DE2060859C3 - Molding compounds based on olefin polymers stabilized against thermal-oxidative degradation - Google Patents

Description

their easy transferability the stabilizing effect. Tertiary aliphatic carbon atoms are not present in mono-meric acenaphthylene. The stabil

Polyolefins are due to their excellent ization of molding compounds on the basis of

mechanical and electrical properties in olefin polymers against thermal oxidative degradation

Increasingly in many areas of technology according to the invention can surprisingly only

used. These numerous possible uses can be achieved with polyacenaphthalene, which is

opportunities, e.g. B. as insulating materials in electrical engineering, in contrast to the well-known stabilizers in poly-

however, assume that these polymers retain their good properties and do not migrate.

Maintain substance properties over a long period of time. The present invention aims to

However, as is known, olefin polymers are oxide-based, stable against thermal-oxidative degradation.

sensitive to movement, d. that is, they are already in the air, based molding compounds based on olefin poly-

Particularly at elevated temperatures, acidic merizates create the disadvantages outlined above

substance degraded. Which no longer show with increasing degradation.

There is now one against thermal-oxidative degradation

severe deterioration in the mechanical and destabilized molding compound, consisting of A) 90 bis

electrical properties. It therefore has 95.5 percent by weight of olefin polymer and B) 10 bis

There has been no lack of attempts through suitable additives 30 0.5 percent by weight of polyacenaphthylene, based on

to retard the oxidation of these polymers by the weight of the olefin polymer. the

to suppress the most favorable trap completely. non-polar oligomeric, preferably polymeric

Known additives, which remain in the autocatalytic bc-hydrocarbon polyacenaphthylene

Accelerated oxidation chain reaction of the olefin poly- due to its polymeric structure in the olefin polymer

merisate have an anti-oxidant effect, are before 35 and protect it effectively against thermal-oxida-

especially low molecular weight compounds, especially tive degradation. It shows a homogeneous stabilizing

hindered phenols and aromatic amines. Effect whereby there is no formation of oxidation and

However, this has the disadvantage that they are often consequently the effective in terms of

have no permanent effect because they are stabilized against oxidative: '· degradation required

Only some of the volatility remains in the polymer. Molding compounds with a

or - what also for polymeric nitrogen-containing hetero content of 2 to 4% based on polyacenaphthylene

cyclen applies as oxidation stabilizers - due to the weight of the olefin polymer, have proven to be

Their polar structure with the olefin polymers proved particularly favorable.

are incompatible and with higher proportions to a With the oxide used according to the invention

Deterioration of the known good electrical 45 stabilizer polyacenaphthylene can olefin

Properties of these polymers can lead. polymers such as B. High or low pressure poly

US Pat. No. 2,761,855 discloses the stabilization of ethylene, isotactic polypropylene, or polybutene-1 lization of polyvinyl chloride, which, as well as mixtures of these polymers, is effective against the stabilization of polyols and is protected by thermal oxidative degradation ,
Fines Object of the Present Invention 50 The poly to be used according to the invention. Thus, acenaphthylene is formed in the breakdown of polyvinyl chloride by known processes, essentially through hydrochloric acid, while in the case of thermal polymerization of acenaphthylene in the case of polyolefins essentially CO ₁ and H ₃ O as 100 to 120 ^° C. or through catalytic polymerization, oxidation products are formed. Even when adding radical formers, such as. B. Diben-15% common comonomers behave the bo- 55 zoyl peroxide at 100 ⁰ C are obtained. High degree of polymerisation, essentially like polyvinyl chloride. The stabilization of Olefinpolymerisatmassen against other known processes by polymerization oxidative degradation, the object of the present invention of acenaphthylene in solution at ^ 0 ⁰ C with boron is not mentioned and also due to the fluoride ether or by Introduction of boron fluoride gas Constitution not possible. 60 can be obtained as a catalyst.

In British patent specification 652 730, the stabilization of the polyacenaphlization obtained by this process of molding compounds based on ethylene can be converted from benzene with methanol Olefin polymers can be used directly against degradation by UV radiation, as this may be the case described, wherein compounds formed with a strong oligomer fractions formed with the polymerization UV absorption spectrum in polyethylene or poly- 65 polyacenaphthylene achieved oxidation-inhibiting wood containing material will not interfere. An even distribution of the can, such as B. naphthalene, anthracene, fluorene stabilizer according to the invention has proven to be special or other aromatic hydrocarbons. It can be turned out to be beneficial. For this purpose, the invention

aem & D used polyacenaphthylene in a very finely divided form incorporated into the non-crosslinked olefin polymers. This can be done by mixing in the iffindunßßssiges oxidation stabilizer in the oil finoolmerisate according to conventional mixing processes.

lS?

According to a preferred embodiment of the invention, the uniform distribution of the polyacenaphthylene to be used in the olefin polymer can be obtained by heating a mechanical mixture of the two polymers above the softening point of the olefin polymer and mixing this mixture in an extruder or in a corresponding device Subjected to kneading or rolling treatment.

In some cases it has been found beneficial to use polvacenaphthylene in an aromatic hydrocarbon to be added dissolved to the olefin polymer. Sas thus stabilized against thermal oxidation Olefin polymer can be added directly to extruded or injection-molded articles, preferably cables or Conductive insulation, processed i.

Stabilization with polyacenaphthylene as a polymer and thus non-migratory antioxidants make themselves in the production of news veiniso-Eungpn from olefin polymers with high take-off speeds be driven, especially noticeable Shaft, especially when it comes to with thixotropic hydrocarbon mixtures

Example 2

Commercially available low pressure polyethylene W ^ °!,?, g / cm », MFI, * / ,,, = 0.25) was without and with poly »Addition of cenuphthylene (4 percent by weight) to lWJf-

™ ^{ien ver} P ^tear > ^where * » ^Poly ^? ^ph ÄV £ a Brabender kneader into the polyethylene at l »u ^

Kneading temperature was mixed in " _he i _tene "

Those obtained at 100.degree. C. on the basis of these films

The r} g shows the aging values in pure oxygen. »·

During the induction period of the unstabilized

Foil (curve Ϊ) is around 80 hours, wiro

this in the case of the roue provided with polyacenaphthylene

(Curve la) after 3500 hours not yet

»5 is enough.

Example 3

Commercially available isotaküsches ^^ S (d = 0.896 g / cm *, MFI ₁₉₀ , * about 16) was without and

* o with the addition of polyacenaphthytes (f percent by weight) pressed into ΙΟΟ-μ-foils, wolv * the Ρ " ¹ ^" ^ ¹ ^^ was mixed in a Brabender kneader into the polypropylene at 210 ⁰ C kneading temperature.

The hai enen at 100 C on the basis of these films

_{You show 5} values of aging in residual oxygen. I. While the induction penode of the film without poly acenaphthylene (curve 3) is only a few hours, this be, the nut ^ {^, »β ^ see film (curve 3a) after 3500 hours

100 ° C shown. Both the unstabilized (curve 1, correct. "

2 and 3) as well as those with polyacenaphthylene versehe- A well-known, reliable andla

nen C'efinpolymerisate (curve la, la and 3 _fl ) of the method for determining the thermal sc ^ en

F ₁ g. I became foils at about 180 ° C (thickness about the stability of polymers is that of the

100 μ) and the oxygen uptake in a ₄ o oxygen uptake in the closed system vg

closed system volumetrically dependent on Journal of apphed polymer science. Vol 1 (W

Addiction

D invention is illustrated by the following examples explained in more detail.

example 1

^^ ^ ^ _practical application is unusable This value is referred to as the f ₁₀ value ( _{cf.ACS Div Org} Coatings Plast. Chem, 161 st meeting 55 3 \ S 639 to 655, in particular Tables V and Vl,

PolyäÄ mixed in at 180 ° C kneading temperature 6o plasticized at 180 ° C and mixed with was pressed into ΙΟΟ-μ-foils. Example 4

SSSSSHSS

S.sSS

of the unstabilized film (curve 1) about 90 hours

not reached yet.

Example 6

2 percent by mass (based on PE) acenaphthylene (corresponds to British patent specification 652 730)

Example 7

4 percent by mass (based on PE) acenaphthylene (corresponds to British patent specification d52 730) These mixtures were homogenized by kneading for a further 2 minutes. The ones from the mixes produced press foils (100 μ) were the oxygen aging subjected.

The measured values were determined in accordance with the following table, which is shown in FIG. graphically are applied.

Table 1

Measured values of the O _t aging on non-furled

LupoIen-1810-D foils 1.1810 D + 2% 2. 1810 D + 4%

Polyacenaphthylene polyacenaphthylene

Material:
Measurements were made on ΙΟΟ-μπι foils (PreD foils).

Measured values:

The readings are on ml / g-Oj uptake and on

Normal conditions have been converted.
Measuring temperature:

100 C.
3. 1810D f 2% 1810D + 4%

Acenaphthylene and acenaphthylene

hours O, ml / g 140 1.2 284 0.7 332 1.5 452 1.3 500 2.0 596 1.1 644 0.5 740 0.2 836 1.1 908 0.8 932 1.4

hours O ₁ ml / g 140 1.0 284 2.3 332 3.0 404 4.5 452 3.8 500 4.5 596 6.4 644 5.5 740 4.9 R40 7.0 908 5.7 932 7.1

hours O, ml / g 140 1.4 260 7.7 332 14.6 404 23.0 452 22.2 500 34.0 596 45.9 620 47.9

hours O, ml / g 140 2.7 260 6.2 308 8.0 404 13.4 452 13.1 500 17.0 596 21.0 644 22.4 740 25.3 836 32.6 908 34.1 932 34.8

This shows that the f, ₀ - "Wcrt in the

1. Mixture not yet achieved after 1000 hours

will,

2. Mixture not yet achieved after 1000 hours

will,

3. Mixing is achieved after only 290 hours.

4. Mixture is already achieved after 350 hours Polyacenaphthylene gives the polyethylene a

far better protection against oxidation than acenaphthylene

1 sheet of drawings

Claims (1)

% 2 of the cited polynuclear compounds, too Claim: which also includes monomeric »acenaphthylene can, no general inference as to that according to the Polymeric acenaphthylene used in the invention stabilized against thermal decomposition Molding compound consisting of bus 5 are drawn. So has monomeric »acenaphthylene A) 90 to 95.5 percent by weight of olefin polymer has a melting point of 92 ° C, is not very volatile and and migrates out easily. It's not im as a stabilizer B) 10 to 0.5 percent by weight of polyacenaphthylene, suitable for the purposes of the present invention. About it based on the weight of the Olefinpolymeri- also result only in the polyacenaphthylene or the sates. xo in the polymerization of acenaphthylene to polyacenaphthylene on tertiary aliphatic carbon atoms existing or emerging Η atoms due to