WO2011131153A1

WO2011131153A1 - Polymer type phosphor-containing flame retardant, preparation method and application thereof

Info

Publication number: WO2011131153A1
Application number: PCT/CN2011/073615
Authority: WO
Inventors: 潘小明; 李执阶; 潘新明
Original assignee: 江苏大明科技有限公司
Priority date: 2010-04-19
Filing date: 2011-05-03
Publication date: 2011-10-27
Also published as: CN101805620A; CN101805620B

Abstract

Disclosed are a polymer type phosphor-containing flame retardant, preparation method and application thereof, which belong to the field of chemical materials. The polymer type phosphor-containing flame retardant PNX is a compound shown in formula (1), wherein n is an integer of 5~8 and the molecular weight of the flame retardant is between 900 and 1400. The method for preparing the flame retardant PNX is as follows: reacting phosphorus oxychloride with ethylene glycol in a nitrogen environment through a chemical reaction shown in the reaction formula (1) to obtain a compound (2), then reacting the compound (2) with anhydrous ethanol through a chemical reaction shown in reaction formula (2) under the action of a catalyst aluminum chloride to produce the flame retardant PNX. The flame retardant PNX belongs to a halogen-free, phosphorous type flame retardant. It coincides with the national concept of green-environmentally-friendly development. The content of phosphor is as high as 18%~20%, and the flame retardant properties are excellent.

Description

Polymer type phosphorus containing agent and preparation and application thereof

Technical field

The invention belongs to the field of chemical materials, and relates to a polymer type phosphorus-containing flame retardant, a preparation method thereof and application thereof.

Background technique

Some halogen-based flame retardants have been banned based on environmental and sustainable development requirements, and some are also treated with caution and applications are limited. Since the promulgation of the two EU ROHS and WEEE directives in 2003, the application of phosphorus-halide flame retardants has also been limited, so that the voice of green halogen-free phosphorus-based flame retardants is getting higher and higher.

Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer type phosphorus-containing flame retardant in view of the above-mentioned deficiencies of the prior art.

Another object of the present invention is to provide a process for preparing the flame retardant.

A further object of the invention is to provide the use of the flame retardant.

The object of the present invention can be achieved by the following technical solutions:

A polymer type phosphorus-containing flame retardant PNX having the following chemical formula:

, n=5~8, the molecular weight of the flame retardant is between 900 and 1400.

Through elemental analysis, the polymer type phosphorus-containing flame retardant of the present invention PNX-type compound element composition is: P 19.75 ~ 19.95, C 32.63 ~ 33.12, H 6.23 ~ 6.37, 0 40 · 8% ~ 40 · 19%.

Infrared absorption spectrum showed characteristic peaks at 1300cm- ^1, prove the existence of P = 0; 1180cm- 1 and 980cm-l characteristic peaks at, prove the existence of P- 0- C; absorption peak ¹ at 1392cm- 1464 cm "and An absorption peak between 2800 and 3000 cm-1 indicates the presence of CH ₂ and CH ₃ .

The preparation process of the flame retardant PNX according to the present invention is characterized in that the compound (2) is obtained by a chemical reaction represented by the formula (1) by using phosphorus oxychloride and ethylene glycol in a nitrogen atmosphere; The flame retardant PNX is obtained by a chemical reaction represented by the reaction formula (2) with anhydrous ethanol under the action of a catalyst aluminum chloride. 〇

(n+1) POCI3 + n HOCH ₂ CH ₂ OH -►CI-P- -OCH ₂ CH ₂ 0-P- ■CI + 2n HCl

Cl

(2)

Reaction formula ( ) n=5~8 (n+3)HCl

Reaction formula ( )

, n=5~8 The preparation process of the flame retardant PNX according to the present invention is specifically composed of the following steps:

(1) Pumping phosphorus oxychloride into reactor No. 1 and cooling to 10~15 °C, introducing nitrogen into the kettle at a flow rate of 0.5~3m ³ /h, protecting and preventing oxidation, and slowly adding B. The diol is heated to 15~25 ° C after the dropwise addition, and the reaction is stirred for 0.5~3 h; the nitrogen gas is stopped, and the excess P0C1 _{3 is} distilled off under reduced pressure. After distillation, the temperature is lowered, and the discharge is passed to the No. 2 reactor;

(2) Put the catalyst A1C1 ₃ into the No. 2 reactor, stir for 0.5~lh, control the temperature at 10~13°C, add absolute ethanol, and after the addition, heat up to 20~30°C, keep warm for 3~6h The catalyst is removed by low pressure suction filtration; the filtrate is washed with water for 2 to 6 times, and after each water washing, the water is distilled off under reduced pressure to obtain a flame retardant PNX.

Wherein, the molar ratio of phosphorus oxychloride, ethylene glycol, absolute ethanol and aluminum chloride is phosphorus oxychloride: ethylene glycol: absolute ethanol: aluminum chloride = 3~7: 1: 3.5- 4.5: 0.004-0.008, preferably 5:1: 4.0 4.2:0.004.

The dropping rate of the dropwise addition of ethylene glycol is 110 to 140 g/min, and the hydrochloric acid produced during the dropwise addition is absorbed by the HC1 absorption tower.

The dropping rate of the dropwise addition of absolute ethanol is 400 to 580 g/min, and the hydrochloric acid produced during the dropwise addition is absorbed by the HC1 absorption tower.

In the step (1), the pressure of the vacuum distillation is -0.1 to -0.05 MPa, and the distillation temperature is 45 to 60 °C.

In the step (2), the pressure of the vacuum distillation is -0.1 to -0.05 MPa, and the distillation temperature is 105 °C.

The purity of the phosphorus oxychloride is greater than or equal to 98.5%, the purity of the ethylene glycol is greater than or equal to 99.5%, and the purity of the anhydrous ethanol is greater than or equal to 99.5%.

The flame retardant PNX according to the invention is used in a flexible polyurethane foam.

None of the matters in the present invention are conventional in the art. The beneficial effects of the invention:

The flame retardant PNX provided by the invention belongs to the halogen-free phosphorus-based flame retardant, and conforms to the national green environmental protection development concept, and the phosphorus content is as high as 18%-20%, and the flame retardant performance is superior. Used in flexible polyurethane foam, the addition amount is less than half of the flame retardant TCPP and MPPDP, and the same flame retardant effect can be obtained without generating toxic fumes.

The preparation method provided by the invention has the advantages of simple process, continuous, high production efficiency and stable product quality.

Specific real fc^:

Example 1

(1) Using a vacuum pump to pump phosphorus oxychloride 767.5Kg into the No. 1 reactor, reduce the temperature to 10~15 °C, and introduce nitrogen into the kettle at a flow rate of 2m ³ /h to protect against oxidation and slow. Ethylene glycol 62Kg was added dropwise, and the addition time was 8 h. After the completion of the dropwise addition, the temperature was raised to 18 ° C, and the material was stirred for ₁ hour; the nitrogen gas was stopped, and the excess POCl ₃ was distilled off under reduced pressure at -O.lMPa, 55 ° C, After the distillation is completed, the temperature is lowered, and the discharge is passed to the No. 2 reactor;

(2) Into the No. 2 reactor, put 533.4g of catalyst AlCl _{3 and} stir for 0.5h, control the reaction temperature to 10~13 V with ice brine, add 184Kg of absolute ethanol, and add the time for 6h. After the addition, the temperature is raised to The reaction was kept at 25 ° C for 4 h; the catalyst was removed by low pressure filtration; the filtrate was washed 3 times, and after each water washing, the flame retardant PNX was obtained by distilling off the water at -O.lMPa, 105 ° C under reduced pressure.

Example 2

In this embodiment, according to the preparation process of Example 1, the molar ratio of the raw materials, the amount of the catalyst, and the reaction temperature were respectively changed through various sets of experiments to obtain an optimum process.

2.1 First step reaction raw material molar ratio

The ratio of phosphorus oxychloride to ethylene glycol in the first step reaction was changed (as shown in Table 1), and the other conditions were the same as in the first step, wherein the temperature refers to the temperature at which ethylene glycol was added dropwise.

Table 1

After analysis, the first group has a degree of polymerization of 10~15, the degree of polymerization is too high, the substance is viscous, and it is solidified after cooling. It is not suitable to stir the reaction with the second step; the degree of polymerization of the second to fourth groups is 5~8, and the degree of polymerization is moderate. , liquid, easy to react in the second step, especially the compound prepared in the third group (2) has the best performance; the fifth group has a degree of polymerization of 1~3, the degree of polymerization is too low, and the phosphorus oxychloride is excessively excessive, energy consumption many. Therefore, the molar ratio of phosphorus oxychloride to ethylene glycol is selected to be 3-7:1, preferably 5:1.

2.2 second step reaction raw material molar ratio

Only the amount of ethanol added in the second step was changed (as shown in Table 2), and other conditions were carried out in the same manner as in Example 1, where the temperature refers to the temperature at which ethylene glycol and ethanol were added dropwise.

Table 2

The results of laboratory analysis showed that the first group reaction was incomplete, and the C1 element remained, the product yield was low, only 60%; the second to fifth groups were completely reacted, the product yield was as high as 82~87%; the sixth group was completely reacted, the product The yield was 87%, but the ethanol fraction was distilled off in the water washing distillation to prove an excess of ethanol. Therefore, the molar ratio of ethylene glycol to ethanol is selected to be 1: 3.5-4.5, wherein the yield of the fourth to fifth groups is the highest, so the molar ratio of ethylene glycol to ethanol is preferably 1: 4.0.

2.3 The second step of the reaction catalyst selection

Only the amount of the second-stage reaction catalyst was changed (as shown in Table 3), and other conditions were carried out in the same manner as in Example 1, wherein the temperature refers to the temperature at which ethylene glycol and ethanol were added dropwise.

table 3

Group 4 5 1 4.0 0.006 10- -15 °C Group 5 5 1 4.0 0.008 10- 15 °C The first and second groups of reaction time need 12h, which is added dropwise for 8h, 4h incubation; Group 2, The reaction time was 8 h, in which 6 h was added dropwise and kept for 2 h; the reaction time of the 3rd to 5th groups was 6 h, and 4 h was added dropwise, and the temperature was kept for 2 h.

Therefore, the ratio of catalyst to ethylene glycol is selected to be 0.004 0.008: 1, preferably 0.004;

2.4 The second step of the choice of reaction temperature

Only the temperature of the second step of the reaction dropwise addition of ethanol was changed (Table 4), and the other conditions were carried out in the same manner as in Example 1.

Table 4

The results showed that the reaction time of Groups 1~3 was longer than 10h, of which 5h was added, the temperature was 5~6h and the yield was up to 73%; the reaction time of Group 4 was 6h, which was added for 5h, heat preservation for lh, high yield 88.2%; Group 5 reaction time 5h, which was added dropwise for 4h, the yield of heat preservation was 80% for 1 h; therefore, 10~15 °C was selected as the second reaction temperature.

In summary, the present invention selects phosphorus oxychloride: ethylene glycol: absolute ethanol: aluminum chloride molar ratio is 3~7: 1: 3.5-4.5: 0.004-0.008, preferably 5: 1: 4.0-4.2 : 0.004; The second step reaction temperature is 10~15 °C.

Example 3

The flame retardant PNX of the present invention and the phosphorus halogen flame retardant T ₁₍₎₁ (tetrakis(β-chloroethyl)-1,2-ethylenediphosphate) are respectively added to a flexible polyurethane foam for automobiles. The preparation process is a conventional process, and the respective formulations and properties are shown in Tables 5 and 6.

Table 5. Formulation and properties of Τ ₁₀ ι flame retardant flexible polyurethane foam

Surfactant 0.20 Elongation 110

Τιοι 5.0 tear strength /kpa 10 melamine 30.0 compression variable (50% deformation) 30%

TDI 57.7 weight loss /g 49

Oxygen index% 31 Table 6. Formulation and properties of PNX flame retardant flexible polyurethane foam

It can be seen from Table 5 and Table 6 that PNX reaches 40% of the T _{1 () 1} addition amount, and the same flame retardant effect can be achieved. The oxygen index is also slightly higher than the T101 flame retardant flexible polyurethane foam, and ΡΝΧ The flame retardant flexible polyurethane foam does not produce toxic fumes when burned, and the T101 flame retardant flexible polyurethane foam produces toxic fumes when burned.

Example 4

The flame retardant bismuth and the phosphorus halogen flame retardant MPPDP of the invention are respectively added to the flexible polyurethane foam, and the preparation process is a conventional process, and the respective formulations and properties are shown in Table 7 and Table 8. Table 7. Formulation and properties of MPPDP flame retardant flexible polyurethane foam

Table 8. Formulation and properties of PNX flame retardant flexible polyurethane foam

It can be seen from Table 7 and Table 8 that 12% of MPPDP flame retardant is added, the flame retardancy is up to V-2, and 12% is added. The PNX flame retardant has a flame retardancy of V-0, while the rest of the performance does not change much.

* The value in parentheses is a blank value.

Claims

Claim

A polymer type phosphorus-containing flame retardant PNX, characterized in that the flame retardant is represented by the formula (1)

Class compound:

(1)

, n = 5~8 integer, the flame retardant molecular weight is between 900~1400.

The method for preparing a flame retardant PNX according to claim 1, wherein the compound (2) is obtained by a chemical reaction represented by the formula (1) by using phosphorus oxychloride and ethylene glycol in a nitrogen atmosphere; (2) obtaining a flame retardant by a chemical reaction represented by the reaction formula (2) with anhydrous ethanol under the action of a catalyst aluminum chloride

PNX;

(n+1) P0C1 ₃ + n HOCH ₂ CH ₂ OH -►

(2)

Reaction formula ( )

n=5~8 integer; (n+3)HCl

Reaction formula ( )

, n = an integer from 5 to 8.

3. The preparation method according to claim 2, wherein the specific steps are as follows:

(1) Injecting phosphorus oxychloride into the No. 1 reactor, cooling to 10~15 °C, introducing nitrogen into the kettle, the flow rate is

0.5~3m ³ /h, and slowly add ethylene glycol, after the addition is completed, the temperature is raised to 15~25 °C, and the reaction is stirred for 0.5~3h;

The nitrogen gas is stopped, the excess phosphorus oxychloride is distilled off under reduced pressure, the distillation is completed, the temperature is lowered, and the liquid obtained in the distillation pot is passed to the No. 2 reactor;

(2) Put the catalyst A1C1 ₃ into the No. 2 reactor, stir for 0.5~lh, control the temperature at 10~15°C, add absolute ethanol, and after the addition, heat up to 20~30°C, keep warm for 3~6h The catalyst is removed by low pressure suction filtration; the filtrate is washed with water for 2 to 6 times, and after each water washing, the water is distilled off under reduced pressure to obtain a flame retardant PNX.

4. The preparation process according to claim 2 or 3, characterized in that the molar ratio of phosphorus oxychloride, ethylene glycol, absolute ethanol and aluminum chloride is phosphorus oxychloride: ethylene glycol: none Water ethanol: Aluminum chloride = 3~7: 1: 3.5-4.5: 0.004-0.008

5. The preparation process according to claim 4, wherein the molar ratio of phosphorus oxychloride, ethylene glycol, absolute ethanol and aluminum chloride is phosphorus oxychloride phosphorus oxychloride: ethylene glycol : Anhydrous ethanol: Aluminum chloride: l

6. The preparation process according to claim 3, characterized in that the dropping rate of the dropwise addition of ethylene glycol is 110 to 140 g/min, and the hydrochloric acid generated during the dropwise addition is absorbed by the HC1 absorption tower.

7. The preparation process according to claim 3, characterized in that the dropping rate of the dropwise addition of absolute ethanol is 400 to 580 g/min, and the hydrochloric acid produced during the dropwise addition is absorbed by the HC1 absorption tower.

The preparation process according to claim 3, characterized in that the pressure of the vacuum distillation in the step (1) is -0.1 to -0.05 MPa, and the distillation temperature is 45 to 60 °C.

9. The preparation process according to claim 3, characterized in that the pressure in the vacuum distillation in the step (2) is -0.1 to -0.05 MPa, and the distillation temperature is 105 Torr.

10. The use of the flame retardant PNX of claim 1 in the preparation of a flexible polyurethane foam.