JPH03503419A - Application to flame retardant ABS resin compositions and ABS polymer systems - 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] Background of the invention for application to flame-retardant ABS resin compositions and ABS polymer systems Hikarigo Public The present invention relates to plastic additive compositions. More specifically, the present invention provides halogen A set of plastic additives containing asymmetrically modified higher alkyl bisphenoxyalkanes. Regarding products. Furthermore, the present invention provides a halogenated asymmetric higher alkyl bisphenol compound. Seeds in non-blooming, flame-retardant ABS resin compositions incorporating sialkane . Plastic additives are used to improve or modify the properties of commercially available polymers. It is used to do things. By using plastic additives, the ratio A relatively small number of commercially available polymers become available for use in many applications. Our technician will It can be extremely difficult to select a specific plastic additive for a given application. It is well known that Therefore, additive manufacturers must conduct very complex and sophisticated studies. and provide a range of additives to achieve the desired results. Must be.

Plastic additive compositions include plasticizers, flame retardants, flow control agents.

or as an impact modifier in resin systems, heat transfer fluids, or pressure fluids. I can do it.

One important use of plastic additive compositions is as a lit fuel agent in resin systems. be. Most flame retardants do not effectively slow down the burning rate of resin systems. For example, flame retardant Many of the agents.

Reduces the impact strength of resin 1. Migration silane is generated from the resin composition to reduce the impact strength of the resin. evaporation from the resin composition: resin Undesirably plasticizes the composition to reduce heat deflection temperatures: or It has a tendency to deteriorate when exposed to light.

Therefore, in addition to its role as a flame retardant, flame retardants can provide the desired properties of the resin composition. The engineer must be specifically compatible with the resin system in order to enhance It is well known that it is extremely difficult to select such specific flame retardants for application. ing.

Furthermore, even if a flame retardant is useful for a particular resin system, There is no guarantee that the agent will also be useful with other resin systems; One type of resin that can be used is

There are acrylonitrile-butadiene-styrene ("ABS") resins.

r”)Iandbook of Plast by Harper ics and EIastomers', published by McGraw-Hill, 1975. Some of the characteristics of typical ABS resins are explained in pp. 1-68. It is.

ABS thermoplastics have good physical and mechanical properties (e.g. good abuse resistance, It has a good balance of thermal properties, moldability, stain resistance, chemical resistance, and surface hardness. Ru. Generally, ABS thermoplastic resin has excellent properties and moderate cost. Because of this, it is widely used. For example, ABS resin is a material with high impact strength. Telephone equipment manufacturers that require fees, subsidiary equipment manufacturers, automobile manufacturers, etc. used by.

In the industry, many flame retardants are used for ABS resins. , 22()ribromophenoxy)-ethane, danΔ(pentabromophenoxy)- Ethane, octabromodiphenyl oxide, decabromodiphenyl oxide, te Trabromobisphenol-A and tribromophenoxyethyl-te All substances such as trabromobisphenol-A and ether.

Used in various ABS systems. In particular, the conventional technology regarding flame retardant ABSvA fat No. 4,016,139 and U.S. Pat. No. 4.567.2. No. 18, which are hereby incorporated by reference. ABS plastic The above-mentioned flame retardants for firewood coatings cannot be said to be fully satisfactory. Because blue thermal migration, thermal instability, ultraviolet instability, discoloration.

Or, it may have a negative effect on properties such as impact strength or fluidity. be.

When applying flame retardants to ABS resin, certain important properties of ABS resin must be preserved. Examples of critical properties that must be maintained include impact strength, photostability, and preservation of the aesthetic properties of the surface, etc.

In particular, manufacturers of computer housings require flame-retardant, light-stable, and They are requesting a thermoplastic ABS resin that does not easily cause blooming.

The use of various bromine-containing compounds as flame retardants is well known in the art. There is. Compositions obtained using these various bromine-containing compounds are 1) It may cause a decrease in surface gloss 2. The surface of the polymer Flame retardant deposits are likely to form on surfaces.

U.S. Pat. No. 3,876.612 to Anderson et al. The specifications disclose ABS plastic compositions containing symmetrical bisphenoxy flame retardants. It shows. The flame retardant composition has the following formula (where Z is bromine or chlorine; m' is an integer having a value of 1 to 5; i and io are integers having a value of 0 to 2; ^^ Cyano group, nitro group, lower alkoxy group, lower alkyl fluorine group. Zial Kylamino group. Phenyl i, /'i lo phenyl group.

benzyl group or halobenzyl group; and R is the following group: (a) CHi-CH(OH)-CHx(b) CHt-C)l (CHzOIl)-Cllt(c) (Cllz), -0-(CHz) , where w-1 to 6 (e) C) lx-C(0)-Clh is expressed by

U.S. Pat. No. 3,876,612 to Anderson et al. Using alkylbisphenoxyalkane as a flame retardant for ABS resin That has not been disclosed.

U.S. Patent No. 3 by Anderson et al. 883. Specification No. 479 is ABS discloses a plastic composition containing a symmetrical bisphenoxy compound. The bisphenoxy compound has the formula 0, where 2 is bromine; i and io are integers having the value l or 2; alkylene is a straight or branched alkylene group having 1 to 6 carbon atoms; and A is a cyano group. Nitro group, lower alkoxy group, lower alkyl group (CH3, Ctl ls, CsH, or C4), fluorine, dialkylamino group, phenyl group, halophenyl group, benzyl group, or halobenzyl group [selected from the group]. U.S. Pat. No. 3,883,4 to Anderson et al. Specification No. 79 is. Asymmetric higher alkyl bisphenoxy alkanes as flame retardants Not disclosing its use.

U.S. Pat. No. 3,892,710 to Anderson et al. Symmetrical halogen Discloses an ABS plastic composition containing an alkyl chloride flame retardant. difficulty The fuel is the formula i and i゛ are integers having values from 0 to 2; H and ho are respectively independently consisting of oxygen, nitrogen, or sulfur only when m and ■゛ are not both oxygen selected from the group; ^ is a cyano group, a nitro group, a lower alkoxy group, a lower alkyl group; Fluorine, dialkylamino group, phenyl group, halophenyl group, benzyl group.

and a halobenzyl group). Anderson et al. U.S. Pat. No. 3,892,710 relates to 10genated aryl flame retardants. and discloses the use of asymmetric higher alkyl bisphenoxy alkanes. has not been disclosed.

U.S. Pat. No. 3,971,758 to Anderson et al. ABS plastic compositions containing phenoxy flame retardant compounds are disclosed. Applicable The flame retardant composition has the formula (wherein Z is bromine or chlorine; I and l' have values from 1 to 5. i and 1° are integers with values between O and 2;) IBCA has 1 to 6 carbon atoms. It is a halide of alkylene group that has been divided into techniques. and A is a cyano group, nitro group, lower alkoxy group, lower alkyl (CI- C4) group, fluorine, dialkylamino group, phenyl group, halophenyl group, benzyl group or 10-benzyl group). Even in this case, U.S. Pat. No. 3,971.758 to Anderson et al. Does not disclose the use of alkylbisphenoxyalkanes as flame retardants .

U.S. Pat. No. 4,016,137 to Anderson et al.

A plastic composition containing ABS and a symmetrical bisphenoxy flame retardant compound is disclosed. and the flame retardant compound has the following formula (wherein Z is bromine; - and ■゛ are 1 is an integer having a value between ~5; and alkylene has 1 to 6 carbon atoms. do.

It has a linear or branched alkylene group).　　′In this case Also, U.S. Pat. No. 4,016,137 discloses an asymmetric higher alkyl bisphene The use of noxyalkanes as flame retardants is not disclosed.

No. 4,016,139 to Anderson et al.

A combination comprising an ABS polymer, a symmetrical bisphenoxy flame retardant, and a flame retardant enhancer. Discloses the product. The bisphenoxy flame retardant has the following formula: (In the formula, Z is bromine; IIl and m' are bromine atoms whose total amount is 6 to 10 is an integer having a value of 1 to 5 such that The rice by Anderson et al. National Patent No. 4.016.139 describes an asymmetrical higher alkyl bisphenoxylate. Sialkane compounds are not disclosed.

U.S. Pat. No. 4,051,105 to Anderson et al. Discloses a dry-coat composition. The plastic composition is made of ABS polymer and the formula (wherein Z is bromine and -l is an integer having a value of 1 to 5; 1 is a value of O to 4 is an integer having a value of 0 to 2; i is an integer having a value of 1 to 5; is an integer having 1 to 6 carbon atoms; alkylene has 1 to 6 carbon atoms. Straight chain or technique is the alkylene group of the chain: and A is chlorine). Contains a noxy compound. U.S. Patent No. 4.051,1 to Anderson et al. No. 05 specification discloses clearly asymmetric higher alkyl bisphenoxy compounds. It has not been.

Broadly speaking, the patent by Anderson et al. covers bromine-containing compounds for ABS resins. It explains how aromatic nuclei can be modified by bromination, alkylation, and various other substituents. discloses the use of symmetrically substituted bisphenoxyalkane compounds. child When using a symmetrical bisphenoxyalkane compound, ABS odor It cannot be said that fully satisfactory results have been obtained, especially in the case of 7. () Libro Symmetrical bisphenoxy compounds such as mophenoxy)-echun are suitable for ABS systems. Blooming or migration to the polymer surface is likely to occur.

Therefore, the main object of the present invention is to develop a novel halogenated asymmetric higher alkyl bisphene. The purpose of the present invention is to provide noxyalkanes.

Another object of the present invention is to provide a halogenated asymmetric higher alkyl bis useful as a flame retardant. Our purpose is to provide phenoxyalkanes.

Yet another object of the invention is to use halogenated flame retardants as non-blooming flame retardants. An object of the present invention is to provide an asymmetric higher alkyl bisphenoxy alkane.

Yet another object of the invention is to reduce blooming, thermal instability, and light sensitivity. problems such as instability and other problems that conventional flame retardants for ABS resins have. A drug capable of making ABS resin compositions flame retardant without exhibiting any drawbacks The aim is to provide agents for

Yet another object of the present invention is to achieve a desired level of An object of the present invention is to provide a flame-retardant ABS resin composition that exhibits flame retardancy.

Still another object of the present invention is to provide a halogenated asymmetric higher alkyl bisphenoxia. The objective is to use Lucan as a flame retardant for ABS resin.

4 groups with light room The above objects and other objects, advantages, and features of the present invention reside in the halogenated asymmetric high grade This can be achieved with new compositions containing alkylbisphenoxyalkanes. The bisphenoxyalkanes used according to the invention are brominated non-paired The preferred brominated bisphenoxyethane is preferably a higher alkyl bisphenoxyethane. Suphenoxyethane contains 40-70% by weight of bromine. Furthermore, the present invention is flame retardant with an effective amount of halogenated asymmetric higher alkyl bisphenoxy alkanes. A 1M flammable ABS resin composition is created by incorporating a reinforcing agent into a normally flammable ABS resin. get something

The compositions of the present invention contain about 50-901i% ABS, based on the weight of one composition. Thermoplastic resin, about 5-30% heavy weight halogenated asymmetric high alkyl bisphenol Preferably, it includes a xyalkane and about 0.1-15% by weight of a flame retardant enhancer.

Mitsuyu Tachisho ■ Tei Douyu According to the present invention, a novel halogen-symmetric higher alkyl bisphenoxy compound The novel composition of the present invention has been found to have the following properties:

Its improved properties distinguish it from known bisphenoxy compositions. The composition is stable to light and heat, has good flame retardant properties, and has the highest L Importantly, compositions incorporating the two new compounds do not cause blooming. .

The novel composition of the present invention has the following formula: [Wherein, X is bromine or chlorine; Z is an integer of 2 to 4; R is methyl (C Hs) to dodecyl (C, □Ls); n is 0, 1. or 2 and y is 0.1. or 2; R o is 3eC-butyl (sec-CJ*) + Pentyl (csH++), Hexyl (CJI z>, Hebuti) Lt (Ctll + s), octyl (Cel11t), /nyl (CqH,,) , decyl (c, .lI!,).

selected from the group consisting of undecyl (CIIL3) and dodecyl (C+Jzs) R3 is a direct alkyl from methyl (CH3) to dodecyl cc+ru□); a linear or branched alkylene group (e.g. cyclohexane); and When i is 1, R+ and R2 are different] halogenated asymmetric higher alkyl The novel compositions of the present invention, which are rubisphenoxyalkanes, contain certain small amounts of halogens. Contains a symmetrical higher alkyl bisphenoxy alkane.

A small amount of halogenated symmetrical higher alkyl bisphenoxyalkane is present in the composition. does not affect the usefulness of the composition as a non-blooming flame retardant. stomach.

If χ is bromine, the bromine content should be about 40-70% by weight. especially Preferred bisphenoxy compounds are 2, for example, X is 3. z is 23 and n is O It is a compound that In the most preferred compounds, X is bromine and R z is octyl (CsLt) or nonyl (C9H19) and R8 is ethyl It's Ren.

A preferred new plastic additive composition (brominated bisphenoxyethane) Produced by two-step synthesis from hydrogenated phenols and dihalogenated ethane. Main synthesis is the standard Williamson ether synthesis method (shown below in unsubstituted form) done according to.

In this case, χ and Y are each independently bromine or chlorine.

A preferred method of synthesis is in a high boiling polar solvent (e.g. propylene glycol). Phenolate salt with minimum alkyl content and large excess of 1,2-dibromoethane (4 moles or more per 11 moles of phenolate). With the synthesis method called be. Excess dibromo is added before reacting the resulting intermediate with another phenolate salt. Preferably, the ethane is removed by distillation.

The compounds listed in Table 1 are examples of compounds synthesized by preferred synthetic methods. 0 The items listed in this table are not all, and the scope of the present invention is limited thereby. Brominated alkylphenols can be obtained from commercially available alkylphenols. Fabricated using methods known to those skilled in the art.

Yu” two branches Halogenated asymmetric higher alkyl bisphenoxy alkanes.

They can be used alone or in combination in plastic formulations. P When using the preferred brominated bisphenoxyethane in the plastic formulation, the It should be used in amounts of 0.5 to 30% by weight of the plastic formulation. Plasti The most preferred weight percent of brominated bisphenoxyethane in the alcoholic formulation is between 5 and 5. It is 20% by weight.

The present invention further provides the use of an asymmetric bisphenoxy compound in ABS resin. Also includes.

Halogenated asymmetric higher alkyl bisphenoxy alkanes.

Novel composition of the present invention useful for producing flame-retardant ABS resin without blooming Due to its improved properties, it is clearly different from known flame-retardant ABS. Become.

Preferred new flame retardant ABS compositions include from about 50 to about 90% by weight thermoplastic ABS resin. Fat: about 5 to about 30% by weight of halogenated asymmetric higher alkyl bisphenoquinoalk and about 0.1 to about 15% by weight of 1!1 as a flame enhancer. In this case, the above percentages are 9, which is a value based on the total weight of the mixture obtained from about 60 to 90% ABS resin: about 10-30% halogenated asymmetric higher alkyl bisph Most preferably, it contains an enoxyalkane compound; and about 2-10% of a flame retardant enhancer. Delicious.

ABS resin combines styrene/acrylonitrile copolymer with butadiene-based rubber. Blend with rubber; styrene/acrylonitrile in butadiene-based rubber grafting chains; or styrene monomers, acrylonitrile monomers, and Any thermoplastic resin obtained by: copolymerizing and butadiene monomers It may be fat. Therefore, each component of the terpolymer can be included in virtually any proportion. and substantially any suitable acrylonitrile-butadiene-styrene composition. can be used. ABS contains stabilizers, plasticizers, dyes, pigments, and fillers. It may contain other additives such as, or it may not substantially contain it.

Preferred plastic composition for producing flame-retardant ABS resin without blooming All additives are asymmetric (i.e., R1 and R2 are different when n months old) 6 Preferred additives according to the invention include 1-D ribromophenoxy) -2-(dibromononylphenoxy)-ethane, 1-(tribromophenoxy) -2-(dibromooctylphenoxy)-ethane, 1-(tribromophenoquine) )-2-(dibromopentylphenoxy)-ethane, 1-(tribromophenoxy) cy)-2-(dibromododecylphenoxy)-ethane 11-(tetrabromomethyl ruphenoxy)-2-(dibromooctylphenoxy)-ethane.

1-(tetrabromomethylphenoxy)-2-(dibromononylphenoxy) -ethane, and 1-(pentabromophenoxy)-2-(dibromononylphenol) xy)-ethane, etc.

The flame retardant ABS composition of the present invention may further include one or more flame retardant enhancers. is desirable. Flame retardancy enhancers useful in the present invention include Group IV-A of the 1-cycle table. Oxides and halides of elements and group V-A elements Niline, nitrogen, boron, or Organic or inorganic compounds of sulfur; and 2 such as zinc, magnesium.

Oxides and halides such as titanium (all of which are disclosed in U.S. Pat. No. 4.016,13) 9); and the like. Preferred flame retardant enhancement according to the invention The agent is an oxide of antimony, arsenic, and bismuth, and the oxide of antimony is Particularly preferred, antimony dioxide is one of the most preferred used in the compositions of the present invention. It is a flame retardant enhancer. As mentioned above, the flame retardant enhancer is about 0.1-15% by weight. Used at the level of Flame retardant enhancers are used at levels of about 2-10% by weight It is preferable to do so.

It is also possible to incorporate other additives into the m-acid, as long as a certain end result is achieved. within the scope of the invention. Such additives include heat stabilizers, 5 light stabilizers, Plasticizer, R agent, preservative.

UV stabilizers, fillers, antioxidants, antistatic agents, and well-known to those skilled in the art other materials (e.g. “Modern Plastics Enc cloe dia″νof, 63. No, 1OA, McGraw-Old It, In c, (1986) J), but are not limited to these. do not have.

The present invention will be illustrated by examples below, but the scope of the present invention is not limited thereby. It's not something you can do. All parts are parts by weight.

1 top Step ■: In a 5F reactor equipped with a mechanical stirrer.

2.4.6-) Libromophenol (856g, 2.6mol), phenol (6g), sodium carbonate (180g, 1.7mol), and propylene glyco (1036 g) was charged. Heat the mixture to 100"C while stirring, This temperature was maintained for 1 hour. 1,2-dibromoethane (1950g, 10.4 mol) were added all at once into the reactor. Raise the temperature again to 100″C and vigorously The mixture was held for an additional 3 hours with stirring.

Stirring was stopped without cooling the reaction mixture and the phases were allowed to separate.

Methanol (6f) was pumped into a 12ff reactor equipped with a mechanical stirrer. , while stirring the methanol vigorously, the lower phase from the above 52 reactor was mixed with methanol. added to. At this time, add the lower phase sufficiently to prevent it from solidifying before finishing adding it. The temperature was maintained at 7. The resulting methanol slurry was filtered to remove the product (β-build). Lomomethyl-2,4,6-tribromophenyl ether, compound Q) was recovered. . 995 g of product with a purity of >98% after drying in a vacuum oven at room temperature (87% of theory) and 1% or less of 1,2-bis(tribromophenoxy)-ethyl Tan was obtained.

Step n, Ia In a 51 reactor equipped with a mechanical stirrer, dibromononylphene is added. Nor (860 g, 2.25 mol), phenol (5 g).

Sodium carbonate C127g, 1.2mol), and propylene glycol (2X OOg) was prepared. The mixture was slowly heated to 150'C while stirring.

Compound Q (995 g, 2 ．． 25 mol) was added portionwise to this mixture. Maintain the light temperature and stirring state for an additional 4 hours. I held it. Then, stirring was stopped and the two reaction mixtures were allowed to cool. Decant the lower phase; The lower phase was dissolved in methylene chloride (11). After washing with dilute hydrochloric acid, distill off the solvent. Wiped film evaporator Volatile components were removed using a vacuum cleaner at 200° C. and 1,0 torr. Living The weight of the product (compound A) was 1530 g (92.5% of theory). two The yield adjusted in time for the process was approximately 80% of the theoretical amount in step ①. Mechanical stirrer and device Taking the Dean-5tark trap Keta! In a 2f2f vessel, dibromononylphenol (2270 g, 6.0 mol) ), phenol (16g), sodium carbonate (382g, 3.6mol), and 3,700g of propylene glyco-J was charged. Add this mixture while stirring. Slowly heat to 100'C for 30-60 minutes) and hold at 100'C for 1 hour. . ■, React all of 2-dibromoethane (4410g, 24.0mol) at once Added to the bowl. Heat the mixture to 1.30°C with vigorous stirring and at light temperature. After cooling the reaction mixture to 90-95 °C for 4 hours, water (300 g) was added. Addition.

This mixture was heated to reflux (~95°C) to form an azeotrope of dibromoethane and water. Collected during a Dean-Stark trap.

Remove dibromoethane and drain water until no more dibromoethane is recovered. When no more dibromoethane is recovered, water is added back into the reactor. Also removed. If water pi becomes acidic during azeotropic distillation, add 1 to the reaction mixture. of sodium carbonate.

Process■, 5I equipped with a mechanical stirrer! into the reactor.

2,4.6-tribromophenol (1985g, 6.0mol), phenol (14 g), sodium carbonate (382 g, 3.6 mol), and propylene Glycol (2500g) was charged. Slowly stir this mixture for 10 minutes while stirring. The mixture was heated to 0°C for 30 to 60 minutes) and held at 100°C for 1 hour.

The reaction mixture from step [was heated to 145°C and 5I! , the contents of the reactor are added to. After returning the temperature to 145°C, one compound was heated to 14°C with vigorous stirring. It was held at 5°C for 4 hours. Stop stirring, cool reactor 1 to 35"C, and remove the upper phase. Decanted. The lower phase was dissolved in methylene chloride (2°52). Wash with dilute hydrochloric acid After that, the solvent was distilled off and heated to 200°C using a wiped film evaporator. .

Volatile components were removed at 1.0 torr. The weight of the product (compound A) is 3,480 g, which was about 79% of the theoretical amount.

1 liter per month Process■, 32 tubes equipped with a mechanical stirrer and a Dean-Starck trap. In the reactor, dibromononylphenol (983g + 2.6mol), sodium carbonate (180 g, 1.7 mol), 1,2-dibromoethane (1950 g, 1 0.4 mol), and tris(2-(2-methoxyethoxy)ethyl)amine, etc. Specifically, TDA-1 (84 g) was charged.

The mixture was heated to 130°C and held at this temperature for 4 hours. After cooling, the main mixture Filter the material and use a wiped film evaporator to 100”C, Excess dibromoethane was removed at 201-ml.

Process■, 3E reactor equipped with mechanical stirrer and Dean-Stark trap. In the reactor, the product from Step I (predominantly β-bromoethyl-dibromononyl fluoride) is phenyl ether and TDA-1).

2.4.6-) Libromophenol (860g, 2.6mol) and sodium carbonate Thorium (180 g, 1.7 mol) was charged. Heat this mixture to 130°C and held at this temperature for 5 hours. 51 reactor equipped with mechanical stirrer and reflux condenser Methylene chloride (2E) was charged into the reactor.

The still hot reactor product was slowly added to the methylene chloride.

This mixture was then washed with dilute hydrochloric acid. After distilling off the methylene chloride, wipe the Using a film evaporator, remove the continuous components at 200°C and 1,01-liter. Removed. The weight of the obtained product (compound A) was 1.410 g, and the theoretical amount It was about 74%.

Urasho mottled soil Step I, in a 51 reactor vessel equipped with a mechanical stirrer and a subsurface gas inlet tube, 2 ．． 4.6-) Ribromophenol (1,160 g, 3.5 mol), hydroxide Charge thium hydrate (7.5g) and ethylene glycol (2000g) is. Heat this mixture to 120°C and, while stirring vigorously, add 3 to 4 g per back Ethylene oxide was introduced below the water surface at a rate of . 1 reactor using pH paper The pH of the compound was checked. Approximately 1 hour later (depending on the addition ratio of ethylene oxide) ), the pH changes from slightly acidic to strongly basic. At this point, ethylene Stop adding oxide. 180-200 g of ethylene oxide was used. anti When the temperature of the reaction mixture was below 100°C, water (750g) was added. temperature When the temperature reaches around 70°C.

This heavy slurry was filtered using a laboratory filtration centrifuge and heated at 70°C on a filter cloth. of water (10f). The product was heated at 80°C in a forced draft oven at a constant weight. It was dried until. The obtained product (β-hydroxoethyl-2,4,6-t The weight of the ribomophenyl ether is 1190g, which is about 91% of the theoretical amount. It was.

Step ■, in a 51 reactor vessel equipped with a mechanical stirrer, the product from step ■ (9 40 g, 2.5 mol), and pyridine (3 mol).The mixture was heated to 5°C. Benzenesulfonyl chloride (883 g, 5 mol) was added to The mixture was added dropwise over 1 hour while being maintained at °C. After stirring at 5°C for 16 hours, The temperature of this compound was slowly raised to room temperature 3, and the generated solid was removed by filtration. rear.

With vigorous stirring, place the book into a 12F reactor halfway filled with the ice/water slurry. The mixture was added gradually. 7. Recover the product by filtration. vacuum oven It was dried in a container until it reached a constant weight. Product (2-(2,4,6-tribromof The weight of ethyl benzenesulfonate] is 1.210 g, and the It was about 94% of the theoretical amount.

Step ■, β-(2,4,6-)ribromophenoxy)-ethyl instead of compound Q except that til benzenesulfonate (1160 g, 2.25 mol) was used. , the same procedure as in step ① of Example 1 was followed. The weight of the product (compound A) is 1540 g, which was 93% of the theoretical amount. The yield when the three steps are combined is the theoretical one. It was about 79% of the amount.

SuJL[jiang[ 20.0 parts of halogenated asymmetric higher alkyl bisphenoxyalkane (compound A); 69.0 parts of HeBS resin [Borg Warner Corporation (B CYCO from org-Warner Corporation Commercially available as LAC) GSM 1000: ]; 5.0 parts of chlorinated polyethylene From Dow Chemical Company TYRIN (commercially available as CPE-42133): 5.0 parts of ammonium dioxide Timon (M & T Chemical Co. city) from Thermoguard (T) IERFIOGtlARD) S ), 0.5 part of stabilizer [Ciba Geigy Corporation (Ciba Ge TINUVIN 770 from igy Corporation Commercially available go and 0.5 part antioxidant [Ciba Geigy Corporation? Irganox (commercially available as Irganox 1076): A flame retardant composition was prepared by

Compound A is 1-(tribromophenoxy)-2-(dibromononylphenoxy) - ethane, an asymmetric halogenated higher alkyl prepared according to Example 1 It is a bisphenoxyalkane.

Brebou Center Bowl (PRSP-center bowl) (Model R 6°C,W, Brabender Instruments Inc. (C,W , Brabender Instruments, :nc), S, / '+-7 Kenzatsuk (S.

Hackensack, NJ) until a homogeneous material is obtained. The compound was blended. The resulting mixture is cooled, ground into chips, and tested. It was molded into a test piece. , 1 oz injection molding machine [Model HT-30RS, New Newbury Industries, Inc. Books using Stries+ Inc.)+-1-Nibury, OH] The chi knob was injection molded. The conditions for injection molding are shown in Table 1. obtained in this way The bromine content of the resulting mixture was 10.8% by weight.

Table ■ Machine parameters for injection molding - Raw solution temperature 430°F Mold temperature 100″F Initial ram pressure 1900 psi Secondary ram pressure 1000 p si total injection time 5 sec Cycle time 255ec For test molded blacks aged at 70°C for at least 2 to 6 weeks. Bloom was recognized. Perform periodic visual inspection to detect deposits on the surface of the specimen. I checked to see if it exists.

XJf! iJ decoy:■ Bisphenoxyalkane compound B, compound C1 compound instead of compound Compound E, Compound G, and Compound r (respectively, in the resulting polymer composition) (in such a proportion that a bromine concentration of 10.8% by weight was maintained) A flame retardant composition was prepared according to the method described in Example 5. Names of these compounds are shown in Table 1.

Table m Compound J, Compound F, Compound, and Compound Ri instead of Compound A (respectively) 2 to maintain a bromine concentration of 10.8% by weight in the resulting polymer composition. The flame retardant composition was prepared according to the method described in Example 5, except that Created.

The names of compounds J, F, K, and L are shown in Table 1.

Example 5 = Flame retardancy and physical properties of various injection molded samples obtained from il It is shown in Table ■. In addition, the test methods applied are also specified in Table ■. (all laws are well known to those skilled in the art).

Table ■ Table 1 shows the experimental evaluation results for various test pieces.

It can be summarized as follows.

Example 5 is a halogenated asymmetric higher alkyl bisphenoxial according to the present invention. It shows a flame retardant ABS compound laced with cans. Achieved flammability rating of v-〇 Bloom was not recognized.

According to Comparative Examples 1 to 4, one prior art symmetrical bisphenoxy compound was When the bisphenoxy compound is used in a compound, the bisphenoxy compound migrates from the ABS resin. room).

Examples 6 to 11 are halogenated asymmetric higher alkyl bisphenes within the scope of the present invention. Figure 2 depicts a flame retardant formulation incorporating a noxyalkane.

Incorporating the halogenated asymmetric higher alkyl bisphene/xyalkane of the present invention. However, bloom does not occur with ABS resin.

Bloom occurs in ABS resin incorporating symmetric bisphene and tuxialkane. It is especially important to keep in mind that migration from resins or resins is likely to occur. It is essential. Furthermore, one halogenated asymmetric higher alkyl bisphenoxia of the present invention ABS resin incorporating Lucan has good photostability and migration of flame retardant due to heat. and have improved physical properties (e.g. impact strength, tensile elongation, etc.) do.

Tsim Chung±■2■ A portion of Compound A is added to ( The method described in Example 5 was followed except that Compound J was substituted (specified in Table V). A flammable composition was prepared.

Kitamoto 1i = Yui Except that Compound J was used in place of Compound J in the proportions specified in Table V of Table 2. A flame retardant composition was prepared according to the method described in Example 5.

Table 7 A8 Table 7 shows the experimental evaluation results for various test pieces, and the key points are as follows: can be approx.

^ The halogenated asymmetric higher alkyl bisphenoxy of the present invention in the BS resin formulation Bloom is suppressed when alkanes are used. ! ? 7. () Ribromofuenoki In the case of c)-ethane (compound J), even if the amount used is large (Comparative Example 5), even if it is small ( Comparative Example 6).

Considerable bloom was observed. Examples 12 to 14 to 1 Flame retardant of the present invention (tribromophenoxy)-ethane (compound J). It can be seen that bloom is not recognized in this case. Therefore, I? X (tribromophe The blooming caused by the presence of (noxy)-ethane (compound ThJ).

Delayed or inhibited by the presence of Compound A.

From the above explanation, those skilled in the art can easily understand the nine essential features of the present invention. and may be adapted to various uses and conditions without departing from the spirit and scope of the invention. Various variations of the invention can be made.

Submission of translation of written amendment (Article 184-7, Paragraph 1 of the Patent Act) February 28, 1990 Director General of the Japan Patent Office Yoshi 1) Moon Takeshi 1, Indication of patent application PCT/US89102796 2. Name of the invention Application to flame-retardant ABS resin compositions and ABS polymer systems 3, patent applicant Name - Great Lakes Chemical Corporation 5, Submission of amendment Day October 17, 1989 Rumor Go 1〒 1. (Correction) Structural formula [Wherein, X is bromine or chlorine; R1 is methyl (CI+, ), ethyl (cz ns), propyl (C, Hff), butyl (C, OW), pentyl (CsHz ).

Hexyl (CiLa), heptyl (Ctil+s), octyl (CaH+t ), nonyl (CJ+q), decyl (CIOH2I), undecyl (Cwll+ w), and dodecyl (C+J□). Straight chain (C+-C tr) or branched chain alkyl; 2 is an integer of 2 to 5; n is 0, 1 ．． or 2; R2 is 5ec-butyl (sec-Cnll*), pentyl ( CsH□), hexyl (Cill+:+), heptyl (Ctllls), o Cutyl (CsH+t), nonyl (C9L?), decyl (C+.Ht+), U selected from the group consisting of decyl (C++fb3) and dodecyl (C+zllts). It will be revealed. straight chain or branched chain alkyl; y is 0, 1. or 2; R1 is methylene (C1lz), ethylene (C, l14), propylene (CJh ).

Butylene (c41(s), pentylene<CsH,.), hexylene (CJ+t) .

Heptylene (C?H14), octylene (CIII6), nonylene (Cv Lm).

(C+Jz<). Straight chain or branched chain alkylene group And: and when n is 1, 2I? , and R, are different) Unsymmetrical homologous alkylbisphenoxyalkane.

2. X is bromine. A composition according to claim 1.

3. The composition according to claim 2, wherein Rt is octyl (C, H, , ) .

4. The composition according to claim 2, wherein R2 is nonyl (CJ+,).

5, R5 is ethylene. A composition according to claim 4.

6゜ Structural formula A halogenated asymmetric higher alkyl bisphenoxy alkane represented by

7. Structural formula A halogenated asymmetric higher alkyl bisphenoxy alkane represented by

8. Structural formula A halogenated asymmetric higher alkyl bisphenoxy alkane represented by

9. (Delete) 10. (Amendment) (a) Usually flammable acrylonitrile-butadiene-styrene resin; (b) Acrylonitrile-butadiene-styrene resin composition as a flame retardant a halogenated asymmetric higher alkyl bisphenoxy in an amount effective to render it flame retardant. Alkane: and (c) @it flame enhancer; Non-blooming flame retardant acrylonitrile-butadiene-styrene resin containing A composition.

In this case, the halogenated asymmetric higher alkyl bisphenoxy alkane has the structural formula [In the formula, X is bromine or chlorine; R9 is Cl""-C+□ linear or is a chain alkyl; 2 is an integer of 2 to 5; n is 0, l, or 2: R is 5ec-butyl (sec C4H9), pentyl (CsL+), xyl (C6H13), heptyl (CJ+s), octyl (C*H+t) , nonyl (CJ+q), decyl (C,.Ht+), undecyl (C11823 ), and dodecyl (CI211□, ). Straight chain or technique He is a chain alkyl; y is 0.1. or 2; R3 is directly between C1 and C1□ It is a linear or branched chain alkylene; and when n is 1, R1 and R2 are different. It is a compound represented by The resin composition.

11. The composition has, based on the weight of the flame retardant ABS composition, (a) about 50 to about 90% ABS resin; (b) about 5 to about 30% halogenated asymmetric type Higher alkyl bisphenoxy alkanes; and (c) about 0.1 to about 15% flame retardant enhancer; Compositions as described.

12. The flame retardant enhancer oxidizes the TV-A group elements and V-^ group elements of the periodic table. compounds and halides; organic compounds and mineralization of phosphorus, nitrogen, boron, or sulfur compound; as well as zinc and magnesium.

or titanium oxides and halides; Claims No. Composition according to item 10.

13. The flame retardant enhancer is antimony trioxide. Claim 10 Compositions as described.

14. The halogenated asymmetric higher alkyl bisphenoxy alkane.

l-(tribromophenoxy)-2-(dibromononylphenoxy)-ethane; 1-(Tribromophenoxy)-2-(dibromooctylphenoxy)-ethane ; ■-(Tribromophenoxy)-2-(dibromopentylphenoxy)-ethane ; 1-(Tribromophenoxy)-2-(dibromododecylphenoxy)-ethane ; 1-(tetrabromomethylphenoxy)-2-(dibromooctylphenoxy) Ethane; ! -(tetrabromomethylphenoxy)-2-(dibromononylphenoxy)- Ethane; 1-(pentabromophenoxy)-2-(dibromononylphenoxy)-ethane ; selected from the group consisting of. A composition according to claim 10.

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Claims (14)

[Claims] 1. Structural formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [Wherein, X is bromine or chlorine; R1 is methyl to dodecyl (C1 to C12)] linear or branched chain alkyl; z is an integer of 2 to 5; n is 0, 1 , or 2; R2 is sec-butyl (sec-C4H9), pentyl (C5 H11), hexyl (C6H13), heptyl (C7H15), octyl (C8 H17), nonyl (C9H19), decyl (C10H21), undecyl (C1 1H23), and dodecyl (C12H25). is branched alkyl; y is 0, 1, or 2; R3 is methyl to a decyl (C1-C12) linear or branched alkylene group; and When n is 1, R1 and R2 are different]. Kirbisphenoxyalkane. 2. A composition according to claim 1, wherein X is bromine. 3. A composition according to claim 2, wherein R2 is octyl (C8H17). 4. A composition according to claim 2, wherein R2 is nonyl (C9H19). 5. 5. A composition according to claim 4, wherein R3 is ethylene. 6. Structural formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A halogenated asymmetric higher alkyl bisphenoxy alkane represented by 7. Structural formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A halogenated asymmetric higher alkyl bisphenoxy alkane represented by 8. Structural formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A halogenated asymmetric higher alkyl bisphenoxy alkane represented by 9. (a) usually flammable acrylonitrile-butadiene-styrene resin; (b) Acrylonitrile-butadiene-styrene resin composition as a flame retardant. a halogenated asymmetric higher alkyl bisphenoxia in an effective amount to render it flame retardant; and (c) a flame retardant enhancer; non-blooming flame-retardant acrylonitrile-butadiene-styrene tree containing Fat composition. 10. The halogenated asymmetric higher alkyl bisphenoxy alkane has the structural formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [Wherein, X is bromine or chlorine; R1 is a C1 to C12 linear or branched chain alkyl; z is an integer of 2 to 5; n is 0, 1, or 2; R2 is sec-butyl (seo-C4H9), pentyl (C5H11), hexyl ( C6H13), heptyl (C7H15), octyl (C8H17), nonyl (C 9H19), decyl (C10H21), undecyl (C11H23), and dode Straight chain or branched chain alkyl selected from the group consisting of sil (C12H25) y is 0, 1, or 2; R3 is C1 to C12 linear or branched; is a chain alkylene group; and when n is 1, R1 and R2 are different] 2. The composition according to claim 1, which is a compound according to claim 1. 11. Based on the weight of the flame retardant ABS composition, the composition may contain (a) from about 50 to about 90% acrylonitrile-butadiene-styrene resin; (b) about 5 to about 30% halogenated asymmetric higher alkyl bisphenoxyalka and (c) about 0.1 to about 15% flame retardant enhancer; Composition. 12. The flame retardant enhancer may be an oxide or an oxide of a group IV-A element and a group V-A element of the periodic table. and halides; organic and inorganic compounds of phosphorus, nitrogen, boron, or sulfur; ; and oxides and halides of zinc, magnesium, or titanium; 10. A composition according to claim 9, which is selected from the group consisting of: 13. Claim 9, wherein the flame retardant enhancer is antimony trioxide. Composition. 14. The halogenated asymmetric higher alkyl bisphenoxy alkane is 1-(tribromophenoxy)-2-(dibromononylphenoxy)-ethane; 1-(Tribromophenoxy)-2-(dibromooctylphenoxy)-ethane ; 1-(Tribromophenoxy)-2-(dibromopentylphenoxy)-ethane ; 1-(Tribromophenoxy)-2-(dibromododecylphenoxy)-ethane ; 1-(tetrabromomethylphenoxy)-2-(dibromooctylphenoxy) -ethane; 1-(tetrabromomethylphenoxy)-2-(dibromononylphenoxy)- ethane; and 1-(pentabromophenoxy)-2-(dibromononylphenoxy)-ethane ; A composition according to claim 9, selected from the group consisting of: