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WO1997032927A1 - Procede visant a inhiber la formation de nitrosamine dans le caoutchouc - Google Patents

Procede visant a inhiber la formation de nitrosamine dans le caoutchouc Download PDF

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Publication number
WO1997032927A1
WO1997032927A1 PCT/GB1997/000602 GB9700602W WO9732927A1 WO 1997032927 A1 WO1997032927 A1 WO 1997032927A1 GB 9700602 W GB9700602 W GB 9700602W WO 9732927 A1 WO9732927 A1 WO 9732927A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
process according
phenate
formulation
phr
Prior art date
Application number
PCT/GB1997/000602
Other languages
English (en)
Inventor
Hugh Wynn Gibbs
Douglas Martin Edward Butcher
Philip Edward Russell Tate
Graham Paul Sexton
Original Assignee
Rhodia Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhodia Limited filed Critical Rhodia Limited
Priority to AU22256/97A priority Critical patent/AU2225697A/en
Publication of WO1997032927A1 publication Critical patent/WO1997032927A1/fr

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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/138—Phenolates
    • 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
    • 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

Definitions

  • Aliphatic N-nitrosamines are known to be carcinogenic in some animals. Significant levels of volatile nitrosamines have been detected in factories manufacturing rubber products both in the products themselves and in the ambient air. Since workers in the rubber industry have been shown to suffer from an increased incidence of certain types of cancer, it has been suggested that nitrosamines contribute to this increase. Concern has also been expressed about nitrosamine levels in certain types of rubber product, more particularly those which come into physical contact with users and those which are used in confined spaces.
  • nitrosamines are generated by the reaction of nitrogen oxides (NO ⁇ ) with secondary amines (or secondary amine residues) present in the rubber formulation. It appears likely that the NO is already present in the ambient atmosphere (produced in vehicle exhausts and/or by industrial combustion) .
  • the nitrogen oxides are absorbed by the fillers customarily used in rubber (carbon black or silica) and are thus brought into contact, during the vulcanisation, with secondary amines generated by many common accelerators used in rubber vulcanisation.
  • accelerators containing secondary amine residues include: N-Morpholinyl-benzothiazole-2-sulphenamide f N , -di-isopropyl-benzothiazole-2-sulphenamide 4-Morpholinyl-2-benzothiazole disulphide
  • alkaline earth metal carboxylates and phenates can advantageously be incorporated into vulcanisable rubber formulations to reduce nitrosamine formation during vulcanisation.
  • Such carboxylates and phenates should desirably have a melting point below 130°C in order to be fully compatible with the rubber formulation during the vulcanisation process.
  • the present invention accordingly provides vulcanisable rubber formulations comprising an alkaline earth metal carboxylate or phenate in an amount sufficient to reduce or inhibit nitrosamine formation.
  • rubber formulations may comprise a vulcanisation accelerator containing secondary amine residues such as one of those mentioned above.
  • alkaline earth metal carboxylates include carboxylates derived from aliphatic and alicyclic acids with 4 to 22 carbons, especially 8 to 20 carbons, or from aromatic acids with 7 to 12 carbons, and from calcium, barium and magnesium, especially barium.
  • Suitable phenates include those derived from aromatic alcohols of 6 to 12 carbons.
  • Preferred materials include calcium, barium and magnesium stearate, especially barium stearate, and barium neodecanoate as well as magnesium and calcium phenate.
  • the carboxylate or phenate employed should generally have a melting point not exceeding 130°C. It has also been found that the addition of calcium oxide as well as the carboxylate/phenate enhances the effect of the latter significantly. Thus an about 40% reduction in nitrosamine concentration due to the addition of barium carboxylate can be increased to about 70% with the addition of calcium oxide as well.
  • the rubber formulation may be of any known kind and based on, for example, natural rubber, styrene butadiene rubber, nitrile rubber, polybutadiene, polychlorophene or EPDM rubber, or any mixture of these, especially EPDM rubber.
  • the alkaline earth metal carboxylate or phenate is suitably incorporated in the vulcanisable formulation at a level of 0.05 to 5 parts, especially 0.5 to 2 parts, per 100 parts by weight of rubber with, optionally, 1 to 20 parts, especially 2 to 10 parts, per 100 parts by weight of the rubber, of calcium oxide. They may be incorporated as pure compound, diluted in a process oil, or supported on a high surface area solid, e.g. silica filler.
  • the manner of providing the alkaline earth metal carboxylate or phenate and, optionally, calcium oxide is chosen to provide ease of handling and mixing with the other ingredients of the formulation.
  • the vulcanisable formulation also contains other ingredients conventionally present in vulcanisable formulations including especially the usual carbon black or silica filler and other materials such as zinc oxide, stearic acid, antioxidant....
  • the vulcanisation itself is brought about in the usual manner by incorporating in the formulation an accelerator/ sulphur mixture and curing the formulation at elevated temperature in the usual way.
  • an accelerator/ sulphur mixture and curing the formulation at elevated temperature in the usual way.
  • Example 1 A rubber master batch was prepared by mixing together: Natural Rubber (SMR CV) 100 parts by weight Carbon Black (FEF 550) 45
  • the accelerator/sulphur mixture (sulphur 0.33 phr, MOR 3 phr, Tetramethylthiuram disulphide 2 phr) was then added on a 2-roll mill and the formulation was then vulcanised.
  • Step 1 Place the cellulose thimble containing the vulcanisate into a Soxhlet Extractor containing 50 ml of methanol containing 0.1 % ascorbic acid. Fit the extractor onto a 150 ml round bottom flask.
  • Step 2 After 24 hours extraction in cold methanol, add a further 30 ml through the Soxhlet. Then reflux over a water bath for 1 hour.
  • Step 3 After cooling, transfer the extract into a volumetric flask and make up to 100 ml.
  • Step 4 Pipette 25 ml of the extract into a glass vial and seal with a crimped cap and PTFE lined rubber septum and were stored in the dark at 0°C prior to their analysis.
  • the ethanolic extract (10 ml) was diluted with water (90 ml) and treated with an internal standard (N-nitrosodipropylamine, 41 ng in ethanol, 0.5 ml), sodium chloride (10 g) and dichloro- ethane (20 ml) ) .
  • the mixture was shaken and allowed to separate.
  • the dichloro ethane layer was recovered, dried (sodium sulphate) and evaporated to convenient small bulk.
  • a part of the concentrate was subjected to gas-chromatography on a glass column packed with Carbowax 20M on Chromosorb P and a chromatogram developed at 145°C (carrier gas argon, ca.
  • TAA thermal energy analyser
  • the eluting species were pyrolysed at 475°C, substances other than nitric oxide were frozen out, and the nitric oxide was mixed with ozone to give a chemiluminescent reaction which was measured by means of a photomultiplier tube.
  • the output of the detector was recorded and the ratio of the response area due to any nitrosamine to that due to the internal standard is calculated.
  • a series of analyses was made in which known quantities of individual nitrosamines were added to water containing 10% of methanol and the solutions subjected to the analysis described above. The response area ratios for each nitrosamine are linear with respect to mass of nitrosamine. From the lines so obtained, the mass of each nitrosamine corresponding to its observed response was calculated.
  • NDMA nitrosodi ethylamine
  • NMOR nitrosomorpholine
  • Example 2 An EPDM compound was prepared using the following basic formulation:
  • Varying amounts of calcium oxide and barium neodedanoate were incorporated separately or together.
  • the formulation was prepared as follows:
  • the carbon black, stearic acid, zinc oxide, EPDM (and calcium oxide and/or barium neodecanoate if used) were mixed together in an internal mixed.
  • the sulphur, MBT and TMTD were added to the previously mixed compound on a 2-roll mill and mixed.
  • the formulation was vulcanised at 170°C with a cure time of T 90 as measured on a Monsanto Rheo eter.
  • the vulcanised sample was extracted and analysed for nitrosamines as in Example 1.
  • alkaline earth metal carboxylates or phenates used in - li ⁇ the present invention may be produced in known manner and some are commercially available.
  • Barium stearate may be, for example, produced as follows:
  • Stearic acid (273 g; 1 mole) was added slowly with stirring to a mixture of barium oxide (51.1 g; 0.33 mole), xylene (500 g) , water (5 g) and hexyl carbitol (50 g) heated at 100°C. The temperature was then raised to 150°C as the aqueous distillate was collected in a Dean & Stark trap. Once the water was removed the temperature was increased to ⁇ 170°C as the remaining xylene was removed, finally under vacuum. The product was allowed to cool to give a waxy solid, melting point 90°C. Barium neodecanoate.
  • neodecanoic acid 287.0 g; 1.64 mole
  • dioxitol 36.6 g
  • mineral oil 300 g
  • the product was filtered under pressure and then allowed to cool to give a clear, dark amber, viscous liquid.

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

Cette invention concerne un procédé visant à réduire ou à inhiber la formation de nitrosamine dans une formulation de caoutchouc vulcanisable, ledit procédé consistant à incorporer à ladite formulation un carboxylate ou phénate de métal rare alcalin.
PCT/GB1997/000602 1996-03-04 1997-03-04 Procede visant a inhiber la formation de nitrosamine dans le caoutchouc WO1997032927A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU22256/97A AU2225697A (en) 1996-03-04 1997-03-04 Inhibiting nitrosamine formation in rubber

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9604601.6 1996-03-04
GB9604601A GB2310858A (en) 1996-03-04 1996-03-04 Inhibiting nitrosamine formation in rubber

Publications (1)

Publication Number Publication Date
WO1997032927A1 true WO1997032927A1 (fr) 1997-09-12

Family

ID=10789834

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1997/000602 WO1997032927A1 (fr) 1996-03-04 1997-03-04 Procede visant a inhiber la formation de nitrosamine dans le caoutchouc

Country Status (3)

Country Link
AU (1) AU2225697A (fr)
GB (1) GB2310858A (fr)
WO (1) WO1997032927A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495065B1 (en) 1999-09-09 2002-12-17 Atofina Chemicals, Inc. Nitrosamine-inhibiting compositions for shortstopping of free radical emulsion polymerizations
EP4035633A2 (fr) 2020-10-22 2022-08-03 Thai Nippon Rubber Industry Public Company Limited Préservatifs en latex de polyisoprène synthétique à teneur réduite en nitrosamine

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0602431D0 (en) * 2006-02-08 2006-03-22 Broadlab Ltd Improvements in or relating to rubber products
CN111751456B (zh) * 2019-09-10 2023-04-28 上海市食品药品包装材料测试所 一种同时定量检测弹性体密封件中亚硝胺和亚硝胺可生成物的方法
JP7568496B2 (ja) * 2020-12-09 2024-10-16 株式会社ブリヂストン ゴム組成物、ゴム－金属複合体、ホース、コンベヤベルト、ゴムクローラ及びタイヤ

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB809743A (en) * 1954-12-21 1959-03-04 Dunlop Rubber Co Improvements in and relating to natural rubber articles
US3310546A (en) * 1963-09-11 1967-03-21 Du Pont Curable chloroprene polymer composition and method of curing same
GB1064189A (en) * 1964-10-30 1967-04-05 Technical Proc Inc Processing aids for rubbers
US5070130A (en) * 1990-09-19 1991-12-03 The B. F. Goodrich Company Alkaline earth oxides and hydroxides to reduce nitrosamine formation from vulcanization accelerators
EP0482470A1 (fr) * 1990-10-25 1992-04-29 Bayer Ag Utilisation de demi-esters d'acide maléique et d'acide fumarique et de leurs sels pour réduire la formation de nitrosamines dans la vulcanisation au soufre

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB770057A (en) * 1953-08-04 1957-03-13 Richardson Co Composition of phenol-aldehyde resins and elastomers for moulding battery cases
NL124560C (fr) * 1961-10-18
DE1302611B (fr) * 1964-07-14 1971-02-25 Chemische Werke Huels Ag
EP0172410A1 (fr) * 1984-08-24 1986-02-26 The Firestone Tire & Rubber Company Procédé pour augmenter le module de caoutchouc vulcanisable

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB809743A (en) * 1954-12-21 1959-03-04 Dunlop Rubber Co Improvements in and relating to natural rubber articles
US3310546A (en) * 1963-09-11 1967-03-21 Du Pont Curable chloroprene polymer composition and method of curing same
GB1064189A (en) * 1964-10-30 1967-04-05 Technical Proc Inc Processing aids for rubbers
US5070130A (en) * 1990-09-19 1991-12-03 The B. F. Goodrich Company Alkaline earth oxides and hydroxides to reduce nitrosamine formation from vulcanization accelerators
EP0482470A1 (fr) * 1990-10-25 1992-04-29 Bayer Ag Utilisation de demi-esters d'acide maléique et d'acide fumarique et de leurs sels pour réduire la formation de nitrosamines dans la vulcanisation au soufre

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6495065B1 (en) 1999-09-09 2002-12-17 Atofina Chemicals, Inc. Nitrosamine-inhibiting compositions for shortstopping of free radical emulsion polymerizations
EP4035633A2 (fr) 2020-10-22 2022-08-03 Thai Nippon Rubber Industry Public Company Limited Préservatifs en latex de polyisoprène synthétique à teneur réduite en nitrosamine

Also Published As

Publication number Publication date
GB2310858A (en) 1997-09-10
GB9604601D0 (en) 1996-05-01
AU2225697A (en) 1997-09-22

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