WO1992013800A1

WO1992013800A1 - Hydroxide compounds of a certain composition, process for making them and their use

Info

Publication number: WO1992013800A1
Application number: PCT/DE1992/000095
Authority: WO
Inventors: Coriolan Razvan; Reinhard Beck; Alfred KÜRZINGER; Michael Rosenthal; Albert W. PÜRZER
Original assignee: Bärlocher Gmbh
Priority date: 1991-02-08
Filing date: 1992-02-07
Publication date: 1992-08-20
Also published as: IE920378A1; DE4103916C2; ZA92831B; AU1224792A; MX9200568A; DE4103916A1; PT100107A

Abstract

The invention describes compounds of general formula (I) in which: X3+ is a trivalent metal; Y2+ is a divalent metal; An- is an inorganic or organic anion with the valency n; 0.1 « a « 0.5; 0 « b « 1; 0 « m « 2; and n is a whole number, and a process for making them. The compounds of the invention are particularly suitable as stabilisers for halogen-containing thermoplastic resins, especially PVC.

Description

Hydroxide compounds with a certain composition, process

for their manufacture and their use

description

The invention relates to compounds of a more specific composition, processes for their preparation and their use as stabilizers for halogen-containing

Thermoplastics.

A halogen-containing thermoplastic resin, e.g.

Polyvinyl chloride, when heated to melt deformation while eliminating hydrogen chloride, changes into a polyene structure, whereby the polymer

discolored. To increase the light and heat stability, stabilizers are therefore usually added to the polymer before processing. As stabilizers

predominantly carboxylates and / or phenolates of metals, e.g. Magnesium, calcium, strontium, barium, tin, cadmium, zinc and lead are used. In addition to these organic salts, inorganic salts, particularly those of lead, such as lead sulfate and phosphite are also used. Stabilizers based on the

Heavy metals barium, cadmium and lead are used. For a long time, attempts have been made to replace these toxic substances with physiologically harmless stabilizers.

With stabilizers based on calcium and

Zinc carboxylates, however, have not been satisfactory

Results in terms of thermal stability and

Weather resistance can be achieved. These shortcomings have been tried through combinations of

Fix carboxylates with effective costabilizers. DE-OS 22 33 743 proposes known ones

PVC stabilizers with a non-activated zeolite too combine. EP-A-0 063 180 describes a combination of β-diketones and hydrotalcite as a PVC stabilizer. U.S. Patent 4,221,687 describes that

Combination of basic, inorganic oxides / hydroxides of non-toxic metals with 1,3-diketones.

DE-OS 38 43 581 uses a for comparison purposes

Hydrotalcite's chemical composition:

Ca ₆ Al ₂ (OH) ₁₆ CO ₃ × 4H ₂ O is used to stabilize PVC, showing that this hydrotalcite is not the desired one

Stabilizer effect achieved.

While some of the proposed combinations of primary and costabilizers provide satisfactory results in terms of thermostability and color retention, problems often arise during or after shaping that affect the intended use of the

Oppose molding. In polymers that contain hydrotalcite and / or zeolite, bubbles form under thermal stress, which are caused by the elimination of volatile constituents from hydrotalcite and / or zeolite.

This leads to problems in further processing

(e.g. when welding profiles) and use.

The invention has for its object to provide new compounds and a process for their preparation, which are particularly suitable as stabilizers for halogen-containing thermoplastic resins, without the above-mentioned disadvantages of the known stabilizers to be classified, in particular classified as non-toxic.

This object is achieved by the

Provision of compounds of the general formula

in which mean:

X is a trivalent metal;

Y ^{2+ is} a divalent metal;

A ^{n -} an inorganic or organic anion with the

Valency n;

0.1 ≤ a ≤ 0.5;

0 ≤ b ≤ 1

0 ≤ m ≤ 2; and

n is an integer.

Among these compounds, preference is given to those in which the trivalent metal X ^{3+ is selected} from Al and Fe and the divalent metal Y ^{2 + is selected} from Sr, Ba, Zn, Sn and Fe.

The anions A ^n- according to the above formula can

suitably selected from chloride, iodide,

Perchlorate, hydroxide, acetate, carbonate, sulfate, thiosulfate, sulfite, thiosulfite, dithionite, borate, hydrogen borate,

Silicate, mono- and di-carboxylates, benzoates, lactate, phosphonates, o-phosphate, m-phosphate and polyphosphates. These anions can be used alone or in combinations.

X-ray diffractometer recordings of the invention

Connections clearly show that it is not

Compounds of the hydrotalcite type are as described, for example, in DE-OS 30 19 632.

Surprisingly, it has been shown that the

Compounds of the invention containing halogen

thermoplastic resins and those made therefrom

Give moldings at least the same heat stability as basic lead sulfates. In this application, the compounds according to the invention do not cause any discoloration of the moldings produced from, for example, rigid PVC, and also the color retention and the weathering stability of those with

Compounds stabilized according to the invention are those with toxic heavy metal compounds

stabilized products at least equivalent.

The invention also relates to a method for

Preparation of the compounds according to the invention, which is characterized in that mixtures of one or more metal compounds of the divalent metal Y ²⁺ , one or more metal compounds of the trivalent

Metal X ³⁺ and optionally calcium salts,

optionally in the presence of organic and / or inorganic acids or their salts in an aqueous medium at a pH of 8-12 in amounts corresponding to the formation of the desired compounds and the

Separates the reaction product in a manner known per se and wins. The reaction is preferably carried out at a pH of 9-11.

The reaction temperatures are preferably between 40 and 100 ° C, particularly preferably between 60 and

85 ° C.

No catalysts or accelerators are required. In the compounds according to the invention that can

Crystal water in whole or in part by thermal

Treatment to be removed.

If calcium salts are used, calcium chloride, its hydroxide and / or oxide is preferably used. As a metal compound of the divalent metal

preferably zinc chloride, its hydroxide and / or oxide used. Aluminum chloride and / or hydroxide and / or sodium aluminate are preferably used as trivalent metal compounds. Sodium hydroxide is preferably used to adjust the pH.

The reaction product obtained in the above reaction is separated off in a manner known per se, preferably by filtration. Working up the

separated reaction product is also carried out in a manner known per se, for example by washing the filter cake with water and drying the washed residue

Temperatures of, for example, 60-150 ° C, preferably at

90-130 ° C.

According to a preferred embodiment, the reaction product obtained directly during the reaction can be carried out before

Separation can be treated with surface-active agents. Examples of such surfactants are fatty acids and their metal salts, silanes and titanates. Stearic acid and / or its metal salts with calcium and / or zinc are preferably used. These agents are used in amounts of 0.01-10% by weight, preferably 0.5-5% by weight, based on the compounds according to the invention. Such a treatment improves the dispersibility of the compounds according to the invention as stabilizers in halogen-containing resins.

Polyvinyl chloride is particularly suitable for stabilization with the compounds according to the invention,

Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene / vinyl acetate copolymer and chlorosulfonated polyethylene. Resins of the polyvinyl chloride type, i.e. Vinyl chloride homo- and copolymers of vinyl chloride with other comonomers

be stabilized. The compounds of the invention can be used with metal soaps, i.e. Salting of

Fatty acids can be combined. Examples of that

Metals used are: magnesium, calcium, strontium, barium, zinc and aluminum. In addition to carboxylates such as ethyl 2-hexanoate, decanate, laurate, stearate, palmitate, oleate,

12-hydroxystearate, fumarate, maleate and benzoate, phenolate salts of the above-mentioned metals can also be used in combination with the compounds according to the invention.

In general, these metal salts can be used in amounts between 0.05% and 10%, preferably between 0.1 and 5% by weight, based on the halogen-containing polymer.

The compounds according to the invention can be used here

Costabilizers such as Polyols, phosphites,

β-diketones, isocyanurates, dihydropyridines,

Combined epoxy compounds or thioglycolic acid esters become .

Polyhydric alcohols, e.g.

Trimethylolpropane, glycerin, pentaerythritol,

Polyvinyl alcohol and their di- or oligomers or partial esters thereof are used.

Suitable phosphites are alkyl or aryl esters of phosphorous acid, e.g. Triphenyl phosphite,

Diphenyldecyl phosphite, tridecyl phosphite or

Trisnonylphenyl phosphite.

As β-diketones e.g. Acetylacetone, dibenzoylmethane, stearoylbenzoylmethane, benzoylacetic acid, 2,2'-methylenebiscyclohexane-1,3-dione, palmitoyltetralone,

Bis- (3,4-methylenedioxylbenzoyl) methane,

Bis (2-hydroxybenzoyl) methane or their metal salts with e.g. Ca, Zn, Mg can be used.

As isocyanurate e.g. Trishydroxyethyl isocyanurate can be used.

A suitable dihydropyridine is e.g.

Dihydro-1,4-dimethyl-2,6-dicarbododecyloxyl-3,5-pyridine.

A suitable thioglycolic acid ester is e.g.

2-ethylhexylthioglycolate.

In addition to the compounds according to the invention, other additives can also be used, for example antioxidants, UV absorbers, such as, for example, benzophenones, benzotriazoles or sterically hindered amines (HALS), pigments, fillers and processing aids. The compounds of the invention are suitable for

Stabilization of both plasticizer-containing and plasticizer-free polymers. Commonly used substances such as e.g.

Di- (2-ethylhexyl) phthalate may be included.

These additives and stabilizers can be added to the polymer individually or as mixtures of several components. The additive and / or stabilizer mixture can be used in powder form, as granules or as a melt product.

The following examples illustrate the invention.

AI Preparation of compounds according to the invention

example 1

An aqueous solution (2.5 1), which contains 294 g CaCl ₂ × 2H ₂ O (2 mol) and 241.5 g AlCl ₃ × 6H ₂ O (1 mol), is heated to 70 ° C., followed by a pH of 10.0 was set in a 50% NaOH solution. The suspension formed is stirred for 2 hours at 85 ° C. and then a solution containing 111 g of tetrasodium pyrophosphate (0.5 mol) is added. After 12 hours, 2 g of stearic acid are added and the reaction product is filtered off, washed and dried in a drying cabinet at 120 ° C. for 5 hours.

Example 2

An aqueous solution (2.5 1) is prepared, which

Contains 195.5 g CaCl ₂ × 2H ₂ O (1.33 mol), 90 g ZnCl ₂ (0.66 mol) and 241 g AlCl ₃ × 6H ₂ O (1.0 mol). This solution is added dropwise to 500 ml of water (65 ° C). During the dropping is adjusted to a pH of 10.0 with a 50% NaOH solution. The resulting suspension is stirred for 2 hours at 80 ° C, then a solution containing 63 g (0.5 mol) Na ₂ SO _{3 is} added. After 18 hours

Reaction time, 2 g of stearic acid are added,

filtered off and washed. The resulting product is dried in a drying cabinet at 120 ° C. for 5 hours.

B) Use of the compounds according to the invention as

Stabilizers

In the following examples, the thermal stability and the initial color of PVC moldings, which

Compounds according to the invention and, for comparison purposes, conventional lead stabilizers have been added.

For the evaluation of the thermal stability the

PVC resin mass homogenized and plasticized on a laboratory rolling mill for 5 minutes at 180 ° C. Square sample sheets with an edge length of 15 mm are cut from the approximately 1 mm thick skin thus produced. The sample sheets are annealed in a heating cabinet at 180 ° C. One leaflet is taken at 10-minute intervals and attached to a test card one after the other. This process is repeated until the test leaves are discolored black. Example 3

Parts by weight

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ABCDEF

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

PVC (K 68) 100 100 100 100 100 100

Polymethyl methacrylate 1 1 1 1 1 1

Chalk 2 2 2 2 2 2

TiO ₂ 3 3 3 3 3 2

Distearyl phthalate 0.5 0.5 0.5 0.5 0.5 0.5

Bisphenol A 0.2 0.2 0.2 0.2 0.2 0.2

Phenyldidecyl phosphite 0.3 0.3 0.3 0.3 0.3 0.3

Lead stearate 0.8 0.8 - - - -

3 PbO.PbSO ₄ .0.5H ₂ O 2.0 3.0 - - - -

Zinc stearate - - 0.8 0.8 0.8 0.8

Calcium stearate - - 0.8 0.8 0.8 0.8

Al _{o, 33} (Ca _{o, 5} Zn _{o, 5} ) _{o, 67}

(SO ₃ ) _{o, 16} (OH) ₂ .0.5 H ₂ O - - 3.0 4.0 - -

Al _{o, 33} Ca _{o, 67} (P ₂ O ₇ ) _0.08 - - - - 3.0 4.0 (OH) ₂ .o, 4H ₂ O The above compositions from A to F were made and tested according to the indicated method. The results are summarized in Table I.

Table I: Results of the thermal evaluation

stability

Time (min.)

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

Together 0 10 20 30 40 60 80 100 120 150 200 composition

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

A 1 1 1 2 4 6 7 7 8 - -

B 1 1 1 1 1 2 4 4 7 7 8

C 1 1 1 2 3 5 7 8 - - -

D 1 1 1 1 1 2 3 5 7 8 -

E 1 1 1 3 3 5 7 8 - - -

F 1 1 1 2 2 3 5 7 8 - -

1 = white; 2 = pale yellow; 3 = yellow; 4 = light gray;

5 = orange; 6 = gray; 7 = brown; 8 = black

Example 4

Parts by weight

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - GHIJK

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

PVC (K 68) 100 100 100 100 100

Polymethyl methacrylate 1 1 1 1 1

Chalk 2 2 2 2 2

TiO ₂ 3 3 3 3 3

Distearyl phthalate 0.5 0.5 0.5 0.5 0.5

Bisphenol A 0.2 0.2 0.2 0.2 0.2

Phenyldidecyl phosphite 0.3 0.3 0.3 0.3 0.3

Zinc stearate 0.8 0.8 0.8 0.8 0.8

Calcium stearate 0.8 0.8 0.8 0.8 0.8

Al _0.33 (Ca _{o, 5} Zn _{o, 5} ) _0.67 3.0 3.0 3.0 3.0 3.0 (SO ₃ ) _{o, 16} (OH) ₂ .0.5H ₂ O

Dipentaerythritol - 0.5 - - -

Trishydroxyethyl isocyanurate - - 0.5 - -

Ethylaminocrotonate - - - 0.3 -

Stearoylbenzoylmethane - - - - 0.1 The above compositions from G to K were prepared and tested according to the indicated method. The results are shown in Table II.

Table II: Results of thermal stability

Time (min.)

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

Together 0 10 20 30 40 60 80 100 120 150 composition

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

G 1 1 1 2 3 5 7 8 - -

H 1 1 1 1 1 3 3 5 6 -

I 1 1 1 1 2 3 5 5 6 -

J 1 1 1 1 1 6 - - - -

K 1 1 1 1 2 2 3 4 5 6

1 = white; 2 = pale yellow; 3 = yellow; 4 = orange;

5 = brown; 6 = black

Example 5

Parts by weight

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - L M N

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

PVC (K 70) 100 100 100

Diisodecyl phthalate 60 60 60

Chalk 30 30 30

Lead stearate 0.6 - -

3 PbO.PbSO ₄ 2.0 - -

Al _{o, 33} (Ca _{o, 5} Zn _{o, 5} ) _{o, 67}

(SO ₃ ) _{o, 16} (OH) ₂ . 0, 5H ₂ O - 3, 0 -

Al _0.33 (Ca _{o, 67} (P ₂ O ₇ ) _0.08 - - 3.0 (OH) ₂ .0.4H ₂ O

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

The above compositions from L to N were prepared and tested according to the indicated method. The results are shown in Table III. Table III: Results of the evaluation of the thermal

stability

Time (min.)

Together 0 10 20 30 40 60 80 100 120 150 200 composition

L 1 1 1 1 1 2 2 2 3 3 4

M 1 1 1 1 1 2 2 3 3 4 -

N 1 1 1 1 2 3 3 3 3 4 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

1 = white; 2 = yellow; 3 = brown; 4 = black

Claims

1. Compounds of the general formula

in which mean:

X ^{3+ is} a trivalent metal;

Y ^{2+ is} a divalent metal;

A ^{n -} an inorganic or organic anion with the

Valency n;

0.1≤ a ≤ 0.5;

0 ≤ b ≤1

0 ≤ m ≤ 2; and

n is an integer.

2. Compounds according to claim 1, wherein the trivalent

Metal X ^{3+ is selected} from AI and Fe.

3. Compounds according to claim 1 and / or 2, wherein the divalent metal Y ^{2+ is selected} from Sr, Ba, Zn, Sn and Fe.

4. A process for the preparation of compounds according to claims 1 to 3, characterized in that

Mixtures of one or more metal compounds of the divalent metal Y ²⁺ , one or more

Metal compounds of the trivalent metal X ³⁺ and

optionally calcium salts, optionally in the presence of organic and / or inorganic acids or their salts in an aqueous medium at a pH of 8-12 in Formation of the desired compounds corresponding amounts and the reaction product is separated in a conventional manner and wins.

5. The method according to claim 4, wherein the reaction is carried out at a pH of 9-11.

6. Use of the compounds according to claims 1 to 3 as stabilizers for halogen-containing, thermoplastic resins, in particular PVC.