CN110272579B - Preparation method of starch wet-process graft modified composite EVA (ethylene-vinyl acetate copolymer) foamed shoe material - Google Patents
Preparation method of starch wet-process graft modified composite EVA (ethylene-vinyl acetate copolymer) foamed shoe material Download PDFInfo
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/0009—Footwear characterised by the material made at least partially of alveolar or honeycomb material
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0033—Use of organic additives containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
Abstract
A preparation method of a starch wet-process graft modified composite EVA (ethylene-vinyl acetate copolymer) foamed shoe material comprises the following steps: using starch wet method to graft unsaturated monomer to synthesize polymer emulsion; the raw materials comprise the following components in parts by weight: 100 parts of starch, 30-120 parts of grafted unsaturated monomer, 1.0-4.0 parts of initiator ammonium persulfate and 180-250 parts of distilled water; step two: spray drying the polymer emulsion to obtain dry powder of the starch wet-process graft polymer; step three: and mixing and foaming the polymer dry powder and EVA to obtain the composite EVA shoe material. The invention has the advantages that: the physical index of the material can be completely comparable with that of a common EVA shoe material, particularly the material density can be lower, the water absorption performance of the material can be controlled according to requirements, the material can completely replace the EVA material of the traditional shoe material, the shoe material can be naturally degraded, in a soil burying method test, a sample is buried in soil with humus, and the degradation weight loss rate of 30 days can reach 35%.
Description
Technical Field
The invention relates to a method for preparing a foaming shoe material by compounding a starch wet-method grafted unsaturated monomer synthetic polymer and EVA in a gradient temperature rise and back evaporation monomer mode, belonging to the field of new materials.
Background
The EVA material is a main variety of shoe materials in China, and the using amount of the EVA material accounts for more than 35% of the sole material. EVA is a random copolymer polymerized mainly from ethylene (CH2= CH2) monomer and vinyl acetate (CH3COOCH = CH2) monomer. CH3 COO-side chain groups are introduced into the main chain of the EVA molecules, so that the order among the molecules is reduced, and the EVA copolymer has better elasticity and lower hardness, but the common EVA shoe material does not have hygroscopicity. The EVA foaming material is prepared with EVA resin as main material, foaming agent, cross-linking agent, stuffing and other assistants, and through mixing, pelletizing in extruder and molding in an injection molding machine. The EVA foaming material for the shoe material is widely applied due to the advantages of lightness, good elasticity, good flexibility, difficult wrinkle, excellent colorability, suitability for various climates and the like, but is easy to cause white pollution to threaten the environment due to the fact that the EVA foaming material does not absorb moisture and is not easy to degrade; meanwhile, the sole is not hygroscopic, so that the insole is easy to cause moisture and odor in the shoe cavity when used as an insole. The foamed shoe material prepared by compounding the unsaturated monomer synthetic polymer grafted by the starch wet method and the EVA in the gradient temperature-rising and anti-steaming monomer mode designed by the invention completely reaches the level of the common EVA in physical property, has good moisture absorption and dehumidification performance and can be naturally degraded.
Disclosure of Invention
The invention aims to provide a starch wet-process graft modified composite EVA (ethylene-vinyl acetate copolymer) foaming shoe material, which solves the problems of no moisture absorption and difficult degradation of the existing EVA foaming material for the shoe material.
The technical scheme of the invention is as follows: a preparation method of a starch wet-process graft modified composite EVA (ethylene-vinyl acetate copolymer) foamed shoe material is characterized by comprising the following steps:
the method comprises the following steps: using starch wet method to graft unsaturated monomer to synthesize polymer emulsion; the raw materials comprise the following components in parts by weight: 100 portions of starch, 30 to 120 portions of grafting unsaturated monomer, 1.0 to 4.0 portions of ammonium persulfate and 180 portions of distilled water;
step two: spray drying the polymer emulsion to obtain dry powder of the starch wet-process graft polymer;
step three: and mixing and foaming the polymer dry powder and EVA to obtain the composite EVA shoe material.
The raw materials are preferably selected from the following raw materials in parts by weight: grafting unsaturated monomer: 40-100, initiator ammonium persulfate: 1.5-2.5, distilled water: 200-210.
The grafted unsaturated monomer comprises: the ratio of the combination of methyl methacrylate and vinyl acetate is 1: 2-1: 3, or the ratio of the combination of ethyl methacrylate and vinyl acetate is 1: 2-1: 3, or vinyl acetate monomer.
The starch comprises one or a mixture of more than two of corn starch, wheat starch and potato starch in any proportion.
The method for synthesizing the polymer emulsion in the first step comprises the following steps:
step 1), adding starch into a four-port reaction kettle according to the parts, adding the parts of distilled water, stirring and transparentizing at 85 ℃ for 15min, and cooling to 60 ℃;
step 2), adding the ammonium persulfate solution in the parts into the solution obtained in the step 1), and uniformly stirring;
step 3), dripping the grafted unsaturated monomer in the solution obtained in the step 2) by adopting a reaction mode of gradient temperature rise at the temperature of 60 ℃, namely dripping a part of the grafted unsaturated monomer in a plurality of temperature gradients of temperature rise every time one temperature gradient is increased until all the grafted unsaturated monomers are dripped;
step 4), when the grafted unsaturated monomer is completely added, strictly controlling the synthesis reaction temperature in the reaction kettle at 66 ℃ until the reaction is finished, wherein the total reaction time is 2.5-3.5 h;
and 5) after the synthesis reaction is finished, heating to 75 ℃, evaporating redundant grafting unsaturated monomers under a condensation condition to obtain the polymer emulsion, and recycling the evaporated redundant grafting unsaturated monomers.
The reaction mode of gradient temperature rise is completed by two steps:
the first step is as follows: when 1/3 of the total amount of the grafted unsaturated monomer is added, heating the reaction kettle to 62 ℃, and continuously dropwise adding the grafted unsaturated monomer;
the second step is that: when 2/3 of the total amount of the grafted unsaturated monomer is added dropwise, the temperature of the reaction kettle is raised to 64 ℃, and the grafted unsaturated monomer is continuously added dropwise until the completion.
The third step of mixing and foaming the polymer dry powder and the EVA comprises the following steps:
step 1), adding a powdery starch graft polymer and EVA into an internal mixer, carrying out internal mixing for 4min at 90 ℃, adding urea, zinc oxide, zinc stearate, sodium bicarbonate and a foaming agent azodicarbonamide AC, carrying out internal mixing for 4min at 90 ℃, then adding talcum powder and dichlorobenzenesulfonic acid, carrying out internal mixing for 3min, adding a crosslinking agent dicumyl peroxide (DCP), carrying out internal mixing for 1min, and discharging;
step 2), mixing the mixture obtained in the step 1) in an open mill for tabletting;
and 3), cutting the mixture sheet obtained in the step 2) into small pieces, and performing compression foaming on the small pieces in a flat vulcanizing machine for 6min at 160 ℃, so as to obtain a finished product of the starch wet-process grafted organic unsaturated monomer and EVA composite foaming shoe material.
The method comprises the following materials in parts by weight:
EVA: 100 parts of powdery starch wet-process graft polymer: 30-80 parts of urea: 2.0 to 4.5 portions of,
zinc oxide: 2.0-4.0 parts of sodium bicarbonate: 0.5-2.0 parts of zinc stearate: 1.0-2.5 parts, dichlorobenzenesulfonic acid: 1.6-2.8 parts of foaming agent Azodicarbonamide (AC): 3.0-7.0 parts, talcum powder: 10.0-12.0 parts of dicumyl peroxide (DCP) as a crosslinking agent: 0.5-0.9 part; the VA content in the EVA is between 7.0% and 22.0%.
The weight parts of the materials used in the above method are preferably:
EVA: 100 parts of powdery starch wet-process graft polymer: 45-70 parts of a solvent; urea: 3.0-4.0 parts; zinc oxide: 3.0-4.0 parts; sodium bicarbonate: 1.0-1.5 parts; zinc stearate: 1.0-2.0 parts; dichlorobenzene sulfonic acid: 1.8-2.5 parts; blowing agent Azodicarbonamide (AC): 3.5-6.0 parts; talc powder: 10.5-11.5 parts; crosslinking agent dicumyl peroxide (DCP): 0.7 to 0.8 portion.
The invention has the advantages that: the modification reaction mode of gradient temperature rise by adopting the addition amount of the grafting unsaturated monomer can ensure that the reaction speed of the monomer is high and the reaction is relatively complete, while the reaction mode of fixed temperature can only be carried out at a lower temperature (such as 62 ℃), the reaction speed is low, the reaction is incomplete, and the amount of the residual grafting unsaturated monomer is large.
After the modification reaction is finished, the grafted unsaturated monomer is heated to 75 ℃ and redundant monomer is evaporated under the condensation condition for recycling, so that the influence of volatile monomer in the post process can be eliminated, the material can be saved, and the production cost can be reduced.
The physical index of the material can be completely compared with that of the common EVA shoe material, and particularly, the material has the lowest density which can reach 0.12g/cm3Can still be used normally.
After soaking for 6 hours, the water absorption rate can reach about 17.5 percent of the self weight; under the conditions of room temperature 23 ℃ and relative humidity 50%, about 90% of the absorbed water can be lost within 6 hours.
The foamed shoe material can replace the traditional shoe material EVA material, the shoe material can be naturally degraded, and in the soil burying method test, the sample is buried in soil with humus, and the degradation weight loss rate of 30 days can reach 35%.
Detailed Description
The invention relates to a preparation method of a starch wet-process graft modified composite EVA (ethylene-vinyl acetate copolymer) foamed shoe material, which comprises the following steps of:
the method comprises the following steps: using starch wet method to graft unsaturated monomer to synthesize polymer emulsion; the raw materials comprise the following components in parts by weight: 100 parts of starch, 30-120 parts of grafted unsaturated monomer, 1.0-4.0 parts of initiator ammonium persulfate and 180-250 parts of distilled water;
step two: spray drying the polymer emulsion to obtain dry powder of the starch wet-process graft polymer;
step three: and mixing and foaming the polymer dry powder and EVA to obtain the composite EVA shoe material.
The grafted unsaturated monomer comprises a combination of methyl methacrylate and vinyl acetate (weight ratio 1: 2), or a combination of ethyl methacrylate and vinyl acetate (weight ratio 1: 2), or a vinyl acetate monomer alone, depending primarily on the final performance objectives of the product.
The amount of the graft unsaturated monomer is 30 to 120 parts, preferably 40 to 100 parts, based on 100 parts of the starch.
The starch comprises one or a mixture of more than two of corn starch, wheat starch and potato starch in any proportion. The starch varieties are different, the performance of the obtained final product is different, and the pure corn starch has the best effect.
The method for synthesizing the polymer emulsion by grafting the unsaturated monomer by the starch wet method comprises the following steps:
step 1), adding 100 parts of starch into a four-port reaction kettle, adding 180-250 parts (preferably 200-210 parts) of distilled water, stirring and transparentizing at the temperature of 85 ℃ for 15min, and cooling to 60 ℃;
step 2), adding an ammonium persulfate solution into the solution obtained in the step 1), and uniformly stirring;
and 3) dropwise adding the grafted unsaturated monomer into the solution obtained in the step 2) at 60 ℃, wherein the speed can be slightly higher when the dropwise adding is started.
Step 4), when 1/3 of the total amount of the grafted unsaturated monomer is added, heating the reaction kettle to 62 ℃, and continuously dropwise adding the grafted unsaturated monomer;
step 5), when 2/3 of the total amount of the grafted unsaturated monomer is dripped, heating the reaction kettle to 64 ℃, and continuously dripping the grafted unsaturated monomer until the completion;
step 6), when the grafted unsaturated monomer is completely added, strictly controlling the reaction temperature to be 66 ℃ until the reaction is finished, wherein the total reaction time is generally 3 hours;
and 7) after the modification reaction is finished, heating to 75 ℃, evaporating redundant grafting unsaturated monomers under a condensation condition to obtain a finished product of the starch wet grafting modified composite EVA foaming shoe material, and recycling the evaporated redundant grafting unsaturated monomers.
The amount of the distilled water used in the synthesis reaction (also called as 'modification reaction') of the polymer emulsion is 180-250 parts, preferably 200-210 parts, within the range of the amount of the distilled water, the grafting reaction can be ensured to be smoothly carried out, and the subsequent spray drying cost can be saved due to higher concentration.
The reaction system of the modification reaction is a gradient temperature-increasing system. Adding an initiator solution into the solution in the reaction kettle at 60 ℃, uniformly stirring, then dropwise adding the grafted unsaturated monomer at 60 ℃, heating to 62 ℃ when the grafted unsaturated monomer is added into 1/3, heating to 64 ℃ when the amount of the grafted unsaturated monomer is added into 2/3, heating to 66 ℃ when the grafted unsaturated monomer is completely added, and strictly controlling the reaction temperature until the reaction is finished. The added monomer not only participates in the reaction but also can serve as a diluent of the reaction system.
After the modification reaction is finished, the temperature is raised to 75 ℃, redundant grafting unsaturated monomers are evaporated under the condensation condition and are recycled, so that the grafting rate is high, materials can be saved, and the cost is reduced.
The initiator used in the modification reaction is ammonium persulfate, and the using amount is 1.0-4.0 parts, preferably 1.5-2.5 parts. The amount of the initiator used may be determined according to the final purpose of the shoe material.
The ammonium persulfate is added in a one-off mode, the grafted unsaturated monomer is added in a dropwise mode, and the vinyl acetate monomer is easy to chain transfer into a stable allyl free radical and has a self-polymerization inhibition effect, so that the grafting reaction is favorably carried out by adopting a quick-first and slow-later adding mode and a gradient heating reaction mode.
The invention comprises the following third step: the method for mixing and foaming the grafted unsaturated monomer polymer dry powder and the EVA comprises the following steps:
step 1): adding powdery starch graft polymer and EVA into an internal mixer, internally mixing for 4min at 90 ℃, adding urea, zinc oxide, zinc stearate, sodium bicarbonate and Azodicarbonamide (AC) serving as a foaming agent, internally mixing for 4min at 90 ℃, then adding talcum powder and dichlorobenzenesulfonic acid, continuously internally mixing for 3min, adding dicumyl peroxide (DCP) serving as a crosslinking agent, internally mixing for 1min, and discharging.
Step 2): and (2) mixing the mixture obtained in the step 1) on an open mill to carry out tabletting.
Step 3): cutting the mixture sheet obtained in the step 2) into small pieces, and performing compression foaming on the small pieces in a flat vulcanizing machine for 6min at the temperature of 160 ℃ to obtain the starch wet-process grafted organic unsaturated monomer and EVA composite foamed shoe material.
The components and contents (in parts by weight of the EVA material) of the material used in the third step of the invention are as follows:
EVA 100 weight portions
Starch wet graft polymer (dry powder): 30-80 parts, preferably: 45-70 parts of a solvent;
urea: 2.0-4.5 parts, preferably: 3.0-4.0 parts;
zinc oxide: 2.0-4.0 parts, preferably: 3.0-4.0 parts;
0.5-2.0 parts of sodium bicarbonate, preferably: 1.0-1.5 parts;
zinc stearate: 1.0-2.5 parts, preferably: 1.0-2.0 parts;
dichlorobenzene sulfonic acid: 1.6-2.8 parts, preferably: 1.8-2.5 parts;
blowing agent Azodicarbonamide (AC): 3.0-7.0 parts, preferably: 3.5-6.0 parts;
talc powder: 10.0-12.0 parts, preferably: 10.5-11.5 parts;
crosslinking agent dicumyl peroxide (DCP): 0.50-0.90 parts, preferably: 0.70-0.80 portion.
The material for the shoes, which is prepared by the invention, can absorb moisture, remove moisture and be biodegradable, is an environment-friendly material, is very suitable for being used as a material for the inner cavity of the shoes, is sanitary and is beneficial to environmental protection.
The starch grafted and modified by the monomer can be completely degraded, and can promote the degradation of the polyolefin synthetic polymer, and the prepared shoe material also has the characteristics. The naturally degradable shoe material prepared by the preparation method of the shoe material can completely replace the conventionally used EVA shoe material, and in the soil burying method test, the sample is buried in the soil with humus, and the degradation weight loss rate of 30 days can reach 35%. Obviously reduces the material cost of the EVA for shoes, and increases the moisture absorption performance and the moisture removal performance of the EVA.
The addition amount of the wet starch graft polymer (dry powder) is 30-80 parts, preferably 45-70 parts, based on 100 parts by weight of the EVA material, and the proportion can enable the physical properties of the wet starch graft polymer and the EVA composite foaming shoe material to reach the best, has excellent moisture absorption and dehumidification properties, and can reduce the cost to the maximum extent.
The VA content in the EVA is between 7.0 and 22.0 percent, the VA content is too small, the hardness of the wet modified starch foaming shoe material is larger, and the VA content is too large, so that the shoe material is easy to stick to a roller in the operation process and even can not be foamed.
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The first step is as follows: preparation of corn starch wet-process grafted unsaturated monomer polymer
Adding 60g of corn starch into a four-port reaction kettle, adding 120g of distilled water, stirring and transparentizing at 85 ℃ for 15min, and cooling to 60 ℃; adding 1.2g of initiator ammonium persulfate solution dissolved in 10ml of distilled water, and stirring for 10 min; dropwise adding 20g of mixed reaction monomers (methyl methacrylate and vinyl acetate =1: 2) at 60 ℃, heating and maintaining at 62 ℃, continuously dropwise adding 20g of the mixed reaction monomers, heating and maintaining at 64 ℃, then adding 20g of the mixed reaction monomers, heating and maintaining at 66 ℃ for reacting for 2 h; heating to 75 ℃, and evaporating unreacted monomers under a condensation condition to obtain the wet starch graft polymer emulsion. The solid content of the product is 43 +/-1 percent, and the pH value is 6.0-6.5.
The second step is that: foamed shoe material prepared from starch wet-process graft polymer and EVA (ethylene-vinyl acetate copolymer)
Carrying out spray drying on the starch wet-method grafted unsaturated monomer polymer obtained in the first step to obtain a powdery starch modified polymer; adding 140g of powdery starch modified polymer, 200g of EVA200g into an internal mixer, internally mixing for 4min at 90 ℃, 6.5g of urea, 5.8g of zinc oxide, 3g of zinc stearate, 2g of sodium bicarbonate and 7g of Azodicarbonamide (AC) serving as a foaming agent, internally mixing for 4min at 90 ℃, then adding 23g of talcum powder and 3.6g of dichlorobenzenesulfonic acid, continuously internally mixing for 3min, adding 1.6g of dicumyl peroxide (DCP) serving as a crosslinking agent, internally mixing for 1min, discharging, and completely transferring to an open mill for open mixing and tabletting after discharging. And (3) cutting the sheet into small pieces, and performing compression foaming on the small pieces in a flat vulcanizing machine for 6min at the temperature of 160 ℃ to obtain the starch wet-process grafted unsaturated monomer polymer and EVA composite foaming shoe material.
The measured physical index is shown in Table 1 below.
TABLE 1 measurement results of foamed shoe material prepared by compounding starch wet-process graft unsaturated monomer polymer and EVA and common EVA
Example 2
The first step is as follows: preparation of corn starch wet-process grafted unsaturated monomer polymer
Adding 60g of corn starch into a four-port reaction kettle, adding 120g of distilled water, stirring and transparentizing at 85 ℃ for 15min, and cooling to 60 ℃; adding 1.2g of initiator ammonium persulfate solution dissolved in 10ml of distilled water, and stirring for 10 min; dropwise adding 17g of mixed reaction monomers (methyl methacrylate and vinyl acetate =1: 2) at 60 ℃, heating and maintaining at 62 ℃, continuously dropwise adding 17g of the mixed reaction monomers, heating and maintaining at 64 ℃, then adding 16g of the mixed reaction monomers, heating and maintaining at 66 ℃ for reaction for 2 h; heating to 75 ℃, and evaporating unreacted monomers under a condensation condition to obtain the wet starch graft polymer emulsion. The solid content of the product is 41 +/-1 percent, and the pH value is 6.0-6.5. .
The second step is that: preparation of starch wet modified polymer composite EVA foamed shoe material
Spray drying the starch wet-process modified polymer obtained in the first step to obtain a powdery starch modified polymer; adding 110g of powdery starch modified polymer and EVA200g into an internal mixer, internally mixing for 3min at 90 ℃, adding 6g of urea, 5g of zinc oxide, 3g of zinc stearate, 2g of sodium bicarbonate and 7.5g of Azodicarbonamide (AC) serving as a foaming agent, internally mixing for 4min at 90 ℃, then adding 21g of talcum powder and 3.6g of dichlorobenzenesulfonic acid, continuously internally mixing for 3min, adding 1.6g of dicumyl peroxide (DCP) serving as a crosslinking agent, internally mixing for 1min, discharging, and completely transferring to an open mill for open mixing and tabletting after discharging. And (3) cutting the sheet into small pieces, and performing compression foaming on the small pieces in a flat vulcanizing machine for 6min at the temperature of 160 ℃ to obtain the starch wet-process grafted unsaturated monomer polymer and EVA composite foaming shoe material.
The measured physical index is shown in Table 2
TABLE 2 determination results of starch wet-process grafting unsaturated monomer polymer and EVA composite foamed shoe material and common EVA
Example 3
The first step is as follows: preparation of wheat starch wet-method grafted unsaturated monomer polymer
Adding 60g of wheat starch into a four-port reaction kettle, adding 120g of distilled water, stirring and transparentizing at 85 ℃ for 15min, and cooling to 60 ℃; adding 1.3g of initiator ammonium persulfate solution dissolved in 20ml of distilled water, and stirring for 10 min; dropwise adding 20g of mixed reaction monomers (ethyl methacrylate and vinyl acetate =1: 2) at 60 ℃, heating and maintaining at 62 ℃, continuously dropwise adding 20g of the mixed reaction monomers, heating and maintaining at 64 ℃, then adding 20g of the mixed reaction monomers, and continuously heating and maintaining at 66 ℃ for reacting for 2 h; heating to 75 ℃, and evaporating unreacted monomers under a condensation condition to obtain the wet starch graft polymer. The solid content of the product is 43 +/-1 percent, and the pH value is 6.0-6.5.
The second step is that: preparation of starch wet modified polymer composite EVA foamed shoe material
Spray drying the starch wet-process graft polymer obtained in the first step to obtain a powdery starch graft polymer; 100g of powdery starch graft polymer and 200g of EVA200g are added into an internal mixer, internal mixing is carried out for 3min at 90 ℃, 6g of urea, 5g of zinc oxide, 3.6g of zinc stearate, 2g of sodium bicarbonate and 7g of Azodicarbonamide (AC) serving as a foaming agent are added, internal mixing is carried out for 4min at 90 ℃, then 23g of talcum powder and 3.5g of dichlorobenzenesulfonic acid are added, internal mixing is continued for 3min, 1.5g of dicumyl peroxide (DCP) serving as a crosslinking agent is added, internal mixing is carried out for 1min, and all the materials are transferred to an open mill for tabletting after being discharged. And (3) cutting the sheet into small pieces, and performing compression foaming on the small pieces in a flat vulcanizing machine for 6min at the temperature of 160 ℃ to obtain the starch wet-process grafted unsaturated monomer polymer and EVA composite foaming shoe material.
The measured physical index is shown in Table 3 below
TABLE 3 determination results of starch wet-process grafting unsaturated monomer polymer and EVA composite foamed shoe material and common EVA
Example 4
The first step is as follows: preparation of potato starch wet-method grafted unsaturated monomer polymer
Adding 60g of potato starch into a four-port reaction kettle, adding 130g of distilled water, stirring and transparentizing at 85 ℃ for 15min, and cooling to 60 ℃; adding 1.4g of initiator ammonium persulfate solution dissolved in 10ml of distilled water, and stirring for 10 min; dripping 20g of reaction monomer (vinyl acetate 100%) at 60 ℃, heating and keeping at 62 ℃, continuing to drip 20g of mixed reaction monomer, heating and keeping at 64 ℃, then adding 20g of mixed reaction monomer, continuing to heat and keep at 66 ℃ for reaction for 2 hours; heating to 75 ℃, and evaporating unreacted monomers under a condensation condition to obtain the wet starch graft polymer. The solid content of the product is 42 +/-1 percent, and the pH value is 6.0-6.5. .
The second step is that: preparation of starch wet modified polymer composite EVA foamed shoe material
Spray drying the starch wet-process modified polymer obtained in the first step to obtain a powdery starch modified polymer; adding 120g of powdery starch modified polymer and 200g of EVA200g into an internal mixer, internally mixing for 3min at 90 ℃, adding 7g of urea, 6g of zinc oxide, 3.2g of zinc stearate, 2g of sodium bicarbonate and 7g of Azodicarbonamide (AC) serving as a foaming agent, internally mixing for 4min at 90 ℃, then adding 22g of talcum powder and 3.5g of dichlorobenzoic acid, continuously internally mixing for 3min, adding 1.5g of dicumyl peroxide (DCP) serving as a crosslinking agent, internally mixing for 1min, discharging, and completely transferring to an open mill for tabletting. And (3) cutting the sheet into small pieces, and performing compression foaming on the small pieces in a flat vulcanizing machine for 7min at the temperature of 160 ℃ to obtain the starch wet-process grafted organic unsaturated monomer polymer and EVA composite foaming shoe material.
The measured physical index is shown in Table 4 below
TABLE 4 determination results of starch wet-process grafting unsaturated monomer polymer and EVA composite foamed shoe material and common EVA
As can be seen from the comparison parameters listed in tables 1-4, the index of the water absorption of the starch wet-modified polymer composite EVA foamed shoe material is obviously superior to that of the common EVA, and other indexes are basically consistent.
The components of the invention are all in parts by weight.
Claims (4)
1. A preparation method of a starch wet grafting modified composite EVA foaming shoe material, which is characterized in that,
the method comprises the following steps: using starch wet method to graft unsaturated monomer to synthesize polymer emulsion; the raw materials comprise the following components in parts by weight: 100 portions of starch, 30 to 120 portions of grafting unsaturated monomer, 1.0 to 4.0 portions of ammonium persulfate and 180 portions of distilled water; the grafted unsaturated monomer comprises: a combination of methyl methacrylate and vinyl acetate, or a combination of ethyl methacrylate and vinyl acetate; wherein the ratio of the combination of methyl methacrylate and vinyl acetate is between 1:2 and 1:3, and the ratio of the combination of ethyl methacrylate and vinyl acetate is between 1:2 and 1:3, or more;
step two: spray drying the polymer emulsion to obtain dry powder of the starch wet-process graft polymer;
step three: mixing and foaming the polymer dry powder and EVA to obtain a composite EVA shoe material;
the method for synthesizing the polymer emulsion in the first step comprises the following steps:
step 1), adding starch into a four-port reaction kettle according to the parts, adding the parts of distilled water, stirring and transparentizing at 85 ℃ for 15min, and cooling to 60 ℃;
step 2), adding the ammonium persulfate solution in the parts into the solution obtained in the step 1), and uniformly stirring;
step 3), dripping the grafted unsaturated monomer in the solution obtained in the step 2) by adopting a reaction mode of gradient temperature rise at the temperature of 60 ℃, namely dripping a part of the grafted unsaturated monomer in a plurality of temperature gradients of temperature rise every time one temperature gradient is increased until all the grafted unsaturated monomers are dripped;
step 4), when the grafted unsaturated monomer is completely added, strictly controlling the synthesis reaction temperature in the reaction kettle at 66 ℃ until the reaction is finished, wherein the total reaction time is 2.5-3.5 h;
step 5), after the synthesis reaction is finished, heating to 75 ℃, evaporating redundant grafting unsaturated monomers under a condensation condition to obtain the polymer emulsion, and recycling the evaporated redundant grafting unsaturated monomers;
the third step of mixing and foaming the polymer dry powder and the EVA comprises the following steps:
step 1), adding a powdery starch graft polymer and EVA into an internal mixer, carrying out internal mixing for 4min at 90 ℃, adding urea, zinc oxide, zinc stearate, sodium bicarbonate and a foaming agent azodicarbonamide, carrying out internal mixing for 4min at 90 ℃, then adding talcum powder and dichlorobenzenesulfonic acid, continuing internal mixing for 3min, adding a crosslinking agent dicumyl peroxide, carrying out internal mixing for 1min, and discharging;
step 2), mixing the mixture obtained in the step 1) in an open mill for tabletting;
and 3) cutting the mixture sheet obtained in the step 2) into small pieces, and performing compression foaming on the small pieces in a flat vulcanizing machine for 6min at 160 ℃, so as to obtain a finished product of the starch wet-process grafted organic unsaturated monomer and EVA composite foaming shoe material.
2. The composite EVA foamed shoe material of claim 1, wherein the starch comprises one or a mixture of two or more of corn starch, wheat starch and potato starch in any proportion.
3. The preparation method of the starch wet grafting modified composite EVA foamed shoe material according to claim 1, wherein the reaction mode of gradient temperature rise is completed in two steps:
the first step is as follows: when 1/3 of the total amount of the grafted unsaturated monomer is added, heating the reaction kettle to 62 ℃, and continuously dropwise adding the grafted unsaturated monomer;
the second step is that: when 2/3 of the total amount of the grafted unsaturated monomer is added dropwise, the temperature of the reaction kettle is raised to 64 ℃, and the grafted unsaturated monomer is continuously added dropwise until the completion.
4. The preparation method of the starch wet grafting modified composite EVA foamed shoe material according to claim 1, wherein the weight parts of the materials used in the method are as follows:
EVA: 100 parts of powdery starch wet-process graft polymer: 30-80 parts of urea: 2.0-4.5 parts of zinc oxide: 2.0-4.0 parts of sodium bicarbonate: 0.5-2.0 parts of zinc stearate: 1.0-2.5 parts, dichlorobenzenesulfonic acid: 1.6-2.8 parts of foaming agent azodicarbonamide: 3.0-7.0 parts, talcum powder: 10.0-12.0 parts of a cross-linking agent dicumyl peroxide: 0.5-0.9 part; the VA content in the EVA is between 7.0% and 22.0%.
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