DE2518040C2 - Process for the production of adhesive mixtures based on rubber-like copolymers of ethylene - Google Patents

Description

The subject of the main patent 24 50 643 is a process / ur production of tacky mixtures based on a rubber-like copolymer of ethylene, at least one other jr-alkylene and one or more polymers and tackifying resins, the copolymer in the non-linear part of the polymer chains C = Contains carbon bonds, the carbon atoms of which contain either two hydrocarbon groups located in the cis-position to one another, which are not part of the same cyclic system, or have at least three hydrocarbon groups, and the mixture of copolymer, tackifying resin and possibly customary additives in the presence of oxygen and a sensitizer is exposed to an artificial light source which emits light with a wavelength between 200 and 800 nanometers and wherein the mixture in the unvulcanized state has an elongation at break of at least 500 ° o and between 1.5 and 50 kg / cm ² Has tensile strength.

It has now been found that it is particularly advantageous to use mixtures of two or more rubber-like EPDM polymers or mixtures of a rubber-like EPDM polymer with others Rubber-type polymers are used. Here, however, it is necessary that these mixtures have necessary mechanical properties such as tensile strength and elongation at break.

The invention relates to a process for the production of non-tacky mixtures based on a chewable

Ischuk-like copolymer of ethylene, at least one other x-alkylene and one or more polyenes and tackifying resins, the copolymer in the non-linear part of the polymer chains containing C = C bonds, the carbon atoms of which contain either two hydrocarbon groups in vicinal cis position to one another which are not part of the same cyclic system sina, or at least * have three hydrocarbon groups, and the mixture containing copolymer, tackifying resin and possibly customary additives, which in the unvulcanized state has an elongation at break of at least 500% and between 1.5 and 50 kg / cm ^{2 has} tensile strength in the presence of oxygen and 0.001 to 1% by weight, based on the rubber-like copolymer, of a sensitizer. an artificial light source is exposed to light with a wavelength between 200 and 800 nanometers

"'emits radiation energy of at least 2 microwatts per cm ² per nm to the mixture according to patent 24 50 643, which is characterized in that the mixture also contains at least one other rubber-like polymer.

The inventive method it is possible with two or more rubber-like polymers, which do not have any inherent tackiness to produce tacky mixtures.

An ethylene-propylene-diene polymer with high tensile strength (green strength) can be combined with an ethylene-propylene dier.polymer with low tensile strength and conventional additives such as carbon black and oil to achieve a mixture with a tensile strength in the range of 1.5 and 50 kg / cm ² and an elongation at break of at least 500s. be mixed. If such a mixture contains C = C bonds in the non-linear part of the polymer chain with the structure defined above and the mixture of the polymer and the adhesive

- "Rig-making component with Lieh! in the presence of a sensitizer and in the presence of oxygen irradiated, excellent tack values can be obtained.

It is also possible to use mixtures of rubber-like polymers of ethylene, propylene and one non-conjugated diene with other polymers such as rubber-like polymers of conjugated Used in particular to use butadiene or isoprene. Examples of these polymers are polybutadiene-styrene, Polybutadienes, polyisoprene, polybutadiene-acrylonitrile, polyisobutene-isoprene (butyl rubber) and other.

These polymers have high molecular weights, for example higher than 10,000, preferably higher than 100,000.
The use of polymer mixtures according to the invention makes it possible in particular to meet the respective requirements with regard to the respective desired intrinsic strength values in a variety of ways.
The following examples illustrate the invention.

example 1

^JS The following polymers were used.

All polymers are copolymers of ethylene, propylene and ethylidene-norbornene (EN).
The following characteristics are recorded for each polymer:

a) The composition (% by weight of ethylene, propylene and EN).
■ "'b) The Mooney viscosity [ml χ (1 + 4) 125 ° C].

c) dsc temperature

d) Tensile strength and elongation at break of the polymer

e) Tensile strength and elongation at break, if according to the compounding specification according to Example 1 of Main patent was compounded.

Polymer A Polymer B Polymer C Polymer D a) 52, 38, 10
b) 68
c) not measurable
d) 2.7, 290%
e) 2.2, 270% 62, 28, 10
59
+ 4.5 ° C
>3.2> 2365%
3.3> 2365% 63, 28, 9
58
+ 7 ° C
44, 1800%
>4.2> 236596 64.31.5
54
+ 7.5 ° C
47, 1350%
14, 2290% Polymer E. Polymer F Polymer G

67, 28, 5 67, 25, 8

54.5 75.5

+ 12 ⁰ C + 16 ⁰ C

^{6 (1} d) 47.5.1110% 54.980% 61.7309b

36, 1950% 76, 121096

Mixtures of polymer A with each of polymers B to G are made. The composition corresponded to the recipe of Example 1 of the main patent. '* ^{! l} '

a) 64, 26, 10 C. b) 71.5 1110% O + 10 ° 2365% d) 47.5, e) 13.7,

Polymer B 25 18 040 Self-adhesive rigkcil Polymer A tensile strenght fracture after 4 hours in kg / cm ² elongation '^ l w 33 irradiation g / 5 mm 100 > I5400 0 90 3.3 > 2365 > 9000 IO SO 3.1 > 2365 > 6400 20th 70 2.9 2160 7000 30th 60 2.9 I860 3800 40 50 2.8 960 2200 50 40 2.7 530 1750 60 . Polymer C. 2.6 280 Polymer A 100 15000 f) 90 > 4.2 > 2365 19000 10 80 3.4 > 2365 > 15800 20th 70 3.0 > 2365 16000 30th 60 2.8 > 2365 11200 40 50 2.8 1590 3800 50 40 3.0 660 2200 60 30th 2.9 460 1500 70 Polymer D. 2.8 290 Polymer A. 100 - 0 90 14th 2290 4800 10 80 > 11.3 > 2365 > 7600 20th 70 > 9y > 2365 > 10400 30th 60 4.2 > 2365 11200 40 50 3.3 > 2365 6800 50 40 3.0 1530 2600 60 30th 2.7 780 1700 70 Polymer B 2.7 320 Adhesion Polymer A tensile strenght fracture after 4 hours in kg / cm ² elongation % w 33 irradiation g / 5 mm 100 2200 0 90 > 13.7 > 2365 6000 10 80 > 10.7 > 2365 > 14600 20th 70 > 4.3 > 2365 > 14400 30th 60 > 3.9 > 2365 > 13600 40 50 3.1 > 2365 8400 50 40 2.9 1450 4200 60 30th 2.9 1180 2100 70 20th 2.8 410 1400 80 Polymer F. 2.7 290 Polymer A. 100 - 0 90 36 1950 - 10 80 29 2150 2000 20th 70 17th 2310 2100 30th 60 > 7.3 > 2365 > 6200 40 50 > 4.3 2365 > 7800 50 40 3.0 2365 > 7400 60 30th 2.7 2365 3600 70 20th 2.6 550 1800 80 Polymer B 2.4 350 Inherent tackiness Polymer A tensile strenght fracture after 4 hours In kg / cm ² elongation % w 33 irradiation g / 5 mm 100 _ 0 90 76 1210 - 10 80 67 1320 - 20th 70 60 1400 _ 30th 60 43 1500 _ 40 30th 1580

Polymer B 25 18 040 Elgenklebrlgkclt continuation after 4 hours Polymer A tensile strenght fracture w 33-inch resolution g / 5 mm 50 In kg / cm * elongation % 2100 40 > 7200 50 30th 21 1820 > 8400 60 20th 11th 1900 1800 70 10 3.7 2260 1350 80 3.0 540 90 2.7 250

example

Mixtures of polymer B with polyisoprene (PIP) (Cariflex IR 305; cis-1.4 content: 92.0% LVN 7.5 dl / g). These mixtures were prepared according to the recipe of Example 1 of the main patent, however, the oil content varied with the polyisoprene content.

Polyisoprene Mixture of Mixture of 25 parts of oil 70 parts PIP 50 parts PIP 30 parts EPDM 30 parts EPDM 32.5 parts of oil 37.5 parts of oil

polymer

Tensile strength 1.5 kg / cm ² 3.3 kg / cm ²

Elongation 750% 2365%

mixture

Tensile strength 6.1 kg / cm ²

Elongation 1650%

Self-tack after 3100 g / 5 mm

Eastbound irradiation with a w 33 fluorescent tube

14.5 kg / cm ² 2365%

1.4 kg / cm ²

141096

1300 g / 5 mm

Example 3
Mixtures were made from the polymer F and polyisoprene (Cariflex IR 305)

60 parts polyisoprene 40 parts EPDM 35 parts oil

70 parts polyisoprene 30 parts EPDM 32.5 parts oil

polymer 12.5 kg / cm ² 4.5 kg / cm ² tensile strenght 1050% 990% strain mixture 6.1 kg / cm ² 1.4 kg / cm ² tensile strenght 1650% 1410% strain 3100 g / 5 mm 1300 g / 5 mm Inherent tack irradiation to the east with a w 33 fluorescent tube Example 4

Mixtures of polymer B with a polyisoprene with a high cis content (Natsyn 2200, cis-1,4 content 96%).

Polyisoprene 25 parts oil

30 parts polyisoprene 70 parts EPDM 42.5 parts oil

Polymer tensile strength elongation

Mixture tensile strength elongation inherent tack after 4 hours of irradiation

1.5 kg / cm ² 200%

0.6 kg / cm ²

8096

600 g / 5 mm

23.5 kg / cm ² 234096

2.4 kg / cm ² > 236596 8000 g / 5 mm

Example 5

Mixtures of EPDM (polymer B) with SBR (SBR 1500) were produced. The compounding took place according to the recipe of example 1 of the main patent with the exception of the amount of oil.

EPDM Parts polymer strain 390 mixture strain Own SBR Oil ever train % > 2365 train sticky wedge 1500 100 parts strength > 2365 strength Polynization kg / cm ² 2140 kg / cm ^! nuisance 1940 0 25th 2200 260 650 100 50 37i 19th > 2365 1.2 > 2365 10800 50 60 40 > 11 2.4 > 2365 12600 40 70 42 ^ > 22 2.6 > 2365 13800 30th 80 45 3i 2.8 > 2365 12000 20th 90 47} 34 2.9 > 2365 11000 10 100 50 33 2.9 > 2365 > 15400 0 > 32 3.3

Optimal values were achieved with 30 parts of SBR. Becomes EPDM with high green strength with SBR mixed, the highest intrinsic tack values are achieved with higher SBR contents.

Example 6

A mixture of butyl rubber (Butyl 218, Enjay) with EPDM-B was produced. You mixed 80 Parts of EPDM-B with 20 parts of butyl rubber together with compounding components according to Example 1 of the main application, but the oil content was 45 parts.

Results: polymer

link

Inherent tackiness
after 4 hours
Irradiation

Tensile strength 22.5 kg / cm ²

Elongation 219096

Tensile strength 2.9 kg / cm ²

Elongation> 236596

g / 5 mm
9800

Claims (27)

Patent claims: 1. A process for the production of tacky mixtures based on a rubber-like copolymer of ethylene, at least one other α-alkylene and one or more polyenes and tackifying resins, the copolymer containing C = C bonds in the non-linear part of the polymer celts, their carbon atoms contain either two hydrocarbon groups in vicinal cis-position to one another, which are not part of the same cyclic system, or have at least three hydrocarbon groups, and the mixture containing copolymer, tackifying resin and possibly customary additives, which in the unvulcanized state has an elongation at break of at least 500% and a tensile strength wedge between 1.5 and 50 kg / cm ² in the presence of oxygen and 0.001 to 1 wt .- 'Ί. based on the rubber-like copolymer, a sensitizer, is exposed to an artificial light source that emits light with a wavelength between 200 and 800 narvometers and the mixture is given a radiation energy of at least 2 microwatts per cm ³ per nm according to patent 24 50 643. characterized that the mixture also contains at least one other rubber-like polymer. 2. The method according to claim 1, characterized in that the mixture is based on a rubber-like copolymers of ethylene, at least one further jr-alkene and one or more Polyenes comprises a mixture of a) a copolymer of ethylene, at least one further ar-alkene and one or more polyenes with a tensile strength of at least 10 kg / cm ² and an ethylene content in the range between 50 and 80% by weight, b) a copolymer of ethylene, at least one further α-alkene and one or more polyenes with a tensile strength of less than 10 kg / cm ² and an ethylene content of less than 65% by weight 3. The method according to claim 2, characterized in that the mixture is based on a rubber-like Copolymers of ethylene, at least one further jr-alkene and one or more Polyenes comprises a mixture of a) a copolymer of ethylene, at least one further α-alkene and one or more polyenes with a tensile strength of at least 10 kg / cm ² and an ethylene content in the range of between 62 and 75% by weight b) a copolymer of ethylene, at least one further α-alkene and one or more polyenes with a tensile strength of less than 10 kg / cm ² and an ethylene content in the range between 50 and 63% by weight. 4. Process according to Claims 1 and 2, characterized in that the ethylene copolymers have a Mooney viscosity ML (I +4) 125 ° of at least 20. 5. The method according to claim 4, characterized in that the ethylene copolymers have a Mooney viscosity ML (I +4) 125 ° of at least 30. 6. The method according to claim 1, characterized in that the mixture on the basis of a rubber-like copolymer of ethylene, at least one further α-alkene and one or more Polyenes comprises a mixture of a) a copolymer of ethylene, at least one further «-alkene and one or more polyenes with a tensile strength of at least 10 kg / cm ² and an ethylene content in the range between 50 to 80% by weight b) one or more rubber-like polymers selected from the group consisting of I polymers and copolymers of butadiene II Polymers and copolymers of isoprene III polymers and copolymers of isobutylene and IV Polymers and copolymers of chloroprene. 7. The method according to claim 6, characterized in that the mixture is based on a rubber-like Copolymers of ethylene, at least one further α-alkene and one or more Polyenes comprises a mixture of a) a copolymer of ethylene, at least one further «-alkene and one or more polyenes with a tensile strength of at least 10 kg / cm ² and an ethylene content in the range of between 62 and 75% by weight b) one or more rubber-like polymers selected from the group consisting of I polybutadiene II Polybutadiene-styrene having a styrene content within the range from 5 to 50% by weight III polybutadlene-acrylonitrile with an acrylonitrile content in the range from 5 to 50% by weight IV polyisoprene V polyisobutylene-isoprene with an isoprene content of 1-5 wt. -96 isoprene and VI polychloroprene. 8. The method according to claims 6 and 7, characterized in that the polymers and copolymers are have a Mooney viscosity of at least 20. 9. The method according to claim 8, characterized in that the polymers and copolymers a Have a Mooney viscosity of at least 30. 10. The method according to claims 6-9, characterized in that the copolymer of ethylene, ' at least one further ar-alkene and one or more polyenes in the mixture in an amount of at least 50% by weight based on the total polymer content is present. 11. The method according to any one of claims 1-10, characterized in that the total amount of radiation energy obtained from UV light with a wavelength between 200 and 400 nm is at most half the total amount of radiation energy obtained from light in the wavelength range from 200 to 600 nm ^lu is. 12. The method according to claim 11, characterized in that the total amount of the UV light with a wave range of 200 to 400 nm obtained radiation energy at most a quarter of the total Amount of radiation energy obtained from light in the wavelength range from 200 to 600 nm. 13. The method according to claim 11, characterized in that the total amount of ^{radiation energy obtained from UV light] <i} from 325 to 400 nm is at most a quarter of the total amount of radiation obtained from light in the wavelength range from 325 to 600 nm. 14. decay according to claim 11, characterized in that the total amount of UV light with A maximum of one sixth of the radiation energy delivered in a wavelength range from 325 to 400 nm Total amount of radiant energy in the wavelength range from 325 to 600 nm. - ° 15. The method according to claims 10 to 14, characterized in that the radiation energy used is above 30 μW / cm ² per nm. 16. The method according to claim 15, characterized in that the radiation energy used is above 200 nW / cm ² per nm. 17. The method according to claim 1 to 16, characterized in that the total amount of radiation energy obtained is below 15 joules / cm ² per nm. 18. The method according to claims 1 to 17, characterized in that the tensile strength of the mixture is between 2 and 30 kg / cm ² , in particular between 3 and 25 kg / cm ² . 19. The method according to claim 18, characterized in that the tensile strength of the mixture below 15 kg / cm ² . 20. The method according to claims 1 to 19, characterized in that the elongation at break of the Mixture exceeds 800%. 21. The method according to claim 20, characterized in that the elongation at break of the mixture 1700% exceeds. 22. The method according to claims 1 to 21, characterized in that the ethylene incorporation of the chew - ' ⁵ chuk-like copolymer is between 60 and 77.5 mol%. 23. The method according to claims 1 to 22, characterized in that the tackifying resin a compound made from alkylphenol and formaldehyde with a molecular weight between 200 and 3000 is used, the alkyl group having 1 to 30 carbon atoms, in particular 8 to 12 carbon atoms, contains. - »n 24. The method according to claims 1 to 23, characterized in that the amount of sensitizer 0.001 to 1% by weight, based on the rubber-like copolymer. 25. The method according to claim 24, characterized in that the sensitizer in an amount of 0.01 to 0.5% by weight is mixed into the rubber. 26. The method according to claims 1 to 25, characterized in that one or ⁴ - ^s several polynuclear aromatics with 3 to 50 aromatic nuclei is used as the sensitizer. 27. The method according to claim 26, characterized in that an aromatic oil is used as the sensitizer with an aromatic incorporation of more than 40% by weight and after dissolving 74 mg in 100 ml of n-hexane resulting light transmission below 95% is used.