CA1309789C - Method for producing red phosphorus flame retardant and nonflammable resinous composition - Google Patents
Method for producing red phosphorus flame retardant and nonflammable resinous compositionInfo
- Publication number
- CA1309789C CA1309789C CA000568936A CA568936A CA1309789C CA 1309789 C CA1309789 C CA 1309789C CA 000568936 A CA000568936 A CA 000568936A CA 568936 A CA568936 A CA 568936A CA 1309789 C CA1309789 C CA 1309789C
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- Prior art keywords
- red phosphorus
- particles
- phosphorus
- resin
- weight
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/003—Phosphorus
- C01B25/006—Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
- C09K21/04—Inorganic materials containing phosphorus
Abstract
METHOD FOR PRODUCING RED PHOSPHORUS FLAME RETARDANT
AND NONFLAMMABLE RESINOUS COMPOSITION
ABSTRACT OF THE DISCLOSURE
Red phosphorus flame retardants for synthetic resin are produced by a method comprising the steps of heating yellow phosphorus at temperatures of 250 to 600 °C to effect a partial conversion of yellow phosphorus to red phosphorus; removing unconverted yellow phosphorus; and coating particles of the resulting red phosphorus with at least one of thermosetting resin and metal hydroxide. The thus obtained red phosphorus flame retardants are very stable because of significantly improved heat resistance, water resistance and weatherability and thus can provide nonflammable resinous compositions which can be used for long period of time. The nonflammable composition consists essentially of 100 parts by weight of polyolefine resin, 20 to 200 parts by weight of hydrated inorganic filler and 0.1 to 30 parts by weight of the coated red phosphorus flame retardant.
AND NONFLAMMABLE RESINOUS COMPOSITION
ABSTRACT OF THE DISCLOSURE
Red phosphorus flame retardants for synthetic resin are produced by a method comprising the steps of heating yellow phosphorus at temperatures of 250 to 600 °C to effect a partial conversion of yellow phosphorus to red phosphorus; removing unconverted yellow phosphorus; and coating particles of the resulting red phosphorus with at least one of thermosetting resin and metal hydroxide. The thus obtained red phosphorus flame retardants are very stable because of significantly improved heat resistance, water resistance and weatherability and thus can provide nonflammable resinous compositions which can be used for long period of time. The nonflammable composition consists essentially of 100 parts by weight of polyolefine resin, 20 to 200 parts by weight of hydrated inorganic filler and 0.1 to 30 parts by weight of the coated red phosphorus flame retardant.
Description
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METHOD FOR PRODUCING RED PHOSPHORUS FLAME RET~RDANT
AND NONFLAMMABLE RESINOUS COMPOSITION
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a method for producing a red phosphorus flame retardant, especially, a highly stabilized red phosphorus flame retardant, and to a nonflammable resinous composition containing the flame retardant.
METHOD FOR PRODUCING RED PHOSPHORUS FLAME RET~RDANT
AND NONFLAMMABLE RESINOUS COMPOSITION
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a method for producing a red phosphorus flame retardant, especially, a highly stabilized red phosphorus flame retardant, and to a nonflammable resinous composition containing the flame retardant.
2. Description of the Prior Art Red phosphorus has been well known as a flame retardant for synthetic resin and has been incorporated into various resins. However, commercially available red phosphorus has hardly been used as it is. In most cases, special stabilizing treatments are required.
This is mainly due to the following reasons. Namely, since red phosphorus is unstable to heat, friction, shock, etc., accidents are apt to occur during the storage and handling and incorporation of it into synthetic resin. Further, red phosphorus reacts with moisture and oxygen in the air, thereby forming toxic and harmful substances. Such undesirable properties of red phosphorus do not permit its safe use as a flame retardant.
Further, red phosphorus does not have a qood compatibili~y with synthetic resin. For these reasons, red phosphorus is usually coated with an inorganic or organic material. However, in recent years, as physical properties required for synthetic resins ~te increasingly severe, more highly stabilized ~.
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flame retardants of red phosphorus have been demanded.
For example, polyolefine resins have been used as covering materials for communication cables, electric cables, etc. In such uses, serious accidents have been experienced due to fires of the cables. Therefore, countermeasure has been urgently needed against such accidents and, at the same time, higher levels of nonflammability are required in the covering resin materials.
Conventionally, for example, polyvinyl chloride and halogen-containing polyolefine have chiefly been used as nonflammable covering resin materials.
However, these halogen-containing polymers have great difficulties to ensure safety and prevent accidents, since they ca~se problems such as evolution of large quantities of smoke and gas, which are highly toxic and corrosive, during a fire. As means for eliminating these di~ficulties, it has been proposed to add a smoke inhibitor, an acid trapping filler, etc.
However, these additives have to be added in large amounts to fully prevent the smoking and gas evolution and, thereby the nonflammability inherent in the foregoing polymers may be considerably impaired. Therefore, under the existing circumstances, the halogen-2S containing polymers can not meet, at the same time, therequirements of reduction of smoking and environmental pollution and good nonflammability.
On the other hand, as a halogen-free nonflammable composition, there has been known a polyolefine composition prepared by incorporating a high-temperature active filler, such as magnesium hydroxide or aluminum hydroxide, which absorbs combustion heat, into polyolefine type resin. However, in the composition, these inorganic fillers are needed in if~: 2 large quantities in order to ensure a sufficient nonflammability, thereby causing an undesirable deterioration of the properties of the used resin, especially with respect to mechanical and electrical properties, heat resistance, water resistance and weatherability.
As previously described, red phosphorus has been well known to be an effective flame retardant for synthetic resin and has been used in practical applications related to electronics, etc.
However~ red phosphorus is disadvantageous, for example, in that it forms phosphine and oxidized products With the lapse Of time, thereby deteriorating the used reSin. Therefore, currently, red phosphorus flame retardants composed of red phosphorus particles coated with a stabilizing agent have been mainly used.
However, even the thus stabilized red phosphorus has only a very insufficient stability for a long-term use under variable environmental conditions, such as for example in cables, and, thus, can not provide good utility for such an actual use.
Nevertheless, there is still now a strong demand for further improvements in the stability of red phosphorus because of the several advantageous propertiPs of red phosphorus. For example, when red phosphorus is used, evolution of smoke and toxic gases is very slight as compared with the foregoing chlorine-containing flame retardant. Since a considerably high flameproofing effect can be obtained with addition of small amounts of red phosphorus, addition of filler which may adversely affect the mechanical properties of resin can be avoided.
Under such circumstances, the present Inventors have considered that the known surface treatments for ,r~
....
1 3 ~ 3 1 ~, stabilizing hava limitations and made many studies on stabilization of red phocphorus flame retardants from a quite different angle. As a result, it has been found that subst~nt;ally ~pheric~1 re~ phos~orus having entirely different s~rface state, physical properties and shape from any known red phosphorus can be obtained by a novel process unknown in the prior production pro~cesses of red phosphorus.
Further, although the novel red phosphorus itself can be sufficiently used as a flame retardant because of its very high stability, it can be f~lrther highly stabilized by surface treating, and, thereby, exhibits significantly improved water resistance, corrosion resistance and heat resistance as compared with those of the red phosphorus flame retardant obtained in the prior art.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a method for producing a red phosphorus flame retardant having improved stability and safety.
A further object of this invention is to provide a resinous nonflammable composition prepared by incorporating the red phosphorus into thermoplastic resin, especially, polyolefine resin, in which problems such as fire and environmental pollution are minimized and significantly improved heat resistance, water resistance and weatherability can be stably ensured over long periods of time.
In accordance to a first aspect of the present invention, a red phosphorus flame retardant is prepared by a method comprising the steps of:
heating yellow phosphorus at temperatures of 250 to 600 C to effect a partial conversion of yellow .
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I phosphorus to red phosphorus;
removing unconverte~ yellow phosphorus7 and coating particles of the resulting substantially spherical red phosphorus with at least one of thermosetting resin and metal h~droxideO
In a further aspect of the present invention, there is provided a nonflammable resinous composition containing the red phosphorus flame retardant prepared by the method specified above. The nonflammable composition consists essentially of 100 parts by weight of polyolefine resin, 20 to 200 parts by weight of hydrated inorganic filler and 01. to 30 parts by weight of the coated red phosphorus flame retardant.
In another aspect of the present invention, a method for producing a red phosphorus flame retardant, said method comprising the steps of:
heating yellow phosphorus at temperatures of 250 to 600C. to effect a partial conversion of not higher than 70% of said yellow phosphorus to red phosphorus;
removing the unconverted yellow phosphorus; and coating the resulting substantially spherical particles of red phosphorus with at least one of thermosetting resin and metal hydroxide, said particles of red phosphorus having been formed without being subjected to a pulverization procedure.
In a further aspect of the present invention, a nonflammable resinous composition consisting essentially of 100 parts by weight of polyolefine resin, 20 to 200 parts by weight of hydrated inorganic filler and 0.1 to 30 parts by weight of substantially spherical particles of red phosphorus flame retardant, said flame retardant being produced by heating yellow phosphorus at temperatures of 250C. to 600C. to effect a partial conversion of not r~ ~ ~
-5a-1 highee than 70% of said yellow phosphorus to red phosphorus; removing the unconverted yellow phosphorus; and coating the resulting substantially spherical particles of red phosphorus with at least one of thermosetting resin and metal hydroxide, said particles of red phosphorus having been formed without being subjected to a pulverization procedure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Red phosphorus has been produced by thermal conversion of yellow phosphorus. In the production process of red phosphorus heretofore employed, yellow phosphorus as a starting material is heated at a temperature near the boiling point of yellow phosphorus over a few days until the conversion reaction is completed, and red phosphorus is obtained in the form of a hard cake-like coagulated mass.
When red phosphorus is incorporated as a flame retardant into synthetic resin, it must be in a powder form.
Therefore, the prior art red phosphorus which is taken out of a conversion vessel as a coagulated mass indispensably requires a pulverizing step. In contrast to this, since conversion conditions according to the method of the present invention are different from those of the above conventional method, the resulting red phosphorus can be obtained in a powder form composed of substantially spherical fine particles and crumbly agglomerates i c, ~ g ~
thereof, and, thereby, does not require ~ pulverizing step.
In practicing the method of the present invention, yellow phosphorus as a raw material is charged into a reactor which has been previously filled with an inert ~ gas and heated to melt and then conversion is commenced. The conversion is continued until the conversion of yellow phosphorus to red phosphorus reaches the desired conversion ratio and the conversion is stopped. After removing unconverted yellow phosphorus from the reactor by an appropriate technique, there c~n ~e obtained substantially sphericAl red phosphorus as a powder form. The present Inventors have unexpectedlyfo~n~
t~at th~ ~uhct~nt;ally sp~er;c~l red phosphor~s ~r obt~;ned by such a partial conversion has a considerably high stability as compared with the known pulverized red phosphorus. The present invention has bPen achieved based on this finding.
It has been found through the Inventors' extensive studies that conversion of yellow phosphorus to red phosphorus commences at a relatively low temperature and becomes rapid at about the boiling point of yellow phosphorus. Thereafter, the reaction rate further increases with an increase in temperature. In a low temperature range, red phosphorus is produced as fine spherical particles in molten yellow phosphorus.
However, with increase in temperature, particles of red phosphorus agglomerate together and their particle size - increases. The growth and agglomeration of the particles are also detected when the conversion is prolonged. Therefore, when the conversion reaction is carried out at a too high temperature or over a too long period of time, it excessively proceeds and most f the yellow phosphorus is converte~ to red phosphorus.
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In such conditions, the red phosphorus can no longer exist in the form of particles, ~orming an agglomerated product. Consequently, it is impossible to obtain red phosphorus in a powder state. Many efforts have been made b~ the present ;nventors in order to avoid the foregoing excessive conversion and thereby make possible the attainment of powdered red phosphorus co~osed of suhstantially spherical fine p~rticles. It has bee folmd that it is necessary to continue the conversion of yellow phosphorus to red phosphorus at 250 to 600 C while maintaining the flowability of the reaction mixture and the flowability of the reaction mixture can be maintained by controlling the conversion ratio to 70%
or lower. The conversion ratio varies depending on the processing temperature and time. Lower processing temperature and shorter time will result in a lower conversion ratio. The conversion ratio can be arbitrarily adjusted by appropriately adjusting the processing temperature and time for the conversion.
When the conversion ratio is controlled to 70% or lower, the reaction mixture is retained in a flowable state and red phosphorus can be obtained in a powder form after removing unconverted yellow phosphorus.
When the tempèrature during the conversion procedure is below 250 C, the reaction rate is very small. Thus, such a lower temperature is unfavorable as a practical processing condition. While temperatures exceeding 600 C result in an excessively high conversion rate and make difficult the control of the reaction. Further, the reaction mixture rapidly loses its flowability and a compact massive product results. Therefore, it is impossible to ohta;n pow~ered red ~hosphorus without a further pulverizinq step, as described in the prior art process.
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As set forth above, when the reaction temperature is low and the reaction time is short, the conversion ratio becomes small and the resulting red phosphorus powder has a small particle size. On the contrary, when the reaction time is long and the conversion ratio becomes large, the degree of agglomeration of red phosphorus particles is increased and the particle size - becomes large. However, w~en th~ thus agglomerated ~rticle~ ~re obtained from a flowable reaction mixture, the particles are, unlike a cake-like compact mass of red phosphorus, very loosely agglomerated and form a crumbly mass which can be readily crumbled to powder by a light mechanical treatment, without any treatment as called pulverizing. Inventors' experimental data ~5 showed that the stability of the agglomerated red phosphorus particles is not adversely affected by the dividing treatment as required for such a crumbly agglomerate and the red phosphorus powder which is obtained by dividing the particles agglomerated also exhibits a high stability. Therefore, the red phosphorus powder of the present invention may also contain the red phosphorus powder obtained by dividing such loosely agglomerated particles. ~he red phosphorus powder obtained according to the present invention and composed of substantially spherical ~rticles has a particle size of the order of few microns to 100 ~m and the particle size ranges in a narrow particle size distribution as compared with that of known pulverized red phosphorus powder and has a high uniformity.
In the present invention, conversion of yellow phosphorus to red phosphorus is performed by a partial conversion of yellow phosphorus and is quite different from d complete conversion heretofore practiced.
Therefore, a removal process of unconverted yellow ~:~, },~
i, _9_ phosphorus is required and the process is readily performed using an appropriate technique, such as distillation, filtration or solvent extraction.
Practically, distillation is carried out in an inert gas atmosphere under reduced pressure or ordinary pressure, after termination of the conversion reaction.
Unconverted yellow phosphorus is removed by this distillation. When filtration is used, the reaction mixture is put into water or an aqueous solution and red phosphorus is separated from unconverted yellow phosphorus by filtration and dried. When solvent extraction is used, unconverted yellow phosphorus is extracted from the reaction mixture, using a solvent capable of dissolving yellow phosphorus. Needless to say, these techniques may be used in combination thereof. In any case, the removed yellow phosphorus may be recycled in a subsequent conversion process to red phosphorus. The red phosphorus obtained accordin~
to the process of the present invention itself has a high stability far superior to red phosphorus stabilized in the prior art. However, when the red phosphorus of the present invention is further surface-treated with at least one of thermosetting resin and metal hydroxide, such as aluminum hydroxide, zinc hydroxide, etc., the stability is surprisingly improved and problems due to deterioration of synthetic resin which may be caused due to addition of the red phosphorus can be almost eliminated. Almost complete water resistance and corrosion resistance can be achieved and heat resistance is considerably improved.
Therefore, the substantially spherical red phosphorus of the present invention can be used as a flame retardant for thermoplastic resin with safety. Such unexpectedly high stability of the red phosphorus flame retardant of the present ~3 7J~ ~
invention is considered to be due to the fact that the surface state of the red phosphorus powder of the present invention is considerably different from that - of the prior art pulverized red phosphorus powder.
When red phosphorus powder is, like the aforesaid prior art, obtained by pulverizing a hard agglomerated mass, the resulting powder has a complicated surface state having acute edges and sharply fractured faces. In contrast to this, since the red phosphorus powder obtained according to the present invention is not suhjecte~ to a pulverizing process, its surface is almost free of fractured faces and edge llnes. It has been confirmed by electron microscopy that the red phosphorus powder of the present invention is composed of particles having naturally formed spherical surfaces and agglomerates thereof. The pulverized red phosphorus powder has many active sites on its surface and readily reacts with moisture and oxygen. On the contra~, the sub-stantially spherical red phsophorus ~rticles of the present invention are almost free of such active sites and the sur~ace state thereof is extremely stable. Therefore, chemical reactions with moisture and oxygen hardly occur and, as a result, the moisture resistance and heat resistance are greatly improved. Further, in the surface-treating with thermosetting resin or metal hydroxide, it is difficult to uniformly and wholly coat the pulverized red - phosphorus due to its surface state and some portions of the surface may be left without a coating. However, the spherical red phosphorus of the present invention can be uniformly and entirely coated. This makes a great difference in its stability The surface treatment of the red phosphorus of the present invention by thermosetting resin or metal hydroxide may be performed in a conventional manner.
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Examples of suitable thermosetting resins include formaldehyde type resins, such as phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, furf ~ 1 alcohol-formaldehyde resin, aniline-formaldehyde resin, etc.; and polyhydric alcohol-polybasic acid resins.
In practicing the present invention, 10 to 100 - parts by weight of the red phosphorus is suspended in 100 parts by weight of water to give a suSpension of red phophorusO To the resulting suspension, a raw material or initial condensation product for the thermosetting resin is added in amounts of 1 to 35 parts by weight with respect to 100 parts by weight of the red phosphorus and stirred at 40 to 100 C for 1 to 3 hours. If necessary, polymerization catalyst and filler such as aluminum hydroxide, magnesium hydroxide or titanium hydroxide may be present in the suspension.
The addition of the filler not only improves the mechanical strength of the resulting resin coating but also provides a beneficial effect of shielding the purplish red color inherent to red phosphorus, thereby making possible a greatly expanded use of the red phosphorus flame retardant of the present invention.
When the red phosphorus is coated with metal hydroxide, for example, aluminum hydroxide or zinc hydroxide, an aqueous solution of sulfate or chloride of aluminum or zinc is added to an aqueous suspension of red phosphorus and aluminum hydroxide or zinc hydroxide is precipitated onto the red phosphorus powder, for example, by neutralization with sodium hydroxide or double decomposition by ammonium bicarbonate. The aqueous suspension of the red phosphorus preferably consists of 10 to 100 parts by weight of the red phosphorus and 100 parts by weight of , ~ 3 ~
water and the concentration of the aqueous solution of the metal salt may be preferably 5 to 30~. The guantity of the resulting metal hydroxide coating is preferably in the range of 1 to 30 parts by weight per 100 parts by weight of the red phosphorus. When the coating with the metal hydroxide is followed by coating with the thermosetting resin, the resulting double-coated red phosphorus has the highest level of stability and, even in use in severe conditions, it is not subject to deterioration. Therefore, in resinous compositions flameproofed by SUCh a highly stabilized red phosphorus flame retardant, deleterious effects due to the use o~ the red phosphorus flame retardant are scarcely observed over long periods of time. When the double-coating procedure is carried out, the quantity of the metal hydroxide coating may be in the range of 0.1 to 30 parts by weight per 100 parts by weight of the red phosphorus.
In the preparation of the nonflammable composition of the present invention, the red phosphorus flame retardant prepared by the method of the present invention is mixed in the proportion of 0.1 to 30 parts by weight with respect to 100 parts by weight of polyolefine resin. When the red phosphorus flame retardant is less than 0.1 parts by weight, a sufficient flameproofing effect can not be obtained.
On the other hand, the use of the red phosphorus flame retardant exceeding 30 parts by weight unfavorably affects physical properties of the resin.
The polyolefine resin may be any resin which can be obtained using olefine type monomers as starting materials and, as such polyolefine resin, there may be mentioned polyolefine type homopolymers, copolymer or mixtures thereof, more specifically, polyethylene, "~,,.~1 , i ~ , ~
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polypropylene, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, polybutene, cross-linked polyethylene, cross-linked polypropylene, ethylene-propylene rubber, poly-4-methylpentene-1, ethylene-butene copolymer, butylrubber, styrene-butadiene rubber and mixtures thereof. These resins are all free of halogen and can be effectively flameproofed by the red phosphorus of the present invention without deterioration of the mechanical and electrical properties. Therefore, the present invention can provide very useful nonflammable resinous compositions minimizing the problems of smoking and environmental pollution and having a superior combination of properties with respect to heat-resistance, water resistance and stability which insures a substantial long useful life. The foregoing properties are especially important for insulating materials used for covering communication cables and other electric cables which are used in widely variable environmental conditions, especially, with regard to temperature and water. According to the present invention, the cable covering materials are first successfully flameproofed with red phosphorus flame retardant to practical levels. Resins flameproofed with the prior art red phosphorus flame retardant are inferior in heat resistance and water resistance and, thus, when they are used to cover the above-mentioned cables, they are readily deteriorated in a short period of time, thereby causing swelling, embrittlement, dlscolorin~, etc. As a result, the mechanical properties and electrical properties of the covering materials are impaired and the cables become impractical from the standpoint of external appearance and safe use. However, in the resinous compositions flameproofed according to the ~ JP~-~?~ 9 present invention, their initial properties are stably retained over a long period of time even under severe conditions, such as heat, water, etc. This makes a great contribution to safe use and cost reduction in long-term use in applications related to the foregoing cables. Also, in other applications, there can be obtained considerable improvements in safe use and durability.
In the present invention, magnesium hydroxide, aluminum hydro~ide, basic magnesium carbonate, etc., may be employed as a filler synergistically increasing the flameproofing effect of the red phosphorus. When the fillers are used in combination with the red phosphorus, they synergistically improve the flameproofing effect of the red phosphorus, achieving high flameproofing effect which can not be obtained when the red phosphorus is used alone. Although the red phosphorus itself causes the evolution of small amounts of smoke, the above filler has an effect of reducing the smoke evolution. The inorganic fillers are preferably added in the range of 20 to 200 parts by weight with respect to 100 parts by weight of polyolefine resin or modified polyolefine resin.
Addition of less than 20 parts by weight can not achieve a sufficient synergistic effect in cooperation with the red phosphorus. On the other hand, when the addition exceeds 200 parts by weight, the physical properties of the resin are adversely affected. If necessary, additives such as dripping inhibitor (e.g., carbon black), lubricant, colorant, dispersant, etc., may be added to the nonflammable composition of the present invention.
Hereinafter, the present invention will now be described in detail with reference to the following _, ~
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examples. In the examples, the term "red phosphorus flame retardant" is used to mean "coated red phosphorus" and percentages are given by weight, unless otherwise specified.
EXAMPLES
Example 1 A stream of nitrogen gas was passed through a stainless steel vessel to displace the air and 500 g of yellow phosphorus was charged into the vessel. After sealing the vessel, the yellow phosphorus was heated at 270 C for four hours to effect conversion of yellow phosphorus to red phosphorus. Unconverted yellow phosphorus was removed from the vessel and there was obtained 211 g of red phosphorus in a flowable powder form having an average particle size of 50 ~m. The resulting substantially spheri.cal re~ phosph~rus ~5 s~spended in 400 ml of w~ter and 150 rnl of a 10% ~ql~eous sol~tion of ~sl~ninLnn sulfate was added to the resulting suspension. Then, 50 ml of a 5~ agueous solution of sodium hydroxide was added dropwise to the suspension while sufficiently stirring and the resulting suspension was heated to 50 C and held at this temperature for 30 minutes. The suspension was filtered, washed with water and dried.
There was obtained 217 g of red phosphorus flame retardant.
Example 2 A stream of nitrogen gas was passed through a high-pressure reactor to displace the air and 100 g of yellow phosphorus was charged into the reactor. After sealing the reactor, the yellow phosphorus was heated to 480 C for 30 minutes, held at that temperature for 10 minutes and cooled in the air. Unconverted yellow phosphorus was removed from the reactor, and 68 g of red phosphorus was obtained in a powder form.
The resulting substantially spherical red p~osphorus was sieve~
t~rough a l~O mesh screen. A]tho~g~ 22 percent of the red phosphorus powder was not passed, the residual red phosphorus powder can be readily crumbled by fingers to entirely pass through a 100 mesh screen.
Thereafter, the powder was suspended in 200 ml of water and 3 g of phenol and 6 g of 37% formalin were added to the resulting suspension. After heating the suspension to 80 C, 2 g of 85% phosphoric acld was added under stirring. After heating the suspension at 80 C for one hour with stirring, the suspension was cooled in the air, filtered and dried. There was obtained 72 g of red phosphorus flame retardant.
Example 3 A stream of nitrogen gas was passed through a reactor and 200 g of yellow phosphorus was charged into the reactor and heated at 280 C for one and a half hours to cau,se conversion of yellow phosphorus to red phosphorus. Vnconverted yellow phosphorus was removed from the reactor and 36 g of powdered red phosphorus having an average particle size of 28 ~m was obtained.
me resulting substantially shperica~ red phosphorus was suspended i~ lOO ml of~1ater. Tcl the suspension, ,~ml of 8%
aluminum sulfate was added and stirred. Then, 10 ml of a 15~ aqueous solution of ammonium bicarbonate was added dropwise to the suspension and the suspension was heated at 60C for 10 minutes. After adding 2 g of B~
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phenol and 4 g of 37% formalin to the suspension, the suspension heated ~o 80 ~C and 1g of 85% phosphoric acid was added under stirring. After stirring the suspension at 80 c for one hour, the suspension was s cooled in the air, filtered and dried. There was obtained 39 g of red phosphorus flame retardant.
Comparative Example 1 Pulverized red phosphorus was subjocted to the same coating treatment as described in _xample 1.
Comparative Example 2 Pulverized red phosphorus was subjected to the same coating treatment as described in Example 2.
Comparative Example 3 Pulverized red phosphorus was subjected to the same coating treatment as described in Example 3.
ThP uncoated red phosphorus obtained in Examples 1 to 3 were tested for the physical properties in comparison with pulverized red phosphorus set forth in Comparative Examples 1 to 3. The results are shown in Table 1.
Further, the stability of the red phosphorus flame retardants set forth in example and comparative examples was tested in accordance with the test procedures described below and the results are shown in Table 2.
Table 1 Physical Properti.es of Red Phosphorus _ _ Red Phosphorus Ignition Evolution or Elution of Average Point(C) Phosphine P2O5Particle (ppm) (mg)Size (llm) -Example No.
345 0.1 31.5 50 2 341 0.1 30.7 80 3 340 0.2 32.4 28 Pulverized Red Phosphorus 291 225.3 . 213.1 100 .
Table 2 Stability of Red Phosphorus Flame Retardant Flame Ignition Evolution ofElution of RetardantPoint(C) Phosphine (ppm)P2O5 (mg) . _ _ . .
- Example No.
348 0.0 5.3 2 355 0.0 5.6 :; 3 357 0.0 3.8 Compa ative Example No.
295 76.3 121.2 2 321 1.4 67.8 3 329 1.2 62.9 . _ _ . ... _ _ _ Measurement Method Ignition Point:
1 g of each sample was placed in a 10 ml porcelain crucible, then put in an electric furnace and heated at a heating rate of 1 C/min to measure ignition point.
Evolution of phosphine:
20 g of each sample was suspended in 40 ml of water contained in a 500 ml flask and was fully shaken. After sealing the flask, the sealed sample was allowed to stand for 24 hours and the amount of phosphine evolved in a space above the suspension was measured.
Elution of P205:
5 g of each sample was suspended in 100 ml of water, was allowed to stand for 100 hours at 121 C at 2 atm. and filtered. ~he P2O5 content in the filtrate was measured.
Examples 4 to 9 Resinous compositions were prepared as test samples in which the red phosphorus (uncoated) or the red phosphorus flame retardants (coated) set forth in Examples 1 to 3 and metal hydroxide were incorporated into polyolefine resin in the proportions shown in Table 3. In Examples 4 and 5, the red phosphorus (uncoated) obtained in Example 1 was used and in Examples 6 to 9, the red phosphorus flame retardants (coated) obtained in Examples 1, 2 and 3 were used.
r?' ~3 Each test sample was tested for nonflammability, moisture absorption and tensile strength reduction and the results are given in Table 4.
Comparative Examples 4 to 9 Comparative resinous compositions were prepared as test samples in which the pulverized red phosphorus (uncoated) or the pulverized red phosphorus flame retardants ~coated) set forth in comparative Examples 1 to 3 and metal hydroxide were incorporated into polyolefine resin in the proportions shown in Table 3.
In Comparative Examples 4 and 5, the pulverized red phosphorus (uncoated) was used and in Examples 6 to 9, the pulverized red phosphorus flame retardants tcoated) obtained in Comparative Examplesl, 2 and 3 were used.
Each test sample was tested for nonflammability, water absorption and tensile strength reduction and the results are given in Table 4.
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Table 3 Mixing Proportion of Resinous Composition (part by weight) Constituents Examples _ _PE_ *1 100_ PP *2 _100 _ EPR *3 _ _ 100 EEA *4 100 EEA *5 100 EVA *6 100 Aluminum 50 20 Hydroxide Magnesium 50 100 80 80 HYdroxide Red Phosphorus or Red Phosphorus 30 25 20 2 5 10 Flame Retardant*7 (1) (1) (2) (3) (3) (1) ; Table 3 ( continued) Constituents Comparative Examples _ _ _ _ _ _ _ PE *1 100 PP *2 100 .
EPR *3 100 _ EEA *4 100 EEA *5 100 EVA *6 100 .
~ 3 ~
Table 3 (continued) ~ Constituents Comparative Examples : 4 5 6 7 8 9 . _ _ _ _ _ ~luminum 50 20 Hydroxide Magnesium 50 100 80 80 Hydroxide Red Phosphorus or Red Phosphorus 30 25 20 2 5 10 Flame Retardant*7 (1) (1) (2) (3) (3) (1) _ Remark:
*1: Polyethylene density 0.92 *2: Polypropylene density 0.91 *3: Ethylene-Propylene rubber *4: Ethylene-Ethylacrylate copolymer containing 5% Acrylate *5: Ethylene-Ethylacrylate copolymer containing 8% Acrylate *6: Ethylene-Vinyl Acetate copolymer containing 10%
Acetate *7: Numbers indicated within ( ) are those of Examples or Comparative Examples.
Table 4 Physical Properties of Resinous Composition Nonflamma- Moisture Tensile External bility Absorption Strength Appearance (UL 94) (%) Reduction(%) Example No.
4 V-O 0.10 3~0 Unchanged V-O 0.11 2.7 Unchanged 6 V-O 0.15 2.7 Unchanged 7 V-O 4.5 5.2 Unchanged 8 V-O 4.2 4.8 Unchanged 9 V-O 3.7 3.1 Unchanged Comparative Example No.
4 V-O 2.1 38 Swelling V-O 2.2 30 Swelling 6 V-O 3.8 32 Swelling 7 V-O 42.1 72 Considerable Swelling 8 V-O 58.5 70 Considerable Swelling 9 V-O 69.2 69 Considerable Swelling Remark:
Nonflammability:
7 ~ '~, r, According to the Vertical Flame Method UL-94 Moisture Absorption:
With respect to Examples 4 to 6 and Comparative Examples 4 to 6, each sample was immersed in water and left at 121 C at 2 a-tm for 100 hours. The percentage of the increase in the weight of the sample was measured.
With respect to Examples 7 to 9 and Comparative Examples 7 to 9, each sample was immersed in hot water at 95C ~or 35 days and the percentage of the increase in the weight of the sample was measured.
Tensile Strength Reduction:
Each sample was treated in hot water in the same manner as described in Moisture Absorption and the tensile strength of the thus treated sample was measured. The reduction is indicated by the percentages of the reductlon in the tensile strength caused by this immersion in hot water to the tensile strength of the sample before immersion. Tensile strength was measured in accordance with ASTM-D638.
As is clear from the tables, the red phosphorus flame retardants prepared by the method of the present invention have a high ignition point, excellent stability to heat and a significantly improved water resistance in comparison with the conventional pulverized red phosphorus. Further, the red phosphorus flame retardants of the present invention are almost free from the formation of toxic phosphine and r~
corrosive acidic substances due to the reaction with moisture. Therefore, the red phosphorus :Elame retardant of the present invention is very useful as a highly stable and safe flame retardant for thermoplastic resin.
This is mainly due to the following reasons. Namely, since red phosphorus is unstable to heat, friction, shock, etc., accidents are apt to occur during the storage and handling and incorporation of it into synthetic resin. Further, red phosphorus reacts with moisture and oxygen in the air, thereby forming toxic and harmful substances. Such undesirable properties of red phosphorus do not permit its safe use as a flame retardant.
Further, red phosphorus does not have a qood compatibili~y with synthetic resin. For these reasons, red phosphorus is usually coated with an inorganic or organic material. However, in recent years, as physical properties required for synthetic resins ~te increasingly severe, more highly stabilized ~.
~ .
7 ~ ~
flame retardants of red phosphorus have been demanded.
For example, polyolefine resins have been used as covering materials for communication cables, electric cables, etc. In such uses, serious accidents have been experienced due to fires of the cables. Therefore, countermeasure has been urgently needed against such accidents and, at the same time, higher levels of nonflammability are required in the covering resin materials.
Conventionally, for example, polyvinyl chloride and halogen-containing polyolefine have chiefly been used as nonflammable covering resin materials.
However, these halogen-containing polymers have great difficulties to ensure safety and prevent accidents, since they ca~se problems such as evolution of large quantities of smoke and gas, which are highly toxic and corrosive, during a fire. As means for eliminating these di~ficulties, it has been proposed to add a smoke inhibitor, an acid trapping filler, etc.
However, these additives have to be added in large amounts to fully prevent the smoking and gas evolution and, thereby the nonflammability inherent in the foregoing polymers may be considerably impaired. Therefore, under the existing circumstances, the halogen-2S containing polymers can not meet, at the same time, therequirements of reduction of smoking and environmental pollution and good nonflammability.
On the other hand, as a halogen-free nonflammable composition, there has been known a polyolefine composition prepared by incorporating a high-temperature active filler, such as magnesium hydroxide or aluminum hydroxide, which absorbs combustion heat, into polyolefine type resin. However, in the composition, these inorganic fillers are needed in if~: 2 large quantities in order to ensure a sufficient nonflammability, thereby causing an undesirable deterioration of the properties of the used resin, especially with respect to mechanical and electrical properties, heat resistance, water resistance and weatherability.
As previously described, red phosphorus has been well known to be an effective flame retardant for synthetic resin and has been used in practical applications related to electronics, etc.
However~ red phosphorus is disadvantageous, for example, in that it forms phosphine and oxidized products With the lapse Of time, thereby deteriorating the used reSin. Therefore, currently, red phosphorus flame retardants composed of red phosphorus particles coated with a stabilizing agent have been mainly used.
However, even the thus stabilized red phosphorus has only a very insufficient stability for a long-term use under variable environmental conditions, such as for example in cables, and, thus, can not provide good utility for such an actual use.
Nevertheless, there is still now a strong demand for further improvements in the stability of red phosphorus because of the several advantageous propertiPs of red phosphorus. For example, when red phosphorus is used, evolution of smoke and toxic gases is very slight as compared with the foregoing chlorine-containing flame retardant. Since a considerably high flameproofing effect can be obtained with addition of small amounts of red phosphorus, addition of filler which may adversely affect the mechanical properties of resin can be avoided.
Under such circumstances, the present Inventors have considered that the known surface treatments for ,r~
....
1 3 ~ 3 1 ~, stabilizing hava limitations and made many studies on stabilization of red phocphorus flame retardants from a quite different angle. As a result, it has been found that subst~nt;ally ~pheric~1 re~ phos~orus having entirely different s~rface state, physical properties and shape from any known red phosphorus can be obtained by a novel process unknown in the prior production pro~cesses of red phosphorus.
Further, although the novel red phosphorus itself can be sufficiently used as a flame retardant because of its very high stability, it can be f~lrther highly stabilized by surface treating, and, thereby, exhibits significantly improved water resistance, corrosion resistance and heat resistance as compared with those of the red phosphorus flame retardant obtained in the prior art.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a method for producing a red phosphorus flame retardant having improved stability and safety.
A further object of this invention is to provide a resinous nonflammable composition prepared by incorporating the red phosphorus into thermoplastic resin, especially, polyolefine resin, in which problems such as fire and environmental pollution are minimized and significantly improved heat resistance, water resistance and weatherability can be stably ensured over long periods of time.
In accordance to a first aspect of the present invention, a red phosphorus flame retardant is prepared by a method comprising the steps of:
heating yellow phosphorus at temperatures of 250 to 600 C to effect a partial conversion of yellow .
~.~
r~ " ~
I phosphorus to red phosphorus;
removing unconverte~ yellow phosphorus7 and coating particles of the resulting substantially spherical red phosphorus with at least one of thermosetting resin and metal h~droxideO
In a further aspect of the present invention, there is provided a nonflammable resinous composition containing the red phosphorus flame retardant prepared by the method specified above. The nonflammable composition consists essentially of 100 parts by weight of polyolefine resin, 20 to 200 parts by weight of hydrated inorganic filler and 01. to 30 parts by weight of the coated red phosphorus flame retardant.
In another aspect of the present invention, a method for producing a red phosphorus flame retardant, said method comprising the steps of:
heating yellow phosphorus at temperatures of 250 to 600C. to effect a partial conversion of not higher than 70% of said yellow phosphorus to red phosphorus;
removing the unconverted yellow phosphorus; and coating the resulting substantially spherical particles of red phosphorus with at least one of thermosetting resin and metal hydroxide, said particles of red phosphorus having been formed without being subjected to a pulverization procedure.
In a further aspect of the present invention, a nonflammable resinous composition consisting essentially of 100 parts by weight of polyolefine resin, 20 to 200 parts by weight of hydrated inorganic filler and 0.1 to 30 parts by weight of substantially spherical particles of red phosphorus flame retardant, said flame retardant being produced by heating yellow phosphorus at temperatures of 250C. to 600C. to effect a partial conversion of not r~ ~ ~
-5a-1 highee than 70% of said yellow phosphorus to red phosphorus; removing the unconverted yellow phosphorus; and coating the resulting substantially spherical particles of red phosphorus with at least one of thermosetting resin and metal hydroxide, said particles of red phosphorus having been formed without being subjected to a pulverization procedure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Red phosphorus has been produced by thermal conversion of yellow phosphorus. In the production process of red phosphorus heretofore employed, yellow phosphorus as a starting material is heated at a temperature near the boiling point of yellow phosphorus over a few days until the conversion reaction is completed, and red phosphorus is obtained in the form of a hard cake-like coagulated mass.
When red phosphorus is incorporated as a flame retardant into synthetic resin, it must be in a powder form.
Therefore, the prior art red phosphorus which is taken out of a conversion vessel as a coagulated mass indispensably requires a pulverizing step. In contrast to this, since conversion conditions according to the method of the present invention are different from those of the above conventional method, the resulting red phosphorus can be obtained in a powder form composed of substantially spherical fine particles and crumbly agglomerates i c, ~ g ~
thereof, and, thereby, does not require ~ pulverizing step.
In practicing the method of the present invention, yellow phosphorus as a raw material is charged into a reactor which has been previously filled with an inert ~ gas and heated to melt and then conversion is commenced. The conversion is continued until the conversion of yellow phosphorus to red phosphorus reaches the desired conversion ratio and the conversion is stopped. After removing unconverted yellow phosphorus from the reactor by an appropriate technique, there c~n ~e obtained substantially sphericAl red phosphorus as a powder form. The present Inventors have unexpectedlyfo~n~
t~at th~ ~uhct~nt;ally sp~er;c~l red phosphor~s ~r obt~;ned by such a partial conversion has a considerably high stability as compared with the known pulverized red phosphorus. The present invention has bPen achieved based on this finding.
It has been found through the Inventors' extensive studies that conversion of yellow phosphorus to red phosphorus commences at a relatively low temperature and becomes rapid at about the boiling point of yellow phosphorus. Thereafter, the reaction rate further increases with an increase in temperature. In a low temperature range, red phosphorus is produced as fine spherical particles in molten yellow phosphorus.
However, with increase in temperature, particles of red phosphorus agglomerate together and their particle size - increases. The growth and agglomeration of the particles are also detected when the conversion is prolonged. Therefore, when the conversion reaction is carried out at a too high temperature or over a too long period of time, it excessively proceeds and most f the yellow phosphorus is converte~ to red phosphorus.
~31 3 cJ ~
In such conditions, the red phosphorus can no longer exist in the form of particles, ~orming an agglomerated product. Consequently, it is impossible to obtain red phosphorus in a powder state. Many efforts have been made b~ the present ;nventors in order to avoid the foregoing excessive conversion and thereby make possible the attainment of powdered red phosphorus co~osed of suhstantially spherical fine p~rticles. It has bee folmd that it is necessary to continue the conversion of yellow phosphorus to red phosphorus at 250 to 600 C while maintaining the flowability of the reaction mixture and the flowability of the reaction mixture can be maintained by controlling the conversion ratio to 70%
or lower. The conversion ratio varies depending on the processing temperature and time. Lower processing temperature and shorter time will result in a lower conversion ratio. The conversion ratio can be arbitrarily adjusted by appropriately adjusting the processing temperature and time for the conversion.
When the conversion ratio is controlled to 70% or lower, the reaction mixture is retained in a flowable state and red phosphorus can be obtained in a powder form after removing unconverted yellow phosphorus.
When the tempèrature during the conversion procedure is below 250 C, the reaction rate is very small. Thus, such a lower temperature is unfavorable as a practical processing condition. While temperatures exceeding 600 C result in an excessively high conversion rate and make difficult the control of the reaction. Further, the reaction mixture rapidly loses its flowability and a compact massive product results. Therefore, it is impossible to ohta;n pow~ered red ~hosphorus without a further pulverizinq step, as described in the prior art process.
~l r~ ~
As set forth above, when the reaction temperature is low and the reaction time is short, the conversion ratio becomes small and the resulting red phosphorus powder has a small particle size. On the contrary, when the reaction time is long and the conversion ratio becomes large, the degree of agglomeration of red phosphorus particles is increased and the particle size - becomes large. However, w~en th~ thus agglomerated ~rticle~ ~re obtained from a flowable reaction mixture, the particles are, unlike a cake-like compact mass of red phosphorus, very loosely agglomerated and form a crumbly mass which can be readily crumbled to powder by a light mechanical treatment, without any treatment as called pulverizing. Inventors' experimental data ~5 showed that the stability of the agglomerated red phosphorus particles is not adversely affected by the dividing treatment as required for such a crumbly agglomerate and the red phosphorus powder which is obtained by dividing the particles agglomerated also exhibits a high stability. Therefore, the red phosphorus powder of the present invention may also contain the red phosphorus powder obtained by dividing such loosely agglomerated particles. ~he red phosphorus powder obtained according to the present invention and composed of substantially spherical ~rticles has a particle size of the order of few microns to 100 ~m and the particle size ranges in a narrow particle size distribution as compared with that of known pulverized red phosphorus powder and has a high uniformity.
In the present invention, conversion of yellow phosphorus to red phosphorus is performed by a partial conversion of yellow phosphorus and is quite different from d complete conversion heretofore practiced.
Therefore, a removal process of unconverted yellow ~:~, },~
i, _9_ phosphorus is required and the process is readily performed using an appropriate technique, such as distillation, filtration or solvent extraction.
Practically, distillation is carried out in an inert gas atmosphere under reduced pressure or ordinary pressure, after termination of the conversion reaction.
Unconverted yellow phosphorus is removed by this distillation. When filtration is used, the reaction mixture is put into water or an aqueous solution and red phosphorus is separated from unconverted yellow phosphorus by filtration and dried. When solvent extraction is used, unconverted yellow phosphorus is extracted from the reaction mixture, using a solvent capable of dissolving yellow phosphorus. Needless to say, these techniques may be used in combination thereof. In any case, the removed yellow phosphorus may be recycled in a subsequent conversion process to red phosphorus. The red phosphorus obtained accordin~
to the process of the present invention itself has a high stability far superior to red phosphorus stabilized in the prior art. However, when the red phosphorus of the present invention is further surface-treated with at least one of thermosetting resin and metal hydroxide, such as aluminum hydroxide, zinc hydroxide, etc., the stability is surprisingly improved and problems due to deterioration of synthetic resin which may be caused due to addition of the red phosphorus can be almost eliminated. Almost complete water resistance and corrosion resistance can be achieved and heat resistance is considerably improved.
Therefore, the substantially spherical red phosphorus of the present invention can be used as a flame retardant for thermoplastic resin with safety. Such unexpectedly high stability of the red phosphorus flame retardant of the present ~3 7J~ ~
invention is considered to be due to the fact that the surface state of the red phosphorus powder of the present invention is considerably different from that - of the prior art pulverized red phosphorus powder.
When red phosphorus powder is, like the aforesaid prior art, obtained by pulverizing a hard agglomerated mass, the resulting powder has a complicated surface state having acute edges and sharply fractured faces. In contrast to this, since the red phosphorus powder obtained according to the present invention is not suhjecte~ to a pulverizing process, its surface is almost free of fractured faces and edge llnes. It has been confirmed by electron microscopy that the red phosphorus powder of the present invention is composed of particles having naturally formed spherical surfaces and agglomerates thereof. The pulverized red phosphorus powder has many active sites on its surface and readily reacts with moisture and oxygen. On the contra~, the sub-stantially spherical red phsophorus ~rticles of the present invention are almost free of such active sites and the sur~ace state thereof is extremely stable. Therefore, chemical reactions with moisture and oxygen hardly occur and, as a result, the moisture resistance and heat resistance are greatly improved. Further, in the surface-treating with thermosetting resin or metal hydroxide, it is difficult to uniformly and wholly coat the pulverized red - phosphorus due to its surface state and some portions of the surface may be left without a coating. However, the spherical red phosphorus of the present invention can be uniformly and entirely coated. This makes a great difference in its stability The surface treatment of the red phosphorus of the present invention by thermosetting resin or metal hydroxide may be performed in a conventional manner.
B~
J ~
Examples of suitable thermosetting resins include formaldehyde type resins, such as phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, furf ~ 1 alcohol-formaldehyde resin, aniline-formaldehyde resin, etc.; and polyhydric alcohol-polybasic acid resins.
In practicing the present invention, 10 to 100 - parts by weight of the red phosphorus is suspended in 100 parts by weight of water to give a suSpension of red phophorusO To the resulting suspension, a raw material or initial condensation product for the thermosetting resin is added in amounts of 1 to 35 parts by weight with respect to 100 parts by weight of the red phosphorus and stirred at 40 to 100 C for 1 to 3 hours. If necessary, polymerization catalyst and filler such as aluminum hydroxide, magnesium hydroxide or titanium hydroxide may be present in the suspension.
The addition of the filler not only improves the mechanical strength of the resulting resin coating but also provides a beneficial effect of shielding the purplish red color inherent to red phosphorus, thereby making possible a greatly expanded use of the red phosphorus flame retardant of the present invention.
When the red phosphorus is coated with metal hydroxide, for example, aluminum hydroxide or zinc hydroxide, an aqueous solution of sulfate or chloride of aluminum or zinc is added to an aqueous suspension of red phosphorus and aluminum hydroxide or zinc hydroxide is precipitated onto the red phosphorus powder, for example, by neutralization with sodium hydroxide or double decomposition by ammonium bicarbonate. The aqueous suspension of the red phosphorus preferably consists of 10 to 100 parts by weight of the red phosphorus and 100 parts by weight of , ~ 3 ~
water and the concentration of the aqueous solution of the metal salt may be preferably 5 to 30~. The guantity of the resulting metal hydroxide coating is preferably in the range of 1 to 30 parts by weight per 100 parts by weight of the red phosphorus. When the coating with the metal hydroxide is followed by coating with the thermosetting resin, the resulting double-coated red phosphorus has the highest level of stability and, even in use in severe conditions, it is not subject to deterioration. Therefore, in resinous compositions flameproofed by SUCh a highly stabilized red phosphorus flame retardant, deleterious effects due to the use o~ the red phosphorus flame retardant are scarcely observed over long periods of time. When the double-coating procedure is carried out, the quantity of the metal hydroxide coating may be in the range of 0.1 to 30 parts by weight per 100 parts by weight of the red phosphorus.
In the preparation of the nonflammable composition of the present invention, the red phosphorus flame retardant prepared by the method of the present invention is mixed in the proportion of 0.1 to 30 parts by weight with respect to 100 parts by weight of polyolefine resin. When the red phosphorus flame retardant is less than 0.1 parts by weight, a sufficient flameproofing effect can not be obtained.
On the other hand, the use of the red phosphorus flame retardant exceeding 30 parts by weight unfavorably affects physical properties of the resin.
The polyolefine resin may be any resin which can be obtained using olefine type monomers as starting materials and, as such polyolefine resin, there may be mentioned polyolefine type homopolymers, copolymer or mixtures thereof, more specifically, polyethylene, "~,,.~1 , i ~ , ~
$ ~
polypropylene, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, polybutene, cross-linked polyethylene, cross-linked polypropylene, ethylene-propylene rubber, poly-4-methylpentene-1, ethylene-butene copolymer, butylrubber, styrene-butadiene rubber and mixtures thereof. These resins are all free of halogen and can be effectively flameproofed by the red phosphorus of the present invention without deterioration of the mechanical and electrical properties. Therefore, the present invention can provide very useful nonflammable resinous compositions minimizing the problems of smoking and environmental pollution and having a superior combination of properties with respect to heat-resistance, water resistance and stability which insures a substantial long useful life. The foregoing properties are especially important for insulating materials used for covering communication cables and other electric cables which are used in widely variable environmental conditions, especially, with regard to temperature and water. According to the present invention, the cable covering materials are first successfully flameproofed with red phosphorus flame retardant to practical levels. Resins flameproofed with the prior art red phosphorus flame retardant are inferior in heat resistance and water resistance and, thus, when they are used to cover the above-mentioned cables, they are readily deteriorated in a short period of time, thereby causing swelling, embrittlement, dlscolorin~, etc. As a result, the mechanical properties and electrical properties of the covering materials are impaired and the cables become impractical from the standpoint of external appearance and safe use. However, in the resinous compositions flameproofed according to the ~ JP~-~?~ 9 present invention, their initial properties are stably retained over a long period of time even under severe conditions, such as heat, water, etc. This makes a great contribution to safe use and cost reduction in long-term use in applications related to the foregoing cables. Also, in other applications, there can be obtained considerable improvements in safe use and durability.
In the present invention, magnesium hydroxide, aluminum hydro~ide, basic magnesium carbonate, etc., may be employed as a filler synergistically increasing the flameproofing effect of the red phosphorus. When the fillers are used in combination with the red phosphorus, they synergistically improve the flameproofing effect of the red phosphorus, achieving high flameproofing effect which can not be obtained when the red phosphorus is used alone. Although the red phosphorus itself causes the evolution of small amounts of smoke, the above filler has an effect of reducing the smoke evolution. The inorganic fillers are preferably added in the range of 20 to 200 parts by weight with respect to 100 parts by weight of polyolefine resin or modified polyolefine resin.
Addition of less than 20 parts by weight can not achieve a sufficient synergistic effect in cooperation with the red phosphorus. On the other hand, when the addition exceeds 200 parts by weight, the physical properties of the resin are adversely affected. If necessary, additives such as dripping inhibitor (e.g., carbon black), lubricant, colorant, dispersant, etc., may be added to the nonflammable composition of the present invention.
Hereinafter, the present invention will now be described in detail with reference to the following _, ~
~ 3 ~
examples. In the examples, the term "red phosphorus flame retardant" is used to mean "coated red phosphorus" and percentages are given by weight, unless otherwise specified.
EXAMPLES
Example 1 A stream of nitrogen gas was passed through a stainless steel vessel to displace the air and 500 g of yellow phosphorus was charged into the vessel. After sealing the vessel, the yellow phosphorus was heated at 270 C for four hours to effect conversion of yellow phosphorus to red phosphorus. Unconverted yellow phosphorus was removed from the vessel and there was obtained 211 g of red phosphorus in a flowable powder form having an average particle size of 50 ~m. The resulting substantially spheri.cal re~ phosph~rus ~5 s~spended in 400 ml of w~ter and 150 rnl of a 10% ~ql~eous sol~tion of ~sl~ninLnn sulfate was added to the resulting suspension. Then, 50 ml of a 5~ agueous solution of sodium hydroxide was added dropwise to the suspension while sufficiently stirring and the resulting suspension was heated to 50 C and held at this temperature for 30 minutes. The suspension was filtered, washed with water and dried.
There was obtained 217 g of red phosphorus flame retardant.
Example 2 A stream of nitrogen gas was passed through a high-pressure reactor to displace the air and 100 g of yellow phosphorus was charged into the reactor. After sealing the reactor, the yellow phosphorus was heated to 480 C for 30 minutes, held at that temperature for 10 minutes and cooled in the air. Unconverted yellow phosphorus was removed from the reactor, and 68 g of red phosphorus was obtained in a powder form.
The resulting substantially spherical red p~osphorus was sieve~
t~rough a l~O mesh screen. A]tho~g~ 22 percent of the red phosphorus powder was not passed, the residual red phosphorus powder can be readily crumbled by fingers to entirely pass through a 100 mesh screen.
Thereafter, the powder was suspended in 200 ml of water and 3 g of phenol and 6 g of 37% formalin were added to the resulting suspension. After heating the suspension to 80 C, 2 g of 85% phosphoric acld was added under stirring. After heating the suspension at 80 C for one hour with stirring, the suspension was cooled in the air, filtered and dried. There was obtained 72 g of red phosphorus flame retardant.
Example 3 A stream of nitrogen gas was passed through a reactor and 200 g of yellow phosphorus was charged into the reactor and heated at 280 C for one and a half hours to cau,se conversion of yellow phosphorus to red phosphorus. Vnconverted yellow phosphorus was removed from the reactor and 36 g of powdered red phosphorus having an average particle size of 28 ~m was obtained.
me resulting substantially shperica~ red phosphorus was suspended i~ lOO ml of~1ater. Tcl the suspension, ,~ml of 8%
aluminum sulfate was added and stirred. Then, 10 ml of a 15~ aqueous solution of ammonium bicarbonate was added dropwise to the suspension and the suspension was heated at 60C for 10 minutes. After adding 2 g of B~
~ 3 ~
phenol and 4 g of 37% formalin to the suspension, the suspension heated ~o 80 ~C and 1g of 85% phosphoric acid was added under stirring. After stirring the suspension at 80 c for one hour, the suspension was s cooled in the air, filtered and dried. There was obtained 39 g of red phosphorus flame retardant.
Comparative Example 1 Pulverized red phosphorus was subjocted to the same coating treatment as described in _xample 1.
Comparative Example 2 Pulverized red phosphorus was subjected to the same coating treatment as described in Example 2.
Comparative Example 3 Pulverized red phosphorus was subjected to the same coating treatment as described in Example 3.
ThP uncoated red phosphorus obtained in Examples 1 to 3 were tested for the physical properties in comparison with pulverized red phosphorus set forth in Comparative Examples 1 to 3. The results are shown in Table 1.
Further, the stability of the red phosphorus flame retardants set forth in example and comparative examples was tested in accordance with the test procedures described below and the results are shown in Table 2.
Table 1 Physical Properti.es of Red Phosphorus _ _ Red Phosphorus Ignition Evolution or Elution of Average Point(C) Phosphine P2O5Particle (ppm) (mg)Size (llm) -Example No.
345 0.1 31.5 50 2 341 0.1 30.7 80 3 340 0.2 32.4 28 Pulverized Red Phosphorus 291 225.3 . 213.1 100 .
Table 2 Stability of Red Phosphorus Flame Retardant Flame Ignition Evolution ofElution of RetardantPoint(C) Phosphine (ppm)P2O5 (mg) . _ _ . .
- Example No.
348 0.0 5.3 2 355 0.0 5.6 :; 3 357 0.0 3.8 Compa ative Example No.
295 76.3 121.2 2 321 1.4 67.8 3 329 1.2 62.9 . _ _ . ... _ _ _ Measurement Method Ignition Point:
1 g of each sample was placed in a 10 ml porcelain crucible, then put in an electric furnace and heated at a heating rate of 1 C/min to measure ignition point.
Evolution of phosphine:
20 g of each sample was suspended in 40 ml of water contained in a 500 ml flask and was fully shaken. After sealing the flask, the sealed sample was allowed to stand for 24 hours and the amount of phosphine evolved in a space above the suspension was measured.
Elution of P205:
5 g of each sample was suspended in 100 ml of water, was allowed to stand for 100 hours at 121 C at 2 atm. and filtered. ~he P2O5 content in the filtrate was measured.
Examples 4 to 9 Resinous compositions were prepared as test samples in which the red phosphorus (uncoated) or the red phosphorus flame retardants (coated) set forth in Examples 1 to 3 and metal hydroxide were incorporated into polyolefine resin in the proportions shown in Table 3. In Examples 4 and 5, the red phosphorus (uncoated) obtained in Example 1 was used and in Examples 6 to 9, the red phosphorus flame retardants (coated) obtained in Examples 1, 2 and 3 were used.
r?' ~3 Each test sample was tested for nonflammability, moisture absorption and tensile strength reduction and the results are given in Table 4.
Comparative Examples 4 to 9 Comparative resinous compositions were prepared as test samples in which the pulverized red phosphorus (uncoated) or the pulverized red phosphorus flame retardants ~coated) set forth in comparative Examples 1 to 3 and metal hydroxide were incorporated into polyolefine resin in the proportions shown in Table 3.
In Comparative Examples 4 and 5, the pulverized red phosphorus (uncoated) was used and in Examples 6 to 9, the pulverized red phosphorus flame retardants tcoated) obtained in Comparative Examplesl, 2 and 3 were used.
Each test sample was tested for nonflammability, water absorption and tensile strength reduction and the results are given in Table 4.
~ 3~
Table 3 Mixing Proportion of Resinous Composition (part by weight) Constituents Examples _ _PE_ *1 100_ PP *2 _100 _ EPR *3 _ _ 100 EEA *4 100 EEA *5 100 EVA *6 100 Aluminum 50 20 Hydroxide Magnesium 50 100 80 80 HYdroxide Red Phosphorus or Red Phosphorus 30 25 20 2 5 10 Flame Retardant*7 (1) (1) (2) (3) (3) (1) ; Table 3 ( continued) Constituents Comparative Examples _ _ _ _ _ _ _ PE *1 100 PP *2 100 .
EPR *3 100 _ EEA *4 100 EEA *5 100 EVA *6 100 .
~ 3 ~
Table 3 (continued) ~ Constituents Comparative Examples : 4 5 6 7 8 9 . _ _ _ _ _ ~luminum 50 20 Hydroxide Magnesium 50 100 80 80 Hydroxide Red Phosphorus or Red Phosphorus 30 25 20 2 5 10 Flame Retardant*7 (1) (1) (2) (3) (3) (1) _ Remark:
*1: Polyethylene density 0.92 *2: Polypropylene density 0.91 *3: Ethylene-Propylene rubber *4: Ethylene-Ethylacrylate copolymer containing 5% Acrylate *5: Ethylene-Ethylacrylate copolymer containing 8% Acrylate *6: Ethylene-Vinyl Acetate copolymer containing 10%
Acetate *7: Numbers indicated within ( ) are those of Examples or Comparative Examples.
Table 4 Physical Properties of Resinous Composition Nonflamma- Moisture Tensile External bility Absorption Strength Appearance (UL 94) (%) Reduction(%) Example No.
4 V-O 0.10 3~0 Unchanged V-O 0.11 2.7 Unchanged 6 V-O 0.15 2.7 Unchanged 7 V-O 4.5 5.2 Unchanged 8 V-O 4.2 4.8 Unchanged 9 V-O 3.7 3.1 Unchanged Comparative Example No.
4 V-O 2.1 38 Swelling V-O 2.2 30 Swelling 6 V-O 3.8 32 Swelling 7 V-O 42.1 72 Considerable Swelling 8 V-O 58.5 70 Considerable Swelling 9 V-O 69.2 69 Considerable Swelling Remark:
Nonflammability:
7 ~ '~, r, According to the Vertical Flame Method UL-94 Moisture Absorption:
With respect to Examples 4 to 6 and Comparative Examples 4 to 6, each sample was immersed in water and left at 121 C at 2 a-tm for 100 hours. The percentage of the increase in the weight of the sample was measured.
With respect to Examples 7 to 9 and Comparative Examples 7 to 9, each sample was immersed in hot water at 95C ~or 35 days and the percentage of the increase in the weight of the sample was measured.
Tensile Strength Reduction:
Each sample was treated in hot water in the same manner as described in Moisture Absorption and the tensile strength of the thus treated sample was measured. The reduction is indicated by the percentages of the reductlon in the tensile strength caused by this immersion in hot water to the tensile strength of the sample before immersion. Tensile strength was measured in accordance with ASTM-D638.
As is clear from the tables, the red phosphorus flame retardants prepared by the method of the present invention have a high ignition point, excellent stability to heat and a significantly improved water resistance in comparison with the conventional pulverized red phosphorus. Further, the red phosphorus flame retardants of the present invention are almost free from the formation of toxic phosphine and r~
corrosive acidic substances due to the reaction with moisture. Therefore, the red phosphorus :Elame retardant of the present invention is very useful as a highly stable and safe flame retardant for thermoplastic resin.
Claims (16)
1. A method for producing a red phosphorus flame retardant, said method comprising the steps of:
heating yellow phosphorus at temperatures of 250°
to 600°C. to effect a partial conversion of not higher than 70% of said yellow phosphorus to red phosphorus;
removing the unconverted yellow phosphorus; and coating the resulting substantially spherical particles of red phosphorus with at least one of thermosetting resin and metal hydroxide, said particles of red phosphorus having been formed without being subjected to a pulverization procedure.
heating yellow phosphorus at temperatures of 250°
to 600°C. to effect a partial conversion of not higher than 70% of said yellow phosphorus to red phosphorus;
removing the unconverted yellow phosphorus; and coating the resulting substantially spherical particles of red phosphorus with at least one of thermosetting resin and metal hydroxide, said particles of red phosphorus having been formed without being subjected to a pulverization procedure.
2. A nonflammable resinous composition consisting essentially of 100 parts by weight of polyolefine resin, 20 to 200 parts by weight of hydrated inorganic filler and 0.1 to 30 parts by weight of substantially spherical particles of red phosphorus flame retardant, said flame retardant being produced by heating yellow phosphorus at temperatures of 250°C. to 600°C. to effect a partial conversion of not higher than 70% of said yellow phosphorus to red phosphorus;
removing the unconverted yellow phosphorus; and coating the resulting substantially spherical particles of red phosphorus with at least one of thermosetting resin and metal hydroxide, said particles of red phosphorus having been formed without being subjected to a pulverization procedure.
removing the unconverted yellow phosphorus; and coating the resulting substantially spherical particles of red phosphorus with at least one of thermosetting resin and metal hydroxide, said particles of red phosphorus having been formed without being subjected to a pulverization procedure.
3. A method for producing a red phosphorus flame retardant, comprising the steps of:
heating yellow phosphorus, in an inert atmosphere, at a temperature of from 250° to 600°C. effective to convert a part of said yellow phosphorus to red phosphorus and form a flowable dispersion of fine substantially spherical particles of red phosphorus having a particle size of up to about 100 µm and friable loose agglomerates thereof dispersed in a matrix of molten yellow phosphorus, until 70%
or lower of said yellow phosphorus has been converted to red phosphorus; then removing unconverted yellow phosphorus from said flowable dispersion and recovering said substantially spherical particles of red phosphorus and agglomerates thereof, which particles are substantially spherical and have external surfaces substantially free of fracture faces and acute edge lines, said surfaces also being substantially free of active sites capable of reacting with moisture and oxygen so that the surfaces of said particles are stable, said particles having been formed without being subjected to a pulverization procedure;
and uniformly and entirely coating said external surfaces or said particles with at least one coating material selected from the group consisting of thermosetting resins and metal hydroxides.
heating yellow phosphorus, in an inert atmosphere, at a temperature of from 250° to 600°C. effective to convert a part of said yellow phosphorus to red phosphorus and form a flowable dispersion of fine substantially spherical particles of red phosphorus having a particle size of up to about 100 µm and friable loose agglomerates thereof dispersed in a matrix of molten yellow phosphorus, until 70%
or lower of said yellow phosphorus has been converted to red phosphorus; then removing unconverted yellow phosphorus from said flowable dispersion and recovering said substantially spherical particles of red phosphorus and agglomerates thereof, which particles are substantially spherical and have external surfaces substantially free of fracture faces and acute edge lines, said surfaces also being substantially free of active sites capable of reacting with moisture and oxygen so that the surfaces of said particles are stable, said particles having been formed without being subjected to a pulverization procedure;
and uniformly and entirely coating said external surfaces or said particles with at least one coating material selected from the group consisting of thermosetting resins and metal hydroxides.
4. A method as claimed in claim 3 in which unconverted yellow phosphorus is removed from said dispersion by distilling off said unconverted yellow phosphorus.
5. A method as claimed in claim 3 in which the amount of said coating material on said red phosphorus particles is from 1 to 35 parts by weight of said coating material per 100 parts by weight of said red phosphorus particles.
6. A nonflammable resin composition consisting essentially of a blend of 100 parts by weight of polyolefin resin, 20 to 200 parts by weight of hydrated inorganic filler and 0.1 to 30 parts by weight of substantially spherical, coated red phosphorus flame retardant particles having a particle size of up to 100 um and friable loose agglomerates of said particles, the external surfaces of said red phosphorus particles being substantially free of fracture faces and acute edge lines and being substantially free of active sites capable of reacting with moisture and oxygen so that the external surfaces of said particles are stable, said particles having been formed without being subjected to a pulverization procedure, said external surfaces of said particles being uniformly and entirely coated with at least one coating material selected from the group consisting of thermosetting resins and metal hydroxides.
7. A nonflammable resin composition as claimed in claim 6 in which said coated particles contain from 1 to 30 parts by weight of said coating material per 100 parts by weight of said red phosphorus particles.
8. A nonflammable resin composition as claimed in claim 6 in which said red phosphorus particles are coated with both of a thermosetting resin and a metal hydroxide.
9. A nonflammable resin composition as claimed in claim 6 in which said coating material is a thermosetting resin selected from the group consisting of phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, furfuryl alcohol-formaldehyde resin, aniline-formaldehyde resin and polyhydric alcohol-polybasic acid resins.
10. A nonflammable resin composition as claimed in claim 6 in which said coating material is aluminum hydroxide or zinc hydroxide.
11. A nonflammable resin composition as claimed in any one of claims 6, 7, 8, 9 or 10 in which said polyolefin resin is selected from the group consisting of polyethylene, polypropylene, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, polybutene, cross-linked polyethylene, cross-linked polypropylene, ethylene-propylene rubber, poly-4-methylpentene-1, ethylene-butene copolymer butyl rubber, styrene-butadiene rubber and mixtures thereof.
12. A nonflammable resin composition as claimed in any one of claims 6, 7, 8, 9 or 10 in which said inorganic filler is selected from the group consisting of aluminum hydroxide, magnesium hydroxide and basic magnesium carbonate.
13. A nonflammable resin composition as claimed in claim 11 in which said inorganic filler is selected from the group consisting of aluminum hydroxide, magnesium hydroxide and basic magnesium carbonate.
14. A method as claimed in any one of claims 1, 3, 4 or 5 wherein said thermosetting resin is selected from the group consisting of phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, furfuyl alcohol-formaldehyde resin, aniline-formaldehyde resin and polyhydric alcohol-polybasic acid resins.
15. A nonflammable resinous composition as claimed in claim 2 wherein said polyolefin resin is selected from the group consisting of polyethylene, polypropylene, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, polybutene, cross-linked polyethylene, cross-linked polypropylene, ethylene-propylene rubber, poly-4-methylpentene-1, ethylene-butene copolymer butyl rubber, styrene-butadiene rubber and mixtures thereof.
16. A nonflammable resinous composition as claimed in claim 2 or claim 15 wherein said inorganic filler is selected from the group consisting of aluminum hydroxide, magnesium hydroxide and basic magnesium carbonate.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-160715 | 1987-06-26 | ||
| JP16071587A JPS644632A (en) | 1987-06-26 | 1987-06-26 | Fire-retardant resin composition |
| JP62261252A JPH0627217B2 (en) | 1987-10-17 | 1987-10-17 | Method for producing red phosphorus flame retardant |
| JP62-261252 | 1987-10-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1309789C true CA1309789C (en) | 1992-11-03 |
Family
ID=26487137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000568936A Expired - Fee Related CA1309789C (en) | 1987-06-26 | 1988-06-08 | Method for producing red phosphorus flame retardant and nonflammable resinous composition |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5041490A (en) |
| EP (1) | EP0296501B1 (en) |
| CA (1) | CA1309789C (en) |
| DE (2) | DE296501T1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2603884B2 (en) * | 1991-03-05 | 1997-04-23 | 出光エヌエスジー株式会社 | Flame retardant resin composition |
| JP2601743B2 (en) * | 1992-02-18 | 1997-04-16 | 燐化学工業株式会社 | Fine powdered red phosphorus and method for producing the same |
| JP2832672B2 (en) * | 1993-08-12 | 1998-12-09 | 燐化学工業株式会社 | Red phosphorus flame retardant and flame retardant resin composition |
| US5543447A (en) * | 1994-09-28 | 1996-08-06 | Southwest Research Institute | Stabilization of red amorphous phosphorus by ordered polymeric structures for the manufacture of non-emissive fire retardant plastics |
| GB9523002D0 (en) * | 1995-11-09 | 1996-01-10 | Raychem Ltd | Flame-retarded adhesive composition |
| DE19651471A1 (en) * | 1996-12-11 | 1998-06-18 | Clariant Gmbh | Flame retardant unsaturated polyester resins |
| TW552291B (en) | 1998-02-23 | 2003-09-11 | Teijin Ltd | Fire-retardant resin compositions |
| EP0985706B1 (en) * | 1998-03-25 | 2005-07-27 | Teijin Limited | Resin composition |
| JP2000281874A (en) * | 1999-03-31 | 2000-10-10 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| DE10126760A1 (en) * | 2001-06-01 | 2002-12-05 | Bayer Ag | Microencapsulated red phosphorus |
| US20090258161A1 (en) * | 2008-04-10 | 2009-10-15 | Japp Robert M | Circuitized substrate with P-aramid dielectric layers and method of making same |
| JP2015504452A (en) | 2011-12-06 | 2015-02-12 | エンパイア テクノロジー ディベロップメント エルエルシー | Phosphorus loading particles and methods of preparing and using them |
| CN109054346A (en) * | 2018-07-23 | 2018-12-21 | 德清顾舒家华高分子材料有限公司 | It is a kind of for promoting the preparation method of the organic-silicon-modified expanded graphite of polyurethane foam flame retardant property |
| CN113174089A (en) * | 2021-05-26 | 2021-07-27 | 兰州大学 | Polystyrene nano-microsphere coated red phosphorus flame retardant and preparation and application thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2339581C2 (en) * | 1973-08-04 | 1983-03-03 | Hoechst Ag, 6000 Frankfurt | Flame-retardant molding compounds based on polyolefins |
| DE2408531B2 (en) * | 1974-02-22 | 1979-12-06 | Basf Ag, 6700 Ludwigshafen | Glass fiber reinforced polyester molding compounds with reduced flammability |
| FR2303837A1 (en) * | 1975-03-13 | 1976-10-08 | Rhone Poulenc Ind | FIRE-RETARDANT THERMOSTABLE COMPOSITIONS BASED ON PREPOLYMERS OBTAINED FROM BIS-IMIDS AND DIAMINES |
| FR2314219A1 (en) * | 1975-06-10 | 1977-01-07 | Rhone Poulenc Ind | COMPOSITIONS INTENDED FOR THE FLAME PROTECTION OF PLASTICS |
| US4071584A (en) * | 1977-01-03 | 1978-01-31 | Monsanto Company | Hydroxyphenylthiophosphoranylidene organophosphorus compounds |
| JPS5439200A (en) * | 1977-09-02 | 1979-03-26 | Hitachi Ltd | Automatic vender |
| JPS5510462A (en) * | 1978-07-11 | 1980-01-24 | Nippon Chem Ind Co Ltd:The | Modified red phosphorus and production thereof |
| DE2945118C2 (en) * | 1979-11-08 | 1981-12-03 | Hoechst Ag, 6000 Frankfurt | Stabilized red phosphorus and process for its manufacture |
| IT1134333B (en) * | 1980-11-19 | 1986-08-13 | F F A Spa Sa | PROCESS TO STABILIZE THE RED PHOSPHORUS BY ENCAPSULATION FOR USE AS A FLAME RETARDANT OF POLYMERIC MATERIALS AND PRODUCT SO OBTAINED |
| US4421728A (en) * | 1982-07-07 | 1983-12-20 | Erco Industries Limited | Stabilization of red phosphorus |
| IT1200424B (en) * | 1985-03-19 | 1989-01-18 | Saffa Spa | RED PHOSPHORUS STABILIZED FOR USE AS A FLAME RETARDANT, ESPECIALLY FOR POLYMER-BASED COMPOSITIONS |
| US4879067A (en) * | 1986-06-19 | 1989-11-07 | Rinkagaku Kogyo Co., Ltd. | Red phosphorus flame retardant and nonflammable resinous composition containing the same |
-
1988
- 1988-06-08 CA CA000568936A patent/CA1309789C/en not_active Expired - Fee Related
- 1988-06-16 DE DE198888109684T patent/DE296501T1/en active Pending
- 1988-06-16 EP EP88109684A patent/EP0296501B1/en not_active Expired - Lifetime
- 1988-06-16 DE DE8888109684T patent/DE3875811T2/en not_active Expired - Fee Related
-
1989
- 1989-11-15 US US07/437,762 patent/US5041490A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3875811D1 (en) | 1992-12-17 |
| EP0296501B1 (en) | 1992-11-11 |
| US5041490A (en) | 1991-08-20 |
| EP0296501A1 (en) | 1988-12-28 |
| DE3875811T2 (en) | 1993-03-18 |
| DE296501T1 (en) | 1989-06-01 |
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