CN103396530B - Synthesizing method of p-cresol-dicyclopentadiene isobutyl resin antioxidant - Google Patents
Synthesizing method of p-cresol-dicyclopentadiene isobutyl resin antioxidant Download PDFInfo
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- CN103396530B CN103396530B CN201310324217.3A CN201310324217A CN103396530B CN 103396530 B CN103396530 B CN 103396530B CN 201310324217 A CN201310324217 A CN 201310324217A CN 103396530 B CN103396530 B CN 103396530B
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- dicyclopentadiene
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- cresol
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Abstract
The invention relates to a synthesizing method of a p-cresol-dicyclopentadiene isobutyl resin antioxidant. The method comprises the following steps of: dissolving p-cresol with dimethylformamide; dropwise adding dicyclopentadiene; performing a reflux reaction for 1 hour; after a condensation reaction, cooling and keeping the temperature at 80 DEG C; adding isobutene; stopping the adding of the isobutene when the isobutene is no longer adsorbed; continuously stirring for 2 hours; after an alkylation reaction, adding sodium hydroxide into a reaction system; evenly mixing; cooling; filtering a solvent from the mixture, thereby obtaining the p-cresol-dicyclopentadiene isobutyl resin antioxidant.
Description
Technical field
The present invention relates to a kind of preparation method of oxidation inhibitor, particularly the preparation method of a kind of hindered phenol antioxygen methylphenol-dicyclopentadiene isobutyl resin antioxidant.
Background technology
The preparation method of methylphenol-dicyclopentadiene isobutyl resin antioxidant is a lot, main method comprises: take p-methyl phenol as main raw material, carry out condensation reaction with dicyclopentadiene and generate phenolic petroleum resin, carry out alkylated reaction with iso-butylene again and obtain, Chinese patent CN 1916060A discloses a kind of method by Paramethyl Phenol-dicyclopentadiene Styrene Chemical Inhibitor Resin.The method adopts a large amount of cyclohexane solvent in reaction process, and decolours with gac in aftertreatment, and technique is loaded down with trivial details.Chinese patent CN 101402721A discloses the method for a kind of p-methyl phenol-dicyclopentadiene isobutyl alkylene antioxidant resin, but the poor product quality that this method is produced, yield is low, and in alkylation process, employ the vitriol oil make catalyzer, product emulsification is easily caused not easily to remove catalyzer, need the neutralization of a large amount of alkali, therefore product colour difference, ash content are high; And the vitriol oil has severe corrosive, serious to equipment corrosion, equipment requirements is high, and uses that atlapulgite is de-urges decolouring can produce a large amount of solid waste, contaminate environment again.
It is that condensation reaction is carried out in catalyzer agent that Chinese patent CN 101967223A discloses a kind of use with boron trifluoride complex, owing to needing to use when absolute with boron trifluoride complex, operation difficulty is strengthened.The products such as the fluoroboric acid left over after being simultaneously difficult to remove reaction make quality product decline." synthesis of Condenced Phenols oxidation inhibitor BPCD " of " Speciality Petrochemicals " magazine publication, in one literary composition, describe and use 3-oxa-polyfluoro penta sulfonic acid as catalyst condensation reaction and alkylated reaction, because 3-oxa-polyfluoro penta sulfonic acid is expensive, remove also quite difficult, condensation reaction simultaneously does not use solvent, and make reaction incomplete, productive rate is not high.
The present invention, through research, finds a kind of method preparing p-methyl phenol-dicyclopentadiene isobutyl alkylene antioxidant resin newly, reacts fully, simple operation, cheap, and yield improves, Quality advance.
Summary of the invention
The invention provides the preparation method of a kind of p-cresol-dicyclopentadiene isobutyl product oxidation inhibitor, described method steps is as follows:
P-methyl phenol dimethyl formamide dissolves, drip dicyclopentadiene, back flow reaction 1 hour, condensation reaction terminates, lower the temperature and maintain the temperature at 65 ~ 100 DEG C, pass into iso-butylene, stop when iso-butylene no longer absorbs passing into, continue stirring 2 hours, alkylated reaction terminates, in reaction system, add sodium hydroxide, mix, after cooling, solvent leached and obtain product.
P-methyl phenol and dicyclopentadiene are carried out condensation reaction to generate phenolic petroleum resin by the present invention, and then phenolic petroleum resin and iso-butylene are carried out alkylated reaction; Finally carry out neutralizing i.e. obtained p-cresol-dicyclopentadiene isobutyl resin antioxidant with soda ash;
Be characterized in: during described condensation reaction, being that solvent is double with dimethyl formamide makees catalyzer, and when feeding intake, the mol ratio of p-methyl phenol and dicyclopentadiene is 2.0 ~ 3.0: 1, the add-on of dimethyl formamide is as the criterion to dissolve p-methyl phenol, can add better to dissolve.Reaction adopts the circumfluence method time to be 1 hour; During alkylated reaction, be still the double catalyzer that does of solvent with dimethyl formamide, temperature of reaction is 65 ~ 100 DEG C, and the reaction times is 1-3h; Reaction terminates rear sodium hydroxide and regulates pH value, makes the 7-8 that pH value arrives, and after cooling, end product is separated out from solvent, filters and obtains product.Sufficient reacting of the present invention, solvent easily removes, and solvent is identical with catalyzer, is that operation simplifies, is easy to remove, reacts and carry out in same solvent, and without the need to changing solvent, directly carry out next step reaction, total yield of products can realize 99%.
Embodiment
Embodiment 1
In the reactor that agitator, reflux exchanger, feeding device and nitrogen protection device 250ml are housed; add 50g p-methyl phenol, add 200g dimethyl formamide; stirring makes p-methyl phenol dissolve completely; add the dicyclopentadiene of 30g; reflux about 1 hour; be cooled to less than 100 DEG C, pass into iso-butylene to not absorbing stopping, adding sodium hydroxide 1.5g and neutralizing; stir; cool to less than 10 DEG C, place 2 hours, filter; dry; obtain product 60g, yield 99%, purity 99%.
Claims (1)
1. a synthetic method for paracresol-dicyclopentadiene isobutylation resin antioxidant, is characterized in that, step is as follows:
P-methyl phenol dimethyl formamide dissolves, drip dicyclopentadiene, back flow reaction 1 hour, condensation reaction terminates, lower the temperature and maintain the temperature at 80 DEG C, pass into iso-butylene, stop when iso-butylene no longer absorbs passing into, continue stirring 2 hours, alkylated reaction terminates, in reaction system, add sodium hydroxide, mix, after cooling, solvent leached and obtain product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310324217.3A CN103396530B (en) | 2013-07-30 | 2013-07-30 | Synthesizing method of p-cresol-dicyclopentadiene isobutyl resin antioxidant |
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| CN201310324217.3A CN103396530B (en) | 2013-07-30 | 2013-07-30 | Synthesizing method of p-cresol-dicyclopentadiene isobutyl resin antioxidant |
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| Publication Number | Publication Date |
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| CN103396530A CN103396530A (en) | 2013-11-20 |
| CN103396530B true CN103396530B (en) | 2015-02-18 |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107032962A (en) * | 2017-06-02 | 2017-08-11 | 江苏飞亚化学工业有限责任公司 | A kind of polymerization type hindered phenol antioxidant and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1068995A (en) * | 1963-06-21 | 1967-05-17 | Goodyear Tire & Rubber | Alkylated condensation products of phenols and dicyclopentadiene and their use as rubber ? antioxidants |
| US3751375A (en) * | 1972-02-29 | 1973-08-07 | Goodyear Tire & Rubber | Stabilization of polyurethane compositions and resins used to prepare polyurethane compositions |
| US4127490A (en) * | 1977-12-05 | 1978-11-28 | Basf Wyandotte Corporation | Fiber finish compositions |
| CN101967223A (en) * | 2010-09-28 | 2011-02-09 | 江苏飞亚化学工业有限责任公司 | Synthesis method of paracresol-dicyclopentadiene isobutylation resin antioxidant |
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2013
- 2013-07-30 CN CN201310324217.3A patent/CN103396530B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1068995A (en) * | 1963-06-21 | 1967-05-17 | Goodyear Tire & Rubber | Alkylated condensation products of phenols and dicyclopentadiene and their use as rubber ? antioxidants |
| US3751375A (en) * | 1972-02-29 | 1973-08-07 | Goodyear Tire & Rubber | Stabilization of polyurethane compositions and resins used to prepare polyurethane compositions |
| US4127490A (en) * | 1977-12-05 | 1978-11-28 | Basf Wyandotte Corporation | Fiber finish compositions |
| CN101967223A (en) * | 2010-09-28 | 2011-02-09 | 江苏飞亚化学工业有限责任公司 | Synthesis method of paracresol-dicyclopentadiene isobutylation resin antioxidant |
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Address after: 276000 50 meters north of the intersection of Huanghai 11th Road and Dashan Road, tuanlin Town, Lingang Economic Development Zone, Linyi City, Shandong Province Patentee after: Shandong Daguan Technology Co.,Ltd. Address before: 272264 resident of chemical industry park, Lingang Development Zone, Linyi City, Shandong Province Patentee before: SHANDONG DAGUAN BIOCHEMICAL TECHNOLOGY CO.,LTD. |
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