phosphorylated alkylphenol/phenol ester mixtures in which the weight ratio of the alkyl moiety to the phenol moiety ranges from 0.05 to about 0.65, and the number of carbon atoms per alkyl moiety ranges from 3 to 16, preferably from 3 to 12, which mixtures have satisfactory viscosity range and impart to polymeric materials and especially to polyvinylchloride plasticized therewith good light and heat stability; a process for producing such phosphorylated alkylphenol/phenol ester mixtures; and polymeric materials plasticized therewith.
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1. A triaryl phosphate composition consisting essentially of a phosphorylated . .alkylphenol/phenol.!. isopropyl phenol/phenol ester mixture wherein the weight ratio of the . .alkyl.!. isopropyl moiety to phenol moiety ranges from 0.05 to about 0.65 . .and the number of carbon atoms per alkyl moiety ranges from 3 to 16.!. which ester is prepared by steps comprising:
(a) alkylating at a temperature of from about 15° to 250° C in the presence of a lewis acid or a bronsted acid as catalyst, phenol . .with an alkylating agent selected from the group consisting of alkyl halides in which the alkyl group is a C1 to C6 straight- or branched-chain alkyl or a C6 to C12 cycloalkyl, C1 to C6 alkanols, and C3 -c16 olefins,.!. with propylene to obtain an . .alkylated phenol.!. isopropyl phenol/phenol reaction mixture having 0.05 to about 0.65 by weight of isopropyl moiety per phenol moiety, and (b) reacting at a temperature of from about 15° to 250°C in the presence of a lewis acid as catalyst, said . .alkylated phenol.!. isopropyl phenol/phenol reaction mixture with a phosphorylating agent selected from the group consisting of phosphorous oxychloride, phosphorous oxybromide and phosphoric acid. . .
2. A composition as defined in
alkyl moiety is an isopropyl moiety..!. 4. A composition as . .claimed.!. defined in claim 1, wherein the phenol starting material is phenol derived from the decomposition of cumene hydroperoxide, or from the sulphonation of benzene, and is in a form free or substantially free from alkylated phenols. 5. A composition as claimed in claim 1, wherein the . .proportion.!. weight ratio of . .alkylating agent.!. alkyl moiety to phenol moiety is within the range of from . .10%.!. #x2205;1 to . .40% by weight based on the weight of the phenol.!.#x2205;4. . .6. A composition as claimed in claim 1, wherein the alkylating agent is propylene, isobutylene or di-isobutylene..!. 7. The product of claim 1 wherein at least part of the alkylation catalyst is removed from the alkylation reaction mixture prior to phosphorylation. 8. A composition according to
9. A composition according to
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This is a reissue application of U.S. Pat. No. 3,576,923 which matured from Ser. No. 645,888, filed June 14, 1967. 28
940 parts of phenol were placed in a reactor fitted with stirrer, dropping funnel, thermometer and reflux condenser. 10 parts of concentrated sulphuric acid were added and the reactor was heated to 100°C 280 parts of caprylene were added dropwise over a period of 1 hour and the reaction mass was then maintained at 100° to 105°C for a further 4 hours. The excess sulphuric acid was neutralized by stirring the reaction mixture with 11 parts of solid sodium carbonate at 100° to 105°C for 2 hours and the solid was removed by filtration after cooling. To the filtrate, which was 1124 parts of a mixture of phenol and capryl phenols, was added 41 parts of androus aluminium chloride, followed by 495 parts of phosphorus oxychloride added over a period of 45 minutes while maintaining the reaction mixture at 50°C The recovery procedure described in Example 1 was then followed.
The ester product, consisting of triphenyl phosphate and mixed phosphates derived from both phenol and capryl phenols, was a pale yellow oil boiling over the range 168° to 280°C at 0.2 millimeter of mercury pressure. It had acid value 0.2 and amounted to 1092 parts.
376 parts of phenol were placed in a reactor fitted with stirrer, dropping funnel, thermometer and reflux condenser. 0.06 part of perchloric acid (specific gravity 1.70) were added and the mixture heated to 45°C 109 parts of cyclohexene were added dropwise over a period of 1 hour maintaining the reaction temperature at 45°C The mixture was stirred at 45°C for a further 1 hour, and then unreacted cyclohexene (amounting to 17 parts) was removed by distillation at 12 millimeters of mercury pressure.
17 parts of anhydrous aluminium chloride were added, followed by 215 parts of phosphorus oxychloride, added over a period of 45 minutes while maintaining the reaction mixture at 50°C The resulting mixture was gradually heated to 150°C over 4 hours and was then maintained at 150°C for a further period of 4 hours.
To the resulting product, after cooling, were added 600 parts by volume of toluene and the mixture was washed with a mixture of 40 parts by volume of concentrated hydrochloric acid and 800 parts by volume of water for 30 minutes at 60°C and then with a mixture of 20 parts by volume of concentrated hydrochloric acid and 800 parts by volume of water for 10 minutes at 60°C This acid washing was then followed by a five-fold washing with 800 parts by volume of water for 10 minutes at 60° C. The toluene present was then removed by distillation and the product subjected to fractional distillation.
The fraction distilling over at boiling range 182° to 250°C at 0.1 millimeter of mercury pressure, amounting to 388 parts, was collected. The fraction was washed, firstly, with a mixture of 12 parts 46% sodium hydroxide solution and 530 parts of water for 3 hours at 40°C and, secondly, with a mixture of 6 parts of 46% sodium hydroxide solution and 530 parts of water for 1 hour at 40°C This alkali wash was then followed by washing twice with 800 parts of water for 30 minutes at 40°C to remove any sodium hydroxide present. The resulting product was dried by heating at 95° to 100°C at 12 to 15 millimeters of mercury pressure.
The phosphate ester produced was pale yellow, oily liquid consisting of a mixture of triphenyl phosphate, and mixed phosphates derived from both phenol and cyclohexyl phenols, and had an acid value of less than 0.1.
Randell, Donald R., Pickles, Wilfred
| Patent | Priority | Assignee | Title |
| 4280945, | Nov 05 1979 | AKZO AMERICA INC , A CORP OF DE | Vinyl chloride compositions plasticized with meta-tertiary-butylphenyl diphenyl phosphate |
| 4351780, | Dec 09 1980 | AKZO AMERICA INC , A CORP OF DE | Process for preparing isopropylphenyl/phenyl phosphate |
| 4378320, | Nov 05 1979 | AKZO AMERICA INC , A CORP OF DE | Meta-tertiary-butylphenyl diphenyl phosphate |
| 4539134, | Dec 02 1982 | Halliburton Company; HYDROCHEM INDUSTRIAL SERVICES, INC | Methods and cleaning compositions for removing organic materials from metallic surfaces |
| 5206404, | Apr 27 1992 | PABU SERVICES, INC | Triaryl phosphate ester composition and process for its preparation |
| Patent | Priority | Assignee | Title |
| 1425393, | |||
| 2071323, | |||
| 2226336, | |||
| 2450903, | |||
| 2473612, | |||
| 2802884, | |||
| 3071549, | |||
| 3553155, | |||
| UK818048, | |||
| UK890642, | |||
| UK992629, | |||
| UK992630, |
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