Method of producing viscoelastic polyurethane plasticised foam plastic with open cells

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing viscoelastic polyurethane plasticised foam plastic with open cells produced from renewable material, used in many engineering fields, particularly inside motorcars, in furniture and mattresses or sound insulation. The method involves reaction of a) polyisocyanates with b) a mixture of polyols and c) foaming agents. The mixture of polyols b) consists of bi) compounds with at least two hydrogen atoms which are active with respect to isocyanate groups, and hydroxyl number ranging from 20 to 100 mg KOH/g, bii) a compound with at least two hydrogen atoms which are active with respect to isocyanate groups, and hydroxyl number ranging from 100 to 800 mg KOH/g, and biii) a compound with at least one and a maximum of two hydrogen atoms which are active with respect to isocyanate groups, and hydroxyl number ranging from 100 to 800 mg KOH/g, wherein each of the components bi) and bii) contains at least one compound which contains renewable material or reaction products thereof.

EFFECT: obtaining viscoelastic polyurethane plasticised foam plastic produced from renewable material, having good mechanical properties, very low smell and emissions, and also have prolonged stability, particularly when stored in a warm humid environment.

13 cl, 4 ex, 1 tbl

The invention relates to a method for viscoelastic plasticized polyurethane foams with open cells when using polyether polyols based on renewable resources, in particular castor oil.

Plasticized polyurethane foams are used in many areas of technology, particularly in upholstery or for noise insulation. Obtaining them carried out typically by reacting polyisocyanates with compounds having at least two active hydrogen atom of the isocyanate groups in the presence of foaming agents and, if necessary, in the presence of catalysts and conventional auxiliary substances and/or additives.

Based on environmental reasons, the market requires increasing the number of foams that contain reproducible raw materials. In the manufacture of polyurethane reproducible raw materials may in the future also constitute an alternative to original products petrochemical way. Foams are mainly through the use of natural compounds containing hydroxyl groups, or polyols, which are produced by joining these compounds alkalisation.

Examples of compounds obtained from the reproducing raw materials are castor oil, polyhydroxyamide acid, castor acid, MoE is oficerowie hydroxyl groups of the oil, such as, for example, grape seed, oil of black cumin oil, pumpkin seed oil from the seeds of borage, soybean oil, oil of wheat germ, canola oil, sunflower oil, peanut oil, oil of apricot pits, oil pistachio seed oil, almond oil, olive oil, oil of macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, hemp oil, kernel of walnut, hazel, evening primrose oil, rosehip oil, hemp oil, Thistle oil (Thistle), walnut oil, modified hydroxyl groups of fatty acids and esters of fatty acids based on myristoleic acid, palmitoleic acid, butyric acid, vaccinology acid, petroselinic acid, gadolinio acid, erucic acid, Neronova acid, linoleic acid and linolenic acid, stearidonic acid, arachidonic acid, timnodonic acid, clupanodons acid, cervanova acid. The greatest technical importance castor oil and gidrirovannoe castor oil.

The interaction of compounds of reproducing raw acceleratedly may be conventional and known manner.

From international application WO 00/44813 known to produce polyether alcohols by alkoxysilane of kastorovogo the oil when using polymethylsilane compounds, often also called DMS-catalysts.

From international application WO 04/20497 know the use of polyether alcohols which have been made by joining alkalisation to organic compounds, in particular castor oil, to obtain a plasticized polyurethane foams with reduced dimming (Fogging). Such foams are used, in particular, in the inner workings of cars.

A special class of materials among plasticized polyurethane foams are viscoelastic foams.

In the framework of the present invention called viscoelastic foam in the case, when he is in the process of testing the torsional strength in accordance with DIN 53445 has a coefficient of losses amounting to more than about 0.15, preferably more than 0.2. Further, it is preferable position, when the foams according to the invention exhibit viscoelastic characteristics in a wide temperature range, i.e. from -20°C to +50°C, but at least from 0 to +40°C.

Viscoelastic foam can also be called in when he has a ball rebound resilience, which is measured in accordance with DIN EN ISO 8307 and is less than 30%, and the preferred way, from 2 to 25%, especially preferred way, from 3 to 20%.

the particular preference is given to the fact that the foam according to the present invention meets both the above criteria in terms of loss factor and criteria in terms of elasticity in the rebound.

In the case of viscoelastic foams according to the invention described above coefiicient attenuation talking about the so-called "tired" foams.

Such foams are used, in particular, for insulation, as well as for the manufacture of mattresses or pillows. In these cases, the application is also very important that the foam had good resistance to aging, in particular, when stored in a moist warm atmosphere. Further, the cleavage of urethane linkages, which can lead to the formation of aromatic amines, should clearly be suppressed.

Therefore, the present invention is to provide a viscoelastic plasticized polyurethane foams that are made on the basis of reproducing materials have good mechanical properties, a slight odor and low emissions, but also have good long-term stability, in particular, when stored in a moist warm atmosphere.

In an unexpected way this problem was solved when receiving plasticized polyurethane foam used is of at least two polyol on the basis of renewable raw materials with different hydroxyl numbers.

Thus, an object of the present invention is a method for viscoelastic plasticized polyurethane foams on the basis of renewable raw materials by interaction

a) polyisocyanates with

b) compounds having active hydrogen atoms with respect to isocyanate groups, which contain:

bi) compounds with at least two active hydrogen atoms with respect to isocyanate groups, and a hydroxyl number constituting from 20 to 100 mg KOH/g, and

bii) compounds with at least two active hydrogen atoms with respect to isocyanate groups and hydroxyl number, comprising from 100 to 800 mg KOH/g, and

biii) connection at least one, maximum two active hydrogen atoms with respect to isocyanate groups and hydroxyl number, comprising from 100 to 800 mg KOH/g, and

c) foaming agents,

characterized in that the components (bi) and (bii) contain at least one compound containing reproducible raw materials or products of the interaction.

The object of the application are then obtained in accordance with this method viscoelastic plasticized polyurethane foams.

Further, the object of the invention is the use of viscoelastic plasticized polyurethane foams with open ACE the kami in the manufacture of furniture and mattresses for interior decoration of the car, in particular for rear fill car mats.

The share of renewable resources in the foam is the preferred way, at least 20, with particular preference given to the value above 30, and in particular above 40 wt.%.

The components (bi) and (bii) can be composed exclusively from compounds of renewable resources.

A preferred way, the component (b) is 5 to 45 wt.%, in particular 10-25 wt.%, from bi)30-90 wt.%, in particular 50-80 wt.% from bii) and 5-40 wt.%, in particular 10-30 wt.% from bii), and the percentage data relate to amounts that are bi), bii) and biii).

As compounds of renewable resources used, in particular, the above-described reproduced reproduced or modified raw materials such as oils, fatty acids and esters of fatty acids of the series that have at least average HE is a functionality equal to from 2 to 16, mostly from 2 to 8, and a very special advantage have values from 2 to 4.

Connection from renewable raw materials are selected, the preferred way, from the group consisting of castor oil, polyhydroxy acid, castor acid modified hydroxyl groups of the oil, such as grape seed, oil of black cumin oil, pumpkin seed oil from the seeds of borage, soy is aslo, the oil of wheat germ, canola oil, sunflower oil, peanut oil, oil of apricot pits, oil pistachio seed oil, almond oil, olive oil, oil of macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, hemp oil, kernel of walnut, hazel, evening primrose oil, rosehip oil, hemp oil, Thistle oil (Thistle), walnut oil, modified with hydroxyl groups of fatty acids and esters of fatty acids based on myristoleic acid, palmitoleic acid, butyric acid, vaccinology acid, petroselinic acid, gadolinio acid, erucic acid, Neronova acid, linoleic acid and linolenic acid, stearidonic acid, arachidonic acid, timnodonic acid, clupanodons acid, cervanova acid.

Products of compounds chemically modified with hydroxyl groups, which are represented in the trade, are, for example, Merginat® PV 204, 206 and 235, or polyhydroxyalkane acid PHF 110 firm "Hamburger Gettheme".

The preferred way, as a connection from renewable raw materials use castor oil and/or gidrirovannoe castor oil.

The interaction of compounds from renewable resources with acceleratedly can be normal and Investlesprom mostly original compound is mixed with a catalyst, and this mixture is subjected to interaction with acceleratedly. Join alkalisation carried out in most cases in the conventional conditions at temperatures lying in the range from 60 to 180°C., preference is also given to the temperature range from 90 to 140°C., in particular the temperature interval from 100 to 130°C. and at a pressure whose values lie in the range from 0 to 20 bar, preference is also given range pressure 0 to 10 bar and in particular, the interval of pressures from 0 to 5 bar. As alkalisation use, the preferred way, ethylene oxide, propylene oxide or any mixture of these compounds.

As catalysts are used, preferably, the basic compound, with the greatest technical importance potassium hydroxide. In addition, polymitarcyidae connection, often referred to as DMC catalysts are used as catalysts, as, for example, described in European patents EP 654302, EP 862947, international applications WO 99/16775, WO 00/74845, WO 00/74843 and WO 00/4844.

As alkalisation can find the use of all known alkalinity, such as ethylene oxide, propylene oxide, butylenes, stimulated. In particular, as alkalisation use ethylene oxide, propylene oxide and mixtures of these compounds.

From n the German patent DE 10240186 know, what polymitarcyidae connection, also frequently referred to as DMC catalysts, are particularly suitable for alkoxysilane renewable resources, such as castor oil. These resultant polyols are preferred manner, the content of cyclic esters of fatty acids of a number equal to a maximum of 10 frequent. per million, and therefore are distinguished by their very low emission characteristics.

Connection bi) have a preferred way, a hydroxyl number of 20 to 100 mg/KOH with a viscosity of whose values are in the range from 400 to 6000 mpuas · sec. The preferred use of the find politicaly on the basis of castor oil with a hydroxyl number lying in the interval from 30 to 80, and the preferred range from 45 to 60 mg KOH/g. They have a preferred way, the content of primary hydroxyl groups of less than 10, the preferred manner less than 5 wt.%, relative to the weight of polyetherpolyols. In particular, the accession of alkalisation is using DMC catalysis.

Connection bii) have a preferred way, a hydroxyl number of 100 to 800 mg/KOH. As compounds from renewable resources are used, in particular, described above, reproduced or modified reproducible raw materials, such as oil, fatty acids and esters of fatty acids are presented. If necessary, they can be subjected to interaction with acceleratedly, such as ethylene oxide, propylene oxide or any mixture of these compounds using suitable catalysts. As connection bii) is particularly preferred use of castor oil.

The components bi) and bii) may have, in addition to the connection of renewable resources, if necessary, and other polyols, in particular polyether alcohols, which can be obtained in accordance with known methods, mainly by catalytic joining alkalisation, in particular of ethylene oxide and/or propylene oxide, to the H-functional initiator substances, or by condensation of tetrahydrofuran. As H-functional initiator substances are used, in particular, multi-functional alcohols and/or amines. The preferred application find water, diatomic alcohols, such as ethylene glycol, propylene glycol or butanediol, trivalent alcohols such as glycerin or trimethylolpropane, as well as polyhydric alcohols such as pentaerythritol, sugar alcohols, for example sucrose, glucose or sorbitol. The used, the preferred way amines are aliphatic amines with carbon atoms up to 10, for example, Ethylenediamine, diet lotrimin, Propylenediamine, and aminoalcohols, such as ethanolamine or diethanolamine. As alkalisation use, the preferred manner, the ethylene oxide and/or propylene oxide, with polyether alcohols, which are used when receiving plasticized polyurethane foams, are very often at the end of the chain ethylenoxide block. As catalysts when attaching alkalisation used are, in particular, the main connection, however, the potassium hydroxide is the most technically preferable. If the content of unsaturated components in the polyester alcohols should be negligible, as catalysts for these polyether alcohols can also be used DMC-catalysts.

For certain applications, in particular for increasing the hardness of plasticized polyurethane foams, can be used as a Supplement also called polyols, polymer-modified. Such polyols can be, for example, obtained by passing in the correct position, i.e. in situ polymerization of monomers, which are unsaturated in terms of ethylene, are preferred manner, the styrene and/or Acrylonitrile in the polyester alcohols. To the polyester alcohols, modified polymers, Tsatsa also polyester polyols, containing dispersion polycarbamide that the preferred way, is produced by the interaction of amines with isocyanates in the polyols.

As connection biii) suitable also monooly and diols with the number of hydroxyl groups is from 100 to 800 mgKOH/g a Special advantage is the use of polyalkylene glycols, benzyl alcohol, monospitovo C4-C18, oxopentanoate C8-C18, such as Lutensol®. A.N, AO, AR, AT, F, ON, TO, XL, XP, AR-marks of BASF AG. A very special way apply polypropyleneoxide, such as Lupranol 1000, 1100 and 1200, and monooly, such as Lutensol® A4N, A03 ON 30, ON 40, t, T03, 30 HA, HA 40, XP-30, XP-40, XL 40 and benzyl alcohol.

Getting viscoelastic plasticized polyurethane foams in accordance with the invention can be carried out using conventional and known methods.

About starting compounds used in the method according to the invention, individually, we can say the following

As polyisocyanates a) in the method according to the invention are used all isocyanates having two or more isocyanate groups in the molecule. This can be used as aliphatic isocyanates, such as hexamethylene diisocyanate (HDI)and isotropy diisocyanate (IPDI), or preferred way, aromatic diisocyanates, such as toluidinovi diisocyanate (TD), diphenylmethane diisocyanate (MDI) or a mixture of diphenylmethane diisocyanate and polymethylene-Polyphenylene polyisocyanates (crude/crude MDI), preference is given to TDI and MDI, and particularly preferred is a TDI. And a very special advantage is a mixture of 80 wt.% 2,4 - and 20 wt.% 2,6-toluylene diisocyanate. It is also possible to use isocyanates which have been modified by embedding urethane, uretdione, isocyanurate, allophanate, uretonimine and other groups are so-called modified isocyanates. Preferred prepolymers are MDI-prepolymers with an NCO content ranging from 20 to 35%, or a mixture thereof with polyethylene-Polyphenylene the polyisocyanates (crude MDI).

Used in accordance with the invention, the polyether alcohols bi), bii) and biii) can be used as such or in combination with other compounds having at least two active hydrogen atoms with respect to isocyanate groups.

As compounds with at least two active hydrogen atoms (b), which can be used together with the polyether alcohols bi), bii) and biii), which are in this case used in accordance with the invention, are taken into account, in particular, polyether alcohols and p is impactfully way polyether alcohols with a functionality equal to 2-16, in particular 2 to 8, the preferred way of 2-4 and an average molecular weight Mw in the range from 400 to 20 000 g/mol, preferably from 1000 to 80000 g/mol.

To compounds having at least two active hydrogen atoms (b)are the means of chain elongation and substance, forming a cross connection in the connection. As a means of lengthening the chain and cross-linking substances are used, the preferred way, 2 - and 3-functional alcohols with a molecular weight in the range from 62 to 800 g/mol, in particular in the range from 60 to 200 g/mol. Examples are ethylene glycol, propylene glycol, diethylene glycol. triethylene glycol, dipropyleneglycol, tripropyleneglycol, low molecular weight polypropylene and polyethylene oxides, such as, for example, Lupranol® 1200, butandiol-1,4, glycerin or trimethylolpropane. As cross-linking agents can also be used diamines, sorbitol, glycerin, alkanolamine. If we use the means of lengthening of the chain and a crosslinking agent, the amount is the preferred way to 5 wt.% with respect to the weight of compounds having at least two active hydrogen atoms.

The method according to the invention are provided mostly in the presence of activators, for example tertiary amines, reorganizes metal compounds, in particular compounds of tin. As compounds of tin are used, the preferred way of divalent salts of fatty acids, as, for example, diktat tin and tin-organic compounds, such as, for example, disutility dilaurate tin.

As the foaming agent (C), which is used to obtain a plasticized polyurethane foams are used, the preferred way, the water which reacts with isocyanate groups with the release in the form of free carbon dioxide. Advantage is water in an amount of from 0.5 to 6 wt.%, as a special advantage is water in an amount of from 1.5 to 5.0 wt.%, in relation to the weight of components b). Together with water or instead of water can also be used physically active foaming agents such as carbon dioxide, for example, n-, ISO - or cyclopentane, cyclohexane, or halogenated hydrocarbons, such as Tetrafluoroethane, pentafluoropropane, Heptafluoropropane, pentafluorobutane, hexaferrite or dichloronaphthalene. The number of physical foaming agents is preferred in the range between 1 and 15 wt.%, in particular from 1 to 10%, and the amount of water is the preferred way, in the interval between 0.5 and 10 wt.%, in particular from 1 to 5 wt.%. Advantage has carbon dioxide as a physical agent wspanialy is, as a special advantage is carbon dioxide in combination with water.

To obtain a plasticized polyurethane foams in accordance with the invention can as usual be used as stabilizers and excipients and additives.

As for the stabilizer, then we can talk primarily about polyester-siloxanes, preferably, soluble in water polyethylsiloxane. These compounds, in General, are so designed that the long-chain copolymerizate of ethylene and of propylene oxide is associated with polydimethylsiloxane balance. Other foam stabilizers are described in patent applications US - US-A-2834748, 2917480 and US-A-3629308.

The interaction is carried out, if necessary, in the presence of auxiliary substances and additives, such as fillers, regulators acetoarsenite, surface-active compounds and/or fire retardant means. The preferred fire retardant means are liquid fire retardant funds received on the basis of halogen and phosphorus, such as trichloropropane, trichlorethylene and not containing halogen-free flame retardant tools such as Exolit® OP 560 (Clariant International Ltd.).

More information about used original substances, catalysts, auxiliary substances and additives can be found, for example, the R, the Handbook of artificial materials (Kunststoffandbuch), volume 7, section "Polyurethanes", publishing house "Karl-Khan-grain-Verlag", Munich, first edition 1966, second edition 1983 and the third edition 1993

To obtain polyurethanes according to the invention the organic polyisocyanates are subjected to interaction with compounds having at least two active hydrogen atoms, in the presence of these foaming agents and, if necessary, in the presence of catalysts and auxiliaries and/or additives.

Upon receipt of the polyurethanes according to the invention are mixed together isocyanate and an integral part of the polyol, and in most cases in such quantities that the equivalent ratio of isocyanate groups to the sum of the active hydrogen atoms is from 0.7 to 1.25, the preferred way of 0.8-1.2.

Obtaining polyurethane foams is carried out, the preferred way, in accordance with the method "oneshot", for example, using technologies such as high and low pressure. The foams can be produced in open or closed metal molds or by continuous application of the reaction mixture on a moving tape automated lines for receiving the foam blocks.

A special advantage in obtaining molded plastic foams is that the work was carried out in the accordance with the so-called two-way, in the course of which the fabrication and foaming polyol as one and isocyanate components. Mixing parts is preferred manner, at a temperature whose value is in the range from 15 to 90°C., preferably in the range from 20 to 60°C., and a special advantage is the temperature interval from 20°to 35 ° C, after which the resulting mixture is placed in a mold or on a moving tape automated lines. The temperature inside the form is in most cases from 20 to 110°C. and the preferred temperature range is 30 to 60°C, special advantage is the range of temperatures between 35 and 55°C.

Plasticized foam blocks can be manufactured on automatic plants operating in batch or continuous mode, as, for example, by the methods 'Planiblock', 'Maxfoam', 'Draka-Petzetakis'.

Plasticized polyurethane foams, for the manufacture of which use polyether polyols from renewable raw material, which is produced by DMC catalysis, compared to foods in which the polyether polyols used in accordance with the invention, were manufactured from renewable raw materials using basic catalysts, different smell, which became significantly less Fogging-values, which are also significantly is anise, significantly reduced cracking, and improved value of the residual compressive deformation before and after aging. Further, the foams produced in accordance with the invention possess a high degree of openness of the cells, for example, that manifests itself in increased breathability.

The residual deformation of the compression block plasticized polyurethane foams is a maximum of 10%after aging in accordance with DIN EN ISO 2440 maximum of 20%.

The permeability of viscoelastic plasticized polyurethane foams obtained according to the invention, is the preferred way, at least 10 DM³/min, particularly preferred more than 30 and, in particular, more than 50 DM³/min

Viscoelastic plasticized polyurethane foams have very good resistance to ageing, in particular, and also in conditions when simultaneously apply heat and moisture. They are hydrophobic and resistant to swelling. The proportion of aromatic amines, in particular 2,4 and 2,6-tolualdehyde or MDA in the foam, less than 1 part per million and not increased even after long term storage.

The plasticized polyurethane foams in accordance with the invention is carried out, the preferred way, in the salons of the car is biles, as well as in furniture and mattresses.

The invention is illustrated in more detail by the following examples.

Getting viscoelastic plasticized polyurethane foams with open cells

Examples 1-4

Original products that are listed in the table were used in the interaction in the proportions shown in the table.

All components except the isocyanate were first United by intensive mixing with the formation of a single polyol as one component. After that, in the conditions of mixing said isocyanate, and the reaction mixture is poured into the open, where it turned into a polyurethane foam. The characteristic values were obtained frothy layers in the table.

In accordance with these regulations, instructions, and control tests identified the following characteristic values:

The definition of the 'Wet-Compression-Set' was carried out in accordance with the Instructions to perform work U10 AA-131-041 from 06.02.02.

With calipers or measuring device of the contact type determines the height of the pre-marked locations of the test foam specimen is, having dimensions of 50 mm × 50 mm × 25 mm, then the samples are placed between two compression plates, and using a remote element size 7.5 mm, with clamping device squeeze together until the desired height.

Maturing in a climatic Cabinet at 50°C and a relative humidity equal to 95%, begins immediately after clamping. After 22 hours the subjects foam samples in a short period of time then removed from the clamping device and temporarily for 30 minutes are placed on the surface with low heating power, namely on the tray, to relieve internal stresses when in normal climatic conditions. Following this, using the same measurement tools to determine the residual height of the marked location.

Parameter 'Wet-Compression-Set' refers to deformation and is calculated as below:

Wet-Compression-Set=h_o-h_r*100/(h_o7.5 mm), %,

where h_o- the initial height, mm;

h_rresidual height of the specimen, mm

1. The method of obtaining the viscoelastic plasticized polyurethane foams with open cells on the basis of renewable resources through collaboration
a) polyisocyanates with
b) a mixture of polyols consisting of
bi) compounds with at least two hydrogen atoms active towards isocyanate groups, and a hydroxyl number constituting from 20 to 100 mg KOH/g, '
and
bii) compounds with at least two hydrogen atoms active towards isocyanate groups and hydroxyl number, comprising from 100 to 800 mg KOH/g, '
and
biii) compounds with at least one and a maximum of two hydrogen atoms active towards isocyanate groups and hydroxyl number, comprising from 100 to 800 mg KOH/g, '
c) and foaming agents,
characterized in that each of the components bi) and bii) contains at least one compound containing renewable raw materials or products of its interaction.

2. The method according to claim 1, characterized in that component b) is 5 to 45 wt.%, from bi)30-90 wt.%, from bii) and 5-40 wt.%, from biii), in each case relative to the sum of the components bi), bii) and biii).

3. The method according to claim 1, characterized in that as component bi) use the interaction products of castor oil with acceleratedly.

4. The method according to claim 1, characterized in that as component bii) use castor oil.

5. The method according to claim 1, characterized in that component b) is 10-25 wt.%, from bi), 50-80 wt.%, from bii) and 10-30 wt.%, from biii), in each case relative to the sum of the components bi), bii) and biii).

6. The method according to claim 1, characterized in that as component bi) using the polyether polyols obtained by the addition of alkalisation to compounds from renewable raw materials using DMC catalysts, the content of cyclic esters of fatty acids of the series constituting a maximum of 10 parts per million

7. The method according to claim 1, characterized in that the connection quality biii) use monooly and/or diols having a number of hydroxyl groups of from 100 to 800 mg KOH/g

8. The method according to claim 1, characterized in that as MDI preferably use a mixture of 80 wt.% 2,4-toluylene diisocyanate and 20 wt.% 2,6-toluylene diisocyanate.

9. The method according to claim 1, characterized in that as a blowing agent, preferably water use.

10. The method according to claim 1, characterized in that the permeability of viscoelastic plasticized polyurethane block foams is at least 10 DM³/min

11. The method according to claim 1, characterized in that the residual strain compression plasticized polyurethane block the foams is a maximum of 7%.

12. The method according to claim 1, characterized in that the residual strain compression plasticized polyurethane block foams is maximum after aging in accordance with DIN EN ISO 2440, a maximum of 15%.

13. The method according to claim 1, characterized in that the proportion of renewable raw materials is at least 20 wt.%, with respect to the polyurethane foam.