DE1694325C3 - Crosslinking of olefin polymers - Google Patents

Description

at least 50 mole percent of an x

The search for new and better crosslinking agents, a class of crosslinking agents, is ongoing in the olefin polymer field
are the mono- and diesters of quinone dioxime, such as

they are described in British patent specification 961 795 .... "v _D -.

are. Although these quinone dioxime esters have excellent pigmentation vulcanizates with marked stability, they have the disadvantage that they blacken the polymer when it cures, so that they are not used for many modern purposes can be. ...

The present invention is now intended to provide a comparison of the general formula network system are proposed, with which

Hi-Fi

various

O - N = C - \ C = C.

I l_c - N - Ο --Α

in which A is an acyl, aryl, alkylsulfonyl, arylsulfonyl, alkylphosphinyl, arylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylcarbamyl or arylcarbamyl group having 1 to 36 carbon atoms, R is a hydrogen atom or a methyl, phenyl or furfuryl radical and R ¹ denotes a hydrogen atom or a nitro group and w, η and ο are 0, 1 or 2, optionally with the use of 0.005 to 2 parts by weight of an accelerator, based on 100 parts by weight of polymer, for crosslinking homopolymers or copolymers of \ - Olefins with at least 50 mole percent of an oleline.

The amount of crosslinking agent used is not critical and can vary widely Moving boundaries, depending to a certain extent on the polymer to be crosslinked. So can Quantities of 0.1 to 30 parts per 100 parts of polymer and preferably 0.5 to 20 parts per 100 parts of polymer can be used (all quantities are based on weight).

Useful crosslinking agents include for example

50 3-hexyne-2,5-dione-dioxime-dislearate,

3-hexene-3-methyl-2,5-dione-dioxime-dichloro

benzoate,
2-nitroterephthalaldehyde-dioxime-di-p-loluenesulfonic acid,

Dimethylglyoxime dimahansulionate, dimethylglyoxime dibutanesulfinate, Dimethylglyoxime dibenzenesulfinate, dimethylglyoxime diphenylphosphinate,

Dimethylglyoxin vdibutylpnosphinate, dimethylglyoxime dichlorophosphinate, Dimethylglyoxime diphenycarbamate, dimethylglyoxime diethylcarbamate, 3-Oclen-5-yn-2,7-dione-dioxime distearate,

4- (l-butyn-3-onyl) benzaldehyde dioxime dioctanoate, 4- (l-butyn-3-onyl) benzaldehyde-dioxime-diacetate, 4- (1-bulin-3-onyl) -zimta! Dehyd-dioxime-dibutyrate, Furfuryl dioxini distearate,

3 4

l-phenyl-l ^ -propandione-dioxim-distearal, turns. If necessary, the accelerator can be used at

Tcrephthalaldehyde dioxime distearate, mixing process to facilitate handling and

Glyoxime distearate, to achieve an even distribution as LÖ-

Glyoxime dibenzoate, solution (ζ. B. 5 to 20 ° / ₀ ig) in a suitable solution

Dimethylglyoxime distearate, 5 medium to be added. This can be done low

Dimethylglyoxime dibenzoate and boiling organic solvents such as

Diphenyl glyoxime distearate. Acetone, isopropanol, ethanol, benzene and the like are used will.

The dioximes can be converted by reaction with the corresponding acid chloride in pyridine to be cured into the additives, such as the desired esters, which are possibly still customary. For example, antioxidants, fillers, pigments, antistatic agents, 10 g of the oxime in 150 ml of pyridine are dissolved in substances, extender oils, plasticizers, tackifying agents in a 500 ml Erlenmeyer flask and given substances and the like. Such materials are in case something heated (up to 50 "C). Then, however, the piston, a 10 ° / ₀ hydrochloric excess is under general, not necessarily, in advance or in swirling premixed 15 of Mischsiufe with the polymer, the acid chloride was added in one In the eye- Suitable fillers are carbon black, clay, silica, mean the ester precipitates immediately, and the mixture of aluminum oxide, carbonates, hydroxides, silicates, dia becomes warm. The flask is then closed and tome earth, talc, kaolin, barium sulfate, calcium The prosulfate, calcium carbonate is then allowed to stand for 1 hour. They can be poured into 2 l of distilled water in amounts up to ductile, filtered off, washed pyridine-free with so to 2C0 parts and more and preferably from 0.05 to water and before Use 100 parts per ICO part of polymer used, dried The spelling of hydrocarbon momers is understood, for example, a Brabender plastograph, a single terminal unsaturated group, a Banbury mixer, a two-roll mixer, and the like of the formula —C-CH. contain. Under "Λ-olefin at suitable temperatures in the range from 25 to polymeric and copolymeric" homopolymers 2C0 C are mixed. The mixing temperature and copolymers including terpolymers is determined by the softening point of the polymer (for EPC standing, in which at least 50% of the polymer is generally 25 to 120 ° C) and is above derived from olefins. For example, the polymers derived from this but below the hardening temperature of the cross-linking agent (ie the temperature at which the ethylene, polypropylene, ethylene / propylene copolyester, respective compound decomposes) belong to the polymers will). Fillers and ethylene / bulylene copolymers, butyl rubber, other ethylene additives can be mixed in with continued stirring of propylene / diene terpolymers and ethylene; vinyl. The veracetate copolymer is then added, provided it contains at least 35 wetting agents and then the accelerator, 50 molar percentages of olefin derived units, if any. These comments contain. These polymers can be even more porous, although they can all have been treated at once and, for example, chlorinated, softened polymers can be added, but will be chlorosulphonated, oxidized, etc.; For example, they are added one after the other to achieve uniform mixing described in U.S. Patent No. 2 212 786, and chlorosulfonated polyethylene as an olefin polymer because it is easier to handle. Mixing is seen in the eye. mine performed for 2 to 15 minutes. For the Her-Dic invention, the finished and copolymers are generally suitable for all oleopolymeric positions of commercial products, but for the sake of simplicity and clarity they are mixed in by extrusion or compression in the following mainly temperatures above the softening point of the poly with respect to ethylene / propylene rubber (ÄPK), but explained in more detail below the hardening temperature of the polymer to be hardened. wetting agent brought into the desired shape. In the context of the invention, together with shaped products, these crosslinking agents can also be accelerated to a higher level, e.g. B. heated temperature, can be used in the case of EPC for example via metal salts or metal chelates, 50 130'C, at which a rapid hardening of the which increases the crosslinking effect and also the polymers takes place.

Use of lower crosslinking temperatures. The following examples were used in the

Uuiben. Mixing stage obtained mass to 0.5 mm thick plaque

As accelerators, salts and chelates can be hardened by placing them in a platen press

Metals such as aluminum, iron, tin, zinc, titanium, 55 2KCO kg / cm ^{s for} 5 minutes to the hardening temperature

Chromium, vanadium, mercury and boron used was heated. For most of the tests, it was

will; suitable compounds are, for example, hardening temperature 225 ° C. However, it depends on the

MCl ₁ , FeCI ₃ , SnCI ₄ , ZnCI ₂ , TiCI ₄ , CrCI ₃ , VCl ₄ , individual cases applicable temperature of

AlBr ₃ , HgCl ₄ , BF ₃ and the like, as well as coordination factors, such as 1. the poly to be hardened

connections, the maximum number of coordinates of which is 60 mers, 2. the type and amount of crosslinking agent *

is saturated before addition to the polymer, which and 3. whether an accelerator is used or

but not when mixed and hardened with the hardener. As a rule, the hardening temperature is at

react. As examples of this last mentioned, the optimal hardening is suggested, i. H. where the

Coordination complexes such as hardness state (the percentage of gel content) cannot be accelerated

E: iscn (III) acetylacetonate, aluminum acetylacclonate, 65 more changed, between 125 and 250 ° C.

Boron fluoride n-butyl etherate and the like can be mentioned. In the examples, all melt indexes were under

The accelerator we «! preferably in amounts according to the conditions specified in ASTMD 1258-52 T.

from 0.005 to 2.0 parts per 100 parts of polymer and the densities of the polymers below those in ASTMD

1505-57 T specified conditions measured. To determine the violet content of the polymers a weighed polymer sample (about 0.5 g) in a cellulose Soxhlet thimble for 24 hours under reflux in n-heptane (which contains 0.3% 2,5-di-tert-butyl-4-methylphenol contained) heated and then weighed the undissolved portion after drying. From it the gel content was calculated as follows:

% Gel =

Weight of the insoluble
Sample weight

100

In all examples, unless otherwise noted, a Brabender Plastograph Model PL-V2 with a recording device for measuring used by changes in torque.

example 1

8.8 g (0.1 mol) of glyoxime were added to 150 ml of pyridine in a 50 ml Erlenmeyer flask. Once all of glyoxime was dissolved, 66.5 g (0.22 mol, 10 ° / ₀ excess) of stearoyl chloride were added while swirling the flask. The reaction mixture was allowed to stand at room temperature for 1 hour and then poured into 1 liter of distilled water. The crude glyoxime distearate was filtered off through a glass filter crucible and then washed four times with 500 ml of distilled water to remove most of the pyridine. The product was then dried ^{in vacuo at 50 ° C. overnight.} The dried glyoxime distearate had a melting point of 105 to 110 ° C and weighed 54.5 g (88% yield). Before use, part of this product was recrystallized from benzene to give pure glyoxime distearate, melting point 111 to 112 ° C.

Example 2

Example 1 was repeated, but replacing the glyoxime with 22.0 g (0.1 mol) of furfuryl dioxime would. 39.1 g (52% yield) of crude ίο Furfuryldioximdistearat were obtained, which after the Recrystallization from Pctrolether had a melting point of 90 to 93 ° C.

Example 3

250 ml of ethyl alcohol, 250 ml of pyridine, 33.5 g (0.25 mol) of terephthalaldehyde and 34.8 g (0.5 mol) of hydroxylamine hydrochloride were placed in a 1 liter volumetric flask. The mixture was refluxed for 2 hours and then cooled to room temperature. The resulting Terephthalaldehyddioxim was abfillricrl and overnight in vacuo at 50 C ^l-dried.

Then the same procedure as in Example 1 was carried out using 16.4 g (0.1 mol) of terephthalaldehyde dioxime, F. 217 to 220 "C. 28.5 g (41% bulge) of terephthalaldehyde dioxime distearate were obtained which has a melting point after recrystallization from methyl alcohol from 145 to 146 ° C.

In the following table 1 are the elemental analyzes and melting ranges of various inventive crosslinking agents.

Table 1
Elemental analysis and melting ranges of various oxime ester surfactants

connection

carbon 55 found Elemental analysis found nitrogen found Melting range theory 73.40 hydrogen 10.11 theory 3.54 73.36 75.37 theory 10.91 3.72 4.14 90 to 93 76.00 75.59 10.17 10.93 3.93 4.05 60 to 61 75.81 73.78 11.05 11.51 4.02 4.5. * 145 to 146 73.51 64.93 10.98 4.08 4.51 9.34 111 to 112 64.86 74.94 11.68 11.62 9.45 4.25 217 to 218 74.02 66.35 4.08 5.09 4.32 8,; o 82 to 83 66.66 77.32 11.80 10.10 8.63 3.53 238 to 239 77.65 4.97 game 5 3.63 90 to 91 10.44 By S

Furfuryl dioxime distearate

1 - phenyl -1,2 - propanedione - dioximdi

stcarat

Teicphthalaldehyde dioxime dislearate ...

Glyoxime distearate

Glyoxime dibenzoate

Dimethyl glyoxime distearate

Dimethylglyoxime dibenzoal

Diphenyl glyoxime distearate

Networking rcaklions
Example 4

37.5 p ethylene propylene rubber (ÄPK) were stirred for 5 minutes at 110 ° C. at 30 rpm. Then 0.012 mol of glyoxime distearate per 100 g of ÄPK were added and the mixture was stirred for a further 5 minutes. The vet mixed material was taken out of the Brabender Plastopraphen and pressed for 5 minutes in a plate press at 2800 kg / cm ² and 225 ° C. to form a 0.5 mm thick plaque. The hardened polymer showed only a slight discoloration, ie it was a light yellow color and had a gel content of 21%.

Example 4 was repeated, but following the addition of the Gi> o \ imdi.; Leai \ Ui 49 mg of iron (IM) acetylacetonate were added to the Plastograph and mixed for a further 5 minutes. The mixed material was taken out of the plastograph and pressed for 5 minutes in a plate press at 2800 kg / cm ² and 150 ° C. to form a 0.5 mm thick plaque. The cured polymer showed little discoloration and had a gel content of 47%. A comparison of Example 4 with Example 5 shows that when an accelerator is used, the crosslinking mechanism

7 8

ralur can be reduced and also the 49 mg iron (III) acetylacetonate was used

Networking effect is increased. Example 5 was at a setting temperature of 250 ⁰ C, a gel content

repeated, but 0.019 moles of glyoxime each of 44% were achieved.

100 g ÄPK and 0.013 g iron (III) acetyIacetonate each In the following examples the usable

100 g of ÄPK introduced and a curing temperature of 5 speed of the crosslinking agent according to the invention for

20O ⁰ C applied. The cured polymer showed only several other polymers shown.

had a slight discoloration and a gel content of. -I _1n

Example 6 37.5 g of butyl rubber with a content of 98%

ίο Isobutylene and 2% butadiene were ½ minutes

37.5 g of ethylene-propylene rubber were stirred for 5 minutes in air at HO ⁰ C at 30 rpm. Then were

Nuts stirred in air at 110 ° C at 30 rpm, in the plastograph 0.012 mol glyoxime distearate each

with 0.012 mol of furfuryl dioxime distearate per 100 g of ÄPK 100 g of butyl rubber are added and a further 5 minutes

added and then stirred for a further 5 minutes. long stirred. The mixed batch was

The mixed material was placed in a platen press and in a platen press for 5 minutes

introduced and there at 2800 kg / cm * and 225 ° C at 2800 kg / cm * and 175 "C to a thickness of 0.5 mm

Pressed for 5 minutes. The cross-linked polymer plaque is pressed. The crosslinked polymer only showed

showed little discoloration and had little discoloration and had a gel content of

Gel content of 50%. 66%. Example 7 ^fl0 Example 11 Example 6 was repeated, but 37.5 g of commercially available polyethylene with a density Place of the furfuryl dioxime distearate was 0.012 mol GIy- of 0.96 and a melt index of 0.7

oxime dibenzoate used per 100 g of ÄPK. The gehär- 10 minutes at 160 ⁰ C with 30 U / min overall in air

The last polymer showed little discoloration and it was stirred. Then 0.009 mol of dimethylglyoxime

had a gel content of 38%. distearate per 100 g of polyethylene added and still

. -ίο stirred for another 10 minutes. The mixed up

Example 8 batch was removed and placed in a platen press Example 6 was repeated, but curing was carried out at 2800 kg / cm * and 225 ° C. for 5 minutes. Place of the furfuryl dioxime distearate 0.012 mol di- 30 The crosslinked polymer showed only slight discoloration

meihylglyoximdibenzoat used per 100 g of ÄPK. and had a gel content of 40%.

The crosslinked polymer showed little discoloration in

and had a violin content of 13%. Example ^

. - ι η Example 11 was repeated, but a

B e 1 s ρ 1 e I 9 ₃₅ commercial polyethylene used, which is up to Example 6 was repeated, but were oxidized to a carbonyl content of 0.3% Place of furfuryl dioxime distearate was 0.012 mol of tere-. Samples of the polymer were each given for 5 minutes

phthalaldehyde dioxime distearate per 100 g ÄPK and one long in a plate press at 2800 kg / cm * and temperature

Hardening temperature of 250 ° C applied. The temperatures of 175, 200 and 225 ° C to 0.5 mm thick

wetted polymers showed only a slight discoloration. 40 plaques pressed. After hardening, the samples

and had a gel content of 30%. ten a gel content of 18, 29 or 50% and

When this example was repeated with the addition of showed only a slight discoloration.

Claims (1)

Claim: Use of 0.1 to 30 parts by weight, based on 100 parts by weight of polymer of a dioxime of the general formula R R \ _t _O —N = C— \ C s C in which A is an acyl, aroyl, alkylsulfonyl, arylsulfonyl, alkylphosphinyl, arylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylcarbamyl or 15 arylcarbamyl group with 1 to 36 carbon atoms, pure hydrogen atom or a methyl,
Phenyl or furfuryl radical and R ¹ denotes a hydrogen atom or a nitro group and m, η ■ · u η ι λΗργ ~> are, if applicable, under and ο equal to 0, 1 or - » ^na - * ^fc ₂ W eightstcilen O ₁ DO) 01s -