CN101967223A - Synthesis method of paracresol-dicyclopentadiene isobutylation resin antioxidant - Google Patents
Synthesis method of paracresol-dicyclopentadiene isobutylation resin antioxidant Download PDFInfo
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Abstract
The invention relates to a synthesis method of a paracresol-dicyclopentadiene isobutylation resin antioxidant, belonging to the technical field of chemical synthesis. The synthesis method comprises the following steps of: carrying out a condensation reaction on paracresol and dicyclopentadiene to produce phenolic type petroleum resin; then, carrying out an alkylation reaction on the phenolic type petroleum resin and isobutene; and finally, neutralizing by using sodium carbonate, and distilling to obtain the paracresol-dicyclopentadiene isobutylation resin antioxidant. The paracresol-dicyclopentadiene isobutylation resin antioxidant is still prepared by using the paracresol, the dicyclopentadiene and the isobutene as raw materials through the two steps of reactions of condensation and alkylation, but the total yield of the product can reach 93-95% through a special process.
Description
Technical field
The invention belongs to chemosynthesis technical field, particularly a kind of synthetic method of hindered phenol antioxygen.
Background technology
At present, the antioxidant that is used for plastics and rubber item technical field has a variety of, relatively is typically phenols and amine antioxidants.Wherein amine antioxidants is mainly used in rubber greatly because of toxicity, and is easy to change in the use, bad with the compatibleness of hydro carbons oil product, and present research direction is compound anti-aging agent of the little phenols of toxicity and aggretion type phenolic antioxidant.Mostly toxicity is low in other type, and phenolic antioxidant is best a kind of in all oxidation inhibitor, can be divided into single phenol, bisphenols oxidation inhibitor, phenolic antioxidant have do not pollute, low toxicity or nontoxic characteristics, also have good resistance of oxidation simultaneously.
The optimum weight of universal phenolic antioxidant is 800～1000, and polymerization type hindered phenol oxidation inhibitor relative molecular mass is greater than 800, and the developing direction of phenolic antioxidant is to improve the relative molecular mass of self from now on.
P-methyl phenol-dicyclopentadiene isobutyl resin oxidation inhibitor is one of several nontoxic, tasteless, look shallow oxidation inhibitor kinds few in number in the phenolic antioxidant, be widely used in rubber, plastics, fiber, tackiness agent, prevent the aging of material, prolong material work-ing life, in oil fuel industry, also be used for suppressing the increase of viscosity and acidity, in food and fodder industry, prevent food spoilage.
P-methyl phenol-dicyclopentadiene isobutyl resin antioxidant product is main raw material usually with the p-methyl phenol, carry out condensation reaction with dicyclopentadiene and generate phenol type petroleum resin, carry out alkylated reaction with iso-butylene again and make, disclose many documents now about phenolic antioxidant.For example: CN 1916060A discloses a kind of method by Paramethyl Phenol-dicyclopentadiene Styrene Chemical Inhibitor Resin.This method adopts a large amount of cyclohexane solvents in reaction process, and decolours with gac in aftertreatment, and technology is loaded down with trivial details.And for example 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, used the vitriol oil to make catalyzer, cause product emulsification to be difficult for removing catalyzer easily, need a large amount of alkali neutralizations, so product colour difference, ash content height; And the vitriol oil has severe corrosive, and is serious to equipment corrosion, the equipment requirements height, and use atlapulgite to take off to urge decolouring to produce a large amount of solid useless, contaminate environment again.
Summary of the invention
The objective of the invention is to seek a kind of novel process of synthetic p-cresol-dicyclopentadiene isobutyl product oxidation inhibitor of efficient, cleaning.
Technical scheme of the present invention is: p-methyl phenol and dicyclopentadiene are carried out condensation reaction generation phenol type petroleum resin, and then phenol type petroleum resin and iso-butylene are carried out alkylated reaction; After neutralizing with soda ash at last,, promptly make p-cresol-dicyclopentadiene isobutyl resin oxidation inhibitor through distillation; Be characterized in: during described condensation reaction, with the boron trifluoride complex is agent, earlier p-methyl phenol is dewatered with solvent and add reactor again after the pre-treatment, when feeding intake, the mol ratio of p-methyl phenol and dicyclopentadiene is 2.0～3.0: 1, temperature of reaction is 70～110 ℃, and the reaction times is 4～10h; During described alkylated reaction, be catalyzer with organic composite sulfoacid, the mass ratio of organic composite sulfoacid and p-methyl phenol is 3～5: 100, and temperature of reaction is 65～100 ℃, and the reaction times is 3～7h; Add organic composite sulfoacid solvent when adding organic composite sulfoacid
It is raw material that the present invention still adopts p-cresol, dicyclopentadiene and iso-butylene, make through condensation, alkylation two steps reaction, but by special technology, total yield of products can realize 93～95%.
Characteristics of the present invention are:
1, during condensation reaction, be agent with the boron trifluoride complex, p-methyl phenol is dewatered with solvent adds reactor after the pre-treatment again, is unlikely to influence the effect of condensation catalyst.The reaction raw materials p-methyl phenol is suitably excessive in the condensation reaction, and time, the temperature of control reaction, to realize the polymerization degree of control reaction product.
2, the present invention only need be used to dissolve the solvent of organic composite sulfoacid on a small quantity, both can improve the efficient of catalyzer, is easy to the carrying out that react, and saves again and uses a large amount of solvents, increases plant factor; Adopt organic composite sulfoacid to make catalyzer in the alkylation process, disposable synthetic this antioxidant product only need react, neutralize, distills just and can obtain high-quality product, and technological process is simple, has save many trivial step.
3, alkylated reaction adopts organic composite sulfoacid catalyzer, and easily washing separates, and product color is good, and ash is low, and water can distill recovery set usefulness, and basic non-wastewater discharge reaches the cleaner production requirement.And facility investment reduces greatly.
4, carry out condensation reaction under the condition that does not add organic solvent, the required chemical composition of the mixture of generation can obtain after the processing below alkylation and the process, can remove the lower boiling component of removal of alkylation reaction by distillation.
In addition, the preferred temperature of reaction of condensation reaction of the present invention is 90～100 ℃, and the reaction times is 6～8h.
The preferred temperature of reaction of alkylated reaction is 70～85 ℃, and the reaction times is 4～6h.
The mol ratio of preferred p-methyl phenol and dicyclopentadiene is 2.4～2.6: 1.
The solvent of described organic composite sulfoacid is any one in benzene, toluene or the dimethylbenzene.
Technology advantage of the present invention: adopt the catalyzer of organic composite sulfoacid as alkylated reaction, improve the quality of products, this catalyzer is cheap and common, and its treating processes is simple, easily washing neutralizes with minute quantity soda ash, and water can distill recovery set and use, almost there are not the three wastes to produce, etching apparatus not, technology clean environment firendly, and the purity height of product, color and luster is good, and ash is low.
Embodiment
Embodiment 1
In the reactor that agitator, reflux exchanger, feeding device and nitrogen protection device 250ml are housed; add 50g to p-methyl phenol (purity 99.5%), 2g boron trifluoride complex catalyzer; be heated to 60～80 ℃, treat that p-methyl phenol melts back unlatching stirring fully and is warming up to 90～100 ℃.Prepare the dicyclopentadiene of 30g simultaneously, slowly add in the reactor by feeding device, after all dicyclopentadiene dropwises, reaction mixture kept reacting about 4 hours again, controlled temperature is at 100～105 ℃, be cooled to then below 100 ℃, negative pressure reclaims unreacted p-cresol (3.04Kpa, 180 ℃), adds toluene again and organic composite sulfoacid catalyzer 1.5g carries out alkylated reaction, feeding iso-butylene at 75 ℃ does not stop to not absorbing, add soda ash 1.5g and neutralize, toluene is reclaimed in distillation, and negative pressure (3.0Kpa) is distilled to 240 ℃ and gets product 58g product, yield 91.8%, 117.5 ℃ of fusing points.
Embodiment 2
With the 800 gram solid p-methyl phenols 3000ml glass still of packing into, use the nitrogen replacement air.Heat temperature raising is opened stirring arm (60～80 rev/mins of rotating speeds) to fusing, adds condensation catalyst boron trifluoride complex 20 grams with dropping funnel, and continues to stir and be warming up to 100 ℃, begins to drip dicyclopentadiene 450g.Temperature of reaction is controlled at 100 ± 2 ℃, and during dropping, stirring velocity is fast slightly.After dripping end, 100 ± 2 ℃ of insulations 1 hour.(3.04Kpa, 180 ℃) steam moisture, unnecessary p-cresol and small-molecule substance under vacuum, finish sampling analysis.Temperature of charge is reduced to below 100 ℃, add toluene (or benzene, or dimethylbenzene), organic composite sulfoacid catalyzer 40g also stirs, and treats that temperature reduces to 80 ± 2 ℃, feeds iso-butylene, control reaction temperature.When iso-butylene no longer absorbs, stop, being incubated 2 hours.After alkylated reaction finishes, slowly add soda ash 40g, after toluene is steamed, under the 3Kpa condition, be distilled to 210 ℃ again, promptly get product 950g, 119 ℃ of fusing points, yield 93%.
Gained antioxidant product of the present invention has following structure:
Its main physico-chemical property:
Outward appearance: unrestricted flow, pale powder fusing point: 〉=115 ℃
Fugitive constituent :≤0.5% ash content :≤0.5%
Average molecular mass: 650 colourities :≤2
Solubleness: can be dissolved in aromatics, ethers, dehydrated alcohol, Virahol equal solvent, the water insoluble and various aqueous solution.
Claims (5)
1. the synthetic method of p-methyl phenol-dicyclopentadiene isobutyl resin oxidation inhibitor is carried out condensation reaction generation phenol type petroleum resin with p-methyl phenol and dicyclopentadiene, and then phenol type petroleum resin and iso-butylene is carried out alkylated reaction; After neutralizing with soda ash at last,, promptly make p-cresol-dicyclopentadiene isobutyl resin oxidation inhibitor through distillation; When it is characterized in that described condensation reaction, with the boron trifluoride complex is agent, earlier p-methyl phenol is dewatered with solvent and add reactor again after the pre-treatment, when feeding intake, the mol ratio of p-methyl phenol and dicyclopentadiene is 2.0～3.0: 1, temperature of reaction is 70～110 ℃, and the reaction times is 4～10h; During described alkylated reaction, be catalyzer with organic composite sulfoacid, the mass ratio of organic composite sulfoacid and p-methyl phenol is 3～5: 100, and temperature of reaction is 65～100 ℃, and the reaction times is 3～7h; Add organic composite sulfoacid solvent when adding organic composite sulfoacid.
2. according to the synthetic method of the described p-methyl phenol of claim 1-dicyclopentadiene isobutyl resin oxidation inhibitor, the temperature of reaction that it is characterized in that condensation reaction is 90～100 ℃, and the reaction times is 6～8h.
3. according to the synthetic method of claim 1 or 2 described p-methyl phenols-dicyclopentadiene isobutyl resin oxidation inhibitor, the temperature of reaction that it is characterized in that alkylated reaction is 70～85 ℃, and the reaction times is 4～6h.
4. according to the synthetic method of the described p-methyl phenol of claim 1-dicyclopentadiene isobutyl resin oxidation inhibitor, the mol ratio that it is characterized in that p-methyl phenol and dicyclopentadiene is 2.4～2.6: 1.
5. according to the synthetic method of the described p-methyl phenol of claim 1-dicyclopentadiene isobutyl resin oxidation inhibitor, it is characterized in that described organic composite sulfoacid solvent is any one in benzene, toluene or the dimethylbenzene.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319315A (en) * | 2013-06-17 | 2013-09-25 | 湖北工业大学 | Method for producing aggregate-type hindered phenol antioxidant |
| CN103396530A (en) * | 2013-07-30 | 2013-11-20 | 江苏飞亚化学工业有限责任公司 | Synthesizing method of p-cresol-dicyclopentadiene isobutyl resin antioxidant |
| CN103420807A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
| CN106317382A (en) * | 2015-06-30 | 2017-01-11 | 江苏圣奥化学科技有限公司 | Preparation method of anti-aging agent |
| CN106542970A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | The method that a kind of synthesis of dicyclopentadiene phenol resin and feedstock circulation are utilized |
| US20170174597A1 (en) * | 2015-12-18 | 2017-06-22 | Kumho Petrochemical Co., Ltd. | Preparing method of a phenolic oligomer antioxidant |
| CN106928496A (en) * | 2017-04-27 | 2017-07-07 | 江苏飞亚化学工业有限责任公司 | A kind of preparation method of anti-coagulation type antioxidant |
| CN107446121A (en) * | 2017-08-18 | 2017-12-08 | 广东新华粤石化集团股份公司 | One pot process paracresol dicyclopentadiene butylation product |
| CN107955277A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of rubber and preparation method thereof |
| CN108440296A (en) * | 2018-04-03 | 2018-08-24 | 吉林市银联科技有限公司 | A kind of poly- phenol monoacrylate and preparation method |
| CN111592638A (en) * | 2020-06-19 | 2020-08-28 | 西安元创化工科技股份有限公司 | Preparation method of high-softening-point light-colored dicyclopentadiene-phenol resin |
| CN112063100A (en) * | 2020-09-14 | 2020-12-11 | 江苏麒祥高新材料有限公司 | Modified resin liquid and preparation method thereof |
| CN113620785A (en) * | 2021-09-23 | 2021-11-09 | 广东希必达新材料科技有限公司 | Preparation method of antioxidant |
| CN113817241A (en) * | 2021-10-25 | 2021-12-21 | 徐州工业职业技术学院 | Anti-aging rubber material and preparation method thereof |
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| CN1916060A (en) * | 2006-08-23 | 2007-02-21 | 杨彦威 | Antioxidant resin through benzene ethylenation of p - methyl phenol - dicyclopentadiene |
| CN101402721A (en) * | 2008-11-04 | 2009-04-08 | 三门峡市峡威化工有限公司 | Process for producing polymerization type hindered phenol antioxidant 616 |
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| CN1916060A (en) * | 2006-08-23 | 2007-02-21 | 杨彦威 | Antioxidant resin through benzene ethylenation of p - methyl phenol - dicyclopentadiene |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420807A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
| CN103319315A (en) * | 2013-06-17 | 2013-09-25 | 湖北工业大学 | Method for producing aggregate-type hindered phenol antioxidant |
| CN103396530A (en) * | 2013-07-30 | 2013-11-20 | 江苏飞亚化学工业有限责任公司 | Synthesizing method of p-cresol-dicyclopentadiene isobutyl resin antioxidant |
| CN103396530B (en) * | 2013-07-30 | 2015-02-18 | 江苏飞亚化学工业有限责任公司 | Synthesizing method of p-cresol-dicyclopentadiene isobutyl resin antioxidant |
| CN106317382A (en) * | 2015-06-30 | 2017-01-11 | 江苏圣奥化学科技有限公司 | Preparation method of anti-aging agent |
| CN106542970A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | The method that a kind of synthesis of dicyclopentadiene phenol resin and feedstock circulation are utilized |
| US9908830B2 (en) * | 2015-12-18 | 2018-03-06 | Kumho Petrochemical Co., Ltd | Preparing method of a phenolic oligomer antioxidant |
| US20170174597A1 (en) * | 2015-12-18 | 2017-06-22 | Kumho Petrochemical Co., Ltd. | Preparing method of a phenolic oligomer antioxidant |
| CN107955277B (en) * | 2016-10-14 | 2020-07-21 | 中国石油化工股份有限公司 | Rubber product and preparation method thereof |
| CN107955277A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of rubber and preparation method thereof |
| CN106928496A (en) * | 2017-04-27 | 2017-07-07 | 江苏飞亚化学工业有限责任公司 | A kind of preparation method of anti-coagulation type antioxidant |
| CN107446121A (en) * | 2017-08-18 | 2017-12-08 | 广东新华粤石化集团股份公司 | One pot process paracresol dicyclopentadiene butylation product |
| CN108440296A (en) * | 2018-04-03 | 2018-08-24 | 吉林市银联科技有限公司 | A kind of poly- phenol monoacrylate and preparation method |
| CN111592638A (en) * | 2020-06-19 | 2020-08-28 | 西安元创化工科技股份有限公司 | Preparation method of high-softening-point light-colored dicyclopentadiene-phenol resin |
| CN112063100A (en) * | 2020-09-14 | 2020-12-11 | 江苏麒祥高新材料有限公司 | Modified resin liquid and preparation method thereof |
| CN113620785A (en) * | 2021-09-23 | 2021-11-09 | 广东希必达新材料科技有限公司 | Preparation method of antioxidant |
| CN113817241A (en) * | 2021-10-25 | 2021-12-21 | 徐州工业职业技术学院 | Anti-aging rubber material and preparation method thereof |
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Application publication date: 20110209 |