DE1906765A1 - Vulcanization process - Google Patents

Description

Folder 21848 - Dr ₀ K ₁
Case Bo20829

Description of the patent application of

Imperial Chemical Industries Ltd », London, Great Britain

concerning
Vulcanization process

Priority: February 14, 1968 - Great Britain

The invention relates to an improved vulcanization process for use with ethylene / propylene terpolymer rubber

Ethylene / propylene terpolymers are copolymers of ethylene, Propylene and a smaller proportion of a diene * such as ZoB "Dicyclopentadieno These terpolymers can be vulcanized by sulfur in the presence of an accelerator system, whereby the accelerator system as the primary glue

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Köfflnü.ichen accelerators, such as ", an accelerator of the 2hiuram or dithiocarbamate type, and as a secondary accelerator a conventional accelerator such as Z ₀ B ₀ an accelerator of the thiazole type. These accelerator systems have the disadvantage that they develop strong surface efflorescence tend and result in only a slow vulcanizate! Gas velocity which cannot be improved if the amount of the primary accelerator is increased »

It has now been found that these disadvantages due to the use

part of the formation of certain dialkylthiophosphoryl sulfides instead of / the

Accelerator system can be eliminated or reduced «.

According to the invention, an improved method for vulcanizing ethylene / propylene terpolymers is proposed, which is stated that you can use the terpolymer Sulfur, a bis (dialkylthiophosphoryl) sulfide, in which the sulfide group is a disulfide, irisulfide or setrasulfide group is, and heated with a conventional accelerator

The preferred bis (dialkylthiophosphoryl) sulfide is bis (diethylthiophosphoryl) trisulfide. If the size of iHkylgruppen rises then falls Viüieanisierungsaktivltäto However, not preferred is the dimethyl compounds because they stink * md somewhat unstable _o The disulfides xmä Tristalfide SSIG - 3n lower

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Seigang sum bloom than the tetrasulfides. It is preferred to use bis (dia23 ylthiopliosphoryl) sulfide to replace the primary accelerator, in which case the conventional accelerator used in the process of the invention is a secondary accelerator _{If f is} like z ₀ B ₀ a thiaaol like Kereaptofcenzthiassol or Dlbenathiazyldisulfid _p or a BenztMasFlsulfenamids like Benathiazylsulfen (cyclohexyl) amid "or a substituted thiourea like Diphenylthiourea or Lthylsnttd.oharnst of f _o

The BisCdialkylthiophosphoryl) sulfide can, however, also the secondary Replace accelerator, in which case the one in the erfindungsgeuäßsn ¥ experienced conventional sulfur-containing accelerators will be a primary accelerator, like a «B» a s, ifie tetramethylthiuram disulfide, tetraethylthiuram disulfide

tiss. ₉ TetramethylthiurammonosTilfid or Dipentamethylenethiuramteiäsasulfids or a dithiocarbamate such as zinc diethyldithiocarbamate, Ziafcdiiaetliyldithiocarbamat or zinc-di-n-butyl-dithiocarbamate ο

If desired, the bis (dialkylthiophosphoryl) sulfide can be added eätalich to a Vtilkanisierungssystera on the basis of conventional rather besides be used, or only a part can be used one or more of the conventional accelerators in a bleeding system for the sulfur vulcanization of the terpolymers »

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«= 4 · -

Dae bis (dialkylthiophosphoryl) sulfide can be used in an amount of 0.5-6 * $ 0 and preferably 1.5-3.5? »» Based on weight of the terpolymer, but larger or smaller amounts can also be used if necessary «.

The conventional sulfur-containing accelerators can be used in amounts of O, 5-3 "O ^ and preferably from 0.5 to 1> 5 #» on the weight of the terpolymer used, but more or less of these quantities can be possibly used also _{o 0}

The sulfur can be used in the usual amount; these is expediently between 0.5 and 3 «Q £, based on the Terpolymer weight o

The inventive method can be carried out at any convenient temperature, for example at 130-200 ⁰ C and preferably at 140-180 ⁰ G, but temperatures outside this range may be used if desired, also "

The sulfur, the bis (dialkylthiophosphoryl) sulfide and the conventional sulfur-containing accelerator can be incorporated into the terpolymer by any conventional method prior to carrying out the process according to the invention, for example on a two-roll mill _{or the like}

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The terpolymer can contain the usual additives and auxiliaries, such as fillers, pigments, antioxidants and processing oils.

The invention is illustrated in more detail by the following examples « The examples are not to be interpreted in a restrictive sense. »All parts and percentages are expressed in weight, provided nothing else is specified

example 1

Rubber compounds are made from the following ingredients adding the polymer to the fillers in a laboratory Banbury mixer and the processing oil are mixed together, after which the addition of sulfur and the accelerator on a two * roller rubber mixers connected.

Ethylene / propylene terpolymer 100 parts

(Shell BOP 900)

Zinc oxide 5 parts

Fast extrusion black 100 parts

Processing oil 30 parts

Sulfur 1.5 parts

Accelerators as indicated in Table X

Table X is the Mooney scorch at 130 ⁰ C, the Oszillationssoheibenviskosimeterwerte at 160 ⁰ C (which the

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Change in dynamic shear modulus over time at, one constant temperature), tensile strength, elongation at break, the module and the pressure deformation (oompreasion set) according to the Vulcanization on ο

Table I.

Hercaptobenzothiazole 0.5
1.5 0.5
1.5 0.5
5.0 0.5
5.0 Bie (di§.thylthiophospbi; fyl) trisulfide 17th 12th 25th 16 Mooney Anvulkanlsation at 150 ⁰ C
(min to min + 10) 52
74 27
76 50
62 25th
86 Oscillation viscometer
at 16000, time to au 90 #
Networking (min)
Torque with 9Q # networking
(in lbs) 97
144
151 122
147
157 80
112
122 140
168
168 V ¹ »! frflni sation
160 ^ 0 ( ^m An) 540
520
265 575
290
265 255
240
215 520
255
215 Tensile strength (kg / cm ² ) 10
20th
50 66
105
125 80
116
150 68
102
116 107
150
150 Elongation at break {%) 10
20th
50 46
19th
14th 21
15th
10 49
25th
16 17th
10
8th Module at 200 ^ iger 10
Elongation (kg / om ² ; ₂ o
50 Druolno deformation 70 ⁰ C 10
(24 st 255 & together * -
printing) ²⁰
50

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Example 2

The procedure of Example 1 is repeated, with the II beauty specified accelerators are used in Ta * _o and the results obtained are give in the Table close _o

Table II

Mercaptobenzothiazole 0.5 0.5 14th - 0.5 0.5 13th 0.5 17th 0.5 0 _e 5 letramethylt muram monosulfide 1.5 - 122 - - - - - Bis (diethylthiophosphoryl) - 1.5 153 3.0 - - - dusulfide 167 Bis (diethylthiophosphoryl) - - 27 380 ca 1.5 27 3.0 24 cm - trisulfide 76 305 77 93 Bis (diethylthiophosphoryl) - - - 275 - - - 1.5 3.0 tetrasulfide 81 Mooney vulcanization at 17th 115 18th 10K2 14th 130 ⁰ C (min hie win * 10) 132 118 139 Oscillating Disc Viscosity 25th 153 156 meter 16O <> C 14th 164 178 Time to 90% networking
(min) 30th 13th 24 385 355 27 24 Torque at $ 0? & Iger ver 75 85 335 255 75 88 mesh (in lbs) 280 250 Vulcanization 76 98 160OG 1min) 111 134 Tensile strength (kg / cm ² ) to 98 132 131 158 119 140 20th 152 163 24 20th 153 163 30th 162 170 15th 12th 164 172 Elongation at break (%) 10 370 370 12th 10 385 370 20th 345 300 335 295 30th 285 245 295 ² .55 Module at 200% elongation 10 68 92 76 95 (kg / cm2) 20 108 124 111; 128 . 30th 125 146 127 148 Krucfererfürnoing at 70 ⁰ C 10 44 21 27- 20th (24 st, 25 # together- 20 19th 12th 16 11th printing) 30 13th 11th 12th 10

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Example 5

The Dao procedure of Example 1 is repeated ₉ using the following ingredients:

Ethylene / propylene terpolymer 100 parts

Zinc oxide. 5! Hurry

Stearic acid 1 part

Fast extrusion black 100 parts

Processing oil 30 parts

Sulfur 1.5 parts accelerator as indicated in Table III

The results obtained are given in Table III.

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Table III

Mercaptobenzothiazole
Tetramethylthiurane ionosulfide
Bis (diisopropylthiophosphoryl) disulfide
Bia (diethylthiophosphoryl) trisulfide 0.5
1.5 0.5
1.5
3.0 0.5
1.5
3.0 0.5
L5
4.0 Mooney scorch at 15O ⁰ C
(min to min + 10) 16 15y2 20th 21 Oscillating disk viscometer 160 ° G
Time to 90 # networking (min)
Torque with 90 # networking
(In lbs) 51
65 24
77 26th
82 26th
78 Viii ksnisierung at
16O ^ü CJ (min) 95
158
151 131
160
166 122
157
158 127
158
162 Tensile strength (kg / cm ² ) 10
20th
50 550
295
275 555
245
225 340
250
205 350
250
205 Elongation at break (S) 10
20th
50, 66
105
120 91
155
151 86
135
150 92
157
155 Module at 200 # expansion 10
(kg / cm2) 20
50 52
26th
19th 42
19th
14th 56
25th
16 62
25th
14th Compression deformation at 7O ⁰ C 10
20th
30th

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Claims (1)

P ₁ at e.fl t . Expectations Process for the vulcanization of ethylene / propylene terpolymers characterized in that the terpolymer with sulfur, a bis (dialkylthiophosphoryl) sulfide, in which the sulfide group has a disulfide, tris-olfid " or tetrasulfide group is «wnd with a conventional one Heated accelerator The method of claim 1, characterized in that _v is the terpolymer with sulfur »heated a bis (diäthylthiophosphoryl) sulfide and a conventional accelerator" Process according to claim 1, characterized in that the terpolymer is heated with sulfur, bis (diethylthiophosphoryl) «= - trisulphide and a conventional accelerator» 4 «Method according to claim 1, 2 or 3, dadursh characterized ₉ that the traditional accelerator is a Selnandary accelerator« ο method according to claim 1, 2 or 5 _? as we have also known that the traditional Bsse'ialeu · = · niger ® is part of a 3 visualization sysateias on the? Base 909838/1504 conventional accelerator is ο ο method according to claim 1, / 6der 5? known thereby draws that the terpolymer with sulfur and a Accelerator system based on a conventional accelerator for the sulfur vulcanization of the terpolymer and a bis-CdialkylthiophosphorjlJ-sulfidi which one Part of replacing one or more of the conventional accelerators, heated ο method according to one of claims 1 to 6 _? characterized in that the bis (dialkylthio <~ phosphoryl) sulfide in an amount of O ₈ , 5-6 * 0? » and preferably = used from 1 _f 5 ~ 3 _f 5f ° t based on the weight of the terpolymers _r * ο Process according to one of Claims 1 to 7, characterized in that the conventional sulfur-containing accelerator is used in an amount of 0 _s 5-3 »0 $, preferably from Ο _Ρ 5 ° * 1» 5 $ »based on weight of the terpolymer ο Method according to one of claims 1 to 8 _f, characterized in that the sulfur is used in a Henge of Ο ₈ 5-3ρΟ ^, based on the weight of the sulfur, PATiMTANWXtTB W1.-1NG.H. FINCKE, DIPL.-ING.H.BÖHI DlPL-ING. S. STAEGH 909838/1504