CN108485560A - A kind of high-performance adhesives for shoes and preparation method thereof - Google Patents
A kind of high-performance adhesives for shoes and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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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
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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- 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
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of high-performance adhesives for shoes, include the raw material of following parts by weight：2~3 parts of 20~30 parts of gum arabic, 17~24 parts of TPU elastic resins, 13~22 parts of epoxy resin, 9~18 parts of ethyl acetate, 4~7 parts of polyisobutene, 6~11 parts of polypropylene, 2~4 parts of rosin, 1~3 part of microwax, 1~2 part of stearic acid, 3~5 parts of modified Nano grade calcium carbonate, 4~7 parts of Modified Starch Adhesive, 3~6 parts of polycarbonate polyol, 1~4 part of dioctyl adipate, 1~2 part of zinc oxide, 2~5 parts of toughener, 1~3 part of anti-aging agent and fungicide.The high-performance adhesives for shoes scientific formulation, rationally, caking ability is high, and mechanical property is good, excellent weather resistance and hard, and corrosion-resistant, and production cost is low.
Description
Technical field
The invention belongs to adhesive technical fields, and in particular to a kind of high-performance adhesives for shoes and preparation method thereof.
Background technology
There are tens populations in the whole world, everyone will wear shoes, there are 1,300,000,000 people in China, is the most state of the number of global wear shoes
Family and the first big country of shoes industry production, existing shoes manufacturing enterprise of China have family more than 20,000, most of producer to use adhesive producing
Shoes.
Adhesive, purposes are bonding Foxing strip for rubber shoes and upper of a shoe, and Foxing strip for rubber shoes film is made to form firm entirety with upper of a shoe.
The leading indicator of judgement Adhensive performance is the adhesive strength of Foxing strip for rubber shoes film and upper of a shoe, usually with the Foxing strip for rubber shoes glue of measurement
The adhesive strength value of piece and upper of a shoe indicates quality of the adhesive to rubber overshoes bond properties.
But adhesive in the prior art is easily led to there are the small mass defect of adhesion strength in process of producing product
Rubber overshoes seep through, rubber overshoes base fabric come to nothing, Foxing strip for rubber shoes delamination and other issues, causes product qualification rate low.
Invention content
The present invention provides a kind of high-performance adhesives for shoes and preparation method thereof, solve the problems in background technology,
The high-performance adhesives for shoes scientific formulation, rationally, caking ability is high, and mechanical property is good, excellent weather resistance and hard, and corrosion-resistant, prevents
Ageing properties are good, and production cost is low.
It is of the existing technology in order to solve the problems, such as, it adopts the following technical scheme that：
A kind of high-performance adhesives for shoes, includes the raw material of following parts by weight：20~30 parts of gum arabic, TPU elastic resins
17~24 parts, 13~22 parts of epoxy resin, 9~18 parts of ethyl acetate, 4~7 parts of polyisobutene, 6~11 parts of polypropylene, rosin 2
~4 parts, 1~3 part of microwax, 1~2 part of stearic acid, 3~5 parts of modified Nano grade calcium carbonate, 4~7 parts of Modified Starch Adhesive,
3~6 parts of polycarbonate polyol, 1~4 part of dioctyl adipate, 1~2 part of zinc oxide, 2~5 parts of toughener, anti-aging agent 1~3
2~3 parts of part and fungicide；
Wherein, the preparation method of the Modified Starch Adhesive is as follows：（1）By weight, following raw material is weighed：Potato starch
20 parts, 5 parts of methacrylic acid, 3 parts of styrene, 3 parts of hydrogen peroxide, 2 parts of odium stearate；（2）By the methacrylic acid,
Styrene and odium stearate carry out 40~50min of emulsion reaction under Ultrasonic Conditions, and emulsion is made；（3）By the starch
Raw material leads to nitrogen protection under Ultrasonic Conditions in room temperature environment, 50min is preheated when temperature is 60~70 DEG C, maintains temperature
60~70 DEG C and 10~15min of hydroperoxidation is added, obtains reactant；（4）To step（3）Step is added in reactant obtained
Suddenly（2）Emulsion obtained carries out chemical reaction 60min, obtains Modified Starch Adhesive.
Preferably, the high-performance adhesives for shoes, includes the raw material of following parts by weight：24~28 parts of gum arabic,
19~22 parts of TPU elastic resins, 15~20 parts of epoxy resin, 10~17 parts of ethyl acetate, 5.2~6.3 parts of polyisobutene, poly- third
6~10 parts of alkene, 2.4~3.6 parts of rosin, 1.7~2.5 parts of microwax, 1.1~1.8 parts of stearic acid, modified Nano grade calcium carbonate
3.2~4.3 parts, 5~6 parts of Modified Starch Adhesive, 4~5 parts of polycarbonate polyol, 2~3 parts of dioctyl adipate, oxidation
2.2~2.7 parts of 1.3~1.7 parts of zinc, 3~4 parts of toughener, 1.5~2.4 parts of anti-aging agent and fungicide.
Preferably, the high-performance adhesives for shoes, includes the raw material of following parts by weight：25 parts of gum arabic, TPU bullets
20 parts of resin of property, 18 parts of epoxy resin, 14 parts of ethyl acetate, 6 parts of polyisobutene, 7 parts of polypropylene, 3 parts of rosin, microwax 2.1
Part, 1.6 parts of stearic acid, 3.9 parts of modified Nano grade calcium carbonate, 5.6 parts of Modified Starch Adhesive, 4.5 parts of polycarbonate polyol,
2.6 parts of 2.3 parts of dioctyl adipate, 1.4 parts of zinc oxide, 3.8 parts of toughener, 2.2 parts of anti-aging agent and fungicide.
Preferably, the preparation method of the modified Nano grade calcium carbonate is as follows：
（1）Weigh the raw material of following parts by weight：5 parts of 80 parts of nanometer grade calcium carbonate, 10 parts of coupling agent, 5 parts of lubricant and dispersant；
（2）Nanometer grade calcium carbonate is put in 80~120 DEG C of oven heat and is dried 3 hours, is cooled to room temperature；
（3）It is added in high-speed mixer and stirs 20 minutes after taking-up, the coupling agent weighed is then added and is stirred for 10 minutes, then according to
Secondary that the dispersant and lubricant that weigh is added, then heating stirring is transferred to stirring in cold mixer and is cooled to≤40 DEG C to 85 DEG C
Material, obtains modified Nano grade calcium carbonate.
Preferably, the fungicide is nano-silver ionic fungicide.
Preferably, the toughener is POE.
A method of the high-performance adhesives for shoes is prepared, is included the following steps：
（1）Gum arabic, TPU elastic resins, epoxy resin, ethyl acetate, polyisobutene, poly- third are weighed by above-mentioned formula
Alkene, rosin, microwax, stearic acid, modified Nano grade calcium carbonate, Modified Starch Adhesive, polycarbonate polyol, adipic acid two
Monooctyl ester, zinc oxide, toughener, anti-aging agent and fungicide, it is spare；
（2）Gum arabic, TPU elastic resins, epoxy resin are first placed in cutter and are crushed, remixes uniformly, then sets
It heats and is kneaded in kneading machine, obtain compounding mixture A, the process that the heating is kneaded is specific as follows：50~60 DEG C are first heated to,
Heat preservation is kneaded 20~30 minutes, is again heated to 75~80 DEG C, heat preservation is kneaded 10~15 minutes, finally heated to 90~95 DEG C, is protected
Temperature is kneaded 8~15 minutes；
（3）Modified Nano grade calcium carbonate, stearic acid and rosin are sequentially added into the compounding mixture A obtained by step, are first stirred
Mixing 7~13 minutes, then ultrasonic wave mix 3~6 minutes, and polypropylene and zinc oxide is then added, is placed in kneading machine, is warming up to
78~84 DEG C, heat preservation is kneaded 5~10 minutes, obtains compounding mixture B；
（4）To step（3）Polyisobutene, microwax and anti-aging agent is first added in the compounding mixture B of gained, it is heated to 100~
It 110 DEG C, is stirred 10~15 minutes, ethyl acetate is then added, insulated and stirred mixes 4~8 minutes, obtains mixture C；
（5）To step（4）Modified Starch Adhesive, polycarbonate polyol, adipic acid two are sequentially added in the mixture C of gained
Monooctyl ester, toughener and fungicide are uniformly mixed to get the high-performance adhesives for shoes.
Preferably, the step（3）The frequency of middle ultrasonic wave mixing is 25KHz.
Compared with prior art, the present invention it has the advantages that：
High-performance adhesives for shoes scientific formulation of the present invention, rationally, caking ability is high, and mechanical property is good, excellent weather resistance and hard, and
Corrosion-resistant, anti ageing property is good, and production cost is low, specific as follows：
（1）High-performance adhesives for shoes of the present invention is using gum arabic, TPU elastic resins, epoxy resin as master
Raw material is wanted, and adds other raw materials, is mutually acted synergistically between raw material, by the high adhesiveness of epoxy resin, heat resistance, chemically-resistant
Moral character, the good amphipathic property of gum arabic, the excellent elasticity of viscosity and elasticity and TPU elastic resins, wearability
It is combined with low temperature flexibility, has obtained the high-performance adhesives for shoes of excellent combination property, the high-performance adhesives for shoes
Caking ability is high, and mechanical property is good, excellent weather resistance and hard；
（2）High-performance association of the present invention adhesives for shoes also added Modified Starch Adhesive in the feed, modified
Amylum adhesive bonding effect is good, can effectively improve the caking property of product；
（3）The present invention also uses polyisobutene, polypropylene, modified Nano grade calcium carbonate, zinc oxide etc. for raw material, is set with Arab
It mutually acts synergistically between glue, TPU elastic resins, epoxy resin, the anti ageing property of product can be effectively improved.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.These embodiments are merely to illustrate the present invention and do not have to
In limiting the scope of the invention.
Embodiment 1
The present embodiment is related to a kind of high-performance adhesives for shoes, includes the raw material of following parts by weight：20 parts of gum arabic, TPU
17 parts of elastic resin, 13 parts of epoxy resin, 9 parts of ethyl acetate, 4 parts of polyisobutene, 6 parts of polypropylene, 2 parts of rosin, microwax 1
Part, 1 part of stearic acid, 3 parts of modified Nano grade calcium carbonate, 4 parts of Modified Starch Adhesive, 3 parts of polycarbonate polyol, adipic acid two
2~3 parts of 1 part of monooctyl ester, 1 part of zinc oxide, toughener 2,1 part of anti-aging agent and fungicide；
Wherein, the preparation method of the Modified Starch Adhesive is as follows：（1）By weight, following raw material is weighed：Potato starch
20 parts, 5 parts of methacrylic acid, 3 parts of styrene, 3 parts of hydrogen peroxide, 2 parts of odium stearate；（2）By the methacrylic acid,
Styrene and odium stearate carry out emulsion reaction 40min under Ultrasonic Conditions, and emulsion is made；（3）By the starch raw material
Under Ultrasonic Conditions, nitrogen protection is led in room temperature environment, 50min is preheated when temperature is 60 DEG C, maintain temperature 60 C and is added
Enter hydroperoxidation 10min, obtains reactant；（4）To step（3）Step is added in reactant obtained（2）Emulsification obtained
Liquid carries out chemical reaction 60min, obtains Modified Starch Adhesive.
Wherein, the preparation method of the modified Nano grade calcium carbonate is as follows：
（1）Weigh the raw material of following parts by weight：5 parts of 80 parts of nanometer grade calcium carbonate, 10 parts of coupling agent, 5 parts of lubricant and dispersant；
（2）Nanometer grade calcium carbonate is put in 80 DEG C of oven heat and is dried 3 hours, is cooled to room temperature；
（3）It is added in high-speed mixer and stirs 20 minutes after taking-up, the coupling agent weighed is then added and is stirred for 10 minutes, then according to
Secondary that the dispersant and lubricant that weigh is added, then heating stirring is transferred to stirring in cold mixer and is cooled to≤40 DEG C to 85 DEG C
Material, obtains modified Nano grade calcium carbonate.
Wherein, the fungicide is nano-silver ionic fungicide.
Wherein, the toughener is POE.
A method of the high-performance adhesives for shoes is prepared, is included the following steps：
（1）Gum arabic, TPU elastic resins, epoxy resin, ethyl acetate, polyisobutene, poly- third are weighed by above-mentioned formula
Alkene, rosin, microwax, stearic acid, modified Nano grade calcium carbonate, Modified Starch Adhesive, polycarbonate polyol, adipic acid two
Monooctyl ester, zinc oxide, toughener, anti-aging agent and fungicide, it is spare；
（2）Gum arabic, TPU elastic resins, epoxy resin are first placed in cutter and are crushed, remixes uniformly, then sets
It heats and is kneaded in kneading machine, obtain compounding mixture A, the process that the heating is kneaded is specific as follows：50 DEG C are first heated to, heat preservation
It is kneaded 20 minutes, is again heated to 75 DEG C, heat preservation is kneaded 10 minutes, and finally heated to 90 DEG C, heat preservation is kneaded 8 minutes；
（3）Modified Nano grade calcium carbonate, stearic acid and rosin are sequentially added into the compounding mixture A obtained by step, are first stirred
Mixing 7 minutes, then ultrasonic wave mix 3 minutes, and polypropylene and zinc oxide is then added, is placed in kneading machine, are warming up to 78 DEG C, protect
Temperature is kneaded 5 minutes, obtains compounding mixture B；
（4）To step（3）Polyisobutene, microwax and anti-aging agent is first added in the compounding mixture B of gained, is heated to 100 DEG C,
It is stirred 10 minutes, ethyl acetate is then added, insulated and stirred mixes 4 minutes, obtains mixture C；
（5）To step（4）Modified Starch Adhesive, polycarbonate polyol, adipic acid two are sequentially added in the mixture C of gained
Monooctyl ester, toughener and fungicide are uniformly mixed to get the high-performance adhesives for shoes.
Wherein, the step（3）The frequency of middle ultrasonic wave mixing is 25KHz.
Embodiment 2
The present embodiment is related to a kind of high-performance adhesives for shoes, includes the raw material of following parts by weight：30 parts of gum arabic, TPU
24 parts of elastic resin, 22 parts of epoxy resin, 18 parts of ethyl acetate, 7 parts of polyisobutene, 11 parts of polypropylene, 4 parts of rosin, microwax 3
Part, 2 parts of stearic acid, 5 parts of modified Nano grade calcium carbonate, 7 parts of Modified Starch Adhesive, 6 parts of polycarbonate polyol, adipic acid two
3 parts of 4 parts of monooctyl ester, 2 parts of zinc oxide, 5 parts of toughener, 3 parts of anti-aging agent and fungicide；
Wherein, the preparation method of the Modified Starch Adhesive is as follows：（1）By weight, following raw material is weighed：Potato starch
20 parts, 5 parts of methacrylic acid, 3 parts of styrene, 3 parts of hydrogen peroxide, 2 parts of odium stearate；（2）By the methacrylic acid,
Styrene and odium stearate carry out 40~50min of emulsion reaction under Ultrasonic Conditions, and emulsion is made；（3）By the starch
Raw material leads to nitrogen protection under Ultrasonic Conditions in room temperature environment, 50min is preheated when temperature is 60~70 DEG C, maintains temperature
60~70 DEG C and 10~15min of hydroperoxidation is added, obtains reactant；（4）To step（3）Step is added in reactant obtained
Suddenly（2）Emulsion obtained carries out chemical reaction 60min, obtains Modified Starch Adhesive.
Wherein, the preparation method of the modified Nano grade calcium carbonate is as follows：
（1）Weigh the raw material of following parts by weight：5 parts of 80 parts of nanometer grade calcium carbonate, 10 parts of coupling agent, 5 parts of lubricant and dispersant；
（2）Nanometer grade calcium carbonate is put in 120 DEG C of oven heat and is dried 3 hours, is cooled to room temperature；
（3）It is added in high-speed mixer and stirs 20 minutes after taking-up, the coupling agent weighed is then added and is stirred for 10 minutes, then according to
Secondary that the dispersant and lubricant that weigh is added, then heating stirring is transferred to stirring in cold mixer and is cooled to≤40 DEG C to 85 DEG C
Material, obtains modified Nano grade calcium carbonate.
Wherein, the fungicide is nano-silver ionic fungicide.
Wherein, the toughener is POE.
A method of the high-performance adhesives for shoes is prepared, is included the following steps：
（1）Gum arabic, TPU elastic resins, epoxy resin, ethyl acetate, polyisobutene, poly- third are weighed by above-mentioned formula
Alkene, rosin, microwax, stearic acid, modified Nano grade calcium carbonate, Modified Starch Adhesive, polycarbonate polyol, adipic acid two
Monooctyl ester, zinc oxide, toughener, anti-aging agent and fungicide, it is spare；
（2）Gum arabic, TPU elastic resins, epoxy resin are first placed in cutter and are crushed, remixes uniformly, then sets
It heats and is kneaded in kneading machine, obtain compounding mixture A, the process that the heating is kneaded is specific as follows：60 DEG C are first heated to, heat preservation
It is kneaded 30 minutes, is again heated to 80 DEG C, heat preservation is kneaded 15 minutes, and finally heated to 95 DEG C, heat preservation is kneaded 15 minutes；
（3）Modified Nano grade calcium carbonate, stearic acid and rosin are sequentially added into the compounding mixture A obtained by step, are first stirred
Mixing 13 minutes, then ultrasonic wave mix 6 minutes, and polypropylene and zinc oxide is then added, is placed in kneading machine, is warming up to 84 DEG C,
Heat preservation is kneaded 10 minutes, obtains compounding mixture B；
（4）To step（3）Polyisobutene, microwax and anti-aging agent is first added in the compounding mixture B of gained, is heated to 110 DEG C,
It is stirred 15 minutes, ethyl acetate is then added, insulated and stirred mixes 8 minutes, obtains mixture C；
（5）To step（4）Modified Starch Adhesive, polycarbonate polyol, adipic acid two are sequentially added in the mixture C of gained
Monooctyl ester, toughener and fungicide are uniformly mixed to get the high-performance adhesives for shoes.
Wherein, the step（3）The frequency of middle ultrasonic wave mixing is 25KHz.
Embodiment 3
The present embodiment is related to a kind of high-performance adhesives for shoes, includes the raw material of following parts by weight：24 parts of gum arabic, TPU
19 parts of elastic resin, 15 parts of epoxy resin, 10 parts of ethyl acetate, 5.2 parts of polyisobutene, 6 parts of polypropylene, 2.4 parts of rosin, crystallite
1.7 parts of wax, 1.1 parts of stearic acid, 3.2 parts of modified Nano grade calcium carbonate, 5 parts of Modified Starch Adhesive, polycarbonate polyol 4
Part, 2 parts of dioctyl adipate, 1.3 parts of zinc oxide, 3 parts of toughener, 1.5 parts of anti-aging agent and 2.2 parts of fungicide；
Wherein, the preparation method of the Modified Starch Adhesive is as follows：（1）By weight, following raw material is weighed：Potato starch
20 parts, 5 parts of methacrylic acid, 3 parts of styrene, 3 parts of hydrogen peroxide, 2 parts of odium stearate；（2）By the methacrylic acid,
Styrene and odium stearate carry out emulsion reaction 42min under Ultrasonic Conditions, and emulsion is made；（3）By the starch raw material
Under Ultrasonic Conditions, nitrogen protection is led in room temperature environment, 50min is preheated when temperature is 63 DEG C, maintain 63 DEG C of temperature and is added
Enter hydroperoxidation 11min, obtains reactant；（4）To step（3）Step is added in reactant obtained（2）Emulsification obtained
Liquid carries out chemical reaction 60min, obtains Modified Starch Adhesive.
Wherein, the preparation method of the modified Nano grade calcium carbonate is as follows：
（1）Weigh the raw material of following parts by weight：5 parts of 80 parts of nanometer grade calcium carbonate, 10 parts of coupling agent, 5 parts of lubricant and dispersant；
（2）Nanometer grade calcium carbonate is put in 90 DEG C of oven heat and is dried 3 hours, is cooled to room temperature；
（3）It is added in high-speed mixer and stirs 20 minutes after taking-up, the coupling agent weighed is then added and is stirred for 10 minutes, then according to
Secondary that the dispersant and lubricant that weigh is added, then heating stirring is transferred to stirring in cold mixer and is cooled to≤40 DEG C to 85 DEG C
Material, obtains modified Nano grade calcium carbonate.
Wherein, the fungicide is nano-silver ionic fungicide.
Wherein, the toughener is POE.
A method of the high-performance adhesives for shoes is prepared, is included the following steps：
（1）Gum arabic, TPU elastic resins, epoxy resin, ethyl acetate, polyisobutene, poly- third are weighed by above-mentioned formula
Alkene, rosin, microwax, stearic acid, modified Nano grade calcium carbonate, Modified Starch Adhesive, polycarbonate polyol, adipic acid two
Monooctyl ester, zinc oxide, toughener, anti-aging agent and fungicide, it is spare；
（2）Gum arabic, TPU elastic resins, epoxy resin are first placed in cutter and are crushed, remixes uniformly, then sets
It heats and is kneaded in kneading machine, obtain compounding mixture A, the process that the heating is kneaded is specific as follows：52 DEG C are first heated to, heat preservation
It is kneaded 23 minutes, is again heated to 76 DEG C, heat preservation is kneaded 11 minutes, and finally heated to 91 DEG C, heat preservation is kneaded 10 minutes；
（3）Modified Nano grade calcium carbonate, stearic acid and rosin are sequentially added into the compounding mixture A obtained by step, are first stirred
Mixing 9 minutes, then ultrasonic wave mix 4 minutes, and polypropylene and zinc oxide is then added, is placed in kneading machine, are warming up to 80 DEG C, protect
Temperature is kneaded 6 minutes, obtains compounding mixture B；
（4）To step（3）Polyisobutene, microwax and anti-aging agent is first added in the compounding mixture B of gained, is heated to 102 DEG C,
It is stirred 12 minutes, ethyl acetate is then added, insulated and stirred mixes 5 minutes, obtains mixture C；
（5）To step（4）Modified Starch Adhesive, polycarbonate polyol, adipic acid two are sequentially added in the mixture C of gained
Monooctyl ester, toughener and fungicide are uniformly mixed to get the high-performance adhesives for shoes.
Wherein, the step（3）The frequency of middle ultrasonic wave mixing is 25KHz.
Embodiment 4
The present embodiment is related to a kind of high-performance adhesives for shoes, includes the raw material of following parts by weight：28 parts of gum arabic, TPU
It is 22 parts of elastic resin, 20 parts of epoxy resin, 17 parts of ethyl acetate, 6.3 parts of polyisobutene, 10 parts of polypropylene, 3.6 parts of rosin, micro-
2.5 parts of brilliant wax, 1.8 parts of stearic acid, 4.3 parts of modified Nano grade calcium carbonate, 6 parts of Modified Starch Adhesive, polycarbonate polyol 5
Part, 3 parts of dioctyl adipate, 1.7 parts of zinc oxide, 4 parts of toughener, 2.4 parts of anti-aging agent and 2.7 parts of fungicide；
Wherein, the preparation method of the Modified Starch Adhesive is as follows：（1）By weight, following raw material is weighed：Potato starch
20 parts, 5 parts of methacrylic acid, 3 parts of styrene, 3 parts of hydrogen peroxide, 2 parts of odium stearate；（2）By the methacrylic acid,
Styrene and odium stearate carry out emulsion reaction 45min under Ultrasonic Conditions, and emulsion is made；（3）By the starch raw material
Under Ultrasonic Conditions, nitrogen protection is led in room temperature environment, 50min is preheated when temperature is 65 DEG C, maintain 65 DEG C of temperature and is added
Enter hydroperoxidation 13min, obtains reactant；（4）To step（3）Step is added in reactant obtained（2）Emulsification obtained
Liquid carries out chemical reaction 60min, obtains Modified Starch Adhesive.
Wherein, the preparation method of the modified Nano grade calcium carbonate is as follows：
（1）Weigh the raw material of following parts by weight：5 parts of 80 parts of nanometer grade calcium carbonate, 10 parts of coupling agent, 5 parts of lubricant and dispersant；
（2）Nanometer grade calcium carbonate is put in 100 DEG C of oven heat and is dried 3 hours, is cooled to room temperature；
（3）It is added in high-speed mixer and stirs 20 minutes after taking-up, the coupling agent weighed is then added and is stirred for 10 minutes, then according to
Secondary that the dispersant and lubricant that weigh is added, then heating stirring is transferred to stirring in cold mixer and is cooled to≤40 DEG C to 85 DEG C
Material, obtains modified Nano grade calcium carbonate.
Wherein, the fungicide is nano-silver ionic fungicide.
Wherein, the toughener is POE.
A method of the high-performance adhesives for shoes is prepared, is included the following steps：
（1）Gum arabic, TPU elastic resins, epoxy resin, ethyl acetate, polyisobutene, poly- third are weighed by above-mentioned formula
Alkene, rosin, microwax, stearic acid, modified Nano grade calcium carbonate, Modified Starch Adhesive, polycarbonate polyol, adipic acid two
Monooctyl ester, zinc oxide, toughener, anti-aging agent and fungicide, it is spare；
（2）Gum arabic, TPU elastic resins, epoxy resin are first placed in cutter and are crushed, remixes uniformly, then sets
It heats and is kneaded in kneading machine, obtain compounding mixture A, the process that the heating is kneaded is specific as follows：55 DEG C are first heated to, heat preservation
It is kneaded 25 minutes, is again heated to 77 DEG C, heat preservation is kneaded 13 minutes, and finally heated to 93 DEG C, heat preservation is kneaded 12 minutes；
（3）Modified Nano grade calcium carbonate, stearic acid and rosin are sequentially added into the compounding mixture A obtained by step, are first stirred
Mixing 10 minutes, then ultrasonic wave mix 5 minutes, and polypropylene and zinc oxide is then added, is placed in kneading machine, is warming up to 91 DEG C,
Heat preservation is kneaded 8 minutes, obtains compounding mixture B；
（4）To step（3）Polyisobutene, microwax and anti-aging agent is first added in the compounding mixture B of gained, is heated to 105 DEG C,
It is stirred 13 minutes, ethyl acetate is then added, insulated and stirred mixes 6 minutes, obtains mixture C；
（5）To step（4）Modified Starch Adhesive, polycarbonate polyol, adipic acid two are sequentially added in the mixture C of gained
Monooctyl ester, toughener and fungicide are uniformly mixed to get the high-performance adhesives for shoes.
Wherein, the step（3）The frequency of middle ultrasonic wave mixing is 25KHz.
Embodiment 5
The present embodiment is related to a kind of high-performance adhesives for shoes, includes the raw material of following parts by weight：25 parts of gum arabic, TPU
20 parts of elastic resin, 18 parts of epoxy resin, 14 parts of ethyl acetate, 6 parts of polyisobutene, 7 parts of polypropylene, 3 parts of rosin, microwax
2.1 parts, 1.6 parts of stearic acid, 3.9 parts of modified Nano grade calcium carbonate, 5.6 parts of Modified Starch Adhesive, polycarbonate polyol 4.5
Part, 2.3 parts of dioctyl adipate, 1.4 parts of zinc oxide, 3.8 parts of toughener, 2.2 parts of anti-aging agent and 2.6 parts of fungicide；
Wherein, the preparation method of the Modified Starch Adhesive is as follows：（1）By weight, following raw material is weighed：Potato starch
20 parts, 5 parts of methacrylic acid, 3 parts of styrene, 3 parts of hydrogen peroxide, 2 parts of odium stearate；（2）By the methacrylic acid,
Styrene and odium stearate carry out emulsion reaction 48min under Ultrasonic Conditions, and emulsion is made；（3）By the starch raw material
Under Ultrasonic Conditions, nitrogen protection is led in room temperature environment, 50min is preheated when temperature is 69 DEG C, maintain 69 DEG C of temperature and is added
Enter hydroperoxidation 14min, obtains reactant；（4）To step（3）Step is added in reactant obtained（2）Emulsification obtained
Liquid carries out chemical reaction 60min, obtains Modified Starch Adhesive.
Wherein, the preparation method of the modified Nano grade calcium carbonate is as follows：
（1）Weigh the raw material of following parts by weight：5 parts of 80 parts of nanometer grade calcium carbonate, 10 parts of coupling agent, 5 parts of lubricant and dispersant；
（2）Nanometer grade calcium carbonate is put in 110 DEG C of oven heat and is dried 3 hours, is cooled to room temperature；
（3）It is added in high-speed mixer and stirs 20 minutes after taking-up, the coupling agent weighed is then added and is stirred for 10 minutes, then according to
Secondary that the dispersant and lubricant that weigh is added, then heating stirring is transferred to stirring in cold mixer and is cooled to≤40 DEG C to 85 DEG C
Material, obtains modified Nano grade calcium carbonate.
Wherein, the fungicide is nano-silver ionic fungicide.
Wherein, the toughener is POE.
A method of the high-performance adhesives for shoes is prepared, is included the following steps：
（1）Gum arabic, TPU elastic resins, epoxy resin, ethyl acetate, polyisobutene, poly- third are weighed by above-mentioned formula
Alkene, rosin, microwax, stearic acid, modified Nano grade calcium carbonate, Modified Starch Adhesive, polycarbonate polyol, adipic acid two
Monooctyl ester, zinc oxide, toughener, anti-aging agent and fungicide, it is spare；
（2）Gum arabic, TPU elastic resins, epoxy resin are first placed in cutter and are crushed, remixes uniformly, then sets
It heats and is kneaded in kneading machine, obtain compounding mixture A, the process that the heating is kneaded is specific as follows：58 DEG C are first heated to, heat preservation
It is kneaded 29 minutes, is again heated to 79 DEG C, heat preservation is kneaded 14 minutes, and finally heated to 93 DEG C, heat preservation is kneaded 14 minutes；
（3）Modified Nano grade calcium carbonate, stearic acid and rosin are sequentially added into the compounding mixture A obtained by step, are first stirred
Mixing 12 minutes, then ultrasonic wave mix 5 minutes, and polypropylene and zinc oxide is then added, is placed in kneading machine, is warming up to 83 DEG C,
Heat preservation is kneaded 9 minutes, obtains compounding mixture B；
（4）To step（3）Polyisobutene, microwax and anti-aging agent is first added in the compounding mixture B of gained, is heated to 108 DEG C,
It is stirred 14 minutes, ethyl acetate is then added, insulated and stirred mixes 7 minutes, obtains mixture C；
（5）To step（4）Modified Starch Adhesive, polycarbonate polyol, adipic acid two are sequentially added in the mixture C of gained
Monooctyl ester, toughener and fungicide are uniformly mixed to get the high-performance adhesives for shoes.
Wherein, the step（3）The frequency of middle ultrasonic wave mixing is 25KHz.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (8)
1. a kind of high-performance adhesives for shoes, which is characterized in that include the raw material of following parts by weight：Gum arabic 20~30
Part, 17~24 parts of TPU elastic resins, 13~22 parts of epoxy resin, 9~18 parts of ethyl acetate, 4~7 parts of polyisobutene, polypropylene
6~11 parts, 2~4 parts of rosin, 1~3 part of microwax, 1~2 part of stearic acid, 3~5 parts of modified Nano grade calcium carbonate, modified starch
4~7 parts of adhesive, 3~6 parts of polycarbonate polyol, 1~4 part of dioctyl adipate, 1~2 part of zinc oxide, toughener 2~5
2~3 parts of part, 1~3 part of anti-aging agent and fungicide；
Wherein, the preparation method of the Modified Starch Adhesive is as follows：（1）By weight, following raw material is weighed：Potato starch
20 parts, 5 parts of methacrylic acid, 3 parts of styrene, 3 parts of hydrogen peroxide, 2 parts of odium stearate；（2）By the methacrylic acid,
Styrene and odium stearate carry out 40~50min of emulsion reaction under Ultrasonic Conditions, and emulsion is made；（3）By the starch
Raw material leads to nitrogen protection under Ultrasonic Conditions in room temperature environment, 50min is preheated when temperature is 60~70 DEG C, maintains temperature
60~70 DEG C and 10~15min of hydroperoxidation is added, obtains reactant；（4）To step（3）Step is added in reactant obtained
Suddenly（2）Emulsion obtained carries out chemical reaction 60min, obtains Modified Starch Adhesive.
2. high-performance adhesives for shoes according to claim 1, which is characterized in that include the raw material of following parts by weight：Ah
Draw 24~28 parts of uncle's natural gum, 19~22 parts of TPU elastic resins, 15~20 parts of epoxy resin, 10~17 parts of ethyl acetate, poly- isobutyl
5.2~6.3 parts of alkene, 6~10 parts of polypropylene, 2.4~3.6 parts of rosin, 1.7~2.5 parts of microwax, 1.1~1.8 parts of stearic acid,
3.2~4.3 parts of modified Nano grade calcium carbonate, 5~6 parts of Modified Starch Adhesive, 4~5 parts of polycarbonate polyol, adipic acid two
2.2~2.7 parts of 2~3 parts of monooctyl ester, 1.3~1.7 parts of zinc oxide, 3~4 parts of toughener, 1.5~2.4 parts of anti-aging agent and fungicide.
3. high-performance adhesives for shoes according to claim 1, which is characterized in that include the raw material of following parts by weight：Ah
Draw uncle natural gum 25 parts, 20 parts of TPU elastic resins, 18 parts of epoxy resin, 14 parts of ethyl acetate, 6 parts of polyisobutene, 7 parts of polypropylene,
3 parts of rosin, 1.6 parts of stearic acid, 3.9 parts of modified Nano grade calcium carbonate, 5.6 parts of Modified Starch Adhesive, gathers 2.1 parts of microwax
4.5 parts of carbonate polyol, 2.3 parts of dioctyl adipate, 1.4 parts of zinc oxide, 3.8 parts of toughener, 2.2 parts of anti-aging agent and sterilization
2.6 parts of agent.
4. high-performance adhesives for shoes according to claim 1, which is characterized in that the system of the modified Nano grade calcium carbonate
Preparation Method is as follows：
（1）Weigh the raw material of following parts by weight：5 parts of 80 parts of nanometer grade calcium carbonate, 10 parts of coupling agent, 5 parts of lubricant and dispersant；
（2）Nanometer grade calcium carbonate is put in 80~120 DEG C of oven heat and is dried 3 hours, is cooled to room temperature；
（3）It is added in high-speed mixer and stirs 20 minutes after taking-up, the coupling agent weighed is then added and is stirred for 10 minutes, then according to
Secondary that the dispersant and lubricant that weigh is added, then heating stirring is transferred to stirring in cold mixer and is cooled to≤40 DEG C to 85 DEG C
Material, obtains modified Nano grade calcium carbonate.
5. high-performance adhesives for shoes according to claim 1, which is characterized in that the fungicide kills for nano-silver ionic
Microbial inoculum.
6. high-performance adhesives for shoes according to claim 1, which is characterized in that the toughener is POE.
7. a kind of method preparing any one of claim 1~6 high-performance adhesives for shoes, which is characterized in that including with
Lower step：
（1）Gum arabic, TPU elastic resins, epoxy resin, ethyl acetate, polyisobutene, poly- third are weighed by above-mentioned formula
Alkene, rosin, microwax, stearic acid, modified Nano grade calcium carbonate, Modified Starch Adhesive, polycarbonate polyol, adipic acid two
Monooctyl ester, zinc oxide, toughener, anti-aging agent and fungicide, it is spare；
（2）Gum arabic, TPU elastic resins, epoxy resin are first placed in cutter and are crushed, remixes uniformly, then sets
It heats and is kneaded in kneading machine, obtain compounding mixture A, the process that the heating is kneaded is specific as follows：50~60 DEG C are first heated to,
Heat preservation is kneaded 20~30 minutes, is again heated to 75~80 DEG C, heat preservation is kneaded 10~15 minutes, finally heated to 90~95 DEG C, is protected
Temperature is kneaded 8~15 minutes；
（3）Modified Nano grade calcium carbonate, stearic acid and rosin are sequentially added into the compounding mixture A obtained by step, are first stirred
Mixing 7~13 minutes, then ultrasonic wave mix 3~6 minutes, and polypropylene and zinc oxide is then added, is placed in kneading machine, is warming up to
78~84 DEG C, heat preservation is kneaded 5~10 minutes, obtains compounding mixture B；
（4）To step（3）Polyisobutene, microwax and anti-aging agent is first added in the compounding mixture B of gained, it is heated to 100~
It 110 DEG C, is stirred 10~15 minutes, ethyl acetate is then added, insulated and stirred mixes 4~8 minutes, obtains mixture C；
（5）To step（4）Modified Starch Adhesive, polycarbonate polyol, adipic acid two are sequentially added in the mixture C of gained
Monooctyl ester, toughener and fungicide are uniformly mixed to get the high-performance adhesives for shoes.
8. preparation method according to claim 7, which is characterized in that the step（3）The frequency of middle ultrasonic wave mixing is
25KHz。
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750815A (en) * | 2019-02-28 | 2019-05-14 | 南京美高美新材料有限公司 | Composite floor board |
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2018
- 2018-04-09 CN CN201810308507.1A patent/CN108485560A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109750815A (en) * | 2019-02-28 | 2019-05-14 | 南京美高美新材料有限公司 | Composite floor board |
| CN109750815B (en) * | 2019-02-28 | 2024-01-12 | 南京美高美新材料有限公司 | Composite floor |
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Application publication date: 20180904 |