CN1104404C - Instytut Ciezkiej Syntezy Organicznej - Google Patents
Instytut Ciezkiej Syntezy Organicznej Download PDFInfo
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- CN1104404C CN1104404C CN97113188A CN97113188A CN1104404C CN 1104404 C CN1104404 C CN 1104404C CN 97113188 A CN97113188 A CN 97113188A CN 97113188 A CN97113188 A CN 97113188A CN 1104404 C CN1104404 C CN 1104404C
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- alkylphenol
- phenol
- alkylation
- alkene
- alkyl phenols
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Abstract
The present invention provides method of obtaining alkyl phenols of light and stable color with phenol and alkene using acid, sulfonic acid ion exchanging resin activator in terms of alkylation method, wherein, the phenol is alkylation processed with alkene in existence of not more than 1 percent (weight) water and 0.5-100 ppm2,4,6-tri-tert-butylphenolato, and alkyl phenols is obtained by distillation from mixture after reaction in existence of at most 15ppm sodium hypophosphite (NaH[2]PO[2]) and 5-100ppm di-substituted hydroxylamine ramification with the general formula of NR[2], in the formula, R[1] and R[2] are alkyl substituent [CH[3]-(CH[2])n-], wherein n is not less than 1, or when one of R[1] or R[2] substituents is benzyl substituent (C[6]H[5]CH[2]-), then added into distilled alkyl phenols at temperature not higher than 100 DEG C.
Description
Theme of the present invention is a method of making the alkylphenol with light colour stable when storing.After just reclaiming, has light colour with the sulfonic acid ion exchange resin catalytic alkylation and by the alkylphenol that distillation obtains from phenol and a kind of alkene.In the process of standing storage, the color of alkylphenol is the armpit look gradually, and this is a kind of important disadvantages and usually hinders product further to use.This change of alkylphenol color is likely owing to being brought out by light and temperature in the presence of oxygen and reacts, and relevant with contained trace impurity in the finished product.
The method of the decolouring of the many alkylphenols in this area and colour stable effect is well-known.Can be used for decolouring and the colour stable of alkylphenol together with other material with oxalic acid and sodium hypophosphite or potassium hypophosphite or with a kind of mixture of Hypophosporous Acid, 50 according to Poland Patent 100082 specification sheetss, the above-mentioned weight ratio that adds in post reaction mixture or the alkylating phenol to the component of 0.01-2% (weight) is 1: 5 or 5: 1.
According to another Poland Patent No.131609 specification sheets, the decolouring of alkylphenol and colour stable effect are by using consumption to be 1-200 as the said components weight ratio of 0.005 to 3% (weight) of alkylphenol weight: 1 the Resorcinol and the mixture of oxalic acid are realized.
With this best situation, the application of aforementioned stable agent is product (nonyl phenol) color of 40 ° of Hz, but when storing further degeneration will be arranged.
According to U.S. Patent No. AP4386224 specification sheets, with the N of 5-50ppm, the N-diethyl hydroxylamine can realize containing C
8-C
13The colour stable effect of monoalkyl phenol of alkyl.After at room temperature preserving 50 days, did the nonylphenol that colour stable is handled with the method for this invention, its color changes to 35 ° of Hz from 20; 60 ℃ stored for 7 weeks after, its color is 45 ° of Hz, 25 ℃ of storages after 31 days, the color that is added with the 4-dodecylphenol after the agent of 20ppm aforementioned stable is stable (65 ° of Hz); 4-dodecylphenol color 60 ℃ of identical times of storage is increased to 110 ° of Hz.
The objective of the invention is to develop a kind of acquisition long storage (being not less than 90 days) and the method for the stable alkylphenol of light colour at high temperature.If after storing the above-mentioned time, the nonyl phenol color is lower than 30 ° of Hz and the dodecyl phenol color is lower than 50 ° of Hz, and then the color of alkylphenol is considered to stable.
Main points of the present invention are in the method that phenol usefulness olefin alkylation in the presence of the acid sulfonic acid ion exchange resin is arranged, and use this method, at water that is no more than 1.0% (weight) and 0.5-100ppm2, and 4, the 6-tri-tert-butyl phenol exists realizes alkylation down.Adding at the most, the 15ppm sodium hypophosphite reclaims product through vacuum distilling.The alkylphenol product that reclaims is mixed mutually with 5-100ppm two substituted hydroxylamine derivatives not being higher than under 100 ℃ the temperature.This hydroxylamine derivative has two alkyl substituents or an alkyl substituent and a benzyl substituting group.
With the alkylphenol that has stable light colour under the inventive method energy production long storage condition.When the possibility that alkylphenol is had effective colour stable effect is studied, be surprised to find that, only carrying out the phenol alkylation with alkene and distilling as mentioned above under the situation that the condition of alkylphenol is met, by the product colour stability of using two substituted hydroxylamine derivatives to obtain to require.
Example I-VII:
In a flow reactor of filling, carry out the phenol alkylated reaction with the macropore of sulfo group styrene diethylene benzene copoly mer form and gel-type ion-exchange resin.Comprise in the reaction system of reactor and circulation vessel by under 60-150 ℃, making one by phenol, alkene, water, 2,4, the mixture that 6-tri-tert-butyl phenol (TTBF) and alkylphenol constitute is by the cation exchanger bed, obtain the alkylphenol concentration of requirement like this, thereby carry out this technology in a continuous manner.The post reaction mixture that vacuum distilling obtains in the presence of sodium hypophosphite and reclaim product.In this product, add azanol.The kind and the consumption of used azanol see Table 2.
Table 1 has shown condition and the product colour that obtains alkylphenol.
Table 2 has shown the holding conditions and the final color thereof of the alkylphenol after the stabilization treatment.
Table 1
| Embodiment number | Alkylating agent | Alkylation conditions | NaH 2PO 2Add-on (distillation before) (ppm) | The color of alkylphenol | |
| Water-content (% weight) | TTBF content (ppm) | 〔°Hz〕 | |||
| I | Tripropylene | 0.1 | 12 | 10 | 5 |
| II | Tripropylene | 0.4 | 0.5 | 5 | 10 |
| III | Tripropylene | 0.4 | - | 15 | 10 |
| IV | Tripropylene | 0.5 | 8 | - | 15 |
| V | Tetrapropylene | 0.2 | 100 | 9 | 40 |
| VI | Tetrapropylene | 0.6 | 5 | - | 65 |
| VII | Tetrapropylene | 0.3 | - | 12 | 45 |
Table 2: alkylphenol colour stability
| Project | Alkylphenol according to Table I embodiment acquisition | Priming color (Hz) | Stablizer | Storage requirement | Final color (° Hz) | ||
| Type | Consumption (ppm) | Temperature (℃) | Time (moon) | ||||
| 1 | Nonyl phenol, example I | 5 | DEHA *) | 10 | 20 | 6 | 10 |
| 2 | Nonyl phenol, example I | 5 | EBHA **) | 30 | 60 | 3 | 20 |
| 3 | Nonyl phenol, example II | 10 | DEHA | 10 | 20 | 6 | 10 |
| 4 | Nonyl phenol, EXAMPLE III | 10 | DEHA | 20 | 20 | 6 | 70 |
| 5 | Nonyl phenol, EXAMPLE IV | 15 | EBHA | 5 | 20 | 6 | 30 |
| 6 | 4-dodecylphenol, EXAMPLE V | 40 | EBHA | 50 | 20 | 6 | 40 |
| 7 | 4-dodecylphenol, EXAMPLE V | 40 | DEHA | 100 | 50 | 3 | 45 |
| 8 | 4-dodecylphenol, example VI | 65 | EBHA | 10 | 20 | 6 | 220 |
| 9 | 4-dodecylphenol, example VI | 45 | DEHA | 75 | 20 | 3 | 150 |
*)N, the N-diethyl hydroxylamine
*) N, N-Ethylbenzyl azanol
Claims (1)
- By phenol and alkene by obtain to have the method for the alkylphenol of stable light colour with alkylation with acid, sulfonic acid ion exchange resin catalyzer, wherein be no more than 1 weight % water and 0.5-100ppm2,4, the 6-tri-tert-butyl phenol exists down makes the phenol alkylation with alkene, in the presence of 15ppm sodium hypophosphite at the most, from react the back mixture, reclaim alkylphenol and be not higher than that the 5-100ppm general formula is NR under 100 ℃ the temperature with this by distillation 1R 2The two substituted hydroxylamine derivatives of OH are added in the distilled alkylphenol R in the general formula 1And R 2Be alkyl substituent CH 3-(CH 2) n-, n in the formula 〉=1 or R 1Or R 2One of substituting group is benzyl substituting group C 6H 5CH 2-.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL31453996A PL181855B1 (en) | 1996-05-28 | 1996-05-28 | Method of obtaining alkyl phenoles of light and stable colour |
| PLP-314539 | 1996-05-28 | ||
| PLP314539 | 1996-05-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1167749A CN1167749A (en) | 1997-12-17 |
| CN1104404C true CN1104404C (en) | 2003-04-02 |
Family
ID=20067660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97113188A Expired - Fee Related CN1104404C (en) | 1996-05-28 | 1997-05-27 | Instytut Ciezkiej Syntezy Organicznej |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1104404C (en) |
| PL (1) | PL181855B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386224A (en) * | 1981-08-31 | 1983-05-31 | Monsanto Company | Color stabilization of monoalkyl phenols |
| CN1096287A (en) * | 1993-04-05 | 1994-12-14 | 通用电气公司 | To using the method for Hypophosporous Acid, 50 stable prod color and luster in the cumylphenol production |
-
1996
- 1996-05-28 PL PL31453996A patent/PL181855B1/en not_active IP Right Cessation
-
1997
- 1997-05-27 CN CN97113188A patent/CN1104404C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386224A (en) * | 1981-08-31 | 1983-05-31 | Monsanto Company | Color stabilization of monoalkyl phenols |
| CN1096287A (en) * | 1993-04-05 | 1994-12-14 | 通用电气公司 | To using the method for Hypophosporous Acid, 50 stable prod color and luster in the cumylphenol production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1167749A (en) | 1997-12-17 |
| PL181855B1 (en) | 2001-09-28 |
| PL314539A1 (en) | 1997-12-08 |
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