CA2153509A1 - Accelerator mixtures - Google Patents
Accelerator mixturesInfo
- Publication number
- CA2153509A1 CA2153509A1 CA002153509A CA2153509A CA2153509A1 CA 2153509 A1 CA2153509 A1 CA 2153509A1 CA 002153509 A CA002153509 A CA 002153509A CA 2153509 A CA2153509 A CA 2153509A CA 2153509 A1 CA2153509 A1 CA 2153509A1
- Authority
- CA
- Canada
- Prior art keywords
- accelerator
- vulcanisation
- sulphur
- sulphenamides
- thiazoles
- 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.)
- Abandoned
Links
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
- C08K5/49—Phosphorus-containing compounds
- C08K5/5398—Phosphorus bound to sulfur
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/44—Sulfenamides
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Process for finding and optimising vulcanisation accelerators based on C6-C12 alkyldithiophosphates for vulcanising non-polar rubbers, wherein a C6-C12 alkyldithiophosphate is mixed with a compound from the group comprising sulphenamides, thiazoles or carbamates, the solubility of the mixture in the non-polar rubber and the vulcanisation kinetics of the accelerator in comparison with a standard accelerator are experimentally optimised and a further compound from the group comprising sulphenamides, thiazoles or carbamates is optionally added.
Description
l ~153509 RC 181-foreign countries _ Accelerator mixtures Rubbers containing double bonds in their main or side chains may be crosslinked with sulphur or sulphur donors.
Any further mention of sulphur below always also includes other sulphur donors. The crosslinking process is also known as vulcanisation. In this process, the sulphur (or sulphur donor) is used together with a vulcanisation accelerator. These accelerators may consist of a single chemical or of two or more chemicals.
The quantity of vulcanisation accelerator in relation to the sulphur and simultaneously in relation to the quantity of double bonds in the rubber used determines the crosslinking rate and the network structure. This in turn determines the physical properties and ageing resistance of the vulcanisate.
Determining the necessary quantity of accelerator for non-polar rubbers, for example EPDM rubber, is particularly problematic. In order to achieve satisfactory vulcanisate properties, it was hitherto necessary to select such a large quantity of accelerator that its solubility limit was exceeded. This results in blooming; the dynamic resistance of vulcanisate mouldings is inter alia impaired.
Most chemicals which are used in customary accelerators lead to the formation of N-nitrosamines, as their decomposition products are usually secondary amines, which react in the rubber itself or in the surrounding gas space with nitrosating agents (NOX) to yield stable, carcinogenic N-nitrosamines.
Hitherto, only few accelerators have been known which are not carcinogenic and are adequately soluble in non-polar rubber.
~1535~
It is also already known that soluble (= bloom-free) accelerator mixtures may be obtained with dithiophosphates, but these lead to the formation of carcinogenic N-nitrosamines.
The object of the invention is to discover accelerator mixtures which form no hazardous N-nitrosamines and no or distinctly less toxicologically questionable vulcanisate vapours, which exhibit vulcanisation kinetics analogous to standard systems and which yield vulcanisates with physical properties in line with those obtained with standard systems.
The present invention provides a process for finding and optimising vulcanisation accelerators based on C6-Cl2 alkyldithiophosphates for vulcanising non-polar rubbers, which process is characterised in that a C6-Cl2 alkyldithiophosphate is mixed with a compound from the group comprising sulphenamides, thiazoles and carbamates, the solubility of the mixture in the non-polar rubber and the vulcanisation kinetics of the accelerator in comparison with a standard accelerator are experimentally optimised and a further hitherto unused compound from the group comprising sulphenamides, thiazoles and carbamates is optionally added.
In detail, C6-Cl2 alkyldithiophosphates may be mixed with per se known compounds, which themselves have an accelerating action, and the.action of these mixtures tested with regard to vulcanisation kinetics and vulcanisation properties. It is necessary to use statistical test planning methods as an aid for this purpose.
A known accelerator from the class of substances comprising sulphenamides, thiazoles and carbamates is first selected ~153509 RC 181 _ 3 as a principal accelerator and the optimum quantity ratio of this selected accelerator to the dithiophosphates, preferably a mixture of zinc alkyldithiophosphate with zinc alkyldithiophosphateamine mixture, is then determined.
Another (known) accelerator from a class of substances other than the stated already used class is then added to this mixture. By way of example, a thiazole was added to the principal sulphenamide accelerator. The result is then a combination of sulphenamide, thiazole and the dithiophosphate mixture.
In parallel, the solubility of the known accelerators in EPDM rubber was determined as no reliable data in this connection were hitherto available. This information provides a concentration limit for each individual accelerator which may not be exceeded if the accelerator mixture is not to cause blooming (which is exhibited as a film on the surface of the vulcanisate). Blooming disrupts the further processing or working of vulcanisates.
The accelerator packages according to the invention obtained in this manner may be incorporated into a crosslinking system consisting of sulphur (and/or sulphur donors), accelerator package and additional accelerators and tested, wherein the quantity ratios of crosslinking agent, accelerator package and additional accelerator may be varied in order to discover the optimum quantity ratio.
As a result, it is possible to state accelerator packages which, in conjunction with sulphur and an additional accelerator, exhibit a slow, medium and fast vulcanisation rate. In this manner, it is possible to establish each desired vulcanisation characteristic which is achieved with suitably selected standard systems. The influence of an accelerator system on vulcanisate properties is marginal. A
decisive factor is the influence of the accelerator system RC 181 _ 4 _ on the vulcanisation rate, on which, in turn, the processability of a rubber compound using a particular process is dependent.
By means of direct comparison of the accelerator systems with standard systems (confirmatory testing), it may be demonstrated that the vulcanisate properties obtained with the accelerators according to the invention are completely in line with those of standard systems and that the vulcanisation rates may also be adjusted to those of standard systems.
3~09 -RC 181 _ 5 _ Example Table 1 shows accelerator packages based on sulphenamide (in this case cyclohexylsulphenamide (CBS)). The figures are parts by weight.
Table 1 Accelerator AP 1 AP 2 AP 3 AP 4 N-cyclohexyl-2- 1.92 1.92 1.92 0.96 benzothiazole-sulphenamide N-tert.-butyl-2- - - - 0.96 benzothiazole-sulphenamide Dibenzothiazole - 1.28 0.96 1.28 disulphide Zinc di-2-ethyl- 1.07 1.07 0.8 1.07 hexyldithio-phosphate These accelerator packages are used together with sulphur and a second accelerator. The figures are again parts by weight.
Table 2 Practical example 1 2 3 4 Sulphur (80%) 1.6 1.6 0.5 1.6 Dithiocaprolactam (80%) Accelerator 4 5.6 4.8 5.6 package (80%) Zinc amine di-2- 2.4 2.4 1 2.4 ethylhexyldithio-phosphate (50~) ~s3~as Table 3 shows accelerator packages based on a thiazole. The figures are parts by weight.
Table 3 Accelerator package AP 5 AP 6 Dithiocaprolactam - 0.88 Dibenzothiazole disulphide 3.20 3.2 Zinc di-2-ethylhexyl- 0.85 0.35 dithiophosphate These accelerator packages are used together with sulphur and a second accelerator.
Table 4 Example 5 6 Sulphur 80~ 1.2 1.4 Accelerator package 80~ 5.7 5.8 Zinc diamine di-2-ethyl- 2.3 2.7 hexyldithiophosphate
Any further mention of sulphur below always also includes other sulphur donors. The crosslinking process is also known as vulcanisation. In this process, the sulphur (or sulphur donor) is used together with a vulcanisation accelerator. These accelerators may consist of a single chemical or of two or more chemicals.
The quantity of vulcanisation accelerator in relation to the sulphur and simultaneously in relation to the quantity of double bonds in the rubber used determines the crosslinking rate and the network structure. This in turn determines the physical properties and ageing resistance of the vulcanisate.
Determining the necessary quantity of accelerator for non-polar rubbers, for example EPDM rubber, is particularly problematic. In order to achieve satisfactory vulcanisate properties, it was hitherto necessary to select such a large quantity of accelerator that its solubility limit was exceeded. This results in blooming; the dynamic resistance of vulcanisate mouldings is inter alia impaired.
Most chemicals which are used in customary accelerators lead to the formation of N-nitrosamines, as their decomposition products are usually secondary amines, which react in the rubber itself or in the surrounding gas space with nitrosating agents (NOX) to yield stable, carcinogenic N-nitrosamines.
Hitherto, only few accelerators have been known which are not carcinogenic and are adequately soluble in non-polar rubber.
~1535~
It is also already known that soluble (= bloom-free) accelerator mixtures may be obtained with dithiophosphates, but these lead to the formation of carcinogenic N-nitrosamines.
The object of the invention is to discover accelerator mixtures which form no hazardous N-nitrosamines and no or distinctly less toxicologically questionable vulcanisate vapours, which exhibit vulcanisation kinetics analogous to standard systems and which yield vulcanisates with physical properties in line with those obtained with standard systems.
The present invention provides a process for finding and optimising vulcanisation accelerators based on C6-Cl2 alkyldithiophosphates for vulcanising non-polar rubbers, which process is characterised in that a C6-Cl2 alkyldithiophosphate is mixed with a compound from the group comprising sulphenamides, thiazoles and carbamates, the solubility of the mixture in the non-polar rubber and the vulcanisation kinetics of the accelerator in comparison with a standard accelerator are experimentally optimised and a further hitherto unused compound from the group comprising sulphenamides, thiazoles and carbamates is optionally added.
In detail, C6-Cl2 alkyldithiophosphates may be mixed with per se known compounds, which themselves have an accelerating action, and the.action of these mixtures tested with regard to vulcanisation kinetics and vulcanisation properties. It is necessary to use statistical test planning methods as an aid for this purpose.
A known accelerator from the class of substances comprising sulphenamides, thiazoles and carbamates is first selected ~153509 RC 181 _ 3 as a principal accelerator and the optimum quantity ratio of this selected accelerator to the dithiophosphates, preferably a mixture of zinc alkyldithiophosphate with zinc alkyldithiophosphateamine mixture, is then determined.
Another (known) accelerator from a class of substances other than the stated already used class is then added to this mixture. By way of example, a thiazole was added to the principal sulphenamide accelerator. The result is then a combination of sulphenamide, thiazole and the dithiophosphate mixture.
In parallel, the solubility of the known accelerators in EPDM rubber was determined as no reliable data in this connection were hitherto available. This information provides a concentration limit for each individual accelerator which may not be exceeded if the accelerator mixture is not to cause blooming (which is exhibited as a film on the surface of the vulcanisate). Blooming disrupts the further processing or working of vulcanisates.
The accelerator packages according to the invention obtained in this manner may be incorporated into a crosslinking system consisting of sulphur (and/or sulphur donors), accelerator package and additional accelerators and tested, wherein the quantity ratios of crosslinking agent, accelerator package and additional accelerator may be varied in order to discover the optimum quantity ratio.
As a result, it is possible to state accelerator packages which, in conjunction with sulphur and an additional accelerator, exhibit a slow, medium and fast vulcanisation rate. In this manner, it is possible to establish each desired vulcanisation characteristic which is achieved with suitably selected standard systems. The influence of an accelerator system on vulcanisate properties is marginal. A
decisive factor is the influence of the accelerator system RC 181 _ 4 _ on the vulcanisation rate, on which, in turn, the processability of a rubber compound using a particular process is dependent.
By means of direct comparison of the accelerator systems with standard systems (confirmatory testing), it may be demonstrated that the vulcanisate properties obtained with the accelerators according to the invention are completely in line with those of standard systems and that the vulcanisation rates may also be adjusted to those of standard systems.
3~09 -RC 181 _ 5 _ Example Table 1 shows accelerator packages based on sulphenamide (in this case cyclohexylsulphenamide (CBS)). The figures are parts by weight.
Table 1 Accelerator AP 1 AP 2 AP 3 AP 4 N-cyclohexyl-2- 1.92 1.92 1.92 0.96 benzothiazole-sulphenamide N-tert.-butyl-2- - - - 0.96 benzothiazole-sulphenamide Dibenzothiazole - 1.28 0.96 1.28 disulphide Zinc di-2-ethyl- 1.07 1.07 0.8 1.07 hexyldithio-phosphate These accelerator packages are used together with sulphur and a second accelerator. The figures are again parts by weight.
Table 2 Practical example 1 2 3 4 Sulphur (80%) 1.6 1.6 0.5 1.6 Dithiocaprolactam (80%) Accelerator 4 5.6 4.8 5.6 package (80%) Zinc amine di-2- 2.4 2.4 1 2.4 ethylhexyldithio-phosphate (50~) ~s3~as Table 3 shows accelerator packages based on a thiazole. The figures are parts by weight.
Table 3 Accelerator package AP 5 AP 6 Dithiocaprolactam - 0.88 Dibenzothiazole disulphide 3.20 3.2 Zinc di-2-ethylhexyl- 0.85 0.35 dithiophosphate These accelerator packages are used together with sulphur and a second accelerator.
Table 4 Example 5 6 Sulphur 80~ 1.2 1.4 Accelerator package 80~ 5.7 5.8 Zinc diamine di-2-ethyl- 2.3 2.7 hexyldithiophosphate
Claims (2)
1. Process for finding and optimising vulcanisation accelerators based on C6-C12 alkyldithiophosphates for vulcanising non-polar rubbers, characterised in that a C6-C12 alkyldithiophosphate is mixed with a compound from the group comprising sulphenamides, thiazoles or carbamates, the solubility of the mixture in the non-polar rubber and the vulcanisation kinetics of the accelerator in comparison with a standard accelerator are experimentally optimised and a further compound from the group comprising sulphenamides, thiazoles or carbamates is optionally added.
2. Process for finding and optimising the accelerator mixtures stated in claim 1, characterised in that the mixtures are experimentally optimised with regard to the quantity ratio to sulphur/sulphur donor and an additional accelerator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4424681A DE4424681A1 (en) | 1994-07-13 | 1994-07-13 | Accelerator mixtures |
| DEP4424681.1 | 1994-07-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2153509A1 true CA2153509A1 (en) | 1996-01-14 |
Family
ID=6523028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002153509A Abandoned CA2153509A1 (en) | 1994-07-13 | 1995-07-10 | Accelerator mixtures |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0692518A1 (en) |
| JP (1) | JPH0848819A (en) |
| KR (1) | KR960004369A (en) |
| CN (1) | CN1127273A (en) |
| CA (1) | CA2153509A1 (en) |
| DE (1) | DE4424681A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6536492B2 (en) | 1998-07-22 | 2003-03-25 | Michelin Recherche Et Technique S.A. | Silica-containing rubber composition vulcanizable with sulfur |
| DE102009023915A1 (en) | 2009-05-27 | 2010-12-02 | Rhein-Chemie Rheinau Gmbh | Mixtures of functionalized diene rubbers with trimethylolpropane and fatty acid, a process for their preparation and their use |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004026317A1 (en) * | 2004-05-26 | 2005-12-15 | Rhein-Chemie Rheinau Gmbh | Process for the preparation of rubber compounds |
| CN103254511B (en) * | 2012-02-20 | 2015-08-19 | 中国石油化工股份有限公司 | A kind of terpolymer EP rubber |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4027114A1 (en) * | 1989-08-29 | 1991-03-28 | Phoenix Ag | EPDM vulcanisation system without toxic nitrosamine(s) - contg. 2-mercapto-benzothiazole etc. and special mixt. of thiuram- and-or di:thiocarbamate and bis-amido-polysulphide-type accelerators |
-
1994
- 1994-07-13 DE DE4424681A patent/DE4424681A1/en not_active Withdrawn
-
1995
- 1995-06-30 EP EP95110225A patent/EP0692518A1/en not_active Withdrawn
- 1995-07-07 JP JP7194116A patent/JPH0848819A/en active Pending
- 1995-07-10 CA CA002153509A patent/CA2153509A1/en not_active Abandoned
- 1995-07-12 CN CN95115014A patent/CN1127273A/en active Pending
- 1995-07-13 KR KR1019950020549A patent/KR960004369A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6536492B2 (en) | 1998-07-22 | 2003-03-25 | Michelin Recherche Et Technique S.A. | Silica-containing rubber composition vulcanizable with sulfur |
| DE102009023915A1 (en) | 2009-05-27 | 2010-12-02 | Rhein-Chemie Rheinau Gmbh | Mixtures of functionalized diene rubbers with trimethylolpropane and fatty acid, a process for their preparation and their use |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0692518A1 (en) | 1996-01-17 |
| JPH0848819A (en) | 1996-02-20 |
| DE4424681A1 (en) | 1996-01-18 |
| CN1127273A (en) | 1996-07-24 |
| KR960004369A (en) | 1996-02-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |