TW526204B - Process for preparing bis(3-t-butyl-4-hydroxyphenyl-2,4-di-t-butylphenyl)resorcinol diphosphate - Google Patents

Abstract

The invention relates to a process for preparing bis(3-t-butyl-4-hydroxyphenyl-2,4-di-t-butylphenyl) resorcinol diphosphate, which has characteristics of high conversion and high selectivity, and which comprises of charging sequentially phenolic compounds, phosphoryl chloride, catalyst and organic base, heating the reaction mixture for carry out a three-stage esterification reaction and improving the purity of the product through molecular designing; dissolving the product in an organic solvent and removing residual hydrochloride salt with a small amount of ammonia gas, thereby achieving the object of purification without generation of waste water and waste product.

Description

526204 A7 B7 ____— V. Description of the Invention (/) Bis- (3 " Third-Butyl-4-Ethylphenyl-2,4-Di-Third-Butylphenyl) Resorcinol Dicanister [ Bis (3-t-butyl-4-hydroxyphenyl, 2,4-di-t-butylphei ^ yl) resorcinol diphosphate (hereinafter referred to as HDP) is a compound of the same series in the manufacturing process, and its structural formula is OH-P-〇II 〇- ι > 1 (1¾Read the precautions on the back before filling this page} HDP is a reactive aromatic phosphorus flame retardant, suitable for bonding monomers such as epoxy resin. After polymerization, the finished product can maintain its physical properties and chemical properties. And weather resistance, the trend of environmentally friendly products in the future.

According to the literature, the synthesis methods of hydroxyl-reactive aromatic phosphorus-based flame retardants, including U.S. Patent Nos. 5,506,313 (1996) and 5,278,212 (1994), all propose that the product is a mixture with a low proportion of main ingredients, which has not been explicitly purified. The method is to wash the product with hydrochloric acid water; the main content is to show that after the reaction of a few base aromatic scale flame retardants, it 'slows down the changes in the chemical and physical properties of the finished product. } f \ 部 中 • Fire guide λ 1ί: Bamboo print The purpose of the present invention is to improve the purity of a single product, the reproducibility of the reaction and simplify the reaction steps, so as to provide the feasibility of mass production. In the present invention, vaporized phosphatidine, resorcinol and magnesium chloride are added to the reaction tank at one time, and the temperature of the reaction solution is heated to 80 to 100t. After 3 hours of reaction, excess phosphine chloride is distilled off; 2,4-bis- The third butyl phenol reacts with an organic base at 120 ~ 130 ° C. 2 This paper is a Chinese standard (CNS) A4 size (210X297 mm) 526204 A7 B7. Description of the invention (>hours; adding the third butyl p-catechol, and reacting at 120 ~ 130 ° C for 2 hours; the three-stage esterification reactions are all detected by a 31P nuclear magnetic resonance spectrometer. After the product is dissolved in an organic solvent, first Filter the organic hydrochloride, replace the remaining hydrochloride with vaporized ammonium with a small amount of ammonia, filter the vaporized ammonium, and evaporate the organic solvent to recover the HDP series compounds; the conversion rate is calculated by resorcinol It is as high as 100% of the theoretical value and the selectivity is more than 80%. According to the present invention, bis- (3-thirdbutyl-4-hydroxyphenyl-2,4-di-thirdbutylphenyl) The preparation of hydroquinone diphosphate (HDP) is carried out in a single kettle. The vaporized phosphorous phosphonium and a small amount of catalyst gasified magnesium are simultaneously added into the reaction tank. A condensation tube and a temperature probe are placed on the reaction tank, and the gas tube is connected to the condensation tube, and the hydrochloric acid can be introduced into the neutralization tank. The first stage heating temperature is 60 ~ 12 (TC, the esterification reaction is carried out at normal pressure, mainly mono-substitution (n = 1) and a small amount of di-substitution (n = 2), as shown in the following equation (!), The preferred temperature control is 80 ~ 10 (TC, a large amount of hydrochloric acid gas released from the reaction when the temperature is too high will take away the vaporized phosphine from the reaction tank; after about 3 hours, a reduced pressure (30 ~ 40mmHg) distillation of the Dong vaporized phosphine is recovered, and the temperature should not exceed 13 (TC to avoid reverse reactions. After about 3 hours, gasification is said after the hydrazone is no longer distilled out; return to room temperature and add 2,4-di-tert-butylphenol and double equivalent organic base for second-stage esterification. The reaction, as shown in the following equation (2), the temperature is controlled at 80 ~ 140 ° C, preferably 120 ~ 131TC for two hours.

Continue adding equivalent third butyl hydroquinone for the third-stage esterification reaction, as shown in the following equation (3), the temperature is controlled at 70 ~ 140 ° C, preferably 120 ~ 130 ° C. This paper is suitable for Sichuan China National Standard ^ 7 (CNS) A4 (210X 297 mm) (诮 Please read the notes on the back before filling out this page} 526204 A7 B7 V. Description of the invention (today) Two hours; After the completion of the three-stage esterification reaction, The end point of the reaction was determined by 31p nuclear magnetic resonance spectrometer test. After the reaction was completed, the product was dissolved in an organic solvent, and the hydrochloride of the organic base was filtered at room temperature, and then the unprecipitated hydrochloride was replaced with a small amount of ammonia gas. Ammonium chloride, filtered and evaporated to recover organic solvents to obtain HDP products. The entire reaction is based on resorcinol, with a conversion rate of up to 100% of the theoretical value and a selectivity of more than 80%. ⑴ POC 丨 3+ H0 ~ 〇H • 丨, ° 〇II (2) CI.P- I Cl 〇II (3) CI.P_ ό · 〇-

〇 II O-PfCI + HCI (g) Cl π = 1,2

〇 II-O-P-CI

OH-Cl + f r3n △ 〇 II CI-P- ^ 0- 〇 II -〇_P.

-CI + R 3 N * HCI

〇 II -0-P—CI +

OH 〇 R, N r ~ \ II Η0- < Π > -0-P- △ 〇

OH 〇

0 will be 0- 沐 〇 会 H

+ r3n * hci Example 1 Weigh 11 grams of resorcinol (0.1 mol) and 92 grams of phosphonium chloride (ο. 6 mol) (read the precautions on the back and write this page)

The size of this paper is stated in the Chinese National Standard (CNS) A4 specification (210X297 mm) 526204 A7 B7 ______ ^ V. Description of the invention (\ | >) and catalyst gasification magnesium 0.36 g (four thousandths of the weight of phosphorus rhenium) ), At the same time into a 250 ml reaction tank, a condenser tube and a temperature probe are placed on the reaction tank, the refrigerant in the condenser tube is maintained at 0 ° C, and an air pipe is connected to the neutralization tank above it; the temperature of the reaction solution rises to 65. (: Start the reaction from left to right, the temperature is maintained between 80 ~ 100 ° C, and the hydrochloric acid gas produced by the reaction will slow down after about an hour. After three hours, the reaction is almost complete, and the external calibration substance three (2-gas ethyl) is added to the sample. ) Soil acid vinegar, [abbreviated as TCEP 'tris (2-chloroethyl) phosphate] was detected with a 31P nuclear magnetic resonance spectrometer, and the conversion rate was converted from the relative integral value. After excess vaporized phosphine was recovered by vacuum distillation, the weight was 33. 36 Grams, and the theoretical calculated value of 33.33 grams, double proof of 100¾ conversion rate 继续 Continue the second stage of the esterification reaction, the intermediate product after distillation is calculated based on the relative integral value of 2,4-di-third butylphenol 37.66 grams (0.183 moles) 33.3 g (0.42 moles) of condensate; the condensing tube is condensed with water, the reaction temperature is maintained at 120 ~ 130 ° C for two hours, and the sample is detected by 31P nuclear magnetic resonance spectrometer. It is a di-substituted product, as shown in Table 1. Following the third stage of the esterification reaction, 31.66 g (0.19 mol) of tertiary butyl p-catechol was added, and the reaction temperature was maintained at 120-130 ° C for two hours, and samples were taken. 31P nuclear magnetic resonance spectrometer The product has been completely reacted into a tri-substituted HDP product. The product was dissolved in 150 g of toluene, and filtered at room temperature for hydrazone hydrochloride. After the toluene was recovered by distillation, a preliminary purified HDP product was obtained. The test values are shown in Table 2. 5 This paper uses the Chinese National Standard (CNS) A4 specification (210X297 mm) Kidney-(that is, read the precautions on the back before reading and writing this page) Order

526204 A7 B7 V. Description of the invention (/) P NMR acronym (ppm reference point is 85% H3P〇4) 31 P〇CI3

TECP 0 〇d〇 会 〇-ί-α ^ Cl

〇IIci-pH 〇II-P--Cl I Cl 2: 3.7ppm (s) 3.4ppm (s): 2.8ppm (s): -6.5ppm (s) and 2.8ppm fe) ⅡII.P · 0 〇〇II 〇-P-(〇) Ί〇Γ0_ ^ Τπ ° · ^ οη: -7ppm (s) and -1 8.6ppm (s): -18ppm (s) 〇II H〇-P-〇-

〇II, 〇-P-〇H: -12 ppm (s) Example two to four The first and third stage esterification reaction conditions are the same as in Example 1, only the temperature and time of the second stage esterification reaction are changed, As shown in Table 1. The size of this paper refers to the state Chinese National Standard (CNS) A4 specification (210X297 mm) (that is, read the precautions on the back before filling this page)

526204 A7 B7 ______ 5. Description of the invention (Examples 5 to 12) (The conditions for the first stage of the esterification are the same as those of the first embodiment for the second stage of the esterification.) The reaction was first dissolved in 150 ml of organic solvent at room temperature, containing 37.66 g (0.2183 mol) of 2,4-di-tert-butylphenol, and triethyl at 25 ° C or 0 ° C. 22.18 g (0.22 mol) of amine was dropped into the reaction solution, and the reaction was detected by a 31P nuclear magnetic resonance spectrometer after 16 hours or 1 hour of reaction. The conversion and selectivity were converted from the relative integral values, as shown in Table 1. Continue the third-stage esterification reaction, add 31.66 g of tert-butylhydroquinone (0.19 mol) to the solution, and drop in 19.19 g (0.19 mol) of triethylamine at 25 ° C. After 16 hours of reaction, the triethylamine hydrochloride was filtered and detected by a 31P nuclear magnetic resonance spectrometer. It was completely converted into HDP and its derivatives (75 ~ 90%) and bis- (2, 4-di-tert-butylbenzene). Group) resorcinol diphosphate [Bis (2,4-di-1-butylphenyl) resorcinol diphosphate] (10 ~ 25¾ Example 13 The three-stage esterification reaction conditions are the same as in Example 1, and it is soluble in toluene only when purified After filtering the bite hydrochloride, a small amount of ammonia gas was passed in. After the solution turned red in about 5 minutes, the ammonia gas was stopped, the gasification of ammonium was filtered, and the toluene was recovered. The product test values are shown in Table 2. Example Fourteen Three The stage esterification reaction and purification conditions were the same as in Example 1. Only the organic solvent was changed to ethyl acetate, and the product test values are shown in Table 2. 7 > Paper size Shizhou 1113 standards (〇 ^) / \ 4 specifications (210乂, 297 mm) 526204 A7 B7 __ ............... ......——-'r " * _ I.-Description of the invention (") Examples The esterification reaction and purification conditions in the fifth and third stages were the same as those in the thirteenth implementation. Only the organic solvent was changed to ethyl acetate. %) mm) This b-pyridine (none) me 2 tree 100 94 ipsm ^ site bite (none) lore 4 stele gQ 85-* JL ·, f Xife & 'JH. ctb-pyridine (none) 7〇rc 100 89 site》 Bite (none) 25TC 18 hours 95 91 triethylamine (acetic acid triturate) 25iC 16 tree 100 88 triethylamine (propyl 25 ° C 16 tree 91 90 triethylamine (ethyl 25t 16 tree 95 77 tml) · ^ Triethylamine (Digas methyl tiger) 25TC 16 tree 95 78 timh, triethylamine (ethyl acetate) 0 ° C 1 tree 89 80 tmyt triethylamine (propyl) 0 ° C 1 to 90 60 mm— Triethylamine (Ethylamine 0 ° C for 1 hour 93 83 Triethylamine (Dimethylethane) ore 1 94 94 Note: Selectivity refers to the ratio of the product of Equation (2). 8 Chinese National Standard (CNS) A4 specification (21〇 乂 297 public attack) ----------- (Read the precautions on the back before writing this page)

, 1T

526204 A7 B7 Table 2. Product test values Color phosphorus content (¾) Gas content (ppm) Several base values (meq / g) Example 1 Light yellow 6.46 1220 1.48 Example 13 light yellow 6.43 245 1.53 Example 14 light Yellow 6.48 8000 1.61 Example 15 Light yellow 6.38 30 L56 Read the precautions on the back before writing this page

、 1T This paper is compliant with China National Standard (CNS) Α4 specification (210X297 mm)

Claims (1)

526204 A8 B8 C8 D8 VI. Patent application scope 1 ~ 1 · 2 times equivalent. 5. The manufacturing method according to item 1 of the scope of patent application, wherein the organic solvent in step (4) is toluene, xylene, ethyl acetate, butyl acetate, and the like. 6 · The method according to item 5 of the scope of patent application, wherein the amount of organic solvent is 5 times the weight of the product. (Please read the notes on the back before this page) 1 #!-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210X297 mm)