JPH03162414A - Surface active agent comprising silicone/polyether copolymer and its manufacture - Google Patents

Abstract

PURPOSE: To obtain a novel silicone polyether copolymer surfactant which has specific pendant groups and is suitable as a stabilizer for producing a rigid polyurethane foam by reacting a polyether copolymer with a monofunctional siloxane.

CONSTITUTION: Ethylene oxide, propylene oxide, and pref. 6% allyl glycidyl ether are reacted. The resultant polyether copolymer is reacted with a monofunctional siloxane which forms pendant groups represented by the formula (wherein R' is a 1-3C group; and (a) and (b) are each 0-3), giving the objective copolymer.

COPYRIGHT: (C)1991,JPO

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates generally to silicone polyether copolymers; in one aspect, this invention relates to novel silicone/polyether block copolymers that are useful as stabilizers in the production of polyurethane foams, particularly rigid 7 ohm. In a further aspect, the present invention relates to a novel method for making copolymers and polyurethane foams made therefrom. In summary, the present invention provides silicone/polyether block copolymers that are useful as surfactants in the production of several types of polyurethane 7 ohms. While conventional copolymers have a polysiloxane backbone with pendant polyethers, the surfactants of the present invention conversely contain pendant siloxanes on the polyether chains. These novel non-hydrolyzable polysiloxane polyalkylene copolymers featuring a "reverse" structure, i.e., a polyalkylene backbone with lateral and/or terminal pendant polysiloxanes, have a narrow molecular weight distribution and a narrow molecular weight distribution. provides seeds of distribution and contains no unreacted polyether or unmodified silicone oil diluent. These surfactants are useful in a variety of urethane foam systems and can also represent aqueous wetting agents. The first disclosure of polysiloxane polyoxyalkylene copolymers is found in US Pat. No. 2,834,748. These compositions were of the hydrolysable type. The first disclosure of subsequent non-hydrolyzable polysiloxane polyoxyalkylene copolymers was in U.S. Pat. No. 2,846,458.
Seen in the issue. In 1958, the application of polysiloxane polyoxyalkylene copolymers to the stabilization of 7-ohm urethanes was first disclosed in British Patent No. 892.136. These polymers were hydrolyzable. Shortly thereafter, the application of non-hydrolyzable copolymers to the production of urethane foams was reported. For those skilled in the art, the purity of non-hydrolyzable silicone polyether compositions used to stabilize urethane foams is typically determined in part by processing polyethers to ensure complete consumption of silane hydrogen from siloxane intermediates. It is known that certain harms are caused by the requirement to use a molar excess of . This requirement stems from competing side reactions of the olefinically terminated polyethers which effectively deactivate a certain proportion of the polyethers. Residual silane hydrogen remaining in the product can lead to product instability and/or when used in urethane foam systems, as is well known to those skilled in the art.
Or it may cause bubble collapse properties. Use of excess process polyether not only results in an effectively diluted product, but also increases manufacturing costs and prevents easy separation of the copolymer product if desired. Unreacted silicone (particularly unmodified cyclics) present as part of the thermodynamic equilibrium of the species present in the equilibrated poly(dimethyl-methylhydrogen) siloxane fluid.
It also reduces the purity of the copolymer products produced therefrom. Moreover, typical copolymer compositions such as those described above invariably exhibit broad molecular weight and composition distributions. This is a function of the nature of the equilibrated siloxane intermediate used. Applications requiring particularly narrow copolymer molecular weight and/or structural distributions for performance are therefore complicated by the presence of a broad distribution. At the very least, copolymer compositions other than special narrow molecular weight and/or structural distributions may serve as expensive diluents for special materials and processes. A description of excess polyether is found in U.S. Pat. No. 3,798.
No. 253, No. 3.957.843, No. 4,059,6
No. 05, No. 4.105.048, and No. 4,160,
775 etc. These patents all address the common theme of modifying the functional moiety of the process polyether to minimize the mechanism that renders a substantial proportion of the polyether inert with respect to its hydrosilanization reactivity. . This method allows for 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 their unmodified counterparts. Furthermore, these methods do not address both the issue of broad molecular weight distribution of copolymer species and the presence of unmodified silicone species. For molecular weight and composition distribution, see U.S. Pat.
No. 0,987. The structure of the disclosed copolymer was such that the polyether pendants in the copolymer structure were uniformly spaced along the siloxane backbone. Although these structures were relatively more homogeneous structures, they still consisted of a distribution of siloxane species in which the degree of polymerization of the siloxane varied due to the nature of the siloxane condensation reaction used. A significant reduction in the amount of unreacted unmodified silicone is due to the loss of silicone lights from either the starting fluid or the copolymer raw material.
It can be achieved by distillation (preferably in vacuum). Both methods are time consuming and expensive, and the latter method can compromise the integrity of the copolymer biomaterial. Although there are a variety of products and technologies in today's silicone surfactant market that thus offer a wide range of performance properties, there is a narrow unimodal distribution and residual unreacted polyether and unreacted polyethers. There are few, if any, products that are substantially free of silicone. With the exception of dimethyl oil, which is sometimes used in HR molding systems, typical silicone surfactants are structurally dependent on the (optionally branched) silicone backbone exhibiting lateral or terminal alkyl, aryl, polyether or other organic pendants. It is a classified copolymer. c in formula R1 and R2 are alkyl, aryl and/or polyether]. Silicone and pendant dimensions, pendant spacing,
Varying the number and type, suitable diluents, and other pervasive structural and organizational characteristics will result in the necessary performance changes required for a particular application. Typical non-hydrolyzable silicone polyether structures used to stabilize urethane 7 ohms feature an (optionally branched) polysiloxane backbone containing terminal and/or lateral polyether pendants. However, in contrast, the molecular “inversion” of the surfactant structure
n) Silicone surfactants with J, ie surfactants of a polyether backbone with silicone pendants, have not been reported in the literature. For purposes of illustration, such an assembly can be represented by the following formula: an organic backbone with pendants of silane or silicone, such as repeating units (Me)Si(OSiMe3)z (I[I) (IV) Those with this are manufactured. However, these polymers contain ester or polyethylene oxide ketal repeat units. Japanese researchers have produced polyetherenolepolyester block copolymers of pendant anolekoxysilanes with pendant silane groups attached through oxygen atoms to the polyether backbone. U.S. Pat. No. 4,514,315 discloses a method for grafting ethylenically unsaturated alkylene silanes onto 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 the total weight. M. L. Wheeler, in U.S. Pat.
An olefinic silicone-organic graft polymer prepared by radically grafting an olefinic silicone onto an organic polymer is disclosed and claimed. This olefinic silicone contains at least one unsaturated group and the graft copolymer thus obtained is heavily crosslinked. In radical grafting, one would expect some of the unsaturated silicone compounds to react within them and free the polymeric compounds. Furthermore, 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, although the prior art discloses structures with silicone pendants from polyester and poly(ethylene oxide monoketal) backbones, as well as structures with silane pendants from polyether or poly(ether-ester) backbones, To date, no silicone pendant polyethers have been disclosed in the literature that have not been prepared by radical methods. Therefore, as mentioned above, since these copolymers have a polyether backbone and a silicone (or silane) pendant, i.e., an inverse arrangement to normal surfactants, they are referred to as "inverted surfactants". Called. One or more of the following objects may thus be achieved by practice of the present invention. It is an object of the present invention to provide new siloxane polyether copolymers. Another object of the present invention is to provide novel silicone polyether compositions that are block copolymer combinations. Another object is to provide silicone polyether copolymers that are useful as surfactants in the production of polyurethane foams. Yet another object of the invention is to
Or to provide a copolymer exhibiting a polyether backbone with lateral siloxane pendants. Another object is to provide a copolymer raw material mixture that is substantially free of both residual unreacted polyether and unreacted silicone and is therefore primarily a copolymer. A further object is to provide a copolymer composition having 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 using the surfactants of the invention. Also provided are methods for making the above copolymers and foams. These and other objects will be readily apparent to those skilled in the art in light of the teachings presented herein. In broad aspects, the present invention relates to silicone polyether copolymers, their preparation and their use as stabilizers in the production of polyurethane foams, and urethane 7 ohms, particularly rigid urethane 7 ohms. As mentioned above, the molecular structure of the copolymers of the present invention is the inverse of the conventional copolymers used in the manufacture of foams, i.e. they have the formula -S i R'', R“. a and b are as described above] is characterized by a polyether backbone having at least three silicone pendants. The use of these polymers avoids the potential problems and disadvantages associated with unreacted polyethers and silicones and results in a narrower copolymer molecular weight and structure distribution. FIG. 1 shows a gel permeation chromatograph of a typical conventional surfactant preceded by a silicone precursor, and FIG. 2 shows a gel permeation chromatograph of a surfactant of the present invention preceded by a silicone precursor. -Shows permeation chromatography. As mentioned above, no molecular "inversion" of the structure of the surfactant, ie, a silicone surfactant having a polyether backbone with silicone pendants, has been reported in the literature. Formula (IF) above generally exemplifies a typical repeating unit of a surfactant having such an inverted structure. In one aspect, the silicone polyether copolymers of the present invention include ethylene oxide, propylene oxide and It is produced by hydrosilanization of polyethers produced by copolymerization of allyl glycidyl ether. Such copolymers consist of random or block repeating units? \SiR', O■R", [wherein R represents hydrogen, lower alkyl, acetyl, etc.; R' represents C, -C,, R" or OR~, provided that R" is SiR'. o .-. represents C, ~C, and R~ represents C, ~C, and W represents a prime number of at least 2, preferably 2 to 10, and within W or of W connected to the polyether. a divalent group optionally containing at least one 2 to 10 selected from O, N and S at the end; a, b and C are 0 to 3, with the proviso that C is preferably 2 or 3: and X and y are 0 or positive integers: and 2 is the average value of at least 3. The group H as used throughout this specification and claims can be exemplified by −
Si3 is H-SiR', O■R" E, where R', R". Preferably the sum of a and b is 3. The copolymer surfactant of the present invention is a suitable polyether monofunctional siloxane. The polyether itself can be prepared by the homopolymerization or copolymerization of one or more olefinically unsaturated groups, at least some of which can be subsequently reacted with a monofunctional siloxane. Similar to commercially available polymeric biomass produced, for example, typically about 6% AGE and Po
Polypropylene oxide (PPO) before vulcanization with the remainder
) Rubber polyether. Many alkylene oxides that can be used to make polyethers include ethylene oxide,
Propylene oxide, butylene oxide, 2,3-epoxybutane, 2-methyl-1,2-epoxypropane,
Includes tetrahydrofuran. Examples of alkylene oxides containing ole7ynic unsaturation include allyl glycidyl ether, vinylcyclohexene monoxide, 3,4-epoxy l-butene, etc.
It is not limited to this. The polyethers used in the preparation of the surfactants of the present invention thus contain repeating units [wherein R 1, , R 4 is hydrogen or lower alkyl, Z has 1 to 6 carbon atoms, and O , N and S; d has a value of O or l; n has a value of 1 to 6; m is O or a positive integer; and W can be exemplified by 1 with 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 polymeric compounds can be prepared as block or random polymers and may consist entirely of units having pendant unsaturated groups. That is, if the polyether is prepared exclusively from unsaturated epoxides such as allyl glycidyl ether, the polymer backbone will contain a large number of pendant unsaturated groups. On the other hand, if only small amounts of unsaturated epoxides are used in the preparation of polyethers, the pendant unsaturated groups will be widely spaced along the polyether backbone, thus reducing the number of possible bonding sites for siloxane groups. However, as mentioned above, the final surfactant must contain on average at least three siloxane groups. Although one siloxane gives the AB structure and two siloxanes give ABA, neither of these are inverted surfactants by definition. Although the surfactant composition will necessarily consist of AB and ABA structures, its contribution to the total structure will decrease as the average number of siloxane pendants becomes substantially more than three. Thus, a satisfactory polyether can be prepared from the copolymerization of a mixture containing 94% propylene oxide and 6% alinoleglycidyl ether if the average molecular weight of such polyether is 5700 g/mol. Ta. The polyether copolymer surfactant of the present invention has a polyether copolymer surfactant of about 650
The polyether backbone has an average molecular weight of ~20,000 and includes multi-a pedant silicone-containing groups. The surfactant (.) has a narrow, unimodal distribution: (b) is essentially free of silicone oil and process polyether; and (C) is free of any unreacted unreacted residues on the polyether backbone. A distinctive feature is that the saturated groups are optionally inactivated. A deactivated unsaturated group, as used in the present invention, refers to a group that has been isomerized such that the olefinically unsaturated group is no longer terminal. For example, an acrylic group can be isomerized or isomerized to a propenyl group, thus for the purposes of this invention there is no point of crosslinking with other polyethers for further reaction or during normal hydrosilanization reaction conditions. It can be thought of as being inactivated with respect to providing. Before discussing the preparation of the silicone polyether copolymers of the present invention, it is important to note that the purity of non-hydrolyzable silicone polyether compositions used to stabilize urethane foams typically requires complete consumption of the silane hydrogen. It should be noted that the siloxane intermediate is affected as a result of the requirement to use a molar excess of process polyether to compensate. This requirement arises because of competing side reactions of the olefinically terminated polyethers which effectively deactivate a certain proportion of the polyethers. Residual silane hydrogen remaining in the raw material can cause foam collapse of the raw material and further imperfections in the raw material assembly 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 prevents easy isolation of the copolymer product. . Furthermore, typical copolymer assemblies such as those described above exhibit broad molecular weight and composition distributions as a function of the nature of the equilibrated siloxane intermediates used. Thus, applications requiring particularly narrow copolymer molecular weight and/or composition distributions for special performance may be complicated by the presence of broad distributions. At the very least, copolymer structures falling outside of a particularly narrow molecular weight and/or structural distribution will represent an expensive diluent to the raw material and process. A particularly important property of the copolymers of the present invention is that, compared to conventional polyether copolymers with pendant siloxanes,
That is, it can be produced with a relatively narrow molecular weight range. Prior to this discovery, there was no precedent or 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 inversion of the structure of the siloxane polyether copolymer would provide moisture and stabilization of the urethane 7 ohm. As mentioned above, the inverted silicone polyether copolymers of the present invention can be conveniently prepared, for example, by hydrosilanization of a suitable polyether with a monofunctional siloxane. The method generally used to prepare the various inverted structures of the present invention employs various multifunctional polyethers in reaction with several separate monofunctional SiH fluids under typical hydrosilanization conditions. . Multifunctionality of the polyethers was introduced by simultaneous alkoxylation of EO and/or PO with allyl glycidyl ether (AGE) or vinyl cyclohexene monoxide (VCM). The monofunctionality of SiH fluids is explained below by silicones such as MM', MD'M, M. Guaranteed by distillation of T', DAD', etc. Typically, hydrosilanization was carried out 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 production is also possible, but this is an example! As shown in (2), there was a lot of heat. The stoichiometry of allyl (or vinyl) and SiH was in the range 1.3:1.0 with excess of SiH. At very high proportions there is a lower silicone content and therefore significant unreacted pendant olefin groups, and at very low proportions there is excess silicone fluid that must be distilled off. A large excess of silicone was not a problem in the raw product as this excess was easily removed by final distillation. However, it has been discovered that even in the presence of excess SiH fluid, these hydrosilanations convert up to 90% of the allyl groups to hydrosilanized bioactive compounds (depending on the exact siloxane). The remaining unsaturation was present as a propenyl functionality. This showed that allyl and propenyl isomerization competes with hydrosilanization in these highly reactive systems to a similar extent as occurs in conventional surfactant preparation. Since there is currently a lack of suitable simplified nomenclature for easy identification of inverted copolymer structures, Tables 1 and 2 are provided to teach important structural differences within the present invention. Part ■
The table shows multifunctional polyether intermediates. Table 1 describes the copolymers produced by the method of the invention together with some analytical data. Examples 1-IF and III illustrate the preparation of typical inversion surfactants based on monofunctional SiH fluids and multifunctional polyethers. Example! ■~x■ are each H. R. Slab stop? (
slabstock), rigid and oval H. R. The evaluation results of urethane foam based on the formulation are shown. For ease of identification, the surfactants of the invention are referred to by the letter designation having the following meanings:
i(CHx)i D (CHs)*SjOzzz D'(CHz)Si(H)Ozz■D" (C
Hz)Si(R)(h7■D3 Cyclic dimethylsiloxane trimer "Si (CHz)3siOsi(CHx)J [(CHs)ssio]ssiH [(CHi)isio] zsi(CHx)H(CHs
)ssio[si(CHs)zo] zsi(CHz)
J(CHs)ssio[si(CHs)solisi(
CHx)zHCHsSiOsz2 SiOa7z H fluid "poly(dimethyl, methyl-hydrogen) MM' M. T'MD'MMD2M' MD. M' T Q Siloxane. The invention will be more easily understood with reference to the drawings. FIG. 1 shows a typical copolymer mother liquor below the GPC of the starting SiH fluid backbone as compared to a typical GPC of an inverted copolymer below the GPC of the starting polyether backbone as shown in FIG. (mother fluid) JIf-like GP
C (gel permeation chromatography). GPC of normal copolymer mother liquors shows a multimodal distribution, whereas inverted copolymer mother liquors are unimodal. Besides the novel structure itself, exhibiting silicone pendants from a polyether backbone as opposed to the reverse in conventional surfactant systems, the mother liquor composition is also unique. As can be seen in the chromatogram, the inverted biomass exhibits a narrow unimodal distribution. This narrowness (relative to conventional surfactants) is a manifestation of the difference between the backbones of the two systems. Typical surfactants are based on equilibrated SiH fluids with a broad structural distribution. On the other hand, the reversing surfactant is n
- Based on multifunctional polyethers "grown" from initiators such as butanol. Although these polyethers are not completely distinct molecular species, they are more uniform in composition than balanced SiH fluids, particularly with respect to molecular weight distribution. As these "more uniform" intermediates react with distinct silicones, such as MM', D'D, etc., a relative degree of uniformity appears in the inverted surfactant composition. This is unlike conventional surfactant systems in which the less homogeneous SiH fluid backbone reacts with a non-discrete allyl-initiated polyether to produce a less homogeneous product. The inverted surfactant distribution is therefore based on less dispersion than conventional systems. GPC confirms this in terms of molecular weight distribution. A second unique feature of the inversion surfactants of the present invention is the absence of diluents (both silicone oil and excess process polyether) present in conventional surfactants. Free silicone oil (ie, D, etc.) is present in conventional systems because it is present in the equilibrated SiH fluid intermediate. Most of the silicone oil in typical copolymer compositions is S
Either the iH fluid precursor or the final copolymer product can be removed from the SiH fluid by harsh distillation. However, even effective distillation has been shown to leave behind linear or cyclic silicone oils greater than about MD, M, and D8. These silicone oils are not present in the inversion system of the present invention if the silicone precursor is purified. Since little or no redistribution is observed during these hydrosilanizations using appropriate conditions, silicone oil is not formed as a by-product and thus is not present in the final inverse copolymer assembly. The excess unreacted polyether present in conventional systems is a result of the required hydrosilanization conditions. Generally, in order to complete the platinum-catalyzed hydrosilanization based on consumption of SiH, 30% allyl-initiated polyether
It must exist in excess. On the other hand, any allyl to propenyl isomerization that occurs within a polyfunctional polyether only serves to deactivate its unsaturated groups and does not deactivate the entire polyether as shown below: Si Any remaining unreacted silicone SiH fluid used here is volatile and easily removed during standard solvent evaporation. It will not cause any problems as it will be removed. GPC, eye C. 11 and "S I mar" were useful tools for characterizing the inverted surfactant materials. GPC confirmed the absence/presence of crosslinking. Careful purification of silicone intermediates and controlled reactions and The processing conditions prevented cross-linked structures. 13Ct++++ is particularly useful for monitoring the degree of conversion of unsaturated groups in multifunctional polyethers after hydrosilanization. Although conversions of 80% or more are often observed, Complete conversion is usually hindered by competing isomerizations of allyl to propenyl.
is the dehydrogenation condensation chemistry (S i H+
HOR-45 i OR + H,) could be shown to be absent. The inversion surfactants of the present invention were evaluated for application to conventional soft HR (former and slab stock) and hard urethane foams. This performance testing method involves an initial screening of different reversal silicone surfactants in a box injection with a final evaluation occurring in an L-panel mold. The L-panel is a suitable and simple identification test by which performance criteria of surfactants such as surface defects, density, density gradient, K-factor and flowability can be effectively measured. Performance in these evaluations is based on foam density and K
- The judgment was made based on the factor (insulation ability) ζ. These evaluations used fast and slow formulations such as in a spray system. Union Carbide
Carp. ) and L-5420 and L-54.
Two conventional hard foam surfactants identified as No. 40 were used as controls. 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 2. In each case a surfactant, all of which contained an unterminated polyether backbone, was introduced on the resin side. The 7 ohm results are presented in Tables V through 1 for the slow formulations and in Table 2 for the 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. do. Such polyols have an average of at least 2 hydroxyl groups per molecule, typically 2.0 to 3.5, and carbon,
It includes compounds consisting of hydrogen and oxygen and compounds which may contain phosphorus, halogen and/or nitrogen. Such polyether polyols are known in the art and are commercially available. Organic polyisocyanates useful in preparing polyether polyurethane 7ohm according to the method of the present invention are well known in the art and are organic compounds containing at least two isocyanate groups, including any such Compounds or mixtures thereof can be used. Toluene diisocyanate is one of the suitable incyanates used commercially for foam production. The urethane foaming reaction is usually carried out in the presence of a small amount of a catalyst, preferably an amine catalyst, usually a tertiary amine. In addition to the amine catalyst, it is also suitable to add a small amount of some kind of metal catalyst during the fractionation of the reaction mixture. Such auxiliary catalysts are well known in the art of producing polyether-based polyurethane foams. For example, useful metal catalysts include organic derivatives of tin, particularly tin compounds of carboxylic acids, such as stannous octoate, stannous oleate, and the like. Foaming can be achieved by using in the reaction mixture a small amount of a polyurethane blowing agent, such as water, which reacts with incyanate to generate carbon dioxide in situ, or by using a blowing agent that evaporates due to the exotherm of the reaction, or by using a blowing agent that evaporates due to the exotherm of the reaction;
A combination of the two can be performed. The polyether-based polyurethane foams of the present invention may be foamed by any of the techniques known in the art, such as especially the "one-shot" technique. According to this method, a foamed product is provided by reacting a polyisocyanate and a polyertepolyol simultaneously with the foaming operation. It is sometimes convenient to add the surfactant to the reaction mixture as a premix with one or more of the blowing agent, polyether, polyol and catalyst component. It is understood that the relative amounts of the various components of the foam composition are not narrowly critical. Polyether polyols and polyisocyanates are present in major amounts in the foam formulation. The relative amounts of these two components and the amounts needed to produce the desired urethane structure of the foam are well known in the art. The blowing agent, catalyst, and surfactant are each present in a small amount sufficient to foam the reaction mixture, and the catalyst is present in a catalytic amount that is the amount necessary to contact both to form the urethane at a reasonable rate. 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 conventional polyether and/or polyester polyurethanes. For example, the foams of the invention can be advantageously used in the manufacture of textile backings, cushions, mattresses, pads, carpet backings, padding, gaskets, sealers, insulation materials, and the like. In the following examples, all reactions involving handling of organometallic compounds were carried out in an inert atmosphere. Commercially available reagents were used without further purification. All glassware is K.
Washed successively with OH/isoprobanol, water, dilute hydrochloric acid, and water and dried in an oven before use. "Cast spectrum is a Fourier transform type barrier 7 (Varia
n) Measured using a CFT-20 spectrometer. "S I mar and additional 13Cast spectra were measured using a JEOL-90Q spectrometer. Samples of..." The GC analysis was carried out on a Hewlett-Packard machine equipped with a 107 Eat
ckard) 5840 A type gas chromatograph. The GC was operated using a helium gas flow of 30 cc/min and a ramp rate of 1 min from 75°C to 350°C with a post-hold time of 20 min. GPC is CHC1
10' to3500 and IOO at 1.0% dilution in 3
A was obtained by operating through a set of four columns at a high pressure of 1080 A and a flow rate of 1/min at room temperature. The following examples illustrate the invention. Example I Preparation of the inverted surfactant I S-5 by hydrosilanization of MM' with polyether I3 A clean, dry 500+nQ 3-tube round bottom flask (3
NRBF), polyether 13 [allyl 6.4%;
OH (diol) 3.52%: allyl glycidyl ether (AGE) 43% by weight, ED 24% and P0 28%]
85.71, MM' (Petraci) 39.217, and toluene 202 were added. This charge showed a 30% excess of allyl groups (relative to SiH) and 60% toluene. However, many similar preparations have been found to be suitable using tri stoichiometric amounts and only 30% by weight toluene. Next, a mantle heater was placed in the reaction vessel.
Equipped with mechanical stirrer, thermometer/temperature monitor, Dean-Stark repair with Friedrich condenser, N2 inlet/outlet and N2 sparge tube. Nitrogen was flushed through the stirring system. The homogeneous solution was mixed with qual platinum # (CPA)/ethanol solution (10+++j Pt/mff) 0. 5mQ
(15 ppm) at 29°C. 4 reaction vessels
Although it was warmed to 0℃, a fever of 35℃ was observed at this point, and l
The temperature reached 75°C for minutes. Next, the reaction vessel was heated to 100
℃ and kept at this temperature for 90 minutes. NaHCO35.
Neutralization was performed by adding 12 and maintaining at 100° C. for 3 hours. The solution was filtered through a 3-4μ filter bed under 40psiN and collected into another 3NRBF. The toluene was then removed by N2 sparge at 100°C. Collected 110.157 of a transparent brown substance (
yield 88%). GPC analysis showed a unimodal biomass distribution with lower retention times than the polyether starting material, consistent with an increase in molecular volume. ``c,,'' indicates the typical 1.2 hydrosilanization of the allyl group and 'Slallr indicates the presence of silicon atoms of M and M'' type only in a l:1 ratio. The percentage of silicon is 9.9 ± 0.1% (calculated value is 1 for 100% reaction).
0.9%). This copolymer product has a surface tension of 22.4 at 25°C and a concentration of 1%.
It was found that down to dynes/cm. Example ■ Preparation of inverted surfactant Is-11 by hydrosilanization of MD'M with polyether l3 Clean dry 500
Add MD' to a 3ml round bottom flask (3NRBF).
M5 0.3 2,? , polyether 13 [allyl I 6.4%; OH (diol) 3.52%: allyl glycidyl ether (AGE) 48% by weight, ED 24% and P0 28%] 74,681? and toluene 2002. This charge showed a 30% excess of allyl groups (relative to SiH) and 60% toluene. However, many similar preparations have a stoichiometry of l:l and 30% by weight.
It was discovered that success was achieved using only toluene. The reaction vessel was then equipped with a heating mantle, mechanical stirrer, thermometer/temperature monitor, Dean-Stark repairer with Friedrich condenser, N2 inlet/outlet, and N2 sparge. Are you stirring? The system was flushed with nitrogen. The homogeneous solution was dissolved in chloroplatinic acid (CPA)/ethanol solution (l Om9 Pt/m(2) 0.4m+2(1
5 ppm) at 65°C. The reactor was warmed to 77°C, at which point an exotherm of 20°C was observed, rising to 97°C over 3 minutes. Next, the reaction vessel was heated to 100,
゜Cf. : Maintained for 34 minutes. N a H C O s
5. Neutralization was performed by adding 0.09. The reaction kettle was kept at 100° C. for an additional 125 minutes, during which time the solution was cooled to room temperature, pressure filtered through a 1-2 μ filter bed under 40 pSiNx, and collected into another 3NRBF. The toluene was then removed by sparging with N at 100°C. Approximately 115,000 pale yellow raw wood? was collected (yield 92%). GPC analysis showed a unimodal biomass distribution with lower retention times than the polyether starting material, consistent with an increase in molecular volume. '3C. ■, indicates the typical 1.2 hydrosilanization of the allyl group; 'Sllllll' indicates the presence of only M and D'' units in a l:1 ratio. This copolymer compound has 2
It was shown to reduce the surface tension of water to 22.4 dynes/am at 5° C. and 1% concentration. Example
Hydrosilanization with M is shown. Example X■ shows the solventless hydrosilanization of MD'M and polyether 13. Example ■ Preparation of the inverted surfactant Is''-35 by hydrosilanization of polyester l'3 with M D 2M' Polyether l'3 [
Allyl 6.4%); OH (diol) 3.52%; Allyl glycidyl ether (AGE) 48% by weight, E02
4% and P028%] 29.0 1 , MDzM'
(See Example xvr) 35.972 and toluene 29. 19I? I put it in. These preparations are allyl: SiH
1:1 stoichiometric ratio and 30% dilution with toluene. The reaction vessel was equipped as in Example 3 for the production of hydrosilanates. Dehydration of the reactor contents was ensured by distillation of the toluene assisted by a small sparge of N2 at 90°C giving a clean, dry toluene distillate. The reaction vessel was cooled to 86°C, and the homogeneous solution was poured into a CPA/ethanol solution (P t l Oml/m12) at 0%. 3
Contacted with mQ (32 ppm). After an induction period of about 1 second, a rapid exotherm of 27°C occurred, bringing the temperature of the reaction kettle to 113°C, followed immediately by a brown color of the solution. The reaction kettle was kept at 105°C for 30 minutes, at which point it was converted to NaHCOslO-151
and kept at 105°C for 120 minutes. The solution was then cooled to 37°C and filtered under 40 psi of N2 through a 7-filter bed of l~2μ and another 500m
Collected in 3NRBF of 2. The toluene was then removed at 105°C with the aid of a N sparge. GC analysis of the distillate after toluene removal revealed unreacted MD. The presence of M'about 22 was shown. Brown non-viscous raw material 5 1. 3 3
, ii' were collected (yield 79%). GPC of the raw material showed a unimodal product distribution. 13Cmmr showed a typical 1.2hydronation of the allyl group and a small amount of propenyl carbon. 'Sl@II+ analysis showed the presence of only M, D and M'' silicone groups in a ratio of l2:l. Gravimetric analysis of % silicon (elemental) was 14.0 ± 0.3%; 50% of theoretical value
Met. Interestingly, 13Cam+ suggested more than 80% reaction completion. This contradiction in analysis remains unresolved. Example ■ MD of polyester l3. Preparation of the inverted surfactant IS"-82 by hydrosilanization with M' Clean 500
In 3NRBF of mQ, M D , M' (see Example
%); OH (diol) 3.52%; allyl glycidyl ether (AGE) 48% by weight, E024% and P02
8%] l6. l22, and toluene 17.15,? I put it in. These charges exhibited a l:l stoichiometry of allyl:SiH and a 30% dilution with toluene. The reaction vessel was equipped as in Example 3 for the production of hydrosilanates. Are the contents of the reaction vessel clean? Dehydration was ensured by distillation of the toluene assisted by a small sparge of N2 at 90'O to give a dry toluene distillate. CPA/ethanol solution (Phill O mji/mQ
) 0. The catalyst was activated by adding 15 mC (26 ppm). After a short induction period, rapid lo'c! fever occurs,
The temperature of the reaction vessel reached 108°C, and the solution soon turned brown. The reaction vessel was kept at 100°C for 60 minutes, at which point it was heated to a moist (lO% water) solution of N a H C
O 35. Neutralize with 0'I and 100°C
for an additional 120 minutes. The solution was then filtered hot through a 3-4 μ filter bed under 40 psi of N and collected in another 500 m (2 of 3 NRBF). The toluene was then removed at 11 O'0 with the aid of a N2 sparge. A brown raw plant 3+.71.9 (yield 79%) was collected. GPC of the raw plant showed a unimodal biochemical distribution. +3cs++++ and 29c,1, Example V Preparation of the inverted surfactant Is"-59 by hydrosilanization of polyesterol I3 with M.T' (Example
■Reference) 32.58y, polyether 13 [allyl l6
．． 4%); OH (diol) 3.52%; allyl glycidyl ether (AGE) 48% by weight, E024% and P
○28%] 27.462, and toluene 26.01,?
I put it in. These preparations are allyl:SiH l:l
The stoichiometric ratio and 30% dilution with toluene were shown. The reaction vessel was equipped as in Example I in the preparation of hydrosilanates. The reactor was heated to 85°C and a light N2 sparge was started. A small amount of clear (dry) toluene was collected to ensure dehydrated starting material. The temperature of the reaction vessel was increased to 108°C, at which point the CPA/ethanol solution (P
t 1 0m,? /m(2)0.2 5m(2( 2
9 ppm). An exotherm of 4°C occurred and the reaction kettle reached 112°C over a period of 3 minutes. CPA/ethanol solution 0.1mQ (1
2 ppm), but no further heat generation occurred. The contents of the reaction kettle turned brown after 20 minutes at llo'o. The reaction kettle was kept at llo'c for an additional 95 minutes to complete the reaction. The solution was then wetted with N a H CO
3 5. Neutralize with 5 2 and heat to 100°C for 120
It lasted for a minute. The solution was then filtered through a 3-4μ filter bed under 40psi of N2 to obtain a clear, brown toluene solution. The toluene was then removed at 100'O with the aid of a N2 sparge. and a clear brown product 25.77,? (yield 4
4.4%) were collected. GC of the distillate removed shows considerable unreacted M. The recovery of T' was shown. GPC of the product showed a typical unimodal biomass distribution. 1c,,,t, revealed approximately 40% conversion of the allyl group to the 1,2-hydrosilation product, while the remainder was isomerized to the propenyl function. Gravimetric analysis for S1 showed the presence of 10.3% Si (100% reaction is calculated as 20.6% Si). As a note,
M. All hydrosilanations performed with T' were observed to be approximately as inert as this preparation. Undoubtedly, the steric bulk of the M,T' units hinders effective and efficient hydrosilanization under the conditions used. In each case "c,...,," reveals the presence of the only propenyl unsaturation remaining in the product after incomplete reaction. Thus, the M, T' of the CPA catalyst under these conditions
On the time scale required for hydrosilanization, isomerization of allyl to propenyl effectively competes to deactivate the unsaturated group. Example ■ D. of polyester l3. Preparation of inverted surfactant Is“-1 by hydrosilanization with D′ clean soomQ
During the 3NRBF, D. D'55.00,? , on polyether [allyl 6.4%): ○H (diol) 3.
52%: Add 48% by weight of allyl glycidyl ether (AGE), 24% EO and 28% P○, and 170.47 liters of toluene. These preparations are SiH
showed a 43% excess of allyl groups and a 62% dilution with toluene. However, many other similar preparations:
It was discovered that using a stoichiometric ratio of 1 and only 30% by weight toluene was effective. The reaction kettle was equipped as in Example 1 and the contents were dehydrated by distillation at 105°C assisted by a N2 sparge. Collected a small amount of water. Cool the reaction vessel to 30°C, and
PA/ethanol solution (Pt1 0ml/m<1)
0.45m (2 (14ppm)) was added to the catalyst. The reaction kettle was heated to 70°C, at which point an exotherm of 21°C occurred and the kettle reached 910C!. KOH, ethanol and water. SiH testing, including addition and measurement of evolved hydrogen gas, showed no detectable SiH residue. The kettle was held at 9500 for 95 minutes, at which point it was flushed with 3.02 NaHCO s. This hot toluene solution was then mixed with 3-4μ of 7
Filtered through a filter bed under 4Qpsi of N2 and collected into another 500+nl2 of 3NRBF. The toluene was then removed at 95°C with the aid of a N2 sparge, leaving a brown raw material 108,? (yield 88%). ? PC analysis showed a unimodal product distribution. "c,,,," indicated that 65% of the allyl groups reacted with the silicone to form the 1.2 hydrosilanated compound.Of the remaining 35% of unreacted unsaturation, 70% of the allyl groups gravimetric analysis of Si showed 16.3% of the raw material (D,
For complete reaction of D' with all allyl groups 21.
1%). This showed 62% completion of the reaction, and compared well with the data of mouth c,.... nS1, revealed that no appreciable ring opening of the cyclic D3D' m occurred during hydrosilanization to polyfunctional polyethers. This inverting surfactant was found to reduce the surface tension of water to 23.2 dynes/cm at a concentration of 1%. Example ■ Preparation of the inversion surfactant Is"-22 by hydrosilanization of polyesters with D4D' Clean 500n+
In 3NRBF of ff, polyether Jodan [Allyl l6
．． 4%). OH (diol) 3.52%: allyl glycidyl ether (AGE) 48% by weight, E024% and P
O28%] 53,273? , D4D' (purity 81%
Distilled to D4; impurities are mainly D4 and D. Non-Si-H containing
) 71.82 & and toluene 752 were added. These charges contain a 30% excess of unsaturation and toluene 38
It expressed no. Furthermore, a stoichiometric amount of l:1 (or D.D'
(excess of D4D) and 30% dilution in toluene
It has been discovered that it can be used successfully in the preparation of A reaction vessel was equipped as in Example ①, and the contents were purged with N2
Dehydration was achieved by sparge-assisted distillation at 100°C. The distillate was clear so the solution appeared dry. Reduce the humidity to 70°C and convert the solution into CPA/
Ethanol solution (PtlOml/m4) 0
．． Contact was made at 5 mff (25 ppm). 75℃
After heating to 33°C, an exotherm of 33°C occurred, and the temperature of the reaction vessel reached 108°C in 1 minute. After about 1 additional minute, the clear contents of the reaction vessel turned brown. The reaction vessel was then kept at 100°C for 30 minutes, at which point it was heated to NaHC○34.4,? It was neutralized. The reaction vessel was then held at 100°C for 120 minutes and cooled to room temperature. The solution was then filtered through a 3-4μ 7 lter bed under Nz 40psi and collected in another 500mQ of 3NRBF. Next, toluene and residual D, D
', D, and Ds were removed by N, sparge-assisted evaporation to <100° C. over 120 min. This evaporation step was continued for an additional 15 hours (to ensure removal of volatile silicone). GPC analysis showed a unimodal growth distribution. The C nmr is 1.2 due to hydrosilanization of the allyl group.
It showed 81% conversion to the monosubstituted raw compound and 19% conversion to the propenyl group by isomerization. "Sinmr showed that the shape of the D.D' ring was retained during the hydrosilanization process. Gravimetric analysis showed that the SiH
gave 5.5% Si compared to the theoretical value of 20.6% Si for complete conversion of . The Si value in this gravimetric analysis indicated 58% conversion of SiH. The origin of the discrepancy between oral Cnmr and gravimetric Si analysis remains unresolved. A 1% solution of this inverted copolymer has a surface tension of 20.7
It has been found that it can be reduced to dynes/cm. Example ■ Preparation of inverted surfactant Is-42 by hydrosilanization with polyether 5 of HSi(OEt)s.
[Allyl 4.2%; OH (monool) 0.45%;
Allyl glycidyl ether (AGE) 13% by weight, E○
34% and P○53% 146.16g and toluene 2
4.06g was added. The reaction vessel was equipped as in Example I and heated to 95°C. At this point, a short period of N2
Sparge assisted evaporation showed that the contents were dehydrated. The contents were cooled to 80'O and H Si (○EO
, 7.77g were added. This preparation is allyl and Si
The l:l stoichiometry of H is indicated. This reaction vessel was
/Ethanol solution (PtlO mg/mQ)0
．． 2no2 (26ppm). After an induction period of about 5 seconds, a lo'o exotherm occurs and the reaction kettle reaches 2
It reached 93°C over a period of minutes. The reaction vessel was kept at 90°C for 10 minutes, at which point it was heated to NaHCO386.
Neutralized with 4g and kept at 90°C for 120 minutes. The contents were then cooled to 33°C and filtered through a 3-4μ filter bed at 90°C under 40psi N2. 36.39g of transparent, pale yellow, viscous raw material was collected (
yield 67%). The GPC chromatograph 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 the secondary hydroxyl terminated polJ ether backbone is considered as a possible cause of the apparent crosslinking. Gravimetric analysis of this material gave 2.1% Si. Complete SiH conversion would give a product of 2.4% Si. This is H
S i (OE t). (The final distilled raw material contained residual unreacted H S
i(O E t)s did not exist). Qualitatively “C”
The nmr showed a lower conversion of the allyl group, but quantification was not possible due to the complexity of the spectrum (particularly due to the overlap of the important resonance band with that of the butyl initiator of the polyether). Example ■ Preparation of inversion surfactant IS-41 by hydrosilanization of HSi(○Et)2Me with polyether 5.
[Allyl 4.2%; OH (monool) 0.45%; Allyl glycidyl ether (AGE) 13% by weight, E03
4% and P053%] 109.90 g, HSiMe(O
Et) * 15.31g and toluene 53.32g (
30% dilution). These preparations are allyl and S
A 1=1 stoichiometry of iH groups was shown. The reaction vessel was equipped as in Example I for the hydrosilanization step. The reaction vessel was heated to 87°C, and the contents were converted into CPA/ethanol solution (Ptl Omg/mf2) 0.3+of
f (17 ppm). After an induction period of approximately 2 minutes, an exotherm of 6°C occurred and the kettle temperature reached 95°C. At this point the clear solution turned from colorless to pale yellow. This was kept at 95°C for 30 minutes, followed by NaH C
Neutralized with Os. The viscosity of the solution is NaHCO. An increase was observed immediately after the addition of . Temperature to 95℃ l20
The contents were then cooled to 35°C. This solution was then passed through a 3-4μ filter bed for 40 ps.
iN, filtered down and collected into another 3NRBF. The toluene was then removed with a N2 sparge at 95°C. 110.68 g of clear yellow, highly viscous product was collected (88% yield). GPC analysis showed one major peak at a retention time roughly consistent with the proposed structure. However (Example ■
Some obvious high molecular weight peaks (to a lesser extent) were also observed. This high molecular weight peak is similar to that of a
It is believed to be attributable to cross-linked substrates as a result of a) transesterification of the alkoxysilane groups with the secondary hydroquine end groups of the polyether and/or b) hydrolysis of the alkoxysilane groups. EXAMPLE Mol:
Allyl glycidyl ether (AGE) 51% by weight and E
367.30 g of 049% and 42.97 g of toluene were added. The reaction vessel was equipped as in Example ①. The polyether/toluene solution was dehydrated by N2 sparge assisted distillation at 95°C to give clear dry toluene. The reaction vessel was cooled to 70°C, and HSiEtz3
2.70g was added. CPA/ethanol solution (PLIO mg/m
Q) 0. 3 mQ (21 ppm) was added at 72°C to effect the catalyst. The temperature was raised to 89°C, at which point an exotherm of 21'O occurred and the kettle temperature rose to 110°C over a period of 3 minutes. At this time, the contents darkened to a typical yellow-brown color. Next, this reaction vessel was heated to 9500°C.
At this point, add 0.14.8 g of NaHC.
and kept at 95°C for 120 minutes, then the solution was cooled to room temperature. The solution was filtered through a 3-4μ filter bed under 40 psi N2 and the clear brown solution was collected in another 5-00 mQ of 3NRBF. From this solution, 99% of toluene was then added with the aid of N and a sparge.
It was removed at 5°C. The distilled raw materials were collected (yield: 68%). GPC analysis of the raw material showed a unimodal raw material distribution with a shorter retention time than that of the polyether for the starting polyether backbone, consistent with the proposed reaction and increase in molecular weight. Gravimetric analysis was performed using S i2. 0%, while complete conversion of the silane would have given a Si value of 8.3%. The observed fs Si values indicated that the conversion of silane to hydrosilanized product was only 16%. Mouth C n
mr is 38 to allyl 1,2-hydrosilane reaction product
% conversion and 62% isomerization of allyl to propenyl. The origin of this discrepancy between C nmr and gravimetric analysis remains unresolved.
on polyether in 3NMBF of

[Allyl 17.1
%; Molecular weight (gpc) - 1020 g/mol; Allyl glycidyl ether (AGE) 51% by weight and E049
%184.76g, MM'4 0.24g and toluene 75g were added. These preparations are allyl: SiH
1.3:l stoichiometry of and 30% dilution with toluene. However, it has been found that a 1:1 stoichiometry and 30% toluene dilution can also be used successfully. The reaction vessel was equipped as in Example I for the hydrosilanization step and heated to 52°C. Then the system is CP
A/Ethanol solution (ptlOmg/mQ) 0.
5 m (2 (25 ppm)). Approximately 10
After an induction period of seconds, a rapid exotherm of 58°C occurs and the reaction kettle rises to 110'C! in about 20 seconds! Became. The reaction kettle was then kept at 110°C for 45 minutes and then heated with NaH.
Neutralized with 4-1 g of COs. The reaction vessel was kept at 100° C. for an additional 120 minutes. At this point the solution was cooled to 40°C, filtered through a 3-4μ filter bed under 40psi N2, and
Collected in 3NRBF of 00v2. The toluene was then removed at 80°C with the aid of a N2 sparge. Then, 113 g of light golden brown raw mushrooms were collected (yield: 90%). GPC analysis of the raw material showed a unimodal product distribution at a shorter retention time than the starting polyether backbone, consistent with an increase in molecular weight. The weight analysis of raw wood was performed using Sil1.
7%, while the conversion of lOO% was Si(I[12.9
It was supposed to give %. The calculated conversion of MM' to raw wood was 87% based on this gravimetric analysis. ''' C nmr indicates that 71% of allyl groups are converted by hydrosilanization, which leads to MM
This corresponds to a conversion of 92% and is in close agreement with the results from gravimetric analysis. 29Sinmr is a 1:l ratio of M and M' as expected for the silicon species in the raw material.
It was revealed that. This inverting surfactant has been shown to reduce the surface tension of water to 22.2 dynes/cm at a concentration of 0.1%.
. Example ■ Preparation of the inverted surfactant Is-46 by hydrosilanization of polyester 7 with MM'.
Allyl glycidyl ether (AGE) 22% by weight and E
77.13 g of O7 8%] and 42.93 g of toluene were added. The reaction vessel was equipped as in Example I for the dehydration and hydrosilanization steps. The solution was heated to 95°C and lightly sparged with <N2 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. Then add the solution to 4
Cooled to 5° C. at which point 22.87 g of MM' was converted to a cloudy yellow heterogeneous suspension. This MM'
The charges in were in stoichiometric amounts relative to the allyl groups of the polyether. The temperature of the system was increased to 52° C. and the system was subsequently contacted with a CPA/ethanol solution (P t I O mg/mQ). 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 increased to 100°C and maintained for 30 minutes. Then increase the temperature to 100'C for another 135 minutes! Please keep it N
aHCO. was added to neutralize. The solution was then cooled to 36°C and passed through a 3-4μ filter bed at 40psi.
of N2 and collected in another 500 mQ of 3NRBF. Toluene was removed at 95°C with the aid of a N2 sparge. When the toluene distillation was finished, the solution was cooled to room temperature and the N2 sparge was continued for 16 hours. Semi-waxy product 7 1. 6 1g was collected (yield 72%)
. GPC analysis of this raw material showed a unimodal product distribution at a shorter retention time than the starting polyether backbone, consistent with the higher molecular weight. Weight analysis of S1 is 7.1
%, while the theoretical value of Si for 100% addition of MM' corresponded to 8.7%. This indicates that the actual conversion of MM' is only 80% based on gravimetric analysis.
;. The C nmr showed that 18% of the allyl group was converted to the 1.2 hydrosilanated product and the remaining 22% was converted to propenyl. This was consistent with the results suggested by gravimetric analysis. "Sinmr is the difference between the two main species of silicon atoms in the product
It shows that M and M' are present in a ratio of 1.0:0.97. There was also a small amount of D'-type silicon atoms present, which may result from either dehydrogenation condensation of some of MM' with the primary hydroxyl end of the polyether backbone or cleavage of the siloxane backbone. The observed ratio of M:M':D' is 1.0.
:0.9720. It was 06. Example Xll1 Preparation of the inverted surfactant Is-65 by hydrosilanization with MM' of polyester l [allyl 3.52%; MW (gpc) =
1050g; Allyl glycidyl ether (AGE
) 12% and E088%] 10.89 g and toluene 34 g were added. The flask was equipped as in Example I for the hydrosilanization step. The temperature was increased to 85°C, at which point the homogeneous system was treated with 0.0% CPA/ethanol solution (Ptl Omg/mQ).
45 mQ (25 ppm). Immediately (2
Fever occurred (within an induction period of seconds). A water bath was immediately placed around the flask. The temperature of the maximum exotherm reached 100°C within 35 seconds and the solution became clear and brown. The reaction kettle was held at 100° C. for 75 minutes at which point 6 g of wet NaH CO s (10% water) was added to neutralize. The temperature was maintained at 100°C for an additional 145 minutes. The solution was then passed through a 3-4μ filter bed for 40
Hot filtered under psiN2, other 50On+12 3N
Gathered at RBF. Toluene was slowly removed at 110°C with the aid of a N2 sparge. Raw materials (wax at room temperature) 1
13.87g was collected (91% yield). GPC analysis showed a unimodal product distribution at 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 inverted surfactant IS-72 by hydrosilanization of polyester 10 with MDM'
OE allyl on polyether in mQ 3NMBF6.
77%; MW (gpc) = l 0 6 5 g/mol; VCM2 4% and EO 76%] 9 1.4 5
3.57 g of gSMD'M3 and 53 g of toluene were added. These charges exhibited a l:l stoichiometry of allyl:SiH and a 30% dilution with toluene. A reaction vessel was equipped as in the example and heated to 95°C. This solution was dissolved in a CPA/ethanol solution (P t 10 m
g/mQ), but no reaction was observed. This system was treated with CPAO after 5 minutes. 4 5 no 2 (2 5
ppm). An exotherm of 5°C was observed. The brown solution was kept at 100° C. for 60 minutes, at which point it was neutralized by adding 5.5 g of wet NaH CO 3 (10% water). The hot solution was then filtered through a 3-4μ filter bed to yield a clear light brown solution that was collected in another 500 mQ NRBF. The toluene was removed with 110'o assisted by a N2 sparge. Raw things (
106.67 g (very viscous/semi-wax) were collected (85% yield). GPC analysis showed a unimodal product distribution at shorter retention times than the starting polyether backbone, consistent with an increase in molecular weight as expected for the proposed raw materials. The presence of a limited amount of toluene in this raw material was also observed,
This showed that the distillation was incomplete. EXAMPLE
0g/mol. AGE9 7% and EO3%) 33.15
g and 53 g of toluene were added. These preparations are l
:1 stoichiometric ratio and 60% toluene. This high amount of toluene was used as a safeguard against the expected high heat of reaction. The reaction vessel was equipped as in Example I for the hydrosilanization step. The system was heated to 70 °C, surrounded by a water bath, and immediately added to the CPA/ethanol solution (
Pt1 0mg/m4) 0.3 0m4 (2 8p
pm) was prepared. Immediately after this, the heat generation increased the temperature of the pot to 105°C (heat generation 35°C). The contents of the reaction vessel slowly turned from yellow to brown. A temperature of 100 °C was maintained for 60 min, at which point moist NaH CO s (ice lO%) was added.
5.5g was added to neutralize. The temperature of the reaction kettle was maintained at 100° C. for an additional 120 minutes. The contents are then passed through a 3-4μ filter bed for approximately 40 ps.
filtered into another 500 mQ of 3NRBF under N2,
A clear, dark brown solution was obtained. Then toluene was heated with vigorous N
The mixture was removed at 100° C. with the aid of two sparges. 58.56 g of transparent, dark brown raw material was obtained (yield 78%). GPC analysis showed a unimodal product distribution with shorter retention times than polyether i-soil, consistent with an increase in molecular weight as in the proposed product. This reaction, when brought to theoretical completion, positions an MM' group at almost every ether linkage along the backbone (excluding the ethylene glycol initiator unit). EXAMPLE
polyether 17 (allyl 1) in 3NRBF of mff
5%; terminal treatment with diacetoxy; OHO%; AG
E4 8%, ED2 4% and P028%) 37.1
3g SMD'M22 1.97g and toluene 150g
I put it in. These charges are allyl: SiH=1.
3:1 and 70% dilution in toluene. A reaction vessel was equipped as in the example construction, and the contents were 100%
Heated to ℃. The contents were then dehydrated by distillation assisted by a N2 sparge. The results showed that the distillate was clear and dry. The temperature was lowered to 808C and the CPA/ethanol solution (Ptl Omg/mQ) 0. 4mQ (1 9
ppm). After an induction period of 30 seconds, an exotherm of 13°C was observed and the reactor was heated to 93°C for approximately 3 minutes.
It became C. After an additional 4 minutes, the contents of the reaction kettle turned dark in color. The temperature was maintained at 100'011 m for 105 min and NaH
It was neutralized with 5.2 g of C○s. The temperature was held at t o 'c for an additional 190 minutes. Cool this solution to room temperature and add another 500 mI of 3NRB under 4 psi of N2 through a 1-2μ filter bed.
Filtered into F. Toluene was removed at 80°C with the aid of a N2 sparge. 53 g of clear, yellow product was collected (88% yield). GPC analysis showed a unimodal product distribution. Si
A gravimetric analysis of showed 14.5% Si. Complete conversion of MD'M would theoretically give 15.4%. 14.5% Si therefore represents a conversion of 91% of the MD'M present. Residual MD'M was removed in a final distillation step. A 1% concentration of this terminated inversion surfactant reduced the surface tension of water to 24.9 dynes/cm. Example XVI+ Preparation of inversion surfactant Is-11 by hydrosilanization of polyester 13 with MD'M
Polyether 13 [allyl
6.4%. OH (diol) 3.52%; allyl glycidyl ether (AGE) 48% by weight, E024% and P
028%]40. OOg and MD'M3 5.5 9g
I put it in. These preparations are allyl:SiH l:1
The stoichiometric ratio is shown. The contents of the reaction vessel were heated to 86°C and a CPA/ethanol solution (Ptl Omg/m(2) 0.2m4 (2
6 ppm). No reaction occurred after about 5 minutes. Next, add CPA/ethanol solution to the reaction vessel.
．． 2 mQ (26 ppm) was added. After a short induction period, an exotherm of 36°C was observed, and even if the reactor was placed in a water bath at the beginning of the exotherm, the reactor would remain in the il.
The temperature has reached 2°C. The reaction vessel quickly becomes transparent and brown;
. The temperature was reduced to 100°C and maintained at this temperature for 60 minutes, at which point the contents of the kettle were poured into moist NaHC○. (10%
Water) was neutralized with 5.5 g. The reaction vessel was heated for an additional 150 minutes.
The temperature was maintained at 0°C and the contents were then filtered through a 3-4μ filter bed. 62.22 g of product was collected (yield 8
2%). GPC showed a small amount of unreacted MD'M. However, GPC in the copolymer region (unimodal distribution)
The chromatogram was qualitatively identical to that of the raw material from Example 2. EXAMPLE l7.1%; MW (gpc)-
1020g/mol. AGE51% and E○49%; I3
Primary hydroxyl end by Cnmr 80%) 9 0.0
8g of HSi(OE)s3, 5.12g of HSi(OE)s3, and 175g of toluene were added. These materials are (SiH
(vs.) showed a 30% excess of allyl groups and 58% dilution with toluene. The reaction vessel was equipped as in Example 3 for the hydrosilanization step. Next, the reaction vessel was heated to CPA/
Dissolved in ethanol! (PtlOmg/n+Q) 0.
Contact was made at 20° C. with 5 mQ (17 ppm). The reaction vessel was heated to 110°C from the outside, and HSi (
○Et). 16.0 grams were reloaded and recontacted with CPA. No observable fever occurred. The system was neutralized with NaHCO3, held at l O O "C for 120 minutes, and filtered under 40 psi of N2. Distillation of toluene assisted by a N2 sparge began at 75 °C. However, the contents of the reaction vessel gelled during this distillation. Transesterification of the methoxyl groups with the primary hydroxyl groups of the polyether is likely responsible for the crosslinking reaction that occurred in the system. Example XIX HSi(OEt)s and polyether 9 HSi(○E
t). Two hydrolytically unstable inverse surfactants 1s-62 and IS, respectively, by hydrochylanation with Me
Preparation of -63 Clean 500 m (2 of 3 NRBF) The following charges were placed: Reactor Polyether 9 HSi(OEt), HS i(OEt) 2Me Toluene A (gm) 82.13 B (gm ) 79.55 25.41 20.88 46.86 43.66 (Polyether tan: allyl 7.67%; molecular weight (gpc
) = 4230 g/mol; AGE 2 2%: and EO
78%: Primary hydroxyl tip by Cnmr (
tip) 90%). In both cases, these charges were 1:1 stoichiometric ratio of allyl and SiH and 30% in toluene.
Represents dilution. The reaction vessel was equipped to carry out the process for hydrosilanization. The reaction vessel was warmed to 90°C, and then the CPA/ethanol solution (Pt
10mg/mQ) 0.3mff was charged. In both reactions, an 8°C exotherm occurred following an induction period of 10 seconds, 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 XX■, 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 Polyether 18 M D +xD 's. One attempt was made to produce a 1:1 adduct of a hydrosilanized multifunctional polyether and a SiH fluid in sM. The polyether was Polyether H with a nominal molecular weight of 1020 and an average functionality of 4.5. Silicones have an average functionality of about 5.5 MD, D's
,sM. The strategy is to use reaction conditions that best produce the l:l adduct, if possible. It has been recognized that crosslinking cannot be completely avoided even under optimal circumstances simply due to structural changes in both the polyether and the silicone which preclude the formation of l:l adducts. Nevertheless, conditions preferred for 1:1 adducts (high dilution) were used to the extent possible. The probability of failure for this experiment was considered high from the outset due to the prerequisites needed for success. 3NRB of looOmQ
In F, polyether 18 (allyl 17.1%; molecular weight (gpc) -1020 g/mol; AGE5i% and E
O (diol) 49%) 19.03g, MD,,D'. s M 17-51 g and toluene 331.
0g was added. This charge exhibited a 30% excess of allyl groups over SiH and a 70% dilution with toluene. The flask was equipped essentially as in I for hydrosilanization preparation. The solution was heated to 95°C and mixed with CPA/ethanol solution (P t l Omg/rrl ) 0.9 mff (
25 ppm). After a short induction period, an exotherm of approximately 7°C occurred. However, within 10 minutes, the entire reaction kettle contents gelled despite the high dilution with toluene. No further processing of this material was undertaken. EXAMPLE XXI SURFACTANT EVALUATION Three inversion surfactants (IS-15, IS-22, and IS-59) were added to two HR slab stocks (Sl
ab stock) formulation. The composition is as follows: Part Polyol E-547 H,O DEOA C-183 T-12 TDI (110 Index) Surfactant results are shown below: Part A 100.0 1 3.2 0J O ．． l5 0.05 41.0 0.2 Part B 00.0 3.2 068 0.15 0.05 38.8 0.2 Example xxn In all evaluations of inversion surfactants, several rigid urethane foam sets Thirty-nine reversal surfactants and mixtures thereof were evaluated in one. The composition is shown in the table below. The results are shown in Tables ① to ②. Example xxm Performance test method applied to high-resilience urethane foam using standard QC thermal formulations.
including an initial selection of different inverted silicone polyether copolymers. The mixing ratio and foaming conditions are shown in the table below. Table Ⅲ HR standard QC formulation and conditions Ingredients TD I (1 0 2 1) 8 0/2 0 Polyol 12-35 Polyol 34-28 Water A-1 DABCO/33LV DEDA Surfactant part 36.8 50.0 50.0 3, 0 0. IO. 5 0.9 Various! 1 184 250 250 15.0 0.5 2.5 4.5 Various Conditions: Mold Temperature Active Agents on Dimensional Control Surfaces of Vented Molds Surfactants were evaluated for their ability to stabilize the fine cell structure without pad shrinkage. The low and high end surfactant effective ranges (minimum and maximum surfactant concentrations that stabilize the bubbles and cause very little shrinkage, respectively) were determined for a potential system. Some of these reversal surfactants investigated showed promise. These contained MM' and MD'M as pendants. A typical problem is severe shrinkage [pad tightness] at the concentration required for bubble stabilization.
strength)] and consequently a very narrow concentration range. Example XXIV Determination of Reduction in Aqueous Surface Tension of Selected Inverting Surfactants In this example, the reduction in aqueous surface tension of various inverting surfactants produced by the method of the present invention was determined. The results obtained are shown in Table A below. Example XXv Contact Angle Measurement The known surfactant SILWET-L-7 is commercially available from Union Carbide.
A comparison of contact angles between T.S. 7 and a typical inversion surfactant (t.S.) of the present invention was made. The results are shown in Table B below. L1″)o 0 0 0 ro
o o b o o b 00 ”If 0
0 CI LO CN 0 LQ u"1roO) C
'J t-'s oNoro's 00--= (') 11C
N-11010:e:! : :I: :e :l:
O: Z gu ==== 工= 工= u:e = =:e GUCo Cn C:r V5 DimensionLi') Dimension u'z
V5 −ICo Co (n (N
('J CN ('J CN (N
+NC%! 01 l:') -m
Co (') − Co one (mcS3(') (O
CQ Ll') eo O') CQ dimensioncQ Ll
') Coichi
ToeI1) Sunto de Toro N Maroto 〇101 1-1 -cy's Low N's Dimension o To flash■〇1111111111cX3N Tree If possible, the structure is l) Oxide charge amount determined based on 2) gpc information 3) 1H and "C n m r results, and/or 4) analysis of % hydroxyl and % unsaturation. AGE = allyl glycidyl ether VCM - vinyl cyclohexene monoxide Silicone D.D'D,D'DsD'D,D'MM'MM'MM'MM'MM'D.D'MD'MMD' M MD'M MD' M MD' M D4o' f-1 D .D'''' RXN% Activator CL Wang ヱ 3.6 2.1 L H 6.3 3.7 1.9 H 9.2 5.7 2.3 H II 5.6 3.7 H 3.6 2.4 0 .7 H 6.3 4.3 1.3 H 9.2 6.2 1.8 H 11 6.7 2.6 H 3.6 2.4 0.7 Ac 3.6 2.2 0.9 Ac 3.6 2.4. 0.7 }] 6.3 4.3 1.3 H 9.2 6.4 1.6 H 11 7.5 1.8 }1 3.6 Ac 3.6 2.5 0.6 H 9. 2 6.2 1.8 Structure and supporting analytical data of 8' Molecular weight target Molecular weight gpc H 1615 1210}1
2880 +{ 1160 2940H
4830 3430H 1200
1250H 2130 21
80H 3090 3050}1
3580 3680Ac 151
0 1370Ac 1930
1500H. 1430 1440}+
2540 2430}1
3680 3350H 4270
3900Ac 1740 150
0H 1850 1600H
4750 3600 molecular weight OH Si
% target Si% weight analysis 1790 21.6
16.33120 21.6 4470 21.6 4150 21.6 9.914.5 14.5 l4.5 10.1 14.5 15,8 11.5 18.1 l8,4 l8,4 18.4 l8 ,4 15.0 23.6 23.6 L. S. No. Silicone 18 D4D"" 19 D. D"・) 20 MD'M 21 MD'lJ 22 D.D'(・) 23 MD'M 24 MM' 25 MM' 26 MM' 27 M.T' 28 1i137' 29 Viscosity T' 30 M, T' 31 D.D' 32 D.D' 33 D.D' 34 ReD'M 35 MD.M' RXN% 20!00 35 784 Chopsticks 1Δ (continued) V R R' 2 ■ H O.7 Ac Ac L.S} [H 1.LH}! 0.6+1}1 4.5HH 1.3}IH 1.7HH 3,6HH 3 .6+{H 3.3HH 5.7}fH 9.6HH O.21{H O.8HH OHH O Bu H O.7 H ■ Molecular weight target 5520 2l60 2040 3600 1850 6680 1700 3000 5570 2380 2380 4 200 7800 1850 2660 4690 5630 l660 Molecular weight gpc 4100 l630 l640 2800 1890 4700 l560 2600 4270 l400 I820 3760 l660 2700 4600 l725 Molecular weight OH Si% target 23.6 20.2 19.0 1 9.0 23.6 18.9 15.2 15.2 15 .2 21.7 21.7 21.7 21.7 23.6 24.3 24.3 6.9 2l,7 Si% weight analysis l5.3 l5.4 15.5 20.3 11,7 11. 1 12.4 9.6 lO.9 l2.2 24 23.7 23.l 5.1l l4 !.S.No. Silicone 36 MD,M' 37 M02M' 38 MD.M' 39 D2M' 40 (Eta )3SiH 41 (EtO)xsiMeH 42 (EtO)isiH 43 Et3SiH 44 Et3SiH 45 MD'M 46 MM' 47 D.D' 48 MM' 49 MD'M 50 D. D' 51 MD'M 52 D. D' 53 MM' RXN% '1.9HH 1.9H}! 1.5HH 3HH HH Bu H 3.6Bu H 9.3HH 5.8HH O. 9HH O. 7HH O. 2HH 1.3HH OHH O. 3HH 2.2HH O. 8HH 1.2HH -131- Molecular weight target 2380 4200 4270 7800 1210 5I40 5280 4910 2640 2350 2110 2780 3660 4070 4810 6050 7l50 5450 Molecular weight gpc l795 30 84 3960 5l60 5095 5370 3810 l820 l750 l675 l870 2700 2835 2925 4644 4960 4l40 Molecular weight OH Si% Target 20.6 20.6 21.6 20,6 Si% weight analysis 3.5 14.2 13.3 14.5 2.14 2,9 2 9.31 7.1 16.57 6.74 9, 67 15.41 9.5 14.14 6.86 Nuricorn MD2! J' MD 2M'MD2M' M, T'M3T' M, T' M. T'MD' M HSi(OEt)+HSi(OEt), MD' M 關'MD' M! JM'MM' D. D'MD' M MD' M RXN% 100 (c) 170 L Table ■ (continued) v R R' HH HH O. 8HH 2.3HH 3.8HH 2.2HH 6. lHH 4HH OHH QHH OHH 011H QHH OHH QHH OHH OHH OHI{ Molecular weight target 6660 2590 4480 2590 4480 1660 6660 6680 5480 5260 l290 l210 4290 4 020 5800 4790 6200 10660 Molecular weight gpc 4100 1600 2780 1170 l940 900 3020 3150 (b) (b) Molecular weight OH Si% target 13.8 l3.8 13.8 13.8 13.8 13.8 13.8 18.9 4.2 4.2 7.2 5.1 73 5.2 5,1 10.9 7.2 72 Si% weight analysis9. l2 9.12 11.8 10.4 4.8 4.8 4.8 16.8 Ko 1 Shin (continued)! ．． S. No. Silicone Polyether
M 10 (c) 18
0 2.1 0 H H73 M
M'3 (c)100
0 5.3 0 H H74 M
M' 4 (e) 170
0 9.1 0 H H75 M
D'lJ 12 (c)57
0 6.30 H H76 D,
D' 10 (c) 18
0 2. l O H H77
D. D' 12 (c)57
0 6.30 H H78 Da
D' l (c) 20
0 1-1 0 H H79 D
．． D' 4 (c) 170
0 9-1 0 H H80 D
．． D' 3 (c) 100
0 5.3 0 FI H81
(MeO)+SiH 18 (c)
+1 0 4.6 0 H H82
MDJ' 13 (C)
4 3-6 3-1 0! l
H83 MM' 21 (
c) 0.70 8.90 H H8
4 MD'M 13 (c
) 4 3.6 3-1 0 H
The H(a) D,D' source contains non-monofunctional SiH fluid impurities that cause some biological substances to deteriorate. (b) Sekimono is gelatinized. (c) NHR was not measured. RXN% is not determined: therefore Z and V are maximum 2 and minimum V Molecular weight target Molecular weight gpc l530 5800 9990 4680 1810 5530 l440 11880 69l0 1580 (b) l850 2370 l430 Molecular weight OH Si% target 11.6 5.1 5.1 11.3 16.3 16.0 10.7 10.8 lO. 8 8.2 23.5 21.1 18.3 Combined with Si% weight analysis. Department; pphp O. 60 0.60 0.60 Panel height: inch 9.51 8.31 8.66 Hard (PIP-37 Paddle weight: g 112.02 111.41 111.70 0.60 0.60 0. 60 0.60 0.60 0.60 0,60 16.50 11.50 13.70 6,20 9.70 0.00 0.00 113.05 111.27 112.08 109.10 111.17 111 .23 112.74 0.60 0.60 0.60 0.60 15.20 16.40 14.20 16.20 112.36 113.27 112.88 112.57 Rating 5 Flow coefficient K7 Acta 9.80 0.141 8.61 0.145 8.95 0.144 Density; pcf 2,60 2.74 2,77 11.06 9. l9 10.02 7.17 8.46 0.00 0.00 0.131 0.138 0.129 0.249 0.14i o. ooo o. ooo 2.03 2.71 2.51 3.44 2.64 0.00 0,00 10.60 11.00 10.15 11.02 0.129 0.147 0.131 0.141 2.33 1 ,99 2.49 2.01 Kotan 1 part; pphp O. 60 0.60 0.60 0.60 0.60 0.60 Panel height: inch 17.20 13.60 17.20 15.50 17.10 15.00 Panel weight: g 112.27 112.75 112.60 113.16 113.29 111.52 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 11.00 12. 50 14.50 15.00 15.00 15.80 16.25 16.21 14.80 15.50 15.80 110.29 111.60 110.18 111.83 111.85 113.87 112.07 112 .70 111.19 112.95 113.59 i (continued) Flow coefficient 11.42 9.92 11.38 10.64 11.27 10.60 K7 Actor 0.130 0.128 0.123 f) -125 0.127 0.132 Density; pcf 1,94 2.56 l996 2.27 1,98 2.30 9.07 +0.00 10.52 10.57 10.56 1 (L69 11.05 10.97 10 .54 10.66 10.72 0.156 0.159 0.130 0.125 0.125 0.125 0.135 0.126 0.128 0.130 0.126 2,89 2,51 2.42 2.3l 2.34 2.26 2,09 2.15 2,32 2,30 2.l7 Part ■ 1.5 number part; I) I) hl) 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 Pall height: inches 13.80 16.60 16.50 5.00 13.00 +5.80 13.70 13.50 0.00 Pap Weight; g 113.51 113.25 113.02 110.01 110.70 113.80 112.46 112.67 0,00 0.60 0.60 0.60 0.60 0.60 0. 60 0.60 12.00 12.50 14.10 11.50 11.30 9.00 8.50 109.96 112.20 111.76 111.54 111.37 111.53 106.26 Length (continued) Flow coefficient 9.93 11.05 11.06 6.6l 9.85 10.69 9.98 9.80 0.00 9.51 9.52 10.20 9.17 9.10 8,48 8.34 K factor 0.12g 0.123 0.126 0.205 0.140 0.129 0.129 0.122 o. ooo 0,35 0.35 0.122 0.34 0.132 0.146 0.137 Density; pcf 2,37 2,01 2.06 2.96 2.28 2.11 2.47 2.52 0 .00 2,55 2.53 2,36 2,66 2,71 2,89 2.67 Formulation No. Height: inch Weight: g11.20
110.2611. 30
112.37 o. oo o. o
o o. oo o. oo o. oo o. oo 0.60 12.63
109.4948 0.60
+4.00
110.8652 0.60
13.37 110.0
635'''' 0.60 13
．． 67 111.22(a) I
．． S. 85 is I. S. 48 and I. S. Weight of 52 5 0
/5 0 combination (continued) Flow coefficient 9.15 9,02 0.00 0.00 0.00 K factor 0.123 0.12g o. ooo o. ooo o. ooo Density; pcf 2.57 2.67 0.00 0.00 0.00 9.31 10.25 10.06 1008 0.129 0.136 0.120 0.124 2.30 2,33 226 230 ! ．． S. Number part; PI) hp 45 1.20 46 1.20 47 1.20 48 +. 20 49 1.20 50 1.20 51 +. 20 52 1.20 53 1.20 A-not measured -135- 5 Riiyu upper rainbow t. 36 1, 34 1, 34 1, 34 1, 35 1, 33 1, 35 1, 33 1, 35 K7 actor 0.55 0,59 0,63 0.55 0. +62 0,58 0.156 0.157 0.156 1. S. No. part; pl) hl) 55 1.11 1.11 Barrel height: inches 12.80 12.80 Notes (Continued) Barrel weight; g Flow coefficient 121.15 8.93 122. 79 8.81 1.67 1,67 1,67 1,67 1.67 I.67 1,67 1.67 15.20 10.30 13.00 14.90 15.20 13.90 12.30 12 .50 122.62 121.32 121.74 122.02 122.55 123.56 122.46 122.63 9.7l 7,98 8,96 9,65 9,72 9.l6 8.65 8.71 2.22 2,22 2.22 2.22 2.22 2.22 15.00 9.90 14.60 12.80 15.50 12.80 124.19 121.32 122.15 121.41 122. 42 121.39 9.52 7.83 9,53 8.9l 9.84 8,9l K factor 0.146 Mitsuri 2 2.58 Air bubble fixation 13 Wagihiki 4 0.144 2.58 13 4 0.1211! 0.148 0.130 0.139 0.142 0.130 0.143 0.141 2,22 3.07 2.32 2.72 2,26 2.46 2.67 2.63 0.127 0.151 0.130 0.136 0.134 0.132 2.l8 3,l3 2, 33 2.70 2.26 2.5l 1.S.No. Department; I)I)hl)55
2.22 56 2.22 Panel height: inch 11.20 12.50 Consideration (continued) Panel weight: g Flow coefficient 121.40 8.31 122.76 8.70 0.56 0,56 0 ,56 0.56 0.56 14.80 12.00 8,00 14.50 l000 121.79 120.38 119.36 122.06 120.27 9.63 8,68 7,24 9,30 7. 94 1.11 1.11 1.11 1.11 1.11 14.90 13.20 10.30 14.70 10.20 121.99 122.16 119.47 123.61 121.16 9.65 9 ,00 8,10 9,45 7.95 45 48 2.22 2.22 2.22 14.80 13.80 16.30 121.91 122.81 119.38 9.62 9.10 10.39 - 137- K7 Actor 0.140 0.141 Density; pcf 2.76 2.70 Air bubble fixation l5 l5 Kanto Sou 4 4 0.132 0.145 0.300 0.139 0.131 2.27 2.75 3,11 2,30 2.80 0.128 0.138 0.217 0.135 0.148 2,20 2.69 2,79 2,30 2.95 0.127 2.09 l7 0.136 2 .57 17 0.139 2.20 17 1. S. Number part: pphp O, 56 0.56 0,56 0.56 0.56 0,56 0.56 Paddle height: inches 14.60 9, 80 11.30 9.20 11.60 13.00 12.60 Hard (LS-49 Bainore weight; g 121.35 119.49 119.83 119.62 121.49 122.56 121.15 1.11 1, 11 1,11 1,11 1. 11 1, 11 1,11 1.11 15.40 to.so 14.60 13.50 15.30 13.80 13.50 +3.90 119.86 118.52 120.19 119.63 120.96 120 .77 119.60 120.91 Flow coefficient K-factor 9.59 0.130 7.91 0.140 g. 46 0.185 7.68 0.211 8.46 0.184 8.90 0.132 8J5 0.132 Density; pcf 2.36 2,99 2,82 3,05 2,74 2,65 2.73 10.01 8.25 9,60 9,31 9.80 9,33 9.31 9.36 0.129 0.143 0.135 0.134 0.130 0.126 0.126 0.125 2. 26 2.9l 2.4l 2.67 2.37 2,50 2,62 2.57 1.5. Number bar height: inch 5.30 0.90 4.60 3.10 5.00 4.00 3,40 3.70 Paper board L (continued Panel weight: g Flow rate 121.90 9. 81 120.15 8.20 121.80 9.55 120.98 9.05 120.29 9.82 121.53 9.35 120.15 9.23 121.95 9.21 2.22 2,22 2 .22 2.22 2.22 2.22 2,22 2.22 5.50 1,00 5.30 3.70 6,20 4.00 3.30 3.70 121.83 119.56 120.99 120.26 123.19 122.33 119.49 119.30 9.89 8.36 9.88 9.33 10.04 9.29 9,24 9,4] K factor 0.122 0.127 0. 126 0.129 0.130 0.126 0.127 0.127 Density; pcf 2.24 2.89 2, 44 2, 66 2,30 2,57 2.60 2.57 0.34 0,20 0 The present invention has been illustrated in the above examples. However, this should not be construed as limited to the materials used herein, but rather pertains to the general field as hereinbefore disclosed.Various modifications and embodiments of the invention can be made without departing from its spirit or scope. Features and aspects of the invention are as follows: 1. On average at least three radicals of the formula -SiR'.0(3-.)R" has 2 to 10 carbon atoms, and has at least one 2 to 10 group of O, N, and S, and is bonded to the main chain of the polyether through the aliphatic groups of O, N, and S. consisting of the polyester main chain, provided that R' represents 01 to C,, R" or OR";R" is S
+ R t Ou; and R III represents C.
-C. and in which a, b and C have values from 0 to 3, the silicone polyether copolymer surfactant having (a) a narrow unimodal distribution; (b) an essential silicone oil and process; The surface activity of the silicone polyether copolymer is characterized in that it does not contain polyether; and (C) any unreacted unsaturated groups on the polyether main chain are optionally inactivated. agent. 2. The above l having a molecular weight of about 650 to about 20,000
copolymer surfactant. 3. The above l having a molecular weight of about 800 to about 10,000.
copolymer surfactant. 4. The copolymer surfactant of item 1 above, wherein the polyether backbone is made in part from at least one alkylene oxide. 5. The copolymer of 1 above, wherein the polyether main chain is partially produced from at least one alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and at least one alkylene oxide containing olefinic unsaturation. Polymeric surfactant. 6. The copolymer surfactant of item 1 above, wherein the polyether backbone is made from an alkylene oxide containing olefinic unsaturation. 7. 5. The copolymer surfactant of 5 above, wherein the alkylene oxide having olefinic unsaturation is allyl glycidyl ether. 8. The alkylene oxy/ having olefinic unsaturation
5. The copolymer surfactant of 5 above, wherein d is vinylcyclohexene monoxide. 9. 5. The copolymer surfactant according to 5 above, wherein the alkylene group having olefinic unsaturation is 1,2-epoxy-3-butene. 10. The copolymer surfactant of 1 above, wherein the polyether backbone is essentially a homopolymer. 11. The copolymer surfactant of 1 above, wherein the polyether main chain is a copolymer. l2, the above l in which the polyether main chain is a terpolymer;
copolymer surfactant. 13. The copolymer surfactant of 1 above, wherein the polyether main chain is a random copolymer. 14. The copolymer surfactant of 1 above, wherein the polyether main chain is a block copolymer. 15. The following random or block repeating units [wherein R represents hydrogen, lower alkyl, acetyl, etc.; R' is C
, ~C,, R" or ○R", where R" is SiR
',04-e and R#' represents C1 to C, W has at least 2 carbon atoms, preferably 2 to IO, and within W or at the end of W connected to the polyether O,N
and at least one divalent group optionally containing 2 to 10 selected from S; a, b and C are O to 3, provided that C is preferably 2 or 3; and X and y are 0 or a positive integer; and 2 is an average value of at least 3]. 16. The copolymer of 1 above, in which the pendant silicone group is derived from MM'i. 17. The above copolymer 1 in which the pendant silicone groups are derived from MD2M'. 18. The copolymer of 1 above, wherein the pendant silicone groups are derived from M D , M'. 19. The copolymer of 1 above, wherein the pendanton silicone group is derived from MD'M. 20. The above copolymer 1, in which the pendant silicone groups are derived from M and T'. 21. The pedant silicone group is D. The above copolymer derived from D'. 22. The above copolymer 1, in which the pedant silicone groups are derived from D and D'. 23, the pendant silicone group is HS1 (OEt)
The copolymer of the above 1 derived from 3. 24. The pendant silicone group is HSi(○Me)s
The above copolymer derived from 1. 25. The pendant silicone group is H S i M e
A copolymer of the above 1 derived from (○Et)2. 26. The pendant silicone group H S iE t3
The above copolymer derived from 1. 27. A polyether copolymer having on average more than two pendant unsaturated groups is hydrosilanized with a silicone compound having only one group that reacts with the pendant unsaturated groups in the presence of a catalytic amount of a hydrosilanization catalyst. 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;
the copolymer surfactant has a ratio of unsaturated groups to (a) a narrow unimodal distribution; (b) is essentially free of silicone oil and process polyether; and (c) the polyether backbone characterized in that any of the above unreacted unsaturated groups is optionally inactivated,
A method for producing a silicone polyether copolymer surfactant according to claim 1. 28. The polyether is a repeating unit [wherein R' to R6 are hydrogen or lower alkyl, and 2
represents a hydrocarbon group having 1 to 6 carbon atoms and optionally containing heteroatoms such as O, N and S; d has a value of 0 or 1; n has a value of 1 to 6; and m has a value of O or a positive integer; and W has an average value of at least 3]. 29. The pendant silicone has the following formula: SIR'aOtsR" [wherein R' represents CI-03, R" or OR~;
R' is S+Rt04-. represents: and R#' is C1
~C, and a, b and C have a value of O~3. 30. 29. The method of 29 above, wherein the polyether backbone is essentially a homopolymer. 31. 29 above, wherein the polyether main chain is a copolymer. 32. The method of 29 above, wherein the polyether main chain is a random copolymer. 33. 29 above, wherein the polyether main chain is a block copolymer. 34. 29 above, wherein the pendant silicone group is derived from MM'. 35, the pendant silicone group is MD. The method of 29 above derived from M'. 36. 29 above, wherein the pendant silicone group is derived from MD, M'. 37. 29. The method of 29 above, wherein the pendant silicone group is derived from MD'M. 38. 29. The method of 29 above, wherein the pendant silicone group is derived from M, T'. 39. The pedant silicone group is D. The method of 29 above derived from D'. 40. 29 above, wherein the pendant silicone group is derived from D4D'. 41. The pendant silicone group is HSi(○Et).
The method of 29 above derived from. 42. The pendant silicone group is HS1 (OMe)
．． The method of 29 above derived from. 43. The pedant silicone group is HSiMe(○Et
) The method of 29 above derived from 2. 44. The pendant silicone group is H S iE t,
The method of 29 above derived from. 45. 29 above, wherein the hydrosilanization catalyst is chloroplatinic acid. 46. A slab of high modulus polyurethane 7 ohm made from a formulation comprising at least one surfactant as defined in 1 above, namely a silicone polyether copolymer surfactant. 47. A high modulus rigid urethane 7 ohm made from a formulation comprising at least one surfactant of I above, namely a silicone polyether copolymer surfactant. 48. High modulus molded polyurethane foam made from a formulation comprising at least one surfactant as defined in 1 above, namely a silicone polyether copolymer surfactant. 49. A wetting agent composition comprising the silicone polyether copolymer of item 1 above.

[Brief explanation of the drawing]

FIG. 1 shows a gel permeation chromatograph of a typical conventional surfactant preceded by a silicone precursor, and FIG. 2 shows a gel permeation chromatograph of a surfactant of the present invention preceded by a silicone precursor. -Shows permeation chromatography.

Claims (1)

[Claims] 1. On average, the formula -SiR'_aO_(_3_-_a_)_/_2R″_
At least three pendant groups of b form the main group of the polyether through divalent aliphatic groups having 2 to 10 carbon atoms and optionally containing at least one heteroatom of the group O, N and S. consisting of the polyether backbone attached to a chain;
However, R' represents C_1 to C_3, R'' or OR''';R'' represents SiR_cO_4_-_c_/_2;
and R''' represents C_1 to C_3; and a, b, and c have values of 0 to 3, the silicone polyether copolymer surfactant having (a) a narrow unimodal distribution; (b) The silicone is essentially free of silicone oil and process polyether; and (c) any unreacted unsaturated groups on the polyether backbone are optionally deactivated. Polyether copolymer surfactant. 2. A polyether copolymer having an average of more than two pendant unsaturated groups is reacted with the pendant unsaturated groups in the presence of a catalytic amount of a hydrosilanization catalyst. hydrosilanizing with a silicone compound having only one group such that the ratio of silicone-containing groups to the copolymer pendant unsaturated groups forms a plurality of silicone-containing groups along the copolymer backbone. and that the resulting polyether copolymer surfactant has (a) a narrow unimodal distribution; (b) essentially free of silicone oil and process polyether; and (c) A method for producing a silicone polyether copolymer surfactant according to claim 1, characterized in that any unreacted unsaturated groups on the ether main chain are optionally inactivated. .