CN110272579A - The preparation method of the compound EVA foam shoe material of starch wet process graft modification - Google Patents
The preparation method of the compound EVA foam shoe material of starch wet process graft modification 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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- 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
- C08J9/0023—Use of organic additives containing oxygen
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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
- C08J9/0028—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
-
- 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
Step 1: a kind of preparation method of the compound EVA foam shoe material of starch wet process graft modification uses starch wet process imping unsaturated monomers synthetic polymer emulsion；The raw material of use includes: starch 100, imping unsaturated monomers 30-120, initiator ammonium persulfate 1.0-4.0, distilled water 180-250 according to parts by weight；Step 2: the polymer emulsion is spray-dried, starch wet process graft polymers dry powder is obtained；Step 3: foaming is kneaded with the polymer dry powder and EVA and obtains compound EVA shoe material.The invention has the advantages that its physical index can compare favourably completely with common EVA shoe material, especially density of material can be accomplished lower, the water absorbing properties of material can be controlled as desired, completely alternative traditional footwear material EVA material uses, footwear material can natural degradation, in soil buries method test, by sample landfill in the soil for having humus, 30 days degradation weight-loss ratios are up to 35%.
Description
Technical field
The present invention relates to gradient increased temperature and it is anti-steam monomeric fashion starch wet process imping unsaturated monomers synthetic polymer with
The compound preparation method for preparing foaming shoe material of EVA, belongs to field of new materials.
Background technique
EVA material is the principal item of China's material for shoes, and dosage accounts for about 35% of sole material or more.EVA mainly by
Random copolymer made of ethylene (CH2=CH2) monomer and vinyl acetate (CH3COOCH=CH2) monomer polymerization.EVA molecule master
On chain introduce CH3COO- side-chain radical, reduce intermolecular order, make EVA copolymer have it is preferable elasticity and compared with
Low hardness, but common EVA shoe material itself does not have hygroscopicity.The main formula of EVA foamed material is based on EVA resin
It wants raw material and to add foaming agent, crosslinking agent, filler and other auxiliary agents uniform through mixer mechanical mixture, made by extruder
Grain most prepares various foamed products through ejaculator compression molding afterwards.EVA foamed material for footwear material is since its is light, bullet
Property it is good, flexible it is good, be not easy to wrinkle, have the advantages that fabulous coloring, be widely used suitable for various weathers, but by
It is non-hygroscopic in itself and do not allow degradable, it be easy to cause white pollution and threatening environment；Itself non-hygroscopic causes simultaneously
It is be easy to cause when being used as insole in shoe cavity moist and smelly.The gradient increased temperature and anti-steaming monomeric fashion starch that the present invention designs
Common EVA is fully achieved in physical property in the foaming shoe material of wet process imping unsaturated monomers synthetic polymer and the compound preparation of EVA
Level, itself have good moisture absorption and dehumidification, can be with natural degradation.
Summary of the invention
It is an object of the invention to provide a kind of compound EVA foam shoe materials of starch wet process graft modification, to solve existing use
It is non-hygroscopic and do not allow problem of easy degradation existing for the EVA foamed material of footwear material.
The technical scheme is that a kind of preparation method of the compound EVA foam shoe material of starch wet process graft modification, special
Sign is, comprising the following steps:
Step 1: starch wet process imping unsaturated monomers synthetic polymer emulsion is used；The raw material of use includes: according to parts by weight
Starch 100, imping unsaturated monomers 30-120, ammonium persulfate 1.0-4.0, distilled water 180-250；
Step 2: the polymer emulsion is spray-dried, starch wet process graft polymers dry powder is obtained；
Step 3: foaming is kneaded with the polymer dry powder and EVA and obtains compound EVA shoe material.
The parts by weight of the raw material are preferred are as follows: imping unsaturated monomers: 40-100, initiator ammonium persulfate: 1.5-
2.5, distilled water: 200-210.
The imping unsaturated monomers include: the combination of methyl methacrylate and vinylacetate, are matched in 1:2--
Between 1:3 or the combination of ethyl methacrylate and vinylacetate, proportion is between 1:2-1:3 or vinyl acetate
Ester monomer.
The starch includes the arbitrary proportion of one or more of cornstarch, wheaten starch and potato starch
Mixture.
In the step one polymer emulsion synthetic method the following steps are included:
Starch is added in four mouthfuls of reaction kettles by the number, and the distilled water of the number is added by step 1), in 85 DEG C of temperature
Lower stirring transparence 15min, cools to 60 DEG C；
Step 2 is added the ammonium persulfate solution of the number, stirs evenly in the solution that step 1) obtains；
In the solution that step 2 obtains, at 60 DEG C, it is unsaturated that grafting is added dropwise using the reactive mode of gradient increased temperature in step 3)
Monomer divides the temperature gradient of several heatings, a part of imping unsaturated monomers are added dropwise in one temperature gradient of every increase, until
Whole imping unsaturated monomers are added dropwise；
Step 4), after imping unsaturated monomers are all added, the synthesis reaction temperature in strict control reaction kettle at 66 DEG C extremely
Reaction terminates, and reaction total time is 2.5-3.5h；
After step 5) synthetic reaction, 75 DEG C are warming up to, extra imping unsaturated monomers are steamed under condensing condition, that is, are made
Obtain the polymer emulsion, the extra imping unsaturated monomers recycling and reusing steamed.
The reactive mode of the gradient increased temperature is completed in two steps:
Step 1: temperature reaction kettle temperature degree continues to be added dropwise to 62 DEG C when addition imping unsaturated monomers amount is the 1/3 of total amount
Imping unsaturated monomers；
Step 2: temperature reaction kettle temperature degree continues to be added dropwise to 64 DEG C when dropwise addition imping unsaturated monomers amount is the 2/3 of total amount
Imping unsaturated monomers to complete.
The method of the step three " be kneaded and foamed with the polymer dry powder and EVA " the following steps are included:
Powdered starch graft polymers and EVA, 90 DEG C of mixing 4min is added in step 1) on mixer, and urea, oxidation is added
Then talcum powder and dichloro-benzenes is added in zinc, zinc stearate, sodium bicarbonate, foaming agent azodicarbonamide AC, 90 DEG C of mixing 4min
Sulfonic acid continues mixing 3min, adds crosslinking agent cumyl peroxide (DCP) mixing 1min discharging；
Step 2, the mixture that step 1) is obtained is in open mill mill tabletting；
The mixture sheet material that step 2 obtains is cut into small pieces by step 3), the moulded from foam on vulcanizing press, time 6min,
160 DEG C of temperature, starch wet process can be obtained and be grafted organic unsaturated monomer and the composite foamed footwear material finished product of EVA.
The parts by weight of material used in the method are as follows:
EVA:100 parts, powdered starch wet process graft polymers: 30-80 parts, urea: 2.0-4.5 parts,
Zinc oxide: 2.0-4.0 parts, sodium bicarbonate: 0.5-2.0 parts, zinc stearate: 1.0-2.5 parts, dichloro benzosulfonic acid: 1.6-2.8
Part, foaming agent azodicarbonamide (AC): 3.0-7.0 parts, talcum powder: 10.0-12.0 parts, crosslinking agent cumyl peroxide
(DCP): 0.5-0.9 parts；VA content is between 7.0%-22.0% in the EVA.
It is preferred using the parts by weight of material in above-mentioned method are as follows:
EVA:100 parts, powdered starch wet process graft polymers: 45-70 parts；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；Dichloro benzosulfonic acid: 1.8-2.5 parts；Foaming agent azodicarbonamide
(AC): 3.5-6.0 parts；Talcum powder: 10.5-11.5 parts；Crosslinking agent cumyl peroxide (DCP): 0.7-0.8 parts.
The invention has the advantages that implement the modified-reaction mode of gradient increased temperature using imping unsaturated monomers additional amount, it can
Guarantee that monomer reaction speed is fast, reaction is also comparatively complete, and the reactive mode of fixed temperature can only be at a lower temperature
It carries out (such as 62 DEG C), reaction speed is slow, and not exclusively, remaining imping unsaturated monomers amount is larger for reaction.
After modified-reaction, imping unsaturated monomers are being warming up to 75 DEG C, are steaming excess monomer recycling under condensing condition
Recycle, after can not only eliminating in technique volatile monomers influence, while material can also be saved, reduce production cost.
Its physical index can compare favourably completely with common EVA shoe material, and especially density of material is minimum, can reach 0.12g/
cm3Remain to normal use.
Water absorption rate is up to 17.5% or so of own wt after the 6h that soaks；In 23 DEG C of room temperature, the condition of relative humidity 50%
Under, 6h, which can about lose, absorbs the 90% of moisture.
The alternative traditional footwear material EVA material of foaming shoe material of the invention uses, footwear material can natural degradation, tested in soil buries method
In, by sample landfill in the soil for having humus, 30 days degradation weight-loss ratios are up to 35%.
Specific embodiment
A kind of preparation method of the compound EVA foam shoe material of starch wet process graft modification of the present invention, comprising the following steps:
Step 1: starch wet process imping unsaturated monomers synthetic polymer emulsion is used；The raw material of use includes: according to parts by weight
Starch 100, imping unsaturated monomers 30-120, initiator ammonium persulfate 1.0-4.0, distilled water 180-250；
Step 2: the polymer emulsion is spray-dried, starch wet process graft polymers dry powder is obtained；
Step 3: foaming is kneaded with the polymer dry powder and EVA and obtains compound EVA shoe material.
The imping unsaturated monomers include methyl methacrylate and vinylacetate combination (weight ratio 1:2), or
Person's ethyl methacrylate and vinylacetate combination (weight ratio 1:2), or Vinyl Acetate Monomer is used alone, mainly
Depending on the final performance target of product.
It is in terms of 100 parts by starch dosage (weight), the dosage of the imping unsaturated monomers is 30-120 parts, preferably 40-
100 parts.
The starch includes the arbitrary proportion of one or more of cornstarch, wheaten starch and potato starch
Mixture.Starch varieties are different, and the performance for obtaining final product is variant, best with pure cornstarch effect.
The step of synthetic method of the step one starch wet process imping unsaturated monomers synthetic polymer emulsion, is as follows:
100 parts of starch are added in four mouthfuls of reaction kettles, and the distillation of 180-250 parts (preferably 200-210 parts) are added by step 1)
Water stirs transparence 15min at a temperature of 85 DEG C, cools to 60 DEG C；
Step 2 is added ammonium persulfate solution, stirs evenly in the solution that step 1) obtains；
Step 3), in the solution that step 2 obtains, 60 DEG C of dropwise addition imping unsaturated monomers, speed can be slightly when starting to be added dropwise
Fastly.
Step 4), when addition imping unsaturated monomers amount is the 1/3 of total amount, temperature reaction kettle temperature degree continues to be added dropwise to 62 DEG C
Imping unsaturated monomers；
Step 5), when dropwise addition imping unsaturated monomers amount is the 2/3 of total amount, temperature reaction kettle temperature degree continues to be added dropwise to 64 DEG C
Imping unsaturated monomers to complete；
Step 6), after imping unsaturated monomers are all added, strict control reaction temperature terminates at 66 DEG C to reaction, general anti-
Answering total time is 3h；
After step 7) modified-reaction, 75 DEG C are warming up to, is obtained after extra imping unsaturated monomers are steamed under condensing condition
Described " the compound EVA foam shoe material of the starch wet process graft modification " finished product, the extra imping unsaturated monomers recycling steamed are sharp again
With.
Amount of distilled water used is 180-250 parts in the synthetic reaction (also referred to as " modified-reaction ") of the polymer emulsion, excellent
200-210 parts are selected, can not only guarantee that graft reaction can be gone on smoothly within the scope of this water consumption, and since concentration is higher also
Subsequent spray drying cost can be saved.
The reactive mode of above-mentioned modified-reaction is that gradient increased temperature mode carries out.60 DEG C of additions of solution in a kettle cause
Agent solution starts that imping unsaturated monomers are added dropwise for 60 DEG C, when imping unsaturated monomers are added 1/3, be warming up to after mixing evenly
62 DEG C, 64 DEG C are warming up to when imping unsaturated monomers amount is added 2/3, after imping unsaturated monomers are all added, is warming up to
66 DEG C and strict control reaction temperature to reaction terminate.The monomer of addition is not only involved in reaction, and can serve as reaction system
Diluent.
After the modified-reaction, 75 DEG C are warming up to, extra imping unsaturated monomers are steamed under condensing condition, recycling is again
It utilizes, not only can guarantee that grafting rate is higher, while material can be saved, reduce cost.
Initiator used is ammonium persulfate in above-mentioned modified-reaction, and dosage is 1.0-4.0 parts, preferably 1.5-2.5 parts.Draw
The usage amount for sending out agent can be depending on the final purpose of footwear material.
The ammonium persulfate uses disposable adding manner, and imping unsaturated monomers are added using dropwise addition mode, due to
Vinyl Acetate Monomer has easily by chain tra nsfer at stable allyl radical from inhibition, so using first quick and back slow
Adding manner and the reactive mode of gradient increased temperature be conducive to the progress of graft reaction.
Step 3 of the present invention: it is as follows that imping unsaturated monomers polymer dry powder is kneaded the step of method of foaming with EVA:
Step 1): being added powdered starch graft polymers and EVA, 90 DEG C of mixing 4min on mixer, and urea, oxidation is added
Then talcum powder and dichloro is added in zinc, zinc stearate, sodium bicarbonate, foaming agent azodicarbonamide (AC), 90 DEG C of mixing 4min
Benzene sulfonic acid continues mixing 3min, adds crosslinking agent cumyl peroxide (DCP) mixing 1min discharging.
Step 2: the mixture that step 1) is obtained is in open mill mill tabletting.
Step 3): being cut into small pieces for the mixture sheet material that step 2 obtains, the moulded from foam on vulcanizing press, the time
6min, can be obtained starch wet process and be grafted organic unsaturated monomer and the composite foamed footwear material of EVA by 160 DEG C of temperature.
Material component used in step 3 of the present invention and content (in terms of the parts by weight of the EVA material) are as follows:
100 parts of EVA dosage
Starch wet process graft polymers (dry powder): 30-80 parts, preferably: 45-70 parts；
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；
Dichloro benzosulfonic acid: 1.6-2.8 parts, preferably: 1.8-2.5 parts；
Foaming agent azodicarbonamide (AC): 3.0-7.0 parts, preferably: 3.5-6.0 parts；
Talcum powder: 10.0-12.0 parts, preferably: 10.5-11.5 parts；
Crosslinking agent cumyl peroxide (DCP): 0.50-0.90 parts, preferably: 0.70-0.80 parts.
It is produced by the present invention can moisture absorption, dehumidification and biodegradable material for shoes be environment-friendly material, very be applicable in
In being used as shoes lumen material, not only health and also be good for the environment.
Not only oneself can be degradable by the starch of monomer graft modification, polyolefins can also be promoted to synthesize macromolecule
Degradation, footwear material obtained also has the characteristics that such.Prepared by material for shoes preparation method of the invention can natural degradation shoes
Material is fully able to substitute conventional use of EVA shoe material, and in soil buries method test, sample is filled in the soil for having humus
In, 30 days degradation weight-loss ratios are up to 35%.Be substantially reduced the material cost of shoes EVA, and increase EVA moisture pick-up properties and
Dehumidification performance.
In terms of 100 parts of weight of the EVA material, wet process starch graft copolymers (dry powder) additional amount is 30-80
Part, preferably 45-70 parts, this proportion can be such that wet process starch graft copolymers and the physical property of the composite foamed footwear material of EVA reach
To best, there is splendid moisture absorption and dehumidification performance, and cost can be reduced to greatest extent.
For VA content between 7.0-22.0%, VA content is too small in the EVA, and the wet-process modified foaming shoe material hardness of starch is inclined
Greatly, VA content is too big, then roll banding is easy in operating procedure, or even can not foam.
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1
Step 1: the preparation of cornstarch wet process imping unsaturated monomers polymer
60g cornstarch is added in four mouthfuls of reaction kettles, and 120g distilled water is added, stirs transparence at a temperature of 85 DEG C
15min cools to 60 DEG C；The 1.2g initiator ammonium persulfate solution of 10ml distilled water dissolution is added, stirs 10min；60 DEG C of drops
Add hybrid reaction monomer (methyl methacrylate and vinylacetate=1:2) 20g, heating is maintained at 62 DEG C, continues that mixing is added dropwise
Reaction monomers 20g, heating are maintained at 64 DEG C, add hybrid reaction monomer 20g, 66 DEG C of reaction 2h of heating and heat preservation；It is warming up to 75
DEG C, unreacted monomer is steamed under condensing condition, and wet process starch graft copolymers lotion can be obtained.The solid content 43 of product ±
1%, pH value 6.0-6.5.
Step 2: the compound EVA of starch wet process graft polymers prepares foaming shoe material
Starch wet process imping unsaturated monomers polymer obtained in the first step is spray-dried, powdered starch is obtained and changes
Property polymer；Addition powdered starch polymer-modified 140g, EVA200g on mixer, 90 DEG C of mixing 4min, urea 6.5g,
Zinc oxide 5.8g, zinc stearate 3g, sodium bicarbonate 2g, foaming agent azodicarbonamide (AC) 7g, 90 DEG C of mixing 4min, then plus
Enter talcum powder 23g and dichloro benzosulfonic acid 3.6g and continue mixing 3min, adds crosslinking agent cumyl peroxide (DCP) 1.6g,
Mixing 1min discharging, is transferred completely into mill tabletting on open mill after discharging.Sheet material is cut into small pieces, in vulcanizing press upper mold
160 DEG C of temperature, starch wet process imping unsaturated monomers polymer and the composite foamed shoes of EVA can be obtained in foam, time 6min
Material.
Actual measurement physical index see the table below 1.
1 starch wet process imping unsaturated monomers polymer of table and EVA it is compound prepare foaming shoe material and common EVA measurement tie
Fruit
Embodiment 2
Step 1: the preparation of cornstarch wet process imping unsaturated monomers polymer
Corn 60g starch is added in four mouthfuls of reaction kettles, 120g distilled water is added, transparence 15min is stirred at a temperature of 85 DEG C,
Cool to 60 DEG C；The 1.2g initiator ammonium persulfate solution of 10ml distilled water dissolution is added, stirs 10min；60 DEG C of dropwise addition mixing
Reaction monomers (methyl methacrylate and vinylacetate=1:2) 17g, heating are maintained at 62 DEG C, continue that hybrid reaction list is added dropwise
Body 17g, heating are maintained at 64 DEG C, add hybrid reaction monomer 16g, 66 DEG C of reaction 2h of heating and heat preservation；75 DEG C are warming up to, condensation
Under the conditions of steam unreacted monomer, wet process starch graft copolymers lotion can be obtained.The solid content 41 ± 1% of product, pH value
For 6.0-6.5.
Step 2: the preparation of the compound EVA foam shoe material of the wet-process modified polymer of starch
The wet-process modified polymer of starch obtained in the first step is spray-dried, it is polymer-modified to obtain powdered starch；?
On mixer be added powdered starch polymer-modified 110g, EVA200g, 90 DEG C of mixing 3min, be added urea 6g, zinc oxide 5g,
Then talcum powder is added in zinc stearate 3g, sodium bicarbonate 2g, foaming agent azodicarbonamide (AC) 7.5g, 90 DEG C of mixing 4min
21g and dichloro benzosulfonic acid 3.6g continues mixing 3min, adds crosslinking agent cumyl peroxide (DCP) 1.6g, mixing 1min
Discharging, is transferred completely into mill tabletting on open mill after discharging.Sheet material is cut into small pieces, the moulded from foam on vulcanizing press,
160 DEG C of temperature, starch wet process imping unsaturated monomers polymer and the composite foamed footwear material of EVA can be obtained in time 6min.
Actual measurement physical index see the table below 2
2 starch wet process imping unsaturated monomers polymer of table and the composite foamed footwear material of EVA and common EVA measurement result
Embodiment 3
Step 1: the preparation of wheaten starch wet process imping unsaturated monomers polymer
60g wheaten starch is added in four mouthfuls of reaction kettles, and 120g distilled water is added, stirs transparence at a temperature of 85 DEG C
15min cools to 60 DEG C；The 1.3g initiator ammonium persulfate solution of 20ml distilled water dissolution is added, stirs 10min；60 DEG C of drops
Add hybrid reaction monomer (ethyl methacrylate and vinylacetate=1:2) 20g, heating is maintained at 62 DEG C, continues that mixing is added dropwise
Reaction monomers 20g, heating are maintained at 64 DEG C, add hybrid reaction monomer 20g, continue 66 DEG C of reaction 2h of heating and heat preservation；Heating
To 75 DEG C, unreacted monomer is steamed under condensing condition, wet process starch graft copolymers can be obtained.The solid content 43 of product ±
1%, pH value 6.0-6.5.
Step 2: the preparation of the compound EVA foam shoe material of the wet-process modified polymer of starch
Starch wet process graft polymers obtained in the first step is spray-dried, powdered starch graft polymers is obtained；?
On mixer be added powdered starch graft polymers 100g, EVA200g, 90 DEG C of mixing 3min, be added urea 6g, zinc oxide 5g,
Talcum powder is then added in zinc stearate 3.6g, sodium bicarbonate 2g, foaming agent azodicarbonamide (AC) 7g, 90 DEG C of mixing 4min
23g and dichloro benzosulfonic acid 3.5g continues mixing 3min, adds crosslinking agent cumyl peroxide (DCP) 1.5g, mixing 1min
Discharging, is transferred completely into mill tabletting on open mill after discharging.Sheet material is cut into small pieces, the moulded from foam on vulcanizing press,
160 DEG C of temperature, starch wet process imping unsaturated monomers polymer and the composite foamed footwear material of EVA can be obtained in time 6min.
Actual measurement physical index see the table below 3
3 starch wet process imping unsaturated monomers polymer of table and the composite foamed footwear material of EVA and common EVA measurement result
Embodiment 4
Step 1: the preparation of potato starch wet process imping unsaturated monomers polymer
60g potato starch is added in four mouthfuls of reaction kettles, and 130g distilled water is added, stirs transparence at a temperature of 85 DEG C
15min cools to 60 DEG C；The 1.4g initiator ammonium persulfate solution of 10ml distilled water dissolution is added, stirs 10min；60 DEG C of drops
Add reaction monomers (vinylacetate 100%) 20g, heating is maintained at 62 DEG C, continues that hybrid reaction monomer 20g is added dropwise, heating is kept
At 64 DEG C, hybrid reaction monomer 20g is added, continues 66 DEG C of reaction 2h of heating and heat preservation；75 DEG C are warming up to, is steamed under condensing condition
Wet process starch graft copolymers can be obtained in unreacted monomer.The solid content 42 ± 1% of product, pH value 6.0-6.5.
Step 2: the preparation of the compound EVA foam shoe material of the wet-process modified polymer of starch
The wet-process modified polymer of starch obtained in the first step is spray-dried, it is polymer-modified to obtain powdered starch；?
On mixer be added powdered starch polymer-modified 120g, EVA200g, 90 DEG C of mixing 3min, be added urea 7g, zinc oxide 6g,
Then talcum powder is added in zinc stearate 3.2g, sodium bicarbonate 2g, foaming agent azodicarbonamide (AC) 7g, 90 DEG C of mixing 4min
22g and dichlorobenzoic acid 3.5g continues mixing 3min, adds crosslinking agent cumyl peroxide (DCP) 1.5g, mixing 1min
Discharging, is transferred completely into mill tabletting on open mill.Sheet material is cut into small pieces, the moulded from foam on vulcanizing press, the time
7min, can be obtained starch wet process and be grafted organic polymerization of unsaturated monomers object and the composite foamed footwear material of EVA by 160 DEG C of temperature.
Actual measurement physical index see the table below 4
4 starch wet process imping unsaturated monomers polymer of table and the composite foamed footwear material of EVA and common EVA measurement result
The reduced parameter listed from table 1- table 4 it is found that the compound EVA foam shoe material of the wet-process modified polymer of starch of the invention suction
The index of water rate is substantially better than common EVA, and other indexs are almost the same.
The all parts by weight of component content according to the present invention.
Claims (9)
1. a kind of preparation method of the compound EVA foam shoe material of starch wet process graft modification, which is characterized in that
Step 1: starch wet process imping unsaturated monomers synthetic polymer emulsion is used；The raw material of use includes: according to parts by weight
Starch 100, imping unsaturated monomers 30-120, ammonium persulfate 1.0-4.0, distilled water 180-250；
Step 2: the polymer emulsion is spray-dried, starch wet process graft polymers dry powder is obtained；
Step 3: foaming is kneaded with the polymer dry powder and EVA and obtains compound EVA shoe material.
2. the compound EVA foam shoe material of starch wet process graft modification according to claim 1, which is characterized in that the raw material
Parts by weight it is preferred are as follows: imping unsaturated monomers: 40-100, initiator ammonium persulfate: 1.5-2.5, distilled water: 200-210.
3. the preparation method of the compound EVA foam shoe material of starch wet process graft modification according to claim 1, feature exist
In, the imping unsaturated monomers include: the combination of methyl methacrylate and vinylacetate, proportion 1:2--1:3 it
Between or ethyl methacrylate and vinylacetate combination, proportion is between 1:2-1:3 or vinylacetate list
Body.
4. the preparation method of the compound EVA foam shoe material of starch wet process graft modification according to claim 1, feature exist
In the starch includes the mixed of the arbitrary proportion of one or more of cornstarch, wheaten starch and potato starch
It is fit.
5. the preparation method of the compound EVA foam shoe material of starch wet process graft modification according to claim 1, feature exist
In, in the step one polymer emulsion synthetic method the following steps are included:
Starch is added in four mouthfuls of reaction kettles by the number, and the distilled water of the number is added by step 1), in 85 DEG C of temperature
Lower stirring transparence 15min, cools to 60 DEG C；
Step 2 is added the ammonium persulfate solution of the number, stirs evenly in the solution that step 1) obtains；
In the solution that step 2 obtains, at 60 DEG C, it is unsaturated that grafting is added dropwise using the reactive mode of gradient increased temperature in step 3)
Monomer divides the temperature gradient of several heatings, a part of imping unsaturated monomers are added dropwise in one temperature gradient of every increase, until
Whole imping unsaturated monomers are added dropwise；
Step 4), after imping unsaturated monomers are all added, the synthesis reaction temperature in strict control reaction kettle at 66 DEG C extremely
Reaction terminates, and reaction total time is 2.5-3.5h；
After step 5) synthetic reaction, 75 DEG C are warming up to, extra imping unsaturated monomers are steamed under condensing condition, that is, are made
Obtain the polymer emulsion, the extra imping unsaturated monomers recycling and reusing steamed.
6. the preparation method of the compound EVA foam shoe material of starch wet process graft modification according to claim 5, feature exist
In the reactive mode of the gradient increased temperature is completed in two steps:
Step 1: temperature reaction kettle temperature degree continues to be added dropwise to 62 DEG C when addition imping unsaturated monomers amount is the 1/3 of total amount
Imping unsaturated monomers；
Step 2: temperature reaction kettle temperature degree continues to be added dropwise to 64 DEG C when dropwise addition imping unsaturated monomers amount is the 2/3 of total amount
Imping unsaturated monomers to complete.
7. the preparation method of the compound EVA foam shoe material of starch wet process graft modification according to claim 1, feature exist
In, the step three " be kneaded and foamed with the polymer dry powder and EVA " method the following steps are included:
Powdered starch graft polymers and EVA, 90 DEG C of mixing 4min is added in step 1) on mixer, and urea, oxidation is added
Then talcum powder and dichloro-benzenes sulphur is added in zinc, zinc stearate, sodium bicarbonate, foaming agent azodicarbonamide, 90 DEG C of mixing 4min
Acid continues mixing 3min, adds crosslinking agent cumyl peroxide mixing 1min discharging；
Step 2, the mixture that step 1) is obtained is in open mill mill tabletting；
The mixture sheet material that step 2 obtains is cut into small pieces by step 3), the moulded from foam on vulcanizing press, time 6min,
160 DEG C of temperature, starch wet process can be obtained and be grafted organic unsaturated monomer and the composite foamed footwear material finished product of EVA.
8. the preparation method of the compound EVA foam shoe material of starch wet process graft modification according to claim 7, feature exist
In the parts by weight of material used in the method are as follows:
EVA:100 parts, powdered starch wet process graft polymers: 30-80 parts, urea: 2.0-4.5 parts,
Zinc oxide: 2.0-4.0 parts, sodium bicarbonate: 0.5-2.0 parts, zinc stearate: 1.0-2.5 parts, dichloro benzosulfonic acid: 1.6-2.8
Part, foaming agent azodicarbonamide: 3.0-7.0 parts, talcum powder: 10.0-12.0 parts, crosslinking agent cumyl peroxide: 0.5-
0.9 part；VA content is between 7.0%-22.0% in the EVA.
9. the compound EVA foam shoe material of starch wet process graft modification according to claim 8, which is characterized in that above-mentioned side
It is preferred using the parts by weight of material in method are as follows:
EVA:100 parts, powdered starch wet process graft polymers: 45-70 parts；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；Dichloro benzosulfonic acid: 1.8-2.5 parts；Two formyl of foaming agent azo
Amine: 3.5-6.0 parts；Talcum powder: 10.5-11.5 parts；Crosslinking agent cumyl peroxide: 0.7-0.8 parts.
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Effective date of registration: 20221220 Address after: 100015 No. 18 Jiangtaixi Road, Chaoyang District, Beijing Patentee after: CHINA LEATHER & FOOTWEAR RESEARCH INSTITUTE CO.,LTD. Patentee after: China light inspection and Certification Co.,Ltd. Address before: 100015 No. 18 Jiangtaixi Road, Chaoyang District, Beijing Patentee before: CHINA LEATHER & FOOTWEAR RESEARCH INSTITUTE CO.,LTD. |