AU779070B2

AU779070B2 - Additive mixture for increasing the fire stability of synthetic form bodies, synthetic form body and two-component system for its manufacturing

Info

Publication number: AU779070B2
Application number: AU16415/01A
Authority: AU
Inventors: Franz Heimpel; Wolfgang Lieberth; Herbert Munzenberger; Gisela Tiefensee
Original assignee: Hilti AG
Current assignee: Hilti AG
Priority date: 2000-02-22
Filing date: 2001-01-24
Publication date: 2005-01-06
Anticipated expiration: 2021-01-24
Also published as: AU1641501A; EP1127937B1; EP1127937A1; DE10007977B4; PL202877B1; PL345991A1; JP2001270998A; DE10007977A1; ATE286105T1

Abstract

Additive mixture for increasing the dimensional stability of plastics moldings in a fire contains acid generator(s), compound(s) giving carbon and particulate metal(s). Independent claims are also included for: (a) plastics moldings containing 10-60, preferably 25-40 wt.% of the additive mixture, homogeneously distributed in the moldings; (b) a two-component system for the production of thermosetting or thermoplastic resin foam moldings of this type.

Description

-1-

AUSTRALIA

PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

Name of Applicant/s: Actual Inventor/s: Address for Service: Hilti Aktiengesellschaft Herbert Munzenberger and Franz Heimpel and Wolfgang Lieberth and Gisela Tiefensee BALDWIN SHELSTON WATERS MARGARET STREET SYDNEY NSW 2000 'ADDITIVE MIXTURE FOR INCREASING THE FIRE STABILITY OF SYNTHETIC FORM BODIES, SYNTHETIC FORM BODY AND TWO- COMPONENT SYSTEM FOR ITS MANUFACTURING' a Invention Title: The following statement is a full description of this invention, including the best method of performing it known to me/us:- File: 30258AUP00

I

la Additive mixture for increasing the fire stability of synthetic form bodies, synthetic form body and twocomponent system for its manufacturing The present invention relates to an additive mixture for increasing the stability of shape of synthetic form bodies in case of a fire, synthetic form bodies containing this additive mixture and a two-component system for its manufacturing.

It is known that synthetic materials and in particular synthetic form bodies undergo a significant change in shape in case of a fire because they melt and thereby deform or are degraded by means of the temperature and flame effect. This is particularly problematic in the case of synthetic form bodies and in particular synthetic foam form bodies, which are used as means of fire protection to close off openings in walls, ceilings and floors, cable ducts, pipe ducts and the like, namely with fire protection foams used on site and in openings to be closed off.

ooo Although it is known that a number of additives can be oeeee used to increase the fire resistance time of such synthetic form bodies such as flame inhibitors and flame protection means to improve the fire stability, ablation filling materials, which peel of in the case of fire by splitting off water and energy consumption, vitrifying or ceramising fillers such as borates, glass frits or sodium silicate, resinifying or carbonating systems or also intumescent systems. This means systems that effect a large increase in volume of the form body in case of a fire, so that the opening to be protected against penetration of fire may withstand the increased 2 temperatures and the flame effect for a longer period of time. Such intumescent materials are, for example, expanded graphite or intumescent systems based on acidifiers, carbon supplying compounds, gas formers and resin binders. These intumescent materials and systems encounter a large increase in volume in case of a fire through the heat effect, so that the closing-off is maintained for a longer period of time.

Fillers and additives, which are generally used for the stabilising of intumescence crusts such as borates, metal oxides, carbonates, silicates, phosphates and the like effect the consolidation of the ash crust through different mechanisms. Borates and phosphates, for example effect a vitrification and serve as binding means, on the other hand, they influence the depolymerisation of the synthetic matrix. Fillers such as carbonates, silicates and the like act as reinforcements for the intumescence oooeo crust. Metal oxides such as iron oxide or titan oxide 20 react with phosphor by forming phosphates, which have a ceramising effect, while aluminium and magnesium hydroxides improve the fire behaviour of the binder by means of splitting off water.

In all previously known systems the synthetic matrix ooooo degrades or melts under the effect of temperature and flames. The additives and admixtures also change state according to their mechanisms of action. Furthermore, a generated intumescence crust is constantly degraded by burning, erosion, melting, disintegration and the like, so that the synthetic form body is more or less quickly used up depending on the layer thickness and density. In the case of fire, a change in the shape of the synthetic form body is always connected thereto, so that until now no synthetic form bodies are known, which maintain their original, geometrical form over longer periods of time under the effect of fire.

It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.

SUMMARY OF THE INVENTION Accordingly, the present invention relates to an additive mixturefor increasing the stability of shape of syntheticform bodies in the case of fire, the mixture including a content of at least one acidifier, at least one carbon supplying compound and at least one particle-shaped metal.

According to a first aspect, the present invention provides an additive mixture for increasing the stability of shape of synthetic form bodies in the case of fire, wherein it contains 10 to 90% by weight of an acidifier selected from the group comprising ammonium phosphate, ammonium polyphosphate, a diamine phosphate, a phosphoric ester acid with monovalent or polyvalent alcohols, a phosphoric acid partial ester or mixed ester 15 with monovalent and/or polyvalent low molecular alcohols, melamine phosphates and boric acid salts; 5 to 45% by weight of a carbon-supplying compound selected from the group comprising carbohydrates, such as sugar or starch, pentaerythritol, dipentaerythritol, a :phenolic resin, a urea resin, a polyurethane, poly(meth)acrylate, polyvinyl acetate, i polyvinyl alcohol, a silicone resin and/or an unvulcanised rubber; and 5 to 45% by weight of a particle-shaped metal, selected from the group comprising aluminum, magnesium, iron and zinc, wherein the particle-shaped metal is provided in form of a powder, laminas and/or scales having a particle size of 0.5 to 10 jim or in the form of fibers, threads and/or i whiskers having a thickness of 0.5 to 10 jim and a length of 10 to 50 Pim.

99***9 S" According to a second aspect the present invention provides the use of the additive mixture according to the invention for increasing the form stability of a synthetic form body in the case of fire, wherein the additive mixture is homogenously distributed in the synthetic mass of the synthetic form body in an amount of 10 to 60% by weight of the synthetic form body.

Unless the context clearly requires otherwise, throughout the description and the claims, the words 'comprise', 'comprising', and the like are to be construed in an inclusive -3asense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".

At least one embodiment of the present invention provides an additive mixture by means of which the form stability of synthetic form bodies is significantly improved in the case of fire, to provide synthetic form bodies of this type and to make available a twocomponent system for manufacturing such synthetic form bodies.

Surprisingly, it has been shown that if the synthetic matrix of the synthetic form body contains an additive mixture, which supplies at least one acidifier, at least one carbon supplying compound and at least one particle-shaped metal, the stability of shape of the synthetic form body can be significantly improved, whereby it transforms into an organic, solid, rock-like, fire-resistant mass in the case of fire without essential change of the geometrical form.

According to a preferred embodiment, the additive mixture contains 10 to 90% by weight, preferably 40 to 70% by weight of the acidifier, 5 to 45% by weight, preferably 15 to 30% by weight of the carbon supplying compound and 5 to o00 o*o* oo••• o*oo o 4 by weight, preferably 15 to 30% by weight of the particleshaped metal.

Preferably, the additive mixture contains as acidifier a salt or an ester of an organic, non-volatile acid selected from sulphuric acid, phosphorous acid and boracic acid.

Particularly preferred acidifiers are ammonium phosphate, ammonium poly-phosphate, diamine phosphate, phosphoric ester with monovalent or polyvalent alcohols, in particular polyhydroxy alcohol such as penta-erythrite, in particular 10 trichlorethylene phosphate, tri(2-chlorisopropylene)phosphate, triphenyl phosphate, tri(2-chlorethylene)phosphate, penta- erythrite phosphate, phosphoric partial I *4 ester or -mixed ester with monovalent and/or polyvalent low- S* molecular alcohols, melamine phosphates, in particular mono- 15 melamine orthophosphate, di-melamine orthophosphate, dimelamine pyrophosphate, melamine poly-phosphate and/or boric S.acid salts, in particular melamine borate.

Preferably the additive mixture contains as carbon supplying compound, a polyhydroxy compound such as, for 20 example a carbohydrate such as sugar or starch, pentaerythrite, di-penta-erythrite, and/or a thermoplastic or duroplastic polymeric resin binder, such as a phenol resin, a urea resin, a polyurethane, polyvinyl chloride, poly(meth)acrylate, polyvinyl acetate, polyvinyl alcohol, a silicon resin and/or an unvulcanised rubber.

According to a preferred embodiment of the invention, the particle-shaped metal is selected from a group comprising aluminium, magnesium, iron and zinc and is preferably provided in form of a powder, laminas, scales, fibres, threads and/or whiskers. Preferably, the particle-shaped 5 metal provided in form of a powder, laminas or scales has a particle size of 50 jim, preferably of 0.5 to 10 jim. If the particle-shaped metal is provided in form of fibres, threads and/or whiskers, the components preferably have a thickness of 0.5 to 10 jim and a length of 10 to 50 pm.

Unless the context clearly requires otherwise, throughout the description and the claims, the words 'comprise', 'comprising', and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive S 10 sense; that is to say, in the sense of "including, but not limited to".

ooooo According to a further preferred embodiment, the additive mixture contains at least one inorganic filler, in particular a metal oxide such as iron oxide, titan oxide, silica oxide, aluminium oxide, heavy spar, a borate, in particular zinc borate, a carbonate, preferably chalk, a silicate, preferably alkali silicate, kaolin and/or glass powder.

A further embodiment of the present invention relates to 20 a synthetic form body with increased stability of shape in the case of fire, wherein it is 10 to 60% by weight, preferably 25 to 40% by weight of the above described additive mixture, relative to the weight of the synthetic form body, homogenously distributed in the synthetic mass.

The synthetic mass is preferably of a conventional duroplastic or thermoplastic resin and conventional auxiliaries. The synthetic mass can be formed of a phenol resin, urea resin, unvulcanised rubber, polyurethane, polyolefine, polyvinyl chloride, poly(meth)acrylate, polyvinyl acetate, polyvinyl alcohol, a silicon resin, polybutene, polybutadiene and conventional auxiliaries.

The synthetic mass can preferably additionally contain inorganic filler in form of inorganic foam, preferably foamed swellable clay, perlite and/or vermiculite, or in form of hollow globules made of a silicate material or glass.

According to a preferred embodiment of the invention, the synthetic mass contains in addition to the thermoplastic resin and the additive mixture an intumescent material, such as in particular expanded graphite. On the other hand, it is also possible to add a gas former for an intumescent material to the synthetic mass such as chloride paraffin, melamine, a melamine compound, in particular melamine cyanuric acid, melamine phosphate, melamine poly-phosphate, tri(hydroxyethylene)cyanuric acid, dicyandiamide and/or guanidine salt, in particular ~guanidine phosphate or guanidine sulphate. The gas former S"together with the acidifier and the carbon supplying compound form an intumescent system, which shows increased form stability in the case of fire through the use of the particle-shaped metal according to the invention.

It is possible, if required, to add one or several flame protection means to the synthetic mass of a synthetic 0 30 form body, such as halogenated flame protection means, metal hydroxides, in particular aluminium hydroxide or magnesium hydroxide, metal oxides such as titan dioxide, red phosphor and/or phosphor compounds, in particular trichlorethylene phosphate, tri(2-chlorisopropylene)phosphate, triphenyl phosphate and tri(2-chlorethylene)phosphate, and also antimony oxide as synergist if required.

The duroplastic or thermoplastic resin of the synthetic form body according to the invention can be provided in form of a dense mass or preferably in form of a foam. Polyurethane foams are preferred, which are conventionally manufactured from a polyisocyanate, a polyhydroxy alcohol and water or a propellant on the basis of liquefied resin or if required, conventional catalysts, additives etc. It is particularly 10 preferred to form the synthetic form body on the basis of such a polyurethane foam when being used on site, in particular for use as building foam in particularly fire protection foam for the foaming of openings in walls, floors, ceilings and for filling the remaining air gaps in pipe and 15 cable ducts through walls, floors or ceilings.

eo A further subject of the invention relates to a twocomponent system for manufacturing this synthetic form body o on site, wherein one packaging container of the two-component oooo system contains at least one polyisocyanate and the other *ooo packaging container at least one polyhydroxy alcohol, one catalyst for the reaction of the polyhydroxy alcohol with the polyisocyanate, a propellant, an intumescence mixture consisting of ammonium poly-phosphate, melamine and pentaerythrite and 5 to 15% by weight of the above described additive mixture. During the application the components are either forced out of the packaging containers by the effect of a propellant contained in the packaging container or by applying mechanical forces, are mixed, and by forming the synthetic form body are foamed in the opening to be closed off and consolidated.

By means of this two-component system, it is possible in a simple manner to generate a fire protection closing-off on site with increased form stability in the case of fire.

The additive mixture according to the invention can be used anywhere where a high elasticity of the synthetic form body on the one hand, and a particularly high fire resistance on the other is required. By using the additive mixture according to the invention, for example flexible plates, cable coatings with maintained function also in the case of fire, protective shields for fuel hoses, foams for aeroplane seats, inserts for pipe clamps, glazing tees, pipe ducts (bellow expansion joint) but also permanently elastic coatings and sealants can be formed, which demonstrate a particularly advantageous form stability in the case of fire.

0006 oO o The improvement of the form stability in the case of fire ooooo achieved according to the invention is achieved in that S the additive mixture added to the organic synthetic mass forms an organic, ceramic-like material in the case of fire through the effect of high temperatures, which does not change over long periods of time even with high temperatures of up to 15000C. In case of intumescent materials, the intumescent crust generated in the case of o oo fire is permanently eroded by the fire and renews itself, however has a significantly increased stability due to the additive mixture according to the invention.

The following examples serve the further description of the invention.

Example 1 Additive mixture The additive mixture according to the invention is prepared by mixing 30 parts by weight of ammonium polyphosphate, 10 parts by weight of di-penta-erythrite and 10 parts by weight of aluminium powder with a particle size of 5 pm.

Example 2 Plate of elastic polyurethane Synthetic mass for the production of an elastic polyurethane form body.

The polyhydroxy alcohol component is prepared by mixing the following components: 100 parts by weight di-functional polyether polyhydroxy alcohol (OH-number about 28) 200 parts by weight tri-functional polyether polyhydroxy alcohol (OH-number about 20 1 part by weight of catalyst (DBTL, DABACO) 10 parts by weight of powdery molecular sieve (10 A) (drying agent) 100 parts by weight of additive mixture according to example 1 As polyisocyanate component 30 GT 4,4'methylenedi(phenylisocyanate) with a NCO content of 31% is used.

The homogenous mixture made of the polyhydroxy alcohol component and the polyisocyanate component is prepared *30 and transforms the mixture to a plate, which after curing has a shore A hardness of about 50 and an elongation tear of 500%.

Example 3 Plate of silicon elastomer Components for the silicon elastomer Component A 200 parts by weight c, w-di-hydroxy-poly-di-methylene siloxane parts by weight SiH-functional silane (cross-linking agent) 100 parts by weight additive mixture according to example 1 Component B 1 part by weight of an organic platinum complex as catalyst 100 parts by weight c, w-di-hydroxy-poly-di-methylene siloxane 20 Component A is mixed with component B and forms the synthetic mass to a plate. After a reaction time of about 10 minutes a silicon elastomer plate is achieved with a shore A hardness of about 30 and an elongation tear of S300%.

Example 4 Plasto-elastic acrylate sealant For the production of a plasto-elastic acrylate sealant following components are mixed: 200 parts by weight of a styrene/butyl acrylate dispersion (high solids content 200 parts by weight calcium carbonate (Omya 5 GU) 100 parts by weight additive mixture according to example 1 This plasto-elastic acrylate sealant results after application to a protective base and the curing in a coating layer with a shore A hardness of about 50 and an elongation tear of about 100%.

Example 5 Polyurethane soft foam Polyhydroxy alcohol component By mixing the following components a polyhydroxy alcohol component is formed: 100 parts by weight di-functional polyether polyhydroxy alcohol (OH-number about 28) 200 parts by weight tri-functional polyether polyhydroxy alcohol (OH-number about 1 part by weight catalyst (DBTL, DABACO) 3 parts by weight water 1 part by weight foam stabiliser 100 parts by weight additive mixture according to .example 1 As polyisocyanate component 30 GT 4,4'methylene- 25 di(phenylisocyanate) with a NCO content of 31% is used.

•After the homogenous mixing of the polyhydroxy alcohol component with the polyisocyanate component polyurethane soft foam is formed.

Example 6 Stability properties in the case of fire If the products of examples 2 to 5 are exposed to a Bunsen burner flame with a temperature of 1200 0 C, in all 12 cases a rock-like mass with the dimensions of the original products is generated. Even after exposure to flames for several hours, these products do not alter their dimensions any further.

If the products are slowly heated in an oven to 1200 0

C,

they also transform to rock-like masses without altering their dimensions.

*oo

Claims

13- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:- 1. An additive mixture for increasing the stability of shape of synthetic form bodies in the case of fire, wherein it contains 10 to 90% by weight of an acidifier selected from the group comprising ammonium phosphate, ammonium polyphosphate, a diamine phosphate, a phosphoric ester acid with monovalent or polyvalent alcohols, a phosphoric acid partial ester or mixed ester with monovalent and/or polyvalent low molecular alcohols, melamine phosphates and boric acid salts; 5 to 45% by weight of a carbon-supplying compound selected from the group comprising carbohydrates, such as sugar or starch, pentaerythritol, dipentaerythritol, a phenolic resin, a urea resin, a polyurethane, poly(meth)acrylate, polyvinyl acetate, polyvinyl alcohol, a silicone resin and/or an unvulcanised rubber; and to 45% by weight of a particle-shaped metal, selected from the group comprising aluminum, magnesium, iron and zinc, wherein the particle-shaped metal is provided in form of a powder, laminas and/or scales having a particle size of 0.5 to 10 [tm or in the form of fibers, threads and/or whiskers having a thickness of 0.5 to 10 pm and a length of 15 10 to 50 tm. 2. The additive mixture according to claim 1, wherein it comprises 40 to 70% by weight of the acidifier, 15 to 30% by weight of the carbon-supplying compound and 15 to by weight of the particle-shaped metal. 3. The additive mixture according to claim 1, comprising as the acidifier a phosphoric 20 ester with a polyhydroxy alcohol. 4. The additive mixture according to claim 3, wherein the acidifier is selected from the Sgroup comprising pentaerythritol phosphate, trichloroethyl phosphate, tris(2-chloro- isopropyl) phosphate, triphenyl phosphate, tris(2-chloro-ethyl) phosphate, monomelamine orthophosphate, di-melamine orthophosphate, di-melamine pyrophosphate and melamine poly-phosphate. The additive mixture according to at least one of the preceding claims, wherein it also contains at least one inorganic filler. -14- 6. The additive mixture according to claim 5, wherein it contains as inorganic filler a metal oxide, heavy spar, a borate, a carbonate, a silicate, kaolin and/or glass powder. 7. The additive mixture according to claim 6, wherein it contains an inorganic filler selected from the group comprising iron oxide, titanium oxide, silica, aluminium oxide, zinc borate, chalk, an alkali silicate, talcum, mica or wollastonite. 8. The use of the additive mixture according to any one of the preceding claims for increasing the form stability of a synthetic form body in the case of fire, wherein the additive mixture is homogenously distributed in the synthetic mass of the synthetic form body in an amount of 10 to 60% by weight of the synthetic form body. 9. The use according to claim 8, wherein the additive mixture is contained in an amount of 25 to 40% by weight of the synthetic form body. The use according to claim 8 or claim 9, wherein the synthetic mass is formed of a conventional duroplastic or thermoplastic resin and conventional auxiliaries. •i 11. The use according to claim 10, wherein the synthetic mass can be formed ofa phenol resin, urea resin, unvulcanised rubber, polyurethane, polyolefine, polyvinyl chloride, poly(meth)acrylate, polyvinyl acetate, polyvinyl alcohol, a silicone resin, polybutene and/or polybutadiene and conventional auxiliaries. 12. The use according to any one of claims 8 to 11, wherein the synthetic mass comprises an inorganic filler in form of inorganic foam or in form of hollow globules made 20 of a silicate material or glass. 13. The use according to claim 12, wherein the inorganic filler is selected from foamed swellable clay, perlite and/or vermiculite.

14. The use according to any one of claims 8 to 14, wherein the synthetic mass contains in addition to the thermoplastic resin and the additive mixture an intumrnescent material.

15. The use according to claim 14, wherein the synthetic mass contains expandable graphite as intumescent material.

16. The use according to any one of claims 8 to 12, wherein the synthetic mass contains in addition to the thermoplastic resin and the additive mixture a gas former for an intumescent material.

17. The use according to claim 16, wherein it contains as gas former chloroparaffin, melamine, a melamine compound, tri(hydroxyethylene)cyanuric acid, dicyandiamide and/or a guanidine salt.

18. The use according to claim 17, wherein the gas former is selected from melamine cyanuric acid, melamine phosphate, melamine polyphosphate, guanidine phosphate and guanidine sulphate.

19. The use according to any one of the preceding claims 8 to 18, wherein the synthetic mass additionally contains one or several flame protection means. The use according to claim 19, wherein the synthetic mass contains as additional flame protecting means a halogenated flame protection means, ammonium phosphate, .metal hydroxide, a metal oxide, red phosphorus and/or a phosphorus compound, and also 15 antimony oxide as synergist if required.

21. The use according to claim 20, wherein the additional flame protecting means 0 comprises as the metal hydroxide aluminum hydroxide or magnesium hydroxide, as the metal oxide titanium oxide and/or as the phosphorus compound a halogenated phosphoric acid ester. 20 22. The use according to claim 21, wherein the halogenated phosphoric acid ester is selected from the group comprising trichloroethylene phosphate, tri(2-chloro-isopropylene) phosphate, triphenyl phosphate and tri(2-chloro-ethylene) phosphate.

23. The use according to any one of claims 9 to 20, wherein the duroplastic or thermoplastic resin is provided in the form of a foam. -16-

24. The use according to claim 23, wherein it comprises as a resin a polyurethane foam formed of a polyisocyanate, a polyhydroxy alcohol and water or a propellant on the basis of liquefied gas. The use according to claim 16, wherein the polyurethane foam is formed during the application on site.

26. The use according to any one of claims 23 to 25, for the manufacture of a synthetic form body with increased stability of shape in case of fire on site, wherein one packaging container contains at least a polyisocyanate and the other packaging container contains at least a polyol, a catalyst for the reaction of the polyol and the polyisocyanate, a propellant, an intumescent mixture consisting of ammonium polyphosphate, melamine and pentaerythritol and 5 to 15% by weight of the additive mixture according to any one of claims 1 to 7, said components are, during the application, forced out of the packaging containers by the effect of a propellant or by applying mechanical forces, are mixed, and by i forming the synthetic form body are foamed in the opening to be closed off and hardened. o*

27. An additive mixture for increasing the stability of shape of synthetic form bodies in the case of fire, substantially as herein described with reference to any one of the embodiments of the invention illustrated in the accompanying drawings and/or examples. 0

28. The use of the additive mixture as defined by any one of claims 1 to 7 for increasing the form stability of a synthetic form body in the case of fire, substantially as herein g 20 described with reference to any one of the embodiments of the invention illustrated in the "accompanying drawings and/or examples. 0 DATED this 2 9 th Day of October 2004 2 Shelston IP Attorneys for HILTI AKTIENGESELLSCHAFT