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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Definitions

• This invention relates to aluminum hydroxide having a diminished tendency to cause discoloration when compounded with a plastic composition at an elevated temperature, typically 180° C.
• the invention relates to aluminum hydroxide in a plastic composition in which the major polymeric component is a vinyl chloride polymer such as polyvinyl chloride, conveniently abbreviated pvc.
• M. Tadenuma et al., U.S. Pat. No. 5,004,776 disclosed a thermally stabilized chlorine-containing resin composition
• a stabilizer consisting essentially of (a) an overbased alkaline earth metal carboxylate or phenolate complex, (b) zeolite, (c) calcium hydroxide and (d) a complex of at least one metal perchlorate selected from the group consisting of sodium, magnesium, calcium and barium perchlorates with at least one compound selected from the group consisting of polyhydric alcohols and their derivatives.
• the chlorine-containing resin composition may further comprise a known stabilizer for chlorine-containing resins, a known co-stabilizer and other known additives, for example (among others) an inorganic metal salt compound.
• the inorganic compound includes, for example, magnesium oxide, calcium oxide, calcium phosphate, aluminum hydroxide, synthetic hydrotalcite and the like.
• U.S. Pat. No. 5,025,051 disclosed a synthetic resin composition
• a synthetic resin composition comprising (A) 100 parts by weight of a synthetic resin, and (B) 0.01 to 10 parts by weight of a mixed product of (a) a compound having at least one piperidyl group, (b) perchloric acid, and (c) optionally an inorganic substance other than perchloric acid.
• the inorganic substance other than perchloric acid there are d disclosed, for example, an oxide, hydroxide, inorganic acid salt, basic inorganic acid salt or double salt of at least one metal selected from the group consisting of Li, Na, K, Mg, C, Sr, Ba, Zn, Al, Sn and Pb, further a metallic aluminum powder, or a metal oxide such as SnO2, TiO2, or ZrO2.
• the oxide of the metal there are mentioned, for example, MgO, CaO, BaO, ZnO, SrO2, or PbO
• the hydroxide of said metal there are mentioned, for example, LiOH, Mg (OH)2, Ca (OH)2 or Al(OH)3.
• K. Bai et al., U.S. Pat. No. 5,034,443 disclosed that a blend of sodium perchlorate hydrate and calcium silicate provides improved long term heat stability to a polyvinyl chloride resin containing a conventional heat stabilizer, and that a combination of a solution of sodium perchlorate in water with calcium silicate and a non-absorbing diluent powder such as calcium carbonate provides a free-flowing powder composition of reduced hazard level.
• Other non-absorbing diluent powders include zeolites, silica, alumina, PVC resins, barium sulfate and the like.
• Watanabe et al., U.S. Pat. No. 5,190,700 disclosed a flame retardant for a powder halogen-containing vinyl resin which comprises (A) 5 to 40 parts by weight of at least one alkali metal compound of lithium, sodium and potassium calculated as the formula M2O where M is said alkali metal (B) 0.2 to 10 parts by weight of a perchloric acid radical in the form of the acid or a salt or amine thereof, calculated as perchloric acid radical (ClO4), and (C) 1-50 parts by weight of a hydrophobic dispersing agent having a boiling point or a decomposition temperature of 200° C.
• antimony pentoxide Sb2O5
• Watanabe also acknowledges that a variety of flame retardants have been used, including inorganic materials such as antimony trioxide (Sb2O3), sodium antimonite, aluminum hydroxide, zirconium oxide, zinc borate and borax.
• inorganic materials such as antimony trioxide (Sb2O3), sodium antimonite, aluminum hydroxide, zirconium oxide, zinc borate and borax.
• compositions comprising (a) pvc, (b) perchloric acid or a perchlorate, (c) a terminal epoxide compound and (d) an antioxidant ('077) and (a) flexible pvc, (b) perchloric acid or a perchlorate, (c) a terminal epoxide compound ('443).
• the compositions can contain further additives.
• fillers and reinforcing materials for example calcium carbonate, silicates, glass fibers, talc, kaolin, chalk, mica, metal oxides and hydroxides, carbon black or graphite.
• the fillers used are, for example, chalk, kaolin, china clay, talc, silicates, glass fibers, glass beads, sawdust, mica, metal oxides or hydroxides, carbon black, graphite, rock flour and barytes.
• an aluminum hydroxide composition having diminished tendency to cause discoloration on heating at 177° C. of a plastic composition whose major polymeric component is polyvinyl chloride, comprising aluminum hydroxide and an amount, effective in diminishing discoloration, of at least one inorganic perchlorate salt selected from the group consisting of alkali metal perchlorates and alkaline earth metal perchlorates.
• the effective amount of the perchlorate salt ranges from 0.03 parts by weight to 3 parts by weight per 100 parts by weight of aluminum hydroxide.
• a plastic composition having diminished tendency to discolor on heating at 177° C. in the presence of aluminum hydroxide comprising polyvinyl chloride, aluminum hydroxide, and an amount, effective in diminishing the tendency to discolor, of at least one inorganic perchlorate salt selected from the group consisting of alkali metal perchlorates and alkaline earth metal perchlorates.
• the amount of aluminum hydroxide is suitably a flame-retardant amount in the range from 15 parts by weight to 150 parts by weight per 100 parts by weight of polyvinyl chloride.
• a masterbatch composition adapted for safe storage, transport, and simplified compounding with a plastic composition whose major polymeric component is polyvinyl chloride, comprising aluminum hydroxide and at least one inorganic perchlorate salt selected from the group consisting of alkali metal perchlorates and alkaline earth metal perchlorates.
• the masterbatch according to the invention can contain from 7 parts by weight to 500 parts by weight of the perchlorate salt, calculated on a dry basis, per 100 parts by weight of aluminum hydroxide.
• the masterbatch according to the invention can additionally include water, calcium silicate, and inert inorganic diluent powder as required.
• a masterbatch according to the invention simplifies the compounding of an aluminum hydroxide containing plastic composition whose major polymeric component is polyvinyl chloride with the effective amount of perchlorate salt required according to the invention by substituting for it a more proportionate quantity of a more easily handled and transported masterbatch as defined, along with additional aluminum hydroxide and other compounding ingredients as required.
• an insulated electrical conductor comprising a metallic conductor, a first insulating layer comprising flexible polyvinyl chloride surrounding the conductor, and a second layer surrounding the first insulating layer as a plenum or jacket.
• the second layer comprises polyvinyl chloride, a sufficient quantity of plasticizer to impart flexibility to the composition, aluminum hydroxide, and an amount, effective in diminishing the tendency to discolor, of at least one inorganic perchlorate salt selected from the group consisting of alkali metal perchlorates and alkaline earth metal perchlorates.
• the amount of aluminum hydroxide is suitably a flame-retardant amount in the range from 15 parts by weight to 150 parts by weight per 100 parts by weight of polyvinyl chloride.
• the flame retardance of pvc compositions according to the invention comprising a flame retardant amount of aluminum hydroxide is enhanced in comparison to similar compositions not including an effective amount of such inorganic perchlorate salt.
• the flame-retardant amount is in the range from 15 to 150 parts by weight of aluminum hydroxide per 100 parts by weight of pvc.
• polyvinyl chloride and its abbreviation pvc are used to refer to vinyl chloride polymers in general, including vinyl chloride homopolymer; copolymers of vinyl chloride as the major monomer with minor amounts of one or more unsaturated monomers such as vinyl acetate, vinylidene chloride, vinyl alkyl ethers, ethylene, propylene, dialkyl maleates and acrylonitrile; and blends of a vinyl chloride polymer with equal or lesser amounts of polymeric modifiers such as acrylic and methacrylic ester polymers, butadiene polymers, styrene polymers, acrylonitrile polymers, and copolymers of two or more of the here indicated monomers, chlorinated polyethylene and chlorinated vinyl chloride polymers.
• the alkali metal and alkaline earth metal perchlorates used according to this invention include barium perchlorate, calcium perchlorate, lithium perchlorate, magnesium perchlorate, potassium perchlorate, sodium perchlorate, and strontium perchlorate.
• Anhydrous solid forms, hydrated solid forms, and aqueous solutions of these perchlorate salts can be used according to the invention.
• Sodium perchlorate is preferred.
• Sodium perchlorate monohydrate is particularly preferred.
• PVC used according to this invention can be rigid or flexible. Flexible PVC is preferred. Flexibility is imparted to PVC as known in the art by such techniques as limiting thickness of unmodified vinyl chloride homopolymer to 0.05 mm or less, by copolymerization of vinyl chloride with 10-20% of such comonomers as vinyl acetate (so-called internal plasticization), and particularly by compounding with compatible liquids known as plasticizers.
• plasticizers are known in the art, including in particular the esters of dicarboxylic and tricarboxylic acids such as adipic, citric, phthalic and trimellitic acids with alcohols having 6-12 carbon atoms, preferably dialkyl phthalates and trialkyl trimellitates having 7 to 11 carbon atoms in the alkyl groups. Additional representatives of the class of suitable plasticizers are disclosed by Wehner et al., U.S. Pat. No. 6,194,494 B1 at column 37 line 36 to column 38 line 51, which disclosure is here incorporated by reference. Use levels of plasticizers when present can range from 5 parts by weight to 125 parts by weight per 100 parts of pvc.
• PVC compositions according to this invention usually contain at least one heat stabilizer.
• any known heat stabilizer can be used. Preference is usually given to environmentally acceptable stabilizers from which such toxic heavy metals as arsenic, cadmium, lead, and thallium are substantially excluded.
• Particularly preferred metal containing heat stabilizers are barium, calcium, magnesium, strontium, and zinc salts of aliphatic and aromatic non-nitrogenous monocarboxylic acids having 6 to 24 carbon atoms.
• non-metallic heat stabilizers are aliphatic and aromatic phosphites, substituted phenols having a molecular weight of at least 200 daltons, ethers and esters having epoxide groups and molecular weight of at least 200 daltons and 1,3-dicarbonyl compounds having molecular weight of at least 200 daltons. Additional categories of suitable heat stabilizers are disclosed by Wehner et al., U.S. Pat. No. 6,194,494 B1, at column 1 line 4 to column 2 line 5, and many individual representatives of these categories are disclosed at column 2 line 46 to column 37 line 25 and column 39 line 8 to column 42 line 27. These disclosures are here incorporated by reference. Use levels of heat stabilizers when present can range from 0.01 to 10 parts by weight per 100 parts of pvc. Larger amounts can be used but are seldom required.
• compositions of the invention were observed in a typical plenum wire compound formulation, that is a formulation of a flexible flame retardant outer sheath or plenum for a wire or other metallic conductor surrounded by a layer of primary insulation and further surrounded by the outer sheath or plenum. All quantities are given in parts by weight.
• the typical plenum wire compound base formulation contained PVC resin 100.0 Phthalate ester plasticizer 50.0 Omya F brand of calcium carbonate 12.0 Antimony trioxide second flame retardant 5.0 Stearic acid 0.25 Ba/Zn solid stabilizer 8.0 ATH aluminum hydroxide 50.0
• NaP-60 60% Na perchlorate monohydrate aqueous solution
• Various amounts of 60% Na perchlorate monohydrate aqueous solution were blended with this base formulation using a two roll mill, as shown below for each Example, and samples cut from each milled sheet were tested for static oven stability at two temperatures, 350° F. (177° C.) sampled at 15 minute intervals and 375° F. (190° C.) sampled at 10 minute intervals.
• EXAMPLE Control A 1 2 3 4 5 NaP-60 parts actual none 0.5 1.0 1.5 2.0 3.0 NaP-60 parts/100 ATH none 1.0 2.0 3.0 4.0 6.0 As dry NaClO 4 per 100 none 0.48 0.96 1.44 1.92 2.88 ATH
• Examples 1-5 At 177° C. oven test, the color change of Examples 1-5 is minimal (no sign of brown color in 120 minutes) and at 190° C. the Examples 1-5 compounds containing the perchlorate and ATH shows improved long term stability compared to Control A. Also the perchlorate containing ATH had improved flame and smoke properties of plenum compounds over that using ATH without perchlorate.
• composition of the invention was observed in a similar plenum base formulation with varied levels of sodium perchlorate monohydrate supplied in two different physical forms.
• PVC resin 100.0 Dialkyl phthalate plasticizer 47.0 Omya F brand of calcium carbonate 12.0
• Antimony trioxide second flame retardant 8.0 Stearic acid 0.3 Ba/Zn solid stabilizer 6.0 ATH aluminum hydroxide 60
• Control B PVC compound without perchlorate initially discolored to brown in 90 minutes at 177° C. and 20 minutes at 205° C. and turned to dark brown in 105 minutes at 177° C. and in 25 minutes at 205° C.
• composition of the invention was observed in the plenum base formulation of Examples 6-12 with varied levels of aluminum hydroxide.
• Control Control Control Control EXAMPLE C D E F G ATH aluminum none none 10 20 40 hydroxide Powder blend actual 0.5 none none none none As NaP-60 parts solution 0.167 none none none As NaP-60 parts/100 N/A none none none none ATH As dry NaClO 4 per 100 N/A none none none none ATH
• Control C and Control D compounds represent a comparison that measures the stabilizing effectiveness of sodium perchlorate in the absence of aluminum hydroxide. Both Control C and Control D also contain the same amount of barium-zinc stabilizer. It can be seen that there is a certain favorable effect of the sodium perchlorate in Control C. Control C showed the first sign of brown discoloration at 105 minutes at 177° C. and at 15 minutes at 205° C., while Control D showed the first sign of brown discoloration at 90 minutes at 177° C. and at 10 minutes at 205° C. Control C also turned to dark brown at 30 minutes at 205° C. while Control D turned to dark brown at 20 minutes at 205° C.
• Controls D, E, F, G and H represent a comparison that measures the effect of increasing levels of aluminum hydroxide from zero to 10, 20, 40, and 60 parts per 100 parts of pvc.

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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)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

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• 2002
  • 2002-01-04 US US10/035,129 patent/US20030153661A1/en not_active Abandoned
  • 2002-12-06 AT AT02806450T patent/ATE345363T1/de not_active IP Right Cessation
  • 2002-12-06 WO PCT/US2002/039225 patent/WO2003059998A1/en active IP Right Grant
  • 2002-12-06 EP EP02806450A patent/EP1461381B1/en not_active Expired - Lifetime
  • 2002-12-06 DE DE60216145T patent/DE60216145T2/de not_active Expired - Lifetime
  • 2002-12-06 JP JP2003560092A patent/JP4439917B2/ja not_active Expired - Fee Related
• 2003
  • 2003-01-03 TW TW092100097A patent/TWI286560B/zh not_active IP Right Cessation
  • 2003-11-26 US US10/724,374 patent/US6984684B2/en not_active Expired - Fee Related
• 2005
  • 2005-08-09 US US11/200,418 patent/US7550525B2/en not_active Expired - Fee Related

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