JPS60141609A - Red phosphorus containing composition and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for stabilizing red phosphorus against oxidation.

[Conventional technology]

It is known that red phosphorus undergoes chemical reactions when stored in a humid atmosphere, forming phosphine and various phosphoric acids, primarily phosphorous and phosphoric acids. The formation of highly toxic phosphine makes working conditions very dangerous and produces unpleasant odors, and the formation of phosphorous and phosphoric acids is undesirable when using red phosphorus.

[Problems to be solved by the present invention]

Aluminum in the form of hydroxide has been widely used to prevent red phosphorus degradation and stabilize red phosphorus as described above. However, relatively large amounts of aluminum are required to achieve substantial stabilization of red phosphorus.

Another problem encountered in prior art aluminum processing is that the product is difficult to process. A layer of alumina is deposited on the red phosphorus particles in the aqueous dispersion of red phosphorus, and the treated red phosphorus is filtered and dried. Effective filtration of treated red phosphorus is difficult to achieve as a result of gelation of the aluminum hydroxide, and large amounts of water are retained by the aluminum hydroxide.

Recently, as described in U.S. Pat. - It has now been found that the red phosphorus thus achieved and further processed can be filtered easily and rapidly. Another advantage of titania-treated red phosphorus is that the red phosphorus can be heated at temperatures up to 300°C without evaporating water, which makes the red phosphorus product suitable for plastics treated at high temperatures. It is suitable for addition to the class.

U.S. Pat. No. 6,092,460, U.S. Pat. No. 6,092,460, U.S. Pat. ing. Red phosphorus particles are 1-10 heavy JI of red phosphorus particles
It is described as being coated with a coating polymer which can be a melamine-formaldehyde resin, a phenolic resin or an epoxy resin in an amount of #L% and an amount of up to 1m-% by weight of the coated particles. There is a general indication that metal oxides or salts can be present in the composition.

Further, US Pat. No. 4,433/197 proposes a method for stabilizing red phosphorus against oxidation by simultaneously treating red phosphorus particles with aluminum hydroxide and a hardened epoxy resin.

Means for Solving the Problems According to the invention, a combination of a certain amount of titanium in the form of titanium dioxide or titanium IJyate and a specific organic resin is particularly effective as a stabilizer for red phosphorus. I recently discovered this unexpectedly. In the present invention, delaying the oxidation of red phosphorus and suppressing phosphine formation is achieved.

According to one aspect of the invention, the invention provides at most about 2 m
In a red phosphorus-containing composition with a particle size of 1N, titanium dioxide or titanium phosphate is added by weight of titanium to 0.1N.
To provide a red phosphorus-containing composition characterized in that the red phosphorus particles have a particle size of at most about ulIM, characterized in that the red phosphorus particles have a particle size of about ulIM at most, and contain o,i to 3.0% by weight of an organic resin. It is something.

According to the present invention, T10. When used in combination with epoxy resin, the improvement achieved in oxidative stability is considerably greater than that achieved using the prior art combination of aluminum hydroxide and epoxy resin.

The present invention also includes a novel method for processing red phosphorus particles to achieve stabilization of the red phosphorus particles. Therefore, according to another aspect of the invention, the invention provides for adding a titanium compound to a slurry of red phosphorus particles in which the red phosphorus particles have a particle size of at most about 2 mm; Adjust to ~l and T1 on red phosphorus particles is about 0.0! Deposition of titanium dioxide or titanium phosphate in an amount of ~7.0 wt. It is an object of the present invention to provide a method for preparing a red phosphorus-containing composition having a particle size of at most 2.0 mm, which comprises separating red phosphorus particles deposited and treated in an amount of 0% by weight from a slurry.

[For production]

The organic resin used in the red phosphorus treatment according to the invention is water-soluble or water-emulsifiable. The seven types of organic resins used in the present invention are epoxy resins. Epoxy resins are thermosetting resins based on the reactivity of epoxy groups. Seven common types of resins are made from shrimp chlorohydrin and co-aromatic and aliphatic polyols such as Corbis-furopane (bisphenol A), which terminate in glycidyl ether structures. Based on
Contains a large number of hydroxyl groups and is easily cured using water-soluble internally modified polyamines. Curing is usually done in an aqueous phase with a pH maintained at about 0 to 9, at a temperature of about 0°C to about 0°C. ℃
It happens in The epoxy resin that can be used in the present invention is generally about/
It has an epoxy equivalent weight of 70 to hoo.

Another type of organic resin used in this invention is melamine-formaldehyde resin. Melamine-formaldehyde resin is an amine resin made from melamine and formaldehyde. The seventh step in forming the melamine-formaldehyde resin is the formation of trimethylolmelamine, a molecule with a ring of three carbon atoms and three nitrogen atoms. Molecules of trimethylolmelamine or polymers of melimethylolmelamine are reacted with formaldehyde. Low molecular weight uncured melamine resins are water soluble syrups and are preferred for use in the present invention. Curing occurs with heat and acidity.

Another type of organic resin used in this invention is urea-formaldehyde resin. Urea-formaldehyde resins are another class of amino resins and are a one-step operation that involves first forming a methylolurea and then thermally curing it by controlling heat and pressure in the presence of an acid catalyst. is formed.

The red phosphorus treated according to the present invention has a large size,
Preferably O0θ/~0. /! It is in the form of microparticles with dimensions of Wll. Red phosphorus particles are treated with titanium dioxide or titanium phosphate and an organic resin. The amount of titanium compound used is expressed as Ti and is approximately θ, θ! ~about/,
The θ weight can be varied by 41%, and the amount of organic resin can vary from 0.1 to 3% by weight.

Preferably, the content can be varied from O, S to 3.0% by weight. In view of the prior art, it is surprising that small amounts of titanium and organic resins as described above can effectively stabilize red phosphorus against oxidation and phosphine formation.

The treatment of red phosphorus particles using titanium dioxide or titanium phosphate and an organic resin is a two-step process in which titanium dioxide or titanium phosphate is first deposited on the red phosphorus particles, and then the organic resin is deposited on the red phosphorus particles. can be done.

Treatment of red phosphorus with titanium dioxide can be carried out in the aqueous phase to deposit titanium hydroxide dioxide on the red phosphorus. In this operation, the red phosphorus particles are preferably suspended in water, and the resulting slurry is heated at about 0°C to about 9θ°C.
, preferably to about goC. The heated slurry is slowly mixed with the required amount of a water-soluble titanium salt 9, such as titanium phosphate, to achieve the desired treatment level at a slightly acidic pH. The pH of the slurry is then adjusted to a range of about 0 to about q to deposit hydrated titanium dioxide onto the red phosphorus particles.

The slurry is then treated with an organic resin. The method and conditions for organic resin treatment depend on the form and nature of the resin used to treat the red phosphorus particles.

The resin is usually added to the slurry in uncured or partially cured form and is cured on the surface of the red phosphorus particles.

If the organic resin is an epoxy resin, an aqueous dispersion of uncured epoxy resin in an amount sufficient to provide the desired treatment level is mixed with a slurry of red phosphorous treated with a titanium compound, followed by an aqueous solution of an epoxy hardener. Add to slurry.

Raise the pH of the slurry to about 65°C to about 65°C, and raise the pH of the slurry to about
The mixture is stirred at a temperature of 100 ml for a period of time to allow crosslinking, usually from about 0.5 to about 2 hours. Thereafter, the pH of the slurry is raised again to about 7-g, and crosslinking is completed in about 10 minutes to about 30 minutes.

When the organic resin is a melamine-formaldehyde resin, an aqueous solution of a thermosetting uncured melamine-formaldehyde resin is added to a slurry of red phosphorus particles treated with a titanium compound, and the pH of the slurry is adjusted from about . The slurry is then heated to about g[theta]C to about 10[theta]C, and the resin is thermally cured for about o,z to about co hours.

If the organic resin is a urea-formaldehyde resin, an aqueous solution of uncured urea-formaldehyde resin is added to the slurry of red phosphorous particles treated with a titanium compound. The pH of the slurry is adjusted to about 0.5 to about q.o, and the slurry is heated to about 0.0 to about 70 0.degree. The resin is cured for about 1 hour.

The treatment of red phosphorus particles with titanium phosphate (orthophosphoric acid, not titanium sulfate alone) is similar to the above-mentioned deposition of titanium dioxide, except that a water-soluble salt of IJ or orthophosphoric acid, such as sodium dihydrogen phosphate and titanium sulfate, is added to the slurry. It can be carried out in the aqueous phase in a similar manner to the aqueous phase treatment for

After titanium phosphate deposition, the slurry is treated with an organic resin as described above for titanium dioxide treatment.

After completion of the resin deposition step, the treated red phosphorus is fractionated, for example by filtration, washed with water, dried and dehydrated in a vacuum oven at a temperature of about 10[theta]C to about /30[deg.]C.

Red phosphorus treated with a specific amount of titanium dioxide or titanium phosphate and a specific amount of a specific organic resin using the present invention has improved properties compared to those of the prior art. Red phosphorus treated with titanium dioxide and epoxy resin has greater stability against degradation from the formation of oxidation products and phosphine than red phosphorus treated with titanium alone at the same titanium concentration level; The same stability can be achieved with less titanium dioxide by using a combination of titanium dioxide and resin. The improved stability reduces the formation of phosphoric acid and reduces the generation of phosphine during storage of the treated red phosphorus. It is clear that the presence of titanium dioxide or titanium phosphate on the red phosphorus contributes to a large extent to the low acid formation, and the presence of organic resins on the red phosphorus contributes to a large extent to the low phosphine formation. It is clear that

Although red phosphorus treated with titanium dioxide and melamine resin has lower stability than red phosphorus treated with titanium dioxide and epoxy resin, it has good properties that are advantageous for certain uses of red phosphorus, such as in the Matsushi industry. Has water dispersibility.

The red phosphorus treated according to the invention requires only a very short time for filtration and exhibits a much lower water retention capacity than the red phosphorus treated with aluminum hydroxide, resulting in the need for operation, unlike the aluminum hydroxide treatment. time is significantly reduced.

〔Example〕

The present invention will be further explained with reference to Examples (hereinafter referred to as just one example unless otherwise specified).

Example/ This example illustrates the stabilization of red phosphorus by a combination of titanium dioxide and epoxy resin.

Typically 0. /! Amorphous red phosphorus (RAP) with a particle size of r -0,0/in is suspended in 100 ml of water at a concentration of the red radish sg and heated to 60° C. with stirring. Adding various amounts of titanium sulfate to samples of slurry;
The pH of the slurry was adjusted to 3 to form a precipitate of hydrated titanium dioxide on the red phosphorus. In this example, the amount of Tiet deposited is expressed as ppm of T1 in Tie.

The aqueous dispersion of uncured epoxy resin was then mixed with the suspension of red phosphorous particles and the solution of epoxy resin and curing agent was added. The epoxy resin used is manufactured by Chemroy Chemicals Ltd.
It is an epoxy resin sold under the trade name DJ, R, , 7 Moss by a). This resin beam, E, R,
,? J/ is a mixture of an epoxy resin and an aliphatic reactive diluent which is an aliphatic glycidyl ether of CH to CI4. D, Hunger R,, 32Q has an epoxy equivalent of /92~-〇　 and a viscosity of 60θ~g00(!I)θ at 25°C. D, Fi, R,,? J/ is the reaction product of bisphenol A and shrimp chlorohydrin, with a weight epoxy equivalent of 1 g-/90 at U S°C and /10 at 23°C.
It has a viscosity of 00~/4000 Cp8. The resin is 7% in the form of an emulsion in water (3I resin in 50 ml of water)
The surfactant Tween 20
(Sorbitol monostearic acid) was added and used. The curing agent is manufactured by Henkel End Corporation (Ho
The curing agent was designated as TSXII-klt# by nkθ1 & Co.).

Hardener T13X Anyori has an amine value of 3g! -S-Gio is an aliphatic amidoamine which is a water reducing agent and was used in the form of an aqueous dispersion (3 g of amine in 0 ml of water).

Next, 5 wt% NaOH was added to adjust the pH to S, and the temperature was increased to 60°C.
The suspension was stirred for 7 hours. Then wt% NaOH was added to raise the pH to 7 and the mixture (suspension) was stirred for an additional 75 minutes to crosslink the resin and form a coating on the RAP particles. Thereafter, the mixture was filtered, and the filter residue was washed with water and dried in a vacuum oven at about 10° C. for about 76 hours.

The stability of treated red phosphorus samples was tested and the results were compared to the stability of untreated red phosphorus, red phosphorus treated with resin only, red phosphorus treated with aluminum hydroxide and epoxy resin, and red phosphorus treated with titanium dioxide only. compared to gender.

The stability of red phosphorus against oxidation was tested by keeping the sample in an oven at a temperature of 70°C under conditions of relative humidity of 100 °C and H3P0. Measure the acidity expressed as . The results obtained are shown in the graph of FIG. The descriptions correspond to the samples listed in Table 1 below.

The results shown in Figure 1 indicate that red phosphorus treated with 10O100Opp and a small amount of resin has approximately the same stability against oxidation as that treated with JOOOppmTi, and is more stable than that treated with resin alone or with aluminum and resin. I'm going to use it.

When the resin is combined with KOθθppm Ti and 3θθQ ppm Ti, the stability is further increased, and T10
．． Alone or A [! It is more stable than the combination of (0H)3 and epoxy resin.

The treated samples described above were also tested for phosphine generation and compared to untreated samples.

Samples were placed together with water in a glass bottle (b 9 cm) with a septum that could be inserted directly with a syringe.
This was stirred. After repeated stirring and standing at room temperature, the phosphine concentration was measured by gas chromatography using a flame spectrophotometer.

The obtained results are listed in the following M1 table: Table 1 (1) / θ, 7g% resin Oo, 2° (2), 2 0.441% resin A O, /A (1) 3, ? 000 ppm Ti+0.7g% resin A
OJ! (1) 'I 2000 ppm Ti, +o, 7gc4oo
1. 0.30! r, 70001; lpm M+0.
71! r% resin (1) A O,, 12 (2) 6 /θ00 ppm T1+0.3A% resin 4to
, tia(2) 7 /θ00 ppm Ti+O,, tθ Chi resin II
O,2II(2) Za -〇〇Q ppm Ti+OJ4% resin yo,
rtt(2) 9 2000 ppm T1-4-0.30% resin e
o, 2g(2) /θ 3θ00 ppm Ti+o,jθ% resin II
O, Ak // 3θθOppm Ti 60,1:J
+31 +2] 7.2-〇00 ppm Ti 10, g□% resin 9
0.2!13 Untreated RAP & jJO Notes: (1) Resin/hardener ratio / / / (2) Resin/hardener ratio // θ, 6 (3) In this experiment, titanium was used as phosphate Deposited.

As can be observed from the results in Table 1, phosphine generation is greatly reduced by treatment with amorphous red phosphorus, either alone or in combination with T1 or M. Phosphine generation was lower in the sample treated with T1 alone.

EXAMPLE This example illustrates the stability of amorphous red phosphorus when stored under humid conditions F.

After processing the red phosphorus, the procedure of Example 1 was repeated except that the red phosphorus was not dried. Oxidative stability and phosphine evolution were determined as described in Example/. The measured values of oxidation stability are plotted on the graph shown in Figure 1, and the measured values of Bosphin generation are listed in the following table:
AP A 20. t, 2 3θO (7ppm Ti 6 k, 93 θθ
θppm 'ri+o, xs epoxy resin 6 /, /
lI ρθθθppm Ti 10,? Chepoxy resin
6 ko, /ro, Tacheboxy resin &, 2. /A
! 000pprnTIA A,/λ From the results shown in Figure 1, it can be observed that the oxidative stability increases when titanium dioxide and epoxy resin are used in combination. The results in Table 1 show that treating wet samples with a combination of titanium dioxide and epoxy resin significantly reduces phosphine generation.

Example 3 This example illustrates the stabilization of red phosphorus by a combination of titanium dioxide and melamine resin.

Typically, amorphous red phosphorus with a particle size of θ, Δ ~ 0,0/#III is mixed with water yoOd and Rico o1! Ti08O4-H,5o4-gH20
10% aqueous solution of 3. Mixed with tough. Next〇Regulations Na
OH was added to bring the pH to 3. A sufficient amount of a 10% aqueous solution of melamine resin to obtain the desired treatment is added to the mixture and the pH is again adjusted to about 3 by addition of S%H,PO,. The suspension was heated to 95° C. with stirring, reacted for 7 hours, and filtered. During the curing of this resin, the pH was controlled at approximately 3. The filtration residue was washed with water and dried in a vacuum oven at about 100° C. for about 76 hours.

The melamine resin used is Mon5ant.
o) Trade name Sufribu Set / 0 / (5cri
It was a methylated melamine-formaldehyde resin sold as pθθt10/). What is this resin?
It is purchased in the form of an aqueous solution. This resin was a polycondensation product of melamine and formaldehyde.

Samples were tested for oxidative stability and phosphine evolution as described in Example 1, and the results were compared to those for samples treated with resin alone and untreated red phosphorus. The oxidative stability results for RAP treated with Sufligset 10/ are plotted in the graphical representation of FIG. 3, and the phosphine generation data for RAP treated with Suffrigset ioi are listed in Table 1 below: Table 1 / , 2000ppmTi-1-7% resin 40J'
1.2. 2000ppm Ti-1-o, 5% resin
AO, A-7j, ) 000ppm Ti 10j% resin Ao, ysri 7% resin Ao, qi s, 2% resin AO, 1:41 6.2θ00pprn T1+o, 3r% epoxy/4
0. AIri Untreated RAP 4 Ko, Ko3 From the results in Figure J, T10. RAP stabilized with and melamine resins is stable against oxidation, but the resins alone are not very effective.

Phosphine generation was T10. compared to untreated RAP and treatment with resin alone. and decreased by treatment with melamine resin.

EXAMPLE This example illustrates the stabilization of red phosphorus by a combination of titanium dioxide and a urea-formaldehyde resin.

The procedure of Example 3 was carried out using a urea-formaldehyde resin of the same type, except that the pH was controlled during curing of the resin and phosphoric acid was used as needed. The treatment operation was repeated. The resin used was from Monsanto under the trade name Regimen (Reday 1mθne) LTX-,7/-4/
and LTX-J/-Roux. LTX
-,? /-A / is the minimum solid content 9g%, 1 at S℃
It is a modified urea-formaldehyde resin with a viscosity of g00 cpB and a density of i, ittg/d at 2/°C. L
TX-J/-b2 is a modified urea-formaldehyde resin with a solids content of 93-97%, a density of 809 g/ml at -3°C, and a viscosity of 400 cps at 21°C.

Samples were tested for oxidative stability and phosphine evolution as described in Examples/and results were compared to samples treated with resin alone and untreated red phosphorus. The oxidative stability results are plotted in the graphical diagram of FIG. 9, and the phosphine generation data are listed in Table 1 below: Table 2/θ, 3% LTX-J/-AI/2 0.1. 7/,
Ochi LTX-,7/-4/ /ko θ,? 3λ000p
pm Ti-1-Oj%LTX-,3/-AI/co
/, 7II 200θppm Ti-1-/, 0% L
TX-J/-AI /J 2.2 (1) Evening 2000ppm Ti +7.0%LTX-, 7/-
4/ /J J76 KoOf717ppm Ti+OJ
%LTX-,7/-i j OJ7 JOOOppm
Ti-1-/, θcl, LTX-J/-&ko r o,
Note: ill T1 was deposited as titanium phosphate.

As can be observed from the results of the graph in Figure 9, T10
．． Alternatively, a combination of titanium phosphate and urea-formaldehyde resin increases stability.

It is more effective to use LTX-J/-AJ resin.

This example is a compilation of data from previous examples and some additional experimental results for purposes of comparison and to draw conclusions from the data.

Selected data from the previous examples are listed in Table 1 below: The following conclusions can be drawn from the above data: (a) The stability of RAP treated with the combination of 'rio□ and epoxy resin is When compared to RAP treated with resin alone, the stability is improved by a factor of about 3, but the combination of N,(on)s and epoxy resin improves stability by only a factor of about -2; (b) Tie, and melamine resin. (c) Tie, (!: The stability of RAP treated with the combination of urea-formaldehyde resins is improved by a factor of two when compared to RAP treated with the resin alone; When compared to that treated alone, it is improved by about 3 times; (RAP using di Ti O2 and epoxy resin
The treatment of RAP with resins in general and epoxy resins in particular gives the best results from all aspects with the best stability against oxidation and the lowest amount of phosphine;
treatment reduces the amount of phosphine generated; (fl
Tie, and AQ(OH)3 stabilize RAP against oxidation, but T10. A1 (0H
)s does not improve the stability of RAP.

To summarize the disclosure herein, the present invention provides that dioxide ≠
The object of the present invention is to provide a novel amorphous red phosphorus having improved oxidation stability and phosphine generation by treatment with titanium or titanium phosphate and an organic resin. Modifications within the scope of this invention can be performed.

[Brief explanation of drawings]

Figure 7 is a graph showing the effect of titanium dioxide and epoxy resin on the oxidative stability of red phosphorus, and Figure 2 is a graph showing the effect of titanium dioxide and epoxy resin on the oxidative stability of wet red phosphorus. Figure 3 is a graph showing the effects of titanium dioxide, titanium phosphate, melamine-formaldehyde, and resin on the oxidative stability of red phosphorus; FIG. 3 is a graph showing the effects of urea-formaldehyde resin and urea-formaldehyde resin.

Claims (1)

[Claims] / In a red phosphorus-containing composition in which the red phosphorus particles have a particle size of at most 2 rays, the titanium dioxide or titanium phosphate expressed as the weight of titanium is 0.0 ~ /
, 0% by weight and an organic resin in o, i~, 0% by weight. A red phosphorus-containing composition having a comparable particle size even if the red phosphorus particles are large. The composition according to claim 1, wherein the organic resin is an epoxy resin, a melamine-formaldehyde resin or a urea-formaldehyde resin. 3. The composition according to claim 1 or 1, which contains 0.5 to 3.0% by weight of an organic resin. Add a titanium compound to a slurry of red phosphorus particles having the same particle size even if the red phosphorus particles are large;
．． Deposition of titanium dioxide or titanium phosphate in an amount of 02~/, 0% by weight is carried out; a water-soluble or water-emulsifiable resin is added to the slurry and the resin is deposited on the red phosphorus particles o,i-
At most, 21AN consists of separating from the slurry the red phosphorus particles deposited and treated in an amount of s, o wt%.
A method for producing a red phosphorus-containing composition having a particle size of . j) The manufacturing method according to claim iZ, wherein the organic resin is an epoxy resin, a melamine-formaldehyde resin, or a urea-formaldehyde resin. 6. Claim tA in which the resin added to the slurry is an uncured resin, and the resin deposited on the red phosphorus particles is cured.
The manufacturing method described in Section ti or Section S gi2. 2. The manufacturing method according to any one of claims d to 6, wherein the titanium compound is titanium sulfate. and the titanium compound is titanium sulfate, and ortho IJ
7. The method according to claim 6, wherein a water-soluble salt of phosphoric acid or phosphoric acid is added to the slurry. Add the uncured epoxy resin and the curing agent for the resin to the slurry, adjust the pH of the slurry to 4/-4, adjust the temperature of the slurry to 0~tθ℃, and add the slurry to OJ~
Claims 1 to 6 wherein the hardened resin is deposited by stirring for one hour, raising the pH of the slurry to a value of 7 to 30 g, and stirring the slurry for 10 to 30 minutes.
The manufacturing method described in any of the paragraphs. /θ uncured melamine-formaldehyde resin or uncured urea-formaldehyde resin is added to the slurry,
The pH of the slurry was adjusted to a value of -47, the temperature of the slurry was adjusted to a value of 0 to 0. f-
A process according to any one of claims d to 9, wherein the hardened resin is deposited by stirring for one hour. // Heating the slurry to a temperature of to-to °C and then adding the titanium compound
The manufacturing method described in any of Section O. /-L Wash the separated red phosphorus particles, 700-730
Claims 7 to 1/1 drying at a temperature of °C.
The manufacturing method described in any of the paragraphs.