DE2420093A1 - HEAT-RESISTANT AND FIRE-RESISTANT SYNTHETIC RESIN MATERIALS CONTAINING INORGANIC SUBSTANCES AND METHOD FOR MANUFACTURING THE SAME - Google Patents

Description

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ijr.'h \ .. Vv. ^ζ - ': - ·: ^ Ί ^ April 25, 1974

K. SCHUMANN - D.PL.-ING. P. JAKOF ^P ^ ^^ 2 4 2 0 0 9

Takashi ISHIKAWA

1355) Oaza Higashine-ko, Higashine-shi, Yamagata-ken,

Heat-resistant and fire-resistant synthetic resin materials containing inorganic substances and methods of making the same

The invention relates to new fire-resistant organic materials obtained by a method for Improvement of the heat resistance and fire resistance properties are made, and in particular on heat-resistant, synthetic materials, which contain inorganic substances, as evidenced by the content of a mixture of synthetic resin material as a matrix and an inorganic high molecular weight substance, or a porous inorganic substance Substances that are cross-linked with one another are distinguished;

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and a method of making the same.

The new materials according to the invention can be viewed as inorganic substances in those inorganic polymers or monomers with molecules of high molecular weight organic compounds are mutually bound., Such materials are useful in many areas, for example in the ceramic industry, including the manufacture of furnace systems, as heat-resistant ones ceramic carriers or coating materials, as impregnation materials and binders. they are also suitable as materials for fire-resistant or refractory structures that can be made into a desired Shape, such as a board, can be shaped and especially as refractories with little Weight for use in construction.

The invention also relates to an improved method of making a foamed synthetic Resin.

There is a method for producing foamed synthetic resin known in the organic High molecular weight and low weight substances that have a particular, chain-like or have branched-chain molecular structure, gradually reacted with a polyisocyanate or with boric acid will. However, this known method has. Disadvantage that special and large devices and special working methods for pouring and foaming are required and that many factors in the

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Mixing of the respective components must be observed. ■ * "''.

The invention includes a method of mixing ingredients using a new stationary Mixer with spiral guide blades, in which a foamed synthetic resin material, the one Has structure in which the components in a physical and chemical manner with one another are bound, is formed.

It is well known that the physical properties of a body made of foamed, high molecular weight Material that consists of foamed, inorganic substances that form between molecules of a synthetic resin are dispersed, significantly changed by a suitable heat treatment and be improved.

The invention consists in providing a material which forms a glass-like surface thereon, when it is heated to high temperatures, and especially in the manufacture of a heat-resistant one A binder which is advantageously used with a composition which hardens by mixing with water and in the formation of a coating material or layer-forming material that has a layer Heat-resistant and flame-resistant properties can form when applied to the surface of a board of inorganic substances or a plate of organic materials or sheet materials that are made with Plates or panels are reinforced, is applied.

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The synthetic resin materials have a porous structure, 'light weight and good moldability, so that these materials, especially materials made of rigid foam, are used for different types of components and auxiliary components are suitable for buildings.

The invention therefore resides in the manufacture of an anti-flame material that is used in panels, sheets. or square bars can be shaped, taking advantage of the good physical properties of the inorganic substances and the properties of organic substances described above in themselves united. The material is made by mixing a suitable synthetic resin with one or two Kinds of suitable, inorganic substances, and although prepared separately or simultaneously, based on the expected mechanism of foaming.

Another feature of the invention is to provide an improved method and method Apparatus for making the material described above.

In general, a polymeric material which has particles or short fibers of an inorganic Contains substance that has the cell-like structure of a foamed polymer, which is essentially made up of a synthetic resin, is bound, due to the reinforcement by the added inorganic Substances and the desired physical properties, such as malleability, organic substances, excellent physical properties.

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Pollich is the high molecular weight organic material containing inorganic substances, of greater value in many uses, particularly in construction, namely in the form of plates, panels, square or round rods and layered panels, as well as material for inside or outside finishing.

The object of the invention is to provide a synthetic resin material excellent in physical properties that contains inorganic substances for use as a material for building purposes and other constructions.

Building materials with good anti-flame properties at high temperature are desirable. The synthetic resins themselves are, however, compared to wood, metal, and ceramic vrenig heat-resistant and weather-resistant. Despite this fact, there will be different synthetic resin materials are widely used because of good moldability. Many tries have been undertaken to further improve the physical properties of these materials. Many suggestions and studies have been published.

In terms of anti-flame properties can The synthetic resins are classified into flame retardant and non-combustible types. The former They continue to burn on contact with a flame, so they are not considered fully fire-resistant materials can be viewed. The latter burn themselves

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not. The materials of the latter type can also be self-extinguishing types that appear on the surface form an incombustible and heat-resistant layer when they come into contact with high temperature come, and non-flammable species that are based on a structure similar to an inorganic material Heat stable, be divided.

However, it is desirable to have materials available that are completely at very high temperature are stable when the material contains an organic substance as a main component.

The object of the invention is therefore also to provide an incombustible, cheap, synthetic resin material, that at high temperature a heat-resistant layer on the surface of the material can form.

It is a further object of the invention to provide sheet materials for use in construction, including incombustible. Side part materials for apartments and various types of layered panels.

According to the invention, the types of panels or panels described above are created, which under Using a simple device can be easily made.

Another object of the invention is to create a new adiabatic material in the form of an ear, a square or round rod, which in large

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technical scale can be produced.

Various methods of producing foamed material are known in which a foaming agent is added to a desired synthetic resin. Different types of foaming agents, for use in these methods are also known.

These artificial foam materials can be which contain organic, high molecular weight compounds as carriers and subdivide those of an inorganic nature will. The former are made of polyethylene, polystyrene or polyurethane and the latter are made of Concrete foam or glass foam. One of the inorganic foam materials is concrete foam with independent Cells containing a double salt of a cement polymer and silicon dioxide and aluminum hydroxide as film-forming agents contains. This polymer is of a different nature than the plastic foam.

The glass foam described above is a fire-resistant material, which by adding a small Amount of powdery soot as a foaming agent to form a powdery glass mass, uniform Mixing the ingredients, heating the mass in the mold for foaming, slow cooling and blowing

after removing the product from the mold will. Antimony trioxide, potassium sulfate, or boric acid can be added to increase the sintering rate of the glass and the rate of foaming through uniform decomposition of the foam

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to vote bildners. However, this procedure is nui? for the production of foamed materials mainly made of glass.

According to the invention there is also a method for producing a new and useful, adiabatic Resin material containing an inorganic high molecular substance, which is a synthetic one Resin an inorganic, high molecular substance including boric acid and its salts and silicic acid and their salts and one or more types of inorganic, foamable substances, such as AL ^ O * and Al ^ O ^ -containing minerals can be added.

Examples of the synthetic resins used as the matrix according to the invention are thermoplastic resins such as vinyl acetate resin, acrylic resin, Polyvinyl alcohol, polystyrene, polyethylene, polypropylene and polyamide, and thermosetting resins such as Condensation products of melamine, urea, phenol and epoxy resin, silicone resin, polyurethane, xylene resin and toluene barz.

The adiabatic material according to the invention is characterized in that it has the above-described, synthetic resin and boric acid and its derivatives, silica or its derivatives containing, and related on dimensional stability (antidefacement), shock absorption (antishock), hardness and dimensional stability normal temperature has excellent properties and that improved anti-flame properties due to the fact that shows a ceramic

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Layer is formed on its surface at a high temperature, and boric acid or its derivatives develop gas at a higher temperature.

For example, when boric acid or its compounds are added to a polyurethane resin raw material in the foaming reaction according to the invention, the physical properties of the resins obtained are significantly improved. In particular, the obtained materials show improved dimensional stability properties, shock-absorbing properties, improved hardness and dimensional stability, as well as excellent anti-flame properties due to a ceramic layer which is formed on the surface by the dehydration reaction of boric acid or its derivatives, although the polyurethane is carbonized. If the material is further heated to a higher temperature, although the polyurethane resin is thermally decomposed, the fire resistance property can be maintained due to the fact that the boric acid or its derivatives evolve gases, liberating their crystal water to cause the particles of the material bind and fill the space in between. The temperature at which thermal decomposition of boric acid occurs is, 200 to 300 C, while the decomposition temperature of salts of boric acid, such as sodium borate, copper borate, lead borate, and zinc borate is 4-50 to 700 ⁰ C.

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In the same way, if silicic acid or its derivatives one. Polyurethane resin raw material is added, the same effect described above is observed. It. has also been found through experiments that materials containing pearlite particles or particles of other inorganic, heat-resistant materials or aluminum oxide clay materials!
keep.

contain, temperatures of 1000 ⁰ C or more withstand-

The materials according to the invention can contain phosphoric acid or phosphates such as sodium phosphate, potassium phosphate, ammonium phosphate, calcium phosphate, magnesium phosphate and aluminum phosphates including AlPO ₄ , Al (H ₂ PO ₄ ) ^, Al (PO ₅ ), and the like.

Silica salts which can be used according to the invention include sodium silicate, calcium silicate, calcium silicate, copper silicate, zinc silicate and the like. Examples of minerals containing aluminum oxide are pearlite (75% SiO ₂ , Al ₂ O ₅ ), vermiculite (water-containing silicate with Al ₂ O ₅₁ Fe and Mg), agalmatolite (pyroferrite containing, for example, 28.3% Al ₃ O ₅ , 66.7% SiO ₂ and 5% H ₂ O), kaolin (a clay of the sericite type of the general formula Al ₂ O ₅ 2SiO _2. 2H ₂ O, for example containing 39.5% Al ₃ O ₅ , 46.5% SiO ₂ , 14.0% H ₂ O) -, sericite, clay and hedenbergite. A suitable clay is one that contains 36.4% Al ₂ O ₅ , 47.9% SiO ₂ , 1.3% Fe ₂ O ^, 0.8% CaO, 0.4% MgO, and 12.3% H ₂ O contains. Examples of suitable borates are potassium borate, sodium borate, magnesium borate, calcium borate, copper borate, lead borate and zinc borate.

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According to the invention, both thermoplastic, such as thermosetting resins used. The former include polyvinyl acetate, acrylate resins, Polyvinyl alcohol, polystyrene, polyethylene, polypropylene and polyamide. The latter include Melamine resins, urea resins, phenolic resins, epoxy resins, silicone resins, polyurethanes, xylene resins, Toluene resins and the like.

Fillers that are added to the organic substances can of course set with water include (hydraulic) substances produced by suitable firing, such as cement and Plaster. These substances can be used in place of the minerals described above.

The invention is illustrated below by means of examples explained in more detail. All parts are based on weight.

example 1

100 parts of a polyvinyl chloride emulsion, 30 parts of aluminum phosphate, 30 parts of aluminum oxide and 30 parts of water were mixed in a mixer at 60 ° C. for 30 minutes and then poured into a mold. ^{After heating to 100 °} C. for 40 minutes, the mixture was slowly cooled and the foamed object was removed from the mold.

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Example 2

100 parts of polyethylene, 30 parts of pearlite particles, 40 parts of aluminum phosphate and 30 parts of water were mixed in a mixer. The mixture was heated in a mold for 20 minutes at 300 ^° C. for foaming. The molded article was removed from the mold to relax it after being slowly cooled.

Example 3

100 parts of polystyrene, 25 parts of powdered Agal- "matolith, 30 parts aluminum oxide and 30 parts of water were mixed in a mixer at 280 ⁰ C for 20 minutes, and poured into a mold and then heated 25 minutes 200 ⁰ C. The molded article was removed from the mold after slow cooling.

Example 4-

100 parts of polyurethane, 25 parts of "vermiculite, 30 parts of sodium phosphate, 30 parts water and 10 parts of glass wool were mixed at 70 ⁰ C 25 minutes in a mixer. The mixture was applied to a 35-minute pressure at 25O ° C to form around an object .

The properties of those obtained according to Examples 1 to 4 Items are shown in Table I below.

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- 13 Table I.

Example 1 Example 2 Example 3 Example 4 Specific 0.12-0.14 0.14-0.16 0.15-0.17 0.16-0.18, weight (g / cm ^) _

Stretching strength 8 - 10 (kg / cm)

Self-extinguishing flammability

7-9

9-10

8-11

resistance

Weather resistance

Heat resistance

non-combustible non-combustible non-combustible bar bar

resistant resistant resistant against against against against .Alkali Alkali Alkali Alkali and black and black and black and weak Acids before acids before acids

no
Change after 12 months of exposure

no

none no change change change after 15- after 15- after 15 months monthly monthly exposure exposure exposure to outside to outside to outside to outside conditions conditions conditions

1810

1330

1340

1350

Example 5

Parts of polyethylene, 30 parts of aluminum oxide, 10 parts of chromic acid, 20 parts of sodium borate and 30 parts of aluminum phosphate were ^{mixed in a mixer at 70 0} C minutes and then put into a mold from a.

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Brought nickel-containing alloy and then heated to 200 ° C for 30 minutes to foam. The foamed one Item was taken out of the form after relaxing. ■ $ -

Example 6

100 parts of polyethylene!, 30 parts of perlite, parts of phosphoric acid, 25 parts of ammonium chromate and 20 parts of sodium borate were mixed in a mixer at 50 ⁰ C for 40 minutes and heated at 300 ° C for 20 minutes to foam. The obtained article was removed from the mold after being relaxed. "

Example 7

100 parts of polystyrene, 35 parts of ammonium phosphate, 30 parts of aluminum chromate, 10 parts of chromic acid and 20 parts of sodium borate, 30 parts of "Shiras balloon" (hollow glass particles) and 10 parts of asbestos wool were mixed in a mixer for 40 minutes at 60 ⁰ C. The mixture was pressed in an oil press. The pressed body was then heated ^{to a temperature of 150 ° C. for 40 minutes.}

The objects obtained according to Examples 5 to 7 had the properties shown in Table II below.

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- 15 Table II

Specific
Weight (g / cnr)

Elongation strength
(ks / cm ² )

Incombustible

resistance

Weather resistance

Heat resistance
( ⁰ C)

Example 5 Example 6 Example 7 0.13-0.15 0.14-0.16 0.15-0.16

8-11-10

9-11

self-extinguishing incombustible incombustible

resistant to alkali
weakness
Acids resistant
against alkali and
weakness
Acids

resistant to alkali and weak acids

no change
after 12 months of exposure to external conditions

1400

no change
after 15 months
Expose
to external conditions

1450

no change after 15 months of exposure to external conditions

1500

Example 8

In a mixture of 100 parts of molten polyethylene and 40 parts of perlite particles was Air is blown in to form an object that contains small, air-enclosing cells. .

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Example 9

In a mixture of 100 parts of molten polyethylene and 40 parts of borax air was blown, and the foamed mixture was brought to the desired shape and heated to 180 to 30O ⁰ C, wherein the blowing hrurde caused by discharge and evaporation of the crystal water of borax.

Example 10

Air was in a mixture of 100 parts aluminum phosphate, 40 parts diatomaceous earth, 20 parts sodium borate and 30 parts of water blown in to mix them together and at 60 to 150 C inorganic To form polymers. The received mass contained small, air-filled cells, each 0.8 to 1.2 mm in diameter, and had a specific gravity from 0.40 to 0.45 g / cm.

Example 11

In a mixture of 100 parts of polyethylene, 40 parts of ammonium phosphate and 20 parts Fatriumborat nitrogen was blown to mix them at 60 to 15O ⁰ G. The mixture was then cooled. The mass obtained had cells with a diameter of 1.3 to 1.5 mm and a specific gravity of 0.25 to 0.30 g / cm.

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Claims (12)

Claims 1. Heat-resistant and fire-resistant, synthetic resin material, marked thereby, that it comprises a synthetic resin as a matrix and, dispersed therein, an inorganic substance, and is capable of evolving gas when heated. 2. Synthetic resin material according to claim 1, characterized in that · characterized in that the synthetic resin is a thermoplastic resin or one by heat curable resin is. 3. Synthetic resin material according to claim 1 or 2, characterized in that the thermoplastic Resin made from polyvinyl acetate, an acrylic resin, polyvinyl alcohol, a styrene resin, polyethylene and Made of polyamide. 4. Synthetic resin material according to claim 1 or 2, characterized in that the by Thermosetting resin made from a melamine resin, urea resin, Phenolic resin, epoxy resin, silicone resin, polyurethane resin, xylene resin or toluene resin. 5- A synthetic resin material according to any one of claims 1 to 4-, characterized in that the inorganic substance consists of boric acid, silica or their salts. 6. A synthetic resin material according to any one of claims 1 to 4, characterized in that 409848/0742 containing the inorganic substance of aluminum Minerals, including pearlite, vermiculite, obsidian, sericite, kaolin, agalmatolite, diatomaceous earth, Clay and mica, ordered. 7- A synthetic resin material according to any one of claims 1 to 4, marked thereby. I mean that the inorganic substance made of a fired, water-setting material, especially the various Types of portland cement and plaster of paris, is made up. 8. Synthetic resin material according to any one of claims 1 to 7j, characterized in that it forms a heat-resistant layer on the surface and the particles of resin material through it Layer are bound to each other. 9- A synthetic resin material according to any one of claims 1 to 8, characterized in that it comes in plates, square and round rods, tubes and Layer panels can be formed. 10. A method for producing a heat-resistant and fire-resistant synthetic resin material according to one of claims 1 to 9 »characterized in that that one in a mixture that consists mainly of a synthetic resin as a base material and an inorganic substance "which is capable of forming gas when it is formed into a mass, the cells are heated, a gas is injected. 409848/0742 11. Use of the synthetic resin materials according to any one of claims 1 to 9 for various Types of building materials, including those for construction, for side panels, for waterproofing, for walls and for floor coverings. 12. Use of the synthetic resin materials according to any one of claims 1 to 9 for impregnation of organic and inorganic boards, plates and sheets, whereby when heated a ceramic Layer is formed on the surface thereof. 13- Use of the synthetic resin materials according to any one of claims 1 to 9 as auxiliary materials for the production of heat-resistant materials, in particular materials for firing systems Additive to various types of water-setting materials. 409848/0742