TW492973B - Process for preparing a mixture of amino-containing phosphazenes - Google Patents

Abstract

The present invention provides a process for preparing a mixture of amino-containing phosphazenes having the following general formula (I) by reacting a (NPCl2)n phosphazene mixture with NH3 and HOR to proceed amination and esterification in the presence of a tertiary amine catalyst: NnPn(NH2)x(OR)2n-x (I), wherein 10 ≥ n ≥ 3, 1 ≤ x < 2n, and R is phenyl or C3-C6 alkyl. In addition to simultaneously carrying out amination and esterification, the process of the present invention also simultaneously performs a regeneration of the catalyst, thereby greatly reducing the processing procedures and reaction time. Furthermore, the invented process is a water-free process without the problem of a large quantitied waste water. Ammonium chloride, a by-product of the invented process, can be recovered and reused.

Description

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 492973 A7 B7 V. Description of the Invention (1) Field of the Invention The present invention relates to a mixture of amine-containing phosphazene compounds that can be used as a hardener and a flame retardant for a resin at the same time. Preparation method, in particular, related to the anhydrous preparation of a mixture of amine-containing phosphazene compounds. BACKGROUND OF THE INVENTION Phosphazenes are a general term for compounds containing a phosphorus-nitrogen double bond structure (-P = N-), and their general molecular formula Expressed as [NPR'2] n, η 値 -3. With the change of R ', such compounds can be derived into tens of millions of different compounds. Except that R 'is different, the structural formula 尙 can be classified into a cyclic compound or a linear compound. When η = 3, its structure is like a benzene ring hexagonal plane compound. When η = 4, it is an octagonal cyclic compound. At present, the cyclic compounds that can be identified more clearly have a maximum η 値 of 10. Compounds of ng 3 may also exist as linear chains. Phosphazene compounds have been considered as potential flame retardants due to their multiplicative effects of phosphorus and nitrogen. When R is a group having an active hydrogen, such as an amine group and a hydroxyl group, it can be used to cure a resin having a functional group capable of reacting with the active hydrogen, such as a polyurethane resin and an epoxy resin. A typical example of amine group-containing phosphazene compounds that can be used as hardeners and flame retardants for polyurethane resins and epoxy resins. l &lt; x &lt; 2n, and R is phenyl or C3-C6 alkyl. The traditional preparation methods of such amine-containing phosphazene compounds can be divided into two types. The first method is first amination and then esterification; the second method is first esterification and then amination. The following is N3P3 (NH2 ) 2 (OC3H7) 4 Synthesis as an example: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------------------- Order --------- ^ I ^ w. (Please read the note on the back? Matters before filling out this page} 492973 A7 __B7 V. Description of the invention (2) Method one

Printed by Cl CI, Intellectual Property Bureau, Ministry of Economic Affairs

-------------------- Order --------- Line (Please read the notes on the back before filling this page) This paper size is applicable to China Standard (CNS) A4 specification (210 X 297 mm) 492973 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Cl OR

N

Rr ° An / &lt; or

Cl OR: 0 ^

n / P <0R NH3 / ether Cl High pressure reaction H2N or: 0 person / &lt;

NH2 OR method two must be fully aminated under pressure during amination, increasing process complexity and safety concerns. The above conventional methods have the disadvantage of many steps in actual operation. Take method one as an example. Step one: amination reaction. Step 2: After the amination reaction, the organic solvent layer and the water layer are separated. Step Three ... The organic solvent was distilled off to obtain N3P3 (NH2) 2C14. Step 4: The intermediate product N3P3 (NH2) 2CU is reacted with NaOC3H7 prepared in advance under heating and reflux. Step 5: After the reaction, wash off the NaCl with water, let it stand and separate the organic solvent. Please read the notes on the back before filling this page.) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) 492973 A7 B7 5. Description of the invention (4) Layer and water layer. Step 6: Dry the remaining water in the organic solvent layer. Step 7: Distill off the solvent to obtain the product. Summary of the Invention The present invention provides a method for simultaneously aminating and esterifying (NPCl2) n phosphazene compound mixture with NH3 &amp; HOR in the presence of a tertiary amine catalyst to prepare several amine group-containing phosphazenes having the following formula Method for a mixture of compounds:

NnPn (NH2) x (OR) 2n-x (I) where 3 $ η $ 10, 1 $ &lt; χ &lt; 2η, and R is phenyl or C3-C6 alkyl. In addition to the simultaneous amination and esterification, the method of the present invention simultaneously performs a regeneration reaction of the catalyst. Therefore, not only the operation steps of the method of the present invention are greatly reduced, but also the reaction time can be shortened. Furthermore, the method of the present invention is an anhydration process without the problem of a large amount of wastewater. The by-product amine chloride produced by the method of the present invention can also be recycled and reused. Brief description of the figure Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Figure 1 is a reaction system suitable for the method of the present invention, in the figure A: thermometer cannula B: feeding tube C: mechanical stirrer D: condensation tube E: Washing Tower-7 · This paper size applies to China National Standard (CNS) A4 (210 x 297 public love) ^ --- 492973 A7 B7 V. Description of the invention () F: NH3 gas flow meter G: reaction bottle H: constant temperature Water tank I: Flow control needle valve J: NH3 gas cylinder Detailed description of the invention The present invention discloses a method for preparing a mixture having the following formula (I) amine-containing phosphazene compound:

NnPn (NH2) x (OR) 2n.x (I) where η is an integer of 3; X is an IS x &lt; 2n integer; and R is phenyl or (: 3-(: 6 alkyl, preferably R is Propyl; the method comprises the following steps: a) introducing NH3 into a mixture of phosphazene compounds containing HO, (NPCl2) n and a tertiary amine reactant mixture at a temperature between 30-100 ° C Reaction for a period of time, in which η and R have the same definitions as above; b) solid-liquid separation of the product mixture produced in step a) and removal of solids containing NH4C1 precipitation therefrom; c) removal of the product produced in step b) by evaporation The highly volatile compounds in the liquid mixture yield a mixture product consisting essentially of several amine-containing phosphazene compounds having the above formula (I). Preferably, the reactant mixture in step a) of the method of the present invention further comprises an organic solvent, preferably chlorobenzene. This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page), T · na— nn ϋ β · 1 ϋ 1 ^ 1 n 1 —. 1 ftn 1 = Mouth line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 492973 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy A7 B7 V. Description of the invention () Preferably, (NPCl2) n phosphorus in step a) The nitrile compound mixture contains 60-70% by weight of 11 = 3 phosphazene compound; 10-20% by weight of 11 = 4 phosphazene compound; and 10-20% by weight: 1 ^ 5 of phosphazene compound. Preferably, the tertiary amine in step a) of the method of the present invention is pyridine. Preferably, the reactant mixture in step a) of the method of the present invention comprises 100-500 parts by weight of a phosphazene compound mixture, 20-150 parts by weight of pyridine and 500-2000 parts by weight of HOC3H7. More preferably, it contains 350 parts by weight of a phosphazene compound mixture, 40-80 parts by weight of batch 11 and 1000 parts by weight of HOC3H7. When the reactant mixture of step a) further comprises chlorobenzene, preferably the reactant mixture of step a) comprises 100-500 parts by weight of a phosphazene compound mixture, 80-360 parts by weight of pyridine, and 300-2400 parts by weight of H0C3H7, and 500-3600 parts by weight of chlorobenzene. More preferably, the reactant mixture of step a) contains 350 parts by weight of the phosphazene compound mixture, and the parts by weight of chlorobenzene are not less than HOC3H7. The present invention will be further understood through the following examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention in any way. Example In this example, NnPn (NH2) x (OC3H7) 2n-x is synthesized, and the reaction formula can be expressed as follows: HOC3H7 / solvent [NPCl2] n -► NnPn (NH2) x (OC3H7) 2n-x catalyst / NH3 This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -------------------- Order --------- line (Please read the notes on the back before filling out this page) 492973 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Because the product is intended to be used for curing of epoxy resin and PU resin, each molecule Must contain at least two NH2 groups. Since the synthesized product is not a single amine-containing phosphazene compound, such as a pure product of N3P3 (NH2) 2 (OC3H7) 4, but a mixture of NnPn (NH2) x (OC3H7) 2n-x, so this implementation Examples will explore the effect of reaction conditions on X 値. This embodiment uses a reaction system as shown in FIG. 1 and includes a reaction flask G placed in a constant temperature water tank. The reaction flask G is provided with a thermometer cannula A, a feeding tube B, a mechanical stirrer C, and a condensation. A pipe D, and an NHs gas introduction pipe, in which an NH3 gas cylinder J is connected to the NH3 gas introduction pipe, and a washing tower E is connected to the condensation pipe D. The NH3 gas introduction pipe is provided with a first-class control needle valve I and a flow meter F. Pyridine (Py), Chlorobenzen (CB), and n-Propanol (NPA) were placed in the reaction flask G in a predetermined amount. (] 12) 11 phosphazene compound mixture (containing 60-70% by weight of 11 = 3 phosphazene compound; 10-20% by weight of 11 = 4 phosphazene compound; 30%); and 10-20% by weight of 11 ^ 5 phosphazene compound). Maintain the reaction solution temperature between 25-3 ° C. After the addition of (NPCl2) n, NH3 gas was started to flow in according to the predetermined NHs gas flow rate, and the reaction temperature was maintained using a constant temperature water bath as follows: first stage 40 ° C 2 hours second stage 50 ° C 2 hours third stage 60 ° C 2 hours Fourth stage 70 ° C 1 hour After the reaction is finished, stop passing NH3 and let it cool down to room temperature. Then pass -10-This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------------------- Order ----- ---- Line (please read the precautions on the back before filling this page) 492973 A7 B7__ V. Description of the invention (8) The solid amine chloride is filtered out, and the liquid part is at a temperature of 90 ° C and a pressure of 30-40t. The Py, CB and NPA were distilled off under rr to obtain a brown product. (Please read the precautions on the back before filling this page.) The reaction mixture of an experiment was tracked by infrared spectroscopy using infrared spectroscopy. An absorption peak appears, indicating that both esterification and amination are in progress. By the fourth hour, the relative positions of the absorption peaks of the two substituents did not change much, indicating that the main substitution reaction was completed.

Since NnPn (NH2) x (OC3H7) 2n_x contains -NH2 and -OC3H7 groups, its infrared spectral absorption is u N-H 3270cm-1 and u -C-H 2965cm · 1, respectively. The intensity of the absorption peak is related to X and 2-x 値. When X 値 is larger, it means that the more -NH2 group is contained, the relative -0CsH7 group content becomes smaller. Therefore, the ratio of the two absorption peaks can predict the degree of amination. Theoretically, the amount of each element is calculated using NnPn (NH2) x (OC3H7) 2n_x as shown in Table 1. Table 1 Molecular formula MW P% Cl% C% H% N% N3P3 (NH2) l (OC3H7) 5 446 20.85 0 40.35 8.30 12.55 N3P3 (NH2) 2 (OC3H?) 4 403 23.08 0 35.73 7.94 17.37 N3P3 (NH2) 2 (OC3H7) 3Cl 379.5 24.50 9.35 28.46 6.59 18.40 N3P3 (NH2) 3 (OC3H7) 3 360 25.83 0 30.00 7.50 23.33 N3P3 (NH2) 3 (OC3H7) 4Cl 336.5 27.64 10.55 21.39 5.94 24.96 N4P4 (NH2) 2 (OC3H7) 6 566 21.91 0 38.16 8.13 14.84 N4P4 (NH2) 3 (OC3H?) 5 523 23.70 0 34.42 7.84 18.73 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The following table 2 lists the different ammonia gas flow rates, CB solvent amount, and Py amount. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 492973 A7 B7 5. Description of the invention () The product amine Of the degree of change. Printed Experiment No. Py NPA CB Nm Gas Flow Speed 514 Time NH2 / OC3H7 IR Absorption Peak Ratio P% Cl% C% H% N% 1 50 360 700 8 * 15min 4 * 15min 16 * 25min 4 * 20min 3 * 90min 2 * 175 min 56.9% 21.64 2.54 2 50 360 700 8 * 10min 16 * 170min 4 * 90min 2 * 80min 85.7% 23.86 2.23 3 50 360 700 4 * 10min 16 * 200min 2 * 110min 93.4% 23.74 2.41 5 50 360 700 4 * 435min 68.4% 23.82 2.88 31.4 7.2 18.4 6 50 360 700 4 * 162min 2 * 240min l * 50min 31.7% 21.32 1.74 38.1 8.0 13.0 7 50 360 700 2 * 420min 54.9% 22.60 3.45 34.3 7.5 14.6 8 150 1000 0 2 * 420min 0% 19.80 1.50 41.7 8.4 9.1 9 1000 400 0 2 * 300min 4 * 60min 8 * 90min 0% 20.45 0.38 40.8 8.2 9.9 -12-------------- ------- Order --------- Line (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 492973 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 10 V. Description of the invention () Note: 1. The amount of (NPCl2) n tested per time is 348 grams. 2. NH3 gas flow rate: In the table, 値 is a flowmeter characterization 値, and its corresponding actual flow rate is as follows: Haitong 値 actual flow rate (ml / min) characterization 値 actual flow rate (ml / min) 1 82 10 655 2 144 12 720 4 320 14 840 6 428 16 930 8 560 20 1036 The relationship between the flow rate and the characterization of 値: y = -1 · 3531χ2 + 78 · 612χ + 4.5309 It can be seen from Tables 1 and 2 that the content of phosphorus element and the ratio of infrared absorption peaks 値When there are two -NΗ2 groups, the infrared absorption peak ratio 値 must be more than 60%. According to the analysis of phosphorus element, the phosphorus content is about 22-24wt%. In addition, the results of the total amount of NH; gas used in Table 2 and the amount used in the first 180 minutes and the ratio of infrared absorption peaks are listed in Table 3. From these, the following preliminary conclusions can be roughly obtained: A. The ratio of the infrared absorption peak ratio 値 is related to the total amount of NH3 gas passed. B. The ratio of the infrared absorption peak ratio 与 is related to the comparison of the flow in the early stage of NH3 ventilation. C. The ratio of infrared absorption peak ratio 値 is related to the solvent. -13-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ------------------- Order --------- (Please read the precautions on the back before filling this page) 492973 A7 B7 V. Description of the invention (11) Table III Total No. Py NPA CB Nrn Ventilation Volume (L) 18 Ventilation Volume (L) Before Excitation NH2 / OC3H7 IR absorption peak ratio 1 50 360 700 88.57 65.53 56.9% 2 50 360 700 204.02 163.7 0 85.7% 3 50 360 700 205.04 161.30 93.4% 5 50 360 700 139.20 57.60 68.4% 6 50 360 700 84.74 54.43 31.7% 7 50 360 700 60.48 25.92 54.9% 8 150 1000 0 60.48 25.92 0% 9 1000 400 0 112.80 25.92 0% (Please read the notes on the back before filling out this page) The Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs prints and uses the gas chromatograph (GC) The relative contents of CB and NPA were analyzed for three experiments. The results are shown in Table 4. The data in Table 4 show that most of the responses were completed within 5 hours. This phenomenon is very consistent with the change in the absorption peak of the infrared absorption spectrum. -14-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 492973 A7 V. Description of the invention (12) Table 4 GC traces the relative content of NPA / CB in the reaction solution Response time (hours) Response One NPA% reaction Two NPA% reaction Three NPA% 0 42.75 43.85 36.83 1 34.47 35.10 32.74 2 30.30 32.21 25.74 3 29.95 23.37 4 32.39 29.49 22.67 5 28.45 21.06 6 31.579 28.99 20.39 7 20.34 8 9 31.10 28.41 21.14 _ (Please read the back first Please note this page to fill in this page) In order to understand the actual influence of NHs gas flow rate, solvent, and Py amount on the degree of amination of the product, the experiments in Table 5 below are performed, and the reaction conditions and results are listed. Remaining printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs π This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 492973 A7 B7 V. Invention Description (13 No. Py NPA CB NH3 gas flow rate t time NH2 / OC3H7 IR absorption peak ratio P% Cl% C% H% N% 1A 80 1000 0 2 * 420 min &lt; 10% 21.13 4.42 37.1 7.6 10.8 1B 80 500 500 2 * 420min &lt; 10% 19.69 4.27 38.7 7.4 10.3 2A 80 1000 0 6 * 420min 48.4% 21.40 0.67 38.0 82 14.1 2B 80 500 500 6 * 420min 69.7% 21.54 1.13 36.1 8.0 16.5. 3A 160 1000 0 2 * 420min 29.0% 19.62 0.42 42.0 8.5 10.0 3B 80 300 700 6 * 420min 73.5% 23.60 1.66 35.5 7.7 17.1 4A 160 1000 0 6 * 360min 2 * 60min 41.0% 20.76 0.97 39.41 12.5 8.3 5A 240 1000 0 6 * 360min 2 * 60min 17.1% 19.60 0.40 40.8 8.5 11.0 6A 160 1000 0 6 * 360min 2 * 60min 40.0% 20.39 0.44 38.6 8.3 13.0 7A 80 1000 0 8 * 300min 4 * 10min 2 * 95min 60.4% 23.06 1.06 33.5 7.8 18.1 8A 80 1000 0 10 * 240min 6 * 120min 2 * 60min 63.4% 23.06 1 Λ Λ l.jj 32.3 7.7 18.9 9A 80 10 0 0 0 8 * 300min 4 * 25min 2 * 120min 55.5% 22.34 0.66 35.0 8.0 17.4 10A 80 1000 0 10 * 160min 4 * 80min 2 * 180min 78.6% 22.90 1.38 33.0 7.8 19.0 11A 40 1000 0 6 * 420min 75.0% 23.42 1.30 31.1 7.7 18.6 12B 180 1200 1800 18 * 360min 4 * 60min 70.0% 22.50 1.63 32.4 7.6 19.4 13B 360 2400 3600 20 * 195min 15 * 90min 10 * 155min 51.0% 19.56 3.36 39.1 7.2 13.7 14B 360 2400 3600 25 * 130min 20 * 210min 15 * 20min 10 * 60min 68.6% 23.48 1.24 34.0 7.7 18.1 15A 80 1000 0 20 * 250min 8 * 170min 83.0% 23.46 1.72 31.7 7.7 20.1 IIIII Remarks: 1. The amount of (NPCl2) n per test is 348 grams. 2. Experiment No. Numbering method: A means solvent is NPA; B means solvent-16.-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). Please read the precautions of © before reading Fill in this page # ^ + ^ 973 A7 B7 V. Description of the invention (14 is the mixing of NPA and CB. 3. Experiment No. 12B uses a 5 liter reaction bottle; Experiments 13B and 14B use a 12 liter reaction bottle; the rest is 3 liter Reaction flask. 4. The flow rate of NH3 gas is described in Experiment Nos. 1-1, 2 and 15. The flowmeter used is the same as in Table 2. Experiment No. 13B and 14B use another flowmeter. Yes: Diurnal flow rate (ml / min) 10 854 15 1500 20 2180 25 2878 Relationship between flow rate and characterization: flow rate = 135.24X-513.2, where X: characterization 値 -------------- ------ Order --------- ^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -1 This paper size applies to Chinese national standards ( CNS) A4 size (210 X 297 mm)

Claims (1)

492973 A8 B8 C8 D8 VI. Application for Patent Scope 1. A method for preparing a mixture of several amine group-containing phosphazene compounds having the following formula (I): (Please read the note on the back? Matters before filling out this page) NnPn (NH2) x (〇R) 2n-X (I) where η is an integer of η-3; X is an IS χ &lt; 2η integer; and R is phenyl or (: 3-(: 6alkyl); the method includes The following steps: a) introduce NH3 into a reactant mixture containing HO, (NPCl2) n and a tertiary amine reactant mixture at a temperature between 30-100 ° C for a period of time, wherein η And R have the same meanings as above; b) the product mixture produced in step a) of the solid-liquid separation from which the solid containing NH4C1 precipitate is removed; and c) the liquid mixture produced in step b) is removed by evaporation Higher volatile compounds, resulting in a mixture product comprising several amine-containing phosphazene compounds having the formula (I) above. 2. The method of claim 1 in which R is -C3H7 alkyl. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3. The method of item 2 of the patent application, wherein the reactant mixture of step a) further comprises an organic solvent. 4. The method according to item 1 of the scope of patent application, wherein the (NPCl2) n compound compound of step a) contains 60-70 min %% of n = 3 of ortho-18-This paper scale applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) 492973 A8 B8 C8 D8 Six. Patent application scope Nitrile compounds; 10-20% by weight of 11 = 4 phosphazene compounds; and 10-20% by weight of 11 ^ 5 phosphorus Nitrile compound. 5. The method of claim 1 in which the tertiary amine of step a) is pyridine. 6. The method according to item 2 of the patent application, wherein the tertiary amine of step a) is pyridine. 7. The method of claim 3, wherein the tertiary amine of step a) is pyridine. ----------- Φ (Please read the notes on the back before filling out this page) * 161: 8. If the method of the 7th scope of the patent application, the organic solvent is chlorobenzene 〇9. The method according to item 6 of the patent application, wherein the reactant mixture of step a) comprises 100-500 parts by weight of a phosphazene compound mixture, 20-150 parts by weight of pyridine and 500-2000 parts by weight of HOC, H7 . 10. The method according to item 9 of the application, wherein the reactant mixture of step a) comprises 350 parts by weight of a phosphazene compound mixture, 40 to 80 parts by weight of pyridine and 1,000 parts by weight of HOC3H7. 11 · Method according to item 8 in the scope of patent application, where the response of step a) -19-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Preparation 492973 A8 B8 C8 D8 Six. Patent application scope The mixture contains 100-500 parts by weight of a phosphazene compound mixture, 80-360 parts by weight of pyridine, 300-2400 parts by weight of HOC3H7, and 500-3600 parts by weight of chlorobenzene . 12. The method according to item 9 of the scope of patent application, wherein the reactant mixture of step a) comprises 350 parts by weight of a phosphazene compound mixture, and the parts by weight of chlorobenzene are not less than HOC3H7. • T image • n ϋ n emm§ mmmmf *-· nn «1- ··-n in« _1 I (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ο 2 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)