CN103627055B - Utilize the method that modified microcrystalline cellulose prepares tire tread glue - Google Patents
Utilize the method that modified microcrystalline cellulose prepares tire tread glue Download PDFInfo
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- CN103627055B CN103627055B CN201310548311.7A CN201310548311A CN103627055B CN 103627055 B CN103627055 B CN 103627055B CN 201310548311 A CN201310548311 A CN 201310548311A CN 103627055 B CN103627055 B CN 103627055B
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- microcrystalline cellulose
- modified microcrystalline
- rubber
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- tire tread
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
The invention discloses a kind of method utilizing modified microcrystalline cellulose to prepare tire tread glue, its step includes: one, utilize functional ionic liquids modified microcrystalline cellulose；Two, modified microcrystalline cellulose is applied in reinforcement tread rubber technique, by conventional calendering process, modified microcrystalline Cellulose part is replaced white carbon and obtains elastomeric compound；Elastomeric compound is carried out sulfuration sizing according to technique sulfurizing time at 130 180 DEG C, i.e. can get vulcanizate.The present invention is by utilizing functional ionic liquids (containing double bond, rubber accelerator or sulfuration base etc.) modified microcrystalline cellulose, it is effectively improved microcrystalline Cellulose to disperse in rubber matrix, improve microcrystalline Cellulose and rubber matrix, the interaction of white carbon, limit the formation of white carbon network structure simultaneously, it is applied in tire tread glue to improve the intensity of tread rubber, significantly improves the anti-slippery of tread rubber, reduce the resistance to rolling of tire simultaneously, preparation technology is simple, non-environmental-pollution.
Description
Technical field
The present invention relates to the preparation technology of a kind of tire tread glue, particularly relate to one and utilize modified microcrystalline cellulose to prepare
The method of tire tread glue.
Background technology
White carbon black, white carbon are as the efficient reinforcing agent of rubber industry, and they have irreplaceablely in reinforcing rubber
Position.But white carbon black is in processing with during using, and there are the following problems: 1. processing pollution is serious, white carbon black producing, accumulating and to rubber
Easily fly upward when glue adds, even banbury is also difficult avoids the infringement to operator's health；2. long processing time, power consumption
Greatly；3. big to the dependency of oil.White carbon black is petrochemicals, and it continues substantial amounts of consumption and is necessarily unprofitable to alleviate oil money
The growing tension in source；4. white carbon black density is higher, so that vulcanite density substantially increases, thus compromises to a certain extent
This key property of macromolecular material light weight, adds the volume cost of rubber.
Cellulose is the natural macromolecular material that plant is synthesized by photosynthesis, it be widely present in plant, animal and
In antibacterial, the producible cellulose of annual nature is up to 1010～1011Ton.Can be prepared as various after native cellulose regeneration
Regenerated cellulose chopped fiber.As a kind of resourceful chopped fiber renewable, degradable, if being applied to rubber material
The reinforcement of material, will inject new vitality for development low cost, high-performance, degradable rubber-base composite material industry.
In recent years, the microcrystalline Cellulose as natural polymers is studied and in high-performance tire at reinforcing rubber
Application cause the extensive concern of people.At present in rubber industry, improve the most frequently used in rubber matrix of microcrystalline Cellulose
Method have two kinds, one be add surface modifier, another kind is chemical grafting treated.Wherein chemical grafting treated method effect
Preferably, but General reactions condition is harsher, processes technics comparing loaded down with trivial details, and production cost is higher.Adding surface modifier is one
Plant method simply and easily.What process microcrystalline Cellulose was the more commonly used at present has silane coupler, titanate coupling agent, surface
The micromolecular compounds such as activating agent.These micromolecular compounds can react with the hydroxyl on white carbon surface, it is generally required to
White carbon is carried out pretreatment, and discharges small-molecule substance, environment and operator are worked the mischief.
At present at Polymeric Industry, the method for modifying for microcrystalline Cellulose is more, the Chinese patent (patent No.
03114288.5) in the water dispersion medium of nano micro crystal cellulose, add hydrophilic colloid and uniformly divide with ultrasound wave
Dissipate, be then dried, pulverize prepared Easily-water dispersible nanocrystalline cellulose.United States Patent (USP) (patent No. 3539365) discloses
By addition hydroxymethyl cellulose is blended in microfine cellulose crystallite (particle diameter minimum reaches micron order), to overcome microfine cellulose micro-
The brilliant reunion also occurred because of surface hydrogen bond action.Chinese patent (patent No. 03126825.0, application number 201210156331.5)
In liquid dispersion medium, under catalyst action, ultra-fine and nano micro crystal cellulose are reacted with esterifying liquid, obtains surface ester
Change modified microcrystalline Cellulose.Chinese patent (application number 201110333820.9) first with anhydrous dimethyl sulphoxide to after drying
Microcrystalline Cellulose carry out swelling, then carry out nanorize process with thionyl chloride, be finally passed through ammonia and be modified, at ultrasound wave
Obtain stable nano-cellulose suspension under auxiliary, the most freeze-dried obtain carboxide modified nanometre cellulose.China
Microcrystalline Cellulose is first carried out surface grafting process by patent (patent No. 200810219532.9), then by micro-for obtained modification
Crystalline cellulose uses traditional rubber processing and compounding rubber, prepares rubber/modified microcrystalline cellulose composite material, and this is multiple
Condensation material has preferable mechanical property.Chinese patent (application number 201010522126.7, application number 201010522109.3)
After nano micro crystal cellulose is first mixed with latex, add in Heveatex, be dried to obtain nano micro crystal cellulose/natural
Rubber composition, is subsequently adding white carbon black or white carbon carries out mixing, obtains the rubber of nano micro crystal cellulose reinforcement.
In view of the foregoing it is apparent that, currently utilize the problem existing for microcrystalline Cellulose reinforced rubber still have following some:
(1) great amount of hydroxy group is contained on microcrystalline Cellulose surface, and therefore microcrystalline Cellulose interphase interaction is relatively strong, at rubber matrix
In dispersed difficulty, especially after the size of microcrystalline Cellulose is reduced to nanoscale by micron order, agglomeration is tighter
Weight, greatly reduces the reinforcing effect of microcrystalline Cellulose.
(2) microcrystalline Cellulose surface polarity is relatively strong, poor with the interfacial adhesion row of conventional nonpolar polydiene,
Interface bond strength is more weak, this reduces the reinforcing effect of microcrystalline Cellulose.
(3) in order to improve the dispersion of microcrystalline Cellulose, typically cellulose first must be total to retrogradation with natural rubber latex, then
Carry out mixing again, complex manufacturing, and relatively costly.
Summary of the invention
In order to solve the problems of the prior art, it is an object of the invention to provide that a kind of technique is simple, low cost, modified effect
The best, the modified microcrystalline cellulose that utilizes required that uses that can meet High-performance green tire prepares the side of tire tread glue
Method.
For reaching above-mentioned purpose, the technology used in the present invention means are: utilize modified microcrystalline cellulose to prepare tire
The method of face glue, its step includes:
One, functional ionic liquids modified microcrystalline cellulose is utilized: first by ionic liquid, deionized water and microcrystalline cellulose
Element joins in reactor, stirs 3h at 80 DEG C, and the product after then stirring being terminated is dried 12h at 80 DEG C, obtained ion
Liquid modifying microcrystalline Cellulose；
Two, modified microcrystalline Cellulose is applied in reinforced rubber technique: mixing, in mill or banbury by base
Body rubber is the most mixing with ion liquid modified microcrystalline Cellulose, is subsequently adding white carbon, adds adjuvant, finally adds sulfur and rush
Entering agent, thin leading to beat bottom sheet after triangle bag 6 times, obtain elastomeric compound, above-mentioned mixing initial temperature is 70-100 DEG C, mixing rotating speed 40-
70 turns/min, mixing total time is 6-10min；Sulfuration is shaped, is vulcanized by elastomeric compound 130-180 DEG C, and cure time is served as reasons
The technique sulfurizing time that vulcameter determines, i.e. can get vulcanizate.
Further, the ionic liquid in described step one is alkyl imidazole halogen, wherein alkyl be containing double bond, polysulfide bond or
Promoting the group of base, anion is Cl-or Br-.
Further, in described step one, ionic liquid: microcrystalline Cellulose: deionized water=1～5: 100:
300。
Further, in described step one, the particle diameter of microcrystalline Cellulose is 1-100um.
Further, microcrystalline Cellulose in described step 2: white carbon is 5～25: 45～25.
Further, in described step 2, adjuvant includes TBBS(NS), Si-69, zinc oxide, stearic acid.
The beneficial effects of the present invention is: improve microcrystalline Cellulose and disperse in rubber matrix, improve processing characteristics；Improve
The interaction of microcrystalline Cellulose rubber matrix；Improve the interaction of microcrystalline Cellulose and white carbon, limit white carbon network
Formation；It is applied to tread rubber, resistance to rolling can be significantly reduced, improve the anti-slippery of tread rubber simultaneously；Preparation technology letter
Single, non-environmental-pollution.
Accompanying drawing explanation
The present invention is described further with embodiment below in conjunction with the accompanying drawings.
Fig. 1 is dynamic mechanical (DMA) performance chart of vulcanizate of the present invention.
Detailed description of the invention
Embodiment 1
Utilizing the method that modified microcrystalline cellulose prepares tire tread glue, its step includes:
Utilize functional ionic liquids modified microcrystalline cellulose: 1g allyl imidazole chlorine ([AMIM] Cl) ion will be filled
Liquid, 100g microcrystalline Cellulose, 300g deionized water is placed in glass reactor, heats and stirring in 80 DEG C of water-baths
3h, the above-mentioned product after then stirring being terminated dries 12h in the vacuum drying oven of 80 DEG C, cool down i.e. obtain ion liquid modified
Microcrystalline Cellulose；Wherein the particle diameter of microcrystalline Cellulose is 20-80um.
Modified microcrystalline Cellulose is applied in reinforced rubber technique: mixing, in banbury by base rubber first with
Ion liquid modified microcrystalline Cellulose is mixing, and mixing initial temperature is 90 DEG C, mixing 60 turns/min of rotating speed, is subsequently adding Linesless charcoal
Black, the most ion liquid modified microcrystalline Cellulose 5, white carbon 45 g, add adjuvant TBBS(NS) 1g and Si-69 3.6g,
Zinc oxide 3g, stearic acid 1g, finally add sulfur 1.76g and diphenylguanidine PG 1g, the thinnest logical beat after triangle bag for 6 times under
Sheet, obtains elastomeric compound, and above-mentioned mixing initial temperature is 70-100 DEG C, mixing rotating speed 40-70 turns/min, and mixing total time is
8min；Sulfuration is shaped, is vulcanized by elastomeric compound 160 DEG C, and cure time is the technique sulfurizing time determined by vulcameter, i.e.
Available vulcanizate.
Embodiment 2
Utilizing the method that modified microcrystalline cellulose prepares tire tread glue, its step includes:
Utilize functional ionic liquids modified microcrystalline cellulose: 1g allyl imidazole chlorine ([AMIM] Cl) ion will be filled
Liquid, 100g microcrystalline Cellulose, 300g deionized water is placed in glass reactor, heats and stirring in 80 DEG C of water-baths
3h, the above-mentioned product after then stirring being terminated dries 12h in the vacuum drying oven of 80 DEG C, cool down i.e. obtain ion liquid modified
Microcrystalline Cellulose；Wherein the particle diameter of microcrystalline Cellulose is 20-80um.
Modified microcrystalline Cellulose is applied in reinforced rubber technique: mixing, in banbury by base rubber first with
Ion liquid modified microcrystalline Cellulose is mixing, and mixing initial temperature is 90 DEG C, mixing 60 turns/min of rotating speed, is subsequently adding Linesless charcoal
Black, the most ion liquid modified microcrystalline Cellulose 10 g, white carbon 40 g, add adjuvant TBBS(NS) 1g and Si-69
3.2g, zinc oxide 3g, stearic acid 1g, finally add sulfur 1.76g and diphenylguanidine PG 1g, the thinnest leading to beats triangle 6 times
Bottom sheet after bag, obtains elastomeric compound, and above-mentioned mixing initial temperature is 70-100 DEG C, mixing rotating speed 40-70 turns/min, mixing total time
For 8min；Sulfuration is shaped, is vulcanized by elastomeric compound 160 DEG C, and cure time is the technique sulfurizing time determined by vulcameter,
I.e. can get vulcanizate.
Embodiment 3
This embodiment is the comparative example of embodiment 1, and difference from Example 1 is: the crystallite wherein added
Cellulose is unmodified microcrystalline Cellulose, and added quality is the most identical.
Embodiment 4
This embodiment is the comparative example of embodiment 2, and difference from Example 2 is: the crystallite wherein added
Cellulose is unmodified microcrystalline Cellulose, and added quality is the most identical.
Embodiment 5
This embodiment is comparative example, and wherein adding white carbon is 50g, is added without microcrystalline Cellulose, the Si-added
69 4g,
Sulfur 1.78g.
The physical and mechanical properties of the vulcanizate obtained in above-mentioned 5 embodiments is as shown in the table.
Above-mentioned experimental data shows, after ion liquid modified cellulose replaces 5phr white carbon, and the physical mechanical of vulcanizate
Performance has raising by a relatively large margin, and after unmodified microcrystalline Cellulose replaces 5phr white carbon, the Physical Mechanical of vulcanizate
Can decline.The dynamic property of vulcanizate is as shown in Figure 1.From fig. 1, it can be seen that the vulcanizate containing ion liquid modified microcrystalline Cellulose exists
Tan δ-value at 0 DEG C is higher, and the tan δ-value at 60 DEG C is relatively low, illustrates that this sizing material has anti-slippery good, rolls resistance simultaneously
The advantage that power is low.
Ionic liquid (ionic liquids) and cellulose have extremely strong interaction, it might even be possible to be partly dissolved fibre
Dimension element.And ionic liquid and white carbon black are by pi-pi bond, can also produce the strongest interaction with white carbon by hydroxyl.This
Invention utilizes and can be with the functional ionic liquids (containing double bond, polysulfide bond or promotion base etc.) of rubber matrix generation chemical action
Modifying agent, can combine closely microcrystalline Cellulose-rubber matrix-reinforced filling, form firm interface cohesion, to rubber
Glue produces significant strengthening action and other modifying functions.The present invention strong phase interaction based on glyoxaline ion liquid with cellulose
With, utilize functional ionic liquids (containing double bond, polysulfide bond or promotion base etc.) modified microcrystalline cellulose, both can effectively prevent
The reunion of cellulose, can improve again the interaction between microcrystalline Cellulose and rubber.The application of this technology, with tread rubber, can be composed
Give the characteristic that below sizing material is excellent:
1. improve microcrystalline Cellulose to disperse in rubber matrix, improve processing characteristics.
2. the interaction of microcrystalline Cellulose rubber matrix is improved.
3. improve microcrystalline Cellulose and white carbon, the interaction of white carbon black, break white carbon black, white carbon network.
4. application and tread rubber, can significantly improve the anti-slippery of tread rubber, reduce the resistance to rolling of tire simultaneously.
5. preparation technology is simple, can use method for pretreating can also during rubber processing in-situ treatment microcrystalline cellulose
Element.
The present embodiment utilizes ionic liquid aqueous solution pretreatment microcrystalline Cellulose, it is also possible to straight during rubber processing
Connect addition functional ionic liquids, in-situ treatment microcrystalline Cellulose during rubber processing.Both technique has modified effect
Fruit is notable, technical process is simple, the feature of green non-pollution.Technical staff, can be easily in the technical scope that the invention discloses
Expect change or replace, all should contain within protection scope of the present invention.
Claims (5)
1. utilize the method that modified microcrystalline cellulose prepares tire tread glue, it is characterised in that step includes:
One, functional ionic liquids modified microcrystalline cellulose is utilized: first ionic liquid, deionized water and microcrystalline Cellulose are added
Entering in reactor, stir 3h at 80 DEG C, the product after then stirring being terminated is dried 12h at 80 DEG C, is obtained ionic liquid
Modified microcrystalline cellulose；
Two, modified microcrystalline Cellulose is applied in reinforced rubber technique: mixing, in mill or banbury by matrix rubber
Glue is the most mixing with modified microcrystalline Cellulose, is subsequently adding white carbon, adds adjuvant, finally adds sulfur and accelerator, thin
Logical beat bottom sheet after triangle bag 6 times, obtain elastomeric compound, above-mentioned mixing initial temperature is 70-100 DEG C, mixing rotating speed 40-70 turn/
Min, mixing total time is 6-10min；Sulfuration is shaped, is vulcanized by elastomeric compound 130-180 DEG C, and cure time is by vulcameter
The technique sulfurizing time determined, i.e. can get vulcanizate；
In described step one, ionic liquid: microcrystalline Cellulose: mass ratio=1 of deionized water～5: 100: 300.
The method utilizing modified microcrystalline cellulose to prepare tire tread glue the most according to claim 1, it is characterised in that: institute
Stating the ionic liquid in step one is alkyl imidazole halogen, and wherein alkyl is double bond containing group, and anion is Cl-, Br-。
The method utilizing modified microcrystalline cellulose to prepare tire tread glue the most according to claim 1, it is characterised in that: institute
Stating the particle diameter of microcrystalline Cellulose in step one is 1-100um.
The method utilizing modified microcrystalline cellulose to prepare tire tread glue the most according to claim 1, it is characterised in that: institute
State the adjuvant in step 2 and include TBBS, Si-69, zinc oxide, stearic acid.
The method utilizing modified microcrystalline cellulose to prepare tire tread glue the most according to claim 1, it is characterised in that: institute
State microcrystalline Cellulose in step 2: the mass ratio of white carbon is 5～25: 45～25.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019053602A1 (en) * | 2017-09-13 | 2019-03-21 | Pirelli Tyre S.P.A. | Tyre for vehicle wheels comprising a composite reinforcing filler |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6449580B2 (en) * | 2014-07-25 | 2019-01-09 | 東洋ゴム工業株式会社 | Pneumatic tire manufacturing method and tire member manufacturing method |
| CN104629105B (en) * | 2015-01-27 | 2017-01-11 | 山东大学 | Microcrystalline cellulose reinforced rubber wear-resistant material and preparation method thereof |
| CN106087411B (en) * | 2016-06-06 | 2018-06-12 | 深圳市新纶科技股份有限公司 | A kind of modifying aramid fiber pulp and preparation method thereof and the brake block manufactured with it |
| CN106519352B (en) * | 2016-09-20 | 2018-12-04 | 青岛科技大学 | Microcrystalline cellulose-nano silicon dioxide hybridization material, preparation method and its application |
| CN106478991A (en) * | 2016-10-11 | 2017-03-08 | 青岛科技大学 | A kind of preparation method and applications of microcrystalline cellulose nano-ZnO hybrid material |
| CN107674254A (en) * | 2017-09-29 | 2018-02-09 | 安徽北马科技有限公司 | A kind of production method of tire tread glue |
| 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 |
| CN114437430B (en) * | 2022-02-28 | 2023-08-11 | 青岛科技大学 | High-wear-resistance rubber-based composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412825A (en) * | 2008-11-28 | 2009-04-22 | 华南理工大学 | Rubber / modified microcrystalline cellulose composite material and preparation thereof |
| CN102002173A (en) * | 2010-10-26 | 2011-04-06 | 华南理工大学 | Preparation method for nanocrystals cellulose/white carbon black/rubber composite material |
| CN102382870A (en) * | 2011-08-10 | 2012-03-21 | 中国科学院西双版纳热带植物园 | Method for pretreating and hydrolyzing microcrystalline cellulose |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007005388A2 (en) * | 2005-06-29 | 2007-01-11 | The University Of Alabama | Ionic liquid reconstituted cellulose composites as solid support matrices |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412825A (en) * | 2008-11-28 | 2009-04-22 | 华南理工大学 | Rubber / modified microcrystalline cellulose composite material and preparation thereof |
| CN102002173A (en) * | 2010-10-26 | 2011-04-06 | 华南理工大学 | Preparation method for nanocrystals cellulose/white carbon black/rubber composite material |
| CN102382870A (en) * | 2011-08-10 | 2012-03-21 | 中国科学院西双版纳热带植物园 | Method for pretreating and hydrolyzing microcrystalline cellulose |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019053602A1 (en) * | 2017-09-13 | 2019-03-21 | Pirelli Tyre S.P.A. | Tyre for vehicle wheels comprising a composite reinforcing filler |
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