HU193706B - Surface treated loading material for polymers and plastic composition - Google Patents

Abstract

Calcium-carbonate based fillers for plastics are surface-treated with, based on the calcium-carbonate, 0.1-4.0 wt% surfactant and 0.01-1.0 wt% organic ortho-titanic-acid derivs. of general formula (R-O)nTiXnYm where R stands for alkyl or substd. alkyl, X means an organic acid radical, Y is a complex-forming organic mol, n is 1, 2 or 3, and m is 0, 1 or 2.

Description

The present invention relates to a surface-treated filler for use with polymers and to a plastic composition prepared thereby.

Fillers for polymers are often used to reduce the price of the product and / or modify its physical properties. The most inorganic fillers used include calcium carbonate, which has the advantage of white color, relatively low hardness, widespread occurrence in nature, etc. The disadvantage of calcium carbonate is that it absorbs moisture on its surface, and thus, during storage, especially in gliders, the ground flour tends to agglomerate under the influence of air humidity, and therefore a dangerous vaulting occurs when the glider is lowered. Due to its hydrophilic nature and tendency to agglomeration, calcium carbonate has poor adhesion to plastics and rubbers, and can only be dispersed with high shear energy when mixed.

SUMMARY OF THE INVENTION The present invention relates to a surface-treated calcium carbonate and to a polymer composition thereby eliminating the above disadvantages.

Surface treatment methods are known that improve adhesion between calcium carbonate and polymers and enhance dispersibility. Surface treatment is most often done with ionic or nonionic surfactants. Treatment of fatty acids with calcium soap and stearin or other organic acids is now conventional (L. I. Hass, Encyclopedia of PVC, M. Dekker, New York 1976). The surfactants proposed for the hydrophobization of fillers have a great variety of chemical structures, e.g. phosphoric acid partial esters (British Patent No. 1,506,578), organic amines (British Patent No. 1,393,721), long-chain alcohols (British Patent Nos. 1,395,700 and 1,421,713), and ethers of multifunctional alcohols (German Patent No. 1,792,086).

The advantage of surface treatment with surfactants is that relatively inexpensive chemicals can be used, although they are 10 to 100 times more expensive than the filler to be treated. The disadvantage of the solution is that only the adhesive interaction between the filler and the surfactant occurs, and thus the high shear forces in the polymer processing sometimes eliminate the adhesion, and therefore the surfactants do not sufficiently reduce the abrasive effect of the filler. A further problem is that the beneficial effect of the surfactant tends to occur only with a narrow optimal surfactant / filler ratio; with little surfactant there is no full coverage, but in the case of overdose, too much surfactant acts as a lubricant on the filler surface and forms a separating layer. Müller et al. 2 (V. Müller, J. Gáhde, S. Tolstaja, G. V. Kozlov, Acta Polimerica 32, 105, 1981), for example, investigated the properties of polyethylene compositions with kaolin as a function of the concentration of octadecylamine surfactant. It was found that the strength obtained at an optimum concentration of 1.5% by weight based on the filler, but worse at 2.5% by weight, than with untreated filler.

Surface treatment agents which enter into chemical bonding with the surface of the filler are also known. One of their main types (the silanes) does not give good results in the case of calcium carbonate because its surface does not contain reactive -Si-OH groups. However, certain derivatives of orthotitanic acid containing one or more readily hydrolyzable alkoxy groups and at least one organic moiety which is difficult to hydrolyze or non-hydrolyze may be usefully employed. The chemical structure of the poorly hydrolyzing group is selected for compatibility with the polymer matrix, using titanate-phosphite complexes (U.S. Pat. Nos. 4,080,353 and 4,052,311), titanate chelates (4,087,402 and 4,098,758). U.S. Patent Nos. 3,697,474 and 3,697,475), fatty acids and oleic acid (U.S. Patent Nos. 3,697,474 and 3,697,475).

The main barrier to the spread of organic titanates is the extremely high price, which is 200 to 1000 times the price of the calcium carbonate to be treated, so even though it is only used at 0.5-1% by volume of filler, the cost of the surface treatment agent is often higher desired filler value. The property improvement achieved is mostly out of proportion to the cost increase.

A major limiting factor becomes the high cost of surface-treated filler when the main purpose of filler use is to reduce manufacturing costs, since filler density is usually two to three times higher than that of the polymer, so that filler costs more than half to one third of the polymer price. , the filler becomes more costly. (The finished product is sold essentially by volume.)

In our studies, we have found that there is a synergistic effect when the surface treatment of calcium carbonate is 0.01 to 1% by weight (RO -) of the organo-ortho-titanium acid derivative (RO -) "TiX ₄ -" the surfactant is applied together or sequentially. R 1 is C 1-8 alkyl; X is a carboxylic acid residue having from 10 to 20 carbon atoms, partially esterified phosphoric acid, pyrophosphoric acid or sulfonic acid residue; n is 1-3. The surfactant used may be a bis acid ester of an organic acid having from 10 to 20 carbon atoms or a carboxylic acid ester of a divalent or polyhydric alcohol or polyether diol having a molecular weight of 400-400. The ratio of the two treatment agents is 1: 1 to 1:20.

As a result of the treatment with the substances according to the invention, the abrasive effect of calcium carbonate is significantly reduced. The ^five surface-treated calcium carbonate is easy to process, good mechanical properties, the compositions can be prepared.

In addition, the cost-effectiveness of surface treatment is greatly increased, since ^{0 of} the expensive titanates requires only a small amount to be applied. A further advantage is that a high polymer composition can be obtained with high filler concentrations. 15

In our view, the synergistic effect is due, firstly, to the fact that the surface of the calcium carbonate is not uniform; in the absence of surface active hydrogen atoms or for other reasons, the ortho-titanoic acid derivative does not bind, but the surfactant also covers these sites and, on the other hand, high shear forces do not remove titanate chemically bound to the filler surface. The finding is due to ⁵ synergistic effects that the amount of expensive ortho-titanium acid derivative can be reduced below the value required for full coverage while maintaining product properties. ³ θ

The surface treatment can be carried out by any of the methods known per se, so that the equipment used hitherto can be used without further ado. The sub ⁴⁰ kalmazandó ortho-titanic acid derivative and the surfactants be added together or separately, in solution or in pure form as well. In general, the order of use of the surfactants is also inert, but in some cases better results have been obtained by first incorporating the ortho-titanoic acid derivative into the calcium carbonate and then adding the surfactant.

The invention is further illustrated by the following examples.

Example 1 24 g of isopropyltri (dioctylpyrophosphate) titanium were added to kg of ground calcium carbonate of mineral origin (having a particle size distribution of 80% by 10 µm, 99% by 20 µm, 100% by 40 µm). and a mixture of 240 g of surfactant (BYK Chemie LP 5026, based on polyethylene glycol esterified with an aliphatic carboxylic acid having an average molecular weight of 1500 to 2500 and 1.68 mmol COOH / g). The material was stirred in a Spangenberg Fluidomat FT 30 GV for 5 minutes at 2500 rpm while maintaining the temperature at ca. The mixture was heated to 80 ° C and stirred for a further 5 minutes at 720 rpm with cooling.

for comparison, two fillers were prepared by the above process, one of which was mixed with 2% by weight of the aforementioned surfactant and 0.2% by weight of isopropyltri (dioctylpyrophosphate) titaniumate.

For the materials, the degree of abrasion was determined. The results are. Table 1 summarizes this.

The abrasion effect on bronze mesh fabric was measured by the Breunig method using an Abrasions Tester AT 1000 for 2 hours. Table 1 shows the weight loss per 1 m ² . Table 1, line 1 shows the surface treatment data for the example. Rows 2 and 3 show data for the same surface treatment agents, while Row 4 shows values for untreated filler.

Table 1

Row- song Quantity of surface treatment agent Wear rate in g / m ² calcium carbonate% by weight calculated surfactant. ortho-titanic acid derivative First 2% 0.2% 41.8 Second 2% - 50.2 Third - 0.2% 47.3 4th - - 54.1

It can be seen that the above-mentioned surface treatment agents each do little to reduce the abrasive effect, but their combined application causes significant improvement.

Example 2

Ground calcium carbonate of mineral origin (having a particle size distribution below 40 pm, 70% below 5 pm, 10 pm 3)

Less than -3193706 95%, less than 15 μιη 99%, less than 20 pm 100%) as described in Example 1 with isopropyltri (dioctylpyrophosphate) titanium 1 and tenside (polyethylene glycol ester type BYK Chemie LPW 5174) compound). From the untreated and different surface treated calcium carbonate samples, 60 g of 40 g of dioxo2 were used.

dispersed in til-phthalate on a Bühler three-cylinder lab-size dispenser with a single pass. Then we measured the viscosity of the dispersion Haake rotational viscometer at a shear rate of 41.2 s ^_1. The data are shown in Table 2.

spreadsheet

Row- Quantity of surface treatment agent Viscosity number based on calcium carbonate mPa · s mass

surfactants ortho-titáiísav- derivative First 0.2 0.02 4.9 Second 0.2 - 19.7 - 0.02 43.8 4th 0.5 - 6.9 5th - - 56.1

It can be seen that the surface treatment according to the invention greatly improves the dispersibility, only 8.7% of the viscosity obtained is observed in the untreated sample. When the surfactant and the ortho-titanium acid derivative were used separately, the viscosity was 4- and 9-fold higher than that of the combination, moreover, a 2.5-fold increase in the surfactant content (to 0.5% by weight). still gives 40% higher viscosity than the synergistic composition of the invention.

Example 3

Example 2 was surface treated with ground calcium carbonate (Table 3, Example 1), and increasing amounts of surfactant (Table 3, Examples 2-4) or ortho-titanium acid derivatives (Table 3, Examples 5-7). with treated and untreated flour, Spangenberg instant mixer produced hard PVC powder blends with the following composition:

suspension PVC value 67) Part weight 100 stabilizer (3 base lead sulfate 0.8 2 2-base lead stearate 0.7 neutral lead stearate 0.5) lubricant (stearic acid 0.3 calcium- stearate 0.1 paraffin 0.1) 0.5 calcium carbonate 6 titanium dioxide 0.1

my carbon black is 0.005

The agitation was carried out until 105 ° C was reached.

The cooled powder blends were rolled at 200 ° C and then pressed at 1 mm thickness at the same temperature. The tensile and tensile strengths of the specimens cut from the plates were measured and are shown in Table 3.

Table 5

Row- Quantity of surface treatment agent based on calcium carbonate% by weight

Tensile strength ₂

K / mm

% Elongation at break

surfactants ortho-titanium acid stem ^- derivatives First 0.2 0.02 55.1 51.5 Second 0.2 - 51.9 23.5 Third 2.0 - 50.8 28.3

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Table 3 (cont.)

Row- Quantity of surface treatment agent Tensile solid- Tensile number based on calcium carbonate tensile strength% N / mtn% surfactant ortho titanium derivatives

4th 4.0 - 5- - 0.02 6th - 0.2 7th - 1.0 8th - -

52.2 26.5 52.5 22.8 52.3 24.7 51.7 29.0 51.9 19.6

It can be seen from the data in Table 3 that the surface treatment does not significantly affect the tensile strength, but increases the tensile strength, i.e. the toughness. The value of the tensile elongation obtained with the synergistic mixture is not reached even at much higher concentrations when applied with the surfactant or the ortho-titanium acid derivative alone, and even with 4% tenside the tensile elongation is slightly reduced.

Example 4

The hard PVC composition described in Example 2 was prepared with 40 parts by weight of filler based on 100 parts by weight of PVC based on calcium carbonate according to the invention. The ratio of the other components of the composition to PVC was unchanged. Sample preparation and testing were performed as in Example 3. The resulting sheet has a tensile strength of 44.2 N / mm ² and an elongation at break of 29%. It can be seen that the surface-treated calcium carbonate of the invention, even when used in such high concentrations, produces a product with good mechanical properties.

Example 5

Ground calcium carbonate having a grain size distribution of 20 mesh: 83% at 10, 99% at 10, 100% at 15, was surface-treated in a Spangenberg Fluidomat FT 30 GV. The surfactant and the ortho-titanoic acid derivative used are the same as in Example 3.

The surface-treated and untreated calcium carbonate in the Pappenmayer instant mixer prepared the PVC powder mixture of Example 3, except that

10 parts by weight of calcium carbonate were added to 100 parts by weight of PVC. From this rotary blend, a Cincinnati-Milacron CM 65 extruder was extruded with a hard PVC tube having a diameter of 105 mm and a wall thickness of 2.7 mm. The quality of the tubes obtained with the wrong filler in the hands was not good, due to the uneven dispersion of the calcium carbonate its surface was marbled and wavy, broken during sawing, blistering during heat treatment, so-called encapsulation.

stress! whitening (micro-cracks) occurred.

The quality of the tubes treated with the surfactant according to the invention and treated with a separate surfactant or ortho-titanium acid derivative was investigated. Tests were performed on specimens cut lengthwise from the finished tube, the data are shown in Table 4.

Table 4

Row- song The amount of surface treatment agent calculated on the basis of calcium carbonate % by weight tensile Strength, N / mm ^ breaking strain % Impact Hcm / cm2 Charpy incised specimen surfactants ortho-titanic acid derivative First 0.8% 0.1% 53.7 30.8 48.5 Second 1.0% - 50.6 20.4 40.8 5th - 0.2 7> 50.7 22.3 42.7

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The quality of the tube obtained with the surface-treated fillers was satisfactory, but the composition of the invention (Table 4, Row 1) provided significantly better mechanical properties than the surface treatment with the surfactant or the ortho-titanium acid alone.

Example 6

The calcium carbonate powder of Example 5 was surface treated in a Spangenberg Fluidomat FT 30 GV rapid mixer. Surfactants one of succinic acid and diethylene glycol: 1 mixture of made by condensation of a polyester was used having a free acid ¹⁵ suspension PVC (K value 70 dioctyl phthalate stabilizer (BACD laurate), lubricants (calcium stearate), calcium carbonate (treated 1-3 .

untreated 4.

The compositions were kneaded in an internal mixer at 170 ° C for 10 minutes and then 1 mm thick plates were extruded. The plates had a content of 1.25 mmol / g and an average molecular weight of 800. The ortho titanium acid derivative used was isopropyl tri (dioctylpyrophosphate titanate).

The surface treatment was carried out according to the invention (Table 5, line 1) with a combination of the surfactant and the ortho-titanium acid derivative, and comparatively separately with the surfactant (Table 5, line 2) and the ortho-titanium acid derivative (5 table row 3).

Soft PVC compositions with different surface treatments and untreated calcium carbonate were prepared with the following composition:

Weight% Weight%

100 34.2 40 13.6

0.9

0.5

Fi 150 51.3

a.) mechanical properties and amounts of surface treatment agent used are given in Table 5.

Table 5

Row ^- Quantity of surface treatment agent calculated on calcium carbonate% by weight

Tensile strength

N / mm ^z

Elongation at break

surfactants ortho-titanic acid-derived. First o, 5 0.1 14.8 195 Second o, '5 - 12.1 174 Third - 0.1 12.7 168 4th - - 11.7 132

It can be seen that the use of the surfactant or the ortho-titanium acid derivative alone significantly increases the tensile elongation and slightly the tensile strength. However, the combined use of the two surface treatment agents still results in a significant improvement in θθ vulval.

Example 7

The calcium carbonate powder of Example 5 was surface-treated as described there.

The ortho-titanoic acid derivative used was isopropyltri (isostearoyl) titanium and the surfactant was stearic acid. The treated and untreated calcium carbonate was mixed with high-density polyethylene (277-73 Soviet HDPE) (10 parts CaCO ₃ per 100 parts PE) and injected into containers. The specimens cut from the crates were subjected to a tensile test. The results are shown in Table 6.

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Table 6

Row- Quantity of surface treatment agent calculated as calcium carbonate% by weight

Tensile Strength

N / mm ^

% Elongation at break

surfactants ortho-titanic acid derivative 1% 0.2% 28.5 313 Second * · 27.2 33

As can be seen, surface treatment significantly improves the elongation at break, i.e. the toughness of the product. It was easy to determine visually that untreated filler distribution is less homogeneous than ²⁰ were treated.

Example 8

Calcium carbonate milled product of Example 5 was surface-treated as described therein, the surfactant used was ⁵ lauric acid, ortho-titanic acid derivatives are tri-isooctyl (lauryl) titanate. M * ^{n was} used in an amount of 1% by weight based on the calcium carbonate. 30

The treated and untreated calcium carbonate is manufactured by Bradender Laboratory

Table 7 was mixed with polypropylene in an internal mixer with the addition of a suitable amount of lubricant, antioxidant and light stabilizer, and 1 mm plates were pressed in a laboratory press.

Composition of the composition:

Polypropylene (TVK, H 601) 100 sliding (calcium stearate) 0.5 antioxidant (Ciba- Geigy Irganox 1010) 0.3 light stabilizer (Ciba- Geigy Tinuvin 144) 0.1 calcium carbonate 15

The mechanical properties of the resulting plates were measured. The data are shown in Table 7.

Row- song The amount of surface treatment agent on the calcium carbonate Tensile strength ₂ N / mm tear strain % calculated, % by weight surfactants ortho-titánsav- derivatives First 1 1 29.3 241 Second - - 27.3 32

Example 9 50

The calcium carbonate powder of Example 5 was surface-treated as described there.

The surfactant used was a stearic acid partial ester of glycerol with an average molecular weight of 400-500. The titanate used was ethyl ether di (dodecobenzenesulfonyl) titanate. The surfactant was applied to the filler in an amount of 0.8% by weight based on the calcium carbonate and 0.05% by weight of the ortho-titanium acid derivative. The half-cured filler was mixed with the high density polyethylene of Example 7 in an amount of 4 parts per 100 parts by weight of polyethylene. The mixture KUASY manufactured reciprocating screw injection molding machine equipped with a homogenizing screw fröccsönfőttünk ⁶ lítórekeszeket ® M30 type fiber. The compartments in all respects achieved the properties of unfilled polyethylene compartments and were even better than the comparator sample in the low temperature drop test. - A compartment made of a surface-treated calcium carbonate polymer according to the invention, after dropping after 6 drops at a load of 25 kg at a temperature of 25 kg, and broken at the third dropping.

Example 10

The calcium carbonate powder of Example 5 was surface-treated as described there. 3% by weight of surfactant based on calcium carbonate was used. The surfactant is polyethylene7

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was a 1: 1 mixture of lauric ester of glycol (1000 to 1500) and fatty acid partial ester of pentaerythritol (400 to 500). Dimethyl di (dicresylphosphate) titaniumate was used as the ortho-titanium acid derivative. The resulting filler was used to prepare a PVC powder blend with the following additives:

Part weight

Suspension PVC 100 (K value 58) Stabilizer dibutyltin di (isooctylthioglycolate) 3 slides: Loxiol G 41.

(Henkel) 2 Polyethylene Wax PA520 (Hoechst) 0.1 Pigments: Titanium Dioxide 0.1 Carbon Black 0.005 Calcium Carbonate 1

The mixture was injection molded, which in all respects achieved the properties of the comparative samples made with Socal N ₂ precipitated calcium carbonate.

Claims (2)

A surface-treated calcium carbonate-based filler for polymers, characterized in that c is 0.01 to 1% by weight, based on calcium carbonate (RO), of the formula "TiX ₄ -" wherein R 1 is C 8 -C 8 alkyl, X and C10-20 carboxylic acid, partially esterified phosphoric acid, or pyro10 phosphoric acid or sulfonic acid residue, and n is an integer from 1 to 3, an organic ortho-titanium acid derivative and 0.1 to 3% carbon-10-20 carbonic acid as a surfactant, two or a carboxylic acid ester of a polyhydric alcohol or polyether diol having a molecular weight of 400-4000, wherein the weight ratio of the ortho-titanium acid derivative to the surfactant is 1: 1 to 1:20. 2. A polymeric composition based on PVC or polyolefin, optionally containing a stabilizer, preferably lead salts, a lubricant, preferably a calcium salt of a saturated fatty acid having from 16 to 20 carbon atoms, a colorant, a plasticizer, preferably phthalic acid esters, 25 to 100 parts by weight of a polymer containing from 1 to 150 parts by weight of surface-treated calcium carbonate according to claim 1.