CN104194109A - Thermo-oxidative ageing resistant epoxidized natural rubber composite material and preparation method thereof - Google Patents
Thermo-oxidative ageing resistant epoxidized natural rubber composite material and preparation method thereof Download PDFInfo
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- CN104194109A CN104194109A CN201410394554.4A CN201410394554A CN104194109A CN 104194109 A CN104194109 A CN 104194109A CN 201410394554 A CN201410394554 A CN 201410394554A CN 104194109 A CN104194109 A CN 104194109A
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- natural rubber
- epoxidized natural
- hydrotalcite
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- rubber composite
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- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 90
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 90
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 230000032683 aging Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 92
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 91
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 91
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229920000126 latex Polymers 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920006173 natural rubber latex Polymers 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 19
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 238000006735 epoxidation reaction Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 239000004816 latex Substances 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- ZUBNXRHITOZMOO-UHFFFAOYSA-N zinc;octadecanoic acid;oxygen(2-) Chemical group [O-2].[Zn+2].CCCCCCCCCCCCCCCCCC(O)=O ZUBNXRHITOZMOO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 abstract description 25
- 238000004073 vulcanization Methods 0.000 abstract description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 abstract description 2
- 230000035882 stress Effects 0.000 description 10
- 238000005987 sulfurization reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
The invention discloses a hydrotalcite/epoxidized natural rubber composite material and a preparation method thereof. The preparation method comprises the following steps: modifying hydrotalcite and dispersing the modified hydrotalcite by using deionized water; adding epoxidized natural rubber latex, continuously and ultrasonically stirring to obtain a hydrotalcite/epoxidized natural rubber composite material at a rubber latex state; and adding vulcanization processing aids, thereby obtaining an ageing-resistant epoxidized natural rubber composite material. The thermo-oxidative ageing resistant epoxidized natural rubber composite material with excellent performance, prepared by the invention, can be used for high-performance tires, medical rubber latex products, rubber tubes, shoe soles and other epoxidized natural rubber products.
Description
[technical field]
The present invention relates to epoxidized natural rubber composite material and preparation method thereof, particularly a kind of heat oxygen aging resistance epoxidized natural rubber composite material and preparation method thereof.
[background technology]
Epoxy natural rubber is a kind ofly natural rubber is carried out to epoxidation modification to obtain, and normally under acidic conditions, is added by natural rubber latex that formic acid or acetic acid and hydrogen peroxide is prepared from.Because epoxy natural rubber is to introduce epoxide group in natural rubber molecule, so cause the increase of the reactive force between polarity and the rubber molecule of rubber molecule, make it have some special performances, such as the resistance to resistance to air loss of excellence, oil-proofness, good anti-slippery and lower rolling resistance and good tackiness.Therefore, epoxy natural rubber is of many uses, particularly in green tire application aspect, because epoxy natural rubber has low rolling resistance and high anti-slippery, is with a wide range of applications at the manufacture view of high-performance green tire.But, epoxy natural rubber goods are easy to be subject to the impact of environmental factors to occur the phenomenon of ageing of rubber in processing or use procedure, therefore epoxy natural rubber goods ubiquity period of storage is short, work-ing life is short, the aging problem such as be clamminess, and has limited to a large extent the application of epoxy natural rubber.
Therefore, a kind of have good mechanical property and ageing resistance also will be provided, can be for medical adhesive milk-product, tire, epoxidized natural rubber composite material of the epoxy natural rubber such as sebific duct, sole goods and preparation method thereof, the application of widening to a large extent epoxy natural rubber.
[summary of the invention]
The object of the present invention is to provide a kind of heat oxygen aging resistance epoxidized natural rubber composite material and preparation method thereof.
Specifically, the present invention is to provide a kind of hydrotalcite/epoxidized natural rubber composite material; Its preparation method is, first hydrotalcite carried out to modification, then disperses with deionized water, adds epoxidized natural latex, continues ultrasonic agitation and obtain the hydrotalcite/epoxidized natural rubber composite material of latex state; Through adding sulfuration processing aid, obtain ageing-resistant epoxidized natural rubber composite material.
A kind of heat oxygen aging resistance epoxidized natural rubber composite material of the present invention, is characterized in that it comprises following component by weight:
By 100 parts of the epoxidized natural latex of dry glue;
3～30 parts of hydrotalcites.
In order to prepare heat oxygen aging resistance epoxidized natural rubber composite material of the present invention, also can select to add the one in 5～10% silane coupling agent or sodium stearate of hydrotalcite consumption;
In order to prepare heat oxygen aging resistance epoxidized natural rubber composite material of the present invention, also can add the Synergist S-421 95 of following formula:
| Material name | Epoxy natural rubber | Sulphur | Accelerator NS | Zinc oxide | Stearic acid |
| Parts by weight | 100 | 1.5 | 1.5 | 5 | 2 |
Weight part of the present invention can be gram or kilogram etc. known content unit.
Epoxy natural rubber of the present invention is that the epoxidation level of being prepared by epoxidation reaction by natural rubber latex is 5～50% epoxidized natural latex;
Hydrotalcite of the present invention, its laminate positively charged ion is Mg
2+or Al
3+, interlayer anion is CO
32-, OH
-, SO
4 2-, NO
3 -or Cl
-, median size is 0.5-1.2 μ m, the amount ratio of the epoxidized natural latex of the epoxidation level 5-50% of itself and 100 parts of dry glue meters is 3～30 parts;
Silane coupling agent of the present invention, the one in optional Si-69 or KH550 or KH560, its consumption is 5～10% of hydrotalcite consumption;
Hydrotalcite/epoxidized natural rubber composite material prepared by the present invention can adopt sulfur cross-linking system (common vulcanization system, semi effcient vulcanization system, efficient vulcanization system), peroxide vulcanizing system to make prevulcanized latex, produces various latex products by impregnation technology; Also can adopt conventional machining technique to carry out mixing sulfuration, make various dry glue goods.
The preparation method of a kind of heat oxygen aging resistance epoxidized natural rubber composite material of the present invention is as follows:
Take a certain amount of hydrotalcite, add a certain amount of deionized water, under the state of ultrasonic dispersion while stirring, add a certain amount of silane coupling agent or sodium stearate, be placed in the water-bath continuously stirring 24h of 30～40 DEG C, add subsequently epoxidized natural latex, continue ultrasonic agitation 0.5～1h, obtain the hydrotalcite/epoxidized natural rubber composite material of latex state; Hydrotalcite/the epoxidized natural rubber composite material of emulsus state is solidified with peptizer to compressing tablet, granulation, the dry hydrotalcite/epoxidized natural rubber composite material that obtains dry gluey state; Add various Synergist S-421 95s to carry out by formula in this matrix material mixing, obtain heat oxygen aging resistance epoxidized natural rubber composite material.
[key point of the present invention]
Key point of the present invention is:
The hydrotalcite that the present invention adopts, claims again layered double hydroxide (Layared Double Hydroxides is called for short LDHs), is a kind of typical anion type laminated compound, and its typical molecular composition is Mg
6al
2(OH)
16cO
34H
2o.Because having compared with strong alkalescence, hydrotalcite surface there is good wetting ability, by add the hydrotalcite of modification in epoxidized natural latex, the a large amount of non-bridge formation hydroxyl that hydrotalcite surface exists reacts with the epoxide group in epoxy natural rubber, make hydrotalcite better key and and be dispersed in rubber particles system, also can absorb simultaneously and in and the free acid that produces in epoxy natural rubber weathering process, suppress the carrying out of weathering process, thereby improve the resistance to deterioration of epoxidized natural rubber composite material.
[beneficial effect of the present invention]
Heat oxygen aging resistance epoxidized natural rubber composite material prepared by the present invention, has following unusual effect:
---tensile strength is 25.2MPa～32.8MPa;
---300% stress at definite elongation is 2.05MPa～2.74MPa;
---tear strength is 31MPa～43MPa;
---after the hot air aging of 100 DEG C × 24h, the stretching strength retentivity of matrix material is 69%～93%, and elongation rate of tensile failure conservation rate is 80%～96%;
---because hydrotalcite has significant restraining effect to the growth of multiple-microorganism and mushroom, there is effective sterilization component high dispersing, germ-killing efficiency high; The features such as matrix material has that heat-dissipating is low, anti-slippery good, hot oxygen and Heat stability is good.Therefore the epoxidized natural rubber composite material that, prepared by the present invention has great application prospect at aspects such as high-performance tire, medical gloves, sebific ducts;
---the present invention hydrotalcite nontoxicity, nonstaining property, preparation method used is simple; With low cost;
---technical matters provided by the invention is simple, is easy to large-scale production.
[embodiment]
Except as otherwise noted, the umber below adopting is weight part.
The test of tensile strength, elongation rate of tensile failure and stress at definite elongation is carried out according to GB/T528-2009; Tear strength test is carried out according to GB/T529-2008.Heat-resistant air aging property: it is to take out sample after aging 24h in the air oven aging test case of 100 DEG C that sample is hung on to experimental temperature at a certain distance, measures its tensile strength and elongation rate of tensile failure.Measured value × 100% before performance measurement value after property retention rate=sample is aging/test is aging.
Embodiment 1
Be first Mg by 3 parts of laminate positively charged ions
2+or Al
3+, interlayer anion is CO
32-, OH
-, SO
4 2-, NO
3 -or Cl
-median size is that the hydrotalcite of 0.5-1.2 μ m adds in the deionized water of 20ml, under the state of ultrasonic dispersion while stirring, add the Si-69 of 5% (weight) of hydrotalcite, be placed in the water-bath continuously stirring 24h of 30 DEG C, add subsequently the epoxidized natural latex of the epoxidation level 5% of 100 parts of dry glue meters, continue ultrasonic agitation 0.6h, obtain the hydrotalcite/epoxidized natural rubber composite material of latex state; Hydrotalcite/the epoxidized natural rubber composite material of emulsus state is solidified with peptizer to compressing tablet, granulation, the dry hydrotalcite/epoxidized natural rubber composite material that obtains dry gluey state.Add various Synergist S-421 95s to carry out the mixing rubber unvulcanizate that obtains by the formula shown in table 1 in this matrix material, after rubber unvulcanizate is at room temperature parked to 3～6h, on vulcanizing press in the sulfuration of 150 DEG C and 15MPa condition, sulfurizing time T
90adopt vulkameter (MDR 2000) to measure.Vulcanized film is at room temperature parked 20h, then measures the physical and mechanical properties of cross-linked rubber.
The basic recipe that table 1 is tested
| Material name | Epoxy natural rubber | Sulphur | Accelerator NS | Zinc oxide | Stearic acid |
| Parts by weight | 100 | 1.5 | 1.5 | 5 | 2 |
Table 2 epoxidation level is the mechanical property of 5% epoxy natural rubber cross-linked rubber
| Project | Tensile strength/MPa | Elongation rate of tensile failure/% | 300% stress at definite elongation/MPa | Tear strength/MPa |
| Do not add hydrotalcite | 18.01 | 720 | 1.53 | 22.86 |
| Add hydrotalcite | 25.21 | 662 | 1.97 | 31.21 |
The stretching strength retentivity of table 3 hydrotalcite/epoxidized natural rubber composite material and elongation rate of tensile failure conservation rate
| Project | Stretching strength retentivity/% | Elongation rate of tensile failure conservation rate/% |
| Do not add hydrotalcite | 65.14 | 71.23 |
| Add hydrotalcite | 76.23 | 85.36 |
The mechanical property of hydrotalcite/epoxidized natural rubber composite material is as shown in table 2.As can be seen from Table 2, the tensile strength of hydrotalcite/epoxidized natural rubber composite material is 25.21Mpa, than the large 7.2Mpa of the cross-linked rubber that does not add hydrotalcite; 300% stress at definite elongation is brought up to 1.97Mpa by 1.53MPa; Tear strength is brought up to 31.21Mpa by 22.86MPa.
Table 3 is hydrotalcite/epoxidized natural rubber composite material stretching strength retentivity and elongation rate of tensile failure conservation rates after hot air aging.As can be seen from Table 3, the ageing resistance of hydrotalcite/epoxidized natural rubber composite material obviously improves, for example, and after 100 DEG C of aging 24h,, hydrotalcite/epoxidized natural rubber composite material tensile strength and elongation rate of tensile failure conservation rate be respectively 76.23% and 85.36%.
Embodiment 2
Be first Mg by 10 parts of laminate positively charged ions
2+or Al
3+, interlayer anion is CO
3 2-, OH
-, SO
4 2-, NO
3 -or Cl
-median size is that the hydrotalcite of 0.5-1.2 μ m adds in the deionized water of 30ml, under the state of ultrasonic dispersion while stirring, add the sodium stearate of 7% (weight) of hydrotalcite, be placed in the water-bath continuously stirring 24h of 35 DEG C, add subsequently the epoxidized natural latex of the epoxidation level 20% of 100 parts of dry glue meters, continue ultrasonic agitation 0.6h, obtain the hydrotalcite/epoxidized natural rubber composite material of latex state; Hydrotalcite/the epoxidized natural rubber composite material of emulsus state is solidified with peptizer to compressing tablet, granulation, the dry hydrotalcite/epoxidized natural rubber composite material that obtains dry gluey state.This matrix material adds various Synergist S-421 95s to carry out mixingly obtaining rubber unvulcanizate by the formula shown in table 1, after rubber unvulcanizate is at room temperature parked to 3～6h, on vulcanizing press in 150 DEG C and the sulfuration of 15MPa condition, sulfurizing time T
90adopt vulkameter (MDR 2000) to measure.Vulcanized film is at room temperature parked 20h, then measures the physical and mechanical properties of cross-linked rubber.
Table 4 epoxidation level is the mechanical property of 20% epoxy natural rubber cross-linked rubber
| Project | Tensile strength/MPa | Elongation rate of tensile failure/% | 300% stress at definite elongation/MPa | Tear strength/MPa |
| Do not add hydrotalcite | 21.52 | 670 | 1.61 | 23.49 |
| Add hydrotalcite | 28.54 | 623 | 2.14 | 32.13 |
The stretching strength retentivity of table 5 hydrotalcite/epoxidized natural rubber composite material and elongation rate of tensile failure conservation rate
| Project | Stretching strength retentivity/% | Elongation rate of tensile failure conservation rate/% |
| Do not add hydrotalcite | 61.14 | 70.56 |
| Add hydrotalcite | 80.23 | 90.21 |
The mechanical property of hydrotalcite/epoxidized natural rubber composite material is as shown in table 4.As can be seen from Table 4, the tensile strength of hydrotalcite/epoxidized natural rubber composite material is 28.54Mpa, than the large 7.02Mpa of the cross-linked rubber that does not add hydrotalcite; 300% stress at definite elongation is brought up to 2.14Mpa by 1.61MPa; Tear strength is brought up to 32.13Mpa by 23.49MPa.
Table 5 is hydrotalcite/epoxidized natural rubber composite material stretching strength retentivity and elongation rate of tensile failure conservation rates after hot air aging.As can be seen from Table 5, the ageing resistance of hydrotalcite/epoxidized natural rubber composite material obviously improves, for example, and after 100 DEG C of aging 24h,, hydrotalcite/epoxidized natural rubber composite material tensile strength and elongation rate of tensile failure conservation rate be respectively 80.23% and 90.21%.
Embodiment 3
Be first Mg by 20 parts of laminate positively charged ions
2+or Al
3+, interlayer anion is CO
3 2-, OH
-, SO
4 2-, NO
3 -or Cl
-median size is that the hydrotalcite of 0.5-1.2 μ m adds in 40ml deionized water, under the state of ultrasonic dispersion while stirring, add the KH 550 of 7% (weight) of hydrotalcite, be placed in the water-bath continuously stirring 24h of 40 DEG C, add subsequently the epoxidized natural latex of the epoxidation level 40% of 100 parts of dry glue meters, continue ultrasonic agitation 1h, obtain the hydrotalcite/epoxidized natural rubber composite material of latex state; Hydrotalcite/the epoxidized natural rubber composite material of emulsus state is solidified with peptizer to compressing tablet, granulation, the dry hydrotalcite/epoxidized natural rubber composite material that obtains dry gluey state.Add various Synergist S-421 95s to carry out the mixing rubber unvulcanizate that obtains by the formula shown in table 1 in this matrix material, after rubber unvulcanizate is at room temperature parked to 3～6h, on vulcanizing press in the sulfuration of 150 DEG C and 15MPa condition, sulfurizing time T
90adopt vulkameter (MDR 2000) to measure.Vulcanized film is at room temperature parked 20h, then measures the physical and mechanical properties of cross-linked rubber.
Table 6 epoxidation level is the mechanical property of 40% epoxy natural rubber cross-linked rubber
| Project | Tensile strength/MPa | Elongation rate of tensile failure/% | 300% stress at definite elongation/MPa | Tear strength/MPa |
| Do not add hydrotalcite | 23.16 | 643 | 1.73 | 22.54 |
| Add hydrotalcite | 31.74 | 616 | 2.21 | 35.81 |
The stretching strength retentivity of table 7 hydrotalcite/epoxidized natural rubber composite material and elongation rate of tensile failure conservation rate
| Project | Stretching strength retentivity/% | Elongation rate of tensile failure conservation rate/% |
| Do not add hydrotalcite | 57.32 | 79.95 |
| Add hydrotalcite | 86.87 | 91.23 |
The mechanical property of hydrotalcite/epoxidized natural rubber composite material is as shown in table 7.As can be seen from Table 7, the tensile strength of hydrotalcite/epoxidized natural rubber composite material is 31.74Mpa, than the large 8.58Mpa of the cross-linked rubber that does not add hydrotalcite; 300% stress at definite elongation is brought up to 2.21Mpa by 1.73MPa; Tear strength is brought up to 35.81Mpa by 22.54MPa.
Table 8 is hydrotalcite/epoxidized natural rubber composite material stretching strength retentivity and elongation rate of tensile failure conservation rates after hot air aging.As can be seen from Table 8, the ageing resistance of hydrotalcite/epoxidized natural rubber composite material obviously improves, for example, after 100 DEG C of aging 24h, the tensile strength of hydrotalcite/epoxidized natural rubber composite material and elongation rate of tensile failure conservation rate are respectively 86.87% and 91.23%.
Embodiment 4
Be first Mg by 30 parts of laminate positively charged ions
2+or Al
3+, interlayer anion is CO
3 2-, OH
-, SO
4 2-, NO
3 -or Cl
-median size is that the hydrotalcite of 0.5-1.2 μ m adds in 50ml deionized water, under the state of ultrasonic dispersion while stirring, add the KH 560 of 10% (weight) of hydrotalcite, be placed in the water-bath continuously stirring 24h of 40 DEG C, add subsequently the epoxidized natural latex of the epoxidation level 50% of 100 parts of dry glue meters, continue ultrasonic agitation 1h, obtain the hydrotalcite/epoxidized natural rubber composite material of latex state; Hydrotalcite/the epoxidized natural rubber composite material of emulsus state is solidified with peptizer to compressing tablet, granulation, the dry hydrotalcite/epoxidized natural rubber composite material that obtains dry gluey state.Add various Synergist S-421 95s to carry out the mixing rubber unvulcanizate that obtains by the formula shown in table 1 in this matrix material, after rubber unvulcanizate is at room temperature parked to 3～6h, on vulcanizing press in the sulfuration of 150 DEG C and 15MPa condition, sulfurizing time T
90adopt vulkameter (MDR 2000) to measure.Vulcanized film is at room temperature parked 20h, then measures the physical and mechanical properties of cross-linked rubber.
Table 9 epoxidation level is the mechanical property of 50% epoxy natural rubber cross-linked rubber
| Project | Tensile strength/MPa | Elongation rate of tensile failure/% | 300% stress at definite elongation/MPa | Tear strength/MPa |
| Do not add hydrotalcite | 24.35 | 632 | 1.78 | 23.87 |
| Add hydrotalcite | 31.67 | 605 | 2.32 | 37.12 |
The stretching strength retentivity of table 10 hydrotalcite/epoxidized natural rubber composite material and elongation rate of tensile failure conservation rate
| Project | Stretching strength retentivity/% | Elongation rate of tensile failure conservation rate/% |
| Do not add hydrotalcite | 58.44 | 81.86 |
| Add hydrotalcite | 89.87 | 94.32 |
The mechanical property of hydrotalcite/epoxidized natural rubber composite material is as shown in table 9.As can be seen from Table 9, the tensile strength of hydrotalcite/epoxidized natural rubber composite material is 31.67Mpa, than the large 7.32Mpa of the cross-linked rubber that does not add hydrotalcite; 300% stress at definite elongation is brought up to 2.32Mpa by 1.78MPa; Tear strength is brought up to 37.12Mpa by 23.87MPa.
Table 10 is hydrotalcite/epoxidized natural rubber composite material stretching strength retentivity and elongation rate of tensile failure conservation rates after hot air aging.As can be seen from Table 10, the ageing resistance of hydrotalcite/epoxidized natural rubber composite material obviously improves, for example, after 100 DEG C of aging 24h, the tensile strength of hydrotalcite/epoxidized natural rubber composite material and elongation rate of tensile failure conservation rate are respectively 89.87% and 94.32%.
Claims (3)
1. a heat oxygen aging resistance epoxidized natural rubber composite material, is characterized in that it comprises following component by weight:
By 100 parts of the epoxidized natural latex of dry glue;
3～30 parts of hydrotalcites;
Described epoxidized natural latex is that the epoxidation level of being prepared by epoxidation reaction by natural rubber latex is 5～50% epoxidized natural latex; Described hydrotalcite, its laminate positively charged ion is Mg
2+or Al
3+, interlayer anion is CO
3 2-, OH
-, SO
4 2-, NO
3 -or Cl
-, median size is 0.5-1.2 μ m.
2. a kind of heat oxygen aging resistance epoxidized natural rubber composite material according to claim 1, while it is characterized in that preparing, also can select to add the one in 5～10% silane coupling agent or sodium stearate of hydrotalcite consumption: and also can add the Synergist S-421 95 of following formula:
Described silane coupling agent is the one in Si-69 or KH550 or KH560.
3. the preparation method of a kind of heat oxygen aging resistance epoxidized natural rubber composite material according to claim 1 and 2, its feature comprises as follows:
Take a certain amount of hydrotalcite, add a certain amount of deionized water, under the state of ultrasonic dispersion while stirring, add a certain amount of silane coupling agent or sodium stearate, be placed in the water-bath continuously stirring 24h of 30～40 DEG C, add subsequently epoxidized natural latex, continue ultrasonic agitation 0.5～1h, obtain the hydrotalcite/epoxidized natural rubber composite material of latex state; Hydrotalcite/the epoxidized natural rubber composite material of emulsus state is solidified with peptizer to compressing tablet, granulation, the dry hydrotalcite/epoxidized natural rubber composite material that obtains dry gluey state; Add various Synergist S-421 95s to carry out by formula in this matrix material mixing, obtain heat oxygen aging resistance epoxidized natural rubber composite material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410394554.4A CN104194109B (en) | 2014-08-12 | 2014-08-12 | A kind of heat oxygen aging resistance epoxidized natural rubber composite material and its preparation method |
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| CN106738532A (en) * | 2016-08-22 | 2017-05-31 | 海南大学 | A kind of quick-drying method of latex |
| CN110713638A (en) * | 2018-07-11 | 2020-01-21 | 北京化工大学 | Hydrotalcite/epoxy natural rubber/styrene butadiene rubber composite material and preparation method thereof |
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