CN109749168A - A kind of nano zine oxide/rubber composite material and preparation method - Google Patents
A kind of nano zine oxide/rubber composite material and preparation method Download PDFInfo
- Publication number
- CN109749168A CN109749168A CN201711067574.0A CN201711067574A CN109749168A CN 109749168 A CN109749168 A CN 109749168A CN 201711067574 A CN201711067574 A CN 201711067574A CN 109749168 A CN109749168 A CN 109749168A
- Authority
- CN
- China
- Prior art keywords
- rubber
- latex
- composite material
- nano zine
- zine oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a kind of nano zine oxide/rubber composite material and preparation methods.The composite material is by including that the raw material of following components is prepared: rubber latex and nano zinc oxide fluid dispersion；The dosage of nano zine oxide is 15~80wt.% of rubber latex；Rubber latex is one of butadiene-vinylpyridine copylymer latex, butadiene styrene vinyl pyridine latex, carboxylic styrene butadiene latex, carboxylic acrylonitrile butadiene rubber latex, epoxy natural latex or combination.Preparation method includes: (1) by nano zinc oxide fluid dispersion 5~60min of ultrasound, obtains stable nano zinc oxide suspension；(2) nano zinc oxide suspension is added slowly to be sufficiently mixed in the rubber latex stirred to the two；(3) flocculation (4) is dry.Method and process of the invention is simple, and while zinc oxide dosage reduces in making rubber compounding, application performance (such as mechanical property) is suitable with conventional oxidation zinc, even more preferably.
Description
Technical field
The present invention relates to technical field of rubber vulcanization, further say, are to be related to a kind of nano zine oxide/rubber composite wood
Material and preparation method.
Background technique
Vulcanization can make natural rubber or synthetic rubber be transformed into valuable vulcanized rubber.Common vulcanizing system is sulphur
Vulcanizing system, for the system, vulcanization accelerator and activator are essential.They can reduce sulfur consumption,
Shorten vulcanization time, reduces curing temperature, while improving the physical and chemical performance etc. of state of cure (vulcanization) and vulcanizate.It is well known that
Zinc oxide is important vulcanizing activator, from nineteen twenty-three it is found that zinc oxide have vulcanization activation since continue to use always to
It is modern.The effect of zinc oxide is embodied in following three aspects: (1) cure activation system；(2) crosslink density of vulcanizate is improved；(3)
Improve the ageing-resistant performance of vulcanizate.
Early in the harmful substance inventory in 2003, European Union's 2003/105/EC regulation just include zinc oxide.This bill refers to
Out, when zinc is released to environment, when into streams, river and ocean, the alloy of certain zinc can poison microorganism and aquatic life
Object.The production of outdoor Rubber (rubber scraps that such as tire generates during braking, acceleration) and zinc oxide
Enterprise may be one of main source of zinc pollution.At the beginning of 2016, California, USA proposes a bill (SB1260),
It is recommended that being limited in tire using zinc or zinc oxide, while forbidding sale containing the tire product higher than a certain amount of zinc.Therefore,
Small environmental pollution and active high vulcanizing activator are developed in recent years, are reduced zinc oxide dosage and are had become important research content.
Conventional oxidation zinc cure activation reaction essence is interfacial reaction, and only the zinc ion in the zinc oxide on surface can be sent out
The effect of waving, a large amount of zinc ion in particle inside are still in zinc oxide lattice.Zinc oxide is thus caused greatly to waste.
In order to improve the service efficiency of zinc oxide and reduce the harm of zinc oxide, one such method is exactly the nanosizing of zinc oxide,
Increase reaction interface, so that more zinc oxide and promotor is formed compound, achieve the effect that decrement.But using nano oxygen
When changing zinc, it has to three problems below considering: first, between hydrophilic nano zine oxide and lipophilic rubber matrix
Affinity is low, poor compatibility；Second, the high surface of nano zine oxide generates reunion between capable of will lead to its particle；Third, nano oxygen
Change zinc aggregate meeting adsorbed water molecule, forms hydroxyl on surface, make zinc oxide that can be hardened.Therefore, nano oxygen is only really solved
Change zinc stronger reunite tendency and poor dispersibility, its nano effect of competence exertion in rubber matrix.
In recent years, during preparing nano zine oxide, different modifying agent is added, adjustable nano zine oxide is dredged
It is aqueous, so that it be made to obtain good dispersion in rubber matrix, more efficient sulfurate activity is played, reduces the use of zinc oxide
Amount.But if the organic modifier of surface of nanometer zinc oxide cladding cannot be sloughed during vulcanization reaction, oxygen certainly will be hindered
Change zinc and stearic acid, promotor etc. to react, so as to cause " inactivation " of nano zine oxide.So being carried out to nano zine oxide
While modified, it is necessary to take into account its polymolecularity and high-sulfurized activity.
Summary of the invention
It is easy to reunite to solve nano-zinc oxide powder in the prior art, and the problems such as with rubber matrix poor compatibility；This
Invention provides a kind of nano zine oxide/rubber composite material and preparation method.Make the hydroxyl and function of surface of nanometer zinc oxide
Functional group in rubber forms hydrogen bond action, to facilitate dispersion of the nano zine oxide in the rubber, realizes and uniformly divides
It dissipates.The advantage of its high-specific surface area is played, so as to achieve the purpose that reduce zinc oxide dosage in rubber compounding.
An object of the present invention is to provide a kind of nano zine oxide/rubber composite material.
The composite material is by including that the raw material of following components is prepared:
Rubber latex and nano zinc oxide fluid dispersion；
The dosage of nano zine oxide is 15~80wt.% of rubber；It is preferred that 20~50wt.%.
Rubber latex is butadiene-vinylpyridine copylymer latex, butadiene styrene vinyl pyridine latex, carboxylic styrene butadiene latex, carboxylic acrylonitrile butadiene rubber latex, epoxy natural latex
One of or combination.The preferred solid content of the rubber latex in 20~50wt.%, wherein the ratio of functional group 3~
50wt.%.
Wherein, preferably:
The Particle Size of Nanometer ZnO range is 20~500nm, more preferably 50~100nm.
The second object of the present invention is to provide nano zine oxide/rubber composite material preparation method described in one kind.
Include:
(1) by nano zinc oxide fluid dispersion 5~60min of ultrasound, stable nano zinc oxide suspension is obtained；
(2) nano zinc oxide suspension is added slowly to be sufficiently mixed in the rubber latex stirred to the two；
(3) it flocculates: the latex that step (2) mixes being poured slowly into flocculant solution while stirring, is flocculated
Object；
(4) dry.
Resulting floccule is drained away the water, is shredded, is placed in air dry oven, dry 2~72h at 40~180 DEG C.
Wherein, preferably:
The concentration of nano zinc oxide fluid dispersion is 15~50wt.%.
Step (2), speed of agitator are 20~800r/min, 10~60min of mixing time；
Step (3), speed of agitator are 20~800r/min.
40~180 DEG C of drying temperature of step (4)；2~72h of drying time.
The flocculant is one of hydrochloric acid, sulfuric acid, calcium chloride, magnesium chloride, aluminium chloride, sodium chloride or combination；
The concentration 1wt.% of flocculant solution is to saturated concentration.
Following technical scheme specifically can be used in the present invention:
(1) nano zine oxide/rubber masterbatch preparation
(a) it is dense that nano-zinc oxide powder the preparation of nano zinc oxide fluid dispersion: is add to deionized water preparation quality
Degree is the zinc oxide fluid dispersion (or commercially available zinc oxide fluid dispersion) of 15~50wt.%, then 5~60min of ultrasound, is obtained steady
Fixed nano zinc oxide suspension.
(b) nano zine oxide/rubber latex is compound: mass fraction of the nano zine oxide in rubber is 15~80wt.%；
Nano zinc oxide fluid dispersion is added slowly in the rubber latex stirred, speed of agitator is 20~800r/min, is stirred
It mixes 10~60min and is sufficiently mixed to the two；
(c) it flocculates:, flocculant solution is prepared, it is under the speed of agitator of 20~800r/min, the latex mixed is slow
It pours into；
(d) dry: resulting floccule being drained away the water, is shredded, is placed in air dry oven, is done at 40~180 DEG C
Dry 2~72h.
(2) it is kneaded and vulcanizes: mixing in rubber is added in nano zine oxide rubber master batch and other rubber chemicals and obtains rubber compound；
Rubber compound obtains vulcanizate by vulcanization.
The nano oxidized partial size can configure dispersion liquid and rubber glue in 20~500nm for nano-zinc oxide powder
Cream is compound；Also nano zinc oxide fluid dispersion can be directly used and latex progress is compound；Preferable particle size is the oxidation of 50~100nm
Zinc.It in addition, zinc oxide is not limited only to pure zinc oxide, while also including support type zinc oxide.
Functional group in the hydroxyl and functional rubber of surface of nanometer zinc oxide of the invention forms hydrogen bond action, to have
Help dispersion of the nano zine oxide in the rubber, realizes evenly dispersed.The advantage of its high-specific surface area is played, so as to reach
To the purpose for reducing zinc oxide dosage in rubber compounding.Also, this nano zine oxide/rubber composite material is applied to rubber sulphur
Change formula substitution conventional oxidation zinc, sulfurate activity with higher and efficiency, the dosage of zinc oxide in sulfurizing formula can be made bright
It is aobvious to reduce.Method and process of the invention is simple, while zinc oxide dosage reduces in making rubber compounding, application performance (such as power
Learn performance) it is suitable with conventional oxidation zinc, even more preferably.
Detailed description of the invention
The SEM photograph of Fig. 1-1 embodiment 1；
The SEM photograph of Fig. 1-2 embodiment 2；
The SEM photograph of Fig. 1-3 embodiment 3；
The SEM photograph of Fig. 1-4 embodiment 4；
The SEM photograph of Fig. 1-5 embodiment 8；
The SEM photograph of Fig. 1-6 comparative example 2；
The SEM photograph of Fig. 1-7 comparative example 3.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Raw materials used in embodiment is commercially available.
Embodiment 1
The preparation of nano zine oxide/butadiene-vinylpyridine rubber rubber master batch: (1) it configures the nano zinc oxide fluid dispersion of 20wt.%: weighing
The nano-zinc oxide powder (zinc oxide partial size is 300nm or so) of 10g, is added in 40g deionized water, ultrasonic 15min is obtained
The nano zinc oxide fluid dispersion of system stable homogeneous, for use；(2) butadiene-vinylpyridine copylymer latex (the vinylpyridine structure list of 20wt.% is configured
First content is 3wt.%): the butadiene-vinylpyridine copylymer latex that 125g solid content is 40wt.% is weighed, 125g deionized water is added to be diluted to
20wt.%；(3) slowly rubber latex is added in nano zinc oxide fluid dispersion, mechanical stirring revolving speed 300r/min, when stirring
Between 30min, obtain uniform and stable dispersion liquid；(4) configure 0.5L 2wt.% calcium chloride solution, by the rubber mixed/
Nano zinc oxide fluid dispersion, which is added in calcium chloride solution, to flocculate；(5) obtained rubber master batch is cut into small pieces, it is dry as 60 DEG C of air blast
In dry case, drying is for 24 hours.The stereoscan photograph of composite material is shown in Fig. 1-1；Compared with comparative example 2, identical nano zine oxide contains
It measures, the dispersion of nano zine oxide is more preferable in butadiene-vinylpyridine rubber.Tensile strength and the stress that composes oneself are higher.
Rubber compounding used are as follows: nano zine oxide/butadiene-vinylpyridine rubber composite material: 5phr (is equivalent to 1phr conventional oxidation
Zinc), the poly- butylbenzene ESBR1502:100phr of cream, stearic acid SA:1phr, carbon black N330:40phr, antioxidant 4010NA: 2phr, rush
Into agent NS:1.7phr, sulphur: 1.5phr and activating agent 5phr.
Rubber processing: banbury rotating speed is set as 60r/min, heating is not opened, after emulsion polymerized styrene butadiene rubber is cut into small pieces
It is added in mixer, plasticate 2min；Load weighted zinc oxide, stearic acid, anti-aging agent 4041NA is added, is kneaded 2min；It is added one
The other half remaining carbon black is added after being kneaded 1min in half load weighted carbon black；It is kneaded 6min back glue.Sizing material stands cooling and is opening
Add accelerator NS and sulphur in mill, keeps rubber compounding uniform by beating triangle bag, rubbing volume with the hands, last slice obtains rubber compound.Glue
After material stands 8h, sulfurizing time is obtained by no rotor vulcameter, obtains required vulcanization on vulcanizing press with 150 DEG C
Glue.It is tested according to national standards, gained performance is shown in Tables 1 and 2.
Compared with comparative example 1 and comparative example 2, nano zine oxide in embodiment 1 due to containing in functional group rubber
Functional group between there are hydrogen bond action, so nano zine oxide has preferably dispersibility.Therefore, 1 data of contrast table, it is real
Example 1 is applied with faster curingprocess rate, i.e. optimum sulfurating time T90 is smaller.In addition, the data in contrast table 2, embodiment 1
The tensile strength of vulcanized rubber has obvious promotion, and 300% stress at definite elongation significantly increases.The crosslinking of stress at definite elongation and rubber
Density is positively correlated, and illustrates that the rubber that embodiment 1 obtains has bigger crosslink density.In conclusion we prepare it is novel
Vulcanizing activator has more preferably effect than nano-zinc oxide powder and nano zine oxide/General Purpose Rubber latex composite material.
Embodiment 2
Unlike the first embodiment, in nano zine oxide/butadiene-vinylpyridine rubber composite material, zinc oxide is in rubber latex
Content is 30wt.% in this embodiment.In addition, the solid content of butadiene styrene vinyl pyridine latex used is 20wt.% in this embodiment.Other
Technique and vulcanization aid type and dosage are same as Example 1.The stereoscan photograph of composite material is shown in Fig. 1-2；
Compared with comparative example 3, the nano zine oxide in embodiment 2 has preferably dispersibility, in addition compares Tables 1 and 2
Data find that embodiment 2 has more preferably curability and mechanical property.
Embodiment 3
Unlike the first embodiment, in butadiene-vinylpyridine copylymer latex, fourth pyrrole strand medium vinyl pyridine structure unit content, this reality
It applies in example as 15wt.%.；In addition, a difference another with embodiment 1 is the concentration of nano zinc oxide fluid dispersion, this implementation
Example is 15wt.%.Other techniques and vulcanization aid type and dosage are same as Example 1.The stereoscan photograph of composite material
See Fig. 1-3；
Embodiment 4
Unlike the first embodiment, in nano zine oxide/butadiene-vinylpyridine rubber composite material, in butadiene styrene vinyl pyridine latex, butylbenzene pyrrole point
Subchain medium vinyl pyridine structure unit content is 50wt.% in this embodiment.In addition, a difference is nano zine oxide
The concentration of dispersion liquid, this embodiment are 50wt.%.Other techniques and vulcanization aid type and dosage are same as Example 1.
Comparing embodiment 1, embodiment 3 and embodiment 4 have differing ethylene yl pyridines knot in three kinds of butadiene-vinylpyridine rubber strands
Structure unit content, with the increase of functional group content, time of scorch is reduced, and is illustrated that the alkalinity of vinylpyridine has reaction and is added
It is quick-acting to answer, but the mechanical property of final vulcanized rubber is close.
Embodiment 5
As different from Example 3, in nano zine oxide/butadiene-vinylpyridine rubber composite material, zinc oxide is in rubber latex
Content is 30wt.% in this embodiment.In addition, speed of agitator is 800r/min, mixing time 10min in this embodiment.Its
His technique and vulcanization aid type and dosage are same as Example 1.The stereoscan photograph of composite material is shown in Fig. 1-4；
Embodiment 6
Unlike the first embodiment, in nano zine oxide/butadiene-vinylpyridine rubber composite material, the type and oxidation of function latex
Content of the zinc in rubber composite material, rubber latex used in this embodiment are that (latex solid content is butadiene styrene vinyl pyridine latex
40wt.% and carboxyl-content are 3wt.%), and content of the zinc oxide in rubber composite material is 15wt.% in this embodiment.Its
His technique and vulcanization aid type and dosage are same as Example 1.
Embodiment 7
Unlike the first embodiment, in nano zine oxide/rubber composite material, the type and zinc oxide of function latex exist
Content in rubber latex, rubber latex used in this embodiment is that (solid content is 40wt.% and ring to epoxy natural latex
Oxygen degree of functionalization is that 25%), content of the zinc oxide in rubber latex is 80wt.%.Other techniques and vulcanization aid type
It is same as Example 1 with dosage.
Comparing embodiment 1, embodiment 6 and embodiment 7 can all make to receive although changing the type of function latex
The rice good dispersion of zinc oxide, the curability and mechanical property of final vulcanized rubber are close.
Embodiment 8
Unlike the first embodiment, in nano zine oxide/butadiene-vinylpyridine rubber composite material, the partial size of zinc oxide, this embodiment
In for 60nm or so.Other techniques and vulcanization aid type and dosage are same as Example 1.The stereoscan photograph of composite material
See Fig. 1-5；
It is compound by lotion even if the partial size of nano zine oxide is reduced to 60nm from 300nm compared with embodiment 1
Method, it still has preferable dispersibility (comparison attached drawing 1-1 and 1-5) in functional rubber (tertiary pyrrole gum).Also, contrast table
Data in 2, Particle Size of Nanometer ZnO is smaller, can obtain bigger tensile strength and (be promoted from 24MPa to 26.97MPa).
Comparative example 1
Be not added nano zine oxide/butadiene-vinylpyridine rubber composite material unlike embodiment 1 is unique, but with traditional handicraft one
Sample uses conventional oxidation zinc.Other techniques and vulcanization aid type and dosage are same as Example 1.
Comparative example 2
It is different from embodiment 1, butadiene-vinylpyridine copylymer latex is replaced using common styrene-butadiene latex.Other techniques and vulcanization aid type
It is same as Example 1 with dosage.Would not there are hydrogen bond action, nano zine oxide between nano zine oxide and rubber molecule in this way
It will be become difficult in the dispersion of rubber.The stereoscan photograph of composite material is shown in Fig. 1-6；
Comparative example 3
It is different from comparative example 2, in nano zine oxide/styrene-butadiene rubber composite material, the content of zinc oxide, in this embodiment
For 30wt.%.The stereoscan photograph of composite material is shown in Fig. 1-7；
The curability of rubber is shown in Table 1
The mechanical property of vulcanization of rubber glue is shown in Table 2
It can be seen that, due to nano zine oxide and contain the rubber of functional group in SEM picture in Figure of description
There are hydrogen bond actions between molecule, and hydrogen bond action is not present between butadiene-styrene rubber and nano zine oxide common in comparative example.
So dispersion of the nano zine oxide in the rubber containing functional group is more uniform, and in straight styrene-butadiene rubber cream, nano oxygen
Change zinc and biggish aggregate, reaction efficiency and mechanical property of the zinc oxide in sulfidation after this certainly will be influenced occurs.
Claims (10)
1. a kind of nano zine oxide/rubber composite material, it is characterised in that the composite material is by the original including following components
Material is prepared:
Rubber latex and nano zinc oxide fluid dispersion；
The dosage of nano zine oxide is 15~80wt.% of rubber latex；
Rubber latex is butadiene-vinylpyridine copylymer latex, in butadiene styrene vinyl pyridine latex, carboxylic styrene butadiene latex, carboxylic acrylonitrile butadiene rubber latex, epoxy natural latex
A kind of or combination.
2. nano zine oxide/rubber composite material as described in claim 1, it is characterised in that:
The dosage of nano zine oxide is 20~50wt.% of rubber latex.
3. nano zine oxide/rubber composite material as described in claim 1, it is characterised in that:
The Particle Size of Nanometer ZnO range is 20~500nm.
4. nano zine oxide/rubber composite material as claimed in claim 3, it is characterised in that:
The Particle Size of Nanometer ZnO range is 50~100nm.
5. nano zine oxide/the rubber composite material as described in claim 1, it is characterised in that:
The rubber latex solid content is in 20~60wt.%, and wherein the ratio of functional group is in 3~50wt.%.
6. a kind of nano zine oxide/rubber composite material preparation method as described in one of Claims 1 to 5, feature exist
In the described method includes:
(1) by nano zinc oxide fluid dispersion 5~60min of ultrasound, stable nano zinc oxide suspension is obtained；
(2) nano zinc oxide suspension is added slowly to be sufficiently mixed in the rubber latex stirred to the two；
(3) it flocculates: the latex that step (2) mixes being poured slowly into flocculant solution while stirring, obtains flocculate；
(4) dry.
7. the preparation method of nano zine oxide/rubber composite material as claimed in claim 6, it is characterised in that:
The concentration of nano zinc oxide fluid dispersion is 15~50wt.%.
8. the preparation method of nano zine oxide/rubber composite material as claimed in claim 6, it is characterised in that:
Step (2), speed of agitator are 20~800r/min, 10~60min of mixing time.
9. the preparation method of nano zine oxide/rubber composite material as claimed in claim 6, it is characterised in that:
40~180 DEG C of drying temperature of step (4)；2~72h of drying time.
10. the preparation method of nano zine oxide/rubber composite material as claimed in claim 6, it is characterised in that:
The flocculant is one of hydrochloric acid, sulfuric acid, calcium chloride, magnesium chloride, aluminium chloride, sodium chloride or combination；
The concentration 1wt.% of flocculant solution is to saturated concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711067574.0A CN109749168B (en) | 2017-11-03 | 2017-11-03 | Nano zinc oxide/rubber composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711067574.0A CN109749168B (en) | 2017-11-03 | 2017-11-03 | Nano zinc oxide/rubber composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109749168A true CN109749168A (en) | 2019-05-14 |
| CN109749168B CN109749168B (en) | 2020-02-14 |
Family
ID=66397993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711067574.0A Active CN109749168B (en) | 2017-11-03 | 2017-11-03 | Nano zinc oxide/rubber composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109749168B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114105182A (en) * | 2020-08-25 | 2022-03-01 | 北京化工大学 | Nano zinc oxide, preparation method, master rubber and tread rubber |
| CN114672082A (en) * | 2022-03-31 | 2022-06-28 | 广东金发科技有限公司 | Carboxylic butyronitrile emulsion and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408762A (en) * | 2001-09-25 | 2003-04-09 | 兰化胶乳研制中心 | Inorganic nano particle-high molecular composite material and its preparing method and use |
| CN1516726A (en) * | 2001-04-12 | 2004-07-28 | Anionically stabilised aqueous dispersions of nanoparticulate zinc oxide, method for production and use thereof | |
| CN103554560A (en) * | 2013-10-29 | 2014-02-05 | 中国热带农业科学院农产品加工研究所 | Method for preparing unsaturated fatty acid zinc salt reinforced natural rubber in in-situ reaction |
| CN104231368A (en) * | 2014-09-21 | 2014-12-24 | 北京化工大学 | Molybdenum disulfide/ butadiene styrene rubber/ butadiene-vinylpyridine rubber nanocomposite material with high wear resistance |
| CN104861858A (en) * | 2015-06-16 | 2015-08-26 | 华东理工大学 | Preparation method of novel ink-jet printing coating |
| JP2015193845A (en) * | 2010-05-11 | 2015-11-05 | 住友ゴム工業株式会社 | Composite body, and method for producing the same |
| CN107177985A (en) * | 2017-05-16 | 2017-09-19 | 浙江理工大学 | A kind of preparation method of the aramid fiber two-bath gum dipping liquid of modified zinc oxide |
-
2017
- 2017-11-03 CN CN201711067574.0A patent/CN109749168B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1516726A (en) * | 2001-04-12 | 2004-07-28 | Anionically stabilised aqueous dispersions of nanoparticulate zinc oxide, method for production and use thereof | |
| CN1408762A (en) * | 2001-09-25 | 2003-04-09 | 兰化胶乳研制中心 | Inorganic nano particle-high molecular composite material and its preparing method and use |
| JP2015193845A (en) * | 2010-05-11 | 2015-11-05 | 住友ゴム工業株式会社 | Composite body, and method for producing the same |
| CN103554560A (en) * | 2013-10-29 | 2014-02-05 | 中国热带农业科学院农产品加工研究所 | Method for preparing unsaturated fatty acid zinc salt reinforced natural rubber in in-situ reaction |
| CN104231368A (en) * | 2014-09-21 | 2014-12-24 | 北京化工大学 | Molybdenum disulfide/ butadiene styrene rubber/ butadiene-vinylpyridine rubber nanocomposite material with high wear resistance |
| CN104861858A (en) * | 2015-06-16 | 2015-08-26 | 华东理工大学 | Preparation method of novel ink-jet printing coating |
| CN107177985A (en) * | 2017-05-16 | 2017-09-19 | 浙江理工大学 | A kind of preparation method of the aramid fiber two-bath gum dipping liquid of modified zinc oxide |
Non-Patent Citations (1)
| Title |
|---|
| 王书忠 等: "无机纳米粒子/丁苯胶乳复合技术的研究", 《功能高分子材料》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114105182A (en) * | 2020-08-25 | 2022-03-01 | 北京化工大学 | Nano zinc oxide, preparation method, master rubber and tread rubber |
| CN114672082A (en) * | 2022-03-31 | 2022-06-28 | 广东金发科技有限公司 | Carboxylic butyronitrile emulsion and preparation method and application thereof |
| CN114672082B (en) * | 2022-03-31 | 2023-08-29 | 广东金发科技有限公司 | Carboxylated nitrile emulsion and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109749168B (en) | 2020-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107501646B (en) | Graphene quantum dot/rubber nano composite material preparation method | |
| JP6502695B2 (en) | Microfibrillated plant fiber-rubber composite, method for producing the same, rubber composition and pneumatic tire | |
| CN101456961B (en) | Method for preparing reactive nano calcium carbonate-native rubber composite material | |
| JP2012144680A (en) | Rubber wet master batch, process for producing the same, rubber composition, and pneumatic tire | |
| JP2012504185A (en) | Tires containing recycled materials | |
| JP2012197375A (en) | Unvulcanized rubber composition, method of producing the same, and pneumatic tire | |
| CN103539976B (en) | A kind of preparation method utilizing hydroxyethyl methylacrylate rubber modified graft copolymer nano-calcium carbonate to strengthen native rubber composite material | |
| JP6030411B2 (en) | Rubber wet masterbatch and method for producing the same, rubber composition and pneumatic tire | |
| CN109749168A (en) | A kind of nano zine oxide/rubber composite material and preparation method | |
| CN108424563A (en) | The high-performance rubber composite material and preparation method of nanofiber is drawn containing Kev | |
| JP2017088747A (en) | Manufacturing method of wet master batch | |
| CN108410032A (en) | A kind of tire tread glue sizing material and preparation method thereof | |
| JP2018119041A (en) | Production method of master batch | |
| US10435522B2 (en) | Method for producing masterbatch | |
| JP5250206B2 (en) | Method for producing natural rubber and / or synthetic isoprene rubber masterbatch using microbially decomposed powder rubber | |
| JP2018070812A (en) | Method for producing master batch | |
| CN107663283A (en) | The preparation method of beta-type silicon carbide whisker/Nano chitosan high intensity antibacterial latex film | |
| CN108250453A (en) | The manufacturing method of rubber wet masterbatch | |
| JP2011079912A (en) | Composite, rubber composition and pneumatic tire | |
| JP6377979B2 (en) | Manufacturing method of rubber wet masterbatch | |
| CN104211837B (en) | A kind of preparation method of carbon black extended SBR rubber master batch | |
| WO2013097263A1 (en) | Method for blending natural latex and silica slurry | |
| CN108299701B (en) | Fiber material and method for producing same, and composite material and method for producing same | |
| CN106479006A (en) | Elastic composites | |
| Guo et al. | Mechanical properties and crosslink density of rare earth‐modified high‐abrasion furnace‐filled powdered natural rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |