CN114437618A - Waterborne polyurethane adhesive and preparation method thereof - Google Patents
Waterborne polyurethane adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN114437618A CN114437618A CN202210219101.2A CN202210219101A CN114437618A CN 114437618 A CN114437618 A CN 114437618A CN 202210219101 A CN202210219101 A CN 202210219101A CN 114437618 A CN114437618 A CN 114437618A
- Authority
- CN
- China
- Prior art keywords
- parts
- resin
- polyurethane adhesive
- waterborne polyurethane
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/04—Printing inks based on proteins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/06—Printing inks based on fatty oils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/08—Printing inks based on natural resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention relates to the technical field of adhesive preparation, in particular to a water-based polyurethane adhesive and a preparation method thereof, wherein each part of the adhesive comprises the following raw materials in parts by mass: 100-110 parts of waterborne polyurethane resin, 1-5 parts of phenolic resin, 2-6 parts of organic silicon flatting agent, 2-4 parts of polysiloxane, 12-20 parts of cross-linking agent, 1-3 parts of triazine ring, 0.7-0.9 part of pH regulator, 10-30 parts of phenol, 2-10 parts of 2-imidazolidinone and 1-3 parts of diethylenetriamine, and the preparation method comprises the following steps: s1, weighing the raw materials according to the formula for later use; and S2, putting the waterborne polyurethane resin into a mixer, sequentially adding the weight-divided resin, the organic silicon leveling agent, the polysiloxane, the cross-linking agent, the phenol, the 2-imidazolidinone and the diethylenetriamine into the mixer, and stirring and mixing for 1-3 hours until the mixture is uniformly stirred. The invention not only can obviously improve the hydrolysis resistance of the waterborne polyurethane adhesive, but also can play a role in purifying formaldehyde molecules, thereby providing good prospect for the application of the waterborne polyurethane adhesive in indoor environment.
Description
Technical Field
The invention relates to the technical field of adhesive preparation, in particular to a water-based polyurethane adhesive and a preparation method thereof.
Background
With the enhancement of the awareness of safety and environmental protection, the research on the waterborne polyurethane adhesive is rapidly developed. The water-based polyurethane adhesive is formed by dissolving or dispersing polyurethane in water, and has the advantages of no solvent, no pollution, good film forming property, strong bonding force, easy mixing with other polymers, particularly emulsion polymers, and the like, compared with a solvent type adhesive. The adhesive has been gradually applied to the aspects of automobile interior trim adhesion, kitchen article manufacturing, composite film manufacturing, sole and upper adhesion, garment processing and the like.
In addition to maintaining the advantages of polyurethane, the waterborne polyurethane adhesive has the disadvantages of insufficient hydrolysis resistance compared with a solvent-based polyurethane adhesive, and when the waterborne polyurethane adhesive is used as an automobile interior adhesive, a kitchen product manufacturing environment and the like in a relatively closed environment, how to reduce the content of formaldehyde molecules in the environment is also a big problem, so that a waterborne polyurethane adhesive and a preparation method thereof are needed to solve the problem.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a water-based polyurethane adhesive and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100-110 parts of waterborne polyurethane resin, 1-5 parts of phenolic resin, 2-6 parts of organic silicon flatting agent, 2-4 parts of polysiloxane, 12-20 parts of cross-linking agent, 1-3 parts of triazine ring, 0.7-0.9 part of pH regulator, 10-30 parts of phenol, 2-10 parts of 2-imidazolidinone and 1-3 parts of diethylenetriamine.
Preferably, the silicone leveling agent is polydimethylsiloxane.
Preferably, the cross-linking agent is formed by mixing amino resin and aluminum phosphate according to the mass ratio of 3: 1.
Preferably, the amino resin is any one of urea-formaldehyde resin, melamine-formaldehyde resin and polyamide polyamine epichlorohydrin.
Preferably, the mass of the phenol is between 1.3 and 1.5 times the mass of the cross-linking agent.
Preferably, the mass ratio of the 2-imidazolidinone to the diethylenetriamine is 3: 1.
A preparation method of a water-based polyurethane adhesive comprises the following steps:
s1, weighing the raw materials according to the formula for later use;
s2, putting the waterborne polyurethane resin into a mixer, sequentially adding the weight-divided resin, the organic silicon leveling agent, the polysiloxane, the cross-linking agent, the phenol, the 2-imidazolidinone and the diethylenetriamine into the mixer, and stirring and mixing for 1-3 hours until the mixture is uniformly stirred;
s3, continuously adding the pH regulator into the mixer until the pH value reaches 7.3, then adding the triazine ring into the mixer, continuously stirring and mixing for 1-2 hours until the mixture is uniformly stirred, and taking out the mixture to obtain the waterborne polyurethane adhesive.
Preferably, the stirring speed in S2 is 1300-1500rpm, and the stirring speed in S3 is 800-900 rpm.
The invention has the beneficial effects that:
1. in the invention, the mixture of amino resin and aluminum phosphate is used as a cross-linking agent, and a proper amount of triazine ring and a little excessive phenol are added, so that the triazine ring with stable structure is introduced into the resin environment of the adhesive, and can be matched with the phenol and effectively improve the hydrolysis resistance of the adhesive.
2. In the invention, on the basis of adding slightly excessive phenol, 2-imidazolidinone and diethylenetriamine are matched, formaldehyde molecules are captured and obtained through the 2-imidazolidinone, so that redundant phenol can quickly contact with formaldehyde and react to generate phenolic resin to improve the thickening effect of the adhesive, the formaldehyde molecules can be captured, and the captured formaldehyde molecules can be prevented from overflowing and scattering again by utilizing the fixing effect of the diethylenetriamine on the formaldehyde molecules, thereby improving the formaldehyde removal and purification effect.
In conclusion, the invention not only can obviously improve the hydrolysis resistance of the waterborne polyurethane adhesive, but also can play a role in purifying formaldehyde molecules, thereby providing good prospects for the application of the waterborne polyurethane adhesive in indoor environment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Example 1:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 16.8 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Example 2:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 105 parts of aqueous polyurethane resin, 3 parts of phenolic resin, 4 parts of polydimethylsiloxane, 3 parts of polysiloxane, 12 parts of urea-formaldehyde resin, 4 parts of aluminum phosphate, 2 parts of triazine ring, 0.8 part of pH regulator, 22.4 parts of phenol, 6 parts of 2-imidazolidinone and 2 parts of diethylenetriamine.
Example 3:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 110 parts of aqueous polyurethane resin, 5 parts of phenolic resin, 6 parts of polydimethylsiloxane, 4 parts of polysiloxane, 15 parts of urea-formaldehyde resin, 5 parts of aluminum phosphate, 3 parts of triazine ring, 0.9 part of pH regulator, 28 parts of phenol, 9 parts of 2-imidazolidinone and 3 parts of diethylenetriamine.
The raw materials of the above examples 1-3 were all processed to prepare aqueous polyurethane adhesives by the following processes:
a preparation method of a water-based polyurethane adhesive comprises the following steps:
s1, weighing the raw materials according to the formula for later use;
s2, putting the waterborne polyurethane resin into a mixer, sequentially adding the weight-divided resin, the organic silicon leveling agent, the polysiloxane, the cross-linking agent, the phenol, the 2-imidazolidinone and the diethylenetriamine into the mixer, and stirring and mixing at the rotating speed of 1300rpm for 3 hours until the mixture is uniformly stirred;
and S3, continuously adding the pH regulator into the mixer until the pH value reaches 7.3, then adding the triazine ring into the mixer, continuously stirring and mixing the mixture for 1 hour at the rotating speed of 800rpm until the mixture is uniformly stirred, and taking the mixture out to obtain the waterborne polyurethane adhesive.
Test one: determination of hydrolysis resistance of aqueous polyurethane adhesive
Experiment I, when the raw material formulation does not add triazine ring, can cancel the addition to pH regulator at the same time, and set up the following comparative example:
comparative example 1:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of waterborne polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 16.8 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Comparative example 2:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 105 parts of aqueous polyurethane resin, 3 parts of phenolic resin, 4 parts of polydimethylsiloxane, 3 parts of polysiloxane, 12 parts of urea-formaldehyde resin, 4 parts of aluminum phosphate, 22.4 parts of phenol, 6 parts of 2-imidazolidinone and 2 parts of diethylenetriamine.
Comparative example 3:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 110 parts of aqueous polyurethane resin, 5 parts of phenolic resin, 6 parts of polydimethylsiloxane, 4 parts of polysiloxane, 15 parts of urea-formaldehyde resin, 5 parts of aluminum phosphate, 28 parts of phenol, 9 parts of 2-imidazolidinone and 3 parts of diethylenetriamine.
The raw materials of comparative examples 1 to 3 above were all prepared into an aqueous polyurethane adhesive by the following procedure:
a preparation method of a water-based polyurethane adhesive comprises the following steps:
s1, weighing the raw materials according to the formula for later use;
and S2, putting the waterborne polyurethane resin into a mixer, sequentially adding the weight-divided resin, the organic silicon leveling agent, the polysiloxane, the cross-linking agent, the phenol, the 2-imidazolidinone and the diethylenetriamine into the mixer, and stirring and mixing at the rotating speed of 1300rpm for 3 hours until the mixture is uniformly stirred to obtain the waterborne polyurethane adhesive.
The following hydrolysis resistance test was performed on the aqueous polyurethane adhesives of the above examples 1 to 3 and comparative examples 1 to 3:
a water-based polyurethane adhesive was used as a sample, which was applied to a polytetrafluoroethylene test plate, allowed to stand at room temperature for 7 days to naturally dry to form a film, the film (thickness: 0.4mm) was cut into a size of 30mm × 30mm, immersed in tap water at 25 ℃ for 24 hours, and the change in mass before and after immersion was observed or weighed, and the water absorption rate was calculated as follows:
as can be seen from the test results in the above table, when each group of tests only differs in the presence or absence of triazine ring, the hydrolysis resistance of the aqueous polyurethane adhesive in the examples is better than that of the aqueous polyurethane adhesive in the comparative examples.
Experiment 2, when the amount of phenol added in the raw material formula is too small or too large, the following examples and comparative examples are set:
example 4:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 15.6 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Example 5:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 18 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Comparative example 4:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 14.4 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Comparative example 5:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 13.2 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Comparative example 6:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 12 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Comparative example 7:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 19.2 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Comparative example 8:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 20.4 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Comparative example 9:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 21.6 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
The preparation processes of the aqueous polyurethane adhesives in the above examples 4 to 5 and comparative examples 4 to 9 were the same as those in examples 1 to 3.
Examples 1, 4-5 and comparative examples 4-9 were each tested according to the procedure of testing hydrolysis resistance in experiment (r), and the test results are reported in the following table:
from the above test results, it can be seen that the water absorption of the waterborne polyurethane adhesive is less than 5.5% when the mass ratio of phenol to the crosslinking agent is between 1.3:1 and 1.5:1, and the water absorption starts to gradually increase when the mass ratio of phenol to the crosslinking agent is less than 1.3:1, and the water absorption starts to gradually increase when the mass ratio of phenol to the crosslinking agent is more than 1.5:1, so that the optimal mass ratio of phenol to crosslinking agent in the formulation is 1.3:1 to 1.5: 1.
And (2) test II: measurement of Formaldehyde purification Effect of aqueous polyurethane adhesive
Experiment (c), when one or two of 2-imidazolidinone and diethylenetriamine is/are added in the raw material formula, the following comparative examples are set:
comparative example 10:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 16.8 parts of phenol and 3 parts of 2-imidazolidinone.
Comparative example 11:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 105 parts of aqueous polyurethane resin, 3 parts of phenolic resin, 4 parts of polydimethylsiloxane, 3 parts of polysiloxane, 12 parts of urea-formaldehyde resin, 4 parts of aluminum phosphate, 2 parts of triazine ring, 0.8 part of pH regulator, 22.4 parts of phenol and 6 parts of 2-imidazolidinone.
Comparative example 12:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 110 parts of aqueous polyurethane resin, 5 parts of phenolic resin, 6 parts of polydimethylsiloxane, 4 parts of polysiloxane, 15 parts of urea-formaldehyde resin, 5 parts of aluminum phosphate, 3 parts of triazine ring, 0.9 part of pH regulator, 28 parts of phenol and 9 parts of 2-imidazolidinone.
The raw materials of the above comparative examples 10 to 12 were all subjected to the following procedure for preparing an aqueous polyurethane adhesive:
a preparation method of a water-based polyurethane adhesive comprises the following steps:
s1, weighing the raw materials according to the formula for later use;
s2, putting the waterborne polyurethane resin into a mixer, sequentially adding the weight-divided resin, the organic silicon leveling agent, the polysiloxane, the cross-linking agent, the phenol and the 2-imidazolidinone into the mixer, and stirring and mixing at the rotating speed of 1300rpm for 3 hours until the mixture is uniformly stirred;
and S3, continuously adding the pH regulator into the mixer until the pH value reaches 7.3, then adding the triazine ring into the mixer, continuously stirring and mixing the mixture for 1 hour at the rotating speed of 800rpm until the mixture is uniformly stirred, and taking the mixture out to obtain the waterborne polyurethane adhesive.
Comparative example 13:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator and 16.8 parts of phenol.
Comparative example 14:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 105 parts of aqueous polyurethane resin, 3 parts of phenolic resin, 4 parts of polydimethylsiloxane, 3 parts of polysiloxane, 12 parts of urea-formaldehyde resin, 4 parts of aluminum phosphate, 2 parts of triazine ring, 0.8 part of pH regulator and 22.4 parts of phenol.
Comparative example 15:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 110 parts of aqueous polyurethane resin, 5 parts of phenolic resin, 6 parts of polydimethylsiloxane, 4 parts of polysiloxane, 15 parts of urea-formaldehyde resin, 5 parts of aluminum phosphate, 3 parts of triazine ring, 0.9 part of pH regulator and 28 parts of phenol.
The raw materials of the above comparative examples 13 to 15 were all subjected to the following procedure for preparing an aqueous polyurethane adhesive:
a preparation method of a water-based polyurethane adhesive comprises the following steps:
s1, weighing the raw materials according to the formula for later use;
s2, putting the waterborne polyurethane resin into a mixer, sequentially adding the weight-divided resin, the organic silicon leveling agent, the polysiloxane, the cross-linking agent and the phenol into the mixer, and stirring and mixing at the rotating speed of 1300rpm for 3 hours until the materials are uniformly stirred;
and S3, continuously adding the pH regulator into the mixer until the pH value reaches 7.3, then adding the triazine ring into the mixer, continuously stirring and mixing the mixture for 1 hour at the rotating speed of 800rpm until the mixture is uniformly stirred, and taking the mixture out to obtain the waterborne polyurethane adhesive.
The aqueous polyurethane adhesives of examples 1 to 3 and comparative examples 10 to 15 described above were subjected to the following tests for formaldehyde purification:
10 artificial boards (with the length of 50mm, the width of 50mm and the thickness of 10mm) are taken for each group of tests, the waterborne polyurethane adhesive used for the group of tests is coated on the surface of the artificial boards (the initial formaldehyde concentration C1 on the artificial boards is measured by a formaldehyde detector before coating), after the coating is finished, the artificial boards are sealed by a vinyl bag, each group of samples are kept at certain intervals, the samples are placed for 7 days under the constant temperature condition of 20 ℃, the formaldehyde concentration C2 on the artificial boards is measured by the formaldehyde detector after 7 days, the C1 and the C2 are average values, and the results are recorded in the following table:
from the above test results, it can be seen that when diethylenetriamine is absent from the formulation of the raw materials in the aqueous polyurethane adhesive (i.e., comparative examples 10 to 12), the formaldehyde-purifying effect of the adhesive is reduced, and when 2-imidazolidinone and diethylenetriamine are absent from the formulation of the raw materials in the aqueous polyurethane adhesive (i.e., comparative examples 13 to 15), the formaldehyde-purifying effect of the adhesive is slightly reduced compared to the former, and thus, the formaldehyde-purifying effect can be more remarkably improved by the combination of 2-imidazolidinone and diethylenetriamine.
Experiment (c), when the amount of phenol added in the raw material formula is too small, taking comparative examples 4-6 set up in experiment (c) as reference of the experiment, and comparing with examples 4-5 set up in example 1 and experiment (c), the following comparative examples are set up:
comparative example 16:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 10.8 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Comparative example 17:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 9.6 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
Comparative example 18:
the waterborne polyurethane adhesive comprises the following raw materials in parts by mass: 100 parts of aqueous polyurethane resin, 1 part of phenolic resin, 2 parts of polydimethylsiloxane, 2 parts of polysiloxane, 9 parts of urea-formaldehyde resin, 3 parts of aluminum phosphate, 1 part of triazine ring, 0.7 part of pH regulator, 8.4 parts of phenol, 3 parts of 2-imidazolidinone and 1 part of diethylenetriamine.
The preparation processes of the aqueous polyurethane adhesives in the above comparative examples 16 to 18 were all in accordance with those of examples 1 to 3.
The above examples and comparative examples were carried out in the same manner as described for the formaldehyde purification test in experiment (c), and the results are reported in the following table:
from the above test results, it can be seen that the removal rate of example 1, example 4 and example 5 can reach 97% or more, while the removal rate of formaldehyde is reduced in comparative examples 4 to 6 and comparative examples 16 to 18 because the content of phenol is reduced, so that the excessive formaldehyde molecules captured and fixed do not react and purify, and the final removal rate of formaldehyde is reduced, and when the ratio of phenol to crosslinking agent is less than 1:1, the reduction of the removal rate is larger, and therefore, it is difficult to completely purify the formaldehyde molecules when the amount of phenol is too small.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The water-based polyurethane adhesive is characterized in that each part of the adhesive comprises the following raw materials in parts by mass: 100-110 parts of waterborne polyurethane resin, 1-5 parts of phenolic resin, 2-6 parts of organic silicon flatting agent, 2-4 parts of polysiloxane, 12-20 parts of cross-linking agent, 1-3 parts of triazine ring, 0.7-0.9 part of pH regulator, 10-30 parts of phenol, 2-10 parts of 2-imidazolidinone and 1-3 parts of diethylenetriamine.
2. The aqueous polyurethane adhesive of claim 1, wherein the silicone leveling agent is polydimethylsiloxane.
3. The waterborne polyurethane adhesive of claim 1, wherein the cross-linking agent is formed by mixing amino resin and aluminum phosphate according to a mass ratio of 3: 1.
4. The waterborne polyurethane adhesive of claim 3, wherein the amino resin is any one of urea formaldehyde resin, melamine formaldehyde resin and polyamide polyamine epichlorohydrin.
5. The aqueous polyurethane adhesive of claim 1, wherein the phenol is present in an amount of 1.3 to 1.5 times the amount of the crosslinking agent.
6. The aqueous polyurethane adhesive according to claim 1, wherein the mass ratio of the 2-imidazolidinone to the diethylenetriamine is 3: 1.
7. The preparation method of the aqueous polyurethane adhesive as claimed in claims 1 to 6, comprising the steps of:
s1, weighing the raw materials according to the formula for later use;
s2, putting the waterborne polyurethane resin into a mixer, sequentially adding the weight-divided resin, the organic silicon leveling agent, the polysiloxane, the cross-linking agent, the phenol, the 2-imidazolidinone and the diethylenetriamine into the mixer, and stirring and mixing for 1-3 hours until the mixture is uniformly stirred;
s3, continuously adding the pH regulator into the mixer until the pH value reaches 7.3, then adding the triazine ring into the mixer, continuously stirring and mixing for 1-2 hours until the mixture is uniformly stirred, and taking out the mixture to obtain the waterborne polyurethane adhesive.
8. The method as claimed in claim 7, wherein the stirring speed in S2 is 1300-1500rpm, and the stirring speed in S3 is 800-900 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219101.2A CN114437618A (en) | 2022-03-08 | 2022-03-08 | Waterborne polyurethane adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219101.2A CN114437618A (en) | 2022-03-08 | 2022-03-08 | Waterborne polyurethane adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114437618A true CN114437618A (en) | 2022-05-06 |
Family
ID=81360258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210219101.2A Withdrawn CN114437618A (en) | 2022-03-08 | 2022-03-08 | Waterborne polyurethane adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114437618A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4197219A (en) * | 1979-01-17 | 1980-04-08 | Lord Corporation | Aqueous polyurethane-phenolic-formaldehyde resin emulsions for use as adhesives, primers and surface coatings |
| JPH0987487A (en) * | 1995-09-21 | 1997-03-31 | Dainippon Ink & Chem Inc | Thermoplastic resin composition, laminated sheet using the same and its production |
| JP2002194043A (en) * | 2000-12-25 | 2002-07-10 | Sumitomo Bakelite Co Ltd | Amino resin composition and decorative sheet using the same |
| JP2006045546A (en) * | 2004-07-05 | 2006-02-16 | Dainippon Ink & Chem Inc | Thermosetting resin composition, boric acid-modified triazine structure-containing novolac resin and their preparation processes |
| CN105385097A (en) * | 2015-12-28 | 2016-03-09 | 上海锦湖日丽塑料有限公司 | Self-formaldehyde-clearing and heat-resistant acrylonitrile butadiene styrene (ABS) material and preparation method thereof |
| CN107868642A (en) * | 2017-12-06 | 2018-04-03 | 安徽格瑞恩园林工程有限公司 | Building Adhesive of the high acid and alkali-resistance of adhesive strength and preparation method thereof |
| CN110835514A (en) * | 2019-11-12 | 2020-02-25 | 江阴市威腾铝箔合成材料有限公司 | Double-component flame-retardant polyurethane adhesive and preparation method thereof |
| CN113617203A (en) * | 2021-08-02 | 2021-11-09 | 柳州佳饰家装饰材料有限公司 | Formaldehyde removal auxiliary agent and preparation method thereof |
| CN113733286A (en) * | 2021-09-08 | 2021-12-03 | 大亚人造板集团有限公司 | Manufacturing process of JIS-18 type shaving board |
-
2022
- 2022-03-08 CN CN202210219101.2A patent/CN114437618A/en not_active Withdrawn
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4197219A (en) * | 1979-01-17 | 1980-04-08 | Lord Corporation | Aqueous polyurethane-phenolic-formaldehyde resin emulsions for use as adhesives, primers and surface coatings |
| JPH0987487A (en) * | 1995-09-21 | 1997-03-31 | Dainippon Ink & Chem Inc | Thermoplastic resin composition, laminated sheet using the same and its production |
| JP2002194043A (en) * | 2000-12-25 | 2002-07-10 | Sumitomo Bakelite Co Ltd | Amino resin composition and decorative sheet using the same |
| JP2006045546A (en) * | 2004-07-05 | 2006-02-16 | Dainippon Ink & Chem Inc | Thermosetting resin composition, boric acid-modified triazine structure-containing novolac resin and their preparation processes |
| CN105385097A (en) * | 2015-12-28 | 2016-03-09 | 上海锦湖日丽塑料有限公司 | Self-formaldehyde-clearing and heat-resistant acrylonitrile butadiene styrene (ABS) material and preparation method thereof |
| CN107868642A (en) * | 2017-12-06 | 2018-04-03 | 安徽格瑞恩园林工程有限公司 | Building Adhesive of the high acid and alkali-resistance of adhesive strength and preparation method thereof |
| CN110835514A (en) * | 2019-11-12 | 2020-02-25 | 江阴市威腾铝箔合成材料有限公司 | Double-component flame-retardant polyurethane adhesive and preparation method thereof |
| CN113617203A (en) * | 2021-08-02 | 2021-11-09 | 柳州佳饰家装饰材料有限公司 | Formaldehyde removal auxiliary agent and preparation method thereof |
| CN113733286A (en) * | 2021-09-08 | 2021-12-03 | 大亚人造板集团有限公司 | Manufacturing process of JIS-18 type shaving board |
Non-Patent Citations (1)
| Title |
|---|
| 方瑞娜等: "胺类甲醛清除剂的甲醛净化效果研究", 《黄河水利职业技术学院学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5547764A (en) | Method of producing PVOH coatings with enhanced properties | |
| CN109749690A (en) | Epoxy resin modified aqueous polyurethane adhesive for building and preparation method thereof | |
| CN112961640B (en) | Polyurethane adhesive film used as absorbent plastic and preparation method and application thereof | |
| CN113265879B (en) | Multi-crosslinking super-hydrophilic fabric and preparation method thereof | |
| CN108707231A (en) | A kind of preparation method of methyl phenyl silicone resin and coating | |
| CN109810622A (en) | The preparation method of normal temperature solidifying water polyurethane/boron nitride nanometer composite coating and its film | |
| CN114437618A (en) | Waterborne polyurethane adhesive and preparation method thereof | |
| CN111019583A (en) | Polyurethane glue and preparation method thereof | |
| CN111057448A (en) | Polyester paint for coiled aluminum sheet handfeel and preparation method thereof | |
| CN114230764A (en) | Water-based closed polyisocyanate curing agent and preparation method and application thereof | |
| US2546575A (en) | Process for treating nonfibrous regenerated cellulose | |
| CN107236494B (en) | A kind of organic fiber cord dip adhesive composition and preparation method thereof | |
| CN103962020A (en) | Diffusion dialysis membrane for recycling acid, as well as preparation method and application thereof | |
| CN114316269B (en) | Preparation method and application of silicone resin | |
| CN106540671B (en) | A kind of poly-aspartate-melamine/absorbent charcoal composite material preparation method and applications | |
| CN103275298A (en) | Organosilicon modified waterborne polyurethane resin and preparation method thereof | |
| CN113699828A (en) | Heat-sealing EAA emulsion, preparation method thereof and composite paper | |
| CN104474924A (en) | Preparation method of polyvinyl alcohol ultra-filtration membrane | |
| US2432542A (en) | Method of producing coated cellulosic sheets | |
| CN113386409A (en) | Waterproof corrosion-resistant polyethylene fabric and preparation method thereof | |
| CN112853336A (en) | Chromium-free surface treating agent for aluminum can cover packaging material, and preparation method and passivation process thereof | |
| CN111799052A (en) | Sintered neodymium iron boron magnet with surface function rete | |
| CN111303329A (en) | Organosilicon modified styrene-acrylic emulsion with good water resistance and preparation method thereof | |
| CN1154707C (en) | Method for producing modified rubber water-proof coatings | |
| CN109294318A (en) | A kind of aqueous inorganic ceramic coating curing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20220506 |