DE1225860B - Stabilized molding compounds based on low-pressure, homo- or copolymers of monoolefins - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German class: 39 b -22/06

Number:
File number:
Registration date:
Display day:

1,225,860
S86636IVc / 39b
August 8, 1963
September 29, 1966

The invention is concerned with the stabilization of molding compositions based on homopolymers or copolymers of monoolefins, which are produced by a low-pressure polymerization process, such as the Ziegler process, can be produced by a combination of various stabilizers. In particular, she deals with stabilized molding compounds of low pressure homopolymers of propylene or copolymers of propylene and other jvionoolefins, such as copolymers of propylene and ethylene.

Polymers of this type are particularly sensitive to the action of light, heat and / or oxygen, whereby they become brittle and inflexible and their tensile strength is reduced. In order to eliminate these disadvantages, it was recommended in Belgian patent specification 605 950 to mix the polymers with a small amount of a stabilizer _{combination, including an organic sulfur compound of the general formula R 1} - SzR ₂ , in which χ is an integer ao and R ₁ and R _{2 represent} similar or different organic groups which are attached to Sa via carbon atoms; are bonded, and a polynuclear polyphenol which consists of a benzene ring containing η 3,5-dialkyl-4-hydroxybenzyl radicals bonded to η different ring carbon atoms and is substituted with 6 - «alkyl radicals on the other ring carbon atoms, where = 3 or 4 means. Stabilized molding compositions obtained by mixing the polymers with these compounds are in fact very resistant to the action of light and heat. However, they are unsuitable for certain uses because not only light, heat or oxygen have an adverse effect on the properties of low-pressure polymers of monoolefins, but also particles of impurities such as catalyst residues or metal particles present in the polymer Can cause degradation of the favorable properties. The same disadvantage occurs when the polymer is in contact with a metallic surface, in particular with a surface made of copper, which is a particular disadvantage when the polymer is used as an insulation material for electrical conductors. With a combination of the above stabilizers it is not possible to effectively protect the polymer against a reduction in its mechanical properties when it is in contact with copper. Polymers stabilized in the manner indicated there are consequently not very suitable for insulation purposes.

Stabilized molding compounds based on
of low pressure, homo- or
-Mixed polymers of monoolefins

Applicant:

Shell Internationale Research Maatschappij

N.V., The Hague

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse
and Dr. E. Frhr. v. Pechmann, patent attorneys,
Munich 9, Schweigerstr. 2

Named as inventor:

Jacob Oepkes,

Adriaan Wouter van Breen, Delft (Netherlands)

Claimed priority:

Netherlands of August 10, 1962 (281943) -

In British Patent 890 761, stabilizer combinations are used to protect the polymer against destruction by contact with copper, which is a diester of a ß-thiodipropionic acid and a bisphenol obtained by condensing 1 mole of a saturated aldehyde or ketone having 4 to 6 carbon atoms or of sulfur dichloride and 2 moles of a phenol with a non-reactive, o-position substituent and an unsubstituted p ring carbon atom. In the French Patent specification 1 269 406 also describes the addition of a diester of iS-thiodipropionic acid in Combination with a certain trisphenolic compound disclosed by condensation of either 1 mole of an unsaturated aldehyde or ketone and 3 moles of phenol with an unreactive one o- or p-hydrocarbon substituents or from 1 mole of a hydroxyaryl-substituted saturated aldehyde or ketone and 2 moles of phenol with a non-reactive o- or p-hydrocarbon substituents is obtained in order to stabilize the polymers against to achieve destruction through contact with copper.

3 4

The stability of such molding compounds which are stable Suitable polynuclear polyphenols are generally

Sator combinations contain, in which, in addition to the common ones, the 1,3,5-trialkyl-2,4,6-tris- (3,5-dialkyl-

mentioned diesters also the above bis- or tris-4-hydroxybenzyi) benzenes and especially those

phenolic compounds are present, compounds whose phenol nuclei have a secondary

however, much to be desired if they have, alike, 5 or tertiary alkyl substituents on either of the two

whether in contact with copper or not, higher Tem ring carbon atoms in o-position to the hydroxyl

exposed to temperatures. Have special difficult groups.

opportunities arise in the manufacture of isolated compounds of the latter are preferred

electrical conductors, as these are coated with three 3,5-di-tert-butyl-4-hydroxybenzyl radicals,

Conductor with a thermoplastic or molten io such as 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-

zenen polymers are produced. As is known, 4-hydroxybenzyl) benzene is used,

The bisphenols or trisphenols of category c) will be used for the application of such coatings

Temperatures of generally more than 150 ° C. produced by known processes. So can

applied. In addition, the so stable are suitable, for example, a trisphenol by reaction of

Sized molding compounds are of course not very good for the one mole of an unsaturated aldehyde or ketone

Covering electrical conductors whose use at 3 moles of one in the o-position with a secondary

higher temperatures is provided. or tertiary alkyl radical substituted phenol in

It has now been found that molding compositions based on the presence of an organic solvent and

Base of low-pressure homo- or mixed-poly of a strong acid, such as hydrochloric acid,

mers of monoolefins are an excellent resistance. A trisphenol is also formed,

Resistance to joint action if, under similar conditions, 1 mole of one

of high temperatures and contact with hydroxylaryl-substituted, saturated aldehydes or

Copper can be bestowed by a stabili- ketone with 2 moles of one in the o-position with a second

Sator mixture of tertiary or tertiary alkyl radical substituted phenol

25 is condensed. Bisphenols can be caused by condensation

a) an organic, non-phenolic sulfur _sat i _{on emes Mo} i _{s of} a saturated aldehyde or compound of the general formula R ₁ -S ₃ TR ₈ , ketone or of sulfur dichloride with 2 mol of one in which χ is an integer and R ₁ and R _{2 m} o-position can be obtained with a secondary or tertiary, identical or different phenol substituted by a carbon-alkyl radical,
* atoms bonded to organic radicals DAR S ₃₀ Particularly suitable bis- or trisphenols will provide unsaturated by reaction of a phenol with a

b) a polynuclear phenol and or saturated aldehyde or ketone with more than . c) another phenolic compound 2 carbon atoms but less than 6 carbon atoms and especially by condensation

with the indicator that the masses as b) one with 35 of phenols with unsaturated aliphatic alde-

n 3,5-dialkyl-4-hydroxybenzyl radicals and with 6-η hyden, such as acrolein or crotonaldehyde.

Alkyl radicals substituted benzene, where n = 3 or Die in the condensation reactions mentioned

4, and as c) contain a bis- or trisphenol, phenols used preferably contain in the o-position

the reaction of a saturated or unsaturated tertiary or secondary alkyl substituent,

Aldehyde or ketone or sulfur dichloride 40 especially a tertiary butyl substituent. she

with one in the o-position through at least one, however, other substituents can also be in the o-position

secondary or tertiary alkyl radicals including η alkyl groups.

Phenol has been obtained. Examples of preferably used bis or

The organic radicals R ₁ and R _{2 of} the sulfur trisphenols are: l, l, 3-tris- (2-methyl-4-hydroxy-

containing compound R ₁ - S _x - R ₂ can be alkyl, 45 5-tert.-butylphenyl) butane, l, l-bis (2-methyl-4-hydroxy-

Arylalkyl or cycloalkyl radicals with preferably 5-tert-butylphenyl) butane, 1,3-bis (2-methyl-4-hydroxy-

at least 8 and at most 25 carbon atoms 5-tert.-butylphenyl) propane and 4,4'-thio-bis (3-methyl-

be, where the number χ is generally not greater than 6-tert-butylphenol). Of these connections are

than is 2. Examples of suitable dialkyl mono- or those mentioned first and last are particularly suitable,

-disulphides are: di-dodecyldisulphide, n-dodecylcetyl- 50 The amount in which the sulfur-containing organ-

sulfide, bis- (n-eicosyl) -suMd and bis- (n-cetyl) -sulfide, niche compound of the formula R ₁ -S _x - R ₂ in the

of which the last compound turns out to be molding compositions to be stabilized particularly according to the invention

proved suitable. The radicals R ₁ and R ₂ can also be included, is usually in the range of 0.01

mean esterified carboxylic acid alkyl radicals, such as. B. up to 1.5 percent by weight, based on the weight

in compounds of general formula 55 amount of polymer, for the other two components the stabilizer mixture is the

O O setting amount generally between 0.01 and

Il 1 1.0 percent by weight. Well stabilized molding compounds

R ₃ O - C - C _m H _am - S - C _m H ₂ m - C - OR ₄ contain, for example, 0.05 to 0.3 percent by weight

60 of the above-mentioned polynuclear polyphenol of

in R ₃ and R ₄ similar or different carbon category b), 0.3 to 1.2 percent by weight of the above

hydrogen radicals, preferably alkyl radicals with 6 to mentioned organic sulfur-containing compounds

20 carbon atoms are and m is an integer of category a) and 0.2 to 0.8 percent by weight

from 1 to 6 means. Of these dialkyl esters of bis- or trisphenolic condensation products

Thiodicarboxylic acids are said to be the symmetrical dialkyl 65 abovementioned category c).

esters of jg-thiodipropionic acid, in particular di- If desired, the inventively stabilized

lauryl-jS-thiodipropionate as particularly suitable formed molding compounds more than a stabilizer compound

thinks. a certain category. So

excellent results are obtained, for example, with preparations which, in addition to a thiobisphenol contain a tris (hydroxyphenyl) butane.

The stabilizer mixtures or their individual components can be prepared by the usual mixing or Blending processes, such as dry blending in, for example, a powder mixer, Grinding, rolling in, Banbury mixing or extrusion, homogeneously into the polymers to be stabilized be introduced. The mixing can take place even during the work-up of the polymer take place.

The molding compositions stabilized according to the invention can, in addition to the stabilizer mixture mentioned, also other stabilizers, such as UV light stabilizers, or commonly used Contain additives such as pigments, fillers, vulcanizing agents or lubricants.

The molding compositions stabilized according to the invention can be molded not only as insulation material of coatings on cables, but also ίο on tubes, plates, foils, layers of film, threads, Process fibers, bottles or injection molded objects.

Table I.

rehearse sulfur
link,
Component a) Weight
percent Multi-core
Phenol,
Component b) Weight
percent Up or
Trisphenol,
Compo
nent c) Weight
percent Heating
in T
without
Contact duration
agen
in
Contact with Cu with Cu 1 al 0.3 b 0.05 el 0.8 80 25th 2 al 0.4 b 0.07 el 0.5 94 36 3 al 0.6 b 0.2 el 0.3 135 55 4th al 0.6 b 0.2 el 0.5 130 57 5 a2 0.3 b 0.05 el 0.8 80 25th 6th a2 0.6 b 0.2 el 0.5 100 40 7th al 0.4 b 0.07 c2 0.5 100 26th 8th al 0.6 b 0.2 c2 0.5 130 44 9 al 0.6 b 0.2 c3 0.5 170 65

Table II

sulfur Weight
percent More Weight
percent Up or Weight
percent Others
Stabilisa
fools Weight
percent Heating time agen
in
Contact rehearse ver
binding,
Compo robust
Phenol,
Compo Tris
phenol,
Compo in T
without
Contact with Cu nent a) 0.3 nente b) 0.05 nent c) with Cu 1 10 al 0.4 b 0.07 100 3 11 al 0.6 b 0.2 - - 120 5 12th al 0.3 b 0.05 - 170 2 13th a2 0.6 b 0.2 - - 110 2 14th a2 0.1 b - 0.1 - 160 2 15 * al 0.5 - el 0.4 20th 15th 16 * al 0.6 el 0.2 - 120 7th 17 ** al 0.6 - c2 0.2 86 6th 18 ** al 0.6 - c3 0.2 - 150 5 19 ** al 0.6 - c4 0.2 105 5 20 ** al 0.6 - c5 0.2 - 90 6th 21 *** al 0.6 - 0.2 c6 dl 0.5 98 10 22nd al 0.6 b - dl 0.2 100 6th 23 **** al 0.6 - 0.2 - dl 0.5 120 13th 24 a2 0.6 b - dl 0.2 86 8th 25 **** a2 0.6 - 0.2 - dl 0.5 112 11 26th a3 0.6 b - dl • 0.2 73 7th 27 **** a3 0.6 - 0.2 - d2 0.5 82 6th 28 al 0.6 b - d2 0.2 110 3 29 ***** al 0.6 - 0.2 - d3 0.5 30th 7th 30th al 0.6 b - d3 0.2 115 3 ₃₁ ***** al 0.6 - 0.2 - d4 0.5 32 8th 32 al 0.6 b d4 0.2 124 4th 33 ***** al 0.6 0.2 d2 0.5 36 8th 34 ***** al 0.6 c2 0.2 d2 1.0 81 6th 32 ***** al 0.6 - c2 0.2 d3 0.5 72 10 3g ***** al 0.6 - c2 0.2 d3 1.0 84 7th 37 ***** al - c2 76

* Rubber + Plastics Age, 42 (1961), p. 541.
** Belgian patents nos. 577252, 582161.
*** French patent specification No. 1247236.

**** Belgian patent specification No. 577252, French patent specification No. 1259294.
***** U.S. Patent No. 3033814.

example

A polypropylene was used as the polymer to be stabilized, which by polymerization made of propylene in the presence of a catalyst from titanium tetrachloride and triethylaluminum had been. Its intrinsic viscosity in decahydronaphthalene at 135 ° C was 3.0.

100 parts by weight of polypropylene powder were mixed with the stabilizer combinations by rolling, fine copper turnings were also incorporated into part of the polymer. From both samples the copper-free as well as the copper-containing, molded bodies were produced (length 200 mm, width 20 mm, Thickness 0.5 mm) and then heated in an oven at a constant temperature of 135 ° C exposed to the action of air. In the following Tables, the last two columns on the right indicate the number of days after which the samples became brittle.

Table I contains nine samples that were stabilized according to the invention, while Table II For comparison purposes, stabilizer mixtures were compared, which were either 2-component mixtures represent or 3-component mixtures in which one component does not comply with the invention specified corresponds to.

The components a), b) and c) used in the molding compositions according to the invention and the to The other stabilizers marked with d) used for comparison purposes were:

al: dilauryl - ^ - thiodipropionate,

a 2: dicetyl sulfide,

a.3; Didodecyl sulfide,

b: l, 3 _? 5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-

4-hydroxybenzyl) benzene,
c 1; l, l, 3-tris- (2-methyl-4-hydroxy-

5-tert-butylphenyl) butane,
c 2; l, l-bis (2-methyl-4-hydroxy-

5-tert-butylphenyl) butane,
c 3: 4,4'-thio-bis (3-methyl-6-tert-butylphenol),
c 4: 2,2'-thio-bis (4-methyl-6-tert-butylphenol),
c 5: 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), c 6: 2,2'-methylene-bis- [4-methyl-

6- (l'-methylcyclohexyl) phenol],
d 1: 4- (2'-hydroxyphenyl) -2,2,4-trimethyl-

5 ', 6-dinonylchroman,
d2: phenyl salicylate,
d 3: p-tert-butyl-phenyl salicylate,
d4: p-octyl phenyl salicylate.

The superiority of the molding compositions stabilized according to the invention in samples 1 to 9 in Table I. versus the samples contained in Table II, which systems of two or more components obtained in which a component essential according to the invention is missing is based on the comparison clearly emerged.

Claims (2)

Patent claims: 1. Molding compounds based on low-pressure homopolymers or copolymers of monoolefins, one against the joint effects of high temperatures and contact with copper protective stabilizer mixture a) an organic non-phenolic sulfur compound the general formula R ₁ - S _x - R ₂ , wherein χ is an integer and R ₁ and R _{2 are the} same or different via carbon atoms on Sa; represent bound organic residues, b) a polynuclear phenol and c) another phenolic compound contain, characterized in that they contain as b) a benzene substituted with η 3,5-dialkyl-4-hydroxybenzyl radicals and 6-w alkyl radicals, where n = 3 or 4, and as c) a bis- or trisphenol, which has been obtained by reaction of a saturated or unsaturated aldehyde or ketone or of sulfur dichloride with a phenol substituted in the o-position by at least one secondary or tertiary alkyl radical. 2. Molding compositions according to claim 1, characterized in that they contain component a) in an amount of not more than 1.5 percent by weight and components b) and c) each in an amount of not more than 1 percent by weight based on the polyolefin. Considered publications: Examined documents of Belgian patents Nos. 577 252, 582162; French patents No. 1 247 236,
259 294; U.S. Patent No. 3,033,814; “Rubber Plast. Age ", 42 (1961), No. 5, p. 541. 609 658/478 9.66 © Bundesdruckerei Berlin