DE1232347B - Molding compounds from olefin homopolymers and / or olefin copolymers and organic metal compounds - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

did. CL:

C08f

German class: 39 b -22/06

Number: 1232347

File number: S 85712IV c / 39 b

Filing date: June 18, 1963

Opened on: January 12, 1967

The invention is concerned with molding compositions which mainly consist of predominantly crystalline polymers and / or predominantly crystalline copolymers of olefins. The molding compositions according to the invention are readily processable products which have greater clarity or transparency and / or improved mechanical properties and, first and foremost, higher impact strength than olefin homopolymers or copolymers without additives. In many cases, products are also obtained which have increased impact strength ^{even at a low temperature of about 0 ° C.}

The invention has an extraordinary advantage if the basic substances in the molding compositions are completely or predominantly crystalline polymers of monoolefinically unsaturated hydrocarbons with 2 to 4 carbon atoms in the molecule, which have been obtained in the presence of catalysts of the Ziegler-Natta type, in particular polypropylene. Those polymers which at least 5 x 10 ~ ⁴ percent by weight aluminum, calculated as metal are preferred which contain.

It has been found that these improved properties are found in molding compositions in which Addition compounds of metal salts of certain carboxylic acids are included. The invention relates to therefore molding compounds made from predominantly crystalline olefin homopolymers and / or olefin copolymers and organic ones Metal compounds, which are characterized in that they are 0.01 to 5 percent by weight as the metal compound at least one addition compound of the general formula

[MO, (OH) _e ZrWCHZ)

and optionally also contain no more than 20 percent by weight of rubber-like polymers and known stabilizers, where in the formula M is a metal and the symbols Z are mutually identical or different and each of these symbols is a carboxyl group a) of a di- or polybasic carboxylic acid or b) represents a monocarboxylic acid containing ring structures and in which ρ and q represent 0 or an integer or a fractional number and r and y represent integers or fractional numbers, where 2p + q + r is the valency of M and χ is a means an integer from 1 to 50,000.

The size of this integer depends on the nature of the metal and the width of ρ and q . The compounds corresponding to this formula thus have molding compositions made from olefin homo- and / or
- copolymers and organic
Metal connections

Applicant:

Shell International 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:
Frederik Lambertus Binsbergen,
Amsterdam, Netherlands)

Claimed priority:

Netherlands of June 18, 1962 (279 854)

in particular has a polymeric character when M is aluminum, ρ is equal to 0 and q has a value of less than 3 and of more than 1, both χ and y being able to have a value between 10 and 50,000. Values above 10 can only be determined by estimation, since such compounds are practically insoluble in all solvents.

The carboxylic acid groups Z of the acid added to the salt and those of the salt added to the acid can be the same or different from one another. You can own groups of carboxylic acids belonging to different classes. However, all symbols Z preferably represent the same carboxyl group.

Representatives of the desired addition compounds include, among others

[Al (OH) ZJ * ■
[Al (OH) Z ₂ I ₂ ; ·
[Al (OH) ZJ * ·
CaZ ₂ - (HZ),
CaZ, 2 (HZ)

1.5 χ (HZ),
0.5x (HZ),

and

NaZ-0.3 (HZ),

in which Z, for example, a benzoic acid group, a p-methylbenzoic acid group, a p-tert-butyl

609 757/446

3 4

benzoic acid group or a cinnamic acid group and χ Very good results are also obtained with the addition an integer between 10 and 50,000, such as compounds of monocarboxylic acids such as ZrOZ ₂ · 2 (HZ) ₃ where Z is, for example, one of those in which the carboxyl group is attached to a cyclo- Mandelic acid group and Zr the element zirconium is bonded to an aliphatic ring, for example in represents. 5 of the cyclohexanecarboxylic acid, the 1-methylcyclohexane carboxylates of silicon, tin or lead as additive carboxylic acid, the trans-4-tert-butylcyclohexanecarboxylic acid to form polymers, including polyacid, the cis-4-neopentylcyclohexanecarboxylic acid and ethylene are made from U.S. Patent 2,985,604 of 1-methylcyclohexene-S-carboxylic acid, or in which are known. In contrast to the metal containing the carboxyl group on a heterocyclic structure according to the invention, they are bound, for example in the 2-furancarboxylic salts, plasticizers which are readily miscible with the polymer with acid or pyrocucic acid or with γ-pyridine. Also that from the Japanese patent carboxylic acid or isonicotinic acid,
font 7577/1960 known basic aluminum The same applies to the addition compounds of stearate and its home solution act as plasticizers. In contrast, the above-mentioned heavy monocarboxylic acids such as monophenylacetic acid, soluble to insoluble metal salts have the effect of diphenylacetic acid, p-nitrophenylacetic acid, crystallization nuclei in the formation of poly- benzilic acid or diphenylglycolic acid, Dimerisate spherulites, to which the property improvement phenylpropionic acid, the j3, / 3-di- (p-tert-butylphenyl) -rung is attributed. α-hydroxypropionic acid, the / J-phenyl-ß-methylbutter-In the molding compositions according to the invention are the 20 acid, the ^ -p-aminophenyl-jS-methylbutyric acid, the addition compounds of saturated aliphatic / Sp-nitrophenyl-ß-methylbutyric acid and cinnamon -Dicarboxylic acids with no more than 12 carbon acids.

atoms in the molecule preferred. These preferred The in the molding compositions according to the invention

Addition compounds generally provide a used addition compounds are known in the art

considerable increase in impact resistance. Made a 25 way. Some such procedures are in the

Examples are given to improve clarity or transparency.

in particular with the aid of addition compounds The addition compounds are obtained in a konder succinic acid, glutaric acid, adipic acid concentration of 0.01 to 5 percent by weight and ins- and tetramethyladipic acid. special in such a range of 0.05 to 2 weight-good results are also used with the addition of 30 percent, based on the total mixture,
It has also been found that a saturated cycloaliphatic dicarboxylic acid such as cis-cyclohexane-1,4-dicarboxylic acid can be obtained from aromatic compounds if the predominantly crystalline polymers contain dicarboxylic acids such as phthalic acid and also more- and / or contain predominantly crystalline copolymers before basic carboxylic acids. Two and more of their crystallization by cooling from the basic carboxylic acids, the unsaturated bonds in a molten state with one or more of the and / or substituents such as halogen atoms, hydroxyl-mentioned addition compounds and additionally with and amino groups, also belong to one or more rubber-like ones Substances of the carboxylic acids, the addition compounds of which are mixed.

suitable for the molding compositions according to the invention. 40 In this way, the impact resistance can even with

With regard to the addition compounds of mono- a temperature below room temperature

carboxylic acids is very particularly an excellent one of, for example, 0 ⁰ C without significant loss of the

Effect with the addition compounds of benzoin yield stress can be increased,
acid and substituted benzoic acids obtained. Suitable rubber-like substances are

These are to be mentioned first, the 45 preferably mixed polymers of two or more

one or more hydrocarbon radicals as substituent olefins such as the rubber-like copolymers

contain ducks, such as the alkyl benzoates of ethylene with propylene and / or with the

acids and especially the p-isopropyl and p-tert-butylenes, in which copolymers as well

Butyl benzoic acid. Other unsaturated compounds such as dicyclo-

by adding addition compounds of the 50 pentadiene, as well as poly-

Oi- or / 3-naphthoic acid can be obtained. Very isobutylene, butyl rubber, mainly the cis-

Also suitable are the addition compounds of 1,4-configuration polybutadienes and the

Benzoic acids, which are used as substituents on a polar amorphous homopolymer of monoolefins, such as

Group or such an atom, for example an amorphous polypropylene. Under the expression

Hydroxyl group, an alkoxy group, an amino 55 "rubber-like substances" are also included

group, a nitro group, an esterified carboxyl natural rubber, polyisoprene, styrene butadiene

group or a halogen atom. These polar rubbers, acrylonitrile butadiene rubbers and

Groups or atoms in the benzoic acids can be understood to mean silicone rubbers, whereby the above

either as the only substituent or as a group of amorphous polymers a glass flux

with one or more alkyl, cycloalkyl and / or 60 temperature, measured according to ASTM: D 1043-51, of

Aryl radicals occur as substituents. Generally less than 10 ° C.

are the most effective compounds in which a The amount of rubber-like substances

Substituent is present in the p-position to the carboxyl group. is not more than 20 percent by weight and is

Suitable examples of benzoic acids with polar preferably between 3 and 15 percent by weight of the

Substituents are p-, o- and m-chlorobenzoic acid, 65 total mixture.

p- and m-hydroxybenzoic acid, p-methoxy- Preferably rubber-like substances are used

benzoic acid, the o-aminobenzoic acid, the p- and with an average molecular weight of

m-nitrobenzoic acid and monomethyl terephthalate. used more than 50000.

5 6

The addition compounds and the rubber compound consists in that the added addition compounds are similar Substances can fertilize the solid homogeneous material in very finely divided form on the polymer and / or copolymers are added and particles are precipitated, whereby a very fundamental resulting mixture then to a temperature mutual mixing of the addition rate Above the melting point of the homo- and / or 5 compounds and the polymer ensured Copolymer are heated. However, it is also will. The in-situ production of the addition connection is possible, One or more additional fertilizers can then be added to the polymer in connection with the vapor substances to be added only after the same aqueous polymer suspension received molten treatment became. take place. It is also possible to isolate the polymer during the mixing of the crystalline polyol, for example by centrifugation, to isolate the polymer and the substances to be added can be washed out with water and if necessary solvents can also be used. The moist cake can then be turned back into the rubber-like substance, for example, without the presence of a wetting agent prior to implementation further during the processing of the crystalline the in-situ preparation of the addition compound in Bring the reaction mixture containing polymer in the form of suspension 201.

be added to a solution. In this case, the mixing of the predominantly crystalline

mixing with the addition compound in polymer and the added substances

dry condition, if desired while accelerating, it is advisable to put the mixtures on one

Addition of a stabilizer. Temperature, which is generally considerable

The compounds are preferably in the form of 20 borrowed above the melting point of the polymer,

a suspension with a suspension of homo- The mixture is usually at a temperature

and / or mixed polymer and the produced or heated to a temperature which is around

then freed of the mixture held from water. for example 20 to 150 ° C above the melting point

In general, aqueous suspensions are laid and then crystallize out by cooling

turns. It is also possible to use suitable suspensions.

Neten organic liquids such as in Cooling to a temperature at which the

Ethanol instead of aqueous suspensions to crystallization can take place as quickly as this

use. Thus, if the metal in addition conduction is allowed to go on, so is

compound an alkali metal such as sodium, slowly over the course of several minutes up to

so this connection is not in water, but for a few hours.

for example made in ethanol. The manner of mixing results in both the addition compound and the poly- very even distribution of the substances used in the crystalline merizate in a suitable manner in ethanol in suspension polymers. These are leveled and mixed with one another, after which moderate distribution remains essentially even while the ethanol is separated from the mixture and the crystallization continues, both when it can be recovered. The aqueous suspension of an addition compound, in the event of a considerable temperature in which the metal is not an alkali metal, can increase the gradient due to the relatively large dimensions of the article to be molded obtained during the manufacture of this compound.
Be reaction mixture. Conversely, the solid substance present in this reaction mixture can, on the other hand, be isolated first, then washed out if desired and the melt retained, so that the injection molding can be resuspended in water, for example at a lower processing temperature after which the resulting mixture can be carried out as an aqueous suspension. Since the addition compound can be used. An aqueous suspension of the predominantly crystalline cooling of its melt at a higher homo- and / or copolymer can, for example, solidify faster than if the additives present in the dry state by suspending this macromolecular polymer melt in water with HiHe does not contain, their processing can also be made of a wetting agent. 50 faster.

It is also possible, the aqueous suspension by means of the form according to the invention

the addition connection with the still moist mass achieved favorable effects it is further-

To mix polymer cake, which is possible from the water, predominantly crystalline polymers with

rigen polymer suspension was obtained, for example a relatively high melt index at low

can be processed by spraying the suspension at the addition temperatures.

link on this cake. Similarly, if desired, the mold of the invention can be used An alcoholic suspension of the addition compounds also disconnects other polyolefin additives that are customary keep mixed with said cake.

will. The before and / or simultaneously with their crystallization

A very advantageous method for producing the 60 taking place shaping of the invention

The molding compositions according to the invention consists in that the molding compositions can be used in any known manner

Addition compounds take place in an aqueous medium. Products such as everyday objects can

produce in which the crystalline homo- and / by casting or injection molding from these mixtures

or mixed polymer prepared beforehand in suspension, films by blowing or extrusion

usually using a wetting agent 65 obtained through a slit; Threads, rods

is, and the resulting mixture then solid or strips can also be extruded

are continuously or essentially completely obtained from water. The same can be used upon request

to free. The advantage of this in-situ production granules, sticks or flakes can be crushed.

a) Preparation of an addition compound of
p-methylbenzoic acid with its sodium salt

4 g of NaOH were dissolved in 200 ml of ethyl alcohol, and further 27.2 g of p-methylbenzoic acid were also dissolved in 200 ml of ethyl alcohol. The solutions were heated to 70 ° C and poured together. The total mixture was cooled and concentrated to approximately 100 ml. The precipitate formed was filtered, washed with cold ethyl alcohol and then dried under a pressure of 16 cm Hg at 7O ⁰ C. The product obtained was composed of NaZ · HZ, where Z is a p-methylbenzoic acid group.

b) Preparation of an addition compound of

Cinnamic acid with its barium salt

A solution of barium cinnamic acid salt was prepared by dissolving 1.00 g of the salt containing 3 mol of crystal water in 100 ml of water. This solution was saturated ^{at approximately 25 ° C.} The solution was heated to 90 ° C, after which 0.6 g of cinnamic acid was added, which slowly dissolved. On cooling, a precipitate was formed which was filtered and then was dried under a pressure of 16 cm Hg at 7O ⁰ C. The product consisted of BaZ ₂ * 2 HZ, where Z is a cinnamic acid group.

c) Preparation of an addition compound of mandelic acid with one of its zirconium salts

_{7.45 g of Zr (NO 3} ) _{4 were} dissolved in a mixture of 300 ml of water and 120 ml of concentrated hydrochloric acid. 20 g of mandelic acid were dissolved in 150 ml of water and this solution was added to the zirconium nitrate solution, a precipitate being formed. The reaction mixture was made up to 1000 ml with water and stirred for some time. The precipitate was then filtered off, washed with a solution of 25 g of mandelic acid and 4 ml of concentrated hydrochloric acid in 500 ml of water washed at 70 ⁰ C under a pressure of 16 cm Hg The composition of the product corresponded to the formula ZrO ₂ -2 HZ, in the Z means a mandelic acid group.

d) Preparation of an addition compound of benzoic acid with a basic aluminum salt thereof

A solution A was prepared by dissolving 6.12 g of Al ₂ (SO ₄ ) S '15 H ₂ O in 100 ml of water. A solution B was obtained by dissolving 2.40 g of NaOH and 7.32 g of benzoic acid in 100 ml of water. Solution A was added to solution B with vigorous stirring, forming a precipitate. This precipitate was first filtered off, washed out with a 2% strength solution of sodium benzoate in water and then ^{dried at 70 °} C. under a pressure of 16 cm Hg. The product was composed of [Al (OH) Z ₂ ] ^ · χ HZ, in which Z denotes a benzoic acid group and χ has a value of more than 10 and can be up to 50,000, it being noted that this high agglomeration value can only be estimated (cf. "Canadian Journal of Chemistry", 35 [1957], pp. 799 to 815).

example 1

From isotactic polypropylene powder and 0.5 percent by weight of the addition compounds a) to d), calculated on the amount of polymer, powdery mixtures were prepared and then pulverized.

The polypropylene was in technical grade isooctane in the presence of a mixture of γ-titanium trichloride and Aluminum diethyl chloride has been produced as catalysts. The polymer had a melt index of 1.0, an intrinsic viscosity of 3.9, measured in decahydronaphthalene at 135 ° C, and a solubility in

ίο cold hexane of 6 percent by weight. The polymer contained 16 x 10 ~ ⁴ weight percent aluminum and 20 x 10- ⁴ percent by weight titanium.

A sample of each of the powdery mixtures and the original polypropylene powder were at ordinary temperature 0.15 percent by weight 4,4'-thio-bis- (6-tert-butyl-m-cresol) and 0.6 percent by weight Dilauryl thiopropionate added as a known stabilizer mixture. The obtained powdery Mixtures were rolled out at 180 ° C. for 5 minutes. From the layered skins obtained in this way 1 mm foils were then pressed at 280 ° C.

The clarity of these films was determined with the aid of depolarization measurements. These measurements were made as follows. A piece of approximately 22 mg of a 1 mm film obtained in the manner described above was ^{pressed between a cover glass and a slit at approximately 200 °} C. to form a layer of 0.04 mm. The polymer was then crystallized out by cooling in air. The microscope material obtained was examined in a polarizing microscope between crossed polarizers. Instead of the eyepiece, a photomultiplier was built into the observation tube. The light intensity falling on the photomultiplier was measured. It was ensured that the part of the sample to be measured did not show any spatial birefringence.

The aperture sections of the converging lens were set so that the pointer of the photomultiplier at the measurement of a standard preparation indicated a light intensity of 100. As a standard preparation any sample can be used, provided that the measured path difference is less than a quarter the wavelength of the light used.

The product to be examined was then measured, the optical system of the microscope maintaining an unchanged setting and the deflection of the pointer indicating the depolarization value Δ .
The results of the depolarization measurements of the foils mentioned are summarized in Table I.

Table I.

Used
Addition connection

no

a) NaZ -HZ

(Z = p-methylbenzoic acid group)

b) BaZ ₂ -2HZ

(Z = succinic acid group)

c) ZrOZ ₂ · 2 HZ

(Z = mandelic acid group)

d) [Al (OH) Z ₂ L • jcHZ

(Z = benzoic acid group)

Depolarization Δ

150
5

20th

ϊ 232

10

In the following example, a polypropylene was used which had been prepared as described above, except that dry hydrogen chloride gas was passed into the resulting reaction mixture after the polymerization had ended. Secondary butanol was then added and the reaction mixture was washed out first with a solution of 0.1 percent by weight of HCl, then with water and finally with an aqueous solution of 0.2 percent by weight of Na ₂ CO ₃ .

After this washout, the suspension was centrifuged in a decanter centrifuge, with a Cake was obtained which was 30 percent by weight of predominantly crystalline polypropylene and another 70 percent by weight technical isooctane contained. A portion of this cake was made for the one described below Attempt used.

This part was suspended in water with HiUe of calcium stearate and the obtained The product is then completely freed from the organic liquid by steam treatment. That Polymer was again separated from the resulting aqueous suspension by centrifugation. A part of the cake obtained, which still contained about 50 percent by weight of water, was with a Wet solution of 5 percent by weight acetone in water.

Example 2

To this mixture was added with vigorous stirring an amount of 0.5 percent by weight of the polymeric additive compound d) having the composition [Al (OH) Z ^ χ · HZ had, wherein Z is a benzoic acid group. The compound was added in the form of an aqueous suspension. After mixing, the solid substance was separated off, again by centrifugation, and finally dried at 60 ° C. under nitrogen. The powdery product obtained consisted of polypropylene, in which 0.5 percent by weight of the addition compound was incorporated in a very homogeneous and very finely divided state. The product also contained approximately 0.3 percent by weight calcium stearate based on polypropylene.

Samples of the product mentioned and of polypropylene powder obtained by direct drying of the Polypropylene cake containing 50% by weight of water was obtained with ordinary Temperature 0.15 percent by weight 4,4'-thiobis (6-tert-butyl-m-cresol) and 0.6 percent by weight Dilauryl thiodipropionate added. The powdery mixtures obtained were for 5 minutes rolled out at 180 ° C. The layered skins obtained in this way became 6.25 mm foils and likewise 1 mm foils pressed at 280 ° C. In accordance with the specifications of the "British Standard Specification" for the determination of the impact strength of bars cut with their Help this impact resistance at 20 ° C was determined. The 1 mm foils were used to measure the yield stress and the depolarization as described in Example 1 is used. The results were as follows:

Table Π

Mixture free of addition compound

Mixture with a
Content of 0.5 percent by weight addition compound

Yield stress

kg / cm ²

326

330

Notched impact strength
at 20 ° C

kg cm / cm ²

6.4

10

Depolarization
Δ

150

Example 3

The experiment described in Example 2 was repeated, but with additional use of a rubber. The impact strength at 0 ° C was measured. Mixtures were used, which by Addition of the pulverulent mixtures prepared according to the information in Example 2 beforehand made of two rubber-like ethylene-propylene copolymers with a propylene content of about 60 weight percent on the roll. That average molecular weights of these copolymers were 123,000 and 360,000. The amount of Copolymers used was 10 percent by weight, based on polypropylene. During the The duration of the mixing of the powdery mixture with the layer skins was the rolling temperature 180 ° C. After the powder was added, rolling was stopped for 5 minutes at this Temperature continued. The layered skins obtained were made in accordance with the information in the example 2 foils are pressed for the measurement of the impact strength and the yield stress. The results are compiled in Table III.

Table III

Polymer addition
links
[Al (OH) Z ₂ L x HZ Mixed polymer Molecular weight Hot stress Notched impact strength
kg cm / cm ² 20 ° C (Z = benzoic acid Molecular weight 360000 6.4 group) 123000 kg / cm ² 0 ° C 9.8 - 326 2.0 14.5 + - 330 2.0 30th - + - 286 6.8 16.6 + + + 287 10 > 40 - + 282 7.8 + - 283 11.8

609 757/446

Claims (1)

Claim: Molding compounds made from predominantly crystalline olefin homopolymers and / or copolymers and organic ones Metal compounds, characterized in that they are used as metal compounds 0.01 to 5 percent by weight of at least one addition compound of the general formula and optionally additionally no more than 20 percent by weight of rubbery polymers as well as known stabilizers, where in the formula M is a metal, Z is identical or different carboxyl groups of a di- or polybasic carboxylic acid and / or a monocarboxylic acid having ring-shaped substituents and ρ and q are 0 or a whole or broken number, r and y are a whole or broken number are, where 2p - {- q + r is equal to the valence of M and χ is a number between 1 and 50,000. Considered publications:
U.S. Patent No. 2985604;
Japanese published publication No. 7577/1960. 609 757/446 1.67 © Bundesdruckerei Berlin