CN1027815C

CN1027815C - Flexible polyurea or polyurea-polyurethane foams prepared from high equivalent weight amine-terminated compounds and process for preparing same

Info

Publication number: CN1027815C
Application number: CN88101942A
Authority: CN
Inventors: 拉尔夫·地普里斯特及尔; 罗纳德·姆赫林顿; 理查德·丹佩弗里
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1987-04-07
Filing date: 1988-04-07
Publication date: 1995-03-08
Anticipated expiration: 2003-04-07
Also published as: AU605860B2; CN1030086A; WO1988008009A1; JPH06102710B2; JPH02500109A; BR8807445A; AU1548588A

Abstract

Flexible polyurethane foams are prepared by reacting a polyisocyanate with certain amine-terminated compounds. The amine-terminated compounds are characterized in having at least 30 percent of their active hydrogen-containing groups in the form of primary aromatic, Lewis acid-blocked primary aliphatic and/or secondary aromatic or aliphatic amine groups. The resulting foams exhibit excellent physical properties, even in the absence of a cross-linker compound.

Description

Flexible polyurea or polyurea-polyurethane foams prepared from high equivalent weight amine-terminated compounds and process for preparing same

The present invention relates to the flexible foam that in the reaction of polyisocyanates and high equivalent weight compound, prepares with many groups that contain reactive hydrogen.

Flexible polyurethane foam has had for many years in industrial application.Their prevailing purposes are to make pad, for example cushion, car mat, mattress, substrate pad and other wadding or pad.Flexible polyurethane foam is to be made by the component reaction that comprises high equivalent weight polyol, polyisocyanates and whipping agent by traditional method.The certain methods of these component reaction is applied.In one approach, make the polyol and the excessive polyisocyanates reaction of stoichiometry of high equivalent weight, generate prepolymer, then, this prepolymer and water and optional other polyol and whipping agent reaction generate foam.In another approach, this polyol mixes with whipping agent and all other components except that polyisocyanates, forms " B-side " composition, and then, foam is made in said composition and polymeric polyisocyanate reaction.

In recent years, wish to produce a kind of foam that has than high bearing capacity, in particular for the foam of cushion material always.In order to produce the foam that has than high bearing capacity, just adopting certain methods.A kind of method comprises the use linking agent, i.e. the polyol or the polyamine of low equivalent, strong reactive behavior.Use this method can prepare foam with higher year He.So-called foamable reaction that is occurred when regrettably, using this class linking agent to tend to destroy the production foam and the balance between the gelling reaction.In order to obtain a kind of open celled foam with good physical behavior, making the reaction of polyol and isocyanic ester and whipping agent generation gas is necessary by suitable order all.If these foam gellings are too fast, foam will shrink after cooling so; If these frothy gels are slow excessively, then can form big and irregular hole; What is more, and the gas that whipping agent produced can all be run away, and generates " airbag ".Owing to this reason, industrial practice has proved that it is difficult using linking agent.In addition, linking agent has also increased the foamy cost significantly, and this is not only the cost that adds linking agent, and because the existence of linking agent also must be used additional polyisocyanates, to adjust.Therefore, always wish when the preparation flexible foam, to use the linking agent of minimum quantity.

Another kind method is to use the differential scattered seed of polymkeric substance packing material.These so-called " polymeric isocyanate " and " polymeric polyhydroxy compound " get by the existence that is dispersed in polyol and the polyisocyanates colloidal state fractionated polymer beads in any one or two kinds of to be strengthened.Various polymer beads are dispersed in polyol and the polyisocyanates by this way, they comprise the ethene polymers class, for example particle of styrene-propene-nitrile (SAN) copolymer analog, polyisocyanate polyaddition (PIPA) polymer class, polyureas and the epoxy particle of use recently.

Use these polymeric dispersants to have some problems.Though they improve load-carrying properties really and help perforate, also be expected further to improve load-carrying properties in some cases, but some more is difficult to control, transportation and processing for they, because the tendency that these discrete particles have gelling and settle out from external phase but on the other hand.Polymeric polyhydroxy compound and polymeric isocyanate cost an arm and a leg with respect to polyol and polyisocyanates itself.In addition, even use these dispersion agents, also require usually to use linking agent, thereby further increased the foamy cost.Have, the molded foam made from the polymeric dispersant in use contraction problem of (under impossible extruding situation) also is a shortcoming again.

Another consideration is to prepare low density foam by the water-content that increases in the foam formulation.Traditional preparation foamy method is that per 100 parts of (weight) polyols use the water of 2～4 parts (weight), so that cellular structure is provided.Recently, made the low density foam of water-content up to 4.6 parts.Up to now, the foam of these high-moistures still is difficult to preparation and processing.Water is often promptly many than the polyol reaction, thereby causes foam foaming too early and contraction.

Be desirable to provide a kind of flexible foam with good load-carrying properties, wherein employed linking agent and polymeric dispersant can reduce to minimum or even fully need not, if desired, can in foam, use high-content water to prepare low density foam.

On the one hand, the present invention is a kind of flexible polyurea or polyureas-polyurethane foam of perforate, and its density is 6 pounds every cubic feet (100 kilograms every cubic metre) or littler, and it is the reaction product of the reaction mixture formed of following component:

(A) a kind of higher normal compound or its mixture; its each molecule on average has 1.5～4 groups that contain reactive hydrogen; the group at least 30% that wherein contains reactive hydrogen is uncle's aryl amine, uncle's fat and/or the secondary fat or the aromatic amino of Lewis acid protection (blocked)

(B) a kind of whipping agent, its consumption are enough to offer foam with vesicular structure,

(C) a kind of per 100 parts of components (A) are lower than the linking agent or the chain extension agent of 5 parts (weight), and

(D) a kind of polyisocyanates.

On the other hand, the present invention is a kind of method for preparing polyurethane foam, is included under the condition that obtains a kind of flexible polyurea or polyureas-polyurethane foam and makes reaction mixture reaction as herein described with single stage method.

Again on the one hand, the present invention is under the situation that has the q.s whipping agent to exist, and by making component reaction, a kind of improvement of the flexible polymer foam process of preparation perforate is 6 pounds every cubic feet or lower (100kg/m so that density is provided ²) foam; this component comprises having many higher normal compounds that contain the group of reactive hydrogen; per 100 parts of component (A) linking agents or chain extension agent are no more than 5 parts (weight); and polyisocyanates; its improvements are: with regard to regard to the high equivalent weight compound; used have in each molecule 1.5～4 groups that contain reactive hydrogen than high equivalent weight compound or its mixture, at least 30% is uncle's aryl amine in this group, uncle's fat and/or the secondary aromatics or the fatty amido of Lewis acid protection.

Also have, the present invention is a kind of composition that contains reactive hydrogen that comprises following component:

(A) a kind of higher normal compound or its mixture, its each molecule on average has 1.5～4 groups that contain reactive hydrogen, and the group at least 30% that wherein contains reactive hydrogen is uncle's aryl amine, uncle's fat and/or the secondary fat or the aryl amine of Lewis acid protection,

(B) per 100 parts of (weight) components (A) water is 3.5～10 parts (weight), and

(C) a kind of linking agent or chain extension agent, per 100 parts of (weight) components (A) are 0.1～4.5 part (weight).

Have been found that use the uncle's fat contain uncle's aryl amine of at least 30%, Lewis acid protection and/or secondary aromatics or fatty amido (hereinafter claiming " end amine compound ") can provide some unexpected benefits than the high equivalent weight compound.This foam has particularly good load-carrying properties, even also is like this not having under the situation of linking agent.When using linking agent, foamy load-carrying properties of the present invention are better than other similar foam of use side hydroxyl high equivalent weight compound usually.Foam of the present invention typically has bearing behavior, it reach in addition when having surpassed the linking agent that uses similar content by the foamy supporting capacity of polymeric dispersant preparation.In addition, foam of the present invention is perforate, and often demonstrates the low-shrinkage energy, available it manufacture and can prevent bubble after the moulding part or other structure broken, that contain inner lead.Employed foam formulation also has the good ability that can flow and be full of complicated die among the present invention.Find that also in some cases, permission to use of the present invention is far above adopting traditional method, industrial possible water-content to prepare foam.

In the present invention, the use side amine compound prepares flexible polyurea or polyureas-polyurethane foam.As term used in the present invention; the end amine compound refers to a kind of higher normal compound or polymkeric substance; or this compound or mixture of polymers; it has many groups that contain reactive hydrogen, and wherein at least 30% is uncle's fat and/or the secondary fat or the ah aromatic amihe-based of primary amine groups, Lewis acid protection.The equivalent of employed here end amine compound more or less depends on foamy particular type to be prepared, but best 400～5000, and the best is 500～2500.On average have 1.5～4 groups that contain reactive hydrogen in end amine compound or each molecule of its mixture, be preferably 1.8～3 groups that contain reactive hydrogen.

The end amine compound can be any easy structure, as long as it does not contain the component of undesirable, interference and polyisocyanates reaction generation polyureas or polyureas-polyurethane foam ability.Particularly Shi Yi end amine compound is to have many groups that contain hydrogen alive, and at least 30% is the uncle's fat of uncle aryl amine, Lewis acid protection and/or the polyethers or the polyester of secondary fat or ah aromatic amihe-based wherein.

The secondary fat amine compound of suitable end comprises the polyol class, and especially making the ratio of contained secondary amine through modification is 30～100%, is preferably 50～100%, and the best is 60～90% polyether polyol and polyester polyol.As United States Patent (USP) 4,153,381 is described, and the secondary fat amine compound of this class end can pass through corresponding polyol and primary amine reaction, and the preparation easily with the hydrogen reduction intermediate product.This primary amine is that alkylamine, Cycloalkyl amine or the benzyl amine of inertia replacement is more favourable.Another kind method holds secondary fat amine compound to prepare in the Michael reaction of corresponding uncle's aliphatic amine and alkylene unsaturated compound.Though the noisy substituent any compound of response capacity that can generate secondary amine with primary amine generation Michael reaction and not contain generating product and polymeric polyisocyanate can use, vinyl cyanide is a kind of suitable especially alkylene unsaturated compound.Uncle's aliphatic amine itself can prepare in the reductive amination of corresponding polyol and ammonia, for example resembles United States Patent (USP) 3,128,311; 3,152,998; 3,654,370; 3,347,926 and 4,014, described in 933 like that.

Suitable end aromatic amine compound comprises polyol class, particularly polyether polyhydroxy-compound and polyester polyol, and they all contain a certain proportion of arylamine group through modification.For example, this compounds can carry out end-blocking by corresponding polyether polyhydroxy-compound or polyester polyol and vulcabond and generate prepolymer, and this prepolymer and water are reacted the free isocyanate group is hydrolyzed into corresponding primary amines and prepares.The compound of these types is because the viscosity height is processed difficulty, because of this time recommended.By another method, can be by making the nitrobenzene compound reaction in corresponding polyether polyhydroxy-compound or polyester polyol and fontanel generation, for example neighbour or p-Nitrophenyl chloride, or DNCB reaction, then nitroreduction is become amine, thereby prepare this compounds.

Best, adopt catalytic hydrogenation to produce this product.Representative method is seen " catalytic hydrogenation on the platinum " (" Catalytic Hydrogenation over platinum Metals'by Paol N.Rylander; 1967; Acaolemic Press, New York N.Y).Comprise that any known of Raney nickel (Raney hickel) can use fragrant nitro-reduction reaction useful catalysts.Preferred catalyzer is made up of the platinum metals, and they comprise ruthenium, handcuffs, palladium, osmium, iridium and platinum.Best, catalyzer is stated from the carrier, for example activated carbon, silica gel, alumina, diatomite, float stone or the like.The accurate ratio of metal element is not a key factor on these carriers.In general, metal can be in 0.05～40%(weight), 0.5～20%(weight more fortunately), be preferably in 5～10%(weight) scope in change.

Desiring the reductive nitro, the ratio of the employed catalyzer of representing with pure metal is preferably in 0.1～1.0mol% scope more favourable in the scope of amount nitro 0.05～10mol% metal.Term " equivalent of nitro " means the nitro equivalent, and it can be tried to achieve by the molecular weight of removing nitro-aromatics (II) with every mole nitro number.

In the liquid phase that has hydrogen and catalyst component to exist, carry out hydrogenation.Generally speaking, this catalyzer need use a kind of solvent, but this solvent is not absolute demand yet.Any knownly can adopt to the useful solvent of catalytic hydrogenation, but it should be an inert for compound (I) and compound (II).For example, following solvent can be used separately or with the form of its mixture: aromatic hydrocarbons, benzene for example, toluene and dimethylbenzene; Alcohols, methyl alcohol for example, ethanol, propyl alcohol and Virahol; Ester class, for example ethyl acetate ethyl propionate and ethyl butyrate; Ethers, for example diox and tetrahydrofuran (THF); And water, they or use separately, or use with above-mentioned solvent.Also can consider to use liquefied ammonia.The consumption of solvent is not crucial substantive issue, thinks that effective any consumption can adopt.The content of nitro-aromatics in the solvent (II) is at least 10%(weight) more favourable, be preferably 20～70%(weight), and the best is 25～50%(weight).

In any given hydrogenation, the accurate selection of temperature is one, for example the function of specific catalytic activity and hydrogen pressure.This temperature better, is preferably in 15～100 ℃ in 0～200 ℃ of scope, best in 20～50 ℃ of scopes.

Similar to the situation of said temperature, the hydrogen pressure that is adopted can be in any useful range, for example from the 15psig(100KPa gauge pressure) to up to any rational operating pressure.In general, this hydrogen pressure will be from the 15pisg(100KPa gauge pressure) to the 200psig(1400KPa gauge pressure), preferably from the 30psig(100KPa gauge pressure) to the 60psig(300KPa gauge pressure).

Being easy to of this reduction reaction controlled hydrogen subsequently and absorbed.Therefore, reduction reaction will end at the theoretical hydrogen amount absorbed that.Another kind method is that this reduction reaction is performed until the degree that hydrogen can be consumed that no longer includes.

In the suitable method of another kind, the polyethers of corresponding terminal hydroxy group or terminal primary amine or polyester can with the lower alkyl ester that for example resembles nitroanisole or para-amino benzoic acid, especially this class substance reaction of methyl esters then is the reduction reaction of nitro, generates the end aromatic amine compound.

The end secondary amine compound can prepare in the michael reaction of corresponding uncle's aromatic amine compound and alkylene unsaturated compound (for example aforesaid vinyl cyanide).No matter be terminal primary amine, still hold secondary amine, the ratio that the end aromatic amine compound contains primary amine groups and/or secondary amine the 30～100% better of the group sum that contains reactive hydrogen that provided than the high equivalent weight compound of serving as reasons is preferably 50～100%, and the best is 70～100%.

Here the uncle's fat amine compound protected that is suitable for can be very expediently be followed after the reductive amination reaction of corresponding terminal hydroxy group compound and ammonia and carries out coordination reaction with Lewis acid (for example Benzoyl chloride, the metal carboxylate or the ALUMINUM CARBOXYLIC of carbonic acid gas and for example tin, zinc, titanium) and make.Lewis acidic consumption is preferably whenever amount primary amine 0.9～1.5 equivalent with whenever amount primary amine groups 0.2～5 equivalent is better.

Any in the aforementioned end amine compound, and it and mixture with suitable normal a kind of polyol are effective, as long as within the specified in the above scope of the ratio of amido, in by the group of the reactive hydrogen of contributing than the high equivalent weight compound, at least 30% be amido promptly.Particularly interested is the mixture of end amine compound and polymeric polyhydroxy compound, the polymeric polyisocyanate polyol dispersion agent (PIPA polyol) of polyureas polyol dispersion agent (PHD polyol), addition polymerization for example, or addition polymer dispersion agent, styrene-acrylonitrile copolymer polyol for example, weight with employed higher normal compound is benchmark, and the weight percent of this polymkeric substance polyol is up to 50%.

Just as previously mentioned, the preferred equivalent of end amine compound depends on that more or less desire prepares foamy type and working method thereof.With regard to prepare the molded polyurethane foam with thermal curing methods with regard to, the equivalent of end amine compound is 500～2500 better, is preferably 700～2000, and the best is 800～1500.As for prepare slab foam or molded polyurethane foam with the cold-curing method, best equivalent is 500～1800.

No matter be the aliphatic polymeric isocyanate class, or the aromatic polyisocyanate class, all can be used for the present invention and prepare foam.For example Shi Yi aliphatic polyisocyanate class comprises two isocyanic acid ethyls, 1,4-tetramethylene diisocyanate, 1,6-two isocyanic acids six methylene esters, 1,12-two isocyanic acid dodecyl esters, tetramethylene-1,3-vulcabond, hexanaphthene-1, the 3-vulcabond, hexanaphthene-1,4-vulcabond, 1,5-two isocyanato-s-3,3, the 5-trimethyl-cyclohexane, 2,4-two isocyanic acid hexahydro-toluene esters and/or 2,6-two isocyanic acid hexahydro-toluene esters, perhydro--carotene 2,4 '-and/or-4,4 '-'-diphenylmethane diisocyanate (H ₁₂MDI) and two isonitrile acid isophorone ester.

For instance, Shi Yi aromatic polyisocyanate comprises 2,4-and/or 2,6-toluene-2,4-diisocyanate (TDI), 2,4 '-'-diphenylmethane diisocyanate, 1,3-and 1, the inferior phenyl ester of 4-two isocyanic acids, 4,4 '-two isocyanic acid ditan esters (comprise they and a small amount of 2,4 '-mixture of isomers), 1,5-two isocyanic acid naphthylidene esters, three benzene toluenes-4,4,4 " triisocyanate and polyphenylene-polymethylene polyisocyanates.When polyisocyanates is the derivative of MDI or MDI, during the particularly a kind of mixture that comprises polymeric MDI, recommending the end amine compound is dual functional basically, promptly has average 1.5～2.2 functionality, is preferably 1.8～2.1, and the best is 1.9～2.05.Have been found that opposite with the polyol of the higher functionality that is used to prepare flexible foam traditionally, be essentially dual functional end amine compound class the use retardation gelling of reaction mixture, and further promoted the high quality foamy to generate with this.Can use actual functionality is that 1.5～1.95 a kind of higher normal compound and another kind of actual functionality are 2.2 or the mixture of higher higher normal compound, and the average functionality of this mixture is 1.5～2.2.

In addition; the derivative of aforementioned polyisocyanates and prepolymer, the derivative and the prepolymer that for example contain the polyisocyanates of urea alkane, carbodiimide, allophanate, isocyanuric acid ester, acidylate urea, biuret, ester and similar group here are of great use.Among them, the prepolymer of TDI and MDI contains carbodiimide and equivalent so-called " liquid MDI " product between 130～150 is particularly important.

In the aforementioned polyisocyanates, TDI, MDI, two isocyanic acid isophorone esters, H ₁₂MDI, two isocyanic acids, six methylene esters, two cyclic isocyanate hexane ester and derivatives thereof, because their price, availability and performance and should be preferred.TDI, the derivative of MDI and MDI are best, and TDI, particularly 2,4-and 2, the 6-mixture of isomers should preferentially be selected for use especially.

It is 60～200 that the consumption of polyisocyanates should be enough to provide isocyanate index, is preferably 90～125, and the best is 95～110.When index is higher, the binary polymerization reaction of polyisocyanates can take place, thereby make foam lose flexibility.When index is low, can occur solidifying insufficient, make the foamy performance inferior.When using the MDI or derivatives thereof as polyisocyanates, the isocyanate index of being recommended is 60～110, is preferably 90～103, because when index is higher than 110, MDI helps to provide slab foam, and index was low to moderate 60 o'clock, and MDI will provide the snappiness foam." isocyanate index " is isocyanate group and 100 times of the ratio that can react the group that generates reactive hydrogen contained in the foamy mixture.

Whipping agent is another key ingredient of the present invention.Whipping agent is any material that can produce gas under the condition of polyisocyanates and polyol reaction.Such material comprises air, and carbonic acid gas, nitrogen, water, formic acid, lower boiling fontanel be for alkanes, finely-divided solid and so-called " azo " whipping agent, for example Cellmic C 121.Preferred blowing agent be water, lower boiling fontanel for alkanes, or their mixture.The reasonable volume of whipping agent is 0.5-6Ib/ft for being enough to provide a kind of volume density ³(8.3-100kg/m ³) or littler, be preferably 0.9-4Ib/ft ³(15-66.6kg/m ³), the best is 1.1-3Ib/ft ³(18.3-50kg/m ³).

Consumption can provide desired density for per 100 parts of fontanels that comprise methylene dichloride, Refrigerant 12 and monochlorodifluoromethane and monochlorotrifluoromethane than 5～50 parts of high equivalent weight compounds usually for alkanes, when with another kind of whipping agent (for example water) when using jointly, its consumption can be smaller.

An outstanding advantage of the present invention is exactly that it can prepare the very low foam of density as whipping agent for water.In the past, for per 100 parts of higher normal polyols, water is limited to 4.6 parts or lower as the consumption of whipping agent, because make water often make foam inferior relatively largely.Adopt the inventive method, the used water yield of per 100 parts of end amine compound can surpass 7.5 parts, so that the foam of the extremely-low density with useful physical character is provided.Therefore,,, be preferably 3.5～8 parts, when the best is 4～6 parts, can provide desirable density when the amount ranges of water is 0.5～10 part for per 100 parts of end amine compound.(density is lower than 1.5 pounds of/cubic feet (10kg/m for the preparation extremely-low density ³) foam, the consumption of water is 5～10 parts.

During foam produced according to the present invention, end amine compound and polyisocyanates catalyst for reaction have also been used.Although known many materials can be used for reaching this purpose, using the catalyzer of the most preferentially selecting for use is tertiary amine catalyst and organo-metallic catalyst.

For example, typical tertiary amine catalyst comprises triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N-coconut morpholine, 1-methyl-4-dimethylaminoethyl piperazine, 3-methoxyl group-N-dimethyl propylamine, N, N-diethyl-3 diethyl aminopropylamine, dimethyl benzylamine and two (2-dimethylaminoethyl) ether.For per 100 parts (weight) end amine compound, the consumption of tertiary amine catalyst be 0.01～5 part better, 0.05～2 part is best.

Typical organo-metallic catalyst comprises the organic salt of metal (for example tin, bismuth, mercury, zinc and lead) and preferred organo-tin compound.For example Shi Yi organotin catalysts comprises tin methide dilaurate, dibutyltin dilaurate and stannous octoate.For example at United States Patent (USP) 2,846, also mention some other suitable catalyzer in 408.Per 100 parts (weight) end amine compound, organo-metallic catalyst is 0.001～0.5(weight) better.

Polyureas or polyureas-polyurethane foam are according to the inventive method end amine compound, whipping agent, polyisocyanates to be contacted with catalyzer, what these component reaction are generated be prepared under poromeric condition.In general, reaction mixture can contain other component, for example linking agent, catalyzer, tensio-active agent, tinting material, pore-creating agent, fire retardant, antioxidant, releasing agent or the like, whether they can be molded or sheet material foam and changing according to required attribute of foamy and foam.

Can use linking agent, especially when producing molded foam or high-elastic sheet material foam, so that improve load-carrying properties and processibility.The linking agent that this class is suitable comprises having in alkanolamine and each molecule and contains 3～8, preferably 200 or other compound of low equivalent more of the group of 3～4 reactive hydrogens.The example of this compound has glycerine and TriMethylolPropane(TMP) and other alkylidene group three alcohols.But, alkanolamine preferably, for example diethanolamine, tri-isopropanolamine, trolamine, diisopropanolamine (DIPA), the adducts of 4～8 moles of ethylene oxide and/or propylene oxide and ethylene diamine; Polyamines class, for example methylene-bis (Ortho-Chloro aniline), ethylene diamine and ammonia.According to its optimum response, what recommended most is diethanolamine.Advantage of foamy of the present invention is that at the weight range of working as of linking agent, foam demonstrates the better load-carrying properties of similar foam that prepare with the end amine compound than not.Therefore, in order to obtain suitable load-carrying properties, reduce or even to save crosslinker compound be possible according to the present invention.But when using, per 100 parts of end amine compound adopt the linking agent that is lower than 5 parts, is preferably 0.1～4 part more favourable.What recommended most is: during use, the total amount of per 100 parts (weight) end amine compound linking agent and chain extension agent is lower than 5 parts.

Can also use chain extension agent, with the further foamy load-carrying properties of improving.For this purpose of the present invention, " chain extension agent " comprises that having the group and the equivalent that contain two reactive hydrogens in the per molecule is 31～300, is preferably 31～150 compound.The chain extension agent of hydroxyl comprises aklylene glycol class and glycol ethers, ethylene glycol for example, 1, ammediol, 1,4-butyleneglycol, hexamethylene glycol, Diethylene Glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and 1,4 cyclohexane dimethanol.The amine chain extension agent comprises diethyl phenyl diamines, phenylenediamine, the methylene-bis (aniline) of methylene-bis (Ortho-Chloro aniline), NaCl block, tolylene diamine, aromatic diamine class (they with at least one carbon atom that each amido links to each other on replaced by alkyl).When using such chain extension agent, more favourable with the trace use, the end amine compound of promptly per 100 parts (weight) is lower than 5 parts (weight).That is recommended most is every 100(weight) hold the total amount of amine compound chain extension agent and linking agent to be lower than 5 parts (weight).But, generally be preferably under the situation that does not have chain extension agent and prepare foam.

In order to prepare stable foam, that is to say a kind of foam that does not subside or contain a large amount of macropores, can use a kind of tensio-active agent.This tensio-active agent makes foamed reaction mixture stable in case subside, and fully is cured to up to this mixture to have kept its profile.Suitable tensio-active agent comprises as mentioned above the multipolymer of polysiloxane/poly-(alkylene oxide) of (as United States Patent (USP) 3,887,500 and 3,957,842 in).In the preparation foam, the selection of this tensio-active agent and use are being known in the art.But, an advantage of the invention is the tensio-active agent that can use reduced amounts, can save tensio-active agent fully sometimes.Therefore, recommend to use a kind of per 100 parts of end amine compound consumptions to be lower than 0.5 part, to be preferably lower than 0.25 part tensio-active agent.In an optimum implementation, under the situation that does not have tensio-active agent basically, prepared foam.

According to the present invention, foamy preparation is finished with a step by mixing total overall reaction component, catalyzer and optional composition and it being reacted.In the preparation of molded foam, can find out advantage of the present invention especially.Prepare in molded polyureas-polyurethane foam, the whole components except that polyisocyanates are preferably carried out blend together and are injected mixing tube with single liquid stream.Moreover, some component, catalyzer or fontanel for the methane whipping agent sometimes also with the polyisocyanates blend.In addition, when making water and tensio-active agent, if need, the liquid stream that they can be independent is introduced.Polyisocyanates joins in the mixing tube with independent liquid stream, and there, it and polyol mixture also inject mould.When implementing mixing and injection molding operation, can adopt traditional low-voltage device, or adopt high pressure bump mixed processes, for example reaction injection molding method.In general, blending ingredients under about room temperature is although can be solid under component such as the pure MDI(room temperature) be heated to more than their fusing point.

In first kind of molding technique (hot molding technology), reactant is placed the mould of room temperature.Filling finishes, and places 150～275 ℃ baking oven to be cured on mould.In second kind of technology (cold mechanography), reactant placed be preheating to 30～75 ℃ mould.After mould is filled with, place 70～150 ℃ baking oven to be cured again.In the third technology, in solidification process, the mould of having filled with is kept at room temperature.In the third technology, can to or can mould not carried out preheating yet.

Enough reaction mixtures are placed mould so that mixture is full of mould fully after expansion.Best, add excessive slightly material, minimum requirements also will be full of mould.After mould filling finishes,, reaction mixture is solidified in mould making molded foam from mould, deviate from and do not take place under the situation of undesirable tension set at least.In typical commercial run, be just to be enough to reach this purpose in 2～30 minutes the set time in the mould.If need, by being heated to 50～120 ℃, last 10 minutes to 24 hours, be preferably 20 minutes to 2 hours, can carry out regelate to foam.

In solidification process or afterwards, perhaps with mechanical means the foamy hole is opened is necessary or desirable.This can by foam is pushed, punching, vacuum extrusion or by making the mould release finish (as United States Patent (USP) 4,579,700 is described) in the suitable stage of solidified.An advantage of the invention is that the insufficient regelate shrinking percentage of bringing of perforate has reduced usually substantially, thereby reduce or saved necessity of mechanical perforate.

In the sheet material foam of preparation time recommendation, reaction mixture preferably also contains a kind of aforesaid tensio-active agent and catalyzer.Although can use linking agent but they often omit from the sheet material composition of raw materials.In sheet material foamy industrial production, component can be, typically is introduced separately in the mixed flow, and there, they carry out thorough mixing and by being metered into the foaming bed.Moreover, if need, but these components of premix (except that polyisocyanates).During blend, these components are more favourable under room temperature or a little higher than room temperature in mixing tube, although in some cases perhaps must be through preheating so that under the fusion room temperature be some components of solid.

Foam use of the present invention a lot, for example as mattress, soft cushion of furniture, liner, substrate pad, the band cushion the substrate pad, automobile headstock baffle plate, vibration isolating pad, door handle, device lining (head liners) and seat.The present invention require good load-carrying properties or require low density and the occasion of high water content under particularly useful.

Provide the following example with explanation the present invention, but never mean and limit the scope of the invention.All umbers and percentage all by weight, except as otherwise noted.

Embodiment 1

In the present embodiment, make a kind of two functional end uncle's arylamine polyethers and polymkeric substance MDI be reacted into molded foam.

No. 1, the formulation flexible foam sample and No. 2 and control sample A and the B that point out by Table I.(Table I is seen the literary composition back)

Each preparation molded foam with No. 1, sample and No. 2 and control sample A and B, method is as follows: mix each component, they are transferred to 8 " * 8 " * 3 that have been preheating to 140 (63 ℃) " (in the mould of 200mm * 200mm * 76mm); after the foaming; mould was placed in the baking oven of 175 ℃ (80 ℃) baking 3 minutes, and made the foam demoulding this moment.The foamy characteristic is shown in the following table II.(the table II is seen the literary composition back)

Can see that the present invention has mainly improved modulus, tearing strength and tensile strength from table II data.Modulus value merits attention especially, because for example the modulus that obtains with the present invention shows that foam will provide comfortable especially seat.It is surprised that these values are made us especially, because sample is for No. 1 and No. 2 not use the linking agent preparation.

Embodiment 2

With No. 3～7, the described formulation flexible foam of following table III sample (the table III is seen the literary composition back)

Prepare foam sample 3～No. 7 according to embodiment 1 described general operation, result such as following table IV are shown.(the table IV is seen the literary composition back)

All foams all have good physical property.It should be noted that sample No. 7, wherein per 100 parts of end amine compound use 7.5 parts of water.Obtained the low-down foam of a kind of density, this foam has good physicals, particularly tensile strength and load-carrying properties.

Embodiment 3

In the present embodiment, make the heterogeneous mixture reaction of a kind of secondary fat amine polyethers of end and a kind of TDI of nominal trifunctional, form a kind of molded foam.

With showing No. 8～10, the formulation flexible foam sample shown in the V.(the table V is seen the literary composition back)

With each the preparation foam in these prescriptions, method is as follows, except that TDI, mixing all ingredients (all the temperature of component is 78 (25 ℃)), in TDI, carry out blend and mixture be poured into 15 " * 15 " * 4.5 that have been preheating to 140 (60 ℃) that " (in the mould of 381mm * 381mm * 114mm); after mould is full of, closed mould also was put in one 250 (121 ℃) baking ovens heating 4 minutes at once, then made the foam demoulding that obtains.The foamy physical property is measured in the cooling back, the results are shown in the table VI.(the table VI is seen the literary composition back)

All foams all have good performance.It should be noted that IFD and modulus value especially.Prepare foam by similar approach, different is to replace ending amino polyether with end hydroxy polyether, and it has 25%IFD value 16 and 65%IFD value 44 usually.The IFD value that foam of the present invention provides is higher basically.Equally, (weight with polyol is benchmark with the mixture of san copolymer polyol, its effective solids content is 12.wt%) preparation foam show, typical 25%IFD value 17～21, the 65%IFD value is 52～59, as can be seen, the load-carrying properties that provide with end amine polyethers equal or exceed the foam with micro-enhancing preparation.In addition, this foamy modulus value is very high, and this is desirable just, and all is difficult to reach with the multipolymer polyol.

Embodiment 4

With the prescription that the following table VII is listed, adopt the common operation among the embodiment 1 to prepare polyurethane foam (No. 11, sample).

The table VII

The composition weight umber

———— ————

End amine polyethers B ^1.75

Multipolymer polyol A ^2.25

Diethanolamine 1.7

Water 3.8

Triethylenediamine solution ^3.0.12

Two (2-dimethylaminoethyl) ether ^4.0.075

Dibutyl tin dilaurate 0.0042

The N-[3-(dimethylamino) propyl group]-N, N ', N '-0.24

Trimethylammonium-1, the 3-propylene diamine ^5.

Pore-creating agent ^5.0.05

80/20 tolylene diisocyanate ^7.105 indexes

1. make the polyethers and the p-Nitrophenyl chloride reaction of a kind of terminal primary amine, 5000 molecular weight, nominal trifunctional then make nitroreduction become primary amine, preparation thus.

2. a kind of 40% solid particulate SAN type multipolymer polyol, it with polyol B as basic polyol.

The solution of 3. a kind of 33% dipropylidene diol (DPG).

4. as the solution among a kind of 10% the end amine polyethers C.

5. Abbott laboratory sale, trade mark Polyca+77.

6. a kind of silicone oil is by the sale of Dow Corning company, trade mark DCF1163.

7. see Table the III note 7.

The foam that obtains has the characteristic of pointing out in the table VIII.

The table VIII

Density, 1b/ft ³(kg/m ³) 2.20(35)

Tensile strength, psi(MPa) ^1.18.0(0.12)

Unit elongation, % ^1.83

Tearing strength 1b/in ^2.(N/m) 1.37(240)

Elasticity, % ^8.36.6

Compression set, % ^4.80

IFD ^⑤

25% 61

65% 148

The hysteresis return rate, % ^5.66

Modulus ^5.2.43

Air flow quantity ft ³/ min(m ³/ s) ^7.6.0(2.8 * 10 ^-3)

1. A STM D-3574-81 tests E

2. A STM D-3574-81 tests F

3. A STM D-3574-81 tests H

4. A STM D-3574-81 tests D

5. A STM D-3574-81 test B IFD is the indentation force amount of deflection

6. modulus=65% IFD/25% IFD

⑦A STM D-3574-81

Indicated as the IFD value of reporting in the table VIII, the combination of end amine compound and multipolymer polyol, provide very large improvement for load-carrying properties here, in No. 4 samples, find out also but be not obvious effects that it has also used the blend of a kind of end amine compound and multipolymer polyol similar.

The table I

Parts by weight

Sample control sample sample control sample

No. 2 B* of No. 1 A* of component

End amine polyethers A ^1.100 0 100 0

Polyol A ^1.0 100 0 100

Diethanolamine 0 0.5 0 0.5

Water 4.5 4.5 4.5 4.5

Amine catalyst ^2.1111

Polysiloxane surfactant A ^3.0 0.75 0 0.75

Polysiloxane surfactant B ^4.0.75 0 0.75 0

Polysiloxane surfactant C ^5.0 0.3 0 0.3

Polysiloxane surfactant D ^6.0.3 0 0.3 0

Polymkeric substance MDI A ^7.80.3 80.3 00

Polymkeric substance MDI B ^8.00 80.3 80.3

* not embodiments of the invention

1. polyol A is a kind of two functional 1000 normal poly-(propylene oxides), and it contains 18%(weight) poly-(ethylene oxide) block of end.End amine polyethers A is by making the reaction of polyol A and p-Nitrophenyl chloride, making nitroreduction become primary amine groups to make subsequently.About 83% hydroxyl is converted to uncle's aryl amine.

2. a kind of sale monopoly tertiary amine catalyst (Union Carbide company sells, trade mark C225 catalyzer)

3. Y-10148 tensio-active agent (sale of Union Carbide company)

4. DC-5043 tensio-active agent (sale of Dow Corning company)

5. L-540 tensio-active agent (sale of Union Carbide company)

6. DC-10140 tensio-active agent (sale of Dow Corning company)

7. a kind of from 12%(weight) 2,4 '-135 normal polymkeric substance MDI(2.2～2.4 functionality of isomer preparation)

8. a kind of from 2.5%(weight) 2,4 '-135 normal polymkeric substance MDI(2.2～2.4 functionality of isomer preparation)

The table II

Sample or control sample numbering

Characteristic 1 A* 2 B*

Density 1b/ft ³(kg/m ³) 2.02(32) 1.91(31) 2.13(31) 2.11(34)

Tensile strength, psi ^1.(MPA) 14.0(0.10 35.1(0.24 12.9(0.09 22.7(0.16))))

Unit elongation % ^1.70 50 82 74

Tearing strength, 1b/in(N/m) 2.14(375) 1.25(220) 2.19(385) 1.22(215)

Elasticity % ^3.28 30 33 35

Compression set, % ^4.81 56 72 55

IFD ^⑤

25% 46 65 54 68

65% 140 137 158 159

Turn back to 25% 22 35 28 37

Hysteresis return rate % ^6.47 54 52 54

Modulus ^6.3.04 2.11 2.93 2.34

Air flow quantity, Ft ³/ min(m ³/ s) ^7.0.41(1.9 * 10 ^-7) 0.18(8.5 * 10 ^-5) 0.14(6.6 * 10 ^-5) 0.43(2 * 10 ^-4)

* non-embodiments of the invention

1. A STM D-3574-81 tests E

2. A STM D-3574-81 tests F

3. A STM D-3574-81 tests H

4. A STM D-3574-81 tests D

5. A STM D-3574-81 test B IFD is the indentation force amount of deflection

6. modulus=65% IFD/25% IFD

⑦A STM D-3574-81

The table III

Parts by weight

Component sample

No. 3 No. 4 No. 5 No. 6 No. 7

End amine polyethers B ^1.100 50 40 60 100

Polyol B ^1.00 60 40 0

Polyol C ^2.0 50 000

Diethanolamine 1.7 1.7 1.7 1.7 1.7

Water 3.8 3.8 3.8 3.8 7.5

Triethylenediamine solution ^3.0.25 0.25 0.25 0.25 0.25

Two (2-dimethyl aminoethyl) ether ^4.0.05 0.05 0.05 0.05 0.05

Silicone surfactant B ^5.1.6 1.6 1.6 1.6 1.6

Pore-creating agent ^6.0.04 0000

80/20 TDI ^⑦48.4 48.4 48.4 48.4 48.4

1. polyol B is 1650 equivalents, the nominal official that contains about 18% ethylene oxide-capped dose can poly(propylene oxide).End amine polyethers B is by making polyol B with the p-Nitrophenyl chloride reaction and make nitroreduction become primary amine groups to prepare.

2. a kind of san copolymer polyol of 25% solid particulate uses polyol B as basic polyol.

3. the solution in the dipropylidene diol a kind of 33%(weight).

4. as the solution among a kind of 10% the end amine polyethers B.

5. DC-5043(Dow Corning company sells).

6. a kind of silicone oil (Dow Coring company sells, trade mark DCF11630).

7. a kind of 80%(weight) 2,4-isomer and 20%(weight) 2, the 6-mixture of isomers.

The table IV

Sample number into spectrum

Characteristic 34567

Density 1b/ft ³(kg/m ³) 1.98(32) 1.92(31) 1.95(31) 1.84(30)

Tensile strength, psi(MPa) ^1.15.0(0.10) 20.9(0.14) 15.8 15.6(0.11) 19.1(0.13)

Unit elongation % ^1.109 104 125 121 91

Tearing strength, ^2.1b/in(N/M) 1.18(207) 1.76(308 1.17 1.23(215 1.40(245)))

Elasticity % 50 49 60 55 46

Compression set, % ^4.41.0 23.1 16.7 14.8 66.5

IFD ^⑤

25% 28 31 19 19 26

65% 66 78 47 46 55

Turn back to 25% 21 23 16 15 15

Hysteresis return rate % ^5.73 75 83 80 59

Modulus ⁶2.36 2.52 2.47 2.42 2.12

* non-embodiments of the invention

1. A STM D-3574-81 tests E

2. A STM D-3574-81 tests F

3. A STM D-3574-81 tests H

4. A STM D-3574-81 tests D

5. A STM D-3574-81 test B IFD is the indentation force amount of deflection

6. modulus=65% IFD/25% IFD

⑦A STM D-3574-81

The table V

Parts by weight

No. 10, No. 9 samples of No. 8 samples of component sample

End amine polyethers C ^1.100 100 100

Diethanolamine 1.5 1.7 1.7

Water 3.8 3.8 3.8

Triethylenediamine solution ^2.0.25 0.12 0.12

Two (2-dimethyl aminoethyl ethers) ^3.0.05 0.075 0.075

Silicone surfactant ^4.2.0 1.65 1.65

Dibutyl tin dilaurate 0.0042 0.0042 0.0042

N-[3-(dimethoxy amino)

Propyl group]-N, N '-N '-0.15 0.24 0.24

Trimethylammonium-1, the 3-propylene diamine ^5.

80/20 toluene 101 101 105

Vulcabond ^6.Index index index

1. by making a kind of uncle end amine, the polyethers and the acrylonitrile reactor of the nominal trifunctional of 5000 molecular weight, until basically all primary amine groups be transformed into secondary amine and prepare.

2. the solution in a kind of 33% the dipropylidene diol (DPG).

3. as the solution among 10% the end amine polyethers C.

4. DC-5043 tensio-active agent (sale of Dow Corning company).

5. see Table the III note.

The table VI

Sample number into spectrum

Characteristic 89 10

Density 1b/ft ³(kg/m ³) 2.02(33) 217(35) 2.20(35)

Tensile strength, psi(MPa) ^1.20.5(0.14) 19.0 18.6(0.13)

Unit elongation, % ^1.184 168 147

Tearing strength 1b/in(N/m) ²1.75 1.55(271) 1.42

Elasticity, % ^3.48 43 51

Compression set, % ^4.15.5 19.7 21.3

IFD ^⑤

25% 22 18 20

65% 65 56 65

Turn back to 25% 17 15 16

Hysteresis return rate % ^5.79 80 79

Modulus ^6.2.95 3.11 3.25

ft ³/min（m ³/s）

1.～7. see Table the IV note 1.～7.

Claims

1, a kind of method for preparing the perforate polyester form, this method is included under the condition that can obtain flexible polyurea or polyureas-polyurethane foam, goes on foot with one and makes the reaction mixture reaction, and wherein reaction mixture contains:

(A) higher normal compound or its mixture, its each molecule on average have 1.5-4 group that contains reactive hydrogen, and the group at least 30% that wherein contains reactive hydrogen is the aliphatic amido of uncle and/or the secondary ah aromatic amihe-based or the aliphatic amido of uncle's aryl amine, Lewis acid protection,

(B) whipping agent, its consumption is lower than 6 pounds every cubic feet (100 kilograms/meter for being enough to provide have ³) foam of density,

(C) per 100 parts of components (A) are lower than the linking agent or the chain extension agent of 5 parts (weight), and

(D) polyisocyanates.

2, according to the process of claim 1 wherein that the average equivalent of component (A) is 500,2,500.

3, according to claim 1 or 2 described methods, wherein component (A) comprising:

(1) a kind of polyethers of end arylamine, or

(2) polyethers of the secondary fat amine of a kind of end.

4, in accordance with the method for claim 3, the polyethers of its middle-end arylamine comprises the reaction product of a kind of polyether polyhydroxy-compound and a kind of nitrohalogen compound, and wherein nitro is reduced into primary amine groups subsequently.

5, in accordance with the method for claim 3, the polyethers of the secondary aliphatic amine of its middle-end comprises a kind of polyethers of terminal primary amine and the Michael addition thing of alkylene unsaturated compound.

6, in accordance with the method for claim 5, the polyethers of the secondary aliphatic amine of its middle-end is to prepare in the reductive amination of polyether polyhydroxy-compound and primary amine.

7, according to the method for claim 1 or 2, wherein the average functionality of (A) is 1.8-3.

8, according to the method for claim 1 or 2, the group that wherein contains reactive hydrogen has 50-100% to be following form:

(1) aryl amine, or

(2) secondary aliphatic amido.

9, in accordance with the method for claim 1, wherein whipping agent contains water, and the content of water is at least 3.5 parts of per 100 parts of components (A) (weight), and the equivalent of component (A) is 500-2, and 500.

10, in accordance with the method for claim 9, wherein the content of water is per 100 parts of components (A) 3.5-8 parts (weight).

11, according to the process of claim 1 wherein that component (C) comprises the heterogeneous mixture of toluene-2,4-diisocyanate, MDI or MDI derivative.

12, in accordance with the method for claim 1, wherein the content of polyisocyanates for being enough to provide the polyisocyanates index of 90-125.

13, according to the method for claim 12, wherein isocyanate index is 95-120.

14, according to the method for claim 1 or 12, wherein polyisocyanates is an aromatic polyisocyanate.

15, in accordance with the method for claim 14, wherein polyisocyanates comprises:

(1) 2,4-and 2, the heterogeneous mixture of 6-tolylene diisocyanate, or

(2) 2,4 '-and 4,4 '-heterogeneous mixture of diphenylmethanediisocyanate or derivatives thereof, and the average functionality of component (A) is 1.9～2.05.

16, according to the process of claim 1 wherein that linking agent is an alkanolamine, its consumption is 0.1-4 part (weight) in per 100 parts of (weight) components (A).

17, according to the method for claim 1, reaction mixture also contains the catalyzer and the tensio-active agents such as tertiary amine of significant quantity.