CN103657723B - Preparation method of catalyst for preparing dodecyl phenol - Google Patents
Preparation method of catalyst for preparing dodecyl phenol Download PDFInfo
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- CN103657723B CN103657723B CN201310724278.9A CN201310724278A CN103657723B CN 103657723 B CN103657723 B CN 103657723B CN 201310724278 A CN201310724278 A CN 201310724278A CN 103657723 B CN103657723 B CN 103657723B
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Abstract
The invention provides a preparation method of a catalyst for preparing dodecyl phenol. In the polymerization, an N,N-dimethylethenesulfonamide monomer is introduced; amido of N,N-dimethylethenesulfonamide is immobilized on a resin framework. The resin catalyst obtained by applying the method provided by the invention is used for preparing dodecyl phenol; the service life of the catalyst is longer than that of an existing resin catalyst; meanwhile, production cost can be reduced; the resin catalyst obtained by applying the method can be well used for replacing foreign like products.
Description
Technical field
The present invention relates to a kind of method of producing cation exchange resin catalyst, particularly a kind of preparation method of the catalyst for the preparation of dodecyl phenol.
Background technology
Dodecyl phenol is mainly for the preparation of the detergent additive (it exists with the calcium of alkalescence and magnesium phenates wherein) of lubricating oil and non-ionic detergent (ethoxylation or propenoxylated dodecyl phenol) and anionic detergent (sulphation or Sulfonated dodecyl phenol).The preparation process of dodecyl phenol utilizes the alkylated reaction of phenol and alkene usually, is catalyst with acid, and in reaction mixture, the concentration of acid can be 1-50% (weight).
CN1078195 discloses under the existence of the cation exchange resin catalyst of sulfonated styrene diethylene benzene copoly mer form, by the method for propylene tetramer alkylated phenol continuous production dodecyl phenol, wherein, by reactant mixture and above-mentioned macroporous type catalyst exposure, its alkylate obtains two kinds of fractions through distillation, reclaim from higher boiling fraction by conventional method subsequently and obtain dodecyl phenol, and low boiling fractions is divided into two liquid streams, previous liquid stream recirculation is entered in alkylation of phenol device, and add water in another liquid stream and make it be divided into hydrocarbon layers and phenol layer, the latter recycles and enters in the synthesis technique of dodecyl phenol after distillation dehydration.
JP6228438 discloses the alkylated reaction of phenol and C12-C30 alkene, and it is with the ion exchange resin of highly acid sulphonated polystyrene for catalyst, and this reaction has high heat endurance and good selective.Due to the concentration of dialkyl group phenol lower (about 3wt%) in alkylate, decompression distillation is not needed it to be separated.
Poland Patent No.167907 discloses under the existence of the ion exchanger catalysts be made up of macropore and gel type cation exchanger, by the successive reaction of C12 olefin alkylation phenol, removes inert material and water by crystallization from reaction medium.The method can obtain high and stable productive rate, has high selective.But in order to phenol and hydrocarbons be separated by solvent extraction from post-crystallization liquor, need added solvent regenerating unit on equipment.
The resin catalyst that above-mentioned patent and known technology use, has poor heat stability, side reaction is many, service life is short, shortcoming that production cost is higher.In order to improve the combination property of resin catalyst, reducing production cost, being necessary further to study, finding the suitable catalyst for the preparation of dodecyl phenol.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, provide a kind of Catalysts and its preparation method for the preparation of dodecyl phenol, this resin catalyst has the advantages such as heat resistance is high, side reaction is few, the reaction time is long.
The party's ratio juris is by N, N-dimethyl ethenyl sulfonamide introduces polystyrene, by N, the amido of N-dimethyl ethenyl sulfonamide is immobilized on the skeleton of resin, described catalyst prod belongs to bronsted acid catalyst, and what play catalytic action in this catalyst is Brewster acidic site on catalyst.When the amount of catalyst is enough, because the Brewster acidic site provided is sufficient, reaction just reaches balance, and the conversion ratio of phenol can reach maximum.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
There is provided a kind of catalyst for the preparation of dodecyl phenol, structural formula is as follows:
The integer of n=1-3000
A kind of preparation method of the catalyst for the preparation of dodecyl phenol is provided, comprises the following steps:
1). the preparation of polymerization Archon
In a kettle., by weight, the styrene of 100 parts, the divinylbenzene (being preferably 12 parts) of 5-20 part, the N of 0.5 ~ 2 part, N-dimethyl ethenyl sulfonamide C is added
4h
9nO
2s is as comonomer, the chain-transferring agent of 0.01 ~ 0.05 part, the pore-foaming agent (being preferably 40 parts) of 20-60 part, 70 DEG C ~ 95 DEG C (being preferably 80 DEG C) reactions 6 ~ 24h (being preferably 18h), terminate reaction, reaction generates polymerization Archon, after oven dry, pore-foaming agent extracting is clean, dry stand-by;
2). sulfonating reaction
By step 1) the polymerization Archon that obtains joins in sulfuric acid, the mass ratio of polymerization Archon and sulfuric acid is 1:1-1:3 (being preferably 1:2), carry out sulfonating reaction 10-30h (being preferably 20h) 80-140 DEG C (being preferably 100 DEG C), obtain the resin catalyst for the preparation of dodecyl phenol.
Step 1) described in the preferred lauryl mercaptan of chain-transferring agent.
Step 1) described in pore-foaming agent be selected from liquid wax, white oil, containing organic alcohols more than 3 carbon atoms or any one or two or more mixtures in gasoline, be preferably liquid wax.
The resin catalyst product that the inventive method obtains has following beneficial effect:
Relative to ordinary resin catalyst, resin catalyst prepared by the inventive method, heat resistance is high, and side reaction is few, and the reaction time is long.The introducing of Long carbon chain, improves the compatibility of catalyst and reactant, improves conversion ratio.Under close pulp furnish, the resin catalyst of application the inventive method gained prepares dodecyl phenol, dodecyl phenol yield is higher than the technique of the existing resin catalyst of application, can reduce production cost, the resin catalyst that therefore the inventive method obtains can perform well in alternative same kind of products at abroad simultaneously.
Detailed description of the invention
Following instance is only further illustrate the present invention, is not restriction the scope of protection of the invention.
Embodiment 1:
1). the preparation of polymerization Archon
In a kettle., by weight, add the styrene of 100 parts, the divinylbenzene of 12 parts, the N of 1 part, N-dimethyl ethenyl sulfonamide is as comonomer, the lauryl mercaptan of 0.02 part, the pore-foaming agent of 40 parts, at 80 DEG C of reaction 18h, terminates reaction, reaction generates polymerization Archon, after oven dry, pore-foaming agent extracting is clean, dry stand-by;
2). sulfonating reaction
By step 1) the polymerization Archon that obtains joins in sulfuric acid, and the mass ratio of polymerization Archon and sulfuric acid is 1:2, carries out sulfonating reaction 20h, obtain the resin catalyst for the preparation of dodecyl phenol at 100 DEG C.Products obtained therefrom is numbered M-1.
Embodiment 2
Step 1) in the N that adds, N-dimethyl ethenyl sulfonamide changes 0.5 part into, the other the same as in Example 1.Products obtained therefrom is numbered M-2.
Embodiment 3
Step 1) in the N that adds, N-dimethyl ethenyl sulfonamide changes 2 parts into, the other the same as in Example 1.Products obtained therefrom is numbered M-3.
Embodiment 4
Step 1) in the lauryl mercaptan that adds change 0.01 part into, the other the same as in Example 1.Products obtained therefrom is numbered M-4.
Embodiment 5
Step 1) in the lauryl mercaptan that adds change 0.01 part into, the other the same as in Example 2.Products obtained therefrom is numbered M-5.
Embodiment 6
Step 1) in the lauryl mercaptan that adds change 0.01 part into, the other the same as in Example 3.Products obtained therefrom is numbered M-6.
Embodiment 7
Step 1) lauryl mercaptan that adds changes 0.05 part into, the other the same as in Example 1.Products obtained therefrom is numbered M-7.
Embodiment 8
Step 1) in the lauryl mercaptan that adds change 0.05 part into, the other the same as in Example 2.Products obtained therefrom is numbered M-8.
Embodiment 9
Step 1) in the lauryl mercaptan that adds change 0.05 part into, the other the same as in Example 3.Products obtained therefrom is numbered M-9.
Comparative example 1:
Step 1) in the N that adds, N-dimethyl ethenyl sulfonamide changes 0 part into, the other the same as in Example 1.Products obtained therefrom is numbered M-10.
Comparative example 2:
Step 1) in the lauryl mercaptan that adds change 0 part into, the other the same as in Example 1.Products obtained therefrom is numbered M-11.
The test in the service life of embodiment 10. resin catalyst:
The resin catalyst product obtained in embodiment 1-9 and comparative example 1-2 is loaded in fixed bed reactors respectively, anhydrous phenol and polypropylene tetramer (different laurylene) are with 2:1(mol) proportioning enter two sections of fixed bed reactors, temperature 120 DEG C, pressure 0.9MPa, polypropylene tetramer air speed 1h
-1, the exit sample analysis in reactor is less than 70% be inefficacy by the yield of two reactor, statistics dealdehyding resin service life, the results are shown in Table 1.Use D001 ion exchange resin to do catalysis to carry out as a comparison simultaneously.Longer 120 DEG C of service lifes, sulfonic acid group gets over difficult drop-off, and heat resistance is better, so service life is the sign of resin catalyst heat resistance.
Table 1: the comparison in test specimen service life that different process is made
| Numbering | Service life sky | Product yield % | Phenol conversion % |
| M－1 | 178 | 71 | 81 |
| M－2 | 150 | 61 | 77 |
| M－3 | 184 | 74 | 84 |
| M－4 | 137 | 62 | 74 |
| M－5 | 124 | 60 | 72 |
| M－6 | 130 | 61 | 72 |
| M－7 | 156 | 66 | 76 |
| M－8 | 174 | 69 | 74 |
| M－9 | 200 | 77 | 83 |
| M－10 | 108 | 54 | 65 |
| M－11 | 112 | 55 | 63 |
| D001 ion exchange resin | 84 | 39 | 51 |
With FTIS, pressing potassium bromide troche does infrared spectrum analysis to synthesized each resin.All at 1730cm in the collection of illustrative plates of M1-M9, M11 sample
-1near there is carbonyl absorption peak, 1380cm
-1and 1150cm
-1near there is sulfonamide characteristic peak; 2980cm
-1neighbouring appearance-CH
3characteristic peak; Have in the collection of illustrative plates of M1-M11 sample in collection of illustrative plates all at 1600cm
-1, 1580cm
-1, 1500cm
-1neighbouring appearance 3 absorption bands, this is the key character of aromatic compound infrared spectrum, can determine to have fragrant nuclear structure in resin accordingly.Therefore can judge successfully to introduce N in this patent polystyrene products, N-dimethyl ethenyl sulfonamide.
Relative to ordinary resin catalyst, resin catalyst prepared by the inventive method, heat resistance is high, side reaction is few, and the reaction time is long, therefore under close pulp furnish, the resin catalyst of application the inventive method gained prepares dodecyl phenol, catalyst service life, can reduce production cost, the resin catalyst that therefore the inventive method obtains can perform well in alternative same kind of products at abroad simultaneously higher than existing resin catalyst.
Claims (5)
1. for the preparation of a preparation method for the catalyst of dodecyl phenol, it is characterized in that, comprise the following steps:
1). the preparation of polymerization Archon
In a kettle., by weight, the styrene of 100 parts, the divinylbenzene of 5-20 part, the N of 0.5 ~ 2 part is added, N-dimethyl ethenyl sulfonamide C
4h
9nO
2s as comonomer, the chain-transferring agent of 0.01 ~ 0.05 part, the pore-foaming agent of 20-60 part, at 70 DEG C ~ 95 DEG C reaction 6 ~ 24h, terminate reaction, reaction generates polymerization Archon, after oven dry, pore-foaming agent extracting is clean, dries stand-by;
2). sulfonating reaction
By step 1) the polymerization Archon that obtains joins in sulfuric acid, and the mass ratio of polymerization Archon and sulfuric acid is 1:1-1:3, carries out sulfonating reaction 10-30h, obtain the resin catalyst for the preparation of dodecyl phenol at 80-140 DEG C;
Step 1) described in chain-transferring agent be lauryl mercaptan.
2. preparation method according to claim 1, is characterized in that: step 1) described in pore-foaming agent be selected from liquid wax, white oil, containing organic alcohols more than 3 carbon atoms or any one or two or more mixtures in gasoline.
3. preparation method according to claim 1, is characterized in that: described pore-foaming agent is liquid wax.
4. according to the catalyst for the preparation of dodecyl phenol that the described preparation method of one of claim 1-3 obtains.
5. the application in dodecyl phenol produced by catalyst at the anhydrous phenol of employing and polypropylene tetramer according to claim 4.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310724278.9A CN103657723B (en) | 2013-12-24 | 2013-12-24 | Preparation method of catalyst for preparing dodecyl phenol |
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|---|---|---|---|
| CN201310724278.9A CN103657723B (en) | 2013-12-24 | 2013-12-24 | Preparation method of catalyst for preparing dodecyl phenol |
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| CN103657723B true CN103657723B (en) | 2015-05-27 |
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| CN112574005A (en) * | 2020-12-23 | 2021-03-30 | 广东新华粤石化集团股份公司 | Preparation method for producing branched-chain dodecylphenol |
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| BR8707843A (en) * | 1986-10-24 | 1989-10-03 | Exxon Research Engineering Co | ALKYLEPHONES AND DERIVATIVES FROM THE SAME VIA PHENOL ALKYLATION BY CRACKED PETROLEUM DISTILLATES |
| PL182406B1 (en) * | 1996-09-19 | 2001-12-31 | Inst Ciezkiej Syntezy Orga | Method of obtaining dodecyl phenol |
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