WO2018078163A1

WO2018078163A1 - Polyurethane-based building product comprising feather

Info

Publication number: WO2018078163A1
Application number: PCT/EP2017/077802
Authority: WO
Inventors: József Major
Original assignee: Eu Pcm Közhasznú Nonprofit Kft.
Priority date: 2016-10-28
Filing date: 2017-10-30
Publication date: 2018-05-03
Also published as: EP3532523A1

Abstract

The invention relates to a heat and sound insulation, particularly airborne sound and step sound insulation building product comprising hard polyurethane comprising animal originated feather, wherein the animal originated feather is involved in the cross-linking of the polyurethane, and thus the amount of the synthetic cross-linking precursor is at most 50 wt% of the amount of the synthetic cross-linking precursor needed for the required hardness in a usual process where no feather is applied.

Description

POLYURETHANE-BASED BUILDING PRODUCT COMPRISING FEATHER

Field of Invention

The invention relates to a building product having excellent mechanical properties (particularly good fire resistance and sound insulation, particularly airborne sound and step sound insulation properties) the main component of the material of which is animal originated feather and polyurethane copolymer. At the same time the invention provides an opportunity for utilization of the animal originated feather considered as a hazardous waste. Background Art

The combination of the animal originated feather (hereinafter: feather) and the plastics are known in the prior art. US 2005/0205226A1 describes a combination of feather and resins, wherein the resin is preferably polyurethane. Particularly heat insulating boards are produced from the manufactured foamed or unfoamed material. During the production the polyurethane precursors conventionally used in the manufacturing of the hard polyurethane plastic materials, see among them the crosslinking polyisocyanate precursor mentioned in paragraph [0014], e.g. in line 16), are mixed with the feather and other conventional auxiliaries. Further, in the pre-treatment of the whole feather, the barbs (also named as fibers) are separated from the quill (also named as shaft) and only the barb part is used in the preparation. This can be the reason that in the preferable embodiment the board comprises fiberglass reinforcement on both sides, and based on the description it cannot be used for interior decoration purposes.

CN 103 882 627A describes materials having insulation effect particularly for use in the apparel industry, which materials comprise 40-60 wt% of feather, 5-10 wt% of polyurethane film, 10-20 wt% of organic material, and 10-20 wt% of polyester. The technical field according to the description differs from the solution based on the present invention, since the polyurethane as a separated phase covers the surface of the feathers only in a filmwise manner.

CN 202 540 875U also describes heat insulation materials comprising natural feather, wherein the feathers are covered by a thermoplastic, e.g. polyurethane. The essential components of the composition are a fibrous material and polyester type plastics. Also in this case the technology relates to layered and isolated chemical structures.

In TW 473 589B feather degreased and washed with alcohol is used together with polypropylene and/or polyethylene. The material is applied for the manufacturing of a building product, however, the chemical combinability with polyurethanes is not mentioned.

In the solution according to F 2 844 816 Al a thermoplastic material is mixed with natural fibres, wherein the feather as a fibrous material is mentioned. The applying of the polyurethane is not disclosed by the description. The material is used for the manufacturing of building products.

We note here that in the case of such solutions, where the surface of the feather is treated with polyurethane, the feather cannot exhibit cross-linking effect (see details below), which is the substantial part of the present invention.

WO2000/017460A1 describes an insulating material used in roof covering, wherein the used animal originated fibrous material can be feather. The application of polyurethane is not mentioned in the description. In Wrzesniewska-Tosik K. et al. (Feathers as a Flame - etardant in Elastic Polyurethane Foam), Fibres & Textiles in Eastern Europe, Vol 22, No. 1. (2014-01-01), pages 119-128 ground (milled) feather is applied together with polyurethane components (precursors) in the preparation of foamed polyurethane, concentrating on the enhanced flame-retardant properties of the obtained material. The composition of the starting materials was not disclosed, and their proportion was declared as a secret know-how (see in the middle column of page 120). There is nothing in the article which would suggest that an atypical polyurethane preparation process is applied (beside the use of ground feather), i.e. there is no any hint in the article which would suggest the elimination of the use of the cross-linking precursor (or at least a remarkable decreasing of the amount of the cross-linking agent). However, grinding procedure was discussed in details, where the feather was ground to a powder having particle size under 0.1 mm (the whole procedure needed about 21 hours to reach the desired particle size). It comes from the article that the very small particle size has a great impact on the properties of the product. Moreover, the time of preparation is not in the range of that of the typical commercial polyurethane production which represent substantially distinct idea.

In Japanese patent application of JP 1993/0160471 (see also under XP-002766226) fine feather powder with particle size of 4 μηι in the preparation of polyurethane. The product is used as surface modifier,

US 5,269,992 discloses a method of producing a feather containing resilient body. In the process the feather is first coated with water, then coated with the prepolymer of polyurethane resin, in the next step the stickness is adjusted and further the polyuretane resin is hardened. The document discloses the use of polyurethane resin prepolymers, which are deemed to be the common prepolymers. There is no mention or hint about the replacement of cross-linking precursor. Thus there is no teaching in the document that the amount of cross-linking agent can be reduced by the use of feather.

It is an object of the invention to provide such a material useful in the building industry, which has excellent mechanical properties, particularly good heat and sound insulation, particularly airborne sound and step sound insulation properties, and it possesses suitable strength and lire resistance, and further it can be produced by an environmentally developed technology. The product according to the invention is characterized in that it comprises feather in a great amount for creating cross-linker binds between the polymer chains, where the created cross-linking is a multidirectional 3D type cross-linking, see below. Thus the present invention allows of utilizing the feather considered as a hazardous waste, in other words, by its help the environmental impact due to the disposal (e.g. incineration) of the feather used for the goal of the present invention can be avoided. Additionally, there is no need for the usual synthetic cross-linkable compounds - which are usually hazardous polyphenol compounds -, as they are substituted by the used feather.

During the poultry meat production, a remarkable amount of poultry feather is forming where a part of it is utilized in a well known manner in the everyday life for e.g. feather pillows, feather coats. The feather, which cannot be used for this goal, is considered as a hazardous waste in Europe and throughout the world, primarily not due to the toxicity of the material, but due to its stability, that is its slow degradation. Only in Hungary the average amount of the slaughtered poultry was 360-480 thousand tons per year between 2010 and 2015 (https://www.ksh.hu/docs/hun/eurostat_tablak/tabl/tag00043.html), accordingly, about 23-30 thousand tons of waste feather is formed yearly the disposal of which should be accomplished. The European Union law (1576/2007/EK Regulation, 1774/2002/EK Regulation, 71/2003 FVM Regulation) strictly define the disposal and deposition of animal by-products not intended for human consumption, thus, among others, the utilization of the milled feather produced form the feather originated from slaughterhouse as a feed is significantly restricted by the valid veterinary regulation. Therefore, such innovative developments and methods are necessary, which enables the utilization the formed waste feather.

Besides some pigment and 1-2% of fat content the feather mainly consists of protein, wherein the 85% of the protein content is keratin. The keratin is a protein containing a high amount of cysteine. The cysteine is significant regarding to the stability, as the disulfide bridges between them result in the extreme stability of the keratin, and thus of the feather.

Brief Description of the Invention

In particular, the invention relates to:

1. A heat and sound insulation building product comprising hard polyurethane, which comprises animal originated feather, wherein the animal originated feather is involved in the multidirectional cross-linking of the polyurethane, and the product is substantially free of synthetic cross-linking agent.

2. A heat and sound insulation building product comprising hard polyurethane, which comprises animal originated feather, wherein the animal originated feather is involved in the multidirectional cross-linking of the polyurethane, and the amount of the synthetic cross-linking precursor being in the product is at most 50 wt% of the amount of the synthetic cross-linking precursor being in a polyurethane made without feather but which is made with synthetic cross-linking precursor and from the same diisocyanate type precursors and diol type precursors and where the hardness of this reference polyurethane is the same as the product's hardness.

3. A heat and sound insulation building product comprising hard polyurethane, which comprises animal originated feather, wherein the animal originated feather is involved in the multidirectional cross-linking of the polyurethane, and the amount of the synthetic cross-linking precursor being in the product is at most 40 wt%, more preferably at most 30 wt%, even more preferably at most 20 wt%, even more preferably at most 10 wt%, and still more preferably at most 5 wt% or 1 wt% of the total amount of all isocyanate compounds being in the product.

4. The building product according to any of points 1 to 3, further comprising one or more auxiliaries selected from the group of flame retardant materials, foaming agents, and polymerization catalysts.

5. The building product according to any of points 1 to 4, wherein the amount of the feather is 5-70 wt%, preferably 10-50 wt% based on the total weight of the product.

6. The building product according to any of points 1 to 5, wherein the polyurethane comprises polypropylene glycol applied as diol type precursor.

7. The building product according to any of points 1 to 6, wherein the polyurethane comprises diphenylmethane diisocyanate applied as diisocyanate type precursor.

8. The building product according to any of points 1 to 7, which is free from added synthetic cross- linking precursor.

9. A method for producing a heat and sound insulation building product according to any of clams 1 to 8, characterized in that it comprises the following steps:

a) diol type precursor of the polyurethane, diisocyanate type precursor of the polyurethane and feather are mixed, optionally together with one or more auxiliary/auxiliaries, without using separately added synthetic cross-linking agent; b) the obtained mixture is poured into a mould;

c) after polymerization the obtained product is removed from the mould.

10. Use of animal originated feather as a multidirectional cross-linking precursor in producing of polyurethane.

11. The building product according to any of points 1 to 8, the method according to point 9 and the use according to point 10, wherein the feather is whole feather.

12. The building product according to any of points 1 to 8, the method according point 9 and the use according to point 10, wherein the feather is ground feather.

13. The building product according to any of points 1 to 8, the method according point 9 and the use according to point 10, wherein the feather is the mixture of whole and ground feather.

14. The building product and the method according to point 12 or 13, wherein the length of the ground feather pieces is typically about 1-15 mm, preferably about 2-10 mm.

Detailed Description of the Invention

The crucial component of the building product according to the present invention is the animal originated feather (which can be whole feather or ground feather or a mixture thereof) typically feather originated from poultry, such as chicken, duck, gosling, goose etc. (hereinafter shortly: feather). If ground feather is applied, then the whole feather is ground, preferably after cleaning, in usual grinding equipments, such as a circular knife grinding equipment. The length of the feather pieces obtained after grinding is typically about 1-15 mm, preferably about 2-10 mm, which particles contains both relatively long quill (shaft) parts (related to a finely ground feather) and barbs. If whole feather is applied, then it has its natural size, which has a length preferably about 2 to 10 cm. In this context the "length" of the feather or a particle obtained from the feather is the length of the maximal diameter of the feather/particle.

It is an obviously advantageous embodiment of the invention when whole feather is applied without any cutting/ground/heat type pre -treatment (excepting washing and airdrying) since in this case a number of long and energy consuming processing steps can be eliminated from the procedure.

Based on our measurements the building product comprising such ground feather has an excellent heat and sound insulation, typically excellent step sound insulation property (which is better than that of building product produced from whole feather), and further excellent strength and fire resistance.

Moreover, based on our measurements, the building product comprising whole feather has an excellent heat and sound insulation, typically excellent airborne sound insulation property (which is better than that of building product produced from ground feather), and further excellent strength and fire resistance.

The applied feather preferably is not useful for producing of a higher value-added product (typically feather pillow, feather coat etc.) or for other goal. Before the use the feather it is preferred if the feather is cleaned in the usual way (typically with water optionally comprising alcohol, preferably ethyl alcohol) during which the impurities and the fat is removed from its surface.

The feather is the 5-70 wt%, preferably 10-50 wt%, even more preferably 15-45 wt%, and still more preferably 20-40 wt% of the product according to the present invention.

The preferable amount of the feather is more in the case of a less foamed product (e.g. 20-40 wt%, within this it can be 25-35 wt%), and is less in the case of a highly foamed product (e.g. 5-19 wt%, within this it can be 7-15 wt%).

The other crucial component of the building product according to the present invention is polyurethane formed by the reaction of compounds comprising isocyanate groups [isocyanate type precursors (containing at least two isocianate groups))] and OH groups [hydroxyl type precursors (containing at least two hydroxyl groups), particularly in the presence of a catalyst. Here we mention that the precursors are often named as monomers (of the polymer) or precursor monomers (of the polymer). The polyurethanes typically are polymers formed by the polyaddition reaction of linear di- and/or triisocyanates and linear diols and/or triols. Their common feature is that their molecules comprise urethane groups ( 1 -NH-CO-0-R2). Except for the simplest cases their structure cannot be defined exactly due to the varied oligomerization reactions of the used monomers and due to that generally several kinds of monomers are used in the preparation even within each monomer type.

Polyurethane -based materials (which are often foamed solid materials) are used in many areas, for example, as a sealant, an insulant. A lot of kinds of the polyurethanes are known from the literature, as the variety of the compounds comprising isocyanate groups and OH groups usable as a precursor is extremely wide, and additionally a lot of variants of them are used in the practice.

Basically two types of polyurethanes can be distinguished: the soft (or flexible) and the hard polyurethanes (in both cases the foamed type is typical in the practice). The hardness/strength of the polyurethane depends on the number of the cross-linking bonds (that is the bonds linking the linear polymer chains to stabilize the structure) formed during the polymerization starting from the precursors. Such precursor monomers are required for the cross-linking, which contain at least three functional groups (which can be isocyanate or hydroxyl groups)— here they are named as cross-linking precursors. Obviously, only linear chains can be formed from diisocyanates (diisocyanate type precursors) and diols (dihydroxy type precursors which are also named as diol type precursors). The production of the soft polyurethanes is disclosed, for example, in patent HU 227871. An example of the prior art documents disclosing the production of the hard polyurethanes is patent EP2111423, where large amount of polyisocyanate cross-linking precursor is applied for the cross-linking..

Accordingly, the polyurethane precursors are those molecules from which the basic structure of polyurethane is built up, i.e. those starting materials which are essential in the formation of the structure of the polyurethane. As it was discussed above, we can speak about isocyanate type precursors (e.g. diisocyanate type precursor monomers), hydroxyl type precursors ( e.g. diol type precursor monomers) and cross-linking precursors, (they are applied only if cross-linking precursor is necessary for the formation of the structure). The cross-linking precursors can be isocyanate type precursors (having at least three - but for better properties (e.g. for better hardening property) substantially more - isocyanate groups, named here as polyisocyanate cross-linking precursor) or hydroxyl type precursors (having at least three - but typically much more - hydroxyl groups, named here as polyol cross-linking precursor), so they form a subgroup within the isocyanate type precursors and hydroxyl type precursors. Accordingly, if diisocyanate type precursor and polyisocyanate cross-linking precursor are applied in the preparation of the polyurethane (beside the diol type precursor), then the amount of isocyanate type precursors is the sum of the amount of diisocyanate type precursor and the amount of polyisocyanate cross-linking precursor (and it is true vica versa for the relating hydroxyl type precursors). Here we underline that these polyfunctional compounds are linear molecules therefore their cross- reaction results in rather a grid-like cross-linked structure.

As it comes from the above definitions, the oligomer type precursor compounds (which are built up from 3 to 5 monomer units) are embraced by the phrase of polyisocyanate and polyol. It should be noted that a cross-linking precursor has better hardening (cross-linking) property if it has a higher degree of polymerization, i.e. when it has more monomers with functional group than a shorter, an oligomer type precursor compound, i.e. when it is really "poly(mer)" type cross-linking precursor compound.

A typical isocyanate type precursor monomer of the soft and hard polyurethane is usually diphenyl methane diisocyanate (diphenylmethane-4,4' -diisocyanate, MDI, also known as methylene biphenyl diisocyanate). Examples of other suitable diisocyanates are 2,4- or 2,6-toluene diisocyanate (TDI) (also known as toluene -2, 4 -diisocyanate and toluene-2,6-diisocyanate), m-phenylene diisocyanate, hexamethylene-1,6- diisocyanate, tetramethylene- 1 ,4-diisocyanate, cyclohexane- 1 ,4-diisocyanate, hexahydrotoluene-2,4- diisocyanate, hexahydrotoluene-2,6-diisocyanate, naphthalene-l,5-diisocyanate, 4,4'-diphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate and 3,3'-dimethyl diphenyl methane -4, 4'-diisocyanate.

Typically, a multi-ring aromatic polyisocyanate compound is used as a cross-linking isocyanate precursor monomer, preferably polyphenylene-polymethylene -polyisocyanate [polymethylene-poly(phenyl- isocyanate)] ensuring the hardness of polyurethane, e.g. polymerized MDI type precursor compound. Preferably, the polyphenylene-polymethylene -polyisocyanate type cross-linking precursor is an oligomer compound, which more preferably comprises significant amount of 3, 4 and/or 5 aromatic phenylene rings, wherein the phenylene rings have isocyanate groups.

Here we mention that - in the practice - a diisocyanate type precursor may contain (and often contains) a small amount of short oligo/polyisocyanate type precursor, too, because such oligo/polyisocyanate type precursor can be formed during the preparation of the diisocyanate precursor, practically as a side product/contamination. Accordingly, a diisocyanate product being on the market may contain oligo/polyisocyanate type precursor in an amount of under 5 wt%, more preferably under 2 wt%, more preferably under 1 wt% based on the total weight of the diisocyanate product. Here we declare that in this description we may use the phrase "free from cross-linking precursor" in the meaning that the product does not contain extra added cross-linking precursor [but may contain a low level of oligo/polyfunctional components deriving from the diisocyanate component where these oligo/polyfunctional components (acting as cross- linking precursor) are only minor components]. So, the phrase of "polyurethane free from cross-linking precursor" can be changed for "polyurethane free from separately added cross-linking precursor" or simply "free from added cross-linking precursor" in such a situation.

It is also important distinctive feature that the cross-linking precursor being in the diisocyanate type precursor (if it is there at all) is short linear type precursor (oligomer type precursor), which is able to make linear bonds between the chains resulting in a grid-type structure in the polyurethane. However, the feather involved into the cross-linking of the polyurethane has a 3D (three-dimensional) structure fixed by covalent disulfide bonds, so the feather can be regarded as a multidirectional 3D cross-linking agent (precursor) which is more effective in hardening than the ususal synthetic cross-linking precursor, since the feather contains various groups at various 3D positions capable to react with the isothiocyanate groups. The other essential component of the soft and hard polyurethanes is the precursor compound having hydroxyl groups (hydroxyl type precursors), the examples of which are diols compounds (diol type precursors), such as ethylene glycol, 1,2-propylene glycol, 1,3 -propylene glycol, 1,4-butylene glycol, 2,3- butylene glycol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, l,4-bis(hydroxy-methyl)-cyclohexane, 2- methyl- 1,3 -propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycols having even more molecular weight, dipropylene glycol and polypropylene glycols, as well as dibutylene glycol and polybutylene glycols and additional oxyalkylene glycols, wherein polypropylene glycol is preferred.

The cross-linking of polyurethane can be achieved with precursors containing more than two - but usually more - OH groups, however, this kind of cross-linking has less practical importance.

The above-mentioned isocyanate type precursors and hydroxyl type precursors can be named here together as synthetic cross-linking precursors. Accordingly, e.g. the phrase "free from added cross-linking precursor" can be understood as "free from added synthetic cross-linking precursor".

It is also declared that when we discuss precursors in the product according to the invention (or in other polyurethane, e.g. in the below discussed reference polyurethane) then - for the sake of simplicity - they mean the relating residue of the precursor as it is built in the polymer structure.

We have surprisingly found that the above-mentioned synthetic cross-linking precursors, which are typically a polyisocyante cross-linking precursors, can be replaced by using the feather as multidirectional 3D cross-linking agent (precursor). Accordingly, the soft polyurethane can be converted into hard polyurethane (having outstanding properties) by using of feather without synthetic cross-linking precursor. However, this fact does not exclude such kind of product according to the invention, which comprises, besides the feather, a conventional synthetic cross-linking precursor in a less amount. A preferred embodiment of the product according to the invention (sometimes named simply as "product") is free from synthetic cross-linking precursors. A further preferred embodiment, wherein at least 50%, more preferably at least 75%, even more preferably at least 90%, still more preferably at least 95% of the cross-linking bonds are provided by the feather added to the product, accordingly, the amount of the synthetic cross-linking precursor used in the product is at most 50 wt%, preferably at most 25 wt%, even more preferably at most 10 wt%, still more preferably at most 5 wt% or at most 1 wt% of the amount of the synthetic cross-linking precursor required for the desired extent of the cross-linking resulting in the desired hardness. This desired hardness is the hardness of a polyurethane (reference polyurethane) which is made without feather but which is made with cross- linking precursor and from the same other precursors (which are diisocyanate and diol type precursors) and where the hardness of this polyurethane is the same as the product's hardness. With other words: this reference polyurethane has no feather but it is made from the diisocyanate and the diol type precursors of the product and the desired hardness is set by the amount of the synthetic cross-linking precursor. Obviously, this reference polyurethane contains much more synthetic cross-linking precursor (resulting in grid-type structure) than the proposed feather-based product since, in the latter case, dominant part of the cross-linking bonds (see above) are provided by the feather added to the product.

As it was discussed above, it cannot be excluded that the diisocyanate component contains a small amount of cross-linking agent of short length. Accordingly, the phrase of "substantially free of cross-linking agent" should be interpreted in line with the above discussions, i.e. it may allow that a smaller part of the cross-linking bonds can be made by synthetic cross-linking precursor, where, simultaneously, the bigger part of the cross-linking bonds are ensured by the applied feather. Here we emphasize that feather-based cross- linking results in a much more complex 3D structure which is fixed by various covalent bonds formed between the keratin protein of the feather and the isothiocyanate functional groups.

As another approach to define the amount of cross-linking precursor, the amount of the synthetic cross- linking precursor (typically synthetic cross-linking isocyanate compound) can be related to the total amount of all isocyanate compounds (precursors) used for the polymerization. In this approach the preferred embodiment is that wherein the amount of the synthetic cross-linking precursor is at most 40 wt%, more preferably at most 30 wt%, even more preferably at most 20 wt%, even more preferably at most 10 wt%, and still more preferably at most 5 wt% or lwt% or 0.1 wt% of the total amount of all isocyanate compounds being in the product [where the less values, as (at most) 10 wt%, 5%, 1 % and 0.1 wt%are more preferred]. We also note here that the most preferred embodiment is the product free from synthetic cross-linking precursor, at least from separately added synthetic cross-linking precursor, but definitely lacking synthetic multidirectional networking agent (synthetic multidirectional 3D cross-linking precursor).

The obtained product possesses excellent heat insulation property (its heat insulating ability is within the range of the best quality building insulants) and has very good mechanical properties (compressive, strech and tensile strength), and further it is a much better sound insulant, preferably step sound and airborne sound insulant, than the corresponding soft polyurethane without feather [e.g. Elastopor H-1221 (BASF)]. Additionally, the utilization of the feather surprisingly improves the fire resistance of the obtained polyurethane, as the obtained composite is more fire resistant than the corresponding soft polyurethane [e.g. Elastopor H-1221 (BASF)] or the feather alone.

A building product having arbitrary size can be formed from the material according to the present invention depending on the used mould. A typical product is the sheet-like product, which can be an interior step resistant floor/tread surface insulation panel, wherein the width and the length is variable in a relatively narrow range (typically in the range of 30-90 cm, preferably in the range of 40-80 cm), while the thickness is typically 25-75 mm, preferably 45-55 mm). When the aim is the production of insulation wall panel (having good airborne sound insulation property), then the preferred range for width and the length is 30-70 cm, preferably 45-55 cm (and the thickness is as above). Auxiliaries

The product according to the invention can comprise, besides the foregoing main components, one or more auxiliaries selected from the following groups.

Flame retardant (fire retardant) materials, such as tris(2-chloro-l-methylethyl)-phosphate, monoammonium phosphate, ammonium sulphate, borax. Borax, at the same time, is an antimicrobial, antifungal and anti -rodent material; however, other excipient having such an effect also can be used.

Examples of the foaming agents, which can be used for the modification of the product density, are CFC (chlorofluorocarbon) compounds, HCFS (hydrogen chlorofluorocarbon) compounds, pentane and methyl formate.

The heat generation during the polyurethane production enables to use foaming additives that evaporate or gas due to the heat generation (e.g. pentane). As, however, the goal for the product is the step resistance, preferably it comprises no or only a small amount of the foaming agent.

Typically, the polyurethanes also comprise a catalyst that provides the suitable rate of the reaction. Examples of these are tin(II) salts or dialkyltin(II) salts of carboxylic acids, amine type compounds, such as benzyldimethylamine, dimethylethanolamine (DMEA), dimethylaminopropylamine (DMAPA) etc., wherein benzyldimethylamine is preferred.

Other excipient conventional in the building industry, such as a colorant, can be used.

We note that such a product according to the invention can be considered suitable, which only consists of a) polyurethane precursors, feather (whole or ground or a mixture thereof), catalyst, flame retardant, foaming agent and colorant;

b) polyurethane precursors, feather (whole or ground or a mixture thereof), catalyst, flame retardant and foaming agent;

c) polyurethane precursors, feather (whole or ground or a mixture thereof), catalyst and flame retardant;

d) polyurethane precursors, feather (whole or ground or a mixture thereof) and catalyst;

e) polyurethane precursors, feather (whole or ground or a mixture thereof) and flame retardant;

f) polyurethane precursors and feather (whole or ground or a mixture thereof).

Production of the polyurethane -based building material according to the invention

In the closest solutions known from the prior art documents - among which we discuss that disclosed in US 2005/0205226A1 below - the precursors mixed with feather are the precursors usually used in the polyurethane production, including the usual polyisocyanate type cross-linking precursors to provide the hardness (see the polyol-polyisocyanate precursors mentioned in the middle of the paragraph [0014]). In the known method polyurethane precursors and feather are mixed in one step, and then the polymerization reaction is started by addition of a catalyst (we note that in the practice the catalyst is typically added together with one of the precursors).

Here we mention that in the above-mentioned Wrzesniewska-Tosik K. et al. article the preparation process is not detailed since it is declared there as a secret know-how knowledge (see in the middle column of page 120). Moreover, the preparation conditions apparently differ from that of typical polyurethane synthesis.

In contrast to the known methods, in the method according to the invention precursors used for the soft polyurethane production are used for the hard polyurethane production, however, not synthetic isocyanate type cross-linking precursor (polyisocyanate), but feather is used for hardening the polyurethane. Surprisingly, by using this method the synthetic cross-linking precursor can be replaced in the hard polyurethane production. We explain this phenomenon by that the proteins forming the main mass of the feather comprise amino acids having numerous such amino-, hydro xyl- and carboxylic groups, which are capable of reacting with isocyanate group, and the spatial multidirectional cross-linking of the linear polymer chains thereby being achieved.

It should be stated that in US 2005/0205226A1 and in the above-mentioned Wrzesniewska-Tosik K. et al. article there is no hint that the amount of the usual synthetic cross-linking precursor can be reduced by the utilization of feather, therefore, it is definitely not referred to that it can be even fully replaced with feather.

As we noted, the feather improves the fire resistance of the product even alone, however, by addition of usual flame retardant materials (e.g. monoammonium phosphate or borax, which is, at the same time, an antimicrobial, antifungal and anti-rodent material) the fire resistance can be enhanced and can be set in a range consistent with the application standard. The coefficients of the thermal conduction of the product are within the range of the best quality insulants, besides the appropriate flexibility and abrasion resistance.

The density and other properties of the product can be also modified with the foaming agents described above (if it is used), wherein 1, 1,1,3,3-pentafluorobutane is preferred. It should be noted that the bulk density of the product produced with ground feather is remarkably higher than the panels produced with whole feather, which preferably increases the load capacity. Typically, polymerization catalyst, preferably benzyldimethylamine can be used in the production to increase the rate of the reaction, which is an exothermal procedure accompanied with heat generation. The catalyst is expediently added (e.g. pre -mixed) together with one of the precursors. The heat generation enables the utilization of such foaming additives, which evaporate or gas due to the heat generation (e.g. pentane). It should be noted that strong foaming is reasonable to use only in that case, if the mechanical strength of the polyurethane panel can be provided by other material.

In our certain tests two precursors of the soft polyurethane [in our exemplified tests the A) and B) components of Elastopor H-1221 (BASF)] were mixed, and subsequently the whole or ground feather was added. Here we underline that if we start out only from the above-mentioned A) and B) component of Elastopor H-1221 (BASF) without added further cross-linking precursor, then a soft polyurethane product is obtained which cannot be used for the purpose of the present invention.

However, when firstly the feather and the precursor having hydroxyl groups [the A) component of Elastopor H-1221 (BASF) which is a diol type precursor] were mixed - optionally together with further auxiliaries -, and subsequently the diisocyanate type precursor [e.g. the B) component of Elastopor H-1221 (BASF)] was added, then a foaming controllable by the amount of the feather was achieved, however, in this case the amount of the mixable feather was less. In other words, the product density (foaminess) also can be controlled by the amount of the feather. EXAMPLES

I. Production examples

IA) Preparation of polyurethane by the use of ground feather Example 1

A panel having size of 800*400*50 mm was produced where the material requirements were as follows:

a) The used polymerization A) (PUR A) component is 0.65 kg of A) component of the commercially available Elastopor H- 1221/43 (BASF, ID No. 30243976/SDS_GEN_HU/HU) product, the composition of which is as follows based on the product catalogue:

Polyol: polypropylene glycol.

Content (W/W): < 25 %.

CAS No.: 25322-69-4.

Catalyst: benzyldimethylamine.

Content (W/W): >= 1 % - < 3 %. CAS No.: 103-83-3.

EU No.: 203-149-1.

INDEX No.: 612-074-00-7.

Flame retardant: tris(2-chloro- 1 -methylethyl)-phosphate.

Content (W/W): >= 3 % - < 20 %.

CAS No.: 13674-84-5.

EU No.: 237-158-7, 911-815-4.

REACH Registry No.:01-2119486772-26.

Propellant (foaming agent): 1,1, 1,3,3-pentafluorobutane.

Content (W/W): >= 4 % - <= 9 %.

CAS No.: 406-58-6. b) The used polymerization B) component (PUR B) is 0.75 kg of B) component of the commercially available Elastopor H-1221/43 (BASF) product, which is diphenylmethane diisocyanate (MDI) [IsoPMDI 92140].

c) Ground poultry feather: 1.1 kg (blend of poultry feathers originated from slaughterhouse, the main mass of which is formed by chicken feather, the grinding was carried out with knife grinding equipment (Wanner 20.20), the size of the ground feather pieces is about 2-10 mm).

d) Borax [(di) sodium tetraborate]: 0.31 kg.

e) Monoammonium phosphate (MAP): 0.31 kg.

The mixing of the base materials is preformed in the following order and manner:

Pentane is added to and mixed with the component PUR A at an ambient temperature under atmospheric pressure in an 80 1 mixer, and borax and monoammonium phosphate (MAP) is added to the obtained mixture, and the mixture is stirred to homogeneity. The component B is mixed in the obtained mixture, and it is homogenized, and subsequently the total amount of the ground feather is added, and then the obtained mixture is stirred evenly.

The obtained mixture is poured into a mould. After the polymerization has been completed the product is removed from the mould and cut to size. IB) Preparation of polyurethane by the use of whole feather

Example 2

a) The used polymerization A) (PUR A) component is 0.58 kg of A) component of the commercially available Elastopor H-1221/43 (BASF, ID No. 30243976/SDS_GEN_HU/HU) product, the composition of which is as follows based on the product catalogue:

Polyol: polypropylene glycol. Content (W/W): < 25 %.

CAS No.: 25322-69-4.

Catalyst: benzyldimethylamine.

Content (W/W): >= 1 % - < 3 %.

CAS No.: 103-83-3.

EU No.: 203-149-1.

INDEX No.: 612-074-00-7. Flame retardant: tris(2-chloro- 1 -methylethyl)-phosphate.

Content (W/W): >= 3 % - < 20 %.

CAS No.: 13674-84-5.

EU No.: 237-158-7, 911-815-4.

REACH Registry No.:01-2119486772-26.

Propellant (foaming agent): 1,1,1,3,3-pentafluorobutane.

Content (W/W): >= 4 % - <= 9 %.

CAS No.: 406-58-6. b) The used polymerization B) component (PUR B) is 0.68 kg of B) component of the commercially available Elastopor H-1221/43 (BASF) product, which is diphenylmethane diisocyanate (MDI) [IsoPMDI 92140].

c) Whole poultry feather: 0.75 kg (blend of poultry feathers originated from slaughterhouse, the main mass of which is formed by chicken feather, the length of the whole feathers is about 2-10 cm).

d) Pentane: 50 ml.

e) Borax [(di)sodium tetraborate]: 0.31 kg.

f) Monoammonium phosphate (MAP): 0.31 kg.

Pentane is added to and mixed with the component PUR A at an ambient temperature under atmospheric pressure in an 80 1 mixer, and borax and monoammonium phosphate (MAP) is added to the obtained mixture, and the mixture is stirred to homogeneity. The component B is mixed in the obtained mixture, and it is homogenized, and subsequently the total amount of the whole feather is added, and then the obtained mixture is stirred evenly. The obtained mixture is poured into a mould. After the polymerization has been completed the product is removed from the mould and cut to size.

Example 3

The procedure according to Example 2 was carried out except that pentane was not used.

Example 4

The procedure according to Example 2 is carried out, but with the following differences.

Borax and monoammonium phosphate (MAP) is added to the component PUR A at an ambient temperature under atmospheric pressure in an 80 1 mixer, and the mixture is stirred to homogeneity. The total amount (0.25 kg) of the feather is mixed in the obtained mixture, and then the component B is added to the obtained mixture and it is stirred evenly. The obtained mixture is poured into a mould. After the polymerization has been completed the product is removed from the mould and cut to size.

IIA. The physical/mechanical properties of the obtained product prepared by the use of ground feather (product of Example 1) A) HEAT INSULATION PROPERTIES

Coefficients of the thermal resistance and thermal transmittance were calculated in accordance with the standard EN ISO 6946:2008. The products were tested in accordance with the standard MSZ EN 12667:2001.

The testing of the test specimens was carried out after a conditioning at laboratory climate. The date of the test: from April 20 to April 25, 2016.

Condition of air in the laboratory: 20-23 °C, cp = 45-52.

Test equipment: HOLOMET IX Rapid-k, RK-80a.

Single specimen, horizontal, asymmetric arrangement, vertical downward heat transfer. Surface of the equipment: 0.3 m x 0.3 m.

Measuring surface: 0.1 m x 0.1 m

Measurement uncertainty: < 5 %.

Calibration date: April 19, 2016.

Test identifier: 16041950.CAL

Validity: May 18, 2016.

Identifier of the reference specimen: CAL 2-09

Material of the reference specimen: EPS (expanded polystyrene)

Thermal resistance of the reference specimen: R = 1.27 m²K / W

Weight change of the specimen during the measurement preparation and the measurement: 0.

Table 1

The specimens in the table are the products produced according to Example 1.

The results demonstrate that the product according to the invention has excellent heat insulation properties.

B) SOUND INSULATION PROPERTIES

The step sound insulation tests were carried out in accordance with the standard MSZ EN ISO 10140- 3:2011. The determination of the weighted sound insulation properties was carried out in accordance with the standard MSZ EN ISO 717-2:2013.

The test equipments were as follows:

- Briiel&Kjaer PULSE 3160A042 LAN -XI measuring system

- Briiel&Kjaer 4190 microphone

- Briiel&Kjaer 2669 microphone preamplifier

- RION NC73 acoustic calibrator

- DS600 performance amplifier

- TOA F-505G sound source

- Briiel&Kjaer 3204 standard step sound generator

The step sound insulation values of the product according to Example 1 are as follows:

Based on the tests it can be stated that the feather panel according to the invention in the floated floor board provides better step sound insulation that the structure produced with similar construction, but with the conventional PUR foam.

C) OTHER MECHANICAL PROPERTIES

The properties according to Table 2 were also tested by the methods specified therein (the designations are the reference designations of the corresponding Hungarian standards) and by the devices according to Table 3.

Table 2: Test methods

Test Test method T (°C) RH (%)

Thickness MSZ EN 823:2013 24 50

Bulk density MSZ EN 1602:2013 24 50

Compressive stress at 10% deformation MSZ EN 826:2013 24 50 Tensile strength perpendicular to surface MSZ EN 1607:2013 25 48

Bending strength MSZ EN 12089:2013 24 50

Table 3: Data of the test devices

RESULTS

a) Thickness and bulk density

Table 4

The size of the tested samples: 200x200x50 mm. Test date: September 7 and September 13, 2016. The tested samples are the products produced according to Example 1. b) Compressive stress at 10% deformation

Table 5

The size of the tested samples: 200x200x50 m; test rate: 5 mm/min. Test date: September 7 and September 13, 2016. The tested samples are the products produced according to Example 1. c) Bending strength

Table 6

The size of the tested samples: 300x150x50 mm; test rate: 10 mm/min. Test date: September 7 and September 13, 2016. The tested samples are the products produced according to Example 1. The results demonstrate that the products according to the invention have such physical and mechanical properties, which excellently meet the requirements of building industry and provide a suitable applicability and constructability, for use particularly in exterior frontage insulation systems as heat and sound insulation layer.

D) FLAME RETARD ANCY

Based on the performed tests the wall comprising the sample made from the material according to Example 1 meets the requirements of the fire safety class B - s2, dO according to the standard MSZ EN 13501- 1 :2007+A1 :2010.

Explanation of the fire safety indicators

Letter - fire behaviour, it provides information on the rate of the fire development and the energy derived from the combustion of the product.

sX - smoke production, it provides information on the amount and the speed of the smoke forming during the combustion.

dY - flaming droplets, it indicates whether such melt is formed or such burning part of material left from the sample, which facilitates the spreading of the fire.

Meaning of the indicators found in the case of the tested samples

a) Fire safety classes: A1>A2>B>C>D>E>F. The fire safety class B is the highest class achievable among materials comprising organic substances at such a high amount.

b) sl>s2>s3: in the case of s2 there is smoke development, typically it should not be located on the escape route according to OTSZ (National Fire Safety Regulation).

c) d0>dl>d2: in the case of dO there are no flaming droplets.

Accordingly, the product according to Example 1 is recommended for use in building industry based on its flame retardancy.

IIB. The physical/mechanical properties of the obtained product prepared by the use of whole feather (product of Example 2)

A) HEAT INSULATION PROPERTIES

Condition of air in the laboratory: 20-23 °C, cp = 45-52.

Test equipment: HOLOMETRIX Rapid-k, RK-80a.

Measuring surface: 0.1 m x 0.1 m

Measurement uncertainty: < 5 %. Calibration date: April 19, 2016.

Test identifier: 16041950.CAL

Validity: May 18, 2016.

Identifier of the reference specimen: CAL 2-09

Material of the reference specimen: EPS (expanded polystyrene)

Thermal resistance of the reference specimen: R = 1.27 m²K / W

Table 1

The specimens in the table are the products produced according to Example 2.

B) SOUND INSULATION PROPERTIES

The airborne sound insulation tests were carried out in accordance with the standard MSZ EN ISO 10140-2:2011. The determination of the weighted sound insulation properties was carried out in accordance with the standard MSZ EN ISO 717-1 :2013.

The sound insulation requirements for bounding constructions are regulated by the standard MSZ 15601 :2007 in Hungary.

The test equipments were as follows:

- Briiel&Kjaer PULSE 3160A042 LAN -XI measuring system

- Briiel&Kjaer 4190 microphone

- Briiel&Kjaer 2669 microphone preamplifier

-RION NC73 acoustic calibrator

- DS600 performance amplifier

TOA F-505G sound source.

The airborne sound insulation value of the product according to Example 2 (5 cm of thickness): Rw =

14 dB.

The airborne sound insulation value of the corresponding product produced without feather (5 cm): Rw = 18 dB.

The results demonstrate that the product according to the invention has excellent sound insulation properties. C) OTHER MECHANICAL PROPERTIES

The properties according to Table 2 were also tested by the methods specified therein (the designations are the reference designations of the corresponding Hungarian standards) and by the devices according to

Table 3.

Table 2: Test methods

Table 3: Data of the test devices

RESULTS

a) Thickness and bulk density

Table 4

The size of the tested samples: 200x200 mm. Test date: September 7 and September 13, 2016.

The tested samples are the products produced according to Example 2. b) Compressive stress at 10% deformation

Table 5

The size of the tested samples: 200x200x50 m; test rate: 5 mm/min. Test date: September 7 and September 13, 2016. The tested samples are the products produced according to Example 2. c) Tensile strength perpendicular to surface of the frontage panel with whole feather

Table 6

The size of the tested samples: 100x100x50 mm; test rate: 10 mm/min. Test date: September 14, 2016.

The tested samples are the products produced according to Example 2. d) Bending strength

Table 7

The size of the tested samples: 300x150x50 mm; test rate: 10 mm/min. Test date: September 7 and September 13, 2016. The tested samples are the products produced according to Example 2.

The results demonstrate that the products according to the invention have such physical and mechanical properties, which excellently meet the requirements of building industry and provide a suitable applicability and constructability, for use particularly in exterior frontage insulation systems as heat and sound insulation layer.

D) FLAME RETARD ANCY

The classification of the flame retardancy of the product of Example 2 is the same like in II/ A, subpoint D. Accordingly, the product according to Example 2 is recommended for use in building industry based on its flame retardancy.

Claims

4. The building product according to any of claims 1 to 3, further comprising one or more auxiliaries selected from the group of flame retardant materials, foaming agents, and polymerization catalysts.

5. The building product according to any of claims 1 to 4, wherein the amount of the feather is 5-70 wt%, preferably 10-50 wt% based on the total weight of the product.

6. The building product according to any of claims 1 to 5, wherein the polyurethane comprises polypropylene glycol applied as diol type precursor.

7. The building product according to any of claims 1 to 6, wherein the polyurethane comprises diphenylmethane diisocyanate applied as diisocyanate type precursor.

8. The building product according to any of claims 1 to 7, which is free from added synthetic cross- linking precursor.

a) diol type precursor of the polyurethane, diisocyanate type precursor of the polyurethane and feather are mixed, optionally together with one or more auxiliary/auxiliaries, without using separately added synthetic cross-linking agent;

b) the obtained mixture is poured into a mould;

c) after polymerization the obtained product is removed from the mould.

11. The building product according to any of claims 1 to 8, the method according to claim 9 and the use according to claim 10, wherein the feather is whole feather.

12. The building product according to any of claims 1 to 8, the method according claim 9 and the use according to claim 10, wherein the feather is ground feather.

13. The building product according to any of claims 1 to 8, the method according claim 9 and the use according to claim 10, wherein the feather is the mixture of whole and ground feather.

14. The building product and the method according to claim 12 or 13, wherein the length of the ground feather pieces is typically about 1-15 mm, preferably about 2-10 mm.