DE1694786A1 - Hot-vulcanizable synthetic rubber mixture - Google Patents

Description

EGG. DU PONT JDB NEM0UH3 AND 00Μ? Α1ΠΓ .., · ' 10th and Market Treeta, Wilmington, Delaware 19 899, V. 3t, A

Hot-volcanic Ktraatkauteohj ^ iaohung

ι. «- i

The invention relates to vullcanieierber · Hieohpolyiatrii * -fc «ii <jlMii ~ gen as well as the core division of eynth« tiaohwi! »Uteolxujltn and Brztugnieeen from the same. _v

Certain kautiohukelaetisohe PolyaerJeate, which in the main fcfjfc | # Have ethylene-unsaturated bonds, laosen eiöh duroh Phenols, β · Β. Bi «-. (Ethylol) -reeole, 'mi products vulcanize rapid physical Efgeneohhaften, play this role in butyl rubber, for which »die toad Bonds belong to the monomer units dee isoprene, the the main chain in 1,4-st θ llung embedded bind. YulkaxiieateJ the duroh T | lkanieiertii ton ButylkadtioAuk «it warwi Phenolhareea are produced, beii4tn a «ftuegeieioiieii ^

■ competence

therefore, against the warmth of the age, '«" f

toeö ^ i / iitt ν

ίο γιο **

1OnAtVi for application tweoke, such as tire vulcanizing oil, to whom the ·· Bigeneohaft is important.

Since a, via the chewed α-Konoolef in-Miachpolymsri- • »it unsaturated side chains have advantageous properties that make their use in important areas of application of rubbers possible, it was investigated whether the advantages that" I get through the crosslinking "it Phenolic resins can be achieved, can also be extended to the Tulkanieate of these copolymers. Ethylene-propylene tripolymers of this type, which contain units of a conjugated line in low concentrations, can be vulcanized with sulfur, but not within ψΧ% of warmable phenolic hareen alone. The ease of vulcanization apparently depends on the type of crosslinking · β part β.

Isohpolynierieate »with low content · α of T, 1-disubstituted or 1,24trieubetituier-tta olefinic groups (i.e.

Groups of Jfrutaaaensctgung USmCB ^ ^^ ode; e CWJ _n ^), can ■ vulcanize it with more rigid Hesols:! without showering special activating sides. The monomeric unit of 5-methyllene-norbornene- (2) in the Mieohpolymerieaten * J8A patent specification 3,093,621 is an example of • a unit, ^ Le has a 1,1-disubstituted olefinic group Isoprene in butyl rubber

SNSPSGTlD

# 9 * 786

10 710

is an abbreviation for a unit which has a 1,1 * 2-trisubstituted olefinic group. However, it was found these copolymers, did all cross-linking in ethylene, Propylene hexadiene chewing chuk 1,2-disubstituted olefin Have side groups in low concentrations, eioh Do not let it vulcanize in this way. To be effective Vulkanieationarustand to achieve, did here rather the addition of a Lewis acid, such as tin (II) chloride dihydrate, as an activating agent required. Baeen, like Sinkoxyd, are allowed in such mixtures should not be included.

Daa vulcanize old beeoles with activation aittela Tin (II) chloride dihydrate, however, is because of the nature of the aioh thereby forming lifting products from Haohteil. Here developed Uj Sioh next large amounts of corrosive hydrogen halides. Aueserde «there is an effect of the metal halide idea set up as an activation agent on the resol, which is the slight Processability binds. Ba would therefore be an advantage if ·· geXKnge »Xthylen-Prbpylen-Miechpolyeeriaate« with reetliohtn 112-diaubated olefinic groups without activating duroh vulcanize metal halides.

9a it has now been found that eioh saturated in the main chain molten hydrogen misohpolyeerieate from alndeatena of a straight

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chain α-monoolefin and at least one non-conjugated diene, which have 1,2-disubstituted ethylene-unsaturated side groups in amounts of preferably at least about 2.0 mol ~ #, look for the addition of (a) a 611ö, thermosetting, monomeric p-alkylphenol or resole with several -CH ₂ -X groups, where X is a halogen atom or a hydroxyl group and the halogen content is at least 1% by weight of the phenolic compound, and (b) a Lewis base, namely zinc oxide, magnesium oxide or tin (II ) -oxide, let vulcanize. The mixed polymer mixed with the vulcanizing agents must be heated to Bweoke vulcanization.

The monoolefins used for the production of the copolymers have the general structural formula R-GH «0H ₂ , where R is an alkyl group with up to 16 carbon atoms or a water oil. Ethylene is by far preferred, and of the remaining monoolefins, the lower members, in which B contains up to 4 carbon atoms, are preferred in view of their ready availability. Also mixtures of monoolefins. may be used who dene A group of dienes are the off en-chain dienes having a terminal carbon-carbon "double bond and a 1,2-dieubstituierten carbon-carbon double bond. The preferred group of such compounds are open-chain dienes with 6 to 22 carbon atoms in the Molcs-

- 4 «.
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HH kül, which have the general formula GH ₂ SsCH-R ₁ -CsC-R ₂ , in which R _{1 is} an alkylene radical and R _{2 is} an alkyl group. A particularly preferred example is hexadiene- (1,4). Another group of non-conjugated dienes are the substituted norbornene (2), in which the second carbon-carbon double bond is 1,2-disubstituted. Examples are 5- (2 ^f -butenyl) -norbornene- (2), 5- (3 * -pentenyl) -norbornene- (2) and dicyclopentadiene. Typical copolymers are described in U.S. Patents 2,933,480 and 3,093,620.

The hydrocarbon copolymers should have more unsaturated bonds in the form of 1,2-di-substituted ethylene unsaturated

■ -, _-- ί. . ■ ■ ■ ■ j

have thick seiton chains than for the usual vulcanization with sulfur is required {and preferably at least about 2.0 mol- ^. Copolymers that are not enough unsaturated Have bonds of this kind (e.g. about 1 MoI- ^,! what in a typical case a Mi ^ chpo-lymerisat with! 0.3 g-mol of carbon-carbon double bonds per kg sprioht) cannot be satisfactorily divided with the aid of the invention vulcanize the vulcanizing agent used. All other things being equal, however, the properties improve of the vulcanizate with increasing amount of unsaturated Bonds in the copolymers

6 '^; ■ ■.

10 710

It su ₁ is particularly noted that the ascending in the side chains' [tatetenden unsaturated bonds of the present invention vulcanizable copolymers are characterized in that they are 1,2-disubstltuiert, so have the structure -CtteÖH-. So far it has not been Böglioh to vulcanize copolymers with such double bonds in a satisfactory manner with thermosetting phenolic resins without the addition of tin (II) chloride dihydrate or other Lewis acids, which are troublesome during vulcanization for the reasons given above. On the other hand, copolymers, if they have only low concentrations of 1,1-disubstituted olefinic double bonds,> 0 »CH ₂ , or 1,1,2-trisubstituted olefinic double bonds,> C« = CH-, can easily be used with thermosetting ones

Phenolic resins vulcanize without Zlnn (II) chloride dihydrate

iug ** «t * t to whoever needs it. j

The pheiiolischen vulcanizing agents to be used according to the invention are oil-soluble monomeric 4-alkylphenols or resols with several -GHgl-öruppen in o-position to the phenolic hydroxyl group, where Z denotes a halogen atom or a hydroxyl group. The monomeric form of these vulcanizing agents corresponds to general formula

OH

16947ββ

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in which R is an alkyl, aryl or alkaryl radical having 4 to 16 carbon atoms and X is a halogen atom or a hydroxyl. group means. Typical compounds of this type are 2,6-dibromomethyl-4-tert.butylphenol, 2,6-dibromomethyl-4-ootylphenol and _2f 6-dibroiraethyl-4-phenylphenol. They can be prepared polymeric resols by using one of the methods described in p -Position hydrocarbon-substituted β-phenol with a molar excess of formaldehyde and heated for the purpose of polymerization. The formaldehyde is preferably used in amounts of about 1.5 to 2.1 hol per hol of phenol. In order to obtain vulcanizing agents suitable for the purposes of the invention, the product is halogenated. Both the monomeric and the polymeric phenolic compounds should contain at least 1 wt. -Φ halogen! preferably the halogen is bromine or chlorine. The 4-position hydrocarbon group is the same as for the monomeric compounds. The polymeric phenol should be oil-soluble and reactive in the water. Typical compounds and methods of making the same are described in U.S. Patents 2,972,600, 3,093,613, and 3,165,496. A particularly preferred compound is "Resin SP-1055", commercially available from the Sichteotady Chemical Company. The substance has a specific gravity of 1.00 to 1.10, a melting point in the range of 51 to 63 ° C *, a bromine content of 3.6 to 3.9 percent and a methylol group content in the range of 10.0 to

- 7 -109835/15 92

■■■ ■ ■ '' S? '

10 710 ^Q

12.5 wt. 36 and is produced by using excess formaldehyde with 1.1 _S 3, 3-Setra diethylbutylphenol.

The resin concentration fcami fluctuate within wide limits »If smaller amounts of resin are used» the yulcanization takes a long time and / or higher vulcanization »temperatures have to be used · Shorter yucanization time © !! or lower vulcanization temperatures can be used with higher resin concentrations. Allgeiaeinen Ia leads iaiiter given Vulkanisatiönsbedingungen a Brhb "himg the K011-a © ntration the resin to eteeis irerbesserten yulJmnisation ^ u · stand * The allowable resin concentration iia area ran ti to 24 Sewichtßteilen, vojpzisgsweie © 12-18 (yev / icfhtate : .- len, per 100 parts by weight of copolymer,

The metal oxides are dissolved with the halogen-containing ones. Phenyl compounds used _for the carbon dioxide miso-polishate ZVL vulcanize "The saturation" of the oxides determines the degree of etching of the improvement of the vulcanization conditione. S & im & oil basic oxides "such as tin dioxide (SnOg), but only act as fillers. The oxides of metals, such as magnesium , zinc and divalent tin, are more basic, and the synthetic chewing mixtures in which they are contained achieve better volcanic properties.

'. .- 8 109835/1692

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state as those »those in the absence of this Oxides are vulcanized.

The metal oxides should be added in concentrations of at least about 2 parts by weight per 100 parts by weight of the copolymer. By adding more than about 10 parts by weight of metal oxide no further advantages are achieved "The forthcoming _t train ten concentrations are for zinc oxide, and tin (Il) -oxyd about 5 weight parts, for magnesium oxide about 5 to 10 parts by weight per 100 Gewiohtsteile copolymer.

The size and type of action that has the Metalioxyd on the properties of the vulcanized material is, sound many factors, such as the Halbgengehalt the phenol compound and the presence or absence affects a reinforcing filler *. If, for example, a synthetic rubber is vulcanized, the greatest advantages that are achieved by using zinc oxide are an increase in the tensile strength and elongation at break of the vulcanizate; the resistance to permanent compression set and the? However, the modulus of the vulcanizate has roughly the same values as if no zinc oxide had been added. In other cases, when furnace ruse is used as a reinforcing filler together with zinc oxide, improvements in terms of permanent deformation and modulus or, generally speaking, improved vulcanization are achieved.

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state of consumption »type and amount of metal oxide to be added Let the specialist for the respective Harg, Metal oxide and the other aggregates as well as depending on the Desired properties of the yulcanizate by Roucinev requests determine.

! The hydrocarbon copolymers can be used for improving ™ the properties of the vulcanizates, the usual additives to Evjb and mineral fillers within a wide range; Concentration range be added. Also the usual plasticizer oils can easily be incorporated into rubber compounds that can be vulcanized by resin, thereby reducing the limits of the filling can be expanded »Paraffinic, naphthenic and aromatic oils.

The resin-vulcanizable, soot-filled rubber ^ mixtures show a good compatibility. With tightness very satisfactory extruded products are obtained, which are characterized by sharp edges, smooth, shiny sides and excellent pore accuracy and dimensionality.

The KunstkautBGhukmisohungen genäse the invention may be in conventional KautsohukoischTorrichtungari, z ', B _c are prepared on a roll mill or in internal mixers such as the Banbury Misoher.

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The vulcanization takes place by heating to about 120 Ms 200 ° C. Higher temperatures than 200 ° 0 are usually considered impractical in seehnik. Temperatures in the range from 160 to 200 ° C are preferred range for a given resin concentration and a given curing time a better state of cure is reached "the Tulkanisationsseit 1st to those skilled optional% Vulkanisatiön & times of 60 to 120 Kinuten, however, have proven advantageous" Ih general, obtained with the same YulkaniBationsmitteln at a given temperature products of improved Vulcanization state when the vulcanization tent is extended »The results of vulcanization tests suggest that the most favorable vulcanization state, generally around 60 to 00 minutes at 200 ° C and after 90 to 120 minutes at 180 ° C, is achieved *

In the following examples refer to file if nothing otherwise stated, on weighted quantities »

Ia the following examples are for the various Ingredients and properties of the vulcanizates used the following symbols

1-098.35 / 1592-,

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Resin A - The phenolic resin "Resin SP-1055" M described above - module at 100 # elongation, kg / cm ² - module at 200 # elongation, kg / om ² T _ß - tensile strength at break, kg / cm Ε, , - elongation at break, $>
SAF - furnace soot for generating high abrasion resistance.

The properties of the vulcanizates are as follows ASTM-P ruf methods determined. The stress-strain properties are, unless otherwise specified, determined at 25 ° G «

Property ASTM method Stress-strain curves D-412-61T Permanent compression set D-395-55 Elasticity according to Yerzley D-945-59 Shore Α hardness Β-676-59Ϊ

example 1

The vulcanization of a copolymer of ethylene and Hexadiene (1,4-) according to the invention is carried out as follows:

Through interpolymerization of clay, ethylene and bexadiene- (1,4) in Setraohloräthylen in the presence of a vanadium tris- (acetyl-

109 835 Π 59 2

acetoiiat) and DiisobutylaluiHiniunmjonoohlorid according to the US Pat. No. 2,935,480 manufactured coordination catalyst, a mixed polymer is produced «The product has one
intrinsic viscosity of 1.28 (determined at 30 ° δ in a
0 _f 1% by weight solution of the copolymer in tetrachlorethylene). Bs contains 51.0% by weight of eexadiene (1 _r 4) units (determined by infrared analysis ©). The content of unsaturated * M bonds, determined by BroiHaufeahme (and corrected for substitution), is 2.62 g »moles of carbon-carbon double bonds per Srg, which is 9 * 22. KoI- ^ corresponds to.

Three samples Cdi © Samples 1 to 3) of this ütlschpolyzaesisatss four- »the processed according to the following instructions see below JKunstkautsehukiaischungen Reduced to 50 ° C and slowly incorporated into the ears » The brewing process is ended by another 5 minutes of picking out at 90 ° C.

WHEEL

13 -

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Ropes

Copolymer 100 100 100 (unsaturated bonds «2.6 mol / kg j effective concentration 9» 22 mol-96}

Furnace soot 50 50 50

Stearic acid 111

Zinc oxide 5 ■ -

Tin (XI) oacyd. . , - 5 Magnesium oxide - ■ - - 5

Resin A 12 12 12

The three rehearsals are dureb. 60 minutes of burning at ISO up to 200 ° 0 Tulkanieiert »The yilcanizates have the following properties:

jBigensohaft M, kg / sqm ²

kg / a ²

Ϊ from e 1 1 e I 1 2 . ”JL Tulkani sa fei ons-
tsiaperaturj ⁰ C 79 83
83 76
84 ISO
200 172 167
202 162
197 180
200 SYS
281 249
2-52 252
292 180
200 * »00
290 290
250 280
280 180
200

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Sabelle I (gorta etching)

Vulcanization property temperature » ⁰ C

Permanent deformation in the event of breakage, #

Permanent bridge deformation, fi _ (22 hours at 70 ° C)

(70 hours at 100 ° 0)

Yerzley elasticity. $
at 100 ^° C

Hardness, Shore A

A fourth sample of the, as described above, with aggregates mixed and vulcanized copolymer, which, however, has been added with ice in metal oxide, produces a vulcanizate with inferior properties.

Example 2

180
200 40
28 34
27 31
25th 200 15th
10 20th
9 14th
10 180
200 29
10 40
21 25th
8th 180
200
180
200 64
73
86
88 67
70
87
88 67
77
88
89

The MischpoXysierisat described in Example 1 from ethylene and Hexadiene (1,4) is following the procedure of Example 1 and the add aggregates to the following gate script:

-15 - ■

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File components

Mixed polymer 100

Furnace soot (SAI), 50

Stearic acid 1

Zinc oxide 5

Three samples are prepared from the above approach, with 6 parts for sample No. _1, 12 parts for sample No. 0 and 18 parts for sample No. 3 being added.

These mixtures are chained for 60 or 150 minutes at 180 ° C and other samples of the same for 30 or 60 minutes at 200 ° Ö iRiX. The properties of the vulcanizates obtained are shown in Table II.

Tabel II 1 2 3 vulcanization
Min _e / ° C 133
144
153
140 158
188
166
176 169
204
176
194 M ₂₀₀ J kg / em ² 60/180
150/180
30/200
60/200 247
280
295
272 277
293
279
249 283
248
263
262 T ₃ , kg / cm ² 60/180
150/180
30/200
60/200 470
430
460
450 330
295
315
275 310
235
285
260 60/180
150/180
30/200
60/200 ..-- .16 - _m 109835/1592

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Tabel II continue ") Permanent deformation
at break, £ 60/180
150/180
30/200
60/200 1 2 3 vulcanization
Ett./°C Remaining pressure
shaping, # _
(70 hours at 100 ° C) 60/180
150/180
30/200
60/200 70
56
60
59 35
26th
35
32 29
23
30th
30th Elasticity according to _
Yerzley, ψ (100 ° C) 60/180
150/180
30/200
60/200 59
34
47
27 32
12th
19th
10 24
11
16
10 Hardness, Shore Λ 60/180
150/180
30/200
60/200 59
59
59
63 71
71
70
70 76
74
73
73 Example 3 83
91
89
90 82
89
88
90 84
89
89
89

Two mixed polymer samples are produced by reacting ethylene, propylene and hexadiene (1,4) at 0 ° in tetrachlorethylene in the presence of a coordination catalyst prepared from vanadium tris-Caoetylaeetonat) and Diisofeutylaluminiuminonoöhlcirid "" sample 1 has an ismer © flsoosity of »1,2. and contains- 37» 0 &&% $ ** $ l © aeinh © it @ a miss. If, 7 ffewo «^ H © ii®ai © aC-1f4) =» fehalt an img @ 0ftttigt <m Bindtragdii-l> 6t? Sgt I ₉

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ORIGINAL

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The copolymer of sample 2 contains 35.2 wt »- # Propylene units and 14.3% by weight of hexadiene-d ^ units; its content of unsaturated bonds is 1.28 g ~ mol Koh lenstoif-carbon «double bonds per kg, corresponding to 4.65

* The copolymers are kneaded on the rubber roller frame at 50 ° C, before slowly 50 parts of furnace black and then 1! Peil stearic acid and 5 parts of zinc oxide are added. After a very good distribution of the constituents has been achieved, 12 ropes of phenolic resin A are slowly added and fully dispersed. From these Kunstkautsehukmisohungen prepared plates and KÜgeichen 60 Hinuten be vulcanized in press at 180 ° Q.

The properties of the vulcanizates are shown in Table III «

$, a be I la III

file

HlgöSipoipseslest ". - ■« 100

100

_s i3 m &
gwasme

10 710

table III (lortsetgnng)

Ropes

Stearic acid
Zinc oxide

Harz Ä

Vulcanization 60 Mn. at 180 ° CM, kg / eni ²
, kg / em ²

kg / cm
kg / cm ²

Permanent deformation in the event of breakage,

1 1 5 5 12th 12th -39 ■ 29 85 61 14? 105 195 192 360 4-ω 11 20th 26th ■ 55 59 -60 77 76

Permanent ufcrsri
(22 hours at 70 ° C)

Elasticity according to
Hardness, Shore A

If the same amounts of Hars A su a Mi from ethylene, propylene and Hes: adiene- {1,4) sugesstst., The outer content of unsaturated bonds is only 1.02 mol · = - ^ is obtained during processing Prepare an old yulcanizate in the manner described for samples 1 and 2. Own

achafteno

- 19-109 835/159

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B e e 1 4

Ethylene, propylene and 5- (2 · -Butenyl) -nörbomen- (2) are continuous at atmospheric pressure of the copolymerization tetrachlorethylene, at 25 ° C in the presence of one of yanadium tris (acetylaoetonate) and diisobutylaluminum monochloride naea of the United States Patent Enforcement 3 093 620! subject »You get two. Misoh polymer samples (Samples 1 and 2). The mixed polymer sample JTr. 1 contains 23 wt * -96 Iro-pylene units and has an inner vieoosit & t hair dryer 2 | 73. The Misohpolyinerieatprobe Fr. 2 contains 37 wt .- ^ propylene units and has an internal viscosity of 2.52 «,

The two mixed polymer samples are placed on the Eautsehukwatzenstuhl With aggregates and vulcanizing bags reriaischi; and vulcanized in the press for 60 minutes at 180 ° C ,, Die Mixing pipes are the following:

Sample Kr, 1
(3.77 mol- # C = C) Sample Hr _g 2 *
(1.07 moles "*? * C ^a 0) Mixed polymer 100 100 SAP furnace soot 50 50 Stearic acid ■ i 1 Zinc oxide 5 5 Resin A 12th 12th

* Not within the scope of the invention; only given for comparison purposes.

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The mixing process -let the following: Bie copolymers
ässanäehet are kneaded on the Ikutschuk roller at 40 to 80 ° C, then the filler is added and mixed in homogeneously, whereupon the stearic acid and zinc oxide are added. Then the temperature of the rolling stock is reduced to 40 ° 0, whereupon the resin Λ is added and well distributed.

The properties of the two vulcanizate samples after 60 minutes long vulcanization at 180 ° ö are the following!

at 1 e

KJ ₀₀ , kg / cm ²

- η

G? _B , kg / cm ²

Permanent deformation in the event of breakage,

Permanent printer perforation »$ {22 hours at 70 ° G)

Yerzley elasticity, ψ hardness »Shore A

* Fleas in the cock of the invention _f only indicated below »

■, 1 ■. -. 82 2 * hard 77 64 28 108 266 264 250 510 '.7; 40 ■ - ■ 15 "'..'.- 40 to

21st

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Example 5 '. '' ■

Propylene and 5- (3'-pentenyl) ~ norboraen- (2) are the

Copolymerization at 25 ° C and atmospheric pressure in tetrachlorethylene in the presence of a vanadium tetrachloride. and SiieobutylaluiBiniumiQonochlorid prepared according to the US Pat. No. 3,095,620. Ee two copolymers are produced. The sample ITr. 1 contains 24 wt * - ^ propylene units and 0.97 g-mol carbon-carbon double bonds per kg (3.4-4 mol ~ 3 & unsaturated bonds); the sample Mr. 2 contains 18 öewo ~? & Propylene units and 1.07 g ~ mol Eohlenstoff-Eohlenstöff-Doppelbindxingen per kg (3 _f 77 Get ~ £ unsaturated bonds) "Me inner Yiscositäten the ProbenUr. 1 and Kr. 2 are 1, δ? or 2.1V

The copolymers are made with those given below Aggregates and vulcanizing agents on the rubber whale jsenetuhl mixed at 50 to 60 ° G and then 60 minutes at 180 ° 0 tulips. From label? the Misohvorsohrifte result and the properties of the vulcanizates obtained.

22 ~

0S838 / 1S92

10 710

la bell e

Mixed polymer 100

(unsaturated bonds 0 »97 mol / kg? 3.44 mol *)

Mixed polymer - 100

(unsaturated bonds 1> 07 mol / kg; 3.77 mol *)

SAP furnace soot Stearic acid

Zinc oxide Resin A

Vulcanization 60 min, at 180 ° Q

"Kg / om ^2/2

"Kg / om ²

Permanent deformation in the event of breakage, 1> Permanent deformation, Jt 38 34 i

(22 hours at 700 C) ^

Hardness, Shore A 80 82 example

Ethylene, propylene and bioyclopentadiene are in tetrachlorethylene in the presence, one of vanadium tetra chloride and diisobutyl / aluminum monochloride according to US Pat. No. 3,000,866

- 23 -

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50 50 1 1 5 5 ia 12th $ 8 74 123 159 196 193 310 245 24 21st 38 34

10 Tto

the

. Bs are two Mse & polyffleriaatprdben (samples Sir I .. vn & - 9s *. 2); manufactured. The " Vx & be Hr, 1 contains O, 79: g ~ Möl

The Sindimgen kg (2 _S 69 mole ~ $ h £ robe Is "Si? -

per kg (6.56

will

WfeS «» i isil% ^ iiP

'ils "

10S835 / 1S

measured üosm. äss i® £ ^a ? ε · ®θθ @ "60 Himmfs ^ ^ ei 1S

"'' IT ^ '/', C- ^ JC." do

3- ^:

T69-4786-

Tabel YI (continued) 1 ;' . 2 104 181 α » _Β , kg / cm 2 ■■ "" ■; ..- ■ '■■' ■ 155 13.0 Η · * '■ 5 5 Permanent Deformation at Fraction, i> 49 16 Permanent Compression deformation «

(22 hours at 70 ° C) Hardness, Shore A 78 82 'I.

Example 7

Ss is a copolymer of ethylene and hexadiene (1,4) manufactured with the following characteristics:

Internal viscosity "1.58 unsaturated bonds β 2.6 g-mol / kg" 9.22 mol- #.

The IBLschpolymerisat is mixed with additives and vulcanizing agents according to the following instructions on the rubber roller frame. All components with the exception of the resin are incorporated at 90 ° 0; the resin is added at 55.degree.

Components q? _e ile

Mixed polymer 100

SA7-0fenruee 50

Zinc oxide 5

Stearic acid 1

Resin A 12

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KujiBtkautaohuInsisclnmg is 60 minutes. at 160 ° 0 rulka-Me results are as follows

Module at £ 200? elongation, kg / oa Module at 300 years leveling, kg / oB ² 272 Tensile strength, kg / ce ² 531 Elongation at break, Jt 365 Permanent deformation at fracture, ^ 50 Permanent Bruolnrerfor »sng, f>

(22 hours at. 70 ° E) 40

(70 hr. At 10O ⁰ C) 71

Hardness, Shore A 89 smoothness naoh Yersley (at 100 ° E) * £ 48.7

Claims (4)

169470b- S * I * you t®- a '1S-β greasy Γ 'r'.r cfier «a : δ -η- .fesfl tui er »' ? ^ C 2 710 ten phenol-formaldehyde-eesols with several GHgX groups, v / obei X a halogen, in particular chlorine or BrOR ₁ - oöes? a hydroxyl group, the hydrocarbon stoffsubotit-ue & t in the monomeric phenol or _o the resole is an alkyl "-, aryl *, aralkyl or cycloalkyl group 1st and the halogen content bsw the monomeric phenols. Resole is at least 1 GeWo ^ ₅ based on the Ph end compound. 2. Artificial chewing mixture according to claim 1, characterized that it contains 12 to 18 parts by weight of phenol compound and 5 to parts by weight of metal oxide for every 100 parts by weight of synthetic polymer 3. Kunstkautschukraisehiing according to claim 1 md 2, dadurah characterized in that they are Vulkanisiert! Ttel © ine contains, which has been obtained by bromination dee from 1 mol of 1 , 1.5 P nethylbutylphenol and 1.5 to 2.1 mol of formaldehyde and a bromine content of'3 »6 to 3» 9 wt .- $ S and a Methylol groups & gehaXt τοώ 10.0 to 12.5 wt 4. Kunat rubber mixture according to claim 1 Ms 3 _1, characterized in that the copolymer is a Mechpolysssrisat of ethylene and hexadiene (1,4) tmd the mixture contains the phenolTÖr- bond in amounts τοη 12 to 18 parts by weight per 100 parts by weight of the copolymer. BAft ORfQWAL