CN110194944A - A kind of structural type antibacterial moisture-curable polyurethane hot melt adhesive and preparation method thereof - Google Patents
A kind of structural type antibacterial moisture-curable polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN110194944A CN110194944A CN201910539161.0A CN201910539161A CN110194944A CN 110194944 A CN110194944 A CN 110194944A CN 201910539161 A CN201910539161 A CN 201910539161A CN 110194944 A CN110194944 A CN 110194944A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/48—Polyethers
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
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- C09J175/06—Polyurethanes from polyesters
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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Abstract
The invention discloses a kind of structural type antibacterial moisture-curable polyurethane hot melt adhesive and preparation method thereof, structural type antibacterial moisture-curable polyurethane hot melt adhesive includes following composition by weight: 20.0~60.0 parts of diisocyanate, 40.0~100.0 parts of oligomer polyol, 1.0~5.0 parts of chain extender, 0.5~1.5 part of antioxidant, 0.01~0.06 part of catalyst, 10.0~35.0 parts of terpene resin, 5.0~20.0 parts of polyurethane elastomer, 0.01~0.1 part of curing catalysts, 4.0~8.0 parts of nanofiller, 4.0~10.0 parts of hydroxyl schiff bases；Hydroxyl schiff bases is made with aniline by reacting by laurine.The disadvantages of for structural type antibacterial moisture-curable polyurethane hot melt adhesive produced by the present invention without additional addition antibacterial agent, anti-microbial property is lasting, effectively overcomes additional addition antibacterial agent, and antibacterial effect is not lasting, easy to migrate, dispersion is uneven.
Description
Technical field
The present invention relates to a kind of hot melt adhesive technology more particularly to a kind of structural type antibacterial moisture-curable polyurethane hot melt adhesive and its
Preparation method.
Background technique
Moisture-curable polyurethane hot melt adhesive is one kind containing end-NCO group polyurethane adhesive.In use, heating melting is applied
Glue, after the cooling physical solidification of glue-line generates preliminary bonding force, end NCO in glue-line again with the moisture or adherend in air
The active hydrogen compounds on surface reacts, and generates chemical crosslinking cure.Moisture-curable polyurethane hot melt adhesive not only has conventional thermoplastic
Hot melt adhesive rapid link positioning, higher initial adhesive strength advantage is provided, also can further solidify crosslinking, make glue-line bonding force,
Cohesive strength etc. can be significantly improved.
Polyurethane hot melt does not discharge solvent, no pollution to the environment, to human body due to having 100% solid content into environment
Nonhazardous meets " environmental protection, health, safety " three environmentally protective adhesives required greatly, and no drying process, and energy consumption is few, behaviour
Facilitate, can be used for high speed continuous production line, improve a series of incomparable advantages such as production efficiency, becomes adhesive neck
More and more important a kind of adhesive in domain.
PVC floor is a kind of home decoration composite floor board emerging in recent years, generally mainly by wearing layer, buffer layer
It is mostly bonded with multilayered structures composition, materials such as bases based on PVC and mountain flour between buffer layer and base with adhesive.
Currently, conventional PVC floor is mostly bonded using solvent-based adhesive, but the VOC content of solvent-based adhesive is generally higher,
Environmental pollution is larger and is harmful to the human body.Gradually attention with people to environmental protection, moisture-curable polyurethane hot melt adhesive is due to it
The relatively safer environmental protection of body and various characteristics such as easy for construction, start in PVC composite floor field application.However, existing
There is the risk of mildew after use without bacteria resistance function in the Moisture-curable hot melt adhesive in technology.As Chinese patent CN108822784A is public
A kind of moisture-curable polyurethane hot melt adhesive and preparation method thereof is opened, which is characterized in that be made of, have the raw material of following mass fraction
Body are as follows: 30~35 parts of polyether polyol, 11~19 parts of liquid polyesters polyalcohol, 11~18 parts of solid polyester polyalcohol, EVA resin
10~15 parts, 0.2~0.5 part of antioxidant, 21.29~23.19 parts of MDI, 0.01 part of catalyst, 1~1.5 part of chain extender and silicon
1.1~1.5 parts of alkane coupling agent；There is the risk of mildew after use without bacteria resistance function in the invention Moisture-curable hot melt adhesive.
And although the certain hot melt adhesive of tradition have certain anti-microbial property, all by the way of outer addition antibacterial agent, and
The disadvantages of outer addition antibacterial agent has antibacterial effect not lasting, easy to migrate, and dispersion is uneven.Such as Chinese patent CN106189876A,
Disclose a kind of antimicrobial form hot melt adhesive comprising adhesive layer and antibiotic layer, wherein adhesive layer, including double-layer structure, one layer is viscous
The aluminium foil adhesive layer in aluminium foil surface is tied, another layer is resin-bonded layer；Antibiotic layer, to contain nanometer Ag2O or nano-TiO2
Aqueous binder, the antibiotic layer is sprayed at the resin-bonded layer side；The present invention uses and is compounded with antibiotic layer structure
Hot melt adhesive, the antibiotic layer are to contain nanometer Ag2O or nano-TiO2Aqueous binder, hot melt adhesive can be realized using the antibiotic layer
Have after heat-sealing from antibiotic property.And such as Chinese patent CN105647402A, disclose a kind of shoes heat with bactericidal effect
Melten gel, including following component: carboxymethyl chitosan, EVA, methyl methacrylate, terpene resin, nano flyash, rosin season
Doutrate, wax class, 2,6- di-tert-butyl-4-methy phenol, dodecyl trimethyl ammonium chloride, montmorillonite, antibacterial agent and
Konjaku glucomannan.
Therefore one kind is developed without additional antibacterial agent, and there is the Moisture-curable hot melt adhesive of good antibacterial functions to meet society for itself
The demand of development.
Summary of the invention
For overcome the deficiencies in the prior art, it is poly- that one of the objects of the present invention is to provide a kind of structural type antibacterial moisturecurings
Urethane hot melt adhesive.
The second object of the present invention is to provide a kind of preparation method of structural type antibacterial moisture-curable polyurethane hot melt adhesive.
An object of the present invention adopts the following technical scheme that realization: a kind of structural type antibacterial moisturecuring polyurethane-hot melt
Glue, including composition as follows by weight: 20.0~60.0 parts of diisocyanate, 40.0~100.0 parts of oligomer polyol,
1.0~5.0 parts of chain extender, 0.01~0.06 part of catalyst, 10.0~35.0 parts of terpene resin, gathers 0.5~1.5 part of antioxidant
5.0~20.0 parts of urethane elastomer, 0.01~0.1 part of curing catalysts, 4.0~8.0 parts of nanofiller, hydroxyl schiff bases 4.0
~10.0 parts；
Wherein, the hydroxyl schiff bases is made with aniline by reacting by laurine.
Structural type antibacterial moisture-curable polyurethane hot melt adhesive of the present invention, wherein the preparation side of the hydroxyl schiff bases
Method is as follows:
With laurine: aniline molar ratio is that 1:1 weighs raw material；In three mouthfuls of reactions equipped with thermometer, blender, condenser pipe
In kettle, the aniline and ethyl alcohol of formula ratio is added, is warming up to 80-82 DEG C of stirring and dissolving, it is in addition that the laurine of formula ratio is molten
In ethyl alcohol, after laurine is completely dissolved, it is slowly dropped in aforesaid reaction vessel；And first acid as catalyst is added,
It is warming up to 82-83 DEG C, reaction 6-8h is stirred at reflux, is cooled to room temperature to fully reacting, purify, it is dry to get hydroxyl Schiff
Alkali.
Structural type antibacterial moisture-curable polyurethane hot melt adhesive of the present invention, wherein the diisocyanate is 4,4 '-two
Methylenebis phenyl isocyanate, toluene di-isocyanate(TDI), isophorone diisocyanate, one in hexamethylene diisocyanate
Kind or several compositions.
Structural type antibacterial moisture-curable polyurethane hot melt adhesive of the present invention, wherein the oligomer polyol is poly- four
Hydrogen furans dihydric alcohol, polycarbonate glycol, polycaprolactone diols, polyethylene oxide polyol, polyether Glycols, poly- second two
The combination of one or more of alcohol, polyoxypropylene polyol；The molecular weight of the oligomer polyol is 1000~5000.
Structural type antibacterial moisture-curable polyurethane hot melt adhesive of the present invention, wherein the chain extender be propylene glycol, 1,
4 butanediols, 1,4- cyclohexanedimethanol, neopentyl glycol, Diethylene Glycol, 2-butyl-2-ethyl-1,3-propanediol, three hydroxyl first
The composition of one or more of base propane.
Structural type antibacterial moisture-curable polyurethane hot melt adhesive of the present invention, wherein the antioxidant be antioxidant 1010,
The composition of one or both of irgasfos 168.
Structural type antibacterial moisture-curable polyurethane hot melt adhesive of the present invention, wherein the catalyst is tin dilaurate two
Butyl tin.
Structural type antibacterial moisture-curable polyurethane hot melt adhesive of the present invention, wherein the curing catalysts are double morpholines
Base Anaesthetie Ether.The curing catalysts are dual-morpholinyl diethyl ether.
Structural type antibacterial moisture-curable polyurethane hot melt adhesive of the present invention, wherein the nanofiller is organic swelling
The composition of one or more of soil, precipitated calcium carbonate, fumed silica.
The second object of the present invention adopts the following technical scheme that realization: a kind of structural type antibacterial moisture-curable polyurethane hot melt adhesive
Preparation method, comprising the following steps:
1) based on formulation weight part, oligomer polyol, chain extender, terpene resin, polyurethane elastomer and antioxidant are added
Into reaction kettle, be heated to 120 DEG C~130 DEG C, stir evenly, under the conditions of vacuum degree < 200Pa be dehydrated 2.0h~
3.0h；
2) be cooled to 65 DEG C~70 DEG C, diisocyanate be added, is stirred to react 0.5~1.0h, be warming up to 100 DEG C~110 DEG C, it is true
0.5h is reacted under empty condition；
3) nanofiller, catalyst and hydroxyl schiff bases is added, is stirred to react 0.5h~1.0h under the conditions of 100 DEG C~105 DEG C；
4) reaction terminates, and curing catalysts are added and stir evenly, keep drop temperature at 100 DEG C~110 DEG C, fast under nitrogen protection
Speed discharging, sealed package to obtain the final product.
Compared with prior art, the beneficial effects of the present invention are:
(1) structural type antibacterial moisture-curable polyurethane hot melt adhesive produced by the present invention is held without additional addition antibacterial agent, anti-microbial property
Long, additional addition antibacterial agent is effectively overcome, the disadvantages of antibacterial effect is not lasting, easy to migrate, dispersion is uneven.
(2) in addition, a little catalyst is added, reaction temperature is reduced, the generation of by-product is reduced.If a little catalysis is not added
Agent needs higher reaction temperatures, and isocyanates has fraction that autohemagglutination does not occur at high temperature.
(3) structural type antibacterial moisture-curable polyurethane hot melt adhesive initial shear strength with higher produced by the present invention
Energy, adhesion strength, peel strength are big, can be applied to PVC composite floor board, automobile and electronics industry etc..
Specific embodiment
In the following, being described further in conjunction with specific embodiment to the present invention, it should be noted that is do not collided
Under the premise of, new embodiment can be formed between various embodiments described below or between each technical characteristic in any combination.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field
Rule method.
A kind of structural type antibacterial moisture-curable polyurethane hot melt adhesive, including composition as follows by weight: diisocyanate
20.0~60.0 parts, 40.0~100.0 parts of oligomer polyol, 1.0~5.0 parts of chain extender, 0.5~1.5 part of antioxidant, urge
0.01~0.06 part of agent, 10.0~35.0 parts of terpene resin, 5.0~20.0 parts of polyurethane elastomer, curing catalysts 0.01
~0.1 part, 4.0~8.0 parts of nanofiller, 4.0~10.0 parts of hydroxyl schiff bases；
Wherein, the hydroxyl schiff bases is made with aniline by reacting by laurine.
Structural type antibacterial moisture-curable polyurethane hot melt adhesive of the present invention, wherein the preparation side of the hydroxyl schiff bases
Method is as follows:
With laurine: aniline molar ratio is that 1:1 weighs raw material；In three mouthfuls of reactions equipped with thermometer, blender, condenser pipe
In kettle, the aniline and ethyl alcohol of formula ratio is added, is warming up to 80-82 DEG C of stirring and dissolving, it is in addition that the laurine of formula ratio is molten
In ethyl alcohol, after laurine is completely dissolved, it is slowly dropped in aforesaid reaction vessel；And first acid as catalyst is added,
It is warming up to 82-83 DEG C, reaction 6-8h is stirred at reflux, is cooled to room temperature to fully reacting, purify, it is dry to get hydroxyl Schiff
Alkali.
Hydroxyl schiff bases has certain antibiotic property, please analyze the addition of hydroxyl schiff bases in addition to excellent antibiotic property
Can be outer, synergistic effect is played with total formula cooperation.
As further embodiment, the diisocyanate is 4,4 '-methyl diphenylene diisocyanates, toluene two
The composition of one or more of isocyanates, isophorone diisocyanate, hexamethylene diisocyanate.
As further embodiment, the oligomer polyol is polytetrahydrofuran dihydric alcohol, polycarbonate binary
Alcohol, polycaprolactone diols, polyethylene oxide polyol, polyether Glycols, polyethylene glycol, one in polyoxypropylene polyol
Kind or several combinations；The molecular weight of the oligomer polyol is 1000~5000.
As further embodiment, the chain extender is propylene glycol, Isosorbide-5-Nitrae butanediol, Isosorbide-5-Nitrae-cyclohexanedimethanol, new
The combination of one or more of pentanediol, Diethylene Glycol, 2-butyl-2-ethyl-1,3-propanediol, trimethylolpropane
Object.
As further embodiment, the antioxidant is one or both of antioxidant 1010, irgasfos 168
Composition.
As further embodiment, the catalyst is dibutyl tin dilaurate.
As further embodiment, the curing catalysts are dual-morpholinyl diethyl ether.The curing catalysts
For dual-morpholinyl diethyl ether.
As further embodiment, the nanofiller is organobentonite, precipitated calcium carbonate, fumed silica
One or more of composition.
As further embodiment, the terpene resin is selected from the terpene resin of dehydration.
As further embodiment, the polyurethane elastomer is selected from the polyurethane elastomer ... of dehydration
The preparation method of above structure type antibacterial moisture-curable polyurethane hot melt adhesive, comprising the following steps:
1) based on formulation weight part, oligomer polyol, chain extender, terpene resin, polyurethane elastomer and antioxidant are added
Into reaction kettle, be heated to 120 DEG C~130 DEG C, stir evenly, under the conditions of vacuum degree < 200Pa be dehydrated 2.0h~
3.0h；
2) be cooled to 65 DEG C~70 DEG C, diisocyanate be added, is stirred to react 0.5~1.0h, be warming up to 100 DEG C~110 DEG C, it is true
0.5h is reacted under empty condition；
3) nanofiller, catalyst and hydroxyl schiff bases is added, is stirred to react 0.5h~1.0h under the conditions of 100 DEG C~105 DEG C；
4) reaction terminates, and curing catalysts are added and stir evenly, keep drop temperature at 100 DEG C~110 DEG C, fast under nitrogen protection
Speed discharging, sealed package to obtain the final product.
It is specific embodiment of the present invention below, used raw material, equipment etc. remove special limit in the following embodiments
It can be obtained by buying pattern outside fixed.
Embodiment 1
Structural type antibacterial moisture-curable polyurethane hot melt adhesive, preparation process are as follows:
1) based on formulation weight part, by 60.5 parts of polycarbonate glycol, 1.5 parts of Isosorbide-5-Nitrae butanediol, 25.0 parts of terpene resin, gather
10.5 parts of urethane elastomer, 0.4 part of antioxidant 1010 and 0.4 part of irgasfos 168, are added in reaction kettle, are heated to
It 120 DEG C, stirs evenly, is dehydrated 3.0h under the conditions of vacuum degree < 200Pa；
2) be cooled to 70 DEG C, 35.0 parts of 4,4 '-methyl diphenylene diisocyanate be added, is stirred to react 0.5, be warming up to 105 DEG C,
0.5h is reacted under vacuum condition；
3) 4.0 parts of organobentonite of addition, 0.05 part of dibutyl tin dilaurate and 6.0 parts of hydroxyl schiff bases, in 105 DEG C of conditions
Under be stirred to react 0.5h；
4) reaction terminates, and is added 0.04 part of curing catalysts and stirs evenly, and keeps drop temperature at 105 DEG C, fast under nitrogen protection
Speed discharging, sealed package to obtain the final product.,
Embodiment 2
Structural type antibacterial moisture-curable polyurethane hot melt adhesive, preparation process are as follows:
1) based on formulation weight part, by 65 parts of polytetrahydrofuran dihydric alcohol, 3.0 parts of Isosorbide-5-Nitrae-cyclohexanedimethanol, terpene resin 15.0
Part, 8.5 parts of polyurethane elastomer, 0.4 part of antioxidant 1010 and 0.4 part of irgasfos 168, are added in reaction kettle, and heating rises
Temperature is stirred evenly to 130 DEG C, is dehydrated 2.0h under the conditions of vacuum degree < 200Pa；
2) it is cooled to 65 DEG C, is added 43.0 parts of toluene di-isocyanate(TDI), is stirred to react 0.5h, be warming up to 100 DEG C, under vacuum condition
React 0.5h；
3) 4.5 parts of fumed silica of addition, 0.04 part of dibutyl tin dilaurate and 7.0 parts of hydroxyl schiff bases, in 105 DEG C of items
0.5h is stirred to react under part；
4) reaction terminates, and 0.04 part of curing catalysts stirs evenly, and keeps drop temperature at 100 DEG C~110 DEG C, under nitrogen protection
Quickly discharging, sealed package to obtain the final product.
Embodiment 3
Structural type antibacterial moisture-curable polyurethane hot melt adhesive, preparation process are as follows:
1) based on formulation weight part, by 45.0 parts of polyethylene oxide polyol, 1.6 parts of Diethylene Glycol, terpene resin 10.0
Part, 10.0 parts of polyurethane elastomer, 0.3 part of antioxidant 1010 and 0.3 part of irgasfos 168, are added in reaction kettle, and heating rises
Temperature is stirred evenly to 120 DEG C, is dehydrated 2.5h under the conditions of vacuum degree < 200Pa；
2) 65 DEG C are cooled to, 39.8 parts of isophorone diisocyanate is added, is stirred to react 1.0h, is warming up to 110 DEG C, vacuum item
0.5h is reacted under part；
3) 5.2 parts of precipitated calcium carbonate of addition, 0.04 part of dibutyl tin dilaurate and 8.0 parts of hydroxyl schiff bases, in 105 DEG C of conditions
Under be stirred to react 0.5h；
4) reaction terminates, and is added 0.03 part of curing catalysts and stirs evenly, and keeps drop temperature at 110 DEG C, fast under nitrogen protection
Speed discharging, sealed package to obtain the final product.
Embodiment 4
Structural type antibacterial moisture-curable polyurethane hot melt adhesive, preparation process are as follows:
1) based on formulation weight part, by 65.5 parts of polycaprolactone diols, 2.8 parts of neopentyl glycol, 35.0 parts of terpene resin, poly- ammonia
7.0 parts of ester elastomer, 0.5 part of antioxidant 1010 and 0.5 part of irgasfos 168, are added in reaction kettle, are heated to 130
DEG C, it stirs evenly, is dehydrated 2.0 under the conditions of vacuum degree < 200Pa；
2) 65 DEG C are cooled to, 47.5 parts of hexamethylene diisocyanate is added, is stirred to react 1.0h, is warming up to 110 DEG C, vacuum item
0.5h is reacted under part；
3) 5.0 parts of fumed silica of addition, 0.05 part of dibutyl tin dilaurate and 9.0 parts of hydroxyl schiff bases, in 105 DEG C of items
1.0h is stirred to react under part；
4) reaction terminates, and is added 0.04 part of curing catalysts and stirs evenly, and keeps drop temperature at 110 DEG C, fast under nitrogen protection
Speed discharging, sealed package to obtain the final product.
Effect assessment and performance detection
1. the test method according to GB/T 2790 measures peel strength, anti-microbial property is tested according to GB/T 21866-2008.It is right
Embodiment 1-4 moisture-curable polyurethane hot melt adhesive and the performance of conventional moisture-curable polyurethane hot melt adhesive are detected, detection project
And result is referring to table 1.
Table 1: 1-4 of the embodiment of the present invention and conventional moisture-curable polyurethane hot melt adhesive (comparative example 1), addition type antibacterial heat
Glue (comparative example 2) contrast properties test index
The peel strength of the embodiment of the present invention is much larger than conventional moisture-curable polyurethane hot melt adhesive, addition as can be seen from Table 1
The peel strength of type Antibacterial hot melt adhesive, antibiotic rate antibacterial effect of the invention is basically unchanged after simulating 1 annual aging, and addition type is anti-
The decline of bacterium hot melt adhesive is obvious, this shows addition type Antibacterial hot melt adhesive, and antibacterial effect is not lasting, and structure of the invention type moist antibacterial is solid
Change polyurethane hot melt durable antibacterial effect.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of structural type antibacterial moisture-curable polyurethane hot melt adhesive, which is characterized in that including composition as follows by weight: two
20.0~60.0 parts of isocyanates, 40.0~100.0 parts of oligomer polyol, 1.0~5.0 parts of chain extender, antioxidant 0.5~
1.5 parts, 0.01~0.06 part of catalyst, 10.0~35.0 parts of terpene resin, 5.0~20.0 parts of polyurethane elastomer, solidification urge
0.01~0.1 part of agent, 4.0~8.0 parts of nanofiller, 4.0~10.0 parts of hydroxyl schiff bases；
Wherein, the hydroxyl schiff bases is made with aniline by reacting by laurine.
2. structural type antibacterial moisture-curable polyurethane hot melt adhesive as described in claim 1, which is characterized in that the hydroxyl schiff bases
The preparation method is as follows:
With laurine: aniline molar ratio is that 1:1 weighs raw material；In three mouthfuls of reactions equipped with thermometer, blender, condenser pipe
In kettle, the aniline and ethyl alcohol of formula ratio is added, is warming up to 80-82 DEG C of stirring and dissolving, it is in addition that the laurine of formula ratio is molten
In ethyl alcohol, after laurine is completely dissolved, it is slowly dropped in aforesaid reaction vessel；And first acid as catalyst is added,
It is warming up to 82-83 DEG C, reaction 6-8h is stirred at reflux, is cooled to room temperature to fully reacting, purify, it is dry to get hydroxyl Schiff
Alkali.
3. structural type antibacterial moisture-curable polyurethane hot melt adhesive as described in claim 1, which is characterized in that the diisocyanate
It is 4,4 '-methyl diphenylene diisocyanates, toluene di-isocyanate(TDI), isophorone diisocyanate, two isocyanide of hexa-methylene
The composition of one or more of acid esters.
4. structural type antibacterial moisture-curable polyurethane hot melt adhesive as described in claim 1, which is characterized in that the oligomer is polynary
Alcohol is polytetrahydrofuran dihydric alcohol, polycarbonate glycol, polycaprolactone diols, polyethylene oxide polyol, polyethers binary
The combination of one or more of alcohol, polyethylene glycol, polyoxypropylene polyol；The molecular weight of the oligomer polyol is
1000~5000.
5. structural type antibacterial moisture-curable polyurethane hot melt adhesive as described in claim 1, which is characterized in that the chain extender is
Propylene glycol, 1,4 butanediols, 1,4- cyclohexanedimethanol, neopentyl glycol, Diethylene Glycol, 2- butyl -2- ethyl -1,3- the third two
The composition of one or more of alcohol, trimethylolpropane.
6. structural type antibacterial moisture-curable polyurethane hot melt adhesive as described in claim 1, which is characterized in that the antioxidant is anti-
The composition of one or both of oxygen agent 1010, irgasfos 168.
7. structural type antibacterial moisture-curable polyurethane hot melt adhesive as described in claim 1, which is characterized in that the catalyst is two
Dibutyl tin laurate.
8. structural type antibacterial moisture-curable polyurethane hot melt adhesive as described in claim 1, which is characterized in that the curing catalysts
For dual-morpholinyl diethyl ether.The curing catalysts are dual-morpholinyl diethyl ether.
9. structural type antibacterial moisture-curable polyurethane hot melt adhesive as described in claim 1, which is characterized in that the nanofiller is
The composition of one or more of organobentonite, precipitated calcium carbonate, fumed silica.
10. a kind of preparation method of structural type antibacterial moisture-curable polyurethane hot melt adhesive, which comprises the following steps:
1) based on formulation weight part, oligomer polyol, chain extender, terpene resin, polyurethane elastomer and antioxidant are added
Into reaction kettle, be heated to 120 DEG C~130 DEG C, stir evenly, under the conditions of vacuum degree < 200Pa be dehydrated 2.0h~
3.0h；
2) be cooled to 65 DEG C~70 DEG C, diisocyanate be added, is stirred to react 0.5~1.0h, be warming up to 100 DEG C~110 DEG C, it is true
0.5h is reacted under empty condition；
3) nanofiller, catalyst and hydroxyl schiff bases is added, is stirred to react 0.5h~1.0h under the conditions of 100 DEG C~105 DEG C；
4) reaction terminates, and curing catalysts are added and stir evenly, keep drop temperature at 100 DEG C~110 DEG C, fast under nitrogen protection
Speed discharging, sealed package to obtain the final product.
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| CN115948141A (en) * | 2022-12-15 | 2023-04-11 | 江苏和和新材料股份有限公司 | TPU (thermoplastic polyurethane) hot melt adhesive film for sole fitting and preparation method and application thereof |
| CN116199841A (en) * | 2023-02-21 | 2023-06-02 | 中国科学院宁波材料技术与工程研究所 | Antibacterial agent and preparation method and application thereof |
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| CN116199841A (en) * | 2023-02-21 | 2023-06-02 | 中国科学院宁波材料技术与工程研究所 | Antibacterial agent and preparation method and application thereof |
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