CN103554561A - High-hardness and extremely-cold-resistant sole material and preparation method thereof - Google Patents
High-hardness and extremely-cold-resistant sole material and preparation method thereof Download PDFInfo
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- CN103554561A CN103554561A CN201310540202.0A CN201310540202A CN103554561A CN 103554561 A CN103554561 A CN 103554561A CN 201310540202 A CN201310540202 A CN 201310540202A CN 103554561 A CN103554561 A CN 103554561A
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Abstract
The invention discloses a high-hardness and extremely-cold-resistant sole material, which comprises natural rubber, butadiene rubber, a vulcanizer, high styrene rubber, a vulcanizing promoter, a vulcanizing active agent, an anti-aging agent, a softening agent and a reinforcing filler in parts by weight. By improving the rubber formula and preparation process and mixing the natural rubber, synthesized rubber and plastics according to a reasonable ratio, the weaknesses of the properties of the natural rubber can be overcome, the functional requirement of a rubber sole in a special environment can be met, a rubber material which is suitable for producing the high-hardness and extreme-cold-resistant sole is selected, the sole produced by adopting the rubber material has good an effect on multiple functions such as slipping resistance, curvature resistance, cold resistance and hardness, the production process is not complicated, and a valuable reference is provided to the production of high-hardness and extremely-cold-resistant functional soles.
Description
Technical field
The present invention relates to rubber processing, particularly a kind of high rigidity, resistance to extremely cold material for sole of shoe and preparation method thereof.
Background technology
Due to outdoor activity in recent years, the movable rises such as motion of exploring, and regional condition difference etc., adapt to the needs of exceedingly odious low temperature environment, some specific function of footwear has been proposed to new requirement.And the outdoor products of current common price can only meet the demand of general summer coolness degree, under the condition of extreme cold, higher to performance requriementss such as the cold tolerance of sole, hardness.Yet snowfield sport shoes for climbing mountain manufacturing process is before complicated, material price is very high, and often market value is tens times even tens times of common footwear, is difficult to meet the demand of ordinary consumer.Therefore, finding a kind of cheap material makes the sole that possesses property and instantly, has certain economic worth.
The technology of having grasped according to current rubber shoe industry, is mainly still used natural rubber to carry out the making of sole for material of main part.Characteristic---chill property because natural rubber itself possesses, in the situation that envrionment temperature is extremely low, very easily produces the accidents such as sole fracture with the sole that natural rubber is made; In order to ensure sole, in cold snowfield, walk and there is enough stability, security and comfortableness, the performances such as cold-resistant, the hardness of sole are had higher requirement.
Summary of the invention
Technical problem to be solved by this invention is: a kind of high rigidity, resistance to extremely cold material for sole of shoe and preparation method thereof are provided, and it can meet the service requirements under cold environment, and guarantees to have good hardness, to overcome the deficiencies in the prior art.
High rigidity, the resistance to extremely cold material for sole of shoe of being achieved in that of the present invention, according to listed as parts by weight, comprise 30～90 parts of natural rubbers, 10～70 parts of cis-butadiene cements, 1～3 part of vulcanizing agent, 20～40 parts of high-phenylethylenes, 1～5 part of vulcanization accelerator, 3～5 parts of vulcanization levellers, 1～2 part, anti-aging agent, 30～70 parts of 5～15 parts of tenderizers and packing strengthening agents.
Preferred scheme is according to listed as parts by weight, to comprise 60 parts of natural rubbers, 40 parts of cis-butadiene cements, 2 parts of vulcanizing agents, 30 parts of high-phenylethylenes, 4.1 parts of vulcanization accelerators, 5 parts of vulcanization levellers, 1.8 parts, anti-aging agent, 58 parts of 11 parts of tenderizers and packing strengthening agents.
Vulcanizing agent is that sulphur, every 4.1 parts of vulcanization accelerators are comprised of 1.6 parts of accelerator CBSs, 1.8 parts of altaxs and vulkacit D 0 .7 part; Every 5 parts of vulcanization levellers are comprised of with 3 parts of nano zine oxides 2 parts of stearic acid; Anti-aging agent is anti-aging agent CD; Tenderizer is that 46# machinery oil, packing strengthening agent are carbon black N220.
The preparation method of high rigidity, resistance to extremely cold material for sole of shoe, gets each component by above-mentioned parts by weight, and operation steps is as follows:
(1) plasticate: natural rubber is plasticated together with high-phenylethylene, make its Wei Shi plasticity number reach 0.53～0.58, obtain broken-(down)rubber;
(2) female refining: get half broken-(down)rubber mixing together with 50 parts of packing strengthening agents and cis-butadiene cement, make master batch;
(3) mixing: remaining broken-(down)rubber to be dropped into together with master batch, vulcanizing agent, vulcanization accelerator, vulcanization leveller, anti-aging agent, tenderizer and remaining packing strengthening agent to Banbury mixer and press refining 2 minutes, after mixing at 90～100 ℃ 3～3.5 minutes discharges of banburying, obtain resistance to extremely cold sole sizing material.
Plasticating described in step 1) be, gets after natural rubber is plasticated 4 minutes 30 seconds-4 minutes 50 seconds on Banbury mixer and add whole high-phenylethylenes again, and continuing refining is plastic emitting in 9-11 minute; Banbury mixer condition is: banburying chamber's temperature 90 pressure 0.2Mpa of～120℃， banburying chamber, closed-smelting machine rotor rotating speed is 1440r/min.
Step 2) female refining described in refers to, 1/2 broken-(down)rubber to be dropped into together with 50 parts of packing strengthening agents and cis-butadiene cement to Banbury mixer to press refining about 2 minutes, throw again remaining broken-(down)rubber, promotor, promoting agent, anti-aging agent, tenderizer and remaining packing strengthening agent, after mixing, in 90～100 ℃ of banburyings 3 minutes～3, minute within 30 seconds, get final product discharge.
In order to verify technique effect of the present invention, carried out following test:
The present invention be through contriver's experiment repeatedly draw, after screening, contrast experiment's Data induction of the main detection index of representative testing data and cold-resistant footwear is arranged, gather as follows:
Note: table 1 physicals testing conditions is according to GB/T 2941-91, and detected temperatures is subzero 40 ℃; Flexion detection method is according to GB/T 13934-92, specimen shape: rectangle, test frequency: 8.3 ± 0.28Hz (500 ± 20r/min).
Table 2 natural rubber and cis-1,4-polybutadiene rubber share cold-resistant and skid resistance test
Note: table 2 physicals testing conditions is according to GB/T 2941-91, and detected temperatures is subzero 40 ℃; Flexion detection method is according to GB/T 13934-92, specimen shape: rectangle, test frequency: 8.3 ± 0.28Hz (500 ± 20r/min).
The testing data of table 2 shows, when purely usining natural rubber while making sole as framework material, there is comparatively excellent wet-sliding resistant performance, but because natural rubber and goods thereof have chill property, when low temperature environment, there is larger hidden danger in this sole, may produce the danger that sole and footwear body come off, produce the accidents such as fracture in also may wearing process when lower temperature environment.When with a certain amount of cis-butadiene cement and with after, on wet-sliding resistant performance, have certain sacrifice, hardness also approximately has decline, but cold tolerance is greatly improved, this has also made up the deficiency of synthetic rubber on wet-sliding resistant performance.
Because snow boot boots may need to fill crampon class article sometimes, this to the hardness of sole require high.In order to meet the high rigidity of snow boot boots, and the Functional Requirement high to cold tolerance, we have added a kind of plastics-high-phenylethylene in table 2 formula used.Adding proportion is done to following test:
Table 3 natural rubber and cis-1,4-polybutadiene rubber share and add plastics (high-phenylethylene) to resist cold and skid resistance test
Note: table 3 physicals testing conditions is according to GB/T 2941-91, and detected temperatures is subzero 40 ℃; Flexion detection method is according to GB/T 13934-92, specimen shape: rectangle, test frequency: 8.3 ± 0.28Hz (500 ± 20r/min).
This method has been passed through repeatedly revision test, and testing data shows that this test circulation ratio is better, and the method is effective.
Test number by above simultaneous test shows: in formula as listed in table 2, natural rubber is 60 parts, and cis-butadiene cement is that this group test-results of 40 parts is comparatively desirable.Testing data also shows, add high-phenylethylene to also having a certain impact by wet-sliding resistant performance and the anti-tortuous performance of rubber soles, but this and with the influenced maximum of formula be the hardness of sole, sole hardness is almost along with the increase journey straight line rising of the add-on of high-phenylethylene.But wet-sliding resistant performance and anti-tortuous performance are also had a certain impact, natural rubber and elastomeric and with formula in add the high-phenylethylene of 30 parts of left and right comparatively suitable.So not only, ensuring than more excellent wet-sliding resistant performance and anti-tortuous performance, can also provide higher hardness, from having met to a great extent the functional requirement of rubber overshoes at exceedingly odious cold environment.And with cheap cost value, reach the physicals of high-end snowfield motion shoe products.
Therefore, according to above testing data, we optimize one group of formulation data that comprehensive comparison is outstanding: calculate in mass ratio, it is by 60 parts of natural rubbers, 40 parts of cis-butadiene cements, 2.0 parts, sulphur; 30 parts of high-phenylethylenes; 4.1 parts of vulcanization accelerators; 5.0 parts of promoting agents; 1.8 parts, anti-aging agent; 11.0 parts of tenderizers; 58 parts of packing strengthening agents are prepared from.Making is to the high high rigidity of Functional Requirement, resistance to extremely cold sole.By this sizing material, in die temperature, be that 145～155 ℃, die pressure are 410 seconds left and right sulfidization moldings of pressurize under 15～17Mpa condition, can make a kind of high rigidity, resistance to extremely cold sole.
When preparing broken-(down)rubber, because high-phenylethylene is harder, need to when plasticating, drop into, there is time enough evenly to mix with natural rubber.Carbon black N220 is as packing strengthening agent, and amount ratio is larger, needs the long period to be mixed into completely in rubber; In addition, the processing characteristics of cis-butadiene cement and natural rubber used time is not fine, therefore need to when refining master batch, drop in the lump yet.
Owing to having adopted technique scheme, compared with prior art, the present invention improves sizing compound formula and preparation technology, mixed by natural rubber and synthetic rubber and plastics having been carried out to rational ratio, overcome the defect of natural rubber in performance own, reached the functional requirement of rubber soles to particular surroundings, filtered out and be a kind ofly suitable for production the present invention and make high rigidity, the sizing material of resistance to extremely cold sole, the sole that adopts this sizing material to produce, anti-slippery, anti-complications, and cold tolerance, on the multiple functions such as hardness, all reached reasonable effect, making processes is also also uncomplicated, give high rigidity, resistance to extremely cold functional type sole is made provides valuable reference.The inventive method is simple, the low cost product of made, and result of use is good.
Embodiment
Embodiments of the invention 1: high rigidity, resistance to extremely cold material for sole of shoe, according to listed as parts by weight, comprise 60 parts of natural rubbers, 40 parts of cis-butadiene cements, 2 parts, sulphur, 30 parts of high-phenylethylenes, 4.1 parts of vulcanization accelerators, 5 parts of vulcanization levellers, 1.8 parts, anti-aging agent, 58 parts of 11 parts of tenderizers and packing strengthening agents.
The preparation method of high rigidity, resistance to extremely cold material for sole of shoe, gets each component by above-mentioned parts by weight, and operation steps is as follows:
(1) plasticate: natural rubber is plasticated together with high-phenylethylene, make its Wei Shi plasticity number reach 0.53～0.58, obtain broken-(down)rubber;
(2) female refining: get half broken-(down)rubber mixing together with 50 parts of packing strengthening agents and cis-butadiene cement, make master batch;
(3) mixing: remaining broken-(down)rubber to be dropped into together with master batch, vulcanizing agent, vulcanization accelerator, vulcanization leveller, anti-aging agent, tenderizer and 8 parts of packing strengthening agents to Banbury mixer and press refining 2 minutes, after mixing at 90～100 ℃ 3～3.5 minutes discharges of banburying, obtain resistance to extremely cold sole sizing material.
Plasticating described in step 1) be, gets after natural rubber is plasticated 4 minutes 30 seconds-4 minutes 50 seconds on Banbury mixer and add whole high-phenylethylenes again, and continuing refining is plastic emitting in about 10 minutes; Banbury mixer condition is: banburying chamber's temperature 90 pressure 0.2Mpa of～120℃， banburying chamber, closed-smelting machine rotor rotating speed is 1440r/min.
Step 2) female refining described in refers to, 1/2 broken-(down)rubber to be dropped into together with packing strengthening agent and cis-butadiene cement to Banbury mixer to press refining about 2 minutes, throw again remaining broken-(down)rubber, promotor, promoting agent, anti-aging agent, tenderizer and packing strengthening agent, after mixing, in 90～100 ℃ of banburyings 3 minutes～3, minute within 30 seconds, get final product discharge.
Embodiments of the invention 2: high rigidity, resistance to extremely cold material for sole of shoe, according to listed as parts by weight, comprise 30 parts of natural rubbers, 70 parts of cis-butadiene cements, 1 part of vulcanizing agent, 20 parts of high-phenylethylenes, 1 part of vulcanization accelerator, 3 parts of vulcanization levellers, 1 part, anti-aging agent, 70 parts of 5 parts of tenderizers and packing strengthening agents.
Preparation method is with embodiment 1.
Embodiments of the invention 3: high rigidity, resistance to extremely cold material for sole of shoe, according to listed as parts by weight, comprise 90 parts of natural rubbers, 10 parts of cis-butadiene cements, 3 parts of vulcanizing agents, 40 parts of high-phenylethylenes, 5 parts of vulcanization accelerators, 5 parts of vulcanization levellers, 2 parts, anti-aging agent, 70 parts of 15 parts of tenderizers and packing strengthening agents.
Preparation method is with embodiment 1.
Claims (6)
1. a high rigidity, resistance to extremely cold material for sole of shoe, it is characterized in that: according to listed as parts by weight, comprise 30～90 parts of natural rubbers, 10～70 parts of cis-butadiene cements, 1～3 part of vulcanizing agent, 20～40 parts of high-phenylethylenes, 1～5 part of vulcanization accelerator, 3～5 parts of vulcanization levellers, 1～2 part, anti-aging agent, 30～70 parts of 5～15 parts of tenderizers and packing strengthening agents.
2. high rigidity according to claim 1, resistance to extremely cold material for sole of shoe, it is characterized in that: according to listed as parts by weight, comprise 60 parts of natural rubbers, 40 parts of cis-butadiene cements, 2 parts of vulcanizing agents, 30 parts of high-phenylethylenes, 4.1 parts of vulcanization accelerators, 5 parts of vulcanization levellers, 1.8 parts, anti-aging agent, 58 parts of 11 parts of tenderizers and packing strengthening agents.
3. high rigidity according to claim 1, resistance to extremely cold material for sole of shoe, is characterized in that: vulcanizing agent is that sulphur, every 4.1 parts of vulcanization accelerators are comprised of 1.6 parts of accelerator CBSs, 1.8 parts of altaxs and vulkacit D 0 .7 part; Every 5 parts of vulcanization levellers are comprised of with 3 parts of nano zine oxides 2 parts of stearic acid; Anti-aging agent is anti-aging agent CD; Tenderizer is that 46# machinery oil, packing strengthening agent are carbon black N220.
4. a preparation method for high rigidity as claimed in claim 1, resistance to extremely cold material for sole of shoe, is characterized in that: by above-mentioned parts by weight, get each component, operation steps is as follows:
(1) plasticate: natural rubber is plasticated together with high-phenylethylene, make its Wei Shi plasticity number reach 0.53～0.58, obtain broken-(down)rubber;
(2) female refining: get half broken-(down)rubber with
50 partspacking strengthening agent and cis-butadiene cement are mixing together, make master batch;
(3) mixing: remaining broken-(down)rubber to be dropped into together with master batch, vulcanizing agent, vulcanization accelerator, vulcanization leveller, anti-aging agent, tenderizer and remaining packing strengthening agent to Banbury mixer and press refining 2 minutes, after mixing at 90～100 ℃ 3～3.5 minutes discharges of banburying, obtain resistance to extremely cold sole sizing material.
5. the preparation method of high rigidity according to claim 4, resistance to extremely cold material for sole of shoe, is characterized in that: plasticating described in step 1) is to get after natural rubber is plasticated 4 minutes 30 seconds-4 minutes 50 seconds on Banbury mixer and add whole high-phenylethylenes again, continuation refining
9-11minute be plastic emitting; Banbury mixer condition is: banburying chamber's temperature 90 pressure 0.2Mpa of～120℃， banburying chamber, closed-smelting machine rotor rotating speed is 1440r/min.
6. the preparation method of high rigidity according to claim 4, resistance to extremely cold material for sole of shoe, it is characterized in that: step 2) described in female refining refer to, 1/2 broken-(down)rubber to be dropped into together with 50 parts of packing strengthening agents and cis-butadiene cement to Banbury mixer to press refining about 2 minutes, throw again remaining broken-(down)rubber, promotor, promoting agent, anti-aging agent, tenderizer and remaining packing strengthening agent, after mixing, in 90 ~ 100 ℃ of banburyings 3 minutes ~ 3, minute within 30 seconds, get final product discharge.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965523A (en) * | 2014-05-20 | 2014-08-06 | 南京东亚橡塑制品有限公司 | Dual-density sole and preparation method thereof |
| CN105218886A (en) * | 2015-11-14 | 2016-01-06 | 际华三五一五皮革皮鞋有限公司 | At the bottom of the extremely cold-resistant high elasticity abrasion-proof glue of one |
| CN105670056A (en) * | 2016-04-11 | 2016-06-15 | 泉州盛达轻工有限公司 | High-strength low-temperature-resistant material for shoes and preparation method of high-strength low-temperature-resistant material |
| CN106084325A (en) * | 2016-06-30 | 2016-11-09 | 嘉兴市哈妮鞋业有限公司 | High rigidity sole sizing material |
| CN106317494A (en) * | 2016-08-30 | 2017-01-11 | 浙江中瑞橡胶高分子材料股份有限公司 | Formula and preparation method of vulcanized rubber heelpiece |
| CN106566014A (en) * | 2016-11-10 | 2017-04-19 | 际华三五五皮革皮鞋有限公司 | Insulated and acid-base-resistant rubber material |
| CN109181041A (en) * | 2018-07-24 | 2019-01-11 | 温州市小林鞋材有限公司 | A kind of ultralight rubber plastic sole material and preparation method thereof |
| CN111019199A (en) * | 2019-12-27 | 2020-04-17 | 惠州麦丰密封科技有限公司 | Sealing ring and preparation method thereof |
| CN111019197A (en) * | 2019-12-24 | 2020-04-17 | 正新橡胶（中国）有限公司 | Anti-aging tire rubber composition and application thereof |
| CN111333922A (en) * | 2019-09-27 | 2020-06-26 | 际华三五三七有限责任公司 | Rubber cement for double-blade scraping of middle base cloth of rubber shoes as well as preparation method and application of rubber cement |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965523A (en) * | 2014-05-20 | 2014-08-06 | 南京东亚橡塑制品有限公司 | Dual-density sole and preparation method thereof |
| CN105218886A (en) * | 2015-11-14 | 2016-01-06 | 际华三五一五皮革皮鞋有限公司 | At the bottom of the extremely cold-resistant high elasticity abrasion-proof glue of one |
| CN105670056A (en) * | 2016-04-11 | 2016-06-15 | 泉州盛达轻工有限公司 | High-strength low-temperature-resistant material for shoes and preparation method of high-strength low-temperature-resistant material |
| CN106084325A (en) * | 2016-06-30 | 2016-11-09 | 嘉兴市哈妮鞋业有限公司 | High rigidity sole sizing material |
| CN106317494A (en) * | 2016-08-30 | 2017-01-11 | 浙江中瑞橡胶高分子材料股份有限公司 | Formula and preparation method of vulcanized rubber heelpiece |
| CN106566014A (en) * | 2016-11-10 | 2017-04-19 | 际华三五五皮革皮鞋有限公司 | Insulated and acid-base-resistant rubber material |
| CN109181041A (en) * | 2018-07-24 | 2019-01-11 | 温州市小林鞋材有限公司 | A kind of ultralight rubber plastic sole material and preparation method thereof |
| CN111333922A (en) * | 2019-09-27 | 2020-06-26 | 际华三五三七有限责任公司 | Rubber cement for double-blade scraping of middle base cloth of rubber shoes as well as preparation method and application of rubber cement |
| CN111019197A (en) * | 2019-12-24 | 2020-04-17 | 正新橡胶（中国）有限公司 | Anti-aging tire rubber composition and application thereof |
| CN111019199A (en) * | 2019-12-27 | 2020-04-17 | 惠州麦丰密封科技有限公司 | Sealing ring and preparation method thereof |
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Application publication date: 20140205 |