CN103937057A - Preparation method of starch modified white carbon black/rubber composite filler - Google Patents
Preparation method of starch modified white carbon black/rubber composite filler Download PDFInfo
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- CN103937057A CN103937057A CN201410175732.4A CN201410175732A CN103937057A CN 103937057 A CN103937057 A CN 103937057A CN 201410175732 A CN201410175732 A CN 201410175732A CN 103937057 A CN103937057 A CN 103937057A
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Abstract
The invention relates to a preparation method of a starch modified white carbon black/rubber composite material, which comprises the following step: by using traditional rubber processing equipment, uniformly dispersing a previously gelatinized starch paste into a white carbon black/rubber composite material to obtain a starch modified white carbon black/rubber composite material. The introduced starch macromolecular chains and silicon hydroxyl groups on the surface of white carbon black interact with each other, so that the dispersion of the filler in the rubber matrix is reinforced, thereby improving the slip resistance and abrasion resistance of the white carbon black/rubber composite material and reducing the rolling resistance of the white carbon black/rubber composite material. According to the invention, the method is simple and easy to implement, does not change the traditional rubber processing mode, is short in production cycle, low in raw material cost, friendly to environment and suitable for preparation of various vulcanized rubber products, and has wide application prospects.
Description
Technical field
The preparation method who the present invention relates to a kind of starch conversion white carbon black/rubber composite, the invention belongs to rubber materials.
Background technology
Hyundai Motor improves day by day to the technical requirements of tyre performance, and tire forward is towards high technology content and the future development that becomes more meticulous.Anti-slippery, low-rolling-resistance, high-performance and multifunctional tire shared ratio in tire continue to increase, and under this historical background, " green tire " arises at the historic moment.So-called " green tire " refer to due to application plastics on new materials and design, and cause rolling resistance little, thereby the radial that oil consumption is low, exhaust gas emission is few.Green tire has low-carbon environment-friendly, reduces oil consumption and optimizes the advantages such as tire lifting safety.Wherein, reduce the rolling resistance of tyre surface and ensure that wet-sliding resistant performance is well the most basic requirement of green tire.While travelling on automobile is having the road surface of water, owing to there being the existence of water between tire and road surface, so the gripping power of tire can significantly reduce.Especially for the higher passenger car of travel speed, the anti-slippery of tire seems particularly important.So reducing as much as possible under the premise that security is guaranteed, the rolling resistance of tire is significant to the development of rubber industry.
Starch is a kind of natural plant polyose, and it is extensively present in the fruit, root, stem of plant with particle form, is the source of the main carbohydrate of the mankind.Starch resource is abundant, cheap, there is again recyclability, closely bound up with the mankind's the survival and development, in recent years, along with day by day strong to environmental requirement of people, environmental protection concept gos deep in industrial design and practical application gradually, and starch application is met to people to energy-conservation and requirement environmental protection in this invention of tire.
Similar to traditional loading material of rubber white carbon black, there is activity hydroxy in starch particle surface, and this makes starch application become possibility in rubber.But native starch has crystallinity, particle is thick, contains great amount of hydroxy group, poor with the consistency of rubber matrix, these characteristic limitations the application of starch in rubber.So, starch be applied in rubber, must first carry out suitable processing to starch, wherein starch pasting is exactly one of most important treatment process.
The gelatinization (Gelatinization) of starch refers at high temperature, and starch is swelling, division forms even pasty state solution.Starch is after gelatinization, and the crystal block section of starch dissolves, and particle is swelling, and grain pattern is loose, and starch aqeous suspension becomes the higher colloid of a kind of translucent viscosity.In forefathers' research, the method that mainly adopts starch latex to condense altogether (LCM) is prepared starch/rubber composite.This method has mainly utilized starch to have gelatinization and most of rubber to have the feature of water miscible liquid, pasted starch or modification pasted starch and latex can be condensed altogether, obtains starch/rubber composite.Adopt in this way, improved the dispersion of starch in rubber matrix, played to a certain extent strengthening action.But this method production cycle is long, complex process, starch amount of filling is limited, and starch is easy to reunite in following process process.
Summary of the invention
The present invention is intended to overcome the existing defect of preparing in starch/rubber composite technology, provides a kind of method simple, with low cost and be easy to industrialized preparation method.Utilized starch have can gelatinization characteristic, the destroyed of starch pasting the association state between crystallinity and the starch molecule of starch.And, the starch after gelatinization, starch granules is loose, and starch molecule is dissolved in water.Under the effect of the strong shearing force of traditional rubber tooling, there is being distributed in white carbon black/rubber composite that more full-bodied starch paste can uniform, fine.And hydroxyl on starch molecular chain can interact with the silicon hydroxyl on white carbon black surface, reduce to a certain extent the reunion between white carbon black, strengthen the dispersiveness of filler, the excellent performance of rubber composite.
A kind of preparation method of starch conversion white carbon black/rubber composite, it is characterized in that: the starch aqeous suspension gelatinization that is 10%-35% by mass concentration, get according to solid content the starch paste that the mass ratio of white carbon black and starch is 67/10-67/2, utilize traditional rubber tooling to be dispersed in white carbon black/rubber composite, obtain starch conversion white carbon black/rubber combined filler.
Further: starch is glutinous rice starch, W-Gum, yam starch or pea starch one or more.
As preferably: starch is glutinous rice starch, W-Gum, yam starch, pea starch.
As preferably: the mass concentration of starch is 10%-35%.
As preferably: the mass ratio of white carbon black and starch is 67/10-67/2.
Beneficial effect
1) preparation method's technique of starch conversion white carbon black/rubber combined filler involved in the present invention is simple, does not change traditional Rubber processing mode, and material cost is cheap, low-carbon environment-friendly;
2) pasted starch can interact with white carbon black, has reduced to a certain extent the reunion of white carbon black, and dispersion effect is strengthened;
3) introducing of starch paste has improved wet-sliding resistant performance and the wear resisting property of white carbon black/rubber composite, has reduced its rolling resistance.
Brief description of the drawings
Fig. 1 is the surface sweeping electron micrograph of the tension fracture face of rubber/starch composite material of preparing of the embodiment of the present invention 7.
Fig. 2 is the surface sweeping electron micrograph of the tension fracture face of rubber/starch composite material of preparing of comparative example 2.
Embodiment
Embodiment 1:
10g glutinous rice starch is joined in the water of 90g, stir and is evenly all mixed with starch suspension, under the condition of 80 DEG C under the condition of gelatinization 30min by its gelatinization; According to solid content, get the starch paste that starch content is 10g, in two roller mills, starch paste is dispersed in white carbon black/styrene-butadiene rubber composite material, basic recipe is in table 3, obtain starch conversion white carbon black/styrene-butadiene rubber composite material, after sulfuration, survey its performance.
Embodiment 2:
10g W-Gum is joined in the water of 56.67g, stir and is evenly all mixed with starch suspension, under the condition of 90 DEG C under the condition of gelatinization 20min by its gelatinization; According to solid content, get the starch paste that starch content is 2g, in Banbury mixer, starch paste is dispersed in white carbon black/styrene-butadiene rubber composite material, basic recipe, in table 3, obtains starch conversion white carbon black/styrene-butadiene rubber composite material, surveys its performance after sulfuration.
Embodiment 3:
10g pea starch is joined in the water of 90g, stir and is evenly all mixed with starch suspension, under the condition of 80 DEG C under the condition of gelatinization 30min by its gelatinization; According to solid content, get the starch paste that starch content is 6g, in two roller mills, starch paste is dispersed in white carbon black/native rubber composite material, basic recipe is in table 3, obtain starch conversion white carbon black/native rubber composite material, after sulfuration, survey its performance.
Embodiment 4:
10g yam starch being joined in the water of 30g, stir and be evenly all mixed with starch suspension, is 350W at microwave power, under the condition that the treatment time is 2min by its gelatinization; According to solid content, get the starch paste that starch content is 6g, in two roller mills, starch paste is dispersed in white carbon black/styrene-butadiene rubber composite material, basic recipe is in table 3, obtain starch conversion white carbon black/styrene-butadiene rubber composite material, after sulfuration, survey its performance.
Embodiment 5:
10g glutinous rice starch being joined in the water of 18.57g, stir and be evenly all mixed with starch suspension, is 350W at microwave power, under the condition that the treatment time is 6min by its gelatinization; According to solid content, get the starch paste that starch content is 2g, in Banbury mixer, starch paste is dispersed in white carbon black/styrene-butadiene rubber composite material, basic recipe, in table 3, obtains starch conversion white carbon black/styrene-butadiene rubber composite material, surveys its performance after sulfuration.
Embodiment 6:
10g W-Gum being joined in the water of 56.67g, stir and be evenly all mixed with starch suspension, is 500W at microwave power, under the condition that the treatment time is 2min by its gelatinization; According to solid content, get the starch paste that starch content is 6g, in Banbury mixer, starch paste is dispersed in white carbon black/styrene-butadiene rubber composite material, basic recipe, in table 3, obtains starch conversion white carbon black/styrene-butadiene rubber composite material, surveys its performance after sulfuration.
Embodiment 7:
10g glutinous rice starch being joined in the water of 56.67g, stir and be evenly all mixed with starch suspension, is 500W at microwave power, under the condition that the treatment time is 2min by its gelatinization; According to solid content, get the starch paste that starch content is 6g, in two roller mills, starch paste is dispersed in white carbon black/native rubber composite material, basic recipe is in table 3, obtain starch conversion white carbon black/native rubber composite material, after sulfuration, survey its performance.
Embodiment 8:
10g glutinous rice starch being joined in the water of 56.67g, stir and be evenly all mixed with starch suspension, is 500W at microwave power, under the condition that the treatment time is 2min by its gelatinization; According to solid content, get the starch paste that starch content is 6g, in two roller mills, starch paste is dispersed in white carbon black/nitile-butadiene rubber composite material, basic recipe is in table 3, obtain starch conversion white carbon black/nitile-butadiene rubber composite material, after sulfuration, survey its performance.
Embodiment 9:
10g glutinous rice starch being joined in the water of 56.67g, stir and be evenly all mixed with starch suspension, is 500W at microwave power, under the condition that the treatment time is 2min by its gelatinization; According to solid content, get the starch paste that starch content is 6g, in the twin screw extruder that is 48:1, starch paste is dispersed in white carbon black/styrene-butadiene rubber composite material in length-to-diameter ratio, basic recipe is in table 3, obtain starch conversion white carbon black/styrene-butadiene rubber composite material, after sulfuration, survey its performance.
Comparative example 1
Obtain white carbon black/rubber composite by basic recipe, after sulfuration, survey its performance.
Comparative example 2
Get 6g glutinous rice starch, in two roller mills, directly glutinous rice starch is dispersed in white carbon black/styrene-butadiene rubber composite material, basic recipe, in table 3, obtains starch/white carbon black/styrene-butadiene rubber composite material, surveys its performance after sulfuration.
Comparative example 3
6g pea starch is joined in the water of 54g, stir and is evenly all mixed with starch suspension, under the condition of 80 DEG C under the condition of gelatinization 30min by its gelatinization; The SBR emulsion that is 25% with 400g solid content by starch good gelatinization mixes, and at room temperature stirs 30min, and the calcium chloride solution that is 2% by massfraction joins in the mixture of starch paste and styrene-butadiene latex, obtains starch/butylbenzene mixture.This mixture is dried to 48 hours in the baking oven of 60 DEG C.In two roller mills, dried starch/butylbenzene mixture is mixing according to formula, basic recipe, in table 3, obtains starch/white carbon black/native rubber composite material, surveys its performance after sulfuration.
The mechanical property of rubber/modified starch composite material, wear hardness, anti-slippery as shown in table 1, rolling resistance performance is as shown in table 2.Wherein, we use the wet-sliding resistant performance of pendulum friction coefficient determinator (BPST) exosyndrome material, and BPST index is higher, and the wet-sliding resistant performance of material is better.By the rolling resistance of rubber rolling resistance test machine exosyndrome material, power loss is lower, and the rolling resistance of material is less.
The mechanical property of vulcanized rubber detected result of table 1. embodiment and comparative example
The cross-linked rubber rolling resistance performance test results of table 2. embodiment and comparative example
Basic recipe formula in table 3. embodiment and comparative example
| Material | Mass parts |
| Rubber | 100 |
| ZnO | 5 |
| SA | 2 |
| White carbon black | 67 |
| Anti-4020NA | 1 |
| Si69 | 3 |
| CZ | 1.2 |
| S | 1.5 |
Claims (2)
1. the preparation method of a starch conversion white carbon black/rubber composite, it is characterized in that: the starch aqeous suspension gelatinization that is 10%-35% by mass concentration, get according to solid content the starch paste that the mass ratio of white carbon black and starch is 67/10-67/2, be dispersed in white carbon black/rubber composite, obtained starch conversion white carbon black/rubber combined filler.
2. a kind of preparation method of starch conversion white carbon black/rubber composite according to claim 1, is characterized in that: starch is glutinous rice starch, W-Gum, yam starch or pea starch one or more.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622841A (en) * | 2015-12-10 | 2016-06-01 | 北京化工大学 | Preparation method of silica/poly(itaconate-isoprene-glycidyl methacrylate) bio-based elastomer composite material |
| CN109266044A (en) * | 2018-11-14 | 2019-01-25 | 陶伟珍 | A kind of preparation method of rubber modification infusorial earth filler |
| CN111793258A (en) * | 2020-07-24 | 2020-10-20 | 吉林农业大学 | Corn byproduct based synthetic rubber environment-friendly material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387696A (en) * | 2013-07-29 | 2013-11-13 | 海南大学 | In-situ polymerization method of nano starch/SiO2 composite particles |
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2014
- 2014-04-28 CN CN201410175732.4A patent/CN103937057A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387696A (en) * | 2013-07-29 | 2013-11-13 | 海南大学 | In-situ polymerization method of nano starch/SiO2 composite particles |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622841A (en) * | 2015-12-10 | 2016-06-01 | 北京化工大学 | Preparation method of silica/poly(itaconate-isoprene-glycidyl methacrylate) bio-based elastomer composite material |
| CN109266044A (en) * | 2018-11-14 | 2019-01-25 | 陶伟珍 | A kind of preparation method of rubber modification infusorial earth filler |
| CN111793258A (en) * | 2020-07-24 | 2020-10-20 | 吉林农业大学 | Corn byproduct based synthetic rubber environment-friendly material and preparation method thereof |
| CN111793258B (en) * | 2020-07-24 | 2022-04-19 | 吉林农业大学 | Corn byproduct based synthetic rubber environment-friendly material and preparation method thereof |
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Application publication date: 20140723 |