MXPA99003058A - Continuous manufacture of silicum copolymers - Google Patents

Abstract

The present invention relates to a continuous process for producing silicone copolymers, with the use of a series of at least one stirred tank reactor, the last of these reactors in the series has a crude product stream, which feeds at least one reactor of cylinder flow, in which this stream of the crude product is sufficiently homogeneous, so that this current upon undergoing a further reaction in the cylinder flow reactor, does not undergo a separation of fa

Description

CONTINUOUS MANUFACTURE OF SILICONE COPOLYMERS FIELD OF THE INVENTION The present invention relates to a process for the continuous production of silicone copolymers and to the novel products produced by the process.

BACKGROUND OF THE INVENTION Silicon copolymers serve as agents that decrease surface tension in agricultural auxiliaries, stabilizers for polyurethane foam, additives for coating applications, defoamers and emulsifiers. The efficient manufacture of silicone copolymers is convenient for two primary reasons - lower cost and less waste. If, in the addition, the equipment necessary for that method or process is less expensive to build, such a method or process will be inherently attractive. Also, there remains the need for a process to prepare silicone copolymers that provide desired properties in the application for which they are intended, this process would offer manufacturers the flexibility to produce product variations, determined by the selection of the manufacturing method.

The chemical reactions can be conducted in a batch form, in a continuous form or in a hybrid form (partially batch or partially continuous). For example, the reagents necessary to prepare a silicone copolymer may be a silicone fluid containing one or more hydrogen atoms, directly attached to the silicon (referred to as a hydrogen siloxane or SiH fluid); and an olefinically-terminated compound (hereinafter referred to as an olefinic compound). The two components are mixed together in the appropriate amounts, and, while stirring sufficiently, the catalyst is added. A vigorous reaction results and the olefin, by hydrosilation, becomes chemically bonded to the silicone. Because most cases, the hydrogen siloxane fluid and the olefinic compound are immiscible, a compatibilizing agent is often used to facilitate the reaction. This agent is often called a solvent, although it is not necessary to use it in sufficient quantity to dissolve both components. If the hydrogen siloxane fluid and the olefinic compound are sufficiently pure of minor trace components, the amount of the "solvent" may decrease, in some cases to zero. However, in those cases, a good agitation becomes even more important, to maximize the contact between the two immiscible (relatively) phases. The reaction between the raw materials does not need to be conducted in a purely batch form. For example, if the reactivity of the hydrogen siloxane fluid is very high, the olefinic compound can be charged to the reactor as a whole, a fraction of the hydrogen siloxane fluid can be charged, the reaction catalyzed by adding a catalyst solution of a noble metal, and the remaining hydrogen siloxane fluid is subsequently added to such a regime, that, after the initial exothermic reaction has begun to subside, the reaction is kept under control. This process is sometimes called de i-lots, or semi-continuous (incorrectly). If both the hydrogen siloxane fluid and the olefinic compound are only partially added initially, and then all the components are added continuously, after starting the reaction, and added until the reactor is full, the reaction is called (correctly ) semi-continuous. In fact, the continuous reaction of the hydrogen siloxane fluid and the olefin, therefore, has not been successfully achieved. This is for several reasons, which will be listed in detail.

There are two main types of continuous reactors for liquid phase systems: continuous stirred tank reactors (known as CSTR) and cylinder flow reactors. In the CSTR, it is inherent that not all reagents can be completely consumed. Nevertheless, the silicone copolymer, which contains an unreacted hydrogen siloxane fluid, is not suitable for obtaining many commercial products. These CSTR by themselves are not good for obtaining silicone copolymers. The presence of the above-described unreacted hydrogen siloxane fluid leaving a CSTR reactor can be avoided by the use of a cylinder flow reactor, where and if there is no continuous mixing, a siloxane fluid of The immiscible hydrogen and the olefinic compound will separate into phases very rapidly, immediately after the initial mixing, thus causing the reaction to proceed more and more slowly. In fact, the reaction ceases rapidly without the current agitation, and then stops proceeding, even with renewed agitation, this effect is believed to cause a gradual irreversible deactivation of the catalyst. Thus, neither of the two standard continuous reactor systems alone is effective in the manufacture of the silicone copolymers.

COMPENDIUM OF THE INVENTION Silicone copolymers, which exhibit improved properties, can be manufactured continuously by the use of a series of at least one CSTR followed by at least one cylinder flow reactor. It has been found that silicone copolymers, produced in this continuous form, can have certain markedly different properties from those analog copolymers produced in batch form. Thus, a process for producing silicone copolymers is taught has the steps of: (a) continuously feeding the hydrogen siloxane, an olefinically substituted compound, capable of reacting with the hydrogen siloxane, and a catalyst for the reaction, at least one (1) continuous stirred tank reactor (CSTR) in series and continuously removing from the last CSTR in the series, a stream of raw product, containing the silicone copolymer and the unreacted hydrogen siloxane and the olefinic compound,, with the condition that the hydrogen siloxane and the olefinic compound are reacted in the series of the CSTR by a sufficient extension so that the stream of the crude product is sufficiently homogeneous, that is to say, does not suffer a phase separation in step (b), and (b) continuously feeding the stream of the crude product to at least one cylinder flow reactor, from which the product is withdrawn.

BRIEF DESCRIPTION OF THE DRAWING Figure 1 is an exemplary production system for the manufacture of silicone copolymers.

DETAILED DESCRIPTION OF THE INVENTION Continuous systems are smaller than batch reactor systems, are less expensive, contain less product, are easier to clean, generate less waste (if cleaning is performed between the use of the reactor system to obtain two different products), and less material is lost from the "lift" of the equipment, thus the overall efficiency is higher. From an operational perspective, continuous systems are also more "controllable" in the sense that the extent or degree of reaction is determined primarily by the design of the reactor or equipment, as opposed to the time elapsed. Neither the CSTR reactor nor the cylinder flow reactor, alone, provide for the continuous manufacture of suitable silicone copolymers, however, when used in combination, the reactor system of the present invention is surprisingly effective in bringing the reaction to its complete state, without undergoing the phenomenon of phase separation and the resulting copolymer provides additional unanticipated benefits. The present invention is applicable to any hydrosilation reaction, typically catalyzed, between a hydrogen siloxane (or SiH fluid) and an olefinically unsaturated compound (hereinafter referred to as the olefinic compound). The hydrogen siloxane can be an organic hydrogen siloxane which comprises any combination of siloxane units, selected from the group consisting of R3Si0j, R2HSiO ^, R2SiO2 2 RHSiO2 / 2, SiO4 / 2 »HSii3 / 2 and RSi? 3/2 # with the proviso that the hydrogen siloxane contains enough siloxane units containing R, to supply an average of 1.0 to 3.0 R radicals per silicon atom and sufficient siloxane units containing H, to supply 0.01 to 1.0 hydrogen atoms attached to silicon per silicon atom and a total of R radicals and hydrogen atoms attached to the silicon from 1.5 to 3.0 per silicon atom. Alternatively, where M = (R) 3SiO? / 2 »M '= (R) 2HSiO? / 2 / D = (R) SiO, D1 = (R) HSiO, and x and y are integers, the preferred structures of the SiH fluid will be MDxD'yM, where x and y are in the respective ranges of 0 < x < 160, 1 < and < 40, and l < + and < 200, and MDxD'yM 'or M'DxD'yM', where x and y are in the respective ranges of 0 < x < 160, 0 < and < 40 y (x + y) < 200. The polymer formulas given herein and elsewhere herein, such as MDxD'yM, will be understood to represent average compositions of statistical polymers, unless otherwise mentioned. The preferred SiH fluids are trisiloxanes of MD'M and M'DM1. Each group R is independently the same or different and represents a hydrocarbon radical or an alkoxy or polyalkylenoxy radical. Illustrative of the appropriate R-radicals are C¿ to C12 alquilo alkyl radicals (such as methyl, ethyl, propyl, butyl, isopentyl, n-hexyl and decyl); cycloaliphatic radicals containing from 5 to 12 carbon atoms (such as cyclohexyl and cyclooctyl); aralkyl radicals (such as phenylethyl) and aryl radicals (such as phenyl optionally substituted with 1 to 6 alkyl groups with up to 6 carbon atoms, such as tolyl and xylyl). Also illustrative radicals R are C1 to C12 alkoxy radicals, such as methoxy, ethoxy, propoxy, butoxy and decyloxy; and polyalkylenoxy radicals, such as CH3? (CH2CH2?) to (CH2CH (CH3) 0) b- in which the subscripts a and b can be from 0 to about 200 and a + b > 0. The preferred radical R is methyl.

The SiH fluids are typically fluid with a hydrogen content (measured by the reaction with an aqueous strong base, to release the hydrogen gas) of about 5 cc / g to 334 cc / g. The viscosities of the fluids can vary from less than 1 cstk (centistoke) to more than 300 cstk (at 250C). The structures of these fluids vary from pure monomer, such as 1,1,2,2-tetramethyldisiloxane (M'M ') to a polymeric, balanced fluid having a MDisoD'ioM structure. The siloxanes blocked at the dimethylhydrogensiloxy end may also be used to prepare linear block copolymers, sometimes referred to as structures (AB) n. The SiH fluids can be mixtures of fluids of different molecular weights and molecular structures. This does not appear to limit the structure of the hydrogen siloxane in addition to imposing (practical) handling aspects such as viscosity, and the desired properties of the copolymer product. The reactive substituent is an olefinically substituted part. Preferred is an olefinic compound of a polyoxyalkylene reagent, corresponding to the formula R1 (OCaH2a) nOR2, it will be understood that the polyoxyalkylene part can be a block or random copolymer of oxyethylene, oxypropylene or oxybutylene units and is typically a mixture of molecules of various chain lengths and compositions. In the above formula, a is from 2 to 4 per unit, n is from 1 to 200, R 'denotes an alkenyl group (preferably an α-olefinic group) containing from 3 to 10 carbon atoms and more preferably a allyl or metalyl group; and R2 denotes a monovalent radical, preferably hydrogen, an alkyl group containing 1 to 5 carbon atoms, an acyl group containing 2 to 5 carbon atoms, a 2-oxacycloalkyl group with 4 to 6 carbon atoms , or a trialkylsilyl group. Alternatively, if it is desired to prepare a copolymer of type (AB) n, R2 can be an alkenyl group (preferably an α-olefinic group) containing from 2 to 10 carbon atoms and more preferably an allyl or methallyl group. Preferred structures of olefinically unsaturated polyether reagents, used, may typically vary from polyalkyleneoxide monoallyl ether of nominal molecular weight of 204 Daltons, all of ethylene oxide, up to 8,000 Daltons of ethylene oxide, 60% of propylene oxide, up to 1500 Daltons all of propylene oxide or 1500 Daltons, all of butylene oxide. If the polyether is capped (for example, a methyl ethyl ether) or unfinished (for example a monoalyl ether) it is immaterial. If the polyether is not capped, it is preferred that an appropriate regulating agent be present, such as any of those described in the U.S. Patent No. 4,847,398, the disclosure of which is incorporated herein by reference. Other olefinically unsaturated olefinic compounds, useful herein, are olefin-initiated alkenes (for example, 1-octene, 1-hexene, ethylene, vinylcyclohexane), an alcohol initiated on olefin, an epoxide substituted with olefin (e.g. glycidyl ether or vinylcyclohexene monoxide), a vinyl substituted alkylamine, a halogenated alkane initiated with olefin, allyl methacrylate, a vinyl initiating nitrile (for example acrylonitrile) or an acetylenically unsaturated material (for example butylated diol). Other specific examples include 4-methyl-1-pentene, styrene or eugenol. Multiple olefinic compounds can be used in a copolymer. For example, ethylene is sometimes used with an allyl polyether to improve compatibility as a surfactant of a polyurethane foam; the vinylcyclohexane monoxide is used as a co-reactant with the allyl polyether, to form a terpolymer used in the softening of textiles, and the eugenol and a polyether are used with a hydrogen siloxane fluid, to produce an antifoam copolymer of Diesel.

The reagents are preferably purified and dried. No non-compatibilizing agent or "solvent" is necessary, but low levels can be added without compromising the effectiveness of the process. However, in that case, a solvent separator system will need to be incorporated; or the solvent will remain in the copolymer product. As previously indicated, the hydrosilation reaction is conducted in the presence of a hydrosilation catalyst, preferably containing a noble metal. Thus, the hydrosilation reaction between the hydrogen siloxane and the olefinically unsaturated reagent is facilitated by the use of catalytic amounts (or effective amounts) of a catalyst containing a noble metal. Such catalysts are well known and include the compounds containing platinum, palladium and rhodium. They are reviewed in the Comprehensive Handbook on Hydrosilylation. edited by B. Marciniec and published by Pergamon Press, NY 1992. In general, platinum catalysts are preferred, and chloroplatinic acid and platinum complexes of 1,3-divinyltetramethyldisoloxane are particularly preferred. The catalyst is used in an effective amount sufficient to initiate, sustain and complete the hydrosilation reaction. The amount of catalyst is usually within the range of about 1 to 100 parts per million (ppm) of a noble metal, based on the total parts of the mixture of the reactants and the solvent. Catalytic concentrations of 2 to 20 ppm are preferred. The hydrosilation reaction may be conducted, optionally, in the presence of additives (or "regulatory" agents) such as the carboxylic acid salts described in U.S. Patent No. 4,847,398. In that patent, the use of the "regulatory" salts is described, these salts have the effect of preventing the dehydrocondensation of the hydroxyl groups with the SiH part. The salt is previously dissolved, preferably in the polyether, before introduction into the CSTR. The concentration used, the salt or other regulator selected and the expected effects are specific processes. The hydrosilylation reaction can be carried out, opsionally, in the presence of sterically clogged nitrogen compounds, disclosed in US Patent No. 5,191,103, or the phosphate salts disclosed in US Pat. No. 5,159,096. . Depending on the manufacturing method, and in the nature of the reagents, one or more of these additives may be present during the hydrosilylation reaction. For example, a low, but sometimes adequate, level of the carboxylic acid salts or the phosphate salts may already be present in the olefinically substituted polyoxyalkylene, followed by the finishing of the initiator polyoxyalkylene with allyl and hydroxyl terminated, with the allyl, metalyl, methyl or acyl groups, or due to the neutralization of basic catalysts with phosphoric acid. In such cases, the use of the additional salt or other additive may not be necessary in achieving the desired effect. A potential product is a silicone polymer of the structure M * DxD * and M *, in which M * is Si01 / 2 (CH3) 2R * or 01 / 2Si (CH3) 3; D is as before; R * is derived from the olefinic compound, discussed above, by the addition of a Si-H bond through an olefin part of the olefinic compound, wherein each * may be the same or different; and x and y are as before. Alternatively, if a copolymer of type [AB] n is produced, it will be of the structure [-B [Si0 (CH3) 2] n] m »where B is the substituent (except derivative of a diolefin or a starting material) difunctional), n is from 1 to 500 and m is from 2 to 500. Likewise, variations of the above structures, for example, using cyclic siloxanes, or using branched siloxanes, containing YES4 / 2 »SÍHO3 / 2 or Si ( CH3) ° 3 / 2f can be produced.

Equipment The present invention is carried out using at least one, and preferably two, continuous agitated tank reactors (CSTR) in series. They can be of any conventional design, effective in carrying out the desired reaction. Each one is equipped with an inlet for the reactants, an outlet for the product stream, and an agitator. The output of at least the last tank reactor stirred in series is connected to the inlet of a cylinder flow reactor, which can be of a conventional design, effective in carrying out the desired reaction. The term "clogged flow reactor" includes its functional equivalent, which may be in series with the CSTRs, although a clogged flow reactor is preferred. See Hill, An Introduction to Chemical Enqeneerins Kinetics and Reactor Desiqn, pages 279-299 (1977), which is incorporated herein by reference. The number of CSTRs will depend somewhat on the identity of the particular reagents and the desired production rate. For some cases, it has been found that one CSTR is sufficient, for example in trisiloxane fluids. For most reactions, the formation of the desired silicone copolymer proceeds at a rate such that two CSTRs are necessary. In other reactions, three or even four (and rarely more) CSTRs are necessary. The number of CSTR needed is generally related to the "clear point" of a reaction in batches of the reactants, as discussed below. In any case, the output of the first CSTR is fed directly to the input of the second CSTR, the output of the second CSTR is fed directly to the input of the third CSTR, if present, etc. The design of CSTRs and cylinder flow reactors are well known in the art and is summarized, for example, in "An Introduction to Reactor Design and Chemical Engineering Kinetics", John Wiley & amp;; Sons, NY, 1977, pages 245 to 304. With reference to the Figure, there is a charge line 1 of the hydrogen siloxane fluid, a charge line 2 of the olefinic compound and a charge line 3 of the catalyst. It is preferred to preheat the olefinic compound in a heat exchanger 4. There is a first CSTR 5, which has a product withdrawal stream 6, which feeds a second CSTR 7, optionally present. The output stream of the second CSTR 8 is fed to the cylinder flow reactor 9, which feeds 10 to the product separator 11. The light products are removed 12 while the heavy products 1 are cooled in a heat exchanger 14. The final copolymer product can be collected in the store 15.

Operation In steady state, the reagents are continuously fed into at least the first CSTR in the series. The catalyst can also be fed continuously, or intermittently. As will be described more fully below, one or both additional reagents and / or catalysts can also be fed to the second and / or successive CSTR. Preferably, the total amount of the olefinic compound (s) fed to the process, represents a stoichiometric excess based on the total amount of the hydrogen siloxane fed, since it is preferred that the product of the silicone copolymer contain no more than trace amounts. of unreacted hydrogen siloxane (ie, less than 0.1 cc / g hydrogen content, as described above) and preferably without unreacted hydrogen siloxane at all. The current leaving the first CSTR and entering the second CSTR (if used) contains reaction products or partial reaction products (ie molecules that still contain some parts of the SiH), unreacted hydrogen siloxane and olefin, and amounts of the catalyst, and its reaction continues in the second CSTR. If the residence time in the CSTR series is prolonged, the catalyst may no longer be active when the reaction mixture enters the cylinder flow reactor. The time required for this to occur is dependent on variables, such as the identity and purity of the olefinic compound, and is thus peculiar to each individual reaction system. However, in general, it is convenient to have not less than 50% by weight and not more than 90% by weight of the reactant limiter reacted at any given CSTR. The rest of the reaction will be completed in the cylinder flow reactor. Optional additional catalyst may be added after the first CSTR, ie the second u, optionally third or other CSTR, to achieve a higher degree of reaction. In a preferred embodiment, the reaction proceeds in the CSTR series to such an extent that the stream (referred to as the "raw product stream") leaving the last CSTR is homogeneous. The flow of the crude product is considered to be sufficiently homogeneous if it does not undergo aseperation as it continues to react under laminar flow conditions in the cylinder flow reactor. It has been found, very surprisingly, that this degree of homogeneity can be achieved in the series of the CSTRs despite the incompatible natures of the hydrogen siloxane and reactants of the reactive olefinic compound, and in spite of the fact that there may be residual amounts of hydrogen silane and unreacted olefinic compound, in still the last of the series of two or more CSTR. It has also been found, all very surprisingly, that even if it is visibly turbid when it leaves the last CSTR, the stream of the crude product does retain homogeneity through the cylinder flow reactor. The point at which the crude product reaches homogeneity, often corresponds to a conversion of 60 to 75%, although sometimes less, of the hydrogen siloxane to the silicone copolymer. This point is sometimes called the "clear point". The number of CSTRs required in the series is generally related to the clear point of a batch reaction, conducted in the same reagents as will be used in the continuous process of the present invention. If the clear point occurs in less than 50% reaction, a single CSTR in the would be sufficient. However, for general processes of a variety of copolymers, a series of at least two CSTRs is preferred, to achieve the degree of homogeneity described above. In those cases where the clear point occurs at more than 90% reaction, a third CSTR may be required. If the stepwise addition, described below, is used, then a third reactor may be required. However, unless stepwise addition is desired, a third reactor is generally not required. Decreasing flow rates to the first CSTR, a third CSTR can be avoided, however, due to the phase separation that will occur before the clear point, it is preferable to use a second CSTR. To help ensure that the product stream has passed the clear point, it is preferred to carry out the reaction in a series of CSTR under conditions such that the stream that flows immediately after the last tank of the series is visibly homogeneous. As noted, the stream still contains unreacted material and thus continues to react in the last CSTR even after having obtained homogeneity. Since deactivation of the catalyst proceeds rapidly at the end of the reaction and because in an idealized CSTR, some of the unreacted components are always present in the leaving mixture, it is preferred that the termination of the reaction occurs in the Cylinder flow system. Thus, the stream of the crude product need not be taken exhaustively to complete the reaction in the CSTR series, to form the silicone copolymer. The cylinder flow reactor must have a flow regime such that a laminar flow exists there. The spatial time (t) and, therefore, the size of the reactor, depend on the catalytic concentration used. The temperature must be the same as, or greater than, the last CSTR. Thus, in one embodiment of the invention, a polyether or olefin, or both, and a hydrogen siloxane fluid, are dosed in a first CSTR, and the temperature of the contents is raised to and maintained between 45 and 1352C. When the first CSTR is half full until full, the flow of the hydrogen siloxane fluid, polyether and olefinic compound is stopped, and the catalyst is added rapidly, a sufficiently large aliquot initially to take all the contents to the desired concentration of noble metal or other active catalytic species, and then only enough to maintain that concentration. After the addition of the catalyst, an exothermic reaction is observed in the first CSTR. After the temperature has reached the desired set point, the flow of the catalyst, the hydrogen siloxane fluid and the olefinic compounds within the reactor begins again, and at the same time or later, the flow begins to exit the first CSTR optionally. in the second CSTR of equal or similar size. The second CSTR is maintained at an effective reaction temperature, usually the same or greater than the first, but preferably within 252C of the temperature in the first CSTR. Once the second CSTR is full, the flow optionally begins in the same way through the third and, optionally, subsequent CSTR or preferably directly to the rinsing cylinder flow reactor, with volume equal to or greater than the previous CSTR. , and it remains within the same temperature range, usually the same as or hotter than the second CSTR. Once the cylinder flow reactor is full, optionally the flow goes to a conventional separator unit to remove volatile trace substances, reducing odor and flammability, or the product can be collected and further processed as, for example, by filtration or separation elsewhere, if necessary. The copolymer leaving the reactor of the cylinder flow does not require any further reaction to be suitable in its use. If a third CSTR is used, it is first filled and then the flow exits to the cylinder flow reactor, as described above. A third CSTR can help to obtain the phase compatibilization by vigorous mechanical agitation for a longer period or to allow the further reaction to be completed if the stepwise addition (discussed below) is employed in the second CSTR. The need for a third CSTR will become evident if a sample of the reaction mixture leaving the second CSTR shows evidence of phase separation - for example, the development of two distinct phases; or if, in the centrifugation to remove air bubbles, the sample remains cloudy. In a preferred embodiment of the reactor system, recirculation loops are provided between the output of the prime CSTR, back to the inflow and from the output of the second CSTR (if used) _ back to the inflow of the first CSTR. Such a recycle stream can be used during startup to reduce reactor size requirements, or to return the product to an earlier CSTR in the series. Thus, an infrared monitor or other monitor detects if the remaining hydrogen content is bonded to the silicon of the output stream of the second CSTR is above a tolerable level and if so, the flow to the outside may be partially or completely recycled back to the first CSTR, which prevents the occurrence of a phase separation in the cylinder flow reactor. The recycle loop from the flow to the outside of the first CSTR back to the inflow can be monitored by the IR detector as well, but is not routinely used in this mode. Rather, it is used during startup to ensure that the reaction has progressed sufficiently before filling the second CSTR. In the most preferred embodiment, a third CSTR is required only if stepwise addition is practiced (described below). In the present invention, the consistent introduction of a second olefinic compound is easily achieved, it can be added to the second CSTR. Because this second component is not present in the first CSTR, the reaction in the first CSTR must occur only between the hydrogen siloxane fluid and the first olefinic compound. Upon entering the second CSTR, the second olefinic compound is available to react with the hydrogen siloxane fluid, along with any unreacted first olefinic compound. Of course, it is not necessary to add any olefinic compound exclusively to a CSTR, this can be fed to two or more CSTR in different ratios. If stepwise addition is used, it is generally preferred not to add any additional reagents to the last of the CSTR series. Thus, in a configuration of three CSTR, the reactants will be added to the first the second CSTR, in the desired proportions, but not to the third CSTR, the hydrosilation reaction can thus effectively extend to the required degree of homogeneity (as discussed below).

Similarly, it becomes apparent that a second different hydrogen siloxane fluid can be introduced in a similar stage form. In fact, any combination of reagents can be combined in the form in stages, and the silicone copolymer product can be obtained in much more reproducible and consistent form than can be achieved in a batch mode, unless the desired products can be obtained in separate batch reactions and then combined after the reactions are complete. The copolymers of the present invention can be used as surfactants, defoamers, agricultural auxiliaries, textile finishes, reactive diluents, coating additives, soaking agents, hydrophobicity agents, inter alia, as will be clear to one skilled in the art. . Some of the copolymers produced by the processes described above are unique and can differ significantly in their properties from the copolymers that are obtained from the same reagents in batch processes. One way in which this unique shape appears is in the performance of the copolymer in the production of the polyurethane foam. The silicone copolymers, obtained according to the present invention, can be used in the production of a polyurethane foam, in the same way as for the known silicone copolymer surfactants. Thus, a foaming mixture is formed, comprising a polyol component, a polyisocyanate, one or more catalysts, an optional auxiliary blowing agent, and the surfactant agent of the silicone copolymer. the composition reacts to produce the polyurethane foam. Compared to the copolymer produced in batches, a continuously produced copolymer can supply a flexible polyurethane foam having a much higher content of open cells. With the copolymer made by the continuous process, it seems to have a wider range of power versus the ability to breathe (ease of air flow through the foam); the foam made with this copolymer remains soft and flexible throughout the molecular weight range of the surfactant, which is practical based on other considerations, such as viscosity. Thus, by producing the copolymer in continuous form, according to the present invention, the manner of the combination of the hydrogen siloxane fluid with the olefinic compound, appears to have been unexpectedly altered, consistent with the observed change in the ability to breathe. This discovery, that the mode of synthesis of the copolymer affects the ability to breathe thereof, provides the very significant advantage that the continuous process of the present invention particularly in contrast to the batch mode - can be purposely modified to cause any of a variety of desired copolymer structures. This aspect can be achieved by carrying out the process of the present invention, using the modality named here as the "stepwise" addition of the reagents. The continuous manufacture of the polymer offers a significant new opportunity to consistently vary the distribution of pendant groups in the copolymer and thus "adapt" the properties to increase the desired characteristics in the application. When stepwise addition is used, a third CSTR is preferred, which allows a higher degree of completion of the reaction, before the mixture enters the cylinder flow reactor. It is also preferred in such cases to add reagents in all CSTRs, as well as in the latter.

EXAMPLES While the scope of the present invention is set forth in the appended claims, the following specific examples illustrate certain aspects of the present invention and, more particularly, indicate methods for evaluating same. It will be understood, therefore, that the examples are designated for illustration only and should not be construed as limitations on the present invention. All parts and percentages are by weight, unless otherwise specified. The following test procedures were used to evaluate the products obtained in the examples.

FOAM TESTING Unless indicated otherwise in the Examples, polyurethane foams were prepared according to the general procedure described in Urethane Chemistry and Applications, KN Edwards, Ed. American Chemical Society Symposium, Serial No. 172, ACS, Washington, DC (1981) page 130, and J. Cellular Plastics, November-December 1981, pages 333-334. The basic steps in the procedures for mixing and foaming the blown polyurethane foam on a laboratory scale are: 1. The ingredients of the formulation were weighed and ready to be added to the predetermined sequence in the mixing container. 2. The ingredients of the formulation (with the exception of the polyisocyanate) were thoroughly mixed and allowed to "degas" for a prescribed time, an auxiliary blowing agent, in addition to water, can be added (if such an auxiliary agent is used), before mixing. The polyisocyanate was added and the formulation mixed again. The mixed formulation was rapidly emptied into an open container at the top, such as a disposable plastic bucket with the top open, for the foam of a thick plate and this foam was allowed to rise. After full elevation, the foam was allowed to stand from the beginning of the mixing process for a total of 3 minutes, and then subsequently cured in an oven at 115 ° C for fifteen minutes. The uniformity of the foam cells (Table I, ST) was judged by the structure of the foam, where a classification of "1" has a small uniform cell structure, and a "14" has a large thick cell structure , not uniform. The foams were evaluated by supplication and the vapors were averaged. The Air Flow of the urethane foam (Table 1, AF) was obtained using a NOPCO instrument in a horizontal thick cut of 1.27 cm from the foam obtained at 7.6 cm from the bottom of the foam. Porosity of the foam was measured in m3 / minute of the air flow through a 1.27 cm thick foam cut.

TURBIDITY POINT The turbidity point is a measure of the solubility of water and, as used herein, is the temperature at which a silicone polyether copolymer, for example, begins to precipitate out of a 1% copolymer solution / 99% water The higher the turbidity point, the greater the solubility of the water (as the temperature increases). The cloud point was determined as follows: A sample of 1 gram in 99 ml of distilled water was dissolved in a 150 ml tube. A stirring bar, covered with plastic, of 2.54 cm, was inserted into the specimen, and this specimen was placed on a mixer / hot plate combination. A thermometer from 0 to 100 was suspended in the solution with the 1.27 cm bulb from the bottom of the specimen. With moderate agitation, the contents of the specimen were heated at a rate of 1 to 2dC per minute. The temperature at which the submerged portion of the thermometer was no longer visible was recorded.

VISCOSITY The viscosity was determined at 252C, using a calibrated Ostwald viscometer, which gives an effusion time of approximately 100 seconds. These measurements were repeated until the effusion time readings corresponded within 0.1 second. The calculations were determined by the equation E x F = Viscosity (cstk), where E = effusion time in seconds, F = calibration factor.

EXAMPLES Examples 1 to 3 with comparatives, wherein the preparation method used a batch hydrosilation process. The following Examples 4 to 6 demonstrate the production of Copolymers employing a Continuous hydrosilation process, using two continuous stirred reactors, followed by a series cylinder flow reactor. Example 1 (in batches) and Example 4 (continuous) use the same raw materials in the same stoichiometric ratios. The olefinically substituted polyether is unfinished and possesses hydroxyl functionality. This material was used in cosmetic formulations where the higher water solubilities and the higher turbidity points are convenient. Example 2 (in batches) and Example 5 (continuous) use the same raw materials in the same stoichiometric ratios. These examples use olefinically substituted polyethers, which are finished in methyl. These products are used in flexible polyurethane foam formulations where good uniformity of cell structure and open cell structure (as measured by increased air flow) is important. Example 3 (in batches) and Example 6 ( continuous) use the same raw materials in the same stoichiometric ratios. These examples teach using olefinically substituted polyethers that are terminated in acetoxy. These products are also used in flexible polyurethane foam formulations and as mentioned, an open cellular structure with good uniformity is convenient.

List of Materials and Abbreviations M = (CH3) 3SÍ01 2, D = (CH3) 2SiO and D »= CH3 (H) SiO 40HA1500-Ome = random polyether of allyl capped in methyl, with 40% by weight of ethylene oxide ( EO) / 60% by weight of propylene oxide (PO) - 1500 of number of Daltons of the average molecular weight (mw). 40HA4000-Ome = allyl random polyether topped with methyl with 40% by weight of ethylene oxide (E0) / 60% by weight of propylene oxide (PO) - mw = 4000 Daltons. 40HA1500-Oac = random polyether of allyl capped with acetoxy, with 40% by weight of ethylene oxide (E0) / 60% by weight of propylene oxide (PO) - mw = 1500 Daltons. 40HA4O00-Oac = random polyether of allyl capped with acetoxy, with 40% by weight of ethylene oxide (EO) / 60% by weight of propylene oxide (PO) - mw = 4000 Daltons.

Example 1 (Comparative) To a 4-neck round bottom flask, equipped with a stirrer, Friedrich condenser, temperature controller and spray tube, 133.3 grams of allyloxypolyethylene glycol (APEG) (molecular weight of 385), 66.8 grams of balanced methyl hydrogen-polysiloxane fluid, having a nominal structure of MDisD'eM, 0.09 grams (500ppm) of sodium propionate. The contents of the flask were stirred and heated to a reaction temperature of 852C with a light nitrogen spray. At a temperature of 852C, the heating and sprinkling of nitrogen were stopped and the reaction was catalyzed with 0.28 cc of a 3.3% chloroplatinic acid solution in ethanol (15 ppm Pt). Within 30 minutes, the reaction was exothermic and the flask temperature reached the crest of 117se. This batch reaction of a copper produced a clear product, free of turbidity, of a viscosity of 344 cstk and provided a water point of turbidity of 50SC. No residual silane hydrogen was detected in the product.

Example 2 (Comparative) To a 4-necked round bottom flask, equipped with a stirrer, Friedrich condenser, a temperature controller and a spray tube, 72.2 grams of 40HA1500-OMe, 75.3 grams of 40HA4000-Ome were charged. , 52.0 grams of balanced methyl hydrogen-polysiloxane fluid, which has a nominal structure of MD7oD'5M. The contents of the flask were stirred and heated to a reaction temperature of 852C with a light nitrogen spray. At a temperature of 852C, the heating and sprinkling of nitrogen were stopped and the reaction was catalyzed with 0.29 ce of a solution of 3.3% chloroplatinic acid in ethanol (15 ppm of Pt). Within 30 minutes, the reaction was exothermic and the flask temperature reached the peak of 94ac. This batch reaction of a copper produced a clear product, free of turbidity, of a viscosity of 1821 cstk and provided a water point of turbidity of 37dC. No residual silane hydrogen was detected in the product.

Example 3 (Comparative) To a 4-neck round bottom flask, equipped with a stirrer, Friedrich condenser, a temperature controller and a spray tube, 73.45 grams of 40HA1500-OAC, 76.15 grams of 40HA4000-OAc were charged. , 50.4 grams of balanced methyl hydrogen-polysiloxane fluid, having a nominal structure of MD7oD'5M. The contents of the flask were stirred and heated to a reaction temperature of 80 ° C. with a light nitrogen spray. At a temperature of 802C, heating and nitrogen sparging were stopped and the reaction was catalyzed with 0.29 ce of a 3.3% chloroplatinic acid solution in ethanol (15 ppm Pt). Within 15 minutes, the reaction was exothermic and the flask temperature reached its peak of 810C. This batch reaction of a copper produced a clear product, free of turbidity, of a viscosity of 3328 cstk and provided a water point of turbidity of 36SC. No residual silane hydrogen was detected in the product.

Example 4 In a steady state operation, 1333.4 grams / hour of allyloxypoliethylene glycol (APEG, molecular weight of 385, which contains 500 ppm of suspended sodium propionate, the same batch of the material used in Example 1), was fed into the first continuous stirred reactor 5, apparatus shown in the Figure, through a line of pipe 2 and 667.5 grams / hour of the balanced methyl hydrogen-polysiloxane fluid, having a nominal structure of MDisD'ßM (the same batch as used in Example 1), was fed over the line of pipe 1. The temperature of the allyloxypolyethylene glycol was fed through the line of pipe 2y was maintained at about 852C and the organic hydrogen-siloxane fluid through the line of pipe 1 at about 282C.The stirred reaction in the first CSTR 5 was continuously catalyzed with a solution of 1% chloroplatinic acid in ethanol, at a rate of 9 ml / hour, which supplied a constant concentration of 15 ppm of platinum in the first CSTR 5 through the line of pipe 3. Due to the continuous exothermic reaction As for hydrosilation, the CSTR 5 was maintained at a constant temperature of about 85-90 ° C by the use of an outer jacket in the first CSTR 5, which I can add or remove heat. The reaction mixture was pumped out of the first CSTR 5 at the same rate at which it entered the first CSTR (2010.8 grams / hour) through the line of pipe 6 and into the second CSTR 7. The temperature in the second CSTR 7 was maintained at 85-902C by the use of an external jacket, heated or cooled, on the second CSTR 7. The reaction mixture left the second reactor stirred at a temperature of 85-902C through the line of pipe 8, as a homogeneous clear liquid, at a rate of 2010.8 grams / hour and entered the cylinder flow reactor 9. The heating and cooling mantle of the cylinder flow reactor 9 was controlled so that the reaction mixture, emerging through the pipe line 10, has a temperature of 85-902C. The average residence time in the combined volume of the three reactors was 4.0 hours. The reaction product was optionally transported to a thin film evaporator 11, in which the product was devolatilized under reduced pressure. The resulting product was cooled to <502C in a heat exchanger 14 and optionally filtered (not shown) to the product storage 15 by means of the pipe line 13. The copolymer product, thus prepared, was a clear, fog-free liquid, having a viscosity of 332 cstk and a water point of turbidity of 57dC. No residual silane hydrogen was detected in the product.

Example 5 In a steady state operation, 2956.8 grams / hour of a homogeneous mixture, composed of 49.1 weight percent 40HA1500-OMe and 50.9 weight percent 40 HA4000-OMe (the same batches of material used in the Example 2), were fed into the first continuous stirred reactor (CSTR 1), apparatus shown in the Figure, through a line of pipe 2 and 1040.2 grams / hour of the balanced methyl hydrogen-polysiloxane fluid, having a nominal structure of MD70D, 5M (the same batch as used in Example 2), was fed over the line of pipe 1. The temperature of the aliloxipoli (oxyethylene) - (oxyplene) was fed through the line of pipe 2 and was maintained at about 852C and the organic hydrogen-siloxane fluid through the line of pipe 1 at about 28oc. The stirred reaction in the first CSTR 5 was continuously catalyzed with a solution of 1% chloatinic acid in ethanol, at a rate of 33 ml / hour, which supplied a constant concentration of 25 ppm of platinum in the first CSTR 5 through the line of pipe 3. Due to the continuous exothermic hydrosilation reaction, the CSTR 5 was maintained at a constant temperature of about 85-90GC by the use of an outer jacket in the first CSTR 5, which I can add or remove heat. The reaction mixture was pumped out of the first CSTR 5 at the same rate at which the combined raw materials entered (4030 grams / hour) through the pipeline 6 and entered the second CSTR 7. The temperature in the second CSTR 7 it was maintained at 85-902C by the use of an external jacket, heated or cooled, on the second CSTR 7. The reaction mixture left the second reactor stirred at a temperature of 85-90ac through line pipe 8, as a homogeneous clear liquid, at a rate of 4030 grams / hour and entered the cylinder flow reactor 9. The heating and cooling mantle of the cylinder flow reactor 9 was controlled so that the reaction mixture, emerging through the pipe line 10, has a temperature of 85-902C. The average residence time of the reaction mixture was about 2.0 hours. The reaction product was optionally transported to a thin film evaporator 11, in which the product was devolatilized under reduced pressure. The resulting product was cooled to < 502C in a heat exchanger 14 and optionally filtered (not shown) to the product storage 15 by means of line pipe 13. The copolymer product, thus prepared, was a clear, fog-free liquid, having a viscosity of 1867 cstk and a water point of turbidity of 382C. No residual silane hydrogen was detected in the product.

Example 6 In a steady state operation, 2893.3 grams / hour of a homogeneous mixture, composed of 49.1 weight percent of 40HA1500-Oac and 50.9 weight percent of 40HA400-Oac (same batches of the material used in Example 3) , were fed into the first continuous stirred reactor 5, apparatus shown in the Figure, through a line of pipe 2 and 1008.5 grams / hour of the balanced methyl hydrogen-polysiloxane fluid, having a nominal structure of MD7oD'5M ( the same batch as the one used in Example 3), was fed on the line of pipe 1. The temperature of the aliloxipoli (oxyethylene) (oxypi-plene) was fed through the line of pipe 2 and was maintained at about 85ac and the organic hydrogen-siloxane fluid through the line of pipe 1 at about 28 ° C. The reaction stirred in the first CSTR 5 was continuously catalyzed with a solution of 1% chloatinic acid in ethanol, at a rate of 33 ml / hour , which supplies a constant concentration of 25 ppm of platinum in the first CSTR 5 through the line of pipe 3. Due to the continuous exothermic hydrosilation reaction, the CSTR 5 was maintained at a constant temperature of about 85-90 ° C by the use of an outer shirt in the first CSTR 5, that I can add or remove heat. The reaction mixture was pumped out of the first CSTR 5 at the same rate at which more raw materials (4034.8 grams / hour) entered through the pipeline 6 and into the second CSTR 7. The temperature in the second CSTR 7 was maintained at 85-90ac by the use of an external jacket, heated or cooled, on the second CSTR 7. The reaction mixture left the second reactor stirred at a temperature of 85-902C through the line of pipe 8, as a liquid homogeneous clear, at a rate of 4034.8 grams / hour and entered the cylinder flow reactor 9.

The heating and cooling mantle of the cylinder flow reactor 9 was controlled so that the reaction mixture, emerging through the pipe line 10, has a temperature of 85-902C. The average residence time in the combined volume of the three reactors was 2.0 hours. The reaction product was optionally transported to a thin film evaporator 11, in which the product was devolatilized under reduced pressure. The resulting product was cooled to < 50QC in a heat exchanger 14 and optionally filtered (not shown) to the product storage 15 by means of the pipe line 13. The copolymer product, thus prepared, was a clear, fog-free liquid, having a viscosity of 2822 cstk and a water point of turbidity of 57ac. No residual silane hydrogen was detected in the product. These data show that a more water-soluble copolymer (by the cloud point) was obtained by the continuous process, which is beneficial for personal care applications. The copolymer obtained by the continuous process also produced more open cell foams than the standard batch copolymers.

TABLE Foam Test Unif Flow from Example Viscosity Conc Point Elev. Type of Process Polyether Application Air Cell of Number cstk Turbidity ° C pphp cm l / sßg foam Care Lot APEG 350 344 50 - - - - Personal Care Continuous APEG 350 332 57 - - - - Personal Foam of 0.5 36.8 224 6 Lot 40HA1500 / 4000-Ome 1821 37 Urethane 0.8 39.0 167 Foam 0.5 34.8 232 7 Continuous 40HA1500 / 4000-Ome 1867 38 Urethane 0.8 37.8 246 6 Foam 0.5 37.6 204 7 Lot 40HA1500 / 4000-Oac 3328 36 Urethane 0.9 40.0 190 6 Foam 0.5 34.8 249 5 Continuous 40HA1500 / 4000-Oac 2822 37 Urethane 0.8 37.8 263 5

Claims (8)

1. CLAIMS 1. A process, which comprises: (a) continually feeding hydrogen siloxane one or more olefinic compounds, capable of reacting with the hydrogen siloxane, and a catalyst for the reaction, to the first of a series of at least one reactor continuously stirred tank (CSTR), and continuously removing from the last CSTR in the series, a stream of crude product, containing a siloxane copolymer and unreacted hydrogen siloxane portions and olefinic compounds; (b) continuously feeding the product stream from step (a) to at least one cylinder flow reactor, wherein a stream of products is continually removed.
2. 2. The process of claim 1, wherein there are at least two tank reactors continuously agitated.
3. 3. The process of claim 3, further comprising feeding one or more of the hydrogen siloxane, the olefinic compound and the catalyst, to the second CSTR in the series.
4. 4. The process of claim 3, wherein the hydrogen siloxane fed to the second CSTR is different from the hydrogen siloxane fed to the first CSTR.
5. 5. The process of claim 1, wherein the hydrogen siloxane comprises any combination of siloxane units, selected from the group consisting of R3SÍ01 / 2, R2HSÍ01 / 2, R2SÍ02 / 2, RHSÍ02 / 2, RSÍ03 2, HSÍ03 / 2 and Si? 4 / 2f with the proviso that the hydrogen siloxane contains sufficient siloxane units containing T, to supply 1.0 to 3.0 radicals of R per silicon atom and sufficient siloxane units containing H, to supply 0.01 at 1.0 hydrogen atoms bonded to silicon per silicon atom and a total of R radicals and hydrogen atoms bonded to silicon from 1.5 to 3.0 per silicon atom and each R group is, independently, the same or different, and each represents an alkyl radical with 1 to 12 carbon atoms, a cycloaliphatic radical containing from 5 to 12 carbon atoms, or a phenyl radical, optionally substituted with 1 to 6 alkyl groups having up to 6 carbon atoms.
6. 6. The process of claim 5, wherein each olefinic compound is a polyoxyalkylene block or random, olefinically substituted, corresponding to the formula: R 1 (OCH 2 CH 2) v (OCH 2 CHR 3) w-OR 2, wherein R 1 denotes an alkenyl group, containing 3 to 10 carbon atoms; each R3 is, independently, methyl or ethyl; R2 denotes a monovalent organic group; and the subscript v has a value from 0 to 200, and the subscript w has a value from 0 to 200, with the proviso that the sum of (v + w) is greater than 0.
7. 7. A product obtained by the process of Claim 1.
8. 8. A process, according to the claim 1, in which there is a recycle stream from the outlet to the inlet of at least one continuously stirred tank reactor.