CN105001454B - The preparation method of hydrotalcite carbon black hydridization material, hydrotalcite carbon black hydridization material/rubber composite and its application - Google Patents
The preparation method of hydrotalcite carbon black hydridization material, hydrotalcite carbon black hydridization material/rubber composite and its application Download PDFInfo
- Publication number
- CN105001454B CN105001454B CN201510543970.0A CN201510543970A CN105001454B CN 105001454 B CN105001454 B CN 105001454B CN 201510543970 A CN201510543970 A CN 201510543970A CN 105001454 B CN105001454 B CN 105001454B
- Authority
- CN
- China
- Prior art keywords
- carbon black
- hydrotalcite
- preparation
- hybrid material
- amination
- 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.)
- Active
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of hydrotalcite carbon black hybrid material, hydrotalcite Carbon Black/Rubber Composites and its application.Surface modification is carried out to carbon black first by amino silane, make its surface amination, meanwhile, hydrotalcite is carried out using acid anhydrides modifying agent surface-functionalized, amination carbon black is uniformly mixed with acid anhydrides hydrotalcite again, co-sedimentation, obtain zinc-aluminum hydrotalcite carbon black hybrid material.Hydrotalcite carbon black hybrid material is further added in rubber using conventional method and obtains rubber composite.Hydrotalcite carbon black hybrid material, which is used for natural rubber, can not only assign the performances such as the excellent mechanical property of material, ageing properties, barrier properties for gases, and what is more important can improve the anti-reversion behaviour of material.
Description
Technical field
The present invention relates to field of rubber materials, and in particular to hydrotalcite-carbon black hybrid material, and hydrotalcite-carbon black are miscellaneous
Change material and be added to the composite that natural rubber is obtained.
Background technology
Natural rubber (NR) is widely applied as a kind of general purpose rubber with good combination property.But,
In sulfur cross-linking system, different degrees of recovery phenomenon occurs in native rubber composite material, causes natural rubber to answer
The hydraulic performance decline of condensation material, significantly limit application of the natural rubber in Industrial Engineering product.In order to solve recovery
The problem of this perplexs people all the time, it is ensured that the vulcanization uniformity of product, people are seeking solution always.
Consider from recovery mechanism, the main method for improving NR anti-reversion behaviour be add containing sulfur-donor or
Offset-type vulcanizing system is to make up the loss of cross-bond.Such as Chinese patent CN103626685A, synthesize a kind of difunctional organic
Thiosulfate, with sulfur-bearing active group and unsaturated double-bond group.In sulfidation, sulfur-bearing active group and rubber are big
Molecule crosslinks reaction, and inserts heat-staple alkyl in sulfur-crosslinked key, improves the heat endurance of cross-bond.Meanwhile, glue
Polysulfide bond in material is heated when decomposing, and unsaturated double-bond therein can occur with the conjugated double bond in rubber molecule structure
Reaction, and new C-C cross-bonds are generated, the cross-linked network of vulcanizate is kept with this, improves the recovery of vulcanizate.In also
State patent CN103739539A, has synthesized a kind of anti-recovery agent 1, double (lemon acid imide methyl) benzene of 3-, in sulfidation
In, when sizing material reverts, it can chemically react with the breaking bonds of sizing material, form new cross-bond, and then compensate sulphur
Change the sulfur-crosslinked chain loss reverted and caused, keep the crosslink density of sizing material, the combination property of stable vulcanizate.But, these resist
The synthesis condition of reversion agent is harsh, it is necessary to which substantial amounts of organic solvent and expensive catalyst, the post processing of product are number
It is tired, easily cause environmental pollution.Therefore, the production cost of such sulfuration resistant reducing agent is high, realizes that large-scale industrial production is deposited
In very big difficulty.Meanwhile, the sulfuration resistant reducing agent of these synthesis is as a kind of rubber used additives, and they, which are only reached, makes up and tie up
Sizing material network cross-linked density is held, ensures the basic performance of product for this.But it assigns product more single performance improvement,
It is difficult to significantly improve the combination property of product.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of hydrotalcite-carbon black hybrid material, carry simultaneously
The composite obtained for hydrotalcite-carbon black hybrid material and rubber mix, the present invention can improve the comprehensive of elastomeric material
Energy.
This programme purpose is realized by following scheme:
A kind of preparation method of hydrotalcite-carbon black hybrid material, comprises the following steps：
(1) acid anhydrides of hydrotalcite：By hydrotalcite ultrasonic disperse in organic solvent, maleation polybutadiene is added
Alkene and catalyst, 4 ~ 24h is reacted in 60 ~ 100 DEG C, is preferable over 80 ~ 90 DEG C of 11 ~ 13h of reaction, is obtained the suspension of acid anhydrides hydrotalcite
Liquid；
(2) amination of carbon black：By carbon black ultrasonic disperse in organic solvent, amino silane is added, in nitrogen environment
Under, 3~24h is reacted in 60~90 DEG C, 80 ~ 90 DEG C of 11 ~ 13h of reaction is preferable over, obtains amination carbon black suspension；
(3) the carbon black uniform suspension that the hydrotacite suspension and step (2) obtained step (1) is obtained is mixed, sunk
Drop, wash, dry, obtain hydrotalcite-carbon black hybrid material.
The mass ratio of the hydrotalcite and maleation polybutadiene is 1/1~1/5.
The mass ratio of the carbon black and amino silane is 1/1~1/15.
The amino silane is gamma-aminopropyl-triethoxy-silane, N- β-(aminoethyl)-γ-aminopropyl trimethoxy
One kind of base silane, g- aminopropyl trimethoxysilanes.
Described catalyst be p-methyl benzenesulfonic acid, benzene sulfonic acid, 2,4- acid dimethyls, 2,5- acid dimethyls,
One kind of 2,4,5- tri-methyl p-toluenesulfonates.
The carbon black be N110, N220, N330, N550, N660, N880, N990, N115, N234, N326, N339,
One kind in N375, N539.
Described organic solvent is one or both of acetone, benzene, toluene, ethanol；Step（2）Described organic solvent
For one or both of acetone, benzene, toluene, ethanol.
The mass ratio of acid anhydrides hydrotalcite and amination carbon black is 1 in step (3):1~25.
Hydrotalcite-Carbon Black/Rubber Composites, is mixed by following mass parts raw material, 100 parts of elastomeric material, neatly
Stone -30-50 parts of carbon black hybrid material.The elastomeric material refers to natural rubber and General Purpose Rubber material.
Hydrotalcite-Carbon Black/Rubber Composites are used for rubber.
The present invention is modified hydrotalcite-carbon black hydridization filler that functionalization is prepared for electrostatic self-assembled by surface, in rubber
Complex filler network structure is introduced in matrix body, the transmission of heat is inhibited to external world, improves material
Heat resistance, reduce the destruction of cross-linked network structure.Meanwhile, surface-functionalized active site can participate in vulcanization, with rubber
Macromolecular crosslinks reaction, so as to generate heat-staple C-C cross-bonds to keep the crosslink density of vulcanizate, improves vulcanization
The recovery of glue, improves the combination property and service life of product.
Specifically, the present invention is related to carries out surface modification using amino silane to carbon black first, make its surface amination.Together
When, hydrotalcite is carried out using acid anhydrides modifying agent surface-functionalized.Then, it is amination carbon black and acid anhydrides hydrotalcite is uniform
Mixing, due to electrostatic interaction, occurs co-sedimentation, obtains zinc-aluminum hydrotalcite-carbon black hybrid material.Carried out again with Heveatex
Uniform mixing, flocculation, washing, drying process obtain zinc-aluminum hydrotalcite-carbon black/natural rubber masterbatch.Further can be using tradition
Processing technology prepares the rubbers such as the sulfurized natural rubber that addition hydrotalcite-carbon black hybrid material is modified.
Compared with prior art, the present invention is advantageous in that：
(1) hydrotalcite-carbon black hybrid material that the present invention is provided is with three functions, and one is sheet hydrotalcite, energy
It is enough effectively to obstruct the infiltration of hot oxygen in the base, the ageing properties of sizing material are improved, weaken the destruction to sizing material strand.Together
When, the polybutadiene oligomer of the modified cladding of hydrotalcite surface can effectively improve the compatibility of filler and rubber matrix,
And long-chain polybutadiene segments can further improve the heat endurance of matrix.Two be containing unsaturated double-bond group, in sulphur
During change, it can react with the double bond in sizing material, so as to provide more crosslinking points when vulcanizate reverts.Three are
Amination carbon black can be effectively improved the ageing properties and mechanical property of rubber.Therefore hydrotalcite-carbon black hydridization filler can have
Improve anti-reversion behaviour, ageing properties and the mechanical property of natural rubber sizing material in effect ground.
(2) hydrotalcite-carbon black hybrid material provided in the present invention can be applied in various general purpose rubbers, equally may be used
Assign the performances such as material excellent mechanical property, ageing properties, barrier properties for gases.
(3) technique of the present invention is simple, reaction condition is gentle, operability and reproducible, meet safety,
Green, the developing direction of environmental protection, therefore with very big development prospect and application potential.
Brief description of the drawings
The scanning electron microscope (SEM) photograph for the zinc-aluminum hydrotalcite that Fig. 1 synthesizes for the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph for zinc-aluminum hydrotalcite-carbon black hybrid material that embodiment 1 is synthesized.
Fig. 3 be embodiment it is 2-in-1 into zinc-aluminum hydrotalcite-carbon black hybrid material scanning electron microscope (SEM) photograph.
Fig. 4 is the scanning electron microscope (SEM) photograph for zinc-aluminum hydrotalcite-carbon black hybrid material that embodiment 3 is synthesized.
Fig. 5 is the scanning electron microscope (SEM) photograph for zinc-aluminum hydrotalcite-carbon black hybrid material that embodiment 4 is synthesized.
Fig. 6 is the scanning electron microscope (SEM) photograph for zinc-aluminum hydrotalcite-carbon black hybrid material that embodiment 5 is synthesized.
Embodiment
Embodiment 1：
(1) acid anhydrides of hydrotalcite：1g zinc-aluminum hydrotalcites ultrasonic disperse is taken in 150mL acetone, 1g Malaysia is added
Acid anhydrides polybutadiene and 0.1g p-methyl benzenesulfonic acids, in the 12h that flowed back at 80 DEG C, obtain flaxen acid anhydrides hydrotalcite.
(2) amination of carbon black：By 1g carbon black N330 ultrasonic disperses in 150mL acetone, 1g γ-aminopropyl is added
Triethoxysilane, in a nitrogen environment, in the 12h that flowed back at 80 DEG C, obtains the amination carbon black of black.
(3) preparation of hydrotalcite-carbon black hybrid material：By the acid anhydrides hydrotalcite obtained in step (1) and step (2)
In obtained amination carbon black with 1:The other ultrasonic disperse formation suspension of 1 mass parts, and uniformly mix, co-sedimentation, drying is washed,
Obtain hydrotalcite-carbon black hybrid material.
(4) preparation of hydrotalcite-Carbon Black/Rubber Composites：The mass parts of natural rubber 100 are taken, step is obtained in (3)
Hydrotalcite-mass parts of carbon black hybrid material 40, using mechanical mixture, obtain hydrotalcite-carbon black/native rubber composite material.
In order to carry out test and comparison, the rubber in hydrotalcite-Carbon Black/Rubber Composites all uses natural rubber in the examples below
The mass parts ratio of glue, rubber and hydrotalcite-carbon black hybrid material is all using 100 mass parts：40 mass parts.
The appearance structure of hydrotalcite-carbon black hybrid material of synthesis is as shown in Fig. 2 hydrotalcite sheets layer surface in step (3)
There is carbon black pellet and small aggregation, and there is part carbon black pellet or aggregation to be coated by hydrotalcite lamella, form structure and answer
Miscellaneous zinc-aluminum hydrotalcite-carbon black hybrid.
Embodiment 2：
(1) acid anhydrides of hydrotalcite：1g zinc-aluminum hydrotalcites ultrasonic disperse is taken in 150mL acetone, 2g Malaysia is added
Acid anhydrides polybutadiene and 0.1g benzene sulfonic acids, in the 11h that flowed back at 90 DEG C, obtain flaxen acid anhydrides hydrotalcite.
(2) amination of carbon black：1g carbon black N330 ultrasonic disperses are taken in 150mL acetone, 3g N- β-(ammonia second is added
Base)-γ-aminopropyltrimethoxysilane, in a nitrogen environment, in the 11h that flowed back at 90 DEG C, obtain the amination carbon black of black.
(3) preparation of hydrotalcite-carbon black hybrid material：Take the acid anhydrides hydrotalcite obtained in step (1) and step (2)
In obtained amination carbon black with 1:The other ultrasonic disperse formation suspension of 5 mass parts, and uniformly mix, co-sedimentation, drying is washed,
Obtain hydrotalcite-carbon black hybrid material.
Remaining implements such as embodiment 1.
The appearance structure of hydrotalcite-carbon black hybrid material of synthesis is as shown in figure 3, hydrotalcite sheets layer surface in step (3)
There is more carbon black aggregate, while thering is some carbon black pellets and aggregation to be embedded in the inside, forming layer by hydrotalcite lamella
Zinc-aluminum hydrotalcite-carbon black hybrid of layer assembling.
Embodiment 3：
(1) acid anhydrides of hydrotalcite：1g zinc-aluminum hydrotalcites ultrasonic disperse is taken in 150mL acetone, 3g Malaysia is added
Acid anhydrides polybutadiene and 0.1g 2,4- acid dimethyl, in the 13h that flowed back at 85 DEG C, obtain flaxen acid anhydrides neatly
Stone.
(2) amination of carbon black：1g carbon black N330 ultrasonic disperses are taken in 150mL acetone, 6g g- aminopropyls are added
Trimethoxy silane, in a nitrogen environment, in the 12h that flowed back at 80 DEG C, obtains the amination carbon black of black.
(3) preparation of hydrotalcite-carbon black hybrid material：By the acid anhydrides hydrotalcite obtained in step (1) and step (2)
In obtained amination carbon black with 1:The other ultrasonic disperse formation suspension of 15 mass parts, and uniformly mix, co-sedimentation, washing is dry
It is dry, obtain hydrotalcite-carbon black hybrid material.
Remaining implements such as embodiment 1.
The appearance structure of hydrotalcite-carbon black hybrid material of synthesis is as shown in figure 4, compared to embodiment 3 in step (3)
The hybrid of preparation, the carbon black aggregate of the hydrotalcite sheets layer surface of the present embodiment synthesis has been reduced, and carbon black pellet is more equal
It is even to be scattered in hydrotalcite sheets layer surface or be embedded in inside lamella.
Embodiment 4：
(1) acid anhydrides of hydrotalcite：1g zinc-aluminum hydrotalcites ultrasonic disperse is taken in 150mL acetone, 4g Malaysia is added
Acid anhydrides polybutadiene and 0.1g p-methyl benzenesulfonic acids, in the 12h that flowed back at 80 DEG C, obtain flaxen acid anhydrides hydrotalcite.
(2) amination of carbon black：1g carbon black N330 ultrasonic disperses are taken in 150mL acetone, 10g γ-ammonia third is added
Ethyl triethoxy silicane alkane, in a nitrogen environment, in the 12h that flowed back at 80 DEG C, obtains the amination carbon black of black.
(3) preparation of hydrotalcite-carbon black hybrid material：By the acid anhydrides hydrotalcite obtained in step (1) and step (2)
In obtained amination carbon black with 1:The other ultrasonic disperse formation suspension of 20 mass parts, and uniformly mix, co-sedimentation, washing is dry
It is dry, obtain hydrotalcite-carbon black hybrid material.
Remaining implements such as embodiment 1.
The appearance structure of hydrotalcite-carbon black hybrid material of synthesis is as shown in figure 5, carbon black pellet is uniformly wrapped in step (3)
It is embedded in inside hydrotalcite lamella, forms the hybrid of self assembly.
Embodiment 5：
(1) acid anhydrides of hydrotalcite：1g zinc-aluminum hydrotalcites ultrasonic disperse is taken in 150mL acetone, 5g Malaysia is added
Acid anhydrides polybutadiene and 0.1g p-methyl benzenesulfonic acids, in the 12h that flowed back at 80 DEG C, obtain flaxen acid anhydrides hydrotalcite.
(2) amination of carbon black：1g carbon black N330 ultrasonic disperses are taken in 150mL acetone, 15g γ-ammonia third is added
Ethyl triethoxy silicane alkane, in a nitrogen environment, in the 12h that flowed back at 80 DEG C, obtains the amination carbon black of black.
(3) preparation of hydrotalcite-carbon black hybrid material：By the acid anhydrides hydrotalcite obtained in step (1) and step (2)
In obtained amination carbon black with 1:The other ultrasonic disperse formation suspension of 25 mass parts, and uniformly mix, co-sedimentation, washing is dry
It is dry, obtain hydrotalcite-carbon black hybrid material.
Remaining implements such as embodiment 1.
In step (3) hydrotalcite-carbon black hybrid material of synthesis appearance structure as shown in figure 5, carbon black aggregate compared with
It is many, what this was caused because carbon black and hydrotalcite are out of proportion.
Hydrotalcite-carbon black/native rubber composite material that embodiment 1 ~ 5 is obtained, is prepared into sizing material, the performance test results
As shown in table 1-4.
Control group sizing material basic recipe (mass parts)：Natural rubber 100, stearic acid 2, zinc oxide 5, sulphur 1.5,
Accelerant CZ 0.5, altax 0.5, antioxidant 4010NA 2, carbon black N330 40.Conditions of vulcanization：150℃×
30min。
The sizing material basic recipe (mass parts) of embodiment 1 ~ 5：From unlike control group, being obtained respectively with 5 embodiments
Hydrotalcite-carbon black hybrid material replace carbon black N330, remaining all same.Conditions of vulcanization：150℃×30min.
Performance test：According to GB/T528-2009, GB/T531.1-2008, tried using UCAN UT-2080 universal materials
The machine cured rubber samples of testing test its performance.
Mechanical property before the NR vulcanizate agings of table 1.
Mechanical property after the NR vulcanizate agings of table 2.
According to GB/T16584-1996, the sulphur that instrument Rheometer MDR2000 test sizing material sample is become using without rotor sulphur
Change performance（Sample after the aging of table 2）, its result is as shown in table 3, and test condition is 150 DEG C × 30min.In this test condition
The data of lower test can represent the trend of reverting of sizing material.
The curability of the NR sizing materials of table 3.
Using crosslink density of the IIC XLDS-15 HT nuclear magnetic resonance crosslink density instrument to the rubber sample after the aging of table 2
Tested.As a result it is as shown in table 4
| Blank | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Crosslink density (× 10-5 mol/cm3) | 11.92 | 12.42 | 12.88 | 13.25 | 13.42 | 13.18 |
Data, which can be seen that, from table 1-4 adds after hydrotalcite-carbon black hydridization filler prepared by 1-5 of the embodiment of the present invention,
The physical property and ageing properties of rubber composite are significantly enhanced.Meanwhile, relative to control sample, add system of the present invention
Standby hydrotalcite-carbon black hybrid material, the crosslink density of sizing material is significantly increased, while extending time of scorch, improves sizing material
Processing characteristics；In addition, after adding hydrotalcite-carbon black hydridization filler prepared by embodiment 1-5, effectively extending the sulfuric of sizing material
Change time T90, and significantly reduce the reversion percentage of system.In summary, hydrotalcite-carbon black hydridization that the present invention is provided
Filler can effectively improve anti-reversion behaviour, mechanical property and the ageing properties of natural rubber.
Claims (8)
1. the preparation method of a kind of hydrotalcite-carbon black hybrid material, it is characterised in that comprise the following steps：
(1) acid anhydrides of hydrotalcite：By hydrotalcite ultrasonic disperse in organic solvent, add maleation polybutadiene and
Catalyst, reacts 4 ~ 24h in 60 ~ 100 DEG C, obtains acid anhydrides hydrotacite suspension；
(2) amination of carbon black：By carbon black ultrasonic disperse in organic solvent, amino silane is added, in a nitrogen environment, in
60~90 DEG C of 3~24h of reaction, obtain amination carbon black suspension；
(3) mixing of carbon black uniform suspension that the hydrotacite suspension and step (2) obtained step (1) is obtained, sedimentation,
Wash, dry, obtain hydrotalcite-carbon black hybrid material.
2. the preparation method as described in claim 1, it is characterised in that：The quality of hydrotalcite and maleation polybutadiene
Than for 1/1~1/5.
3. the preparation method as described in claim 1, it is characterised in that：The mass ratio of carbon black and amino silane is 1/1~1/
15。
4. the preparation method as described in claim 1 or 3, it is characterised in that：The amino silane is the second of γ-aminopropyl three
TMOS, N- β-(aminoethyl)-γ-aminopropyl trimethoxysilane, one kind of γ-aminopropyl trimethoxysilane.
5. the preparation method as described in claim 1, it is characterised in that：Described catalyst is p-methyl benzenesulfonic acid, benzene sulphur
Acid, 2,4- acid dimethyls, 2,5- acid dimethyls, one kind of 2,4,5- tri-methyl p-toluenesulfonates.
6. the preparation method as described in claim 1, it is characterised in that：The carbon black be N110, N220, N330, N550,
One kind in N660, N880, N990, N115, N234, N326, N339, N375, N539.
7. the preparation method as described in claim 1, it is characterised in that：Step（1）Described organic solvent is acetone, benzene, first
One or both of benzene, ethanol；Step（2）Described organic solvent is one or both of acetone, benzene, toluene, ethanol.
8. the preparation method as described in claim 1, it is characterised in that：Acid anhydrides hydrotalcite and amination charcoal in step (3)
Black mass ratio is 1:1~25.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510543970.0A CN105001454B (en) | 2015-08-29 | 2015-08-29 | The preparation method of hydrotalcite carbon black hydridization material, hydrotalcite carbon black hydridization material/rubber composite and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510543970.0A CN105001454B (en) | 2015-08-29 | 2015-08-29 | The preparation method of hydrotalcite carbon black hydridization material, hydrotalcite carbon black hydridization material/rubber composite and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105001454A CN105001454A (en) | 2015-10-28 |
| CN105001454B true CN105001454B (en) | 2017-10-13 |
Family
ID=54374339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510543970.0A Active CN105001454B (en) | 2015-08-29 | 2015-08-29 | The preparation method of hydrotalcite carbon black hydridization material, hydrotalcite carbon black hydridization material/rubber composite and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105001454B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750991B (en) * | 2016-12-14 | 2019-03-26 | 湖北大洋塑胶有限公司 | The PPR pipe and preparation method thereof of heat-resistant impact |
| CN112812363B (en) * | 2021-02-07 | 2022-12-27 | 广东辉海现代家居用品有限公司 | Plasticizer for plastic processing and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509214A (en) * | 2013-08-13 | 2014-01-15 | 北京化工大学 | Preparation method of preprocessed clay/rubber nano composite material |
| CN104558724A (en) * | 2015-01-26 | 2015-04-29 | 北京化工大学 | Preparation method of high-performance hydrotalcite/silicon dioxide/rubber nano composite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4127916B2 (en) * | 1999-01-12 | 2008-07-30 | 横浜ゴム株式会社 | Pneumatic tire |
| JP2002003677A (en) * | 2000-04-18 | 2002-01-09 | Nippon Mektron Ltd | Fluorine-containing elastomer composition |
-
2015
- 2015-08-29 CN CN201510543970.0A patent/CN105001454B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509214A (en) * | 2013-08-13 | 2014-01-15 | 北京化工大学 | Preparation method of preprocessed clay/rubber nano composite material |
| CN104558724A (en) * | 2015-01-26 | 2015-04-29 | 北京化工大学 | Preparation method of high-performance hydrotalcite/silicon dioxide/rubber nano composite material |
Non-Patent Citations (2)
| Title |
|---|
| Direct growth of hydrotalcite nanolayers on carbon fibers by electrospinning;Luis B, et al.;《Applied Clay Science》;20140926;第101卷;第461-467页 * |
| Layered double hydroxide/multiwalled carbon nanotube hybrids as reinforcing filler in silicone rubber;B. Pradhan, et al.;《Composites: Part A》;20131024;第56卷;第290-299页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105001454A (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107325590B (en) | A kind of cable shielding layer material of modified sulfur-bearing graphene doping and its application | |
| CN109467770B (en) | Rubber composite material using cardanol glycidyl ether modified white carbon black and preparation method thereof | |
| CN108219392B (en) | Plastic auxiliary agent with ultraviolet aging resistance and moisture retention functions as well as preparation method and application thereof | |
| CN108641150B (en) | Rubber material capable of being repeatedly processed and preparation method thereof | |
| CN106700160A (en) | Preparation method of supported rubber vulcanizing agent and application thereof | |
| CN102942743A (en) | Simple preparation method of graphene sheet nano composite material | |
| CN110819048A (en) | Graphene modified composite emulsion for rubber material and preparation method thereof | |
| CN104650400A (en) | Cyclopentadiene-modified carbon nanotube/rubber composite material and preparation method thereof | |
| CN105001454B (en) | The preparation method of hydrotalcite carbon black hydridization material, hydrotalcite carbon black hydridization material/rubber composite and its application | |
| CN104650419B (en) | A kind of preparation method of modified white carbon black/solution polymerized rubber composite | |
| CN106608989A (en) | Rubber composition, vulcanized rubber and preparation method thereof | |
| CN113480862A (en) | Lignin-silicon dioxide composite material and preparation method and application thereof | |
| CN109666299A (en) | Antistatic sealing material of a kind of space grade and the preparation method and application thereof | |
| Yu et al. | Dispersing carbon dots in non-polar rubber by slurry compounding and in situ compatibilizing | |
| CN109734960A (en) | A kind of application of modified white carbon black in blend rubber | |
| CN109627502B (en) | Composite material of natural rubber and preparation method thereof | |
| Li et al. | Recent progress of elastomer–silica nanocomposites toward green tires: simulation and experiment | |
| CN104356434A (en) | Nanocrystalline cellulose blended rubber composite based on wood fibers and preparing method thereof | |
| CN108395584A (en) | A kind of automobile tire inner tube of a tyre and preparation method thereof | |
| CN116041820A (en) | Preparation method and application of modified slag composite material | |
| CN109306129A (en) | A kind of cable insulating layer material of modified sulfur-bearing nano silica enhancing and its application | |
| CN107011551B (en) | A kind of modification silicon compound/tread rubber composite material and preparation method with high wet-sliding resistant | |
| CN113956538A (en) | Novel anti-aging agent and preparation method and application thereof | |
| CN104403380A (en) | Method for improving carbon black coupling efficiency and increasing content of combined rubber in rubber | |
| CN114213721B (en) | Rubber composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Peng Hualong Inventor after: Yao Xiang Inventor after: Yin Xingchang Inventor after: Fang Jianming Inventor after: Wang Yingying Inventor after: Zhang Wenguang Inventor before: Peng Hualong Inventor before: Yao Xiang Inventor before: Yin Xingchang Inventor before: Fang Jianming Inventor before: Wang Yingying |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220617 Address after: 100044 room 2-315, floor a 331, Zhongguancun, Haidian District, Beijing Patentee after: Wang Yimin Address before: 223005 No. 1, Shi Lian Road, salt chemical industry zone, Jiangsu Economic Development Zone, Huaian Patentee before: JIANGSU CHEESHINE PERFORMANCE MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230807 Address after: 256102 South West Point (Building 4, Standardization Plant) at the intersection of Xingyuan Road and Zhenxing Road, Yiyuan County, Zibo City, Shandong Province Patentee after: Shandong Light Chemical Zhiyuan New Material Technology Co.,Ltd. Address before: 100044 room 2-315, floor a 331, Zhongguancun, Haidian District, Beijing Patentee before: Wang Yimin |