MXPA97005754A - Copolymers of polyeteros and polisiloxano manufactured with double me cyanide catalysts - Google Patents

Abstract

The invention discloses a new class of silicone surfactants and their use for the preparation of a flexible urethane foam. The surfactants incorporate high molecular weight polyethers, prepared with narrower molecular weight distributions than conventional polyethers. These polyethers are prepared using a double metal cyanide catalyst ("DMC"). These surfactants are better foam stabilizers compared to analogous surfactants, conventional polyether preparations

Description

COPOLYMERS OF POLYETERES AND POLISILOXA OR MANUFACTURED WITH CATALYZERS OF DOUBLE METAL CYANIDE DESCRIPTION Background and field of the invention In the manufacture of polyurethane foam, surfactants are required to stabilize the foam until the chemical reactions of formation of the product are sufficiently complete so that the foam is self-supporting and does not suffer a significant subsidence. Taking into account the complex interaction of these physicochemical and rheological phenomena, it is not possible, in an easy way, to predict the effect of small changes in the composition on the overall performance of a surfactant agent even for those experts in the field. High power silicone surfactants are generally understood to be those that provide a high lifting height and little sinking at the top to minimum levels of use, these are desirable because the foams sink a significant degree before hardening they have high densities and objectionable density gradients. In general, it is preferred that surfactant products produce high elevations, little or no subsidence at the top, and high airflow performance. The last feature refers to the ability of air to pass through the foam and is also known as foam breathing capacity (breathability). Silicone surfactants for making polyurethane foams are typically materials having siloxane backbones and polyether pendant groups. For example, United States Patent No. 4,147,847 discloses certain polysiloxane-polyoxyalkylene copolymer surfactants ("Copolymers") having mixed alkylene oxide polyethers of feed, with molecular weights of up to about 5500. The patent No. 4,025,456 discloses that a key to excellent performance is to use a mixture of polyethers with a molecular weight distribution where a significant portion of the high molecular weight polyether is preferred. With respect to such descriptions, unfortunately, conventional alkylene oxide polymerization catalysts such as KOH can not produce polyethers with molecular weights greater than 5000, if more than about 20% propylene oxide is present.

(PO) in the alkylene oxide feed. Since the state of the art describes or shows the need to use PO (or higher alkylene oxides) in the polyethers, this is an important limitation. With conventional catalysts such as KOH, small amounts of PO are continuously rearranged to provide allyl alcohol which functions as a new source of unsaturated initiator in competition with the original initiator. Eventually the conditions are stabilized when the subsequent addition of PO no longer increases the general molecular weight of the polyether product. In other words, in the attempt to increase the molecular weight, more low molecular weight species are generated which compete with the existing oligomers for chain growth and the total average molecular weight number of the polyether product does not increase. With the KOH catalyst, for example, the average total number of molecular weight reaches approximately 5000 daltons for these mixed polyethers. Furthermore, due to the reactivity of KOH, the polyethers produced by it do not have a random distribution of alkylene oxide units when a mixed feed is used. In contrast, when a polyether is prepared from a mixed feed of ethylene oxide (EO) and propylene oxide (PO), the distal portions of the polyether (from the initiator) are rich in PO when compared to its proximal end . This loss of total distribution affects the performance of the polyether. When analyzed by size exclusion chromatography, large molecular weights, ie, >; 5000 of molecular weight, polyethers made with significant amounts of PO and KOH catalysts show a wider distribution of molecular weights (they generally have a polydiversity greater than 1.4) and contain a significant amount of low molecular weight polyether contaminant. These low molecular weight pollutants compete with the high molecular weight polyethers during the synthesis of the silicone surfactants and effectively reduce the amount of high molecular weight slopes attached to the silicone backbone. Only the lower molecular weight polyethers (ie, <5,000 molecular weight) usually have a polydiversity < 1.5. Since the prior art discloses that high molecular weight earrings are important for potency, a high content of low molecular weight polyethers does not contribute to good performance and therefore is undesirable. The double metal cyanide (DMC) catalysts have been used in the preparation of silicone surfactants as reported in Japanese Kokai 05-117,352 in which the DMC synthesis of poly (ethylene) polyethers (PO) of conventional molecular weights is described. Subsequent addition of ethylene oxide (EO) parts to these products using conventional KOH technology (final molecular weight less than 3000 daltons). Therefore, the polyethers described therein have a block and non-random distribution of EO and PO units. Moreover, this process requires the additional step of removing the KOH before the subsequent hydrosilation reaction because the residual KOH reacts preferentially with the functional groups of hydrido siloxane (SiH) and reduces the efficiency of the insertion of the polyether to the Main structure of siloxane during hydrosilation and produces hydrogen gas, a very dangerous process. European application 0,573,864 A2 describes the use of DMC catalysts for the addition of epoxides (PO and allyl glycidyl ether to non-hydrolyzable siloxane-polyether copolymers having uncoated hydroxyl groups.) Thus, the epoxides were added directly to the polysiloxane, instead of forming a polyether separately as is usual in the state of the art Such synthesis does not provide the ability to obtain a surfactant wherein the pending polyethers have varied molecular weights or compositions.

The present invention provides non-hydrolyzable Copolymer surfactants which offer good potency and have the generalized average formula M "DxD" and M "where: M" represents (CH3) 3SiO? / 2 or R (CH3) 2Si012 / D represents ( CH3) 2Si02 / 2; D "represents (CH3) (R) Si022, x is from about 40 to about 220 / e and is from about 5 to about 34 / R are polyether-containing substituents obtained from a mixture of at least two different polyethers selected from the following two groups: 1) -Cn? 2n.O (C2H40) a '(CsHeOb'R "portions having molecular masses greater than 3000 where the distribution of -C2H4O- ("EO") and -C3H60- groups ("PO") is random where n 'is 3-4 / a' and b 'are positive numbers so that 0 < a '/ (a' + b ') < 0.6, R "represents -H, an alkyl group of 1 to 8 carbon atoms, -C (0) RIH, -C (0) OR '" or -C (0) NHR' "/ R1" represents an aryl group or a monofunctional alkyl; The random block of EO / PO of the polyether that has been produced using a double metal cyanide catalyst and 2) portions -Cn "H2n" 0 (C2H40) a »(C3H60) b" R "having average molecular masses in the range of 300-4000 where n "is 3-4 / a" and b "are independently 0 or a positive number so that the total molecular weight of the polyether is between 300 and 3000 / yy the portions RM and R '" are as defined above; wherein the average molecular weight of the mixture of the polyethers is between 1100 and 3000 and wherein there may be more than one polyether of any group, but at least one of the first group. Still further, the present invention describes polyethers and their preparation, and which are suitable for use in surfactants.

It is a great advantage of the present invention to use polyethers of very high molecular weight of good purity, ie, polyethers terminated in allyl with a narrow molecular weight distribution, prepared with DMC catalyst to produce surface active agents of copolymers with superior performances. In particular, polyethers produced with DMC using metalylalcohol or ring alcohol based initiators and / or with significant amounts of PO in the feed alkylene oxide will contain less polyether contaminants terminated in propenyl than would be encountered with the standard processes. Since the propenyl terminated polyethers are not reactive in the copolymer synthesis, they are undesirable and uneconomic. The use of polyethers produced with DMC results in a more efficient use of the raw material when these polyethers are used to produce copolymers. In addition, the resulting polyethers are much more uniform (ie narrow) in the molecular weight distribution, having polydiversities of 1.1 to 1.4 in molecular weights greater than 5000, which again avoids the low-molecular weight antieconomic polyethers.

Another advantage of the invention is the elimination of the polyether purification step in which the alkoxylation catalyst of the crude polyether product must be removed.

A further advantage is that the polyether-siloxane copolymers have high molecular weight polyethers with narrow molecular weight distributions that can be achieved using polyethers from the conventional KOH process.

Still another advantage is that of providing high-power surfactants for the stabilization of flexible polyurethane foams. Since the present invention allows the use of lower levels of surfactant use and the Copolymer product has a lower silicone content, this results in a significant economic benefit.

The preferred copolymer to be used here has the general average formula: M "DxD" and M "with x = 40-145, y = 5.0-23, and D: (D" + M ") < 10: 1. preferred within this class has the average general formula: MMDxDMyMM with x = 65-135, y = 7-22, and D: (D "+ MH) < 10: 1 The average molecular weight of the mixture (BAMW) is the weighted number of the average molecular weight of the mixture of terminally unsaturated polyethers, the weighting takes into consideration the relative amounts of the materials in the mixture. The BAMW of a double polyether surfactant is preferably 1100-2400 daltons. In the case that more than two polyethers are used, the total BAMW of the polyethers will be in the range of 1900-3000 daltons and the molar ratio of the first and second polyether groups should be between 0.8 and 2.5. The first group of polyether slopes is prepared by means of DMC catalysis using a monofunctional alcohol as initiator, and therefore there is a random distribution of EO and PO units within that polyether. Monofunctional alcohol initiators that either contain only a hydrosilatable group (such as a vinyl, allyl, methallyl, or an alkyne portion) or are monoles which will then be capped with a group containing a hydrosilatable group (e.g. an allyl group of polyethers initiated with butane). Examples of hydrosilatable portions in polyethers are well known in the state of the art (for example: US Pat. Nos. 3,879,433, 3,957,843, 5,191,103, and 5,359,113. It is understood by random distribution that there is no block of EO followed by a block of PO within the polyether, nor sections of the polyether particularly rich in EO or PO unless present in the initiator or corona group). Preferably, the two different types of oxides are intercalated with each other essentially randomly in the polyether. It should be noted that higher alkylene oxides such as butylene oxide can also be used, in addition to or instead of the PO with the DMC catalyst. Within the first group of polyether slopes there is a preferred subgroup which is composed of about 40% by weight of EO residues. It is preferred that such polyethers have BAMW greater than 4000 daltons, more preferably above 5000 daltons and even more preferably above 6000 daltons. In addition, R "is preferably -C (0) CH3, -CH3, or - (t-butyl) .Some suitable R 'groups are methyl, ethyl, propyl, benzyl and phenyl. Within the second group of polyethers there is a preferred subgroup that contains <; 20% by weight of PO and has an average molecular mass in the range of 300-750 daltons. A more preferred polyether of this group is composed of approximately 100% by weight of EO and has a BAMW of 400-600 daltons. In these materials of low molecular weight, R "is preferably -C (0) CH3, -CH3, or - (t-butyl) .These low molecular weight EOs are conveniently produced by means of conventional processes such as KOH or BF3-etherate catalysts.

Method of preparation The processes for synthesizing non-hydrolysable copolymers are well known in the state of the art.

Generally, surfactants are prepared by causing a polyhydridiloxane of generalized average formula MDxD'jM and / or M'DD'j 'to react with an appropriately chosen mixture of polyethers terminated in allyl, in the presence of a hydrosilation catalyst, such as hexachloroplatinic acid. In the formulas of the polyhydridosiloxanes, M and D are as defined above, M 'is (CH3) 2 (H) Si012, and D' represents (CH3) (H) SiO2 / 2. The allyl-terminated polyethers are polyether polymers having a terminal unsaturated hydrocarbon capable of undergoing hydrosilation (such as an allyl alcohol), which may be optionally substituted (such as a metal alcohol), and which contain multiple units of alkylene oxides (that is, EO or PO). The reagents are mixed, optionally in a solvent such as toluene, saturated polyethers, or dipropylene glycol, heated to about 75-95 ° C, then the hydrosilation catalyst is added. If a volatile solvent was used, it is removed by vacuum and, optionally, the mixture (if it is acidic) can be neutralized with a weak base such as NaHCO 3 or a trialkylamine. To produce polyethers with more than 60% by weight of EO in the second group, conventional processes should be used because the DMC catalyst is very active for high EO feeds and will preferentially produce polyethylene glycols. In such processes a terminally unsaturated alcohol is combined, optionally bearing a substituent at the 2-position, with EO, PO or both, in the presence of a Lewis acid or base, to provide the desired polyether with a terminal hydroxyl group. The epoxides may be distributed in blocks or randomly along the polyether chain. The resulting polyethers are generally capped by means of a subsequent reaction (optionally in the presence of a catalyst) with an alkylating agent or an acylating agent such as a methyl halide, allyl chloride (in the case of saturated mono-initiators) such as n-butanol), isobutylene, acetic anhydride, phenyl isocyanate or alkyl carbonates, using procedures well known in the art. In contrast, the first group of polyethers are made using double metal cyanide catalysts (DMC) described in the United States patents of North America Nos. 3,427,256, 3,427,334, 3,427,335, 3,829,505, 4,242,490, 4,472,560, and 4,477,589 (which are incorporated herein by reference) that do not promote the rearrangement PO-allyl alcohol. Examples of such catalysts include: Zn [Fe (CN) 5N0], Ni3 [Mn (CN) 5CNS] _, Cr [Fe (CN) 5NCS], and Fe [Fe (CN) 5OH]. Of particular utility is the zinc hexacyanocobaltate catalyst Zn3 [Co (CN) 6] 2-x 'ZnCl2-y * (alcohol) -z'H20 wherein the alcohol is typically glyme (ethylene glycol dimethyl ether) or t-butanol , and the values x *, y ', and z * depend on the exact method of preparation. The DMC catalysts can give substantially unlimited molecular weight polyethers with almost the same number of polyether equivalents as equivalents of the unit used as the initiator for the polymerization. A second advantage of the DMC catalyst is that it does not promote the allyl-propenyl rearrange in the allyl alcohol initiator (the most preferred initiator) as KOH does. DMC catalysis can, therefore, produce polyethers with molecular weights equal to, or much larger than, those that can be produced with KOH technology but without impurities. PO / EO mixtures containing up to 60% by weight of EO are successfully copolymerized with DMC catalysis as a single stage mixed feed and the monomers are added to a known feed ratio so as to produce polyethers in which the monomer are distributed in a randomized mode in the same ratio as the feed monomer. With KOH catalysis and mixed EO / PO feeds, the EO tends to react more quickly resulting in polyether chains that are rich in EO in the proximal part to the monol initiator and rich in PO in the distal part. In this way, the polyethers produced by means of DMC catalysis have a monomer distribution different from that of conventional polyethers. With the mixed alkylene oxide fed to the DMC catalyst, it is important to start ("activate") the catalyst with pure PO with at least two to four weight percent of the total PO to be fed to the reaction. Preferably this is done after mixing the catalyst and initiator alcohol. Once the catalyst has been started, the desired mixed feed of EO and PO can be initiated (up to 60% by weight EO). This results in a negligibly short PO block at the start (approximately 4 units of PO) with the rest of the material composed of randomly distributed EO and PO units. A continuous process could be carried out by having an upstream feed separate all POs to activate the catalyst and subsequently a mixed feed downstream where there is active catalyst after initiation. The reaction usually takes place until the EO and the PO are consumed. In the case of the allylic alcohol initiator, the polyethers, which are crowned at the hydroxy end, can subsequently be crowned with units such as methyl, acetoxy or t-butyl. Alternatively, a saturated monol such as an n-butanol can be used as an initiator and the polyether capped with an unsaturated unit, such as allyl or methallyl. It is important to use high quality raw materials free of contaminants (such as KOH or acetic anhydride) that can poison or interfere in some other way with the stability, activity and selectivity of the hydrosilation catalyst. However, the DMC is non-reactive and does not require removal. The treatment of the crude polyethers with a neutralizing agent to remove the KOH and distillation in vacuo after the acetoxy-capped are examples of routine process steps to ensure that the polyethers will be of acceptable hydrosilation reactivity. It has been found that some of the compositions of this invention have relatively high viscosities and are preferably dissolved in a vehicle of lower viscosity before evaluations of foam performance to achieve good and reproducible results. It is preferred to dilute the surfactant to approximately a viscosity of less than 2,000 centistoks at 25 ° C. Typical diluents include saturated, polar and high-boiling polyethers or polyols.

Applications The surfactants of the present invention are used in the manufacture of polyurethane foam in the manner known in the state of the art which is generally manufactured by reacting a mixture of (a) a polyether or polyol polyester containing an average of more than two. hydroxyl groups per molecule, (b) an organic isocyanate having at least two isocyanate groups per molecule, (c) at least one catalyst, (d) optionally, an auxiliary blowing agent such as methylene chloride, (e) water, and (f) a siloxane-oxyalkylene copolymer surfactant as described hereinbefore. The relative amounts of the different components of the foam formulation are not narrowly critical. The polyether or the polyester polyol and the isocyanate are present in a larger amount and the relative amount of these two components is well known in the state of the art. The blowing agent, the catalyst and the surfactant are each present in a smaller amount sufficient to foam the reaction mixture. The catalyst is present in a catalytic amount, ie, that amount necessary to catalyze the reactions to produce the urethane at a reasonable speed, and the surfactant is present in an effective and sufficient amount to stabilize the foam and achieve the desired properties, typically about 0.1 to 8 parts per hundred parts polyol (pphp), preferably 0.3 to 3 pphp. Polyols that can be used in the present invention include, but are not limited to, the following polyether polyols: (a) alkylene oxide adducts of polyhydroxyalkanes, (b) alkylene oxide adducts of non-reducing sugars and derivatives of sugar, (c) alkylene oxide adducts of polyphenols / and (d) alkylene oxide adducts of polyamines and polyhydroxyamines. Alkylene oxides having two to four carbon atoms are generally employed, with propylene oxide, ethylene oxide and mixtures thereof being particularly preferred. Any material that has active hydrogens, as determined by the Zerewitinoff method, can be used to some degree and is therefore included within the broad definition of polyols. For example, polyether polyols terminated by amine, polybutadiene polyols terminated by hydroxyl and many others are known and can be used as a minimum component in combination with the conventional polyether polyols identified above. In general, the polyol component should have an equivalent weight in the range of about 400 to about 1500 grams / equivalent and an ethylene oxide content of less than 20%. Preferably the equivalent weight is in the range of about 500 to about 1300 grams / equivalent, and more preferably between about 750 and 1250 grams / equivalent. The polyol or the polyol mixture should have an average hydroxy functionality of at least 2. The equivalent weight is determined from the hydroxyl number measured. The hydroxyl number is defined as the number of milligrams of potassium hydroxide required for the complete hydrolysis of all the acetylated derivative prepared from one gram of polyol. The ratio between the hydroxyl number and the equivalent weight is defined by the equation: OH = 56,100 / equivalent weight, where OH is equal to the hydroxyl number of polyol. Thus, the polyols have hydroxyl numbers preferably in the range of about 43 to about 110, and more preferably in the range of about 45 to about 75. Preferably the polyols should include the poly (oxypropylene) and poly (oxyethylene-oxypropylene) triols. . The ethylene oxide, when used, can be incorporated in any mode along the polymer chain. In other words, ethylene oxide can be incorporated either in internal blocks, as terminal blocks, or it can be randomly distributed along the polyol chain. However, the manner of incorporation and the ethylene oxide content of the polyol is preferably as indicated above. Thus, the ethylene oxide is used at a level below about 20% by weight, preferably below about 15% by weight, and is located primarily within the interior of the polyol chain. Therefore, preferably the polyols are substantially secondary hydroxyl. Preferably, part or all of the polyol component can be added in the form of a polyol polymer in which the reactive monomers have been polymerized within a polyol to form a stable dispersion of the polymer solids within the polyol. The amount of polyol used is determined by the amount of product to be produced. Such quantities can easily be determined by a person with average knowledge in the field. The organic isocyanates useful in the production of polyurethane foam according to the present invention are organic compounds containing, on average, between about one and a half to about six isocyanate groups, and preferably about two isocyanate groups. Suitable organic polyisocyanates include the hydrocarbon diisocyanates, for example, the alkylene diisocyanates and the aryl disocyanates and more specifically, diphenylmethane diisocyanate and toluene diisocyanate ("TDI"). The preferred polyisocyanates are toluene-2,4 and 2,6-diisocyanate and their mixtures having a functionality of about 2, which are hereby broadly referred to simply as TDI. The most preferred polyisocyanate is 80/20 TDI (ie, a mixture of 80% toluene-2, -diisocyanate and 20% toluene-2,6-diisocyanate). The amount of isocyanate to be used is dependent on the desired foam index and the desired final properties of the foam to be formed. If the index is 100, then there is a stoichiometric equivalent of the amount of isocyanate needed to react with the polyol component and the other components containing active hydrogen in the system. While the present invention can be practiced in a wide variety of indices, for example 60-120, the preferred range of use is indexes between 80 and 115 / and more preferably the range of indices is from 85 to 95. Water is the preferred expanding agent, to produce carbon dioxide by reaction with isocyanate. Water should be used at about 1 to 12 pphp (percent polyol parts) and preferably between 2 and 10 pphp. At foam rates lower than 100, the stequimetric excess of water cools and expands by means of vaporization, not as part of the reaction to produce carbon dioxide. Other expanding or expanding agents can be used here, in addition to or even in place of water, such as carbon dioxide, methylene chloride, halocarbons of 1 to 3 carbon atoms, and other equivalent inert blowing agents. The catalyst component is one or a combination of standard organometallic polyurethane and tertiary amine catalysts which should be present at about 0.0001 to 5 weight percent of the reaction mixture. Suitable catalysts include, but are not limited to, dialkyltin carboxylic acid salts, tin salts of organic acids, triethylenediamine (EDTA), bis (2,2-dimethylaminoethyl) ether, and similar compounds that are well known in the medium. The relative amounts of the different components of the foam formulation are not narrowly critical. The polyether and polyisocyanate polyols are present in a larger amount and the relative amount of these two components is well known in the medium. The blowing agent, the catalyst and the surfactant are each present in a smaller amount sufficient to foam the reaction mixture. The catalyst is present in a catalytic amount, ie, that amount necessary to catalyze the reactions to produce the rigid, flexible, edge polyurethane foam, microcellular molding and high elasticity or resilience, at a reasonable speed, and the surfactant is present in an effective amount and sufficient to stabilize the foam and achieve the desired properties, typically about 0.1 to 8 parts per hundred parts polyol (pphp), preferably 0.3 to 3 pphp.

Examples In the following examples, all reactions involving the handling of organometallic compounds were carried out in an inert atmosphere. Commercial reagents were used without further purification. The following terms are used here as defined below. The term "potency" refers to the ability of a surfactant to stabilize the foam during processing. High-power surface active agents allow high lifting heights and relatively only small amounts of subsidence at the top during the manufacture of the foam. In general, large and / or good elevations are desired at lower levels of surfactant use. The phrase "process amplitude" refers to the ability of a foam composition to tolerate changes in its ingredients or amounts thereof, while still producing product having the desired properties. This is often reflected by high (or constant) performance of breathing capacity (breathability) at higher levels of surfactant or catalyst use. The terms "breathing capacity" and "air flow" refer to the ability of a cured foam to allow the passage of a gas. A "sealed" foam has low breathing capacity, while an "open" foam is said to have a high capacity for respiration and allows a gas to pass through it quickly. The constant breathing capability refers to the property of a surfactant to function in a foam composition at low, common and high levels, while still producing product foams having relatively constant breathing capabilities. Low usage levels are usually between 0.7 and 1.0 pphp. Common levels are between 1 to 3 pphp and high levels are greater than 3 pphp. In general, high and constant breathing capacity performances are preferred.

The compounds designated as L-620, DC-5160 and B8021 are copolymer surfactants obtainable from Witco Corp., OrganoSilicones Group, Dow Corning Chemical Company of Midland, MI and Th. Goldschmidt Company of Germany, respectively. L-620 and DC-5160 are non-hydrolysable and B8021 is hydrolysable and blocked from alkoxy end. The expansive agent U-ll. is CC13F. ARCOL® Polyol 16-56 is a commercial product of ARCO Company, Inc., and has the registration number CAS 9082-00-2. Toluene diisocyanate (TDI) was a mixture of approximately 80% of the 2,4- and 20% isomer of the 2,6- isomer, and was used in excess. The NIAX® A-200 catalyst is commercially available from Witco Corp., OrganoSilicones Group, and is a mixture of tertiary amines and a glycol.

Preparation of High Molecular Weight Monoles Using a Double Metal Cyanide Catalyst.

Since allyl alcohol is very toxic, a propoxylated derivative such as APPG-200 can also be used (allyl alcohol topped with approximately 3 PO units, which can be obtained commercially from Union Carbide Corp.) as an initiator, especially in laboratory-level experiments where attention to toxicity may be more critical. APPG-200 (8.9 g) and 12 ml of heptane were charged to a 500 ml autoclave. Zinc hexacyanocobaltate / glyme complex (0.071 g) was added and the reactor was purged three times with nitrogen to remove the air. The mixture was heated to 105 ° C, the excess pressure was vented, PO (10g) was charged, and the mixture was stirred until a pressure drop indicated catalyst activation. A mixture of PO and EO (containing 204.6 g of PO and 136.4 g of EO) was fed into the reactor at a rate to maintain the pressure below 50 psig. The resulting polyether was subjected to vacuum distillation to remove all alkylene oxides that did not react. The product had a viscosity of 5700 cSt (at 25 ° C), a hydroxyl number 7.8 mg KOH / g and an unsaturation of 0.115 meq / g (approximate molecular weight of 8000 daltons).

Preparation of MDxD Surfactants "and M A typical preparation was carried out as follows: a flask provided with a mechanical stirrer, a reflux condenser, and a thermometer under positive nitrogen pressure was charged with the desired MDxDy] M fluid, polyether mixture, and solvent (if used) . BHT (0.6 g, 0.1 weight percent) was added and, where indicated, regulatory solution (sodium propionate), the mixture was stirred and heated to 80 ° C, and an ethanol solution of hexachloroplatinic acid (25 ppm Pt) was added. An exotherm of 5-15 ° C followed, after which the reaction was allowed to proceed for about 40 minutes. All volatile solvents or by-products were removed by vacuum, and the resulting copolymer product was cooled to room temperature, and optionally neutralized with sodium bicarbonate or tertiary amines (if acidic). Table 1 provides the exact feedstock loads for each copolymer. Examples 1 to 3 employ polyethers with molecular weights similar to those used in the state of the art but prepared by means of DMC catalysis. This allows a direct comparison with the conventional technology (designated as Control in Table 4) which was prepared by means of the above procedure using conventional KOH process polyethers.

Table 1: Specifications of Surface Agent Synthesis.

Copoly- Identification of the Fluid Weight SiH Number Polyether (g) BAM (a) (weight in g) Comments 40HA400AC 27.0 1200 MD100D'16.7M High viscosity APEG550AC 18.5 15.0 40HA4000AC 47.0 1500 MD65D'7.7M APEG550AC 19.3 24.0 40HA4OG0AC 55.0 1800 M065D'7.7M High viscosity APEG550AC 15.0 21.2 40HA8000AC 24.9 1200 MD100D'16.7M APEG550AC 20.6 15.0 40HA12000AC 24.25 1200 MD100D'16.7 M APEG550AC 21.3 15.0 0HA800AC 33.8 1800 MD65D'7.7M APEG550AC 12.9 14.1 40HA8000AC 22.4 1200 MD65D'7.7M APEG550AC 18.5 18.5 40HA8000AC 28.9 1500 MD65D'7.7M APEG550AG 15.3 16.0 40HA8000tBu 26.3 1300 MD100D'16.7M 750ppm NaPro adi-Magn. cured before APEG550tBu 20.3 14.2 hydrosilation Diluent 12.2 polyether 40HA8000tBu 26.3 1300 MD100D'16.7M 750ppm NaPro added before APEG550tBu 20.3 14.2 Hydrosilation Diluent 12.2 polyether 40HA8000tBu 24.4 1200 MD100D'16.7M 750ppm NaPro added before APEG550tBu- 21.1 15.0 hydrosilation Magn. Diluent 12.2 polyether 40HA8000tBu 27.0 1300 MD100D'16.7M 75 Oppm NaPro added before hydrosilation APEG550tBu- 19.6 14.2 Magn. Diluent 12.2 polyether 40HA8000tBu 26.3 1300 MD100D'16.7M Without treatment APEG550tBu 20.3 14.2 of MAGNESOL. 40HA8000tBu 17.35 1300 MD100D'16.7M both polyethers -Magn. submitted to APEG550tBu- 13.4 9.35 treatment of Magn. MAGNESOL. 40HA6000tBu 27.0 1300 MD100D'16.7M Without MAGNESOL treatment. APEG550tBu 19.6 14.2 40HA6000tBu 27.0 1300 MD100D'16.7M Low molecular weight polyether subjected to treatment APEG550tBu- 15.5 14.2 Magn. MAGNESOL. APEG550tBu 4.1 40HA6000AC 51.1 1200 MD100D'16.7M APEG550AC 39.9 30.0 40HA10,000Ac 49.0 1200 MD100D '16. 7M APEG550AC 42.0 30.0 55HA6000AC 51.1 1200 MD100D'16.7M APEG550AC 39.9 30.0 55HA10,000Ac 49.0 1200 MD100D'16.7M APEG550AC 42.0 30.0 40HA8000AC 41.1 1300 MD100D'16.7M Product separated into two phases APEG550AC 28.7 21.25 40HA8000AC 22.4 1200 MD65D'7.7M APEG550AC 18.5 18.5 Diluent 11.9 of Polyether 40HA8000AC 24.75 1300 MD65D'7.7M APEG550AC 17.35 17.6 Diluent 11.9 of polyether 40HA8000AC 30.65 1600 MD65D'7.7M APEG55AC 14.4 15.6 Diluent 12.1 of polyether 40HA8000AC 27.9 1450 MD65D ' 7.7M APEG550AC 15.8 16.3 Diluent 12.0 polyether 40HA8000AC 33.1 1750 MD65D'7.7M APEG550AC 13.2 14.3 Diluent 12.2 polyether 27 40HA10,000Ac 118.6 1955 MD65D'7.7M * Prepared via KOH technology APEG550AC * 26.3 52.7 (Comparative) 40HA1500AC * 92.8 Toluene 48 28 4OHA4, O00Ac * -1400 MD65D'7.7M Control: similar to # 27 with all PE APEG550AC * Prepared via KOH technology; Same 40HA1500AC * Number of moles of diluent of each Polyether. polyether (20%) (Comparative) a) BMAW of the terminally unsaturated polyethers, excluding the retained solvents or diluents. b) Polyether mixture components used in the synthesis of the surfactant. Symbolism: initial number followed by H indicates nominal percentage of EO residues in a polyether based on EO and PO, letter A indicates that the polyether is initiated from allylic alcohol, the numbers that follow the capital letters indicate the nominal molecular weight of the polyether / the letters -Ac, -t-Bu indicate acetoxy and t-butyl crown respectively, APEG means polyethylene glycol, initiated from allyl. Unless otherwise indicated, APEG-550Ac was produced via the KOH process after ion exchange to remove the KOH before being crowned with acetoxy, all other polyethers were crowned as received. "Magn" indicates that the polyether was treated with MAGNESOL® before being used. "NaPro" indicates regulatory solution of sodium propionate. The surfactants of Table 1 were evaluated in the polyurethane foam Formulation Test A (Table 2). The procedure for the evaluation is as follows: a 32 oz. Paper container was charged with NIAX® 16-56 polyol (250 g), the surfactant to be evaluated ("pphp" refers to parts of surfactant per 100 parts polyol), amine / water premix (containing 13.75 g of water and 0.5 gram of NIAX® A-200 catalyst), and methylene chloride (25 g). A brass mixer baffle with four vertical baffles equidistantly spaced apart and 0.5 inch wide in the container was inserted, and the mixture was stirred for 15 seconds at 2150 rpm using a drill with a marine blade. After 20 seconds stannous octoate (0.575 g, 0.46 ml) was added to the reaction mixture. A timer was initialized and the mixture was stirred for eight seconds before adding TDI 80/20 (173.6 g) with continuous stirring for seven additional seconds. The stirring was then stopped and the reaction mixture was emptied into a previously weighed 5 gallon plastic bucket. The container was inverted over the cuvette for a total of 10 seconds. As the foam began to rise, a small square (one inch) of aluminum foil was placed on its top to support a fixed length wire that floated in a calibrated support tube to record the heights of the foam in inches. The maximum height of the foam in the expansion, the amount of subsidence in the upper part after one minute, and the time of elevation were recorded. The foam was placed in a low temperature oven at 120 ° C for about 10 minutes and then allowed to cool to room temperature overnight. The height of the foam was measured in centimeters, then the foam was cut open using a tape seal and samples were taken for evaluation. Pieces of 4"x4" xl / 2"were cut from the center using a bread cutter For each sample the cell size (commonly referred to as the" structure "of the foam) and the ability to breath through were determined. of the foam was determined using a Nopco breathing capacity apparatus (adjusted to a counter pressure of 0.5 inches of water and reading of air flow in standard cubic feet per minute.) Generally speaking, coarse foam structures are undesirable and therefore General results in very low breathing capabilities Extremely coarse, spongy or partially sunken foams were not examined for cell size or air flows.

Table 2: Polyurethane Foam Test Formulation A Material pphp (weight) Polyol NIAX® 16-56 100 Distilled water 5.5 Catalyst NIAX® A-200 0.2 Methylene chloride 10.0 Stannous octoate 0.23 TDI 69.44 Varied surfactant3 a) Samples of surfactant containing diluent were evaluated so that the copolymer contained was the same as in other materials ("pphp" in tables 3 and 4 refers to the copolymer contained).

Table 3 shows a comparison of Copolymer number 4 against several products currently commercially available and a Control which represents a Copolymer with the same nominal structure of Copolymer 4 except with polyethers generated via conventional KOH technology so that the EO and the PO there are not randomly distributed. Copolymer 4 clearly shows higher elevation with equal or superior performance of breathing capacity. Copolymer 4 continued to show good low performance of 0.5 pphp, well below the normal range where commercial materials of the state of the art (usually using more than 0.7 pphp) failed. Even with pphp as low as 0.3 Copolymer 4 showed excellent lifting performance (foam structure began to deteriorate indicating that the use of lower levels would equally fail). It will be clear that the present invention provides better lifting performance and shows a higher power than the state of the art.

Table 3: Competitive Results of the Foam Test (Formulation A) # of Corri identif. Elevation gives of the Cop. pphp (cm)% TC AF Str Comments 1 4 1.25 41.2 1.7 7.0 M Control 1.25 39.8 1.2 6.3 NR L-620 1.25 39.3 1.8 3.6 NR GS-1 1.25 39.3 2.3 6.3 NR DC-1 1.0 39.3 2.4 5.5 NR L-620 0.85 38.6 3.6 4.7 NR GS-1 0.85 36.8 7.3 6.6 NR 2 Example 0.7 40.5 2.5 6.7 M 4 Control 0.7 38.1 2.6 6.0 NR L-620 0.7 38.2 ND 5.1 NR GS-1 0.7 Sunken Fault DC-1 0.6 37.1 6.7 6.0 NR 3 Example 0.5 40.2 3.2 6.3 C 4 Control 0.5 38.3 3.4 6.3 NR L-620 0.5 37.3 6.7 6.6 NR DC-1 0.5 Sunken Fault 4 Example 0.4 40.1 3.1 3.3 C 4 Control 0.4 38.0 3.4 6.8 NR L-620 0.4 36.3 4.1 5.5 NR Near Fault Example 0.3 39.6 8.6 0.9 C Still powerful 4 NR = not reported, ND = not determined /% TC = percent of subsidence in the upper part / AF = breathing capacity (Nopco air flow units). Str = cell structure, F = fine, M = medium, C = coarse. The breadth of the present invention is demonstrated by means of the copolymers described above as evaluated in table 4. Copolymers 1 to 8 demonstrated that proper handling of the silicone architecture and the polyether blend will produce copolymers with outstanding performance with range of elevation and, in many cases, constant breathing capabilities (a desirable characteristic). Evaluations of Example 2 repeated several days later gave essentially identical results. The Copolymers 9 to 16 demonstrated that polyethers capped with a non-polar portion such as the t-butyl group are as efficient as the polyethers crowned with acetoxy. Since the MAGNESOL® treatment is often used for conventional KOH technology, the impact of this treatment was tested and no foam performance advantages were found. Buffer solutions were precatalyzed with sodium propionate and it was also found that it was not necessary to obtain excellent performance. Copolymer 21 showed phase separation due presumably to weak reactivity and side reactions. The effects of this problem can be mediated by mixing with a diluent to achieve a more homogeneous material (note the improved lifting performance in the dilution). The addition of diluent before catalysis ensures lower viscosity of the reaction mixture as well as better solubility of the components in the two-phase reaction mixture. The resulting materials (Copolymers 22-26) were evaluated with the retained diluent and clearly showed superior performance. Note that with the Copolymer .25 the breathing capacity performance is the inverse of normal (conventional surfactants usually show a decrease in breathing capacity with higher levels of use). Copolymer 27 is an example of a three polyether copolymer employing a polyether of intermediate molecular weight (between 1400 and 3000 daltons). While these three polyether systems generally show less power than the two polyether systems since some of the grafted sites in the main silicone structure are occupied by lower molecular weight polyethers, they have only found utility in some applications. In this case, the intermediate molecular weight polyether was prepared via a conventional KOH process (the polyether could have been prepared via the DMC process in which the intermediate molecular weight polyethers can be isolated due to limitations of the equipment construction factor) . The foam elevation and breathing capacity performance were superior to the Control made with polyethers of conventional processes (Copolymer 28, a commercial copolymer made in accordance with the patent of the United States of America No. 4,857,583). The use of high molecular weight polyethers made with the DMC catalyst results in copolymers with higher potencies and constant breathing capabilities compared to the Control which has been optimized with the raw materials available from the KOH technology.

Table 4: results of the foam test (formulation A) # of Eleva¬ Coplation mere pphp (c)% TC AF Str Comments 1 1.25 34.0 16.8 No Sinking Partial registration 0.7 32.0 25.5 No Sinking Partial registration 0.5 28.7 1.8 7.0 M Partial collapse 1.25 40.9 1.9 4.5 F Constant breathing capacity 0.7 39.9 3.8 5.3 F 0.4 39.1 1.3 4.0 F 1.25 39.6 1.9 4.5 F Repeated evaluation (Same 0. 7 39.4 3.9 5.0 F results) 0. 4 37.9 0.7 2.4 F 1.25 41.2 1.2 2.3 F Constant breathing capacity 0.7 40.4 3.1 2.8 F 0.4 39.1 5.1 1.7 M 1.25 41.1 1 1..88 7 7..00 MM Constant breathing capacity 0.7 40.6 2.5 6.8 M 0.5 40.4 3.1 6.3 M 0.4 40.1 3.7 3.3 M 0.3 39.6 3.8 0.9 C 1.25 38.4 5.7 5.3 C 0.7 37.6 7.0 4.5 C 1.25 40.4 2.5 4.0 M Consistent breathing capacity 0.7 40.1 3.2 4.3 M 1.25 39.1 3.8 1.0 M 0.7 38.9 4.4 0.1 M 0.45 39.1 3.2 3.8 F 1.25 27.7 30.3 ND F Partial collapse. 0. 7 28.2 28.8 ND F Partial collapse. 1. 25 37.6 3.5 5.5 F Constant breathing capacity. 0. 7 37.1 4.8 5.5 F 0.4 36.3 6.3 5.8 F 1.25 35.8 6.4 5.8 F Consistent breathing capacity. 0. 7 36.3 5.5 6.5 F 0.4 34.3 7.4 5.8 F 1.25 34.8 7.3 4.8 F Consistent breathing capacity 0.7 35.8 6.4 6.0 F 0.4 36.6 4.9 6.5 F 0.3 33.8 10.7 6.0 F 1.25 39.6 2.5 6.0 F Consistent breathing capacity. 0.7 39.4 3.3 6.5 F 0.4 37.8 6.1 6.0 F 1.25 34.8 10.2 2.5 F Constant breathing capacity 0.7 34.0 12.6 2.5 F 0.4 32.0 16.6 2.1 M 1.25 39.1 3.2 4.0 M Constant breathing capacity 0.7 39.1 3.2 4.5 M 0.4 38.1 6.0 5.0 M 1.25 36.6 6.3 2.2 M 0.7 33.0 15.2 1.8 M 0.4 37.1 6.7 4.0 M 11..2255 3311..00 2222..33 33..00 MM Top layer. 1. 25 34.5 11.0 5.3 M Lower layer. 1. 25 34.5 11.0 1.1 C Mixed combined layers. 0.7 37.6 3.5 0.4 C With 20% polyether diluent and returned 0.45 38.1 2.0 0.4 C to be tested. 1.25 38.8 2.6 4.5 M 0.7 38.3 4.6 1.2 C 0.4 37.8 4.0 0.5 C 1.25 39.1 2.6 4.8 F 0.7 39.4 3.2 3.5 M 0.4 38.1 5.2 1.2 C 1.25 40.1 1.2 3.8 F Consistent breathing capacity 0. 7 40.4 1.3 4.8 F 0.4 39.1 2.6 3.5 F 1.25 41.1 2.4 5.3 F Breathing capacity. 0.7 39.6 1.9 4.8 F 0.4 39.4 3.9 3.5 F 1.25 41.1 2.4 4.0 F Consistent breathing capacity. 0. 7 40.4 1.9 4.0 F 0.4 39.1 3.9 3.3 F 1.30 38.8 0.0 5 F Dilution before evaluation. 0. 5 38.1 1.7 3 C 0.4 36.6 5.7 3 C 0.3 35.6 9.0 3 C 28 1 37.1 1.1 4 F Dilution before evaluation. 0.5 35.5 4.9 9 F Non-constant breathing capacity. 0.4 27.2 31.1 ND Gaps Partial collapse NR = not reported, ND = not determined /% TC = percent of subsidence in the upper part / AF = breathing capacity (Nopco air flow units). Str = cell structure, F = fine, M = medium, C = coarse. * Control for example # 27 (comparative, not of this invention).

Claims (24)

1. A surfactant having the generalized average formula M "DxD" and M "characterized by M" represents (CH3) 3Si01 / 2 or R (CH3) 2Si01 / 2 / D represents (CH3) 2Si022 / D "represents (CH3) (R ) Si02 / 2 / x is from about 40 to about 220 / and is from about 5 to about 34 / R are polyether-containing substituents obtained from a mixture of at least two different polyethers selected from the following two groups: 1) portions -Cn? 2NO (C2H40) _ • (C3H60) b '"having average molecular masses greater than 3000 daltons where the distribution of the groups -C2H40- and -C3H60- is random (or contains a random block), and where n 'is 3-4 / a' and b "are positive numbers such as 0 <a7 (a '+ b') <0.6; R" represents -H, an alkyl group of 1 to 8 carbon atoms, -C (0) R "', -C (0) OR"' OR -C (0) NHR "'/ R"' represents monofunctional aryl or alkyl groups / The random block of EO / PO of the polyether has been p b) using a double metal cyanide catalyst / and 2) portions -Cn? 2n "0 (C2H40) a" (C3H60) b "R" having average molecular masses in the range of 300 to 3000 daltons where n "is 3-4 / a "and b" are independently 0 or a positive number such that the total molecular weight of the polyether is from 300 to 3000 daltons / and the portions Rp and R "'are as defined above / wherein from the two different polyethers, at least one is selected from the group (1) of polyethers and the average molecular weight of the mixture of the polyethers is between 1100 and 3000 daltons.

2. A surfactant according to claim 1, further characterized in that the polyethers have a mixture average molecular weight of 1100 to 2100.

3. A surfactant according to claim 1, further characterized by D: (D "+ M ") < 10: 1.

4. A surfactant according to claim 1, further characterized in that x = 65-135 and y = 7 to 22.

5. A surfactant according to claim 1, further characterized in that the molar ratio of the first group of polyethers to the second group of polyethers is between 0.8 and 2.5.

6. A surfactant according to claim 1, further characterized in that it contains at least three different R groups.

7. A surfactant according to claim 1, further characterized in that it further comprises a diluent in an amount such that the viscosity of the surfactant is less than 2,000 centistokes at 25 ° C.

8. A surfactant according to claim 1, further characterized in that the double metal cyanide catalyst is Zn3 [Co (CN) 6] 2-x'ZnCl2-y '(alcohol) -z'H20) wherein ( alcohol) is glyme or t-butanol.

9. A process for manufacturing polyurethane foam characterized in that it comprises reacting a mixture of (a) a polyether or polyester polyol having an average of more than two hydroxyl groups per molecule / (b) an organic isocyanate having at least two groups isocyanate per molecule / (c) at least one catalyst / (d) optionally, an auxiliary blowing agent / (e) water / and (f) a surfactant as defined in claim 1.

10. A process in accordance with claim 9, further characterized in that the polyether-containing substituents in the surfactant have an average molecular weight of mixture of 1100 to 2100.

11. A process according to claim 9, further characterized in that D: (D "+ M") < 10: 1

12. A process according to claim 9, further characterized in that x = 65-135 and y = 7 to 22.

13. A process according to claim 9, further characterized in that the molar ratio of the first group of polyethers to the second group of polyethers it is between 0.8 and 2.5.

14. A process according to claim 9, further characterized in that the surfactant contains at least three different R groups.

15. A process in accordance with the claim 9, further characterized in that in addition the surfactant comprises a diluent in an amount such that the viscosity of the surfactant is less than 2,000 centistokes at 25 ° C.

16. A process in accordance with the claim 9, further characterized in that the double metal cyanide catalyst is Zn3 [Co (CN) 6] 2-x'ZnCl2-y '(alcohol) -z'H20) wherein (alcohol) is glyme or t-butanol.

17. Polyurethane foam produced by the process of claim 9.

18. Polyurethane foam produced by means of the process of claim 10.

19. Polyurethane foam produced by means of the process of claim 11.

20. Polyurethane foam. produced by means of the process of claim 12.

21. Polyurethane foam produced by means of the process of claim 13.

22. Polyurethane foam produced by means of the process of claim 14.

23. Polyurethane foam produced by means of the process of claim 15.

24. Polyurethane foam produced by means of the process of claim 16.