GB2120953A - Catalyst for the production of alkyl phenols - Google Patents
Catalyst for the production of alkyl phenols Download PDFInfo
- Publication number
- GB2120953A GB2120953A GB8314161A GB8314161A GB2120953A GB 2120953 A GB2120953 A GB 2120953A GB 8314161 A GB8314161 A GB 8314161A GB 8314161 A GB8314161 A GB 8314161A GB 2120953 A GB2120953 A GB 2120953A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- phenol
- ester
- alkyl
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0259—Phosphorus acids or phosphorus acid esters comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/049—Pillared clays
Abstract
A catalyst for the reaction of an olefine which has 3 to 16 carbon atoms with phenol comprises an expanding layer clay and a mono- or di-ester of a phosphoric or phosphorous acid. The catalyst achieves a high selectivity in the production of para alkyl phenols.
Description
SPECIFICATION
Production of alkyl phenols
The present invention is concerned with the production of alkyl phenols.
Alkyl phenols, for example octyl phenol are usually made by reaction of olefines for example di-isobutene with phenol. Di-isobutene is a mixed C8 product produced by dimerisation of isobutene and consists mainly of 2,4,4-trimethyl pentene-1 and -2. The reaction of di-isobutene with phenol produces a mixture of substituted phenols, primarily the desired 4-octylphenol with 2-octylphenol and 2,4-dioctylphenol as by-products.
Various catalysts have been proposed for the reaction of an olefine with a phenol to produce an alkyl-phenol, which catalysts include toluene sulphonic acid, various activated clays; boron trifluoride, sulphuric acid and various sulphonated resins. One catalyst which has been used is the combination of phosphoric acid and fullers' earth. With this catalyst, a relatively high selectivity towards 4-octylphenol may be achieved but it is still necessary either to carry out a distillation to remove the above by-products or to accept a lower quality octylphenol containing such by-products. There is therefore an incentive to devise a process of higher selectivity towards 4-octylphenol.
According to the present invention, a catalyst for the reaction of an olefine which has 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms, and is preferably tertiary, with phenol comprises, in combination, an expanding layer clay and a mono- or diester or orthophosphoric or phosphorous acid.
Expanding layer clays are quite widely used in the chemical industry and are readily available products.
They are usuallyvermiculites, halloysites and especially montmorillonites, among which latter the bentonites are especially of value. Our preferred catalyst combination uses fullers' earth.
The ester which is used may, as indicated, be a mono- or diester and is an ester of either orthophosphoric acid or phosphorous acid. Thus it will include in its structure an acidic hydrogen atom. The ester may be an alkyl ester or an aryl ester and, in the case of a diester, the alky or aryl groups may be the same or different or the ester may be an alkyl aryl ester. Each alkyl or aryl group may contain for example 1 to 20 and preferably 1 to 8 carbon atoms. Mixtures of esters may also be used, for example a mixture of a monoester with the corresponding diester.
Suitable esters for use in the catalyst include mono- and dimethyl phosphate and phosphite; mono- and diethyl phosphate and phosphite; mono- and di- n-butyl, sec. butyl and tert. butyl phosphate and phosphite; mono- and diphenyl phosphate and phosphite; methyl ethyl phosphate and phosphite; and the alkyl phosphates and phosphites in which the or each alkyl group contains 5 to 7 carbon atoms.
In reacting an olefine for example di-isobutene with phenol using the improved catalyst according to the present invention, it is preferred that the molar ratio of the two reactants should be such that the phenol is in molar excess. However, because by using this catalyst the selectivity towards the mono-substituted phenol product is high, it is not necessary to use a large excess of phenol so as to inhibit formation of di-alkyl phenols. Thus the molar ratio of phenol to olefine is preferably greater than one to one and may amount to two to one or more but a preferred molar ratio is in the range 1:1 to 1.5:1 and more preferably in the range
1:1 to 1.2:1.
The quantity of catalyst clay employed in the reaction may usefully amount to 0.5 to 5 per cent by weight,
based on the weight of phenol, and is preferably in the range 0.5 to 2 per cent, especially about 1 per cent, by weight.
The weight of ester employed is most easily expressed in terms of a phosphoric acid equivalent, based on the number of free acid hydrogen atoms in the ester. In other words, for calculating the weight of ester, it is convenient to regard three moles of di-ester as being equivalent to 2 moles of the corresponding mono-ester or one mole of the corresponding acid. On this basis, the weight of ester employed is usefully such as corresponds to a weight of acid of 10 to 10,000 parts per million (ppm), based on phenol, especially 500 to
5,000 ppm.
The conditions under which the reaction is carried out may be those conventionally used. The reaction is
exothermic and the temperature may therefore be controlled by the rate of addition of the reactants and/or
by the provision of cooling. In general, the temperature may be maintained between 30 and 90"C, preferably at a level of about 700C.
The alkyl phenol produced by the reaction may be separated from by-products, unreacted starting
materials and catalyst by distillation, leaving soldi catalyst behind in the still bottoms. As an alternative, the
solids may be removed by filtration before a distillation step in which unwanted components of the reaction
mixture are distilled off overhead, the product with minor amounts of impurities being the bottoms product from the distillation.
The invention will now be further described by means of the following Examples:
Examples 1 to 7
In Examples 1 to 6,375 g of phenol, 3.8 g of fullers' earth and the weight of phosphate or phosphite ester
indicated below were placed under nitrogen in a one-litre flask equipped with a mild steel stirrer. 418.3 g of
di-isobutene was added continuously over a period of about 4 hours and the reaction mixture was stirred for
a further hour while the temperature was held unchanged. The mixture was then cooled by about ten degrees and filtered to remove solid catalyst.
Example 7 represents a conventional process using phosphoric acid and fullers' earth and is included for the purpose of comparison. The example was in fact carried out in a 5-litre flask fitted with a stainless steel stirrer and using in each case five times the quantity of reactants used in the other examples, with 1.2 g of 82% phosphoric acid. However, to aid comparison, the weight of acid and the total weight of octyl phenols produced have been divided by five for inclusion in the following table.
TABLE 1
Wt% of products in octyl
Wt. of Reaction Wt. of Phenols mixture
Example Catalyst ester Catalyst Temp. octyl phenols
No. (g) ( C) (g) 2-octyl 4-octyl 2,4-dioctyl phenol phenol phenol 1 Di-n-butyl phosphate 1.0 73 551.64 1.45 96.62 1.93 2 Monophenyl .524 72 632.76 0.88 98.36 0.76 3 Monophenyl phosphate .524 70-72 622.12 0.20 99.02 0.78 4 Diphenyl phosphate 1.0 73 556.49 1.14 96.78 2.08 5 Diethyl phosphite 1.0 72 190.71 2.17 97.04 0.79 6 70% monoethyl phosphate 0.43 72 661.73 1.22 97.28 1.50 30% diethyl phosphate 7 (Phosphoric acid) 0.24 73 619.28 0.97 95.08 3.95 As will be seen, the catalyst according to the present invention is more selective towards the production pf 4-octyl phenol than is the conventional catalyst with in several cases an equivalent or improved total yield of octyl phenols.
Example 8
Phenol (375 g), fullers' earth (9.5 g) and phosphoric acid (0.35 g of 85% H3PO4) or the equivalent as described above of mono- or di-phenyl phosphate were placed under nitrogen in a flask equipped with a stirrer. Propylene trimer (436.5 g) was added continuously over a period of about 3 hours at a temperature of 92"C and stirred at that temperature for a further 1 hour. The reaction product after removal of the catalyst had the following composition in percentages by weight.
TABLE 2
Catalyst 2-n on yl 24-dinonyl phenol phenol H3PO4Fullers' Earth 3.4 4.3 (average of two
preparations) C6H5H2PO4/Fullers' Earth 3.3 1.9 (C6H5)2HPO4/Fullers' Earth 3.5 2.5
The balance of the reaction product was approximately 13% phenol, 5% unreacted nonenes, 1% ethers the rest being essentially 4-nonyl phenol.
The above results show an increased selectivity of reaction to the production of 4-nonyl phenol when catalysts according to the invention are used.
Claims (14)
1. A catalyst for the reaction of an olefine with phenol which comprises an expanding layer clay and a mono- or di-ester of ortho-phosphoric or phosphorous acid.
2. A catalyst as claimed in claim 1 in which the expanding layer clay is fullers' earth.
3. A catalyst as claimed in claim 1 or 2 in which the mono- or di-ester of orthophosphoric or phosphorous acid is an alkyl, aryl or alkyl aryl ester each alkyl or aryl group containing 1 to 8 carbon atoms.
4. A process in which the alkyl phenol is produced by reacting an olefine which has 3 to 16 carbon atoms with phenol in the presence of a catalyst as claimed in any preceding claim.
5. A process as claimed in claim 4 in which the olefin is di-isobutene.
6. A process as claimed in claim 4 or 5 in which the phenol is present in molar excess.
7. A process as claimed in claim 6 in which the molar ratio of phenol to olefine is in the range 1:1 to 1.5:1.
8. A proces as claimed in any of claims 4 to 7 in which the quantity of catalyst clay is 0.5 to 5% by weight based on the weight of the phenol.
9. A process as claimed in any of claims 4 to 8 in which the weight of ester present corresponds to a weight of acid as hereinbefore described of 500 to 5,000 parts per million based on the phenol.
10. A process as claimed in any of claims 4to 9 whenever carried out at a temperature in the range 30 to 90"C.
11. A process as claimed in any of claims 4 to 10 whenever carried out substantially as described in any of Examples 1 to 7.
12. A catalyst as claimed in any of claims 1 to 3 which is substantially as described in any of Examples 1 to7.
13. A process as claimed in any of claims 4 to 10 whenever carried out substantially as described in the experiment of Example 8.
14. A catalyst as claimed in any of claims 1 to 3 substantially as described in ExampleS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8314161A GB2120953B (en) | 1982-06-01 | 1983-05-23 | Catalyst for the production of alkyl phenols |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8215862 | 1982-06-01 | ||
| GB8314161A GB2120953B (en) | 1982-06-01 | 1983-05-23 | Catalyst for the production of alkyl phenols |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8314161D0 GB8314161D0 (en) | 1983-06-29 |
| GB2120953A true GB2120953A (en) | 1983-12-14 |
| GB2120953B GB2120953B (en) | 1986-02-12 |
Family
ID=26282997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8314161A Expired GB2120953B (en) | 1982-06-01 | 1983-05-23 | Catalyst for the production of alkyl phenols |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2120953B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2179563A (en) * | 1985-07-27 | 1987-03-11 | British Petroleum Co Plc | Use of modified layered clay catalysts in reactions capable of catalysis by protons |
| US5334775A (en) * | 1993-06-02 | 1994-08-02 | Exxon Chemical Patents Inc. | Polymer Alkylation of hydroxyaromatic compounds |
| CN1088625C (en) * | 1995-12-06 | 2002-08-07 | 南京师范大学 | Catalyst series for synthesizing 1-,2- and 3- substituted alkylphenols with different proportion by one-step process |
-
1983
- 1983-05-23 GB GB8314161A patent/GB2120953B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2179563A (en) * | 1985-07-27 | 1987-03-11 | British Petroleum Co Plc | Use of modified layered clay catalysts in reactions capable of catalysis by protons |
| US5334775A (en) * | 1993-06-02 | 1994-08-02 | Exxon Chemical Patents Inc. | Polymer Alkylation of hydroxyaromatic compounds |
| CN1088625C (en) * | 1995-12-06 | 2002-08-07 | 南京师范大学 | Catalyst series for synthesizing 1-,2- and 3- substituted alkylphenols with different proportion by one-step process |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8314161D0 (en) | 1983-06-29 |
| GB2120953B (en) | 1986-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7351339B2 (en) | Method for the separation of acids from chemical reaction mixtures by means of ionic fluids | |
| CA2508337C (en) | A selective synthesis of organophosphites | |
| US3061621A (en) | Process for producing carboxylic acids from olefins, carbon monoxide and water | |
| US3036132A (en) | Production of organophosphorus compounds | |
| US2728790A (en) | Catalyzed process for preparation of phosphates and phosphites | |
| US6232485B1 (en) | Production of phosphate esters | |
| US3152164A (en) | Novel cyclic phosphite esters and process involving transesterification of a phosphite diester with a glycol | |
| US2745863A (en) | Preparation of alkaryl phosphoric acids | |
| US4532368A (en) | Process for making meta- and para-alkylphenols | |
| GB2120953A (en) | Catalyst for the production of alkyl phenols | |
| US2716657A (en) | Method of producing orthophosphoric acid esters | |
| EP0008164B1 (en) | Phosphinites and phosphonites, their preparation and use as acrylonitrile dimerisation catalysts | |
| EP0054986A1 (en) | A process for the hydroformylation of olefins | |
| US2470190A (en) | Production of olefin polymers | |
| US3318982A (en) | Process for the manufacture of mixtures of acid orthophosphoric acid esters | |
| US5344951A (en) | Production of alkyl phosphites | |
| EP0347835A2 (en) | Process for preparing aryl-ethyl phenols having one or more alkyl substituents in the ethyl group and their use | |
| US2786878A (en) | Olefin polymerization process | |
| US4443384A (en) | Process for the manufacture of mixed phosphoric acid ester compositions | |
| US4414161A (en) | Process for producing low temperature stable tert-butylphenyl diphenyl phosphate | |
| US2863900A (en) | Synthesis of organic phosphorus compounds | |
| EP0226110A1 (en) | Improved process for preparing bis(dialkylphenyl)pentaerythritol diphosphites | |
| US3128296A (en) | Organic phosphinyloxyaluminum compounds and the preparation thereof | |
| EP0039218B1 (en) | Improvement in process for the alkylation of benzene with propylene | |
| US2758143A (en) | Olefin polymerization process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930523 |