CN109354651A - A kind of footwear material insole board glue and preparation method thereof - Google Patents
A kind of footwear material insole board glue and preparation method thereof Download PDFInfo
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- CN109354651A CN109354651A CN201811252146.XA CN201811252146A CN109354651A CN 109354651 A CN109354651 A CN 109354651A CN 201811252146 A CN201811252146 A CN 201811252146A CN 109354651 A CN109354651 A CN 109354651A
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- footwear material
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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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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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
- C09J113/00—Adhesives based on rubbers containing carboxyl groups
- C09J113/02—Latex
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention discloses a kind of footwear material insole board glue, are related to latex field, according to the mass fraction, including 30~50 parts of ethylene, 50~70 parts of butadiene, 2~4 parts of functional monomer, 0.5~3 part of auxiliary monomer, 2~4 parts of crosslinking agent, 0.5~2 part of emulsifier, 0.5~1 part of ammonium persulfate, 1~2 part of age resister, 2~4 parts of thiocarboxylic acid methyl esters, 2~4 parts and 4~8 parts of starch of calcium chloride.By using above-mentioned technical proposal, after insole board is coated with the hydroxyl styrene-butadiene latex of the application, the toughness of insole board and the property held can be effectively improved, to be conducive to extend its service life.Also, in the process of wearing, once a large amount of sweat occurs in foot, sweat can also be dried and be absorbed to calcium chloride and starch in latex.To ensure that the aridity in shoes.Meanwhile review step is also relatively simple, and scale words is suitble to be produced.
Description
Technical field
The present invention relates to latex field, in particular to a kind of footwear material insole board glue and preparation method thereof.
Background technique
With people's living standard constantly being promoted, the requirement that people dress itself is also higher and higher, such as
In terms of the dress of shoes, people are also to pay special attention to.And the bottom plate of shoes is very heavy for the quality of shoes entirety
The position wanted, the sole of high quality give people and are comfortably through sense.
And general sole is divided into Outer Bottom Plating, insole board and inner bottom plating, and insole board is as undertaking layer, it is whole for sole
Play the role of again for body vital.
And in the prior art, insole board easy to wear, bending under constantly the jamming on of foot, loosely, fracture influences stiffness and to wear
Comfort.
Summary of the invention
The object of the present invention is to provide a kind of footwear material insole board glue, and being coated on indsole plate surface can effectively improve
The mechanical performance of insole board is conducive to extend its service life.Meanwhile production preparation process is simple, pollution is small, is appropriate for
Large-scale production.
Above-mentioned technical purpose of the invention has the technical scheme that
A kind of footwear material insole board glue, raw material are according to the mass fraction, including 30~50 parts of ethylene, 50~70 parts of butadiene, functional
It is 2~4 parts of monomer, 0.5~3 part of auxiliary monomer, 2~4 parts of crosslinking agent, 0.5~2 part of emulsifier, 0.5~1 part of ammonium persulfate, anti-ageing
1~2 part of agent, 2~4 parts of thiocarboxylic acid methyl esters, 2~4 parts and 4~8 parts of starch of calcium chloride.
It can be effectively after insole board is coated with the hydroxyl styrene-butadiene latex of the application by using above-mentioned technical proposal
The toughness of insole board and the property held are improved, to be conducive to extend its service life.
Also, in the process of wearing, once a large amount of sweat occurs in foot, calcium chloride and starch in latex can also be dried
With absorption sweat.Also, it is intermolecular that starch molecule can fully be distributed in polymeric latex during latex molecule cross-link, and forms sediment
Powder molecule itself is also macromolecule, and mutual can also be connected, thus after starch molecule absorbs sweat, it will
It is easy to transmit to surrounding, and distributes to outside shoes.To ensure that the aridity in shoes.
Preferably, the functional monomer is one of itaconic acid, methacrylic acid, fumaric acid and acrylic acid or two
Kind.
By using above-mentioned technical proposal, itaconic acid, methacrylic acid, fumaric acid and acrylic acid are unsaturated acids,
Polycondensation can occur with styrene, butadiene etc., to introduce carboxyl in latex molecule.Conducive to the stabilization for improving latex entirety
Preferably, the auxiliary monomer is one of acrylonitrile, methacrylonitrile and methyl methacrylate.
Preferably, the crosslinking agent is one of N hydroxymethyl acrylamide and N- alkoxy-methyl acrylamide amine or two
Kind.
Preferably, the emulsifier is in sulfosuccinic acid diisobutyl ester sodium sulfonate and Sodium docusate
It is a kind of.
By using above-mentioned technical proposal, select N hydroxymethyl acrylamide or N- alkoxy-methyl acrylamide amine as crosslinking
Agent and selection sulfosuccinic acid diisobutyl ester sodium sulfonate or Sodium docusate can not only guarantee as emulsifier
Effect to crosslinking and the emulsification of reaction system.Meanwhile after in insole board, when insect creeps in shoes, N- hydroxyl first
Base acrylamide or N- alkoxy-methyl acrylamide amine and sulfosuccinic acid diisobutyl ester sodium sulfonate or dioctylsulfosuccinat
Sodium is easy for entering the internal of insect.And N hydroxymethyl acrylamide or N- alkoxy-methyl acrylamide amine will destroy elder brother at this time
Polypide wall chitin, and sulfosuccinic acid diisobutyl ester sodium sulfonate or Sodium docusate can be molten by body wall wax coat
Solution, as soon as and be attached to and form waterproof and air-locked tunic above, to can also make insect air-hole blockage simultaneously death by suffocation
It dies, also just plays desinsection, pest-resistant function in this way, and then be also beneficial to improve the cleanliness in shoes.
Preferably, mixture of the age resister for potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and two
The mass ratio of person is 0.5~2:1.
By using above-mentioned technical method, the lithium ion in lithium iodide can also be with the carbonyl in carboxylic styrene butadiene latex molecule
Between there are mating reactions, produce the structure of similar network, hinder carboxylic styrene butadiene latex strand and corresponding free radical
Movement, thus make polymer molecular chain that need to overcome bigger energy barrier than entirely free on his strand when being thermally decomposed, thus, have
Conducive to promote carboxylic styrene butadiene latex have higher thermal decomposition temperature.
Moreover, lithium iodide and 2-hydroxy-4-n-octoxybenzophenone synergistic effect, additionally it is possible to further increase latex
Oxidation resistant performance and weather resistance.
Preferably, the thiocarboxylic acid methyl esters is one of methyl thiofuroate and thio acetate.
In the past in the production process of carboxylic styrene butadiene latex, often using sulfur alcohol compound as molecular regulation
Agent, sulfur alcohol compound have special stink, it is difficult to and it volatilizees, pollutes environment, it is toxic, reduce final product quality.And they
It is all hazardous chemical, transport, storage, use process need specially treated, not only troublesome and costly.
And select thiocarboxylic acid methyl esters to replace sulfur alcohol compound, not only due to its it is the same with sulfur alcohol compound can
The effect of molecular regulation is effectively acted as, meanwhile, also in that its smell is small, and even with some fragrance, and nontoxic, nothing
Pollution is conducive to the total quality for improving carpet.
A kind of preparation method of footwear material insole board glue, comprising the following steps:
S1, first polymeric kettle is vacuumized, backward polymeric kettle in be added 200~300 parts of soft water, and be added 30~50 parts of styrene
With 50~70 parts of butadiene, after stirring, make the fully dispersed mixing in soft water of styrene and butadiene；
S2,2~4 parts of functional monomer are put into again into polymeric kettle, 0.5~3 part of auxiliary monomer, 0.5~1 part of ammonium persulfate and cream
0.5~2 part of agent, 70~80 DEG C are gradually preheated to while being stirred, and keep 0.5h；
S3,2~4 parts of crosslinking agent of the addition into the polymeric kettle of S2,1~2 part of age resister, 2~4 parts of thiocarboxylic acid methyl esters, chlorination
2~4 parts and 4~8 parts of starch of calcium, and continue to be stirred, while gradually rising temperature to 120 DEG C~150 DEG C, wait react conversion
When rate reaches 93%, stop heating, fall its temperature gradually to 40 DEG C after rise, is deaerated later using pulling vacuum direct steam, together
When, pH value is adjusted to 7~8 using lye, later until temperature is down to room temperature, obtains finished product carboxylic styrene butadiene latex.
By using above-mentioned technical proposal, seed latex, styrene and butadiene are mixed first, in this way convenient for kind
Sub- latex, styrene and butadiene can be pre-mixed uniformly.
And then other raw materials are added and are preheated, facilitate to be promoted so subsequent in the generation of the surface of seed latex
The efficiency of polymerization.
Furthermore it is deaerated using pulling vacuum direct steam, can be subtracted so quickly except the micro-molecular gas that dereaction generates
Few exhaust gas enters directly into environment and influences staff's health.
Preferably, being constantly passed through air in the backward lotion of completion to be de-gassed in S3.
By using above-mentioned technical proposal, the dioxygen oxidation facilitated in air in this way remains in the monomer in latex.From
And be conducive to make manufactured goods meet the requirement of environmental protection.
In conclusion the invention has the following advantages:
1, the insole board after being coated with the hydroxyl styrene-butadiene latex of the application, toughness and folding resistance, which have, to be obviously improved, to have
Conducive to prolonging the service life；
2, contain calcium chloride and starch in the carboxylic styrene butadiene latex of the application, help to enhance the moisture-proof function in shoes；
3, lithium iodide and 2-hydroxy-4-n-octoxybenzophenone mixing are used as age resister, not only effectively improve carboxyl
The anti-aging property of styrene-butadiene latex, while also improving the thermostabilization and weather-proof performance of carboxylic styrene butadiene latex；
4, N hydroxymethyl acrylamide and/or N- alkoxy-methyl acrylamide amine and sulfosuccinic acid diisobutyl ester sodium sulfonate or sulfo group
Dioctyl succinate sodium adds together, effectively improves the insect resistace of carboxylic styrene butadiene latex, exists to advantageously reduce insect
It creeps in shoes.
Detailed description of the invention
Fig. 1 is the preparation flow figure of footwear material insole board glue.
Specific embodiment
Below in conjunction with attached drawing 1, invention is further described in detail.
Embodiment one:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in be added 200 parts of soft water, styrene 30Kg and butadiene 70Kg,
It is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of styrene and butadiene；
Step 2: itaconic acid 2Kg, acrylonitrile 0.5Kg, ammonium persulfate 0.5Kg and sulfosuccinic acid two are put into again into polymeric kettle
Isobutyl ester sodium sulfonate 2Kg, and mixing is stirred with revolving speed 400rpm, and 70 DEG C are gradually preheated to mixture, it keeps the temperature later
Continue 0.5h；
Step 3: N hydroxymethyl acrylamide 2Kg, age resister 1Kg, methyl thiofuroate are added into the polymeric kettle of step 2
2Kg, calcium chloride 2Kg and starch 4Kg, and continue to be stirred, while being gradually heated to 120 DEG C in 1h, it is reached to reaction conversion ratio
When to 93%, stop heating, fall its temperature gradually to 40 DEG C after rise, is deaerated later using pulling vacuum direct steam, obtain cream
Liquid；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and the matter of the two
Amount is than being 0.5:1.
Embodiment two:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in 250Kg soft water is added, and styrene 40Kg and fourth two is added
Alkene 60Kg is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of styrene and butadiene；
Step 2: methacrylic acid 3Kg, methacrylonitrile 1.7Kg, ammonium persulfate 0.7Kg and sulfo group are put into again into polymeric kettle
Dioctyl succinate sodium 1.2Kg, and mixing is stirred with revolving speed 400rpm, and 75 DEG C are gradually preheated to mixture, later
It keeps the temperature and continues 0.5h；
Step 3: N- alkoxy-methyl acrylamide amine 3Kg, age resister 1.5Kg, thioacetic acid are added into the polymeric kettle of step 2
Methyl esters 3Kg, calcium chloride 3Kg and starch 6Kg, and continue to be stirred, while being gradually heated to 135 DEG C in 1h, wait react conversion
When rate reaches 93%, stop heating, fall its temperature gradually to 40 DEG C after rise, is deaerated, obtained using pulling vacuum direct steam later
To lotion；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and the matter of the two
Amount is than being 1:1.
Embodiment three:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in 300Kg soft water is added, and styrene 50Kg and fourth two is added
Alkene 50Kg is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of styrene and butadiene；
Step 2: fumaric acid 4Kg, methyl methacrylate 3Kg, ammonium persulfate 1Kg and sulfosuccinic are put into again into polymeric kettle
Sour diisobutyl ester sodium sulfonate 2Kg, and mixing is stirred with revolving speed 400rpm, and 80 DEG C are gradually preheated to mixture, later
It keeps the temperature and continues 0.5h；
Step 3: N hydroxymethyl acrylamide 2Kg, N- alkoxy-methyl acrylamide amine 2Kg being added into the polymeric kettle of step 2, resist
Aging agent 2Kg, thio acetate 3Kg, calcium chloride 4Kg and starch 8Kg, and continue to be stirred, while being gradually warmed up in 1h
To 150 DEG C, when reaching 93% to reaction conversion ratio, stops heating, fall its temperature gradually to 40 DEG C after rise, later using drawing
The degassing of vacuum direct steam, obtains lotion；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and the matter of the two
Amount is than being 2:1.
Example IV:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in 280Kg soft water is added, and styrene 35Kg and fourth two is added
Alkene 65Kg is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of seed latex, styrene and butadiene；
Step 2: acrylic acid 4Kg, acrylonitrile 0.5Kg, ammonium persulfate 0.8Kg and sulfosuccinic acid two are put into again into polymeric kettle
Monooctyl ester sodium 1.5Kg, and mixing is stirred with revolving speed 400rpm, and 40 DEG C are gradually preheated to mixture, heat preservation continues later
0.5h；
Step 3: N hydroxymethyl acrylamide 2Kg, age resister 1.3Kg, thio-furoic acid first are added into the polymeric kettle of step 2
Ester 4Kg, calcium chloride 3Kg and starch 6Kg, and continue to be stirred, while being gradually heated to 130 DEG C in 1h, to reaction conversion ratio
When reaching 93%, stop heating, fall its temperature gradually to 40 DEG C after rise, is deaerated, obtained using pulling vacuum direct steam later
Lotion；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and the matter of the two
Amount is than being 1.5:1.
Embodiment five:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in 230Kg soft water is added, and styrene 45Kg and fourth two is added
Alkene 55Kg is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of styrene and butadiene；
Step 2: itaconic acid 1Kg, fumaric acid 2Kg, methyl methacrylate 1.4Kg, ammonium persulfate are put into again into polymeric kettle
0.6Kg and Sodium docusate 1.2Kg, and mixing is stirred with revolving speed 400rpm, and gradually preheat to mixture
To 76 DEG C, keeps the temperature continue 0.5h later；
Step 3: N- alkoxy-methyl acrylamide amine 3.2Kg, age resister 1.7Kg, thio chaff are added into the polymeric kettle of step 2
Sour methyl esters 4Kg, calcium chloride 3.4Kg and starch 5.8Kg, and continue to be stirred, while being gradually heated to 145 DEG C in 1h, to anti-
When answering conversion ratio to reach 93%, stop heating, fall its temperature gradually to 40 DEG C after rise, uses pulling vacuum direct steam later
Degassing, obtains lotion；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and the matter of the two
Amount is than being 1:1.
Comparative example one to comparative example three and the difference of embodiment three is only that, as follows:
Comparative example one:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in 300Kg soft water is added, and styrene 50Kg and fourth two is added
Alkene 50Kg is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of styrene and butadiene；
Step 2: fumaric acid 4Kg, methacrylonitrile 3Kg, ammonium persulfate 1Kg and sulfosuccinic acid two are put into again into polymeric kettle
Isobutyl ester sodium sulfonate 2Kg, and mixing is stirred with revolving speed 400rpm, and 80 DEG C are gradually preheated to mixture, it keeps the temperature later
Continue 0.5h；
Step 3: N hydroxymethyl acrylamide 2Kg, N- alkoxy-methyl acrylamide amine 2Kg being added into the polymeric kettle of step 2, resist
Aging agent 2Kg, thio acetate 3Kg, calcium chloride 12Kg, and continue to be stirred, while being gradually heated to 150 DEG C in 1h,
When reaching 93% to reaction conversion ratio, stops heating, fall its temperature gradually to 40 DEG C after rise, it is direct using pulling vacuum later
Steam degassing, obtains lotion；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and the matter of the two
Amount is than being 2:1.
Comparative example two:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in 300Kg soft water is added, and styrene 50Kg and fourth two is added
Alkene 50Kg is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of styrene and butadiene；
Step 2: fumaric acid 4Kg, methacrylonitrile 3Kg, ammonium persulfate 1Kg and sulfosuccinic acid two are put into again into polymeric kettle
Isobutyl ester sodium sulfonate 2Kg, and mixing is stirred with revolving speed 400rpm, and 80 DEG C are gradually preheated to mixture, it keeps the temperature later
Continue 0.5h；
Step 3: N hydroxymethyl acrylamide 2Kg, N- alkoxy-methyl acrylamide amine 2Kg being added into the polymeric kettle of step 2, resist
Aging agent 2Kg, thio acetate 3Kg, starch 12Kg, and continue to be stirred, while being gradually heated to 150 DEG C in 1h, to
When reaction conversion ratio reaches 93%, stop heating, fall its temperature gradually to 40 DEG C after rise, is directly steamed using pulling vacuum later
Vapour degassing, obtains lotion；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and the matter of the two
Amount is than being 2:1.
Comparative example three:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in 300Kg soft water is added, and styrene 50Kg and fourth two is added
Alkene 50Kg is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of styrene and butadiene；
Step 2: fumaric acid 4Kg, methacrylonitrile 3Kg, ammonium persulfate 1Kg and sulfosuccinic acid two are put into again into polymeric kettle
Isobutyl ester sodium sulfonate 2Kg, and mixing is stirred with revolving speed 400rpm, and 80 DEG C are gradually preheated to mixture, it keeps the temperature later
Continue 0.5h；
Step 3: N hydroxymethyl acrylamide 2Kg, N- alkoxy-methyl acrylamide amine 2Kg being added into the polymeric kettle of step 2, resist
Aging agent 2Kg and thio acetate 3Kg, and continue to be stirred, while being gradually heated to 150 DEG C in 1h, wait react conversion
When rate reaches 93%, stop heating, fall its temperature gradually to 40 DEG C after rise, is deaerated, obtained using pulling vacuum direct steam later
To lotion；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and the matter of the two
Amount is than being 2:1.
Comparative example four:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in 300Kg soft water is added, and styrene 40Kg and fourth two is added
Alkene 60Kg is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of styrene and butadiene；
Step 2: fumaric acid 4Kg, methacrylonitrile 3Kg, ammonium persulfate 1Kg and sulfosuccinic acid two are put into again into polymeric kettle
Isobutyl ester sodium sulfonate 2Kg, and mixing is stirred with revolving speed 400rpm, and 80 DEG C are gradually preheated to mixture, it keeps the temperature later
Continue 0.5h；
Step 3: N hydroxymethyl acrylamide 2Kg, N- alkoxy-methyl acrylamide amine 2Kg being added into the polymeric kettle of step 2, resist
Aging agent 2Kg, thio acetate 3Kg, calcium chloride 4Kg and starch 8Kg, and continue to be stirred, while being gradually warmed up in 1h
To 150 DEG C, when reaching 93% to reaction conversion ratio, stops heating, fall its temperature gradually to 40 DEG C after rise, later using drawing
The degassing of vacuum direct steam, obtains lotion；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of potassium iodide and 2-hydroxy-4-n-octoxybenzophenone, and the matter of the two
Amount is than being 2:1.
Comparative example five:
A kind of preparation method of footwear material insole board glue, comprising the following steps:
Step 1: vacuumizing polymeric kettle, backward polymeric kettle in 300Kg soft water is added, and styrene 50Kg and fourth two is added
Alkene 50Kg is stirred with revolving speed 300rpm, makes the fully dispersed mixing in soft water of styrene and butadiene；
Step 2: fumaric acid 4Kg, methacrylonitrile 3Kg, ammonium persulfate 1Kg and octyl phenol polyoxy second are put into again into polymeric kettle
Alkene ether 2Kg, and mixing is stirred with revolving speed 400rpm, and 80 DEG C are gradually preheated to mixture, it keeps the temperature continue 0.5h later；
Step 3: N hydroxymethyl acrylamide 2Kg, N- alkoxy-methyl acrylamide amine 2Kg being added into the polymeric kettle of step 2, resist
Aging agent 2Kg, thio acetate 3Kg, calcium chloride 4Kg and starch 8Kg, and continue to be stirred, while being gradually warmed up in 1h
To 150 DEG C, when reaching 93% to reaction conversion ratio, stops heating, fall its temperature gradually to 40 DEG C after rise, later using drawing
The degassing of vacuum direct steam, obtains lotion；
Step 4: being constantly passed through air into the obtained lotion of step 3, meanwhile, the pH value of lotion is adjusted using potassium hydroxide
To 7~8, so that the temperature of polymeric kettle is down to room temperature later, finally obtain finished product carboxylic styrene butadiene latex.
Wherein, age resister is the mixture of cuprous iodide and 2-hydroxy-4-n-octoxybenzophenone, and the two
Mass ratio is 2:1.
To embodiment one to embodiment five and comparative example one to comparative example five do total solid content, pH value, mechanical stability,
Chemical stability, anti-aging, weather-proof, partial size, pest-resistant, the moisture-proof test such as dry.Specific testing standard or method are as follows:
Insect resistace: carboxylic styrene butadiene latex is coated in insole board, then select 50 can only normal activity adult cockroach in
Bottom plate is placed in the same space and exists, and the survival condition of cockroach is observed after 24 hours；
It is moisture-proof to dry；In the insole board of the application hydroxyl styrene-butadiene latex, shoes are then made, user tests shoes after wearing one day
Interior humidity；
It is anti-aging: after ultraviolet irradiation 12 hours, the color change situation of the insole board of observation coating hydroxyl styrene-butadiene latex；
It is weather-proof: 2 hours in the case of being placed in 50 DEG C, then to be placed in -10 DEG C 2 hours, hydroxyl fourth is coated with to observation after repeating above-mentioned 3 times
The cracking situation of the insole board of benzene latex.
Flexural strength: using bending resistance testing machine respectively to coating the application hydroxyl styrene-butadiene latex insole board into
Row test, the insole board of selection are the BD plate of safe woods footwear material (Guangzhou) Co., Ltd.
Tensile strength: respectively testing the insole board of coating the application hydroxyl styrene-butadiene latex using anti-folding tester,
The insole board of selection is the BD plate of safe woods footwear material (Guangzhou) Co., Ltd.
Following table is the test result of every test:
| Test item | Embodiment one | Embodiment two | Embodiment three | Example IV | Embodiment five | Comparative example one | Comparative example two | Comparative example three | Comparative example four | Comparative example five |
| Cockroach survival volume (only) | 2 | 0 | 1 | 1 | 0 | 1 | 2 | 1 | 45 | 43 |
| Ground dry and wet situation | It is dry | It is dry | It is dry | It is dry | It is dry | It is slightly moist | It is slightly moist | It is obvious moist | It is dry | It is dry |
| Color change situation | It is unchanged | It is unchanged | It is unchanged | It is unchanged | It is unchanged | It is unchanged | It is unchanged | It is unchanged | Jaundice | Micro- Huang |
| Crack situation | Without cracking | Without cracking | Without cracking | Without cracking | Without cracking | Without cracking | Without cracking | Without cracking | Cracking is obvious | Subtle cracking |
| Before coating, flexural strength/MPa | 46 | 46 | 46 | 46 | 46 | / | / | / | / | / |
| Before coating, tensile strength/MPa | 59 | 61 | 64 | 58 | 62 | / | / | / | / | / |
| After coating, flexural strength/MPa | 51 | 51 | 51 | 51 | 51 | / | / | / | / | / |
| After coating, flexural strength/MPa | 63 | 64 | 66 | 63 | 65 | / | / | / | / | / |
As can be seen from the above table, the hydroxyl styrene-butadiene latex of the application not only has good mechanical stability and chemical stability, together
When from comparative example one to comparative example three with the comparison of embodiment three as can be seen that be added to the Carboxy after calcium chloride and starch
Latex has the good moisture-proof performance dried.Secondly, from comparative example four and comparative example five and embodiment three compare after can
To find out, while using N hydroxymethyl acrylamide or N- alkoxy-methyl acrylamide amine and sulfosuccinic acid diisobutyl ester sodium sulfonate
Or Sodium docusate, additionally aid the insect resistace for increasing hydroxyl styrene-butadiene latex.Furthermore from comparative example four and comparative example
Five in the comparison process of embodiment three it can also be seen that being mixed using potassium iodide and 2-hydroxy-4-n-octoxybenzophenone
The age resister of type, can either improve anti-aging property can play weatherability again.Moreover, being furnished with from each embodiment to being not coated with
After the measuring mechanical property of the insole board of the application hydroxyl styrene-butadiene latex and the insole board for being coated with the application hydroxyl styrene-butadiene latex
As can be seen that the hydroxyl styrene-butadiene latex of the application can effectively improve the mechanical performance of insole board, especially toughness and folding
Property.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (9)
1. a kind of footwear material insole board glue, it is characterised in that: raw material according to the mass fraction, including 30~50 parts of styrene, butadiene
50~70 parts, 2~4 parts of functional monomer, 0.5~3 part of auxiliary monomer, 2~4 parts of crosslinking agent, 0.5~2 part of emulsifier, persulfuric acid
0.5~1 part of ammonium, 1~2 part of age resister, 2~4 parts of thiocarboxylic acid methyl esters, 2~4 parts and 4~8 parts of starch of calcium chloride.
2. a kind of footwear material insole board glue according to claim 1, it is characterised in that: the functional monomer be itaconic acid,
One or both of methacrylic acid, fumaric acid and acrylic acid.
3. a kind of footwear material insole board glue according to claim 1, it is characterised in that: the auxiliary monomer is acrylonitrile, first
One of base acrylonitrile and methyl methacrylate.
4. a kind of footwear material insole board glue according to claim 1, it is characterised in that: the crosslinking agent is N- methylol propylene
One or both of amide and N- alkoxy-methyl acrylamide amine.
5. a kind of footwear material insole board glue according to claim 1, it is characterised in that: the emulsifier is sulfosuccinic acid two
One of isobutyl ester sodium sulfonate and Sodium docusate.
6. a kind of footwear material insole board glue according to claim 1, it is characterised in that: the age resister is potassium iodide and 2-
The mixture of hydroxyl -4- oxy-octyl benzophenone, and the mass ratio of the two is 0.5~2:1.
7. a kind of footwear material insole board glue according to claim 1, it is characterised in that: the thiocarboxylic acid methyl esters is thio chaff
One of sour methyl esters and thio acetate.
8. a kind of preparation method of footwear material insole board glue as described in any one of claim 1 to 7 claim, including with
Lower step:
S1, first polymeric kettle is vacuumized, backward polymeric kettle in be added 200~300 parts of soft water, and be added 30~50 parts of styrene
With 50~70 parts of butadiene, after stirring, make the fully dispersed mixing in soft water of styrene and butadiene；
S2,2~4 parts of functional monomer are put into again into polymeric kettle, 0.5~3 part of auxiliary monomer, 0.5~1 part of ammonium persulfate and cream
0.5~2 part of agent, 70~80 DEG C are gradually preheated to while being stirred, and keep 0.5h；
S3,2~4 parts of crosslinking agent of the addition into the polymeric kettle of S2,1~2 part of age resister, 2~4 parts of thiocarboxylic acid methyl esters, chlorination
2~4 parts and 4~8 parts of starch of calcium, and continue to be stirred, while gradually rising temperature to 120 DEG C~150 DEG C, wait react conversion
When rate reaches 93%, stop heating, fall its temperature gradually to 40 DEG C after rise, is deaerated later using pulling vacuum direct steam, together
When, pH value is adjusted to 7~8 using lye, later until temperature is down to room temperature, obtains finished product carboxylic styrene butadiene latex.
9. a kind of preparation method of footwear material insole board glue according to claim 8, it is characterised in that: completion to be de-gassed in S3
Backward lotion in be constantly passed through air.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6038415A (en) * | 1983-08-12 | 1985-02-28 | Nippon Zeon Co Ltd | Production of copolymer latex |
| CN103755872A (en) * | 2013-12-23 | 2014-04-30 | 日照广大建筑材料有限公司 | Preparation method of carboxylic butadiene-styrene latex for printed carpet |
| CN104558439A (en) * | 2015-01-14 | 2015-04-29 | 日照广大建筑材料有限公司 | Carboxylic butadiene-styrene latex for textured paper and preparation method thereof |
| CN107254020A (en) * | 2017-06-29 | 2017-10-17 | 襄阳福源兴盛科技有限公司 | A kind of carboxylic acid styrene-butadiene latex and its production method |
-
2018
- 2018-10-25 CN CN201811252146.XA patent/CN109354651A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6038415A (en) * | 1983-08-12 | 1985-02-28 | Nippon Zeon Co Ltd | Production of copolymer latex |
| CN103755872A (en) * | 2013-12-23 | 2014-04-30 | 日照广大建筑材料有限公司 | Preparation method of carboxylic butadiene-styrene latex for printed carpet |
| CN104558439A (en) * | 2015-01-14 | 2015-04-29 | 日照广大建筑材料有限公司 | Carboxylic butadiene-styrene latex for textured paper and preparation method thereof |
| CN107254020A (en) * | 2017-06-29 | 2017-10-17 | 襄阳福源兴盛科技有限公司 | A kind of carboxylic acid styrene-butadiene latex and its production method |
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Application publication date: 20190219 |