrylate hybrid emulsion is characterized by comprising the following steps of: the method comprises the following steps:
a. synthesis of polyurethane prepolymer:
a1: respectively drying hydroxyl-terminated polybutadiene, hydroxyl-terminated polyethylene glycol and castor oil at the temperature of 75-85 ℃ for 2-3 hours;
a2: mixing 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 a 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 to 5.5): (1.52-1.60): 1, a step of;
b. synthesis of polyurethane and acrylate monomer blending pre-emulsion:
b1: mixing polyolefin 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;
b2: mixing the obtained product in the step b1 with water at a high speed for emulsification for 30-60 min at a rotating speed of 1200-1250r/min, mixing with a chain extender, and reacting for 60min to obtain polyurethane and acrylate monomer blending pre-emulsion, wherein the weight ratio of the obtained product in the step b1 to the water to the chain extender is 50: (25-40): (0.2 to 0.3);
c. polyurethane-acrylate hybrid emulsion polymerization:
uniformly mixing 15-25 parts by weight of water, 0.025-0.035 part by weight of initiator and 0.015-0.025 part by weight of NaHCO3 to obtain a mixed solution, heating to 80-84 ℃, dropwise adding polyurethane and acrylate monomer blending pre-emulsion, dropwise adding for 2.0-2.5 h, reacting for 0.8-1.2 h after the dropwise adding is finished, 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 method for preparing the environment-friendly polyurethane-acrylate hybrid emulsion according to claim 1, which is characterized in that: the initiator comprises ammonium persulfate and/or sodium persulfate.
3. The method for preparing the environment-friendly polyurethane-acrylate hybrid emulsion according to claim 1, which is characterized in that: the chain extender is 1, 4-butanediol and/or sorbitol.
4. The method for preparing the environment-friendly polyurethane-acrylate hybrid emulsion according to claim 1, which is characterized in that: the castor oil is modified castor oil obtained by modifying the castor oil by using maleic anhydride as a modifier.
5. The method for preparing the environment-friendly polyurethane-acrylate hybrid emulsion according to claim 4, which is characterized in that: the modified castor oil is prepared by the following method:
at the temperature of 118-122 ℃, the weight ratio is (2.5-3.5): and (1) mixing and stirring maleic anhydride and castor oil, and reacting for 4-4.5 h until the acid value is lower than 145mgKOH/g, and stopping the reaction to obtain the modified castor oil.
6. A polyurethane-acrylate hybrid emulsion prepared by the method for preparing the environment-friendly polyurethane-acrylate hybrid emulsion according to any one of claims 1-5.
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| 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 |
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| 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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| Title |
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| Polymers from renewable resources.IX.Interpenetrating polymer networks based on castor oil polyurethane poly(hydroxyethyl methacrylate):synthesis, chemical , thermal, and mechanial properties;Pritishree Nayak;《Journal of Applied Polymer Science》;19981231;672-679 * |
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