Title of Invention	PROCESS FOR CONTINUOUS POLYMER-ANALOGOUS REACTIONS
Abstract	In the continuous process for the polymer-analogous reaction of polymers bearing functional groups with reactive compounds, in a first step, a mixture is prepared from the polymers bearing functional groups and the reactive compounds and in a second step, the mixture is conducted continuously through a reaction zone and brought to reaction there.

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The invention relates to a continuous process for the polymer-analogous reaction of polymers bearing functional groups with reactive compounds. Continuous processes are used in the chemical industry everywhere where they are superior to the batch processes owing to the improved space-time yield, increased flexibility, owing to safety considerations, because of the product quality and/or the product mass to be dealt with. A further advantage of continuous processes is that the quality of the resultant product can be controlled by on-line analysis during the running production process by changing reaction parameters, such as flow rate, temperature etc. The continuous processes which have been described hitherto in the chemical industry describe the reaction of monomeric compounds to give novel likewise monomeric compounds or the preparation of polymers from monomers and/or oligomers, e.g. by polycondensation or polymerization J Examples of the first process from silane chemistry are the continuous gas-phase hydrosilylation of silanes by compounds bearing organic double bonds or triple bonds, e.g. a trichlorosilane by acetylene, disclosed by M. Bogdan et al. , Appl. Organomet, Chem. 1 (3), 1987 pp. 267 to 73. In these processes, the starting materials are always, and generally the products also, gaseous or low-viscosity compounds under reaction conditions. In the case of volatile starting materials (b.p. time and a longer thermal stress of the product. For polymer preparation, there are likewise a number of different continuous processes. Thus, for example, EP-A-382 366 describes the hydrolysis and condensation of dimethylchlorosilanes to give oligomeric siloxanes in continuous operation. Processes which are not known are continuous processes for polymer-analogous reactions, polymer-analogous reactions being defined as chemical reactions on macromolecules which do not cause changes in their backbone and leave their degree of polymerization unchanged. An example of these is the saponification of poly(vinyl acetate). The object was to develop a continuous process by which reactive groups on polymers can be continuously reacted in a polymer-analogous manner with monomeric, oligomeric or polymeric reactants. The invention relates to a continuous process for the polymer-analogous reaction of polymers bearing functional groups with reactive compounds in which, in a first step, from the polymers bearing functional groups and the reactive compounds, a mixture is prepared and in a second step the mixture is conducted continuously through a reaction zone and brought to reaction there. In the continuous process, the starting materials are continuously conducted once through a reaction zone and continuously brought to reaction. In this process the polymers bearing functional groups need not be homogeneously miscible with the reactive compounds. Using the present process, the polymers can be reacted with monomeric, oligomeric or polymeric reactants. Polymer is taken to mean a substance whose molecules are characterized by multiple repetition of one or more types of atoms or groups of atoms (units) . The number of units linked together here is so high that the properties of the substance do not change by the addition or release of one or more units. In particular, in the present application, a polymer is made up on average of at least eight units. Oligomer is taken to mean a substance in whose molecules a few atoms or groups of atoms (units) are repeatedly linked with one another. The physical properties change by addition or release of one or more units. In particular, in the present application, an oligomer is made up of from 2 to 7 units. In comparison with the batch preparation process and even in comparison with some continuous monomer preparation processes, e.g. with the hydrosilylation of silanes, very short residence times of the starting materials in the reaction zone are sufficient to achieve a complete conversion in one reactor path. Complete is termed the degree of conversion when at least 95 mol% of the function groups on the polymer backbone are reacted. Calorimetric experiments show that in the case of the polymer-analogous hydrosilylation in a batch process, the polymer-analogous hydrosilylation reaction is in a time window from approximately 3 to 3 0 minutes up to complete conversion. The particular time is dependent on the starting materials. If appropriate, in the batch process, the catalyst or a starting material must again be replenished, in order to achieve a complete conversion. In the present continuous process, however, the mean residence time is in a time window which, with comparable starting materials, is lower by a factor of from 5 to 3 00, without taking into account the heating-up and cooling-down phases which are of long duration in a batch process. The main reason for the short residence times in the reaction zone is that, in the continuous process, in each volume element new, highly reactive catalyst and as yet thermally unstressed starting materials are brought to reaction. In contrast, in the batch process, although the reaction starts off rapidly, the rate of reaction decreases with time, since the catalyst activity decreases and/or the starting materials during the long thermal stress participate in chemical side-reactions, for example -olefin rearrangement, which remove them from the actual polymer-analogous reaction. A further reason is the considerably improved local mixing and more uniform temperature .....distribution per volume element in the present continuous process. The shortened thermal stress in the present continuous process further leads to a significant product improvement. To explain the process, reference is made below to Fig. 1. The starting materials and, if appropriate, the catalyst are metered from reservoirs (1,2) continuously via valves (3,4) into premixing chamber (6) provided with a mixer (5) or into the premixing zone of the continuous reactor. After this mixing operation, the starting material mixture is transported via valve (7) and metering unit (8) into the reaction zone (10) of the continuous reactor. On passing through the reaction zone (10), the starting material mixture reaches the reaction temperature, reacts to completion and leaves the reaction zone (10) of the continuous reactor again. The product can, if appropriate, be subjected to yet further process steps, such as a short-path distillation or a filtration. The product is then cooled and collected in the receiver (12). In the case of catalytic processes, it is necessary to meter a catalyst via metering unit (9). The catalyst can be present here in the licjuid or solid state or dissolved in suitable solvents or as a fixed-bed catalyst. The catalyst can be metered in this process continuously at various positions at various time points. The catalyst can be added in the premixing chamber (6) or in the premixing zone or in the heating-up zone. In a third variant, the catalyst can be added continuously directly in the reaction zone (10) only when the desired reaction temperature of the starting materials is achieved. The catalyst can be metered by suitable pumping systems. Suitable pumping systems are in this case, for example, microprecision metering pumps, piston pumps etc. The amounts of the catalyst added continuously are defined exactly here, e.g. via the free length of travel of the micrometering pump. When suitable fluidized-bed catalysts are used, metering of catalyst is not necessary. The starting materials can be metered continuously in the ratio required via pumps, pressure lines or suction lines. Amounts can be determined here in combination with balances or flow meter devices. The starting materials here can have temperatures of from -2 0°C to 100°C, preferably from 0°C to 60°C and particularly preferably from 10°C to 35°C. When pressure lines and pumps are used, the entire flowthrough process can be controlled by the pumps or the line pressure (e.g. nitrogen pressure line), i.e. the residence time of the starting materials in the reaction zone (10) of the continuous reactor is determined via the pumping rate or the line pressure present. In the process variant having an upstream temperature-controllable continuous premixing chamber, the starting material mixture can be pumped from a separate pump into the continuous reactor. In this variant, controlling the residence time of the starting materials in the reaction zone (10) of the continuous reactor,is possible using this one pump. The metering of starting materials is likewise possible at various places, at different temperatures and time points, similarly to the metering of catalyst. The starting materials can be mixed in the mixing chamber by suitable mixing devices (5). Suitable mixing devices (5) are, for example, agitators, ultrasound etc. The temperature in the premixing chamber (6) can be chosen freely in this case. Preference is given to from 10°C to 35°C. In the continuous reactor, mixing can be performed, for example, by static mixers or active mixing by agitator tools running parallel to the longitudinal axis of the reactor vessel. These agitator tools can be driven externally or can be set in motion by the liquid flowing past.. Mixing and swirling effects in the continuous reactor can also be achieved by fixed or exchangeable vortex disrupters on the wall of the reactor. In the continuous reactor, the mixing can also be achieved by means of charged packings. Suitable packings are for example glass spheres, hollow ceramic or glass bodies, metal turnings etc. Use can be made of all current reactor geometries and shapes, such as are described, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, J. Wiley & Sons, 4th edition, volume 20, pages 1007 to 1059. Particular preference is given to a cylindrical reactor shape, where the ratio of diameter to length can be varied as desired, such as from 1 to 10 to 1 to 2500. The position of the reactor is as desired. The reactor material can vary from metal, such as chrome-vanadium-steel reactors, enameled steel reactors to glass reactors. The reactor is operated in a temperature range from -50°C to +400°C. Preference is given to from 0°C to 2 50°C and particular preference to from 60 °C to 2 00°C. The heating/cooling can be achieved by suitable heating/cooling devices (11) . Suitable heating/cooling devices (11) are here an oil circuit for heating and cooling, or two independent cooling and heating circuits based on oil or brime, radiant furnaces, heating fans and vapor heating systems of all types, such as steam heating. The reactor can be operated at the above specified operating temperatures in an absolute pressure range from vacuum, i.e. 1 mbar, to 3 00 bar. The throughput, i.e. the flowthrough of starting material or product per time unit, can vary as a function of reactor size, i.e. reactor length and diameter, reaction parameters, i.e. reaction temperature, viscosity of the starting materials and of the product, exothermy of the reaction etc., and reaction kinetics, from 100 g per hour to 1000 kg per hour of starting material. Preference is given to turnovers of from 1 kg per hour to 500 kg per hour. Particular preference is given to from 10 kg to 100 kg per hour throughput of starting material. The throughput can be controlled as described above via the continuous metering units (8) . Another possibility of controlling throughput of starting material is an electronically actuatable or manually operable outlet valve or control valve at any desired point in the reactor downstream of the reaction zone (10) or at the end of the reactor. In this case, the transport devices, such as pumps, pressure lines etc., must transport not only against the viscosity of the starting materials and products, but also against a certain constant, freely settable pressure, of the built-in control valve. This type of flow control is particularly preferred. Optionally, downstream of the reaction zone, any desired heating/cooling zone can be connected, in order to set the resultant products to a temperature optimum for the further processing or process steps. The product quality is preferably continuously monitored by on-line measurement methods. Suitable measurement methods are all those which can detect the degree of conversion of the reaction in a sufficiently short time. These are, for example, spectroscopic measurement methods, such as near infrared spectroscopy, FT-IR spectroscopy, Raman and FT-Raman spectroscopy. The mixture prepared in the first step of the present continuous process is preferably liquid at the conditions prevailing in the reaction zone (10) . Preferably, the mixture has a viscosity of at most 10,000 mPa*s. The present continuous process is suitable for all polymer-analogous reactions, such as addition reactions, e.g. hydrosilylations, Michael addition, condensation reactions, metathesis reactions, nucleophilic substitutions, such as esterifications, ester cleavages etc., and electrophilic substitutions etc. Preferably, in the present continuous process, as polymers, use is made of polyethers such as functional polyethylene oxides, polypropylene oxides, polyorganosiloxanes or mixed polyethylene polypropylene oxides. Preferred polyethylene oxides, polypropylene oxides and polyethylene polypropylene oxides have the general formula 1 R' - (CH2CH20) n (CHCH3CH2O) m-R " (1) , where R' and R' are each a hydroxyl group, a primary, secondary or tertiary amino group, a mercapto group or a hydrocarbon radical which is unsubstituted or substituted by Ci-Cio-alkoxy groups, cyano groups or fluorine, chlorine or bromine and has at least one aliphatically unsaturated functional group, n and m are each from 0 to 100 and the sum of n + m has a mean value of at least 8. Preferably, the hydrocarbon radicals R' and R' have a maximum of 6 carbon atoms. Preferably, the sum of n + m has mean values of at least 20. Preferred polyethylene polypropylene oxides of the general formula 1 are freely variable in structure from block copolymers to strictly alternating copolymers. Particularly preferably in the present continuous process, as polymers, use is made of polyorganosiloxanes which have at least one unit of the general formula 2 AaEbSiO 4-a-o where A is a functional group E is an inert group a is 1, 2 or 3 and b is 0, 1 or 2. Preferably, the functional groups A are selected from the groups -H, -OH, -X, -OR, -R1, -0~M+, where X is fluorine, chlorine or bromine, R is a Ci-C2o-hydrocarbon radical which is unsubstituted or substituted by Ci-Cio-alkoxy groups, cyano groups or fluorine, chlorine or bromine, and R1 is a C2- to Ceo-hydrocarbon radical which bears one or more double and/or triple bonds, may be interrupted by heteroatoms, such as O, S, N, and P, and can be unsubstituted or substituted by cyano groups, isocyanate groups, fluorine, chlorine or bromine, primary, secondary or tertiary amino groups, carboxylic acid groups or derivatives thereof, primary, secondary or tertiary alcohols or phenols, aldehyde, keto, epoxide or vinyl ether groups and M+ is metal cations. Examples of R1 are the ethylene, propene or acetylene radical, the acrylate or methacrylate radical, esters, anhydrides etc. Preferably, R is an unsubstituted or substituted C1-C6-hydrocarbon radical. Preferably, R1 is an unsubstituted or substituted C1-C12-hydrocarbon radical. Compounds which are particularly suitable for the present continuous process are the polyorganosiloxanes in which the functional groups A are the group -H. Preferred metal cations are the alkali metal cations and alkaline earth metal cations, and the cations of aluminum. Preferably, the inert groups E are selected from C1- to C2o-hydrocarbon radicals which are unsubstituted or substituted by C1-C10-alkoxy groups, cyano groups or fluorine, chlorine or bromine atoms. Examples Example 1) Hydrosilylation Using a gearwheel pump (ISMATEC BVZ), a starting material mixture is pumped through a heatable cylindrical stainless steel reactor (V4A steel, in-house construction) having a length of 1 m and a nominal capacity of 50 ml. When catalyst solutions are used, these are pumped with a micrometering pump (Havard Apparatus 44). The catalyst solution used is a 1% strength by weight solution of hexachloroplatinic acid in isopropanol. The reactor is packed with approximately 17 g of glass tubes of length approximately 0.5 cm and diameter approximately 0.3 cm. In the case of fixed-bed catalysts, there is no metering of catalyst or charging the reactor with glass pieces. Downstream of the reaction zone, the product is cooled to room temperature by a cooler and collected in a product vessel. The starting materials, solvents and catalysts used, the preparation conditions, such as flow per unit time, reaction temperature (Treactor) / residence time in the reactor (tres) and the products thus prepared are summarized below in tabular form. Fixed-bed catalyst 1: 5% by weight platinum on aluminum oxide, obtainable from Heraeus, type Bd 2/2 8 Fixed-bed catalyst 2: 5% by weight platinum on activated carbon, obtainable from Heraeus, type Dcl3/13 Fixed-bed catalyst 3: 5% by weight platinum on aluminum oxide, obtainable from Heraeus, type K-0156 1) H2C=CHCH20 (CH2CH20) 6OAc (Griinau) 2) H2C=CHCH20 (CHCH3CH20) 9CH3 (BASF) 3)(=CCH20 (CH2CH20) 3OCOCH=CH2) 2 (BASF) 4) Reaction is run at 5 bar gauge pressure. 5) The residence time of the starting materials and of the product is calculated from equation 1: tres ("reactor - Vpacking) / Pproduct flow rate [min] where p = density of the product in g/cm3 Vreactor = nominal capacity of the reactor Vpacking = (weight of the packing) (density of the packing) The resultant products all have a hydrogen number which corresponds to an Si-H group conversion rate greater than 95 mol%. In addition, the compounds prepared using fixed-bed catalysts no longer contain detectable platinum and are colorless clear products. Example 2) Continuous hydrosilylation with variable metering of starting material The reactor structure is identical to that described in Example 1. However, in addition, a third starting material is further added to the continuous reactor downstream of a reaction path of 65 cm to the first two starting materials which by then have already reacted completely to form an intermediate which is not isolated. The catalyst solution used is a 1% strength by weight solution of hexachloroplatinic acid in isopropanol. rable 2: Continuous hydrosilylation using two hydrosilylable starting materials added successively The resultant products all have a hydrogen number which corresponds to an Si-H group conversion greater than 96 mol%. Example 3) Continuous nucleophilic substitution The reactor structure is identical to that in Example 1, with the difference that no catalyst is added. The products produced in the continuous process are subsequently purified via a short-path distillation and a filtration. uantitative Si-O-C linkage is demonstrated in 29Si-NMR. xample 4) Two-stage synthesis in the continuous eactor rocess: The reactor structure is identical to that in Ixample 1. The catalyst solution used for the Lydrosilylation is a 1% strength by weight solution of Lexachloroplatinic acid in isopropanol. In departure from Example 1, in addition, p-toluenesulfonic acid, 5% by weight in toluene, is added at approximately one third of the reactor length as catalyst for the ester cleavage via a microprecision pump. leaction: In the first third of the reactor, a lydrosilylation is carried out. This is then followed, without isolation of the intermediate, by an acid ester lydrolysis catalyzed by p-toluene sulfonic acid, with elimination of butene. The resultant product is then further purified continuously by a short-path distillation. The exact reaction parameters are given in Table 4. Table 4; Preparation of a siloxane oil comprising free carboxylic acid groups The resultant products are characterized by 1H-NMR WE CLAIM: 1. A continuous process for the polymer-analogous hydrosilylation of polyorganosiloxanes bearing functional groups with reactive compounds in which in a first step, from the polyorganosiloxanes bearing functional groups and the reactive compounds, a mixture is prepared and in a second step the mixture is conducted continuously through a reaction zone and brought to reaction there, wherein use is made of polyorganosiloxanes which have at least one unit of the general formula 2 AaEbSiO 4-a-b 2 where A is a functional group which is selected from groups -H, -R1, where R1 is a C2- to C60-hydrocarbon radical which bears one or more double and/or triple bonds, may be interrupted by heteroatoms, such as 0,S,N and P, and can be unsubstituted or substituted by cyano groups, isocyanate groups or derivatives thereof, primary, secondary or tertiary alcohols or phenols, aldehyde, keto, epoxide or vinyl ether groups, E is an inert group a is 1,2 or 3 and b is 0,1 or 2 2. Process according to claim 1, wherein the polyorganosiloxanes have the functional groups = SiH. 3. Process according to Claim 1 to 2, wherein the inert group E are selected from C1 - to C2o-hydrocarbon radical which are unsubstituted or substituted by Cl-ClO-alkoxy groups, cyano groups or fluorine, chlorine or bromine.

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