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WO1990000165A1 - Alcanes bisphenoxy d'alkyle superieur ignifuges et leur application a des systemes polymeres abs - Google Patents

Alcanes bisphenoxy d'alkyle superieur ignifuges et leur application a des systemes polymeres abs Download PDF

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Publication number
WO1990000165A1
WO1990000165A1 PCT/US1989/002796 US8902796W WO9000165A1 WO 1990000165 A1 WO1990000165 A1 WO 1990000165A1 US 8902796 W US8902796 W US 8902796W WO 9000165 A1 WO9000165 A1 WO 9000165A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
flame retardant
halogenated
higher alkyl
ethane
Prior art date
Application number
PCT/US1989/002796
Other languages
English (en)
Inventor
Enrico J. Termine
Nicolai A. Favstritsky
Dennis M. Borden
Original Assignee
Great Lakes Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/213,540 external-priority patent/US4891449A/en
Priority claimed from US07/213,538 external-priority patent/US4880862A/en
Application filed by Great Lakes Chemical Corporation filed Critical Great Lakes Chemical Corporation
Priority to KR1019900700438A priority Critical patent/KR900701715A/ko
Publication of WO1990000165A1 publication Critical patent/WO1990000165A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

Definitions

  • the present invention relates to a plastic additive composition and more particularly to a plastic additive composition
  • this invention relates to a nonblooming flame retardant ABS resin composition incorporating the halogenated unsymmetrical higher bisphenoxy alkanes.
  • plastic additive compositions are an important class of industrial materials. Plastic additives are used to enhance or modify the properties of commercially available polymers. The use of plastic additives allows a relatively small number of commercially available polymers to be tailored to a myriad of uses. Those skilled in the art will know that the selection of an application of a specific plastic additive is unpredictable at best. Therefore, additive manufacturers must take a sophisticated approach and offer a range of products to achieve the desired result.
  • Plastic additive compositions can be used as plasticizers, flame retardants, flow modifiers, or impact modifiers in resin systems, heat transfer fluids, or hydraulic fluids.
  • One important use of plastic additive compositions is as flame retardant agents in resin systems.
  • Most flame retardant agents although efficient in their function of retarding the rate of combustion in a resin system, have a tendency to affect adversely one or more key properties of the resin. For example, many flame retardant additives tend to reduce the impact strength of the resin; to migrate from the resin composition, resulting in a phenomena known as "bloom"; to
  • ABS thermoplastics offer a good balance of
  • ABS thermoplastics are used in. a wide variety of applications because of their properties and moderate costs.
  • ABS thermoplastics are used by telephone equipment, electronic, and automotive manufacturers who require materials of high impact strength.
  • retardant agents require that certain key properties be maintained.
  • key properties include impact strength, light stability and retention of surface aesthetic properties.
  • manufacturers of computer housings desire a thermoplastic ABS resin which is flame retardant, light stable, and resistant to bloom.
  • compositions obtained using these various bromine containing compounds have a tendency to change color on exposure to light, to develop a reduction in surface gloss, and to form deposits of flame retardant agents on the polymer surface.
  • compositions of the flame retardants are depicted by the following formula:
  • A is a cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl,
  • R is chosen from the following group:
  • U.S. Patent No. 3,883,479 issued to Anderson, .et al. discloses plastic compositions containing ABS and symmetrical bisphenoxy compounds.
  • the bisphenoxy compounds have the formula: wherein Z is bromine, m and m' are integers having a value of 1-4, i and i' are integers having a value of 1 or 2.
  • the alkylene is a straight or branched chain alkylene group having from 1 to 6 carbon atoms.
  • A is to be selected from the group consisting of cyano, nitro, lower alkoxy, lower alkyl (defined as CH 3 , C 2 H 5 , C 3 H 7 or C 4 H 9 ), fluorine, dialkylamino, phenyl,
  • the flame retardants have the formula:
  • A is chosen from the group consisting of cyano, nitro, lower alkoxy, lower alkyl, fluorine, diakylamino, phenyl, halo-phenyl, benzyl or halo-benzyl group.
  • compositions of the flame retardants have the formula:
  • Z is bromine or chlorine
  • m and m' are integers having a value of 1 to 5
  • i and i' are integers having a value of 0 to 2
  • HBCA is a halo-branched alkylene group having from 1 to 6 carbon atoms
  • A is cyano, nitro, lower alkoxy, lower alkyl (C 1 -C 4 ), fluorine, dialkylamino, phenyl, halo-phenyl, benzyl or
  • n and m' are integers having a value between 1 and 5 and the alkylene is a straight or branched alkylene group containing 1 to 6 carbon atoms.
  • Anderson, et al., U.S. Patent No. 4,016,139 disclose a composition containing an ABS polymer, a symmetrical bisphenoxy flame retardant and a flame retardant enhancing agent.
  • the bisphenoxy flame retardant has the following formula: wherein Z is bromine, m and m' are integers having a value of 1 to 5 so that the total bromine atom content ranges from 6 to 10 atoms, and T is a straight chain or branched chain carbon group having 1 to 4 carbon atoms.
  • composition contains an ABS polymer and a symmetrical bisphenoxy compound having the formula:
  • alkylene is a straight or branched chain alkylene group having from 1 to 6 carbon atoms and A is chlorine.
  • a primary object of this invention is to provide new unsymmetrical higher alkyl halogenated bisphenoxy alkanes.
  • Another object of the invention is to provide halogenated unsymmetrical higher alkyl bisphenoxy alkanes having utility as flame retardant agents.
  • Yet another object of the invention is to provide halogenated unsymmetrical higher alkyl bisphenoxy alkanes having utility as non-blooming flame
  • An additional object of the present invention is to provide an agent capable of flame retarding ABS resin compositions without exhibiting problems of bloom, heat or light instability or any of the other disadvantages of the prior art ABS flame retardant agents.
  • the bisphenoxy alkane used in accordance with this invention is a brominated unsymmetrical higher alkyl bisphenoxy ethane.
  • the preferred bisphenoxy alkane used in accordance with this invention is a brominated unsymmetrical higher alkyl bisphenoxy ethane.
  • brominated bisphenoxy ethane contains between 40 and 70 percent by weight of bromine.
  • the invention contemplates incorporating an effective amount of halogenated unsymmetrical higher alkyl bisphenoxy alkane and an enhancing agent into a normally combustible ABS resin to obtain a flame retardant ABS resin composition.
  • the compositions of this invention preferably comprise about 50 to 90 percent ABS thermoplastic resin, about 5 to 30 percent halogenated unsymmetrical higher alkyl bisphenoxy alkane and about 0.1 to 15 percent enhancing agent, all by weight of the composition.
  • novel compositions of this invention are distinguished from the known bisphenoxy compositions by improved properties.
  • compositions are stable to light and heat, have good flame retardant properties, and, most importantly, compositions incorporating the novel compounds do not bloom.
  • compositions of matter are halogenated unsymmetrical higher alkyl bisphenoxy alkanes of the following formula:
  • R 3 is a straight or branched alkylene group from methyl (CH 3 ) to dodecyl (C 12 H 25 ) such as cyclohexane for example; and if n is 1, R 1 is not R 2 .
  • the novel composition of matter contains some minor amounts of symmetrical halogenated higher alkyl bisphenoxy alkanes. The minor amounts in the composition do not effect the utility of the composition as a non-blooming flame retardant agent.
  • X is bromine
  • the bromine content should be between approximately 40 percent and 70 percent by weight.
  • Especially preferred bisphenoxy compounds are those compounds where x is 3, z is 2, and n is zero.
  • X is bromine
  • R 2 is either octyl (C 8 H 17 ) or nonyl (C 9 H 19 ) and R 3 is ethylene.
  • the preferred novel plastic additive compositions, brominated bisphenoxy ethanes are prepared in a
  • X and Y are independently bromine or chlorine.
  • the preferred method of synthesis is to react the phenate salt containing the least alkyl content with a large excess of 1,2-dibromoethane (>4 moles/mole phenate) in a polar, high-boiling solvent such as propylene glycol. The excess dibromoethane is then preferably removed by distillation before reacting the intermediate with the second phenate salt.
  • the compounds listed in Table 1 are examples of compounds synthesized by the preferred synthesis method. The list is not intended to be exhaustive or to limit the scope of the invention.
  • the brominated alkyl phenols were produced from commercially available alkyl phenols using techniques known in the art.
  • bisphenoxy ethane is used in a plastic formulation, it should be employed in amounts of 0.5 to 30 percent by weight of plastic formulation.
  • the most preferred weight percent of brominated bisphenoxy ethane in the plastic formulation is 5 percent to 20 percent.
  • This invention also encompasses use of
  • bisphenoxy alkanes are useful in the preparation of non-blooming flame retardant ABS resins.
  • novel compositions of this invention are distinguished from known flame retardant ABS compositions by improved properties.
  • ABS Preferred novel flame retardant ABS
  • compositions may be prepared by admixing from about 50% to about 90% by weight thermoplastic ABS resin; from about 5% to about 30% by weight halogented unsymmetrical higher alkyl bisphenoxy alkane compounds; from about 0.1% to about 15% by weight enhancing agent, where the percentages are based on the total weight of the resulting admixture of these three components.
  • the compositions of this invention comprise about 60 to 90% ABS resin; about 10 to 30% halogenated unsymmetrical higher alkyl bisphenoxy alkane compound; and about 2 to 10% enhancing agent.
  • the ABS resin may be any thermoplastic resin formed by blending a styrene/acrylonitrile copolymer with butadiene-based rubber, or by grafting
  • substantially any suitable acrylonitri le-butadiene-styrene composition may be used, containing each component of the terpolymer in substantially any proportion.
  • the ABS may contain or may be substantially free of other additives such as stabilizers , plasticizers , dyes , pigments , fillers and the like .
  • the preferred plastic composition additives in the preparation of non-blooming flame retardant ABS resins are all unsymmetrical , that i s R 1 is not R 2 where n is 1 .
  • the preferred additives in accordance with this invention include :
  • ABS flame retardant compositions of this invention also desirably incorporate one or more
  • accordance with this invention comprise the oxides and halides of groups IV-A and V-A of the periodic table; organic or inorganic compounds of
  • Preferred enhancing agents in accordance with this invention are the oxides of antimony, arsenic and bismuth, with the oxides of antimony being
  • Antimony trioxide is the most preferred enhancing agent used in the compositions of this invention. As noted, the enhancing agent is supplied at the level of about 0.1-15 percent by
  • the enhancing agent is used at a level of about 2-10 percent by weight.
  • additives include, without limitation, heat
  • Step I 2,4,6-Tribromophenol (856 grams, 2.6 moles), phenol (6 grams), sodium carbonate (180 grams, 1.7 moles) and propylene glycol (1036 grams) are combined in a five-liter reactor equipped with a mechanical stirrer. The mixture is brought to 100oC with agitation and held for one hour.
  • 1,2-Dibromoethane (1950 grams, 10.4 moles) is added to the reactor all at once. The temperature is returned to 100oC and held for an additional three hours with high agitation. Without allowing the reaction mixture to cool, agitation is discontinued, the phases are allowed to separate. Methanol (6 liters) is placed in a 12-liter reactor with
  • Step I Dibromononylphenol (2270 grams, 6.0
  • Step II 2,4,6-Tribromophenol (1985 grams, 6.0 moles), phenol (14 grams), sodium carbonate (382
  • the mixture is held at 145oC with vigorous agitation for four hours. With the stirrer off, the reactor is cooled to 35oC and the upper phase decanted. The lower phase is dissolved in methylene chloride (2.5 liter). After washing with dilute hydrochloric acid, the solvent is
  • Step I Dibromononylphenol (983 grams, 2.6 moles), sodium carbonate (180 grams, 1.7 moles), 1,2-dibromoethane (1950 grams, 10.4 moles),
  • TDA-1 tris(2-(2-methoxyethoxy)ethyl) amine or TDA-1 (84 grams) are combined in a 3-liter reactor equipped with a mechanical stirrer and Dean-Stark trap. The mixture is heated to 130oC and held for four hours. After cooling, the mixture is filtered, and the excess dibromoethane is removed using a wiped film evaporator at 100oC and 20 torr vacuum.
  • Step II The product from Step I which is predominantly 3-bromoethyl-dibromononylphenyl ether and TDA-1 is combined with 2,4, 6-tribromophenol (860 grams, 2.6 moles) and sodium carbonate (180 grams, 1.7 moles) in a 3-liter reactor equipped with mechanical stirrer and Dean-Stark trap. The mixture is heated to 130oC and held for five hours.
  • 2,4, 6-tribromophenol 860 grams, 2.6 moles
  • sodium carbonate 180 grams, 1.7 moles
  • Step I 2,4,6-Tribromophenol (1,160 grams, 3.5 moles), lithium hydroxide monohydrate (7.5 grams), and ethylene glycol (2000 grams) are combined in a 5-liter reactor equipped with mechanical stirrer and subsurface gas inlet tube. The mixture is heated to 120oC and ethylene oxide is introduced subsurface at a rate of three to four grams per minute with vigorous stirring. The pH of the reaction mixture is monitored with dampened pH indicator paper.
  • Step II Product from Step I (940 grams, 2.5 moles), and pyridine (3 liters) are combined in a 5-liter reactor equipped with mechanical stirrer. After cooling the mixture to ⁇ 5oC, benzenesulfonyl chloride (883 grams, 5 moles) is added dropwise over one hour while keeping the temperature at ⁇ 5oC. The mixture is allowed to slowly warm to room
  • Step III Same as Step II of Example 1 except ⁇ -(2,4,6-tribromophenoxy)-ethyl benzenesulfonate (1,160 grams, 2.25 moles) is used in place of
  • a flame retardant composition was prepared by blending 20.0 parts halogenated unsymmetrical higher alkyl bisphenoxy alkane (Compound A); 69.0 parts ABS resin, which is available from Borg-Warner
  • chlorinated polyethylene which is available from The Dow Chemical Company as TYRIN CPE-4213S; 5.0 parts antimony trioxide, which is available from M & T Chemical Company as THERMOGUARD S; 0.5 parts stabilizer, which is available from Ciba Geigy
  • antioxidant which is available from Ciba Geigy Corporation as Irganox 1076.
  • Compound A is 1-(tribromophenoxy)- 2-(dibromononyIphenoxy)-ethane, a halogenated unsymmetrical higher alkyl bisphenoxy alkane
  • the resultant mixture was blended in a
  • Flame retardant compositions were prepared using the method of Example 5 , except that Compound A was replaced by Compound J, Compound F, Compound K, and Compound L, respectively in a proportion so as to maintain a 10.8 percent by weight bromine concentration in the resulting polymer composition. Identity for these Compounds J, F, K, and L are listed in Table III.
  • Table IV shows the results of the experimental evaluations of various test specimens and may be summarized as follows.
  • Example 5 illustrates a flame retardant ABS formulation incorporating halogenated unsymmetrical higher alkyl bisphenoxy alkane in accordance with this invention. A flammability rating of V-O was achieved, and bloom was not observed.
  • Comparative Examples 1-4 show that prior art symmetrical bisphenoxy compound, when used in V-O formulation, migrate (bloom) from ABS resin.
  • Examples 6-11 illustrate flame retardant formulations incorporating other halogenated
  • ABS resins incorporating halogenated unsymmetrical higher alkyl bisphenoxy alkanes of this invention do not bloom whereas symmetrical bisphenoxy alkanes do bloom or tend to migrate from the resin
  • ABS resins incorporating the halogenated unsymmetrical higher alkyl bisphenoxy alkanes of this invention exhibit excellent resistance to light instability, to thermal migration of flame retarding agents, and have improved physical properties, such as impact strength and tensile elongation.
  • Flame retardant compositions were prepared using the method of Example 5, except that Compound A was partially replaced by Compound J in proportion as specified in Table V, so as to maintain a constant weight of bromine-containing flame retardant.
  • a flame retardant composition was prepared using the method of Example 5, except that Compound A was replaced by Compound J in proportion as specified in Table V.
  • Table V shows the results of experimental evaluation of the various test specimens and may be summarized as follows:
  • Example 5 Example 5
  • Examples 12-14 show no evidence of bloom in compositions comprising mixtures of the agents of this invention with bis(tribromophenoxy)-ethane (Compound J).
  • Compound J bis(tribromophenoxy)-ethane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des alcanes bisphénoxy d'alkyle supérieur non symétriques halogénés sont utiles comme agents ignifuges sans efflorescence. On peut notamment utiliser des alcanes bisphénoxy d'alkyle supérieur non symétriques halogénés avec un agent d'exaltation pour rendre une résine ABS ignifuge.
PCT/US1989/002796 1988-06-30 1989-06-29 Alcanes bisphenoxy d'alkyle superieur ignifuges et leur application a des systemes polymeres abs WO1990000165A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019900700438A KR900701715A (ko) 1988-06-30 1989-06-29 방염성 abs수지 조성물 및 abs중합체계에 대한 그의 용도

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/213,540 US4891449A (en) 1988-06-30 1988-06-30 Halogenated unsymmetrical higher alkyl phenoxy alkanes
US07/213,538 US4880862A (en) 1988-06-30 1988-06-30 Flame retardant ABS resin composition
US213,538 1988-06-30
US213,540 1988-06-30

Publications (1)

Publication Number Publication Date
WO1990000165A1 true WO1990000165A1 (fr) 1990-01-11

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PCT/US1989/002796 WO1990000165A1 (fr) 1988-06-30 1989-06-29 Alcanes bisphenoxy d'alkyle superieur ignifuges et leur application a des systemes polymeres abs

Country Status (5)

Country Link
EP (1) EP0388445A4 (fr)
JP (1) JPH03503419A (fr)
KR (1) KR900701715A (fr)
CA (1) CA1317603C (fr)
WO (1) WO1990000165A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3660351A (en) * 1970-03-12 1972-05-02 American Cyanamid Co Flame resistant acrylonitrile polymers
US3876612A (en) * 1972-06-06 1975-04-08 Michigan Chem Corp Abs plastic compositions containing bis-phenoxy flame retardants
US3883479A (en) * 1972-06-06 1975-05-13 Michigan Chem Corp ABS plastic compositions containing bio-phenoxy flame retardants
US3892710A (en) * 1972-06-06 1975-07-01 Michigan Chem Corp ABS plastic compositions containing halogenated aryl flame retardants
US3971758A (en) * 1972-06-06 1976-07-27 Michigan Chemical Corporation Plastic compositions containing acrylonitrile-butadiene-styrene polymer and a bis-phenoxy flame retardant
US4016139A (en) * 1973-02-08 1977-04-05 Michigan Chemical Corporation Plastic composition comprising acrylonitrile-butadiene-styrene polymer, a bis-phenoxy flame retardant and a flame retardant enhancing agent
US4016137A (en) * 1972-06-06 1977-04-05 Michigan Chemical Corporation Plastic compositions
US4051105A (en) * 1972-06-06 1977-09-27 Velsicol Chemical Corporation Plastic compositions
US4059561A (en) * 1975-02-07 1977-11-22 Showa Denko Kabushiki Kaisha Flame-resistant composition containing a norbornene derivative polymer
US4171330A (en) * 1977-01-27 1979-10-16 Unitika Ltd. Fire-retardant resin composition
US4567218A (en) * 1984-02-01 1986-01-28 Great Lakes Chemical Corporation Halogenated bisphenol A ether flame retardant for ABS polymers

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3660351A (en) * 1970-03-12 1972-05-02 American Cyanamid Co Flame resistant acrylonitrile polymers
US3876612A (en) * 1972-06-06 1975-04-08 Michigan Chem Corp Abs plastic compositions containing bis-phenoxy flame retardants
US3883479A (en) * 1972-06-06 1975-05-13 Michigan Chem Corp ABS plastic compositions containing bio-phenoxy flame retardants
US3892710A (en) * 1972-06-06 1975-07-01 Michigan Chem Corp ABS plastic compositions containing halogenated aryl flame retardants
US3971758A (en) * 1972-06-06 1976-07-27 Michigan Chemical Corporation Plastic compositions containing acrylonitrile-butadiene-styrene polymer and a bis-phenoxy flame retardant
US4016137A (en) * 1972-06-06 1977-04-05 Michigan Chemical Corporation Plastic compositions
US4051105A (en) * 1972-06-06 1977-09-27 Velsicol Chemical Corporation Plastic compositions
US4016139A (en) * 1973-02-08 1977-04-05 Michigan Chemical Corporation Plastic composition comprising acrylonitrile-butadiene-styrene polymer, a bis-phenoxy flame retardant and a flame retardant enhancing agent
US4059561A (en) * 1975-02-07 1977-11-22 Showa Denko Kabushiki Kaisha Flame-resistant composition containing a norbornene derivative polymer
US4171330A (en) * 1977-01-27 1979-10-16 Unitika Ltd. Fire-retardant resin composition
US4567218A (en) * 1984-02-01 1986-01-28 Great Lakes Chemical Corporation Halogenated bisphenol A ether flame retardant for ABS polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0388445A4 *

Also Published As

Publication number Publication date
EP0388445A1 (fr) 1990-09-26
KR900701715A (ko) 1990-12-04
JPH03503419A (ja) 1991-08-01
EP0388445A4 (en) 1991-07-03
CA1317603C (fr) 1993-05-11

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