JPH0747630B2 - Silicone polyether copolymer surfactant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates generally to silicone polyether copolymers. In one aspect, the present invention relates to novel silicone / polyether block copolymers useful as stabilizers in the manufacture of polyurethane foams, especially rigid foams. Regarding polymers. In a further aspect, the present invention relates to a process for the production of the novel copolymer and the polyurethane foam produced therefrom.

In summary, the present invention provides silicone / polyether block copolymers that are useful as surfactants in the manufacture of several types of polyurethane foam. Whereas conventional copolymers have a polysiloxane backbone containing pendant polyethers, the surfactants of the present invention, conversely, contain pendant siloxanes on the polyether chain. Non-hydrolyzable polysiloxane polyalkylene copolymers featuring these novel "reverse" structures, ie polyalkylene backbones with lateral and / or terminal pendant polysiloxanes, have narrow molecular weight and composition distributions. , And contains no unreacted polyether or unmodified silicone oil diluent. These surfactants are useful in various urethane foam systems and can also represent aqueous wetting agents.

A first disclosure of polysiloxane polyoxyalkylene copolymers can be found in US Pat. No. 2,834,748. These compositions were of the hydrolyzable type. A subsequent first disclosure of non-hydrolyzable polysiloxane polyoxyalkylene copolymers can be found in US Pat. No. 2,846,458. 195
In 1988, the application of polysiloxane polyoxyalkylene copolymers to the stabilization of urethane foam was first disclosed in British Patent No. 892,136. These polymers were hydrolyzable. Shortly thereafter, the application of non-hydrolyzable copolymers for the production of urethane foam was reported.

For those skilled in the art, the purity of the non-hydrolyzable silicone polyether composition used to stabilize the urethane foam typically depends on the process polyether to ensure complete consumption of silane hydrogen from some siloxane intermediates. It is known to suffer some damage due to the requirement to use a molar excess. This requirement stems from the competing side reactions of the olefinic terminated polyethers that effectively inactivate a proportion of the polyethers. Residual silane hydrogen remaining in the product, as is well known to those skilled in the art, results in product instability and / or when used in urethane foam systems.
Or it may bring about bubble collapse. The use of excess process polyether not only results in an effectively diluted product, but also increases manufacturing costs and optionally hinders easy separation of the copolymer product.

Unreacted silicone present as part of the thermodynamic equilibrium of the species present in the equilibrated poly (dimethyl-methylhydrogen) siloxane fluid (especially unmodified cyclics)
Also reduces the purity of the copolymer product produced therefrom.

Further, the typical copolymer composition as described above always exhibits a broad molecular weight distribution and composition distribution. This is a function of the properties of the equilibrated siloxane intermediate used in part. Therefore, applications that require a particular narrow copolymer molecular weight and / or composition distribution for performance are complicated by the presence of a wide distribution. Very at least a copolymer composition other than a particular narrow molecular weight and / or composition distribution will serve as an expensive diluent for a particular product and process.

A description of excess polyether is found in US Pat. No. 3,798,253.
No. 3,957,843, 4,059,605, 4,105,048,
And No. 4,160,775. All of these patents address the common theme of modifying the functional moieties of the process polyethers to minimize the mechanism that inactivates a substantial proportion of the polyethers with respect to their hydrosilation reactivity. . This method contemplates a somewhat purer polyether lacking substantially unreacted polyether diluent. Unfortunately, the reactivity of the modified process polyethers in these examples is significantly reduced compared to its unmodified counterpart. Furthermore, these methods do not address both the issue of broad molecular weight distribution of the copolymer species and the presence of unmodified silicone species.

See US Pat. No. 4,090,987 for molecular weight and composition distribution.
Are discussed in the issue. The structure of the disclosed copolymer was such that the polyether pendants in the copolymer structure are evenly spaced along the siloxane backbone. Although these structures are relatively more uniform structures,
Due to the nature of the siloxane condensation reaction used, it still consisted of a distribution of siloxane species that changed the degree of polymerization of the siloxane.

Significant reductions in the amount of unreacted unmodified silicone can be achieved by lard (preferably vacuum) distillation of silicone lights from either the starting fluid or the copolymer product. . Both methods are time consuming and expensive and the latter method can compromise the integrity of the copolymer product.

Thus, various products and technologies are provided in the market for silicone surfactants today which offer a wide range of performance characteristics, but have a narrow unimodal distribution and residual unreacted polyethers and unreacted There are few, if any, products that are substantially free of silicone.

Except for dimethyl oil, which is sometimes used in HR molding systems, conventional silicone surfactants are structurally represented by a (optionally branched) silicone backbone that exhibits lateral or terminal alkyl, aryl, polyether or other organic pendants. It is a copolymer classified.

[Wherein R ₁ and R ₂ are alkyl, aryl and / or polyether].

Silicone and pendant dimensions, pendant spacing,
Varying the number and type, suitable diluents, and other extended structural and compositional properties will result in the necessary performance changes needed for the particular application.

Typical non-hydrolyzable silicone polyether compositions used to stabilize urethane foams feature a (optionally branched) polysiloxane backbone containing terminal and / or lateral polyether pendants. However, in contrast, silicone surfactants with a molecular "inversion" of the surfactant structure, ie polyether backbone surfactants with silicone pendants, have not been reported in the literature. For illustrative purposes, such a composition can be represented by the formula: Organic backbones with silane or silicone pendants, eg repeating units Are manufactured. However, these polymers contain ester or polyethylene oxide-ketal repeating units.

Japanese researchers have produced alkoxysilane pendant polyether-polyester block copolymers having pendant silane groups attached to the polyether backbone through oxygen atoms.

U.S. Pat. No. 4,514,315 discloses a method for grafting ethylenically unsaturated alkylene silanes to polyalkylene oxide polymers for use in aluminum corrosion inhibitor packages. The amount of silane monomer grafted onto the polyalkylene oxide polymer was up to 60% by weight of total product.

ML Wheeler, in US Pat. Nos. 3,418,354 and 3,573,334, is an olefin prepared by radically grafting an olefinic silicone to an uncrosslinked (ie, liquid) organic polymer containing a polyether. Disclosed and Claimed Functional Silicone-Organic Graft Polymers. The olefinic silicone contains at least one unsaturated group and the graft copolymer thus obtained is badly crosslinked.

In radical grafting, some of the unsaturated silicone compounds would be expected to react within them to form polymeric compounds. Further, since a siloxane having at least one unsaturated group is used, it would also be expected to be grafted with a silicone having more than one functional group to crosslink the polyether.

That is, the prior art discloses a structure having a silicone pendant from a polyester and a poly (ethylene oxide-ketal) backbone, and further a structure having a silane pendant from a polyether or poly (ether-ester) backbone. To date, silicone pendant polyethers that have not been prepared by the radical method have not been disclosed in the literature. Therefore, as mentioned above, these copolymers have a polyether backbone and a silicone (or silane) pendant, ie they have the opposite arrangement of the usual surfactants, so that they are referred to as "reversing surfactants". be called.

Thus, one or more of the following objects will be met by the practice of the invention. It is an object of the present invention to provide new siloxane polyether copolymers. Another object of the present invention is to provide a novel silicone polyether composition which is a block copolymer composition. Another object is to provide silicone polyether copolymers that are useful as surfactants in the production of polyurethane foam. Yet another object of the present invention is to provide a terminal and / or
Or to provide a copolymer exhibiting a polyether backbone with lateral siloxane pendants. Another object is to provide a copolymer product mixture which is substantially free of both residual unreacted polyether and unreacted silicone and is therefore predominantly a copolymer. A further object is to provide copolymer compositions which have a narrower molecular weight distribution than conventional copolymers. A still further object is to provide a copolymer composition that is an effective stabilizer, especially for rigid polyurethane foams. Another object is to provide rigid polyurethane foams made with the surfactants of this invention. Further provided are methods of making the above copolymers and foams. These and other objects will be readily apparent to one of ordinary skill in the art in light of the teachings provided herein.

In a broad aspect, the present invention relates to silicone polyether copolymers, a process for their preparation and their use as stabilizers in the production of polyurethane foams, and urethane foams, especially rigid urethane foams.

As mentioned above, the molecular structure of the copolymers of the present invention is the reverse of the usual copolymers used in the production of foams, i.e. they have the formula [Wherein R ′, R ″, a and b are as described above] characterized by a polyether backbone with at least three silicone pendants.

The use of these polymers avoids the potential problems and drawbacks associated with unreacted polyethers and silicones and results in narrower copolymer molecular weight and composition distributions.

FIG. 1 shows a gel permeation chromatograph of a typical conventional surfactant preceded by a silicone precursor, and FIG. 2 shows a surfactant of the present invention preceded by a silicone precursor. A gel permeation chromatograph is shown.

As mentioned above, no silicone "reversal" of the structure of the surfactants, i.e. silicone surfactants with a polyether backbone with silicone pendants, has been reported in the literature.
Formula (II) above generally illustrates a typical repeating unit of a surfactant having such an inverted structure.

In one aspect, the silicone polyether copolymers of the present invention are prepared by hydrosilation of a polyether prepared by the copolymerization of ethylene oxide, propylene oxide and allyl glycidyl ether. Such copolymers are composed of the following random or block repeating units: [Wherein R represents hydrogen, lower alkyl, acetyl, etc .; R'represents a C ₁ -C ₃ saturated alkyl group, or R ",
However, R ″ is W has at least 2, preferably 2-10, carbon atoms and is O, N in W or at the end of W linked to the polyether.
And S is a divalent group optionally containing at least one heteroatom; a, b and c are 0-3 and a + b = 3, where c is preferably 2 Or 3; and x and y are 0 or positive integers; and z is an average value of at least 3].

The group H-as used throughout this specification and claims
Si≡ is [Wherein R ′, R ″, a and b are as described above].

The copolymer surfactants of this invention can be prepared by hydrosilation of a suitable polyether with a monofunctional siloxane. A commercially available polymer product prepared by one or more homopolymerizations or copolymerizations containing olefinic unsaturated groups which can themselves be reacted at least in part with the monofunctional siloxane. It is the same. For example, a polyether of polypropylene oxide (PPO) rubber before vulcanization, which typically has about 6% AGE and PO balance. Many of the alkylene oxides that can be used to make the polyether include ethylene oxide, propylene oxide, butylene oxide, 2,3-epoxybutane, 2-methyl-1,2-epoxypropane, tetrahydrofuran and the like.

Examples of alkylene oxides containing olefinic unsaturation include, but are not limited to, allyl glycidyl ether, vinyl cyclohexene monoxide, 3,4-epoxy-1-butene, and the like.

Thus, the polyether used in the production of the surfactant of the present invention comprises repeating units [Wherein R ^{1 to} R ⁴ are hydrogen or lower alkyl, Z represents a hydrocarbon group having 1 to 6 carbon atoms and optionally having a hetero atom such as O, N and S; d has a value of 0 or 1; n has a value of 1 to 6 and m is 0
Or has a positive integer value; and w has an average value of at least 3].

Homopolymerization and copolymerization of alkylene oxides are well known for the production of polymers such as polypropylene oxide rubber. Of course, the polymer compound can be produced as a block or random polymer and may be entirely composed of units having pendant unsaturated groups. Thus, if the polyether is made entirely of unsaturated epoxides such as allyl glycidyl ether, the polymer backbone will contain a large number of pendant unsaturated groups. On the other hand, if unsaturated epoxides are used in small amounts in the production of polyethers, the pendant unsaturated groups will be widely spaced along the polyether backbone, thus leaving less points for siloxane groups to attach.

However, as mentioned above, the final surfactant must contain an average of at least 3 siloxane groups. One siloxane gives the AB structure and two siloxanes give ABA, but neither of these is a reversal surfactant by definition. The surfactant composition must be AB
And ABA structure, but its contribution to the total composition will decrease as the average number of siloxane pendants increases substantially above 3. That is, a satisfactory polyether has an average molecular weight of such a polyether>
If it was 5700 g / mol, it could be prepared from the copolymerization of a mixture containing 94% propylene oxide and 6% acrylic glycidyl ether.

The polyether copolymer surfactants of the present invention have a molecular weight of from about 650 to
It has an average molecular weight of about 20,000 and has a polyether backbone containing a plurality of pendant silicone-containing groups. The surfactant comprises: (a) a narrow, unimodal distribution; (b) essentially free of silicone oil and process polyethers; and (c) any unreacted impurities on the polyether backbone. The feature is that the saturated group is inactivated at any time. An inactivated unsaturated group, as used in the present invention, means an isomerized group such that the olefinic unsaturated group is no longer located at the terminal. For example, the acrylic group may be isomerized or may be isomerized to a propenyl group, thus, for the purposes of the present invention, the point of crosslinking with other polyethers for further reaction or during normal hydrosilation reaction conditions. It can be considered inactivated in terms of providing.

Prior to discussing the production of the silicone polyether copolymers of the present invention, the purity of the non-hydrolyzable silicone polyether composition used to stabilize the urethane foam typically determines the complete consumption of silane hydrogen. It should be noted that the siloxane intermediate is affected as a result of the requirement of using a molar excess of process polyether to compensate. This requirement arises due to competing side reactions of the olefinic terminated polyethers that effectively inactivate a proportion of the polyethers. Residual silane hydrogens remaining in the product can lead to product foam collapse and further product composition imperfections when used in urethane foam systems, as is well known to those skilled in the art. The use of excess process polyether to overcome this problem not only results in an effectively diluted product, but also increases manufacturing costs and interferes with easy isolation of the copolymer product.

Moreover, typical copolymer compositions such as those described above exhibit a broad molecular weight distribution and composition distribution as a function of the nature of the equilibrated siloxane intermediate used. Thus, applications requiring particularly narrow copolymer molecular weight and / or composition distributions for special performance can be complicated by the presence of a wide distribution. Very at least copolymer structures that fall outside of the particularly narrow molecular weight and / or composition distribution will be expensive diluents for products and processes.

A particularly important property of the copolymers of the present invention is that, compared to common polyether copolymers with pendant siloxanes,
That is, it can be produced with a relatively narrow molecular weight range. Prior to this discovery, there was neither precedent nor reason to believe that high copolymer purity and narrow molecular weight distribution could be achieved in a single copolymer species. Furthermore, there was no reason to believe that the reversal of the structure of the siloxane polyether copolymer provided wetting and stabilization of the urethane foam.

As mentioned above, the inverted silicone polyether copolymers of the present invention can be conveniently prepared, for example, by hydrosilation of a suitable polyether with a monofunctional siloxane. In general, the method used to prepare the various inversion structures of the present invention uses various multifunctional polyethers in reaction with several separate monofunctional SiH fluids under typical hydrosilanization conditions. . The polyfunctionality of polyethers is that of EO and / or PO, allyl glycidyl ether (AGE) or vinylcyclohexene monoxide (V
It was introduced by simultaneous alkoxylation of CM). The monofunctionality of SiH fluids is described below in silicones such as MM ',
Guaranteed by distillation of MD'M, M ₃ T ', D ₃ D', etc.

Typically, the hydrosilanization was performed without difficulty, but often gave a sharp exotherm. The amount of solvent was often as high as 60% to help control heat dissipation. Solvent-free preparation is also possible, but very exothermic as shown in Example XVII. The stoichiometric amount of allyl (or vinyl) and SiH is SiH
It was in the range of 1.3: 1.0 for the excess of. There is a lower silicone content than in the case of a very high proportion and thus a considerable amount of unreacted pendant olefin groups, and in a very low proportion there is an excess of silicone fluid which has to be distilled off. Many excesses of silicone were not problematic in the product as this excess was easily removed by final evaporation. However, even in the presence of excess SiH fluid, it was discovered that these hydrosilanations convert less than 90% of allyl groups to hydrosilanated products (also depending on the exact siloxane). The remaining unsaturation was present as a propenyl functionality. This showed that the isomerization of allyl and propenyl competes with hydrosilation in these highly reactive systems to a degree similar to that which occurs in conventional surfactant preparation.

Tables I and II are provided to teach important structural differences within the present invention, as there is currently a lack of simplified nomenclature suitable for simple identification of inversion copolymer production. I
The table shows polyfunctional polyether intermediates. Table II describes the copolymers produced by the method of this invention along with some analytical data. Examples I-XV and XIX are monofunctional Si
Figure 3 shows the preparation of typical reversal surfactants based on H-fluid and multifunctional polyethers.

Examples X XI to X XII are respectively HR slabstock (slastock
bstock), and the results of urethane foam evaluation based on hard and molded HR formulations.

For ease of identification, the surfactants of the present invention are referred to by a letter designation having the following meanings: M O _1/2 Si (CH ₃ ) ₃ D (CH ₃ ) ₂ SiO _2/2 D '. (CH ₃ ) Si (H) O _2/2 D ″ (CH ₃ ) Si (R) O _2/2 D ₃ cyclic dimethylsiloxane trimer D ₄ cyclic dimethylsiloxane tetramer _{MM '(CH 3) 3 SiOSi} (CH 3) 2 HM 3 T' [(CH 3) 3 SiO] 3 SiH MD'M [(CH 3) 3 SiO] 2 Si (CH 3) H MD 2 M '( CH ₃ ) ₃ SiO [Si (CH ₃ ) ₂ O] ₂ Si (CH ₃ ) ₂ H MD ₃ M ′ (CH ₃ ) ₃ SiO [Si (CH ₃ ) ₂ O] ₃ Si (CH ₃ ) ₂ H T CH ₃ SiO _3/2 Q SiO _4/2 “SiH fluid” poly (dimethyl, methyl-hydrogen) siloxane.

The present invention will be more readily understood with reference to the drawings. FIG. 1 is a comparison of a typical GPC of a GPC or less reversed copolymer of a starting polyether backbone as shown in FIG.
Ordinary copolymer mother liquor below the GPC of the starting SiH fluid backbone (moth
er fluid) typical GPC (gel permeation
Chromatography). GP of normal copolymer mother liquor
C shows a multimodal distribution, while the inversion copolymer mother liquor is unimodal.

The composition of the mother liquor is also unique, in addition to the novel structure itself, which shows a silicone pendant from a polyether backbone as opposed to the converse in conventional surfactant systems.

As seen in the chromatogram, the inversion products show a narrow unimodal distribution. This narrowness (relative to conventional surfactants) is a manifestation of the difference between the backbones of the two systems. Common surfactants are based on equilibrated SiH fluids with a broad composition distribution. On the other hand, the reversal surfactant is n-
Based on multifunctional polyethers "grown" from an initiator such as butanol. These polyethers, although not completely distinct molecular species, are more compositionally uniform than the equilibrated SiH fluid, especially with respect to molecular weight distribution. These "more uniform" intermediates are distinct silicones such as
MM ', D'D _3, from reacting with such degree of relative homogeneity appears to reverse the surfactant product. This is not similar to conventional surfactant systems in which the less homogeneous SiH fluid backbone composition reacts with non-discrete allyl-initiated polyethers to produce less homogeneous products. Therefore, the distribution of inverted surfactant is expected to be less dispersive than in conventional systems. GPC confirms this in terms of molecular weight distribution.

A second unique feature of the reversal surfactants of the present invention is the absence of the diluents (both silicone oil and excess process polyether) present in conventional surfactants.
Free silicone oil (ie D ₄ , D ₅ etc.) was equilibrated
It exists in the normal system because it exists in the SiH fluid intermediate.

Most of the silicone oils in conventional copolymer compositions are Si
It can be removed from the SiH fluid by rigorous distillation of either the H 2 fluid precursor or the final copolymer product. However, even effective distillation was shown to leave linear or cyclic silicone oils greater than about MD ₇ M and D ₈ . These silicone oils are not present in the inversion system of the present invention if the silicone precursor has been purified. Since little or no redistribution is observed during these hydrosilanizations using the appropriate conditions, the silicone oil does not form as a by-product and thus is not present in the final reverse copolymer composition.

The excess unreacted polyether present in conventional systems is a result of the required hydrosilation conditions. Generally, in order to complete the platinum-catalyzed hydrosilation based on SiH consumption, the allyl-initiated polyether must be present in a 30% excess.

On the other hand, any allylic to propenyl isomerization that occurs within the polyfunctional polyethers serves only to deactivate its unsaturated groups, and does not deactivate the entire polyether as shown below: [In the formula, H-Si≡ is as described above. Is equivalent to].

Any remaining unreacted silicone SiH fluid does not pose a problem as the one used here is volatile and is easily removed during standard solvent evaporation.

GPC, ¹³ C _nmr and ²⁹ Si _nmr were useful tools for characterizing inverted surfactant products. GPC confirmed the absence / presence of crosslinks. In general, careful purification of silicone intermediates and controlled reaction and processing conditions prevented cross-linking structures. ¹³ C _nmr is particularly useful for monitoring the degree of conversion of unsaturated groups of polyfunctional polyethers after hydrosilanation, 80
Although greater than% conversion is often observed, complete conversion is usually hindered by competing isomerizations of allyl to propenyl. Furthermore, ¹³ C _nmr could be shown to be free of O-dehydrogenative condensation chemistry (SiH + HOR → SiOR + H ₂ ) during hydrosilation in unterminated polyfunctional polyether systems.

The reversal surfactants of the present invention have been evaluated for application to conventional soft HR (molding and slabstock) and hard urethane foam. This performance test method allows for the initial screening of different reversing silicone surfactants in box injection.
Included with the final evaluation occurring in the L-panel format. This L-panel is a proper and simple discriminating test by which surfactant performance criteria such as surface defects, density, density gradient, K-factor and flowability can be effectively measured.
The performance in these evaluations was judged by the density of the form and the K-factor (insulating ability). For these evaluations a fast and smooth formulation such as in a spray system was used.

Two conventional hard foam surfactants sold by Union Carbide Corp. and identified as L-5420 and L-5440 were used as targets. All reversal surfactant evaluations were performed using either or both of these conventional surfactants as controls.

The formulations used to evaluate these performances are shown in Table IV. In each case a surface-active agent (all containing unterminated polyether backbones) was introduced on the resin side. The foam results are presented in Tables V-VII for slow formulations and in Table VIII for fast formulations.

As is known in the art, the production of polyurethane foams using the surfactants of the present invention requires one or more polyether polyols to react with the polyisocyanate reactant to provide urethane linkages. An average of at least two such polyols per molecule, typically
It includes compounds having 2.0 to 3.5 hydroxyl groups and consisting of carbon, hydrogen and oxygen and optionally phosphorus, halogen and / or nitrogen. Such polyether polyols are known in the art and are commercially available.

Organic polyisocyanates useful for making polyether polyurethane foams according to the method of the present invention are well known in the art and are organic compounds containing at least two isocyanate groups, Any compound or a mixture thereof can be used. Toluene diisocyanate is a suitable isocyanate among those used commercially in the production of foam.

The urethane foaming reaction is usually carried out in the presence of a small amount of catalyst, preferably an amine catalyst, usually a tertiary amine.

In addition to the amine catalyst, it is also suitable to add small amounts of certain metal catalysts to the components of the reaction mixture. Such auxiliary catalysts are well known in the art of making polyether-based polyurethane foams. For example, useful metal catalysts include organic derivatives of tin, especially tin compounds of carboxylic acids such as stannous octoate, stannous oleate and the like.

Foaming is accomplished by using water in the reaction mixture which reacts with a small amount of a polyurethane foaming agent such as isocyanate to generate carbon dioxide in situ, or by using a foaming agent which evaporates due to the exotherm of the reaction, or These two
Can be performed in combination. The polyether-based polyurethane foams of the present invention may be foamed by any of the techniques known in the art, such as, in particular, the "one-shot" technique. According to this method, a foamed product is provided by reacting a polyisocyanate and a polyether polyol simultaneously with the foaming operation. Sometimes it is convenient to add the surfactant to the reaction mixture as a premix with one or more of the blowing agent, polyether, polyol and catalyst components.

It is understood that the relative amounts of the various components of the foam composition are narrow and inexact. The polyether polyols and polyisocyanates are present in major amounts in the foam forming formulation. The relative amounts of these two components in the amounts required to produce the desired urethane structure of the foam and such relative amounts are well known in the art. The blowing agent, catalyst and surfactant are each present in a small enough amount to foam the reaction mixture and the catalyst is in a catalytic amount which is the amount required to contact both to produce urethane at a reasonable rate. Is present, and the surfactant is present in an amount sufficient to impart the desired properties. The polyurethanes produced according to the invention can be used in the same fields as customary polyether and / or polyester polyurethanes. For example, the foams of the present invention can be advantageously used in the manufacture of textile backings, cushions, mattresses, pads, carpet backings, fillings, gaskets, sealers, insulations, and the like.

In the following examples, all reactions involving the handling of organometallic compounds were conducted in an inert atmosphere. Commercially available reagents were used without further purification. All glassware is KO
It was washed successively with H / isopropanol, water, dilute hydrochloric acid, and water and oven dried before use. ¹³ C _nmr spectra were measured using a Fourier Transform Varian CFT-20 spectrometer. ^{The 29} Si _nmr and further ¹³ C _nmr spectra were measured using a JEOL-90Q spectrometer. NMR samples were prepared by dissolving the sample in deuterated chloroform or deuterated benzene containing 0.03 M Cr (acac) ₃ relaxant. GC analysis is based on a Hewlett Packard 5840A equipped with a 10 foot x 1/8 stainless steel column packed with Chromosolve W loaded with OV101.
It was performed using a gas chromatograph. The GC was operated using a helium gas flow of 30 cc / min and heating from 75 ° C. to 350 ° C. at a rate of 1 minute and a holding time of 20 minutes. GPC in CHCl ₃
1.0% diluted with 10 ^4, 10 ^3, it was obtained by operating at a flow rate of 10 ml / min under high pressure 1080A and room temperature through 500 and four Karamusetsuto of 100A.

The following example illustrates the invention.

Example I Preparation of Inverted Surfactant IS-5 by Hydrosilation of MM 'with Polyether 13 Clean, dry 500 ml 3 neck round bottom flask (3NRBF).
Polyether 13 [allyl 16.4%; OH (diol) 3.5
2%; allyl glycidyl ether (AGE) 48% by weight, ED24
% And PO28%] 85.79g, and MM '(petrarch) 39.21g
And 20 g of toluene were added. This charge has allyl groups of 3
It showed 0% excess (relative to SiH) and 60% toluene. However, many similar preparations have 1: 1 stoichiometry and 3
It has been found suitable with only 0% by weight of toluene. Then in the reaction kettle a mantle heater, mechanical stirrer, thermometer / temperature monitor, Dane-Stark collector with Friedrich coagulator, N ₂ inlet / outlet and N ₂
Equipped with a sparge tube. The stirring system was flushed with nitrogen.

The homogeneous solution was contacted with 0.5 ml (15 ppm) of chloroplatinic acid (CPA) / ethanol solution (10 mg Pt / ml) at 29 ° C. The reaction kettle was warmed to 40 ° C, at which point an exotherm of 35 ° C was observed, reaching 75 ° C over 1 minute. Next, add 10 reaction kettles.
It was brought to 0 ° C. and kept at this temperature for 90 minutes. Neutralization was carried out by adding 5.1 g of NaHCO ₃ and maintaining at 100 ° C. for 3 hours. Pass this solution through a 3-4 μ filter bed to 40 psi N ₂
Filtered down and collected in another 3NRBF. Then add 1 part of toluene
It was removed by N ₂ sparge at 00 ° C. Transparent brown substance
110.15 g was collected (88% yield).

GPC analysis showed a unimodal product distribution with a lower retention time than the polyether starting material, consistent with an increase in molecular volume. ¹³ C _nmr showed typical 1,2 hydrosilanation of allyl groups and ²⁹ Si _nmr showed the presence of silicon atoms of only M and M ″ forms in a 1: 1 ratio. The percentage of silicon was 9.9 ± 0.1%. It was found that the calculated value was 10.9% for 100% reaction. This copolymer product could reduce the surface tension of water to 22.4 dynes / cm at 25 ° C and 1% concentration. It's been found.

Example II Preparation of Inverting Surfactant IS-11 by Hydrosilation of MD'M with Polyether 13 Clean, dry 500 ml 3 neck round bottom frothco (3NRBF)
, MD′M 50.32g, polyether 13 [allyl 16.4%; OH
(Diol) 3.52%; allyl glycidyl ether (AG
E) 48% by weight, ED 24% and PO 28%] 74.68 g and toluene 2
I added 00g. This charge has a 30% excess of allyl groups (SiH
) And toluene 60%. However, many similar preparations were found to be successful with a 1: 1 stoichiometry and only 30% by weight of toluene.

The reactor was then equipped with a mantle heater, mechanical stirrer, thermometer / temperature monitor, Dane-Scoot collector with Friedrich condenser, N ₂ inlet / outlet and N ₂ sparge tube. The stirring system was flushed with nitrogen.

The homogeneous solution was contacted with 0.4 ml (15 ppm) of chloroplatinic acid (CPA) / ethanol solution (10 mg Pt / ml) at 65 ° C. The reaction kettle was loosened to 77 ° C, at which point an exotherm of 20 ° C was observed, reaching 97 ° C over 3 minutes. Next, add 10 reaction kettles.
Hold at 0 ° C for 34 minutes. Neutralization was carried out by adding 5.0 g of NaHCO ₃ . Keep the reaction kettle at 100 ° C for an additional 125 minutes,
At this time the solution was cooled to room temperature, pressure filtered through a 1-2 μ filter bed under 40 psi N ₂ and collected in another 3 NRBF. The toluene was then removed by N ₂ sparge at 100 ° C. About 115 g of a pale yellow product was collected (92% yield).

GPC analysis showed a unimodal product distribution with a lower retention time than the polyether starting material, consistent with an increase in molecular volume. ¹³ C _nmr showed typical 1,2 hydrosilanation of allyl groups and ²⁹ Si _nmr showed the presence of only M and D ″ units in a 1: 1 ratio. It was shown to reduce the surface tension of water to 22.4 dynes / cm at a concentration of%.

Example X VI shows a hydrosilation with a similar MD'M to the acetoxy-terminated homolog of Polyether 13 , ie Polyether 17 . Example X VII shows solventless hydrosilation of MD'M and polyether 13 .

Example III Preparation of Inverting Surfactant IS ″ -35 by Hydrosilation of Polyester 13 with MD ₂ M ′ Polyether 13 [allyl 1
6.4%); OH (diol) 3.52%; allyl glycidyl ether (AGE) 48% by weight, EO 24% and PO 28%] 29.04 g, MD ₂
35.97 g of M '(see Example XVI) and 29.19 g of toluene were added. These feeds exhibited a 1: 1 stoichiometric ratio of allyl: SiH and a 30% dilution with toluene.

The reaction kettle was equipped as in Example I in the preparation of the hydrosilanized product. The contents of the reaction kettle ensured dehydration by distillation of toluene assisted by a small amount of N ₂ sparging at 90 ° C., which gave a clean, dry toluene distillate. Cool the reaction kettle to 86 ° C to obtain a uniform solution.
CPA / ethanol solution (Pt 10 mg / ml) 0.3 ml (32 ppm). After an induction period of about 1 second, a rapid exotherm of 27 ° C occurred, the temperature of the reaction vessel was 113 ° C, followed immediately by the browning of the solution. Keep this reaction kettle at 105 ° C for 30 minutes,
At this point it was neutralized with 10.15 g NaHCO ₃ and 105 ° C.
Kept for 120 minutes. The solution is then cooled to 37 ° C and
Filter through a 2μ filter bed under 40 psi of N ₂ and collect in another 500 ml of 3NRBF. The toluene was then removed at 105 ° C. with the assistance of N ₂ sparge. GC analysis of the distillate after removal of toluene showed the presence of approximately 2 g of unreacted MD ₂ M ′. 51.33 g of a brown, non-viscous product was collected (79% yield).

The GPC of the product showed a distribution of unimodal products. ¹³ C
_nmr showed typical 1,2-hydrosilanation of the allyl group and a small amount of propenyl carbon. ²⁹ Si _nmr analysis showed the presence of only M, D and M ″ silicone groups in a 1: 2: 1 ratio.
The gravimetric analysis of silicon (element)% was 14.0 ± 0.3%, which was 50% of the theoretical value. Interestingly, ¹³ C _nmr suggested that more than 80% of the reactions were complete. The contradiction of this analysis has not yet been resolved.

Example IV Preparation of Reversing Surfactant IS ″ -82 by Hydrosilanation of Polyester 13 with MD ₃ M ′ 23.88 g MD ₃ M ′ (see Example XVII), polyether 13 [in a clean 500 ml 3NRBF. Allyl 16.4%); OH (diol) 3.52%; Allyl glycidyl ether (AGE) 48
% By weight, EO 24% and PO 28%] 16.12 g, and toluene 17.1
I put 5g. These feeds exhibited a 1: 1 stoichiometric ratio of allyl: SiH and a 30% dilution with toluene.

The reaction kettle was equipped as in Example I in the preparation of the hydrosilanized product. The contents of the reaction kettle ensured dehydration by distillation of toluene assisted by a small amount of N ₂ sparging at 90 ° C., which gave a clean, dry toluene distillate. CPA / ethanol solution (Pt10mg / ml) 0.15m
The catalyst was activated by the addition of 1 (26 ppm). After a short induction period, a rapid exotherm of 10 ° C occurred and the temperature of the reaction kettle increased.
At 108 ° C., the solution immediately turned brown. The reaction kettle was kept at 100 ° C. for 60 minutes, at which point it was neutralized with 5.0 g of moist (10% water) NaHCO ₃ and further heated to 100 ° C. for 120 min.
Hold for a minute. The solution was then hot filtered through a 3-4μ filter bed under 40 psi of N ₂ and collected in another 500 ml of 3NRBF. Next, with the aid of N ₂ sparge, 110 toluene was added.
Removed at ° C. As a result, 31.71 g of a brown product (yield 79
%).

The product GPC showed a unimodal product distribution. ¹³ C
_nmr and ²⁹ Si _nmr are consistent with the proposed product.

'During the reverse surface active agent IS "-59 manufacturing clean 500ml of by hydrosilation with 3NRBF, M ₃ T' Example V M ₃ T of polyester 13 (see Example X VIII) 32.58g, polyether 13 [ Allyl 16.4%); OH (diol) 3.52%; Allyl glycidyl ether (AGE) 48
% By weight, EO 24% and PO 28%] 27.46 g, and toluene 26.0
I put 1g. These feeds exhibited a 1: 1 stoichiometric ratio of allyl: SiH and a 30% dilution with toluene. The reaction kettle was equipped as in Example I in the preparation of the hydrosilanized product.

The reaction kettle was heated to 85 ° C. and a light N ₂ sparge was begun. A small amount of clear (dry) toluene was collected to assure dehydrated starting material. Raise the temperature of the reaction kettle to 108 ° C, at which point CPA / ethanol solution (Pt10mg / ml) 0.25m
The catalyst was activated by the addition of 1 (29 ppm). An exotherm of 4 ° C occurred and the reaction kettle reached 112 ° C over 3 minutes. Re-contact with 0.1 ml (12 ppm) of CPA / ethanol solution did not generate further heat. The contents of the reaction kettle are 20 at 110 ° C.
It turned brown after a minute. The reaction vessel was held at 110 ° C for an additional 95 minutes to complete the reaction. The solution is then moistened with NaHCO ₃ .
Neutralized with 5 g and kept at 100 ° C. for 120 minutes. The solution was then filtered through a 3-4μ filter bed under 40 psi of N ₂ to give a clear, brown toluene solution. The toluene was then removed at 100 ° C. with the assistance of N ₂ spade. And 25.77 g (44.4% yield) of a clear brown product was collected. GC of the distillate distilled off showed significant recovery of unreacted M ₃ T '.

The product GPC showed a typical unimodal product distribution. ¹³ C _nmr revealed approximately 40% reaction of the allyl group to the 1,2-hydrosilanated product, while the rest isomerized to the propenyl functionality. Si gravimetric analysis for Si 10.3%
(100% reaction is calculated as Si 20.6%). As Note, M ₃ T 'in all hydrosilation was conducted was observed to be inactive of same extent approximately with the production. Undoubtedly, interfering with the effective hydrosilation than efficiency under the conditions used in bulkiness of the three-dimensional of M ₃ T 'units. In each case ¹³ C _nmr reveals the presence of the only propenyl unsaturation remaining in the product after incomplete reaction. Thus, on the time scale required for CPA-catalyzed M ₃ T ′ hydrosilanation under these conditions, the isomerization of allyl to propenyl effectively competes to deactivate unsaturated groups.

In Example VI of reversing surface active agents IS "-1 manufacturing clean 500ml by hydrosilation with D ₃ D 'of polyester 13 3NRBF, D ₃ D'55.00g, polyether 13 [16.4% allyl); OH ( Diol) 3.52%; allyl glycidyl ether (AGE) 48% by weight, EO 24% and PO% 2
8%] 70.47 g and 200 g of toluene were added. These feeds showed a 43% excess of allyl groups with respect to SiH and a 62% dilution with toluene. However, many other similar preparations have been found to be successful using a 1: 1 stoichiometry and only 30 wt% toluene.

A reaction kettle was equipped as in Example I and the contents were dehydrated by distillation at 105 ° C assisted by N ₂ sparge. A small amount of water was collected. The reaction kettle was cooled to 30 ° C. and 0.45 ml (14 ppm) of CPA / ethanol solution (Pt10 mg / ml) was added as a catalyst. The reaction kettle was heated to 70 ° C, at which point an exotherm of 21 ° C occurred and the kettle reached 91 ° C. SiH tests, including the addition of KOH, ethanol and water and measurement of the hydrogen gas evolved, showed no detectable SiH residue. The reaction kettle was kept at 95 ° C. for 95 minutes, at which point it was neutralized with 3.0 g of NaHCO ₃ . The hot toluene solution was then filtered through a 3-4μ filter bed under 40 psi of N ₂ and another 500 ml of 3N.
Collected during RBF. Toluene was then removed at 95 ° C. with the assistance of N ₂ sparging to give 108 g (88% yield) of a brown product.

GPC analysis showed a unimodal product distribution. ¹³ C
_nmr showed that 65% of the allyl groups had reacted with the silicone to form the 1,2 hydrosilanated product. Of the remaining 35% of unreacted unsaturation, 70% is present as allyl and 30%
It was present as a propenyl functional group. Si gravimetric analysis showed 16.3% product (21.1% For complete reaction of D ₃ D 'and all allyl groups). This showed 62% completion of the reaction, which was in good contrast to the ¹³ C _nmr data. ²⁹ Si _nmr revealed that there was no appreciable ring opening of the cyclic D ₃ D'ring during the hydrosilation of polyfunctional polyethers.

It has been found that this reversal surfactant reduces the surface tension of water to 23.2 dynes / cm at a concentration of 1%.

Example VII Preparation of Inverting Surfactant IS ″ -22 by Hydrosilation of Polyester 13 at D ₄ D ′ Polyether 13 [allyl 1
6.4%); OH (diol) 3.52%; allyl glycidyl ether (AGE) 48% by weight, EO 24% and PO 28%] 53.27 g, D
71.82 g of ₄ D ′ (distilled to a purity of 1%; impurities were mainly non-Si—H containing D ₄ and D ₅ ) and 75 g of toluene were added.
These charges represented a 30% excess of unsaturation and 38 g of toluene. It was further discovered that a 1: 1 stoichiometry (or excess of D ₄ D ') and a 30% dilution with toluene could be successfully used for preparation of similar D ₄ D'.

The reaction kettle was equipped as in Example I and the contents were dehydrated by distillation at 100 ° C assisted by N ₂ sparge.
The distillate was clear and thus the solution appeared dry. The humidity was lowered to 70 ° C. and the solution was contacted with 0.5 ml (25 ppm) of CPA / ethanol solution (Pt10 mg / ml). 75 ° C
After heating up to 33 ° C, a fever of 33 ° C occurs and the reaction kettle is heated to 10
It reached 8 ° C. After about another 1 minute, the clear contents of the reaction kettle turned brown. The reactor was then held at 100 ° C. for 30 minutes, at which point it was neutralized with 4.4 g of NaHCO ₃ . The reaction kettle was then held at 100 ° C for 120 minutes and cooled to room temperature.
The solution was then passed through a 3-4μ filter bed to N ₂ 40 psi.
Filtered down and collected in another 500 ml of 3NRBF. Then toluene and residual D ₄ D ', the D ₄ and D _5, the distillation was assisted with N ₂ sparge was cotton connexion removed under 100 ° to 120 minutes. This evaporation process was continued for another 15 hours (to ensure removal of volatile silicone).

GPC analysis showed a unimodal product distribution. ¹³ Cnm
r showed 81% conversion of the allyl group to the 1,2-substituted product by hydrosilation and 19% conversion to the propenyl group by isomerization. ²⁹ Sinmr showed that the shape of the D ₄ D'ring was retained during the hydrosilanization process. Gravimetric analysis Si
Compared to the theoretical value of Si 20.6% for the complete conversion of H, S
il gave 15.5%. Si value in this gravimetric analysis is 58% of SiH
It showed conversion. The origin of the discrepancy between ¹³ Cnmr and gravimetric Si analyzes is unsolved.

A 1% solution of this inversion copolymer was found to reduce the surface tension of water to 20.7 dynes / cm.

Example VIII Preparation of Inverting Surfactant IS-42 by Hydrosilanization with Polyether 5 of HSi (OFt) ₃ Polyether 5 [allyl 4.2%; OH (monool) 0.45%; allyl in a clean dry 250 ml 3NRBF. 13% by weight of glycidyl ether (AGE), 34% of EO and 53% of PO] 46.16 g and 24.06 g of toluene were added. The reaction kettle was equipped as in Example I and brought to 95 ° C. At this point for a short time
Evaporation assisted by N ₂ sparge indicated that the contents were dehydrated. Cool the contents to 80 ° C and
t) ₃ 7.77 g was added. This charge is allyl and SiH 1:
1 Stoichiometric amount is shown. The reaction kettle was contacted with 0.2 ml (26 ppm) of CPA / ethanol solution (Pt10 mg / ml). About 5
After a second induction period, an exotherm of 10 ° C occurred and the reaction kettle was brought to 93 ° C for 2 minutes. The reaction kettle was kept at 90 ° C. for 10 minutes, at which time it was neutralized with 8.4 g of NaHCO ₃ , and 90
Hold at 120 ° C for 120 minutes. Then cool the contents to 33 ° C,
Filter at 90 ° C. under 40 psi N ₂ through a 3-4 μ filter bed. 36.39 g of a clear, pale yellow viscous product was collected (yield 67%).

The GPC chromatogram of this material showed a complex appearance with several peaks of higher molecular weight than expected. Some hydrolysis of the alkoxysilane groups or transesterification with a polyether backbone terminated with secondary hydroxyl groups is believed to be a possible cause of apparent crosslinking. Gravimetric analysis of this material gave Si 2.1%. Si2.4% conversion of complete SiH
Would give the product of This is 85% of HSi (OEt) ₃ .
Reaction conversion (there was no residual unreacted HSi (OEt) _{3 in the} final product distilled off). Qualitatively, ¹³ Cnmr showed a lower conversion of the allyl group but was not quantifiable due to spectral complexity (due to the particularly important resonance band overlapping with that of the butyl initiator of the polyether). It was

Example IX Preparation of Reverse Surfactant IS-41 by Hydrosilation with Polyether 5 of HSi (OEt) ₂ Me Polyether 5 [allyl 4.2%; OH (monool) 0.45% in clean dry 500 ml 3NRBF; Allyl glycidyl ether (AGE) 13% by weight, EO34% and PO53%] 109.90 g,
HSiMe (OEt) ₂ 15.31g and toluene 53.32g (30% dilution)
I put it in. These feeds showed a 1: 1 stoichiometry of allyl and SiH groups. The reaction kettle was equipped as in Example I for the hydrosilanation step.

The reaction kettle was heated to 87 ° C. and the contents were contacted with 0.3 ml (17 ppm) of CPA / ethanol solution (Pt10 mg / ml). After an induction period of about 2 minutes an exotherm of 6 ° C occurred and the kettle temperature reached 95 ° C. The clear solution at this point turned from colorless to pale yellow. It was kept at 95 ° C. for 30 minutes and subsequently neutralized with NaHCO ₃ . It was observed that the viscosity of the solution increased immediately after the addition of NaHCO ₃ . The temperature was maintained at 95 ° C for 120 minutes, then the contents were cooled to 35 ° C. The solution was then filtered through a 3-4μ filter bed under 40 psi N ₂ and collected in another 3NRBF. The toluene was then removed by N ₂ sparge at 95 ° C. 110.68 g of a clear yellow, highly viscous product was collected (yield 88
%).

GPC analysis showed one major peak at retention time that was roughly consistent with the proposed structure. However (Example VIII
Some clear high molecular weight peaks were also observed (to a lesser extent than in. This high molecular weight peak is, as in Example VIII, a) of an alkoxysilane group,
It is believed to be attributed to the crosslinked product as a result of transesterification of the polyether with secondary hydroxy end groups and / or b) hydrolysis of the alkoxysilane groups.

Example X Preparation of Reversing Surfactant IS-44 by Hydrosilanization with Polyether 19 of HSiEt ₃ Polyether 19 [allyl 17.1%; molecular weight (gpc) = 1800 g / mol; (AGE) 51% by weight and EO49%] 67.30 g and toluene 42.97 g were added. The reaction kettle was equipped as in Example I. The polyether / toluene solution was dehydrated at 95 ° C. by N ₂ sparge assisted distillation to give clear dry toluene. Cool the reaction kettle to 70 ° C and add HSiEt ₃
32.70 g was added.

CPA / ethanol solution (Pt10mg / ml) 0.3ml (21ppm) 72
It was added at 0 ° C. to act the catalyst. The temperature was raised to 89 ° C, at which point an exotherm of 21 ° C occurred and the kettle temperature was 110 ° C over 3 minutes. At this time, the contents darkened to a typical tan color. The reaction kettle was then held at 95 ° C for 30 minutes, at which point it was neutralized with 14.8 g NaHCO ₃ , and
Hold at 5 ° C for 120 minutes and then cool the solution to room temperature. The solution was filtered through a 3-4μ filter bed under 40 psi of N ₂ and the clear, brown solution was collected in another 500 ml of 3NRBF. The toluene was then removed from this solution at 95 ° C with the aid of N ₂ sparging. Then, the distilled-off products were collected (yield 68%).

GPC analysis of the product showed a unimodal product distribution with a shorter retention time than the polyether 19 of the starting polyether backbone, consistent with the proposed reaction and increasing molecular weight. Gravimetric analysis shows Si 2.0%, while complete conversion of silane is Si
It should give a value of 8.3%. The observed Si values showed that the conversion of silane to hydrosilation product was only 16%. ¹³ Cnmr gives 38% conversion of allyl to 1,2-hydrosilanation product and 62% of allyl to propenyl.
It showed a% isomerization. The origin of this discrepancy between ¹³ C nmr and gravimetric analysis is unsolved.

Example XI Preparation of the Inverted Surfactant IS-24 by Hydrosilation of Polyether 18 with MM 'Polyether 18 [allyl 1
7.1%; molecular weight (gpc) = 1020 g / mol; allyl glycidyl ether (AGE) 51% by weight and EO 49%] 84.76 g, MM'40.
24 g and 75 g of toluene were added. These feeds exhibited a 1.3: 1 stoichiometric ratio of allyl: SiH and a 30% dilution with toluene. However, it was found that 1: 1 stoichiometry and 30% toluene dilution could also be used successfully.

The reaction kettle was equipped as in Example I for the hydrosilanization step and heated to 52 ° C. The system was then contacted with 0.5 ml (25 ppm) of CPA / ethanol solution (Pt 10 mg / ml). After an induction period of about 10 seconds, a rapid exotherm of 58 ° C occurred, and the reaction vessel reached 110 ° C in about 20 seconds. The reactor was then held at 110 ° C for 45 minutes, followed by 4.1 g of NaHCO ₃
Neutralized with. The reaction kettle was held at 100 ° C for an additional 120 minutes.

At this point the solution was cooled to 40 ° C. and filtered through a 3-4 μ filter bed under 40 psi of N ₂ and another 500 ml of 3NRBF.
Collected inside. Then, with the aid of N ₂ sparge,
Removed at 80 ° C. Then 113 g of a light golden brown product was collected (yield 90%).

GPC analysis of the product showed a unimodal product distribution with a shorter retention time than the starting polyether backbone, consistent with increasing molecular weight. Gravimetric analysis of the product showed Si 11.7%, while 100% conversion should give a Si value of 12.9%. The calculated conversion of MM 'to product was 87% based on this gravimetric analysis. ¹³ Cnmr showed that 71% of the allyl groups were converted by hydrosilation, corresponding to a conversion of MM 'of 92% and in good agreement with the results from gravimetric analysis. ²⁹ Sinmr revealed that the silicon species in the product were, as expected, a 1: 1 ratio of M and M '.
This reversal surfactant increases the surface tension of water at a concentration of 0.1%.
It was shown to reduce to 2 dynes / cm.

Example XII Preparation of Reversing Surfactant IS-46 by Hydrosilation of Polyether 7 with MM 'Polyether 7 [allyl 8.
19%; MW (qpc) = 1640g; allyl glycidyl ether (AG
E) 22% by weight and 78% EO] 77.13 g and 42.93 g toluene. The reaction kettle was equipped as in Example I for the dehydration and hydrosilanation steps. The solution was heated to 95 ° C. and lightly sparged with N ₂ to facilitate distillation. The initial distillate was cloudy, indicating a small amount of water in the system. Distillation was continued until the distillate was clear and dry. The solution was then cooled to 45 ° C. at which point MM'22.87g was added to give a cloudy yellow heterogeneous suspension. The charge in this MM 'was stoichiometric with respect to the allyl groups of the polyether.

The temperature of the system was raised to 52 ° C. and then the system was contacted with a CPA / ethanol solution (Pt10 mg / ml). After an induction period of about 2 minutes, an exotherm of 16 ° C was observed and the kettle reached 68 ° C in 4 minutes. The temperature was then raised to 100 ° C and held for 30 minutes. Then, while maintaining the temperature at 100 ° C for another 135 minutes, NaHC
O ₃ was added to neutralize. The solution is then cooled to 36 ° C,
Filter through a 3-4μ filter bed under 40 psi of N ₂ and collect in another 500 ml of 3NRBF. Toluene was removed at 95 ° C with the assistance of N ₂ sparging. When the toluene had finished distilling, the solution was cooled to room temperature and N ₂ sparge was continued for 16 hours. 71.61 g of semi-waxy product was collected (yield 72
%).

GPC analysis of this product was consistent with the higher molecular weight,
It showed a unimodal product distribution with a shorter retention time than the starting polyether backbone. The gravimetric analysis of Si was 7.1%, while the theoretical value of Si for 100% addition of MM 'corresponded to 8.7%. This indicated that the actual conversion of MM 'was only 80% based on gravimetric analysis. ¹³ Cnmr is an allyl group
It was shown that 78% was converted to the 1,2 hydrosilation product and the remaining 22% was converted to propenyl. This was in agreement with the results suggested by gravimetric analysis. ²⁹ Sinmr shows that the two main types of silicon atoms M and M ′ in the product are present in a ratio of 1.0: 0.97. There was also a small amount of some of the MM 'D'type silicon atoms that could be formed either by dehydrogenative condensation with the primary hydroxyl end of the polyether backbone or by cleavage of the siloxane backbone. The observed M: M ′: D ¹ ratio was 1.0: 0.97: 0.06.

Example XIII Polyether 1 reversal table by hydrosilation with MM '.
Preparation of Surfactant IS-65 In a clean, dry 500 ml of 3NMRBF, polyether1
[Allyl 3.52%; MW (gpc) = 1050 g; allyl glycidyl
Ether (AGE) 12% and EO 88%] 110.89g and toluene 34
I put g. This flask is involved in the hydrosilation process
Equipped as in Example I. Temperature up to 85 ℃
At this point, raise the homogeneous system to a CPA / ethanol solution.
(Pt 10 mg / ml) 0.45 ml (25 ppm) was contacted. Immediately
Fever occurred (within a 2-second induction period). Hula soon
An ice bath was placed around Sco. Maximum fever temperature is 35 seconds or less
Reaching 100 ° C, and the solution becomes clear and brown
It was The reaction kettle was kept at 100 ° C for 75 minutes, at which point it was moistened with NaH.
CO₃6 g of (10% water) was added to neutralize. Temperature for another 145 minutes
The temperature was maintained at 100 ° C. Then add the solution to a 3-4μ filter.
ー 40psiN through the floor₂Filter down when hot, another 500ml 3NRB
Collected in F. Toluene N₂At 110 ° C while assisting with sparging
Removed. Collected 113.87 g of product (wax at room temperature)
(Yield 91%).

GPC analysis showed a unimodal product distribution with a shorter retention time than the starting polyether backbone, consistent with an increase in molecular weight as expected from the proposed product.

Example XIV Preparation of Inverting Surfactant IS-72 by Hydrosilation of Polyether 10 with MDM 'Polyether 10 [allyl 6.77%; MW (gpc) = 1065 g / mol; VCM24 in 500 ml of clean, dry 3 NMBF. % And EO76
%] 91.45 g, MD′M 33.57 g, and toluene 53 g were added.
These feeds exhibited a 1: 1 stoichiometric ratio of allyl: SiH and a 30% dilution with toluene. A reaction kettle was equipped as in Example I and heated to 95 ° C. When this solution was contacted with a CPA / ethanol solution (Pt10 mg / ml), no reaction was observed. The system was recontacted after 5 minutes with 0.45 ml (25 ppm) CPA. An exotherm of 5 ° C was observed. 100 brown solution
Hold at 60 ° C for 60 minutes, at which point 5.5 g of damp NaHCO ₃ (10% water)
Was added to neutralize. The hot solution was then filtered through a 3-4μ filter bed to give a clear light brown solution,
This was collected in another 500 ml NRBF. Toluene was removed at 110 ° C. with the assistance of N ₂ sparge. 106.67 g of product (very viscous / semi-wax) was collected (yield 85%). GPC analysis showed a unimodal product distribution with a shorter retention time than the starting polyether backbone, consistent with the expected increase in molecular weight for the proposed product. The presence of a limited amount of toluene was also observed in this product, indicating incomplete distillation.

Example XV Preparation of the Inverting Surfactant IS-83 by Hydrosilation of Polyether 21 with MM 'Polyether 21 (Allyl 34.9: MW (gpc) = 1050 g / mol; AGE 97% and in a clean dry 250 ml 3NRBF. EO3%) 33.
15 g and 53 g of toluene were added. These charges are 1: 1
The stoichiometric ratio and 60% toluene were shown. This high amount of toluene was used for safety protection against the expected high heat of reaction. Example I for a hydrosilanization process of a reaction kettle
Equipped as in. The system is heated to 70 ° C, surrounded by an ice bath and immediately CPA / ethanol solution (Pt10mg / ml) 0.3
0 ml (28 ppm) was charged. Immediately after this, the heat is generated
The temperature was raised to 105 ° C (exothermic 35 ° C). The contents of the reaction kettle slowly changed from yellow to brown. The temperature of 100 ° C. was maintained for 60 minutes, at which point 5.5 g of damp NaHCO ₃ (10% water) was added to neutralize.

The temperature of the reaction kettle was maintained at 100 ° C for an additional 120 minutes. The contents were then filtered through a 3-4 μ filter bed under N _{2 at} about 40 psi into another 500 ml of 3NRBF to give a clear, dark brown solution. Then toluene was assisted with a vigorous N ₂ sparge 10
Removed at 0 ° C. 58.56 g of a clear, dark brown product was obtained (78% yield).

Analysis of GPC showed a unimodal product distribution with a shorter retention time than polyether 21, consistent with an increase in molecular weight as in the proposed product. This reaction places the MM 'group on most of the ether linkages along the backbone (excluding the ethylene glycol initiator unit) when theoretically complete.

Example XVI Preparation of Reversing Surfactant IS-15 by Hydrosilation with Polyether 17 MD'M Polyether 17 (15% allyl; end treatment with diacetoxy; OH 0%; AGE48) in 500 ml of clean, dry 3NRBF. %,
ED24% and PO28%) 37.13g, MD′M221.97g and toluene
I put 150g. These charges are allyl: SiH = 1.3: 1
And 70% dilution with toluene.

A reaction kettle is equipped as in Example I and the contents are 100 ° C.
Heated up. The contents were then dehydrated by distillation assisted by N ₂ sparge. As a result, the distillate was found to be transparent and dry. The temperature was lowered to 80 ° C., and contact was made with 0.4 ml (19 ppm) of CPA / ethanol solution (Pt10 mg / ml). After a 30 second induction period, an exotherm of 13 ° C was observed and the reaction kettle was brought to 93 ° C for about 3 minutes. After a further 4 minutes, the contents of the reaction kettle became dark. The temperature was maintained at 100 ° C. for 105 minutes and neutralized with 5.2 g NaHCO ₃ . The temperature was held at 100 ° C for an additional 190 minutes.

The solution was cooled to room temperature and filtered through a 1-2 μ filter bed under 4 psi of N ₂ into another 500 ml of 3NRBF. Toluene was removed at 80 ° C. with the assistance of N ₂ sparge. 53 g of a clear, yellow product was collected (88% yield).

The GPC analysis showed a unimodal product distribution. Gravimetric analysis of Si showed Si 14.5%. A complete conversion of MD'M would theoretically give 15.4%. Therefore 14.5% Si represents 91% conversion of MD'M present. The remaining MD'M was removed in the final distillation step. A 1% concentration of this end-capped inverted surfactant reduced the surface tension of water to 24.9 dynes / cm.

Example XVII Preparation of Reversing Surfactant IS-11 by Hydrosilation of Polyether 13 with MD'M Polyether 13 [allyl 16.4%; OH (diol) 3.52%; allyl glycidyl in 250 mL of clean, dry 3NRBF. Ether (AGE) 48% by weight, EO 24% and PO 28%] 40.00 g
And MD'M 35.59g. These charges are allyl:
The 1: 1 stoichiometry of SiH is shown.

The contents of the reaction kettle were heated to 86 ° C. and contacted with 0.2 ml (26 ppm) of CPA / ethanol solution (Pt10 mg / ml). The reaction did not occur after about 5 minutes. Next, 0.2 ml (26 ppm) of CPA / ethanol solution was added to the reaction kettle. An exotherm of 36 ° C was observed after a short induction period and the reaction kettle reached 112 ° C even if the reaction vessel was placed in an ice bath early in the exotherm. The reaction kettle immediately turned clear and brown. The temperature was reduced to 100 ° C. and maintained at this temperature for 60 minutes, at which time the kettle contents were neutralized with 5.5 g of moist NaHCO ₃ (10% water). Further reaction kettle
Hold at 100 ° C. for 150 minutes, then filter the contents through a 3-4 μ filter bed. 62.22 g of product was collected (yield 82
%). GPC showed a small amount of unreacted MD'M. However, the GPC chromatogram in the copolymer region (unimodal distribution) was qualitatively identical to that of the product from Example II.

Example XVIII Preparation of Hydrolytically Instable Inverting Surfactant IS-81 by Hydrosilation of Polyether 18 with HSi (OMe) ₃ Polyether 18 (allyl 17.1%; allyl 17.1%; in clean dry 500 ml 3NRBF; MW (gpc) = 1020 g / mol; AGE51% and EO49
%; Primary hydroxyl end 80% by ¹³ Cnmr) 90.08 g, HSi
(OE) ₃ 35.12 g and toluene 175 g were added. These feeds showed a 30% excess of allyl groups (relative to SiH) and a 58% dilution with toluene. The reaction kettle was equipped as in Example I for the hydrosilanization step. Then add 2 mL of CPA / ethanol solution (Pt10mg / ml) 0.5ml (17ppm) to the reaction kettle.
Contact was performed at 0 ° C. The reaction kettle was externally heated to 110 ° C., 16.0 g of HSi (OEt) ₃ was charged again, and re-contact was performed with CPA. No observable fever occurred. The system is NaHCO ₃
Neutralized with 100 ° C. for 120 minutes and filtered under 40 psi of N ₂ . N ₂ sparge assisted distillation of toluene started at 75 ° C. However, the contents of the reaction kettle gelled during this distillation. Transesterification of the methoxyl group with the primary hydroxyl group of the polyether appears to be the cause of the crosslinking reaction taking place in the system.

Example XIX Preparation of two hydrolytically labile inverse surfactants IS-62 and IS-63 respectively by hydroxylation of poiether 9 with HSi (OEt) ₃ and HSi (OEt) ₂ Me. The following charges in 500 ml of 3NRBF were added: (Polyether 9 : allyl 7.67%; molecular weight (gpc) = 423
0 g / mole; AGE 22%; and EO 78%; ¹³ % Cnmr primary hydroxyl tip 90%). In both cases, these feeds consisted of a 1: 1 stoichiometry of allyl and SiH and in toluene.
Represented a 30% dilution. A reaction kettle was equipped as in Example I for the preparation process for hydrosilation. Warm the reaction kettle to 90 ° C, then CPA / ethanol solution (Pt 10mg / m
l) 0.3 ml was charged. In both reactions, an induction period of 10 seconds was followed by an exotherm of 8 ° C, bringing the contents to 98 ° C. The contents of Reaction A gelled in 2 minutes and the contents of Reaction B gelled in 2 minutes. As in Example XXI, the presence of primary hydroxyl groups on the polyether appeared to readily transesterify with the ethoxyl groups of the silane to give a highly crosslinked system responsible for gelation.

Example XX Hydrosilation of Polyether 18 with MD ₁₃ D' _5.5 M One attempt was made to produce a 1: 1 adduct of a multifunctional polyether and a SiH fluid. This polyether was Poly Ale 18 with a molecular weight of 1020 per unit weight and an average functionality of 4.5. Silicone has an average functionality of about 5.5 MD ₁₃ D '
It was _5.5M . The strategy was to use reaction conditions that most favorably produced the 1: 1 adduct.

It was observed that cross-linking could not be completely avoided, even under optimal circumstances, due to structural changes in both polyethers and silicones, which precluded the formation of 1: 1 adducts. Nevertheless, to the extent possible, favorable conditions (high dilution) were used for the 1: 1 adduct. The chances of failure for this experiment were considered high from the beginning due to the requirements needed for success. Polyether 18 (allyl 17.1%; molecular weight (gpc) = 1020 g / mol in 1000 ml 3NRBF;
AGE 51% and EO (diol) 49%) 19.03g, MD ₁₃ D' _5.5 M
17.51 g and 331.0 g of toluene were added. This charge is Si
It showed a 30% excess of allyl groups with respect to H and a 70% dilution with toluene. The flask was equipped as in Example I for the hydrosilanation preparation.

The solution was heated between 95 ° C and the CPA / ethanol solution (Pt
Contact was made with 0.9 ml (25 ppm). An exotherm of approximately 7 ° C occurred after a short induction period. However, within 10 minutes, the entire kettle contents gelled despite the high dilution with toluene. No further processing of this material was promised.

Example XXI Surfactant Evaluation Three Reversing Surfactants (IS-15, IS-22, and IS-59)
Was evaluated on two HR Slab stock formulations. The composition is as follows: Example XXII Evaluation of Reversing Surfactants In all, 39 reversing surfactants and mixtures thereof were evaluated in several rigid urethane foam compositions. The composition is shown in the table below. The results are shown in Tables III-VI.

In addition, "pphp" in the table represents the number of parts (parts by weight) per 100 parts of polyol.

Example XX III Application to Molded High Elastic Urethane Foam The performance test method involves the initial screening of 12 different reversed silicone polyether copolymers using standard QC thermoforming formulations. The ingredients and foaming conditions are shown in the table below.

Surfactants were evaluated for their ability to stabilize the fine cell structure without pad shrinkage. Other end and higher end surfactant coverage (minimum and maximum surfactant concentrations that stabilize the bubbles and cause very little shrinkage, respectively)
Was determined for one possible system. The results are shown below. Note that some of these reversal surfactants examined were promising. These contained MM 'and MD'M as pendants. A typical problem was severe shrinkage [pat tightness] in the concentration required for bubble stabilization and consequently a very narrow concentration range.

Example XX IV Determination of Aqueous Surface Tension Reduction for Selected Reversing Surfactants In this example, the reduction in aqueous surface tension of various reversing surfactants made by the method of the present invention was determined. The results obtained are shown in Table A below.

Example XXV Contact Angle Measurements Comparison of contact angles between the known surfactant SILWET-L-77 commercially available from Union Carbide and a typical inverted surfactant (IS) of the present invention. Was done.

The results are shown in Table B below.

* Where possible, structures were determined based on 1) oxide loading 2) gpc information 3) ¹ H and ¹³ Cnmr results and / or 4)% hydroxyl and% unsaturation analysis. ⁺ AGE = allyl glycidyl ether VCM = vinyl cyclohexene monoxide Although the present invention has been illustrated in the above examples, this should not be seen as limited to the materials used herein, but rather to the general field as previously disclosed in the present invention. Various modifications and embodiments of the invention may be made without departing from its spirit or scope.

The features and related matters of the present invention are as follows: 1. Formula on average The backbone of the polyether through a divalent aliphatic group in which at least three pendant groups of C have from 2 to 10 carbon atoms and may contain at least one heteroatom of the group O, N and S R'represents a C ₁ -C ₃ saturated alkyl group, R "or OR; R" is R represents a C ₁ -C ₃ saturated alkyl group; and a, b and c have a value of 0 to 3, and a + b
= 3, a silicone polyether copolymer surfactant having: (a) a narrow unimodal distribution; (b) essentially free of silicone oil and process polyether; and (c) the polyether. The silicone polyether copolymer surfactant, characterized in that any unreacted main chain and unsaturated groups are inactivated at any time.

2. The copolymer surfactant of 1 above having a molecular weight of about 650 to about 20,000.

3. The copolymer surfactant according to 1 above, wherein the molecular weight is about 800 to about 10,000.

4. The copolymer surfactant according to the above 1, wherein the polyether main chain is partially produced from at least one alkylene oxide.

5. A co-polymer of the above 1 wherein the polyether backbone is prepared from at least one alkylene oxide selected in part from the group consisting of ethylene oxide, propylene oxide, butylene oxyd and at least one alkylene oxide containing olefinic unsaturation. Polymer surfactant.

6. The copolymer surfactant according to 1 above, wherein the polyether main chain is produced from an alkylene oxide containing olefinic unsaturation.

7. The copolymer surfactant according to the above 5, wherein the alkylene oxide having olefinic unsaturation is allyl glycidyl ether.

8. The copolymer surfactant according to the above 5, wherein the alkylene oxide having olefinic unsaturation is vinylcyclohexene monoxide.

9. The alkylene oxide having olefinic unsaturation
The copolymer surfactant according to the above 5, which is 1,2-epoxy-3-butene.

10. The copolymer surfactant according to 1 above, wherein the polyether main chain is essentially a homopolymer.

11. The copolymer surfactant as described in 1 above, wherein the polyether main chain is a copolymer.

12. The copolymer surfactant as described in 1 above, wherein the polyether main chain is a terpolymer.

13. The copolymer surfactant as described in 1 above, wherein the polyether main chain is a random copolymer.

14. The copolymer surfactant as described in 1 above, wherein the polyether main chain is a block copolymer.

15. Next Random or Block Repeating Unit [Wherein R represents hydrogen, lower alkyl, acetyl, etc .; R'represents a C ₁ -C ₃ saturated alkyl group, R "or OR, wherein R" represents And R represents a C ₁ -C ₃ saturated alkyl group; W has a carbon number of at least 2, preferably 2 to 10 and is O, N in W or at the end of W linked to the polyether. And S is a divalent group optionally containing at least one heteroatom; a, b and c are 0 to 3, provided that c
Is preferably 2 or 3 and a + b = 3; and x and y are 0 or a positive integer; and z
Is an average value of at least 3].

16. The above 1 in which the pendant silicone group is derived from MM '
Copolymer of.

17. The copolymer according to 1 above, wherein the pendant silicone group is derived from MD ₂ M ′.

18. The copolymer according to 1 above, wherein the pendant silicone group is derived from MD ₃ M ′.

19. The copolymer according to 1 above, wherein the pendant silicone group is derived from MD'M.

20. The above 1 in which the pendant silicone group is derived from M ₃ T ′
Copolymer of.

21. The above 1 in which the pendant silicone group is derived from D ₃ D ′
Copolymer of.

22. The above 1 in which the pendant silicone group is derived from D ₄ D ′
Copolymer of.

23. The copolymer according to 1 above, wherein the pendant silicone group is derived from HSi (OEt) ₃ .

24. The copolymer according to 1 above, wherein the pendant silicone group is derived from HSi (OMe) ₃ .

25. The copolymer according to 1 above, wherein the pendant silicone group is derived from HSiMe (OEt) ₂ .

26. The copolymer according to 1 above, wherein the pendant silicone group is derived from HSiEt ₃ .

27. Polyether copolymers having on average more than two pendant unsaturated groups are treated with a silicone compound having only one group which reacts with said pendant unsaturated groups in the presence of a catalytic amount of a hydrosilation catalyst. Hydrosilating, provided that the ratio of silicone-containing groups to the copolymer pendant unsaturated groups is sufficient to form a plurality of silicone-containing groups along the copolymer backbone and is obtained. (A) the polyether copolymer surfactant is (a) narrowly unimodal in distribution; (b) is essentially free of silicone oil and process polyethers; and (c) is free of any of the polyether backbone. The production of a silicone polyether copolymer surfactant according to claim 1, characterized in that the unsaturated group of the reaction is optionally inactivated. Law.

28. The polyether is a repeating unit [Wherein R ^{1 to} R ⁴ are hydrogen or lower alkyl, Z represents a hydrocarbon group having 1 to 6 carbon atoms and optionally containing a hetero atom such as O, N and S; d has a value of 0 or 1; n has a value of 1 to 6 and m is 0
Or has a positive integer value; and w has an average value of at least 3].

29. The pendant silicone is the following formula [Wherein, R'is a C ₁ -C ₃ saturated alkyl group, R "or OR
Represents R; And R represents a C ₁ -C ₃ saturated alkyl group;
The method of 27 above, wherein b and c have values from 0 to 3 and a + b = 3.

30. The method of 29 above, wherein the polyether backbone is essentially a homopolymer.

31. The method according to 29 above, wherein the polyether main chain is a copolymer.

32. The above 2 in which the polyether main chain is a random copolymer
9 ways.

33. The above 2 in which the polyether main chain is a block copolymer
9 ways.

34. The above 29, wherein the pendant silicone group is derived from MM ′.
the method of.

35. The above 2 in which the pendant silicone group is derived from MD ₂ M ′.
9 ways.

36. The above 2 in which the pendant silicone group is derived from MD ₃ M ′.
9 ways.

37. The above 2 in which the pendant silicone group is derived from MD'M.
9 ways.

38. The above-mentioned 29, wherein the pendant silicone group is derived from M ₃ T ′.
the method of.

39. The above-mentioned 29, wherein the pendant silicone group is derived from D ₃ D ′.
the method of.

40. The above-mentioned 29, wherein the pendant silicone group is derived from D ₄ D ′.
the method of.

41. The method of 29 above, wherein the pendant silicone group is derived from HSi (OEt) ₃ .

42. The method of 29 above, wherein the pendant silicone group is derived from HSi (OMe) ₃ .

43. The method of 29 above, wherein the pendant silicone group is derived from HSiMe (OEt) ₂ .

44. The above 2 in which the pendant silicone group is derived from HSiEt _3.
9 ways.

45. The above-mentioned 29, wherein the hydrosilation catalyst is chloroplatinic acid.
the method of.

46. A slab of high resilience polyurethane foam made from a formulation comprising at least one surfactant of 1, above, a silicone polyether copolymer surfactant.

47. A high resilience rigid urethane foam made from a formulation comprising at least one surfactant of 1, above, a silicone polyether copolymer surfactant.

48. A high resilience molded polyurethane foam made from a formulation comprising at least one surfactant of 1, above, ie a silicone polyether copolymer surfactant.

49. A wetting agent composition comprising the silicone polyether copolymer of 1 above.

[Brief description of drawings]

FIG. 1 shows a gel permeation chromatograph of a typical conventional surfactant preceded by a silicone precursor, and FIG. 2 shows a surfactant of the present invention preceded by a silicone precursor. A gel permeation chromatograph is shown.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location B01F 17/54 (72) Inventor Gerardo Joseph Marhuy 12590 Watts Pinj Years Folls Brandei Lane 83 (72) Inventor The George Homer Green 10520 Croton-on-Hudson Amberlands 2J Ray, New York, USA (56) References JP-A-52-81399 (JP, A) JP-A-51- 103200 (JP, A) JP 64-87633 (JP, A) JP 63-172737 (JP, A) JP 52-84289 (JP, A) JP 56-22395 (JP, A) JP-A-56-18620 (JP, A) JP-A-3-79627 (JP, A) British patent 1058385 (GB, A)

Claims (1)

[Claims] 1. A formula on average The backbone of the polyether through a divalent aliphatic group in which at least three pendant groups of C have from 2 to 10 carbon atoms and may contain at least one heteroatom of the group O, N and S R'represents a C ₁ -C ₃ saturated alkyl group, or R ";
But A silicone polyether copolymer surfactant in which a, b and c have a value of 0 to 3 and a + b = 3, (a) a narrow unimodal distribution; (b) Essentially free of silicone oils and process polyethers; and (c) any unreacted unsaturated groups on the polyether backbone are optionally deactivated. Silicone polyether copolymer surfactant used in manufacturing.