CN101225062A - Nonyl phenol sulfide oligomer and method for preparing same - Google Patents
Nonyl phenol sulfide oligomer and method for preparing same Download PDFInfo
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- CN101225062A CN101225062A CNA2008100260304A CN200810026030A CN101225062A CN 101225062 A CN101225062 A CN 101225062A CN A2008100260304 A CNA2008100260304 A CN A2008100260304A CN 200810026030 A CN200810026030 A CN 200810026030A CN 101225062 A CN101225062 A CN 101225062A
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- nonyl phenol
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- sulfur monochloride
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Abstract
The invention relates to a nonyl sulfide oligomer used as hypochromic antioxidant and a preparation method, in particular to a nonyl sulfide oligomer used as hypochromic antioxidant for the rosin and the deeply processed products and a preparation method; wherein, the structural formula of the nonyl sulfide oligomer is shown in the above formula, where x being 0 to 2, y1 being 0 to 3 and y2 being 0 to 3. The preparation method for nonyl sulfide oligomer used as hypochromic antioxidant has the advantages that the rosin and the deeply processed products are enabled to effectively resist oxidation and reduce color so as to meet the requirements of different industrial fields; and application range is wider.
Description
[technical field]
The present invention relates to a kind of as the antioxygen nonyl phenol sulfide oligomer of agent and preparation method thereof of losing lustre, especially as the antioxygen of rosin and deep processed product thereof the nonyl phenol sulfide oligomer of agent and preparation method thereof of losing lustre.
[background technology]
The rosin industry is China's new industry, and gross industrial output value is above 1,500,000,000 yuan/year.Rosin and deep processed product thereof are widely used in papermaking, printing ink, tackiness agent, coating, industrial circles such as electronics and rubber.Along with scientific-technical progress and development and national economy, be that the world or domestic market all propose requirements at the higher level to rosin and Gum Rosin quality, as thermostability, color and luster and package stability etc.But defectives such as at present all there are easy oxidation in rosin and deep processed product thereof, and color is dark, thereby limited the application of rosin product.For improving the quality of rosin and deep processed product thereof, the rosin special assistant plays more and more important effect.Yet up to now, do not see to have heat-resisting oxidation on the market, the special assistant of the double effects of losing lustre.
[summary of the invention]
The present invention aims to provide a kind of antioxygen that is used for rosin and deep processed product thereof nonyl phenol sulfide oligomer of agent and preparation method thereof of losing lustre.
Nonyl phenol sulfide oligomer of the present invention, its structural formula is:
Wherein, x=0-2, y
1=0-3, y
2=0-3.
Its every physicals such as table 1.
Table 1: the physicals of nonyl phenol sulfide oligomer
| Project | Value |
| Outward appearance | The yellowish brown thick liquid |
| Total sulfur content, % | 9.4～10.6 |
| Free sulphur content, % | ＜0.1 |
| Chloride content, % | ＜0.1 |
| Viscosity, PaS, 25 ℃ | 55～70 |
The preparation method of nonyl phenol sulfide oligomer of the present invention, operation steps is:
1) sulfur monochloride is synthetic and refining
In SULPHUR POWDER, feed excessive chlorine, obtain thick sulfur dichloride, in thick sulfur dichloride, add massfraction and be 33% SULPHUR POWDER and massfraction and be 1% gac and distill pure system, collect 135 ℃ cut, promptly obtain the purified sulfur monochloride;
2) thio reaction
Dissolve nonyl phenol and above-mentioned purified sulfur monochloride respectively with solvent oil, drip sulfur monochloride solution then in being cooled to 10 ℃ nonyl phenol solution, the molar ratio of nonyl phenol and sulfur monochloride is 1, and does not stop stirring when dripping; After dropwising, leave standstill half an hour; In solution, add 5% sodium sulfite aqueous solution then, continue to stir, and solution temperature is increased to 50 ℃; Leave standstill to layering the aqueous solution of lower floor is discharged; And reuse 5% sodium sulfite aqueous solution washed twice.Wash with pure water again; Solvent oil is removed in last underpressure distillation, gets final product.
Preferred No. 6 solvent oils of wherein said solvent oil.
The control solution temperature remains on 10 ℃ in the dropping process.
Absorb the hydrogen chloride gas that generates with sodium hydroxide solution when dripping sulfur monochloride solution.
Drip preferred 3 hours of the time of sulfur monochloride solution.
Nonyl phenol sulfide oligomer of the present invention can make rosin and deep processed product thereof effectively resist oxidation, reduces color and luster, enables to satisfy the requirement of different industrial circles, and the scope of application is more extensive.In addition, preparation method of the present invention is simple, the productive rate height.
[embodiment]
Embodiment one:
1) sulfur monochloride is synthetic and refining
In SULPHUR POWDER, feed excessive chlorine, obtain thick sulfur dichloride, in thick sulfur dichloride, add massfraction and be 33% SULPHUR POWDER and massfraction and be 1% gac and distill pure system, collect 135 ℃ cut, promptly obtain the purified sulfur monochloride.
2) thio reaction
With 3 liters of No. 6 solvent oils dissolvings, 234 gram nonyl phenols, 4 liters of No. 6 solvent oils dissolvings 135 restrain sulfur monochlorides respectively; Nonyl phenol solution is cooled to 10 ℃ then, drips sulfur monochloride solution in nonyl phenol solution, and the dropping time is 3 hours, does not stop in the time of dropping to stir, and makes solution temperature remain on 10 ℃, absorbs the hydrogen chloride gas that generates with sodium hydroxide solution; After dropwising, leave standstill half an hour.Add 10 liter of 5% sodium sulfite aqueous solution then, continue to stir, and solution temperature is increased to 50 ℃.Leave standstill to layering the aqueous solution of lower floor is discharged.And reuse 5% sodium sulfite aqueous solution washed twice.Add 10 liters of pure water washings again.Solvent oil is removed in last underpressure distillation, can obtain 366 gram products.
Embodiment two:
By the product of liquid chromatography map analysis embodiment one gained, wherein contain nonyl phenol 1.83%, sulfur monochloride 0.56%, nonyl phenol sulfide oligomer 97.61%, promptly productive rate is 96.8%.
The molecular structure that records nonyl phenol sulfide oligomer with nucleus magnetic resonance is as follows:
Wherein, x=0-2, y
1=0-3, y
2=0-3.
In addition, record its every physicals such as table 2.
Table 2: the physicals of nonyl phenol sulfide oligomer
| Project | Value |
| Outward appearance | The yellowish brown thick liquid |
| Total sulfur content, % | 9.50 |
| Free sulphur content, % | 0.06 |
| Chloride content, % | 0.03 |
| Viscosity, PaS, 25 ℃ | 60 |
Embodiment three:
The additive that in four-hole bottle, adds a certain amount of rosin and quality 0.15% thereof, deaeration in condenser, nitrogen protection heating down; after the rosin fusion, stir and be warming up to 270 ℃, be incubated cooling discharge after 4 hours; detect the every quality index of rosiny that different additive makes respectively, result such as table 3.
Table 3: the rosiny physicals that different additive makes
| Additive | Color (iron cobalt method) | Acid value, mgg -1 | Softening temperature, ℃ | Abietic acid, % | The dehydrogenation abietic acid, % |
| Blank | 6 + | 168 | 75.2 | 33.1 | 16.6 |
| The present invention | 2 + | 167.2 | 75.6 | 19.3 | 30.5 |
| Antioxidant 1010 | 6 | 167.0 | 75.4 | 33.3 | 16.1 |
| Antioxidant 1076 | 6 + | 163.4 | 76.3 | 37.1 | 12.6 |
| Oxidation inhibitor 1425 | 6 + | 163.6 | 76.5 | 36.4 | 11.7 |
Annotate: rosiny acid value, softening temperature are stipulated test according to standard GB/T8146-2003.
By table 3 as seen, nonyl phenol sulfide oligomer of the present invention is best to the rosiny antioxygen and the effect of discoloring.
Embodiment four:
In four-hole bottle, add a certain amount of rosin and the additive of quality 0.3% thereof, 0.1% inferior sodium phosphate, 0.05% zinc oxide; deaeration in condenser; nitrogen protection is heating down, wait the rosin fusion after, stir and be warming up to 200 ℃; drip the glycerine of rosin quality 12%; continue to be warming up to 270 ℃, be incubated 4 hours, vacuumize cooling discharge after 1 hour; detect the every quality index of rosiny that different additive makes respectively, result such as table 4.
Table 4: the rosiny physicals that different additive makes
| Additive | Color (iron cobalt method) | Acid number, KOH mgg -1 | Softening temperature, ℃ (ring and ball method) | Solubleness (with benzene 1: 1) |
| GY-323 | 2 + | 9.8 | 89 | Clearly |
| Antioxidant 1010 | 6 | 12.1 | 88 | Clearly |
| Antioxidant 1076 | 6 | 11.8 | 87.5 | Clearly |
| Oxidation inhibitor 1425 | 5 + | 14.5 | 87 | Not really clear |
By table 4 as seen, nonyl phenol sulfide oligomer of the present invention is best to the rosiny effect of discoloring.
Embodiment 5:
The nonyl phenol sulfide oligomer of the present invention that in four-hole bottle, adds a certain amount of rosin and quality 0.15% thereof; deaeration in condenser; nitrogen protection is heating down; after the rosin fusion; stirring also is warming up to 270 ℃; be incubated cooling discharge after 10 hours, detect the every quality index of rosiny, result such as table 5.
Table 5: rosiny physicals
| Color (iron cobalt method) | Acid value, mgg -1 | Softening temperature, ℃ | Abietic acid, % | The dehydrogenation abietic acid, % |
| 2 + | 167.2 | 75.6 | 3.7 | 30.5 |
Claims (9)
1. nonyl phenol sulfide oligomer is characterized in that structural formula is
Wherein, x=0-2, y
1=0-3, y
2=0-3.
2. nonyl phenol sulfide oligomer as claimed in claim 1 is characterized in that being the yellowish brown thick liquid, and total sulfur content is 9.4～10.6%, and free sulphur content is＜0.1%, and chloride content is＜0.1%, and viscosity is 55～70PaS under 25 ℃.
3. method for preparing nonyl phenol sulfide oligomer as claimed in claim 1 is characterized in that operation steps is:
1) sulfur monochloride is synthetic and refining
In SULPHUR POWDER, feed excessive chlorine, obtain thick sulfur dichloride, in thick sulfur dichloride, add massfraction and be 33% SULPHUR POWDER and massfraction and be 1% gac and distill pure system, collect 135 ℃ cut, promptly obtain the purified sulfur monochloride;
2) thio reaction
Dissolve nonyl phenol and above-mentioned purified sulfur monochloride respectively with solvent oil, drip sulfur monochloride solution then in being cooled to 10 ℃ nonyl phenol solution, the molar ratio of nonyl phenol and sulfur monochloride is 1, and does not stop stirring when dripping; After dropwising, leave standstill half an hour; In solution, add 5% sodium sulfite aqueous solution then, continue to stir, and solution temperature is increased to 50 ℃; Leave standstill to layering the aqueous solution of lower floor is discharged; And reuse 5% sodium sulfite aqueous solution washed twice; Wash with pure water again; Solvent oil is removed in last underpressure distillation, gets final product.
4. method as claimed in claim 3 is characterized in that described solvent is No. 6 solvent oils.
5. method as claimed in claim 3 is characterized in that in the dropping process solution temperature being remained on 10 ℃.
6. method as claimed in claim 3 absorbs the hydrogen chloride gas that generates with sodium hydroxide solution when it is characterized in that dripping sulfur monochloride solution.
7. method as claimed in claim 3, the time that it is characterized in that dripping sulfur monochloride solution is 3 hours.
8. as claim 4 or 5 or 6 or 7 described methods, it is characterized in that operation steps is:
1) sulfur monochloride is synthetic and refining
In SULPHUR POWDER, feed excessive chlorine, obtain thick sulfur dichloride, in thick sulfur dichloride, add massfraction and be 33% SULPHUR POWDER and massfraction and be 1% gac and distill pure system, collect 135 ℃ cut, promptly obtain the purified sulfur monochloride;
2) thio reaction
With 3 liters of No. 6 solvent oils dissolvings, 234 gram nonyl phenols, 4 liters of No. 6 solvent oils dissolvings 135 restrain sulfur monochlorides respectively; Nonyl phenol solution is cooled to 10 ℃ then, drips sulfur monochloride solution in nonyl phenol solution, and the dropping time is 3 hours, does not stop in the time of dropping to stir, and makes solution temperature remain on 10 ℃, absorbs the hydrogen chloride gas that generates with sodium hydroxide solution; After dropwising, leave standstill half an hour; Add 10 liter of 5% sodium sulfite aqueous solution then, continue to stir, and solution temperature is increased to 50 ℃; Leave standstill to layering the aqueous solution of lower floor is discharged; And reuse 5% sodium sulfite aqueous solution washed twice; Add 10 liters of pure water washings again; Solvent oil is removed in last underpressure distillation, can obtain 366 gram products.
9. method as claimed in claim 8 is characterized in that the product that makes is the yellowish brown thick liquid, and total sulfur content is 9.50%, and free sulphur content is 0.06%, and chloride content is 0.03%, and viscosity is 60PaS down at 25 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293252A (en) * | 2014-09-02 | 2015-01-21 | 叶旗 | Petroleum resin modified rosin resin dispersion |
| CN107619642A (en) * | 2017-09-25 | 2018-01-23 | 广西众昌树脂有限公司 | The preparation method of liquid rosin resin |
| CN114989051A (en) * | 2022-08-03 | 2022-09-02 | 淄博万科化工有限公司 | Production method of low-chlorine-content antioxidant 323 |
| CN117534599A (en) * | 2024-01-10 | 2024-02-09 | 淄博万科化工有限公司 | Solvent-free production method of antioxidant 323 with low chlorine content |
-
2008
- 2008-01-25 CN CNA2008100260304A patent/CN101225062A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293252A (en) * | 2014-09-02 | 2015-01-21 | 叶旗 | Petroleum resin modified rosin resin dispersion |
| CN107619642A (en) * | 2017-09-25 | 2018-01-23 | 广西众昌树脂有限公司 | The preparation method of liquid rosin resin |
| CN114989051A (en) * | 2022-08-03 | 2022-09-02 | 淄博万科化工有限公司 | Production method of low-chlorine-content antioxidant 323 |
| CN114989051B (en) * | 2022-08-03 | 2022-10-21 | 淄博万科化工有限公司 | Production method of low-chlorine-content antioxidant 323 |
| CN117534599A (en) * | 2024-01-10 | 2024-02-09 | 淄博万科化工有限公司 | Solvent-free production method of antioxidant 323 with low chlorine content |
| CN117534599B (en) * | 2024-01-10 | 2024-03-19 | 淄博万科化工有限公司 | Solvent-free production method of antioxidant 323 with low chlorine content |
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Open date: 20080723 |