CN1152093C - Process for modifying carbon black with ethyl monomer - Google Patents
Process for modifying carbon black with ethyl monomer Download PDFInfo
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- CN1152093C CN1152093C CNB001172336A CN00117233A CN1152093C CN 1152093 C CN1152093 C CN 1152093C CN B001172336 A CNB001172336 A CN B001172336A CN 00117233 A CN00117233 A CN 00117233A CN 1152093 C CN1152093 C CN 1152093C
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- carbon black
- rubber
- vinyl monomer
- correcting agent
- properties
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Abstract
The present invention relates to a method for modifying carbon black with a vinyl monomer. A vinyl monomer modifying agent and the carbon black are sufficiently stirred and evenly mixed to be heated in a static state or a stirring state. A weight proportion to the carbon black and the vinyl monomer modifying agent is 100: 0.1 to 30. The carbon black modified by the method of the present invention has reinforcing action on rubber which is obviously better than carbon black which is not processed. The modified carbon black has the advantages of high physical and mechanical properties and obvious enhancement of a performance conservation rate after ageing. Some special functions can be provided for rubber composite material. Meanwhile, the modified carbon black can be granulated. Consequently, environmental pollution caused by carbon black flying can be prevented.
Description
The present invention relates to the treatment process of inorganic materials, particularly adopt vinyl monomer that carbon black is carried out modification, to improve the comprehensive physical and mechanical properties of rubber.
Carbon black is the reinforced filling that generally adopts in the rubber industry, in most rubber items such as tire, sebific duct, adhesive tape in order to improve the physical and mechanical properties of rubber, as tensile strength, stress at definite elongation, tear strength, abrasion etc.But the carbon black of present industrial employing obviously exists many deficiencies, as: behind the rubber thermo-oxidative ageing with these black-reinforceds, the property retention rate is generally not high, high elongation rate and high stress at definite elongation, high rigidity particularly thorny; Carbon black flies upward cause seriously polluted or the like.
The objective of the invention is to be used for the deficiency that reinforced rubber exists at existing carbon black, a kind of method of modifying carbon black with ethyl monomer is provided, with vinyl monomer carbon black is carried out modification, make carbon black after the modification significantly improve the comprehensive physical and mechanical properties of rubber, particularly make the property retention rate after aging reach higher level.
The method of modifying carbon black with ethyl monomer of the present invention is that vinyl monomer properties-correcting agent is fully mixed with carbon black, and heating is 5 minutes～6 hours under static or stirring, and Heating temperature is 30 ℃～300 ℃, and stirring velocity is 0 rev/min～3000 rev/mins; The weight proportion of described carbon black, vinyl monomer properties-correcting agent is as follows:
100 parts of carbon blacks
0.1～30 part of vinyl monomer properties-correcting agent
Described vinyl monomer properties-correcting agent is acid, acid anhydrides or the ester that contains vinyl, for example toxilic acid, maleic anhydride or maleic acid ester, fumaric acid, fumaric acid anhydride or fumarate, vinylformic acid and ester thereof, methacrylic acid and ester etc. thereof can mix use by one or more compositions.
When carbon black, vinyl monomer properties-correcting agent adopt following weight proportion, to strengthening action the best of rubber:
100 parts of carbon blacks
0.5～10 part of vinyl monomer properties-correcting agent
The modified carbon black that the inventive method obtains can be used in all tire carcass glue such as tire tread glue, tire tire shoulder glue, cord ply compound; Also can in all other rubber items, use.
The technology that the modified carbon black that the inventive method obtains is used for reinforcing rubber is identical with existing rubber processing, promptly adopt Banbury mixer or mill or twin screw extruder that modified carbon black is mixing in rubber, gained rubber unvulcanizate performance obviously is better than adopting the sooty sizing material that is untreated.
The carbon black of the present invention after with the vinyl monomer modification can significantly improve the comprehensive physical and mechanical properties of rubber, gives rubber some new performance and functions simultaneously, as Reinforced Rubber and polymkeric substance cord bonding, reduce the rolling resistance of rubber etc.
The contriver has studied the mechanism that the monomers such as acid, acid anhydrides or ester that contain vinyl of the present invention carry out modification to carbon black by exploitative experiment, thinks that Chemical bond has taken place for vinyl monomer properties-correcting agent and carbon blacksurface.Because there is the general character of surface chemical property in all kinds of carbon blacks, method of the present invention is adapted to the carbon black of all brands and model.The modified carbon black that the inventive method obtains is to the mechanism of action of rubber performance, the contriver thinks that the C=C that forms chemically combined vinyl monomer properties-correcting agent with carbon blacksurface has participated in the sulfidation of rubber, thereby between carbon black-carbon black, carbon black-rubber, rubber-rubber, formed the overall chemical network, promptly formed the overall network effect.Therefore, the modified carbon black that obtains of the inventive method is applicable to the synthetic rubber and the natural rubber of all kinds and the trade mark to the improvement of rubber performance.
The present invention compared with prior art has following advantage:
(1) through the carbon black of the inventive method modification the strengthening action of rubber obviously is better than unmodified carbon black, have higher physical and mechanical properties and significantly improve the aged properties conservation rate, solved the contradiction between high stress at definite elongation, high rigidity and high elongation rate preferably;
(2) can give rubber composite some specific functions through the carbon black of the inventive method modification,, reduce the rolling resistance of vulcanized rubber etc. as the bond properties of obvious Reinforced Rubber and impregnation polymkeric substance cord;
(3) but through the carbon black granulation of the inventive method modification, thereby the environmental pollution of avoiding carbon black to fly upward causing.
Below by embodiment the present invention is done further narration.
Example 1 usefulness maleic anhydride (MAH) modified carbon black (N330)
The basic recipe of table 1 sizing material (part)
A B
Natural rubber (SNR20) 100 100
Carbon black (N330) 25 0
MAH modified carbon black (N330) 0 25
White carbon black 10 10
Zinc oxide 88
Stearic acid 22
Process oil 44
Accelerant CZ 0.6 0.6
Accelerant N OBS 0.6 0.6
Insoluble sulfur 2.5 2.5
100 gram carbon blacks, 30 gram MAH are mixed, in 300 ℃ of maintenances 5 minutes, obtain the MAH modified carbon black under stirring, add in the sizing material.The basic recipe of sizing material is as shown in table 1, and the sizing material of the N330 that is untreated is adopted in the A representative in the table 1, and the sizing material of MAH modification N330 is adopted in the B representative.
Table 2 has been listed the influence of MAH modified carbon black to the cross-linked rubber physical and mechanical properties.As can be seen from the table, the MAH modified carbon black makes aging preceding cross-linked rubber tensile strength, 300% stress at definite elongation, 500% stress at definite elongation and tensile yield than adopting unmodified carbon black to improve to some extent, and (Shao Shi A) is constant substantially for tear strength, hardness; And the cross-linked rubber after aging still can keep higher draw tensile strength and tensile yield, particularly tensile yield still can remain on more than 500% when adopting the MAH modified carbon black, and the aging resistance rate of descent of cross-linked rubber is than low many of the sizing material of employing unmodified carbon black.This life-time service to rubber item is highly beneficial.
The physical and mechanical properties of table 2 cross-linked rubber
A B
After wearing out before aging preceding aging back is aging
300% stress at definite elongation (MPa) 7.3 12.8 7.7 10.8
500% stress at definite elongation (Mpa) 17.2--19.6 21.4
Tensile strength (Mpa) 25.2 19.0 26.7 23.1
Tensile yield (%) 604 404 624 516
Tear strength (KN/m) 170 129 169 133
Hardness (Shao Shi A) 61 66 61 64
Nylon 66 cord H extract power (KN/m) 20.0--21.6--out
Nylon 66 cord sticking power (KN/m) 13.7 7.0 19.6 10.0
Aging condition: in the air, 100 ℃, 24 hours.
Table 2 has also been listed the influence of MAH modified carbon black to natural rubber sizing material and nylon 66 rubberized cord bonding adhesive attractions, and as can be seen, the MAH modified carbon black all is significantly increased the bonding adhesive attraction of nylon 66 rubberized cords and natural rubber sizing material before and after aging.
In addition, the DMA test result to cross-linked rubber shows: the application of MAH modified carbon black can also reduce the rolling resistance of sizing material effectively.
Example 2: with methacrylic acid (MAA) modified carbon black (N539)
100 gram carbon blacks, 0.1 gram MAA are mixed, in 30 ℃ of maintenances 6 hours, obtain MAA modification N539 under stirring, add in the sizing material.The sizing material of unmodified N539 is adopted in the C representative in the table 3 and 4, and the sizing material of MAA modification N539 is adopted in the D representative.
Table 3 basic recipe
*
C D
Carbon black (N539) 25 0
MAH modified carbon black (N539) 0 25
*Other components are with table 1
The physical and mechanical properties of table 4 cross-linked rubber
C D
After wearing out before aging preceding aging back is aging
300% stress at definite elongation (MPa) 6.9 11.5 8.1 12.4
500% stress at definite elongation (MPa) 17.0--20.3--
Tensile strength (MPa) 24.9 17.6 25.8 21.2
Tensile yield (%) 576 365 605 473
Tear strength (KN/m) 160 119 161 122
Hardness (Shao Shi A, degree) 61 66 62 67
Aging condition: in the air, 100 ℃, 24 hours.
As can be seen from Table 4, except that the influence of tear strength and hardness is less, methacrylic acid (MAA) modified carbon black (N539) makes tensile strength, 300% stress at definite elongation, 500% stress at definite elongation and the tensile yield of aging preceding cross-linked rubber than adopting unmodified carbon black all to improve to some extent, and improves the most obvious with 300% stress at definite elongation, 500% stress at definite elongation; Simultaneously, make the cross-linked rubber after wearing out still can keep higher draw tensile strength and tensile yield, particularly aging back tensile yield still reaches 473%, and the tensile yield of the sizing material that adopts unmodified carbon black after aging only is 365%, and the aging resistance rate of descent of cross-linked rubber is than low many of the sizing material of employing unmodified carbon black.This life-time service to rubber item is highly beneficial.
Example 3: butyl methacrylate (BA) modified carbon black (N220).
100 gram carbon blacks, 15 gram BA are mixed, stir down in 150 ℃ of maintenances 3 hours.Obtain BA modification N220, add in the sizing material.The sizing material of unmodified N220 is adopted in the E representative in table 5 and the table 6, and the sizing material of BA modification N220 is adopted in the F representative.
Table 5 basic recipe
*
E F
Carbon black (N220) 25 0
MAH modified carbon black (N220) 0 25
*Other components are with table 1
The physical and mechanical properties of table 6 cross-linked rubber
E F
After wearing out before aging preceding aging back is aging
300% stress at definite elongation (MPa) 7.5 11.9 6.9 10.4
500% stress at definite elongation (MPa) 17.6--16.5 21.4
Tensile strength (MPa) 26.1 19.6 27.7 22.7
Tensile yield (%) 608 388 668 512
Tear strength (KN/m) 175 133 171 133
Hardness (Shao Shi A, degree) 61 66 61 66
Aging condition: in the air, 100 ℃, 24 hours.
As can be seen from Table 6, butyl methacrylate modified carbon black (N220) makes the tensile strength of aging preceding cross-linked rubber and elongation at break obviously improve than the employing unmodified carbon black, hardness and tear strength are constant substantially, and 300% stress at definite elongation, 500% stress at definite elongation slightly reduce; Make the cross-linked rubber after wearing out still can keep higher draw tensile strength and tensile yield simultaneously, particularly tensile yield still can remain on 512%, and the elongation at break of the sizing material that adopts unmodified carbon black after aging only is 388%, and the aging resistance rate of descent of cross-linked rubber is than low many of the sizing material of employing unmodified carbon black.This life-time service to rubber item is highly beneficial.
Claims (2)
1, a kind of method of modifying carbon black with ethyl monomer, it is characterized in that vinyl monomer properties-correcting agent is fully mixed with carbon black, heating is 5 minutes～6 hours under static or stirring, and Heating temperature is 30 ℃～300 ℃, and stirring velocity is 0 rev/min～3000 rev/mins; The weight proportion of described carbon black, vinyl monomer properties-correcting agent is as follows:
100 parts of carbon blacks
0.1～30 part of vinyl monomer properties-correcting agent
Described vinyl monomer properties-correcting agent is acid, acid anhydrides or the ester that contains vinyl, can mix use by one or more compositions.
2,, it is characterized in that the weight proportion of described carbon black, vinyl monomer properties-correcting agent is as follows according to the method for the described modifying carbon black with ethyl monomer of claim 1:
100 parts of carbon blacks
0.5～10 part of vinyl monomer properties-correcting agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001172336A CN1152093C (en) | 2000-07-07 | 2000-07-07 | Process for modifying carbon black with ethyl monomer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001172336A CN1152093C (en) | 2000-07-07 | 2000-07-07 | Process for modifying carbon black with ethyl monomer |
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| CN1279260A CN1279260A (en) | 2001-01-10 |
| CN1152093C true CN1152093C (en) | 2004-06-02 |
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| CNB001172336A Expired - Fee Related CN1152093C (en) | 2000-07-07 | 2000-07-07 | Process for modifying carbon black with ethyl monomer |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100365076C (en) * | 2004-09-28 | 2008-01-30 | 华东理工大学 | Nano carbon black with in-situ grafted organic compound and its producing method |
| CN100406526C (en) * | 2006-03-23 | 2008-07-30 | 华东理工大学 | Water-soluble conductive macromolecular surface modification carbon black and method for preparing same |
| CN100577746C (en) * | 2007-11-02 | 2010-01-06 | 山东大学 | Modification processing method for highly structural-superconducting carbon black BP2000 |
| CN103497357A (en) | 2013-10-10 | 2014-01-08 | 张义纲 | Modified carbon black and preparation method thereof |
| CN111662576A (en) * | 2019-03-07 | 2020-09-15 | 青岛四维化工有限公司 | Preparation method of quasi-in-situ modified pyrolytic carbon black |
| CN110041876B (en) * | 2019-04-01 | 2021-09-21 | 矽时代材料科技股份有限公司 | Ultraviolet curing adhesive, preparation method and application |
| CN113968953A (en) * | 2020-07-24 | 2022-01-25 | 江苏锐嘉新能源科技有限公司 | Preparation process of heat-conducting shockproof polyurethane foam |
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