CN105061808A - Rubber antioxidant preparing method - Google Patents
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- CN105061808A CN105061808A CN201510539169.9A CN201510539169A CN105061808A CN 105061808 A CN105061808 A CN 105061808A CN 201510539169 A CN201510539169 A CN 201510539169A CN 105061808 A CN105061808 A CN 105061808A
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Abstract
The invention discloses a rubber antioxidant preparing method. The method includes the flowing steps that 1, antiager dispersed liquid is prepared, wherein p-phenylenediamine antiager is added to an organic solvent to be evenly dispersed in a ultrasonic mode at the normal temperature, and the antiager dispersed liquid is obtained; 2, a monomer grafting reaction is conducted; water and polymerization inhibitor are added to the antiager dispersed liquid obtained in the step1 to be evenly stirred, then methacrylate monomers are dropwise added, and the reaction temperature is controlled in the range of from 60 DEG C to 70 DEG C; 3, aging is conducted, after the methacrylate monomers are dropwise added, the mixture is continuously stirred for more than 20 minutes and then heated to 80 DEG C to 90 DEG C, a heat preservation reaction is conducted for 11 hours to 13 hours, then the mixture is cooled to the room temperature, and rubber antioxidant is obtained after extraction, washing and drying. According to the rubber antioxidant preparing method, p-phenylenediamine antiager is modified through glycidyl methacrylate, various functional active points are introduced so as to achieve improvement of comprehensive performance, and the aging function of the p-phenylenediamine antiager can be guaranteed while the p-phenylenediamine antiager generates a grafting cross-linking reaction on a rubber molecular chain in the vulcanizing process, so that the migration pollution phenomenon is reduced, and vulcanizing promoting and reinforcing of rubber are improved greatly.
Description
Technical field
The present invention relates to a kind of preparation method of Novel rubber antioxidant, be specifically related to a kind of preparation method of glycidyl methacrylate graft modification p phenylenediamine type antioxidant.
Background technology
Rubber item is being deposited with in use procedure, is subject to the impact of the environmental factorss such as oxygen, ozone, light, heat, variable color, bloom can occur, be clamminess, hardening, embrittlement, crackle etc.; Occur the phenomenons such as the mechanical property of rubber reduces, intensity and elongation etc. significantly decline, ventilation property strengthens, dielectric properties weaken, these are all on the security of rubber item with produce great impact work-ing life simultaneously.
At present, natural rubber (NR) is the maximum rubber item of usage quantity, has excellent mechanics and processing characteristics, and low price, but it is because of containing a large amount of unsaturated link(age)s, is easy to generation chemical reaction, makes its aging resistance not ideal enough.In order to delay the ageing-resistant performance of unsaturated rubber, in sizing material of being everlasting, adding anti-aging agent, its object is to disruptive oxidation chain reaction, catching free radical, stop the carrying out that living chain suppresses or delaying retrogradation reacts.Before 60 or seven ten years, the anti-aging agent of amine primary structure is just brought into use, especially p phenylenediamine type antioxidant, has good heat resistanceheat resistant oxygen and ozone resistance, is a kind of rubber anti-aging agent of excellent property.
In recent years, along with the development of rubber item and macromolecular material, the anti-aging agent of simple function can not meet its demand.In order to solve the single anti-aging problem of rubber item, people prepare a kind of multi-functional anti-aging agent to amines antioxidants by methods such as composite, chemical reactions, while reaching good antiageing effect, also impact is created on the over-all properties of rubber item.The method of current anti-aging agent modification is more, as Chinese patent CN1858035A, with 4-ADPA and containing the aliphatic ketone of two methyl for raw material, prepared novel Ursol D rubber antioxidant FA0-7, and be applied to the anti-aging of rubber.And for example, Chinese patent CN101165086A has prepared spherical p-phenylenediamine rubber aging inhibitor N-1,3 dimethylbutyl-N'-diphenyl-para-phenylene diamines and N-sec.-propyl-N'-diphenyl-para-phenylene diamine, be conducive to the mixing of rubber ingredients in compounding rubber and dispersion, and in rubber, reach anti-aging effect.But these method of modifying exist a common problem, prepare a kind ofly being applied in rubber the p phenylenediamine type antioxidant only having single anti-aging effect exactly, the sulfuration for elastomeric material promotes that performance, mechanical property etc. improve and does not have an impact.Meanwhile, when consumption reaches certain value, easily migrate to surface, pollute, affect the quality of rubber product.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of glycidyl methacrylate graft modification p phenylenediamine type antioxidant, the present invention is ultrasonic preparation anti-aging agent dispersion liquid first in organic solvent, then in dispersion liquid, glycidyl methacrylate is added, and under the effect of catalyzer and stopper, complete the modification of p phenylenediamine type antioxidant.
The present invention is achieved through the following technical solutions:
A preparation method for rubber antioxidant, comprises the following steps:
(1) anti-aging agent dispersion liquid: p phenylenediamine type antioxidant is added in organic solvent, under normal temperature, ultrasonic disperse is even, obtains anti-aging agent dispersion liquid; Described normal temperature refers to 25-30 DEG C;
(2) monomer-grafted reaction: add deionized water in the anti-aging agent dispersion liquid under agitation obtained to step (1)
And stopper, drip methacrylate-based monomer after stirring, temperature of reaction controls at 50 ~ 70 DEG C;
(3) ageing: after methacrylate-based monomer drips, continues to stir more than 20min, is then warming up to 80 ~ 90 DEG C, insulation reaction 11-13h, is cooled to room temperature afterwards, obtain product after extracting, washing, oven dry.
Described p phenylenediamine type antioxidant and the mol ratio of methacrylate-based monomer are 1:2.05 ~ 2.15.
Described p phenylenediamine type antioxidant is N-sec.-propyl-N'-diphenyl-para-phenylene diamine, N-cyclohexyl-N'-phenyl-1,4-Ursol D, N, N'-bis--iso-octyl Ursol D, N, N'-bis-(2-naphthyl) Ursol D, N, the one of N'-di tolyl p phenylenediamine or N-(1,3-dimethylbutyl)-N'-diphenyl-para-phenylene diamine.Described methacrylate-based monomer is glycidyl methacrylate.
The consumption of described stopper is 1% ~ 5% of p phenylenediamine type antioxidant quality, and the consumption of water is 10% ~ 20% of p phenylenediamine type antioxidant quality.
Described stopper is the one of Resorcinol, Resorcinol monobutyl ether, the tertiary butyl neck dihydroxy-benzene, 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone.
Described organic solvent is one or more of acetone, toluene, vinyl acetic monomer, methylene dichloride, methyl alcohol, ethanol, acetonitrile or tetrahydrofuran (THF).
Below the reaction mechanism of glycidyl methacrylate graft modification p phenylenediamine type antioxidant, the graft modification for N-sec.-propyl-N '-diphenyl-para-phenylene diamine:
Glycidyl methacrylate has unstable ring texture, and chemical property is active, easily reacts.Non-share electron pair in Ursol D on nitrogen-atoms and the electronic cloud on phenyl ring form conjugated system, and reaction just occurs on nitrogen-atoms.Although glycidyl methacrylate and p phenylenediamine type antioxidant are all non-polar molecules, due to the existence of polar organic solvent, meanwhile, using water as catalyzer, be conducive to carrying out smoothly of addition reaction.Water and glycidyl methacrylate can be dissolved each other, and make N-sec.-propyl-N '-phenyl-Isosorbide-5-Nitrae-phenylenediamine be basic solution, and under alkaline state, in molecule ,-NH steric hindrance is more weak, and therefore, the ring-opening reaction of oxo bridge fracture comparatively easily occurs.
Compared with prior art, tool has the following advantages in the present invention:
First p phenylenediamine type antioxidant dispersion liquid and glycidyl methacrylate mix by the present invention, under the effect of catalyzer and stopper, epoxy group(ing) in glycidyl methacrylate can nitrogen-atoms in attack p phenylenediamine type antioxidant, realizes open loop grafting.
The present invention is by glycidyl methacrylate modification p phenylenediamine type antioxidant, introduce various functionalization active site to reach the lifting of over-all properties, and there is the methyl acrylic ester graft modification p phenylenediamine type antioxidant of epoxide group, not only can ensure the solarization of p phenylenediamine type antioxidant, simultaneously by introducing unsaturated active site, make anti-aging agent that graft crosslinking reaction occur in sulfidation on rubber molecular chain, thus reduce the generation of migration stain phenomenon, the sulfuration promotion of rubber and reinforcement tool are had greatly improved simultaneously, be conducive to the potential range of application expanding rubber anti-aging agent further.
Accompanying drawing explanation
Fig. 1 is the infrared spectra collection of illustrative plates of antioxidant 4010, antioxidant 4010NA.
Fig. 2 is the infrared spectrogram of glycidyl methacrylate.
The infrared spectrogram of the glycidyl methacrylate graft modification antioxidant 4010NA of Fig. 3 prepared by embodiment 1 ~ 3.
The infrared spectrogram of the glycidyl methacrylate graft modification antioxidant 4010 of Fig. 4 prepared by embodiment 4 ~ 5.
This collection of illustrative plates records with " the Migna760 Fourier transformation infrared spectrometer that Nicolet company of the U.S. produces ".
For glycidyl methacrylate, 2900 ~ 3100cm
-1place's peak band belongs to-CH
3,-CH
2symmetry and asymmetrical stretching vibration, 1720cm
-1the stretching vibration absorption peak of C=O, 1638cm
-1the stretching vibration absorption peak of C=C double bond, 1435 and 1296cm
-1c-H in-plane bending vibration absorption peak, 908cm
-1, 844cm
-1and 815cm
-1it is then epoxy skeletal vibration charateristic avsorption band.Antioxidant 4010 is consistent with the infrared spectra collection of illustrative plates of antioxidant 4010NA substantially.3350cm
-1having occurred stronger absorption peak near place, is the stretching vibration absorption peak that belongs to-NH, 2860 ~ 3050cm
-1place's absorption peak band belongs to-CH
3,-CH
2symmetry and asymmetrical stretching vibration, and the C-H stretching vibration absorption peak on phenyl ring, 1598cm
-1the stretching vibration absorption peak of C-N, 1497cm
-1and 1515cm
-1it is the vibration performance absorption peak of monosubstituted phenyl ring and disubstituted benzene ring.And the antioxidant 4010 of glycidyl methacrylate graft modification and antioxidant 4010NA, at 3300 ~ 3650cm
-1having there is obvious broad peak in place, is to generate the vibration absorption peak that-OH produces in epoxy ring-opening process of grafting, meanwhile, at 908cm
-1, 844cm
-1and 815cm
-1the epoxy skeletal vibration charateristic avsorption band at place disappears substantially, and the successful generation of open loop graft reaction is described.In addition, in collection of illustrative plates, also there is the stretching vibration absorption peak (1720cm of C=O
-1) and the stretching vibration absorption peak (1638cm of C=C double bond
-1).Can find out, the present invention is successfully prepared into a kind of glycidyl methacrylate graft modification antioxidant 4010 and antioxidant 4010NA.
Embodiment
Embodiment 1:
(1) anti-aging agent dispersion liquid: 4.93g (0.01mol) N-sec.-propyl-N'-diphenyl-para-phenylene diamine (4010NA) is added in 200ml acetone, ultrasonic disperse 1h under normal temperature, obtains uniform anti-aging agent dispersion liquid;
(2) monomer-grafted reaction: the anti-aging agent dispersion liquid obtained in step (1) is transferred to and has in the there-necked flask of condensing works, and add 0.5g deionized water and 0.05g Resorcinol, continuing magnetic force is kept to stir afterwards, slow dropping 2.911g (0.0205mol) glycidyl methacrylate, in dropping process, temperature of reaction controls at 60 ~ 70 DEG C;
(3) ageing: after glycidyl methacrylate drips, reaction solution continues to stir 30min, then 80 ~ 90 DEG C are warming up to, insulation reaction 12h, naturally cool to room temperature afterwards, namely extracting, washing, oven dry obtain glycidyl methacrylate graft modification p phenylenediamine type antioxidant.
The glycidyl methacrylate graft modification p phenylenediamine type antioxidant obtained, going out percentage of grafting in conjunction with the change calculations of p phenylenediamine type antioxidant quality before and after graft modification is 22.5%.
Embodiment 2:
(1) anti-aging agent dispersion liquid: 4.93g (0.01mol) N-sec.-propyl-N'-diphenyl-para-phenylene diamine (4010NA) is added in 200ml acetone, ultrasonic disperse 1h under normal temperature, obtains uniform anti-aging agent dispersion liquid;
(2) monomer-grafted reaction: the anti-aging agent dispersion liquid obtained in step (1) is transferred to and has in the there-necked flask of condensing works, and add 0.75g deionized water and 0.15g Resorcinol, continuing magnetic force is kept to stir afterwards, slow dropping 2.982g (0.021mol) glycidyl methacrylate, in dropping process, temperature of reaction controls at 60 ~ 70 DEG C;
(3) ageing: after methacrylate-based monomer drips, continue to stir 30min, be then warming up to 80 ~ 90 DEG C, insulation reaction 12h, naturally cool to room temperature afterwards, namely extracting, washing and oven dry obtain glycidyl methacrylate graft modification p phenylenediamine type antioxidant.
The glycidyl methacrylate graft modification p phenylenediamine type antioxidant obtained, going out percentage of grafting in conjunction with the change calculations of p phenylenediamine type antioxidant quality before and after graft modification is 28.2%.
Embodiment 3:
(1) anti-aging agent dispersion liquid: 4.93g (0.01mol) N-sec.-propyl-N'-diphenyl-para-phenylene diamine (4010NA) is added in 200ml acetone, ultrasonic disperse 1h under normal temperature, obtains uniform anti-aging agent dispersion liquid;
(2) monomer-grafted reaction: the anti-aging agent dispersion liquid obtained in step (1) is transferred to and has in the there-necked flask of condensing works, and add 1.0g deionized water and 0.25g Resorcinol, continuing magnetic force is kept to stir afterwards, slow dropping 3.053g (0.0215mol) glycidyl methacrylate, in dropping process, temperature of reaction controls at 60 ~ 70 DEG C;
(3) ageing: after methacrylate-based monomer drips, continue to stir 30min, be then warming up to 80 ~ 90 DEG C, insulation reaction 12h, naturally cool to room temperature afterwards, namely extracting, washing, oven dry obtain glycidyl methacrylate graft modification p phenylenediamine type antioxidant.
The glycidyl methacrylate graft modification p phenylenediamine type antioxidant obtained, going out percentage of grafting in conjunction with the change calculations of p phenylenediamine type antioxidant quality before and after graft modification is 23.6%.
Embodiment 4:
(1) anti-aging agent dispersion liquid: 2.66g (0.01mol) N cyclohexyl N' phenyl P phenylene diamine (4010) is added in 200ml acetone, ultrasonic disperse 1h under normal temperature, obtains uniform anti-aging agent dispersion liquid;
(2) monomer-grafted reaction: the anti-aging agent dispersion liquid obtained in step (1) is transferred to and has in the there-necked flask of condensing works, and add 0.3g deionized water and 0.0266g Resorcinol, continuing magnetic force is kept to stir afterwards, slow dropping 2.911g (0.0205mol) glycidyl methacrylate, in dropping process, temperature of reaction controls at 60 ~ 70 DEG C;
(3) ageing: after methacrylate-based monomer drips, continue to stir 30min, be then warming up to 80 ~ 90 DEG C, insulation reaction 12h, naturally cool to room temperature afterwards, namely extracting, washing, oven dry obtain glycidyl methacrylate graft modification p phenylenediamine type antioxidant.
The glycidyl methacrylate graft modification p phenylenediamine type antioxidant obtained, going out percentage of grafting in conjunction with the change calculations of p phenylenediamine type antioxidant quality before and after graft modification is 29.1%.
Embodiment 5:
(1) anti-aging agent dispersion liquid: 2.66g (0.01mol) N cyclohexyl N' phenyl P phenylene diamine (4010) is added in 200ml acetone, ultrasonic disperse 1h under normal temperature, obtains uniform anti-aging agent dispersion liquid;
(2) monomer-grafted reaction: the anti-aging agent dispersion liquid obtained in step (1) is transferred to and has in the there-necked flask of condensing works, and add 0.55g deionized water and 0.015g Resorcinol, continuing magnetic force is kept to stir afterwards, slow dropping 3.053g (0.0215mol) glycidyl methacrylate, in dropping process, temperature of reaction controls at 60 ~ 70 DEG C;
(3) ageing: after methacrylate-based monomer drips, continue to stir 30min, be then warming up to 80 ~ 90 DEG C, insulation reaction 12h, naturally cool to room temperature afterwards, namely extracting, washing, oven dry obtain glycidyl methacrylate graft modification p phenylenediamine type antioxidant.
The glycidyl methacrylate graft modification p phenylenediamine type antioxidant obtained, going out percentage of grafting in conjunction with the change calculations of p phenylenediamine type antioxidant quality before and after graft modification is 26.7%.
By proportioning shown in table 1, difference manufacture native rubber composite material in conventional manner, preparation technology's flow process is: natural rubber (NR) → → zinc oxide of plasticating, stearic acid → accelerant CZ, altax → anti-aging agent → sulphur (S); Obtain aging front NR composite materials property as shown in table 2.In order to investigate ageing-resistant performance further, thermo-oxidative ageing process 72 hours under 100 ° of C in ageing oven, obtain aging after NR composite materials property as shown in table 3.
Table 1. rubber test proportioning
| Embodiment | Contrast 1 | Contrast 2 | 1 | 2 | 3 | 4 | 5 |
| NR | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Zinc oxide | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Stearic acid | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Carbon black N330 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| Accelerant CZ | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Altax | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant 4010 | 1 | --- | --- | --- | --- | --- | --- |
| Antioxidant 4010NA | --- | 1 | --- | --- | --- | --- | --- |
| Modification-antioxidant 4010 NA | --- | --- | 1 | 1 | 1 | --- | --- |
| Modification-antioxidant 4010 | --- | --- | --- | --- | --- | 1 | 1 |
| Sulphur (S) | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
Before table 2. thermo-oxidative ageing, the mechanical property of NR matrix material
| Embodiment | Blank 1 | Blank 2 | 1 | 2 | 3 | 4 | 5 | Remarks |
| Tensile strength/MPa | 27.48 | 27.92 | 29.15 | 30.35 | 30.71 | 29.90 | 31.26 | GB/T528-1998 |
| Tensile yield/% | 549.24 | 558.08 | 607.60 | 600.68 | 590.85 | 619.40 | 588.78 | GB/T528-1998 |
| 300% stress at definite elongation/MPa | 9.80 | 9.39 | 10.82 | 11.08 | 11.20 | 10.98 | 11.34 | GB/T528-1998 |
| Tear strength/KNm -1 | 45.85 | 42.46 | 49.65 | 53.68 | 56.55 | 47.85 | 52.92 | GB/T529-1999 |
| Shao A hardness | 52 | 52 | 53 | 54 | 54 | 53 | 54 | GB/T531-1999 |
After table 3. thermo-oxidative ageing, the mechanical property of NR matrix material
| Embodiment | Blank 1 | Blank 2 | 1 | 2 | 3 | 4 | 5 | Remarks |
| Tensile strength/MPa | 18.86 | 19.40 | 20.84 | 22.15 | 23.34 | 21.56 | 23.07 | GB/T528-1998 |
| Tensile yield/% | 311.42 | 320.78 | 359.70 | 366.41 | 371.05 | 372.29 | 367.40 | GB/T528-1998 |
| 300% stress at definite elongation/MPa | 6.76 | 6.52 | 7.73 | 8.09 | 8.51 | 7.92 | 8.37 | GB/T528-1998 |
| Shao A hardness | 60 | 60 | 61 | 62 | 62 | 61 | 62 | GB/T531-1999 |
Note: contrast 1 sample in table 1 and with the addition of 1 part of antioxidant 4010; Contrast 2 samples and with the addition of 1 part of antioxidant 4010NA; Embodiment 1 ~ 3 sample with the addition of the glycidyl methacrylate graft modification antioxidant 4010NA prepared by 1 part respectively; Embodiment 4 ~ 5 with the addition of the glycidyl methacrylate graft modification antioxidant 4010 prepared by 1 part respectively.
Claims (8)
1. a preparation method for rubber antioxidant, is characterized in that comprising the following steps:
(1) anti-aging agent dispersion liquid: p phenylenediamine type antioxidant is added in organic solvent, under normal temperature, ultrasonic disperse is even, obtains anti-aging agent dispersion liquid;
(2) monomer-grafted reaction: add water and stopper in the anti-aging agent dispersion liquid under agitation obtained to step (1), drip methacrylate-based monomer after stirring, temperature of reaction controls at 60 ~ 70 DEG C;
(3) ageing: after methacrylate-based monomer drips, continues to stir more than 20min, is then warming up to 80 ~ 90 DEG C, insulation reaction 11-13h, is cooled to room temperature afterwards, obtain product after extracting, washing, oven dry.
2. the preparation method of a kind of rubber antioxidant as claimed in claim 1, is characterized in that: described p phenylenediamine type antioxidant and the mol ratio of methacrylate-based monomer are 1:2.05 ~ 2.15.
3. the preparation method of a kind of Novel rubber antioxidant as claimed in claim 1 or 2, it is characterized in that: described p phenylenediamine type antioxidant is N-sec.-propyl-N'-diphenyl-para-phenylene diamine, N-cyclohexyl-N'-phenyl-1,4-Ursol D, N, N'-bis--iso-octyl Ursol D, N, N'-bis-(2-naphthyl) Ursol D, N, the one of N'-di tolyl p phenylenediamine or N-(1,3-dimethylbutyl)-N'-diphenyl-para-phenylene diamine.
4. the preparation method of a kind of Novel rubber antioxidant as claimed in claim 1 or 2, is characterized in that: described methacrylate-based monomer is glycidyl methacrylate.
5. the preparation method of a kind of Novel rubber antioxidant as claimed in claim 1, is characterized in that: the consumption of described stopper is 1% ~ 5% of p phenylenediamine type antioxidant quality, and the consumption of water is 10% ~ 20% of p phenylenediamine type antioxidant quality.
6. the preparation method of a kind of rubber antioxidant as described in claim 1 or 5, is characterized in that: described stopper is the one of Resorcinol, Resorcinol monobutyl ether, the tertiary butyl neck dihydroxy-benzene, 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone.
7. the preparation method of a kind of Novel rubber antioxidant as described in claim 1 or 5, is characterized in that: described water is deionized water.
8. the preparation method of a kind of rubber antioxidant as claimed in claim 1, is characterized in that: described organic solvent is one or more of acetone, toluene, vinyl acetic monomer, methylene dichloride, methyl alcohol, ethanol, acetonitrile or tetrahydrofuran (THF).
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