CN109206680A - A kind of method of reinforcement natural rubber - Google Patents
A kind of method of reinforcement natural rubber Download PDFInfo
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Abstract
The invention discloses a kind of method of reinforcement natural rubber, concrete technology is, first by nanometer calcium carbonate, the Nano diamond after oxidation is used coupling agent modified respectively, dispersing agent is then added, the ball milling modification in water phase is added in Heveatex solution；Stirring, cohesion is dry to prepare natural rubber rubber master batch, and vulcanization aid, mixing is added, and vulcanization prepares rubber compound.The present invention effectively raises the mechanical property of natural rubber, while effectively raising its heating conduction, expands the application field of natural rubber.
Description
Technical field
The present invention relates to the reinforcement process of rubber, specifically a kind of method of reinforcement natural rubber.
Background technique
In recent years, with the fast development of modern science and technology, increasingly higher demands are proposed to engineering material.And it passes
The homogenous material of system, if metal material, ceramic material and high molecular material cannot fully meet diversified requirement, then respectively
Kind high-performance compound material comes into being.For example, macromolecule/inorganic filler obtained very high attention and is ground in past 10 years
Study carefully.In rubber production field, natural rubber widely applies to automobile because of properties such as its good insulating properties, elasticity, air-tightness
Tire, conveyor belts, various sealing devices etc., but with the development of science and technology, the continuous extension in rubber applications field, people
For rubber mechanical strength and its functional higher requirements are also raised.Such as applied between tire pad glue-line it is natural
Rubber composite material not only needs good mechanical property, but also should have low-heat-generation, high thermal conductivity, rub resistance, low resistance to sliding
The features such as.Natural rubber/inorganic filler purpose is not only with inorganic particle filled natural rubber, it is often more important that is being filled
In the process, inorganic particulate is reacted with natural rubber parent, crosslinking, so that producing a kind of has new functional macromolecule material
Material, especially promotes its mechanical performance.
Meanwhile people require increasingly harshness to rubber product in daily life, as rubber product will not only have excellent power
Performance is learned, heating conduction is also good, so breaking through single filler, produces Multifunctional rubber system using two kinds or even a variety of fillers
Product have been trends of the times.
In addition, the mixed method of rubber compound is mostly dry blending at present, the disadvantage is that easily causing from production technology
It is dusty, worker's health is endangered, and easily cause mixing uneven.
Summary of the invention
The object of the present invention is to provide a kind of methods of reinforcement natural rubber, a kind of same with excellent mechanical performance to provide
When have both the natural vulcanized rubber and its production method of heating conduction.
The object of the present invention is achieved like this: a kind of method of reinforcement natural rubber, method includes the following steps:
A, by Nano diamond, heating progress oxidation processes are obtained in reaction kettle under the conditions of potassium permanganate, dense sulfuric acid treatment
Oxidation nanometer diamond；Remix modified after nanometer calcium carbonate and gained oxidation nanometer diamond are reacted with coupling agent respectively
Filler, or modified filler is reacted to obtain with coupling agent after nanometer calcium carbonate and gained oxidation nanometer diamond are mixed；
B, dispersing agent, water are added in gained modified filler, is dispersed by ball milling or the method for shearing, modification is obtained
Reinforced filling aqueous solution；
C, the reinforced filling aqueous solution is added in Heveatex, is uniformly mixed, and is agglomerated, dry, prepares natural rubber master batch；
D, the mixing together with vulcanization aid by natural rubber master batch, vulcanization, obtains reinforcement natural rubber.
The method of reinforcement natural rubber of the present invention, Nano diamond particle size described in step a are 4nm~10
μm, the Nano diamond is the Nano diamond original powder or amination Nano diamond using detonation synthesis；The nanometer
Calcium carbonate partial size≤100nm.
The method of reinforcement natural rubber of the present invention, in step a nanometer calcium carbonate and/or oxidation nanometer diamond with
The detailed process of coupling agent reaction is: by the alcohol solution of nanometer calcium carbonate and/or oxidation nanometer diamond and coupling agent in anti-
Reaction 0.1 under the conditions of 20~80 DEG C~for 24 hours is answered in kettle, by the Mass Calculation of component contained by reaction system, nano-calcium carbonate in system
Calcium and/or oxidation nanometer diamond: coupling agent=0.1-50: 1, nanometer calcium carbonate and/or oxidation nanometer diamond: ethyl alcohol: water
=1: 0.1-50: 0.1-50.
Preferably, the method for reinforcement natural rubber of the present invention, nanometer calcium carbonate and/or oxidation nanometer gold in system
Hard rock: coupling agent=1-20: 1, nanometer calcium carbonate and/or oxidation nanometer diamond: ethyl alcohol: water=1: 1-10: 1-10.
The method of reinforcement natural rubber of the present invention, the preparation process of oxidation nanometer diamond is specifically: by nanometer
Diamond and potassium permanganate, the concentrated sulfuric acid in mass ratio 1: 1~1.5: 15~20, react under the conditions of 200~300 DEG C in reaction kettle
After 4~6h, reactant is cleaned to neutrality to get oxidation nanometer diamond with deionized water.
The method of reinforcement natural rubber of the present invention, the coupling agent are sulfur-containing organosilicon compounds.
The method of reinforcement natural rubber of the present invention, dispersing agent described in step b are ionic surfactant.
The method of reinforcement natural rubber of the present invention, nanometer calcium carbonate and oxidation nanometer Buddha's warrior attendant in the modified filler
Stone mass ratio is 0.1~10: 1.
The method of reinforcement natural rubber of the present invention, the dispersing agent are lauryl sodium sulfate, dispersing agent and modification
Filler, water mass ratio be 1: 10: 550；The condition of mechanical milling process is: ball milling pearl diameter is 2-5mm, ball milling pearl amount in ball mill
The 60%~75% of ball milling self-contained volume, Ball-milling Time 2h are accounted for, revolving speed is set as 560rpm.
The method of reinforcement natural rubber of the present invention, the mass fraction of the Heveatex are 60%, and modification is filled out
Material is 0.001~2: 1 with contained natural rubber dry glue quality ratio in the Heveatex；With contained natural in the Heveatex
Based on the quality of rubber dry glue, vulcanization aid described in step d and its additive amount are as follows: sulphur 0.4-2.5phr, zinc oxide
5phr, altax 0.5-4phr, antioxidant 4010NA 1.5phr, stearic acid 2phr；Mixing condition is: smelting temperature 60-90
DEG C, mixing time 5-8min, banbury rotating speed 30rpm；Conditions of vulcanization is: 145 DEG C of curing temperature, vulcanization time 12min.
Preferably, modified filler and contained natural rubber dry glue quality ratio in the Heveatex are 0.01~0.2: 1.
Method of the invention has following progressive effect:
1, method and technology technics comparing of the invention is simple, and large-scale production easy to accomplish solves dry blending and eats powder
Difficult problem.
2, it is easy to get in the present invention using filler is cheap, is conducive to enterprise scale production.
3, multi-functional natural rubber prepared by the present invention has strong mechanical performance, has both certain heating conduction, widens
The application field of natural rubber.
4, the natural rubber obtained by the present invention, can be used for colorful rubber product, compensates for the black filler reinforcement such as carbon black
The defect of natural rubber.
Specific embodiment
Experimental material mentioned by the present invention can be obtained by known method or commercially available approach.
Technical solution of the present invention will be further elaborated below in a manner of specific embodiment, but does not limit right and want
The range asked.
Embodiment 1
Prepare modified reinforced filling aqueous solution:
(1) surface of reinforced filling is modified
1. preparing modified Nano diamond:
Using detonation synthesis Nano diamond, Nano diamond original powder obtained does not carry out any processing, nanogold
Hard rock content is in 55wt%~75wt%, and particle size is from several hundred nanometers to more than ten microns.
Nano diamond original powder 10 obtained is placed in 250mL three-neck flask, and adds the 150g concentrated sulfuric acid
(98%), 10g potassium permanganate is then weighed, fine particle is ground to；Three-neck flask is heated to 100 DEG C, preheats 30min, slowly
Ground potassium permanganate is added, 5h is reacted under the conditions of 220 DEG C, end of reaction takes out reaction liquid, centrifugation to the left side pH=4
The right side, it is dry, obtain oxidation nanometer diamond.
The oxidation nanometer diamond of 1 parts by weight is dissolved in the dehydrated alcohol and 4.5 parts by weight water of 4.5 weight point, then taken
Double-(γ-triethoxy silicon substrate propyl) tetrasulfide (abbreviation Si-69) of 0.05 parts by weight is dissolved in 1 parts by weight dehydrated alcohol
10min is hydrolyzed, is then added in the alcohol solution of oxidation nanometer diamond, 4h, end of reaction alcohol is reacted under the conditions of 80 DEG C
It washes 3 times, washes 3 times, 80 DEG C of dryings for 24 hours, obtain modified Nano diamond.
2. preparing modified nano calcium carbonate:
By 1 parts by weight nanometer calcium carbonate (Nano-CaCO3) it is dissolved in 4.5 parts by weight dehydrated alcohols and the mixing of 4.5 parts by weight water
In liquid, takes 0.05 parts by weight Si-69 to be dissolved in 1 parts by weight dehydrated alcohol and hydrolyze 10min, be then added to the alcohol of nanometer calcium carbonate
4h is reacted in aqueous solution at 80 DEG C, alcohol is washed 3 times, is washed 3 times, 80 DEG C of dryings for 24 hours, obtain modified nano calcium carbonate.
3. modified Nano diamond and modified nano calcium carbonate (Nano-CaCO3) ball-milling treatment
It is that 100 parts by weight (15g) is counted by natural rubber dry glue, weighed modified Nano diamond (ODND) 1-20 is weighed
Measure part and modified nanometer calcium carbonate (Nano-CaCO3) 1-20 parts by weight, 267 parts by weight agate balls (40g) addition ball grinder
In, meanwhile, the lauryl sodium sulfate of two kinds of modified filler gross masses 1/10 is added, it is 1/ that distilled water, which is added, and is made into mass concentration
50 solution, ball milling 2h under the revolving speed of 560rpm, obtains modified reinforced filling aqueous solution.
Embodiment 2
(1) by natural rubber dry glue be 100 parts by weight (15g) in terms of, weigh 2 parts by weight of modified Nano diamond (0.3g),
Modified nano calcium carbonate (Nano-CaCO3) 8 parts by weight (1.2g), 267 parts by weight of agate ball (40g) be added ball grinder in, together
When, the lauryl sodium sulfate 0.15g of two kinds of modified filler gross masses 1/10 is added, 550 parts by weight (82.5g) distilled water is added
It is made into the solution that mass concentration is 1/50, ball milling 2h under the revolving speed of 560rpm obtains modified reinforced filling aqueous solution.
(2) reinforcement natural rubber is prepared
The reinforced filling aqueous solution of obtained modification is added in the Heveatex that 25g mass fraction is 60%, is added
493 parts by weight (74g) distilled water is made into 10% latex solution, stirs for 24 hours, with 20% CaCl2Alcohol solution (1 parts by weight
Anhydrous CaCl2, 2 parts by weight dehydrated alcohols, 2 parts by weight distilled water) and demulsification, it repeatedly extrudes, is then cut into little particle, distill water logging
For 24 hours, 60 DEG C of dryings are wait refine for bubble.
Table 1: rubber constituent
| Heveatex (NR60%) | 100phr |
| S | 2.5 |
| ZnO | 5 |
| Altax | 0.5 |
| Antioxidant 4010NA | 1.5 |
| Stearic acid SA | 2 |
| Modified nano calcium carbonate+modified Nano diamond | 8+2 |
Ingredient table as above, at 60 DEG C, plasticate 2min under mixer 30rpm revolving speed, and the above vulcanization aid, then mixing is added
6min removes the good rubber of mixing, is cut into particle, vulcanizes again overnight.Vulcanization preheats 2min using hot press elder generation 0Mpa, then
15MPa vulcanizes 10min at 145 DEG C.
Table 2: performance test
Embodiment 3
By natural rubber dry glue be 100 (15g) parts by weight in terms of, weigh 3 parts by weight of modified Nano diamond (ODND)
7 parts by weight (1.05g) of (0.45g) and modified nanometer calcium carbonate (Nano-CaCO3), 267 parts by weight (40g) agate bead add
Enter in ball grinder, meanwhile, the lauryl sodium sulfate (0.15g) of two kinds of modified filler gross masses 1/10 is added, 550 weight are added
Part (82.5g) distilled water is made into the solution that mass concentration is 1/50, ball milling 2h under the revolving speed of 560rpm.
The good the two filler mixing liquid of ball milling is added in the Heveatex that 25g mass fraction is 60%, is added 493
Parts by weight (74g) distilled water is made into 10% latex solution, stirs for 24 hours, with 20% CaCl2(1 parts by weight are anhydrous for alcohol solution
CaCl2,2 parts by weight dehydrated alcohols, 2 parts by weight distilled water) demulsification, it repeatedly extrudes, is then cut into little particle, distilled water immersion
For 24 hours, 60 DEG C of dryings are wait refine.
Table 3: rubber constituent
| Heveatex (NR60%) | 100phr |
| S | 1 |
| ZnO | 5 |
| Altax | 1 |
| Antioxidant 4010NA | 1.5 |
| Stearic acid SA | 2 |
| Modified nano calcium carbonate+modified Nano diamond | 7+3 |
Ingredient table as above, at 80 DEG C, plasticate 2min under mixer 30rpm revolving speed, and the above vulcanization aid, then mixing is added
6min removes the good rubber of mixing, is cut into particle, vulcanizes again overnight.Vulcanization preheats 2min using hot press elder generation 0Mpa, then
15MPa vulcanizes 10min at 145 DEG C.
Table 4: performance test
Embodiment 4
By natural rubber dry glue be 100 (15g) parts by weight in terms of, weigh 8 parts by weight of modified Nano diamond (ODND)
12 parts by weight (1.8g) of (1.2g) and modified nanometer calcium carbonate (Nano-CaCO3), 267 (40g) parts by weight agate beads are added
In ball grinder, meanwhile, the lauryl sodium sulfate (0.3g) of two kinds of modified filler gross masses 1/10 is added, 776 parts by weight are added
(115g) distilled water is made into the solution that mass concentration is 1/50, ball milling 2h under the revolving speed of 560rpm.
The good the two filler mixing liquid of ball milling is added in the Heveatex that 25g mass fraction is 60%, is added 387
Parts by weight (58g) distilled water is made into 10% latex solution, and for 24 hours, with 20% CaCl2 alcohol solution, (1 parts by weight are anhydrous for stirring
CaCl2,2 parts by weight dehydrated alcohols, 2 parts by weight distilled water) demulsification, it repeatedly extrudes, is then cut into little particle, distilled water immersion
For 24 hours, 60 DEG C of dryings are wait refine.
Table 5: rubber constituent
| Heveatex (NR60%) | 100phr |
| S | 0.4 |
| ZnO | 5 |
| Altax | 4 |
| Antioxidant 4010NA | 1.5 |
| Stearic acid SA | 2 |
| Modified nano calcium carbonate+modified Nano diamond | 12+8 |
Ingredient table as above, at 60 DEG C, plasticate 2min under mixer 30rpm revolving speed, and the above vulcanization aid, then mixing is added
6min removes the good rubber of mixing, is cut into particle, vulcanizes again overnight.Vulcanization preheats 2min using hot press elder generation 0Mpa, then
15MPa vulcanizes 10min at 145 DEG C.
Table 6: performance test
Embodiment 5
By natural rubber dry glue be 100 (15g) parts by weight in terms of, weigh modified 5 weight of oxidation nanometer diamond (ODND)
Measure part (0.75g) and modified nanometer calcium carbonate (Nano-CaCO3) 5 parts by weight (0.75g), 267 (40g) parts by weight agates
Pearl is added in ball grinder, meanwhile, the lauryl sodium sulfate (0.15g) of two kinds of modified filler gross masses 1/10 is added, is added 550
Parts by weight (82.5g) distilled water is made into the solution that mass concentration is 1/50, ball milling 2h under the revolving speed of 560rpm.
The good the two filler mixing liquid of ball milling is added in the Heveatex that 25g mass fraction is 60%, is added 493
Parts by weight (74g) distilled water is made into 10% latex solution, and for 24 hours, with 20% CaCl2 alcohol solution, (1 parts by weight are anhydrous for stirring
CaCl2, 2 parts by weight dehydrated alcohols, 2 parts by weight distilled water) and demulsification, it repeatedly extrudes, is then cut into little particle, distilled water immersion
For 24 hours, 60 DEG C of dryings are wait refine.
Table 7: rubber constituent
| Heveatex (NR60%) | 100phr |
| S | 0.4 |
| ZnO | 5 |
| Altax | 4 |
| Antioxidant 4010NA | 1.5 |
| Stearic acid SA | 2 |
| Modified nano calcium carbonate+modified Nano diamond | 5+5 |
Ingredient table as above, at 70 DEG C, plasticate 2min under mixer 30rpm revolving speed, and the above vulcanization aid, then mixing is added
6min removes the good rubber of mixing, is cut into particle, vulcanizes again overnight.Vulcanization preheats 2min using hot press elder generation 0Mpa,
15MPa vulcanizes 10min at 145 DEG C.
Table 8: performance test
Embodiment 6: relative to embodiment 5, modified oxidation nanometer diamond (ODND) inventory is 10 parts by weight
(1.5g), modified nanometer calcium carbonate (Nano-CaCO3) inventory be 0, it is other constant.
Embodiment 7: relative to embodiment 5, modified oxidation nanometer diamond (ODND) inventory is 0, modified
Nanometer calcium carbonate (Nano-CaCO3) inventory be 10 parts by weight (1.5g), it is other constant.
Table 9: performance test
The several examples spoken of in this specification be example is illustrated for this patent, although, it is above-mentioned text in
Be described in detail, but on the basis of the present invention, can to further improvement, this belongs to the range of this technology protection
Within.Therefore, the modification made on the basis of without departing substantially from the present invention, falls within the scope of the claimed invention.
Claims (10)
1. a kind of method of reinforcement natural rubber, which comprises the following steps:
A, by Nano diamond, heating progress oxidation processes must be aoxidized in reaction kettle under the conditions of potassium permanganate, dense sulfuric acid treatment
Nano diamond；It remixes to be modified after nanometer calcium carbonate and gained oxidation nanometer diamond are reacted with coupling agent respectively and fill out
Material, or modified filler is reacted to obtain with coupling agent after nanometer calcium carbonate and gained oxidation nanometer diamond are mixed；
B, dispersing agent, water are added in gained modified filler, is dispersed by ball milling or the method for shearing, obtains modified reinforcement
Filler aqueous solution；
C, the reinforced filling aqueous solution is added in Heveatex, is uniformly mixed, and is agglomerated, dry, prepares natural rubber master batch；
D, the mixing together with vulcanization aid by natural rubber master batch, vulcanization, obtains reinforcement natural rubber.
2. the method for reinforcement natural rubber according to claim 1, which is characterized in that Nano diamond described in step a
Particle size is 4nm ~ 10 μm, and the Nano diamond is the Nano diamond original powder or amination nanometer using detonation synthesis
Diamond；Nanometer calcium carbonate partial size≤the 100nm.
3. the method for reinforcement natural rubber according to claim 1 or 2, which is characterized in that nanometer calcium carbonate in step a
And/or the detailed process that oxidation nanometer diamond is reacted with coupling agent is: by nanometer calcium carbonate and/or oxidation nanometer diamond with
The alcohol solution of coupling agent reaction 0.1 under the conditions of 20 ~ 80 DEG C ~ for 24 hours in reaction kettle, based on the quality of the component contained by the reaction system
Calculate, nanometer calcium carbonate and/or oxidation nanometer diamond in system: coupling agent=0.1-50: 1, nanometer calcium carbonate and/or oxidation are received
Rice diamond: ethyl alcohol: water=1: 0.1-50: 0.1-50.
4. the method for reinforcement natural rubber according to claim 3, which is characterized in that in system nanometer calcium carbonate and/or
Oxidation nanometer diamond: coupling agent=1-20: 1, nanometer calcium carbonate and/or oxidation nanometer diamond: ethyl alcohol: water=1: 1-10: 1-
10。
5. the method for reinforcement natural rubber according to claim 2, which is characterized in that the preparation of oxidation nanometer diamond
Journey is specifically: by Nano diamond and potassium permanganate, the concentrated sulfuric acid in mass ratio 1: 1 ~ 1.5: 15 ~ 20,200 ~ 300 in reaction kettle
After reacting 4 ~ 6h under the conditions of DEG C, reactant is cleaned to neutrality to get oxidation nanometer diamond with deionized water.
6. the method for reinforcement natural rubber according to claim 3, which is characterized in that the coupling agent is sulfur-containing organosilicon
Compound.
7. the method for the reinforcement natural rubber according to claim 1, which is characterized in that dispersing agent described in step b be from
Subtype surfactant.
8. the method for the reinforcement natural rubber according to claim 1, which is characterized in that nano-sized carbon in the modified filler
Sour calcium and oxidation nanometer diamond quality ratio are 0.1 ~ 10: 1.
9. the method for reinforcement natural rubber according to claim 7, which is characterized in that the dispersing agent is dodecyl sulphate
The mass ratio of sodium, dispersing agent and modified filler, water is 1: 10: 550；The condition of mechanical milling process is: ball milling pearl diameter in ball mill
For 2-5mm, ball milling pearl amount accounts for the 60%~75% of ball milling self-contained volume, and Ball-milling Time 2h, revolving speed is set as 560rpm.
10. the method for the reinforcement natural rubber according to claim 1, which is characterized in that the quality of the Heveatex
Score is 60%, and contained natural rubber dry glue quality ratio is 0.001 ~ 2: 1 in modified filler and the Heveatex；With the day
In right latex based on the quality of contained natural rubber dry glue, vulcanization aid described in step d and its additive amount are as follows: sulphur 0.4-
2.5phr, zinc oxide 5phr, altax 0.5-4phr, antioxidant 4010NA 1.5phr, stearic acid 2phr；Mixing condition is:
60-90 DEG C of smelting temperature, mixing time 5-8min, banbury rotating speed 30rpm；Conditions of vulcanization is: 145 DEG C of curing temperature, vulcanization
Time 12min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110734585A (en) * | 2019-10-24 | 2020-01-31 | 江苏清荷材料科技有限公司 | rubber master batch and preparation method thereof, and rubber and preparation method thereof |
| CN115785536A (en) * | 2022-12-07 | 2023-03-14 | 丰泽智能装备股份有限公司 | Modified natural rubber, preparation method thereof and building shock insulation rubber support |
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| JP2003041064A (en) * | 2001-07-30 | 2003-02-13 | Ube Ind Ltd | Rubber composition for hose |
| CN106589945A (en) * | 2016-12-30 | 2017-04-26 | 郑州掌盟网络科技有限公司 | Rubber material with damping effect and preparation method thereof |
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| JP2003041064A (en) * | 2001-07-30 | 2003-02-13 | Ube Ind Ltd | Rubber composition for hose |
| CN106589945A (en) * | 2016-12-30 | 2017-04-26 | 郑州掌盟网络科技有限公司 | Rubber material with damping effect and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734585A (en) * | 2019-10-24 | 2020-01-31 | 江苏清荷材料科技有限公司 | rubber master batch and preparation method thereof, and rubber and preparation method thereof |
| CN115785536A (en) * | 2022-12-07 | 2023-03-14 | 丰泽智能装备股份有限公司 | Modified natural rubber, preparation method thereof and building shock insulation rubber support |
| CN115785536B (en) * | 2022-12-07 | 2024-05-24 | 丰泽智能装备股份有限公司 | Modified natural rubber, preparation method thereof and building shock insulation rubber support |
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| CN109206680B (en) | 2020-08-25 |
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