JP2008024813A - Polyol composition, polyurethane foam and its preparation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition useful for preparing an aliphatic isocyanate non-yellowing soft polyurethane foam. <P>SOLUTION: This polyol composition contains (1) 70-100 wt.% highly functional polyol having 3.2-6 average nominal functional value or a polyol blend, (2) about 0-about 20 wt.% at least a chain elongation agent having OH or NH, or NH2 group as a functional group, having at least a functional valence of 2 and an equivalent weight of 330 at most, and, if necessary, (3) 3-30 wt.% stably dispersed polymer polyol. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel polyol composition, a polyurethane foam prepared from the polyol composition, and a method for preparing the polyol composition and the polyurethane foam. It relates to the preparation of yellow-modified aliphatic isocyanate-based flexible polyurethane foams.

  In recent years, polyurethane foam has been widely used as an elastic material in various fields. In particular, in the fields of textiles, medicine and food packaging, the polyurethane must have no yellowing. Polyurethane foams are typically (1) polyols, (2) polyisocyanates, (3) silicone surfactants such as foam stabilizers, (4) water, (5) amine and tin catalysts, and (6) Made from various other additive compositions such as auxiliary blowing agents, fillers, and flame retardants.

  For polyisocyanates, diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI) are the two isocyanates most commonly used in the preparation of polyurethane foams due to their high reactivity. In the case of these two aromatic polyisocyanates, the polyurethanes thus produced turn yellow when irradiated with light or exposed to oxygen. Yellowing properties can be avoided by using aliphatic polyisocyanates as isocyanates in the preparation of polyurethane foams. However, due to the far lower reactivity of aliphatic polyisocyanates, they are very rarely used in the preparation of polyurethane foams.

Morimoto et al., US Pat. No. 5,147,897, dated September 15, 1992, discloses the production of non-yellowing polyurethane foams using aliphatic polyisocyanate prepolymers. The method of this invention, C ₂ -C ₁₀ in the presence of potassium or sodium salt or diazabicycloalkene catalyst of alkanoic acids, isocyanate equivalent of from 0.4 to 5 times the amount of water and an aliphatic polyisocyanate prepolymer And reacting. The prepolymer is obtained by addition polymerization of an aliphatic polyisocyanate having an amount of 1.4 to 2.6 times the amount of hydroxy equivalent and a polyol having an average molecular weight of 100 to 5,000. It is a prepolymer. The reactivity of aliphatic isocyanates is usually lower than that of aromatic isocyanates. When an aliphatic isocyanate is formed into a prepolymer, the mobility of the molecule is further slowed and the reactivity is further lowered. Due to the relatively slow reactivity and high viscosity of the prepolymer, the Morimoto et al. Process cannot be used in the preparation of polyurethane foam having a density of less than 80 kg / m ³ .

Du Prez et al., US Pat. No. 6,242,555, dated June 5, 2001, describes microporous or non-porous, light-resistant, soft or semi-soft polyurethane having a density of at least 900 kg / m ^3. A reaction injection molding (RIM) process for manufacturing is described. The process of this invention is an isocyanate reaction with an isophorone diisocyanate (IPDI) trimer / monomer mixture having an NCO content of 24.5-34% in the presence of a catalyst selected from organolead, organobismuth, and organotin catalysts. Reaction with the sex composition. The isocyanate-reactive composition was made from (1) a DMC (double metal cyanide) catalyst as described in US Pat. No. 5,470,813 and US Pat. No. 5,498,583. A low unsaturated polyether polyol having an average nominal functionality and an average equivalent weight of 800 to 4,000, (2) an aliphatic or cycloaliphatic OH group as a functional group, a functionality of 2, a maximum of 80 equivalents, and From about 3 to about 20% by weight of at least one chain extender having a primary OH content of at least 50%, (3) a catalyst having 2-3 functional aliphatic NH, NH2 or OH groups, and up to 150 equivalents About 2 to about 10% by weight of a cocatalyst system containing At least one of the catalysts is a secondary or primary amino group, and at least one of the catalysts is an amine initiated catalyst. The present invention provides a method for producing a non-yellowing polyurethane material. However, this method can only be used in the reaction injection molding process and in the production of dense molded parts.

  Japanese Patent No. 52997/1977 discloses a so-called “one-shot” process for the preparation of polyurethane foam. In the case of the one-shot process, polyisocyanate, polyol, polymerization catalyst and water are mixed and stirred for polymerization. In the case of this patent publication, an aliphatic polyurethane foam is produced by first mixing the polyurethane composition and pouring the composition onto a conveyor. However, in this process, both the polyol and the isocyanate must be preheated to about 60 ° C. An oven for additional heating is required and installed at the top of the conveyor for further heating. Due to the additional heating and exotherm of the foam due to the reaction of isocyanate and hydroxy groups, the system easily exceeds the autoignition temperature of the foam, ie 175 ° C. This method can therefore only be used for the production of foam sheets with a low height.

The one-shot process has several advantages over prepolymer processes that require two or more steps and can produce low density polyurethane foam. However, since the reactivity of aliphatic isocyanates is relatively low, the production of non-yellowing flexible polyurethane foam having a density of less than 80 kg / m ³ using a one-shot process has not yet been reported.

The inventor has conducted extensive research to invent a method for producing low density non-yellowing flexible polyurethane foam using a one-shot process. Surprisingly, it has been discovered that a one-shot process can be used to prepare non-yellowing flexible polyurethane foams with high functional polyols, or polyol blends and aliphatic polyisocyanates.
US Pat. No. 5,147,897 US Pat. No. 6,242,555 US Pat. No. 5,470,813 US Pat. No. 5,498,583 Japanese Patent No. 52997/1977 U.S. Pat. No. 4,272,619 U.S. Pat. No. 4,640,935 US Pat. No. 5,494,957 US Pat. No. 5,194,453

  The object of the present invention is to provide a novel polyol composition suitable for the preparation of non-yellowing flexible polyurethane foam.

  Another object of the present invention is to provide a one-shot process in the preparation of a non-yellowing polyurethane material having a relatively low density.

  Another object of the present invention is to provide a process for the preparation of non-yellowing aliphatic polyurethane foam.

  Another object of the present invention is to provide a new, non-yellowing polyurethane foam useful in the fields of textile, medical and food packaging.

One embodiment of the present invention discloses a polyol composition useful in preparing non-yellowing flexible polyurethane foam. The polyol composition of the present invention includes the following.
(1) 70-100 wt% functional polyol or polyol blend having an equivalent weight of 800-4,000 and an average nominal functionality of 3.2-6.
(2) from about 0 to about 20% by weight of at least one chain extender component having an OH or NH or NH2 group as a functional group, a functionality of at least 2 and an equivalent of up to 330

  Optionally with a base polyol having a nominal functionality of 2.4 to 5.5, an equivalent weight of 800 to 2,000, and an ethylene oxide content of 4 to 28% based on the weight of the base polyol. From 3 to 30% by weight of a stablely dispersed polymer polyol based on the total polyol composition made can be included in the polyol composition.

  In another embodiment, the invention relates to a process for preparing a non-yellowing flexible polyurethane foam. The process of the present invention comprises the steps of preparing a foam formulation containing a polyol component, an aliphatic polyisocyanate, water, a catalyst for forming urethane bonds in the foam formulation, and a foam stabilizer / surfactant, and thereafter A foam formulation foaming step followed by a foam formulation curing step. The polyol component is selected from the above polyol composition.

  In yet another embodiment, the present invention relates to a method for producing a non-yellowing flexible polyurethane foam using a one-shot process.

In yet another embodiment, the present invention relates to a non-yellowing flexible polyurethane foam prepared by the above process and having a density of less than 80 kg / m ³ .

In yet another embodiment, the present invention relates to a non-yellowing flexible polyurethane foam having a density of less than 80 kg / m ³ . In preparing the polyurethane foams of the present invention, no specific modification of the current polyurethane foam production equipment is necessary.

  When the polyol composition of the present invention is used, the range of compounding components in the preparation of a non-yellowing flexible polyurethane foam having a wide density and load range is expanded.

The present invention relates to a novel polyol composition useful in the preparation of non-yellowing flexible polyurethane foam having a density of less than 80 kg / m ³ . When aliphatic isocyanate is used as the isocyanate component, the present invention provides excellent processing properties and excellent foam elasticity. Furthermore, the present invention discloses a one-shot method for preparing a non-yellowing flexible polyurethane foam with a wide loading range without the use of an additional auxiliary blowing agent.

  The present invention discloses a novel aliphatic isocyanate-based polyurethane material. The polyurethane material of the present invention is suitable for the production of non-yellowing flexible polyurethane foam which is useful as a material in the fields of textiles, medicine, food packaging and the like.

  In the case of the one-shot process of the present invention, the compounded materials are simultaneously injected into the mixing head and injected into a mold or conveyor. The reaction is very fast, depending on the catalyst used, and is completed within 2 to 30 minutes. The resulting foam is then post-cured for about 24 hours to achieve its final properties.

  In the case of the process of the present invention, the reaction composition comprises an aliphatic isocyanate component A, an isocyanate-reactive component B, at least one catalyst, at least one surfactant, and at least one blowing agent. Use other foaming aids such as pigments / dyes, antioxidants, UV absorbers, flame retardants, fillers, recycled foam powders, stabilizers, antibacterial compounds, and antistatic agents when necessary be able to.

  Isocyanate component A is an aliphatic isocyanate monomer or aliphatic isocyanate monomer having an NCO content of 24.5 to 54%, preferably 26 to 51%, and an average calculated functionality of 2.0 to 2.7 / Trimmer blends may be used. The aliphatic isocyanate may be at least one selected from the following without limitation. Hexamethylene diisocyanate, hexamethylene triisocyanate, bicycloheptane triisocyanate, undecane triisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dimethylcyclohexane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate , Its dimer and its trimmer. Of these isocyanates, hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred.

  In addition to the aliphatic isocyanate monomer and trimer, the isocyanate component may optionally further include an aliphatic isocyanate prepolymer having up to 15% by weight of 2-4 isocyanate functional groups, based on the total weight of component A. Polymers can be included.

  Isocyanate-reactive component B comprises (b1) a highly functional polyol or polyol blend having an average nominal functionality of 3.2-6, and (b2) OH or NH as a functional group, or an NH2 group, at least two functional groups And a chain extender component having an equivalent weight of up to 330. Optionally made from a base polyol having a nominal functionality of 2.4 to 5.5, an equivalent weight of 800 to 2,000, and an ethylene oxide content of 4 to 28% based on the weight of the base polyol. Furthermore, 3 to 30% by weight of the total polyol composition of the stably dispersed polymer polyol (b3) can be incorporated in the isocyanate-reactive component.

  In the case of the said polyol composition, it is preferable that the component (b3) is not included.

  In the component (b1), the high-functional polyol that can be used in the present invention has an average nominal functionality of 3.2 to 6; ethylene oxide content of 8 to 25% and 800 to 4,000, preferably 1 It may be any polyalkylene oxide polyol or blend of such polyols having an equivalent weight of 1,000 to 3,500, more preferably 1,200 to 3,000. These polyols and their process of preparation are well known to those skilled in the art to which this invention relates.

  The polyols useful in the present invention include various compounds. Suitable examples of these compounds include, but are not limited to: (A) alkylene oxide adduct of polyhydroxyalkane; (b) alkylene oxide adduct and sugar derivative of non-reducing sugar.

  Examples of the above-mentioned alkylene oxide adduct of polyhydroxyalkane include 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 1,2,3-trihydroxyhexane, glycerin, pentaerythritol, Examples include polycaprolactone, xylitol, arabitol, sorbitol, and alkylene oxide adducts of mannitol. Of the alkylene oxides used, ethylene oxide, propylene oxide, and butylene oxide are most preferred.

  Another type of polyol that can be used in the present invention is the above alkylene oxide adducts of non-reducing sugars. Non-reducing sugars and sugar derivatives to be considered include sucrose; alkyl glycosides such as methyl glucoside and ethyl glucoside; ethylene glycol glycoside, propylene glycol glycoside, glycerol glucoside and 1,2, Glycol glycosides such as 6-hexanetriol glycoside; and alkylene oxide adducts of alkyl glycosides. Of the alkylene oxides used, ethylene oxide, propylene oxide, and butylene oxide are most preferred.

  In practice, any material having active hydrogen as measured by the Zerevichinov test can be used as a component of the polyol. For example, amine-terminated polyether polyols are well known and can be used.

  The most preferred polyol for use in the present invention comprises poly (oxypropylene-oxyethylene) glycol. If used, ethylene oxide can be incorporated along the polymer chain in any manner. Ethylene oxide can be incorporated in the inner block as a terminal block, or can be randomly dispersed along the polyol chain.

  The chain extender component (b2) has a functional group of OH or NH, or NH2, more particularly an aliphatic or cycloaliphatic OH or NH having a functionality of at least 2 and an equivalent of up to 330, or It may be a chain extender having an NH2 group. The chain extender component (b2) can be used in an amount of about 0 to about 20% by weight, preferably 0.8 to 15% by weight, based on the weight of components b1 and b2. Depending on the required loading properties of the foam, in combination with hand and mechanical strength, these chain extenders preferably have a functionality of at least 2 and at most an equivalent of 330.

  Representative examples of the chain extender (b2) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of less than 600, propylene glycol, dipropylene glycol, Polypropylene glycol having a molecular weight of less than 450, propanediol, pentanediol, butanediol, pentanediol, hexanediol, glycerin, poly (oxypropylene-oxyethylene), poly (oxypropylene), poly (oxyethylene), 2-methyl -1,3-propanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, ethylene diamine, Bruno ethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, N- methyl - ethanolamine, isophorone diamine, and hydrazine and the like. Suitable examples of chain extenders are poly (oxypropylene) and diethanolamine. If desired, blends of several chain extenders can also be used.

  The stably dispersed polymer polyol component (b3) may be any polyalkylene oxide polyol having a polymer in which monomers that are not ethylenically saturated are dispersed. Typical examples of polymer polyols stably dispersed include polyalkylene oxide polyols and polyureas in which poly (styrene acrylonitrile) is dispersed. The stably dispersed polymer polyols are Bayer (under the trade name “Polymer Polyol”), BASF (under the trade name “Graft Polyol”), Dow (under the trade name “Copolymer Polyol”) and It is commercially available from several companies including Mobay (under the trade name “PHD polyol”). In the case of Bayer, BASF and Dow products, poly (styrene acrylonitrile) is described in US Pat. No. 4,272,619; US Pat. No. 4,640,935 and US Pat. No. 5,494,957. Dispersed within the polyol by the process described, while the Mobay product disperses polyurea within the polyalkylene oxide polyol. Table I below shows examples of commercially available, stably dispersed polymer polyols.

  Stablely dispersed polymer polyols are described by Oertel in the “Polyurethane Handbook” (1985, Hanser Publisher, G. Ortel's Polyurethane Handbook, ISBN 0-02-948920-2). Can be prepared. Any polyalkylene oxide polyol can be used as a dispersion base in the production of such stably dispersed polymer polyols. The reactivity of such a stably dispersed polymer polyol depends mainly on the reactivity of the base polyol used in the preparation of such a stably dispersed polymer polyol. Since the reactivity of the aliphatic polyisocyanate used in the present invention is relatively low, a nominal functionality of 2.4 to 6 (preferably 2.4 to 5.6, most preferably 2.4 to 5.4) is used. 4 to 28 (preferably 4 based on the weight, equivalent weight of 800 to 2,000 (preferably 800 to 1,600, most preferably 1,000 to 1,600) and the weight of the base polyol. 24) Base polyols having an ethylene oxide content of% by weight are preferred.

A number of commercially available polyurethane catalysts can be used in preparing the non-yellowing aliphatic polyurethane foam of the present invention. The normal usage level of the catalyst is 0.01-2 php. Typical catalysts include (1) bis (2,2′-dimethylamino) ethyl ether, N-methylmorpholine, N, N-ethylmorpholine, N, N-dimethylbenzylamine, N, N— Tertiary amines such as dimethylethanolamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine, pentamethyldipropylenetriamine, trimethylamine, triethylamine, triethanolamine, triethylenediamine, and oxidized pyridine (2) bis (dimethylaminoethyl) ether, 1,5-diazabicyclo- (4,3,0) nonene-5, 1,8-diazabicyclo- (5,4,0) undecene-7, 1,8- Diazabicyclo- (5,3,0) decene-7,1,5-diazabicyclo- (5,4,0) undecene-5,1,4-di Zabicyclo- (3,3,0) octane-4, and diazobicycloalkenes such as organic salts of diazabicycloalkenes such as phenol salts; (3) Alkali and alkaline earth metal alkoxides, hydroxides, and phenoxides (4) Acidic metal salts of strong acids such as stannous chloride, ferric chloride, antimony trichloride, bismuth chloride and nitrates; (5) Be, Mg, Zn, Pb, Ti, Zr , Including various metals such as Sn, Bi, Mo, Mn, Fe, Co and Ni, acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetone Imines, bis-acetylacetone-alkylene diimines, and sari Various metals as obtained from Le aldehyde imine _{chelate; (6) Sn (OR)} 4, Sn (OR) 2, Ti (OR) 4 and Al _{(OR) 3} various metal alcoholates and phenolates such as In this case, R is alkyl or allyl, and alkoxides containing 2- (N, N-dialkylamino) alkanols such as carboxylic acids, β-diketones, and chelates of titanium obtained by this or equivalent procedures. (7) of organic acids including various metals such as alkali metals and alkaline earth metals such as calcium hexanoate, stannous acetate, stannous octylate and stannous oleate. (8) organometallic derivatives of tetravalent tin, trivalent and pentavalent As, Sb and Bi, and metal carbonyls of iron and cobalt.

  Among the above catalysts, organotin compounds have been found to be particularly useful in preparing the aliphatic low density flexible polyurethane foams of the present invention. Suitable organotin compounds include dialkyltin salts of carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, and dioctyltin diacetate. Other useful organotin compounds include trialkyltin hydroxides, dialkyltin oxides, dialkoxide dialkyltins, and dialkyltin dichlorides. Examples of these compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin dichloride, and dioctyltin dichloride.

  One or more surfactants can also be used in the foam-forming composition. Surfactants lower the bulk surface tension, promote foam nucleation, stabilize the expanding foam, and emulsify incompatible ingredients. Surfactants commonly used in polyurethane foam applications are polysiloxane-polyoxyalkylene copolymers, usually from about 0.5 to about 3 based on the total isocyanate-reactive components (b1) and (b2). It is used at a level of wt%, preferably about 0.6 to about 2.5 wt%. Conventional surfactants used in conventional aromatic polyurethane foams can also be used in the present invention.

  In order to act as a blowing agent on the foam, an amount of 0.5-6.5 php of water is used to generate carbon dioxide by reaction with isocyanate. In addition, combinations of water and other well-known auxiliary blowing agents can be used if desired. Of particular interest is the direct use of gaseous or liquid carbon dioxide as an auxiliary blowing agent in addition to water. Also, in the present invention, it is particularly preferred to adjust atmospheric pressure and / or use foaming as disclosed in US Pat. No. 5,194,453 to change the density of the foam.

  If necessary, other additives can be incorporated into the foam-forming composition of the present invention. Other additives include, but are not limited to, pigments, antioxidants, UV absorbers, flame retardants, fillers, recycled foam powders, stabilizers, antibacterial compounds and antistatic agents. Such additives should not adversely affect the properties of the final aliphatic polyurethane foam.

<Embodiment>
In the detailed description below, symbols, terms and abbreviations used are defined as follows.

  ISO 1 relates to 50 wt% NCO hexamethylene diisocyanate commercially available from Mitsui-Takeda.

  ISO2 relates to 3-isocyanate methyl-3,5,5-trimethylcyclohexyl-isocyanate.

  ISO 3 relates to toluene diisocyanate in a composition of 80% by weight 2,4-toluene diisocyanate and 20% by weight 2,6-toluene diisocyanate commercially available from Bayer AG.

  P1 relates to a glycerin-initiated 4,800 molecular weight PO-EO polyether polyol with EO capping having a primary hydroxyl content of 28% and a hydroxyl number of 33.5.

  P2 relates to a glycerin-initiated 6,000 molecular weight PO-EO polyether polyol with EO capping having a primary hydroxyl content of 34% and a hydroxyl number of 28.5.

  P3 refers to all glycerol-initiated 700 molecular weight PO polyether polyols having a hydroxyl value of 235.

  P4 contains 84% primary OH groups and 15.9% EO content, has a viscosity at 25 ° C. of 1,470 cps, has a nominal functionality of 6, and has a hydroxyl value of 28. Of the polyalkylene oxide.

  P5 relates to a highly functional polyalkylene oxide starting with a mixture of sugar and glycerin having a hydroxyl value of 31 and an EO content of about 69%.

  P6 relates to a graft polymer polyol comprising 44% by weight of a dispersed styrene-acrylonitrile copolymer having a hydroxyl value of 30.5. The base polyol is a randomly supplied EO-PO polyol triol having an equivalent of 1,050.

  P7 is a trademark of ACL AIM 6300, a DMC (double metal cyanide) catalyst, marketed by Bayer AG, having a molecular weight of 6,000 and a functionality of 3, made by adding PO to a glycerin initiator. And a low unsaturated polyether polyol.

  DEOA means diethanolamine.

  PEG 400 is a polyethylene glycol having a molecular weight of 400.

  B-8681 is a trademark of Tegostab B-8681, Th. It is a silicon surfactant marketed by Goldschmidt.

  Dabco 33LV is a solution of 33% triethylene diamine in dipropylene glycol, commercially available from Air Products and Chemicals.

  Dabco BL11 is a 70% bis (2-dimethylaminoethyl) ether solution dissolved in dipropylene glycol, commercially available from Air Products and Chemicals.

  SO means stannous octylate.

  DBTDL means dibutyltin dilaurate.

  Flame retardant V88 is a mixture of tris- (mono-chloropropyl) phosphate and tris- (2-chloroethyl) phosphate sold by Rhodia.

  Tinuvin 765 is bis (1,2,2,6,6-pentamethyl-1--4-piperidinyl) sebacate with a chemical extraction number of 41666-6-7, commercially available from Ciba-Geigy.

  “Index” means the ratio of the total amount of reactive isocyanate groups in the reaction mixture divided by the total amount of active hydrogen groups in the reaction mixture and multiplied by 100.

  pbw means parts by weight.

  In the detailed description below, the properties of the polyurethane foams shown in the examples were measured by the following test methods. The density was measured by the DIN 53420 method.

  “IFD (pushing force deflection) 40%” means the load at the time of 40% compression measured by the method of BS4443, 2A-88 parts.

  Tensile strength was measured by the ASTM D-3574-91 method.

  Elongation was measured by the ASTM D-3574-91 method.

  The tear strength was measured by ASTM D-3574-91 method.

  The elasticity value was measured by ASTM D-3574-91 method.

  “Comp.Set” means a compression set measured by the DIN 53572-11-86 method.

  UV stability is a measure of the color fastness obtained by AATCC 16-1990, Option E method. A sample of foam was placed under a xenon arc lamp and exposed to ultraviolet light for 20 hours. Results are expressed on a scale of 1 to 5 when compared to a standard gray scale card. A rating of 5 means that there was no color change and a rating of 1 means almost black. A rating of 4 and above means that visual changes cannot be discerned with the naked eye.

  The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the invention in any way. Unless otherwise indicated, all parts and percentages are parts by weight and percentages by weight.

<Examples 1 to 11 and Comparative Examples C-1 to C-10>
The aliphatic polyurethane foams of Examples 1-11 and Comparative Examples C-1 to C-10 were prepared by mixing the ingredients shown in Tables II to IV in a laboratory bench top scale cup. All components except the organometallic compound and isocyanate were premixed together in a 1.5 liter steel beaker with a Cowles type mixer for 20 seconds at 2050 rpm prior to addition of the organometallic compound. After premixing, if used, the organometallic compound was added into the beaker and mixed again at 2050 rpm for 20 seconds. The selected isocyanate compound was then added to the mixture and mixed with the composition at 2050 rpm for 5 seconds. The mixture was then poured into a wooden box lined with 40 cm (width) * 40 cm (length) * 40 cm (height) paper and allowed to inflate. The height of the inflating foam was recorded with an ultrasonic head set attached on top of the inflating foam.

Examples 1-3 show the processing characteristics of the present invention when compared to standard polyurethane foam formulations (Comparative Examples C1-C3), both containing conventional polyols and DMC low unsaturated polyols. Examples 1-3 show that a wide range of chain extender levels can be used in the present invention for a foam density of 30 kg / m ³ .

  Table III shows the superior processing characteristics of the present invention in preparing low density foams. As can be seen in Examples 4-7, different levels of chain extender and isocyanate index can be used to adjust the resulting foam loading. This indicates that various foam loads, from very soft to very hard, can be produced according to the present invention without the use of additional auxiliary blowing agents.

  Table IV further illustrates the versatility and other advantages of the present invention. In the case of Comparative Examples C-6 to C-7, the graft polymer polyol was used to increase foam loading. Graft polymer polyols can be used to increase foam loading, but these polyols also increased foam loading within conventional aromatic polyurethane foam formulations, so the graft polymer polyols Low reactivity has a significant effect on the breadth of the formulation. Low levels of graft polymer increase the foam load of the present invention while adversely affecting other foam properties such as compression set, elasticity, tear strength, tensile strength, elongation, and the like. The foam collapses when the graft polymer polyol level reaches 40 pbw. As can be seen in Examples 8-11, the present invention can be used to generate a wide range of foam loads without reducing the physical properties of the foam.

  Table V shows the yellowing problem of conventional aromatic polyurethane foams. Comparative Examples 8, 9 and 10 were prepared for comparison. As can be seen from Example 9, even with high levels of UV stabilizers, conventional aromatic polyurethane foams turn black during the UV stability test.

  While the invention has been illustrated and described with reference to preferred embodiments, those skilled in the art will make these and other changes to the invention without departing from the spirit and scope of the invention. You will understand that you can.

Claims (32)

A method for preparing a polyurethane material, comprising:
Preparing a foam formulation comprising a polyol composition, an aliphatic polyisocyanate, and at least one catalyst;
Foaming the foam formulation;
Curing the foam, the polyol composition comprising:
(1) 70-100% by weight polyol or polyol blend having an ethylene oxide content of 8-25%, an average nominal functionality of 3.2-6, and an equivalent weight of 800-4,000;
(2) A method comprising OH or NH as a functional group, or NH2 group, 0 to 20% by weight of at least one chain extender having a functionality of at least 2 and an equivalent weight of up to 330.   A base polyol having a nominal functionality of 2.4 to 5.5, an equivalent weight of 800 to 2,000, and an ethylene oxide content of 4 to 28% based on the weight of the base polyol. The process of claim 1 further comprising 3 to 30% by weight of a stably dispersed polymer polyol prepared in   The method of claim 1 wherein the average nominal functionality of the polyol composition is 3.2-6.   The method of claim 1, wherein the polyol blend contains a polyalkylene oxide polyol.   The process according to claim 1, wherein the polyol contains a polyalkylene oxide polyol having an equivalent weight of 1,000 to 3,500.   6. The method of claim 5, wherein the polyol contains a polyalkylene oxide polyol having an equivalent weight of 1,200 to 3,000.   The method of claim 1, wherein the polyol comprises a poly (oxyethylene-oxypropylene) polyol.   The aliphatic polyisocyanate has an aliphatic isocyanate monomer or an aliphatic isocyanate monomer / trimer blend having an NCO content of 24.5-54% and an average calculated functionality of 2.0-2.7 The method of claim 1.   9. The method of claim 8, wherein the aliphatic polyisocyanate has 26-51% NCO.   The aliphatic isocyanate is hexamethylene diisocyanate, hexamethylene triisocyanate, bicycloheptane triisocyanate, undecane triisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dimethylcyclohexane diisocyanate, xylylene diisocyanate, 9. The method of claim 8, comprising at least one selected from the group consisting of tetramethylxylylene diisocyanate, its dimer and its trimer.   11. The method of claim 10, wherein the aliphatic isocyanate comprises hexamethylene diisocyanate, its dimer or trimer.   11. The method of claim 10, wherein the isocyanate comprises isophorone diisocyanate, dimer or trimer thereof. A foam formulation comprising a polyol composition, an aliphatic polyisocyanate, and at least one catalyst, the polyol composition comprising:
(1) 70-100% by weight polyol or polyol blend having an ethylene oxide content of 8-25%, an average nominal functionality of 3.2-6, and an equivalent weight of 800-4,000;
(2) Foam formulations containing OH or NH as functional groups, or NH2 groups, 0-20 wt% of at least one chain extender having a functionality of at least 2 and an equivalent weight of up to 330.   The base composition having a nominal functionality of 2.4 to 5.5, an equivalent weight of 800 to 2,000, and an ethylene oxide content of 4 to 28% based on the weight of the base polyol. The foam formulation of claim 13, further comprising 3 to 30% by weight of a stably dispersed polymer polyol prepared with a polyol.   The foam formulation of claim 13, wherein the average nominal functionality of the polyol composition is 3.2-6.   The foam formulation of claim 13, wherein the polyol blend contains a polyalkylene oxide polyol.   The foam formulation of claim 13, wherein the polyol contains a polyalkylene oxide polyol having an equivalent weight of 1,000 to 3,500.   The foam formulation of claim 17, wherein the polyol contains a polyalkylene oxide polyol having an equivalent weight of 1,200 to 3,000.   The foam formulation of claim 13, wherein the polyol contains a poly (oxyethylene-oxypropylene) polyol.   The aliphatic polyisocyanate contains an aliphatic isocyanate monomer or an aliphatic isocyanate monomer / trimer blend having an NCO content of 24.5-54% and an average calculated functionality of 2.0-2.7 A foam formulation according to claim 13.   21. A foam formulation according to claim 20, wherein the aliphatic polyisocyanate has an NCO of 26-51%.   The aliphatic isocyanate is hexamethylene diisocyanate, hexamethylene triisocyanate, bicycloheptane triisocyanate, undecane triisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dimethylcyclohexane diisocyanate, xylylene diisocyanate, 21. A foam formulation according to claim 20, comprising at least one selected from the group consisting of tetramethylxylylene diisocyanate, dimers thereof and trimers thereof.   23. A foam formulation according to claim 22 wherein the aliphatic isocyanate comprises hexamethylene diisocyanate, dimer or trimer thereof.   23. A foam formulation according to claim 22 wherein the isocyanate comprises isophorone diisocyanate, dimer or trimer thereof. A polyol composition for preparing a foam material, comprising:
(1) 70-100% by weight polyol or polyol blend having an ethylene oxide content of 8-25%, an average nominal functionality of 3.2-6, and an equivalent weight of 800-4,000;
(2) A polyol composition containing OH or NH as a functional group, or NH2 group, 0 to 20% by weight of at least one chain extender having a functionality of at least 2 and an equivalent weight of at most 330.   3 prepared with said base polyol having a nominal functionality of 2.4 to 5.5, an equivalent weight of 800 to 2,000, and an ethylene oxide content of 4 to 28% based on the weight of the base polyol. 26. The polyol composition of claim 25, further comprising 30% by weight of a stably dispersed polymer polyol.   The polyol composition according to claim 25, wherein an average nominal functionality of the polyol composition is 3.2-6.   26. The polyol composition of claim 25, wherein the polyol blend contains a polyalkylene oxide polyol.   26. The polyol composition according to claim 25, wherein the polyol contains a polyalkylene oxide polyol having an equivalent weight of 1,000 to 3,500.   30. The polyol composition of claim 29, wherein the polyol contains a polyalkylene oxide polyol having an equivalent weight of 1,200 to 3,000.   The polyol composition according to claim 25, wherein the polyol contains a poly (oxyethylene-oxypropylene) polyol.   A polyurethane foam material prepared by the method of any one of claims 1-12.