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WO2008023249A1 - Composition de poly(chlorure de vinyle) - Google Patents

Composition de poly(chlorure de vinyle) Download PDF

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Publication number
WO2008023249A1
WO2008023249A1 PCT/IB2007/002406 IB2007002406W WO2008023249A1 WO 2008023249 A1 WO2008023249 A1 WO 2008023249A1 IB 2007002406 W IB2007002406 W IB 2007002406W WO 2008023249 A1 WO2008023249 A1 WO 2008023249A1
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alkyl
compounds
pvc
obs
acid
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Alan Baillie King
Charles Gilbert Biddulph
Timothy Paul Cooper
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CHEMFIT SPECIALITY CHEMICALS Pty Ltd
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CHEMFIT SPECIALITY CHEMICALS Pty Ltd
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    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • 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

Definitions

  • THIS invention relates to a polyvinylchloride (PVC) composition
  • PVC is a commodity polymer, developed in the late 1800s and first patented in 1912. Despite many attempts to reduce its consumption over the years, mainly due to ecological reasons, it remains one of the most used polymers today, and around 200 thousand tonnes are consumed in South Africa per annum.
  • HCI is naturally evolved when PVC is heated according to the following scheme:
  • the HCI evolved in the first step acts to initiate further loss, which unchecked proceeds to loss of all of the chlorine as HCI.
  • This invention relates to a PVC composition, particularly for use in PVC pipes, the composition including an organic based stabilizer (OBS), typically based on a uracil compound, and a smoke suppressant.
  • OBS organic based stabilizer
  • the OBS and smoke suppressant are present in amounts which are synergistic in reducing smoke and HCI emission in the event of the PVC composition combusting.
  • the OBS may include a compound of the Formula 1 :
  • Y is O or S
  • Ri, R 2 , and R 3 are monovalent substituents selected from the group consisting of hydrogen, halogen, hydroxyl, alkyl, aryl, aralkyl, acyl, amino, aminoalkyl, aminoaryl, and hydrazine
  • Y is O; R 1 and R 2 are alkyl, phenyl or hydrogen; and R 3 is an electron-donating group.
  • the organic based stabiliser is preferably a combination of A) at least one compound of Formula I:
  • R 1 and R 2 are each independently of the other CVCi 2 alkyl, C 3 -Ce alkenyl,
  • C 5 -C 8 cycloalkyl that is unsubstituted or substituted by from 1 to 3 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl or by hydroxy groups or by chlorine atoms, or C 7 -C 9 phenylalkyl that is unsubstituted or substituted at the phenyl ring from 1 to 3 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl or by hydroxy groups or chlorine atoms, and R 1 and R 2 may additionally be hydrogen and C 1 -C 12 alkyl, and
  • Y is S or O
  • the smoke suppressant is preferably heavy-metal free and based on a magnesium / zinc complex oxide of the general formula (Mg 7 Zn)O, containing typically 60% as MgO and which is free of Antimony.
  • the ratio of OBS to smoke suppressant is from 1 :2 to 1 :1 (by mass).
  • the OBS typically comprises 1-3, preferably 1-2 phr of the PVC composition and the smoke suppressant typically comprises 1-4, preferably 1-2 phr of the PVC composition.
  • the PVC composition excludes acid scavengers such as calcium stearate, carbonate, oxide or hydroxide, magnesium stearate, carbonate or hydroxide, or zinc stearate or hydroxide.
  • acid scavengers such as calcium stearate, carbonate, oxide or hydroxide, magnesium stearate, carbonate or hydroxide, or zinc stearate or hydroxide.
  • the invention also relates to a method of manufacturing a stabilised PVC product, the method including the steps of mixing PVC and OBS until the mixture reaches a temperature from 10O 0 C to 12O 0 C, cooling the mixture to a temperature below 6O 0 C, typically about 40 0 C, and then adding a smoke suppressant to the cooled mixture.
  • composition of the stabilised PVC product is as described above.
  • This invention relates to a PVC composition, particularly for use in PVC pipes, which is both environmentally friendly and has smoke-suppressant properties, includes an organic based stabilizer (OBS) and a smoke suppressant, which are synergistic in reducing smoke and toxic gas (HCI) emission in the event of the PVC composition combusting.
  • OBS organic based stabilizer
  • HAI smoke and toxic gas
  • the OBS may include a compound of the Formula 1 :
  • Y is O or S, preferably O 1 and R 1 , R 2 , and R 3 are monovalent substituents selected from the group consisting of hydrogen, halogen, hydroxyl, alkyl, aryl, aralkyl, acyl, amino, aminoalkyl, aminoaryl, and hydrazino.
  • the OBS used in this invention is preferably that described in US 5,925,969 (the content of which is incorporated herein by reference). A description of the OBS, from the specification of US 5,925,969 is provided below:
  • the OBS is preferably a combination of A) at least one compound of Formula 1 :
  • R 3 is NH 2
  • Ri and R 2 are each independently of the other C 1 -C 12 alkyl, C 3 -C 6 alkenyl, C 5 -C 8 cycloalkyl that is unsubstituted or substituted by from 1 to 3 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl or by hydroxy groups or by chlorine atoms, or C 7 -C 9 phenylalkyl that is unsubstituted or substituted at the phenyl ring from 1 to 3 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl or by hydroxy groups or chlorine atoms, and R 1 and R 2 may additionally be hydrogen and Ci-C 12 alkyl, and Y is S or O;
  • perchlorate compounds glycidil compounds, beta-diketones and beta-keto esters dihydropyridines and polydihydropyridines, polyols and disaccharide alcohols, sterically hindered amines (tetraalkylpiperidine compounds), al
  • C 1 -C 4 Alkyl is, for example: methyl, ethyl, n-propyl, isopropyl, n-, iso- , sec- or tert-butyl.
  • C 1 -C 12 Alkyl is, for example, in addition to the radicals just mentioned, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, nonyl, undecyl or dodecyl.
  • C 1 -C 4 Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.
  • Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Phenylalkyl is, for example, benzyl, 1- or 2-phenylethyl, 3- phenylpropyl, ⁇ , ⁇ -dimethylbenzyl or 2-phenylisopropyl, preferably benzyl.
  • C 3 -C 6 Alkenyl is, for example, vinyl, allyl, methallyl, 1-butenyl or 1-hexenyl, preferably allyl.
  • R 1 and R 2 are each independently of the other Ci -C 4 alkyl and hydrogen. Especially preferably, either R 1 and R 2 are identical and are methyl, ethyl, propyl, butyl or allyl, or they are different and are ethyl and allyl.
  • Examples are those of formula M(CIO 4 ) n , wherein M is Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce. According to the value of M, the index n is 1 , 2 or 3.
  • the perchlorate salts may be complexed with alcohols (polyols, cyclodextrins) or ether alcohols or ester alcohols.
  • the ester alcohols include also the polyol partial esters.
  • polyhydric alcohols or polyols are their dinners, trimers, oligomers and polymers, such as di-, tri-, tetra- and poly-glycols, and di-, tri- and tetra-pentaerythritol or polyvinyl alcohol in various degrees of polymerisation.
  • the perchlorate salts can be introduced in various known forms, for example in the form of a salt or an aqueous solution applied to a substrate, such as PVC, calcium silicate, zeolites or hydrotalcites, or bound in a hydrotalcite by chemical reaction.
  • Glycerol monoethers and glycerol monothioethers are preferred as polyol partial ethers.
  • the perchlorates can be used in an amount of, for example, from 0.001 to 5, advantageously from 0.01 to 3, especially from 0.01 to 2, parts by weight, based on 100 parts by weight PVC.
  • Glycidyl and ⁇ -methylglycidyl esters obtainable by reacting a compound having at least one carboxy group in the molecule with epichlorohydrin or glycerol dichlorohydrin or b-methyl-epichlorohydrin.
  • the reaction is advantageously carried out in the presence of bases.
  • Aliphatic carboxylic acids may be used as compounds having at least one carboxy group in the molecule.
  • carboxylic acids examples include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerised or trimerised linoleic acid, acrylic acid and methacrylic acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid and pelargonic acid, and the acids mentioned in connection with the organic zinc compounds.
  • cycloaliphatic carboxylic acids such as cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4- methylhexahydrophthalic acid.
  • aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.
  • Carboxy-terminated adducts for example of trimellitic acid and polyols, such as glycerol or 2,2-bis(4-hydroxycyclohexyl)propane can also be used.
  • trimellitic acid and polyols such as glycerol or 2,2-bis(4-hydroxycyclohexyl)propane
  • Other epoxide compounds that can be used within the scope of this invention are to be found in EP 0 506 617.
  • Glycidyl or ( ⁇ -methylglycidyl) ethers obtainable by reacting a compound having at least one free alcoholic hydroxy group and/or phenolic hydroxy group and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acid catalyst with subsequent treatment with an alkali.
  • Ethers of that type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane-1 ,2-diol, or poly(oxypropylene) glycols, propane-1 ,3-diol, butane-1 ,4-diol, poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane- 1 ,6-diol, hexane-2,4,6-triol, glycerol, 1 ,1 ,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and from polyepichlorohydrins, butanol, amyl alcohol, pentanol, and from monofunctional alcohols, such as isooctanol, 2-ethylhexanol, isodecanol
  • cycloaliphatic alcohols such as 1,3- or 1 ,4- dihydroxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4- hydroxycyclohexyl)propane or 1 ,1-bis(hydroxymethyl)cyclohex ⁇ 3-ene, or they have aromatic nuclei, such as N,N-bis(2-hydroxyethyl)aniline or p,p'- bis(2-hydroxyethylamino)diphenylmethane.
  • the epoxide compounds can also be derived from mononuclear phenols, such as phenol, resorcinol or hydroquinone, or they are based on polynuclear phenols, such as bis(4- hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-di bromo-4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenylsulfone, or on condensation products of phenols with formaldehyde obtained under acid conditions, such as phenol novolaks.
  • mononuclear phenols such as phenol, resorcinol or hydroquinone
  • polynuclear phenols such as bis(4- hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-di bromo-4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyls
  • terminal epoxides are, for example: glycidyl-1 -naphthyl ether, glycidyl-2-phenylphenyl ether, 2- biphenylglycidyl ether, N-(2,3-epoxypropyl) phthalimide and 2,3- epoxypropyl-4-methoxyphenyl ether.
  • N-Glycidyl compounds obtainable by dehydrochlorinating the reaction products of epichlorohydrin with amines containing at least one aminohydrogen atom.
  • amines are, for example, aniline, N- methylaniline, toluidine, n-butylamine, bis(4-aminophenyl)methane, m- xylylenediamine or bis(4-methylaminophenyl)methane, but also N 1 N 1 O- triglycidyl-m-aminophenol or N,N,O-triglycidyl-p-aminophenol.
  • the (N- glycidyl) compounds also include, however, N,N'-di-, N,N',N"-tri and N,N',N",N'"-tetra-glycidyl derivatives of cycloalkyleneureas, such as ethyleneurea or 1 ,3-propyleneurea, and N,N'-diglycidyl derivatives of hydantoins, such as 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.
  • cycloalkyleneureas such as ethyleneurea or 1 ,3-propyleneurea
  • N,N'-diglycidyl derivatives of hydantoins such as 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.
  • S-Glycidyl compounds such as di-S-glycidyl derivatives, that are derived from dithiols, such as ethane-1 ,2-dithiol or bis(4- mercaptomethylphenyl) ether.
  • Epoxide compounds containing a radical of formula I wherein R 1 and R 3 together are -CH 2 -CH 2 — and n is 0 are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentylglycidyl ether or
  • An epoxy resin containing a radical of formula I wherein R 1 and R 3 together are -CH 2 -CH 2 - and n is 1 is, for example, 3,4-epoxy-6-methylcyclohexanecarboxylic acid (3',4-epoxy- 6'-methylcyclohexyl)-methyl ester.
  • Suitable terminal epoxides are, for example (TMdenotes®): a) liquid diglycidyl ethers of bisphenol A, such as Araldite.TM.GY 240, Araldite.TM.AGY 250, Araldite.TM.GY 260, Araldite.TM.GY 266, Araldite.TM.GY 2600, Araldite.TM.MY 790;
  • liquid diglycidyl ethers of bisphenol F such as Araldite.TM.GY 281, Araldite.TM.PY 302, Araldite.TM.PY 306;
  • solid and liquid polyglycidyl ethers of o-cresolformaldehyde novolak such as ECN 1235, ECN 1273, ECN 1280, ECN 1299;
  • liquid glycidyl ethers of alcohols such as Shell.TM.glycidyl ether 162, Araldite.TM.DY 0390, Araldite.TM.DY 0391;
  • liquid glycidyl ethers of carboxylic acids such as Shell.TM. Cardura E terephthalic acid ester, trimellitic acid ester, Araldite.TM.PY 284;
  • solid heterocyclic epoxy resins such as Araldite.TM.PT 810;
  • liquid cycloaliphatic epoxy resins such as Araldite.TM.CY 179;
  • epoxide compounds having two functional groups Preference is given to the use of epoxide compounds having two functional groups. It is, however, also possible in principle to use epoxide compounds having one, three or more functional groups. There are predominantly used epoxide compounds, especially diglycidyl compounds, having aromatic groups. Where appropriate, a mixture of different epoxide compounds can also be used. Especially preferred as terminal epoxide compounds are diglycidyl ethers based on bisphenols, such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4- hydroxyphenyl)-methane or mixtures of bis(ortho/para- hydroxyphenyl)methane (bisphenol F). The terminal epoxide compounds can be used in an amount of, preferably, at least 0.1 part, for example from 0.1 to 5, advantageously from 1 to 5 based on 100 parts by weight PVC.
  • bisphenol A 2,2-bis(4-hydroxyphenyl)propane
  • Beta-diketones, beta-keto esters are Beta-diketones, beta-keto esters:
  • 1.3-Dicarbonyl compounds that can be used may be linear or cyclic dicarbonyl compounds. Preference is given to the use of dicarbonyl compounds of the following formula:
  • R ⁇ is C r C 22 alkyl, C 5 -C 10 hydroxyalkyl, C 2 -C 18 alkenyl, phenyl, phenyl substituted by OH, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or by halogen, C 7 -Ci 0 phenylalkyl, C 5 -C 12 cycloalkyl, C 5 -C 12 cycloalkyl substituted by C 1 -C 4 alkyl, or is a group --R' 5 -S--R' 6 or -R' 5 -O--R' 6 ,
  • R' 2 is hydrogen, C 1 -C 8 alkyl, C 2 -C 12 alkenyl, phenyl, C 7 -C 12 alkylphenyl, C 7 -Ci 0 phenylalkyl or a group -CO-R 4 ,
  • R' 3 has one of the meanings given for R 1 ! or is C-i -C 18 alkoxy
  • R' 4 is C 1 -C 4 alkyl or phenyl
  • R'5 is Ci-Ci 0 alkylene
  • R'e is C 1 -C 12 alkyl, phenyl, C 7 -C 18 alkylphenyl or C 7 -C 10 phenylalkyl.
  • R'i and R' 3 as alkyl may be, especially, C 1 -C 18 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.
  • R'i and R' 3 as hydroxyalkyl are, especially, a group — (CH 2)n —OH, wherein n is 5, 6 or 7.
  • R'-i and R' 3 as alkenyl may be, for example, vinyl, allyl, methallyl, 1- butenyl, 1-hexenyl or oleyl, preferably allyl.
  • R 1 ! and R' 3 as phenyl substituted by OH, alkyl, alkoxy or halogen may be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.
  • R ⁇ and R' 3 as phenylalkyl are especially benzyl.
  • R' 2 and R' 3 as cycloalkyl or alkylcycloalkyl are especially cyclohexyl or methylcyclohexyl.
  • R' 2 as alkyl may be, especially, C 1 -C 4 alkyl.
  • R' 2 as C 2 -C 12 alkenyl may be, especially, allyl.
  • R' 2 as alkylphenyl may be, especially, tolyl.
  • R' 2 as phenylalkyl may be, especially, benzyl.
  • R' 2 is preferably hydrogen.
  • R' 3 as alkoxy may be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy.
  • R' 5 as C 1 -Ci 0 alkylene is especially C 2 -C 4 alkylene.
  • R' 6 as alkyl is especially C 4 -Ci 2 alkyl, such as butyl, hexyl, octyl, decyl or dodecyl.
  • R' 6 as alkylphenyl is especially tolyl.
  • R' 6 as phenylalkyl is especially benzyl.
  • Examples of 1 ,3-dicarbonyl compounds of the above formula and their alkali metal, alkaline earth metal and zinc chelates are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-heptane-2,4-dione, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoyl-benzoylmethane, stearoyl-benzoylmethane, isooctylbenzoylmethane, 5-hydroxycapronyl- benzoylmethane, tribenzoylmethane, bis(4-methylbenzoyl)methane, benzoyl-p-chlorobenzoylmethane, bis(2-hydroxybenzoyl)methane, A- methoxybenzoyl-benzoy
  • R ⁇ is C 1 -C 18 alkyl, phenyl, phenyl substituted by OH, methyl or by methoxy, C 7 -C 10 phenylalkyl or cyclohexyl
  • R' 2 is hydrogen and R' 3 has one of the meanings given for RV
  • the 1 ,3-diketo compounds can be used in an amount of, for example, from 0.01 to 10, advantageously from 0.01 to 3, and especially from 0.01 to 2, parts by weight, based on 100 parts by weight PVC.
  • Suitable monomeric, dihydropyridines are described, for example, in FR 20 39 496, EP 2007, EP 0 362 012, EP 0 286 887 and EP 0 024 754.
  • Suitable polydihydropyridines are especially compounds of the following formula
  • T is C 1 -C 22 alkyl that is unsubstituted or substituted by C 1 -Ci 8 alkoxy, C 1 -C 18 alkylthio, hydroxy, acryloyloxy, methacryloyloxy, halogen, phenyl or by naphthyl;
  • L has the same meanings as T or is a tri- or poly-valent radical from an unsubstituted or Ci -C 12 alkoxy-, C 1 -C 12 thioalkoxy-, C 6 -C 10 aryl-, C 1 -C 12 carboxy- or hydroxy-substituted straight-chained or branched alkyl group,
  • R and R' are each independently of the other methylene or phenylene or an alkylene group of the type ⁇ (-C p H 2p -X-) t C p H 2p - - that is unsubstituted or carries substituents from the series C 1 -Ci 2 alkoxy, CrCi 2 thioalkoxy, C 6 -Ci 0 aryl, Ci-C 12 carboxy and hydroxy,
  • o p is from 2 to 18,
  • o t is from O to 10
  • o X is oxygen or sulfur
  • R" is hydrogen, or C 1 -C 18 alkyl, C 2 -Ci 8 alkoxycarbonyl or C 6 -Ci 0 aryl each of which is unsubstituted or substituted by one or more C 1 -Ci 2 alkyl, C 1 -C 8 alkoxy, halogen or NO 2 substituents, • and the two R 1 " radicals are identical or different and are hydrogen, C 1 -C 18 alkyl, C 1 -C 18 -hydroxyalkyl or C 1 -C 18 alkoxyalkyl or together are uninterrupted or O-interrupted C 3 -C 5 alkylene,
  • Thiodiethylene-bis[5-methoxycarbonyl-2,6-dimethyl-1 ,4-dihydropyridine- 3-carboxylate] is especially preferred.
  • the (Poly-)Dihydropyridine can be present in chlorine containing polymer in an amount of from 0,001 to 5 parts and especially 0,005 to 1 parts by weight based on 100 parts by weight PVC.
  • Suitable compounds of that type are: pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, bistrimethylolethane, trismethylolpropane, inosite, polyvinylalcohol, sorbitol, maltite, isomaltite, lactite, lycasin, mannitol, lactose, leucrose, tris(hydroxyethyl) isocyanurate, palatinite, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcyclopyranol, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-0- ⁇ -D-glycopyranosyl-D-mannitol dihydrate.
  • the polyols can be used in an amount of, for example, from 0.01 to 5, advantageously from 0.1 to 5, parts by weight, based on 100 parts by weight PVC.
  • Sterically hindered amines (tetraalkylpiperidine compounds):
  • the sterically hindered amines, especially piperidine compounds that can be used according to the invention are known especially as light stabilisers. Those compounds contain one or more groups of the formula
  • T Jp 1 CtU They may be compounds of relatively low molecular weight ( ⁇ 700) or of relatively high molecular weight. In the latter case they may be oligomeric or polymeric products. Preference is given to tetramethylpiperidine compounds having a molecular weight of more than 700 that contain no ester groups.
  • stabilisers are the following classes of tetramethylpiperidine compounds.
  • n is a number from 1 to 4, preferably 1 or 2,
  • Ri is hydrogen, oxy, C 1 -Ci 2 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 7 - C 12 aralkyl, C 1 -C 8 alkanoyl, C 3 -C 5 alkenoyl, glycidyl or a group --CH 2 CH(OH)-Z, wherein Z is hydrogen, methyl or phenyl, R 1 being preferably C 1 -C 4 alkyl, allyl, benzyl, acetyl or acryloyl, and,
  • R 2 is hydrogen, C 1 -C 18 alkyl that is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, an ⁇ , ⁇ -unsaturated carboxylic acid having from 3 to 5 carbon atoms or an aromatic carboxylic acid having from 7 to 15 carbon atoms, and, when n is 2, R 2 is C 1 -Ci 2 -alkylene, C 4 -Ci 2 alkenylene, xylylene, a divalent radical of an aliphatic, cyclo
  • substituents are C 1 -C 12 alky!, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2- ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • R 2 may be, for example, the groups listed above and, in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
  • R- I is C 3 -C 8 alkenyl, it may be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2- butenyl.
  • R- I as C 3 -C 8 alkynyl is preferably propargyl.
  • R 1 is especially phenethyl and more especially benzyl.
  • R 1 as C 1 -C 8 alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and as C 3 -C 5 alkenoyl is especially acryloyl.
  • R 2 is a monovalent radical of a carboxylic acid, it is, for example, an acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid radical.
  • R 2 is a divalent radical of a dicarboxylic acid
  • it is, for example, a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl-(3,5di-tert-butyl-4-hydroxybenzyl)-malonic acid or bicycloheptenedicarboxylic acid radical.
  • R 2 is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitic acid or nitrilotriacetic acid radical.
  • R 2 is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-1 ,2,3,4-tetracarboxylic acid or of pyromellitic acid.
  • R 2 is a divalent radical of a dicarbamic acid, it is, for example, a hexamethylenedicarbamic acid or a 2,4-toluylene- dicarbamic acid radical.
  • n is the number 1 or 2
  • R 3 is hydrogen, C 1 -Ci 2 alkyl, C 2 -C 5 hydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -Ci 8 alkanoyl, C 3 -C 5 alkenoyl or benzoyl, and,
  • R 4 is hydrogen, C 1 -Ci 8 alkyl, C 3 -C 8 alkenyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula --CH 2 -CH(OH)-Z or of the formula -CONH--Z, wherein Z is hydrogen, methyl or phenyl; and, when n is 2, R 4 is C 2 -C 12 alkylene, C 6 -C 12 arylene, xylylene, a -CH 2 -CH(OH)-CH 2 - group or a group -CH 2 -CH(OH)-CH 2 -0-D-O-, wherein D is C 2 -C 10 alkylene, C 6 - Ci 5 arylene or C 6 -C 12 cycloalkylene, or,
  • R 3 is not alkanoyl, alkenoyl or benzoyl
  • R 4 may also be a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or also the group — CO- or, • when n is 1 , R 3 and R 4 together may be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1 ,2- or 1 ,3-dicarboxylic acid.
  • any of the substituents are C 1 -C 12 - or C 1 -C 18 -alkyl, they are as already defined above under a).
  • any of the substituents are C 5 -C 7 cycloalkyl, they are especially cyclohexyl.
  • R 3 is especially phenylethyl or more especially benzyl.
  • R 3 is especially 2-hydroxyethyl or 2-hydroxypropyl.
  • R 3 as C 2 -C 18 alkanoyl is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and as C 3 - C 5 alkenoyl is especially acryloyl.
  • R 4 is C 2 -C 8 alkenyl, then it is, for example, allyl, methallyl, 2- butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
  • R 4 as C 1 -C 4 alkyl substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2- cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbony!-ethy).
  • substituents are C 2 -C 12 alkylene, they are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • any of the substituents are C 6 -C 15 arylene, they are, for example, o-, m- or p-phenylene, 1 ,4-naphthylene or 4,4'-diphenylene.
  • D is especially cyclohexylene.
  • n is the number 1 or 2
  • R- I is as defined under a) and
  • R 5 is C 2 -C 8 alkylene or C 2 -C 8 hydroxyalkylene or C4-C22 acyloxyalkylene, and, when n is 2, R 5 is the group ( ⁇ CH 2 ) 2 C(CH 2 - ) 2 .
  • R 5 is C 2 -C 8 alkylene or C 2 -C 8 hydroxyalkylene, it is, for example, ethylene, 1-methyl-ethylene, propylene, 2-ethyl-propylene or 2-ethyl-2- hydroxymethylpropylene.
  • R 5 is, for example, 2-ethyl-2- acetoxymethylpropylene.
  • n is the number 1 or 2
  • R- I is as defined under a
  • R 6 is hydrogen, C r Ci 2 alkyl, allyl, benzyl, glycidyl or C 2 -C 6 alkoxyalkyl and,
  • R 7 is hydrogen, C 1 -Ci 2 alkyl, C 3 -C 5 alkenyl, C 7 -C 9 aralkyl, C 5 -C 7 cycloalkyl, C 2 -C 4 hydroxyalkyl, C 2 -C 6 alkoxyalkyl, C 6 - Cio aryl, glycidyl or a group of the formula ⁇ (CH 2 ) P — COO— Q or of the formula -(CH 2 ) p -0-C0 ⁇ Q, wherein p is 1 or 2 and Q is C r C 4 alkyl or phenyl, and, when n is 2, R 7 is C 2 -C 12 alkylene, C 4 -C 12 alkenylene, C 6 -C 12 arylene, a group --CH 2 -CH(OH)-CH 2 -0-D- CH 2 -CH(OH)-CH 2 --, wherein D is C 2 -C 10 alkylene
  • any of the substituents are C 1 -C 12 alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2- ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • C 1 -C- I8 alkyl may be, for example, the groups listed above and in addition, for example, n-tridecyl, n- tetradecyl, n-hexadecyl or n-octadecyl.
  • substituents are C 2 -C 6 alkoxyalkyl, they are, for example, methoxymethyl, ethoxymethyl, propoxy methyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
  • R 7 is C 3 -C 5 alkenyl, it is, for example, 1-propenyl, allyl, methallyl, 2butenyl or 2-pentenyl.
  • R, T 1 and T 2 are especially phenethyl or more especially benzyl.
  • that ring may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
  • R 7 is C 2 -C 4 hydroxyalkyl, it is, for example, 2-hydroxyethyl, 2- hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
  • R7 , T 1 and T 2 are especially phenyl, a- or ⁇ -naphthyl, which are unsubstituted or substituted by halogen or by C 1 -C 4 alkyl.
  • R 7 is C 2 -C t2 alkylene, it is, for example, ethylene, propylene, 2,2dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
  • R 7 is especially 2-butenylene, 2-pentenylene or 3- hexenylene.
  • R 7 is C 6 -C 12 arylene, it is, for example, o-, m- or p-phenylene, 1 ,4naphthylene or 4,4'-diphenylene.
  • Z' is C 2 -C 12 alkanoyl, it is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.
  • n is the number 1 or 2 and R 3 is a group of the formula
  • R 1 is as defined under a
  • A is C 2 -C 6 alkylene or — (CH 2)3 -O- and
  • R 9 is identical to R 8 or is one of the groups -NRn Ri 2 , -O 13 , - NHCH 2 OR 13 or -N(CH 2 OR 13 ) 2 ,
  • R 12 is C 1 -C 12 alkyl, cyclohexyl, benzyl, C 1 -C 4 hydroxyalkyl and
  • R 13 is hydrogen, C 1 -C 12 alkyl or phenyl, or
  • R 11 and R 12 together are C 4 -C 5 alkylene or C 4 -C5 oxaalkylene, for example
  • R 11 and R 12 are each a group of the formula
  • any of the substituents are C 1 -C 12 alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2- ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
  • substituents are C 1 -C 4 hydroxyalkyl, they are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
  • A is C 2 -C 6 alkylene, it is, for example, ethylene, propylene, 2,2- dimethylpropylene, tetramethylene or hexamethylene.
  • R 11 and R 12 together are C 4 -C 5 alkylene or C 4 -C 5 oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene .
  • Oligomeric or polymeric compounds the structural repeating unit of which contains one or more 2,2,6,6-tetraalkylpiperidine radicals of formula (I), especially polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, polysiloxanes, poly(meth)acrylamides and the copolymers thereof that contain such radicals.
  • 2,2,6,6-tetraalkylpiperidine radicals of formula (I) especially polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, polysiloxanes, poly(meth)acrylamides and the copolymers thereof that contain such radicals.
  • 2,2,6,6-polyalkylpiperidine light stabilisers of that class are the compounds of the following formulae wherein m is a number from 2 to approximately 200.
  • classes e) and f) are especially suitable, especially those tetraalkylpiperidine compounds that contain s-triazine groups. Also especially suitable are compounds 74, 76, 84, 87, 92, 95 and 96.
  • N-piperidinyl-triazines The preparation of the N-piperidinyl-triazines is known from the literature (cf., for example, Houben-Weyl "Methoden der organischen Chemie", Vol. ViII, p. 233-237, 3 rd Ed., Thieme Verlag Stuttgart 1971). There may be used as starting material for the reaction with various N-piperidylamines cyanuric chloride, diamino-chloro-1,3,5-triazine or variously substituted bisdialkylamino-chloro-1 ,3,5-triazines or dialkylamino- or alkylamino- dichloro-1 ,3,5-triazines.
  • tetra- and penta-alkylpiperidine compounds are: bis(2,2,6,6-tetramethyl-piperidyl) sebacate, bis(2,2,6,6tetramethyl-piperidyl) succinate, bis(1 ,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-S. ⁇ -di-tert-butyl ⁇ -hydroxybenzyl-malonic acid bis(1 ,2,2,6,6pentamethylpiperidyl) ester, the condensation product of 1- hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid, the condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidy()- hexamethyienediamine and 4-tert-octylamino-2,6-dichloro-1 ,3,5-s-triazine, tris(2,2,6,6-tetramethyl)
  • the amount of sterically hindered amine added depends on the desired degree of stabilisation. In general, from 0.01 to 0.5% by weight, especially from 0.05 to 0.5% by weight, based on the polymer, is added.
  • Hydrotalcites and alkali (alkaline earth) aluminosilicates (zeolites) The chemical composition of these compounds is known to a person skilled in the art, for example from patent specifications DE 38 43 581 , U.S.
  • M 2+ one or more of the metals from the group Mg, Ca, Sr, Zn or Sn,
  • a n is an anion having the valency n
  • o b is a number from 1 to 2
  • m is a number from 0 to 20.
  • hydrotalcites examples are
  • Zeolites alkali and alkaline earth aluminosilicates
  • VIII M x /n [(AIO 2)X (SiO 2 ) y ].wH 2 0(VIII) wherein n is the charge of the cation M;
  • M is an element of Group I or Group II, such as Li, Na, K, Mg, Ca, Sr or Ba;
  • y:x is a number from 0.8 to 15, preferably from 0.8 to 1.2;
  • w is a number from 0 to 300, preferably from 0.5 to 30.
  • zeolites sodium aluminosilicates of the formulae
  • X OH, halogen, CIO 4 [sodalite]; Na 6 Al 6 Si 30 O 72 . 24 H 2 O; Na 8 Al 8 Si 40 O 96 .
  • Preferred zeolites correspond to the formulae
  • the zeolites listed may also have a lower water content or may be anhydrous.
  • Other suitable zeolites are:
  • That zeolite generally occurs in variants Na-P- 1 , Na-P-2 and Na-P-3, which are differentiated by their cubic, tetragonal or orthorhombic structure (R. M. Barrer, B. M. Munday, J. Chem. Soc. A 1971 , 2909-2914).
  • the literature just mentioned also describes the preparation of zeolite P- 1 and P-2.
  • zeolite P-3 is very rare and is therefore of little practical interest.
  • the structure of zeolite P-1 corresponds to the gismondite structure known from the above-mentioned Atlas of Zeolite Structures.
  • zeolite B or P c cubic
  • zeolite P 1 tetragonal
  • zeolites of the P type that publication also mentions relatively new zeolites of the P type having Si:AI ratios of less than 1.07:1. Those are zeolites designated MAP or MA-P for "Maximum Aluminium P".
  • zeolite P may contain small quantities of other zeolites. Very pure zeolite P has been described in WO 94/26662.
  • Sodium zeolite A and sodium zeolite P are very especially preferred.
  • the hydrotalcites and/or zeolites can be used in amounts of, for example, from 0.1 to 10 parts by weight, based on 100 parts by weight of halogen-containing polymer.
  • Alkali aluminocarbonates (dawsonites) These are compounds of the formula
  • M is H, Li, Na, K, Mgi /2 , Cai /2 , Sri /2 or Zn 1/2 ;
  • Z is CO 2 , SO 2 , (Cl 2 Oz) 1Z2 , B 4 O 6 , S 2 O 2 (thiosulfate) or C 2 O 2 (oxalate):
  • m is a number from 1 to 2 when M is Mg 1 ⁇ 2 or Ca 1Z2 , and in all other cases is a number from 1 to 3;
  • n is a number from 1 to 4;
  • o is a number from 2 to 4; and
  • p is a number from 0 to 30.
  • the alumino salt compounds of formula (I) that can be used according to the invention may be naturally occurring minerals or synthetically prepared compounds.
  • the metals may partially replace one another.
  • the mentioned alumino salt compounds are crystalline, partially crystalline or amorphous or may be present in the form of a dried gel.
  • the alumino salt compounds may also be present in relatively rare crystalline modifications. A process for the preparation of such compounds is described in EP 394 670. Examples of naturally occurring alumino salt compounds are indigirite, tunisite, aluminohydrocalcite, para-aluminohydrocalcite, strontiodresserite and hydrostrontiodresserite.
  • alumino salt compounds are potassium aluminocarbonate ((K 2 O) 1 (AI 2 O 3) .(CO 2)2 .2H 2 O ⁇ , sodium aluminothiosulfate ⁇ (Na 2 O).
  • the mixed alumino salt compounds can be obtained in accordance with processes known per se by cation exchange, preferably from the alkali alumino salt compounds or by combined precipitation (see, for example, U.S. Pat. No. 5,055,284).
  • M is Na or K
  • Z is CO 2 , SO 2 or (Cl 2 O 7 ) i/2
  • m is 1-3
  • n is 1-4
  • o is 2- 4
  • p is 0-20.
  • Z is especially CO 2 .
  • DASC sodium aluminodihydroxycarbonate
  • DAPC homologous potassium compound
  • Dawsonites may also be substituted by lithium-alumohydroxycarbonates or lithium-magnesium-alumohydroxycarbonates, as described in EP 549,340 and DE 4,425,266.
  • the dawsonites can be used in an amount of, for example, from 0.01 to 5, advantageously from 0.1 to 3, especially from 0.1 to 2, parts by weight, based on 10O parts by weight of halogen-containing polymer.
  • the stabiliser combination preferably comprises component A) and, as component B), at least one substance from the following groups: perchlorate compounds, glycidyl compounds, or dihydropyridines and polydihydropyridines.
  • perchlorate compounds glycidyl compounds
  • dihydropyridines glycidyl compounds
  • polydihydropyridines glycidyl compounds
  • Other organic based stabilizers are described in more detail in United States Patents Nos. 6,194,494, 6,232,375, and 6,274,654, the contents of which are incorporated herein by reference.
  • Preferred organic based stabilizers are Mark OBSTM101 and other Mark OBSTM100 series stabilisers available from Chemtura Corporation.
  • the smoke-suppressant is preferably based on a magnesium/zinc complex oxide of the general formula (Mg 1 Zn)O and containing typically 60% as MgO, and which is free of Antimony.
  • the smoke suppressant is specifically considered to be heavy-metal free.
  • the preferred smoke suppressant is OngardTM2 available from Chemtura Corporation.
  • An object of this invention is to reduce smoke and emission of HCI from PVC.
  • the OBS in addition to its primary function as stabilizer, assists with the reduction of smoke due to preventing the formation of benzenes.
  • the heavy metal free smoke suppressant in addition to its primary function as a smoke suppressant assists with heat stability by its reaction with HCI formed during burning. Apart from the fact that the combination of these compounds has not been practiced in the past, it has surprisingly been found the use of these together to be synergistic in reducing the amount of smoke and HCI emitted; and the amount of HCI is reduced in comparison to a PVC composition containing a Pb stabiliser.
  • a PVC composition containing the smoke-suppressant based on a magnesium/zinc complex which is heavy metal free does not require the inclusion of "acid scavengers" (i.e. basic compounds that react with HCI to form a metal chloride such as calcium stearate, carbonate, oxide or hydroxide, magnesium stearate, carbonate or hydroxide, or zinc stearate or hydroxide).
  • acid scavengers i.e. basic compounds that react with HCI to form a metal chloride such as calcium stearate, carbonate, oxide or hydroxide, magnesium stearate, carbonate or hydroxide, or zinc stearate or hydroxide.
  • compositions of the invention are environmentally friendly, making use of environmental synergies between organic based stabilizer (based on a uracil compound) and a smoke suppressant (based on a magnesium/zinc complex).
  • organic based stabilizer based on a uracil compound
  • smoke suppressant based on a magnesium/zinc complex.
  • the reduction in smoke and HCI emission coupled with absence of heavy metals is desirous.
  • the use of the combination is also desirous to a more environmentally friendly application.
  • the organic based stabilizer may be used at 1.5-3% by mass in rigid PVC articles, together with lubricants, fillers and impact modifiers.
  • the smoke suppressant may be used in rigid PVC articles at 1-4% by mass.
  • the stabiliser is Mark OBSTM101
  • smoke suppressant is OngardTM2, both available from the Chemtura Corporation.
  • the Pb stabiliser was a one-pack containing Tribasic lead sulphate plus lubricants.
  • a typical formulation comprised of:
  • Titanium dioxide 1.0 phr
  • Results - Plaques of 75x75x10 mm were compression moulded.
  • the prepared plaques were tested in a Smoke Density Chamber according to ASTM E662 for smoke generation, and ASTM D2863 for flammability as limiting oxygen index. The results are shown in Table 1 below:
  • PVC compounds were produced by mixing PVC powder, stabilizer, lubricants and chlorinated polyethylene as impact modifier in a high speed mixer according to the formulations shown. The mix was dropped to a cooler mixer at 110 0 C and cooled to 4O 0 C before processing. The mixes were compression moulded into plaques of 76mm x 76mm x 5mm for further testing.
  • Conductivity was measured according to IEC 60754-2. 1 mg compound is weighed into a combustion boat which is placed in a furnace and heated to 900 0 C. The gases from the combustion of the PVC, which include HCI are led into a wash bottle containing deionised water. The conductivity of the water is measured after 30 minutes. The higher the conductivity the higher the level of HCI dissolved in the water and consequently emitted from the sample.
  • the combination of the OBS and Ongard has lower HCl emissions than a combination of a Pb stabiliser and Ongard;

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Abstract

L'invention concerne une composition de poly(chlorure de vinyle) (PVC) pour une utilisation dans des tuyaux en PVC, laquelle composition est écologique et possède des propriétés de suppression de la fumée. La composition de PVC comprend un stabilisant à base organique (OBS) et un agent de suppression de la fumée, qui agissent en synergie pour réduire les émissions de fumée et de gaz toxiques (HCl) dans le cas de la combustion de la composition de PVC.
PCT/IB2007/002406 2006-08-24 2007-08-22 Composition de poly(chlorure de vinyle) Ceased WO2008023249A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008018872A1 (de) 2008-04-14 2009-10-15 Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg Stabilisatorsystem für halogenhaltige Polymere
DE102008020203A1 (de) 2008-04-22 2009-10-29 Catena Additives Gmbh & Co. Kg Lösemittelfreie High Solids (One-Pack)-Stabilisatoren für halogenhaltige Polymere
DE102010020486A1 (de) 2010-05-14 2011-11-17 Catena Additives Gmbh & Co. Kg Flammgeschützte halogenhaltige Polymere mit verbesserter Thermostabilität
US8835449B2 (en) 2011-11-11 2014-09-16 Pfizer Inc. 2-thiopyrimidinones
WO2014143623A1 (fr) * 2013-03-15 2014-09-18 The Lubrizol Corporation Compositions cpvc exemptes de métaux lourds
US9771332B2 (en) 2015-05-05 2017-09-26 Pfizer Inc. 2-thiopyrimidinones
US12168011B2 (en) 2022-02-21 2024-12-17 Verona Pharma Plc Formulation production process
US12251384B1 (en) 2023-06-26 2025-03-18 Verona Pharma Plc Particulate composition

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GB1523531A (en) * 1976-05-05 1978-09-06 Nl Industries Inc Fire retardant compositions
GB2033908A (en) * 1978-11-15 1980-05-29 Ciba Geigy Ag Smoke suppressant for plasticised PVC
EP0930332A2 (fr) * 1998-01-16 1999-07-21 Witco Vinyl Additives GmbH Système de stabilisateurs pour les polymères chlorés

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
GB1523531A (en) * 1976-05-05 1978-09-06 Nl Industries Inc Fire retardant compositions
GB2033908A (en) * 1978-11-15 1980-05-29 Ciba Geigy Ag Smoke suppressant for plasticised PVC
EP0930332A2 (fr) * 1998-01-16 1999-07-21 Witco Vinyl Additives GmbH Système de stabilisateurs pour les polymères chlorés

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008018872A1 (de) 2008-04-14 2009-10-15 Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg Stabilisatorsystem für halogenhaltige Polymere
EP2110405A1 (fr) 2008-04-14 2009-10-21 IKA Innovative Kunststoffaufbereitung Gmbh & Co.Kg Systèmes de stabilisateur pour polymères contenant de l'halogène
EP2792707A2 (fr) 2008-04-14 2014-10-22 IKA Innovative Kunststoffaufbereitung Gmbh & Co.Kg Systèmes de stabilisateur pour polymères contenant de l'halogène
DE102008020203A1 (de) 2008-04-22 2009-10-29 Catena Additives Gmbh & Co. Kg Lösemittelfreie High Solids (One-Pack)-Stabilisatoren für halogenhaltige Polymere
EP2392612A1 (fr) 2010-05-14 2011-12-07 CATENA Additives GmbH & Co. KG Polymères contenant un halogène ignifuge ayant une stabilité thermique améliorée
DE102010020486A1 (de) 2010-05-14 2011-11-17 Catena Additives Gmbh & Co. Kg Flammgeschützte halogenhaltige Polymere mit verbesserter Thermostabilität
US9399626B2 (en) 2011-11-11 2016-07-26 Pfizer Inc. 2-thiopyrimidinones
US9873673B2 (en) 2011-11-11 2018-01-23 Pfizer Inc. 2-thiopyrimidinones
US8841314B2 (en) 2011-11-11 2014-09-23 Pfizer Inc. 2-Thiopyrimidinones
US8835449B2 (en) 2011-11-11 2014-09-16 Pfizer Inc. 2-thiopyrimidinones
EP2970631B1 (fr) 2013-03-15 2017-05-03 Lubrizol Advanced Materials, Inc. Composition comprennant de chlorure de polyvinyle chloré sans métaux lourds
CN105209532A (zh) * 2013-03-15 2015-12-30 路博润先进材料公司 不含重金属的cpvc组合物
WO2014143623A1 (fr) * 2013-03-15 2014-09-18 The Lubrizol Corporation Compositions cpvc exemptes de métaux lourds
US10202500B2 (en) 2013-03-15 2019-02-12 Lubrizol Advanced Materials, Inc. Heavy metal free CPVC compounds
US9771332B2 (en) 2015-05-05 2017-09-26 Pfizer Inc. 2-thiopyrimidinones
US12168011B2 (en) 2022-02-21 2024-12-17 Verona Pharma Plc Formulation production process
US12409180B2 (en) 2022-02-21 2025-09-09 Verona Pharma Plc Formulation production process
US12251384B1 (en) 2023-06-26 2025-03-18 Verona Pharma Plc Particulate composition

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