CN107722914A - A kind of Hot-melt adhesives for shoemaking and preparation method thereof - Google Patents
A kind of Hot-melt adhesives for shoemaking and preparation method thereof Download PDFInfo
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- CN107722914A CN107722914A CN201710978683.1A CN201710978683A CN107722914A CN 107722914 A CN107722914 A CN 107722914A CN 201710978683 A CN201710978683 A CN 201710978683A CN 107722914 A CN107722914 A CN 107722914A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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 discloses a kind of Hot-melt adhesives for shoemaking and preparation method thereof, the material composition and its mass percent of Hot-melt adhesives for shoemaking material are：20 parts~30 parts of polyether Glycols, 20 parts~30 parts of polyisocyanates, 10 parts~20 parts of ethylene/vinyl acetate copolymer, 0.01 part~0.1 part of catalyst, 5 parts~10 parts of hydrogenated rosin glyceride, 5 parts~10 parts of naphthenic oil, 1 part~3 parts of microwax.The PUR of the present invention has preferable flexibility, hydrolytic resistance and heat-resisting quantity, and preparation method is easy, low manufacture cost, is easy to large-scale promotion.
Description
Technical field
The invention belongs to adhesive area, more particularly to a kind of Hot-melt adhesives for shoemaking and preparation method thereof.
Background technology
Flour paste, synthetic resin polyvinyl acetate, polyvinyl alcohol etc. belong to cold property glue mostly, and its caking property is poor, work
The sequence time is longer, is gradually eliminated by people.PUR has that bonding force is strong, broad application temperature range, heat-resisting cold resistance
With the performance such as heat endurance is good, stationarity is good, its physical state in certain temperature range changes and changed with temperature, and chemical
Characteristic is constant, nonpoisonous and tasteless, belongs to environmentally friendly machine, is widely used in the fields such as yarn fabric, books and periodicals dress, edge sealing of furniture.
Chinese patent CN103289065A discloses a kind of preparation method of shoemaking polyester hot-melt adhesive, including following step
Suddenly：Terephthalic acid (TPA), M-phthalic acid, adipic acid and butanediol, hexylene glycol, diethylene glycol (DEG) are pressed one in tin/titanium complex catalyst
Certainty ratio carries out esterification；Add stabilizer in the product, antioxidant carries out decompression polycondensation reaction, you can obtain the poly- of footwear
Ester PUR product.Because the standby PUR of the patent system is PEPA, contain ester bond, easily hydrolysis, so polyester-type
Adhesive water resistance it is poor.
Chinese patent CN106289606A discloses a kind of Hot-melt adhesives for shoemaking, by EVA resin, ethylene propylene diene rubber thickening tree
Fat, OPE, agstone, zirconium oxide, antioxidant 1010, antioxidant, antioxidant 2246-S, the second of acetyl tributyl citrate three
Ester, epoxy tetrahydro-2-ethylhexyl phthalate component are made.The EVA type PURs of the patent have preferable cryogenic property, melt
It is suitable to melt viscosity, but heat-resisting quantity is poor, adhesive strength lowers more during high temperature.
Therefore, it is good to be badly in need of a kind of thermal viscosity, high temperature resistant, water-fast connecing property are strong, and preparation technology is easy, cheap PUR
And preparation method thereof.
The content of the invention
The present invention is in view of the above-mentioned problems, provide a kind of Hot-melt adhesives for shoemaking and preparation method thereof.
Technical scheme is used by the present invention solves the above problems：A kind of Hot-melt adhesives for shoemaking, prepare the footwear hot melt
The raw material and its parts by weight of glue be：20 parts~30 parts of polyether Glycols, 20 parts~30 parts of polyisocyanates, ethylene/vinyl acetate
0 part~20 parts of copolymer 1,0.01 part~0.1 part of catalyst, 5 parts~10 parts of hydrogenated rosin glyceride, 5 parts~10 parts of naphthenic oil,
1~3 part of microwax.
Wherein, using PPG, because diether linkage structure unit belongs to flexible chain, and ehter bond not facile hydrolysis, it is made
PUR there is preferable flexibility, hydrolytic resistance and heat-resisting quantity；Add tackifier hydrogenated rosin glyceride and viscosity is adjusted
Agent microwax is saved, the viscosity and the physical property of product of prepolymer and product is adjusted, enhances product performance.
Further, catalyst includes any of butyl titanate, stannous octoate, dibutyl tin laurate or several
Kind.
Further, the raw material and its parts by weight for preparing Hot-melt adhesives for shoemaking be：23~27 parts of polyether Glycols, polyisocyanic acid
24 parts~26 parts of ester, 13 parts~17 parts of ethylene/vinyl acetate copolymer, 0.03 part~0.08 part of catalyst, hydrogenated rosin glycerine
6 parts~8 parts of ester, 7 parts~9 parts of naphthenic oil, 1 part~3 parts of microwax.
Further, the raw material and its parts by weight for preparing Hot-melt adhesives for shoemaking be：25 parts of polyether Glycols, polyisocyanates 25
Part, 15 parts of ethylene/vinyl acetate copolymer, 0.06 part of catalyst, 8 parts of hydrogenated rosin glyceride, 7 parts of naphthenic oil, microwax 2
Part.
Further, the raw material and its parts by weight for preparing Hot-melt adhesives for shoemaking be：30 parts of polyether Glycols, polyisocyanates 25
Part, 10 parts of ethylene/vinyl acetate copolymer, 0.09 part of catalyst, 10 parts of hydrogenated rosin glyceride, 5 parts of naphthenic oil, microwax 2
Part.
Another goal of the invention of the present invention, is to provide a kind of preparation method of above-mentioned Hot-melt adhesives for shoemaking, including following step
Suddenly：
Step S10, by the polyisocyanates of the parts by weight, ethylene/vinyl acetate, naphthenic oil, hydrogenated rosin glycerine
Ester, microwax are mixed in normal pressure, obtain mixture A；
Step S20, the mixture A that step S10 is obtained is transferred in vacuum plant, adds the polyethers two of the parts by weight
First alcohol and catalyst, vacuum plant is closed, it is 125 DEG C~135 DEG C to keep vacuum plant temperature, is reacted, when solution becomes
Uniform thick liquid, bubble-free produces in vacuum plant, stops reaction, vacuum outgas, and discharges while hot under nitrogen protection,
Obtain Hot-melt adhesives for shoemaking.
Wherein, mesogens molecules of the moisture-curable polyurethane hot melt adhesive after moisturecuring is crosslinked form network structure, this structure
Glue is not heated melting again, but also the water resistance, solvent resistance, lower temperature resistance of glue-line can be provided；During applying glue,
Base material can be glued after heating immediately, through supercooling fixation and moisturecuring process, can not only be used in lower temperature range,
It can use and arrive high temperature range.
Further, in step S10, mixing is specially：
Step S11, the polyisocyanates of the parts by weight, ethylene/vinyl acetate are put into Minton dryer, done
Dry 2 hours；
Step S12, reactor is preheated into 10min~15min, preheating temperature is 85 DEG C~90 DEG C, by the parts by weight
Naphthenic oil is put into warmed-up reactor, then adds the polyisocyanates handled through step S11, ethylene/vinyl acetate,
Hydrogenated rosin glyceride, the microwax of the parts by weight are added, the heating stirring under 120 DEG C~135 DEG C of temperature conditionss.
Further, in step S20, the time of reaction is 2h~3h.
Further, in step S20, when reaction temperature is 125 DEG C~129 DEG C, the catalyst of addition is stannous octoate
And dibutyl tin laurate, and both mass percents are 2:1.
Wherein, by stannous octoate catalyst and dibutyltin dilaurate catalyst compounding use, accelerate reaction speed, protect
Card catalyzes and synthesizes effect.
Further, in step S30, when reaction temperature is 130 DEG C~135 DEG C, the catalyst of addition is the fourth of metatitanic acid four
Ester.
It is an advantage of the invention that：
1. mesogens molecules of the present invention after moisturecuring is crosslinked form network structure, the structure not only makes glue not add again
Heat fusing, and also improve the water resistance, solvent resistance and resistance to elevated temperatures of glue-line；
2. the present invention is catalyst compounded using stannous octoate and dibutyl tin laurate, accelerate reaction speed；Using poly-
Ethoxylated polyhydric alcohol, because diether linkage structure unit belongs to flexible chain, and ehter bond not facile hydrolysis, therefore it has preferable flexibility, resistance to
Water-disintegrable and heat-resisting quantity；
3. PUR prepared by the present invention is not aqueous and other solvents, it is easy to transport and stores, service life length, security
Height, the health of secondary pollution and harmful to human will not be caused to environment；
4. the preparation method of Hot-melt adhesives for shoemaking of the present invention is easy, low manufacture cost, it is easy to large-scale promotion.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to embodiment, the present invention is further detailed explanation.
Embodiment
The present invention is described in detail with reference to embodiments, but the present invention can be defined by the claims and cover
Multitude of different ways implement.
Embodiment 1
A kind of Hot-melt adhesives for shoemaking and preparation method thereof
Hot-melt adhesives for shoemaking raw material forms：(unit：kg)
Polyether Glycols 25, polyisocyanates 25, ethylene/vinyl acetate copolymer 15, stannous octoate 0.04, tin dilaurate
Dibutyl tin 0.02, hydrogenated rosin glyceride 8, naphthenic oil 7, microwax 2.
Preparation method, comprise the following steps：
Step S10, by the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate, naphthenic oil, hydrogenated rosin glycerine
Ester, microwax are mixed in normal pressure, obtain mixture A；
Wherein, mixing is specially：
Step S11, the polyisocyanates of the parts by weight, ethylene/vinyl acetate are put into Minton dryer, done
Dry 2 hours；
Step S12, reactor is preheated into 10min, preheating temperature is 85 DEG C, the naphthenic oil of above-mentioned parts by weight is put into pre-
In the reactor of heat, the polyisocyanates handled through step S11, ethylene/vinyl acetate are then added, adds above-mentioned weight
The hydrogenated rosin glyceride, microwax of part, the heating stirring under 120 DEG C of temperature conditionss.
Step S20, the mixture A that step S10 is obtained is transferred in vacuum plant, adds the polyethers two of above-mentioned parts by weight
First alcohol and catalyst, vacuum plant is closed, it is 125 DEG C to keep vacuum plant temperature, reaction 2h is carried out, when solution becomes uniform
Thick liquid, bubble-free produces in vacuum plant, stops reaction, vacuum outgas, and discharges while hot under nitrogen protection, obtains footwear
Use PUR.
Embodiment 2
A kind of Hot-melt adhesives for shoemaking and preparation method thereof
Hot-melt adhesives for shoemaking raw material forms：(unit：kg)
Polyether Glycols 30, polyisocyanates 25, ethylene/vinyl acetate copolymer 10, stannous octoate 0.06, tin dilaurate
Dibutyl tin 0.03, hydrogenated rosin glyceride 10, naphthenic oil 5, microwax 2.
It is prepared via a method which：
Preparation method, comprise the following steps：
Step S10, by the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate, naphthenic oil, hydrogenated rosin glycerine
Ester, microwax are mixed in normal pressure, obtain mixture A；
Wherein, mixing is specially：
Step S11, the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate are put into Minton dryer, done
Dry 2 hours；
Step S12, reactor is preheated into 15min, preheating temperature is 90 DEG C, the naphthenic oil of above-mentioned parts by weight is put into pre-
In the reactor of heat, the polyisocyanates handled through step S11, ethylene/vinyl acetate are then added, adds above-mentioned weight
The hydrogenated rosin glyceride, microwax of part, the heating stirring under 135 DEG C of temperature conditionss.
Step S20, the mixture A that step S10 is obtained is transferred in vacuum plant, adds the polyethers two of above-mentioned parts by weight
First alcohol and catalyst, vacuum plant is closed, it is 129 DEG C to keep vacuum plant temperature, reaction 3h is carried out, when solution becomes uniform
Thick liquid, bubble-free produces in vacuum plant, stops reaction, vacuum outgas, and discharges while hot under nitrogen protection, obtains footwear
Use PUR.
Embodiment 3
A kind of Hot-melt adhesives for shoemaking and preparation method thereof
Hot-melt adhesives for shoemaking raw material forms：(unit：kg)
Polyether Glycols 20, polyisocyanates 30, ethylene/vinyl acetate copolymer 20, butyl titanate 0.01, hydrogenation pine
Fragrant glyceride 5, naphthenic oil 10, microwax 3.
It is prepared via a method which：
Preparation method, comprise the following steps：
Step S10, by the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate, naphthenic oil, hydrogenated rosin glycerine
Ester, microwax are mixed in normal pressure, obtain mixture A；
Wherein, mixing is specially：
Step S11, the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate are put into Minton dryer, done
Dry 2 hours；
Step S12, reactor is preheated into 12min, preheating temperature is 88 DEG C, the naphthenic oil of the parts by weight is put into pre-
In the reactor of heat, the polyisocyanates handled through step S11, ethylene/vinyl acetate are then added, adds the weight
The hydrogenated rosin glyceride, microwax of part, the heating stirring under 130 DEG C of temperature conditionss.
Step S20, the mixture A that step S10 is obtained is transferred in vacuum plant, adds the polyethers two of above-mentioned parts by weight
First alcohol and catalyst, vacuum plant is closed, it is 130 DEG C to keep vacuum plant temperature, reaction 2.5h is carried out, when solution becomes uniform
Thick liquid, bubble-free produces in vacuum plant, stops reaction, vacuum outgas, and discharges while hot under nitrogen protection, obtains
Hot-melt adhesives for shoemaking.
Embodiment 4
A kind of Hot-melt adhesives for shoemaking and preparation method thereof
Hot-melt adhesives for shoemaking raw material forms：(unit：kg)
Polyether Glycols 23, polyisocyanates 26, ethylene/vinyl acetate copolymer 13, butyl titanate 0.08, hydrogenation pine
Fragrant glyceride 5, naphthenic oil 10, microwax 1.
It is prepared via a method which：
Preparation method, comprise the following steps：
Step S10, by the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate, naphthenic oil, hydrogenated rosin glycerine
Ester, microwax are mixed in normal pressure, obtain mixture A；
Wherein, mixing is specially：
Step S11, the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate are put into Minton dryer, done
Dry 2 hours；
Step S12, reactor is preheated into 14min, preheating temperature is 88 DEG C, the naphthenic oil of above-mentioned parts by weight is put into pre-
In the reactor of heat, the polyisocyanates handled through step S11, ethylene/vinyl acetate are then added, adds above-mentioned weight
The hydrogenated rosin glyceride, microwax of part, the heating stirring under 132 DEG C of temperature conditionss.
Step S20, the mixture A that step S10 is obtained is transferred in vacuum plant, adds the polyethers two of above-mentioned parts by weight
First alcohol and catalyst, vacuum plant is closed, it is 135 DEG C to keep vacuum plant temperature, reaction 2.2h is carried out, when solution becomes uniform
Thick liquid, bubble-free produces in vacuum plant, stops reaction, vacuum outgas, and discharges while hot under nitrogen protection, obtains
Hot-melt adhesives for shoemaking.
Embodiment 5
A kind of Hot-melt adhesives for shoemaking and preparation method thereof
Hot-melt adhesives for shoemaking raw material forms：
Polyether Glycols 27, polyisocyanates 24, ethylene/vinyl acetate copolymer 17, butyl titanate 0.01, octanoic acid are sub-
Tin 0.02, hydrogenated rosin glyceride 6, naphthenic oil 9, microwax 2.
It is prepared via a method which：
Preparation method, comprise the following steps：
Step S10, by the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate, naphthenic oil, hydrogenated rosin glycerine
Ester, microwax are mixed in normal pressure, obtain mixture A；
Wherein, mixing is specially：
Step S11, the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate are put into Minton dryer, done
Dry 2 hours；
Step S12, reactor is preheated into 11min, preheating temperature is 86 DEG C, the naphthenic oil of above-mentioned parts by weight is put into pre-
In the reactor of heat, the polyisocyanates handled through step S11, ethylene/vinyl acetate are then added, adds above-mentioned weight
The hydrogenated rosin glyceride, microwax of part, the heating stirring under 123 DEG C of temperature conditionss.
Step S20, the mixture A that step S10 is obtained is transferred in vacuum plant, adds the polyethers two of above-mentioned parts by weight
First alcohol and catalyst, vacuum plant is closed, it is 132 DEG C to keep vacuum plant temperature, reaction 2h is carried out, when solution becomes uniform
Thick liquid, bubble-free produces in vacuum plant, stops reaction, vacuum outgas, and discharges while hot under nitrogen protection, obtains footwear
Use PUR.
Embodiment 6
A kind of Hot-melt adhesives for shoemaking and preparation method thereof
Hot-melt adhesives for shoemaking raw material forms：(unit：kg)
Polyether Glycols 25, polyisocyanates 25, ethylene/vinyl acetate copolymer 13, butyl titanate 0.03, octanoic acid are sub-
Tin 0.02, dibutyl tin laurate 0.05, hydrogenated rosin glyceride 5, naphthenic oil 10, microwax 1.
It is prepared via a method which：
Preparation method, comprise the following steps：
Step S10, by the polyisocyanates of above-mentioned parts by weight, ethylene/vinyl acetate, naphthenic oil, hydrogenated rosin glycerine
Ester, microwax are mixed in normal pressure, obtain mixture A；
Wherein, mixing is specially：
Step S11, the polyisocyanates of the parts by weight, ethylene/vinyl acetate are put into Minton dryer, done
Dry 2 hours；
Step S12, reactor is preheated into 13min, preheating temperature is 85 DEG C, the naphthenic oil of above-mentioned parts by weight is put into pre-
In the reactor of heat, the polyisocyanates handled through step S11, ethylene/vinyl acetate are then added, adds above-mentioned weight
The hydrogenated rosin glyceride, microwax of part, the heating stirring under 120 DEG C of temperature conditionss.
Step S20, the mixture A that step S10 is obtained is transferred in vacuum plant, adds the polyethers two of above-mentioned parts by weight
First alcohol and catalyst, vacuum plant is closed, it is 127 DEG C to keep vacuum plant temperature, reaction 3h is carried out, when solution becomes uniform
Thick liquid, bubble-free produces in vacuum plant, stops reaction, vacuum outgas, and discharges while hot under nitrogen protection, obtains footwear
Use PUR.
Experimental example
In this experimental example, the performance of the PUR prepared by the experiment test embodiment of the present invention 1~6.
1. experiment material
Experimental group：PUR prepared by the embodiment of the present invention 1~6；
Control group：Common PUR.
2. experimental method
(1) it is PUR prepared by the embodiment of the present invention 1~6 and common PUR progress 120 DEG C of melting viscosities, glued membranes is soft
Toughness, resistance to elevated temperatures test, wherein resistance to elevated temperatures mainly investigates 80 DEG C of test temperature, the PUR of 24 hours testing times
Foaming characteristic, experimental result such as table 1.
(2) to the leather shoes outer bottom and the advance gluing in interior bottom of the production of certain Shoes Factory, room temperature vulcanizing, chain extension is after 7 days at room temperature, and 65
DEG C thermal activation, carry out peel strength to it and glue point start degumming washing times performance test, experimental result such as table 2.
3. experimental result
The quantitative measurement of PUR prepared by the embodiment of the present invention 1~6 and common PUR the results are shown in Table 1.
PUR physical test results made from the embodiment 1~6 of table 1.
The physical test results of PUR made from the embodiment 1~6 of table 2.
Test result indicates that compared with common PUR, PUR prepared by the embodiment of the present invention 1~6 is in square one
Under melting viscosity, glued membrane suppleness, resistance to elevated temperatures test result be better than common PUR, show that footwear prepared by the present invention are used
PUR cementability is good, pliability is high, resistance to elevated temperatures is good, and preparation method is adapted to promote, and product quality is more preferably.
The preferred embodiments of the present invention and experimental example are these are only, is not intended to limit the invention, for this area
Technical staff for, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made appoints
What modification, equivalent substitution, improvement etc., should be included within the protection domain of invention.
Claims (10)
1. a kind of Hot-melt adhesives for shoemaking, it is characterised in that the raw material and its parts by weight for preparing the Hot-melt adhesives for shoemaking be：Polyethers binary
20 parts~30 parts of alcohol, 20 parts~30 parts of polyisocyanates, 10 parts~20 parts of ethylene/vinyl acetate copolymer, 0.01 part of catalyst
~0.1 part, 5 parts~10 parts of hydrogenated rosin glyceride, 5 parts~10 parts of naphthenic oil, 1~3 part of microwax.
2. Hot-melt adhesives for shoemaking according to claim 1, it is characterised in that the catalyst includes butyl titanate, octanoic acid
Any of stannous, dibutyl tin laurate are several.
3. Hot-melt adhesives for shoemaking according to claim 1, it is characterised in that prepare the raw material and its again of the Hot-melt adhesives for shoemaking
Measuring part is：23~27 parts of polyether Glycols, 24 parts~26 parts of polyisocyanates, 13 parts~17 parts of ethylene/vinyl acetate copolymer,
0.03 part~0.08 part of catalyst, 6 parts~8 parts of hydrogenated rosin glyceride, 7 parts~9 parts of naphthenic oil, 1 part~3 parts of microwax.
4. Hot-melt adhesives for shoemaking according to claim 1, it is characterised in that prepare the raw material and its again of the Hot-melt adhesives for shoemaking
Measuring part is：25 parts of polyether Glycols, 25 parts of polyisocyanates, 15 parts of ethylene/vinyl acetate copolymer, 0.06 part of catalyst, hydrogen
Change 8 parts of ester gum, 7 parts of naphthenic oil, 2 parts of microwax.
5. Hot-melt adhesives for shoemaking according to claim 1, it is characterised in that prepare the raw material and its again of the Hot-melt adhesives for shoemaking
Measuring part is：30 parts of polyether Glycols, 25 parts of polyisocyanates, 10 parts of ethylene/vinyl acetate copolymer, 0.09 part of catalyst, hydrogen
Change 10 parts of ester gum, 5 parts of naphthenic oil, 2 parts of microwax.
A kind of 6. preparation method according to Hot-melt adhesives for shoemaking according to any one of claims 1 to 5, it is characterised in that including
Following steps：
Step S10, by the polyisocyanates of the parts by weight, ethylene/vinyl acetate, naphthenic oil, hydrogenated rosin glyceride, micro-
Brilliant wax is mixed in normal pressure, obtains mixture A；
Step S20, the mixture A that step S10 is obtained is transferred in vacuum plant, adds the polyether Glycols of the parts by weight
And catalyst, vacuum plant is closed, it is 125 DEG C~135 DEG C to keep vacuum plant temperature, is reacted, when solution becomes uniform
Thick liquid, bubble-free produces in vacuum plant, stops reaction, vacuum outgas, and discharges while hot under nitrogen protection, obtains
Hot-melt adhesives for shoemaking.
7. preparation method according to claim 6, it is characterised in that in step S10, the mixing is specially：
Step S11, the polyisocyanates of the parts by weight, ethylene/vinyl acetate are put into Minton dryer, dry 2
Hour；
Step S12, reactor is preheated into 10min~15min, preheating temperature is 85 DEG C~90 DEG C, by the cycloalkanes of the parts by weight
Oil is put into warmed-up reactor, then adds the polyisocyanates handled through step S11, ethylene/vinyl acetate, then add
Enter hydrogenated rosin glyceride, the microwax of the parts by weight, the heating stirring under 120 DEG C~135 DEG C of temperature conditionss.
8. preparation method according to claim 6, it is characterised in that in step S20, time of the reaction for 2h~
3h。
9. preparation method according to claim 6, it is characterised in that in step S20, when reaction temperature is 125 DEG C~129
DEG C when, the catalyst of addition is stannous octoate and dibutyl tin laurate, and both mass percents are 2:1.
10. preparation method according to claim 6, it is characterised in that in step S30, when reaction temperature be 130 DEG C~
At 135 DEG C, the catalyst of addition is butyl titanate.
Priority Applications (1)
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| US20050049358A1 (en) * | 2003-08-27 | 2005-03-03 | Great Eastern Resins Industrial Co., Ltd. | Water dispersible polyisocyanate composition bearing urea and/or biuret and its uses |
| CN101255327A (en) * | 2008-04-03 | 2008-09-03 | 武汉理工大学 | Preparation method of wet-curing reaction type polyurethane hot melt adhesives for shoes |
| CN101787250A (en) * | 2010-01-22 | 2010-07-28 | 山东久隆高分子材料有限公司 | EVA hot melt adhesive composition containing linear hydroxyl-terminated polyurethane resin |
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