DE2804980A1 - STABILIZED INORGANIC ADDITIVES CONTAINING PROPYLENE POLYMER COMPOUNDS - Google Patents

Description

T n " \ £ f> - patent attorneys:

IIEDTKE - BUHLING - IVlNNE - tjRUPF. Dipl.-Ing. H. Tiedtke

Dipl.-Chem. G. Bühling Dipl.-Ing. R. Kinne

- ³ - 28Q498Q

Bavariaring 4, PO Box 202403 8000 Munich 2

Tel .: (0 89) 53 9653 Telex: 5-24845 tipat

cable: Germaniapatent Munich February 6, 1978 B 8724 / ICI case Po 29327

Imperial Chemical Industries Limited

London / Great Britain

Stabilized propylene polymer compositions containing inorganic additives

The invention relates to propylene polymers that Contain adsorptive, inorganic additives such as talc, asbestos, chalk or limestone, through which the stabilization is made difficult or prevented by propylene polymers.

The term "propylene polymers" are homopolymers of propylene or copolymers to be understood that at least Contain 50% by weight of polymerized propylene.

Make adsorptive, inorganic additives more difficult or prevent the stabilization of propylene polymers probably by the fact that they the sterically hindered, phenolic compounds commonly found in propylene polymers are used as antioxidants, adsorb. British Patent 1,247,802

_{XI / 17} 809832/0900

Dresdner Bank (Munich) Account 3939 844 Postscheck (Munich) Account 670-43-804

it is therefore proposed to use different propylene polymers Substances, e.g. B. uncrosslinked epoxy resins to be added to the hindered phenolic antioxidants preferably to the inorganic additive

5 are adsorbed. Many of these substances, in particular

the epoxy resins suitable for the stated purpose expensive, and many substances are viscous liquids that are difficult to disperse in the propylene polymers. According to the invention it has now been found, surprisingly, that advantageous improvements in stabilization can be achieved, without the use of a substance such as. B. an epoxy compound is necessary if you want the sterically hindered, phenolic antioxidant group binds to an isocyanurate ring and, together with the usual, synergistically active, organic sulfur compounds are used. These improvements are achieved in spite of the fact that isocyanurate antioxidants differ from that in the British Patent 1,259,179 when used in propylene polymers do not have the most effective antioxidants

20 are dation agents.

According to the invention, a propylene polymer composition is accordingly used provided the

a) 10% by weight to 85% by weight, preferably 15% by weight to 60% by weight (based on the weight of the mass) of an adsorbent, inorganic additive,

b) an isocyanurate antioxidant in the form of a sterically hindered, phenolic isocyanuric acid

esters and

c) contains an organic sulfur compound of the type associated with hindered phenolic antioxidants

35 chemicals works synergistically.

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The isocyanurate preferably has the general formula

O = C C = O

ι ι

A ₃ -X ₃ -CH ₂ -N N-CH ₂ -X ₂ -A _{2 f}

C Il 0

wherein A _{1 is} a group containing a sterically hindered phenol,

wherein A ₂ and A ₃ , independently of one another, denote hydrogen, an alkyl group with up to 11 carbon atoms or preferably a group which contains a sterically hindered phenol, it being particularly preferred that A 1, A ₂ and A _{3 are} the same Group are

wherein Xj, X ₂ and X ₃ , independently of one another, are either the group ~ ( ^CH 2 ^ _n ~ ° of the aie group

O
- (CH ₂ ) _p -OC- (CH ₂ ) _m -

mean,
25th

where η and p, independently of one another, are 0, 1, 2 or 3 and where ro is 1, 2, 3 or 4. Preferably η is O, ρ 1 and ra 2.

The hindered phenols contain a sterically hindered one Hydroxyl group. The hydroxyl group is preferably hindered by t-butyl groups which are in the o-position of the hydroxyl group. The hindered phenol is preferably through one with the rest of the isocyanate compound Bond, which is in p-position to the adiinderten hydro-

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xyl group is located. The two preferred isocyanurates (i.e. the isocyanurates where η is O or where ρ is 1 and m 2) therefore have the formulas:

OH

-t-but

CH ₀

C C

I I

N N

CH ₂ ^ C CH,

t-Buty ^ JJ

t-but t-but

and

\ A

CC II

Il
0

wherein t-but is t-butyl and wherein B

O t-but

-CH ₂ -CH ₂ -OC-CH ₂ -CH ₂ - ^ 3

The masses preferably contain 0.01% by weight to
6% by weight (generally 0.08% to 1% by weight) of the isocyanurate when not for use as premixes

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are provided (in this case they can be up to 12% by weight des isocyanurates).

Examples of organic sulfur compounds with Sterically hindered, phenolic antioxidants act synergistically, are long-chain mercaptans and sulfides (e.g. with 10 to 22 carbon atoms), but the preferred compounds are the dialkyl esters of thiodialkanoic acids, especially when the alkyl groups contain 10 to 22 and the alkanoic acids contain 2 to 6 carbon atoms. Individual examples are the Dilauryl ester and the distearyl ester of thiodipropionic acid. The masses preferably contain 0.01% by weight to 10% by weight (generally 0.1% to 0.5% by weight) of the organic sulfur compound when not for use as premixes are provided (in this case they can contain up to 15% by weight of the organic sulfur compound). The compositions can in particular contain 0.5% to 3% of the organic sulfur compound (based on the propylene polymer).

The propylene polymers are preferably crystalline and / or thermoplastic and preferably have a melt index from 0.5 g to 50 g (generally from 1 g to 20 g) per 10 min (measured according to British Standard 2782: part 1/105 C / 1970 using a load of 2.16 kg, but carried out at 230 C). The copolymers preferably contain 2% by weight to 20% by weight ethylene and 98% by weight accordingly up to 80% by weight propylene.

Examples of adsorbent, inorganic additives are not only talc and carbon, but also Asbestos, calcium carbonate (especially limestone and coccolithic chalk) as well as slate powder, mica, clay, barium sulfate and hollow bodies made of various aluminum silicones

35caten exist as z. B. British Patent

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1 292 112 have been described. The average particle size (number average) of the inorganic additives is preferably below 30 μm and often between 0.1 μm and 15 psa, but the carbon blacks used can be particle-

Have 5 sizes of 10 ηπ.

Although the use of substances such as B. epoxy compounds, which are preferentially adsorbed on the inorganic additives over the antioxidants, is not essential for the performance of the compositions according to the invention, but can be achieved through the use of such substances a further improvement in the stabilization of the propylenepolyra can be achieved. The invention Accordingly, masses can additionally contain 0.01% by weight to 5% by weight (preferably 0.1% by weight to 1.3% by weight), based on the Weight of the inorganic additive, containing a substance that is preferred over the isocyanurate to the inorganic Additive is adsorbed and in this way hindering the stabilization of the mass by the inorganic Additive reduced. If the mass is to be used as a premix, it can contain up to 15% by weight contained in the substance. The substance preferably contains a polar group in order to adsorb to the inorganic To facilitate additive, and a non-polar group to improve compatibility with the organic polymer, and it preferably has a molecular weight greater than 300.

Examples of such substances are *

a) amides, e.g. B. N, N'-ethylene-bis-stearic acid amide or

the condensation products of diethanolamine and carboxylic acids,

35 b) polymethyl methacrylate,

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r \

. B.

c) aliphatic polyols, e.g. polyethylene glycol,

Glycerine or mannitol,

d) sulphides, ζ. B. bis (diiaethylthiocarbainoyipdisulfide, 5

e) aminobenzoic acids,

f) long-chain, aliphatic amines, 10 g) polyethers and

h) epoxides, which are most preferred.

These substances are described in the British patent 1 247 802 described in more detail.

The preferred epoxides are the uncrosslinked epoxy resins of the type described in "Encyclopedia of Chemical Technology", 2nd Edition, Volume 8, pages 294-306, edited by R E Kirk and D F Othraer, John Wiley, New York will. The most widely used epoxy resins are condensation products of epichlorohydrin and bisphenol A. The effectiveness of the isocyanurate in terms of stabilization is greater if the epoxy resin that is used is a viscous one

25 is liquid.

Many representatives of the adsorptive, inorganic additives contain transition metals, possibly as impurities, and it is well known that such ions catalyze the oxidative degradation of propylene polymers can. It is therefore sometimes advantageous to add so-called "metal deactivators" to the compositions according to the invention. to be added. Metal deactivators are organic compounds that form complexes with transition metal ions and in this way the ability of the ion to catalyze

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the oxidative degradation (of the propylene polymers. Typical metal deactivators are used in the UK Patents 1,219,783 and 1,166,949. Among the metal deactivators that are of particular importance Of interest include pentaerythritol, N-salicyl-N'-salicylic idenhydr a ζ in, oxanilide, oxamide and preferably melamine or oxalic acid bis (benzylidene hydrazide).

The masses can be known additives such. B. light stabilizers, pigments, antacid substances (e.g. Calcium oxide) and processing aids (e.g. soaps such as sodium or calcium stearate).

The compositions of the invention are suitable for use in the production of technical components for the propylene polymers are needed which, when hot, have increased resistance to deformation and which are subject to less shrinkage on cooling, especially on cooling after molding. Typical components which can be produced from the compositions according to the invention are distributor heads, rocker arm housing covers and housing cover for the camshaft drive in motor vehicles. By extrusion and / or rolling processes films can also be produced from the masses. Examples of typical rolling processes are calendering and chill roll casting and in particular the appropriate modification of the calendering process in which the molten mass is fed from an extruder or from an intensive mixer to the gap between a parallel pair of rollers. In the Foils produced in such a way with a thickness of preferably 0.05 mm to 0.5 mm can by a Thermoforra process, z. B. to form containers for edible fats, documents for chocolate goods and boxes for horticultural purposes. Thicker films, e.g. Be with a thickness of 0.5 mm to 2.0 mm, can be made by thermoforming,

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ζ. B. Forming in a vacuum, with the formation of products such as automotive components, such as equipment such as dashboards, Door panels, floor and ceiling coverings, wheel arches, car seat fittings and luggage compartments, processed will. They can also be used to manufacture cooling tower packings and packings for the treatment of Effluents can be used. For certain products it can be advantageous to coat the shaped article with a suitable, cellular foam material, e.g. B. to be filled with polyurethane foam, or with another support structure. One can also use the process of vacuum deformation.

The foils can, preferably, by means of an embossing tool a pressure roller, are embossed and / or they can with other plate or web-shaped materials, eg. B.

with films or foils, with woven, knitted, knitted, felted and other non-woven, textile fabrics or be laminated with textiles coated with plastic. The lamination can be done while running of the rolling process used to form the films, or it can be carried out by the molten mass is extruded onto the sheet or sheet material.

The invention is illustrated in more detail by the following examples, examples A to H being comparative examples are. The percentages given are% by weight, based on the weight of the mass.

30 Examples 1 to 6 and A to E.

A propylene homopolymer with a melt index of 4 was made with 40% talc, 2% calcium oxide, 1 % carbon black, 0.2% calcium tearate and various amounts of dilauryl thiodipropionate (DLTDP) together with various amounts of the in

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Table 1 indicated ^ antioxidants and epoxy resins mixed in the melt. The epoxy resins were condensates of epichlorohydrin and bisphenol A (trademark "Araldite" or "Epikote" 1002).

The resulting masses were forming 1.6 well thick plates molded. The panels were placed in a hot air oven installed on top of the temperature indicated in Table 1 was maintained. the

10 samples showed after being over a number of days

were cracked on the surface in the air-heated oven. Table 1 shows the time it took for cracks to appear.

The isocyanurate antioxidant can be seen to increase at an antioxidant concentration of 0.2% gives better results than Antioxidants I and II, although I and II are used together with an epoxy resin will. You can also see that the performance

of the isocyanurate is even better if that

Isocyanurate is used in combination with an epoxy resin.

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Table 1

ο co 00 Ca> ro

O CO O O

example Antioxidants "
option: ittel lot lot
of
DLTDP Epoxy verb in-
manure lot Oven-
temperature
( ⁰ C) time to
to the crack
education (d) 1
2 Isocyanurate
Isocyanurate 0.2
0.2 0.5
0.5 - 160
150 12th
31 A.
B. HHHHH
H H 0.2
0.3
0.3
0.2
0.4 0.5
0.5
0.5
0.5
0.75 "Araldite"
"Araldite"
"Araldite"
"Araldite"
"Araldite" 0.5
0.75
1, 00
0.5
0.75 150
150
150
150
150 19th
29
34
19th
22nd 3
4th
5
6th Isocyanurate
Isocyanurate
Isocyanurate
Isocyanurate 0.2
0.3
0.2
0.4 0.5
0.75
0.5
0.5 "Araldite"
"Araldite"
"Epikote" 1002
"Epikote" 1002 0.5
0.75
0.5
0.5 150
150
150
150 34
70
63
70 Isocyanurate: 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate.
Antioxidant I: Pentaerythritol tetra [ß- (di-t-butyl-4-hydroxyphenyl) propionate].
Antioxidant II: 1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane.

At 160 ° C, therefore, the result of 12 resulted in approximately half the time as at 150 ⁰ C, i.e., at 160 ° C.

In Examples D and E, sodium stearate was used instead of calcium stearate.

u>

Cd oo

OO

OC)

B 8724

Examples F to H '

To the effectiveness of the antioxidant in the event the absence of adsorbent additives To compare talc and carbon black, identical samples were molded from a propylene homopolymer containing only 0.5% Dilauryl thiodipropionate, 0.2% calcium stearate and 0.2% of an antioxidant as indicated in Table 2. The samples were placed in a hot air heated Brought oven kept at 150 ° C. The time it took for cracks to appear is shown in the table specified.

Table 2

Ib example Antioxidants Time to crack (d) F. Isocyanurate 80 G ⁺ I 114 H ⁺ II 90 20th

As defined in Table 1.

The superiority of isocyanurate in the presence of adsorptive, inorganic additives is in a stark contrast to its inferior properties in the absence of such additives,

In the case of masses that contain substances that are preferred to the inorganic ones over the antioxidants When additives are adsorbed, the concentration of isocyanurates and sulfur compounds becomes appropriate in% by weight, based on the weight of the propylene polymer contained in the composition. For example, a such mass 0.01 wt% to 6 wt%, preferably

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0.08% by weight to 1% by weight, isocyanurate and 0.1% by weight to 10% by weight, preferably 0.5% by weight to 3% by weight, of the sulfur compound based on the weight of the propylene polymer in bulk. The propylene polymer can

z. B. be a homopolymer or a copolymer of propylene with up to 20 wt .-% ethylene. Also in the presence of the preferably adsorbed substances, the concentration range of the additives can be extended to 3% by weight to 95% by weight, based on the weight of the mass.

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Claims (5)

Claims 1. Propylene polymer composition containing 10 wt .-% to 85% by weight of an absorbable, inorganic additive, 0.1% to 15% by weight of an organic sulfur compound of the type that acts synergistically with hindered phenolic antioxidants and 0.01% by weight up to 12% by weight of an antioxidant which contains a sterically hindered phenolic group, characterized in that that the antioxidant is an isocyanuric acid ester. 2. propylene polymer composition according to claim 1, characterized in that that the adsorbent, inorganic additive is talc. 3. Modified propylene polymer composition according to claim 1, containing 3 wt. up to 95% by weight of an organic organic adsorbent additive, 0.1 wt% to 10 wt% (based on the weight of the propylene polymer in bulk) an organic sulfur compound of the type with hindered phenolic antioxidants acts synergistically, and 0.01 wt .-% to 6 wt .- * (based on the weight of the propylene polymer in the mass) of an antioxidant which contains a sterically hindered phenolic group, characterized in that that the mass also 0.01 wt .-% to 5 wt .-% (based on the weight of the inorganic additive in the mass) 809832/0900 XI / Ί / ORIGSMAL INSPECTED contains a substance which, compared to the isocyanurate, prefers the adsorptive, inorganic additive is adsorbed and that the antioxidant is an isocyanuric acid ester. 4. propylene polymer composition according to claim 3, characterized in that the inorganic additive talc, Carbon, calcium carbonate, slate powder, mica or clay or is in the form of hollow bodies made of 10 aluminum silicates consist. 5. film, characterized in that it is made by extruding and / or rolling a Propylenpolymerraasse one of the preceding claims has been produced. 809832/0900