Polyol as one composition, elastic latexlady polyurethane foam and molded product

 

(57) Abstract:

Describes polyol as one composition containing polyol with stably dispersed therein a polymer and a polyol. Different composition that contains (a) 80-99,5 wt.h. polymer polyol containing primary polyol having a molecular weight in the range from 2500 to 6500, an average nominal functionality of Fn is not less than 2.0 and a primary hydroxyl content of at least 40%, and stably dispersed therein a polymer, and up to a total weight of 100 wt.h.; (b) 0.5 to 20 wt.h. hydrophilic polyol having a molecular weight ranging from 2000 to 5500, the content of ethylene oxide is not less than 40 wt.% and a primary hydroxyl content of at least 50%. Also described elastic latexlady polyurethane foam and the molded product. The technical result - the reduction of the number of the polyols and the ability to use water as the sole blowing agent. 3 S. and 7 C.p. f-crystals, 2 tab.

The present invention relates to polyol as one recipe, suitable for latexotica flexible foams, latecapitalist elastic polyurethane foams obtained from this polyol as one recipe, and molded products containing this pevnymi fields of application are the automotive and aviation industry, finishing facilities and technical products. For example, the entire foam seat top cushion for seats and restraints for back and head, all made of flexible polyurethane foam, are widely used in automobiles and airplanes. Other applications include the use of flexible polyurethane foam as the basis for carpet, foam saddles for motorcycles, gaskets between the car body and Windows, sealing edges of air filters for engines and the insulating layer on automobile parts and engine parts to reduce noise and vibration. It should be noted that each individual case of application imposes compliance requirements to the used elastic foam. Important characteristics in this regard are the density, firmness, elasticity and hydration of the foam, and in order to meet the requirements of each application, these characteristics must be balanced and adjusted. The present invention aims at creating a polyol as one formulation, suitable for the production of flexible foams having latokartano characteristic stress/deformation, i.e. soft start Cam is th elasticity and hardness of the foam.

In the International patent application N W0 95/09886 considered latexotica foams, which are obtained by the interaction of three different polyols, isocyanate having a functionality of from 0.2 to 2.7 and isocyanate index of from 75 to 100, water and auxiliary blowing agent and amine catalyst. Used polyols are (i) the principal amount trilogo polyol having a primary hydroxyl content of 50-80%, the content of ethylene oxide 10-25% and the molecular weight of 3000-6500; (ii) the minimum amount of polymer trilogo polyol having a molecular weight of 3000-6500; and (iii) a very small number trilogo polyol having a primary hydroxyl content of 50-90% and a content of ethylene oxide 40-90%. Should be an advantage in terms of cost perspective, if the number of polyols can be reduced while obtaining a flexible polyurethane foam gives latexlady appearance and characteristics. In addition, the choice of using water as the sole blowing agent, when you can still get latexlady polyurethane foam would be desirable from the point of view of ecology and the effectiveness and efficiency of the method. The present invention, accordingly, is the only blowing agent, while it turns out latexlady foam.

In the description of U.S. patent N 5011908 treated polymer polyol as one composition to obtain a flexible polyurethane foam, which contains the main amount of the high functionality polyol, the minimum number of auxiliary polyalkyleneglycol polyol and stably dispersed polymer. The high functionality polyol, respectively, has an average polyol as one functionality of at least 3, the content of ethylene oxide 8-25% and an equivalent weight of 1000-3000. From consideration, it follows that this high functionality polyol are at least two different polyalkylbenzene polyol, as clearly shown by the working examples. Auxiliary polyalkyloxy polyol, respectively, has an average nominal functionality to 8, the content of ethylene oxide 30-100% and the molecular weight 450-30000 with a clear preference for low molecular weight (450-2000) liquids. Recipe both polyol as one of the components must have an average nominal functionality of not less than a 3.0. Finally, the polymer is present in an amount of from 2 to 50 wt.% in relation to the total weight of the polymer polyol as one of the components and condensation multifunctional glycol or glycolamine and diisocyanate. The preferred polymers are styrene-Acrylonitrile copolymers and styrene-Acrylonitrile-vinylidene copolymers.

Although discussed in the description of U.S. patent N 5011908 elastic polyurethane foam obtained from a polymer polyol as one composition, have good elasticity, used the recipe is relatively complicated, thus, there is a need for a simple recipe. In addition, one of the aims of this patent is the creation of a polymer polyol as one of the compositions for the preparation of elastic polyurethane foam with high elasticity, having a density below 28,8 kg/m3as also clearly shown by the working examples. Finally, in the description of U.S. patent N 5011908 not mention any latexotica appearance or behavior considered elastic foams. The present invention aims at creating a simplified polyol as one recipe that will provide flexible foams, showing excellent elasticity, even at high density, i.e., above 28,8 kg/m3and at the same time showing the above-mentioned latexotica characteristics. More specifically, the present invention aims at the creation of polio is Ristiku stress/deformation, what, therefore, makes these foams very suitable as a cushioning material, which can be used in numerous applications, such fully foam seat top seat cushions and limiters for back and head mentioned above.

It is established that all the above objectives can be achieved by using polyol as one formulation containing a major amount of a polymer polyol and the minimum number of hydrophilic polyol, meeting some of the requirements.

Accordingly, the present invention relates to polyol as one recipe that contains

(a) 80-99,5 mass parts (wt.h), preferably 90-99 wt. including a polymer polyol containing primary polyol having a molecular weight in the range from 2500 to 6500, an average nominal functionality (Fn) is not less than 2.0, a primary hydroxyl content of at least 40% and the polymer is stably dispersed therein; and up to a total weight of 100 wt.h.,

(b) 0.5 to 20 wt. hours, preferably 1-10 wt.h. hydrophilic polyol having a molecular weight ranging from 2000 to 5500, the content of ethylene oxide is not less than 40 wt.% and a primary hydroxyl content not drugoi hand, results in a polyol as one recipe, suitable for latexotica polyurethane foam, is rather unexpected, as these polyols are typically used separately to control the hardness of the polyurethane foam. Namely, it is known that polymeric polyol is used to increase the hardness of the polyurethane, while it is known that hydrophilic polyols are used to reduce the hardness.

It is possible that one or both polyol as one of the component (a) and (b) are a mixture of polyols or dilution of polyols, provided that the average molecular weight and functionality, the primary hydroxyl content and, when ethylene oxide is present, the content of ethylene oxide mixture or dilution falls within the limits required for the relevant component (s) of the formulation of the invention.

In General the polymeric polyol is a dispersion of solid polymer in a liquid polyol. Such systems are well known in the art and are generally obtained by polymerization of one or more monomers with ethylene unsaturation in the presence of a free radical catalyst. Examples of such polymeric polyol as one of the systems and methods for their production are considered, for example, in the descriptions of esults as the dispersed polymer in the polymer polyols instead of polymers based on monomers with ethylene unsaturation.

For the purposes of the present invention uses a special polymer polyol, therefore, in particular, the main polyol must meet certain special requirements. The main polyol used in the component (a), then is a polyol having a molecular weight in the range from 2500 to 6500, an average nominal functionality (Fn) is not less than 2.0 and a primary hydroxyl content of at least 40%. Preferred basic polyols are polyols, having a content of ethylene oxide in the range of 5 to 50 wt.%, preferably from 10 to 30 wt.% and more preferably 10-25 wt.% Established by the special advantage of the use of primary polyols having a molecular weight of from 3000 to 6000, Fn in the range from 2.5 to 6.0, and a primary hydroxyl content in the range from 50 to 100%, more preferably from 70 to 95%, not necessarily with the content of ethylene oxide in the range from 10 to 25%, more preferably 15-20%. Very suitable basic polyols that are commercially available are CARADOL MC 36-03 and CARADOL SA 36-01 (CARADOL - brand).

The polymer dispersed in the main polyol can be, in principle, any known polymer used for this purpose. Thus, according to the career vinylaromatic hydrocarbons, such styrene, -methylstyrene, methylstyrene and various other the alkyl substituted styrene. Among them, the use of styrene is preferred. Vinylaromatic monomer may be used alone or in combination with other monomers with ethylene unsaturation, such as Acrylonitrile, Methacrylonitrile, vinylidenechloride, various acrylates and related dieny similar to 1,3-butadiene and isoprene. The preferred polymers, however, are polystyrene and copolymers of styrene with Acrylonitrile (CAH). Another suitable class of polymers are the polyurea and polyurethane polymers. In particular, is used in this regard are the polycondensation products of primary amines or amines polyhydric alcohols and aromatic diisocyanates. Particularly preferred resin is a polycondensation product of triethanolamine and colordistance (TDI). Dispersed a suitable polymer is present in an amount of 5 to 40% wt. in relation to the total weight of the polymer polyol. In the case where the polymer is polystyrene or a copolymer of CAH, the preferred dry matter content ranges from 5 to 35 wt.%, whereas in the case of polyurea/palmatary commercially available polymer polyol as one of the compositions, which can be suitable used as component (a) polyol as one of the formulations in accordance with the present invention, are discussed in the description of the International patent N WO 95/09886. Such examples include polyurethane polyols CARADOL SP 50-01 and DESMOPHEN 7652, as well as polystyrene polyols CARADOL MD 25-01 and CARADOL MD 30-01 (CARADOL AND DESMOPHEN - brand).

The polyol used as component (b) should be hydrophilic in nature. This is one of the main requirements to obtain, ultimately, latokartano elastic foam, as described previously. In addition, the hydrophilic polyol must meet certain requirements with regard to its molecular weight ranging from 2000 to 5500, the content of ethylene oxide is not less than 40 wt.% and a primary hydroxyl content of at least 50%. Preferred hydrophilic polyols used as component (b) are polyols having a molecular weight ranging from 3000 to 5000, the content of ethylene oxide from 50 to 80 wt.% and a primary hydroxyl content of from 70 to 95%. Commercially available hydrophilic polyols meeting the above requirements are CARADOL SA36-02, DESMOPHEN 7040, VORANOL CP 1421, to polymeric polyol and a hydrophilic polyol polyol as one formulation may contain additional components and excipients, used in the manufacture of flexible foams. For example, polyol as one formulation may further comprise a foaming accelerator and/or a crosslinking agent. In addition, there may be excipients such as fillers, flame retardants, foam stabilizers, foaming agents, and dyes.

Suitable polyol as one formulation further comprises in wt.h. on 100 wt. PM refers to the amount in wt.h. on 100 wt.h. polymer polyol plus hydrophilic polyol):

(c) 0.01 to 2 wt. hours at 100 wt.h. one or more polyurethane catalysts; and

(d) 0-10,0 wt. hours at 100 wt.h., suitable 0-3,0 wt.h. on 100 wt.h. cross-linking agent.

Polyurethane catalysts are known in science and include many different compounds. A wide range of polyurethane catalysts is, for example, in the description of U.S. patent N 5011908. For the purposes of the present invention, however, found particularly advantageous use of a tin catalyst. Tin catalysts include salts of tin and salt dialkylamino carboxylic acids, such as octoate tin (II) oleate, tin (II), dibutyltindilaurate, dibutylaminoethanol and dibutylaminoethanol. Of these the most frequently s of the present invention tin catalyst is octoate tin (II), as it was found that this catalyst gives elastic foam that has excellent properties, especially in terms of elasticity and density. In addition to the tin catalyst may also be used one or more tertiary amine catalysts. Such tertiary amine catalysts are used widely and include, for example, bis(2,2'-dimethylamino)ethyl ether, trimethylamine, triethylamine, triethylenediamine and dimethylethanolamine.

Examples of commercially available tertiary amine catalysts are catalysts that are supplied under the brands NIAX, HEGOUMEN and DABCO (all trademarks). The catalyst is typically used in amounts ranging from 0.01 to 2.0 wt.h. on 100 wt.h. Preferred amounts of catalyst are in the range of 0.05 to 1.0 wt.h. on 100 wt.h.

Using cross-linking agents in obtaining polyurethane foams is well known. It is known that for this purpose polyfunctional glycolamine. The polyfunctional glycolamine, which is most often used and is preferred for use in the present polyol as one recipe is diethanolamin, often abbreviated as deja. Eli 3 wt.h. on 100 wt.h., but the most used are suitable amount in the range of 0.2 to 1.5 wt.h. on 100 wt.h.

In polyol as one recipe can also be added foaming agents. Appropriate foaming agents include water, acetone, (liquid) carbon dioxide, halogenated hydrocarbons, aliphatic alkanes and alicyclic alkanes. Thanks shoesthomasine effect completely chlorinated, fluorinated alkanes (CFC"s), the use of a blowing agent of this type is usually preferred, although it can be used in the scope of the present invention. Halogenated alkanes, in which at least one hydrogen atom is not substituted by a halogen atom (the so-called HCFC"s, have no or almost no asnosciowego effect and therefore are the preferred halogenated hydrocarbons used in physically expanded onto the foam. Very suitable blowing agent HCFC-type is 1-chloro-1,1-differetn. Water quality (chemical) a blowing agent is also well known. Water reacts with isocyanate groups in accordance with well-known NCO/H2O reaction, which is allocated DV were developed aliphatic and alicyclic alkanes. Examples of such alkanes are n-pentane and n-hexane (aliphatic alkanes) and cyclopentane and cyclohexane (alicyclic alkanes). It should be clear that the above foaming agents can be used individually or in mixtures of two or more of them. Found that of these foaming agents, water and carbon dioxide are particularly suitable as blowing agent for the purpose of the present invention. Of these, water is the most preferred. The number that should be used foaming agents, are traditionally used quantities, i.e. in the range from 0.1 to 5 wt.h. on 100 wt.h. in the case of the water and in the range from about 0.1 to 20 wt.h. on 100 wt. h in the case of halogenated hydrocarbons, aliphatic alkanes and alicyclic alkanes.

In addition, you can also use other well-known additives such as flame retardants, foam stabilizers (surfactants) and fillers. As foam stabilizers in polyurethane production are the most widely used silicone surfactants. A wide range of such organosilicon surfactants produced industrial the polyol as one of the reagent and the polyisocyanate reactant.

Polyol as one formulation according to the present invention is very suitable for the production of flexible foams. In order to obtain such elastic foam, polyol as one formulation interacts with the polyisocyanate, so isocyanate index (i.e., the equivalent ratio of isocyanate groups to hydroxyl groups) has a value in the range from 80 to 120. Very good results are obtained when the interaction polyol as one recipe and MDI in such quantities, at which the isocyanate index is in the range of from 85 to 110.

Accordingly, the present invention also relates to an elastic latecapitalist polyurethane foams obtained by foaming a composition containing polyol as one formulation of the invention and a polyisocyanate component. In the case when used polyol as one recipe only contains a polymeric polyol and a hydrophilic polyol, a catalyst, a crosslinking agent, a blowing agent and, if desired, or it seems necessary, foam stabilizers and other additives shall be entered separately in the polyol as one formulation, the polyisocyanate or the reaction mixture containing both components.

The composition from which rooted in the polyol, as defined above;

(b) 0.5 to 20 wt. 'clock to 100 wt.h. to the sum of (a), the hydrophilic polyol as defined above;

(C) 0.01 to 1.0 wt. hours at 100 wt.h. tin catalyst, preferably of octoate tin (II);

(d) 0-1,0 wt.h. on 100 wt.h. the tertiary amine catalyst;

(e) 0.2 to 1.5 wt.h. on 100 wt.h. cross-linking agent, preferably deja;

(f) 0.1 to 5 wt.h. on 100 wt.h. water as a blowing agent;

(g) up to 5 wt.% in relation to the total weight of the composition of silicone foam stabilizer;

(h) optionally, other additives and

(i) a polyisocyanate component in an amount such that the isocyanate index was in the range of from 80 to 120.

Of these components the components (a) and (b) in any case present in the polyol as one formulation of the present invention, while one or more components from (c) to (h) may also be present in this polyol as one structure.

The polyisocyanates which may be used are polyisocyanates commonly used in the production of flexible foams. Used polyisocyanates must have at least two isocyanate groups and include aliphatic, usually alkylen-, isocyanate-and aromaticheskikh foams. You can also use a mixture of two or more of these aliphatic and/or aromatic polyisocyanates. Examples of suitable polyisocyanates include 2,4-colorvision (2,4-TDI), 2,6-colorvision (2,6-TDI), a mixture of 2,4-TDI and 2,6-TDI, 1,5-attendaient, 2,4-methoxyphenylhydrazine, 4,4'-diphenylmethanediisocyanate (MDI), 4,4'-biphenylenediisocyanate, 3,3%-dimethoxy-4,4'-biphenylenediisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate and 3,3'-dimethyl-4,4' -diphenylmethanediisocyanate, 4,4', 4"-triphenyltetrazolium, 2,4,6-colortration, 4,4'-dimethyl-2,2', 5,5'-diphenylmethanediisocyanate, polietilen-polyphenylisocyanate and a mixture of two or more of them. Can also be used polymeric MDI, a mixture of MDI with MDI as the main component. It is established that for the purpose of the present invention, the polyisocyanate component is particularly preferable to use 2,4-TDI, 2,6-TDI, or their mixture. Very good results are achieved with a mixture of 2,4-TDI and 2,6-TDI in the mass ratio of 2,4-TDI:2,6-TDI about 80:20. This mixture is produced by the industry as KARAGAT 80 (KARAGAT - brand).

Elastic latexlady polyurethane foam according to the present invention can be obtained as block the car seat and upholstery accessories) and molded mats, and sound absorbing panel for use, for example, in vehicles containing the above flexible polyurethane foam, are also part of the present invention.

The invention will now be illustrated by the following examples.

EXAMPLE 1

Two polyol as one of the formulations obtained from trietanolaminesalicylate polyurethane polymer polyol (Polyol A) with molecular weight of 4700, Fn = 3, a primary hydroxyl content of 84% and a content of ethylene oxide 18 wt.%, containing 10 wt.% the dry polymer, of a hydrophilic polymer (Polyol) with a molecular weight of 4700, Fn = 3, a primary hydroxyl content of 90% and a content of ethylene oxide 75 wt.%

Both polyol as one recipe sequentially mixed in the foaming formulation FF-1 and FF-2 with water, amine catalyst (trade mark NIAX B2, supplier - Witco), octoate tin (P) as a tin catalyst silicone surface-active agent (trade mark AGOSTA B8681, supplier - Goldschmidt AG), diethanolamine (deja) and CARDAMOM 80 as MDI, and then there is the reaction of the foaming formulations with education latokartano polyurethane foam.

is lauretano are given in table I.

Deformation under compression load (BPS) is defined to characterize the stress-strain behavior of the foam. It is determined by the compression of the entire area of the test sample. Pressure (kPa) required to achieve a certain compression ratio (in%) is BPS.

From table I it is seen that a fully foamed water foam has a high density and excellent elasticity more than 50% and at the same time shows latokartano characteristic stress/deformation, i.e., primary soft touch (as shown by the low pressure required to achieve a 5% compression), and then support increases rapidly with further compression, as illustrated by the rapid increase in the pressure to achieve from 20 to 70% compression.

EXAMPLE 2

Analogously to example 1 two additional polyol as one of the formulations are used to obtain latexotica foams, this time with 100% polystyrene polymer polyol.

Thus, to obtain a polyol as one of the formulations together with hydrophilic polyol (polyol B from example 1) is used polyol With 100% polystyrene polymer polyol having a dry matter content of 10 wt.%, the average molecular weight of 5500, funktsionalnos is by water, the first amine catalyst (trade mark NIAX A1, supplier - Witco), the second amine catalyst (trademark DECO 331Y, supplier Air products), dibutyltindilaurate (trade mark DABCO T-12, the supplier Air products) as a tin catalyst silicone surface-active agent (trade mark AGOSTA B8681, supplier - Goldschmidt AG), diethanolamine (deja) and CARDAMOM 80 as MDI with obtaining foaming formulations FF-3 and FF-4, which then has a reaction with the formation of latexotica foams.

Components of the formulations and properties of the obtained foams are given in table II.

1. Polyol as one composition containing polyol with stably dispersed therein a polymer and a polyol, characterized in that it contains: (a) the 80 to 99.5 wt.h. polymer polyol containing primary polyol having a molecular weight in the range from 2500 to 6500, an average nominal functionality of Fn is not less than 2.0 and a primary hydroxyl content of at least 40%, and stably dispersed therein a polymer, and up to a total weight of 100 wt.h. (b) 0.5 to 20 wt.h. hydrophilic polyol having a molecular weight ranging from 2000 to 5500, contents of atilano the p. 1, characterized in that the main polyol has a molecular weight ranging from 3000 to 6000, Fn in the range from 2.5 to 6.0, and a primary hydroxyl content in the range from 70 to 95%.

3. Polyol as one composition under item 1 or 2, characterized in that the main polyol has a content of ethylene oxide in the range of 5 to 50 wt.%.

4. Polyol as one song on the PP.1 to 3, characterized in that the polymer is polystyrene, styrene-Acrylonitrile copolymer (SAN) or polyurethane polymer obtained as a product of polycondensation of triethanolamine and colordistance.

5. Polyol as one song on the PP.1 to 4, characterized in that the hydrophilic polyol has a molecular weight ranging from 3000 to 5000, contents of ethylene oxide in the range from 50 to 80 wt.% and a primary hydroxyl content in the range from 70 to 95%.

6. Polyol as one song on the PP.1 to 5, characterized in that it further comprises 100 wt.h. polymer polyol and a hydrophilic polyol: (C) 0.01 to 2 wt.h. catalyst, and (d) not more than 3.0 wt.h. cross-linking agent, preferably diethanolamine.

7. Polyol as one composition on p. 6, characterized in that the catalyst is a tin catalyst, optionally used in acatalasemia is octoate tin (II).

9. Elastic latexlady polyurethane foam obtained by foaming composition containing polyol as one composition and a polyisocyanate component, wherein the composition contains a polyol as one piece on PP.1 - 8.

10. Molded product that contains elastic latexlady polyurethane foam under item 9.

 

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