JPS62149738A - Granular fire retardant, its production and use and product - 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 The present invention relates to a granular flame retardant, a method for producing the same, a method for imparting flame retardant properties to a plastic material using the flame retardant, and a flame retardant plastic 4itK obtained by the method. It is.

In particular, the present invention contemplates the use of halogenated hydrocarbon flame retardants alone or in combination with other organic or inorganic flame retardants and synergists.
- Use of a mixture of Rogge/Carbonized Hydrocarbon Xi refueling agent.

The use of halogenated hydrocarbons to impart flame retardancy (PR) to flammable plastics is well known in the prior art (
Are known. A series of commercially available flame retardants include decabromodiphenyl oxide, penta- and octabromodiphenyl oxide, hexabromocyclododecane, and tetrabromobisphenol A. Using mixtures of two or more of these halogenated hydrocarbons in solid or non-solid form and/or mixtures containing inorganic flame retardants or synergistic flame retardants such as antimony oxide or melamine isocyanurate. It is also known that Examples of non-solid flame retardants include penta and bromodiphenyl oxide. Other 43M additives such as binders or carriers, lubricants, smoke arresters, anti-painting agents such as DPFA, and heat stabilizers are often used in admixture with flame retardant compositions.

However, .--rogenated flame retardants are usually in the form of a fine powder, and this powder form poses some problems. Dispersion of flame retardant compounds within processed plastics is often not uniform (contamination problems due to dust formation are significant, and some additives such as antimony oxide are toxic).

Thus, for example, by combining a plastic master bunch with a highly concentrated flame retardant composition, preparing a colloidal suspension of the flame retardant compound and then mixing this with the monomer.
Alternatively, some solutions have been attempted to avoid the use of powdered flame retardant compositions, such as by using binders to create agglomerates of the flame retardant compounds.

It has now been discovered that compacting and crushing allows the use of relatively large grain sizes (2-4 mm) and that core grains can be obtained without the addition of any binder. This is the purpose of the invention.

Another object of the present invention is to provide a method of imparting flammability to polymers that eliminates the dust generation and health hazards present in methods known to the industry.

Furthermore, the flame-retardant plastic material obtained by using the granular 4 flame retardant composition of the present invention does not show any particular difference compared to the plastic material obtained by using the same flame retardant in powder form. discovered. In addition, two types of flame-retardant formulations (
IE compacted flame retardant treatment and powder treatment)
No difference in processability is observed between the two.

This is also a further object of the invention.

The flame retardant composition of the present invention and the process for its preparation, as will become apparent hereinafter, overcome many of the disadvantages of known methods and, moreover, offer certain advantages as will become clear from the description. be.

The granular flame retardant composition according to the present invention, in compacted and granulated form, contains only one or more genated hydrocarbon flame retardant compounds or the halogenated hydrocarbons. It is characterized by containing a mixture of a compound and an organic or inorganic flame retardant or a flame retardant synergist compound.

Preferably, the compacted form is cold compacted.

Cold compacting refers to the fact that no external heat is applied during the compacting operation to aid or promote compacting, and that compacting is performed under substantially no mechanical pressure. means that it is done in

However, as will be clear to those skilled in the art, in some cases during processing or at one or more process steps of processing, it is possible to facilitate the removal of volatile substances contained, for example, in a solid flame release agent or flame retardant mixture. For some purposes, it may be advantageous to maintain temperatures below room temperature. Thus, for example, decabromodiphenyl ether (DECA) m powder may contain 1,000 volatile materials, the removal of which may be aided by a slight increase in temperature to an upper limit of 40°C. Although done for such purposes, such heating of the flame retardant material during processing does not materially alter or affect the compaction process described herein. do not have. It is not beyond the scope of the present invention to use any process step in which such heating is used for purposes unrelated to the compacting process, but to temperatures that do not affect the mechanical properties of the material to be granulated.

The particle size distribution preferably falls within the range of about 2 to 4.0. Additives that may be mixed with the flame retardant compound or compounds include, for example, lubricants, heat stabilizers, non-polymeric binders, smoke suppressants, and carriers.

Suitable smoke suppressants used in the art are, for example, am/monicum molybdate, zinc borate, and bismuth salts.

According to a preferred embodiment of the present invention, halogenated hydrocarbon J
is pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A and its derivatives, tetrabromobisphenol A bis(allyl ether), dibromoneopentyl glycol, tribromoneopentyl alcohol, hexabromocyclododeca/, tribromo Phenylallyl ether, tetrabromodiphenylpentaerythritol, bis(tribromophenoxy)ethane,
Among ethylene bis(dibromonolbornane) dicarboxylic diimide, tetrabromobisphenol S bis(2,3-dibromopropyl) ether, poly(pentabromobenzyl acrylate), and dodecachloropenta-7-crooctadecyl-7,15-diene To be elected. The inorganic flame retardant/synergist compound is selected from antimony oxide, magnesium oxide, magnesium hydroxide, ferric oxide, ammonium salts, cyanurate derivatives.

The green compact produced according to the present invention has at least 0.3
has a diameter crushing strength of ν billion. As will be appreciated by those skilled in the art, diametric crush strength is an important parameter in order for the granules to be strong enough not to disintegrate during normal handling. As will be readily understood by those skilled in the art, too high a value of crushing strength presents difficulties during the process due to, for example, difficulty in disintegrating the grains. In such cases, as will be apparent to those skilled in the art, it is necessary to adjust the crushing strength to the operating condition parameters used during the process. It consists of a mixture of the hydrogenated hydrocarbon and flame retardant synergists such as metal oxides, metal sulfides, and organic salts of antimony, boron, arsenic, and zinc borate.

The process of manufacturing the composition of the present invention involves the following steps:
It is furrowed.

a) Feed the ljA fuel or mixture to the compacting device.

b) Compacting the composition of the flame retardant or mixture thereof in a compacting device.

C) Supply the obtained green compact to a granulator.

d) Granulating the compact in a granulator.

C) Take out both parts having the desired size distribution from the throughput of the granulator.

f) Optionally recycling a portion of the granulation that is of undesirable size into the compaction device.

I love this invention! According to Mr. A, the compacting device is a roll compactor. According to another embodiment of the invention, the granulator is a sieve granulator.

Granulated flame retardant compositions produced by the method of the invention also form part of the invention.

The method of manufacturing an aC article according to the invention consists in mixing the material desired to be tIA flammable-4 with the granular composition according to the invention during its processing.

Flame retardant articles produced by this method also form part of the invention.

It is very difficult to distribute powders well in polymers. Therefore, the advantage of using particulate materials that are more easily dispersed in polymers, together with the aforementioned advantages, constitutes an important Ifi!!a of the present invention. Plastic processing equipment usually includes a nozzle, and the problem of nozzle clogging must be overcome.For this purpose, common technology uses several methods to avoid clogging and particle size problems. , very fine powders or colloidal suspensions of flame retardant materials have been used.However, the flame retardants of the present invention dispersed in polymers melt with or disintegrate within the polymer itself, and thus Because they are dispersed, the grains of the present invention can be used in large sizes, such as 2 to 4 grains.

In the case of granules containing substances that do not melt at the processing temperatures of the polymer, such as antimony oxide or DECA, when the granules melt or disintegrate, the substances that do not melt at the processing temperatures of the polymer are released in fine powder form into the polymer. Care must be taken to ensure a fine pre-dispersion in the grains so that they are evenly distributed.

When using a powdered material, it should be noted that uniform dispersion of the material into the polymer may also be hindered by the formation of lumps of flame retardant material. This is avoided when using the procedure of the present invention.

Another advantage of the present invention is that it provides a greater bulk density than the same flame retardant powdered. As will be clear to those skilled in the art, compared to powders,
This fact is advantageous both in shipping and storage since the flame retardant of the present invention requires processing of a smaller volume of flame retardant. Table 1 below shows three compositions, namely decabromodiphenyl ether (I) ECA alone.
), D E C of DECA and antimo oxide/(AO)
The bulk density values of a mixture with an A/A O ratio of 3:1 and poly(pentapromope/dylacrylar)) (PBB-PA) are shown.

It can be seen that the bulkiness of DgCA and pgcA/AO mixtures increases due to compaction, but does not change in PBB-FA.

No. 1 DECA 1.043 1.583
DgCVAO(3:1) 1.017
1.694PBB-PA 1.249
1.249 Bulk density is not a parameter of absolute value since it depends somewhat on the way the sample was prepared, but such variations are not too large (see above). The numerical value is an index showing the change in bulk density due to compaction and granulation.

The proportions of halogen-containing compound and synergist compound vary depending on the stability of the halogen-containing compound, the reactivity of the particular synergist used, and the plastic material used. Generally, this proportion can be varied within a wide range from 95 parts synergist and 5 parts .loge/containing compound to 5 parts synergist and 90 parts .loge/containing compound.

In addition to the major advantage that the compounds and methods of the present invention are dust-free, the granules of the present invention are substantially free of carrier and binder materials and therefore have a very high effective content of flame retardant compositions. These and other features and advantages of the invention will be better understood from the following examples which illustrate the invention but do not limit it.

The compacting properties of various flame retardant/synergist formulation examples were evaluated using a diameter compression test (April 1963 issue, No. 2) to measure tensile strength.
Experiments were conducted using the method described on pages 83-284) to test at foreign temperatures.

The apparatus used a cylindrical specimen, compressed diametrically between two flat plates. The maximum tensile stress appears perpendicular to the direction of the applied load, and its directivity is proportional to the applied stress.

The loading produces a biaxial stress distribution within the specimen. The maximum tensile stress acting in the direction of breaking the diameter in the loading direction is expressed by the following formula.

In this equation, T8 is the ultimate tensile strength, P is the applied load, and t is the thickness of the specimen.

This test method is! Qualitatively, it allows only tensile stress to be determined, not shear failure or compressive failure.

In diameter compression specimens, the amount of material subjected to stress is proportional to both length and diameter. It has been discovered that antimony oxide alone, without any additives, cannot be compressed into a green compact, even at high pressures such as 500 to 2000 ky/crd.

Surprisingly, it has been found that by incorporating an amount of antimony in the range of 10% to 90%, it is possible to obtain grains of strongly loaded antimony. Its diameter crushing strength is Q, 3ky/clE. The following table shows the combination of antimony oxide (AO) and two flame retardant compounds, namely DECA and tetrabromobisphenol A (T).
Diameter crushing strength of grains obtained from a mixture of BBA))-
This is a summary of the results of DO8).

■Table 1 90 - 10 2000 3.82 75 -
25 2000 2.83 75 25 2000
0.64 50 50 2000 1.25 5
0 - 50 2000 8.66 25 37.5
37.5 2000 4.4 (2) Bromine
Compounds Lim1ted Loss DICCA (
3) Bromine Compounds Lim
lted TBBA This table shows that it is possible to obtain a high diameter crushing strength and that by controlling the composition of the flame release agent made and the pressure used, the DC
You can see that you can combine 8 values.

The following examples illustrate the preparation of particulate flame retardant compositions. In all compaction experiments, an aS-δ compactor (Bepex, Germany) was used, unless otherwise stated.

In all experiments, the oil pressure was 40 bar, the pressure in the accumulator was also 40 bar, and the force due to pressure was 70 K.
It was IJ. In all examples compaction was carried out without binder.

800f octabromodiphenyl ether (ocTA
) through the screw feeder using a roll speed of 7 revolutions per minute. It was supplied to the E-compressor. The compacting material in the form of briquettes leaving the compactor is sent to a sieve granulator. The granulator crushes the briquettes obtained by the compressor. A sieve placed at the bottom of the sieve granulator allows grains with the desired size distribution to be separated. On the other hand, particles with a smaller size distribution are recycled to the compressor.

57% of the granulator throughput is based on the desired size distribution (2-4
■), 43% of which was found to be recycled to the compressor.

Example 3 The same seagull as in Practical Example 2 was operated. However, OC'II' A7
A mixture of 5% and 25% antimony d-oxide was used.

Size distribution 2-3. I chose the grain with ■ as Uruyo 5.

It was found that 30% of what came out of the granulator had the desired canine distribution and the remainder was recycled to the compressor. As will be apparent to those skilled in the art, further limiting the product size range resulted in a much higher proportion of what was recycled as expected.

Example 4 The procedure of Example 3 was repeated. However, pure DECA was used as the one-grain material, and the speed of the roll was 5 revolutions per minute. The results obtained were similar to Example 3.

Example 5 The procedure of Example 2 was repeated. However, DECA75% and A
A mixture of 5% O2 was used. Approximately 50% of the products have the required size distribution 2-4. Also with.

O recovered from the pelletizer Example 6 The procedure of Example 3 was repeated. However, PBB-FA was used as the material to be granulated, and the speed of the rolls was 125 revolutions per minute. Approximately 30% of the throughput was recovered as particulate material with the desired 2-3 inch size distribution, and the remainder was recycled to the compressor.

Example 7 The operation in Example column 6 was repeated i. However, PBB-PA73.
1 and 8b20324.4% and calcium stearate 2
．． A 5% mixture was used. The results obtained were comparable to those of Example 6.

Example 8 The operation of Example 6 was repeated. However, hexabromo7 clododecane (HBCD) was used as the material to be granulated.

25% of the material was recovered from the granulator with the desired dog-tooth distribution of 2-3 m, and the remaining fraction was recycled to the EE compressor.

The procedure of Example 2 was repeated. However, compressor L20015
Using 0P (Bepex), the force due to pressure is 40
A mixture of 77% HBCD, 19.3% tribromophenyl allyl ether, 3.7% lubricant, and heat stabilizer was used. It was found that 54% of the granulator throughput had the desired size distribution (2=4 ym).

The following examples illustrate the production of flame retardant polymeric materials using compositions known to those of the present invention.

Example 10 DECA in powder form, granulated (l) obtained in Example 4
E DECA in compacted form (granules), 75% DECA in compacted form (granules) obtained in Example 5 and AO
Three experiments were conducted to produce flame-retardant impact-resistant polystyrene (IPS) using three flammability agent compositions in a 25% mixture. In all cases it was ensured that products with the same total Br content of 10% were obtained.

grains (or DECA powder) in each case HIP8
(Israel Petrochemical En
Manufactured by terprises () Hliren Q 8B
-5) thoroughly by dry mixing with JL8, then B
uss Kneader RR46 type extruder (Bus8
Ltd., Switzerland) and the processing temperature was set at 160℃.
−190°C.

A test specimen was made by injection molding at 210-230C using an A11rounder-221-75-350 injection molding machine (manufactured by Arburg). Made like this-
The flammability and general properties of flammable HIPS were tested in each case. The results of these tests are summarized in Table 11I.

Example 11 Three types of flame retardant compositions, namely PBB-PA in powder form;
Material B obtained in Example 6, PBB-FA in the form of an ant (compacted powder) (composition engineering), and PBB-FA in the compacted form (granules) obtained in Example 7. PBB-PA 73.1%
An experiment was conducted to produce flame-retardant poly(butylene terephthalate) (PBT) using a mixture (composition n) of AO24.4% and stearyl 4-calcium 2.5% (composition n).

In each case, the flame retardant was thoroughly mixed with PBT and processed as in Example 10. Processing temperature is 260-275
The injection molding temperature was 240-2500°C. The results of these tests are summarized and presented in the following section.

The data reported below in the margins above were obtained in accordance with the following standard test method.

-Melt flow index: Tinus Olse
Flow rate by extrusion plasticity meter using nModel Me4-78 extrusion type plasticity meter (A3TM D1238-7
9) - Flammability: - UL in combustion hood (according to UL)
-94 direct combustion test; 8tanton Redcr
oft company F'rAFlammability Unit
Ultimate Oxygen Index (LOI) (ASTM D
2863-77) It depends on the IT exam #.

Impact energy with one eye zone and non-chip: (A8TMD
z56-81), Zwick pendulum
By impact tester5102.

Single impact tensile energy: (ASTM D 1822-
79) Zwick Penctulum impac
According to t tester type 51Q2.

-HDT: Bending load (18,5 insult/d) Deflection temperature (
Ai9TM D 648-72), CEk8'l'
According to 6055.

- UV Stability: Accelerated Exposure Test - Measures color change by color shift after 205 hours of irradiation, Accelerat
ed Weathering Te5ter Q-U
-V (B rung) (The Q -Panel C
o, ) according to.

- Color shift: measure color and compare with reference sample, 5Pe
ctro Co1or Meter 8CM-90(
Techno-Instruments Ltd.
)by.

The foregoing examples and descriptions are given for illustrative purposes and are not intended to limit the invention. Many changes may be made in the compositions, methods, and steps without departing from the scope of the invention.

Daikin Bentonshi 〾　　Fuji　　Yuu 1 other person

Claims (1)

[Scope of Claims] 1 One or more halogenated hydrocarbon flame retardant compounds alone, or a mixture of the compound and an organic or inorganic flame retardant compound or a flame retardant synergist compound and/or additives, in a green compact A granular flame retardant composition comprising a granulated flame retardant composition. 2. The composition according to claim 1, wherein the compacted and granulated form is a cold compacted form. 3. Composition according to claim 1 or 2, characterized in that it has a particle size distribution between about 2 mm and about 4 mm. 4. A composition according to claim 3, characterized in that the additives include a lubricant, a heat stabilizer, a non-polymeric binder, an anti-smoke agent, an anti-dripping agent, and a carrier. 5 The halogenated hydrocarbon is pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A and its derivatives, tetrabromobisphenol A bis(allyl ether), dibromoneopentyl glycol, tribromoneopentyl alcohol, hexabromo Cyclododecane, tribromophenyl allyl ether, tetrabromodipentaerythritol, bis(tribromophenoxy)ethane, ethylenebis(dibromonolfornan)dicarboximide, tetrabromobisphenol S
Claims characterized in that it is selected from among bis(2,3-dibromopropyl)ether, poly(pentabromopencyl acrylate) and dodecachloropentacyclooctadeca-7,15-diene. The composition according to any one of items 1 to 3 in the range 1 to 3. 6. Claims characterized in that the inorganic flame retardant synergist compound is selected from among antimony oxide, magnesium oxide, magnesium hydroxide, ferric oxide, ammonium salts, and cyanurate derivatives. A composition according to any one of Ranges 1 to 3. 7a) feeding the flame retardant substance or mixture into a compacting device; b) compacting the flame retardant substance or mixture in the compacting device; and c) compressing the obtained compacted material. d) granulating the compacted material in the granulator; e) removing from the granulator a fraction of the throughput having a desired size distribution; f) 7. A process according to any one of claims 1 to 6, characterized in that it comprises the steps of optionally recycling a fraction of the undesired size of the granulate to the compacting device. A method for producing the composition according to item 1. 8. The method according to claim 7, wherein the compacting device is a roll compactor. 9. The method according to claim 7, wherein the granulator is a sieve granulator. 10 The granulated flame retardant composition according to any one of claims 1 to 6, produced by the method according to any one of claims 7 to 9. thing. 11. Flame-retardant product, characterized in that the material desired to impart flame-retardant properties is mixed with the composition according to any one of claims 1 to 6 during processing. How to manufacture. 12. All flame-retardant products manufactured by the method described in claim 11.