GB1570178A - Compositions for stabilisation of vinyl chloride polymers - Google Patents
Compositions for stabilisation of vinyl chloride polymers Download PDFInfo
- Publication number
- GB1570178A GB1570178A GB20759/79A GB2075979A GB1570178A GB 1570178 A GB1570178 A GB 1570178A GB 20759/79 A GB20759/79 A GB 20759/79A GB 2075979 A GB2075979 A GB 2075979A GB 1570178 A GB1570178 A GB 1570178A
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- United Kingdom
- Prior art keywords
- composition according
- source
- calcium carbonate
- vinyl chloride
- lead
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 61
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 22
- 229920000642 polymer Polymers 0.000 title claims description 21
- 230000006641 stabilisation Effects 0.000 title description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000012188 paraffin wax Substances 0.000 claims description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- 239000004608 Heat Stabiliser Substances 0.000 claims description 15
- 150000002611 lead compounds Chemical class 0.000 claims description 15
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 11
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical group [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 8
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims description 6
- 239000004135 Bone phosphate Substances 0.000 claims description 6
- QKUNKVYPGIOQNP-UHFFFAOYSA-N 4,8,11,14,17,21-hexachlorotetracosane Chemical compound CCCC(Cl)CCCC(Cl)CCC(Cl)CCC(Cl)CCC(Cl)CCCC(Cl)CCC QKUNKVYPGIOQNP-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001260 acyclic compounds Chemical class 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 150000001923 cyclic compounds Chemical class 0.000 claims description 4
- 239000012765 fibrous filler Substances 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- QZFAGHFGBLEISM-DBQHITQZSA-N 3-[(1r)-1-hydroxy-2-(methylamino)ethyl]phenol;4-[1-hydroxy-2-(propan-2-ylamino)butyl]benzene-1,2-diol;dihydrochloride Chemical compound Cl.Cl.CNC[C@H](O)C1=CC=CC(O)=C1.CC(C)NC(CC)C(O)C1=CC=C(O)C(O)=C1 QZFAGHFGBLEISM-DBQHITQZSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000003019 stabilising effect Effects 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 description 28
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 2
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- XIWRCSVXKPGGAJ-UHFFFAOYSA-N 1-(5-tert-butyl-2-phenylpyrazol-3-yl)-3-(4-chlorophenyl)urea Chemical compound C=1C=CC=CC=1N1N=C(C(C)(C)C)C=C1NC(=O)NC1=CC=C(Cl)C=C1 XIWRCSVXKPGGAJ-UHFFFAOYSA-N 0.000 description 1
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 150000005006 2-aminopyrimidines Chemical class 0.000 description 1
- BJEXWFRASFTKNJ-UHFFFAOYSA-N 2-anilinoguanidine Chemical compound NC(=N)NNC1=CC=CC=C1 BJEXWFRASFTKNJ-UHFFFAOYSA-N 0.000 description 1
- GGHBKCSNURXPNB-UHFFFAOYSA-N 2-n,4-n,6-n-triphenyl-1,3,5-triazine-2,4,6-triamine Chemical compound N=1C(NC=2C=CC=CC=2)=NC(NC=2C=CC=CC=2)=NC=1NC1=CC=CC=C1 GGHBKCSNURXPNB-UHFFFAOYSA-N 0.000 description 1
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 1
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IJFPVINAQGWBRJ-UHFFFAOYSA-N Diisooctyl phthalate Chemical compound CC(C)CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC(C)C IJFPVINAQGWBRJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- HMOHOVASWYMMHA-UHFFFAOYSA-L barium(2+);diphenoxide Chemical compound [Ba+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 HMOHOVASWYMMHA-UHFFFAOYSA-L 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940065285 cadmium compound Drugs 0.000 description 1
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 description 1
- RXROCZREIWVERD-UHFFFAOYSA-L cadmium(2+);2-ethylhexanoate Chemical compound [Cd+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O RXROCZREIWVERD-UHFFFAOYSA-L 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LUPKFGPEBRKPGP-UHFFFAOYSA-N ethyl (ne)-n-[amino-(cyanoamino)methylidene]carbamate Chemical compound CCOC(=O)NC(=N)NC#N LUPKFGPEBRKPGP-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NGGXACLSAZXJGM-UHFFFAOYSA-N n-(diaminomethylidene)acetamide Chemical compound CC(=O)N=C(N)N NGGXACLSAZXJGM-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229940100888 zinc compound Drugs 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/10—Metal compounds
- C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
(54) COMPOSITION FOR STABILISATION OF VINYL
CHLORIDE POLYMERS
(71) We, DURHAM CHEMICALS LIMITED, a British Company of
Birtley, Chester-Le-Street, County Durham, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a composition for the stabilisation of vinyl chloride polymers.
Our co-pending Patent Application No. 42642/75 (Serial No. 1,570,177) describes and claims stablised vinyl chloride polymer compositions comprising
(a) a vinyl chloride polymer
(b) an ester which is a plasticiser for vinyl chloride polymers
(c) a chlorinated paraffin which is a plasticiser for vinyl chloride polymers
(d) a metal compound which is a heat stabiliser for vinyl chloride polymers
(e) a non-fibrous filler, and
(f) a stabiliser which is an organic nitrogen-containing compound.
The present invention provides a stabilising composition for use in the production of a stabilised vinyl chloride polymer composition including a chlorinated paraffin plasticiser and a non-fibrous filler, comprising
(1) an organic nitrogen containing compound and
(2) a poly basic inorganic lead compound which is a heat stabiliser for a vinyl
chloride polymer, the weight ratio of the lead compound to the organic nitrogen-containing compound being 4:1 to 100:1.
Suitable nitrogen containing compounds include: 1. alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, mono-, di- and tri-propanolamines and butanolamines; 2. urea: quinolines such as a hydroxy-quinoline e.g. 8-hydroxy quinoline or 2,2,4 trimethyl-l ,2-dihydroxy quinoline (Flectrol H); intercyclic dicarboxylic acid amides such as phthalimide; or Chloramine -T, (sodium p-toluene-sulphochloramine); and 3. cyclic or acyclic compounds containing the molecular grouping
This last-mentioned class of compounds (3) represents a preferred class of organic nitrogen containing compound and includes, as cyclic compounds, the various nitrogen substituted triazines such as melamine, dimers and trimers of melamine (melam and melem), N,N',N"-triphenylmelamine; 2-aminopyrimidines, an imidazole such as 2-aminoimidazole and 1,2-dimethylimidazole; acyclic compounds which can be used include the various guanidines or dicyandiamides such as dicyandiamide itself, diphenylguanidine, acetylguanidine, aminoguanidine, phenylaminoguanidine, N-oxymethyl N'-cyanguanidine, N-carboethoxy N'cyanguanidine and N-methylguanidine. Aromatic amines, alkylamines and thioureas are not recommended as they do not always have a beneficial influence on both colour and heat stability of the composition.
The polybasic inorganic lead compound used in the composition of the invention will normally be a tribasic lead sulphate. Other inorganic leads such as white lead or dibasic lead phosphite may also be used.
The composition may additionally contain at least one further heat stabiliser for the vinyl chloride polymer which is an organic lead compound or a barium, cadmium, calcium, zinc or tin containing compound, the weight ratio of the total heat stabiliser to the organic nitrogen containing compound being 4:1 to 100:1. The further heat stabiliser may be, for example, (I) organic lead compounds such as dibasic lead phthalate; (2) metal soaps such as lead stearate, barium stearate, cadmium stearate, calcium stearate or zinc stearate; (3) solvent soluble compounds such as barium phenolate or cadmium 2-ethylhexanoate or (4) organo-tin compounds such as dibutyl tin maleate or di-n-octyl tin thioglycollate.The lead compounds will normally be present in amounts of 110%, preferably 15% by weight of the vinyl chloride polymer, and, when used, the barium, cadmium, calcium or zinc compounds in an amount of 13% by weight of the vinyl chloride polymer and the tin compounds in an amount of 0.5 to 2% by weight of the vinyl chloride polymer. Heat stabilisers (I) identified above are to be preferred, particularly a mixture of tribasic lead sulphate and lead stearate.
It is essential that the weight ratio of the heat stabiliser present in the composition to the organic nitrogen containing compound present in the composition be 4:1 to 100:1, preferably 10:1 to 25:1 e.g. 20:1.
The composition of this invention is prepared by mixing the organic nitrogen containing compound with the polybasic inorganic lead compound and the resulting composition can then be incorporated in a vinyl chloride polymer together with the two plasticisers, the filler and any optional components to form the composition of the parent application.
The following Examples are given to illustrate the invention.
EXAMPLES 1--6 and EXPERIMENTS A-B.
Compositions were prepared by compounding the ingredients given in Table I below in the proportions given in Table 1 below in the following way.
The ingredients of each formulation were weighed into a beaker and mixed with a palette knife. The contents of the beaker were then transferred onto a 2 roll mill operating at 1700C., from which after gelation and mixing for 3 minutes the composition was removed as a sheet. From this specimens were cut for heat stability tests. The PVC resin used was a vinyl chloride homopolymer which is a cable grade resin sold under the Registered Trade Mark Corvic D60/13. D.I.O.P. is an ester plasticiser di-isooctylphthalate. The chlorinated paraffin used, Cereclor
S45 is a chlorinated paraffin containing 45% by weight chlorine of approximate molecular weight 610.
T.B.L.S./lead stearate 4:1 is a mixture of tribasic lead sulphate and lead stearate in a 4:1 ratio by weight. Bisphenol A is the known antioxidant 2,2-(bis-phydroxyphenyl)-propane. In the Table below, the amounts given are in parts by weight. Experiments A-B are not in accordance with the invention and are included for comparison purposes.
TABLE 1
Expt. Expt.
Example A 1 B 2 3 4 5 6 PVC Resin 100 100 100 100 100 100 100 100 Calcium Carbonate 50 50 50 50 50 50 50 50 D.I.O.P. 28 28 28 28 28 28 28 28 Cereclor S45 28 28 28 28 28 28 28 28 TBLS/Lead Stearate 4:1 5 5 4.5 4.5 4.5 4.33 4.33 4.33 Bisphenol A 0.5 0.25 0.25 0.42 0.42 0.42 Triethanolamine 0.25 0.25 Melamine 0.25 0.25 0.5 Dicyandiamide 0.25 The compositions formulated as indicated above were then subjected to a heat stability test. In this test, the specimens were placed in an oven and @eated at 180 C., and were removed at 15 minute intervals and examined for general discolouration (yellowing) and for the appearance of spots. The samples were assessed visually on each occasion and given a discolouration index on a scale of 0 (white sample no discolouration) to 10 (sample completely black). The following results set out in Table 1A were obtained.
TABLE 1A
I o Time mins.
Example 0 15 30 45 60 75 90 105 120 135 150 165 180 A 0 1 2X 4XX 5XXX 7XXXX 1 0 0 1 2X 3X 3X 4X 6XX 6XX 7XX 7XXX v, X m 0 0 1 1 2 2 2 4 oXo oo x ro4 xx x x 5 0 0 1 1 2 3 3 4 6 8 9 -- x o x x bo tx x > ux) x w7 x x x N x x vr vx} mx f x t x esx x N > n O X X , b1 m H o o o H o o < ev C~ o o o o o o o o / E < < m g t m ç X = slightly spotty
XX = spotty
XXX = very spotty
XXXX = almost completely covered by spots These results show that the presence of the chlorinated paraffin plasticiser leads to a very rapid discolouration and spotting of the samples while the spotting problem is eliminated substantially completely and the discolouration occurs much more slowly when the organic nitrogen containing compound is included in the composition.
In addition to exhibiting the favourable heat stability as illustrated above, the compositions of the invention show a significant improvement in stability as measured by the congo red test which is particularly important in compositions to be used in cable making.
EXAMPLES 724 and EXPERIMENTS C-M.
In these Experiments, further information about certain components is given after Experiment M.
EXPERIMENT C
The following components were formulated into test specimens as described in
Examples 1--6.
PVC resin (source (i)) 100 gm.
Diisooctyl phthalate (D.I.O.P.) 50 gm.
Calcium Carbonate (source 1) 50 gm.
Tribasic lead sulphate (T.B.L.S.)/lead stearate 4:1 blend 4.75 gm.
2,2-(bis-p-hydroxyphenyl)propane 0.25 gm.
The specimens were then cut for heat stability and congo red tests.
EXPERIMENT D
The procedure of Experiment C was repeated but part of the D.I.O.P. was replaced by chlorinated paraffin and the quantities adjusted to give a similar plasticising effect. The composition was as follows:
PVC resin (source (i)) 100 gm.
D.I.O.P. 28 gm.
Chlorinated paraffin (source A) 28 gm.
Calcium carbonate (source 1) 50 gm.
T.B.L.S./1ead stearate, 4:1 blend 4.75 gm.
2,2-(bis-p-hydroxyphenyl)propane 0.25 gm.
EXAMPLES 7718.
Specimens were prepared as described in Experiment D but with the following modifications and additions. Unless otherwise indicated the procedure, components and proportions are as in Experiment D.
Weight of 4:1
TBLS/lead stearate N compound
Example mixture
7 4.5 g. 0.1 g. triethanolamine
8 4.5 g. 0.25 g. triethanolamine
9 4.5 g. 0.5 g. triethanolamine
10 4.5 g. 0.75 g. triethanolamine
11 4.5 g. 0.1 g. melamine
12 4.5 g. 0.25 g. melamine
13 4.5 g. 0.5 g. melamine
14 4.5 g. 0.75 g. melamine
15 4.5 g. 0.25 g. urea
16 4.5 g. 0.25 g. Flectol H
(2,2,4-trimethyl-1,2-dihydroxy
quinoline)
17 4.5 g. 0.25 g. 1,2-dimethylimidazole
18 4.5 g. 0.25 g. diethanolamine (Flectol is a Registered Trade Mark)
EXPERIMENT E
The procedure of Experiment C was repeated using the following composition:
PVC resin (source (i)) 100 gm.
D.I.O.P. * 28 gm.
Chlorinated paraffin (source A) 28 gm.
Calcium carbonate (source 2) 50 gm.
T.B.L.S./lead stearate 4:1 blend 4.75 gm.
2,2-(bis-p-hydroxyphenyl)propane 0.25 gm.
EXPERIMENT 19
The procedure of Example C was repeated using the following composition:
PVC resin (source (i)) 100 gm.
D.I.O.P. 28 gm.
Chlorinated paraffin (source A) 28 gm.
Calcium carbonate (source 2) 50 gm.
T.B.L.S./lead stearate 4:1 blend 4.5 gm.
2,2-(bis-p-hydroxyphenyl)-propane 0.25 gm.
Triethanolamine 0.25 gm.
EXPERIMENT F
Experiment E was repeated but calcium carbonate (source 3) was used as the filler.
EXAMPLE 20.
Example 19 was repeated but calcium carbonate (source 3) was used as the filler.
EXPERIMENT G Experiment E was repeated but china clay was used as the filler.
EXAMPLE 21.
Example 19 was repeated but china clay was used as the filler.
EXPERIMENT H
Experiment D was repeated but chlorinated paraffin (source B) was substituted for chlorinated paraffin (source A).
EXAMPLE 22.
Example 12 was repeated but chlorinated paraffin (source B) was substituted for chlorinated paraffin (source A).
EXPERIMENT J
Experiment D was repeated but with the substitution of PVC resin (source (ii)) in place of PVC resin (source (i)).
EXAMPLE 23.
Example 8 was repeated but with the substitution of PVC resin (source (ii)) in place of PVC resin (source (i)).
EXPERIMENT K Experiment D was repeated but with the substitution of PVC resin (source (iii)) in place of PVC resin (source (i)).
EXAMPLE 24.
Example 8 was repeated but with the substitution of PVC resin (source (iii)) in place of PVC resin (source (i)).
EXPERIMENT L
Experiment C was repeated using the following composition:
PVC resin (source (i)) 100 gm.
D.I.O.P. 50 gm.
Calcium carbonate (source l) 50 gm.
T.B.L.S./leadstearate4:1 blend 4.5 gm.
2,2-(bis-p-hydroxyphenyl)-propane 0.25 gm.
Triethanolamine 0.25 gm.
EXPERIMENT M
Experiment L was repeated but with the substitution of melamine for triethanolamine.
The origin of various components in Examples 7-24 and Experiments C-M is given below.
PVC source (i) Corvic D60/13 ex I.C.I. Ltd.
PVC source (ii) Scon 5410 ex Vinatex Ltd.
PVC source (iii) Breon S125/l0 ex B.P. Chemicals Ltd.
Calcium carbonate source 1 Snowcal 6ML ground natural calcium
carbonate ex Cement Marketing Co. Ltd.
Calcium carbonate source 2 Winnofil S precipitated coated calcium
carbonate ex I.C.I. Ltd.
Calcium carbonate source 3 Polycarb S ground coated natural
calcium carbonate ex English China
Clays Ltd.
China clay M l00 ex English China Clays Ltd.
Chlorinated paraffin
Source A Cereclor S45 ex I.C.I. Ltd.
Chlorinated paraffin
Source B Chloroparaffin 45 ex Hoechst.
Scon, Breon, Polycarb, Snowcal and Winnofil are all Registered Trade Marks.
WHAT WE CLAIM IS:
1. A stabilising composition for use in the production of a stabilised vinyl chloride polymer composition including a chlorinated paraffin plasticiser and a non-fibrous filler, comprising (l) an organic nitrogen containing compound and
(2) a poly basic inorganic lead compound which is a heat stabiliser for a vinyl chloride polymer, the weight rafio of the lead compound to the organic nitrogen-containing compound being 4:1 to 100:1.
2. A composition according to claim 1 wherein the ratio is 10:1 to 25:1.
3. A composition according to claim 1 or 2 wherein Component (1) is an alkanolamine.
4. A composition according to claim 3 wherein the alkanolamine is triethanolamine.
5. A composition according to claim 1 or 2 wherein Component (1) is a cyclic or acyclic compound containing the molecular grouping
6. A composition according to claim 5 wherein Component (1) is melamine.
7. A composition according to claim 5 wherein Component (l) is an imidazole or a guanidine.
8. A composition according to claim 1 or 2 wherein Component (l) is urea or a hydroxy quinoline.
9. A composition according to any one of the preceding claims wherein the lead compound is tribasic lead sulphate.
10. A composition according to any one of the preceding claims wherein the composition additionally contains at least one further heat stabiliser for the vinyl chloride polymer which is an organic lead compound or is a barium, cadmium,
calcium, zinc or tin containing compound, the weight ratio of total heat stabiliser to the organic nitrogen containing compound being 4:1 to 100:1.
11. A composition according to claim 10 wherein the further heat stabiliser is lead stearate.
12. A composition according to claim l substantially as hereinbefore described with reference to any one of the Examples.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (12)
1. A stabilising composition for use in the production of a stabilised vinyl chloride polymer composition including a chlorinated paraffin plasticiser and a non-fibrous filler, comprising (l) an organic nitrogen containing compound and
(2) a poly basic inorganic lead compound which is a heat stabiliser for a vinyl chloride polymer, the weight rafio of the lead compound to the organic nitrogen-containing compound being 4:1 to 100:1.
2. A composition according to claim 1 wherein the ratio is 10:1 to 25:1.
3. A composition according to claim 1 or 2 wherein Component (1) is an alkanolamine.
4. A composition according to claim 3 wherein the alkanolamine is triethanolamine.
5. A composition according to claim 1 or 2 wherein Component (1) is a cyclic or acyclic compound containing the molecular grouping
6. A composition according to claim 5 wherein Component (1) is melamine.
7. A composition according to claim 5 wherein Component (l) is an imidazole or a guanidine.
8. A composition according to claim 1 or 2 wherein Component (l) is urea or a hydroxy quinoline.
9. A composition according to any one of the preceding claims wherein the lead compound is tribasic lead sulphate.
10. A composition according to any one of the preceding claims wherein the composition additionally contains at least one further heat stabiliser for the vinyl chloride polymer which is an organic lead compound or is a barium, cadmium,
calcium, zinc or tin containing compound, the weight ratio of total heat stabiliser to the organic nitrogen containing compound being 4:1 to 100:1.
11. A composition according to claim 10 wherein the further heat stabiliser is lead stearate.
12. A composition according to claim l substantially as hereinbefore described with reference to any one of the Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB20759/79A GB1570178A (en) | 1976-10-15 | 1976-10-15 | Compositions for stabilisation of vinyl chloride polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB20759/79A GB1570178A (en) | 1976-10-15 | 1976-10-15 | Compositions for stabilisation of vinyl chloride polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1570178A true GB1570178A (en) | 1980-06-25 |
Family
ID=10151186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB20759/79A Expired GB1570178A (en) | 1976-10-15 | 1976-10-15 | Compositions for stabilisation of vinyl chloride polymers |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1570178A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0524513A2 (en) * | 1991-07-26 | 1993-01-27 | BASF Aktiengesellschaft | Aqueous polymer dispersions |
-
1976
- 1976-10-15 GB GB20759/79A patent/GB1570178A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0524513A2 (en) * | 1991-07-26 | 1993-01-27 | BASF Aktiengesellschaft | Aqueous polymer dispersions |
| EP0524513A3 (en) * | 1991-07-26 | 1993-08-04 | Basf Aktiengesellschaft | Aqueous polymer dispersions |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |