CN112574005A - Preparation method for producing branched-chain dodecylphenol - Google Patents
Preparation method for producing branched-chain dodecylphenol Download PDFInfo
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- CN112574005A CN112574005A CN202011534876.6A CN202011534876A CN112574005A CN 112574005 A CN112574005 A CN 112574005A CN 202011534876 A CN202011534876 A CN 202011534876A CN 112574005 A CN112574005 A CN 112574005A
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- dodecylphenol
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- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 5
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 claims abstract description 63
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 238000009826 distribution Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 230000002152 alkylating effect Effects 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 238000010626 work up procedure Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 16
- 230000007547 defect Effects 0.000 abstract description 3
- 230000008014 freezing Effects 0.000 abstract description 3
- 238000007710 freezing Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 35
- 239000000047 product Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 21
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- -1 aliphatic alcohols Chemical class 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 229940069096 dodecene Drugs 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- DRHABPMHZRIRAH-UHFFFAOYSA-N 2,4,4,6,6-pentamethylhept-2-ene Chemical group CC(C)=CC(C)(C)CC(C)(C)C DRHABPMHZRIRAH-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YOSVDFBKVKLOQU-UHFFFAOYSA-N [Pb].C=CC.C=CC.C=CC.C=CC Chemical compound [Pb].C=CC.C=CC.C=CC.C=CC YOSVDFBKVKLOQU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of branched-chain dodecylphenol synthesis, in particular to a preparation method for producing branched-chain dodecylphenol. A process for preparing branched-chain dodecylphenol includes alkylation reaction of phenol and tetrapropylene in the presence of resin whose functional group is sulfonic acid group. The invention aims to overcome the defects in the prior art, the branched-chain dodecylphenol is prepared by taking the phenol and the tetrapropylene as raw materials, the branched-chain dodecylphenol with high selectivity and high yield can be obtained in a short time under mild conditions, and the method is simple to operate and high in efficiency. Compared with branched dodecylphenol obtained by other methods, the branched dodecylphenol obtained by the method has higher branched degree of the side chain, lower freezing point and higher dispersing capacity, and is more widely applied to surfactants.
Description
Technical Field
The invention relates to the technical field of branched-chain dodecylphenol synthesis, in particular to a preparation method for producing branched-chain dodecylphenol.
Background
Alkylphenols are produced by the alkylation of olefins, aliphatic alcohols or halogenated hydrocarbons with phenols, and alkylphenols which are important in industrial production are obtained by the alkylation of phenol with olefins. The alkylphenol is not only an important intermediate for producing anionic surfactants such as alkylphenol polyoxyethylene ether nonionic surfactants and alkylphenol polyoxyethylene ether sulfate ester phosphates, but also a chemical intermediate for producing bactericides, plasticizers, stabilizers and the like.
Dodecylphenol is one of the important raw materials for preparing lubricating oil additives, industrial surfactants and the like. Because the dodecylphenol belongs to long-chain alkylphenol, the compound is synthesized by alkylating phenol with long-chain terminal olefin or long-chain halogenated hydrocarbon which is mainly used as a raw material. At present, the main methods for producing the dodecylphenol at home and abroad comprise the following steps: (1) the alkyl phenol is synthesized by catalyzing dodecene as an alkylating reagent. (2) Halogenated dodecyl alkane is used as an alkylating reagent to catalyze and synthesize alkylphenol. (3) The alkyl phenol is synthesized by catalyzing with n-dodecanol as an alkylating reagent. At present, the raw materials for synthesizing the dodecylphenol mostly use the triisobutylene, the branched chain degree of the triisobutylene is low, the reaction activity is low, and simultaneously, the catalyst can cause the depolymerization of the raw materials along with the extension of the reaction time, so that the yield is reduced, and the cost is increased.
Disclosure of Invention
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention. The sources of components not mentioned in the present invention are all commercially available.
The invention aims to solve the defects of the prior art and provides a method for producing branched dodecylphenol by using tetrapropylene as a raw material, which has high conversion rate and good selectivity and is suitable for industrial production.
The tetrapropylene is obtained by four times of auto-polymerization of propylene as a reaction raw material, and usually, long-chain olefins obtained by auto-polymerization of olefins having more than two carbon atoms are branched olefin products having a relatively high branching degree, so that the tetrapropylene obtained by four times of auto-polymerization of propylene has many isomers each having a branch and is reacted with phenol to obtain branched dodecylphenol.
Generally, a relatively large amount of linear dodecylphenol is used to obtain linear dodecenes by reaction, wherein the linear dodecenes are obtained only by two ways of extraction from kerosene or animal and vegetable oil and self-polymerization of ethylene, and thus the application of the linear dodecenes is limited to a certain extent.
Researches find that the branched dodecylphenol has lower freezing point, is in a liquid form at normal temperature, is more convenient to use compared with the linear dodecylphenol, does not need to add additional auxiliary agents to enable the branched dodecylphenol to be better compatible with a system, and therefore, the application range of the branched dodecylphenol is wider.
The invention provides a preparation method for producing branched dodecylphenol, which comprises the steps of taking phenol and tetrapropylene as raw materials, and carrying out alkylation reaction in the presence of resin with a functional group of a sulfonic acid group.
The phenol which is one of the raw materials is not limited in any way in the present invention, and any one of those which are industrially available can be generally used. To obtain a better quality of the reaction product, phenol with a water content of less than 10% is preferred.
The tetrapropylene may be obtained by tetramerization of propylene or may be separated from a C10-C14 fraction obtained by cracking paraffin, and is preferably a tetrapropylene obtained by tetramerization of propylene; in such tetrapropylenes, it is preferred that the C12 distribution in the tetrapropylene is more than 60% by weight, since the self-polymerization of propylene has a broad molecular weight distribution in the polymerization; more preferably, the distribution of C12 in the tetrapropylene is more than 90 wt%, the distribution of C10-C11 in the tetrapropylene is between 7 and 10 wt%, and most preferably, the distribution of C12 in the tetrapropylene is more than 95 wt%, and the distribution of C10-C11 in the tetrapropylene is between 3 and 5 wt%. Herein, C12, C10, C11 refer to dodecene, decene and undecene, respectively.
The research finds that the carbon distribution in the tetrapropylene has a great influence on the reaction activity, wherein the carbon distribution specifically refers to the content distribution of dodecene and undecene contained in the tetrapropylene raw material, and the content distribution is expressed by the weight ratio of dodecene or undecene in the total tetrapropylene.
In the method of the present invention, when raw materials of tetrapropylene are studied, it is unexpectedly found that different molar ratios of the reactants phenol and tetrapropylene lead to different reactivity, and the preferred molar ratio of phenol to tetrapropylene is (2-5): 1, more preferably 3: 1. when the molar ratio is too large or too small, the reaction completion time is affected, and due to the undecene contained in the carbon distribution in the tetrapropylene, when a part of the catalyst acts on the tetrapropylene, the undecene with small molecular weight exists to replace the depolymerization of the dodecene, so that the dodecene in the system still keeps high reactivity, and the undecene with small amount can be removed by the post-depolymerization treatment along with the progress of the reaction.
In the alkylation reaction of phenol and tetrapropylene, the method of the invention does not make any requirement on the adding sequence, generally the reaction purity is higher, and the tetrapropylene is preferably added dropwise after the phenol, and is usually added within 0.5-2 h after the phenol is added.
In order to obtain a product with a higher yield, an ionic liquid acid or an ultra-strong solid acid is generally used as a catalyst, and in addition, an ion exchange resin can be used for catalytic reaction, specifically, the ion exchange resin has a good pore structure, a large surface area and a high activity type in a liquid phase reaction and is widely used compared with the former two.
In the invention, the resin with a sulfonic acid group as a functional group is preferably adopted as the ion exchange resin to carry out catalytic reaction, and in order to obtain higher selectivity, the resin framework with the sulfonic acid group is preferably styrene divinylbenzene copolymer; in view of the swellability in the reaction, the resin particle diameter is more preferably 0.6 to 1 mm.
The preferred type of the resin skeleton is related to the selection of tetrapropylene, in general, in the prior art, in order to avoid depolymerization of the reaction raw material alkyl alkene, and therefore the preferred temperature is below 60 ℃, and in order to solve the problem of depolymerization, the reaction temperature is controlled to 70-100 ℃ by the method of the present invention, and in consideration of the influence of the melting point of the polymer skeleton as the resin and the difference of thermal stability on the catalytic performance of the resin, the molecular skeleton with better thermal stability is preferably a styrene divinylbenzene copolymer sulfonic acid group resin, and as such a resin, the most suitable resin of the present invention includes, but is not limited to IRI20h of rocheus.
By way of investigation, in the process of the invention, preferably IRI20h is used in an amount of 5 to 15 wt.%, more preferably 5 to 10 wt.%, based on the mass of phenol. The reaction activity is too high when the catalyst is used in an excessive amount, so that the probability of the reverse reaction of alkyl cation to olefin is increased, and the probability of excessive swelling of resin in the catalytic process is increased. Causing a decrease in yield; and if the content is too low, the catalytic activity is insufficient, and the reaction yield is also influenced.
According to the invention, through the selection of the raw materials and the catalytic system, the alkylation reaction can be completed after reacting for 2-4 h at 70-100 ℃. After the reaction is completed, the branched dodecylphenol with high yield and high selectivity can be finally obtained by carrying out post-treatment on the reaction liquid.
Specifically, the post-treatment method includes filtration, washing and distillation under reduced pressure.
Further, it is preferable that the reaction mixture is subjected to suction filtration while it is hot for the filtration treatment. The washing treatment is preferably carried out by washing the reaction solution with hot water at 50-80 ℃, the hot water washing can be carried out for 1-5 times, and then, alkali liquor is added to neutralize the reaction solution until the reaction solution is neutral, and then liquid separation is carried out; the alkaline solution used here can be any of the alkaline solutions commonly used, for example sodium hydroxide. For the reduced pressure distillation treatment, preferably, the oil phase is subjected to reduced pressure distillation, vacuum pumping is performed, and the reduced pressure distillation is performed under the protection of nitrogen to obtain a dodecylphenol product.
Has the advantages that: the invention aims to overcome the defects in the prior art, the branched-chain dodecylphenol is prepared by taking the phenol and the tetrapropylene as raw materials, the branched-chain dodecylphenol with high selectivity and high yield can be obtained in a short time under mild conditions, and the method is simple to operate and high in efficiency. Compared with branched dodecylphenol obtained by other methods, the branched dodecylphenol obtained by the method has higher branched degree of the side chain, lower freezing point and higher dispersing capacity, and is more widely applied to surfactants.
Detailed Description
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
If not stated otherwise, the tetrapropylene used in the following examples was about 95 wt% in C12 distribution and about 3 wt% in C10-C11 distribution, and the raw material was obtained from Shanghai chess Industrial Co., Ltd, and then separated and purified; the resin catalyst was IRI20h from rohm and haas.
Example 1
282g of phenol, 168g of tetrapropylene and 14.1g of resin catalyst are taken, the phenol and the catalyst are firstly added into a flask, the temperature is raised to 85 ℃ by stirring, the tetrapropylene is dripped, the reaction is continued for 2h under the condition of 85 ℃ after 0.5h of dripping is finished, the hot reaction mixture is filtered while the reaction is finished, the product and the catalyst are separated by suction filtration to prepare a branched-chain dodecylphenol mixture, the mixture is washed by hot water with the temperature of 50-80 ℃, the hot water washing can be 3 times, then alkali liquor is added to neutralize the reaction liquid to be neutral, liquid is separated, oil is taken, the residual phenol is separated by vacuum distillation under reduced pressure under the protection of nitrogen, and the branched-chain dodecylphenol product is prepared.
The components of the branched dodecylphenol mixture were analyzed by a chromatograph, wherein the mass percentage of the tetrapropylene was 0.5%, the mass percentage of the branched dodecylphenol was 52.2%, and the total weight of the branched dodecylphenol mixture was 450g, so that the mass of the reacted tetrapropylene was 2.25g, and the mass of the branched dodecylphenol actually produced was 234.9 g.
Theoretically, the molecular weight of the branched dodecylphenol is 1, 262.43g, 262.43 g;
the tetrapropylene conversion rate (tetrapropylene mass before reaction-tetrapropylene mass after reaction) 100%/tetrapropylene mass before reaction (168-2.25) 100%/168: 98.6%;
the selectivity of branched dodecylphenol is 100% of the mass of branched dodecylphenol actually produced/89.5% of branched dodecylphenol theoretically produced, 234.9 100% of branched dodecylphenol/262.43;
in example 1, the molar ratio of phenol to tetrapropylene was 3: 1, the amount of the catalyst accounts for 5% of the mass of phenol, and the following experiment was performed by adjusting the molar ratio of the raw materials and the amount of the catalyst.
Example 2
Taking 235g of phenol, 168g of tetrapropylene and 11.75g of resin catalyst, adding the phenol and the catalyst into a flask, stirring and heating to 85 ℃, beginning to dropwise add the tetrapropylene, continuing to react for 2 hours at 85 ℃ after 0.5 hour of dropwise addition is finished, filtering and separating a product and the catalyst while the mixture is hot after the reaction is finished to prepare a branched-chain dodecylphenol mixture, washing the mixture with hot water at 50-80 ℃ for 3 times, then adding alkali liquor to neutralize the reaction solution to be neutral, separating the solution, taking oil, performing vacuum distillation under reduced pressure, distilling and vacuumizing to separate excess phenol under nitrogen protection, and preparing a branched-chain dodecylphenol product. According to the performance test method of the embodiment 1, the conversion rate of the tetrapropylene in the reaction is 97 percent, and the selectivity of the branched dodecylphenol is 89 percent.
Example 3
188g of phenol, 168g of tetrapropylene and 9.4g of resin catalyst are taken, the phenol and the catalyst are added into a flask, the temperature is raised to 85 ℃ by stirring, the tetrapropylene is dripped, the reaction is continued for 2 hours at the temperature of 85 ℃ after 0.5 hour of dripping, the product and the catalyst are filtered and separated while the reaction is hot after the reaction is finished, a branched-chain dodecylphenol mixture is prepared, and redundant phenol is separated from the mixture by reduced pressure rectification, so that a branched-chain dodecylphenol product is prepared. According to the performance test method of the example 1, the conversion rate of the tetrapropylene in the reaction is 96.5 percent, and the selectivity of the branched dodecylphenol is 88.4 percent.
Example 4
282g of phenol, 168g of tetrapropylene and 16.92g of resin catalyst are taken, the phenol and the catalyst are firstly added into a flask, the temperature is raised to 85 ℃ by stirring, the tetrapropylene is dripped, the reaction is continued for 2 hours at 85 ℃ after 0.5 hour of dripping, the product and the catalyst are filtered and separated while the reaction is hot after the reaction is finished, a branched-chain dodecylphenol mixture is prepared, and redundant phenol is separated from the mixture by reduced pressure rectification, so that a branched-chain dodecylphenol product is prepared. According to the performance test method of the embodiment 1, the conversion rate of the tetrapropylene in the reaction is 99 percent, and the selectivity of the branched dodecylphenol is 90 percent.
Example 5
282g of phenol, 168g of tetrapropylene and 19.74g of resin catalyst are taken, the phenol and the catalyst are firstly added into a flask, the temperature is raised to 85 ℃ by stirring, the tetrapropylene is dripped, the reaction is continued for 2 hours at 85 ℃ after 0.5 hour of dripping, the product and the catalyst are filtered and separated while the reaction is hot after the reaction is finished, a branched-chain dodecylphenol mixture is prepared, and redundant phenol is separated from the mixture by reduced pressure rectification, so that a branched-chain dodecylphenol product is prepared. According to the performance test method of the embodiment 1, the conversion rate of the tetrapropylene in the reaction is 99.3 percent, and the selectivity of the branched dodecylphenol is 91 percent.
Example 6
Taking 235g of phenol, 168g of tetrapropylene and 14.1g of resin catalyst, adding the phenol and the catalyst into a flask, stirring and heating to 85 ℃, beginning to dropwise add the tetrapropylene, continuing to react for 2 hours at 85 ℃ after 0.5 hour of dropwise addition, filtering and separating a product and the catalyst while the product is hot after the reaction is finished to prepare a branched-chain dodecylphenol mixture, and performing reduced pressure rectification on the mixture to separate redundant phenol to prepare a branched-chain dodecylphenol product. According to the performance test method of the example 1, the conversion rate of the tetrapropylene in the reaction is 98.5 percent, and the selectivity of the branched dodecylphenol is 89 percent.
Example 7
Taking 235g of phenol, 168g of tetrapropylene and 16.45g of resin catalyst, adding the phenol and the catalyst into a flask, stirring and heating to 85 ℃, beginning to dropwise add the tetrapropylene, continuing to react for 2 hours at 85 ℃ after 0.5 hour of dropwise addition, filtering and separating a product and the catalyst while the product is hot after the reaction is finished to prepare a branched-chain dodecylphenol mixture, and performing reduced pressure rectification on the mixture to separate redundant phenol to prepare a branched-chain dodecylphenol product. According to the performance test method of the example 1, the conversion rate of the tetrapropylene in the reaction is 99.1%, and the selectivity of the branched dodecylphenol is 89.6%.
Analysis of the data from the above examples shows that when the molar ratio of phenol to tetrapropylene is 3: 1, when the catalyst amount accounts for 7 percent of the mass of the phenol, the conversion rate of the tetrapropylene and the selectivity of the branched-chain dodecylphenol are both better, and the following experiment is carried out by adjusting the reaction temperature according to the condition.
Example 8
282g of phenol, 168g of tetrapropylene and 19.74g of resin catalyst are taken, the phenol and the catalyst are firstly added into a flask, the temperature is raised to 85 ℃ by stirring, the tetrapropylene is dripped, the reaction is continued for 2 hours at the temperature of 90 ℃ after 0.5 hour of dripping is finished, the product and the catalyst are filtered and separated while the reaction is hot after the reaction is finished, a branched-chain dodecylphenol mixture is prepared, and redundant phenol is separated from the mixture by reduced pressure rectification, so that a branched-chain dodecylphenol product is prepared. According to the performance test method of the example 1, the conversion rate of the tetrapropylene in the reaction is 99.5 percent, and the selectivity of the branched dodecylphenol is 91 percent.
Examples9
282g of phenol, 168g of tetrapropylene and 19.74g of resin catalyst are taken, the phenol and the catalyst are firstly added into a flask, the temperature is raised to 85 ℃ by stirring, the tetrapropylene is dripped, the reaction is continued for 2 hours at the temperature of 95 ℃ after 0.5 hour of dripping, the product and the catalyst are filtered and separated while hot after the reaction is finished, a branched-chain dodecylphenol mixture is prepared, and redundant phenol is separated from the mixture by reduced pressure rectification, so that a branched-chain dodecylphenol product is prepared. According to the performance test method of the example 1, the conversion rate of the tetrapropylene in the reaction is 99.9 percent, and the selectivity of the branched dodecylphenol is 89 percent.
According to examples 8 and 9, it was found that the tetrapropylene conversion increased with increasing reaction temperature, without distinction in the selectivity of branched dodecylphenol, and even with a significant decrease above 95 ℃.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A process for preparing branched-chain dodecylphenol includes such steps as alkylating reaction on phenol and tetrapropylene in the presence of resin whose functional group is sulfonic acid group.
2. The process according to claim 1, wherein the molar ratio of phenol to tetrapropylene is (2-5): 1.
3. the method of claim 2 wherein the tetrapropylene has a C12 distribution of greater than 60 wt%.
4. The method according to claim 3, wherein the resin having the sulfonic acid group as the functional group has a particle diameter of 0.6 to 1 mm.
5. The method of claim 4, wherein the resin architecture is a styrene divinylbenzene copolymer.
6. The method of claim 5, wherein the resin is used in an amount of 5 to 15 wt% based on the mass of phenol.
7. The method of claim 6, wherein the resin is present in an amount of about 5 wt% to about 10 wt% based on the mass of phenol.
8. The process of claim 7, wherein the alkylation reaction temperature is from 70 ℃ to 100 ℃.
9. The method according to any one of claims 1 to 8, wherein the work-up method after the end of the alkylation reaction comprises filtration, washing and distillation under reduced pressure.
10. The method of claim 9, wherein the washing is: washing the reaction solution with hot water of 50-80 deg.c, and neutralizing the reaction solution with alkali solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114456042A (en) * | 2021-05-27 | 2022-05-10 | 广东新华粤石化集团股份公司 | Preparation method of p-dodecylphenol |
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