CN113388356A - Preparation method and application of high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive - Google Patents
Preparation method and application of high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive Download PDFInfo
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- CN113388356A CN113388356A CN202010171983.0A CN202010171983A CN113388356A CN 113388356 A CN113388356 A CN 113388356A CN 202010171983 A CN202010171983 A CN 202010171983A CN 113388356 A CN113388356 A CN 113388356A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Laminated Bodies (AREA)
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Abstract
The invention provides a preparation method and application of a high-solid-content waterborne polyurethane-polyacrylate hybrid emulsion laminating adhesive, which comprises the steps of preparing an isocyanate-terminated polyurethane prepolymer, then preparing a modified polyurethane prepolymer with a terminal group containing partial double bonds, then adding partial acrylate monomers with different hardness, stirring to dilute and reduce viscosity, and then adding water to disperse at high speed to prepare a waterborne polyurethane dispersoid containing double bonds; and finally, slowly dripping the residual acrylate monomer and the initiator into the polyurethane dispersion while stirring at a proper temperature to finally prepare the water-based polyurethane polyacrylate hybrid emulsion. According to the invention, the polyurethane and polyacrylate in the hybrid emulsion have good performance complementarity, the peel strength is greatly improved, and organic solvents such as acetone and the like are not introduced in the process, so that the hybrid emulsion has the characteristics of high drying speed, low cost, greenness and no pollution compared with the traditional waterborne polyurethane.
Description
Technical Field
The invention relates to the technical field of production of plastic/plastic composite materials in flexible packaging industry, in particular to a preparation method and application of a high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive.
Background
The polyurethane adhesive has excellent performance and wide application, but the existing polyurethane adhesive mainly adopts a solvent type, and an organic solvent is inflammable, explosive, volatile and toxic, so that pollution is caused when the polyurethane adhesive is used, and the pollution is brought to public nuisance. Along with the continuous enhancement of the life health, production safety and environmental protection consciousness of people and the continuous establishment of environmental regulations of various countries, the use of the solvent type polyurethane adhesive is more and more limited, so that the pollution-free and environment-friendly water-based polyurethane adhesive becomes a hotspot of research of people, but the water-based polyurethane has the following defects: 1. due to the introduction of hydrophilic groups, the waterproof performance of the adhesive is poor, the thermal stability is not ideal, and the adhesive strength is poor compared with that of a solvent type; 2. the solid content of the water-based polyurethane dispersoid used in the current market is lower, and the solid mass fraction is usually 20 to 40 percent; 3. the cost of raw materials is high; 4. the traditional acetone method preparation process consumes energy, contains organic solvent and has large pollution; thus, appropriate modification is necessary.
Acrylate has the advantages of good adhesion, weather and water resistance, and low price, so it is commonly used to modify waterborne polyurethanes, but simply mixing these two different polymer dispersions will result in poor film properties because of the poor compatibility of the two polymers, which can lead to macroscopic phase separation.
At present, organic solvents such as acetone and the like are usually introduced in the preparation process of polyurethane-polyacrylate emulsion in the market, the organic solvents such as acetone and the like need to be removed in the later period, the acetone is difficult to recover, the energy consumption is high, in addition, the solid content is mostly lower than 50%, when the polyurethane-polyacrylate emulsion is applied to flexible package plastic/plastic structure compounding, the bonding effect and the drying speed are not ideal.
Therefore, it is necessary to invent a preparation method and application of a high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive to solve the problems.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method and application of a high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive. 1. The polyurethane and the polyacrylate in the hybrid emulsion form molecular-level composition, so that the incompatibility problem of two different polymers is solved, and the performances of the polyurethane and the polyacrylate can be tightly combined; 2. in the preparation process, no organic solvent is introduced, so that the later desolventizing process is avoided, the production process is simplified, and the environmental pollution and energy consumption are reduced; 3. the hybrid emulsion laminating adhesive with high solid content (more than 50%) can be prepared, has the advantages of high equipment utilization rate, low transportation cost, low energy consumption of unit products and the like, and is endowed with higher drying speed in the using process.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method and the application of the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion laminating adhesive are characterized in that the formula of the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion laminating adhesive comprises the following components in percentage by weight: 0.1-0.5% of crosslinking monomer, 1-5% of chain extender, 0.5-2% of hydrophilic chain extender, 10-20% of polyester or polyether polyol, 6-16% of aliphatic diisocyanate, 10-15% of acrylate monomer, 0.1-0.5% of initiator, 0.01-0.06% of catalyst and 40-50% of water, firstly preparing isocyanate-terminated polyurethane prepolymer through bulk polymerization, then reacting terminal isocyanate group with hydroxyl-containing acrylate monomer to prepare modified polyurethane prepolymer with partial double bonds at terminal group, then adding part of acrylate monomers with different degrees, stirring to dilute and reduce the hardness, and then adding water to disperse at high speed to prepare the aqueous polyurethane dispersion with the double bonds; and finally, slowly dripping the rest acrylate monomer and the initiator into the polyurethane dispersion while stirring at a proper temperature to finally prepare the waterborne polyurethane-polyacrylate hybrid emulsion, wherein the specific preparation method comprises the following steps:
s1: firstly, all polyester or polyether polyol is dehydrated for 2 hours in vacuum at the temperature of 120 ℃ under the condition of stirring.
S2: adding all aliphatic diisocyanate at 80-100 ℃ at one time, carrying out heat preservation reaction for 1h, then continuously adding a crosslinking monomer and a micromolecule chain extender, and carrying out heat preservation reaction for 3h at 80-100 ℃.
S3: cooling to 60-80 ℃, adding a hydroxyl-containing acrylate monomer into the reaction system, carrying out heat preservation reaction for 1h under the stirring condition, adding part of acrylate monomers with different hardness to dilute, cooling to 30-50 ℃, continuously transferring to a high-speed dispersion machine, and adding water to carry out high-speed dispersion for 30 minutes.
S4: dissolving an initiator in part of acrylate monomers, slowly dropwise adding the initiator into the dispersion machine under the stirring condition at 75 ℃ for 2-4 h, then heating to 82 ℃, continuously carrying out heat preservation reaction for 1-2 h, cooling to below 40 ℃, and discharging.
Preferably, no organic solvent is introduced in the preparation process of the high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive.
Preferably, the crosslinking monomer is a crosslinking monomer having three or more hydroxyl groups, such as glycerol, trimethylolpropane, pentaerythritol, or the like. The acrylate monomer containing hydroxyl is one of hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate; the acrylate monomer is at least one of butyl acrylate, ethyl acrylate, methyl methacrylate, butyl methacrylate, methyl acrylate, hydroxypropyl methacrylate and hydroxyethyl methacrylate.
Preferably, the initiator is at least one of dibenzoyl peroxide and azobisisobutyronitrile.
Preferably, the polyester or polyether polyol is at least one of polybutylene adipate glycol, polycaprolactone glycol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol.
Preferably, the mass fraction of polyacrylate in the preparation system of the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion laminating adhesive can be adjusted, when the mass fraction is 30%, the hybrid emulsion has the best adhesive property on plastic/plastic compounding, and meanwhile, the hybrid emulsion formed by bonding polyacrylate and polyurethane in a chemical bond mode has better chemical stability.
Preferably, the content of the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion can reach 55%, and the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion has a high drying speed and is convenient to construct.
Preferably, the high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive has better peel strength when being applied to plastic/plastic compounding.
The invention has the beneficial effects that:
(1) the invention selects the polyester polyol or polyether polyol with a certain molecular weight range and the proper isocyanate index R, so that the finally prepared polyurethane prepolymer can be subjected to phase transition as early as possible in the dispersing process to obtain the emulsion with high solid content and low viscosity, thereby reducing the water volatilization load, shortening the film forming and drying time, saving more energy in process and improving the production efficiency.
(2) According to the invention, acrylate monomers with different hardness and different proportion are selected to be compounded with the polyurethane dispersoid according to different proportion, and finally the molecular-level compound polyurethane-polyacrylate hybrid emulsion is formed, so that better initial adhesion and peel strength can be achieved on plastic/plastic compounding.
(3) According to the invention, the polyurethane prepolymer is diluted and viscosity reduced by adopting a part of acrylate monomers to replace organic solvents (acetone, butanone and the like) in the traditional method, so that the use of the organic solvents is avoided, and the polyurethane prepolymer is more green, environment-friendly and safe, and the complex process of later desolventizing is avoided, the energy consumption is reduced, and the characteristics of energy conservation and environmental protection are realized.
Detailed Description
The present invention will be further described with reference to specific embodiments for the purpose of facilitating an understanding of technical means, characteristics of creation, objectives and functions realized by the present invention, but the following embodiments are only preferred embodiments of the present invention, and are not intended to be exhaustive. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention. The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The first embodiment is as follows:
a preparation method of a high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive comprises the following steps:
adding 83.05g of polybutylene adipate glycol with the molecular weight of 1000g/mol into a four-neck flask, carrying out vacuum dehydration for 2h at the temperature of 120 ℃, then cooling to 90 ℃, adding 55.85g of isophorone diisocyanate, carrying out heat preservation reaction for 1h, adding 1.5g of trimethylolpropane, 7.35g of dimethylolpropionic acid, 2.25g of 1, 4-butanediol and 7.35g of N-methylpyrrolidone, continuing to react for 3h at the temperature of 90 ℃, then cooling to 75 ℃, adding 9.1g of hydroxyethyl acrylate, stirring and reacting for 1h, cooling to 50 ℃, adding 30g of methyl methacrylate and 15g of butyl acrylate, diluting uniformly, then adding 277.8g of water, and dispersing at a high speed for 30 min at the condition of 2000 r/min; dissolving 1.1g of azobisisobutyronitrile into a mixed solution of 15.5g of methyl methacrylate and 7.7g of butyl acrylate, slowly dropwise adding into the dispersion within 3h at 80 ℃, heating to 82 ℃ after dropwise adding, keeping the temperature for 1.5h, cooling to below 40 ℃, and discharging to obtain the waterborne polyurethane-polyacrylate hybrid emulsion.
Example two:
a preparation method of a high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive comprises the following steps:
adding 19.28g of polypropylene glycol with the molecular weight of 1000g/mol and 77.11g of polybutylene adipate glycol with the molecular weight of 1000g/mol into a four-neck flask, carrying out vacuum dehydration for 2h at 120 ℃, then cooling to 90 ℃, adding 33.87g of hexamethylene diisocyanate, carrying out heat preservation reaction for 1h, adding 1.8g of trimethylolpropane, 7.53g of dimethylolpropionic acid, 2.12g of 1, 4-butanediol and 7.53g of N-methylpyrrolidone, continuing to react for 3h at 90 ℃, then cooling to 75 ℃, adding 7.6g of hydroxyethyl methacrylate, stirring and reacting for 1h, cooling to 50 ℃ after the reaction is finished, adding 35g of methyl methacrylate and 10g of butyl acrylate, diluting uniformly, then adding 277.8g of water, and carrying out high-speed dispersion for 30 min at 2000 r/min; dissolving 1.1g of azobisisobutyronitrile into a mixed solution of 10.5g of methyl methacrylate and 12.7g of butyl acrylate, slowly dropwise adding into the dispersion within 3h at 80 ℃, heating to 82 ℃ after dropwise adding, keeping the temperature for 1.5h, cooling to below 40 ℃, and discharging to obtain the waterborne polyurethane-polyacrylate hybrid emulsion.
The adhesives prepared in examples 1-2 were coated on a dry film coater, and the results are shown in tables 1-2 below.
TABLE 1
TABLE 2
The data in the table show that the water-based laminating adhesive has better peel strength when applied to plastic-plastic compounding.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A preparation method of a high solid content waterborne polyurethane polyacrylate hybrid emulsion laminating adhesive is characterized by comprising the following steps: the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion laminating adhesive comprises the following components in percentage by weight: 0.1-0.5% of crosslinking monomer, 1-5% of chain extender, 0.5-2% of hydrophilic chain extender, 10-20% of polyester or polyether polyol, 6-16% of aliphatic diisocyanate, 10-15% of acrylate monomer, 0.1-0.5% of initiator, 0.01-0.06% of catalyst and 40-50% of water, firstly preparing isocyanate-terminated polyurethane prepolymer through bulk polymerization, then reacting terminal isocyanate group with hydroxyl-containing acrylate monomer to prepare modified polyurethane prepolymer with partial double bonds at terminal group, then adding part of acrylate monomers with different degrees, stirring to dilute and reduce the hardness, and then adding water to disperse at high speed to prepare the aqueous polyurethane dispersion with the double bonds; and finally, slowly dripping the rest acrylate monomer and the initiator into the polyurethane dispersion while stirring at a proper temperature to finally prepare the waterborne polyurethane-polyacrylate hybrid emulsion, wherein the specific preparation method comprises the following steps:
s1: firstly, all polyester or polyether polyol is dehydrated for 2 hours in vacuum at the temperature of 120 ℃ under the condition of stirring.
S2: adding all aliphatic diisocyanate at 80-100 ℃ at one time, carrying out heat preservation reaction for 1h, then continuously adding a crosslinking monomer and a micromolecule chain extender, and carrying out heat preservation reaction for 3h at 80-100 ℃.
S3: cooling to 60-80 ℃, adding a hydroxyl-containing acrylate monomer into the reaction system, carrying out heat preservation reaction for 1h under the stirring condition, adding part of acrylate monomers with different hardness to dilute, cooling to 30-50 ℃, continuously transferring to a high-speed dispersion machine, and adding water to carry out high-speed dispersion for 30 minutes.
S4: dissolving an initiator in part of acrylate monomers, slowly dropwise adding the initiator into the dispersion machine under the stirring condition at 75 ℃ for 2-4 h, then heating to 82 ℃, continuously carrying out heat preservation reaction for 1-2 h, cooling to below 40 ℃, and discharging.
2. The preparation method of the high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive according to claim 1, which is characterized by comprising the following steps: no organic solvent is introduced in the preparation process of the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion laminating adhesive.
3. The preparation method of the high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive according to claim 1, which is characterized by comprising the following steps: the crosslinking monomer is a crosslinking monomer containing more than three hydroxyl groups, such as glycerol, trimethylolpropane, pentaerythritol and the like. The acrylate monomer containing hydroxyl is one of hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate; the acrylate monomer is at least one of butyl acrylate, ethyl acrylate, methyl methacrylate, butyl methacrylate, methyl acrylate, hydroxypropyl methacrylate and hydroxyethyl methacrylate.
4. The preparation method of the high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive according to claim 1, which is characterized by comprising the following steps: the initiator is at least one of dibenzoyl peroxide and azobisisobutyronitrile.
5. The preparation method of the high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive according to claim 1, which is characterized by comprising the following steps: the polyester or polyether polyol is at least one of polybutylene adipate glycol, polycaprolactone glycol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol.
6. The preparation method of the high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive according to claim 1, which is characterized by comprising the following steps: in the preparation system of the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion laminating adhesive, the mass fraction of polyacrylate can be adjusted, when the mass fraction is 30%, the hybrid emulsion has the best adhesive property on plastic/plastic compounding, and meanwhile, the hybrid emulsion formed by bonding polyacrylate and polyurethane in a chemical bond mode has better chemical stability.
7. The preparation method of the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion laminating adhesive as claimed in claim 1, is characterized in that: the content of the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion can be 55%, and the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion has a high drying speed and is convenient to construct.
8. The application of the high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive as described in any one of claims 1 to 7, wherein the high-solid-content water-based polyurethane polyacrylate hybrid emulsion laminating adhesive comprises the following components in percentage by weight: the high-solid-content waterborne polyurethane polyacrylate hybrid emulsion laminating adhesive has better peel strength when being applied to plastic/plastic compounding.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956824A (en) * | 2021-10-19 | 2022-01-21 | 安徽匠星联创新材料科技有限公司 | Reactive all-solid-containing cationic polyurethane-acrylate copolymer adhesive and synthesis method and application thereof |
| CN115074061A (en) * | 2022-07-05 | 2022-09-20 | 湖南林特科技有限公司 | Surface coating adhesive for impregnated paper and preparation method thereof |
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| CN101357978A (en) * | 2007-07-31 | 2009-02-04 | 中科院嘉兴中心应用化学分中心 | Waterborne polyurethane-polyacrylate emulsion and preparation method thereof |
| CN101768416A (en) * | 2008-12-29 | 2010-07-07 | 北京高盟化工有限公司 | Aqueous composite adhesive and preparation method and use thereof |
| CN106065049A (en) * | 2016-06-01 | 2016-11-02 | 南雄市瑞晟化学工业有限公司 | High solids content environment-friendly water-based polyurethane acrylate composite emulsion and preparation method thereof |
| US20170107319A1 (en) * | 2015-10-19 | 2017-04-20 | Nan Ya Plastics Corporation | Process for preparing solvent-free aqueous polyurethane dispersion |
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2020
- 2020-03-12 CN CN202010171983.0A patent/CN113388356A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357978A (en) * | 2007-07-31 | 2009-02-04 | 中科院嘉兴中心应用化学分中心 | Waterborne polyurethane-polyacrylate emulsion and preparation method thereof |
| CN101768416A (en) * | 2008-12-29 | 2010-07-07 | 北京高盟化工有限公司 | Aqueous composite adhesive and preparation method and use thereof |
| US20170107319A1 (en) * | 2015-10-19 | 2017-04-20 | Nan Ya Plastics Corporation | Process for preparing solvent-free aqueous polyurethane dispersion |
| CN106065049A (en) * | 2016-06-01 | 2016-11-02 | 南雄市瑞晟化学工业有限公司 | High solids content environment-friendly water-based polyurethane acrylate composite emulsion and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956824A (en) * | 2021-10-19 | 2022-01-21 | 安徽匠星联创新材料科技有限公司 | Reactive all-solid-containing cationic polyurethane-acrylate copolymer adhesive and synthesis method and application thereof |
| CN113956824B (en) * | 2021-10-19 | 2022-10-25 | 安徽匠星联创新材料科技有限公司 | Reactive full-solid-content cationic polyurethane-acrylate copolymer adhesive and synthesis method and application thereof |
| CN115074061A (en) * | 2022-07-05 | 2022-09-20 | 湖南林特科技有限公司 | Surface coating adhesive for impregnated paper and preparation method thereof |
| CN115074061B (en) * | 2022-07-05 | 2024-04-12 | 湖南林特科技有限公司 | Surface coating adhesive for impregnated paper and preparation method thereof |
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