DE2010301A1 - Process for welding rubbers and polyethylene of various types - Google Patents

Description

Dipl.-Ing. Adolf H. Fischer
Dipl.-Ing. Wolf-Dieter Fischer
67 Ludwigshafen am Ehein
Richard-Wagner-Strasse 22

Process for welding various types of rubber and polyethylene

The invention "relates to a limitation period for welding of rubbers, especially with a low degree of unsaturation and chlorosulfonated polyethylene and consists in that the foils or the like to be connected to one another are printed on one another when exposed to heat at the points to be connected.

The connection of vulcanized elastomers is so far carried out in various ways. One can, for example, glue based on polychloroprene or Use cyanoacrylate. However, these adhesives have only a low temperature resistance, because this ends at about 80 ° C * Certain special tars in connection with epoxy resins have also been used for this bonding. One more way

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consists in using adhesion promoters such as isocyanates in rubber compounds to be built in. However, these adhesion promoters only become effective with the subsequent vulcanization. You can of course also incorporate them into self-vulcanizing adhesive solutions, which means that when they are joined together two vulcanized elastomers have a high adhesive strength. The latter procedure is very common for Rubber-fabric and rubber-metal compounds are used.

The invention has the task of providing a method for welding rubber and polyethylene of the most varied Art to create without using glue or adhesion promoters and similar materials have to.

The solution to this problem has now been found in the fact that rubbers, especially those with a low degree of unsaturation, are used and chlorosulfonated polyethylene has welded to one another under the action of heat and pressure, whereby one of the previous finding was based on the fact that rubbers were dissolved by chlorinated hydrocarbons permit.

The process according to the invention can be carried out in such a way that at temperatures from 100.degree. C. to 140.degree a pressure of 10 to 70 kgf / cm over a period of 1 to 10 minutes is exercised.

If necessary, however, the process can also be carried out in such a way that a pressure of 3 to 40 kp / cm ^{2 is} exerted at a temperature of 160 ° C. to 180 ° C. over a period of 1 to 10 minutes.

109842/0616

In an earlier application by the same applicant, a method for vulcanizing rubbers is disclosed Proposed with a low degree of unsaturation, in particular of isobutylene-isoprene copolymers (IIR), ethylene-propylene-diene terpolymers (EPDM) or their mixtures, using sulfur, a dithiocarbamate accelerator and a thiazole accelerator, plus that in addition to sulfur, the dithiocarbamate accelerator and the thiazole accelerator a guanidine accelerator and at least one 'further' - · Dithiocarbamate accelerators can be used.

It has now been shown that vulcanized rubbers with low unsaturation, vulcanized in the above-mentioned manner, very good are weldable if they are fully vulcanized according to the invention Condition at temperatures of 100 ° C to 180 ° C, a pressure of 5 to 70 kp / cm a time exposed for 1 to 10 minutes.

According to the invention you can treat vulcanizates that vulcanized either under pressure or without pressure.

In some cases it is advantageous to use gasoline or benzene or ketones or chlorinated vulcanizates Activate hydrocarbons.

Further features of the invention emerge from the following description of exemplary embodiments in FIG Connection with the claims.

For the sake of simplicity, various compounds with the usual abbreviations are taken from the specialist literature designated.

109842/0616

It means:

EPDM corresponds

HR "Hypalon" RSS "Buna S" factis Gloria "

Ethylene-propylene terpolymer rubber

Isobutylene-isoprene rubber chlorosulfonated polyethylene Ribbed smoked sheets But ad i en-Styrο1 Sulfur rapeseed oil factice

During the processing according to the invention, the following results could be achieved at HR, depending on time, temperature and pressure:

A) at a temperature of 10O ⁰ C resulted:

Pressure kp / cm Time / min. Peel strength kp / cm 10 2 1.27 10 10 1.0 20th • 10 1.0 - 30 10 0.94 50 10 2.80

B) at a temperature of 120 ⁰ C resulted:

Pressure kp / cm time / min. Peel strength kp / cm

10 20 30 30 70

3 3 3 5

0.3 0.4

0.65 1.25 0.5

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C) "at a temperature of 140 ⁰ C resulted in:

Pressure kp / cm time / min. Peel strength kp / cm

30th . -3 Time / min. 2.0 ■ 30th 5 2 4.0 50 3 5 1.45 50 5 10 3.85 60 1 2 3.25 70 1 4th 2.45 5 •. 4 ' at a temperature of 160 1 C resulted in: ο ■
Pressure kp / cm 2 Peel strength kp / cm 3 3 0.60 3 4th 0.87 3 . 5 1.47 5 1 0.88 5 2 2.75 5 3 3.10 10 5 2.70 10 3.20 .10 3.88 10 4.42 ' 10 4.22 15th 2.06 15th 2.62 15th 2.60 15th 2.88

20 1 3.25

40 -1 2.70

40, 4.00

109842/0616

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With the inventive method, the unexpected result was obtained that, for example, occurred "ATII at a pressure of 10 and" at a temperature of 160 ⁰ C after one to two minutes, a very high peel strength which is more than twice as high as the strength previously achieved by gluing. It is also interesting that aging tests have shown another increase in the peel strength of 14 days at 80 ⁰ C in all these cases.

A few examples should be given for further explanation be cited.

example 1

This example compares an EPDM mixture with conventional acceleration (A) with a mixture shown with acceleration according to the invention (B), activated with and without solvent (C).

Basic recipe .,

EPDM (0.7 mole % unsaturation) 100.0

Zinc oxide 5.0

Stearic acid 1 »0

FEF carbon black 50.0

SRF carbon black 50.0

HAF carbon black 20.0

naphthenic processing oil 50.0

109842/0616

Vulcanization system ABC

Tetramethylthiuram monosulfide 0.8 1.5 -

2-mercaptobenzothiazole - 0.5 0.5

Pentamethylene thiuram tetrasulfide 0.8 - -

Zinc diethyl dithiocarbamate 3.0

Sulfur 1.5 '1.5 1.2

Zinc dibutyldithiocarbamate - - 1.5

Diphenyl guanidine - - 0.5

Zinc ethyl phenyldithiocarbamate - - 0.7

Peel strengths . .. · ^

Pressure kp / cm time / mini. Peel strength

kp / cm

Activation by A
Methylene chloride

Without activation

A. 10 3 0 B. 10 3 - 1Λ5 C. . 10 3 2.40 A. 10 3 O ^ B. 10 3 1.00 0 10 3 2.00

It can therefore be seen that if one works according to the proposal according to the invention, the crosslinking rate increases EPDM also gives a higher peel strength. It should be noted that the acceleration According to the applicant's older proposal, the primary effect here results, while the dissolution of the remaining one thermoplastic component represents the secondary effect. This should be based on an example of the peel strength an aging of EPDM shown in an example 1C " are, as in the other examples 2 and 3 for the peel strength of butadiene-styrene and üfatur- or • Isoprene rubber with an unsaturation level of

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80 mol%, with A more conventional and B the acceleration according to the applicant's earlier invention for EPDM and Butyl rubber.

Example 1 C

In this example, the peel strength is retained after aging for two weeks at 70 ⁰ C.

Pressure kp / cm time / min. Peel strength kp / cm

Activation by methylene chloride

without activation

10

6.00

5.50

Example 2 100.0 Example 3 100.0 Basic recipe 50.0 Basic recipe 5.0 Buna S 25.0 RSS 3.0 SRF soot 2.0 zinc oxide 4-5.0 HAF carbon black 5.0 Stearic acid 8.0 Stearic acid 5.0 SRF soot 3. ^ Zinc oxide. 1.0 aromatic ver
working oil 2, C aromatic ver
working oil Factis Gloria N-phenyl-N * isopropyl-
p-phenylenediamine N-phenyl-N'isopro-
pyl-p-phenylenediamine Accelerator system

Tetramethylthiuram disulfide 2-mercaptobenzothiazole diphenyl guanide in

Zinc ethyl phenyldithiocarbamate

Zinc dibutyldithiocarbamate sulfur

0.5 0.5 0.7

1.5 1.2

0.5
1.5
1.5

0.5 0.5 0.7

1.5 1.2

1 0 9 8 2Γ 2 ⁹ / D 6 1 β

It can be seen that with styrene-butadiene and Natural or isoprene rubber, both accelerator systems with and without activation by solvents do not cause the vulcanized test pieces to adhere.

As a function of time, temperature and pressure were obtained with EPDM with this side proposed acceleration very substantial bond strengths that still increase significantly after aging for two weeks at 7O ⁰ C. ' · ··. *

1. at a temperature of 120 ⁰ C resulted in: "~"

ρ
Pressure kp / cm Time / min. Peel strength after aging speed kp / cm 14 days 70 ° C 10 2 0.75 3.80 10 3 1.30 • 3.56 20 ■ 2 0.40 3.50. 20th 3 2.00 4.65 30th 2 1.80 4.10 - 40 3 1.90 4.10 50 5 3.75 > 6.5O

2. at a temperature of 160 ⁰ C resulted in: ρ '

2 speed kp / cm 14 days 70 ⁰ C 10 1 3.00 4.00 10 1 3.10 > 6.00 10 1 3.40 > 6.50 20th 2 5.00 •> 6.00 30th 1 3.00 > 6.50 40 2 .4.00 > 6.00 40 1 4.00 •> 6.5O 50 3.75 > 6.50 - 10 - 109842 / 0B16

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Finally, the adhesive strength of two vulcanized IIR pieces, which were accelerated under pressure with conventional accelerators with tetramethylthiuram disulfide, 2-mercaptobenzothiazole, zinc diethyldithiocarbamate and sulfur, was compared with those where the proposals here were followed, with and without activation by solvents ; Information about this is given in the following examples 4 and 5:

Example 4 basic recipe

Example 5 Basic door

HR (1 mol% 100.0 HR (1 mol% 100.0 Unsaturation) Unsaturation) SRF soot 30.0 SEF carbon black 30.0 FEF soot 20.0 FEF soot 45.0 HAF carbon black 20.0 HAP soot 20.0 kaolin 50.0 ZnO active 5.0 ZnO active 5.0 Light protection wax 3.0 Light protection wax 3.0 N-phenyl-N-isopropyl %O N-phenyl-N-isopropyl 1.0 -p-phenylenediamine -p -phenylenediamine Extender oil ΛΟ, Ο Extender oil 10.0 Stearic acid 1.0 Stearic acid 1.0

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'109842/061 6

OMGINAL INSPECTED Accelerator system

Tetramethylthiuram disulfide 2-mercaptobenzothiazole

Zinc ethylphenyldithiocarbamate Zinc dibutyldithiocarbamate zinc diethyldithiocarbamate Diphenylguanidine

sulfur

Mooney t 5

Mopney t 35

Vulcanization temperature ^{0 C}

Vulcanization time min. 20 20

Peel strength

. Example pressure kp / cm ² time / min. Peeling

speed kp / cm

Activation '4 10 3 0.

by

Solvent 5 10 3 3.65

without 4 10 '3 O

solvent

5 10 3 1.95

1.0 _ 0.5 0.5 - 0.7, - 1.5 0.3 - - 0.5 1.5 1.2 12'30 "'··' • 6 ¹ OO 21 ¹ OO ^11. '. 12Ί5 " 160 ⁰ O 16O ⁰ C

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109842/0616

Claims (6)

Claims 1) ϊMethods for welding rubbers, in particular with a low degree of unsaturation and chlorosulfonated polyethylene, characterized in that the foils to be connected to one another or the like "on the action of heat at the points to be connected are pressed on each other. 2) Method according to claim 1, characterized in that that at temperatures of 100 ° C to 140 ° C Pressure of 10 to 70 kgf / cm is applied over a period of 1 to 10 minutes. 3) Method according to claim 1, characterized in that that at a temperature of 160 ° C to 180 ° C, a pressure of 3 to 40 kp / cm over a time of 1 to 10 minutes is exercised. 4) Method according to claim 1 to 3, characterized in that that vulcanized rubbers with a low degree of unsaturation, in addition to their vulcanization Sulfur, a dithiocarbamate accelerator, a thiazole accelerator, a guanidine accelerator and at least one further dithiocarbamate accelerator were used in the fully cured state Temperatures from 100 ° C "to 180 ° C, a pressure from 3" to 70 kp / cm a time from 1 to 10 minutes get abandoned. . 5) Method according to claim 4-, characterized in that that vulcanized vulcanizates are used under pressure or without pressure. 6) Method according to claim 1 to 5, characterized in that the vulcanizates activated by gasoline or benzene or ketones or chlorinated hydrocarbons " will. 1098-2 / 0-16