TWI452062B - Method for producing phosphorous nsp flame retardant - Google Patents

Description

Method for producing phosphorus-based nano-barium flame retardant

The present invention relates to a flame retardant, and more particularly, to a method of producing a phosphorus nano tablet flame retardant.

In the special electronic materials, the flame retardant properties of the polymer are strictly required, so it is often necessary to add a flame retardant. Flame retardants can be classified into inorganic and organic. The inorganic system is mainly a metal oxide or a hydroxide, and the organic system is mainly a halogen-containing material. However, halogen-containing flame retardants produce corrosive and toxic gases and are therefore gradually replaced by phosphorus-containing special chemicals.

Hexachlorotriphosphazene (HCP) is one of the raw materials for phosphorus-based flame retardants and is soluble in monochlorobenzene (MCB). Figure 1 shows the synthesis of HCP with commercial poly(oxyalkylene)-amines to produce a polyetheramine phosphorus-based flame retardant. However, polyfunctional group reactants are prone to cross-linking reactions. To avoid cross-linking, the polyfunctional reactant must be diluted with a solvent. However, after the reaction, the solvent must be removed, and then the appropriate solvent is added to continue the reaction, which is quite complicated and time consuming and energy consuming.

In addition, in order to more effectively improve the flame retardancy of the flame retardant, an inorganic substance (such as a crucible having a high aspect ratio) may be added to prepare an organic-inorganic composite material. However, due to its high stacking and hydrophilicity, natural bracts not only cause most of the bakelite composites to be intercalated, but also increase the difficulty of introducing organic matter into bracts and reduce the barrier properties and utilization of bracts.

The present invention thus proposes a new process with a view to improving the above-mentioned deficiency.

It is an object of the present invention to provide a method for producing a composite of a phosphorus-containing polyetheramine and a nano-powder tablet, which does not require solvent removal during the process, and which is easy to separate; and the method for producing a phosphorus-containing polyetheramine in the process does not require high temperature. No cross-linking will occur.

The method for producing a phosphorus-containing polyetheramine of the present invention mainly comprises the following steps:

(a) Dissolving the polyetheramine in an organic solvent at a concentration of 30 to 95 wt%, 50 to 85 wt%, and 65 to 80 wt%. The polyetheramine comprises at least two terminal amine groups (-NH ₂ ), which are mainly composed of a polypropylene ether functional group and have a molecular weight in the range of 200 to 4000, preferably 300 to 2,500. The organic solvent is preferably an alcohol or an aprotic solvent, more preferably isopropanol (IPA) or tetrahydrofuran (THF).

(b) Adding hexachlorotriphosphorus nitrogen (HCP) to the polyetheramine solution of step (a), the molar ratio of HCP to polyetheramine is from 1/1 to 1/100, preferably 1/1~ 1/20, more preferably 1/3~1/10. The reaction temperature is between 0 and 80 ° C, preferably 0 to 60 ° C, more preferably 0 to 30 ° C, so that at least one chlorine of the hexachlorotriphosphoric nitrogen ring, preferably 3 to 6 chlorine, is aggregated. The etheramine is substituted to synthesize a phosphorus-containing polyetheramine (HCP-polyetheramine). The HCP can be first dissolved in an aprotic solvent (e.g., MCB) at a concentration of 25 to 50 wt%, preferably 30 to 45 wt%.

The above method may further comprise the following steps:

(c) adding a base to the phosphorus-containing polyetheramine solution of the step (b) to neutralize the hydrochloric acid produced by the reaction. The base may be an organic base such as pyridine or an inorganic base such as NaOH, preferably triethylamine (TEA). The molar ratio of HCP to alkali may be from 1/0.1 to 1/50, preferably from 1/1 to 1/20, more preferably from 1/3 to 1/10.

(d) The salt of step (c) is removed by filtration.

The phosphorus-based nano-powder flame retardant can be produced by the phosphorus-containing polyetheramine produced by the above steps, and the steps are as follows:

(e) blending a phosphorus-containing polyetheramine into an aqueous solution of nanocrystalline bismuth tablets, the weight ratio of the phosphorus-containing polyetheramine to the nano sized tablet is from 100/1 to 1/50, preferably from 10/1 to 1 More preferably, it is 2/1 to 1/10, and the reaction temperature is 5 to 50 ° C, preferably 20 to 30 ° C, so that the amine group of the phosphorus-containing polyetheramine is ion-bonded with the nano-platelet ion vacancy. To synthesize a composite of a phosphorus-containing polyetheramine and a nano-powder tablet, that is, a phosphorus-based nano-powder flame retardant; wherein, the phosphorus-containing polyether amine refers to at least one of a hexachlorotriphosphonate (HCP) ring. Chlorine, preferably 3-6, is replaced by a polyetheramine having a polypropylene ether and a molecular weight of 200 to 4000; a nanosheet is a layer of each layer which is completely separated after the layered clay is completely separated. .

The product obtained in the step (e) has a low critical solution temperature (LCST) property and can be separated by the following steps:

(f) heating the solution of step (e) to 60 to 95 ° C, preferably 70 to 90 ° C, and filtering.

The phosphorus-based nano-powder flame retardant obtained by the method of the invention, that is, the composite of phosphorus-containing polyetheramine and nano-ruthenium tablets (NSP). Among them, the characteristics and content ratios of the phosphorus-containing polyetheramine and the nano-ruthenium tablets are as defined above.

(1) Raw materials

(1) Hexachlorotriphosphazene (HCP); Mw = 347.6 g/mole, purchased from National Day Chemical.

(2) Polyetheramine: Poly(oxypropylene)-amines, available from Hunstsman Chemical Co., D-amine series products. The backbone is a polyoxypropylene (OP) segment. The structure is as follows:

D230 (x=2~3); Mw~230 g/mole; POP-D230

D400 (x=5~6); Mw~400 g/mole; POP-D400

D2000 (x=33); Mw~2000 g/mole; POP-D2000

(3) Nano sputum tablets: Nano Silicate Plate (NSP); 10 wt% in water, purchased from the Czech Republic. Each layer of layered clay such as montmorillonite (Na ⁺ -MMT) or mica is completely separated (exfoliation), and exists in each individual sheet form; CEC = 1.2 meq / g, the aspect ratio is about (80×80-120×120)×1 nm ³ , the average chip diameter ratio is about 100×100×1 nm ³ , the surface area is about 700-800 m ² /g, and the ion charge density is about 18,000-20,000 ions/piece. The average number of units per unit weight is about 4×10 ¹⁶ pieces/g. The isoelectric point (IEP) of the aqueous solution appears at pH=6.4; it can be rearranged when dispersed in the solution, such as double-layer plate or two pieces. A group of structural units.

(4) Monochlorobenzene: Monochlorobenzene (MCB), a solvent for HCP.

(5) Isopropanol: isopropyl alcohol (IPA), a solvent for polyetheramine and/or HCP.

(6) Tetrahydrofuran: tetrahydrofuran (THF), a solvent for polyetheramine and/or HCP.

(7) Triethylamine: Triethylamine (TEA); Mw = 101 g/mole, available from Sigma-Aldrich, Inc. For removing hydrochloric acid generated by the reaction, an organic base pyridine or an inorganic base NaOH or the like can also be used.

(2) Preparation method Example 1

(a) D400 (50 g, 125 mmole) and isopropanol (IPA, 15 g) were stirred in a three-necked flask.

(b) HCP (20.7 g, 35 wt% in MCB, 20.8 mmole) was slowly dropped into a three-necked flask and mixed with the above D400 solution to synthesize HCP-D400. The reaction temperature was 5 ° C and the solution was transparent.

(c) After half an hour, TEA (12.6 g, 124.8 mmole) was slowly dropped into a three-necked flask to remove hydrochloric acid produced by the reaction, and the solution turned white. The Mobi HCP/D400/TEA is 1/6/9 (1/6/6). The reaction time is about 24 hours.

(d) The hydrochloride salt of TEA was separated by filtration through a filter paper to obtain a liquid product HCP-D400 (65 wt%).

(e) An aqueous NSP solution (50 g, 10 wt%) was taken to a beaker, water was added to 100 g, and stirred at 25 ° C for 1 hour. HCP-D400 (7.7 g, 65 wt%) was blended into an aqueous NSP solution to synthesize HCP-D400/NSP (5/5). The reaction temperature was 25 ° C and the reaction time was about 3 hours.

(f) The HCP-D400/NSP solution was heated to 80 ° C to produce a precipitate. The solution was filtered to separate the solvent to give the solid product HCP-D400/NSP (5/5 by weight). The manufacturing process is shown in Figure 2.

Example 2

The procedure was the same as in Example 1, except that the amount of HCP-D400 added was changed to 3.3 g, and finally the product HCP-D400/NSP (weight ratio 3/7) was obtained.

Example 3

The procedure was the same as in Example 1, except that the amount of HCP-D400 added was changed to 17.9 g, and finally the product HCP-D400/NSP (weight ratio 7/3) was obtained.

Example 4

The procedure was the same as in Example 1, except that the amount of HCP-D400 added was changed to 0.86 g, and finally the product HCP-D400/NSP (weight ratio 1/9) was obtained.

Example 5

The procedure was the same as in Example 1, except that the isopropanol of step (a) was changed to tetrahydrofuran (THF, 150 g) and the reaction temperature was changed to 30 °C. Finally, the product HCP-D400/NSP (weight ratio 7/3) was obtained.

Example 6 (formerly Comparative Example 3)

The procedure was the same as in Example 1, except that the polyetheramine D-400 of step (a) was changed to D-2000. After half an hour, the HCP-D2000 product was produced. Finally, the product HCP-D2000/NSP (weight ratio 5/5) was obtained.

Comparative example 1

The procedure was the same as in (a) and (b) of Example 1, but no isopropanol was added. After half an hour, the cross-linking reaction produced a gelatinous product.

Comparative example 2

The procedure was the same as in (a) and (b) of Example 1, except that isopropanol was not added, and the reaction temperature was changed to 30 °C. After half an hour, the cross-linking reaction produced a gelatinous product.

Table 1 compares the results of synthesizing HCP-D400 under different operating conditions.

Analysis and discussion of experimental results:

1. HCP and polyetheramine D400 were subjected to a nucleophilic substitution reaction to obtain HCP-D400 having a molecular weight of Mw = 1700 g/mol. The molecular weight distribution index (PDI) = 2.49, so the reactants are polyfunctional. Since the reaction is carried out at a high concentration, the reaction at room temperature causes cross-linking, and the reaction temperature is lowered to lower the reaction rate. This can achieve direct feeding and avoid cross-linking, reducing operating procedures.

2. The HCP-polyetheramine is reacted with NSP in proportion to form an organic/inorganic composite material, and the material has LCST characteristics. Since the polyetheramine used in the present invention has a propylene ether functional group, when the molecular weight of the propylene ether is increased, the hydrogen bonding force is remarkable, thereby causing an LCST phenomenon. Figure 3 shows the transmittance at a wavelength of 550 nm at different temperatures before and after D400 and D2000 were compared with HCP by UV analysis. HCP-D400/NSP composites have good dispersibility at low temperatures, but are difficult to separate from solvents. By using the LCST characteristics of the material to raise the temperature of the solution, the product can be rapidly phase separated from the solvent to obtain a product.

3. The polyetheramine-phosphorus and nano-powder composite flame retardant process connects the operation sequence in series to allow the synthesis reaction to be coherent with the organic/inorganic composite. This process allows the polyfunctional reaction to proceed at high concentrations and avoid cross-linking. In addition, the synthetic polymer flame retardant can be introduced into the delaminated clay by a simple blending method to obtain a composite flame resistant material. And by using the LCST characteristics of the material, the product is separated from the solvent by raising the temperature, achieving environmental protection, energy saving and time saving effects, and more in line with industrial production requirements.

Figure 1 shows a prior art process for the synthesis of a phosphorus-containing polyetheramine flame retardant by the synthesis of HCP and polyetheramine.

Fig. 2 is a view showing the manufacturing process of the composite of the phosphorus-containing polyetheramine and the nanopellet tablet of the present invention.

Figure 3 shows the comparison of the UV transmittance at different temperatures before and after the reaction of D400 and D2000 with HCP.

Claims (7)

A phosphorus-based nano-tantale flame retardant comprising at least a composite of a phosphorus-containing polyetheramine and a nano-ruthenium tablet (NSP), wherein the phosphorus-containing polyetheramine-based amine group and the nano-platelet ion vacancy are ions Bonding; wherein, the phosphorus-containing polyether amine means that at least one chlorine of the hexachlorotriphosphorus nitrogen ring (HCP) shown in the following figure is replaced by a polypropylene ether, a polyether amine having a molecular weight of 200 to 4000, and HCP and The molar ratio of polyetheramine is 1/1~1/100. x=2~3, 5~6 or 33; nano-ply film means that each layer of the layered clay is completely separated, and each individual sheet has a film-to-diameter ratio of about (80×80~120×120). ×1 nm ³ ; the weight ratio of the phosphorus-containing polyetheramine to the nano-powder tablet is 100/1 to 1/50. A method for producing a phosphorus-based nano-powder flame retardant, comprising the steps of: blending a phosphorus-containing polyetheramine into an aqueous solution of nano-barium, the weight ratio of the phosphorus-containing polyetheramine to the nano-powder tablet is 100 /1~1/50, the reaction temperature is 5~50 °C, the ionic bond of the phosphorus-containing polyetheramine and the nano-platelet ion vacancy are ion-bonded to synthesize the composite of phosphorus-containing polyetheramine and nano-pate a phosphorus-based nano-powder flame retardant; wherein, the phosphorus-containing polyether amine means that at least one chlorine of the hexachlorotriphosphorus nitrogen ring (HCP) shown in the following figure is a polypropylene ether and has a molecular weight of 200. ~4000 polyetheramine substitution, x=2~3, 5~6 or 33; nano-ply film means that each layer of the layered clay is completely separated, and each individual sheet has a film-to-diameter ratio of about (80×80~120×120). ×1nm ³ . The method of claim 2, wherein the phosphorus-containing polyether amine means that 3 to 6 chlorines of the hexachlorotriphosphorus nitrogen ring (HCP) are substituted by a polyether amine having a backbone of polypropylene ether and a molecular weight of 200 to 4000. The method of claim 2 further includes the following steps: The solution was heated to 60-95 ° C and filtered. The method of claim 2, wherein the phosphorus-containing polyetheramine is first dissolved in an organic solvent. The method of claim 5, wherein the organic solvent is an alcohol or tetrahydrofuran. The method of claim 5, wherein the organic solvent is isopropanol.