DE2146164B2 - RESIN COMPOSITION MADE OF THERMOPLASTIC RESIN - Google Patents

Description

The invention relates to a synthetic resin composition made of thermoplastic resin with iron oxide containing Aggregates.

It is known to improve the properties »5 of plastics, in particular of thermoplastics, to be admixed with these metal oxides, the content of iron oxide is more than 5%, in particular 15 to 40%, of the total weight of the finished mixture. However, through such admixtures, the stress-rupture resistance are practically not improved by thermoplastics, so that such modified Thermoplastics for applications where stress-rupture resistance is important, practically out of the question. as

The object of the invention is to provide synthetic resin compositions made from thermoplastic resin which have excellent stress-rupture resistance and are therefore suitable for the preparation of various Moldings are suitable for which a high stress resistance is essential.

The synthetic resin composition made of thermoplastic resin according to the invention is characterized by a content of 100 parts by weight of a thermoplastic polyolefin consisting of, for. B. polyethylene, polypropylene, Ethylene-vinyl acetate copolymer and / or polystyrene, and 5 to 1200 parts by weight of a pyrite burn and optionally filler or pigment.

The synthetic resin compositions according to the invention are characterized by a particularly high stress-rupture resistance, Heat resistance, non-flammability, antistatic property as well as further characterized by a particularly high specific weight. As a result, the masses according to the invention are as Raw materials are particularly suitable for the production of shaped bodies, in particular shaped bodies in the construction industry, including the wood processing industry.

The masses according to the invention have in general a specific weight of over 1. They can be used for building blocks, panels, tiles, roof panels or roof tiles, containers and industrial pipes are produced. The masses are easy to process and are also suitable for gluing with other fabrics.

Has the high specific weight of the article produced from the masses according to the invention furthermore the advantage that, in contrast to conventional plastics, they do not float on the water, so that waste materials that arise in the processing of the masses according to the invention, sunk in the sea can be. As such, the compositions of the invention do not present the problems of environmental pollution as usual plastics. Another advantage is that the masses according to the invention from cheap raw and waste products can be produced.

The slag or burnup used in accordance with the invention is used in calcination 164

obtained from pyrite in the form of fine powders containing the main component is an iron oxide. Typical composition, specific weight and particle size distribution of the pyrite burn-up are shown in Tables I, II and III below.

Table I.

Composition.

Weight percent

SiO ₂ } ²

Al ₂ O ₃ J.5

CaO ^ ⁹

Fe ₂ O ₃ ⁸ ξ.5

MgO Μ

S ° ' ²

A total of ¹⁰ °

Table II

Specific weight 5.2.

Table III

Particle size distribution of the dried combustion

Weight percent

0 on a 12 mesh sieve

0.314 on a 20 mesh screen

1 * 387 on a 48 mesh sieve

3 * 475 on a sieve of 80 mesh

1.460 on a 100 mesh screen

8 * 145 on a 150 mesh sieve

40,500 on a 200 mesh screen

44,719 going through 200 mesh

All in all:

100.00

The mesh size shows the sieve size, defined by Tyler standard sieves (Tyler Co. in USA).

Since it is generally reddish-brown in color, the burn-off gives a reddish-brown polymer mass and corresponding molded articles while various coloring by compoundingi a suitable amount of carbon black or pigments can be obtained herewith.

As the thermoplastic resin usable in the present invention, various kinds can be mentioned including polyolefins such as ethylene polymers or copolymers, e.g. B. ethylene-vinyl acetate copolymer and propylene copolymers or copolymers; Polyvinyl or polyvinylidene resins, such as polystyrene, polyvinyl chloride and polyvinylidene chloride; Acrylic resins, including copolymers, such as ABS resin; Polyamide resins, polyester resins, etc.

The thermoplastic resins according to the invention can be used not only as a fresh resin in the form of Kügelchtn (pellets) or powders, but also as so-called rejects are used in the form already formed objects, including foams, such as film, panels, rods, containers and Blocks or debris from it depending on the deformation methods and the use of the object to be formed. If such scrap is used, the already formed Item contain some amount of water or contamination.

The burn-up acts as a kind of filler and can be used alone or together with other inorganic substances Fillers such as calcium carbonate, carbon black, talc, clay,

Silicon dioxide, asbestos, cement, earth and sand, fiberglass, Metal salts and metal oxides can be used.

Since the mass of the invention is accessible for gluing with metals, paper, fibers, asbestos, concrete, Plaster of paris and clay, it is suitable for the production of composite bodies connected with these materials. The connection can be effected by adhering the materials to the molded article can adhere from the mass or, alternatively, by simultaneously making a mixture of the mass and deformed the material to form a solidified object.

The composition of the invention gives a molded article not only by a general molding method, such as extrusion, injection, blowing, compression or rotational molding, but also after one for these masses suitable special method of melt casting, which is explained below.

The mass and the shaped object can be produced therefrom according to the invention as follows:

1. Mixing and molding method

The thermoplastic resin and the burnout are mixed and kneaded by a general method using a mixer roll, Banbury mixer or extruder and into a web. Grains, flakes or blocks formed from the mass, which is the raw material for the manufacture of various represent shaped objects. If a Banbury mixer or extruder is used, the burn-up should preferably be dried, and a ventilation-type extruder should be preferred.

According to this method, 100 parts by weight of the thermoplastic resin and 5 to 1200 parts are preferred 20 to 1000 parts by weight of the burnup used. If the amount of burnup is less than 5 parts by weight, the effect of the invention cannot be obtained, and in cases where the amount of the The burn-up is more than 1200 parts by weight, the resulting mass can hardly be molded and can be practical Not used. Furthermore, the compounding ratio varies as the mass is molded of the burn-off to the thermoplastic resin depending on the molding methods and the applications of the molded body. When the mass is subjected to extrusion molding to produce a Web to be deformed, the mass is made by compounding the burnup with the resin or prepared by diluting a base or sample with the resin in such a way that the Compounding ratio. based on weight, amounts to 5 to 100/100. The one corresponding to this value Compounding ratio mass becomes an object of extrusion molding, such as pipes or rods or rods, supplied with an uneven cross-section.

When the composition is injection molded, the compounding ratio should be 5 to 300/100 parts by weight, and that prepared by the same method as described above The mass is molded by means of a general injection molding machine. This mass will supplied to blow molding. In compression molding, the compounding ratio can be up to Be 1000/100, and the mass can be made by mixing and kneading the resin and burning using a mixing roller. When forming a foam, there is a compounding ratio up to 900/100 allowed.

2. Melt casting method

By this method it is possible to make the composition of the invention from 100 parts by weight of the thermoplastic Resin and up to 300 parts by weight of the burn-up to form, with a mass of 20 to 200 parts by weight per 100 parts by weight of the resin

ίο as a result of the superior properties of the molded Subject is preferred. Although a compound with a compounding ratio of less than 20/100 can be formed, it is insufficient due to its low specific weight to the To achieve characteristic of the invention. In contrast, there is a mass with a ratio of more than 300/100 in terms of their use due to the low compressive strength of the molded Subject limited. With this method

ao the resin can either be in the form of fresh grains (Granules) or powders or in the form of used molded objects or in the form of scrap uses v / earth. The use in the latter form brings about the characteristic of this method rather than the former.

The shape of the object to be molded is not limited to any specific shapes, and building blocks, rods and rods, tubes, etc., which can be formed by casting, are preferred manufactured according to this method.

The method is carried out by mixing and heating while a mixture of the thermoplastic Resin and burning in a crucible at a temperature above the melting point The resin is stirred by pouring the molten mixture into a mold or sand mold with it of a desired configuration and by cooling to obtain the molded article in question. The dimensional accuracy of this method is slightly inferior to that of conventional methods, however The items can be beneficial for building materials, underwater trestles for fishing and industrial materials come into use.

The invention is explained in more detail by means of examples which fall within the scope of the invention not restrict.

example 1

Burned pyrite and polyethylene (melt index = 1.5 g / 10 min., Density = 0.923 g / cm ³ ) were mixed and kneaded with a mixing roller so that the specific weight of the resulting mass became 1.1. The resulting mass was subjected to compression molding to form a web.

Furthermore, masses with a specific weight of 1.1 from iron oxide, lead peroxide, zinc powder, Iron powder or zinc white produced instead of pyrite burn-off and converted into one using the same method Railway processed.

The environmental breakage resistance of the resulting sheets was determined by the test method according to ASTM D 1693-60T in a test solution containing 30 percent by weight nonylphenoxypolyethanol as a surfactant.

The results of the test are shown in Table IV, which shows that the composition of the invention each of the comparative masses is superior.

Table IV

filler

Amount of
used
Filler
Weight percent Time required
until the break of
50% of the samples
H

Time required
until break
; ". X, samples

Burn-off 20th 2.03 4.67 Iron oxide 20th 1.00 2.17 Lead peroxide 18th 1.00 2.08 Zinc powder 19th 1.33 3.00 Iron powder 18th 0.97 2.50 Zinc white 19th 0.50 1.08 nothing 0.49 1.28

It can be seen that, compared to iron oxide alone, pyrite burn-off gives a significant effect despite the fact that its main component is iron oxide. The characteristic of burn-off is believed to be a combination of iron oxide, the other metal and non-metal oxides and sulfur according to Table I.

Example 2

A mass was produced by the same methods as in Example 1, with the exception that the polyethylene used had a melt index = 7 g / 10 min. And a density of 0.920 g / cm ³ . The mass was subjected to compression molding under the condition of 175 ° C for 15 minutes to form brick sheets and roof tiles.

The physical properties of the molded article are shown in Table V.

Table V

represents is in units of tensile strength after specimens are irradiated in a weatherometer became.

Table VI Before the at Tensile strength (kg / enr) 400h 600 h 800 h Amount of Irradiation after 112 116 114 used 106 111 110 Burn-off 110 109 111 Weight 200 h [3 percent 120 117 5 112 102 17th 114 104 23 game

Amount of

used

Burn-off

Weight percent A

Surface Shore hardness

Abrasion specific loss *) sches

weight

mg

80 100 71 283 2.65 85 100 72 298 3.00 90 100 83 305 3.40

*) The abrasion loss was measured under a load of 1000 g and the rotation of an abrasion ring (CS-17) of 1000 determined by the Taber abrasion tester.

The weatherability of the molded article is shown in Table VI, which shows the strength

Table VII

A sample batch consisting of polyethylene (melt index = 7 g / 10 min., Density = 0.920 g / cm ³ ) and pyrite burn was diluted with the same polyethylene to obtain a compound with a compounding ratio of burn to polyethylene of 25/100.

Another mass was produced by the same procedure as above with the proviso that that ethylene-vinyl acetate copolymer (content of vinyl acetate unit = 10 percent by weight, melt index = 1.5) was used instead of polyethylene.

The masses were extruded through an extruder into a sheet with a thickness of 0.35 mm. the physical properties of the webs were determined and the results are shown in Table VII.

It can be seen that the polymer incorporated with pyrite burn-up has a high-frequency welding property has been improved considerably.

sample EVA *) EVA E *) E. D 2021 D 2021 L 705 L 705 Amount of burn-up used _ 20th __ 20th (Weight percent) Tensile strength (kg / cm ² ) 160/150 115/80 150/140 110/80 Strain (%) 470/550 325/355 450/500 330/350 Tensile strength (kg / cm) 47/60 47/81 40/50 40/50 Impact strength (kg-cm) 25th 20th 15th 14th Heat seal strength 6.6 5.6 5.0 4.7 (kg / 15 mm width) High frequency seal strength 0 4.7 0 6.0 (kg / 15 mm width) Moisture permeability (g / m ² 24 h) 2.1 2.5 1.8 2.1

*) EVA = ethylene-vinyl acetate mixed polymer, E = polyethylene.

Example 4

A mass was produced by kneading a mixture of 60 parts by weight of pyrite burned off and 40 parts by weight of polyethylene (Schmelziidex = 20 g / 10 min., Density = 0.919 g / cm ³ ) using a mixing roller. Roof tiles, building tiles and other molded articles were formed by subjecting the mass to injection molding using a screw-type injection device under the following conditions.

Q C, C, D Mold temperature (° C) 180 200 210 210 Injection pressure (kg / cm ² ) 800 Injection speed 50 (mm / min.) Injection time (sec.) 10 Cooling time (sec.) 50 Mold temperature ( ⁰ C) 40

The resulting molded articles have a good appearance. With regard to impact resistance, the roof tiles are not broken, torn or burst even if Ut is dropped ten times from a height of 3 m. The roof tiles have such good weatherproof properties that the tiles show no change after irradiating them for 1000 hours in a two-carbon sheet weathering apparatus (supplied by Shimazu Manufacturing Co.). The good flame retardancy of the roof tiles is shown in the fact that the tiles do not burn, but turn dark on their surface when exposed to a town gas flame at a distance of 3 cm for 5 minutes.

Example 5

There was prepared a paste by mixing the following materials were mixed in the amounts listed below for 10 minutes by a mixing roll at a temperature of 120 ⁰ C and kneaded.

Weight parts

Ethylene-vinyl acetate copolymer
(Content of vinyl acetate unit = 15 percent by weight, melt index = 1.5 g /

10 min.) 100

Pyrite burn 25

Crosslinking agent 3

Foam wraps 5

Zinc stearate (excipient) 3

A foamed body was produced by placing the mass in a mold with a dimension of 200 × 200 × 10 mm and subjecting the mass to foaming under a pressure of 100 kg / cm ² at a temperature of 175 ° C. for 15 minutes .

The resulting foam is good in appearance and has a bulk density of 0.27 g / cm ³ , a hardness (ASKER type C) of 58, a rectangular tear strength of 20 kg / cm ² , a tensile strength of 25 kg / cm *, an elongation at break of 200% and a compression reduction at 40 ^° C. of 65%.

In further experiments it was observed that the resulting foam increased with increasing burnup became soft and rubbery.

Example 6

There was prepared a paste by mixing 100 parts by weight of polypropylene and 140 parts by weight Pyritabbrand were mixed in a Banbury mixer, which was maintained at 190 ⁰ C and kneaded. A sheet was made from the mass. Under

ίο Using the web as core material, a layered plank or plate was produced by placing the web between two webs of pure aluminum sheet with a thickness of 0.5 mm, which were degreased with trichlorethylene, and the composite under a pressure of 50 kg / cm ^{2 was} compressed at a temperature of 200 ° C. for 10 minutes by means of a compression device which was provided with a measuring device for determining the strength of the compressed composite.

For comparison, a layered plate with a core was made using the same procedures the specified pure polypropylene web instead of the web made of the mass and with an additional adhesive film a thickness of 50 μ made of ethylene vinyl acetate

Mixed polymer (EVA) or made of ethylene glycidyl methacrylate (EGM) between the sheet from the mass and each of the aluminum panels is made.

The bond strength between the two different materials is determined according to ASTM D 906-49 a pulling speed of 5 mm / min. The tensile strengths when peeling off the layered Plates are listed in Table VIII.

Table VIII

Laminate Tensile strength when peeling Propylene and aluminum 0 kg / cm ^{2 40} mass and aluminum 5 kg / cm ² Bulk, EVA and aluminum 7 kg / cm ² Ground, EGM and aluminum 10 kg / cm ²

The layered board of the invention can be used as a hardly flammable building material and is, as shown in Table VIII, better in terms of accessibility for adhering to a metal than the layered sheet made of polypropylene.

Example 7

This example illustrates a cylindrical block made from a molded article Resins.

A number of mixtures were prepared by burning pyrite in amounts of 20, 30, 50, 60 and 70 percent by weight, based on the resulting mixture, with blown polyethylene film (thickness: 0.05 mm, fold diameter 210 mm), and for 6 months aged after manufacture. The mixture was placed in a cylindrical iron crucible having a diameter of 120 mm and a height of 300 mm, and the film was melted by keeping the temperature of the contents at 250 to 360 ^° C. The contents of the crucible were poured into a cylindrical shape with a diameter of

knives of 52 mm and a height of 150 mm cast and obtained a cylindrical block chilled.

Two rows of cylindrical blocks were made by the same procedure as described above, made using polypropylene film as resin (thickness: 0.07mm, folding diameter: 210 mm), and the 4 months after

was aged during manufacture or using bottles made of high-impact polystyrene as resin.

The physical properties of the resulting blocks are shown in Table IX, which further includes those Properties of concrete made from Portland cereal after hardening for 20 days are also listed for comparison purposes.

Table IX

Samples and amount of added charring weight percent

Specific
weight

Compression strength *)

kg

Hardness after
Rockwell

Polyethylene film alone 0.81

Polyethylene film + burn-off 30 1.08

Polyethylene film + burn-off 50 1.37

Polyethylene film + burn-off 60 1.62

Polyethylene film + burn-off 70 1.98

Polypropylene film alone 0.75

Polypropylene film + burn-off 30 1.08

Polypropylene film + burn-off 50 1.46

Polypropylene film + burn-off 60 1.67

Polypropylene fiun + burn-off 70 1.96

Polystyrene bottles alone 0.94

Polystyrene bottles + burned 20 1.08

Polystyrene bottles + burned 30 1.25

Polystyrene bottles + burned off 50 1.54

Polystyrene bottles + burned off 60 1.78

Portland cement alone 3.7 ^C

Portland cement + sand 50 3.73

*) Load when breaking a cylindrical sample with a diameter of 100 mm, tested in accordance with JIS A 1108-1963 with the aid of Shi

2150 47 1990 48 2110 48 2080 51 1200 1820 60 2000 63 1850 58 1700 55 600 3900 82 4000 80 4080 78 4360 76 3800 76 1600 1580 - he of 50 mm and a height

The stability of the blocks against mineral acid, alkali and salt water is in units of weight gain (Weight percent) shown in Table X after 30 days of immersion at room temperature.

Table X

10% 30% H ₁ SO ₁ 10% NaOH 10% NaCl

Polyethylene + burned off 50 percent by weight Polypropylene + burned off 50 percent by weight Polystyrene + burned off 50 percent by weight

Example 8

Two rows of pipes, containing pyrite burnup in different amounts, were passed through the same Procedures prepared as in Example 7, with the proviso that the resins used are polypropylene and polystyrene, and the amounts of the burn-up mixed were 40 and 30 percent by weight

Table XI

+0.07 +0.04 +0.02 +0.05 + 0.02 +0.02 +0.05 +0.02 +0.02

+0.05 +0.03 +0.05

so and that the shape used has an outer diameter of 150 mm, an inner diameter of 100 mm and a length of 90 mm.

The compression strength of the resulting pipes was determined according to the method according to HS A 5302-1961

measure up. The results are together with those of concrete pipes after one month of hardening shown for comparison in Table XI

Outer

~ who inner length

Diameter diameter

mm

Compressive strength kg

Polypropylene + burned off 40 percent by weight 150

Polystyrene + burn-off 30 percent by weight 150

Portland cement concrete after 1 month hardening 155

108
100

90 500 90 290 90 100

Example 9

The block containing 30 percent by weight of charring, produced according to Example 7, was comminuted into ballast-like aggregates for concrete. A concrete cylinder 42 mm in diameter and 150 mm in height was made by a general method using a mixture of equal weights of the aggregate and cement .

The compression strength of the cylinder was measured according to JIS A 1108-1963 together with that of a concrete cylinder containing ballast and having the same dimension for comparison . The results are shown in Table XII and demonstrate that the mass can be used as an aggregate for concrete.

Table XII

Concrete cylinder

Compression strength *)
kg

Containing the mass
Containing ballast

1720
1530

Example 10

A series of blocks containing pyrite burn was made by the same procedures as in Bei-S game 7 produced, with the proviso that the resins used are polyvinyl chloride (content of dioctyl phthalate = 30 percent by weight), polyvinylidene film, ABS, polyamide film (30 μ thickness), polyester film (30 μ Starch), and the amount of burn-up mixed in was 60% by weight.

The physical properties of the resulting blocks are shown in Table XIII.

Table XIII

Samples Enamel Specific Compress

temperature weight sion

strength*)

⁰ C g / cm "kg

*) The compression strength is by means of the Shimazu All performance test device measured at a compression speed of 3 mm / min.

Polyvinyl chloride

Polyvinylidene chloride
SECTION
polyamide
polyester

170 to 250
120 to 200

220 to 300
270 to 350
270 to 360

1.73 1.75

1.70 1.68 1.69

1500 1300

1850 4050 3900

*) The compression strength was determined according to JIS A 1108-196: measured by the same procedure as in Example 7

Claims (1)

21 Claim: Thermoplastic molding compounds with additives containing iron oxide, consisting of 100 parts by weight of a polyolefin and 5 to 1200 parts by weight of a pyrite burnout and optionally filler or pigment.