CN100569839C - Ozone oxidation improves the method for EVA/PE blending foaming material performance - Google Patents
Ozone oxidation improves the method for EVA/PE blending foaming material performance Download PDFInfo
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- CN100569839C CN100569839C CNB2007100499984A CN200710049998A CN100569839C CN 100569839 C CN100569839 C CN 100569839C CN B2007100499984 A CNB2007100499984 A CN B2007100499984A CN 200710049998 A CN200710049998 A CN 200710049998A CN 100569839 C CN100569839 C CN 100569839C
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Abstract
The present invention discloses the method that a kind of ozone oxidation improves the EVA/PE blending foaming material performance.(a) polyethylene (PE) powder is carried out ozone Oxidation Treatment under 20～90 ℃ of conditions, concentration of ozone gas 10～75mg/L, ozone oxidation time 10～180min; (b) 90: 10～60: 40 uniform mixing of the polyethylene of ethylene-vinyl acetate copolymer (EVA) and above-mentioned ozone Oxidation Treatment being pressed mass ratio, get above-mentioned blend 100 mass parts, dicumyl peroxide (DCP) 0.5～0.8 mass parts, whipping agent 2.0～4.0 mass parts, zinc oxide (ZnO) 0.4～1.2 mass parts, stearic acid (HSt) 0～0.6 mass parts, Zinic stearas (ZnSt) 0～0.6 mass parts and inorganic mineral powder 0～10 mass parts, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, mixing time is 10～15min, obtains the EVA/PE blended complex.(c) place vulcanizing press to carry out moulded from foam above-mentioned blended complex, blowing temperature is that 160～170 ℃, molding pressure are 10～15MPa, and the moulded from foam time is 15～35min, promptly makes the EVA/PE blending foaming material.
Description
Technical field:
The present invention relates to a kind of preparation method of EVA/PE blending foaming material, belong to polymer processing field.
Background technology:
Ethene-vinyl acetate copolymerized resin (EVA) is the thermoplastic elastic material of a class excellent performance, because the existence of the vinyl acetate of random copolymerization in the molecular chain structure, the regularity and the degree of crystallinity of PE molecular chain are declined to a great extent, the kindliness of molecular chain improves, the thermal motion ability strengthens, show as snappiness on the macroscopic view, EVA can be used for making the obturator-type foam materials of high foamability, has light weight, shockproof, soft, rebound resilience is good, compressive set is little, performances such as good weatherability, be widely used in industry, construction industry, water industry is especially in the material for shoes field.But EVA foam material cost is higher, the physical strength of product, and tearing toughness is relatively poor, has limited the further expansion of its Application Areas.
Polyvinyl resin (PE) cost is cheap than EVA, the PE foam materials is tough, flexible good, corrosion-resistant simultaneously, adopt PE that the EVA foam material is carried out blending and modifying and not only can improve its over-all properties, obtain the foam materials of less dense, and can effectively reduce product cost, broadened application scope.Though contain the PE structural unit on the EVA macromolecular chain, but, the ethylene-vinyl acetate copolymerization mode of synthetic EVA is random copolymerization, vinyl acetate between to for plastic ester units polarity is stronger, the consistency of the non-polar polymer PE homopolar polymer EVA of the whole degree of higher rule segment is unsatisfactory, for density and the higher light foam material of performance requriements, how to reach good phase dispersion effect and phase interface bonding strength, and then obtain the very important important factor of EVA/PE blending foaming material that uniform obturator-type foam structure is the preparation high comprehensive performance.But this problem not being furtherd investigate in the common application, only is to adopt simple blend scheme [research of LDPE/EVA Foamed Sole Materials, Lian RongBing, Zhang Weiqin, leaf Shengjing city, plastics industry, the 33rd the 5th phase 2005 of volume; The development of LDPE/EVA foam material, Li Xuefeng, Peng Shaoxian, Li Huaxing, modern plastics processed and applied, the 12nd the 3rd phase 2000 of volume; The development of EVA/PE foam material, Wang Huimin, Kou Yazhi, Ni officers and people print during chemical industry, the phase 1999].CN1370798 discloses the method that a kind of cross-linking radiation prepares the ethylene-vinyl acetate copolymer/linear low-density polyethylene porous plastics, but this method is not done improvement to EVA, PE consistency; CN1970611 discloses a kind of preparation method of EVA/PE/ starch composite foam material, by adopting surface-modifying agent to improve EVA, PE interfacial adhesion, but the adding of surface-modifying agent is difficult to change the high-regularity of PE macromolecular chain, modified effect is not obvious, not only increased product cost, its production process also pollutes environment easily simultaneously.
Summary of the invention:
Main purpose of the present invention is the method that a kind of EVA/PE of raising foam performance is provided at the deficiencies in the prior art.Pass through ozonation technology, on the PE macromolecular chain, directly introduce and contain the oxygen polar group, thereby improve polarity, the reduction segment regularity of PE, optimized the consistency of PE with EVA, adopt this method to prepare lightweight EVA/PE blending foaming material, when improving the eva foam over-all properties, obtaining the less dense foam materials, can effectively reduce product cost, the broadened application scope is particularly useful for the production application of light foam footwear material.
Purpose of the present invention is realized by following technical measures.Wherein said raw material umber is parts by weight except that specified otherwise.
Ozone oxidation improves the method for EVA/PE blending foaming material performance:
(1) polyethylene (PE) powder is carried out ozone Oxidation Treatment under 20～90 ℃ of conditions, concentration of ozone gas 10～75mg/L, ozone oxidation time 10～180min;
(2) 90: 10～60: 40 uniform mixing of the polyethylene of ethylene-vinyl acetate copolymer (EVA) and above-mentioned ozone Oxidation Treatment being pressed mass ratio, get above-mentioned blend 100 mass parts, dicumyl peroxide (DCP) 0.5～0.8 mass parts, whipping agent 2.0～4.0 mass parts, zinc oxide (ZnO) 0.4～1.2 mass parts, stearic acid (HSt) 0～0.6 mass parts, Zinic stearas (ZnSt) 0～0.6 mass parts and inorganic mineral powder 0～10 mass parts, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, mixing time is 10～15min, obtains the EVA/PE blended complex.
(3) place vulcanizing press to carry out moulded from foam above-mentioned blended complex, blowing temperature is that 160～170 ℃, molding pressure are 10～15MPa, and the moulded from foam time is 15～35min, can make the EVA/PE blending foaming material.
Wherein, polyethylene is that molecular weight is any one in 10,000～1,000,000 new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE) or the high density polyethylene(HDPE) (HDPE), wherein preferred new LDPE (film grade).
EVA is 12～30% ethylene-vinyl acetate random copolymers for VA content, and wherein preferred VA content is 21% EVA.
Whipping agent is Cellmic C 121 (AC) or AC whipping agent and N, and N-2 dinitroso five methyne tetramines (DPT) were by 1: 4～4: the 1 composite mixed foaming agents of part by weight.
The inorganic mineral powder is a particle diameter less than any one or its mixture, wherein any one in preferably talc powder, the lime carbonate in the talcum powder of 100 μ m, lime carbonate, wilkinite, the kaolin.
The blending foaming material test performance is as shown in table 1, accompanying drawing is the stereoscan photograph of its abscess microtexture, the result shows, ozone Oxidation Treatment can effectively improve the consistency of PE with EVA, the cell uniformity of blending foaming material be improved significantly, density reduces, and the tensile strength of material, elongation at break and permanent compression set also improve, and specific tenacity significantly improves.
The alternative EVA foam material of EVA/PE blending foaming material is widely used in industry, building, field such as civilian, is particularly useful for the material for sole of shoe of lightweight sports shoes.
Present method has following obvious advantage:
1. by ozone oxidation PE, significantly improved EVA/PE two-phase consistency, the blending foaming material cell uniformity improves, and density is lower, improved combination properties, and specific tenacity significantly improves.
2. with respect to the eva foam material, the blending foaming material cost significantly reduces.
3. easy and simple to handle, the environmentally safe of this method and be easy to suitability for industrialized production.
Description of drawings
Fig. 1: the micro-electromicroscopic photograph of comparison example sample
The micro-electromicroscopic photograph of Fig. 2: embodiment 1 sample
The micro-electromicroscopic photograph of Fig. 3: embodiment 2 samples
Embodiment
Below be the present invention to be specifically described by embodiment; be necessary to be pointed out that at this following examples can only be used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1: LDPE is inserted in the ozone reactor 80 ℃ of temperature of reaction, react 40min under the ozone concn 55mg/L condition, obtain o-LDPE, with o-LDPE 30g, EVA 70g, DCP 0.65g, AC whipping agent 3.2g, 0.8 part of ZnO, HSt 0.4g and ZnSt 0.4g, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, slice behind mixing 10～15min, the EVA/PE blended complex that obtains places vulcanizing press to carry out moulded from foam, blowing temperature is 160～170 ℃, molding pressure is 10～15MPa, the moulded from foam time is 15～35min, makes EVA/PE blend foam materials.
Embodiment 2: LDPE is inserted in the ozone reactor 80 ℃ of temperature of reaction, react 40min under the ozone concn 55mg/L condition, obtain o-LDPE, with o-LDPE 15g, EVA 85g, DCP 0.65g, AC whipping agent 3.2g, 0.8 part of ZnO, HSt 0.4g and ZnSt 0.4g, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, slice behind mixing 10～15min, the EVA/PE blended complex that obtains places vulcanizing press to carry out moulded from foam, blowing temperature is 160～170 ℃, molding pressure is 10～15MPa, the moulded from foam time is 15～35min, makes EVA/PE blend foam materials.
Embodiment 3: LDPE is inserted in the ozone reactor 80 ℃ of temperature of reaction, react 60min under the ozone concn 55mg/L condition, obtain o-LDPE, with o-LDPE 30g, EVA 70g, DCP 0.65g, AC whipping agent 3.2g, 0.8 part of ZnO, HSt 0.4g and ZnSt 0.4g, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, slice behind mixing 10～15min, the EVA/PE blended complex that obtains places vulcanizing press to carry out moulded from foam, blowing temperature is 160～170 ℃, molding pressure is 10～15MPa, the moulded from foam time is 15～35min, makes EVA/PE blend foam materials.
Embodiment 4; LLDPE is inserted in the ozone reactor 60 ℃ of temperature of reaction, react 180min under the ozone concn 10mg/L condition, obtain o-LLDPE, with o-LLDPE 50g, EVA 50g, DCP 0.60g, AC whipping agent 2.8g, ZnO 1.0g, HSt 0.5g, ZnSt 0.5g, talcum powder 10g, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, slice behind mixing 10～1 5min, the EVA/PE blended complex that obtains places vulcanizing press to carry out moulded from foam, blowing temperature is 160～170 ℃, molding pressure is 10～15MPa, the moulded from foam time is 15～35min, makes EVA/PE blend foam materials.
Embodiment 5: HDPE is inserted in the ozone reactor 25 ℃ of temperature of reaction, react 120min under the ozone concn 75mg/L condition, obtain o-HDPE, with o-HDPE 60g, EVA 40g, DCP 0.60g, AC-DPT composite foamable agent 4.8g, ZnO 1.2g, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, slice behind mixing 10～15min, the EVA/PE blended complex that obtains places vulcanizing press to carry out moulded from foam, blowing temperature is 160～170 ℃, molding pressure is 10～15MPa, the moulded from foam time is 15～35min, makes EVA/PE blend foam materials.
Embodiment 6: LDPE is inserted in the ozone reactor 80 ℃ of temperature of reaction, react 40min under the ozone concn 55mg/L condition, obtain o-LDPE, with o-LDPE 30g, EVA 70g, DCP 0.6g, AC-DPT composite foamable agent 5.2g, 0.4 part of ZnO, HSt 0.2g, ZnSt 0.2g, talcum powder 10g, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, slice behind mixing 10～15min, the EVA/PE blended complex that obtains places vulcanizing press to carry out moulded from foam, blowing temperature is 160～170 ℃, molding pressure is 10～15MPa, the moulded from foam time is 15～35min, makes EVA/PE blend foam materials.
Comparison example: will be without LDPE 30g, EVA 70g, DCP 0.65g, 0.8 part of AC whipping agent 3.2g, ZnO, HSt 0.4g and the ZnSt 0.4g of ozone Oxidation Treatment, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, slice behind mixing 10～15min, the EVA/PE blended complex that obtains places vulcanizing press to carry out moulded from foam, blowing temperature is that 160～170 ℃, molding pressure are 10～15MPa, the moulded from foam time is 15～35min, makes EVA/PE blend foam materials.
The physics and the mechanical property of table 1.EVA/PE blending foaming material
Claims (5)
1. ozone oxidation improves the method for EVA/PE blending foaming material performance, it is characterized in that:
(1) polyethylene powder is carried out ozone Oxidation Treatment under 20～90 ℃ of conditions, concentration of ozone gas 10～75mg/L, ozone oxidation time 10～180min;
(2) 90: 10～60: 40 uniform mixing of the polyethylene of ethylene-vinyl acetate copolymer and above-mentioned ozone Oxidation Treatment being pressed mass ratio, get above-mentioned blend 100 mass parts, dicumyl peroxide 0.5～0.8 mass parts, Cellmic C 121 or Cellmic C 121 and N, N-2 dinitroso five methyne tetramines were by 1: 4～4: 1 composite mixed foaming agent 2.0～4.0 mass parts of part by weight, zinc oxide 0.4～1.2 mass parts, stearic acid 0～0.6 mass parts, Zinic stearas 0～0.6 mass parts and particle diameter are less than the talcum powder of 100 μ m, lime carbonate, wilkinite, in the kaolin any one or its mixture 0～10 mass parts, add on the double roll mill and carry out melting mixing, melting temperature is 105～130 ℃, mixing time is 10～15min, obtains the EVA/PE blended complex;
(3) place vulcanizing press to carry out moulded from foam above-mentioned blended complex, blowing temperature is that 160～170 ℃, molding pressure are 10～15MPa, and the moulded from foam time is 15～35min, can make the EVA/PE blending foaming material.
2. ozone oxidation improves the method for EVA/PE blending foaming material performance according to claim 1, it is characterized in that polyethylene is that molecular weight is any one in 10,000～1,000,000 new LDPE (film grade), linear low density polyethylene or the high density polyethylene(HDPE).
3. ozone oxidation improves the method for EVA/PE blending foaming material performance according to claim 1, it is characterized in that EVA is 12～30% ethylene-vinyl acetate random copolymers for VA content.
4. the EVA/PE blending foaming material for preparing of method according to claim 1.
5. as the purposes of EVA/PE blending foaming material as described in the claim 4, it is characterized in that this blending foaming material is used for the footwear material aspect of industry, building, civilian all kinds of buffering and shock preventing materials, wrapping material, lagging material, sports shoes.
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| CN101423632B (en) * | 2007-10-29 | 2011-08-17 | 比亚迪股份有限公司 | Composition for foaming material and foaming material |
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| CN103113653B (en) * | 2013-02-06 | 2015-05-13 | 常州大学 | HDPE (high-density polyethylene)/LDPE (low-density polyethylene) blended foam material and preparation method thereof |
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| CN104231415A (en) * | 2014-10-08 | 2014-12-24 | 金猴集团威海鞋业有限公司 | Modified EVA foaming shoe material containing hemp powder and preparation method thereof |
| US9694521B2 (en) * | 2015-03-23 | 2017-07-04 | Yeti Coolers, Llc | Ozone adhesion process for insulating container manufacture |
| CN104788800B (en) * | 2015-05-04 | 2017-07-04 | 安庆泰亚鞋业有限公司 | EVA foam shoe material and its manufacture method between closed pore and perforate |
| CN105085725A (en) * | 2015-08-24 | 2015-11-25 | 华南理工大学 | Device and method for preparing oxidized polypropylene through ozone oxidation process |
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| CN112795080B (en) * | 2021-02-03 | 2022-10-14 | 长链轻材(南京)科技有限公司 | EVA/LDPE supercritical solid foaming material and preparation method thereof |
| CN115057954A (en) * | 2022-05-13 | 2022-09-16 | 华南理工大学 | Ozone-based controllable functionalized polyethylene resin and preparation method thereof |
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| CN1032943A (en) * | 1988-06-30 | 1989-05-17 | 哈尔滨市泡沫塑料制品厂 | A kind of polyethylene foams |
| CN1087575A (en) * | 1992-11-30 | 1994-06-08 | 聚上企业股份有限公司 | The direct foaming of ethylene-vinyl acetate copolymer integral forming method of sole |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032943A (en) * | 1988-06-30 | 1989-05-17 | 哈尔滨市泡沫塑料制品厂 | A kind of polyethylene foams |
| CN1087575A (en) * | 1992-11-30 | 1994-06-08 | 聚上企业股份有限公司 | The direct foaming of ethylene-vinyl acetate copolymer integral forming method of sole |
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