Information for the Rubber Industry. Selected Processing Additives in CR. content Introduction. Test equipment, Methods and Parameter

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1 -KONTKT 40 Information for the Rubber Industry elected Processing dditives in CR content 1. Introduction 2. Test equipment, Methods and Parameter 3. effects of different Processing dditives in CR 3.1 Conventional, black CR-Compound 3.2 etu-free / MTT-ystem 3.3 etu-free / ulphur-ystem 3.4 Conventional, light coloured CR-Compound DOG 002_Kontakt_40_engl_rz.ind Use and Rating of Processing dditives in CR-Compounds 5. General Product Information 6. ppendix Complete Overview of all Test eries :54:25 Uhr

2 -KONTKT 40 Content Page Page 1. Introduction Product urvey 3 2. Test Equipment, 3 Methods and Parameter 3. Effects of different Processing 4 dditives in CR 3.1 conventional, black 4 CR-Compound Influence on the 4 processing properties Influence on the 5 physical properties 3.2 ETU-free / MTT-ystem Influence on the 6 processing properties Influence on the 7 physical properties 3.3 ETU-free / ulphur-ystem Influence on the 8 processing properties Influence on the 9 physical properties 3.4 Conventional, light coloured 10 CR-Compound Influence on the 10 processing properties Influence on the 11 physical properties 4. Use and Rating of Processing 12 dditives in CR-Compounds 5. General Product Information ppendix Complete 14 Overview of all Test eries 6.1 Conventional, black 14 CR-Compound 6.2 ETU-free / MTT-ystem ETU-free / ulphur-ystem Conventional, light coloured 18 CR-Compound Imprint Editor: DOG Deutsche Oelfabrik Gesellschaft für chemische Erzeugnisse mbh & Co. KG info@dog-chemie.de uthors: Dr. Bernd Bornemann, Manfred Heide, imone Materlik, Ralph Mehl, tephan Müller, tefan Oettlein, ndre Rittmann Layout/Production: EHRENBERG WERBUNG info@ehrenberg.de

3 1. Introduction for many years Polychloroprene rubber (cr) is available in different grades. although there is a large variety of cr-polymers available in the market it is necessary to use processing additives in the majority of these applications. Processing additives show significant positive effects e.g. optimization of the flow- and vulcanization properties and play an important role in improving the efficiency and quality of cr-compounds. for cr-compounds which tend to stick to the mill, Processing additives are essential for a trouble-free production. the DOG product range offers an efficient and competent solution for processing and optimization of cr-compounds. furthermore, many production problems can be solved by using DOG Processing additives. the brochure kontakt 40 elected Processing additives in cr provides recommendations for the use of, and Deosol in Polychloroprene rubber. kontakt 40 demonstrates the effect of these Processing additives and facilitates the specific choice of the most suitable product. although these additives are only used in small quantities the selection of the best product is of the highest importance. the use of zinc soaps in Polychloroprene rubber compounds for example leads to undesired effects such as lower heat resistance or shorter curing time. for this reason we do not recommend the DOG Dispergum product group (zinc soaps) for this elastomer. a further important additive for the processing of Polychloroprene rubber is DOG-factice (cross-linked Native Oils), which has a significant function in many formulations. Detailed information regarding DOG factice is described in our brochure kontakt 38. kontakt 40 replaces the information published in kontakt Product urvey deoflow deoflow deoflow deosol H deogum Processing dditive, based on a mixture of fatty alcohols and fatty acid esters based on calcium salts of fatty acids and amides based on pentaerythritol-tetrastearate emulsion based lubricant and dispersing agent special Processing dditive for a broad range of applications 2. Test Equipment, Methods and Parameter Compounding Internal Mixer farrel br banbury / volume 1.6 l Open Mill laboratory roller Mixer / 260 mm / friction 1 : 1.1 Test equipment for unvulcanized compounds Mooney Viscosimeter Montech V-MV 3000 rheometer MDr 2000 Göttfert rheovulkameter Test methods for vulcanized compounds tensile trength / Elongation DIN 53504, test specimen 2 tear resistance DIN IO 34-1, test specimen a hardness hore a DIN rebound DIN compression et DIN IO 815 3

4 -KONTKT Effects of different Processing dditives in CR 3.1 Conventional, black CR-Compound Recipe 251 C deoflow deoflow deoflow deogum deosol H Baypren neoprene WHV Carbon Black n Plasticizer do MgO tearic cid OdP deoflow 3 deoflow 3 deoflow 3 deogum 3 deosol H 3 ZnO MBT etu Total phr Influence on the processing properties MU Mooney ML 1+4, 100 C phr min Mooney corch 130 C, t phr Deosol H 8.5 Deosol H cm³ Injected volume after 70 s Injection Moulding Test phr cm³ Injected volume after 70 s Capillary Rheometer Test at 90 C phr Deosol H 0.0 Deosol H 4

5 all DOG-products tested show a positive influence on the processing properties of the rubber compounds, and the best effects are achieved with a and. In comparison to the reference compound the Mooney Viscosity can be reduced by approximately 8 points by adding only phr a. the Mooney corch time t 5 at 130 c is an indicatior for the processing safety. at a dosage of there are no significant negative effects. for the evaluation of processing at higher shear rates which are typical in the elastomer industry, representative trials have been made with the rheovulkameter. as it can be seen from the Injection Moulding test (moulded goods), shows its benefits as an external lubricant and dispersing agent due to the fatty acid amides content. a acts as an internal lubricant and provides a significant improvement of the flow and dispersion of the compound Influence on the physical properties hore Hardness hore phr MPa Tensile trength phr 60 Deosol H 14.5 Deosol H MPa Modulus 200 % Deosol H phr % Compression et 24 h / 100 C phr Deosol H the physical properties of conventional cr-compounds are slightly influenced by the addition of the Processing additives. the only exception: for applications where the compression et (c) is important, is not recommended as it may effect the c value. Especially a and are wellestablished as Processing additives in conventional black cr-compounds. further details and results of the test series can be found in the appendix. 5

6 -KONTKT ETU-free / MTT-ystem Recipe 251 C deoflow deoflow deoflow deogum Baypren neoprene WHV Carbon black n Plasticizer do MgO tearic acid OdP deoflow 3 deoflow 3 deoflow 3 deogum 3 ZnO MTT Total phr Mtt (3-Methyl-thiazolidine-thione-2) is used as a worker-friendly alternative for Etu (ethylene thiourea) in Polychloroprene rubber. the following test series indicate that an interaction with Processing additives is possible Influence on the processing properties Mooney ML 1+ 4, 100 C 25 Mooney corch 130 C, t MU min the tests with the Mtt-system show, that a and are extremely effective. both products have no adverse effect on the vulcanization characteristics of the compound. a and lead to a small optimization of the Mooney corch t 5 values as well as a distinct improvement of the flow. shows a slight activation of the vulcanization process, which can result in a loss of processing safety (corch time). 6

7 cm³ Injected volume after 70 s Injection Moulding Test cm³ Injected volume after 70 s Capillary Rheometer Test 90 C leads to a strong influence on the vulcanization, which is documented by a significantly longer corch time or vulcanization time. the result of the Injection Moulding test must be evaluated under consideration of the long corch time Influence on the physical properties hore Hardness hore MPa Tensile trength MPa Modulus 200 % % Compression et 24 h / 100 C Once again a and are recommanded due to their small influence on the physical properties. the influence of on the vulcanization is indicated by the reduction of the Modulus and a higher compression et (c). 7

8 -KONTKT ETU-Free / ulphur-ystem Recipe 251 C deoflow deoflow deoflow deogum Baypren neoprene WHV Carbon black n Plasticizer do MgO tearic acid OdP deoflow 3 deoflow 3 deoflow 3 deogum 3 ZnO TMTM dotg ulphur Total phr Influence on the processing properties MU Mooney ML 1+ 4, 100 C min Mooney corch 130 C, t Injected volume after 70 s Injection Moulding Test Injected volume after 70 s Capillary Rheometer Test 90 C cm³ cm³

9 ulphur-systems are often used for cr-compounds, requiring a high processing safety. therefore the use of Processing additives is highly recommended. Once again a is well balanced, closely followed by. both products cause a significant reduction of the viscosity, ensuring good flow and processing safety. as described at 3.1.1, shows its particular advantage as an external lubricant and a mould release agent Influence on the physical properties 65 Hardness hore Tensile trength hore MPa Modulus 200 % Compression et 24 h / 100 C MPa % the influence of the Processing additives on the physical properties is relatively low. the use of a and leads to a lower value of the hore a hardness. furthermore causes an increase of the compression et. 9

10 -KONTKT Conventional, light coloured CR-Compound Recipe 251 C deoflow deoflow deoflow deogum Baypren neoprene WHV Clay ilica (BeT 125 m²/g) Plasticizer do MgO tearic acid Vulkanox BKf deoflow 3 deoflow 3 deoflow 3 deogum 3 ZnO MBT etu Total phr Influence on the processing properties Mooney ML 1+ 4, 100 C Mooney corch 130 C, t MU 40 min Injected volume after 70 s Injection Moulding Test Injected volume after 70 s Capillary Rheometer Test 90 C cm³ cm³

11 the positive effect of using Processing additives in combination with light fillers in rubber compounds is obvious. all DOG-products tested reduce the viscosity and provide an optimized flow of the compound. the homogeneous distribution of light fillers is quite often difficult, therefore a and are recommended to improve the dispersion. this effect on the dispersion of light fillers is documented by the following physical values Influence on the physical properties 66 Hardness hore 18.0 Tensile trength 17.7 hore MPa MPa Modulus 300 % % Compression et 24 h / 100 C With regards to a low impact on the physicalmechanical properties, the use of is recommended since the mechanical values are almost unchanged. by using a noticeable influence on the vulcanization can be observed. Overall a can be deemed as the most efficient Processing additive, because it strongly improves the viscosity without significantly influencing the mechanical properties. 11

12 -KONTKT Use and Rating of Processing dditives in CR-Compounds Deosol / M H 294 Comprehensive urvey Conventional, black QQQ QQ 1) QQ QQ Q QQ CR-compound ETU-free ystem QQQ QQ 1) QQ QQ Q QQ (sulphur) ETU-free / MTT-ystem QQQ Q 2) QQ Q Q QQ Conventional, light coloured QQQ QQ 1) QQQ QQ Q QQ CR-compound 1) may bloom 2) Influence on vulcanization possible QQQ excellent QQ good Q possible deoflow Deosol Homo- Deotack P / M H 294 genisator Deotack DL Main Effects Flow Improvement QQQ QQQ QQ QQQ QQ Release QQ QQQ QQ QQQ Tack QQQ QQQ Dispersion QQQ QQ QQQ QQ QQ QQ QQQ excellent QQ good QQQ ehr gut QQ Gut Q Möglich 12

13 5. General Product Information Zinc-free Dispersing gents Type ppearance Density Dropping sh BfR 1) FD 2) Dosage [g/cm 3 ] Point [ C] [%] [phr] beige pellets ± or flakes M beige pellets ± D beige-grey pellets ± ± beige pellets ± ± or flakes yellowish flakes ± pecial Performing gents Type ppearance Density Dropping sh BfR 1) FD 2) Dosage [g/cm 3 ] Point [ C] [%] [phr] yellowish flakes ± 5 3 ± light brown pellets ± Emulsion based Dispersing gent Type ppearance Density Dropping sh BfR 1) FD 2) Dosage [g/cm 3 ] Point [ C] [%] [phr] Deosol H beige pellets ± 5 20 ± Homogenizing and Tackifying Resins Type ppearance Density oftening sh BfR 1) FD 2) Dosage [g/cm 3 ] Point [ C] [%] [phr] Homogenisator light yellow pellets ± or flakes Homogenisator dark yellow flakes ± D Deotack R yellow pellets ± Resinous Plasticizer / Tackifier Type ppearance Density ctive sh BfR 1) FD 2) Dosage [g/cm 3 ] ubstance [%] [%] [phr] Deotack P yellow high viscous liquid Deotack 70 DL white powder ± ) BfR: Bundesinstitut für Risikobewertung, recommendation XXI. 2) FD: Listed in Food and Drug dministration

14 -KONTKT ppendix Complete Overview of all Test eries 6.1 Conventional, black CR-compound deoflow deoflow deosol H 251C phr phr phr baypren 110 / Neoprene Wrt baypren 230 / Neoprene WhV carbon black N Plasticizer DO MgO tearic acid ODPa Processing agent ZnO Mbt Etu total phr Mooney Viscosity Ml c Mooney corch 130 C time t 5 [min] after 4 weeks, time t 5 [min] Rheometer MDR C / 6 min ' min [Nm] ' max [Nm] t 10 [min] t 90 [min] Vulcanization: 30 min / 155 C, specimen 6 mm hardness [hore a] rebound [%] Vulcanization: 20 min / 155 C, 2-specimen tensile trength [MPa] Elongation at break [%] Modulus 200% [MPa] tear resistance [N/mm] Hot ir geing 72 h / 100 C retention tensile trength [%] retention Elongation at break [%] change in hardness [hore a] Compression et 24 h / 70 c [%] h / 100 c [%] Rheovulkameter Inject. Moulding Test, press. 60 bar, inject. time 70 s, cap. / piston 100 C, mould 1 C Volume after 70 s [cm³] Volume peed [mm³/s] Rheovulkameter Capillary Test, pressure 60 bar, injection time 70 s, capillary / piston 90 C Volume after 70 s [cm³] Volume peed [mm³/s]

15 deoflow deogum deogum Homo genisator deotack P phr phr phr 251C baypren 110 / Neoprene Wrt baypren 230 / Neoprene WhV carbon black N Plasticizer DO MgO tearic acid ODPa Processing agent ZnO Mbt Etu total phr Ml c Mooney Viscosity Mooney corch 130 C time t 5 [min] after 4 weeks, time t 5 [min] Rheometer MDR C / 6 min ' min [Nm] ' max [Nm] t 10 [min] t 90 [min] Vulcanization: 30 min / 155 C. specimen 6 mm hardness [hore a] rebound [%] Vulcanization: 20 min / 155 C, 2-specimen tensile trength [MPa] Elongation at break [%] Modulus 200% [MPa] tear resistance [N/mm] Hot ir geing 72 h / 100 C retention tensile trength [%] retention Elongation at break [%] change in hardness [hore a] Compression et h / 70 c [%] h / 100 c [%] Rheovulkameter Inject. Moulding Test, press. 60 bar, inject. time 70 s, cap. / piston 100 C, mould 1 C Volume after 70 s [cm³] Volume peed [mm³/s] Rheovulkameter Capillary Test, pressure 60 bar, injection time 70 s, capillary / piston 90 C Volume after 70 s [cm³] Volume peed [mm³/s] 15

16 -KONTKT ETU-free / MTT-ystem deoflow deoflow deoflow deogum 251C baypren 110 / Neoprene Wrt baypren / Neoprene WhV carbon black N Plasticizer DO MgO tearic acid Octamine Processing agent ZnO rhenocure crv/lg total phr Mooney Viscosity Ml c Mooney corch 130 C time t 5 [min] after 4 weeks, time t 5 [min] Rheometer MDR C / 6 min ' min [Nm] ' max [Nm] t 10 [min] t 90 [min] Vulcanization: 30 min / 155 C, 6 mm specimen hardness [hore a] rebound [%] Vulcanization: 20 min / 155 C, 2-specimen tensile trength [MPa] Elongation at break [%] Modulus 200% [MPa] tear resistance [N/mm] Hot ir geing 72 h / 100 C retention tensile trength [%] retention Elongation at break [%] change in hardness [hore a] Compression et 24 h / 70 c [%] h / 100 c [%] Rheovulkameter Injection Moulding Test, pressure 60 bar, injection time 70 s, capillary / piston 100 C, mould 1 C Volume after 70 s [cm³] Volume peed [mm³/s] Rheovulkameter Capillary Test, pressure 60 bar, injection time 70 s, capillary / piston 90 C Volume after 70 s [cm³] Volume peed [mm³/s]

17 6.3 ETU-free / ulphur-ystem deoflow deoflow deoflow deogum 251C baypren 110 / Neoprene Wrt baypren / Neoprene WhV carbon black N Plasticizer DO MgO tearic acid Octamine Processing agent ZnO tmtm DOtG ulphur total phr Mooney Viscosity Ml c Mooney corch 130 C time t 5 [min] after 4 weeks, time t 5 [min] Rheometer MDR C / 6 min ' min [Nm] ' max [Nm] t 10 [min] t 90 [min] Vulcanization: 30 min / 155 C, 6 mm specimen hardness [hore a] rebound [%] Vulcanization: 20 min / 155 C, 2-specimen tensile trength [MPa] Elongation at break [%] Modulus 200% [MPa] tear resistance [N/mm] Hot ir geing 72 h / 100 C retention tensile trength [%] retention Elongation at break [%] change in hardness [hore a] Compression et 24 h / 70 c [%] h / 100 c [%] Rheovulkameter Injection Moulding Test, pressure 60 bar, injection time 70 s, capillary / piston 100 C, mould 1 C Volume after 70 s [cm³] Volume peed [mm³/s] Rheovulkameter Capillary Test, pressure 60 bar, injection time 70 s, capillary / piston 90 C Volume after 70 s [cm³] Volume peed [mm³/s]

18 -KONTKT Conventional, light coloured CR-compound 252C deofl. deofl. deofl. deog. deosol Hom o- H ge n deot. dl baypren 110 / Neoprene Wrt baypren 230 / Neoprene WhV china clay Perkasil k Plasticizer DO MgO tearic acid Vulkanox bkf a Deosol h 3 homogenisator Deotack 70 Dl 4.5 ZnO Mbt Etu total phr Mooney Viscosity Ml c Mooney corch 130 C time t 5 [min] after 4 weeks, time t 5 [min] Rheometer MDR C / 6 min ' min [Nm] ' max [Nm] t 10 [min] t 90 [min] Vulcanization: 30 min / 155 C, 6 mm specimen hardness [hore a] rebound [%] Vulcanization: 20 min / 155 C, 2-specimen tensile trength [MPa] Elongation at break [%] Modulus 300% [MPa] tear resistance [N/mm]

19 6.4 Conventional, light coloured CR-compound (continued) 252C deofl. deofl. deofl. deog. deosol H Hom o- ge n deot. dl Hot ir geing 72 h / 100 C retention tensile trength [%] ret. Elongation at break [%] change in hardness [hore a] ±0 Compression et 24 h / 70 c [%] h / 100 c [%] Rheovulkameter Injection Moulding Test, pressure 60 bar, injection time 70 s, capillary / piston 100 C, mould 1 C Volume after 70 s [cm³] Volume peed [mm³/s] Rheovulkameter Capillary Test, pressure 60 bar, injection time 70 s, capillary / piston 90 C Volume after 70 s [cm³] Volume peed [mm³/s]

20 -KONTKT 40 add efficiency... in more than 70 countries worldwide Hamburg Issue: March 2008; ubject to changes and alterations.,, Deolink, Deovulc and Dispergum are registered trademarks of DOG Deutsche Oelfabrik. Europe sia merica frica ustralia l ustria l Belarus l Belgium l Bosnia and Herzegovina l Bulgaria l Croatia l Czech Republic l Denmark l Estonia l Finland l France l Germany l Great Britain l Greece l Hungary l Ireland l Italy l Latvia l Lithuania l Luxembourg l Macedonia l Malta l Norway l Poland l Portugal l Romania l Russia l erbia l lovakia l lovenia l pain l weden l witzerland l The Netherlands l Turkey l Ukraine l China (PRC) l India l Indonesia l Iran l Israel l Japan l Cambodia l Kazakhstan l Laos l Lebanon l Malaysia l Myanmar l Pakistan l The Philippines l ingapore l outh Korea l ri Lanka l Taiwan (ROC) l Thailand l United rab Emirates l Vietnam l rgentina l Brazil l Canada l Chile l Colombia l Costa Rica l Mexico l Peru l U l Venezuela l Morocco l outh frica l Zimbabwe Use of text and pictures even in extracts is subject to approval of the editor and is illegal to copyright. This also applies to copies, translations, micro recording, saving on data carrier and/or commercial use of addresses and names especially sales to third parties. l ustralia l New-Zealand ny technical consultation provided by us merely constitutes a guideline without any committal even with regard to any third party s rights and will not dispense from the clients examination of the products supplied by us. Processing operations, application and use of our products will be the client s exclusive responsibility. We guarantee the faultless quality of our goods, as defined in our general terms of sale and delivery. DOG Deutsche Oelfabrik Gesellschaft für chemische Erzeugnisse mbh & Co. KG Ellerholzdamm Hamburg Germany Post Box D Hamburg Germany Phone +49(0)40 / Fax + 49(0)40 / info@dog-chemie.de