DE1962071A1 - Crosslinkable mixtures based on terpolymers of ethylene and propylene - Google Patents

Description

The invention relates to mixtures which are crosslinkable at room temperature and are based on terpolymers of ethylene-propylene-non conjugated diene and of ketone peroxides, optionally combined with accelerators, and also the use these mixtures as components of grout «

It is known that terpolymers of ethylene-propylene do not have conjugated diene, which are crosslinked by means of organic peroxides, which are usually used for the crosslinking of polyolefins In many cases, insufficient mechanical properties are used «

On the other hand, a major drawback associated with the use of feroxides is that they do Use of elevated temperatures requires customer but proves on the crebi ^ gene of metal! construction and building

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advertise the use of elevated temperatures for crosslinking of the jointing compounds based on the terpolymers mentioned are difficult to carry out Degree of networking sometimes only low "

The ketone peroxides were found to be excellent Crosslinking agents for terpolymers of ethylene-propylene-non-conjugated diene prove, and that they are the Allow crosslinking to be carried out at room temperature. The aim of the invention is accordingly to be crosslinkable at room temperature Mixtures containing terpolymers of ethylene-propylene-non-conjugated Diene and ketone peroxides, optionally combined with accelerators, include *

The invention is even more surprising because Ketonperoxyde not for cross-linking polyethylene and copolymers of ethylene-propylene at room temperature or even at elevated temperatures of about 160 ⁰ G eigneno

These findings are supported by those in the following Table I and II confirmed the results given »

The mixtures on the basis of polyethylene and copolymers of ethylene-propylene, which include the ingredients set forth in Tables I and II have been prepared in a plastograph Brabender at 106 ° 0 'Fachdem the plates at 165 ⁰ G in the case of mixtures of the table I ge

the

were pressed, one aBxKigft »» ii & a ££ 88 breaking stress and the elongation at break determined according to the test ASTM D 412 "has In the case of the mixtures of Table II the plates were molded at 106 ⁰ O (5 min _e) and then in a isothermal room kept at 2O ⁰ C «After an arbitrary dwell time. the properties are determined as just mentioned »

For comparison, the dicumyl peroxide was considered a real one Networking enabling agent choseno

The results contained in Table I show that the ketone peroxides not for the denial of polyethylene and the copolymers ethylene-propylene are suitable at elevated temperature compared to a peroxide, which among these

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Conditions is useful, namely the dicumyl peroxide. Table II shows that even at room temperature the ketone peroxides Do not cross-link polyethylene and its copolymers "

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mixture
G Polyethylene (1)
Mixed polymer
Ethylene propylene (2)
Soot HAP
Dicumyl peroxide
^v "utanox M 50 (3)
Irigonox HM 80 (4)
sulfur Table I. - 50 IfIl 5 4th 4th 1 I t I 5
0.375 4th
0.375 4th
0.375 Properties after networking
at 165 ⁰ O for 60 minutes 100 128
24 177
126 No Vernet
unused
bare plates
(pastenar
tig or
holey) H-
4.6
> 1000 216
654 3.6
233 I.
!
3
132 Stress at break, kg / cm
Elongation at break $ • 2
(1) Polyethylene of MI = 7 with a specific weight of 0.918 kg / dnr (Alkathene WNGr 14)
(2) Copolymer with a Mooney viscosity: 46 and a propylene content of 0.47 mol / mol
(3) Peroxide of methyl ethyl ketone dissolved in dimethyl phthalate with 50 $ active material
(4) Peroxide of methyl isobutyl ketone dissolved in dimethyl phthalate with 80 fo active material » 100 - 0Q9827 / 2 ο
ro

mixture Polyethylene (1) Table II 100 I. 1 DO 50 - 4th - 4th - I. 8.1 / 201 0.47 moles / mole io active material S. Mixed polymer - - 4th 4th VJl 9/213 with 50 fo active material cobalt Ethylene propylene (2) - 0.375 - - - 11.1 / 232 (4-) Peroxide of methyl isobutyl ketone dissolved in dimethyl phthalate with 80 Soot HAF - - 2 2 2 14/226 (5) Solution of cobalt octoate in white spirit with a salary of $ 1 Butanox M 50 (3) kg / dm ⁵ (Alkathene WNG 14) (6) The first number refers to the breaking stress in kg / cm Triganox HM 80 (4) Propylene content of The second number refers to the elongation at break in $ * Sulfur " 97/20 110/17 111/16 7.6 / 155 Cobalt Accelerator (5) 107/20 122/16 112/15 12.1 / 205 O Properties (6) measured after a 76/16 94/17 11 2/23 18.1 / 276 CD
OO Residence time at 20 ⁰ C of 84/17 79/18 110/23 11.5 / 252 K)
-J O days (1) Polyethylene of MoIo = 7 with a specific weight of 0.918 5 days (2) Interpolymer with Mooney viscosity = 46 and one σ 15 days (3) Peroxide of methyl ethyl ketone dissolved in dimethyl phthalate 35 days

CD CJ)

The invention also relates to room temperature crosslinkable Jointing compounds which consist of the above-mentioned crosslinkable mixtures, a filling, oils and a solvent

The terpolymers and the jointing compounds crosslinked in this way have excellent physical properties and in particular a high breaking stress o

They also have permanent elasticity, which makes them particularly suitable for use in the fields of metal construction and the building industry, _etc.

All ethylene-propylene-non-conjugated diene terpolymers can be crosslinked by the process according to the invention and are suitable for the production of crosslinkable mixtures and of jointing compounds according to the invention

For Verfugungsmassen one will preferably select terpolymer having a Mooney viscosity at 100 ⁰ C between 20 and 120 (test ASTM D 927/53 T).

The composition of the ethylene-propylene non-conjugated diene terpolymers is not critical, provided that it is are elastomers »

The terpolymers with a propylene content between 20 and molar $, preferably between 25 and 50 molar $, are suitable especially for obtaining grout with the desired properties,

The non-conjugated dienes which are used in conjunction with ethylene and propylene in the terpolymers are preferred under :

- the non-conjugated aliphatic dienes, such as ζ · Β _β pentadienes ^ »hexadiene-1e5 and hexadiene-1.4»

- the non-conjugated monocyclic dienes of the type of 4-vinyloyclohexene, 1.3-divinyloyolohexane, oyoloheptadiene-1e4 »oyclooctadiene-1.5 _t

- the non-conjugated alioyoliach serve with endooyolic Bridge like ζ · Β · dicyclopentadiene, norbornadiene, Methylene norbornene and ethylidene norbornene, selected »

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_ 7 -

Terpolymers of particular interest as useful elastomers for the production of the jointing compounds according to the invention are the terpolymers based on ethylene, propylene and dicyclopentadienes hexadiene-1 "4, methylennorbornene and Ethylidene norbornene

The peroxides of are preferably used as ketone peroxides Methyl ethyl ketone and methyl isobutyl ketone «»

The amounts of ketone peroxides used are between 0.1 and 10 parts by weight per 100 parts by weight of the terpolymers "

Sometimes it is advantageous to incorporate crosslinking accelerators and in particular cobalt naphtenate and dimethylaniline _{or the like}

When the curing times are relatively long and vary between 24 hours and -35 days or even more can, this does not represent a disadvantage for the applications in question ©

The fillers which can be used in the production of the jointing compounds according to the invention are generally talc, chalk, Kaolin, clay, soot, asbestos and precipitated calcium carbonate

Useful oils are preferably aliphatic, naphthenic and aromatic mineral oils _e are particularly advantageous naphthenic oils for the composition of the products in Verfugungsmassen ΊΠΠϋτηΐΤΈ Hanael under the names Oircosol nose, Circo Light and "Sunpar 115 (Sun Oil Cy) available ₀

An aromatic oil that can also be used successfully is that commercially available under the name Sundex 8180 (Sun Oil Cy) available © You can also use a solvent to dilute the jointing compounds based on the terpolymers, use a filler material and the oil. A preferred solvent is xylene «

Various other constituents can also be incorporated into the jointing compounds according to the invention before they are crosslinked; these additives are used to impart certain desirable properties to the various ones upcoming applications selected «

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In this regard, one can use synthetic oils, e.g. liquid Polybutenes and polyisobutenes and especially that commercially available under the name Indopol (Amoco Chemical Corp) Use product. Part of the mineral or synthetic impulse can also be obtained by a plasticizer of the type an ester, such as an adipate or a sebacate, replace o

You can also use coumarone resins, rosin, non-reactive phenol-formaldehyde resins, such as Z ₀ B ₀ which are commercially available under the name Amb-jrol SoT. 137 X (Rohm and Haas) and Bakelite 435 products, polyterpene resins and other similar products ",

The incorporation of the above-mentioned resins in amounts of 1 20 fo, preferably 2 - 10 $, based on the weight of the jointing compound, improves the adhesion of these compounds »

The grouting compounds according to the invention can be any suitable known processes are produced. A preferred manufacturing process when using black fillers, ZoBe carbon black HAF, used ^ is described below

An uncooled roller kneader is used to mix the oil and terpolymer. After cooling the rolls, the solvent (xylene) and the crosslinking accelerator is adds "Then one introduces the filler and the Ketonperoxyd and terminated by 10 Kreuzwalzungen _o

If you use a light-colored filling (chalk, calcium carbonate or the like), you are interested in working as follows:

in
An equal-part mixture of terpolymer and oil is produced on an uncooled roller kneader; this mixture is then introduced into a refrigerated Meili kneader and kneaded. Mixture, then SetAt be the missing ingredients added, with the exception of xylene, and kneads the whole to obtain complete homogeneity ₀ Only then are added, the xylene and homogenized "

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Examples 1-5

The mixtures based on a terpolymer of ethylene-propylene-dicyclopentadiene were mixed in a roller kneader After obtaining a mass of sufficient homogeneity, orepes were rolled, from which pattern bars for the determination of the tensile properties according to the ASTM D 412 test «

Part of the bar specimens was used to determine the initial characteristics, the others were kept in an isothermal chamber at 2O ⁰ G Man has in this way the development of the properties of mixtures after 5 "10, 15, can track 20 and 25 days"

It should be noted that the ketone peroxides are very good for crosslinking of the terpolymers from ethylene-propylene-not conju_ Gated diene are suitable, and that the crosslinked products have excellent tensile properties and, in particular, increased Have breaking stress "

The stress at break (first number) and elongation at break (second number) can be found in Table III.

For comparison, example R1 is given, which related to terpolymers crosslinked by means of benzoyl peroxide

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Table III

Examples Misrepresentation
G Royals 200 (1)
Benzoyl peroxide
Methyl ethyl ketone peroxide (2)
Methyl isobutyl ketone peroxide (
Cobalt accelerator R1 2 3 4th VJl 100 6th
3) - 4th 4th
4th 4th · ■ «
* m
4th
4th properties
(first number; breaking stress in kg / cm)
(second number: elongation at break in $) 8/139
32/247
54/287
76/268
107/313
127/300 9/125
89/236
128/282
170/282
193/275
163/216 9/149
27/268
57/217
110/357
131/327
167/305 7/103
87/199.
.130 / 258
126/221
188/226
221/219 Dwell time after days
0
5
10
15th
20th
25th 25/100
63/82
47/73
41/68
55/82
40/66

(1) Terpolymer Ethylene Propylene Non Conjugated Diene sold by UoS

(2) dissolved in dimethyl phthalate, 50 % active material

(3) dissolved in dimethyl phthalate, $ 80 active material

(4) dissolved in dimethyl phthalate with a content of 1 <fo cobalt

Rubber

CD cn K) O

- 11 examples 6-16

In the following the properties of various combinations of Verfugungsmassen on the basis of a terpolymer of Ithylen-propylene non-conjugated diene, a mineral oil and a Füllmaterial'angegeben are _β

The jointing compounds containing carbon black HAF (Examples 6-10) were produced as follows: In an uncooled roller kneader the oil was incorporated into the terpolymer. After cooling the rollers, the solvent (xylene) and the crosslinking accelerator added. Then the carbon black and the ketone peroxide were added and finished with 10 cross-rolls «

If you have a white filling, for example calcium carbonate (Examples 11-16) is used, one works as follows; One sets an equal-part kneader on an uncooled Y / alz kneader Mixture of terpolymer and oil. This mixture is then introduced into a cooled Meili kneader, and after that Kneading the mixture, the missing ingredients with the exception of the solvent are added. Knead until received a complete homogeneity. Then add the xylene and homogenize *

The various compositions of the grouting compounds are given in Table IV below *

An examination of Table IV clearly shows the excellent properties in terms of tensile strength at break of the crosslinked jointing compounds, which match those of Thiokol based grouting compounds, which are of the order of 20 kg / cm have, are superior »

Without the use according to the invention of ketone peroxides, the jointing compounds have a breaking stress of the order of magnitude of 5 kg / cm

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Table IY

Examples 6th 7th 8th 9 10 11th 12th 13th 14th 15th 16 Terpolymer (1) 600 500 700 500 750 300 225 350 500 350 600 Soot HAF 300 300 200 200 100 Calcium carbonate 650 650 550 400 400 250 mixture Oil Sunpar 115 (2) 100 200 100 250 150 50 125 100 100 250 150 G Methyl ethyl ketone
peroxide (3) 24 20th 28 22nd 30th 12th 9 14th 20th 14th 24 Xylene 380 267 . 460 233 457 300 150 500 700 210 500

hJ ■ -J

Breaking stress after 30 days (test ASTM D 412) kg / cm ²

111 32 29 25 46 37 24 86 34 41

28

(1) Terpolymer ethylene-propylene-dicyclopentalen with a content of 38 fo propylene,

an unsaturation of 0.28 groups g / kg

and a Mooney viscosity MX MI at 100 ⁰ O according to the standard ASTM D 927/53 T of 43,

(2) Paraffin oil from Sun Oil Cy *

(3) dissolved in whore thylpht alate with 50 $ active material * »

Claims (1)

- 13 claims 1o Mixtures crosslinkable at room temperature, comprising terpolymers Ethylene-propylene-non-conjugated diene and ketone peroxides, possibly with the addition of accelerators «» 2o mixtures according to claim!, Characterized in that the 'ferpolymeric ethylene-propylene non-conjugated diene contain 25 - 75 mol ₀ - ^, preferably 30 50 Iflolo- ^, propylene * 3. Mixtures according to the preceding claims, characterized characterized in that the non-conjugated diene is a non-conjugated aliphatic diene, preferably Pentadiene-1,4, hexadiene-1c4 and hexadiene-1 "5 isto 4. Mixtures according to the preceding claims, d a d u r oh characterized in that the non-conjugated diene a non-conjugated monocyanic diene, preferably ⁰ vinyl 4-vinylcyclohexene-1.3, DiSof «K ^ £ c ^ clohexane, cyclooctadiene-1 · 5 and cycloheptadiene-1 · 4 is « 5. Mixtures according to the preceding claims, characterized characterized in that the non-conjugated diene is a non-conjugated alicyclic diene, preferably Is dicyclopentadiene and norbornadiene «, 6 »Mixtures according to the preceding claims, thereby characterized in that the ketone peroxide is methyl peroxide
ethyl ketone / is » 7 »Mixtures according to the preceding claims, characterized in that the ketone peroside Methyliso i 8 · At room temperature curable? Erfugungsmasssn _f beaäahaad from the blends is vorhergehandan claims, a filler, an oil, and a solvent. 1QR7H71 9β Yerfugungsmassen according to claim 8, characterized that the oil used is an aliphatic, naphthenic or aromatic mineral oil * 1oo compositions according to claim 8 and 9 »characterized gekennzeichne.t that the filler is carbon black ₀ 11 «masses according to claim 8 and 9» characterized in that that the filling material is calcium carbonate * 12o masses according to claim 8-11, characterized that the solvent used is xylene » 09827/2021