CN102718996B - Ultra-light foamed TPR material synthesized of modified thermoplastic rubber and preparation method thereof - Google Patents
Ultra-light foamed TPR material synthesized of modified thermoplastic rubber and preparation method thereof Download PDFInfo
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- CN102718996B CN102718996B CN201210205035XA CN201210205035A CN102718996B CN 102718996 B CN102718996 B CN 102718996B CN 201210205035X A CN201210205035X A CN 201210205035XA CN 201210205035 A CN201210205035 A CN 201210205035A CN 102718996 B CN102718996 B CN 102718996B
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- paracril
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Abstract
The invention discloses an ultra-light foamed TPR material synthesized of modified thermoplastic rubber and a preparation method thereof, and belongs to the technical field of chemical materials. The invention provides a novel TPR material and a preparation method thereof, wherein the TPR material has the advantages of great foaming capacity, low density, tear resistance, bend resistance and wear resistance, and is produced through the melt blending of acrylonitrile-butadiene rubber, which has high viscosity, and linear three embedded copolymers(SEBS), which uses ethylene-butene copolymers as a middle elastic embedded segment and has high rebound resilience. The novel TPR material and the preparation method have the characteristics of batch production and low production cost.
Description
Technical field
The present invention relates to the elastomeric material of chemical material field, the especially a kind of ultralight foaming of modification TPR material that has added SEBS and paracril and microballoon whipping agent on the basis of traditional TPR and preparation method thereof.
Background technology
At present on the market material for sole of shoe have following several, 1, traditional TPR; 2, rubber; 3, EVA foam material; 4, polyurethane foam material; 5, PVC material.
TPR material owner wanted material for sole of shoe and one of body-building apparatus material and toy material, developed so far many decades from 1963, and product is constantly updated and regenerated, but still exist, density is too high (is generally 0.9-1.2/cm
3), and surface irregularity, generally by adding whipping agent and anti-wear agent, solve on the market density and the wear-resisting problem of TPR, but because density reduces, the tearing power of material, anti-tortuosity reduces again naturally, does not reach the requirement of use fully, although after the interpolation anti-wear agent, the material wear-resistant coefficient is improved, the anti-tear tensile strength of corresponding material is fully not up to standard.The mode that proposes to add the EVA material copolymerization banburying of 20-25% and pass through physical blowing in TPR in CN102031010 is to reduce the density of TPR, there is several places shortcoming in this formula, at first add the EVA of vast scale like this, not possibility copolymerization banburying, the raw material of producing is very sticky, and hardness is very hard, granulation is very difficult, next is that EVA material foam theory is the chemical foaming method, produce gas foaming by high temperature vulcanized promotor and AC whipping agent, if can not have the foaming factor by additional whipping agent after banburying, even finally produce product, but the sole viscose glue of producing is very poor, must manual polishing can viscose glue, cost is too high, marketing exists hardly.
Elastomeric material is material for sole of shoe the most remote, but density too high (1.1-1.4), and sulfuration production process very not environmental protection, yield poorly down, sole smell weight, meet cold meeting and tell the frost whiting, can the oxidation hardening after of long duration.And not recyclable use.
EVA foam material proportion is light (0.23-0.4) very, extensively applied on sports shoes and cooling slippers, but due to character own, wear resistance is low, although while starting, elasticity is fine, through trample for a long time with oxidation after, will harden, and, after dress for a long time, human hair combing waste is smelly, ventilation property is very poor, and production process rubber like, also to vulcanize, yield poorly down, not recyclable.This material is produced monochrome only, if need double-coloredly, needs other materials after artificial adhesive rubber, and cost is too high.
Polyurethane material is emerging material for sole of shoe, existing being widely used on sandals and single footwear, and density is low, and surfacing is attractive in appearance, wear-resisting good.But price is too high, anti-skid factor is not high, not on-slip.The surface processing of all need to spraying paint, particularly cold-resistant, although release cold-resistant material, but still do not reach low temperature resistant standard, meet cold easy division, so produce only sandals and single footwear, cotton-padded shoes adopt this material hardly.Monochromatic production only, although can produce double-coloredly by board transformation, remain and take TPU as double-colored basis, keeps away the shortcoming of unavoidable physical property: not recyclable.
The PVC material is a kind of plastic material, be widely used on slippers, be low-end product, meet cold easily broken, country the forbids import such as and not environmental protection, contain adjacent benzene and heavy metal substance, American-European.
Last-mentioned, be although that the EVA material that occurs in the market and the synthetic rubber foam material of SEBS material combination have solved density and shaggy problem, need to be by sulfuration process production, output is too low, and cost value is too high.
Summary of the invention
For the deficiencies in the prior art, the melt blending that the invention provides the high resilience of the linearity three embedding multipolymers (SEBS) that a kind of high viscosity of utilizing paracril is middle elastomeric block in conjunction with ethylene-butene copolymer produce the high-foaming low density and anti-tearly draw, anti-complications, wear-resisting new TP R material and preparation method thereof, but this material and preparation method possess volume production and the low characteristic of production cost.
The composition of material of the present invention and proportioning:
Described SBS of the present invention can be F675, the F475 of 4452 or Maoming Petrochemical of Yanshan Petrochemical.
Described SEBS of the present invention can be 602,503 of Yueyang petrochemical industry.
Weighting material of the present invention is that calcium carbonate or talcum powder all can.
Paracril of the present invention is the high viscosity quality, can select the high viscosity paracril 8561-Z of Cang County Bang Qing rubber plant.
Microballoon swelling agent of the present invention can be Japan's this microballoon of pine production of low-temperature foaming agent.
The preferred Cellmic C 121 of AC whipping agent of the present invention.
The preparation method of the ultralight foaming TPR material that modified thermoplastic paracril of the present invention and SBS are synthetic is: first the SEBS of the SBS of 50-60 part and 10-20 part is first filled to naphthenic oil and stir more than 60 minutes, again paracril is cut into small pieces to put into and stirs more than 30 minutes simultaneously, fully mix, put into other raw material stirring except the AC whipping agent in the described proportioning ratio of claim 1 again, allow during paracril incorporates mixture in the process stirred, put into the Banbury mixer melt blending, extruding pelletization after banburying, mix the AC whipping agent again, after being put into to injection moulding machine, particle heats to the 170-180 degree, finally inject mould through cooling aftershaping.
Advantage of the present invention is: great advantage is to solve the problem that traditional TPR material is heavy and has also solved the strength problem of foaming TPR material simultaneously by adding paracril and SEBS, density of material of the present invention low (0.45-0.7), wear-resisting, oil resistant, acidproof, anti-complications, high resilience, and because technique is simple, production capacity exceeds the 20-30% of traditional TPR technique, exceeds PU, EVA, rubber process 40-60%.And cost is low, the finished product unit price of making is than low 10% left and right of traditional TPR, lower than PU, EVA, rubber product 20-50%. and reduce energy consumption than traditional TPR material and reach 30-50%.
Below in conjunction with embodiment, the present invention is described further.
Embodiment
embodiment mono-
Material composition and the proportioning of the present embodiment are as follows:
SBS (Yanshan Petrochemical 4452): 50 parts, SEBS (Yueyang petrochemical industry 602): 10 parts, paracril (8561-Z): 10 parts, polystyrene: 13 parts, naphthenic oil: 15 parts, white carbon black: 5 parts, calcium carbonate: 4 parts, microballoon production of low-temperature foaming agent (Japan pine this): 5 parts, Cellmic C 121: 3 parts, high molecular abrasion-proof agent: 2 parts, oxidation inhibitor: 0.5 part, anti-purple agent: 0.5 part.
Preparation method's step of the present embodiment is as follows:
50 parts of SBS (Yanshan Petrochemical 4452) and 10 parts of SEBS (Yueyang petrochemical industry 602) are first filled to 15 parts of naphthenic oils to be stirred 70 minutes, again 10 parts of paracrils are cut into small pieces to put into and stir 35 minutes simultaneously, fully mix, put into other raw material stirring except Cellmic C 121 in the said ratio ratio again, allow during paracril incorporates mixture in the process stirred, put into the Banbury mixer melt blending, extruding pelletization after banburying, mix whipping agent again, heat to 170 degree after particle is put into to injection moulding machine, finally inject mould through cooling aftershaping.
Its physical index is table one:
embodiment bis-
Material composition and the proportioning of the present embodiment are as follows:
SBS (F675 of Maoming Petrochemical): 55 parts, SEBS (Yueyang petrochemical industry 503): 15 parts, paracril (8561-Z): 16 parts, polystyrene: 15 parts, naphthenic oil: 17 parts, white carbon black: 7 parts, calcium carbonate: 5 parts, microballoon production of low-temperature foaming agent (Japan pine this): 7 parts, Cellmic C 121: 4 parts, high molecular abrasion-proof agent: 4 parts, oxidation inhibitor: 1 part, anti-purple agent: 1 part.
Preparation method's step of the present embodiment is as follows:
55 parts of SBS (F675 of Maoming Petrochemical) and 15 parts of SEBS (Yueyang petrochemical industry 503) are first filled to 17 parts of naphthenic oils to be stirred 80 minutes, again 16 parts of paracrils are cut into small pieces to put into and stir 50 minutes simultaneously, fully mix, put into other raw material stirring except Cellmic C 121 in the said ratio ratio again, allow during paracril incorporates mixture in the process stirred, put into the Banbury mixer melt blending, extruding pelletization after banburying, mix whipping agent again, heat to 175 degree after particle is put into to injection moulding machine, finally inject mould through cooling aftershaping.
Its physical index is table two:
embodiment tri-
Material composition and the proportioning of the present embodiment are as follows:
SBS (F475 of Maoming Petrochemical): 60 parts, SEBS (Yueyang petrochemical industry 602): 10 parts, paracril (8561-Z): 12 parts, polystyrene: 20 parts, naphthenic oil: 20 parts, white carbon black: 5 parts, calcium carbonate: 3 parts, microballoon production of low-temperature foaming agent (Japan pine this): 5 parts, Cellmic C 121: 5 parts, high molecular abrasion-proof agent: 2 parts, oxidation inhibitor: 2 parts, anti-purple agent: 2 parts.
Preparation method's step of the present embodiment is as follows:
60 parts of SBS (F475 of Maoming Petrochemical) and 10 parts of SEBS (Yueyang petrochemical industry 602) are first filled to 20 parts of naphthenic oils to be stirred 90 minutes, again 12 parts of paracrils (8561-Z) are cut into small pieces to put into and stir 60 minutes simultaneously, fully mix, put into other raw material stirring except Cellmic C 121 in the said ratio ratio again, allow during paracril incorporates mixture in the process stirred, put into the Banbury mixer melt blending, extruding pelletization after banburying, mix whipping agent again, heat to 175 degree after particle is put into to injection moulding machine, finally inject mould through cooling aftershaping.
Its physical index is table three:
embodiment tetra-
Material composition and the proportioning of the present embodiment are as follows:
SBS (Yanshan Petrochemical 4452): 50 parts, SEBS (Yueyang petrochemical industry 503): 20 parts, paracril (8561-Z): 25 parts, polystyrene: 20 parts, naphthenic oil: 18 parts, white carbon black: 8 parts, calcium carbonate: 10 parts, microballoon production of low-temperature foaming agent (Japan pine this): 8 parts, Cellmic C 121: 5 parts, high molecular abrasion-proof agent: 5 parts, oxidation inhibitor: 1 part, anti-purple agent: 1 part.
Preparation method's step of the present embodiment is as follows:
50 parts of SBS (Yanshan Petrochemical 4452) and 20 parts of SEBS (Yueyang petrochemical industry 503) are first filled to 18 parts of naphthenic oils to be stirred 100 minutes, again 12 parts of paracrils (8561-Z) are cut into small pieces to put into and stir 60 minutes simultaneously, fully mix, put into other raw material stirring except Cellmic C 121 in the said ratio ratio again, allow during paracril incorporates mixture in the process stirred, put into the Banbury mixer melt blending, extruding pelletization after banburying, mix whipping agent again, heat to 180 degree after particle is put into to injection moulding machine, finally inject mould through cooling aftershaping.
Its physical index is table four:
Claims (5)
1. the synthetic ultralight foaming TPR material of a modified thermoplastic rubber, it is characterized in that: its composition structure is: linearity three embedding multipolymer SEBS, paracril, microballoon swelling agent, AC whipping agent, polystyrene (PS), naphthenic oil, white carbon black (SiO2nH2O), anti-wear agent, oxidation inhibitor, anti-purple agent that thermoplastic styrene butadiene rubber SBS, ethylene-butene copolymer are middle elastomeric block, and its proportioning is counted with mass fraction:
2. the ultralight foaming TPR material that a kind of modified thermoplastic rubber according to claim 1 synthesizes, it is characterized in that: described weighting material is calcium carbonate or talcum powder.
3. the ultralight foaming TPR material that a kind of modified thermoplastic rubber according to claim 1 synthesizes, it is characterized in that: described paracril is the high viscosity quality.
4. the ultralight foaming TPR material that a kind of modified thermoplastic rubber according to claim 1 synthesizes, it is characterized in that: described AC whipping agent is Cellmic C 121.
5. the preparation method of the ultralight foaming TPR material that a kind of modified thermoplastic rubber according to claim 1 synthesizes, it is characterized in that comprising the following steps: first by first oil-filled stirring of the SEBS of the SBS of 50-60 part and 10-20 part more than 60 minutes, again paracril is cut into small pieces to put into and stirs more than 30 minutes simultaneously, fully mix, put into other raw material stirring except the AC whipping agent in the described proportioning ratio of claim 1 again, allow during paracril incorporates mixture in the process stirred, put into the Banbury mixer melt blending, extruding pelletization after banburying, mix the AC whipping agent again, after being put into to injection moulding machine, particle heats to the 170-180 degree, finally inject mould through cooling aftershaping.
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| CN105295200A (en) * | 2014-06-24 | 2016-02-03 | 晋江凯基高分子材料有限公司 | TPV (thermoplastic vulcanizate) foam injection molded shoe sole material and preparation method thereof |
| CN104262886A (en) * | 2014-08-29 | 2015-01-07 | 广东志达行新材料有限公司 | TRB (thermoplastic rubber) high-physical-property composite injection-molding rubber material |
| CN105602049B (en) * | 2016-02-24 | 2017-11-17 | 芜湖三鼎鞋业有限公司 | The preparation method at a kind of felt shoes bottom dipping solution and impregnation felt shoes bottom, a kind of footwear |
| CN105670199B (en) * | 2016-03-11 | 2018-06-15 | 福州市昊旺材料科技有限公司 | A kind of thermoplastic elastomer expanded material FRB and preparation 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 |
| CN106221113A (en) * | 2016-08-18 | 2016-12-14 | 泉州福达纳米科技发展有限公司 | The material for sole of shoe that in rubber pattern, the processing method of expanded material and the method prepare |
| CN107629387A (en) * | 2017-04-14 | 2018-01-26 | 莆田市三迪鞋服有限公司 | A kind of improved TPR ultra-light sole materials |
| CN107459688A (en) * | 2017-08-07 | 2017-12-12 | 青阳县吉祥塑胶有限公司 | A kind of EVA rubber synthesizes expanded material |
| CN108359151A (en) * | 2018-02-05 | 2018-08-03 | 厦门塑时代新材料有限公司 | A kind of composition for thermoplastic elastomer and preparation method thereof |
| CN109912918A (en) * | 2019-02-26 | 2019-06-21 | 嘉兴市捷豪清洁用品有限公司 | A kind of modified thermoplastic rubber synthesising biological composite material and preparation method thereof |
| CN110028714A (en) * | 2019-04-30 | 2019-07-19 | 温州市宜和鞋材有限公司 | A kind of formula and preparation process of ultralight one-pass molding composite sole |
| CN113583409A (en) * | 2021-08-11 | 2021-11-02 | 福建斯达新材料科技有限公司 | Injection-molded sole material, sole comprising injection-molded sole material, and preparation method and application of injection-molded sole material |
| CN115594936A (en) * | 2022-08-15 | 2023-01-13 | 莆田市万升鞋业有限公司（Cn） | Ultra-light TPR plastic and preparation method thereof |
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| TW200505973A (en) * | 2003-08-04 | 2005-02-16 | Microcell Composite Company | Foaming process for producing thermoplastic elastomer composite material |
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| CN1884367A (en) * | 2006-06-04 | 2006-12-27 | 浙江三博聚合物有限公司 | Expansion type low-smoke halogen-free thermoplastic flame-retardant rubber and its production method |
| CN101519520A (en) * | 2009-03-26 | 2009-09-02 | 南京工程学院 | Artificial turf thermoplastic rubber filler particles and method fro preparing same |
| CN102031010A (en) * | 2010-11-17 | 2011-04-27 | 福州安健志远国际贸易有限公司 | Ultra-light modified thermoplastic rubber TE material |
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