CA2176650A1 - Stabilized cpvc (chlorinated pvc) - Google Patents
Stabilized cpvc (chlorinated pvc)Info
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- CA2176650A1 CA2176650A1 CA002176650A CA2176650A CA2176650A1 CA 2176650 A1 CA2176650 A1 CA 2176650A1 CA 002176650 A CA002176650 A CA 002176650A CA 2176650 A CA2176650 A CA 2176650A CA 2176650 A1 CA2176650 A1 CA 2176650A1
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- cpvc
- coo
- c18alkyl
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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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
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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
- 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
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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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Lubricants (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Chlorinated PVC (CPVC) is stabilized by addition of a combination of organotin compounds and alkali metal or alkaline earth metal oxides and/or hydroxides against thermal and fric-tional stresses.
Description
7 b6~ 0 Stabilized CPVC (chlorinated PVC) The invention relates to compositions comprising chlorinated PVC and a stabilizer combi-nation comprising organotin stabilizer and alkali metal oxide or hydroxide or alkaline earth metal oxide or hydroxide, and to the stabilizer combination itself, and to the use thereof.
Organotin compounds have long been known as stabilizers for PVC (cf. for example US
4,743,640, columns 4 to 6 and US 4,839,409, columns 4 to 9) and are also employed, for example, in the injection moulding of chlorinated polyvinyl chloride (CPVC) (G.T. Dalal, J.
Vinyl. Techn. 7, 36 (1985); US 4,347,205; WO 90 03 999; US 4,331,775; US 4,345,040). In this process, the material can be stressed in two ways: firstly by shear forces (fricative stress) and secondly by high temperatures. In both cases, the stress loading increases as the residence times in the processing equipment become longer. For such conditions, there continues to be a search for effective stabilizer combinations which offer maximum protec-tion against degradation by thermal and fricative stress.
Surprisingly, the combination of organotin stabilizers with oxides or hydroxides of alkali metals or of alkaline earth metals brings about a substantial improvement in the ability of CPVC to withstand themmal and mechanical stress during processing.
The invention accordingly provides a composition comprising chlorinated PVC (CPVC) and as stabilizer combination A) at least one organotin compound of one of the fommulae I to Vll [R']~Sn[-Q-R2]4 ~ (1) [ Sln-Q-R -CO(~ (Il) 2 1 7665û
[ Sl -S-R3-coo-R7-o-co-R3-S ]k (~
RI~s R3 coo R7 o-CO-R3-S 1~
~S-R3-Coo-R7 o-co-R3-s-sn \~ (IV) \~ -R3 -Coo-R7-o-co-R3-s/
R' Rl I
R8-COO~Sn-X~i~Sn-O-CO-R8 (V) Rl Rl RpSnSq (Vl) or [RpSnSq]r (Vll) in which R and R' independently of one another are C1-C,2alkyl or C3-C"alkoxycarbonyl-ethyl, Q is -S- or-O-CO-, and R2, if Q is -S-, is C8-C,8alkyl or a radical -R3-Coo-R4 or -R3-o-Co-R4, and R2, if Q is -O-CO-, is C,-C,8alkyl, C2-C,8alkenyl, phenyl, C,-C4alkyl substituted phenyl, or a radical -CH=CH-Coo-R5, R3 is methylene, ethylene or o-phenylene, R4 is C5-C,8alkyl, R5 is C,-C,8alkyl, C5-C7cycloalkyl or benzyl, R6, if Q is -S-, is methylene, ethylene or o-phenylene, and R6, if Q is -O-CO-, is C1-C8alkylene, o-phenylene or a group -CH=CH-, R7is C2-C4alkylene oris C4-C8alkylene interrupted by -O-, R8 is C1-C18alkyl, C2-C18alkenyl, phenyl, C1-C4alkyl-substituted phenyl, or a radical -CH=CH-Coo-R5, X independently at each occurrence is -O- or-O-CO-R9-COO-, 3 ~1 76~
R9 is C,-C8alkylene, o-phenylene or a group -CH=CH-, p is 1 or2, q is (4-p)/2, and r> 1, i is 1 or 2, j is a number from 1 to 6, k is a number from 1 to 3 and m is a number from 1 to 4, and B) at least one oxide and/or hydroxide of an alkali metal or alkaline earth metal.
Examples of R, R', R2, R4, R5 and R8 as alkyl within the scope of the definitions given are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
Isooctyl denotes the alkyl radicals of the mixture, originating from the oxo process, of primary branched alcohols R'CH20H, in which R' is a branched heptyl group (Merck Index 1Oth.ed., 5041).
R as alkyl is preferably n-alkyl or isoalkyl, especially preferably methyl, ethyl or n-butyl.
R' as alkyl is preferably methyl, butyl or octyl.
R and R1 as C3-C11alkoxycarbonylethyl are C1-C8alkyl-O-CO-CH2-CH2-.
R2 and R8 as C2-C18alkenyl are, for example, ethenyl (vinyl), propenyl, isopropenyl, 2-butenyl, 3-butenyl, Isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-heptadec-8-enyl, n-octadec-2-enyl, n-octadec-4-enyl.
R2and R8 as C1-C4alkyl-substituted phenyl are, for example, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl or tert-butylphenyl.
R2, R6, R8 and R9 as -CH=CH-Coo-R5 or, respectively, -CH=CH- are derived from maleic acid or fumaric acid, preferably from maleic acid.
R5 as C5-C7cycloalkyl is cyclopentyl, cyclohexyl or cycloheptyl, preferably cyclopentyl or cyclohexyl, especially cyclohexyl.
2 l 7 ~G~O
R6 and R7 as alkylene are a divalent alkyl radical; within the scope of the chain lengths given, R6 and R7 are, for example, methylene, ethylene, -CH(CH3)-CH2-, -(CH2)3-, -(CH2)4-, -(CH2)6-, -(CH2)B-, -CH2-CH(C2H5)-(CH2)4-, -CH2-C(CH3)2-CH2-; straight-chain radicals are preferred. As C4-C8alkylene interrupted by -O-, R7 is, for example, -(CH2)2-O-(CH2)2-, -(CH2)3-O-(CH2)3, -(CH2)2-O-(CH2)4- or-(CH2)4-O-(CH2)4-, especially-(CH2)2-O-(CH2)2-. The unit (O-CH2-CH2) can also be present more than once. Examples of such radicals are -(CH2)2-(O-CH2CH2-)2- and -(CH2)2-(O-CH2CH2-)3-.
There is no upper limit on the index r, because the sulfides may be amorphous, coordina-tively crosslinked lattice structures. It is also possible, as in fommula Vl, to omit the represen-tation of this state of affairs. Accordingly, formulae Vl and Vll are essentially interchange-able. Examples of structures of the sulfides can be found below under "Typical sulfides".
Chlorinated PVC (post-chlorinated polyvinyl chloride), CPVC, is obtained by subsequent chlorination of PVC. After chlorination, the chlorine content is above the level of approxima-tely 57% which is customary for PVC; it may be up to 74% and is commonly from 63 to 69%
(in this respect, cf. G.T. Dalal, J. Vinyl. Techn. 7, 36 (1985)].
The PVC can be post-chlorinated in various ways, for example in suspension under UV light (US 4,345,040; US 2,996,489; US 3,100 762). In this context, the PVC is preferably em-ployed in coarsely granulated form, and may be of high or low molecular weight, with pre-ference being given to the use of high molecular weight PVC.
The CPVC is used, for example, for pipes, conduits, containers, workpieces, valves and fittings, electrical components, automotive parts and other rigid articles. It is particularly suitable for applications in which relatively high pressures and temperatures occur simul-taneously. Examples of areas of application are plant construction, hot water systems, filter units and roof guttering.
Alkali metals or alkaline earth metals may, for example, be Li, Na, K, Mg, Ca, Sr or Ba.
Particularly suitable oxides and hydroxides thereof are CaO, Ca(OH)2, MgO, Mg(OH)2, KOH, and NaOH. CaO, Ca(OH)2, MgO and Mg(OH)2are preferred.
21 7~650 The invention also provides the stabilizer combination for CPVC, comprising the above-described components A) and B) and also, if desired, further additives.
The organotin compounds of the formulae I to Vll are known (cf. for example the literature references cited at the outset and also US 5,021,491 and those referred to therein: US
2,731,482, US 2,731,484, US 2,713,585, US 2,648,650, US 3,507,827). They may, inparticular, be carboxylates, mercaptides and sulfides.
Typical mercaptides are: methyltin tris(alkylthioglycolate) or tris(alkylthiopropionate), n-butyltin tris(alkylthioglycolate), n-butoxycarbonylethyltin tris(alkylthioglycolate), dimethyltin bis(alkylthioglycolate) or bis(alkylthiopropionate); di-n-butyltin bis(alkylthioglycolate) or bis(alkylthiopropionate); bis(n-butoxycarbonylethyl)tin bis(alkylthioglycolate), and n-octyltin tris(isooctylthioglycolate) .
Typical sulfides are those of the formulae Vl and Vll, for example r~Bu ~ \ and r~ ;n - n~
Typical carboxylates are di-n-butyltin bis(methylmaleate), di-n-butyltin bis(butylmaleate) and polymeric di-n-butyltin maleate.
Preferably, in the compounds of the formulae I to IV:
R is C,-C12alkyl, R2, if Q is -S-, is C8-C,8alkyl or a radical -R~-Coo-R4, and R2, if Q is -O-CO-, is C7-C18alkyl, C8-C18alkenyl, phenyl, or a radical -CH=CH-Coo-R5, R~ is methylene, ethylene or o-phenylene, R4 is C5-C,8alkyl, 6 ~ 1 766~
R5 is C1-C,8alkyl or Cs-C7cycloalkyl, R6, if Q is -S-, is methylene, ethylene or o-phenylene, and R6, if Q is -O-CO-, is C,-C4alkylene, o-phenylene or a group -CH=CH-, R7 is C2-C4alkylene or is C4-C8alkylene interrupted by -O-, i is 1 or 2, j is a number from 1 to 6 and k is a number from 1 to 3.
Particularly preferably, in the compounds of the formulae I to IV:
R' is C3-Cgalkyl, R2, if Q is -S-, is a radical -R3-Coo-R4, and R2, if Q is -O-CO-, is C7-C"alkyl, or a radical -CH=CH-Coo-R5, R3is methylene or ethylene, R4is c8-c12alkyl1 R5is C,-C,8alkyl or cyclohexyl, R6, if Q is -S-, is methylene or ethylene, R5, if Q is -O-CO-, is a group -CH=CH-, R7is C2-H4- and i is 1 or 2, j is a number from 1 to 6 and k is a number from 1 to 3.
The substituents on the abovementioned groups -CH=CH- are particularly preferably in the cis position (Z configuration) and, in the compounds, are derived from maleic acid.
Very particular preference is given to compositions comprising, as compound(s) of com-ponent A), those of the formulae I and/or 111 in which R'is butyl or octyl, R3is-CH2-, R7is -C2H4- and R2, if Q is S, is -CH2-Coo-R4, where R4is c8-c12alkyll and R2, if Q is O-CO, is -CH=CH-Coo-R5, where R5is C,-C,8alkyl.
The proportion of component A) in the CPVC is preferably from 0.5 to 5% by weight, in particular from 1.5 to 2.5 % by weight, and that of component B) is preferably from 0.1 to 4% by weight, in particular from 0.5 to 1.5% by weight.
The compositions according to the invention preferably contain a mixture of compounds as component A). However, compositions containing only one compound as component A) are also part of the invention and have the same advantageous properties.
7 211~6~f~
From the chemistry of organotin stabilizers, it is known that these stabilizers are often no longer present in the stabilized substrate in the same form as that in which they were added. Usually, reaction (comproportionation) products are formed. The invention of course also embraces the compositions comprising such products formed from the compounds of component A).
Together with the compounds of component A) of the formulae I to Vll, it is also possible for the compositions according to the invention to contain further tin stabilizers, provided they do not impair the improved properties obtained by the abovementioned compounds. Pre-ference, however, is given to those compositions according to the invention which, other than the above-described organotin compounds of component A) and their comproportio-nation products, contain no other tin stabilizers.
The invention additionally provides for the use of the organotin compounds of component A) in combination with the oxides and/or hydroxides defined above as component B) for stabilizing CPVC. In this context, for example, 0.5 - 5 parts by weight of at least one of the organotin compounds defined above as component A), in combination with 0.1-4.0 parts by weight (per 100 parts by weight of CPVC) of at least one of the oxides or hydroxides of alkali metals or alkaline earth metals defined above as component B3 are added to 100 parts by weight of CPVC. To this extent, the invention also provides a method of stabilizing CPVC by the addition of the componants A) and B) defined at the outset.
The CPVC stabilized in accordance with the invention is ideally suited to processing by in-jection moulding. With this type of processing, the advantages are particularly evident. In particular, surprisingly good stabilization is achieved under high shear stress, thus enabling processing by the injection moulding technique to be carried out without any problems.
In addition to the stabilizer combination according to the invention, the CPVC can also com-prise other customary stabilizers.
Examples are antioxidants, perchlorates, fillers and reinforcing agents, metal soaps, beta-diketones (1,3-diketo compounds), zeolites, hydrotalcites, organophosphites, UV absorbers and light stabilizers, lubricants, dihydropyridines, sterically hindered amines (HALS), fatty acid esters, paraffins, blowing agents, fluorescent whiteners, pigments, flameproofing -8- 2 1 766~U
agents, antistatic agents"~-aminocrotonates (as mentioned for example in EP 0 465 405, p.6, lines 9-14), pyrroles (ibid.), naphthols, hydroxydiphenylamines, phenylindoles, phos-phates, thiophosphates, gelling aids, modifiers (for example impact modifiers), other metal stabilizers and complexing agents for Lewis acids.
The person skilled in the art is familiar with which substances belong to said groups. Some of those which may be mentioned by way of example are:
Perchlorates (or perchloric acid) are of the formula M(ClO4)n where M+ is H+, NH4+, Na+, K+, Mg2+, Ca2+, Ba2+ or Al3+. Depending on the valency of M, the index n is 1, 2 or 3.
In this context, the perchloric acid or respective perchlorate can be employed in a variety of common fomms, for example as a salt or aqueous solution applied to a carrier material, such as PVC, calcium silicate, zeolites or hydrotalcites, or bonded by chemical reaction into a hydrotalcite.
They can be employed in a quantity of, for example, from 0.001 to 5 parts by weight, advan-tageously from 0.01 to 3 parts by weight, particularly preferably from 0.01 to 2.0 parts by weight, based on 100 parts by weight of CPVC.
Examples of fillers are chalk, kaolin, china clay, talc, silicates, glass fibres, glass beads, wood flour, mica, carbon black, graphite, ground minerals or heavy spar. Talc and chalk are preferred.
The fillers can be employed in a quantity of preferably at least 1 part by weight, for example from 5 to 200 parts by weight, advantageously from 10 to 150 parts by weight and, in parti-cular, from 15 to 100 parts by weight, based on 100 parts by weight of CPVC.
Metal soaps are primarily metal carboxylates, preferably of relatively long-chain carboxylic acids. Common examples are stearates, laurates, and also oleates and salts of shorter-chain alkylcarboxylic acids. Use is often made of so-called synergistic mixtures, such as barium/zinc, magnesium/zinc, calcium/zinc or calcium/magnesium/zinc stabilizers. The metal soaps can be employed individually or in mixtures. A review of common metal soaps 9 2 i 7 66513 can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. Vol. A16 (1985) p.
361 .
Other metal stabilizers which may be mentioned are antimony stabilizers, for example those of the formula Sb(SCH2COO-isoctyl) (cf. US 4,743,640).
Possible ,B-diketones or 1,3-dicarbonyl compounds which may be used are linear or cyclic dicarbonyl compounds. Customary examples are given in "Plastics Additives", edited by R.
Gachter and H. Muller, Hanser Verlag, 3rd Edition, 1990, p. 306 ff. Examples of 1 ,3-dicar-bonyl compounds are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-2,4-heptanedione, benzoylacetone, di-benzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoyl-methane, isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis(4-methylbenzoyl)methane, benzoyl-p-chlorobenzoylmethane, bis(2-hydroxybenzoyl)-methane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane, 1-benzoyl-1-acetylnonane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tert-butylbenzoyl)methane, benzoyl-formylmethane, benzoylphenylacetylmethane, bis(cyclo-hexanoyl)methane, di(pivaloyl)methane, methyl, ethyl, hexyl, octyl, dodecyl or octadecyl acetoacetate, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl benzoylacetate, ethyl, propyl, butyl, hexyl or octyl stearoylacetate, and dehydracetic acid and its zinc, calcium or magnesium salts.
The 1,3-diketo compounds can be employed in a quantity of, for example, from 0.01 to 10 parts by weight, advantageously from 0.01 to 3 parts by weight and, in particular, from 0.01 to 2 parts by weight, based on 100 parts by weight of CPVC.
Suitable antioxidants are primarily those containing a sterically hindered phenol group. The best-known example is 2,6-di-tert-butyl-4-methylphenol (BHT). Also worthy of mention are the esters of b-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, di-ethylene glycol, triethylene glycol, pentaerythritol, dipentaerythritol, tris-(hydroxyethyl) iso-cyanurate, N,N'-bis-(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, tri--10- 2 1 766~
methylhexanediol, trimethylolpropane, di-trimethylolpropane, and 4-hydroxymethyl-1-phos-pha-2,6,7-trioxabicyclol2.2.2]-octane.
The antioxidants can be employed in a quantity of, for example, from 0.01 to 10 parts by weight, advantageously from 0.1 to 10 parts by weight and, in particular, from 0.1 to 5 parts by weight, based on 100 parts by weight of CPVC.
Suitable UV absorbers and light stabilizers are primarily benzophenone derivatives and benzotriazole derivatives; known products can be found in "Plastics Additives" edited by R.
Gachter and H. Muller, Hanser Verlag, 3rd edition, 1990, p. 205 ff.
Examples of suitable lubricants are montan wax, fatty acid esters, complex esters, PE
waxes, amide waxes, chlorinated paraffins, glycerol esters and alkaline earth metal soaps.
Lubricants which can be used are also described in "Plastics Additives", edited by R. Gach-ter and H. Muller, Hanser Verlag, 3rd edition, 1990, chapter 6, pages 423-480 and in "Kunststoff Handbuch PVC" [Plastics handbook PVC] 2/1, 20th edition 1986, pp. 570-595.
Suitable organic phosphites are those of the general fommula P(OR')3 in which the radicals R' are identical or different alkyl, alkenyl, aryl or aralkyl radicals.
Particularly suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, tri-oleyl, triphenyl, tricresyl, tris-p-nonylphenyl or tricyclohexyl phosphite, and particular prefe-rence is given to the aryl dialkyl and the alkyl diaryl phosphites, for example phenyl didecyl phosphite, (2,4-di-tert-butylphenyl) didodecyl phosphite, (2,6-di-tert-butylphenyl) didodecyl phosphite, and the dialkyl and diaryl pentaerythritol diphosphites, such as distearyl penta-erythritol diphosphite, and also nonstoichiometric triaryl phosphites, for example those with the composition (H1gCg-C6H4)O1 5P(OC12/13H25/27)1 5. Preferred organic phosphites are di-stearyl pentaerythritol diphosphite, trisnonylphenyl phosphite and phenyl didecyl phosphite.
The organic phosphites can be employed in a quantity of, for example, from 0.01 to 10 parts by weight, advantageously from 0.05 to 5 parts by weight and, in particular, from 0.1 to 3 parts by weight, based on 100 parts by weight of CPVC.
2176~C
Suitable compounds from the series consisting of the hydrotalcites or zeolites are both the naturally occurring minerals and synthetic compounds. The additional use of hydrotalcites and/or zeolites in the compositions according to the invention is preferred since these com-pounds may synergistically increase the stabilizing effect.
The chemical composition of the hydrotalcites and zeolites is familiar to the person skilled in the art.
Examples of hydrotalcites are Al203.6MgO.C02. 1 2H20, Mg4,5AI2(0H)13.C03.3.5H20, 4MgO.AI203.C02.9H20, 4MgO.AI203.C02.6H20, ZnO.3MgO.AI203.CO2.8-9H20 or ZnO.3MgO.AI203.CO2.5-6H20 Examples of zeolites are sodium alumosilicates of the fommulae Na12AI12Si12048 . 27 H20 [zeolite A], Na6AI6Si6024 . 2 NaX . 7.5 H20, where X = OH, halogen or Cl04 [sodalite]
Na6AI6Si30072 . 24 H20, Na8AI8Si40096 . 24 H20, Na,6AI16Si24080 . 16 H20, Na16AI16Si32096 . 16 H20, Na56AI56Si1360384 . 250 H20, [zeolite Y]
N~6AIOGSj1060384 . 264 H20 [zeolite X]
or the zeolites which can be prepared by complete or partial substitution of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na,K),OAl,OSi22064 . 20 H20 Ca4sNa3[(AI02),2(SiO2),2] . 30 H20 -12- i 1 /6~0 KgNa:3[(AI02),2(SiO2),2] . 27 H20.
The hydrotalcites and/or zeolites can be employed in quantities of, for example, from 0.1 to 20 parts by weight, advantageously from 0.1 to 10 parts by weight and, in particular, from 0.1 to 5 parts by weight, based on 100 parts by weight of CPVC.
The compositions according to the invention are prepared by known methods. The stabili-zers are admixed with the CPVC in a known manner prior to processing. A homogeneous mixture can be obtained prior to processing, for example, with the aid of a heating-cooling mixer, customarily at up to 120C in the heating phase.
The examples which follow illustrate the invention in more detail without limiting it. As in the rest of the description, parts and percentages are by weight unless stated otherwise.
Example:
57 9 of the CPVC compound (composition according to Table 1) are subjected, in the knea-ding chamber of a Brabender Plasticorder at 35 rpm, to thermal (1 90C) and fricative stress, i.e. by shear forces. At 5-minute intervals, samples of the plasticated CPVC mass are with-drawn and are subsequently compression-moulded at 1 80C for 1.5 minutes to fomm test specimens. The yellowness index (Yl; DIN 5033, ASTM 1925-70) of these samples is deter-mined by colorimetric determination. Low yellowness indices denote good stabilizer action.
In addition, the long-term thermal stability of the samples is characterized by the period of time until there is a rise in the torque, caused by crosslinking of the polymer material (Bra-bender decomposition time). Long decomposition times, accordingly, denote good stabiliza-tion. The results are summarized in Table I below. It is evident that stabilization with the organotin compound and CaO is superior to that with the organotin compound alone.
-13- 2 1 7 665~
Table l: Brabender Heat test at 1 90C
Mixture 1 2 Acrylate impact modifier 3 3 PMMA flow aid 1.5 1.5 Partially oxidized PE wax 0.6 0.6 Fatty acid ester 0.6 0.6 TiO2 0.5 0.5 Calcium stearate 0.5 0.5 Organotinmercaptide') 0.8 0.8 Calcium oxide -- 1.0 Brabender decomposition time [minutes] 42 56 Yl after 15 minutes 20.7 20.7 Yl after 20 minutes 26.1 23.6 Yl after 25 minutes 31.0 28.2 Yl after30 minutes 38.5 35.1 Yl after 35 minutes 53.4 42.4 1)Mixture of 70 parts by weight of (C4H9)2Sn[SCH2COO-CH2CH(C2Hs)c4H9]2 and 30 parts by weight of C4HgSn[SCH2COO-CH2CH(C2H5)C4Hg]3
Organotin compounds have long been known as stabilizers for PVC (cf. for example US
4,743,640, columns 4 to 6 and US 4,839,409, columns 4 to 9) and are also employed, for example, in the injection moulding of chlorinated polyvinyl chloride (CPVC) (G.T. Dalal, J.
Vinyl. Techn. 7, 36 (1985); US 4,347,205; WO 90 03 999; US 4,331,775; US 4,345,040). In this process, the material can be stressed in two ways: firstly by shear forces (fricative stress) and secondly by high temperatures. In both cases, the stress loading increases as the residence times in the processing equipment become longer. For such conditions, there continues to be a search for effective stabilizer combinations which offer maximum protec-tion against degradation by thermal and fricative stress.
Surprisingly, the combination of organotin stabilizers with oxides or hydroxides of alkali metals or of alkaline earth metals brings about a substantial improvement in the ability of CPVC to withstand themmal and mechanical stress during processing.
The invention accordingly provides a composition comprising chlorinated PVC (CPVC) and as stabilizer combination A) at least one organotin compound of one of the fommulae I to Vll [R']~Sn[-Q-R2]4 ~ (1) [ Sln-Q-R -CO(~ (Il) 2 1 7665û
[ Sl -S-R3-coo-R7-o-co-R3-S ]k (~
RI~s R3 coo R7 o-CO-R3-S 1~
~S-R3-Coo-R7 o-co-R3-s-sn \~ (IV) \~ -R3 -Coo-R7-o-co-R3-s/
R' Rl I
R8-COO~Sn-X~i~Sn-O-CO-R8 (V) Rl Rl RpSnSq (Vl) or [RpSnSq]r (Vll) in which R and R' independently of one another are C1-C,2alkyl or C3-C"alkoxycarbonyl-ethyl, Q is -S- or-O-CO-, and R2, if Q is -S-, is C8-C,8alkyl or a radical -R3-Coo-R4 or -R3-o-Co-R4, and R2, if Q is -O-CO-, is C,-C,8alkyl, C2-C,8alkenyl, phenyl, C,-C4alkyl substituted phenyl, or a radical -CH=CH-Coo-R5, R3 is methylene, ethylene or o-phenylene, R4 is C5-C,8alkyl, R5 is C,-C,8alkyl, C5-C7cycloalkyl or benzyl, R6, if Q is -S-, is methylene, ethylene or o-phenylene, and R6, if Q is -O-CO-, is C1-C8alkylene, o-phenylene or a group -CH=CH-, R7is C2-C4alkylene oris C4-C8alkylene interrupted by -O-, R8 is C1-C18alkyl, C2-C18alkenyl, phenyl, C1-C4alkyl-substituted phenyl, or a radical -CH=CH-Coo-R5, X independently at each occurrence is -O- or-O-CO-R9-COO-, 3 ~1 76~
R9 is C,-C8alkylene, o-phenylene or a group -CH=CH-, p is 1 or2, q is (4-p)/2, and r> 1, i is 1 or 2, j is a number from 1 to 6, k is a number from 1 to 3 and m is a number from 1 to 4, and B) at least one oxide and/or hydroxide of an alkali metal or alkaline earth metal.
Examples of R, R', R2, R4, R5 and R8 as alkyl within the scope of the definitions given are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
Isooctyl denotes the alkyl radicals of the mixture, originating from the oxo process, of primary branched alcohols R'CH20H, in which R' is a branched heptyl group (Merck Index 1Oth.ed., 5041).
R as alkyl is preferably n-alkyl or isoalkyl, especially preferably methyl, ethyl or n-butyl.
R' as alkyl is preferably methyl, butyl or octyl.
R and R1 as C3-C11alkoxycarbonylethyl are C1-C8alkyl-O-CO-CH2-CH2-.
R2 and R8 as C2-C18alkenyl are, for example, ethenyl (vinyl), propenyl, isopropenyl, 2-butenyl, 3-butenyl, Isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-heptadec-8-enyl, n-octadec-2-enyl, n-octadec-4-enyl.
R2and R8 as C1-C4alkyl-substituted phenyl are, for example, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl or tert-butylphenyl.
R2, R6, R8 and R9 as -CH=CH-Coo-R5 or, respectively, -CH=CH- are derived from maleic acid or fumaric acid, preferably from maleic acid.
R5 as C5-C7cycloalkyl is cyclopentyl, cyclohexyl or cycloheptyl, preferably cyclopentyl or cyclohexyl, especially cyclohexyl.
2 l 7 ~G~O
R6 and R7 as alkylene are a divalent alkyl radical; within the scope of the chain lengths given, R6 and R7 are, for example, methylene, ethylene, -CH(CH3)-CH2-, -(CH2)3-, -(CH2)4-, -(CH2)6-, -(CH2)B-, -CH2-CH(C2H5)-(CH2)4-, -CH2-C(CH3)2-CH2-; straight-chain radicals are preferred. As C4-C8alkylene interrupted by -O-, R7 is, for example, -(CH2)2-O-(CH2)2-, -(CH2)3-O-(CH2)3, -(CH2)2-O-(CH2)4- or-(CH2)4-O-(CH2)4-, especially-(CH2)2-O-(CH2)2-. The unit (O-CH2-CH2) can also be present more than once. Examples of such radicals are -(CH2)2-(O-CH2CH2-)2- and -(CH2)2-(O-CH2CH2-)3-.
There is no upper limit on the index r, because the sulfides may be amorphous, coordina-tively crosslinked lattice structures. It is also possible, as in fommula Vl, to omit the represen-tation of this state of affairs. Accordingly, formulae Vl and Vll are essentially interchange-able. Examples of structures of the sulfides can be found below under "Typical sulfides".
Chlorinated PVC (post-chlorinated polyvinyl chloride), CPVC, is obtained by subsequent chlorination of PVC. After chlorination, the chlorine content is above the level of approxima-tely 57% which is customary for PVC; it may be up to 74% and is commonly from 63 to 69%
(in this respect, cf. G.T. Dalal, J. Vinyl. Techn. 7, 36 (1985)].
The PVC can be post-chlorinated in various ways, for example in suspension under UV light (US 4,345,040; US 2,996,489; US 3,100 762). In this context, the PVC is preferably em-ployed in coarsely granulated form, and may be of high or low molecular weight, with pre-ference being given to the use of high molecular weight PVC.
The CPVC is used, for example, for pipes, conduits, containers, workpieces, valves and fittings, electrical components, automotive parts and other rigid articles. It is particularly suitable for applications in which relatively high pressures and temperatures occur simul-taneously. Examples of areas of application are plant construction, hot water systems, filter units and roof guttering.
Alkali metals or alkaline earth metals may, for example, be Li, Na, K, Mg, Ca, Sr or Ba.
Particularly suitable oxides and hydroxides thereof are CaO, Ca(OH)2, MgO, Mg(OH)2, KOH, and NaOH. CaO, Ca(OH)2, MgO and Mg(OH)2are preferred.
21 7~650 The invention also provides the stabilizer combination for CPVC, comprising the above-described components A) and B) and also, if desired, further additives.
The organotin compounds of the formulae I to Vll are known (cf. for example the literature references cited at the outset and also US 5,021,491 and those referred to therein: US
2,731,482, US 2,731,484, US 2,713,585, US 2,648,650, US 3,507,827). They may, inparticular, be carboxylates, mercaptides and sulfides.
Typical mercaptides are: methyltin tris(alkylthioglycolate) or tris(alkylthiopropionate), n-butyltin tris(alkylthioglycolate), n-butoxycarbonylethyltin tris(alkylthioglycolate), dimethyltin bis(alkylthioglycolate) or bis(alkylthiopropionate); di-n-butyltin bis(alkylthioglycolate) or bis(alkylthiopropionate); bis(n-butoxycarbonylethyl)tin bis(alkylthioglycolate), and n-octyltin tris(isooctylthioglycolate) .
Typical sulfides are those of the formulae Vl and Vll, for example r~Bu ~ \ and r~ ;n - n~
Typical carboxylates are di-n-butyltin bis(methylmaleate), di-n-butyltin bis(butylmaleate) and polymeric di-n-butyltin maleate.
Preferably, in the compounds of the formulae I to IV:
R is C,-C12alkyl, R2, if Q is -S-, is C8-C,8alkyl or a radical -R~-Coo-R4, and R2, if Q is -O-CO-, is C7-C18alkyl, C8-C18alkenyl, phenyl, or a radical -CH=CH-Coo-R5, R~ is methylene, ethylene or o-phenylene, R4 is C5-C,8alkyl, 6 ~ 1 766~
R5 is C1-C,8alkyl or Cs-C7cycloalkyl, R6, if Q is -S-, is methylene, ethylene or o-phenylene, and R6, if Q is -O-CO-, is C,-C4alkylene, o-phenylene or a group -CH=CH-, R7 is C2-C4alkylene or is C4-C8alkylene interrupted by -O-, i is 1 or 2, j is a number from 1 to 6 and k is a number from 1 to 3.
Particularly preferably, in the compounds of the formulae I to IV:
R' is C3-Cgalkyl, R2, if Q is -S-, is a radical -R3-Coo-R4, and R2, if Q is -O-CO-, is C7-C"alkyl, or a radical -CH=CH-Coo-R5, R3is methylene or ethylene, R4is c8-c12alkyl1 R5is C,-C,8alkyl or cyclohexyl, R6, if Q is -S-, is methylene or ethylene, R5, if Q is -O-CO-, is a group -CH=CH-, R7is C2-H4- and i is 1 or 2, j is a number from 1 to 6 and k is a number from 1 to 3.
The substituents on the abovementioned groups -CH=CH- are particularly preferably in the cis position (Z configuration) and, in the compounds, are derived from maleic acid.
Very particular preference is given to compositions comprising, as compound(s) of com-ponent A), those of the formulae I and/or 111 in which R'is butyl or octyl, R3is-CH2-, R7is -C2H4- and R2, if Q is S, is -CH2-Coo-R4, where R4is c8-c12alkyll and R2, if Q is O-CO, is -CH=CH-Coo-R5, where R5is C,-C,8alkyl.
The proportion of component A) in the CPVC is preferably from 0.5 to 5% by weight, in particular from 1.5 to 2.5 % by weight, and that of component B) is preferably from 0.1 to 4% by weight, in particular from 0.5 to 1.5% by weight.
The compositions according to the invention preferably contain a mixture of compounds as component A). However, compositions containing only one compound as component A) are also part of the invention and have the same advantageous properties.
7 211~6~f~
From the chemistry of organotin stabilizers, it is known that these stabilizers are often no longer present in the stabilized substrate in the same form as that in which they were added. Usually, reaction (comproportionation) products are formed. The invention of course also embraces the compositions comprising such products formed from the compounds of component A).
Together with the compounds of component A) of the formulae I to Vll, it is also possible for the compositions according to the invention to contain further tin stabilizers, provided they do not impair the improved properties obtained by the abovementioned compounds. Pre-ference, however, is given to those compositions according to the invention which, other than the above-described organotin compounds of component A) and their comproportio-nation products, contain no other tin stabilizers.
The invention additionally provides for the use of the organotin compounds of component A) in combination with the oxides and/or hydroxides defined above as component B) for stabilizing CPVC. In this context, for example, 0.5 - 5 parts by weight of at least one of the organotin compounds defined above as component A), in combination with 0.1-4.0 parts by weight (per 100 parts by weight of CPVC) of at least one of the oxides or hydroxides of alkali metals or alkaline earth metals defined above as component B3 are added to 100 parts by weight of CPVC. To this extent, the invention also provides a method of stabilizing CPVC by the addition of the componants A) and B) defined at the outset.
The CPVC stabilized in accordance with the invention is ideally suited to processing by in-jection moulding. With this type of processing, the advantages are particularly evident. In particular, surprisingly good stabilization is achieved under high shear stress, thus enabling processing by the injection moulding technique to be carried out without any problems.
In addition to the stabilizer combination according to the invention, the CPVC can also com-prise other customary stabilizers.
Examples are antioxidants, perchlorates, fillers and reinforcing agents, metal soaps, beta-diketones (1,3-diketo compounds), zeolites, hydrotalcites, organophosphites, UV absorbers and light stabilizers, lubricants, dihydropyridines, sterically hindered amines (HALS), fatty acid esters, paraffins, blowing agents, fluorescent whiteners, pigments, flameproofing -8- 2 1 766~U
agents, antistatic agents"~-aminocrotonates (as mentioned for example in EP 0 465 405, p.6, lines 9-14), pyrroles (ibid.), naphthols, hydroxydiphenylamines, phenylindoles, phos-phates, thiophosphates, gelling aids, modifiers (for example impact modifiers), other metal stabilizers and complexing agents for Lewis acids.
The person skilled in the art is familiar with which substances belong to said groups. Some of those which may be mentioned by way of example are:
Perchlorates (or perchloric acid) are of the formula M(ClO4)n where M+ is H+, NH4+, Na+, K+, Mg2+, Ca2+, Ba2+ or Al3+. Depending on the valency of M, the index n is 1, 2 or 3.
In this context, the perchloric acid or respective perchlorate can be employed in a variety of common fomms, for example as a salt or aqueous solution applied to a carrier material, such as PVC, calcium silicate, zeolites or hydrotalcites, or bonded by chemical reaction into a hydrotalcite.
They can be employed in a quantity of, for example, from 0.001 to 5 parts by weight, advan-tageously from 0.01 to 3 parts by weight, particularly preferably from 0.01 to 2.0 parts by weight, based on 100 parts by weight of CPVC.
Examples of fillers are chalk, kaolin, china clay, talc, silicates, glass fibres, glass beads, wood flour, mica, carbon black, graphite, ground minerals or heavy spar. Talc and chalk are preferred.
The fillers can be employed in a quantity of preferably at least 1 part by weight, for example from 5 to 200 parts by weight, advantageously from 10 to 150 parts by weight and, in parti-cular, from 15 to 100 parts by weight, based on 100 parts by weight of CPVC.
Metal soaps are primarily metal carboxylates, preferably of relatively long-chain carboxylic acids. Common examples are stearates, laurates, and also oleates and salts of shorter-chain alkylcarboxylic acids. Use is often made of so-called synergistic mixtures, such as barium/zinc, magnesium/zinc, calcium/zinc or calcium/magnesium/zinc stabilizers. The metal soaps can be employed individually or in mixtures. A review of common metal soaps 9 2 i 7 66513 can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. Vol. A16 (1985) p.
361 .
Other metal stabilizers which may be mentioned are antimony stabilizers, for example those of the formula Sb(SCH2COO-isoctyl) (cf. US 4,743,640).
Possible ,B-diketones or 1,3-dicarbonyl compounds which may be used are linear or cyclic dicarbonyl compounds. Customary examples are given in "Plastics Additives", edited by R.
Gachter and H. Muller, Hanser Verlag, 3rd Edition, 1990, p. 306 ff. Examples of 1 ,3-dicar-bonyl compounds are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-2,4-heptanedione, benzoylacetone, di-benzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoyl-methane, isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis(4-methylbenzoyl)methane, benzoyl-p-chlorobenzoylmethane, bis(2-hydroxybenzoyl)-methane, 4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane, 1-benzoyl-1-acetylnonane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tert-butylbenzoyl)methane, benzoyl-formylmethane, benzoylphenylacetylmethane, bis(cyclo-hexanoyl)methane, di(pivaloyl)methane, methyl, ethyl, hexyl, octyl, dodecyl or octadecyl acetoacetate, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl benzoylacetate, ethyl, propyl, butyl, hexyl or octyl stearoylacetate, and dehydracetic acid and its zinc, calcium or magnesium salts.
The 1,3-diketo compounds can be employed in a quantity of, for example, from 0.01 to 10 parts by weight, advantageously from 0.01 to 3 parts by weight and, in particular, from 0.01 to 2 parts by weight, based on 100 parts by weight of CPVC.
Suitable antioxidants are primarily those containing a sterically hindered phenol group. The best-known example is 2,6-di-tert-butyl-4-methylphenol (BHT). Also worthy of mention are the esters of b-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, di-ethylene glycol, triethylene glycol, pentaerythritol, dipentaerythritol, tris-(hydroxyethyl) iso-cyanurate, N,N'-bis-(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, tri--10- 2 1 766~
methylhexanediol, trimethylolpropane, di-trimethylolpropane, and 4-hydroxymethyl-1-phos-pha-2,6,7-trioxabicyclol2.2.2]-octane.
The antioxidants can be employed in a quantity of, for example, from 0.01 to 10 parts by weight, advantageously from 0.1 to 10 parts by weight and, in particular, from 0.1 to 5 parts by weight, based on 100 parts by weight of CPVC.
Suitable UV absorbers and light stabilizers are primarily benzophenone derivatives and benzotriazole derivatives; known products can be found in "Plastics Additives" edited by R.
Gachter and H. Muller, Hanser Verlag, 3rd edition, 1990, p. 205 ff.
Examples of suitable lubricants are montan wax, fatty acid esters, complex esters, PE
waxes, amide waxes, chlorinated paraffins, glycerol esters and alkaline earth metal soaps.
Lubricants which can be used are also described in "Plastics Additives", edited by R. Gach-ter and H. Muller, Hanser Verlag, 3rd edition, 1990, chapter 6, pages 423-480 and in "Kunststoff Handbuch PVC" [Plastics handbook PVC] 2/1, 20th edition 1986, pp. 570-595.
Suitable organic phosphites are those of the general fommula P(OR')3 in which the radicals R' are identical or different alkyl, alkenyl, aryl or aralkyl radicals.
Particularly suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, tri-oleyl, triphenyl, tricresyl, tris-p-nonylphenyl or tricyclohexyl phosphite, and particular prefe-rence is given to the aryl dialkyl and the alkyl diaryl phosphites, for example phenyl didecyl phosphite, (2,4-di-tert-butylphenyl) didodecyl phosphite, (2,6-di-tert-butylphenyl) didodecyl phosphite, and the dialkyl and diaryl pentaerythritol diphosphites, such as distearyl penta-erythritol diphosphite, and also nonstoichiometric triaryl phosphites, for example those with the composition (H1gCg-C6H4)O1 5P(OC12/13H25/27)1 5. Preferred organic phosphites are di-stearyl pentaerythritol diphosphite, trisnonylphenyl phosphite and phenyl didecyl phosphite.
The organic phosphites can be employed in a quantity of, for example, from 0.01 to 10 parts by weight, advantageously from 0.05 to 5 parts by weight and, in particular, from 0.1 to 3 parts by weight, based on 100 parts by weight of CPVC.
2176~C
Suitable compounds from the series consisting of the hydrotalcites or zeolites are both the naturally occurring minerals and synthetic compounds. The additional use of hydrotalcites and/or zeolites in the compositions according to the invention is preferred since these com-pounds may synergistically increase the stabilizing effect.
The chemical composition of the hydrotalcites and zeolites is familiar to the person skilled in the art.
Examples of hydrotalcites are Al203.6MgO.C02. 1 2H20, Mg4,5AI2(0H)13.C03.3.5H20, 4MgO.AI203.C02.9H20, 4MgO.AI203.C02.6H20, ZnO.3MgO.AI203.CO2.8-9H20 or ZnO.3MgO.AI203.CO2.5-6H20 Examples of zeolites are sodium alumosilicates of the fommulae Na12AI12Si12048 . 27 H20 [zeolite A], Na6AI6Si6024 . 2 NaX . 7.5 H20, where X = OH, halogen or Cl04 [sodalite]
Na6AI6Si30072 . 24 H20, Na8AI8Si40096 . 24 H20, Na,6AI16Si24080 . 16 H20, Na16AI16Si32096 . 16 H20, Na56AI56Si1360384 . 250 H20, [zeolite Y]
N~6AIOGSj1060384 . 264 H20 [zeolite X]
or the zeolites which can be prepared by complete or partial substitution of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na,K),OAl,OSi22064 . 20 H20 Ca4sNa3[(AI02),2(SiO2),2] . 30 H20 -12- i 1 /6~0 KgNa:3[(AI02),2(SiO2),2] . 27 H20.
The hydrotalcites and/or zeolites can be employed in quantities of, for example, from 0.1 to 20 parts by weight, advantageously from 0.1 to 10 parts by weight and, in particular, from 0.1 to 5 parts by weight, based on 100 parts by weight of CPVC.
The compositions according to the invention are prepared by known methods. The stabili-zers are admixed with the CPVC in a known manner prior to processing. A homogeneous mixture can be obtained prior to processing, for example, with the aid of a heating-cooling mixer, customarily at up to 120C in the heating phase.
The examples which follow illustrate the invention in more detail without limiting it. As in the rest of the description, parts and percentages are by weight unless stated otherwise.
Example:
57 9 of the CPVC compound (composition according to Table 1) are subjected, in the knea-ding chamber of a Brabender Plasticorder at 35 rpm, to thermal (1 90C) and fricative stress, i.e. by shear forces. At 5-minute intervals, samples of the plasticated CPVC mass are with-drawn and are subsequently compression-moulded at 1 80C for 1.5 minutes to fomm test specimens. The yellowness index (Yl; DIN 5033, ASTM 1925-70) of these samples is deter-mined by colorimetric determination. Low yellowness indices denote good stabilizer action.
In addition, the long-term thermal stability of the samples is characterized by the period of time until there is a rise in the torque, caused by crosslinking of the polymer material (Bra-bender decomposition time). Long decomposition times, accordingly, denote good stabiliza-tion. The results are summarized in Table I below. It is evident that stabilization with the organotin compound and CaO is superior to that with the organotin compound alone.
-13- 2 1 7 665~
Table l: Brabender Heat test at 1 90C
Mixture 1 2 Acrylate impact modifier 3 3 PMMA flow aid 1.5 1.5 Partially oxidized PE wax 0.6 0.6 Fatty acid ester 0.6 0.6 TiO2 0.5 0.5 Calcium stearate 0.5 0.5 Organotinmercaptide') 0.8 0.8 Calcium oxide -- 1.0 Brabender decomposition time [minutes] 42 56 Yl after 15 minutes 20.7 20.7 Yl after 20 minutes 26.1 23.6 Yl after 25 minutes 31.0 28.2 Yl after30 minutes 38.5 35.1 Yl after 35 minutes 53.4 42.4 1)Mixture of 70 parts by weight of (C4H9)2Sn[SCH2COO-CH2CH(C2Hs)c4H9]2 and 30 parts by weight of C4HgSn[SCH2COO-CH2CH(C2H5)C4Hg]3
Claims (9)
1. A composition comprising chlorinated PVC (CPVC) and as stabilizer combinationA) at least one organotin compound of one of the formulae I to VII
(I) (II) (III) (IV) (V) RpSnSq (VI) or [RpSnSq]?, (VII) in which R and R1 independently of one another are C1-C12alkyl or C3-C11alkoxycarbonyl-ethyl, Q is -S- or-O-CO-, and R, if Q is -S-, is Ca-C18alkyl or a radical -R3-COO-R4 or -R3-O-CO-R4, and R, if Q is -O-CO-, is C1-C18alkyl, C2-C18alkenyl, phenyl, C1-C4alkyl substituted phenyl, or a radical -CH=CH-COO-R5, R3 is methylene, ethylene or o-phenylene, R4 is C5-C18alkyl, R5 is C1-C18alkyl, C5-C7cycloalkyl or benzyl, R6, if Q is -S-, is methylene, ethylene or o-phenylene, and R6, if Q is -O-CO-, is C1-C8alkylene, o-phenylene or a group -CH=CH-, R7 is C2-C4alkylene or is C4-C8alkylene interrupted by -O-, R8 is C1-C18alkyl, C2-C18alkenyl, phenyl, C1-C4alkyl-substituted phenyl, or a radical -CH=CH-COO-R5, X independently at each occurrence is -O- or -O-CO-R9-COO-, R9 is C1-C8alkylene, o-phenylene or a group -CH=CH-, p is 1 or 2,q is(4-p)/2,and r>1, i is 1 or 2, j is a number from 1 to 6, k is a number from 1 to 3 and m is a number from 1 to 4, and B) at least one oxide and/or hydroxide of an alkali metal or alkaline earth metal.
(I) (II) (III) (IV) (V) RpSnSq (VI) or [RpSnSq]?, (VII) in which R and R1 independently of one another are C1-C12alkyl or C3-C11alkoxycarbonyl-ethyl, Q is -S- or-O-CO-, and R, if Q is -S-, is Ca-C18alkyl or a radical -R3-COO-R4 or -R3-O-CO-R4, and R, if Q is -O-CO-, is C1-C18alkyl, C2-C18alkenyl, phenyl, C1-C4alkyl substituted phenyl, or a radical -CH=CH-COO-R5, R3 is methylene, ethylene or o-phenylene, R4 is C5-C18alkyl, R5 is C1-C18alkyl, C5-C7cycloalkyl or benzyl, R6, if Q is -S-, is methylene, ethylene or o-phenylene, and R6, if Q is -O-CO-, is C1-C8alkylene, o-phenylene or a group -CH=CH-, R7 is C2-C4alkylene or is C4-C8alkylene interrupted by -O-, R8 is C1-C18alkyl, C2-C18alkenyl, phenyl, C1-C4alkyl-substituted phenyl, or a radical -CH=CH-COO-R5, X independently at each occurrence is -O- or -O-CO-R9-COO-, R9 is C1-C8alkylene, o-phenylene or a group -CH=CH-, p is 1 or 2,q is(4-p)/2,and r>1, i is 1 or 2, j is a number from 1 to 6, k is a number from 1 to 3 and m is a number from 1 to 4, and B) at least one oxide and/or hydroxide of an alkali metal or alkaline earth metal.
2. A composition according to claim 1, wherein in the compounds of the formulae I to IV
R1 is C1-C12alkyl, R, if Q is -S-, is C8-C18alkyl or a radical -R3-COO-R4, and R, if Q is -O-CO-, is C7-C18alkyl, C8-C18alkenyl, phenyl, or a radical -CH=CH-COO-R5, R3 is methylene, ethylene or o-phenylene, R4 is C5-C18alkyl, R5 is C1-C18alkyl or C5-C7cycloalkyl, R6, if Q is -S-, is methylene, ethylene or o-phenylene, and R6, if Q is -O-CO-, is C1-C4alkylene, o-phenylene or a group -CH=CH-, R7 is C2-C4alkylene or is C4-C8alkylene interrupted by -O-, and i is 1 or 2, j is a number from 1 to 6 and k is a number from 1 to 3.
R1 is C1-C12alkyl, R, if Q is -S-, is C8-C18alkyl or a radical -R3-COO-R4, and R, if Q is -O-CO-, is C7-C18alkyl, C8-C18alkenyl, phenyl, or a radical -CH=CH-COO-R5, R3 is methylene, ethylene or o-phenylene, R4 is C5-C18alkyl, R5 is C1-C18alkyl or C5-C7cycloalkyl, R6, if Q is -S-, is methylene, ethylene or o-phenylene, and R6, if Q is -O-CO-, is C1-C4alkylene, o-phenylene or a group -CH=CH-, R7 is C2-C4alkylene or is C4-C8alkylene interrupted by -O-, and i is 1 or 2, j is a number from 1 to 6 and k is a number from 1 to 3.
3. A composition according to claim 1, wherein in the compounds of the formulae I to IV
R1 is C3-C9alkyl, R, if Q is -S-, is a radical -R3-COO-R4, and R, if Q is -O-CO-, is C7-C11alkyl, or a radical -CH=CH-COO-R5, R3 is methylene or ethylene, R4 is C8-C12alkyl, R5 is C1-C18alkyl or cyclohexyl, R6, if Q is -S-, is methylene or ethylene, R6, if Q is -O-CO-, is a group -CH=CH-, R7 is C2-H4-and i is 1 or 2, j is a number from 1 to 6 and k is a number from 1 to 3.
R1 is C3-C9alkyl, R, if Q is -S-, is a radical -R3-COO-R4, and R, if Q is -O-CO-, is C7-C11alkyl, or a radical -CH=CH-COO-R5, R3 is methylene or ethylene, R4 is C8-C12alkyl, R5 is C1-C18alkyl or cyclohexyl, R6, if Q is -S-, is methylene or ethylene, R6, if Q is -O-CO-, is a group -CH=CH-, R7 is C2-H4-and i is 1 or 2, j is a number from 1 to 6 and k is a number from 1 to 3.
4. A composition according to claim 1, which comprises, as compound(s) of component A), those of the formulae I and/or III in which R1 is butyl or octyl, R3 is-CH2-, R7 is -C2H4- and R, if Q is S, is -CH2-COO-R4, where R4 is C8-C12alkyl, and R, if Q is O-CO, is-CH=CH-COO-R5, where R5 is C1-C18alkyl.
5. A composition according to claim 1, comprising as component B) at least one of the substances CaO, Ca(OH)2, MgO and Mg(OH)2.
6. A composition according to claim 1, where the proportion of component A) in the CPVC
is from 0.5 to 5% by weight (based on CPVC) and the proportion of component B) in the CPVC is from 0.1 to 4% by weight (based on CPVC).
is from 0.5 to 5% by weight (based on CPVC) and the proportion of component B) in the CPVC is from 0.1 to 4% by weight (based on CPVC).
7. A composition according to claim 1, where the proportion of component A) in the CPVC
is from 1.5 to 2.5% by weight (based on CPVC) and the proportion of component B) in the CPVC is from 0.5 to 1.5% by weight (based on CPVC).
is from 1.5 to 2.5% by weight (based on CPVC) and the proportion of component B) in the CPVC is from 0.5 to 1.5% by weight (based on CPVC).
8. A stabilizer combination for CPVC, comprising the components A) and B) described in claim 1.
9. A method of stabilizing CPVC by adding a stabilizer combination according to claim 8.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH145895 | 1995-05-17 | ||
| CH1458/95 | 1995-05-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2176650A1 true CA2176650A1 (en) | 1996-11-18 |
Family
ID=4210945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002176650A Abandoned CA2176650A1 (en) | 1995-05-17 | 1996-05-15 | Stabilized cpvc (chlorinated pvc) |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0743339B1 (en) |
| JP (1) | JPH08311286A (en) |
| BR (1) | BR9602295A (en) |
| CA (1) | CA2176650A1 (en) |
| DE (1) | DE59602223D1 (en) |
| DK (1) | DK0743339T3 (en) |
| ES (1) | ES2135862T3 (en) |
| IL (1) | IL118261A0 (en) |
| NO (1) | NO310662B1 (en) |
| TW (1) | TW527389B (en) |
| ZA (1) | ZA963898B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6306950B1 (en) | 1997-12-03 | 2001-10-23 | Kaneka Corporation | Chlorinated vinyl chloride resin composition |
| EP2310451A2 (en) * | 2008-08-05 | 2011-04-20 | PolyOne Corporation | High flow polyvinyl halide compound and methods of making and using same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19914798A1 (en) * | 1999-03-31 | 2000-10-05 | Baerlocher Gmbh | Stabilizer combination for halogenated thermoplastic resin, e.g. rigid polyvinyl chloride for outdoor use, comprises calcium (hydr)oxide, organo-tin compound with organyloxy or organylthio groups and zinc compound |
| WO2019161884A1 (en) | 2018-02-20 | 2019-08-29 | Emery Oleochemicals Gmbh | Lubricant for processing chlorinated polyvinylchloride |
| CN116162189A (en) * | 2019-03-29 | 2023-05-26 | 积水化学工业株式会社 | Chlorinated polyvinyl chloride resin |
| WO2020203858A1 (en) * | 2019-03-29 | 2020-10-08 | 積水化学工業株式会社 | Chlorinated vinyl chloride resin |
| JP7016992B1 (en) | 2020-03-31 | 2022-02-07 | 積水化学工業株式会社 | Chlorinated vinyl chloride resin |
| JP7221396B2 (en) | 2020-03-31 | 2023-02-13 | 積水化学工業株式会社 | Chlorinated vinyl chloride resin |
| US20230128429A1 (en) | 2020-03-31 | 2023-04-27 | Sekisui Chemical Co., Ltd. | Chlorinated vinyl chloride-based resin |
| KR20220162731A (en) | 2020-03-31 | 2022-12-08 | 세키스이가가쿠 고교가부시키가이샤 | Chlorinated vinyl chloride resin |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1229521A (en) * | 1968-09-16 | 1971-04-21 | ||
| GB1229522A (en) * | 1968-09-16 | 1971-04-21 | ||
| GB1392092A (en) * | 1971-02-18 | 1975-04-23 | Dart Ind Inc | Organotin stabilizer systems |
| JPH0236146B2 (en) * | 1982-12-27 | 1990-08-15 | Adeka Argus Chemical Co Ltd | ENSOKAENKABINIRUJUSHISOSEIBUTSU |
| US5030676A (en) * | 1989-07-14 | 1991-07-09 | Certainteed Corporation | UV light stabilized polyvinyl chloride composition |
| ATE178341T1 (en) * | 1993-12-14 | 1999-04-15 | Witco Vinyl Additives Gmbh | STABILIZER FOR POLYMERS CONTAINING CHLORINE |
-
1996
- 1996-05-06 EP EP96810294A patent/EP0743339B1/en not_active Expired - Lifetime
- 1996-05-06 ES ES96810294T patent/ES2135862T3/en not_active Expired - Lifetime
- 1996-05-06 DE DE59602223T patent/DE59602223D1/en not_active Expired - Fee Related
- 1996-05-06 DK DK96810294T patent/DK0743339T3/en active
- 1996-05-11 TW TW085105582A patent/TW527389B/en not_active IP Right Cessation
- 1996-05-15 NO NO19962009A patent/NO310662B1/en unknown
- 1996-05-15 IL IL11826196A patent/IL118261A0/en unknown
- 1996-05-15 CA CA002176650A patent/CA2176650A1/en not_active Abandoned
- 1996-05-16 BR BR9602295A patent/BR9602295A/en not_active Application Discontinuation
- 1996-05-16 ZA ZA963898A patent/ZA963898B/en unknown
- 1996-05-17 JP JP8148040A patent/JPH08311286A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6306950B1 (en) | 1997-12-03 | 2001-10-23 | Kaneka Corporation | Chlorinated vinyl chloride resin composition |
| EP2310451A2 (en) * | 2008-08-05 | 2011-04-20 | PolyOne Corporation | High flow polyvinyl halide compound and methods of making and using same |
| EP2310451A4 (en) * | 2008-08-05 | 2013-12-18 | Polyone Corp | High flow polyvinyl halide compound and methods of making and using same |
Also Published As
| Publication number | Publication date |
|---|---|
| NO962009D0 (en) | 1996-05-15 |
| DE59602223D1 (en) | 1999-07-22 |
| TW527389B (en) | 2003-04-11 |
| ES2135862T3 (en) | 1999-11-01 |
| NO962009L (en) | 1996-11-18 |
| IL118261A0 (en) | 1996-09-12 |
| ZA963898B (en) | 1996-11-18 |
| EP0743339A1 (en) | 1996-11-20 |
| EP0743339B1 (en) | 1999-06-16 |
| JPH08311286A (en) | 1996-11-26 |
| DK0743339T3 (en) | 1999-11-22 |
| BR9602295A (en) | 1998-01-13 |
| NO310662B1 (en) | 2001-08-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |