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WO2014075289A1 - Composition polymère thermoplastique comprenant un sel hypophosphite de métal alcalin - Google Patents

Composition polymère thermoplastique comprenant un sel hypophosphite de métal alcalin Download PDF

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Publication number
WO2014075289A1
WO2014075289A1 PCT/CN2012/084734 CN2012084734W WO2014075289A1 WO 2014075289 A1 WO2014075289 A1 WO 2014075289A1 CN 2012084734 W CN2012084734 W CN 2012084734W WO 2014075289 A1 WO2014075289 A1 WO 2014075289A1
Authority
WO
WIPO (PCT)
Prior art keywords
salt
composition
alkali metal
acid
organic dicarboxylic
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/CN2012/084734
Other languages
English (en)
Inventor
Junli Li
Gary Woodward
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
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
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Priority to EP12888559.7A priority Critical patent/EP2920234A4/fr
Priority to CN201280077110.7A priority patent/CN104781326A/zh
Priority to PCT/CN2012/084734 priority patent/WO2014075289A1/fr
Publication of WO2014075289A1 publication Critical patent/WO2014075289A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the present invention concerns compositions comprising at least a thermoplastic polymer matrix, an alkali metal hypophosphite salt, and an organic dicarboxylic acid or a salt thereof, having a first pkA ⁇ 5; based on the weight of the alkali metal hypophosphite salt; and method to prepare such compositions.
  • Calcium hypophosphite is known and reported in the industry and the academy as a good flame retardant (FR) for plastics. However, even if calcium hypophosphite has brought a lot of interest no industrial application in thermoplastics are reported today because of its unpredictable thermal stability that can generate phosphine and catch fire.
  • US20070082995 and US2010160523A claim the use of hypophosphite salts as FR for polyesters and polyamide.
  • additives such as inorganic hydrates and/ organic salt to improve the stability of plastic but looking at the results it looks like that in several instances they burn the plastic during the compounding which could be due to hypophosphite salts make the crossHnking or degradation of polymer in the thermal processing
  • hypophosphite salts have been claimed to be good to excellent flame retardants for a wide range of plastics but so far they have not been successfully commercialized. There is then a need to develop thermoplastic formulations comprising hypophosphite salts as FR additives having an improved melt stability to decrease variations of its viscosity.
  • thermoplastic polymer matrix permits to avoid deficiencies of the prior art and notably enables a thermoplastic composition that avoids an increase in viscosity and related crosslinking of the thermoplastic matrix.
  • the combination of the present invention also permits a low variation in the viscosity of the thermoplastic resin, while in comparison the use of other salts of organic acids leads to a drop of matrix integrity, and then also a drop of mechanical properties.
  • the invention then provides a convenient method which avoids obtaining a crosslinked polymer as a resul of the use of an alkali metal hypophosphite salt, such as calcium hypophosphite, within the thermoplastic polymer matrix.
  • the invention then improves the processing stability of alkali metal hypophosphite salt formulation at high temperatures, notably around 300°C.
  • This invention can also protect alkali metal hypophosphite salt in thermal processing and reduce the PH 3 generated from alkali metal hypophosphite salt decomposition.
  • the invention provides a way to improve the stability of alkali metal hypophosphite salt in polymer as well as a unique way to measure and track formulation behavior.
  • thermoplastic polymer matrix (a) a thermoplastic polymer matrix
  • the present invention also concerns a method to prepare a composition by blending at least :
  • thermoplastic polymer matrix (a) a thermoplastic polymer matrix
  • the thermoplastic polymer present in composition of the invention is selected from the group consisting in polyethylene, polypropylene, polyphenylene ethers; polyamides, especially PA66, PA6, PA6.10, high temperature polyamides such as PPA, PA4.6, PA9T, PA66.6T, PAIOT, PA6.6T and blends of polyamides, such as PA/PET, PA/ABS or PA/PP; polyesters as polybutylene terephthalate (PBT); polycarbonates; epoxy resins; phenolic resins; acrylonitrile butadiene styrene (ABS); styrene acrilonitrile (SAN); mixtures of high impact polystyrene (HIPS) and polyphenylene ethers such as PPO/HIPS; styrene butadiene rubber and lattices (SB and SB); expandable polystyrene (EPS); halogenated polymers such as polyvinyl chloride (PVC), and mixture
  • Polyamides are preferably chosen among PA66, PA6, PA6.10, PA 10.10, PA11 and PA12, and high temperature polyamides such as PPA, PA4.6, PA9T, PA66.6T, PA10T, PA6.6T and blends of polyamides, such as PA/PET, PA/ABS or PA/PP.
  • thermoplastic polymer (a) is comprised between 40% and 90%, based on the total weight of the composition, more preferably between 30% and 60%.
  • Preferred weight proportion of alkali metal hypophosphite salt (b) is comprised between 1 and 30 wt %, based on the total weight of the composition, more preferably between 8% and 25%.
  • hypophosphite salt present in the composition according to the invention is preferably of the formula (1) below : O
  • n 1 , 2 or 3 ;
  • M is a metal selected from the group consisting alkali metal, alkaline earth metal, aluminium, titanium and zinc.
  • M is calcium or aluminium.
  • the hypophosphite salt may be heat stabilized so as that when it is heated during 3 hours at 298K under a flow of argon flushing at rate 58 mL/mins, it generates less than 0.5 mL of phosphine per gram of hypophosphite salt.
  • the hypophosphite salt preferably includes and is advantageously a calcium hypophosphite.
  • the hypophosphite salt present in the compositions of the invention is so heat stabilized that ,when it is heated during 3 hours at 298°C under a flow of argon flushing at rate 58 mL/min, it generates less than 0.5 mL of phosphine per gram of hypophosphite salt.
  • Preferably according to this test it generates less than 0.1, more preferably less than 0.05, particularly less than preferably less than 0.02 mL of phosphine per gram of calcium hypophosphite.
  • the heat stability of the hypophosphite salt at 298 °C may especially be tested by using a Gastec tube to detect P3 ⁇ 4, as illustrated in the appended examples.
  • hypophosphite salts and, especially, calcium hypophosphite can be prepared for example from white phosphorus (P 4 ) reacted under alkaline conditions with calcium hydroxide or calcium oxide and water as taught by US 5,225,052. It is also possible to obtain calcium hypophosphite by reaction of a calcium salt or simply from lime as taught by Chinese patent CN101332982, with hypophosphorous acid. For example the lime suspension is simply neutralized with hypophosphorous acid, the impurities are removed by filtration and the product isolated in a same way as previously described. It is also possible to obtain calcium hypophosphite from other metallic hypophosphites or the acid by ion exchange process.
  • the process for stabilizing the starting hypophosphite salt which is useful for preparing the polymer composition of the invention can be batch, continuous or semi-continuous and be performed in a close or open system under inert atmosphere. That inert atmosphere can be for example carbon dioxide, argon, or nitrogen.
  • the process for stabilizing the starting hypophosphite salt can be performed under atmospheric pressure, under pressure or under vacuum.
  • the quality of the hypophosphite salts may be determined use of thermal analysis tools such as ARC (Adiabatic Reaction Calorimeter) and TGA (Thermal Gravimetric Analysis). The test can be carried out at any stage during the heating process described before.
  • Another way to check the quality of the heat stabilized hypophosphite salt used in the instant invention is to perform a stability test at elevated temperature on the product, alone or mixed with plastic and measure the amount of phosphine generated during the test. It is also possible to measure the amount of phosphine generated when the product is compounded with plastics such as polyamide.
  • Preferred weight proportion of the organic dicarboxylic acid or a salt thereof (c) is comprised between 0.1% and 10%, based on the total weight of the composition, more preferably between 1 % and 7%.
  • the logarithmic constant, pKa which is equal to -logio a, is also referred to the acid dissociation constant of the organic dicarboxylic acids of the present invention.
  • This constant is classically measured in a water solution at a temperature of 25 C.
  • the constant for dissociation of the first proton may be denoted as Kal and the constant for dissociation of successive protons as Ka2.
  • the first pKa as defined above corresponds to pKal .
  • the first pKa of the salt of the organic dicarboxylic acids (c) of the present invention is inferior or equal to 4.3, more preferably inferior or equal to 4.2 and well more preferably comprised between 0 and 4.2.
  • Salt of an organic dicarboxylic acids (c) may be for example alkali-metal or alkali-earth salts, such as sodium, magnesium, calcium, and/or potassium.
  • Organic dicarboxylic acid or salt thereof (c) may be used to coat the alkali metal hypophosphite salt (b) previously to the blend with the thermoplastic polymer matrix (a). It is also perfectly possible to blend the organic dicarboxylic acid or salt thereof (c), the alkali metal hypophosphite salt (b) and the thermoplastic polymer matrix (a) without a pre-blend of the organic dicarboxylic acid or salt thereof (c) and the alkali metal hypophosphite salt (b) In a general way, the coating of the organic dicarboxylic acid or salt thereof (c) on the alkali metal hypophosphite salt (b) may be carried out with different methods.
  • the alkali metal hypophosphite salt (b) may be surface-coated by intimate contacting of the alkali metal hypophosphite salt (b) and the organic dicarboxylic acid or salt thereof (c), possibly in a solvent, such as water and/or alcohol, and eventually followed by filtering and/or drying of the product thus obtained.
  • a solvent such as water and/or alcohol
  • the alkali metal hypophosphite salt (b) may be surface-coated by the organic dicarboxylic acid or salt thereof (c), by mixing them as dry powders.
  • the alkali metal hypophosphite salt (b) may notably be surface-coated by the organic dicarboxylic acid or salt thereof (c) by mechanical grinding in a milling machine and optionally mixing the dry powders, notably in a slow or high speed mechanical mixer.
  • a binding agent may be used in the surface-coating process improve the adhesion of the coating compound to the surface of the alkali metal hypophosphite salt (b).
  • binding agents are organic binders, such as synthetic or natural waxes, modified waxes, liquid hydrocarbons or epoxide resins.
  • composition of the present invention may also comprise one or several flame retardant additives.
  • Different types of flame retardant additives may be used according to the invention. They can provide several mechanisms of function such as endothermic degradation, thermal shielding, dilution of gas phase, dilution of combustible portion, and radical quenching.
  • Flame retardant additives for polymer compositions are notably described in Plastics Additives, Gachter/Muller, Hansen, 1996, page 709 and passim.
  • Useful Flame retardant additives are notably cited in the following patents: US6344158, US6365071, US6211402 and US6255371.
  • Flame retardant additives used in the composition of the instant invention are preferably chosen in the group comprising :
  • Phosphorous containing flame retardant additives such as:
  • phosphine oxide such as for example triphenylphosphine oxide, tri-(3-hydroxypropyl) phosphine oxide and tri-(3-hydroxy-2-methylpropyl) phosphine oxide.
  • phosphonic acids and their salts such as for example phosphinic acid of zinc, magnesium, calcium, aluminium or manganese, notably aluminium salt of diethylphosphinic acid, aluminium salt of dimethylphosphinic acid, or zinc salt of dimethylphosphinic acid.
  • cyclic phosphonates such as diphosphate cyclic esters that is for example Antiblaze 1045.
  • organic phosphates such as triphenylphosphate.
  • inorganic phosphates such as ammonium polyphosphates and sodium polyphosphates.
  • red phosphorous that can may be found under several shapes such as stabilized, coated, as a powder,
  • Nitrogen containing flame retardant additives such as : triazines, cyanuric acid and/or isocyanuric acid, melamine or its derivatives such as cyanurate, oxalate, phtalate, borate, sulfate, phosphate, polyphosphate and/or pyrophosphate, condensed products of melamine such as melem, melam, melon, tris(hydroxyethyl) isocyanurate, benzoguanamine, guanidine, allanto ' ine and glycoluril.
  • triazines such as : triazines, cyanuric acid and/or isocyanuric acid, melamine or its derivatives such as cyanurate, oxalate, phtalate, borate, sulfate, phosphate, polyphosphate and/or pyrophosphate, condensed products of melamine such as melem, melam, melon, tris(hydroxyethyl
  • Halogen containing flame retardant additives such as:
  • Bromine containing flame retardant additives such as polybromodiphenyl oxydes (PBDPO), brominated polystyrene (BrPS), poly(pentabromobenzylacrylate), brominated indane, tetradecabromodiphenoxybenzene (Saytex 120), ethane- l,2-bis(pentabromophenyl) or Saytex 8010 of Albemarle, tetrabromobisphenol A and brominated epoxy oligomers.
  • PBDPO polybromodiphenyl oxydes
  • BrPS brominated polystyrene
  • PrPS poly(pentabromobenzylacrylate)
  • brominated indane tetradecabromodiphenoxybenzene
  • Saytex 120 tetradecabromodiphenoxybenzene
  • ethane- l,2-bis(pentabromophenyl) or Saytex 8010 of Albemarle, tetrabromobis
  • PDBS-80 from Chemtura, Saytex HP 3010 from Albemarle or FR-803P from Dea Sea Bromine Group, FR-1210 from Dea Sea Bromine Group, octabromodiphenylether (OBPE), FR-245 from Dead Sea Bromine Group, FR- 1025 from Dead Sea Bromine Group and F-2300 or F2400 from Dead Sea Bromine Group.
  • OBPE octabromodiphenylether
  • Chlorine containing flame retardant additives such as Dechlorane plus® from OxyChem (CAS 13560-89-9).
  • Inorganic flame retardant additives such as antimony trioxide, aluminium hydroxide, magnesium hydroxide, cerium oxide, boron containing compounds such as calcium borate.
  • Charring agents and charring catalysts may also be used if necessary.
  • composition according to the present invention may notably comprise:
  • red phosphorous notably a masterbatch made of polymer and comprising red phosphorous.
  • the composition according to the invention may also comprise additives normally used for the manufacture of polymer compositions, especially intended to be moulded.
  • additives normally used for the manufacture of polymer compositions, especially intended to be moulded.
  • the fillers and additives may be added to by any conventional means suitable, for instance during the polymerization or as a molten mixture.
  • the additives are preferably added to the polymer in a melt process, in particular during a step of extrusion, or in a solid process in a mechanical mixer; the solid mixture may then be melted, for example by means of an extrusion process.
  • compositions according to the invention may be used as raw material in the field of plastics processing, for example for the preparation of articles formed by injection-moulding, by injection/blow-moulding, by extrusion or by extrusion/blow-moulding.
  • the modified polyamide is extruded in the form of rods, for example in a twin-screw extrusion device, said rods then being chopped into granules.
  • the moulded components are then prepared by melting the granules produced above and feeding the molten composition into injection-moulding devices.
  • articles obtained from the composition according to the invention mention may, for example, be made of articles in the motor vehicle industry, such as components under the engine hood, bodywork components, tubes and tanks, or articles in the electrical and electronics field, such as connecters.
  • Weight ratio organic dicarboxylic acid or a salt thereof (c), based on the weight of the alkali metal hypophosphite salt (b).
  • thermoplastic resin permits to keep a low variation in the viscosity of the thermoplastic resin, while in comparison the use of other salts of organic acids leads to a drop of matrix integrity, and then also a drop of mechanical properties, even with lower proportions.
  • 0,9g CaHypo HT was mixed with 10% succinate calcium before formulating. Then the resulting salt mixture was formulated with 0.9g Exolit op 1230, 3g glass fiber and 5.2g PA66 26A and then put into microcompounder at 300°C with screw speed lOOrmp/min for 3mins. In this process, screw force changing was monitored along time. 0.9g CaHypo HT was mixed with 10% phthalate calciumbefore formulating. Then the resulting salt mixture was formulated with 0.9g Exolit opl230, 3g glass fiber and 5.2g PA66 26A and then put into microcompounder at 300°C with screw speed lOOrmp/min for 3mins. In this process, screw force changing was monitored along time,
  • 0.9g CaHypo HT was mixed with 0.9g Exolit op 1230, 3g glass fiber and 5,2g PA66 26A and then put into microcompounder at 300°C with screw speed 1 OOrmp/min for 3mins. In this process, screw force changing was monitored along time.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition comprenant au moins une matrice polymère thermoplastique, un sel hypophosphite de métal alcalin et 0,1 à 30 % en poids d'un acide dicarboxylique organique ou de son sel, ayant un premier pkA ≤ 5; sur la base du poids du sel hypophosphite de métal alcalin; et un procédé de préparation de ladite composition.
PCT/CN2012/084734 2012-11-16 2012-11-16 Composition polymère thermoplastique comprenant un sel hypophosphite de métal alcalin Ceased WO2014075289A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP12888559.7A EP2920234A4 (fr) 2012-11-16 2012-11-16 Composition polymère thermoplastique comprenant un sel hypophosphite de métal alcalin
CN201280077110.7A CN104781326A (zh) 2012-11-16 2012-11-16 包含碱金属次磷酸盐的热塑性聚合物组合物
PCT/CN2012/084734 WO2014075289A1 (fr) 2012-11-16 2012-11-16 Composition polymère thermoplastique comprenant un sel hypophosphite de métal alcalin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2012/084734 WO2014075289A1 (fr) 2012-11-16 2012-11-16 Composition polymère thermoplastique comprenant un sel hypophosphite de métal alcalin

Publications (1)

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WO2014075289A1 true WO2014075289A1 (fr) 2014-05-22

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EP (1) EP2920234A4 (fr)
CN (1) CN104781326A (fr)
WO (1) WO2014075289A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190249004A1 (en) * 2016-10-18 2019-08-15 Bromine Compounds Ltd. Flame-retarded polyester compositions
CN107573666A (zh) * 2017-08-16 2018-01-12 上海金发科技发展有限公司 耐候pc/pet合金及其制备方法

Citations (4)

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CN101688017A (zh) * 2007-07-13 2010-03-31 意特麦琪化工有限公司 无卤阻燃添加剂
WO2012013308A1 (fr) * 2010-07-28 2012-02-02 Krohne Messtechnik Gmbh & Co. Kg Circuiterie dotée de capacités de compensation pour générer des oscillations hyperfréquence
WO2012113307A1 (fr) * 2011-02-24 2012-08-30 Rhodia Operations Compositions polymères ignifuges comprenant des sels d'hypophosphite stabilisés
CN102775676A (zh) * 2011-05-11 2012-11-14 上海安凸塑料添加剂有限公司 一种用于注塑有优良耐候性的体育场阻燃塑料座椅的材料

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JPH10168177A (ja) * 1996-12-12 1998-06-23 Mitsubishi Chem Corp 金属塩及びその製造方法
US6084056A (en) * 1998-12-22 2000-07-04 E. I. Dupont De Nemours & Company Process for the hydrolysis of adiponitrile and the production of nylon 6,6 utilizing low catalyst levels
FR2871166B1 (fr) * 2004-06-04 2006-12-01 Creca Sa Composition thermoplastique biodegradable et procede de preparation
TWI488859B (zh) * 2009-09-09 2015-06-21 Nissan Chemical Ind Ltd 膦酸金屬鹽之製造方法及含有膦酸金屬鹽之熱塑性樹脂組成物

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CN101688017A (zh) * 2007-07-13 2010-03-31 意特麦琪化工有限公司 无卤阻燃添加剂
WO2012013308A1 (fr) * 2010-07-28 2012-02-02 Krohne Messtechnik Gmbh & Co. Kg Circuiterie dotée de capacités de compensation pour générer des oscillations hyperfréquence
WO2012113307A1 (fr) * 2011-02-24 2012-08-30 Rhodia Operations Compositions polymères ignifuges comprenant des sels d'hypophosphite stabilisés
CN102775676A (zh) * 2011-05-11 2012-11-14 上海安凸塑料添加剂有限公司 一种用于注塑有优良耐候性的体育场阻燃塑料座椅的材料

Non-Patent Citations (1)

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Title
See also references of EP2920234A4 *

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EP2920234A4 (fr) 2016-07-06
EP2920234A1 (fr) 2015-09-23
CN104781326A (zh) 2015-07-15

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