CN101333304A - Rubber antiager and method for preparing same - Google Patents
Rubber antiager and method for preparing same Download PDFInfo
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- CN101333304A CN101333304A CNA200810023039XA CN200810023039A CN101333304A CN 101333304 A CN101333304 A CN 101333304A CN A200810023039X A CNA200810023039X A CN A200810023039XA CN 200810023039 A CN200810023039 A CN 200810023039A CN 101333304 A CN101333304 A CN 101333304A
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Abstract
The invention discloses a rubber antioxidant and a preparation method thereof. The rubber antioxidant is prepared through the complex reaction of para-phenylene diamine antioxidant and autunite-zinc polymethyl terephthalate; wherein the weight ratio of para-phenylene diamine antioxidant to autunite-zinc polymethyl terephthalate is 2:1-3:1. The preparation method includes the following steps: 1)dissolving para-phenylene diamine antioxidant in acetone solution based on weight ratio of 1:1-1.5:1, producing a mixture solution; 2)adding autunite-zinc polymethyl terephthalate aqueous solution and hyamine catalyzer at the same time into a reactor and blending the two; 3)introducing high temperature steam to the jacket of the reactor and when the temperature reaches 110-120 DEG C, adding the mixture ssolution prepared in step 1); 4) conducting complex reaction for 1.5-3h when the material is at infinite reflux state and finally distilling and recovering the acetone. The rubber antioxidant is of excellent ageing resistance and is free from problems of serious color deterioration, fusion and agglomeration.
Description
Technical field
The present invention relates to a kind of rubber antioxidant and preparation method thereof, particularly a kind of Ursol D class rubber antioxidant and preparation method thereof.
Background technology
As everyone knows, N-sec.-propyl-N '-diphenyl-para-phenylene diamine (rubber antioxidant 4010NA) and N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (rubber antioxidant 4020) is two kinds of best p phenylenediamine type antioxidants of present over-all properties.Performances such as they have good thermo oxidative aging, anti-ozone ageing, anti-flex crack is aging and anti-harmful metal ion wears out.But also there is following shortcoming in these two kinds of anti-aging agent.
N-sec.-propyl-N '-diphenyl-para-phenylene diamine is extracted out loss (can reach 50%) by water or solvent easily, influences long-acting performance.And variable color migration easily, thereby goods are formed pollution.Stimulate toxicity in addition, cause allergic easily.
For N-sec.-propyl-N '-diphenyl-para-phenylene diamine, (1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine runs off in water-fast extraction N-, anti-solvent extract out to run off and toxicity aspect slightly better, but still have the serious problem of variable color.And melt easily, lump, thereby be unfavorable for transportation, process and store, particularly when summer temperature is higher or in the freight container accumulation transportation, very easily melt or the self-adhesion caking.
Summary of the invention
The objective of the invention is to overcome the problems referred to above, a kind of good anti ageing property that both had is provided, can not produce variable color rubber antioxidant serious, easily problem such as fusing caking and preparation method thereof again.
Realization the present invention wherein a kind of technical scheme of purpose is: a kind of rubber antioxidant, by p phenylenediamine type antioxidant and poly-methyl terephthalic acid calcium zinc salt is that raw material carries out complex reaction and obtains, and wherein the weight ratio of p phenylenediamine type antioxidant and poly-methyl terephthalic acid calcium zinc salt is 2: 1～3: 1.
Described p phenylenediamine type antioxidant is N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine or N-sec.-propyl-N '-diphenyl-para-phenylene diamine.
The technical scheme that realizes the another kind of purpose of the present invention is: a kind of preparation method of rubber antioxidant has following steps:
1. p phenylenediamine type antioxidant is dissolved in the acetone soln, obtains behind the mixing solutions stand-byly, wherein the weight ratio of p phenylenediamine type antioxidant and acetone soln is 1: 1～1.5: 1; 2. the aqueous solution and the quaternary ammonium salt catalyst that add poly-methyl terephthalic acid calcium zinc salt in reactor simultaneously stir with the rotating speed of 400r/min～600r/min; Described reactor has cooling and reflux device; 3. feed high-temperature steam in the chuck of reactor, when temperature of charge reaches 110 ℃～120 ℃, add the mixing solutions of step in 1., wherein the weight ratio of p phenylenediamine type antioxidant and poly-methyl terephthalic acid calcium zinc salt is 2: 1～3: 1; 4. make material carry out complex reaction 1.5h～3h under the state of total reflux, distillation is at last reclaimed acetone and is promptly got rubber antioxidant.
The concentration of the aqueous solution of the poly-methyl terephthalic acid calcium zinc salt of above-mentioned steps described in 2. is 50wt%～70wt%.
The quaternary ammonium salt catalyst of above-mentioned steps described in 2. is TBAC tetrabutylammonium chloride, and the weight ratio of p phenylenediamine type antioxidant and quaternary ammonium salt catalyst is 500: 1～600: 1.
The above-mentioned steps 3. adding speed of middle mixing solutions is 8kg/min～12kg/min.
The p phenylenediamine type antioxidant of above-mentioned steps described in 1. is N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine or N-sec.-propyl-N '-diphenyl-para-phenylene diamine.
The present invention has positive effect: (1) rubber antioxidant of the present invention is a kind of rubber antioxidant of solvay-type.By the complexing modification; the excellent anti ageing property that has not only kept original anti-aging agent; but also because the complexing of original anti-aging agent institute be a kind of organic salt; make that under both synergies solvent-proof stability greatly improves: promptly effectively improved water-fast extraction or anti-solvent extraction performance; extract content has reduced 80%～90%, thereby has improved the long-effective protection performance to goods.(2) under the influence of above-mentioned complexing modification, obviously improved the variable color migration performance of anti-aging agent, make the product appearance quality that obvious lifting arranged; Also effectively reduce toxicity to human body.(3) by the complexing modification, when being original rubber antioxidant, its highest consumption still the bloom phenomenon can not take place 5-6 times the time, illustrate that its solubleness in rubber greatly increases.
(4), solved the high temperature time and stacked the fusing agglomeration problems of transporting in the storage process by the complexing modification; Improved dispersed homogeneous degree to a certain extent.
Embodiment
(embodiment 1)
The rubber antioxidant of present embodiment is an optimization type rubber antioxidant, is that raw material carries out complex reaction and obtains by N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine and poly-methyl terephthalic acid calcium zinc salt, and both weight ratios are 2.5: 1.
Wherein the structural formula of poly-methyl terephthalic acid calcium zinc salt is:
The preparation method of this optimization type rubber antioxidant comprises:
1. N-(1, the 3-dimethylbutyl)-the N '-diphenyl-para-phenylene diamine with 250kg is dissolved in the acetone soln of 250kg, obtain mixing solutions after, add in the scale tank stand-by.
2. in the enamel reaction still of the band cooling and reflux device of 1000L, add 166kg concentration simultaneously and be the aqueous solution of poly-methyl terephthalic acid calcium zinc salt of 60wt% and the TBAC tetrabutylammonium chloride of 0.5kg, and stir with the rotating speed of 500r/min.
3. in the chuck of the enamel reaction still of step in 2., feed high-temperature steam, make the material in the reactor be warming up to 115 ℃, at this moment the speed with 10kg/min adds the 500kg mixing solutions that is 1. obtained by step in the scale tank in the enamel reaction still, and make the weight ratio of N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine and poly-methyl terephthalic acid calcium zinc salt is 2.5: 1;
4. continue in the chuck of enamel reaction still, to feed high-temperature steam, and make the material in the reactor that has cooling and reflux device under the state of total reflux, carry out complex reaction 2h, the resultant of reaction is N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine and poly-methyl terephthalic acid calcium zinc salt complex compound.Its molecular structural formula is:
N 〉=3 wherein.M is poly-methyl terephthalic acid calcium zinc salt.
Then temperature of charge is reduced to about 80 ℃, reclaim acetone by the distillatory method again.
Acetone reclaims the back and opens drain hole material is injected wash trough, and to neutral, the material after will washing then is centrifugal, oven dry, crushing screening, promptly get optimization type rubber antioxidant finished product with the deionized water wash material.The transformation efficiency of present embodiment reaches 99.5%.Finished product can dispatch from the factory after check, metering and packing.
The physical index of gained finished product sees Table 1.
Table 1
| Index | Numerical value |
| Outward appearance | The Zijin look is to the atropurpureus powder |
| The dry product ctystallizing point | ≥44.0℃ |
| Weight loss on heating (35 ℃ * 2h) | ≤0.5％ |
| Calcination rear oxidation thing content | ≤16.8％ |
On the finished product visual appearance, the optimization type rubber antioxidant of present embodiment can reduce outward appearance because of the variable color that bloom causes, has improved the visual appearance of tire finished product.
(application examples 1)
1# tread glue formula: 13.5 parts of 70 parts of NR, 30 parts of BR, 4 parts of zinc oxide, 3 parts of stearic acid, 1.5 parts of protection waxes, 1.5 parts of RD, 1 part of common N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine rubber antioxidant, 50 parts of carbon blacks, 2.0 parts of sulphur promotor, other Synergist S-421 95s.
2# tread glue formula: 13.5 parts of the optimization type rubber antioxidant of 70 parts of NR, 30 parts of BR, 4 parts of zinc oxide, 3 parts of stearic acid, 1.5 parts of protection waxes, 1.5 parts of RD, 1 part of embodiment 1,50 parts of carbon blacks, 2.0 parts of sulphur promotor, other Synergist S-421 95s.
1# sidewall rubber prescription: 22.5 parts of 60 parts of NR, 15 parts of BR, 25 parts of SBR, 5 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of protection waxes, 1.5 parts of RD, 1.5 parts of common N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine rubber antioxidant, 60 parts of carbon blacks, 2.35 parts of sulphur promotor, other Synergist S-421 95s.
2# sidewall rubber prescription: 22.5 parts of the optimization type rubber antioxidant of 60 parts of NR, 15 parts of BR, 25 parts of SBR, 5 parts of zinc oxide, 2 parts of stearic acid, 1.5 parts of protection waxes, 1.5 parts of RD, 1.5 parts of embodiment 1,60 parts of carbon blacks, 2.35 parts of sulphur promotor, other Synergist S-421 95s.
Water-fast extraction performance sees Table 2.
Table 2
| Prescription | The soak solution color |
| The 1# tread rubber | Shallow dark brown |
| The 2# tread rubber | Very shallow dark brown |
| The 1# sidewall rubber | Shallow dark brown |
| The 2# sidewall rubber | Very shallow dark brown |
As can be seen from Table 2, the water-fast extraction performance of the optimization type rubber antioxidant of embodiment 1 is better than common N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine rubber antioxidant.
(embodiment 2)
The rubber antioxidant of present embodiment is an optimization type rubber antioxidant, is that raw material carries out complex reaction and obtains by N-sec.-propyl-N '-diphenyl-para-phenylene diamine and poly-methyl terephthalic acid calcium zinc salt, and both weight ratios are 3: 1.
The preparation method of this optimization type rubber antioxidant comprises:
1. N-sec.-propyl-N '-diphenyl-para-phenylene diamine with 300kg is dissolved in the acetone soln of 200kg, obtain mixing solutions after, add in the scale tank stand-by.
2. in the enamel reaction still of the band cooling and reflux device of 1000L, add 160kg concentration simultaneously and be the aqueous solution of poly-methyl terephthalic acid calcium zinc salt of 66wt% and the TBAC tetrabutylammonium chloride of 0.5kg, and stir with the rotating speed of 550r/min.
3. in the chuck of the enamel reaction still of step in 2., feed high-temperature steam, make the material in the reactor be warming up to 120 ℃, at this moment the 500kg mixing solutions that by step 1. obtained of speed from scale tank with 12kg/min adds enamel reaction still, is 3: 1 and make the weight ratio of N-sec.-propyl-N '-diphenyl-para-phenylene diamine and poly-methyl terephthalic acid calcium zinc salt;
4. continue in the chuck of enamel reaction still, to feed high-temperature steam, and making the material in the reactor that has cooling and reflux device under the state of total reflux, carry out complex reaction 1.8h, the resultant of reaction is N-sec.-propyl-N '-diphenyl-para-phenylene diamine and poly-methyl terephthalic acid calcium zinc salt complex compound.Its molecular structural formula is:
N 〉=3 wherein.M is poly-methyl terephthalic acid calcium zinc salt.
Then temperature of charge is reduced to about 80 ℃, reclaim acetone by the distillatory method again.
Acetone reclaims the back and opens drain hole material is injected wash trough, and to neutral, the material after will washing then is centrifugal, oven dry, crushing screening, promptly get optimization type rubber antioxidant finished product with the deionized water wash material.The transformation efficiency of present embodiment reaches 99.3%.Finished product can dispatch from the factory after check, metering and packing.
The physical index of gained finished product sees Table 3.
Table 3
| Index | Numerical value |
| Outward appearance | Pale red to the red-purple powder |
| Dry product is fusing point just | ≥70℃ |
| Weight loss on heating (50 ℃ * 2h) | ≤0.5％ |
| Calcination rear oxidation thing content | ≤16.8％ |
(application examples 2)
1# prescription: 100 parts of SCR-5 natural rubbers, 5 parts of zinc oxide, 0.5 part of stearic acid, 0.7 part of captax, 3 parts of sulphur, 2 parts of common N-sec.-propyl-N '-diphenyl-para-phenylene diamine rubber antioxidants.
2# prescription: the optimization type rubber antioxidant of 100 parts of SCR-5 natural rubbers, 5 parts of zinc oxide, 0.5 part of stearic acid, 0.7 part of captax, 3 parts of sulphur, 2 parts of embodiment 2.
Water-fast extraction performance sees Table 4.
Table 4
As can be seen from Table 4, the water-fast extraction performance of the optimization type rubber antioxidant of embodiment 2 is better than common N-sec.-propyl-N '-diphenyl-para-phenylene diamine anti-aging agent, is more suitable for using under the environment of humidity.This mainly is because poly-methyl terephthalic acid calcium zinc salt has the effect of surface modification, thereby has improved the consistency of anti-aging agent and SCR-5 natural rubber, has reduced its solubleness in water, thereby has improved its water-fast extraction performance.
Claims (7)
1, a kind of rubber antioxidant, it is characterized in that: by p phenylenediamine type antioxidant and poly-methyl terephthalic acid calcium zinc salt is that raw material carries out complex reaction and obtains, and wherein the weight ratio of p phenylenediamine type antioxidant and poly-methyl terephthalic acid calcium zinc salt is 2: 1～3: 1.
2, rubber antioxidant according to claim 1 is characterized in that: described p phenylenediamine type antioxidant is N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine or N-sec.-propyl-N '-diphenyl-para-phenylene diamine.
3, the preparation method of the described rubber antioxidant of a kind of claim 1 is characterized in that having following steps:
1. p phenylenediamine type antioxidant is dissolved in the acetone soln, obtains behind the mixing solutions stand-byly, wherein the weight ratio of p phenylenediamine type antioxidant and acetone soln is 1: 1～1.5: 1;
2. the aqueous solution and the quaternary ammonium salt catalyst that add poly-methyl terephthalic acid calcium zinc salt in reactor simultaneously stir with the rotating speed of 400r/min～600r/min; Described reactor has cooling and reflux device;
3. feed high-temperature steam in the chuck of reactor, when temperature of charge reaches 110 ℃～120 ℃, add the mixing solutions of step in 1., wherein the weight ratio of p phenylenediamine type antioxidant and poly-methyl terephthalic acid calcium zinc salt is 2: 1～3: 1;
4. make material carry out complex reaction 1.5h～3h under the state of total reflux, distillation is at last reclaimed acetone and is promptly got rubber antioxidant.
4, the preparation method of rubber antioxidant according to claim 3 is characterized in that: the concentration of the aqueous solution of the poly-methyl terephthalic acid calcium zinc salt of step described in 2. is 50wt%～70wt%.
5, the preparation method of rubber antioxidant according to claim 3 is characterized in that: the quaternary ammonium salt catalyst of step described in 2. is TBAC tetrabutylammonium chloride, and the weight ratio of p phenylenediamine type antioxidant and quaternary ammonium salt catalyst is 500: 1～600: 1.
6, the preparation method of rubber antioxidant according to claim 3 is characterized in that: the step 3. adding speed of middle mixing solutions is 8kg/min～12kg/min.
7, according to the preparation method of the described rubber antioxidant of one of claim 3 to 6, it is characterized in that: the p phenylenediamine type antioxidant of step described in 1. is N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine or N-sec.-propyl-N '-diphenyl-para-phenylene diamine.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102061023A (en) * | 2010-12-07 | 2011-05-18 | 江苏爱特恩高分子材料有限公司 | Novel rubber antioxidant and preparation method thereof |
| CN104072823A (en) * | 2014-07-09 | 2014-10-01 | 常州市五洲化工有限公司 | Rubber antiager |
| CN107312250A (en) * | 2017-07-04 | 2017-11-03 | 合肥择浚电气设备有限公司 | A kind of excavator mechanical rubber crawler belt and preparation method thereof |
| CN110156919A (en) * | 2018-02-10 | 2019-08-23 | 北京化工大学 | A kind of rubber antioxidant and preparation method thereof |
| CN110922586A (en) * | 2019-12-23 | 2020-03-27 | 黑龙江大学 | Polyamide containing triarylamine with isopropyl directly bonded with nitrogen atom, and preparation method and application thereof |
| CN110922638A (en) * | 2019-12-23 | 2020-03-27 | 常州市五洲环保科技有限公司 | Method for preparing protective material for rubber by recycling textile white mud |
| CN111393665A (en) * | 2020-05-04 | 2020-07-10 | 常州市五好新材料科技有限公司 | Preparation method and application of calcium metal organic framework material |
| CN112521609A (en) * | 2020-12-31 | 2021-03-19 | 常州市五洲化工有限公司 | Preparation method of oil-resistant sealing modified anti-aging agent |
| CN113603930A (en) * | 2021-08-27 | 2021-11-05 | 江苏麒祥高新材料有限公司 | Modified anti-aging agent and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB751630A (en) * | 1953-02-19 | 1956-07-04 | Monsanto Chemicals | Production of vulcanized rubber of improved resistance to cracking and compounds for use therein |
| JP2001172238A (en) * | 1999-12-17 | 2001-06-26 | Toyobo Co Ltd | Aromatic diamine/aromatic dicarboxylic acid salt and method for producing the same |
| CN1686871A (en) * | 2005-04-23 | 2005-10-26 | 陈一鸣 | Method for preparing antiager from wastewater of alkali weight reduction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061023A (en) * | 2010-12-07 | 2011-05-18 | 江苏爱特恩高分子材料有限公司 | Novel rubber antioxidant and preparation method thereof |
| CN104072823A (en) * | 2014-07-09 | 2014-10-01 | 常州市五洲化工有限公司 | Rubber antiager |
| CN104072823B (en) * | 2014-07-09 | 2016-03-23 | 常州市五洲化工有限公司 | A kind of rubber antioxidant |
| CN107312250A (en) * | 2017-07-04 | 2017-11-03 | 合肥择浚电气设备有限公司 | A kind of excavator mechanical rubber crawler belt and preparation method thereof |
| CN110156919A (en) * | 2018-02-10 | 2019-08-23 | 北京化工大学 | A kind of rubber antioxidant and preparation method thereof |
| CN110156919B (en) * | 2018-02-10 | 2020-07-28 | 北京化工大学 | Rubber antioxidant and preparation method thereof |
| CN110922586A (en) * | 2019-12-23 | 2020-03-27 | 黑龙江大学 | Polyamide containing triarylamine with isopropyl directly bonded with nitrogen atom, and preparation method and application thereof |
| CN110922638A (en) * | 2019-12-23 | 2020-03-27 | 常州市五洲环保科技有限公司 | Method for preparing protective material for rubber by recycling textile white mud |
| CN110922586B (en) * | 2019-12-23 | 2022-02-15 | 黑龙江大学 | Polyamide containing triarylamine with isopropyl directly bonded with nitrogen atom, and preparation method and application thereof |
| CN111393665A (en) * | 2020-05-04 | 2020-07-10 | 常州市五好新材料科技有限公司 | Preparation method and application of calcium metal organic framework material |
| CN112521609A (en) * | 2020-12-31 | 2021-03-19 | 常州市五洲化工有限公司 | Preparation method of oil-resistant sealing modified anti-aging agent |
| CN113603930A (en) * | 2021-08-27 | 2021-11-05 | 江苏麒祥高新材料有限公司 | Modified anti-aging agent and preparation method and application thereof |
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