GB2110697A - Vinyl chloride polymer compositions - Google Patents
Vinyl chloride polymer compositions Download PDFInfo
- Publication number
- GB2110697A GB2110697A GB08231465A GB8231465A GB2110697A GB 2110697 A GB2110697 A GB 2110697A GB 08231465 A GB08231465 A GB 08231465A GB 8231465 A GB8231465 A GB 8231465A GB 2110697 A GB2110697 A GB 2110697A
- Authority
- GB
- United Kingdom
- Prior art keywords
- carboxylate
- composition
- vinyl chloride
- chloride polymer
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 229920000642 polymer Polymers 0.000 title claims description 18
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 17
- -1 zinc carboxylate Chemical class 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 19
- 239000011701 zinc Substances 0.000 claims abstract description 19
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 8
- 239000003017 thermal stabilizer Substances 0.000 claims abstract description 8
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 6
- 239000008116 calcium stearate Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 7
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 2
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 239000004608 Heat Stabiliser Substances 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229940065285 cadmium compound Drugs 0.000 description 1
- 150000001662 cadmium compounds Chemical class 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 235000013969 calcium salts of fatty acid Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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)
Abstract
A thermal stabiliser for poly vinyl chloride compositions comprises a basic zinc carboxylate having the empirical formula (RCOO)6Zn4O where R is a branched chain alkyl, cycloalkyl, aryl, aralkyl or alkaryl group, e.g. 2 ethyl hexyl. The carboxylate has a tetrahedral structure with the four zinc atoms at the corners, the oxygen atom at the centre and the six carboxylate groups arranged along the sides. The basic zinc salt is preferably used in combination with another metal carboxylate e.g. calcium stearate.
Description
SPECIFICATION
Vinyl chloride polymer compositions
The present invention relates to stabilised vinyl chloride polymer compositions containing basic zinc carboxylates.
Vinyl chloride polymers, are widely used in the manufacture of plastics articles. They may be homopolymers, or copolymers with other copolymerisable monomers, and may be used plasticised or unplasticised. Vinyl chloride polymers tend to degrade when subjected to heat and it is therefore necessary to add a stabiliser to the polymer to retard this degradation.
Certain metal carboxylate mixtures, e.g. cadmium/barium/zinc carboxylate compounds and cadmium/zinc carboxylate mixtures are known as thermal stabilisers for polyvinyl chloride. However, the toxicity of cadmium compounds has led to attempts to stabilise polyvinyl chloride with additives which do not contain cadmium. Additives comprising calcium and zinc carboxylates have been used as stabilisers but they are generally less effective as thermal stabilisers than additives containing cadmium.
The applicants have found that a basic zinc carboxylate having a particular structure is an effective thermal stabiliser for poly vinyl chloride, particularly when used in combination with another metal carboxylate such as, for example, calcium stearate. The basic zinc carboxylate is a more effective thermal stabiliser than conventional zinc carboxylates.
According to the present invention a composition comprising a vinyl chloride polymer and a zinc carboxylate as a thermal stabiliser is characterised in that the zinc carboxylate is a basic zinc carboxylate having the emperical formula (RCO0)6Zn40 where R is a branched chain alkyl, cycloalkyl, aryl, aralkyl, or alkaryl group, the salt having a tetrahedral structure with the four zinc atoms at the corners, the oxygen atom at the centre and the six carboxylate groups arranged along the sides.
The production of basic zinc salts of the above structure is disclosed in British Patent No.
1142195.
The vinyl chloride polymer may be a homopolymer or a copolymer with another copolymerisable monomer e.g. vinyl acetate. Where a copolymer is used it may for example contain up to 30% by weight of the comonomer.
The vinyl chloride polymer may be a polymer made by mass, suspension, microsuspension, or emulsion polymerisation.
The zinc salts which may be used in the process of the present invention are preferably those in which R in the formula (RCO0)6Zn40 contains not more than 24 carbon atoms and not less than 3.
Preferably R is a branched chain alkyl group having not more than 1 8 and not less than 5 carbon atoms. R may for example be 2-ethyl hexyl.
The quantity of zinc salt used in the compositions of the present inventions may vary over a moderately wide range for example from 0.2 to 5% by weight of the vinyl chloride polymer, more preferably 0.5 to 2.5%.
The zinc salt is preferably used together with other metal carboxylates e.g. calcium carboxylate.
Suitable calcium carboxylates include calcium salts of fatty acids having from 10 to 22 carbon atoms in the molecule, such as calcium stearate.
The quantity of calcium salt used may vary over a moderately wide range for example 0.2% by weight to 5% by weight based on weight of vinyl chloride polymer.
The vinyl chloride polymer composition may contain the usual materials conventionally used in making vinyl chloride polymer compounds e.g. fillers, pigments, process aids, impact modifiers.
Although the basic zinc carboxylate of the present invention has been referred to as a thermal stabiliser throughout this specification it has also been found that the compound may act as an activator for the blowing agent in the production of foamed polyvinyl chloride i.e. it can lower the temperature at which the foaming agent azodicarbonamide decompses to produce nitrogen.
The invention will now be illustrated by reference to the following Examples.
Comparative Test
A polyvinyl chloride blend was prepared from the following ingredients:
parts by weight
Vinyl chloride homopolymer made by the suspension process and having
an ISO viscosity number of about 110 100 Dioctyl adipate 23
Commercial heat stabiliser (a blend of Ca and Zn salts of long chain, fatty
acids sold as Lankromark LZ 330) 3.3
Glyceryl Mono-oleate (sold as Estol 651) 0.1
Wax (sold as Glokem D2S) 1.0
Epoxidised Soyabean Oil (sold as Paraplex G 62) 5.5
The ingredients were mixed together on a 'Kenwood' ('Kenwood' is a Trade Mark) mixer and then milled to give a clear PVC flexible sheet. The sheet was cut into discs of diameter 25.4 mm (1 inch) which were placed in an oven at 1 800 C. Discs were removed from the oven at 10 minute intervals for up to 2 hours.The colour of the discs changed from the initial water-white colour to dark brown as heating continued.
Example 1
An experiment was carried out as in the Comparative Test except that the commercial stabiiiser was replaced by a mixture of 1.65 parts by weight of the basic zinc 2-ethyl hexanoate, and 1.65 parts by weight of calcium stearate.
Example 2
An experiment was carried out as in Example 1 except that the quantity of basic zinc salt was 2.0 parts by weight and the quantity of calcium stearate was 1.3 parts by weight.
A comparison of the discs showed that degradation (as shown by discoloration) proceeded more slowly with the compositions of the invention than when the commercial stabiliser was used. The composition of Example 1 was slightly better than the composition of Example 2.
The basic zinc 2-ethyl hexanoate used in Examples 1 and 2 had an emperical formula (RCO0)6Zn40 where R is a 2-ethyl hexyl group. The compound had a tetrahedral structure with the four ziiic atoms at the corners, the oxygen atom at the centre and the six 2-ethyl hexyl groups arranged along the sides. The preparation of the basic zinc carboxylate is disclosed in British Patent No.
1142195.
Claims (10)
1. A composition comprising a vinyl chloride polymer and a zinc carboxylate, as a thermal stabiliser, characterised in that the zinc carboxylate is a basic zinc carboxylate having the empirical formula (RCO0)6 Zn40 where R is a branched chain alkyl, cycloalkyl, aryl, aralkyl or alkaryl group, the salt having a tetrahedral structure with the four zinc atoms at the corners, the oxygen atom at the centre and the six carboxylate groups arranged along the sides.
2. A composition as claimed in claim 1 characterised in that the number of carbon atoms in the group R of the basic zinc salt is from 3 to 24.
3. A composition as claimed in claim 2 characterised in that R is a branched chain alkyl group having from 5 to 18 carbon atoms.
4. A composition as claimed in claim 3 characterised in that R is 2 ethyl hexyl.
5. A composition as claimed in any of claims 1 to 4 characterised in that the amount of the basic zinc carboxylate is in the range 0.2 to 5% by weight of the vinyl chloride polymer.
6. A composition as claimed in claim 5 characterised in that the amount of the basic zinc carboxylate is in the range 0.5 to 2.5% by weight of the vinyl chloride polymer.
7. A composition as claimed in any of claims 1 to 6 characterised in that the composition also contains a calcium carboxylate having from 10 to 22 carbon atoms.
8. A composition as claimed in claim 7 characterised in that the calcium carboxylate is calcium stearate.
9. A composition as claimed in either of claims 7 or 8 characterised in that the amount of calcium carboxylate is in the range 0.2 to 5% by weight of the vinyl chloride polymer.
10. A composition substantially as described with reference ho the Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08231465A GB2110697B (en) | 1981-11-07 | 1982-11-03 | Vinyl chloride polymer compositions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8133638 | 1981-11-07 | ||
| GB08231465A GB2110697B (en) | 1981-11-07 | 1982-11-03 | Vinyl chloride polymer compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2110697A true GB2110697A (en) | 1983-06-22 |
| GB2110697B GB2110697B (en) | 1985-02-06 |
Family
ID=26281191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08231465A Expired GB2110697B (en) | 1981-11-07 | 1982-11-03 | Vinyl chloride polymer compositions |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2110697B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000046173A1 (en) * | 1999-02-03 | 2000-08-10 | Cognis Deutschland Gmbh | Method for producing overbased zinc soaps |
-
1982
- 1982-11-03 GB GB08231465A patent/GB2110697B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000046173A1 (en) * | 1999-02-03 | 2000-08-10 | Cognis Deutschland Gmbh | Method for producing overbased zinc soaps |
| US6649585B1 (en) | 1999-02-03 | 2003-11-18 | Cognis Deutschland Gmbh & Co. Kg | Processes for preparing superbasic zinc soaps and methods of using said soaps |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2110697B (en) | 1985-02-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |