CN105622987B - Ethylene-vinyl acetate copolymer mixture foaming material with high plant source content, and manufacturing method and application thereof - Google Patents
Ethylene-vinyl acetate copolymer mixture foaming material with high plant source content, and manufacturing method and application thereof Download PDFInfo
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- CN105622987B CN105622987B CN201510824180.XA CN201510824180A CN105622987B CN 105622987 B CN105622987 B CN 105622987B CN 201510824180 A CN201510824180 A CN 201510824180A CN 105622987 B CN105622987 B CN 105622987B
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- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 239000005038 ethylene vinyl acetate Substances 0.000 title claims abstract description 60
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000005187 foaming Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 239000007822 coupling agent Substances 0.000 claims abstract description 30
- 229920002472 Starch Polymers 0.000 claims abstract description 27
- 239000008107 starch Substances 0.000 claims abstract description 27
- 235000019698 starch Nutrition 0.000 claims abstract description 27
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 241000196324 Embryophyta Species 0.000 claims description 91
- 230000004048 modification Effects 0.000 claims description 40
- 238000012986 modification Methods 0.000 claims description 40
- 229920001971 elastomer Polymers 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 19
- 238000005461 lubrication Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- -1 aliphatic ester Chemical class 0.000 claims description 14
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 11
- 229920001038 ethylene copolymer Polymers 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000806 elastomer Substances 0.000 claims description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- 239000005060 rubber Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000004156 Azodicarbonamide Substances 0.000 claims description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 241001330002 Bambuseae Species 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000004645 aluminates Chemical class 0.000 claims description 5
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 5
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 4
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical compound CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical compound C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims description 2
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 claims 1
- 239000006260 foam Substances 0.000 claims 1
- 239000006261 foam material Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000000314 lubricant Substances 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- ACOGMWBDRJJKNB-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.CC(O)=O ACOGMWBDRJJKNB-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an ethylene-vinyl acetate copolymer mixture foaming material with high plant source content, which has the water content of less than 1 percent and comprises 30-60 percent by weight of uniformly mixed modified plant source powder, 40-70 percent by weight of ethylene-vinyl acetate copolymer, 0-30 percent by weight of toughening agent, less than 2 percent by weight of bridging agent and less than 10 percent by weight of foaming agent; the modified plant source powder comprises uniformly mixed plant source powder with the water content of less than 5%, a modifier, a plasticizer, a lubricant, a coupling agent and a functional auxiliary agent; according to the invention, the moisture content of the modified plant source powder is regulated and controlled to be below 1% in the manufacturing process, so that the problems that excessive moisture and water are easily absorbed by starch, the shrinkage rate of a foamed product is too large, the product is easily deformed and has defects or the quality is unstable can be solved.
Description
Technical field
The present invention relates to a kind of ethylene-vinyl acetate copolymer more particularly to a kind of ethyl vinyl acetates of high plant source content
Ethylene copolymer blend.
Background technique
Ethylene-vinyl acetate copolymer (Poly ethylene-co-vinyl acetate, EVA) is light and has good
Chemical stability, tackness, processability and resistance to ag(e)ing, be an excellent high molecular material, be particularly suited for use in footwear, slow
The foamed products such as punching pad.But its source relies primarily on petroleum, but as petroleum-based energy gradually decreases, and how to reduce and produces this
The petroleum dosage of class product is the big trend to be solved.
For raw material petroleum dosage needed for reducing ethylene-vinyl acetate copolymer, the ethene-vinyl acetate of starch is added
Copolymer correlation foamed products come into being, though starch can reach the efficiency for reducing quantity of plastics and foaming, make in production
During making, the starch of gelatinization is easy excessive moisture absorption, water suction, causes foamed products shrinking percentage big, product be easily deformed flaw or
It is the unstable problem of quality.And addition starch can be such that the physical property of product reduces, and need additionally to add bridging agent to remain good
Physical property, however bridging agent but makes foamed products be not easy to crush, and increases that recycling is difficult, noise more not environmentally is generated, so one
As ethylene-vinyl acetate copolymer foamed product content of starch only about 10~30%, alternative petroleum limitation.
In addition, the foamed products moisture content of addition starch is typically larger than 5%, high water content is easy to produce Signs of Mould,
Therefore additional addition mould inhibitor is needed, if but be used in the product for contacting human skin for a long time, there may be security concerns.
Summary of the invention
In order to solve, existing ethylene-vinyl acetate copolymer need to be dependent on bulk petroleum raw material, addition bridging agent causes to recycle
Property decline, foaming quality is unstable and need to additionally add the variety of problems such as mould inhibitor, the present invention provides a kind of second of high plant source content
Alkene-acetate ethylene copolymer mixture foamed material, the modification plant source powder it includes a mixed uniformly moisture content less than 1%
Weight percent 30~60%, ethylene-vinyl acetate copolymer weight percent 40~70%, toughener weight percent 0~30%,
2% or less bridging agent weight percent and 10% or less blowing agent composition weight percentage；Wherein, which includes equal
A plant source powder, modification agent, plasticizer, lubrication prescription, coupling agent and function additive of the even mixed water content less than 5%.
Wherein, which comprising mixed uniformly starch and is selected from bamboo powder, straw powder, bran powder or ground coffee
One or more mixtures；The modification agent includes maleic anhydride, ethylene acid esters, acrylate, isocyanates, aliphatic ester
One or more mixtures；The plasticizer includes one kind of ethylene glycol, glycerine, sorbierite, polyethylene glycol, citric acid, urea
Or a variety of mixtures；The lubrication prescription includes stearic acid, stearate, the one or more mixtures of polyethylene ceride；The coupling agent packet
Silane-containing coupling agent, titanate esters coupling agent, Aluminate coupling agent one or more mixtures；The bridging agent includes peroxidating two
Isopropylbenzene；The foaming agent includes azodicarbonamide or blowing promotor zinc oxide；And the function additive includes filler, colorant
Or fire retardant.
Wherein, 100 composition by weight of plant source powder；0.5~5 composition by weight of modification agent；1~20 weight of plasticizer
Component；0.5~2 composition by weight of lubrication prescription；0.5~5 composition by weight of coupling agent；And 2~10 composition by weight of function additive.
It wherein, further include 2~10 composition by weight of glue calcium or calcium chloride.
The present invention further provides a kind of ethylene-vinyl acetate copolymer mixture foamed materials of high plant source content
Manufacturing method, it includes: a dry plant source powder is to moisture content less than 5%；According to permanent order by plasticizer, modification agent,
Coupling agent, lubrication prescription and function additive and the plant source powder are uniformly added with 80~100 DEG C of temperature, 800~1200rpm of revolving speed
Enter and mixes 5~30 minutes to obtain a modification plant source powder of the moisture content less than 1% jointly；And by the modification plant source powder
Body, peroxide initiator and ethylene-vinyl acetate copolymer carry out the ethyl vinyl acetate that reactive grafting obtains a high plant source content
Ethylene copolymer blend master batch.
Wherein, further by the ethylene-vinyl acetate copolymer mixture master batch of the high plant source content and toughener, frame
Bridge agent, foaming agent and blowing promotor uniformly mix and be granulated with 100~140 DEG C of temperature high plant source content ethylene-vinegar
Sour ethylene copolymer blend foamed material, then the foamed material is shaped with shooting foaming or hot-pressing and foaming.
The present invention further provides a kind of footwear material and a kind of fender, is by the ethylene-of a high plant source content
Made by acetate ethylene copolymer mixture foamed material, the ethylene-vinyl acetate copolymer mixture of the high plant source content
Foamed material includes modification plant source powder weight percent 30~60%, ethylene-of the mixed uniformly moisture content less than 1%
Acetate ethylene copolymer weight percent 30~70%, toughener weight percent 0~30%, bridging agent weight percent 2%
Below and 10% or less blowing agent composition weight percentage；Wherein, which includes that mixed uniformly water content is small
In 5% a plant source powder, modification agent, plasticizer, lubrication prescription, coupling agent and function additive；Wherein toughener includes elasticity
Body, such as POE, TPE or rubber, such as BR, NR.
Wherein, 100 composition by weight of plant source powder；0.5~5 composition by weight of modification agent；1~20 weight of plasticizer
Component；0.5~2 composition by weight of lubrication prescription；0.5~5 composition by weight of coupling agent；And 2~10 composition by weight of function additive.
As shown in the above description, the invention has the following advantages that
1. the present invention substitutes part petroleum resources plastics using starch and botanical material, reach the dosage for reducing petroleum material.
2. due to ethylene-vinyl acetate copolymer (EVA) Yu Huishou physical crushing when can generate high temperature, if adding in the middle
Add starch and botanical material, makes the structure of EVA generate more defect points using high temperature, it is easier to which dispersion and fining increases
Add recyclability, improves existing the shortcomings that can not crushing recycling because add bridging agent, and relative to only 10~20% shallow lake existing EVA
Powder content, the present invention is by regulating and controlling the moisture content 1% of plant source powder hereinafter, making EVA that can add up to 40% or more in processing procedure
Plant-derived component, relatively it is existing addition starch EVA be more easier to crush, have more excellent recycling characteristic.
3. the relatively existing amyloid EVA of the present invention, in addition to it can add the starch of higher amount, further addition is planted
Object source powder, to improve the shortcomings that addition starch causes foamed products physical property to reduce, plant origin powder can increase foaming and produce
The physical property of product, abrasion performance can more increase the content of plant derived material of the present invention.
4. the present invention is easy to draw by regulating and controlling the moisture content 1% of plant source powder in processing procedure hereinafter, can improve starch
Moisture and moisture content are measured, causes foamed products shrinking percentage excessive, product is easily deformed flaw or the unstable problem of quality.
5. foamed products moisture content of the invention, less than 1%, more other biology product-deriveds have low hydroscopicity, it is unfavorable for mould
Increase, and Activities of Some Plants source material inherently has the function of beneficial bacteria, can reduce or be not required to addition mould inhibitor, increase the safety of product.
Detailed description of the invention
Fig. 1 is the ethylene-vinyl acetate copolymer mixture foaming material of the high plant source content of present pre-ferred embodiments
The manufacturing flow chart of material.
Specific embodiment
To understand convenient for those skilled in the art the technical solution of the utility model and beneficial effect, spy combines attached
Figure is described below specific embodiment.
As shown in Figure 1, the manufacture of the ethylene-vinyl acetate copolymer mixture foamed material of the high plant source content of the present invention
One preferred embodiment of method, it includes:
Step 1: will be comprising starch and selected from one or more mixtures of bamboo powder, straw powder, bran powder or ground coffee
A plant source powder first with oven drying to moisture content less than 5%；
Step 2: by the plant source powder be placed in high-speed mixer after, in stirring simultaneously, by modification agent, plasticizer, lubrication prescription,
The plant source powder is added according to permanent order in coupling agent and function additive, the process temperatures 80~120 DEG C, revolving speed 800~
1200rpm, uniform hybrid reaction 5~30 minutes obtain a modification plant source powder of the moisture content less than 1% eventually.It is aforementioned so-called
Permanent order is that plasticizer is first added to destroy starch script internal structure, after keeping it more loose, adds modification agent, allow its not
Only to be reacted with the starch polymer on surface, more can on a small quantity with internal starch generate esterification, finally add coupling agent,
Lubrication prescription and function additive are mixed together into high-speed mixer.
The above-mentioned modification agent include maleic anhydride, ethylene acid esters, acrylate, isocyanates, aliphatic ester one kind or
A variety of mixtures, the plasticizer include ethylene glycol, glycerine, sorbierite, polyethylene glycol, citric acid, urea it is one or more
Mixture, the lubrication prescription include stearic acid, stearate, the one or more mixtures of polyethylene ceride, which includes silane
Coupling agent, titanate esters coupling agent, Aluminate coupling agent one or more mixtures.The aforementioned plant source powder and each addition
The additive amount of agent is 100 composition by weight of plant source powder, 0.5~5 composition by weight of modification agent, 1~20 weight of plasticizer
Component, 0.5~2 composition by weight of lubrication prescription, 0.5~5 composition by weight of coupling agent, can further add such as glue calcium or calcium chloride
Deng addition 2~10 composition by weight of auxiliary agent.
Step 3: the modification plant source powder and ethylene-vinyl acetate copolymer being carried out in twin screw compounder anti-
It should be grafted, obtain the ethylene-vinyl acetate copolymer mixture master batch of a high plant source content.Wherein, the modification plant source powder
The weight percent content of body is 30~60%, which is 40~70%.Second above-mentioned
When alkene-acetate ethylene copolymer addition, a small amount of polyethylene (Polyethylene, PE) can be further added.
Step 4: by the ethylene-vinyl acetate copolymer mixture master batch of the high plant source content and toughener weight percent
Machine is taken in benefit than 2% or less 0~30%, bridging agent weight percent, foaming agent and 10% or less blowing promotor weight percent
Uniformly mix and be granulated with 100~140 DEG C of temperature high plant source content ethylene-vinyl acetate copolymer mixture foaming
Material, then the material is produced to the ethylene-vinyl acetate copolymer of high plant source content with shooting foaming or hot-pressing and foaming processing procedure
The foamed products of mixture, such as foamed thin sheet, footwear material or fender.Wherein, which includes cumyl peroxide
(DCP), the toughener includes elastomer, such as POE elastomer, TPE elastomer or rubber, such as butadiene rubber (Butadiene
Rubber, BR) or natural rubber (Nature Rubber, NR), which includes azodicarbonamide (AC foaming agent), should
Blowing promotor includes zinc oxide (ZnO).
Table 1 is please referred to, is the formula table of present pre-ferred embodiments:
Table 1
| Material (unit: component) | Embodiment A | Embodiment B | Embodiment C |
| EVA 629 | 30 | 20 | 25 |
| EVA 633 | 10 | 20 | 10 |
| Modify plant source powder | 45 | 45 | 50 |
| Other materials | 15 | 15 | 15 |
Other materials described in table 1 includes AC foaming agent, DCP bridging agent, zinc oxide, zinc stearate and elastomer or rubber
Glue；The modification plant source powder includes 100 composition by weight of plant source powder, 0.5~5 composition by weight of modification agent, plasticizer 1~20
Composition by weight, 2~10 composition by weight of 0.5~2 composition by weight of lubrication prescription, 0.5~5 composition by weight of coupling agent and function additive；It should
Function additive can be filler, colorant or fire retardant etc. and add according to the property requirements of final products.
Table 2 is please referred to, is present pre-ferred embodiments compared with the physical property measurement result of existing EVA foamed products, by
Test result it was found that, the physical property of various embodiments of the present invention is suitable with the physical property of existing EVA foaming material, not because add plant source
Material and the physical property of product is reduced, but can reach substitution petroleum resources plastics advantage.
Table 2
As shown in the above description, the invention has the following advantages that
1. the present invention substitutes part petroleum resources plastics using starch and botanical material, reaches and reduce petroleum material
Dosage.
2. due to ethylene-vinyl acetate copolymer (EVA) Yu Huishou physical crushing when can generate high temperature, if adding in the middle
Add starch and botanical material, makes the structure of EVA generate more defect points using high temperature, it is easier to which dispersion and fining increases
Add recyclability, improves existing the shortcomings that can not crushing recycling because adding bridging agent.And relative to existing EVA only 10~20% form sediment
Powder content, the present invention is by regulating and controlling the moisture content 1% of plant source powder hereinafter, making EVA that can add up to 40% or more in processing procedure
Plant-derived component, relatively it is existing addition starch EVA be more easier to crush, have more excellent recycling characteristic.
3. the relatively existing amyloid EVA of the present invention, in addition to it can add the starch of higher amount, further addition is planted
Object source powder, to improve the shortcomings that addition starch causes foamed products physical property to reduce, plant origin powder can increase foaming and produce
The physical property of product, abrasion performance can more increase the content of plant derived material of the present invention.
4. the present invention is easy to draw by regulating and controlling the moisture content 1% of plant source powder in processing procedure hereinafter, can improve starch
Moisture and moisture content are measured, causes foamed products shrinking percentage excessive, product, which is easily deformed, flaw or the unstable problem of quality occurs.
5. foamed products moisture content of the invention, less than 1%, more other biology product-deriveds have low hydroscopicity, it is unfavorable for mould
Bacterium increases, and Activities of Some Plants source material inherently has the function of beneficial bacteria, can reduce or be not required to addition mould inhibitor, increase the peace of product
Quan Xing.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of ethylene-vinyl acetate copolymer mixture foamed material of high plant source content, which is characterized in that it includes equal
Modification plant source powder weight percent 30~60%, peroxide initiator, second of one moisture content of even mixing less than 1%
Alkene-acetate ethylene copolymer weight percent 40~70%, toughener weight percent 0~30%, bridging agent weight percent
2% or less and 10% or less blowing agent composition weight percentage；Wherein, the modification plant source powder includes mixed uniformly aqueous
Measure a plant source powder, modification agent, plasticizer, lubrication prescription, coupling agent and the function additive less than 5%；Wherein, by the modification
Plant source powder, peroxide initiator and ethylene-vinyl acetate copolymer carry out reactive grafting and obtain a high plant source content
Ethylene-vinyl acetate copolymer mixture master batch；The ethylene-vinyl acetate copolymer mixture of the high plant source content is female
Grain is uniformly mixed and is granulated and to be obtained high plant source with 100~140 DEG C of temperature with toughener, bridging agent, foaming agent and blowing promotor
The ethylene-vinyl acetate copolymer mixture foamed material of content, then the foamed material is sent out with shooting foaming or hot pressing
Foam forming.
2. the ethylene-vinyl acetate copolymer mixture foamed material of high plant source content as described in claim 1, feature
It is, in which:
The plant source powder includes mixed uniformly starch and one kind selected from bamboo powder, straw powder, bran powder or ground coffee
Or a variety of mixtures；
The modification agent is mixed comprising maleic anhydride, ethylene acid esters, acrylate, isocyanates, the one or more of aliphatic ester
Close object；
The plasticizer includes one or more mixing of ethylene glycol, glycerine, sorbierite, polyethylene glycol, citric acid, urea
Object；
The lubrication prescription includes stearic acid, stearate, the one or more mixtures of polyethylene ceride；
The coupling agent includes one or more mixtures of silane coupling agent, titanate esters coupling agent, Aluminate coupling agent；
The bridging agent includes cumyl peroxide；
The foaming agent includes azodicarbonamide and blowing promotor zinc oxide；
The function additive includes filler, colorant or fire retardant；
The toughener includes POE elastomer, TPE elastomer or rubber；And
The rubber includes butadiene rubber or natural rubber.
3. the ethylene-vinyl acetate copolymer mixture foamed material of high plant source content as claimed in claim 1 or 2,
It is characterized in that, includes 100 composition by weight of plant source powder, 0.5~5 weight of the modification agent in the modification plant source powder
Measure component, 1~20 composition by weight of the plasticizer, 0.5~2 composition by weight of the lubrication prescription, 0.5~5 weight group of the coupling agent
Part and 2~10 composition by weight of the function additive.
4. the ethylene-vinyl acetate copolymer mixture foamed material of high plant source content as claimed in claim 2, feature
It is, further includes 2~10 composition by weight of glue calcium or calcium chloride.
5. a kind of manufacturing method of the ethylene-vinyl acetate copolymer mixture foamed material of high plant source content, feature exist
In, it includes:
A dry plant source powder is to moisture content less than 5%；
According to permanent order by plasticizer, modification agent, coupling agent, lubrication prescription and function additive and the plant source powder with temperature 80
~100 DEG C, 800~1200rpm of revolving speed are uniformly added into and mix 5~30 minutes to obtain a modification plant of the moisture content less than 1% jointly
Material resource powder；
The modification plant source powder, peroxide initiator and ethylene-vinyl acetate copolymer progress reactive grafting are obtained one
The ethylene-vinyl acetate copolymer mixture master batch of high plant source content；And
By the ethylene-vinyl acetate copolymer mixture master batch of the high plant source content and toughener, bridging agent, foaming agent and
Blowing promotor uniformly mix and be granulated with 100~140 DEG C of temperature high plant source content ethylene-vinyl acetate copolymer it is mixed
Object foamed material is closed, then the foamed material is shaped with shooting foaming or hot-pressing and foaming.
6. a kind of footwear material, which is characterized in that it is foamed by the ethylene-vinyl acetate copolymer mixture of a high plant source content
Made by material, the ethylene-vinyl acetate copolymer mixture foamed material of the high plant source content includes mixed uniformly one
Modification plant source powder weight percent 30~60%, peroxide initiator, ethene-vinyl acetate of the moisture content less than 1%
Copolymer weight percentage 40~70%, toughener weight percent 0~30%, 2% or less bridging agent weight percent and
10% or less blowing agent composition weight percentage；Wherein, the modification plant source powder includes mixed uniformly water content less than 5%
One plant source powder, modification agent, plasticizer, lubrication prescription, coupling agent and function additive；Wherein, by the modification plant source powder,
Peroxide initiator and ethylene-vinyl acetate copolymer carry out the ethyl vinyl acetate second that reactive grafting obtains a high plant source content
Alkene copolymer mixture master batch；By the ethylene-vinyl acetate copolymer mixture master batch of the high plant source content and toughener,
Bridging agent, foaming agent and blowing promotor uniformly mix and be granulated with 100~140 DEG C of temperature high plant source content ethylene-
Acetate ethylene copolymer mixture foamed material, then the foamed material is configured to the shoes with shooting foaming or hot-pressing and foaming
Material.
7. footwear material as claimed in claim 6, which is characterized in that wherein:
100 composition by weight of plant source powder, comprising mixed uniformly starch and selected from bamboo powder, straw powder, bran powder or
One or more mixtures of ground coffee；
0.5~5 composition by weight of modification agent includes maleic anhydride, ethylene acid esters, acrylate, isocyanates, aliphatic ester
One or more mixtures；
1~20 composition by weight of the plasticizer, comprising ethylene glycol, glycerine, sorbierite, polyethylene glycol, citric acid, urea one
Kind or a variety of mixtures；
0.5~2 composition by weight of lubrication prescription includes stearic acid, stearate, the one or more mixtures of polyethylene ceride；
0.5~5 composition by weight of coupling agent, comprising silane coupling agent, titanate esters coupling agent, Aluminate coupling agent one kind or
A variety of mixtures；
The bridging agent includes cumyl peroxide；
The foaming agent includes azodicarbonamide and blowing promotor zinc oxide；
2~10 composition by weight of function additive includes filler, colorant or fire retardant；
The toughener includes POE elastomer, TPE elastomer or rubber；And
The rubber includes butadiene rubber or natural rubber.
8. a kind of fender, which is characterized in that it is sent out by the ethylene-vinyl acetate copolymer mixture of a high plant source content
Made by foam material, the ethylene-vinyl acetate copolymer mixture foamed material of the high plant source content includes mixed uniformly
Modification plant source powder weight percent 30~60%, peroxide initiator, ethyl vinyl acetate second of one moisture content less than 1%
Alkene copolymer weight percent 40~70%, toughener weight percent 0~30%, 2% or less bridging agent weight percent with
And below 10% weight percent of foaming agent；Wherein, the modification plant source powder includes mixed uniformly water content less than 5%
A plant source powder, modification agent, plasticizer, lubrication prescription, coupling agent and function additive；Wherein, by the modification plant source powder
Body, peroxide initiator and ethylene-vinyl acetate copolymer carry out the ethyl vinyl acetate that reactive grafting obtains a high plant source content
Ethylene copolymer blend master batch；By the ethylene-vinyl acetate copolymer mixture master batch and toughening of the high plant source content
Agent, bridging agent, foaming agent and blowing promotor uniformly mix and be granulated with 100~140 DEG C of temperature high plant source content second
Alkene-acetate ethylene copolymer mixture foamed material, then the foamed material is configured to shooting foaming or hot-pressing and foaming
The fender.
9. fender as claimed in claim 8, which is characterized in that wherein:
100 composition by weight of plant source powder, comprising mixed uniformly starch and selected from bamboo powder, straw powder, bran powder or
One or more mixtures of ground coffee；
0.5~5 composition by weight of modification agent includes maleic anhydride, ethylene acid esters, acrylate, isocyanates, aliphatic ester
One or more mixtures；
1~20 composition by weight of the plasticizer, comprising ethylene glycol, glycerine, sorbierite, polyethylene glycol, citric acid, urea one
Kind or a variety of mixtures；
0.5~2 composition by weight of lubrication prescription includes stearic acid, stearate, the one or more mixtures of polyethylene ceride；
0.5~5 composition by weight of coupling agent, comprising silane coupling agent, titanate esters coupling agent, Aluminate coupling agent one kind or
A variety of mixtures；
The bridging agent includes cumyl peroxide；
The foaming agent includes azodicarbonamide and blowing promotor zinc oxide；
2~10 composition by weight of function additive includes filler, colorant or fire retardant；
The toughener includes POE elastomer, TPE elastomer or rubber；And
The rubber includes butadiene rubber or natural rubber.
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| TW103140747 | 2014-11-25 | ||
| TW103140747 | 2014-11-25 |
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| CN107603001B (en) * | 2016-07-11 | 2020-08-11 | 鸿明环保科技股份有限公司 | Low-foaming-ratio biomass composite foamed sheet and manufacturing method thereof |
| CN106317744B (en) * | 2016-08-18 | 2017-07-07 | 福建斯达新材料科技有限公司 | The even processing method and the material of side injection material for sole of shoe and even side injection shoes and processing method |
| CN106800790B (en) * | 2016-12-23 | 2018-01-12 | 盐城工学院 | A kind of heat preservation and soundproof moisture-proof composite material for building and preparation method thereof |
| CN115340721A (en) * | 2022-09-01 | 2022-11-15 | 东莞市国立飞织制品有限公司 | Shoe material containing bio-based EVA (ethylene vinyl acetate) and preparation method and application thereof |
| CN115594993B (en) * | 2022-10-12 | 2023-12-05 | 江西广源化工有限责任公司 | Aluminate coupling agent and preparation method and application thereof |
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| MY132134A (en) * | 1995-03-14 | 2007-09-28 | Daicel Chem | Barrier composite films and a method for producing the same |
| JPH1076593A (en) * | 1996-09-03 | 1998-03-24 | Daicel Chem Ind Ltd | Barrier composite film and its manufacture |
| FR2947558B1 (en) * | 2009-07-03 | 2011-08-19 | Total Raffinage Marketing | TERPOLYMER AND ETHYLENE / VINYL ACETATE / UNSATURATED ESTERS AS ADDITIVES TO ENHANCE COLD LIQUID HYDROCARBONS LIKE MEDIUM DISTILLATES AND FUELS OR COMBUSTIBLES |
| CN102019705B (en) * | 2009-09-21 | 2013-07-31 | 逢甲大学 | Method for manufacturing biobased macromolecule shoe material |
| CN102504398B (en) * | 2011-10-11 | 2013-11-27 | 中国人民解放军总后勤部军需装备研究所 | Modified EVA foaming body and preparation method and application of same |
| CN102786734B (en) * | 2012-07-24 | 2014-08-06 | 福州大学 | Composite foamed shoe material formed by polyolefin and polyolefin elastomers grafted with starch in dry process |
| SG10201704213XA (en) * | 2012-12-21 | 2017-06-29 | Quarzwerke Gmbh | Thermotropic polymers |
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