JPH02500109A - Flexible polyurea or polyurea-polyurethane foam made from high-equivalent amine-terminated compounds and method for producing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Flexible polyureas or polyurea polymers made from high equivalent weight amine terminated compounds. Urethane foam and method for producing the same A flexible foam produced in the reaction of a high equivalent weight compound with a polyisocyanate. Regarding.

Flexible polyurethane foams have been used in industry for many years.

Its most common uses are under furniture and automobile cushions, bedding, and carpets. bedding, and other fillings or cushions.

Flexible polyurethane foams have traditionally been made using high equivalent weight polyols, polyisocyanates and It was manufactured by reacting components comprising a blowing agent and a blowing agent. Reverse these A number of methods have been used to respond. In one method, high equivalent weight polyols are React with a stoichiometric excess of polyisocyanate to form a prepolymer, which is then React with water and optionally other polyols and blowing agents to form a foam . In other methods, the polyol is added to the blowing agent and all ingredients (polyisocyanate). ) to form a “B-side” composition, which is then mixed with Reacts with anate to form a form.

Recently, it has become desirable to form highly resistant cafforms, particularly sheet materials.

Many methods have been used to produce highly resistant cafoams. One method is crosslinking including the use of low equivalent weight highly reactive polyols or polyamines. this Use of the method produces a highly durable cafform. Unfortunately, the use of cross-linking agents The balance between the so-called foaming reaction and gelling reaction that occurs during the manufacture of ohms is disrupted. There is a tendency to In order to obtain open cell foam with good physical properties, polyol It is necessary to accurately continue the reaction between the isocyanate and the isocyanate and the generation of gas by the blowing agent. be. If the foam gels too quickly, the foam will shrink after cooling. cormorant. If the foam gels too slowly, large inhomogeneous bubbles may form or Worse, the gas generated by the blowing agent can escape and create an "air bag." child The use of crosslinking agents has proven to be industrially difficult for the following reasons. Furthermore, the crosslinking agent Crosslinking not only due to price but also due to the additional polyisocyanate to compensate for the presence of crosslinker. The crosslinking agent fully measures the price of the foam. Therefore, in the production of flexible foams the minimum It is desirable to use a level of crosslinking agent.

Another method is to use microdispersions of polymeric filler materials. This so-called “ ``polymer polyol'' and ``polymer isocyanate'' are polyols and polymers. Due to the presence of colloidal polymers dispersed in one or both of the isocyanates, Gives reinforcement. In this method, a wide variety of polymer particles are combined with polyols and polymers. Dispersed in lysocyanate. The polymer particles are vinyl polymers, e.g. Ren-acrylonitrile (SAN) copolymer, polyisocyanate polyaddition (P IPA) polymers, polyurea particles, and recently epoxy particles.

There are problems with the use of this polymer dispersion. This dispersion improves yield strength and In some cases, it may be desirable to further increase the yield strength. stomach. Additionally, this tends to cause dispersed particles to aggregate and settle out of the continuous phase. This makes handling, transportation and processing somewhat difficult. Polymer polyols and and polyisocyanates compared to polyols and polyisocyanates themselves. It's expensive. Furthermore, even with this dispersion, it is usually necessary to use a crosslinking agent. Yes, and increase the price of the form. In addition, polyester in applications where crushing is not possible. The problem of shrinkage of molded forms made from mer dispersions is a drawback.

Another idea is to create lower density foams by increasing the amount of water in the foam formulation. be. Conventionally, the foam is 2 to 100 parts by weight of polyol to give a cellular structure. It was manufactured using 4 parts by weight of water. Recently, low-density phosphatide using up to 4.6 parts of water has been developed. The system was manufactured. To date, this highly water-containing foam has been difficult to manufacture and process. It was. Water reacts faster than polyols, causing premature foaming and foaming. There was a tendency to crush.

Has good yield strength and minimizes or eliminates the use of crosslinkers and polymer dispersions. , and optionally soft foams produced at low densities with large amounts of water in the formulation. It is desirable to provide a

In one embodiment, the present invention provides 6 bonds/ft3 (100 kg/ft3) or less. Open-cell flexible polyurea or polyurea-polyurethane with a density of foam, which contains (A) an average of 1.5 to 4 active hydrogen-containing groups per molecule. or a mixture thereof having at least 3 active hydrogen-containing groups. 0 percent is primary aromatic, Lewis acid blocked primary aliphatic and/or secondary fatty aliphatic or aromatic amine group), (B) a blowing agent in an amount sufficient to impart a cellular structure to the foam; (C) 1 of component (A); less than 5 parts by weight of a crosslinker or chain extender per 00 parts; and (D) Polyisocyanate is a reaction product of a reaction mixture comprising.

In another aspect, the invention is a method of making polyurethane foam, Under conditions such that a urea or polyurea-polyurethane foam is obtained. reacting the reaction mixture in a step process.

In other embodiments, the present invention also provides a in the presence of a blowing agent in an amount sufficient to provide a foam having a density of less than or equal to Relatively high equivalent weight compound having a large number of active hydrogen-containing groups, per 100 parts of component (A) Contains less than 5 parts by weight of crosslinking agent or chain extender and polyisocyanate. A method for producing open-cell flexible polymer foam by reacting components consisting of This improvement is a relatively high equivalent weight compound with 1.5 to 4 active molecules per molecule. This method involves using relatively high equivalent weight compounds or mixtures thereof having hydrogen-containing groups. and at least 30 percent of the groups are primary aromatic, Lewis acid blocks A first aliphatic and/or a second aromatic or aliphatic amine group.

In yet other embodiments, the invention provides (A) Relatively high equivalent compound having an average of 1.5 to 4 active hydrogen-containing groups per molecule or mixtures thereof (at least 30 percent of the active hydrogen-containing groups are primary aromatic groups, Lewis acid blocks primary aliphatic and/or secondary aliphatic or aromatic amino acids. ), (B) 3.5 to 10 parts by weight of water per 100 parts by weight of component (A), and (C) 0.1 to 4.5 parts by weight of crosslinking agent per 100 parts by weight of component (A) or chain extender An active hydrogen-containing composition comprising:

At least 30% primary aromatic, Lewis acid blocked primary aliphatic and/or or a second aromatic or aliphatic amine group (hereinafter referred to as “amine-terminated compound”). It has been found that the use of relatively high equivalent weight compounds containing compounds provides a number of unexpected advantages.

This foam has particularly good load-bearing properties even in the absence of crosslinkers. crosslinking agent When used, the forms of the present invention typically employ only hydroxy-terminated high equivalent weight compounds. It has better yield strength than similar foams produced. Forms of the invention typically include may be similar to foams made from polymer dispersions using the same level of crosslinking agent. It has a yield strength of at least 100% or more. Furthermore, the foam of the present invention is open-celled. , often exhibit low shrinkage and contain internal wires or other structures that prevent post-foam failure. It can be used to manufacture parts that Foam formulation used in the present invention has an excellent ability to fill even more complex molds. In some cases, the invention also enabling the production of foams using much larger amounts of water than using traditional methods; I understand.

In the present invention, flexible polyurea or polyurea-polyurethane foam is used. Amine-terminated compounds are used for the production. Amine terminal used in the present invention A compound has a large number of active hydrogen-containing groups, with at least 30 percent of the groups is the first aromatic, the Lewis acid block is the first aliphatic and/or the second aliphatic or Relatively high equivalent weight compounds or polymers that are aromatic amine groups; means a mixture of compounds. The equivalent amount of amine-terminated compound used is the form to be produced. Advantageously 400 to 5000, preferably 50 It is 0-2500. The amine-terminated compound or mixture thereof has an average of 1 per molecule. ．． It has 5 to 4, preferably 1.8 to 3, active hydrogen-containing groups.

Amine-terminated compounds can be used to form polyurea or polyurea-polyurethane foams. Placements that undesirably affect the ability to react with polyisocyanates to form Any structure may be used as long as it does not contain a substituent. Particularly suitable amine-terminated compounds have a large number of active hydrogen-containing groups, at least 30 percent of which are primary aromatic , Lewis acid blocks primary aliphatic and/or secondary aliphatic or aromatic amines It is a polyether or polyester group.

Suitable secondary aromatic amine terminated compounds are polyols, especially 30 to 100 percent g, preferably 50-100%, more preferably 60-90% Polyether and polyester polymers modified to contain a proportion of secondary amine groups Such secondary aliphatic amine terminated compounds, including lyols, have previously been described in U.S. Pat. No. 153,381, the corresponding polyols are combined with primary amines. It is produced by reacting and reducing the resulting intermediate with hydrogen. First A amine is advantageously internally substituted alkyl-, cycloalkyl-1 or benzyl It is an amine. In addition, the secondary aliphatic amine terminal compound may be It is produced in the Michael addition reaction between amine and ethylenically unsaturated compounds. Aku Rylonitrile is a particularly preferred ethylenically unsaturated compound, although it does not mix well with primary amines. It undergoes frog addition reaction to form a secondary amine and reacts with polyisocyanate. Use any compound that does not contain substituents that adversely affect the ability of the resulting product to It's okay to stay. The primary aliphatic amines themselves are described in US Pat. No. 3,128,311; No. 3.152.998; No. 3,654,370; No. 3.347,926; and the corresponding by ammonia as taught in No. 4,014,933. Produced in reductive amination of polyols.

Suitable aromatic amine terminated compounds include polyols, especially those containing certain aromatic amine groups. Contains improved polyether and polyester polyols. like that The compounds can be prepared, for example, by di-dilyzing the corresponding polyether or polyester polyols. cap with a soocyanate to form a prepolymer, and then add water to the prepolymer. by reacting with and hydrolyzing the free isocyanate groups to the corresponding primary amines. manufactured by This type is difficult to process due to its relatively high viscosity, which makes it difficult to process. In addition to this, such compounds are not preferred. The polyester polyol can be combined with a halogenated nitrobenzene compound, e.g. React with p-nitrochlorobenzene or dinitrochlorobenzene, then Produced by reduction of the nitro group to an amine.

Preferably, the product is produced by a catalytic hydrogenation process. The typical method is rcata lytic Hydrogenation over PlatinumMet als”, Paul N, Rylander, 1967, Academic See Press, New York. It is said to be effective in producing aromatic nitro groups. Any known catalyst may be used, including Raney nickel. The preferred catalyst is Contains thenium, rhodium, palladium, osmium, isodium, and platinum Consists of platinum group metals. Preferably, the catalyst is supported on a support such as activated carbon, silica gel, etc. , supported on alumina, diatomaceous earth, pumice, etc. If the elemental metal is present on the support The exact percentage that is used is not an important factor. Generally, this metal has a weight percent of 0.05 to 40 -cent, preferably 0.5 to 20 weight percent, most preferably 5 to 10 weight percent Volume percentage.

The proportion of the catalyst used expressed as pure metal to the nitro groups to be reduced is: Preferably from 0.05 to 10 mole percent metal per equivalent of nitro groups. good Preferably, this range is 0.1 to 1.0 mole percent. "Nitro group equivalent" is the molecular weight of the nitroaromatic compound (I[) divided by the number of nitro groups per molecule. means the nitro equivalent obtained by

Hydrogenation is carried out in the liquid phase in the presence of hydrogen and catalyst components and generally requires the use of solvents. Required, but not absolutely necessary. Compounds that are effective in catalytic hydrogenation methods Solvents that are inert to (1) and (II) are used. Typically, the following solutions The media may be used alone or in mixtures. Aromatic hydrocarbons, e.g. benzene toluene and xylene; alcohols such as methanol, ethanol, Ropatool and isopropatool; esters such as ethyl acetate, ethyl lupropionate and ethyl butyrate; ethers such as dioxane and Tetrahydrofuran; and water, liquid solution alone or in combination with the above solvents. The use of ammonia is also conceivable. The amount of solvent is not a problem per se, but as long as it is effective. Any amount may be used. Advantageously, the nitroaromatic compound (n) is not present in the center of the solvent. 10% by weight, preferably 20-70% by weight, most preferably It is used at 25-50 weight percent.

The exact choice of temperature in hydrogenation is correlated with the specific catalyst activity and hydrogen pressure, for example. There is. Advantageously, this temperature is between O'C and 200°C, preferably between 15°C and 10 0''C5 most preferably within the range of 20°C to 50°C.

Similarly, within the above temperatures, the hydrogen pressure used was 15 psig (100 kPa gauge). ) to proper operating pressure (covers the effective range).

Generally, this pressure is between 15 psig (100 kPa gauge) and 200 psig (1400kPa gauge), preferably 30 (100) to 60 psig (3 00kPa gauge).

The progress of the reduction can be easily followed by monitoring hydrogen uptake. Therefore, reduction is stopped when the stoichiometric amount of hydrogen has been absorbed. In addition to this, the reduction is no more than hydrogen. continues until it is no longer consumed.

In another preferred method, the corresponding hydroxy- or primary amine-terminated polyether polyester or polyester with nitroanthol or p-aminobenzoic acid. reaction with substances such as alkyl esters, particularly methyl esters, followed by nitro Reduction of the group forms an aromatic amine terminated compound.

The secondary amine-terminated compound is the corresponding primary aromatic amine compound and the acrylonitrile compound described above. It is produced in a Michael reaction with ethylenically unsaturated compounds such as lyle. aroma The group amine-terminated compounds advantageously have either a primary or a secondary amine-terminated 30 to 100 of the total number of active hydrogen-containing groups provided by the equivalent compound, preferably 50 to 100, more preferably 70 to 100 percent of the first and/or or contain a secondary amine group.

Suitable blocked primary aliphatic amine compounds are advantageously treated with ammonia. Reductive amination of hydroxy-terminated compounds followed by Lewis acids such as benzoyl lorides, carbon dioxide and metal carboxylates such as tin, zinc, titanium and its complexation with aluminum carboxylates. Lewis The acid advantageously contains 0.2 to 5, preferably 0.9 to 1.5, per equivalent of primary amine groups. Used in equivalent amounts.

Together with the amine-terminated compound, the proportion of amine groups is within the above range, i.e. relatively high. The total amount of active hydrogen-containing groups contributed by the equivalent compounds is at least 30 percent Mixtures thereof with suitable equivalent amounts of polyols are also advantageous. especially polymers Polyols, such as polyurea polyol dispersions (PHD polyols), polyadditions Polyisocyanate polyol dispersion (PIPA polyol) or addition polyol mer dispersions, e.g. amide with styrene-acrylonitrile copolymer polyols. a mixture of terminal compounds (up to 50% by weight based on the weight of the relatively high equivalent weight material used) The amount of polymer polyol (including the percent polymer polyol) is important.

As mentioned above, the preferred equivalent weight of the amine-terminated compound depends on the type of form being produced. and its manufacturing method. Produce molded polyurethane foam using thermosetting method For this purpose, the amine-terminated compound preferably has an 00-2000, most preferably 800-1500. by cold curing method To produce slabstock foam or molded polyurethane foam, the most The preferred equivalent weight is 500-1800.

In the present invention, aliphatic or aromatic polyisocyanates are used to produce foams. Either of these may be used. Suitable aliphatic polyisocyanates are, for example, ethylene Diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexa Methylene diisocyanate, 1,12-dodecene diisocyanate, cyclobuta -1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate Isocyanate, 1゜5-diisocyanato-3,3,5-)limethylcyclobenzene San, 2,4- and/or 2,6-hexahydrotoluene diisocyanate , perhydro-2,4' and/or -4,4'-diphenylmethane diisosilane Contains anate (H+tMDI) and isophorone diisocyanate.

Suitable aromatic polyisocyanates are for example 2.4- and/or 2.6-) Luene diisocyanate (TDI), 2.

4-diphenylmethane diisocyanate, 1,3- and 1°4-phenylenedi isocyanate, 4,4'-diphenylmethane diisocyanate (a small amount of 2,4 '-isomer), 1,5-naphthylene diisocyanate, trif phenylmethane-4,4'4''-1-diisocyanate and polyphenyl-poly Contains methylene polyisocyanate. Polyisocyanate is MDI or MDI In the case of a mixture containing derivatives of MDI, especially polymeric MDI, the amine-terminated compound is substantially difunctionality, i.e. 1.5 to 2.2, preferably 1.8 to 2.1, etc. It is preferred to have an average functionality of 1.9 to 2.05. Soft foam Substantially difunctional compared to the highly functional polyols traditionally used in the production of The use of amine-terminated compounds retards the gelation of the reaction mixture, thereby making it even better. was found to promote the formation of high-quality foam. 1.5-1.95 actual Relatively high equivalent weight compounds with functionality and other ratios with actual functionality greater than or equal to 2.2 A mixture of relatively high equivalent weight compounds (the average functionality of this mixture is 1.5-2.2) In addition, urethane, carbodiimide, allophanate, isocyanure such as those containing esters, acylated ureas, biurets, esters, and similar groups. Derivatives and prepolymers of the polyisocyanates mentioned above are also useful. These utensils TDI containing a carbodiimide group and having an equivalent weight of 130 to 150 and Of particular interest are prepolymers of MDI as well as so-called "liquid MDIJ products."

Among the polyisocyanates, TDl is preferred due to its price, commercial availability and performance. ,,MDI, isophorone diisocyanate, H1□MDI, hexamethylene diisocyanate Preference is given to isocyanate, cyclohexane diisocyanate and its derivatives.

Most preferred are TDI, MDI and derivatives of MDI. TDI, especially 2.4- Particularly preferred are mixtures of the and 2,6-isomers.

The polyisocyanate has a molecular weight of 60 to 200, preferably 90 to 125, more preferably A sufficient amount is used to give an isocyanate index of 95-110.

At higher indices, trimerization of the polyisocyanate occurs and the form Lower indexes that result in loss of flexibility indicate insufficient curing and reduce the properties of the foam. Sexuality becomes worse. When using MDI or its derivatives as polyisocyanate In this case, the preferred isocyanate index is 60 to 110, and 70 to 103. is more preferable. It is a plate-like form with an MDI of 110 or higher. This is because an index of less than 60 gives a fairly elastic form. be. "Incyanate index" is a mixture that reacts to form a foam. 100 times the ratio of incyanate groups to active hydrogen-containing groups contained in .

Blowing agents are another important component of the invention. The blowing agent is polyisocyanate and polio. Any substance that can generate gas under the conditions of a reaction. Such substances are Air, carbon dioxide, nitrogen, water, formic acid, low boiling halogenated alkanes, finely ground solids and and so-called "azo" blowing agents, such as azobis(formamide). water, low Boiling point halogenated alkanes, or mixtures thereof, are preferred. The blowing agent is advantageously 0.5-6, preferably 0.9-4, more preferably 1.1-3 lb/ft" is used in an amount sufficient to give a lump density of . Methylene chloride, dichlorodifluoro Methane and monochlorotrifluoromethane and monochlorotrifluorometa The halogenated alkanes containing gives the desired density when used in amounts of 50%. When used with other blowing agents, e.g. water. If so, lower amounts may be effective.

One of the advantages of the present invention is the production of very low density foams using water as a blowing agent. is possible. Traditionally, the use of water as a blowing agent has been It was limited to no more than 4.6 copies per 100 copies of the book. When it is used in larger quantities This is because it tends to give a poor form. The present invention provides effective physical properties per 100 parts of amine-terminated compound to give a very low density foam with More than 7.5 parts of water is used. Therefore, water per 100 parts of amine-terminated compound used in an amount of 0.5 to 10, preferably 3.5 to 8, more preferably 4 to 6 parts. give the desired density. Ultra-low density foam (1.5 lb/rt' (10 5 to 10 parts of water are used.

Catalysts for the reaction of amine-terminated compounds with polyisocyanates may also be used in the form according to the invention. used in the production of A wide variety of substances are known to be effective for this purpose; , the most widely used and preferred catalysts are tertiary amine catalysts and organometallic catalysts. be.

Examples of tertiary amine catalysts include, for example, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N-cocomorpholine, 1- Methyl-4-dimethylaminoethylpiperazine, 3-methoxy-N-dimethylpropylene Lopylamine, N,N-diethyl-3-diethylaminopropylamine, diethyl Contains rubenzylamine and bis(2-dimethylaminoethyl) ether. No. The triamine catalyst advantageously contains from 0.01 to 5 parts per 100 parts by weight of amine-terminated compound, Preferably it is used in an amount of 0.05 to 2 parts.

Examples of organometallic catalysts are metals such as tin, bismuth, iron, mercury, zinc and lead. Suitable organotins include, for example, dimethyltin, with organotin compounds being preferred. dilaurate, dibutyltin dilaurate, and stannous octoate. other Suitable catalysts are taught, for example, in US Pat. No. 2,846,408. advantageous contains o, ooi to 0.5 parts by weight of organometallic catalyst per 100 parts of amine-terminated compound. medium is used.

Polyurea or polyurea-polyurethane foams are amine-terminated compounds, This component reacts with the foaming agent, polyisocyanate, and catalyst to form a cellular polymer. produced according to the invention by contacting under conditions of. Usually the reaction mixture are crosslinking agents, catalysts, surfactants, colorants, cell openers, flame retardants, antioxidants, mold release agents. may contain additional ingredients such as depending on whether it is molded or slab material form.

Crosslinking agents can be used to form molded forms or highly elastic steels, especially to improve yield strength and processability. May be used in the production of rubber foam. Suitable such crosslinking agents are alkano amine and 3 to 8, preferably 3 to 4 active hydrogen-containing groups per molecule. 200 or less equivalents of other compounds.

Examples of such compounds are glycerin and trimethylolpropane, as well as other It is an alkylene triol. However, alkanolamines such as jetano triamine, triisopropanolamine, triethanolamine, diisopropanolamine tool amine, 4 to 8 moles of ethylene oxide and/or propylene oxide and ethylene oxide Adducts of diamines as well as polyamines such as methylenebis(0-chloroamine) (niline), ethylenediamine and ammonia are preferred. Its optimal reactivity Most preferred as a standard is jetanolamine. Noform 1 of the present invention One advantage is that at equivalent levels of crosslinker, this form can be used with amine-terminated compounds. The purpose of this invention is to exhibit superior load-bearing properties to similar foams manufactured without the use of carbon fibers. follow Therefore, it is also a good idea to reduce or even eliminate crosslinking compounds to obtain equal yield strength. It is possible by invention. However, if used, advantageously 100% of the amine-terminated compound Less than 5 parts per part, preferably 0.1 to 4 parts of crosslinking agent are used. Linked with crosslinking agent The combined weight of chain extender (if used) is per 100 parts by weight of amine-terminated compound. Most preferably, the amount is less than 5 parts.

Chain extenders may be used to further improve the foam's yield strength. for the present invention The chain extender has 2 active hydrogen-containing groups per molecule and 31 to 300, preferably contains compounds having an equivalent weight of 31 to 150, the hydroxy-containing chain extender is an alkaline Kylene glycol and glycol ethers such as ethylene glycol, 1. 3-propylene glycol, 1,4-butylene glycol, l,6-hexamethylene Ren glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and 1,4-cyclohexane dimeta Contains tools. Amine chain extenders are diethyltoluenediamine, phenylene diamine Min, methylenebis(O-chloroaniline), NaCf7”lock methylenebis (aniline), toluenediamine, a small number (both one carbon) adjacent to each amine group. Contains aromatic diamines substituted with alkyl atoms. Such chain extenders are in small amounts, i.e. less than 5 parts by weight per 100 parts by weight of amine-terminated compound. It is advantageous to Most preferably, the combined weight of chain extender and crosslinker is It is less than 5 parts by weight per 100 parts by weight of the amine-terminated compound. However, chain extenders It is usually preferred to manufacture the foam without using any.

Produces a stable form, i.e. one that does not collapse or contain large amounts of large pores. foaming against cell collapse until the mixture is sufficiently cured to hold its shape. Surfactants may be used to stabilize the reaction mixture. Suitable surfactants are for example Described in U.S. Patent Nos. 3,887,500 and 3,957,842 siloxane poly(alkylene oxide) copolymers such as siloxane poly(alkylene oxide) copolymers. Made of foam The selection and use of such surfactants in formulations are known in the art. Ru. However, one of the advantages of the present invention is that low levels of surfactants are used and sometimes It is possible to exclude surfactants. Therefore, per 100 parts of amine-terminated compound It is preferred to use the surfactant in an amount of less than 0.5 part, preferably less than 0.25 part. Delicious. In particularly preferred embodiments, the foam is substantially surfactant-free. Manufactured without.

In accordance with the present invention, all reaction components, catalyst, and desired components are mixed and reacted simultaneously. The foam is manufactured by a one-shot method by applying the following steps. The advantages of the present invention are seen in the production of molded foam. Made of molded polyurea-polyurethane foam Advantageously, all components except the polyisocyanate are mixed together in a single stream. into the mixing head as However, certain components, such as catalysts or halogens, Genated methane blowing agents are sometimes mixed with polyisocyanates. In addition, water and Surfactants (if used) may be added separately if desired.

The polyisocyanate is added as a separate stream to the mix head where the polyol It is mixed with a mixture and injected into a mold. Traditionally when performing the mixing and mold filling process Low pressure equipment may be used or high pressure impingement mixing methods such as reaction injection molding may be used. Normally, the ingredients are mixed at about room temperature, but pure MDI, which is solid and fluorine at room temperature, The components may be heated to elevated temperatures above their melting points.

In one molding method (aged mold method), the reactants are placed in a mold at ambient temperature. After filling, harden To do this, the mold is placed in an oven at a temperature of 150°C to 275°C. second (cold molding method), the reactants are placed in a mold preheated to 30°C to 75°C. put in. After filling the mold, it is placed in an oven at 70°C to 150’C for curing. It will be done.

In a third method, the filled mold is kept at ambient temperature during the curing process. this third In the method, the mold may or may not be preheated.

After foaming, enough reaction mixture is placed in the mold so that the mixture components completely fill the mold.

Advantageously, a small excess of material is added than the minimum necessary to fill the mold. Mold filling After filling, the molded form can be removed from the mold without at least undesired deformation. The reaction mixture is cured in a mold to an extruded state. In typical industrial methods, this An in-mold curing time of 2 to 30 minutes is appropriate for the target. If necessary, 50°C ~ 1 Heat to a temperature of 20°C for 10 minutes to 24 hours, preferably 20 minutes to 2 hours. The foam may also be post-cured.

It may be necessary to mechanically release bubbles in the foam during or after curing or is desirable. As taught in U.S. Pat. No. 4,579,700, crush the foam, destroy the foam, vacuum crush the foam, or This is done by releasing the pressure inside the mold during the initial stage of the process.

An advantage of the present invention is that post-cure shrinkage associated with improper cell opening is typically reduced, thereby The need to mechanically open bubbles is reduced (or eliminated).

In the production of less preferred slab stock forms, the reaction mixture is preferably Contains surfactants and catalysts such as those listed below. Cross-linking agents may be used, but are often Excluded from rubwood formulations. In the industrial production of slab timber forms, the ingredients are They are typically placed separately in a mixing end where they are thoroughly mixed and foamed. is sent to the head. However, premixing of components other than polyisocyanate is also desirable. You may do so by

The ingredients are at or slightly elevated temperature when mixed in a mix head, but are solid at room temperature. Preheating is necessary to melt the components.

The foam of the present invention can be used, for example, in bedding, furniture cushions, stuffing, carpet underlays, accessories, etc. Genus cushion carpet lining, automobile headrest, compression pad, door handle, Effective as a headliner and sheet. The present invention has particularly good yield characteristics. It is useful for applications where a low density high moisture formulation is desired or where a low density high moisture formulation is desired.

The following examples illustrate the invention but do not limit its scope.

All parts and percentages are by weight unless otherwise indicated.

Goto In this example, a difunctional primary aromatic amine endpoint is used to form a molded form. The riether was reacted with polymeric MDI.

Soft foam samples Nα1 and 2 and comparative samples A and B are shown in Table I. Manufactured from the same composition.

l--1 Weight part Amine-terminated polyether A"' 100 0 100 0 Polyol A"' 0 100 0 100 Diethanolamine OO, 500, 5 Water 4.5 4. 5 4.5 4.5 Amine catalyst +z+ l l l l 1 Silicone surfactant A”ゝゝ　0　0.75　0　0.75Silicone surfactant Agent B") 0.75 0 0.75 0 Silicone surfactant C" 0 0.3 0 0.3 Silicone surfactant D'&) 0.3 0 0.3 0 Polymer M DIA"+ 80.3 80.3 0 0 Polymer? 1DIB"' 0 0 80 ．． 3.80.31 This is not an example of the present invention.

(1) Polyol A is 18% by weight terminal poly(ethylene oxide) block. It is a difunctional, 1000 equivalent weight poly(propylene oxide) containing Amine powder Edge polyether A is prepared by reacting polyol A with p-nitrochlorobenzene and then by reducing the nitro group to a primary amine group. Hydroxy group approx. 83% is converted to primary aromatic amine groups.

” Union Carbide Corporation as a C255 catalyst Proprietary tertiary amine catalyst sold by ”) Y-10148 surfactant, Llinion Carbide Corp.

DC-5043 surfactant, sold by Dow Corning Corp. L-540 surfactant, sold by Union Carbide Corp. 6) DC-10140 surfactant, sold by Dow Corning Corp. (135 equivalent polymer M made from 12 weight percent of the 712,41-isomer DI (2,2-2.4 functionality)”’214’-isomer from 2.5 percent by weight The 135 equivalent polymeric MDI (2,2 to 2.4 functionality) components to be produced were mixed and 1 8” x 8” x 3” (200mm 200mm x 76++o) Transfer to a mold, and after foaming, mold the mold to 1756F (80’C) Place the sample in the oven for 3 minutes and remove the foam. Molded foams were produced from each of kl and 2 and comparative samples A and B. . This foam had the properties shown in Table H below.

As is clear from the data in Table ■, the present invention improves modulus, tensile strength, and A major improvement in tear strength was obtained. The modulus obtained by the present invention is The modulus value is particularly sufficient as it indicates that the ohm gives a particularly comfortable seat. Ru. This value is particularly important because samples No. 1 and 2 were manufactured without using a crosslinking agent. That's surprising.

courage Soft foam samples 3 to 7 were manufactured from the compositions shown in Table 1 below.

Form samples Nα3 to 7 were manufactured according to the method described in Example 1, and the results are shown in the table below. Shown below.

All foams had good physical properties. Especially amine-terminated compounds 100 It is important to prepare the sample using 7.5 parts per part of water. Good physical properties, special A very low density foam with good tensile and yield properties was obtained.

five lords In this example, a nominally trifunctional secondary aliphatic amine terminated polyether with different TDI A molded foam was formed by reacting with a mixture of polymers.

Molding soft foam samples Nα8 to 10 from the composition shown in Table V Amine-terminated polyether C”+ 100 100 100 diethanolamine 1.5 1.7 1.7 Water 3.8 3.8 3.8 Triethylenediamine solution is 0.25 0.12 0.12 silicone interface Activator B 2.0 1.65 1.65 Dibutyltin dilaurate 0.0 042 0.0042 0.004280/20) Luen 101 101 105 Diisocyanate L&) Index Index Index ( 1) primary amine powder until essentially all primary amine groups have been converted to secondary amine groups. A 5000 molecular weight, nominally trifunctional polyether is reacted with acrylonitrile. It was manufactured by

(2) 33% solution in dipropylene glycol (DPG) l) Amine-terminated polyester DC-0910% solution” sold by Dow Corning Corp. 5043 surfactant"Polycat 77 as Abbott Labor Sold by atories (6) See footnote in table ■ Mix all ingredients except TDI at 786F (25°C) and mix in TDI. and preheated this mixture to 140'F (60°C). X15"X 4.5" (381mmX 381mmX 114mm) Gold Foams were made from each of the compositions by pouring into molds. After filling the mold, Close it and immediately put it in the open at 250°C (121°C) for 4 minutes, then remove the resulting photo. I took out the room. After cooling, the physical properties of the foam were measured and are shown in Table 3.

All foams had good properties. Especially when the IFD and modulus values are is important. Hydroxy-terminated polyether instead of amine-terminated polyether Foams made similarly except using 25% IDF of 16 and 65% IDF of 44. The IDF values obtained were substantially higher. Similarly, 1 based on the weight of the polyol Incorporation of SAN copolymer polyol at an effective solids level of 2.5 weight basis The foam produced using the compound had an IDF value of 17 of 25 percent and 52 to It showed an IDF value of 59 and 65 percent. The use of amine-terminated polyether is minute can provide equivalent or better yield strength than foams made with reinforcing agents. Understood. Furthermore, the modulus value of this form is desirable and copolymer – so high that it is difficult to achieve using polyols.

Goto Molded polyurethane foam was prepared using the composition shown in Table 1 below and the method shown in Example 1. (Sample Nα11) was manufactured.

−Table 112■ Amine-terminated polyether B (+) 75 Copolymer polyol A (2) 25 Diethanolamine 1.7 Water 3.8 Triethylenediamine? Liquid (3) 0.12bis(2-dimethylaminoethyl ) Ether (4' 0.075 dibutyltin dilaurate 0.0042 bubbles open) agent (610,05 80/20) 105 Index (1) First A P-nitrochloroben-terminated, 5000 molecular weight, nominally trifunctional polyether It was prepared by reaction with zene and subsequent reduction of the nitro group to the primary amine.

(2) 40% solid SAN type with polyol B as the base polyol copolymer polyol (3) 33% solution in dipropylene glycol (DPG) (4) Amine terminal port 10% solution in Liether C"Polycat 77 as Abbott La Sold by boratories (6) DCF 11630 as Dow Co Silicone oil sold by Rning Corp. (7) See footnote to table ■ The obtained foam had the properties shown in Table 3.

Table-1■ Density, 1 b/ft3 (kg/bo) 2.20 (35) Tensile strength, psi (M Pa)”’ 18.0 (0,12) Elongation, % (-) 83 Tear strength, 1 b / in” (N / m) 1.37 (24 [)) Elasticity, %”36.6 Compression set, % (4) 80 1)’ D(S) 25% 61 65% 148 % hysteresis recovery <s> 66 Modulus (’) 2.43 Airflow, ft3/ll1in (rrf/S)” 6.0 (2,8 xlO-3)") ASTM D-3574-81 Test E.

” ASTM D-3574-81 Test F.

(3) ASTM D-3574-81 Test H0(') ASTM D-35 74-81 Test D.

” ASTM D-3574-81 Test B, IFD is Indentation Force Deflection i) Modulus = 65% IFD / 25% IFD.

” ASTM D-3574-81゜ Combinations of amine-terminated compounds and copolymer polyols are determined according to the IFD values in Table 1. As shown in the figure, the yield strength was dramatically improved.

A similar but slightly inferior effect was also observed for sample N004, and this sample also A mixture of amine-terminated compounds and copolymer polyols was used.

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Claims (1)

[Claims] having a density of 1.6 pounds/ft3 (100 kg/m2) or less; (A) Relatively high equivalent compound having an average of 1.5 to 4 active hydrogen-containing groups per molecule or mixtures thereof (at least 30 percent of the active hydrogen-containing groups are primary aromatic groups, Lewis acid blocks primary aliphatic and/or secondary aliphatic or aromatic amino acids. ), (B) a blowing agent in an amount sufficient to provide a cellular structure to the foam; (C) one of component (A); less than 5 parts by weight of a crosslinker or chain extender per 00 parts; and (D) Polyisocyanate open cell flexible polyurea or polyurea which is the reaction product of a reaction mixture comprising Riurea polyurethane foam. 2. Polyisocyanate gives an isocyanate index of 90-125 2. The foam of claim 1, wherein the foam is present in an amount sufficient to . 3. The blowing agent contains water and has a weight of at least 3.5 parts per 100 parts of component (A). parts of the component and component (A) has an equivalent weight of 500 to 2500. Form described in 2. 4. Polyisocyanate is (1) An isomer mixture of 2,4- and 2,6-toluene diisocyanate, and teeth (2) 2,4'- and 4,4'-diphenylmethane diisocyanate or isomeric mixtures of those derivatives, and component (A) is comprised between 1.9 and 2. Foam according to any of the preceding claims, having an average functionality of 0.05. 5. Ingredient (A) (1) Aromatic amine-terminated polyether or (2) Secondary aliphatic amine-terminated polyether 4. A foam according to any one of claims 1 to 3, comprising a foam. 6. Aromatic amine-terminated polyethers are combined with polyether polyols and halogenated nitrides. Reaction products with lobenzene compounds (where the nitro group is then reduced to the primary amine group) 6. The form of claim 5, comprising: 7. A secondary aliphatic amine-terminated polyether is a primary amine-terminated polyether and an ethylene 6. The foam of claim 5 comprising a Michael addition product with an unsaturated compound. Mu. 8. The secondary aliphatic amine-terminated polyether is a polyether polyether with a primary amine. 8. A foam according to claim 7, which is produced by reductive amination of a polymer. 9. A method for producing open-cell polyurethane foam, the method comprising: is reacted and mixed in a one-step process under conditions such that a polyurea-polyurethane foam is obtained. the reaction mixture is (A) Relatively high equivalent compound having an average of 1.5 to 4 active hydrogen-containing groups per molecule or mixtures thereof (at least 30 percent of the active hydrogen-containing groups are primary aromatic groups, Lewis acid blocks primary aliphatic and/or secondary aliphatic or aromatic amino acids. ), (B) Sufficient to provide a foam with a density of 6 pounds/ft3 (100 kg/m2) amount of blowing agent, (C) less than 5 parts by weight of a crosslinking agent or chain extender per 100 parts of component (A); and (D) Polyisocyanate How to include. 10. Component (A) has an average equivalent weight of 500 to 2500, and component (C) has toluene. diisocyanate, comprising an isomeric mixture of MDI or a derivative of MDI , and the reaction mixture further comprises an effective amount of a catalyst and a surfactant. The method according to item 9. 11. (A) has an equivalent weight of 500 to 2500 and an average functionality of 1.8 to 3; call (1) Aromatic amine group or (2) Secondary aliphatic amine group polyethers having 50 to 100 percent active hydrogen-containing groups of the form; (B) 3.5 to 8 parts of water per 100 parts by weight of component (A); (C) an effective amount of the third Amine catalyst; (D) 0.1 to 4 parts of alkanolamine crosslinking per 100 parts by weight of component (A) agent; and (E) a sufficient amount of aromatic polymers to give an isocyanate index of 95 to 120; isocyanate 6 lb/ft3 produced by reacting a reaction mixture comprising (100 kg/m2) or less Polyurea polyurethane foam. 12. (A) Relatively high abundance with an average of 1.5 to 4 active hydrogen-containing groups per molecule compound or mixture thereof (at least 30 percent of the active hydrogen-containing groups are monoaromatic, Lewis acid block primary aliphatic and/or secondary aliphatic or aromatic group amine group), (B) 3.5 to 10 parts by weight of water per 100 parts by weight of component (A); and (C) 0.1 to 4.5 parts by weight of crosslinking agent per 100 parts by weight of component (A) or chain extender, An active hydrogen-containing composition comprising: