CN111826118A - Solvent-free three-component polyurethane adhesive and preparation method thereof - Google Patents
Solvent-free three-component polyurethane adhesive and preparation method thereof Download PDFInfo
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- 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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- C08G18/30—Low-molecular-weight compounds
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- C08G18/3206—Polyhydroxy compounds aliphatic
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Abstract
The invention provides a solvent-free three-component polyurethane adhesive and a preparation method thereof, wherein the preparation method comprises the following steps: heating the temperature of the reaction kettle to 40-85 ℃, adding polyether polyol, then adding polyester polyol, a cross-linking agent, a catalyst, a filler and a chain extender, and stirring uniformly to obtain a component A; adding isocyanate and polyester polyol into a reaction kettle, then adding a catalyst, heating for reaction, and stopping when the NCO content is stable to obtain a component B; mixing hydrogen-terminated polydimethylsiloxane and single-ended allyl polycaprolactone, adding a solvent, standing until the mixed solution is clear and transparent, adding a Caster catalyst, continuously stirring, standing, taking the lower clear solution, and distilling to remove low-boiling-point substances to obtain a component C; and (2) mixing and stirring 20-25 parts by mass of the component A and 10-15 parts by mass of the component B, then adding 0.6-1.5 parts by mass of the component C, and stirring to obtain the polyurethane adhesive. The invention can improve the surface smoothness of the composite material.
Description
Technical Field
The invention relates to a polyurethane adhesive, in particular to a solvent-free three-component polyurethane adhesive and a preparation method thereof.
Background
The polyurethane adhesive refers to an adhesive containing a carbamate group (-NHCOO-) or an isocyanate group (-NCO) in a molecular chain. In the lithium battery flexible packaging industry, polyurethane adhesives are mainly used for material compounding, and at present, the polyurethane adhesives commonly and mature used in the lithium battery flexible packaging industry are mainly of two types: the solvent-based double-component and solvent-free double-component polyurethane adhesives comprise a main agent and a curing agent, and the existing double-component polyurethane adhesives are poor in wettability, so that pockmarks or white spots are easy to appear during material compounding, the surface smoothness of a product is poor, the attractiveness is low, and the yield of the product is greatly reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a solvent-free three-component polyurethane adhesive and a preparation method thereof, which can improve the wettability and the anti-shrinkage property of a base material, improve the leveling property, reduce the generation of pockmarks or white spots on the surface of a product, improve the surface smoothness of the product and improve the composite quality.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a solvent-free three-component polyurethane adhesive comprises the following steps:
(1) preparation of the component A:
(1.1) Material preparation: weighing the following raw materials in parts by mass
(1.2) preparing a component A: heating the temperature of the reaction kettle to 40-85 ℃, adding polyether polyol, starting stirring, then adding polyester polyol, a cross-linking agent, a catalyst, a filler and a chain extender, continuously stirring until the mixture is uniform, then vacuumizing and dehydrating until the water content is less than 0.05%, and finally cooling, sealing and storing to obtain a component A;
(2) b, preparation of a component:
(2.1) Material preparation: weighing the following raw materials in parts by mass
90-100 parts of isocyanate,
100-110 parts of polyester polyol,
0.7-1 part of a catalyst;
(2.2) preparing a component B: adding isocyanate and polyester polyol into a reaction kettle, stirring uniformly at normal temperature, then vacuumizing and dehydrating, then adding a catalyst under the protection of nitrogen, heating to 70-90 ℃, testing the content of NOC at regular intervals after reacting for 1-2 hours, stopping the reaction when the content of NCO is stable, and finally cooling and sealing for storage to obtain a component B;
(3) and C, preparation of a component:
(3.1) Material preparation: weighing the following raw materials in parts by mass
(3.2) preparing a component C: mixing hydrogen-terminated polydimethylsiloxane and single-ended allyl polycaprolactone, stirring for 20-40 min, adding a solvent, continuously stirring for 20-40 min, standing until the mixed solution is clear and transparent, heating to 80-90 ℃ through a water bath, adding a Caster catalyst, continuously stirring for reacting for 4-8 h, standing for a period of time, taking a lower-layer clear solution, and removing low-boiling-point substances through distillation to obtain a component C;
(4) preparing a polyurethane adhesive: mixing and stirring 20-25 parts by mass of the component A and 10-15 parts by mass of the component B for 5-15 min, then adding 0.6-1.5 parts by mass of the component C, continuously stirring for 40-80 min, and standing for 20-40 min to obtain the polyurethane adhesive.
As a preferable scheme, in the step (1.1), castor oil is used as the polyester polyol, and calcium carbonate is used as the filler.
Preferably, the polyether polyol in step (1.1) is one or more selected from polypropylene glycol, epoxidized soybean oil modified polyol, low molecular weight liquid polyethylene glycol and polytetrahydrofuran glycol.
As a preferable scheme, the cross-linking agent in the step (1.1) is selected from one of xylitol, sorbitol and mannitol.
As a preferable scheme, in the step (1.1), the catalyst is one of dibutyltin dilaurate and stannous octoate, and the chain extender is one of 2, 6-diethylaniline and 1, 4-butanediol.
In a preferable embodiment, in step (2.1), the isocyanate is one or more selected from dicyclohexyl diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate, and the polyester polyol is castor oil.
As a preferable scheme, one or two of dibutyltin dilaurate and triethylenediamine are used as the catalyst in the step (2.1).
As a preferable scheme, the solvent in the step (3.1) is one of toluene and ethyl acetate.
As a preferable scheme, when the component A and the component B are mixed and stirred in the step (4), the humidity is less than or equal to 50 percent.
The solvent-free three-component polyurethane adhesive is prepared by the preparation method.
Compared with the prior art, the invention has obvious advantages and beneficial effects, specifically, the component C is added, so that the wettability of the polyurethane adhesive to the base material can be effectively improved, the leveling effect is improved, the fluidity of the polyurethane adhesive on the surface of the base material is improved, the phenomenon that the base material generates pockmarks or white spots after being compounded is avoided, the surface glossiness and the surface smoothness of the product are improved, and the compounding quality of the product is greatly improved.
To more clearly illustrate the structural features and technical means of the present invention and the specific objects and functions attained thereby, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments:
drawings
FIG. 1 is an external view of a product obtained by compounding a conventional polyurethane adhesive;
FIG. 2 is an appearance diagram of a product obtained by compounding the polyurethane adhesive of the present invention.
Detailed Description
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the positions or elements referred to must have specific orientations, be constructed and operated in specific orientations, and thus, are not to be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood as appropriate by those of ordinary skill in the art.
As described above, in the first aspect, the present invention provides a method for preparing a solvent-free three-component polyurethane adhesive, the method comprising the steps of:
(1) preparation of the component A:
(1.1) Material preparation: weighing the following raw materials in parts by mass
(1.2) preparing a component A: heating the temperature of the reaction kettle to 40-85 ℃, adding polyether polyol, starting stirring, then adding polyester polyol, a cross-linking agent, a catalyst, a filler and a chain extender, continuously stirring until the mixture is uniform, then vacuumizing and dehydrating until the water content is less than 0.05%, and finally cooling, sealing and storing to obtain a component A;
(2) b, preparation of a component:
(2.1) Material preparation: weighing the following raw materials in parts by mass
90-100 parts of isocyanate,
100-110 parts of polyester polyol,
0.7-1 part of a catalyst;
(2.2) preparing a component B: adding isocyanate and polyester polyol into a reaction kettle, stirring uniformly at normal temperature, then vacuumizing and dehydrating, then adding a catalyst under the protection of nitrogen, heating to 70-90 ℃, testing the content of NOC at regular intervals after reacting for 1-2 hours, stopping the reaction when the content of NCO is stable, and finally cooling and sealing for storage to obtain a component B;
(3) and C, preparation of a component:
(3.1) Material preparation: weighing the following raw materials in parts by mass
(3.2) preparing a component C: mixing hydrogen-terminated polydimethylsiloxane and single-ended allyl polycaprolactone, stirring for 20-40 min, adding a solvent, continuously stirring for 20-40 min, standing until the mixed solution is clear and transparent, heating to 80-90 ℃ through a water bath, adding a Caster catalyst, continuously stirring for reacting for 4-8 h, standing for a period of time, taking a lower-layer clear solution, and removing low-boiling-point substances through distillation to obtain a component C;
(4) preparing a polyurethane adhesive: mixing and stirring 20-25 parts by mass of the component A and 10-15 parts by mass of the component B for 5-15 min, then adding 0.6-1.5 parts by mass of the component C, continuously stirring for 40-80 min, and standing for 20-40 min to obtain the polyurethane adhesive.
According to the invention, the castor oil is more environment-friendly, the functionality is higher, and the castor oil has a long-chain fatty group, so that the prepared polyurethane product has good hydrolysis resistance, flexibility and low temperature resistance, and therefore the castor oil is selected as the polyester polyol in the step (1.1). In order to better increase the bonding strength and reduce the production cost, calcium carbonate is selected as the filler. The polyether polyol is one or more of polypropylene glycol, epoxy soybean oil modified polyol, low molecular weight liquid polyethylene glycol and polytetrahydrofuran glycol. The cross-linking agent is selected from one of xylitol, sorbitol and mannitol, is all natural polysaccharide, is environment-friendly, contains a plurality of hydroxyl groups, and can improve the cross-linking density of a cured product and the bonding fastness by adding the cross-linking agent into a polyurethane adhesive. The catalyst is one of dibutyltin dilaurate and stannous octoate, and the chain extender is one of 2, 6-diethylaniline and 1, 4-butanediol.
In the invention, in the step (2.1), the isocyanate is one or more of dicyclohexyl diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate, and the polyester polyol is castor oil. The catalyst is one or two of dibutyltin dilaurate and triethylenediamine.
In the invention, the solvent in the step (3.1) is one of toluene and ethyl acetate.
In the invention, when the component A and the component B in the step (4) are mixed and stirred, the humidity is less than or equal to 50 percent.
The invention provides a solvent-free three-component polyurethane adhesive, which is prepared by the preparation method.
The present invention will be described in detail below by way of specific examples.
Example 1
This example is provided to illustrate a method for preparing a solvent-free three-component polyurethane adhesive, which comprises the following steps:
(1) preparation of the component A:
heating the temperature of a reaction kettle to 40-85 ℃, adding 60 parts by mass of polypropylene glycol and 25 parts by mass of epoxidized soybean oil modified polyol, starting stirring, then adding 30 parts by mass of castor oil, 5 parts by mass of xylitol, 0.5 part by mass of dibutyltin dilaurate, 1 part by mass of calcium carbonate and 1 part by mass of 2, 6-diethylaniline, continuously stirring until the mixture is uniform, then vacuumizing and dehydrating until the water content is less than 0.05%, and finally cooling, sealing and storing to obtain a component A;
(2) b, preparation of a component:
adding 90 parts by mass of dicyclohexyl diisocyanate and 110 parts by mass of castor oil into a reaction kettle, stirring uniformly at normal temperature, vacuumizing and dehydrating, adding 0.3 part by mass of dibutyltin dilaurate and 0.4 part by mass of triethylenediamine under the protection of nitrogen, heating to 70-90 ℃, reacting for 1-2 hours, testing the content of NOC at regular intervals, stopping the reaction when the content of NCO is stable, cooling, sealing and storing to obtain a component B;
(3) and C, preparation of a component:
mixing 120 parts by mass of hydrogen-terminated polydimethylsiloxane and 60 parts by mass of single-ended allyl polycaprolactone, stirring for 20-40 min, adding 40 parts by mass of toluene, continuing to stir for 20-40 min, standing until the mixed solution is clear and transparent, then heating to 80-90 ℃ through a water bath, then adding 1 part by mass of a Kanster catalyst, continuing to stir for reaction for 4-8 h, standing for a period of time, taking a lower-layer clear solution, and removing low-boiling-point substances through distillation to obtain a component C;
(4) preparing a polyurethane adhesive: under the condition that the humidity is less than or equal to 50%, 20 parts by mass of the component A and 15 parts by mass of the component B are mixed and stirred for 5-15 min, then 1 part by mass of the component C is added, stirring is continued for 40-80 min, and standing is carried out for 20-40 min, so that the polyurethane adhesive is obtained.
Example 2
This example is provided to illustrate a method for preparing a solvent-free three-component polyurethane adhesive, which comprises the following steps:
(1) preparation of the component A:
heating the temperature of a reaction kettle to 40-85 ℃, adding 50 parts by mass of low-molecular-weight liquid polyethylene glycol and 50 parts by mass of polytetrahydrofuran diol, starting stirring, then adding 15 parts by mass of castor oil, 8 parts by mass of sorbitol, 0.7 part by mass of stannous octoate, 1 part by mass of calcium carbonate and 1, 4-butanediol, continuously stirring until the mixture is uniform, then vacuumizing and dehydrating until the water content is less than 0.05%, and finally cooling, sealing and storing to obtain a component A;
(2) b, preparation of a component:
adding 95 parts by mass of toluene diisocyanate and 105 parts by mass of castor oil into a reaction kettle, stirring uniformly at normal temperature, vacuumizing and dehydrating, adding 1 part by mass of dibutyltin dilaurate under the protection of nitrogen, heating to 70-90 ℃, reacting for 1-2 h, testing the content of NOC at regular intervals, stopping the reaction when the content of NCO is stable, cooling, and storing in a sealed manner to obtain a component B;
(3) and C, preparation of a component:
mixing 100 parts by mass of hydrogen-terminated polydimethylsiloxane and 80 parts by mass of single-ended allyl polycaprolactone, stirring for 20-40 min, adding 35 parts by mass of ethyl acetate, continuing to stir for 20-40 min, standing until the mixed solution is clear and transparent, then heating to 80-90 ℃ through a water bath, then adding 0.8 part by mass of a Kanster catalyst, continuing to stir for reaction for 4-8 h, standing for a period of time, taking a lower-layer clear solution, and removing low-boiling-point substances through distillation to obtain a component C;
(4) preparing a polyurethane adhesive: under the condition that the humidity is less than or equal to 50%, 22 parts by mass of the component A and 13 parts by mass of the component B are mixed and stirred for 5-15 min, then 1 part by mass of the component C is added, stirring is continued for 40-80 min, and standing is carried out for 20-40 min, so that the polyurethane adhesive is obtained.
Example 3
This example is provided to illustrate a method for preparing a solvent-free three-component polyurethane adhesive, which comprises the following steps:
(1) preparation of the component A:
heating the temperature of a reaction kettle to 40-85 ℃, adding 95 parts by mass of polypropylene glycol, starting stirring, then adding 15 parts by mass of castor oil, 10 parts by mass of mannitol, 1 part by mass of stannous octoate, 0.8 part by mass of calcium carbonate and 1, 4-butanediol, continuously stirring until the mixture is uniform, then vacuumizing and dehydrating until the water content is less than 0.05%, and finally cooling, sealing and storing to obtain a component A;
(2) b, preparation of a component:
adding 40 parts by mass of toluene diisocyanate, 60 parts by mass of diphenylmethane diisocyanate and 100 parts by mass of castor oil into a reaction kettle, stirring uniformly at normal temperature, then vacuumizing and dehydrating, adding 1 part by mass of triethylene diamine under the protection of nitrogen, heating to 70-90 ℃, reacting for 1-2 h, testing the content of NOC at regular intervals, stopping the reaction when the content of NCO is stable, cooling, and sealing for storage to obtain a component B;
(3) and C, preparation of a component:
mixing 60 parts by mass of hydrogen-terminated polydimethylsiloxane and 100 parts by mass of single-ended allyl polycaprolactone, stirring for 20-40 min, adding 40 parts by mass of toluene, continuing to stir for 20-40 min, standing until the mixed solution is clear and transparent, then heating to 80-90 ℃ through a water bath, then adding 0.6 part by mass of a Kanster catalyst, continuing to stir for reaction for 4-8 h, standing for a period of time, taking the lower-layer clear solution, and removing low-boiling-point substances through distillation to obtain a component C;
(4) preparing a polyurethane adhesive: under the condition that the humidity is less than or equal to 50%, 20 parts by mass of the component A and 15 parts by mass of the component B are mixed and stirred for 5-15 min, then 1 part by mass of the component C is added, stirring is continued for 40-80 min, and standing is carried out for 20-40 min, so that the polyurethane adhesive is obtained.
As shown in fig. 1, the surface of the product obtained by compounding the existing polyurethane adhesive has pockmarks or white spots, which results in low smoothness of the product appearance and uneven surface; as shown in figure 2, the product compounded by the polyurethane adhesive prepared by the invention has higher surface flatness and consistency, no pockmark or white spot and greatly improved compounding quality.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the present invention, so that any modifications, equivalents, improvements, etc. made to the above embodiment according to the present invention are within the scope of the present invention.
Claims (10)
1. A preparation method of a solvent-free three-component polyurethane adhesive is characterized by comprising the following steps:
(1) preparation of the component A:
(1.1) Material preparation: weighing the following raw materials in parts by mass
(1.2) preparing a component A: heating the temperature of the reaction kettle to 40-85 ℃, adding polyether polyol, starting stirring, then adding polyester polyol, a cross-linking agent, a catalyst, a filler and a chain extender, continuously stirring until the mixture is uniform, then vacuumizing and dehydrating until the water content is less than 0.05%, and finally cooling, sealing and storing to obtain a component A;
(2) b, preparation of a component:
(2.1) Material preparation: weighing the following raw materials in parts by mass
90-100 parts of isocyanate,
100-110 parts of polyester polyol,
0.7-1 part of a catalyst;
(2.2) preparing a component B: adding isocyanate and polyester polyol into a reaction kettle, stirring uniformly at normal temperature, then vacuumizing and dehydrating, then adding a catalyst under the protection of nitrogen, heating to 70-90 ℃, testing the content of NOC at regular intervals after reacting for 1-2 hours, stopping the reaction when the content of NCO is stable, and finally cooling and sealing for storage to obtain a component B;
(3) and C, preparation of a component:
(3.1) Material preparation: weighing the following raw materials in parts by mass
(3.2) preparing a component C: mixing hydrogen-terminated polydimethylsiloxane and single-ended allyl polycaprolactone, stirring for 20-40 min, adding a solvent, continuously stirring for 20-40 min, standing until the mixed solution is clear and transparent, heating to 80-90 ℃ through a water bath, adding a Caster catalyst, continuously stirring for reacting for 4-8 h, standing for a period of time, taking a lower-layer clear solution, and removing low-boiling-point substances through distillation to obtain a component C;
(4) preparing a polyurethane adhesive: mixing and stirring 20-25 parts by mass of the component A and 10-15 parts by mass of the component B for 5-15 min, then adding 0.6-1.5 parts by mass of the component C, continuously stirring for 40-80 min, and standing for 20-40 min to obtain the polyurethane adhesive.
2. The method for preparing a solvent-free three-component polyurethane adhesive according to claim 1, wherein in step (1.1), the polyester polyol is castor oil and the filler is calcium carbonate.
3. The method for preparing a solvent-free three-component polyurethane adhesive according to claim 1, wherein the polyether polyol in step (1.1) is selected from one or more of polypropylene glycol, epoxy soybean oil modified polyol, low molecular weight liquid polyethylene glycol, and polytetrahydrofuran glycol.
4. The method for preparing a solvent-free three-component polyurethane adhesive according to claim 1, wherein the cross-linking agent in step (1.1) is selected from one of xylitol, sorbitol and mannitol.
5. The method for preparing a solvent-free three-component polyurethane adhesive according to claim 1, wherein in the step (1.1), the catalyst is one of dibutyltin dilaurate and stannous octoate, and the chain extender is one of 2, 6-diethylaniline and 1, 4-butanediol.
6. The method for preparing a solvent-free three-component polyurethane adhesive according to claim 1, wherein in the step (2.1), the isocyanate is one or more selected from dicyclohexyl diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate, and the polyester polyol is castor oil.
7. The method for preparing a solvent-free three-component polyurethane adhesive according to claim 1, wherein the catalyst in step (2.1) is one or two of dibutyltin dilaurate and triethylenediamine.
8. The method for preparing a solvent-free three-component polyurethane adhesive according to claim 1, wherein the solvent in step (3.1) is one of toluene and ethyl acetate.
9. The method for preparing a solvent-free three-component polyurethane adhesive according to claim 1, wherein the humidity of the mixture of the component A and the component B in the step (4) is less than or equal to 50%.
10. A solvent-free three-component polyurethane adhesive prepared by the method of any one of claims 1 to 9.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103102862A (en) * | 2013-01-29 | 2013-05-15 | 浙江华宝油墨有限公司 | Preparation method of dual-component solvent-free type polyurethane adhesive for composite flexible packaging |
| CN107674486A (en) * | 2017-09-06 | 2018-02-09 | 上海优卡化工科技有限公司 | A kind of polyester resin change properties of organic silicon levelling agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103102862A (en) * | 2013-01-29 | 2013-05-15 | 浙江华宝油墨有限公司 | Preparation method of dual-component solvent-free type polyurethane adhesive for composite flexible packaging |
| CN107674486A (en) * | 2017-09-06 | 2018-02-09 | 上海优卡化工科技有限公司 | A kind of polyester resin change properties of organic silicon levelling agent and preparation method thereof |
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Application publication date: 20201027 |