MXPA00009645A - Polyisocyanurate foams - Google Patents

Abstract

The invention provides polyisocyanurate systems for manufacture of polyisocyanurate foam components such as those from SRIM processes. The reaction systems include a polyisocyanate and a polyisocyanate reactive component that includes a trimerization catalyst, polyol, and a carboxylic acid blowing agent, optionally with water as a co-blowing agent. The reaction systems can be blown exclusively with carboxylic acid to produce SRIM products which can be demolded with reduced mold residence time.

Description

POLY I FOAM IANURATE FOAMS FIELD OF THE INVENTION [0001] The present invention relates to foams of po 1 i i or oi anur a t, to compositions used in the preparation of such foams and to molded articles prepared from such foams.

BACKGROUND OF THE INVENTION LD S molded cellular and non-cellular foam articles have found many applications in the automotive and construction industries. Illustrative automotive applications include the use of such foams in items such as consoles, door panels, pillars and seat backs. Examples of non-automotive uses include modular housing and shower supports and doors. Although many foam parts are produced by reaction injection molding processes (J3.IM), woven or nonwoven fiber reinforcements are known to provide the foam parts with higher tensile strength and flexural moduli. Such molding processes are known as reaction injection molding processes (RIM).

SRIM processes generally entail the pouring or injection of a liquid foam composition into a closed or open mold which, if opened, is substantially closed during the foaming reaction. Prior to pouring into the liquid foam composition, the reinforced fiberglass continuous plates and / or other suitable reinforced plastic parts can be placed in the open mold. In some cases, a cosmetic coating or cover supply material would initially be in the open mold prior to the placement of the twisting materials and / or the liquid foam composition. When such supply materials are used and the foam composition is substantially poured into the partially filled mold, the process is known as an SRIM backfill or backfill process. Although SRIM molders are faced with the only problems for their particular processes, they are also faced with the problems that accompany any traditional polyurethane molding process. In any molding operation, considerations of efficiency and cost mean that the length of time required to make each pair t as minimized as possible. As a result, it is highly desirable that each part be removed from the mold as quickly and as easily as possible. However, those skilled in the art will appreciate that molded polyurethane parts tend to require longer molding resistance times. The longer molding resistance time is highly disadvantageous as it adds significantly to the cost per part. Polyurethane foams have been used in a variety of applications including the spillage behind the structural reinforcement of rigid fiber foamed fiber made by reaction injection molding (LD-SRIM). In these applications, the components that form the foam are introduced into a mold, foamed in the mold and eliminated as the finished part. The mold may contain a reinforced mesh armor. In these processes e_s _ b e n f f ic t t e r as a limit a residence time of molding as possible to increase the productivity. Further, . There is little or no mold expansion beforehand to avoid the manufacture of defective parts. The methods of the prior art reduce the residence time of the manufactured parts of LD-SRIM which have focused on the modifications for the polyurethane formulations. These methods have been deficient, however, because the high exothermic temperatures exceed the initial softness point of the immature polymer. Therefore there continues to be a need for foam formulations that have particular utility in LD-SRIM applications and which can be molded with minimal residence time.

BRIEF DESCRIPTION OF THE INVENTION The invention described relates to the reaction system for foams of p or 1 i is ocianu r a t o. The reaction system includes a polyisocyanate component, and a reactive polyisocyanate component. The reactive polyisocyanate component can include a polyol, a carboxylic acid, water, a catalyst, and other additives. The polyisocyanate can be any of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, polyisocyanates to alaulophates, aromatic polyisocyanates and mixtures of isocyanates and modified polyisocyanates by the introduction of at least one of the residues of urethane, allophanate, urea, biuret, cardiimide, uretonimine or isocyanurate. The carboxylic acid component is a substituted or unsubstituted carboxylic acid or partial esters thereof selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, heterocyclic carboxylic acids. The polymerization catalyst is any of potassium hydroxide, potassium hydroxide with fatty acid and metal carboxylates at 1 c to 1 in or soluble or mixtures of the same. The reaction system of the present invention can be molded into SRIM and LD-SRIM with minimum molding strength time, especially when compared to systems of p 1 or r_e t_ano. Oxygen reaction systems can provide significant advantages such as decreased cycle time. Other benefits include high vitreous transition temperature, reduced post mold expansion, higher heat deflection temperature and easier mold removal. Having summarized the invention, the invention will now be described in detail as set forth in the following description and non-limiting examples.

DETAILED DESCRIPTION OF THE INVENTION Glossary: The following materials of. Brand names are defined in the following: Dabco 8800 Delayed action gelation catalyst from Air Products. Dsabco K-15 2 - e t i lh potassium exanoate, at 15% by weight in catalysis of T r im r i z ation of Air Products. Daltorez P-716 polyesterdiol; poly- [(ethylene, die iLej? o) -adipate]; hydroxyl value = 56; MW of approximately 2000, and a nominal functionality of 2.0, of ICI Ame ricas. DEG: diethylene glycol. J e f a HLÍ n e T p o 1 i (oxip r op i 1 in o) t r i am i n 5000: glyceryl, 5000 MW, functionality = 3; by Hunstman P e t r o chemi c a_l. The amine groups are primary aliphatic. Keme ster 5721 Triaclorate stearate from Witco Chemi ca 1 s.

Lioxol G-71S a complex fatty polyester which is the reaction product of adipic acid, pentaerythritol and oleic acid from Henkel Corporation, Niax L-1000 methyl siloxane oxide polyalkylene copolymer from Witco (OSI). Niax L 5420: Methyl polyalkylene oxide siloxane copolymer from Witco (OSI). Niax L 6980 methyl siloxane oxide polyalkylene copolymer from Witco (OSI). Poly G-55-173 polyether polyol from Olin. Chemical, Polycat DBU: catalyst di a z abi c i clounde Ceno from Ai r Products. Pripol 1013: a polymerized fatty trimer acid, nominal functionality = 2 of Uniquema.

Pripol 1040: a polymerized fatty acid dimer, nominal functionality =? 3 of Uniquema.

Priolube 1414 i s obut ilolea t oé s t e of commercial grade oleic acid. Rubinol R-015 triol; propoxylated glycerol; Hydroxy value 1 or = 650 of ICI Americas. Rubinol R-180 sucrose mezcal p r opox i 1 a da / de ile ileglicol (Approximately 72:28 P p of propoxylated products); total hydroxyl value = 440; functionality of number p r omedio = 6.42 of ICI Americas. R u b i n o l F 4 3 5 primary hydroxyl of po 1 i or Ipo 1 i ter finished with a hydroxyl value of 35 and a nominal functionality of 3; of ICI Americas. R u b i n o l - F - 4 5 5 triol 3000 MW finished with primary hydroxyl from ICI Americas. Rubinol F-459 dipropylene glycol oxypropyl alcohol with 20.7% by weight of ethylene oxide; hydroxyl value = 30; diol of ICI Americas. - Rubina to 1680 MDl 4,4 'of u r e t onimina -modi f i to the final NCO content of 29.3%; liquid at room temperature; of I C I Ame ricas. Rubinate 1790 polymer of 4,4 '-MDl with mixture of low MW glycols (TPG, 1,3 -BDO, and PG, at approximately 60:20:20 by weight) For final% NCO of 23.3% (pure MDl variant) of ICI Ame ricas, Rubinate 7302 MDL prepolymer and flexible polyether triol 4000 MW, NCO content = 28% by weight.

Rubinato 7400: MDL prepolymer and flexible polyether triol 2000 MW, NCO content = 28% by weight. Rub nano 8700 polymeric methylene diisocyanate (MDL of NCO content = 31.5% of ICI Ame ricas Rubinato 9410 MDI isocyanate mixture, pr od number functional = 2.3, 32.5% NCO by weight Stepanpol PS- oleyol-based oliol -4002: phthalate with a hydroxyl value of 400 and a nominal functionality of 2.0 Stepan Co. SR-242 (NIAX L- surfactant available from WITCO 5420) (OSi Corp.).

S up r as e c DNR polymeric MDl that has NCO content of 31.5% by weight, functionality of average number = 2.7 of ICI. Tegos tab B a polysiloxane surfactant 8465: modified polyether from Th.Goldschmidt. Unitol DSR: fatty acids of bait oil (mixture of oleic and linoleic acids in the unpurified form); Acid No. 191. Blowing agent, and IMR coadjutor. Available from Union Camp.

COMPONENTS The foams of the present invention are prepared from the compositions which include a polyisocyanate, and an isocyanate reactive component including polyol, a blowing agent including carboxylic acid, catalyst, crosslinker, stabilizer. Each of these is described in the following.

Polyisocyanates Any polyisocyanate previously used in the preparation of polyacrylamide coupons can be used. Preferably, the polyisocyanate has a viscosity (at 25 ° C) of about 35 cps to about 400 cps, more preferably about 200 cps. Examples of useful polyisocyanates include aliphatic polyisocyanates, cycloaliphatic polyisocyanates, polyisocyanates for 1 to 1, aromatic polyisocyanates and mixtures of isocyanates and modified polyisocyanates by the introduction of at least one urethane residue, allophanate , urea, biuret, carbodiimide, uretonimine, or isocyanate. The organic polyisocyanates useful in the present invention include, for example, 1-6-hexamethylene diisocyanate, isophorone diisocyanate, 1,4-diisocyanate of cyclohexane, 4-diisocyanate, di-cycloheximene, 1,4-xylylene diisocyanate, 1,4-phenyl-1-ene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-cyanocide diisocyanate (4,4 'MDl) ) 2,4 '-diphenylmethane diisocyanate (2,4' MDl), polyisocyanates of polymethyl enpo 1 if en i 1 ene. { MDl without p u r i c e) and 1,5-naphthylene diisocyanate. The polyisocyanate component is preferably an aqueous polyisocyanate. The aromatic polyisocyanates can be any of 4,4'-di-isocyanate diisocyanate, 2, 4'-diisocyanate, polymeric diphenylmethane diisocyanate, diphenylmethane diisocyanate variants and mixtures thereof. More preferably, the aromatic polyisocyanate is an MD1 composition of about 0.01 to about 3.0, still more preferably about 2.2 to about 2.7. Polyol The polyol is preferably a flexible polyether polyol predominantly based on propylene oxide and preferably contains minor amounts of ethylene oxide as a cap. Useful polyols include p or 1 ié t di di or 1 / t i ole s flexible. An example of a useful flexible polyether polyol is ethylene oxide capped ethylene oxide based MW polyol average number of ap about 1500 to about 10,000 and average number functionality of approximately 1.5 to about 8. The flexible polyols are of preferably included in the isocyanate reactive component. Flexible polyether polyols are the longest single ingredient by weight of the isocyanate reactive component. More preferably, the flexible polyol is present to a greater extent than about 50% by weight of the isocyanate reactive component, even more preferably about 60 to about 85% by weight; and most preferably about 70 to about by weight based on the total isocyanate reactive component. The flexible polyether polyols can be finished primary or secondary -OH, preferably-primary finished OH. Preferably, the polyether-polyol polyols have an average number equivalent weight of about 1000. The equivalent weight range can range from more than about 300 to about 10,000 (average number), preferably greater than about 500. to approximately 2,000; more preferably about 800 to about 1,500; even more preferably about 900 to about 1,200; and more preferably about 1,000. The flexible polyether polyols employed have an average functionality number of from about 1.5 to about 8; preferably about 2 to about 4; more preferably about 2 to about 3; and more preferably about 2.5 to about 3. The ethylene oxide (EO) content of the flexible polyols is preferably completely present as a cap although some EO may be in the main chain. The preferred EO cap level is from about 5 to about 30%, ie more preferably from about 8 to about 18%, and more preferably from 9 to 10% (EO percentages by weight). preferably employed as a single polyol, although a mixture of flexible polyols may be used.

Blowing agents Carboxylic acids are essential blowing agents in the present invention. The carboxylic acid anhydrides may be used but are less preferred. The carboxylic acids react with isocyanates to form C02 and an amide linkage. The carboxylic acids which can be used in the invention include 1-fatacy, cycloaliphatic, aromatic and / or heterocyclic and / or can be substituted (for example, with halogen atoms) and / or unsaturated. Examples of suitable carboxylic acids and anhydrides include succinic acid; adipic acid; suberic acid; acelaic acid; cebasic acid; italic acid; isophthalic acid; terephthalic acid; trimellitic acid; phthalic acid anhydride; tetrahydrofetic acid anhydride; hexahydrophthalic acid anhydride; tetrachlorophthalic acid anhydride; anhydride of endomethylene t e t rahid rof tal acid; glutaric acid anhydride; maleic acid; maleic acid anhydride; fumaric acid; monomeric fatty acids; dimeric and trimeric such as those of oleic acid which may be mixed with monomeric fatty acids. The partial esters of polycarboxylic acids can also be used, such as terephthalic acid, mono-methylene glycol, ethylene glycol mono-ester of terephthalic acid and mixtures thereof. Preferred carboxylic acids are liquid or soluble in the reactive isocyanate component. The most preferred carboxylic acids are aliphatic carboxylic acids such as mono, di, or t-hydrocarboxylic acid acids having 10 carbon atoms or more, more preferably 16 carbons or more. Suitable carboxylic acids may include, for example, lauric, palmitic, ricinoleic, stearic acid, oleic acid, linoleic acid, linolenic acid, adipic acid, behenic acid, arachidic acid, montanic acids, isostearic acid and similar acids as well as mixtures thereof. The water can be used with the carboxylic acid as a co-blowing agent.

Catalyst In the formulations of the invention, the amount of catalyst can be varied to achieve the desired process and property characteristics as should be apparent to the person skilled in the art. A wide variety of known reaction catalysts to promote therm ation can be used. Preferred titration catalysts include soluble alkali metal carboxylates such as 2-yl exoat or potassium, and potassium acetate, sodium acetate, sodium octoate, potassium octoate, carboxylate tetras, ammonium carboxylate, potassium hydroxide, more preferably potassium hydroxide with fatty acid with the molar excess acid, ie, more -COH groups than KOH groups. The co-catalysts can be used in combination with the trime r i z ation catalyst. These additional catalysts include tertiary amines-and transition metal esters, especially tin fatty esters optionally with alkyl groups attached to the tin atom. A preferred class of co-catalysts is bismuth fatty esters, especially products available under the "Bicat" series from Shepherd Chemical. Another class of preferred high co-catalysts are strong basic amidines and guadinins that are free of isocyanate reactive (-NH) or NH2 groups. A particularly preferred example is a cyclic aliphatic amidine known as Policat DB U (dia z ab i c i cl or unde ce no), from Air Products Co.

Crosslinkers and / or Chain Extenders Chain Extenders and / or Retractors such as DEG and glycerol can be included in the reaction systems of the chain or chain. the invention. Chain Extenders and / or Reagents are minor constituents typically by weight of the total reactive-isocyanate component formulation. A catalytic carrier such as diethylene glycol (DEG) or dipropylene glycol (DPG) can be used as a chain extender. Nevertheless, where the catalyst is soluble in the resin component (polyol _JD-acid), a carrier is not necessary, a wide range of reagents and chain extenders can be used. The chain extenders. useful include diols of average number or absolute MW of up to about 300, preferably of less than about 300, more preferably less than about 250. Examples of these diols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1 -butadine 1 and propylene glycol 400. Suitable chain extenders can be selected from polyols such as oxyethylene or oxypropylene based on diols having a molecular weight of up to about 600. Examples of other useful diols include 1, 8-octa nodi or 1, neopentyl glycol, cyclohexanodimeta no 1, 2-methyl, 3-propanediol, 1,3-bu t anodiol, 1,6 hexahexadione, 1,5-pentanediol and tripropylene glycol; the aliphatic and aromatic amines, for example, 4,4'-rae ti lendi an i 1a having an alkyl substituent on the lower side, placed ortho to each N atom. Preferred crosslinkers with functional polyols of about 3 to about 4, more preferably triols having an average MW number of about 250 or less. Glycol is a higher preferred crosslinker. Stabilizers Stabilized surfactants can also be used in the reaction systems of the invention. Useful foam stabilizing surfactants include but are not limited to copolymers of s i 1 i with -p or 1 i e t e r. Examples of copolymers of s i 1 i with -p or 1 i e t that can be employed in the compositions of the invention include rigid foam surfactants such as Tegostab B-8465.Other additives Other materials conventionally used in the preparation of polyurethane foam may be included as additives in the reaction systems of the invention. Particularly useful additives include internal mold release additives, preferably silicone-free internal mold release agents such as fatty acids, fatty steamers, fatty polyesters, especially combinations thereof. Reinforced materials can also be included in the reaction system. In general, the reinforced material can be directly placed in the mold and the liquid foam composition poured therein. However, alternatively or in addition thereto, the chopped fibers and other fillers may be added to the system component of the system, the isocyanate reactive component or both, in amounts up to about 70% by weight of the SRIM part. Fiber reinforcements are preferably included in the reaction systems of the invention. A wide range of fiber reinforcement amounts can be included. The fiber materials may be woven or non-woven (random) or combinations thereof. The fibers include synthetic fibers of nylon, polyester, aramid, polyesters, polymers, polyamides, silicon charcoal, and the like; natural fibers such as cellulose, cotton, cannabis, linens and jute; and mineral or ceramic fibers including Wolastonite, aluminum, glass fibers and carbon fibers. Fiberglass, whether woven or non-woven, is the preferred reinforced material due to its low cost and physical properties. One or more layers of reinforcement may be used depending on the desired fiber weight. Preferably, these reinforcements are fiber reinforcements and / or continuous plate reinforcements, more preferably glass fibers and / or glass continuous plates. Continuous plates (or long fibers) are particularly preferred. Continuous glass fiber plates are more preferable. Preferably -, - the reinforced material is greater than 0 to about 70% by weight, more preferably about -10% to about 50 in weight, and more preferably approximately % to about 40% by weight of the final part The "chopped" fibers that have a length of about 12.5 mm at a time of 10 10 mm can also be used.

PREPARATION OF FOAMS The foams are preferably prepared by reacting an isocyanate with an isocyanate reactive component that includes a polyol, an alkali metal carboxylate hydroxide trimer catalyst, and an alkaline agent. acid, mono or polycarboxylic blowing ~ in a high index formulation. In an alternative embodiment, the isocyanate reactive component can include carboxylic acids, reactants, and / or chain extenders and be polyol free. The amide reaction of carboxylic acid isocyanate provides at least part of the foam expansion and helps to promote the synthesis of bromide. Opc. ona l e_nt e_, the a uua can be used as a de-blowing agent with the carboxylic acid. The components are mixed for 1 or g r ar? N? from about 200 to about 1500, preferably about 250 to about 700. The isocyanate reactive component can be either a single polyol or a mixed polyol. It is suggested that most of the polyols and additives are in the reactive isocyanate component. The additives can also be placed in the isocyanate component if they are chemically compatible with the isocyanate. The carboxylic acids and the catalysts are included in the isocyanate reactive component. When a polyol is used, a portion of the polyol can be reacted with isocyanate to form a polypropylene wedge. In this embodiment, all or most of the polyol can be in the isocyanate quasi-prepolymer. Although two component formulations are highly preferred, the invention can be practiced with formulations having more than two components.

Process for the formation of foam compositions- "~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ are possible with these compositions Useful molding methods include LD-SRIM fiber cutting techniques. The LD-SRIM uses plate reinforcements with inua-glass and fiber-cutting techniques and uses high-aspect ratio glass fibers and involves cutting fiber reinforcements and injecting them into the side-components. A and B side combined in the main mix. Generally, the reactive components in the formulation are mixed and processed in quantities that provide for compliance to a desired foam density, index and A: B ratios. Details of how to mix the components of the formulation will be apparent to those of ordinary skill in the art. The polymer foams prepared according to the invention have molded densities of less than about 1.2 (spg). The preferred density is from about 0.8 spg to about 0.1 spg, more preferably from about 0.75 spg to about 0.2 spg, even more preferably from about 0.7 spg to about 0.25 spg, more preferably from about 0.6 spg to about 0.3 spg. If the reinforcement is present, then the density is measured including the reinforcement. The invention is illustrated but not limited by the following examples which relate to two component systems in which the A side is diisocyanate and the B side is a mixture of polyol or polyols, reticulum is chain extenders, cataphoresis izers, blowing agents and other additives. In Examples 1-9, unless stated otherwise, a polyisocyanurate foam is prepared by manually mixing the various components shown in Table 1 and allowing the foams to rise in free form. The properties of the resulting foams are shown in Table 1. As used herein, "index" means the ratio of NCO equivalents to equivalents of the total isocyanate reactive group multiplied by 100%. The A / B ratio means the weight ratio of isocyanate to the isocyanate reactive components. This is the weight ratio in which the components of a two-component system are me z c 1 an. The cream time means the time, in seconds, of when sides A and B are mixed first until an initial increase in volume is observed. The gel time means the time, in seconds, of when the side A and B are mixed first to produce a liquid mixture until the liquid mixture becomes solid. The Tack Free time means the time in seconds, when the sides A and B are first mixed until the surface of the resulting foam is free of viscosity to the tuque. End of lift time means the time in seconds, to mix until the foam stops lifting. 1. Appearance of good foam 2. Machine reacities 3. index 4. Ratio A: B 5. 45 &KOH Examples 6A-6F: The formulation of Example 6 is repeated except that the A: B ratios and the indices are varied. Results are shown in table 2 1. Seconds _ Examples 6G-6L: The formulation of Example 6 is repeated except that the isocyanate, the A: B ratios remain constant at 2.25 and the indices are varied. The results are shown in Table 3.

Seconds Example 10: This example illustrates the use of an amine based polyol with an acid blowing agent. Side A Rubinate 8700; index 290; ratio A: B 1.8 B side Compose Rubinol F-455 57.99 Jeffamine T-5000 8.39 Rubinol R-015 14.4 Glycerin 3.62 Unitol DSR 6.06 Loxiol G71S 0.6 Priolube 1414 0.07 Tegos tag B-8465 1.62 50% KOH + 50% Water 0.78 Water 0.37 The reaction system is mixed for 7 seconds The resulting foam has: Cream Time = 36 seconds Gel Time = lQ2 seconds Vi scosi d Free Time = 124 seconds Hardness Time = 142 seconds Good Foam Appearance EXAMPLE 11 This example illustrates the use of polypropylene reactors on the B side to prepare a free-standing foam. In this example, the A-side and B-side components are blended for 25 seconds to produce a free standing pore foam using a potassium catalyst.

Side A Rubinate 8700; Index = 355; A / B = 1.0 Side B Component e PBW Daltorez P-716 100.0"50% KOH + 50% H2O 0.8 Dabco 8800 2.0 Tegostab B-8465 2.0 Unitol DSR 7.5 Lioxol G71S 7.5 Priolube 1414 0.8 Water 0.8 Example 12: The procedure of example 11 is employed except that the mixing time is 15 seconds. The resulting mixture is poured into a mold that measures 15.24"cm by 20.32 cm by .396 cm (6 ~ p ~ u X 8 inches X 5/32 inches) The mold was maintained at 87.7 ° C (190 ° F) in a Carver pressure under a clamping force of 6803.886 kg (15,000 pounds) to form a plaque.The composition was demolded in 2 minutes 30 seconds.The resulting polymer was extremely flexible with the demoulding.After demolding, the part gained dimensional stability Over time, the products produced using this composition will be useful as thermoformable parts that require significant flexibility.

Example 13: The system formulation shown in the following is formed on a plate used in the procedure of Example 12 except that the system is mixed for 10 seconds and the demoulding is done in 1 minute 45 seconds. Side A Rubinate 8700; Index = 355; A / B = l ~ 45 Side B Component PBtore Daltorez P-716 100.0 Ethylene glycol 3.0 50% KOH + 50% H2O 0.8 Tegostab B-8465 2.0 Unitol DSR 7.5 Lioxol G71S 7.5 Priolube 1414 0.8 Water 0.8 Ethylene glycol improves polymer stiffness with example 12.

EXAMPLE 14 The system formulation shown in the following was formed on a plate using the procedure of Example 12 except that the system is mixed for 13 seconds and the demolding is done in 3 minutes 45 seconds. Side A Rubinate 8700; Index = 355; A / B = 2.94 Side B Compliant PBW Daltorez P-716 100.0 Ethylene glycol 15.0 50% KOH + 50% H2O 0.8 Tegostab B-8465 2.0 Unitol DSR 7.5 Lioxol G71S 7.5 Priolube 1414 0.8 Water 0.8 This system shows the stiffening effect in impact of ethylene glycol addition. The plate was even more rigid and less brittle than in Example 13.

E xemployment 15: This example illustrates the use of ortho-phthalate polyester polyols on the B side to produce a free-flowing foam. The mixing time is 12 seconds.

Side A Rubinate 8700; Index = 355; A / B = 2.10 Side B Comp on e n t n PBW _ Stepanpol PS-4002 100.0 50% KOH + 50% H2O 0.8 Tegostab B-8465 2.0 Unitol DSR 7.5 Lioxol G71S 7.5 Priolube 1414 0.8 Water 0.8 This system shows the top surface cure. The free standing foam source has: Cream time = 1 minute 16 seconds; gel time = 1 minute 56 seconds; Viscosity free time = 2 minutes 15 seconds.

Example 16: The system formulation shown in the following was formed on a plate using the procedure of Example 12 except that the system is mixed for 7 seconds and the demolding is done in 3 minutes 30 seconds. Side A Rubinate 8700; Index = 355; A / B = 2.10 Side B Component PBW Stepanpol PS-4002 1 0 0. 0 50% KOH + 50% H2O 0. 8 Tegostab B-8465 2. 0 Unitol DSR 7. 5 Lioxol G71S 7. 5 Priolube 1414 0. 8 - Water 0. 8 The plate shows superior dimensional stability compared to adipate polyesters.

Example 17: This example illustrates the use of di-acids on the B side as blowing agents for making foam foams or cyan sprays. The mixing time is 7 seconds.

Side A Rubinate 8700; Index = 270; A / B = 2.33 B side Comp on te PBW _ Rubinol F-436 70.0 Rubinol R-015 30.0 50% KOH + 50% H2O 0.8 ~ Tegostab B-8465 2.0 Pripol 1013 7.5 Lioxol G71S 7.5 Priolube 1414 0.8 Water 0.8 Foam of pol iis oc i anu at o has a: Cream time = 21 seconds; gel time = 1 minute 27 seconds; viscosity free time = 2 minutes 44 seconds.

EXAMPLE 18 This example illustrates the use of tri-acids in la d_o B as blowing agents to produce a free-standing foam. The mixing time is 7 seconds. Side A Rubinate 8700; Index = 270; A / B = 2.33 ~ Side B Comp onen te PBW Rubinol F-436 70.0 Rubinol R-015 30.0 50% KOH + 50% H2O 0.8 Tegostab B-8465 2.0 Pripol 1040 7.5 Lioxol G71S 7.5 Priolube 1414 0.8 Water 0.8 Polyisocyanate foam has one: Cream time = 21 seconds; time of ge 1 = 1 minute 43 seconds; viscosity free time = 2 minutes 20 seconds. Examples 19 and 20 illustrate the reduced time for demolding the produced parts with the foam reaction systems of the invention. Example 19 shows. the demolding time with a polyurethane system. Example 20 shows 1 s of demolding with the reaction systems of the invention.

Example 19: Polyurethane system Comp. PBW Rubinol R015 100.0 Glycerin 7.5 Policat 8 3.5 Dabco 8800 1.0 Unitol DSR 6.5 Lioxol G71S 10.0 Kemester 5721 1.1 Niax L-6980 1.5 Water 1.6 ratio AB = 1.70 with Rubinate 8700 Index = 105 __ Temperatures Lower upper mold = 73.889 ° C (165 ° F) Release time = 90 seconds Example 20: Polyisocyanurate Systems of the Invention Component PBW Rubinol F-455 85.0 Rubinol R-015 15.0 Unitol DSR 7.5 Lioxol G7 IS 7.5 Priolube 1414 0.83 Tegostab B-8465 2.0 KOH + water 0.65 Water 0.60 Ratio A: B = 1.80 with Rubinate 8700 Index = 405 upper and lower molding temperatures (180 ° F) Release time = 55 seconds

Claims (26)

1. Reaction system for polyisocyanate foams comprising a polyisocyanate component and a reactive polyisocyanate component, the reactive polyisocyanate component comprises a polyol, a carboxylic acid and a catalyst of t r ime r a tion.

2. Reaction system of the claim 1, wherein the polyisocyanate component is selected from the group of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, polyisocyanates for 1 to ions, aromatic polyisocyanates and mixtures of modified isocyanates and polyisocyanates by introducing at least one of the residues of urethane, allophanate, urea, biuret, carbodiimide, uretonimine or isocyanurate.

3. Reaction system of the claim 2, wherein the polyisocyanate component is an aromatic polyisocyanate selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 2,4'-di-furanyl di-isocyanate, polymeric diphenylmethane diisocyanate, variants of diisocyanate di f.eni lme tanoy and mixtures thereof.

4. Reaction system of claim 3, wherein the aromatic polyisocyanate is a diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate or mixtures of diisocyanate di ffimene and polymeric diphenylmethane diisocyanate of functionality -NCO average number from about 2.0 to about 3.0.

5. Reaction system of claim 2, wherein the carboxylic acid component is a substituted or unsubstituted carboxylic acid or partial ester thereof selected from the group consisting of saturated or unsaturated aliphatic carboxylic acids, aromatic carboxylic acids, heterocyclic carboxylic acids.

6. Reaction system of the claim 5, wherein the carboxylic acid is an aliphatic carboxylic acid.

7. Reaction system of the reagent indication 6, wherein the aliphatic carboxylic acid is selected from the group consisting of mono-, di-, or tri-carboxylic acid acids having two carbon atoms or more.

8. Reaction system of the claim 7, wherein the aliphatic carboxylic acid has 16 carbon atoms or more.

9. The reaction system of claim 2, wherein the catalyst is selected from the group consisting of potassium hydroxide, potassium hydroxide with fatty acid, and soluble alkali metal carboxylates.

10. Reaction system of the claim 9, wherein the soluble alkali metal carboxylate is selected from the group consisting of potassium 2-ethylhexoate, and potassium acetate, sodium acetate, sodium octoate, potassium octoate.

11. Reaction system of claim 2, wherein the carboxylic acid blowing agent is tetra-alkylammonium carboxylate.

12. The reaction system of claim 9, wherein the catalyst is a potassium hydroxide with a fatty acid.

13. Method for manufacturing foam products by the SRIM process, the improvement wherein the foam is produced from a reaction system comprising, a polyisocyanate component, a reactive component of polyisocyanate, the reactive component of polyisocyanate comprises a polyol, a carboxylic acid, and a trimerization catalyst.

14. The method of claim 13, wherein the polyisocyanate component is selected from the group of aliphatic polyisocyanates, cyclic organic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates and mixtures of modified isocyanates and polyisocyanates by introducing at least one of the residues of urethane, allophanate, urea, biuret, ca bodiimide, uretonimine or isocyanurate.

15. The method of claim 14, wherein the polyisocyanate component is an aromatic polyisocyanates selected from the group consisting of 4,4 'diisocyanate-di-ethyl ester, 2,4'-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate. , diphenylmethane diisocyanate variants and mixtures thereof.

16. The method of claim 15, wherein the aromatic polyisocyanate is a diphenylmethane diisocyanate or polymeric diphenylmethane diisocyanate of NCO-average functionality from about 2.0 to about 3.0.

17. The method of claim 13, wherein the carboxylic acid component is a substituted or unsubstituted carboxylic acid or partial esters thereof selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, heterocyclic carboxylic acids.

18. The method of claim 16, wherein the carboxylic acid is an aliphatic carboxylic acid.

19. The method of claim 18, wherein the aliphatic carboxylic acid is selected from the group consisting of mono, di or tri-carboxylic fatty acids having 10 or more carbon atoms.

20. The method of claim 19, wherein the aliphatic carboxylic acid? It has 16 carbons or more.

21. Reaction system for polyfoam foams comprising, for example, cyanase and an isocyanate reactive component comprising a complex fatty polyester which is the reaction product of adipic acid, pentaerythritol and oleic acid, an isobutyl ester of oleic acid, a propoxylated glycerol, a triol, a polyether modified polysiloxane surfactant and io potassium hydroxide.

22. Reaction system of claim 21, wherein the propoxylated glycerol has a hydroxyl value of 650.

23. Reaction system of the claim 22, where the triol has a molecular weight of 3000. "

24. Reaction system of the claim 23, where the fatty acid of bait oil is a mixture of oleic and linoleic acids.

25. Reaction system of claim 24, wherein the polymer is polymeric methylene diisocyanate.

26. Reaction product of the reation system of claim 1.