WO2007078028A1

WO2007078028A1 - Salt of carboxyethyl phosphinate ester and flame retardant thermoplastic resin composition containing the same

Info

Publication number: WO2007078028A1
Application number: PCT/KR2006/001191
Authority: WO
Inventors: Sang Hyun Hong; Jeong Hwan Ku; Su Hak Bea; Jin Hwan Choi; Jin Hwan Kim; Min Soo Lee
Original assignee: Cheil Industries Inc.
Priority date: 2005-12-30
Filing date: 2006-03-31
Publication date: 2007-07-12
Also published as: EP1968989A1; US20070155872A1; TW200838869A; US7939588B2; KR100654525B1; CN101351468B; CN101351468A; JP2009522252A; EP1968989A4; TWI336705B

Abstract

Disclosed herein is a salt of carboxyethyl phosphinate ester and flame retardant thermoplastic resin composition containing the same. The salt of carboxyethyl phosphinate ester of this invention has excellent flame retardancy, heat stability and hygroscopicity, and also, the flame retardant thermoplastic resin composition of this invention is environmentally friendly because it does not use a halogenated flame retardant, which causes environmental pollution, and has excellent color heat stability and hygroscopicity.

Description

SALT OF CARBOXYETHYL PHOSPHINATE ESTER AND

FLAME RETARDANT THERMOPLASTIC RESIN

COMPOSITION CONTAINING THE SAME

Technical Field

[1]

[2] The present invention relates, in general, to a novel salt of carboxyethyl phosphinate ester and a flame retardant thermoplastic resin composition containing the same and, more particularly, to a novel salt of carboxyethyl phosphinate ester having excellent flame retardancy and high heat stability and hygroscopicity, and to a flame retardant thermoplastic resin composition containing the same.

[3]

Background Art

[4] Generally, thermoplastic resins are used in almost all electronic products by virtue of the excellent processibility and mechanical properties thereof. However, thermoplastic resins themselves have high combustibility and are not fire resistant. Thus, thermoplastic resin is easily burned in a fire and thus may cause fires to spread. Accordingly, the required use of polymer resin that satisfies a standard for flame retardancy has been legislated in USA, Japan, and European countries, so as to assure the resistance of electronic products to fire.

[5] As conventional methods of retarding fire, methods of mixing thermoplastic resin with a halogenated flame retardant together with an antimony flame retardant to exhibit flame retardancy have been mainly used. As such, examples of the halogenated flame retardant include polybromodiphenylether, tetrabromobisphenol A, bromine- substituted epoxy compounds, and chlorinated polyethylene. Examples of the antimony flame retardant include antimony trioxide and antimony pentoxide.

[6] Although the method of realizing flame retardancy using a halogenated compound together with an antimony compound is advantageous because flame retardancy may be easily achieved and other properties are only slightly deteriorated, it suffers because halogenated hydrogen gas, generated upon processing, may negatively affect the human body, which has been proven through experimentation. In particular, typically represented by the halogenated flame retardant, polybrominated diphenylether has a high probability of generating poisonous gas, such as dioxins or furans, upon combustion. Therefore, methods of realizing flame retardancy without the use of such halogenated compounds are receiving attention.

[7] As methods of realizing flame retardancy of thermoplastic resin without the use of a halogenated flame retardant, methods of using aromatic phosphoric acid ester as a flame retardant have been proposed. However, in the case of styrene resin, it is difficult to achieve flame retardancy corresponding to at least UL 94 Vl using an aromatic phosphoric acid ester compound alone.

[8] Therefore, with the goal of solving the problems, methods of mixing a blend of styrene resin and polyphenylene ether resin or polycarbonate resin with aromatic phosphoric acid ester as a flame retardant have been known. US Patent No. 3,639,506 discloses mono aromatic phosphoric acid ester to be added to a resin blend of high impact polystyrene resin (HIPS) and polyphenylene ether resin. In addition, US Patent No. 5,061,745 discloses mono phosphoric acid ester to be added as a flame retardant to a blend of ABS resin and polycarbonate resin. US Patent No. 5,204,394 discloses oligomeric aromatic phosphoric acid ester to be added as a flame retardant to a resin blend of ABS resin and polycarbonate resin.

[9] Korean Patent Laid-open Publication No. 2002-0007814 discloses a technique for mixing polystyrene resin with carboxy phosphinic acid and phosphoric acid derivative as flame retardants. However, this patent is disadvantageous because carboxy phosphinic acid has low heat stability and high hygroscopicity.

[10]

Disclosure of Invention Technical Problem

[11] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a salt of carboxyethyl phosphinate ester which improves on the low flame retardancy of conventional aromatic phosphoric acid esters and on the low heat stability and high hygroscopicity of carboxy phosphinic acid compounds.

[12] Another object of the present invention is to provide a flame retardant thermoplastic resin composition containing a salt of carboxyethyl phosphinate ester without using a halogenated flame retardant, thus exhibiting excellent flame retardancy and high heat stability and heat resistance, while being environmentally friendly.

[13] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description and preferred embodiments.

[14]

Technical Solution

[15] In order to accomplish the above objects, the present invention provides the salt of carboxyethyl phosphinate ester represented by Formula 1 below:

[16] Formula 1 [17]

[18] wherein R is independently selected from the group consisting of a C1-C6 alkyl group, a C6-C20 aryl group or a C6-C20 alkyl-substituted aryl group, R2 is independently selected from the group consisting of a C1-C6 alkyl group, a C6-C30 aryl group or a C6-C30 alkyl-substituted aryl group, n is an integer from 1 to 3, and M is a metallic ion or a charged amine.

[19] In addition, the present invention provides a flame retardant thermoplastic resin composition comprising a thermoplastic resin and 0.1 ~50 parts by weight of the compound represented by Formula 1, based on 100 parts by weight of the thermoplastic resin.

[20] Hereinafter, a detailed description will be given of the present invention.

[21] The novel salt of carboxy ethyl phosphinate ester of the present invention is a salt of carboxyethyl phosphinate ester represented by Formula 1 below, which is used alone or in a combination:

[22] Formula 1

[23]

[24] wherein R is independently selected from the group consisting of a C1-C6 alkyl group, a C6-C20 aryl group or a C6-C20 alkyl-substituted aryl group, R2 is independently selected from the group consisting of a C1-C6 alkyl group, a C6-C30 aryl group or a C6-C30 alkyl-substituted aryl group, n is an integer from 1 to 3, and M is a metallic ion or a charged amine.

[25] In the compound of Formula 1 , R is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, hexyl and phenyl, and R2 is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, hexyl and phenyl. Further, M may be metal, such as Al, Zn, Ca, Ba or Mg, or an amine compound selected from the group consisting of ammonium, melamine, melem, alkyl ammonium, and alkyl imidazole.

[26] In addition, the present invention pertains to a flame retardant thermoplastic resin composition, comprising a thermoplastic resin, and 0.1-50 parts by weight of the salt of carboxyethyl phosphinate ester represented by Formula 1, based on 100 parts by weight of the thermoplastic resin.

[27] Particularly, individual components of the flame retardant thermoplastic resin composition of the present invention are described below.

[28] (A) Salt of Carboxyethyl Phosphinate Ester

[29] The salt of carboxyethyl phosphinate ester represented by Formula 1, which is used alone or in a combination, is contained in the thermoplastic resin composition of the present invention in an amount of 0.1-50 parts by weight, and preferably 1-40 parts by weight.

[30] (B) Thermoplastic Resin

[31] The type of thermoplastic resin used in the present invention is not particularly limited, and specific examples thereof are as follows. That is, examples of the preferred thermoplastic resin composition include, but are not limited to, polystyrene resin (PS resin), acrylonitrile-butadiene-styrene terpolymer resin (ABS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene-acrylate terpolymer resin (ASA resin), acrylonitrile-styrene copolymer resin (SAN resin), methylmethacrylate- butadiene-styrene terpolymer resin (MBS resin), acrylonitrile-ethylacrylate-styrene terpolymer resin (AES resin), polycarbonate resin (PC resin), polyphenylene ether resin (PPE resin), polyethylene resin (PE resin), polypropylene resin (PP resin), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polyamide (PA) resin, copolymers thereof, or alloys thereof.

[32] In particular, the thermoplastic resin is preferably selected from the group consisting of polycarbonate resin, polyphenylene ether resin, styrene polymer, rubber modified acrylonitrile-styrene copolymer, copolymers thereof, and alloys thereof. More preferably, the thermoplastic resin is polybutylene terephthalate.

[33] Further, the thermoplastic resin is preferably a blend of the polyphenylene ether resin and the high impact polystyrene resin, and more preferably the polyphenylene ether resin constituting the thermoplastic resin is poly(2,6-dimethyl-l,4-phenylene ether).

[34] In order to improve flame retardancy, the flame retardant thermoplastic resin composition of the present invention may further comprise commercially available flame retardants and flame retardant aids, such as organic phosphoric acid ester compounds, cyanurate compounds, metal salts, fluorinated polyolefins, etc., in addition to the above-mentioned salt of carboxyethyl phosphinate ester.

[35] The flame retardant thermoplastic resin composition of the present invention preferably further includes 0.1-40 parts by weight of organic phosphoric acid ester based on 100 parts by weight of the thermoplastic resin. More preferably, the organic phosphoric acid ester is aromatic phosphoric acid ester represented by Formula 2 below:

[36] Formula 2 [37]

[38] wherein R , R and R are each independently hydrogen or a C1-C4 alkyl group, X is a C6-C20 aryl group or a C6-C20 alkyl-substituted aryl group which is derived from dialcohol such as resorcinol, hydroquinol or bisphenol-A, and n ranges from 0 to 4.

[39] Examples of the organic phosphoric acid ester include monomeric phosphoric acid esters, such as triphenyl phosphate and tricresyl phosphate, and oligomeric condensed phosphoric acid esters derived from divalent alcohols such as resorcinol, hydroquinone and bisphenol-A.

[40] The flame retardant thermoplastic resin composition of the present invention may further comprise a flame retardant aid, including metal salts, and an anti-dropping agent, including fluorinated polyolefin resins. The usable metal salt includes widely known metal sulfonates, and examples of the fluorinated polyolefin resin usable as the anti-dropping agent include, but are not limited to, typically usable resins, such as polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/vinylidene fluoride copolymer, tetrafluoroethylene/hexafluoropropylene copolymer and ethylene/ tetrafluoroethylene copolymer. The flame retardant aid and the anti-dropping agent may be used alone or in a combination of two or more that are different from each other, and may be contained in an amount of 0.1~30 parts by weight based on 100 parts by weight of the thermoplastic resin.

[41] In addition, the flame retardant thermoplastic resin composition of the present invention may further comprise an additive, such as a lubricant, a releasing agent, a nucleation agent, an antistatic agent, a heat stabilizer, an antioxidant, a compatibilizer, a light stabilizer, a reinforcement, an inorganic additive, a pigment, or a dye, depending on the end use. These additives may be used alone or in a combination. Examples of the inorganic additive include asbestos, glass fiber, talc, ceramic, and sulfates. The above additive is preferably contained in an amount of 0~60 parts by weight, based on 100 parts by weight of the thermoplastic resin. [42]

Advantageous Effects

[43] The salt of carboxy phosphinic acid ester of the present invention has excellent flame retardancy and high heat stability and hygroscopicity.

[44] Further, the flame retardant thermoplastic resin composition of the present invention, containing the salt of carboxyethyl phosphinate ester, has fire resistance and is environmentally friendly without the use of a halogenated flame retardant, which causes environmental pollution upon combustion, with excellent color heat stability and hygroscopicity.

[45]

Brief Description of the Drawings

[46] FIG. 1 shows the result of NMR analysis of methyl carboxyethyl methylphosphinate, obtained in a preparative example of the present invention;

[47] FIG. 2 shows the result of NMR analysis of ethyl carboxyethyl methylphosphinate, obtained in another preparative example of the present invention; and

[48] FIG. 3 shows the result of NMR analysis of methyl carboxyethyl phenylphosphinate, obtained in a further preparative example of the present invention.

[49]

Mode for the Invention

[50] A better understanding of the present invention may be obtained through the following examples and comparative examples which are set forth to illustrate, but are not to be construed as the limit of the present invention.

[51] (A) Preparative Examples of Salt of Carboxyethyl Phosphinate Ester

[52] The salt of carboxyethyl phosphinate ester was obtained by reacting

2-methyl-l,2-oxaphosphinolan-5-one-2-oxide with alcohol to prepare carboxyethyl phosphinate ester, which was then salified.

[53] Al) Aluminum Salt of Methyl Carboxyethyl Methylphosphinate Ester

[54] Into a four-necked flask fitted with a thermometer, a condenser, a stirrer and a dropping funnel, dichloromethylphosphine (0.5 mol, 58.46 g) was added and then stirred at 8O⁰C for 1 hour in a nitrogen atmosphere while dropping excess acrylic acid in an amount of 1.2 times that required (0.6 mol, 43.24 g) thereon. The temperature was increased to 13O⁰C and the reaction mixture was further stirred for 2 hours. Subsequently, the temperature was decreased to 5O⁰C, after which the reaction mixture was allowed to react for about 2 hours while dropping acetic anhydride (0.6 mol, 174.64 g) thereon. After the completion of the reaction, the resultant reaction solution was cooled to room temperature, precipitated using ether, and then vacuum filtered. The residual ether was removed in a vacuum oven. The resultant

2-methyl-l,2-oxaphosphinolan-5-one-2-oxide (0.5 mol, 67.04 g) was added along with methanol (0.6 mol, 19.22 g) into a flask and then refluxed at 5O⁰C for about 10 hours. After the completion of the reaction, the reaction solution was vacuum distilled, thus obtaining a product. The result of NMR analysis of the product is shown in FIG. 1.

[55] Methyl carboxyethyl methylphosphinate (1 mol, 134.0 g) thus obtained and aluminum trihydroxide (0.33 mol, 35.0 g) were added to 500 ml of water, and the reaction mixture was stirred at 17O⁰C for 6 hours using a mechanical stirrer. After the completion of the reaction, the temperature was decreased to 5O⁰C, and the precipitate was filtered and then washed with water. Subsequently, water was removed at 100⁰C under reduced pressure, therefore obtaining an aluminum salt of methyl carboxyethyl methylphosphinate ester.

[56]

[57] A2) Aluminum Salt of Ethyl Carboxyethyl Methylphosphinate Ester

[58] The title compound was prepared in the same manner as in Al), with the exception that 2-methyl-l,2-oxaphosphinolan-5-one-2-oxide was reacted with ethanol to prepare ethyl carboxyethyl methylphosphinate. The result of NMR analysis of the resultant compound is shown in FIG. 2.

[59]

[60] A3) Aluminum Salt of Methyl Carboxyethyl Phenylphosphinate Ester

[61] The title compound was prepared in the same manner as in Al), with the exception that 2-phenyl-l,2-oxaphosphinolan-5-one-2-oxide was reacted with methanol to prepare methyl carboxyethyl phenylphosphinate. The result of NMR analysis of the resultant compound is shown in FIG. 3.

[62]

[63] (B) Thermoplastic Resin

[64] Bl) Rubber Modified SAN Copolymer Resin (ABS Resin)

[65] Bl D g-ABS Resin

[66] 50 parts by weight of a solid content of butadiene rubber latex was added with 36 parts by weight of styrene and 14 parts by weight of acylonitrile as grafting monomers and 150 parts by weight of deionized water. Subsequently, based on the total solid content, 1.0 part by weight of potassium oleate, 0.4 parts by weight of cumene hydroperoxide, 0.2 parts by weight of a mercaptan chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, and 0.3 parts by weight of sodium pyrophosphate were added, and then the reaction mixture was allowed to stand at 75⁰C for 5 hours. After the completion of the reaction, graft latex was prepared, added with 0.4 parts by weight of sulfuric acid based on the solid content of the resin, and then solidified, thus preparing graft copolymer resin (g-ABS) powder. [67]

[68] B 12) SAN Copolymer Resin

[69] 75 parts by weight of styrene, 25 parts by weight of acrylonitrile, 120 parts by weight of deionized water, 0.15 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate, and 0.2 parts by weight of a mercaptan chain transfer agent were added. After the reaction temperature was increased from room temperature to 8O⁰C over 90 min, the reaction mixture was allowed to stand at the increased temperature for 180 min to prepare copolymer resin (SAN), which was then washed with water, dehydrated, and dried, thus preparing SAN powder. [70] The rubber modified SAN copolymer resin was obtained by compounding 30 parts by weight of B 11) g-ABS resin and 70 parts by weight of B 12) SAN copolymer resin. [71]

[72] 62) High Impact Polystyrene Resin (HIPS Resin)

[73] High impact polystyrene resin HG- 1730, available from Cheil Industries Inc.,

Korea, was used, which had 7.5% rubber content and an average rubber particle size of

0.4 D. [74]

[75] B3) Polyphenylene Ether Resin (PPE Resin)

[76] Poly(2,6-dimethyl-phenylether) (trade name: S-202), available from Asahi Kasehi

Corp. Japan, in the form of powder having an average particle size of tens of D, was used. [77] [78] B4) Glass Fiber Reinforced Polybutylene Terephthalte Resin (Glass Reinforced

PBT Resin) [79] 70 wt% of polybutylene terephthalte resin (trade name: Tribit 1500), available from

Samyang Corp., Korea, was reinforced with 30 wt% of glass fiber and then used. [80]

[81] (C) Carboxy Phosphinic Acid Compound

[82] 2-Carboxyethyl methylphosphinate was used.

[83]

[84] (D) Organic Phosphoric Acid Ester

[85] Bisphenol-A diphenyl phosphate (trade name: CR-741) was used.

[86]

[87] Examples 1-9 and Comparative Examples 1-6

[88] Each of the thermoplastic resin compositions of Examples 1-9 and Comparative

Examples 1-6 was prepared according to the composition ratios shown in Tables 1 and 2 below using the above components. As such, individual components were extruded at 200~280°C using a twin screw extruder to prepare pellets, which were then dried at 80⁰C for 2 hours and thereafter injection molded under conditions of a molding temperature of 180~280°C and a mold temperature of 40~80°C using a 6 Oz injection molding machine, thus manufacturing a sample. The properties of each sample were evaluated. The results are given in Tables 1 and 2 below.

[89] TABLE 1 [90]

[91] TABLE 2 [92]

[93] Evaluation of Properties [94] (1) UL 94 VB Flame Retardancv [95] The sample was produced to a thickness of 1/8" and measured for flame retardancy according to the UL 94 VB method.

[96] (2) Color Heat Stability (AE) [97] The sample was injection molded into a 5cmx20cm sample at a molding temperature of 27O⁰C for a residence time of 10 min using a pinpoint gate mold of a 6 Oz injection molding machine. The sample before and after the residence time was observed using a Minolta spectrophotometer, and thus color heat stability was judged.

[98] (3) Hygroscopicitv (%)

[99] A lOcmx 10cmx0.32cm injected sample was allowed to stand in a thermostatic bath at 6O⁰C for 24 hours. The difference in weight before and after the sample was allowed to stand was measured and thus hygroscopicity was determined.

[100] From the results of Tables 1 and 2, it can be confirmed that the salt of carboxyethyl phosphinate ester of the present invention has excellent flame retardancy, and in particular, color heat stability and hygroscopicity thereof are more greatly improved compared to the case of conventional carboxyethyl phosphinic acid compounds.

Claims

[1] A salt of carboxy ethyl phosphinate ester represented by Formula 1 below:

Formula 1

wherein R is independently selected from the group consisting of C1-C6 alkyl group, C6-C20 aryl group and C6-C20 alkyl-substituted aryl group, R is independently selected from the group consisting of C1-C6 alkyl , C6-C30 aryl group and C6-C30 alkyl-substituted aryl group, n is an integer from 1 to 3, and M is a metallic ion or a charged amine.

[2] The salt according to claim 1 , wherein the R is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, hexyl or phenyl.

[3] The salt according to claim 1, wherein the R is independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, hexyl or phenyl.

[4] The salt according to claim 1, wherein the M is selected from the group consisting of Al, Zn, Ca, Ba, Mg, ammonium, melamine, melem, alkyl ammonium, or alkyl imidazole.

[5] A flame retardant thermoplastic resin composition, comprising: a thermoplastic resin; and

0.1-50 parts by weight of a salt of carboxyethyl phosphinate ester represented by Formula 1 below, which is used alone or in a combination, based on 100 parts by weight of the thermoplastic resin: Formula 1

[6] The composition according to claim 5, wherein the thermoplastic resin is selected from the group consisting of polystyrene resin (PS resin), acrylonitrile- butadiene-styrene terpolymer resin (ABS resin), rubber-modified high impact polystyrene resin (HIPS), acrylonitrile-styrene-acrylate terpolymer resin (ASA resin), acrylonitrile-styrene copolymer resin (SAN resin), methylmethacrylate- butadiene-styrene terpolymer resin (MBS resin), acrylonitrile-ethy- lacrylate-styrene terpolymer resin (AES resin), polycarbonate resin (PC resin), polypheny lene ether resin (PPE resin), polyethylene resin (PE resin), polypropylene resin (PP resin), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polyamide (PA) resin, copolymers thereof, and alloys thereof.

[7] The composition according to claim 5, wherein the thermoplastic resin is polybutylene terephthalate. [8] The composition according to claim 5, wherein the thermoplastic resin is a blend of the polyphenylene ether resin and the high impact polystyrene resin. [9] The composition according to claim 8, wherein the polyphenylene ether resin is poly(2,6-dimethyl- 1 ,4-phenylene ether). [10] The composition according to claim 5, further comprising 0.1-40 parts by weight of organic phosphoric acid ester based on 100 parts by weight of the thermoplastic resin.

[H] The composition according to claim 10, wherein the organic phosphoric acid ester is aromatic phosphoric acid ester represented by Formula 2 below: Formula 2

wherein R , R and R are each independently hydrogen or a C1-C4 alkyl group, X is a C6-C20 aryl group or a C6-C20 alkyl-substituted aryl group which is derived from dialcohol including resorcinol, hydroquinol or bisphenol-A, and n ranges from 0 to 4.

[12] The composition according to any one of claims 5, 10 and 11, further comprising a flame retardant aid including metal sulfonate and an anti-dropping agent including fluorinated polyolefϊn resin selected from the group consisting of poly- tetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/vinylidene fluoride copolymer, tetrafluoroethylene/hexafluoropropylene copolymer and ethylene/tetrafluoroethylene copolymer, the flame retardant aid and the anti- dropping agent being used alone or in a combination and being contained in an amount of 0.1-30 parts by weight based on 100 parts by weight of the thermoplastic resin.

[13] The composition according to claim 5, further comprising 0~60 parts by weight of at least one additive selected from the group consisting of a lubricant, a releasing agent, a nucleation agent, an antistatic agent, a heat stabilizer, an antioxidant, a compatibilizer, a light stabilizer, a reinforcement, an inorganic additive, a pigment, a dye, and mixtures thereof, based on 100 parts by weight of the thermoplastic resin.