WO2003006955A1 - Method and instrument for measuring mooney viscosity, and method and apparatus for producing polymer - Google Patents

Abstract

A method for measuring a Moony viscosity which comprises a step of measuring a solution viscosity of a uniform solution prepared by adding a solvent to a liquid polymerization reaction mixture by the use of a vibration viscometer and a step of calculating a Moony viscosity of a polymer contained in the uniform solution from the measured value of solution viscosity. The method allows the measurement of a Moony viscosity of a polymer contained in the uniform solution in a short time and with high precision, since the measurement of a solution viscosity of a uniform solution by the use of a vibration viscometer can be carried out with simple and easy operations with high precision and in a short time.

Description

 Patent application title: METHOD AND APPARATUS FOR MEASURING MU-1-1 VISCOSITY, AND METHOD AND APPARATUS FOR PRODUCING POLYMER

 The present invention relates to a method and an apparatus for measuring the Mooney viscosity of a polymer in a polymerization reaction solution, and a method and an apparatus for producing a polymer using the method. Background art

 The viscosity of a polymer is widely used as one of the indexes indicating the properties of a polymer, particularly, the size of a molecule. For example, in a synthetic rubber manufacturing plant, the viscosity of a rubber is constantly measured in order to control a polymerization process, a drying process, and the like, or to control the quality of a target rubber product.

 The Mooney viscosity is measured using a Mooney viscometer from the torque applied to a rotating rotor in a polymer filled container. When the Mooney viscosity of a polymer is to be measured during the course of the polymerization reaction, it is necessary to separate the polymer from the polymerization reaction solution for the measurement using the polymer itself. Therefore, there was a problem that it took too much time to measure the viscosity. For this reason, for example, when the Mooney viscosity is measured to determine the end time of the reaction, when the measurement result is obtained, a situation may occur in which the target exceeds the target Moore viscosity. As described above, there is a problem in using the Muchu viscosity for controlling the polymerization reaction in the emulsion polymerization step.

 Therefore, a method for determining Mooney viscosity without separating the polymer from the polymerization reaction solution is being studied. For example, a method has been proposed in which a polymerization reaction solution is diluted with a solvent such as tetrahydrofuran, analyzed by gel permeation chromatography, and the viscosity is estimated from measured values such as peak positions. (JP-A-59-47213, JP-A-59-47214).

However, in the case of emulsion polymerization, since the polymerization reaction solution contains water, the peak positions of the polymer and water sometimes overlapped in gel permeation chromatography. In addition, since the polarity of water was high, the peak of the polymer was broadened, and the error in the measured value was sometimes large. In order to reduce errors in measured values, it was necessary to spend time on analysis, and it was difficult to make accurate measurements in a short time. Disclosure of the invention

 An object of the present invention is to provide a method for measuring the viscosity of a polymer contained in the polymerization reaction solution in a short time and accurately from a polymerization reaction solution. The purpose of this is to provide an extension device. Further, the present invention provides a method for producing a polymer capable of industrially producing a polymer having a desired viscosity having a predetermined viscosity without delaying the completion of the reaction. The purpose is also to do.

 The present inventors separate the polymer from the polymerization reaction solution, and can measure the Mooney viscosity of the polymer in a relatively short time, instead of directly measuring the Mooney viscosity, and have a correlation with the Moieux viscosity. We explored physical properties that could be. As a result, it was found that there was a predetermined correlation between the solution viscosity of a homogeneous solution prepared by adding a solvent to the polymerization reaction solution and the Mooney viscosity of the polymer contained in the polymerization reaction solution. . It was also found that the use of a vibrating viscometer allows the solution viscosity of the homogeneous solution to be measured in a short time with high measurement accuracy. Based on these findings, the present invention has been completed.

 That is, according to the present invention,

 Measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the polymerization reaction solution using a vibrating viscometer; and

 Calculating a Mooney viscosity value of the polymer contained in the homogeneous solution from the measured solution viscosity value.

 The method for measuring the viscosity according to the present invention can be realized by, for example, the following device.

 Apparatus for measuring the Mooney viscosity of the polymer according to the present invention,

 Concentration measuring means for measuring the solid content concentration of the polymerization reaction solution,

Based on the value of the solid concentration measured by the concentration measuring means, a predetermined amount of the polymer is An amount determining means for determining the amount of the polymerization reaction solution or the amount of the solvent to be included,

 Adding a predetermined amount of solvent to the amount of polymerization reaction solution determined by the amount determination means, or adding the determined amount of solvent to a predetermined amount of polymerization reaction solution to prepare a uniform solution Preparation means;

 A vibrating viscometer for measuring the solution viscosity of the uniform solution prepared by the uniform solution preparation means,

 A viscosity calculating means for calculating a viscosity of the polymer contained in the homogeneous solution from a solution viscosity measured by the viscometer.

 The apparatus according to the present invention preferably further comprises a sampling unit for sampling a predetermined amount of a polymerization reaction solution for measuring a solid content concentration.

 According to these inventions, the viscosity of a polymer contained in a polymerization reaction solution is not directly measured, but a solution of a homogeneous solution prepared by adding a solvent to the polymerization reaction solution, which is a substitute physical property. The viscosity is measured using a vibrating viscometer, and the value of the viscosity of the polymer is calculated from the measured value of the solution viscosity. Since the solution viscosity of the homogeneous solution is measured using a vibrating viscometer, the solution viscosity of the uniform solution can be obtained with a simple operation with high measurement accuracy and in a short time. Therefore, the value of the viscosity of the polymer contained in the polymerization reaction solution can be accurately measured in a short time and accurately from the polymerization reaction solution.

 According to the present invention,

 A step of obtaining an emulsion polymerization reaction liquid by an emulsion polymerization reaction,

 A step of measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the emulsion polymerization reaction solution, using a vibrating viscometer,

 From the value of the measured solution viscosity, a step of calculating the value of Mooney viscosity of the polymer contained in the homogeneous solution,

 Changing the polymerization reaction factor in accordance with the calculated Mooney viscosity of the polymer.

 According to the present invention,

A raw material supply step of supplying a raw material comprising a monomer, a polymerization initiator, a molecular weight regulator, and other polymerization auxiliary materials to a polymerization reaction tank; A method for producing a polymer, comprising: an emulsion polymerization step of polymerizing monomers in the polymerization reaction tank to obtain an emulsion polymerization reaction solution; and a polymerization termination step of terminating the emulsion polymerization at a predetermined Mooney viscosity.

 Measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the emulsion polymerization reaction solution collected from the polymerization reaction tank using a vibrating viscometer;

 From the value of the measured solution viscosity, a step of calculating the value of mu-1-1 viscosity of the polymer contained in the homogeneous solution,

 The calculated value of the Mooney viscosity of the polymer is transmitted to at least one step selected from the raw material supply step, the emulsification polymerization step, and the polymerization termination step, and the polymerization reaction factor in each step is changed. And a factor changing step of producing the polymer.

 The method for producing each polymer according to the present invention can be realized by, for example, the following apparatus.

 The apparatus for producing a polymer according to the present invention includes:

 A polymerization reaction tank for obtaining an emulsion polymerization reaction solution by an emulsion polymerization reaction,

 A vibrating viscometer for measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the emulsion polymerization reaction solution collected from the polymerization reaction tank;

 From the value of the solution viscosity measured by the viscometer, to calculate the Moieux viscosity value of the polymer contained in the homogeneous solution, a viscosity calculating means,

 A factor changing means for changing a polymerization reaction factor in accordance with the value of the viscosity of the polymer calculated by the viscosity calculating means.

 According to these inventions, a desired quality polymer having a predetermined viscosity can be industrially advantageously produced without delaying the completion of the reaction.

 According to the present invention,

 A step of obtaining an emulsion polymerization reaction liquid by an emulsion polymerization reaction,

 A step of measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the emulsion polymerization reaction solution, using a vibrating viscometer,

Depending on the value of the measured solution viscosity, and a step of changing the polymerization factor, polymer production method of a is provided _n According to the present invention,

 A raw material supply step of supplying a raw material composed of a monomer, a polymerization initiator, a molecular weight modifier, and other polymerization auxiliary materials to a polymerization reaction tank;

 A method for producing a polymer, comprising: an emulsion polymerization step of polymerizing monomers in the polymerization reaction tank to obtain an emulsion polymerization reaction liquid; and a polymerization termination step of terminating the emulsion polymerization at a predetermined viscosity. hand,

 Measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the emulsion polymerization reaction solution collected from the polymerization reaction tank using a vibrating viscometer;

 A factor changing step of transmitting the measured solution viscosity value to at least one step selected from the raw material supply step, the emulsion polymerization step, and the polymerization termination step, thereby changing a polymerization reaction factor in each step. And a method for producing a polymer having the following. The method for producing each polymer according to the present invention can be realized by, for example, the following apparatus.

 The apparatus for producing a polymer according to the present invention includes:

 A polymerization reaction tank for obtaining an emulsion polymerization reaction solution by an emulsion polymerization reaction,

 A vibrating viscometer for measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the emulsion polymerization reaction solution collected from the polymerization reaction tank;

 And a factor changing means for changing a polymerization reaction factor in accordance with the value of the solution viscosity measured by the viscometer.

 As described above, the present inventors have found that a predetermined correlation exists between the solution viscosity of a homogeneous solution prepared by adding a solvent to a polymerization reaction solution and the Mooney viscosity of a polymer contained in the polymerization reaction solution. Based on the finding that there is, the same effect can be obtained by controlling the solution viscosity of the uniform solution without calculating the Mooney viscosity from the solution viscosity of the uniform solution. That is, according to these inventions, a polymer having a desired Mooney viscosity and a desired quality can be industrially advantageously produced without losing the end of the reaction.

 In the present invention, it is preferable to use a tuning-fork vibrating viscometer to measure the solution viscosity of the homogeneous solution with higher measurement accuracy and in a shorter time.

In the present invention, it is preferable to use an emulsion polymerization reaction liquid as the polymerization reaction liquid. In the present invention, it is preferable to use an emulsion polymerization reaction solution of a copolymer composed of unsaturated nitrile and a conjugated diene.

 In the present invention, 20. It is preferable to use a solvent having a water solubility of 5% by weight or more in C.

 In the present invention, it is preferable to use a ketone or a cyclic ether solvent as the solvent.

In the present invention, the polymer content is from 0.5 to 6 wt _^0/0 homogeneous solution preferable to use arbitrary.

 In the present invention, the polymerization reaction factor is at least one selected from a raw material supply element, an emulsion polymerization element, and a polymerization termination element,

 The raw material supply element is at least one selected from a monomer, a polymerization initiator, a molecular weight modifier, and other polymerization auxiliary materials, whether or not additional input is performed, a timing of additional input, and an additional input amount;

 The emulsion polymerization element is at least one selected from a flow rate of a refrigerant or a heat medium that controls a reaction temperature, a reaction pressure, a stirring speed of a polymerization reaction tank, and a method of stirring a polymerization reaction tank,

 It is preferable that the polymerization terminating element is at least one selected from charging of a polymerization terminator, cooling in the polymerization reaction vessel, and reduced pressure in the polymerization reaction vessel.

 In the present invention, the calculated value of the Mooney viscosity of the polymer is transmitted to the raw material supply step, and at least one selected from the presence or absence of additional input of each raw material, the timing of additional input, and the additional input amount is changed. Preferably.

 In the present invention, the measured value of the solution viscosity is transmitted to the raw material supply step, and at least one selected from the presence / absence of additional input of each raw material, the timing of additional input, and the additional input amount is changed. preferable.

In the present invention, the calculated value of the Mooney viscosity of the polymer is transmitted to the polymerization terminating step, and is selected from the addition of a polymerization terminator, the cooling in the polymerization reaction vessel, and the reduced pressure in the polymerization reaction vessel. Preferably, the polymerization reaction is stopped by at least one method. In the present invention, the measured value of the solution viscosity is transmitted to the polymerization stopping step, and a small amount selected from the addition of a polymerization terminator, the cooling in the polymerization reaction tank, and the reduced pressure in the polymerization reaction tank. It is preferred to terminate the polymerization reaction by at least one method.

 In the present invention, it is preferable to use unsaturated nitrile and a conjugated diene as monomers. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a block diagram showing an example of an apparatus for realizing a method for producing a polymer by patch-type emulsion polymerization according to an embodiment of the present invention.

 FIG. 2 is a diagram showing the relationship between the solution viscosity and mu-1-1 viscosity in Example 1 (however, the straight line in the diagram shows the relationship obtained by regression analysis).

 FIG. 3 is a diagram showing the relationship between the solution viscosity and the mu-1-1 viscosity in Example 6 (however, the straight line in the diagram shows the relationship obtained by regression analysis).

 FIG. 4 is a graph showing the change in viscosity measured by the method of the present invention over time after the start of polymerization in Example 11;

 FIG. 5 is a block diagram showing an example of an apparatus for realizing the method for measuring Mooney viscosity according to the present invention,

 FIG. 6 is a conceptual diagram conceptually showing the vibration type viscometer in FIG. 5,

 Fig. 7 is a flow chart of the measurement of Moey's viscosity.

 FIG. 8 is a diagram showing the relationship between solution viscosity and Mooney viscosity in Example 12 (however, a straight line in the diagram shows a relationship obtained by regression analysis).

 FIG. 9 is a diagram showing the relationship between solution viscosity and Mooney viscosity in Example 13 (however, the straight line in the diagram shows the relationship obtained by regression analysis).

 FIG. 10 is a diagram showing the relationship between solution viscosity and Mooney viscosity in Example 14 (however, the straight line in the diagram shows the relationship obtained by regression analysis). BEST MODE FOR CARRYING OUT THE INVENTION

 In the following description, a method for measuring the Mooney viscosity according to the present invention, an apparatus as an example for realizing the method, a method for producing a polymer using the method, and an example for realizing the production method The manufacturing apparatus will be described in this order.

The polymerization reaction liquid applicable to the present invention is one obtained by solution polymerization. Or may be obtained by means other than solution polymerization. An example of the latter is a polymeric emulsion. In the following description, a case where a polymer emulsion is used as the polymerization reaction liquid will be exemplified.

 Examples of the polymer emulsion applicable to the present invention include a homo- or copolymer composed only of a conjugated gen such as a butadiene polymer, an isoprene polymer, a butadiene-isoprene copolymer; and an acrylonitrile-butadiene copolymer. Conjugated with unsaturated-tolyl such as polymers, acrylonitrile-butadiene-isoprene copolymer, atari-mouth ethyryl-isoprene copolymer, atariloritrile-styrene-butadiene copolymer, atarilonitrile-styrene-styrene-isoprene copolymer, etc. Copolymers composed of styrene and conjugated aromatic vinyl such as styrene-butadiene copolymer and styrene-isoprene copolymer other than copolymers composed of unsaturated nitrile and conjugated gen. Constituent copolymer; Ethyl acrylate polymer, Ethyl acrylate -N-butyl acrylate copolymer, ethyl ^ / acrylate-η-butyl acrylate-2-methoxyshetyl acrylate copolymer, homopolymer or copolymer composed of only acrylate; Emulsion. Among them, a copolymer composed of unsaturated nitrile and a conjugated gen, and a homo- or copolymer emulsion composed only of atalylate are preferable, and a copolymer composed of an unsaturated nitrile and a conjugated gen are preferable. Emulsion is more preferred, and particularly preferred is an emulsion of Atari mouth-tolyl-butadiene copolymer. The polymer emulsion can be obtained by, for example, emulsion polymerization, seeding emulsion polymerization, fine suspension polymerization, or seeding fine suspension polymerization.In the present invention, the emulsion polymerization reaction solution obtained by emulsion polymerization is used. Is preferred. The emulsion polymerization reaction liquid often contains an emulsifier, an unreacted monomer and a polymerization initiator or a residue of a polymerization initiator, in addition to the above polymer and water. In addition, it may contain a molecular weight regulator, a co-catalyst, a ρΗ regulator and the like. Further, the emulsion polymerization reaction liquid may be in the course of emulsion polymerization or may be one after the completion of emulsion polymerization.

Polymer content of Emarujiyon of polymer (solids concentration) is preferably from 5 to 6 0 wt _^0/0, more preferably 1 0-5 0 weight _^0/0, and particularly preferably 2 0-3 5 weight ⁰ / ₀ . If the polymer content is too small, the homogeneous solution described below may be excessively diluted. Yes, if it is too large, the viscosity of the emulsion is so high that preparation of a homogeneous solution may take time or may not be uniform.

The water content of Emarujiyon the polymer is preferably 4 0-9 5 wt%, more preferred properly 5 0-9 0 weight _^0/0 or less, particularly preferably 6 5-8 0% by weight or less. If the water content of the emulsion is too small, there is the same problem as when the polymer content is too large.On the other hand, if the water content is too large, it is the same as if the polymer content is too small. There's a problem.

 The unreacted monomer content of the polymer emulsion is usually 30% by weight. /. Hereinafter, it is preferably at most 20% by weight, more preferably at most 15% by weight, particularly preferably at most 10% by weight. If the unreacted monomer content is too large, the error in viscosity may increase.

The emulsifier contained in the polymer emulsion may be selected from anionic surfactants, nonionic surfactants, cationic surfactants, fluorine surfactants, and the like, depending on the type and equipment of the target polymer. Although various substances such as a silicone-based surfactant and a polymer dispersant are used, the method of the present invention can be applied to those using any of these. The emulsifier content of the polymer emulsion is preferably from 0.1 to 10% by weight, more preferably from 0.25 to 5% by weight. / ₀ , particularly preferably 0.5 to 3% by weight. If the emulsifier content is too high, the measurement error of the solution viscosity increases. Conversely, if the emulsifier content is too small, the polymer particles will be large, and it may take time to prepare a homogeneous solution.

In the present invention, the solvent added to the emulsion of the polymer in order to prepare a homogeneous solution may be determined in consideration of the polymer in the emulsion, but the solubility of water at 20 ° C. is preferably 5 wt% or more, more preferably suitably 1 0 weight _^0/0 or more. If the solubility of water is too low, the water is easily separated and it is difficult to prepare a homogeneous solution. Specific solvents include ketones such as acetone and methylethyl ketone; cyclic ether solvents such as tetrahydrofuran, tetrahydropyran, and dioxane; pyridine solvents such as pyridine and methylpyridine; 2-butanol, phenols such as n-butanol; monocarboxylic acid amides such as N, N-dimethylinoacetamide and N, N-dimethylformamide; formaldehyde, amide Aldehydes such as cetoaldehyde; carboxylic acids such as formic acid, acetic acid, and propionic acid; esters such as methyl formate and ethyl acetate; Among them, ketones and cyclic ether solvents are preferable. Among ketones, methylethyl ketone is particularly preferred. Of the cyclic ether solvents, tetrahydrofuran is particularly preferred. Methyl ethyl ketone is a preferred solvent, but when dissolving low polarity rubber, if the water content in the milk solution is high, the amount of the dissolved emulsion may not be large. On the other hand, tetrahydrofuran is particularly preferable in comparison with other solvents because it has a very high solubility in water and well dissolves the rubber such as the acrylo-tolyl-butadiene copolymer over an extremely wide range of polarities.

For example, when an acrylo-tolyl-butadiene copolymer emulsion is used, the δ value of the solubility parameter is preferably 15.5 to 23.5ΜΡa ^1/2 , and more preferably 16.5 to 22.5MPa. Use a ^1/2 solvent. If the solubility parameter is too small, water will easily separate from the solvent, and if it is too large, the polymer will not dissolve and precipitate out, making it impossible to prepare a homogeneous solution. Specifically, in addition to single solvents such as acetone, methyl ketone, tetrahydrofuran, pyridine, 2-butanol, acetic acid, acetate aldehyde, and methyl formate, a mixture of ethanol and getyl ether in a weight ratio of 1: 1. A mixture of multiple solvents to meet the conditions, such as a solvent, a mixed solvent of methanol and ethyl hexanoate at a weight ratio of 1: 3, a mixed solvent of ethyl acetate and ethylene glycol at a weight ratio of 4: 1, etc. Solvents. The homogeneous solution applicable to the present invention is prepared by diluting a polymer emulsion with a solvent, and is prepared to have a constant polymer content.

 The polymer content of the homogeneous solution is preferably 0.5-6% by weight, more preferably 1-5% by weight, particularly preferably 1.5-4% by weight. If the polymer content of the homogeneous solution is too small, the Mooney viscosity measurement error may increase. Conversely, if the amount is too large, it may be difficult to uniformly dissolve the polymer.

The amount of the homogeneous solution used for measuring the solution viscosity is preferably constant. The amount is not particularly limited, but is preferably 10 to 50 Om 1, more preferably 30 to 300 ml, and particularly preferably 100 to 150 ml. If the amount of the homogeneous solution is too small, the viscosity of the solution cannot be measured with the viscometer In some cases, the error may become large. In the present invention, when an emulsion polymerization reaction solution is used, a sample is collected in an amount such that the yield of the polymer in the homogeneous solution is not significantly reduced or the polymerization conditions are not changed. Prepare a homogeneous solution with volume of.

 In the present invention, a vibrating viscometer is used for measuring the solution viscosity. A vibrating viscometer vibrates a vibrator (also called a sensitive plate) at a constant frequency and amplitude in a solution sample, and determines the difference between the driving force required to drive the vibrator or the magnitude of vibration damping and the viscosity of the solution sample. This is a device for measuring the viscosity of a solution sample by the correlation of By using this viscometer, measurement accuracy can be improved.

 There are various types of vibration type viscometers. For example, it is one of the “single vibration type” that vibrates one vibrator like a pendulum, and the “ultrasonic vibration type” that vibrates one vibrator like a pendulum by ultrasonic waves. There are “torsional vibration type”, in which one vibrator is torsionally vibrated, and “tuning fork vibration type”, in which two vibrators resonate.

 There are two types of simple vibration type: one to measure the attenuation of the amplitude due to viscosity, and the other to measure the current value required for maintaining a constant amplitude. There is a disadvantage that since it is a simple vibration, external influences such as reflected vibration from the container are relatively large. In the torsional vibration type, the detection terminal vibrates in the rotational direction so as to be in a resonance state at a certain frequency, the tip (detection end) of the detection terminal is immersed in a liquid, and the amplitude of the vibration changes depending on the magnitude of the liquid viscosity. This is interpreted as a change in angular acceleration and converted to an electronic signal for measurement. The tuning-fork type vibrator utilizes the fact that the amount of current required to maintain the vibrator at a constant frequency and a constant amplitude increases and decreases as the viscosity of the sample increases and decreases. It is measured and converted to a viscosity value.

In the present invention, each of the above types can be appropriately selected and used. However, when a higher measurement accuracy and a shorter measurement time are desired, it is preferable to use a tuning fork vibrating viscometer. The tuning fork vibrating viscometer vibrates in opposite directions when the two vibrators resonate, so that external influences such as vibration reflected from the container are easily offset, and the measurement error compared to other types Is small and the response is excellent. Measurement range of solution viscosity vibratory viscometer, Ru cormorants are affected by actually used device, but in order to reduce the measurement error is preferably 0. 3~20mP a · _S, Ri yo preferably 1~15mP a · s, particularly preferably 2 to 1 OmP a · s. In the present invention, the value of the Moieux viscosity of the polymer contained in the uniform solution is calculated from the measured solution viscosity value (measured value) of the uniform solution based on a predetermined conversion formula. The value of the Mooney viscosity may be calculated manually, but it is easy to shorten the calculation time by using an information processing device such as a computer.

 The method for calculating the value of the Mu-I viscosity from the measured value of the solution viscosity of the homogeneous solution is to previously determine the solution viscosity of the uniform solution having a certain polymer content and the amount of the polymer contained in the homogeneous solution. The relationship with the viscosity value may be obtained in the form of a conversion formula, and the calculation may be performed based on the conversion formula.

The conversion formula to the value of the Mooney viscosity can usually be determined by regression analysis. Alternatively, an initial conversion formula may be obtained, and this may be optimized over time. The initial conversion formula f () is based on, for example, preparing several kinds of polymers having a viscosity in the range of 5-100 (ML _{1 + 4} , 100 ° C) measured at 100 ° C according to JIS-K6300. However, the solution viscosity of a homogeneous solution of emulsion containing them can be measured and determined by the least square method of the solution viscosity and the mu-1-1 viscosity. Next, during the polymerization, the solution viscosity P of a homogeneous solution prepared by adding a solvent to the emulsion of the polymer after polymerization is measured, and ML is calculated using ML ₍ = f ( ₂ )). By measuring the last ML, we can obtain the optimized formula (( ²⁾ (ρ) based on the new data of p ₍₂ ) and ML ( _2. This f ₍₂ ) (p) As a method of making, for example, autoregression, moving average, autoregression moving average, etc. can be mentioned.

 The viscosity of the polymer used for obtaining the calibration curve may be measured by recovering the polymer from the emulsion of the polymer according to a conventional method. The method for recovering the polymer may be a conventional method.For example, a large amount of a poor solvent is added to the emulsion to precipitate the polymer, and the polymer is thoroughly washed to remove the residue of the poor solvent and the polymerization initiator. Dry thoroughly.

When the solution viscosity of the homogeneous solution in the present invention and the Mooney viscosity of the polymer recovered from the emulsion are analyzed, the correlation coefficient of the calibration curve is 0.8 or more, preferably 0.9 or more, more preferably 0.95 or more. The range of the mu-one viscosity (L i +4, 100 ° C.) that can be measured by the method for measuring Mooney viscosity according to the present invention is usually 5 to 100, preferably 10 to 9 5, more preferably 25 to 85. Measurements outside the range tend to increase measurement errors.

 In the method for measuring the Mooney viscosity according to the present invention, the time from collection of the emulsion to completion of the measurement is preferably within 15 minutes, more preferably within 10 minutes, and particularly preferably within 7 minutes. You can save time. For this reason, it is possible to smoothly convert the value to the subsequent value of the Moie viscosity and to the change in the polymerization reaction factor described later. That is, when a vibrating viscometer is used to measure the solution viscosity of the homogeneous solution, the feed batch to the next batch can be performed in a short time.

 As a result, the calculated value of the muie viscosity calculated by the method for measuring muie viscosity according to the present invention, and the muie knee viscosity actually measured by recovering the polymer from the emulsion according to a conventional method. An error from the actual measurement value can be reduced. Specifically, the difference between the calculated value and the actually measured value can be suppressed to an absolute value, preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

 In order to realize the above-described method for measuring the Moieux viscosity according to the present invention, for example, an apparatus 100 for measuring the Mooney viscosity having the configuration shown in FIG. 5 can be used. In the following example, the description will be made on the assumption that the Mooney viscosity of the polymer in the emulsion polymerization reaction liquid in the polymerization reaction tank 1 shown in FIG. 1 described later is measured.

 An apparatus for measuring Mooney viscosity according to the present embodiment (hereinafter sometimes simply referred to as a measuring apparatus) 100 is a sampling apparatus as a sampling means for collecting a part of the emulsion polymerization reaction liquid in the polymerization reaction tank 1. With 3. The sampling device 3 may be configured to be able to automatically collect the sample from the polymerization reaction tank 1 or may be configured to collect the sample manually.

The sampling device 3 is connected to a concentration measuring device 11 as a concentration measuring means. Here, the concentration of the solid content of the emulsion polymerization reaction liquid collected by the sampling device 3 is measured. In the present embodiment, as the concentration measuring device 11, an electronic balance 111, a dryer (plate heater) 114 mounted on the balance 111, and a dryer 111 Having an aluminum container 1 16 mounted on the A halogen moisture analyzer with a balance (halogen lamp dryer) is used. However, for the dryers 114, various dryers other than the plate heaters (for example, steam dryers, electric heaters, hot air dryers, etc.) can be used. Also, the dryer 114 and the electronic balance 112 need not be integrated. The concentration measuring device 11 may be configured to automatically measure the solid content concentration when a part of the emulsion polymerization reaction liquid is introduced, or may be configured to measure manually.

 The concentration measuring device 11 is connected to an amount determining device 7 serving as an amount determining means. Here, a predetermined amount of the polymer is determined based on the value of the solid concentration measured by the concentration measuring device 11. The amount of the emulsion polymerization reaction solution or the amount of the solvent to be included is determined. As the quantity determining device 7, a computer device is usually used.

 A uniform solution preparation device 8 as a uniform solution preparation means is connected to the sampling device 3 .Here, a predetermined amount of a solvent is added to the amount of the emulsion polymerization reaction solution determined by the amount determination device 7, Alternatively, the determined amount of the solvent is added to a predetermined amount of the emulsion polymerization reaction solution to prepare a homogeneous solution 49. In the present embodiment, the homogeneous solution preparation device 8 includes an electronic balance 81, a container 86 mounted on the balance 81, a solvent tank 82 connected to the container 86, and a solvent tank 8 And a model syringe pump 84 for feeding the solvent in 2 into the container 86.

 The viscosity measuring unit 4 is connected to the uniform solution preparation device 8, and here, the solution viscosity of the uniform solution 49 is measured. The viscosity measuring section 4 has a vibrating viscometer 42 and a thermostatic bath 44 for maintaining a uniform solution 49 measured by the viscometer 42 at a predetermined temperature.

As shown in FIG. 6, the vibrating viscometer 42 used in the present embodiment is a tuning fork vibrating viscometer, and is suspended and supported by a device main body (not shown) via a holding portion 42. I have. A pair of support members 424 are attached to the holding portion 422. A vibrator 4 26 is attached to the tip of each support member 4 2 4. Each support member 4 24 is provided with an electromagnetic drive unit (not shown) for vibrating the vibrator 4 26. The electromagnetic force generated in this electromagnetic drive unit (not shown) and the support member Due to the elasticity of 4 24, the vibrator 4 26 vibrates in the homogeneous solution 49 (see FIG. 5). The vibrator when placed in the uniform solution 49 A displacement sensor 427 is attached which can detect the viscous resistance generated between the 426 and the uniform solution 49 as a change in the amplitude value of the vibrator 426. The holding section 4 2 2 between the pair of support members 4 2 4 and 4 2 4 includes a liquid level sensor (a water level sensor) for controlling the positional relationship between the viscometer 42 and the liquid level of the uniform solution 49. 4 4 5 is attached. The liquid level sensor 425 is not particularly limited, and any type such as a light refractive index sensor type can be used.

 As shown in FIG. 5, an estimation calculating device 5 as Mooney viscosity calculating means is connected to the viscosity measuring unit 4, and here, the viscosity of the homogeneous solution 49 measured by the viscometer 42 is measured. From the value, the value of the Mooney viscosity of the polymer contained in the homogeneous solution 49 is calculated. As the estimation calculation device 5, a computer device is usually used.

 Next, the operation of the measuring apparatus 100 will be described with reference to FIGS.

 First, a predetermined amount of the emulsion polymerization reaction solution (after termination of polymerization) is sampled from the polymerization reaction tank 1 using the sampling device 3 (Step 1 S 1). Do you sample? The amount of the L-polymerization reaction solution is preferably an amount expected to be used for the measurement of the solid content concentration described later and the preparation of a homogeneous solution. Usually, it is about 50 cc.

 Next, a predetermined amount (for example, about 2 to 3 grams) is weighed from the sampled emulsion polymerization reaction solution to obtain a solid content concentration measurement sample (step 2 "'S2).

 However, before weighing a predetermined amount, the emulsified polymerization reaction liquid sampled from the polymerization reaction tank 1 is transferred to a degassing vessel (not shown), and the unreacted monomer components contained in the emulsion polymerization reaction liquid are removed. Degassing is preferred (step 2, --- S 2 '). This is because, before degassing, unreacted monomer components may remain in the emulsion polymerization reaction liquid. Although the concentration measurement sample is weighed manually in the present embodiment, a weighing mechanism is provided in the sampling device 3 described above, and after weighing a predetermined amount, the sample is introduced into the concentration measurement device 11. Anyway.

Next, the solid content concentration (TS) of the weighed sample is measured (step 3—S3). Specifically, a sample for measurement was introduced into an aluminum container 116 of the concentration measuring device 111, and the sample was thermally dried with a dryer 114, and then the weight of the polymer after drying was measured electronically. Measure with a balance 1 1 2 and then weigh the dried sample. Calculate the value of the solid concentration of the measurement sample by dividing by the amount of pull. Next, the value of the solid content concentration calculated by the concentration measuring device 11 is introduced as a predetermined output signal into the amount determining device 7, where a predetermined amount (for example, about 2.5 grams) is used in the present embodiment. The amount of the emulsion polymerization reaction solution containing the above polymer is determined (Step 4—S 4). The determined amount of the emulsion polymerization reaction solution is the amount of the emulsion polymerization reaction solution added to a fixed amount (for example, 100 milliliter) of the solvent, and is usually about 8 grams.

 Next, the amount of the emulsion polymerization reaction solution determined by the amount determination device 7 is weighed from the emulsion polymerization reaction solution sampled by the sampling device 3 in step 1 to obtain a sample for preparing a uniform solution (step 5). S5). In the present embodiment, the preparation sample is weighed manually, but a weighing mechanism is provided in the sampling device 3, where a predetermined amount is weighed and then introduced into the uniform solution preparation device 8. Oh good.

 Next, a uniform amount (for example, 100 milliliters) of a solvent is added to the weighed sample to prepare a homogeneous solution (Step 6-S6). Specifically, a fixed amount (for example, 100 milliliters) of a solvent is supplied from a solvent tank 82 of the homogeneous solution preparation device 8 to a container 86 through a model syringe pump 84, and this is stirred. The weighed sample is dropped and dissolved in the place where the measurement is performed. The dropping time of the sample is usually 30 seconds to 5 minutes, preferably about 1 to 3 minutes. If dripped too soon, it may take a long time to dissolve. In this embodiment, tetrahydrofuran (THF) is used as a solvent to be added.

Next, the viscosity of the prepared homogeneous solution is measured (Step 7—S7). Specifically, in the present embodiment, the container 86 in which the homogeneous solution has been prepared is transferred into the thermostatic bath 44 of the viscosity measuring unit 4 using an automatic transfer device (not shown) such as an arm robot. Then, the homogeneous solution 49 in the container 86 is kept at about 25 ° C. Then, the liquid level sensor 4 2 5 vibratory viscometer ⁴ 2, after placing in a fixed position at the vibrator 4 2 6 in a homogeneous solution 4 9, by operating the electromagnetic drive unit (not shown) The vibrators 426 are vibrated in opposite phases and at the same period. At this time, the viscous resistance generated between the vibrator 4 26 arranged in the uniform solution 49 and the uniform solution 49 is The solution viscosity of the homogeneous solution 49 is measured by detecting the change in the amplitude value of the vibrator 426 with the displacement sensor 427. Since a predetermined relationship is established between the amplitude value of the vibrator 426 and the viscous resistance, the viscosity of the homogeneous solution 4.9 can be measured by measuring the change in the amplitude value.

 Next, the value of the solution viscosity of the homogeneous solution measured by the vibrating viscometer 42 is introduced as a predetermined output signal into the estimating arithmetic unit 5, and the value of the mu viscosity is calculated (step 8). '"S 8).

 On the other hand, after the value of the solution viscosity of the homogeneous solution 49 is introduced into the estimating arithmetic unit 5, the viscometer 42 is washed for the next measurement (step 9—S9). Washing of the viscometer 42 is not particularly limited, and may be performed by, for example, showering a solvent (not shown) before the viscometer 42 is dried, or may be cleaned by blowing air. Natural drying may be used. In any case, it is preferable to automatically wash the viscometer 42, but it may be done manually. In addition, the homogeneous solution 49 after the viscosity measurement is automatically discarded, and the container 86 after the uniform solution 49 is discarded is automatically or manually washed and dried, and then set at the original position. A total of 4 2 and others may be automatically returned to their original positions.

 In the present embodiment, the amount determining device 7 is configured to determine the amount of the emulsion polymerization reaction solution containing a predetermined amount of the polymer based on the value of the solid concentration measured by the concentration measuring device 11. However, a configuration in which the amount of the solvent is determined based on the value of the measured solid concentration may be adopted. In this case, the homogeneous solution 49 may be prepared by adding the determined amount of the solvent to a predetermined amount (for example, about 10 g) of the emulsion polymerization reaction solution to prepare the homogeneous solution 49. .

 In the method for producing a polymer according to the present invention, the polymerization reaction factor is changed according to the value of the Mooney viscosity in the emulsion polymerization reaction solution calculated as described above.

As the polymerization reaction factors, as a raw material supply element, the addition of monomers, a polymerization initiator, a molecular weight regulator and other polymerization auxiliary materials, the presence or absence of additional input, the timing of the additional input, and the additional amount; as an emulsion polymerization element The flow rate of the refrigerant or heat medium controlling the reaction temperature, the reaction pressure, the stirring speed of the polymerization reaction tank and the method of stirring the polymerization reaction tank; and the addition of a polymerization terminator as a polymerization termination element, and the polymerization reaction. Cooling in the tank and depressurization in the polymerization reaction tank; And the like. In the present invention, it is preferable that at least one selected from these polymerization reaction factors is appropriately selected and changed. By changing the various polymerization reaction factors as described above, the deviation from the target quality can be adjusted by changing the reaction conditions. In particular, changing the additional amount of the molecular weight modifier added to the polymerization system as a polymerization reaction factor is effective in adjusting the Mooney viscosity of the obtained polymer. The method of determining the amount that changes the polymerization reaction factor is not particularly controlled. For example, proportional control, proportional integral control, proportional integral derivative control, fuzzy control, adaptive control, etc. can be applied as the control algorithm.

 In addition, in the case of patch-type (batch-type) polymerization, the viscosity of the polymer after the polymerization is measured in a short time, and depending on whether the viscosity is within the range of the target muny viscosity, It is also preferable to select the post-treatment, which is to be sent to the combined separation / recovery process or to the disposal process, and then to execute it. By carrying out in this manner, when the polymerization is repeated until the required amount of the target polymer is obtained, the time during which the polymerization reaction is not performed inside the polymerization reactor can be shortened, and the production efficiency can be increased.

In addition, in this invention, you may apply to not only batch type polymerization but continuous type polymerization. The polymer obtained by the production method of the present invention, when measured at 100 ° C according to JIS-K630, is usually 5 to 100, preferably 10 to 95, more preferably Has a Mooney viscosity (ML _{1 +4} , 100 ° C.) of about 25 to 85.

 In the present embodiment, the viscosity of the polymer contained in the emulsion polymerization reaction solution is not directly measured, but a uniform solution prepared by adding a solvent to the emulsion polymerization reaction solution, which is a substitute physical property. Is measured using a vibrating viscometer, and the value of the Mooney viscosity of the polymer is calculated from the measured value of the solution viscosity. Therefore, the value of the Moieux viscosity of the polymer contained in the emulsion polymerization reaction solution can be measured in a short time and accurately. As a result, a desired quality polymer having a predetermined viscosity can be industrially advantageously produced without losing the end time of the reaction.

In the present invention, the “target quality” is not limited to the polymer's viscosity, molecular weight, molecular weight distribution, etc., and the production efficiency such as the yield of the polymer relative to the amount of monomer used is not limited. It is used in the sense including also. For example, in a patch-type polymerization, the polymer is not polymerized by multiple patch-type polymerizations, such as the time during which the polymerization reaction does not progress in the polymerization reactor. Includes the efficiency of use of manufacturing equipment when manufacturing

 In order to realize the above-described method for producing a polymer according to the present invention, for example, a polymer production apparatus 300 having the configuration shown in FIG. 1 can be used.

 As shown in FIG. 1, the production apparatus 300 has a polymerization reaction tank 1 for obtaining an emulsion polymerization reaction solution by an emulsion polymerization reaction. The polymerization reaction tank 1 has a line 200 for supplying deionized water 20, a line 210 for supplying a monomer 21, a line 220 for supplying an emulsifier 22, and a line for supplying a polymerization initiator 23. 230, a line 240 to which the co-catalyst 24 is supplied, and a line 250 to which the molecular weight modifier 25 is supplied. Lines 200, 210, 220, 230, 240, 250 are provided with automatic regulating valves 209, 219, 229, 239, 249, 259. The automatic control valves 209 to 259 are based on data sent from the flow meters 208, 218, 228, 238, 248, and 258, and based on the data sent from the polymerization reaction tank 1, deionized water 20, monomer 21, emulsifier 22, and polymerization initiator. 23, its opening is adjusted to change the input amount of the promoter 24 and the molecular weight regulator 25. The polymerization reaction tank 1 may be connected to another line (not shown) for supplying other polymerization auxiliary materials.

 A temperature control member 29 is mounted around the polymerization reaction tank 1. A line 260 to which the refrigerant or the heat medium 26 is supplied is connected to the temperature adjusting member 29. An automatic regulating valve 269 is arranged on the line 260. The automatic adjustment valve 269 controls the flow of the refrigerant or heat medium 26 to the temperature adjustment member 29 based on the data sent from the adjuster 267 based on the data from the thermometer 10 that measures the temperature in the polymerization reactor 1. The opening is adjusted in order to change the volume and, consequently, the temperature in the polymerization reactor 1.

 A pressure reduction adjustment line 280 is connected to the upper part of the polymerization reaction tank 1. In the line 280, an automatic regulating valve 289 and a compressor 286 as a pressure reducing means are arranged. The opening of the automatic adjustment valve 289 is adjusted based on the data sent from the regulator 287 to change the degree of pressure reduction in the polymerization reaction tank 1.

The transfer tank 2 is connected to the polymerization reaction tank 1 through a line 70. A line 270 to which the polymerization terminator 27 is supplied is connected to the transfer tank 2. line At 270 an automatic regulating valve 279 is arranged. The opening of the automatic adjusting valve 279 is adjusted based on data sent from the flow meter 278 to change the amount of the polymerization terminator 27 injected into the transfer tank 2.

 In the present embodiment, the configuration is such that the polymerization terminator 27 is charged into the transfer tank 2, but the present invention is not limited to this. The line 270 may be connected to the polymerization reaction tank 1, and the polymerization terminator 27 may be added to the emulsion polymerization reaction liquid in the polymerization reaction tank 1. Also, the polymerization terminator 27 should be injected into the line 70 connecting the polymerization reaction tank 1 and the transfer tank 2, that is, during the transfer of the emulsion polymerization reaction liquid from the polymerization reaction tank 1 to the transfer tank 2. It can be a simple configuration.

 In the present embodiment, the measuring apparatus 100 shown in FIG. 5 described above is connected to the polymerization reaction tank 1. The calculated value of mu-viscosity calculated by the measuring device 100 is input as a predetermined output signal to the control operation device 6 as a factor changing means. The control calculation device 6 controls the flow meters 208, 2 18, 22, 8, 238, 248, 258, 278 based on the output signal from the measuring device 100, and pulls the automatic adjustment valve 209, 2 1 9, 2 29, 2 3 9, 24 9, 25 9, 2 6 9, 2 7 9, 289 are controlled.

 Next, the operation of the manufacturing apparatus 300 according to the present embodiment will be described with reference to FIGS. 1, 5 and 6.

 First, deionized water 20, monomer 21, emulsifier 22, polymerization initiator 23, cocatalyst 24 and molecular weight regulator 25 force Flowmeter 208, 2 18, 228, 238, 248 and 2 Automatic control valve controlled by the data from 58, 209, 219, 229, 239, 249, and 259, and a certain amount is injected into the polymerization reactor 1 ( Raw material supply step), emulsion polymerization is started.

The monomer 21, in this embodiment, the _{c-unsaturated} nitrile using the unsaturated nitrile and a conjugated diene, acrylonitrile; _alpha - black port acrylonitrile, such as α- promo acrylate Roni Torino Les _alpha - Harogenoakuriro two Tolyl; high alkyl acrylonitrile such as methacrylonitrile and ethacrylo-tolyl; and the like. Among them, acrylonitrile is preferred. These unsaturated-tolyls may be used alone or in combination of two or more. Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethynole-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and 2,4-hexadiene. Among them, 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is particularly preferred. These conjugated gens may be used alone or in combination of two or more.

 From the start to the end of the polymerization, the flow rate of the refrigerant or the heat medium 26 is adjusted by the automatic adjustment valve 269 controlled by the controller 267 based on the data from the thermometer 10, and the temperature in the polymerization reactor 1 is adjusted. (Emulsion polymerization step).

 As the polymerization progresses, after a predetermined time has elapsed since the start of polymerization,? A part of the L-polymerization reaction liquid is withdrawn from the polymerization reaction tank 1 and introduced into the measuring apparatus 100 according to the present embodiment shown in FIGS. 5 and 6, where the polymer contained in the emulsion polymerization reaction liquid is removed. The viscosity is calculated. The principle from the sampling from the polymerization reactor 1 to the calculation of the Mooney viscosity is as described above.

 The calculated value of the viscosity is transmitted to the control arithmetic unit 6 as a predetermined output signal. In the control arithmetic unit 6, first, the input value of the viscosity is compared with a preset Mooney viscosity target value. Next, based on this comparison result, additional introduction of monomer 21, polymerization initiator 23, molecular weight regulator 25 and other polymerization auxiliary materials (deionized water 20, emulsifier 22, and cocatalyst 24) Presence / absence, additional charge timing and additional charge (raw material supply element); flow rate of refrigerant or heat medium 26 controlling reaction temperature, reaction pressure, stirring speed of polymerization reaction tank 1 and stirring method of polymerization reaction tank 1 (emulsion And a control signal for changing at least one selected from the group consisting of: a polymerization terminator 27, cooling in the polymerization reaction tank 1 and depressurization in the polymerization reaction tank 1 (polymerization termination element). . Finally, the generated control signal is transmitted to at least one selected from the controllers 207, 217, 227, 237, 247, 257, 267, 277, and 287.

The regulators 207 to 257 receiving the signal issue instructions to adjust the flow to the flow meters 208, 218, 228, 238, 248, and 258, and the automatic regulators 209, 219, 229, 239, 249 For 259, an appropriate opening degree is set so that the determined additional component and the determined amount are additionally added to the polymerization reactor 1. Adjust to

 The controller 2667 receives the signal and adjusts the opening to an appropriate value so that the cooling medium or the heating medium 26 flows at an appropriate flow rate to the automatic adjusting valve 269. Thereby, the temperature in the polymerization reaction tank 1 is adjusted.

 When the predetermined viscosity is reached, the emulsion polymerization reaction liquid is transferred to the transfer tank 2 based on the data from the control arithmetic unit 6.

 Also, when the control signal generated by the control arithmetic unit 6 is sent to the regulator 277, the regulator 277 receiving the signal issues an instruction to adjust the flow rate by the flowmeter 278, For the automatic adjustment valve 27, an appropriate opening is adjusted so that a certain amount of the polymerization terminator 27 is charged into the transfer tank 2. When a polymerization terminator 27 is charged into the transfer tank 2, the polymerization reaction is stopped (polymerization termination step).

 When the control operation unit 6 determines that the polymerization is stopped, in addition to the addition of the polymerization terminator 27, the control signal generated by the control operation unit 6 is transmitted to the automatic adjustment valve 28 disposed on the pressure reduction adjustment line 280. The automatic control valve 289 receives this signal, fully opens the valve, activates the compressor 286, and sucks the pressure inside the polymerization reaction tank 1 through the line 280 under reduced pressure. (Polymerization stopping step). The degree of pressure reduction at this time may be set so as to be equal to or less than the pressure (gauge pressure) in the polymerization reactor 1, for example, −80 kPa. When the pressure in the polymerization reaction tank 1 is reduced to remove the monomer, the polymerization reaction stops. If the opening degree of the automatic control valve 26 is adjusted and the amount of the refrigerant 26 flowing in the temperature control member 29 is increased, the inside of the polymerization reaction tank 1 is cooled (polymerization stop step). The polymerization reaction can also be stopped by a method.

 Thereafter, the polymerization reaction tank 1 in which the polymerization has been stopped is washed and prepared so that the next polymerization can be performed.

 In the present embodiment, an example has been described in which the polymerization terminator 27 is charged in the transfer tank 2.However, for example, when the transfer from the polymerization reaction tank 1 to the transfer tank 2 takes time, , A polymerization terminator 27 may be added.

As described above, the embodiments of the present invention have been described. However, the present invention is not limited to these embodiments at all, and may be implemented in various modes without departing from the gist of the present invention. Of course. For example, in the above-described embodiment, the value of the viscosity of the polymer is calculated from the value of the solution viscosity of the homogeneous solution measured using the vibrating viscometer, and the calculated mu-viscosity of the polymer is calculated. The polymerization reaction factor is changed according to the value. However, the present invention is not limited to this method, and the polymerization reaction factor may be changed according to the value of the measured solution viscosity of the homogeneous solution. This is because there is a predetermined correlation between the solution viscosity of the homogeneous solution prepared by adding a solvent to the polymerization reaction solution and the Mooney viscosity of the polymer contained in the polymerization reaction solution. Even if the polymerization reaction factor is changed in accordance with the value, the same effect is obtained, that is, a polymer of the desired quality having a predetermined Mooney viscosity without losing the reaction end time is industrially advantageous. Because it can be manufactured in In this case, the estimating device 5 (see FIG. 5) of the corresponding device 100 and step 8 (see FIG. 7) of calculating the Mooney viscosity by the device 5 can be omitted. The solution viscosity data output from the apparatus 100 is introduced into the control arithmetic unit 6 of the apparatus 300 (see FIGS. 1 and 5), and is used for subsequent control. Example

 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Parts and percentages are by weight unless otherwise specified. The calculated Mooney viscosity was a value rounded to the nearest whole number.

 In addition, each measured value was measured as follows.

 (1) The solid content concentration of the emulsion polymerization reaction solution was measured in accordance with JIS-K6387-2.

 (2) The polymerization conversion of the emulsion polymerization reaction solution was calculated from the solid content concentration and the amount of monomer added to the reaction solution.

 (3) The water content and the monomer content of the emulsion polymerization reaction solution were measured by gas chromatography.

(4) The content of the milk polymerization agent (sodium dodecyl sulfate) in the emulsion polymerization reaction solution was determined by dissolving the emulsion polymerization reaction solution in methyl ethyl ketone, pouring it into methanol, reprecipitating the polymer, filtering off, and concentrating the filtrate. Then, it was determined by performing NMR measurement. (5) The molecular weight regulator (dodecyl mercaptan) is prepared by dissolving the emulsion polymerization reaction solution in a mixed solvent of methyl ethyl ketone and isopropyl alcohol (weight ratio of methyl ethyl ketone and isopropyl alcohol 7: 3). And titrated with silver nitrate for measurement.

 (6) The content of the polymerization initiator (peroxide at the mouth of tamenhydride) was measured by gas chromatography.

 Example 1

 In a polymerization reactor, 285 parts of deionized water, 30 parts of acrylonitrile, 70 parts of butadiene, 3 parts of sodium dodecinole sulfate, 0.1 part of iron sulfate, 0.1 part of sodium formaldehyde aldehydesulfoxylate 0.1 part I put in 01 copies. Further, 0.556 parts of dodecyl mercaptan, which is a molecular weight modifier, was added, and the mixture was maintained at 10 ° C with sufficient stirring so that the mixture became uniform.After about 10 hours, when the polymerization conversion reached 90%, The reaction was stopped by adding 0.1 part of hydroxylamine sulfate and 0.1 part of sodium hydroxide. This polymerization was performed three times in total. Further, the polymerization was carried out three times each with the amounts of dodecyl mercaptan being 0.549, 0.527, 0.505 and 0.484 parts.

10 g of each obtained emulsion polymerization reaction solution was collected and converted to methyl ethyl ketone (solubility of water at 20 ° C 9.9%, δ value of solubility parameter 19. OMP a ^1/2 ) 80. After dissolution, 15 kinds of 90 g (about 110 m 1) of a homogeneous solution (polymer content: 2.6%) were prepared. These homogeneous solutions were measured at 25 ° C using a tuning fork vibrating viscometer (A'and'h CJ V5000).

1250 parts of each emulsion polymerization reaction solution was added to 2500 parts of a 10% aqueous sodium chloride solution at 60 ° C. to precipitate a polymer, and the precipitated polymer was collected by filtration and collected with 3500 parts of deionized water. After washing twice, it was dried under hot air at 80 ° C. for 90 minutes. The viscosity of the resulting 15 types of polymers (ML _{1 + 4} , 100 ° C) was measured using a Mooney viscometer (島 VIS COMET ER SMV-202 manufactured by Shimadzu Corporation) according to 'JIS-K6300. Measured at 100 ° C.

Assuming that the measured solution viscosity is X (mPas) and the viscosity of the solution is y, the following correlation was found between χ and y. This relational expression is shown in 阅 2. y = 2 8 .0 1-2 0 .4 4

 (Correlation coefficient 9 8 6)

 Examples 2 to 5

 Except that the amount of dodecyl mercaptan was set to the amount shown in Table 1, polymerization was performed only once in the same manner as in Example 1, and a homogeneous solution (polymer content: 2.6% by weight) was prepared from the emulsion polymerization reaction solution in the same manner. The solution viscosity was measured, and the viscosity of the polymer in the emulsion polymerization reaction liquid was calculated using the relationship between the solution viscosity and the viscosity measured in Example 1 as a calibration curve. Table 1 shows the polymer content, water content, monomer content, emulsifier content, solution viscosity, and calculated viscosity. The time from collection of the emulsion polymerization reaction solution to calculation of the Mooney viscosity was about 7 minutes in each case. The measurement error in Table 1 is the absolute value of the difference between the calculated Mooney viscosities of Examples 2 to 5 and the actually measured Moieux viscosities measured in Comparative Examples 1 to 4 below.

 Comparative example:! ~ Four

 Except for using the emulsion polymerization reaction liquid obtained in Examples 2 to 5 instead of the emulsion polymerization reaction liquid obtained in Example 1, the polymer was recovered in the same manner as in Example 1, and the Muney viscosity was measured. It was measured. Table 1 shows the amount of polymer recovered and the measured Mooney viscosity. ? The time from collection of the Wander polymerization reaction solution to completion of the Mooney viscosity measurement was about 150 minutes in each case.

(Hereinafter, margin)

Dodecyl 0.500 0.496 0.492 0.488 Mercaptan (parts)

Example 2 3 4 5

Polymerization conversion (%) 90.0 89.9 89.6 90.2 Solid concentration (%) 23.4 23.4 23.3 23.4 Containing polymer 22.4 22.4 22.3 22.4 Water 74.3 74.3 74.4 74.3 Yes Single a: Form 2.3 2.3 2.3 2.3 Emulsifier 0.8 0.8 0.8 0.8 ri Molecular weight regulator 0.010 0.011 0.011 0.013

(%) Polymerization catalyst 0.001 0.001 0.001 0.001 Homogeneous solution

Solution viscosity (mPa ■ s) 3.57 3.64 3.64 3.68 Calculated Mooney viscosity 80 82 82 84 Comparative example 1 2 3 4 Polymer recovery ω 285 285 286 286 Actual measured Mooney viscosity 80 81 82 84

Example 6

 Polymerization was carried out in the same manner as in Example 1 except that the amount of deionized water was changed to 200 parts. A uniform solution (polymer content: 3.4%) was prepared from the emulsion polymerization reaction solution, and the solution viscosity was measured. The viscosity was calculated.

 Further, 950 parts of this emulsion polymerization reaction solution was used instead of 125 parts of the emulsion polymerization reaction solution obtained in Example 1, and 8.9 93 parts of this emulsion polymerization reaction solution was used instead of 250 parts of a 10% aqueous sodium chloride solution. % Aqueous sodium chloride solution (250 parts of sodium chloride dissolved in 250 parts of deionized water) The polymer was recovered in the same manner as in Example 1 except that 280 parts of sodium chloride was used. I—The viscosity was measured.

 Assuming that the solution viscosity is X (mPas) and the measured Mooney viscosity is y, the following correlation was found between x and y. This relation is shown in FIG. y = 1 7 .2 6-1 2 .8 1

 (Correlation coefficient 0.992)

 Example 7-: L 0

 Same as Example 1 except that the deionized water was set to 200 parts by weight and the amount of dodecyl mercaptan was set to 0.488, 0.492, 0.496, and 0.5 parts. A homogeneous solution (polymer content: 3.4%) was prepared from the emulsion polymerization reaction solution, the solution viscosity was measured, and the Mooney viscosity of the polymer in the emulsion polymerization reaction solution was determined in Example 6. The relational expression between viscosity and Mooney viscosity was calculated as a calibration curve. Table 2 shows the polymerization conversion rate, solid content concentration, water content, monomer content, molecular weight modifier content, polymerization catalyst content, solution viscosity, and calculated mu-viscosity of the emulsion polymerization reaction solution. The time from collection of the emulsion polymerization reaction solution to calculation of the viscosity was approximately 7 minutes in all cases. The measurement error in Table 2 is the absolute value of the difference between the calculated Mooney viscosities of Examples 7 to 10 and the actually measured Mooney viscosities measured in Comparative Examples 5 to 8 below.

 Comparative Examples 5 to 8

The polymer was recovered in the same manner as in Example 2 except that the emulsion polymerization reaction liquid obtained in Examples 8 to 11 was used instead of the emulsion polymerization reaction liquid obtained in Example 1, and Mooney viscosity was measured. Table 2 shows the amount of polymer recovered and the measured Mooney viscosity. _ _ 2

Comparative Example 9

 Polymerization was performed only once, as in Example 1, except that 200 parts by weight of deionized water and 0.562 parts of dodecyl mercaptan were used.10 parts of the emulsion polymerization reaction solution was collected and dissolved in 80 parts of THF. Then, 5 ml of THF was added to 59 mg of the solution to make a homogeneous solution, which was subjected to gel chromatography analysis. For gel chromatography analysis, an HLC-820GPCZSC-8020 device, TSK-ge1 GMH HR-M (S) column, and a differential refractive index detector manufactured by Tosoh Corporation were used. The measurement conditions were a THF flow rate of 1 m 1 / m i η and 40 ° C. It took about 150 minutes from collecting the emulsion polymerization reaction solution to obtaining the weight average molecular weight and the like.

 Comparative Examples 10 to 12

 Instead of a tuning fork vibrating viscometer, a B-type viscometer (Pisco Tech's Pisco Elite), a capillary viscometer (Shibata Kagaku's Ubbelohde viscometer) or a coaxial double cylindrical viscometer (Pisco Tech's RC-20) The solution viscosity of the emulsion polymerization reaction solution of Example 1 was measured in the same manner as in Example 1 except for using. Next, the Mooney viscosity was measured.

 Assuming that the measured solution viscosity is X (mPas) and the actually measured Mooney viscosity is y, the following correlation was found between X and y.

 When using a B-type viscometer, y = 26.13 X-9.55

 (Correlation coefficient) 0.947

When using a capillary viscometer, y = 26.92 X-16.73

 (Correlation coefficient) 0.983

When using a coaxial double cylindrical viscometer, y = 32.88 X-37.03

 (Correlation coefficient) 0.938

Then, the solution viscosity of the emulsion polymerization reaction solution obtained in Example 2 was measured in the same manner as in Example 2 except that the above-mentioned viscometer was used instead of the tuning fork vibrating viscometer, and the emulsion polymerization reaction was performed based on the above equation. The viscosity of the polymer in the liquid was calculated. About 1 5 minutes time taken to calculate the collection or ram one knee viscosity of the emulsion polymerization reaction in each of the viscometer, about 30 minutes, it took about ² 5 minutes. Next, the viscosity of the polymer was measured in the same manner as in Comparative Example 1. Table 3 shows the measured solution viscosity and Mooney viscosity. The measurement error in Table 3 Is the absolute value of the difference between the calculated Moieux viscosity and the actually measured viscosity.

(Hereinafter, margin)

CO

 Example 2 Comparative Example 10 Comparative Example 12 Comparative Example 13

Vibration type tuning fork type B type Capillary type Coaxial double cylindrical type Solution viscosity (mPas) 3.57 3.70 3.62 3.63

Calculated Mooney viscosity 80 87 81 82

From collection of emulsion polymerization liquid

Time required to calculate the Mooney viscosity (min) 7 15 30 25

Actual Mooney viscosity 80

Measurement error 0 1 7 1 1 1 2

Example 1 1

 The polymerization was started in the same manner as in Example 1 except that a polymerization reaction tank having a different shape was used.Emulsion was collected every 30 minutes from the third hour from the start of the polymerization, and the solution viscosity of the homogeneous solution and mu The viscosity was measured and a calibration curve was prepared. The polymer content of the homogeneous solution when measuring the solution viscosity was adjusted to 2.6%. FIG. 4 shows the change in the viscosity of the polymer in the emulsion measured from the value of the solution viscosity of the homogeneous solution as the polymerization proceeds. Assuming that the measured viscosity is y and the solution viscosity is X (mPa · s), there was the following correlation between X and y.

y = 2 3 .8 7 X-5.7 2

 (Correlation coefficient 0.995)

 Polymerization was started in the same composition and in the same polymerization reactor as above with the target product viscosity being 80, and the emulsion was collected every 30 minutes from the third hour after the start of polymerization, as in Example 1. Then, a homogeneous solution was prepared so that the polymer content became 2.6%, the solution viscosity was measured, and the Mooney viscosity was calculated from the measured value by the above calibration curve. The calculated Mooney viscosity reached 61 at 8 hours and 30 minutes and 70 at 9 hours from the start of the polymerization. As a result, it was considered that the Mooney viscosity reached 80 in about 9 hours and 30 minutes after the start of the polymerization. Since it takes about 7 minutes to calculate the viscosity, it is calculated that the viscosity after 9 hours and 15 minutes is calculated to be 75 after 9 hours and 22 minutes. I understand. Therefore, since the change in Mooney viscosity was 5 in 15 minutes, it was determined that the Mooney viscosity reached the target value of 80 at 9 hours and 30 minutes, and at 9 hours and 30 minutes To stop the reaction.

 The viscosity of the obtained polymer was 81 as a value calculated from the value of the solution viscosity, and 80 as a measured value.

As shown in Comparative Examples 1 to 8, it takes time to measure Mooney viscosity. Further, it takes time to calculate the viscosity of the gel by gel-mouth analysis shown in Comparative Example 9. Calculation of the viscosity of the solution from the value of the solution viscosity measured by the B-type viscometer shown in Comparative Example 10 is relatively short, but has a large error from the actually measured value. When the Mooney viscosity was calculated from the solution viscosity value measured by the cavitary type viscometer shown in Comparative Example 11 or the coaxial double cylindrical viscometer shown in Comparative Example 12, the error from the measured value was small. But it takes time.

 On the other hand, the solution viscosity was measured by a method using a tuning fork vibrating viscometer, and was prepared based on the solution viscosity measured in advance by the method and the actually measured Mooney viscosity as in Examples 1 and 6. According to the measurement method of the present invention for calculating the Mooney viscosity using a calibration curve, as shown in Examples 2 to 5 and Examples 7 to 10, the Mooney viscosity can be measured with high accuracy in a short time. Can be measured.

 Further, as shown in Example 11, the method for measuring mu-viscosity of the present invention can be measured in a short time and the accuracy of the measured mu-viscosity is high. It can be used for control to efficiently produce the target polymer.

 Example 12

 In a polymerization reactor, 285 parts of deionized water, 50 parts of acrylonitrile, 50 parts of butadiene, 3 parts of sodium dodecyl sulfate, 0.1 part of iron sulfate, 0.1 part of sodium formaldehyde hydrosulfoxylate and 0.1 part of cumenehydroxide We have added 0.01 parts. Further, 0.556 parts of dodecyl mercaptan, which is a molecular weight modifier, was added, and the mixture was maintained at 10 ° C with sufficient stirring so that the mixture became uniform.After about 10 hours, when the polymerization conversion reached 90%, The reaction was stopped by adding 0.1 part of hydroxylamine sulfate and 0.1 part of sodium hydroxide. This polymerization was performed twice in total. Further, the amount of dodecyl mercaptan was adjusted to 0.549, 0.527, 0.505, and 0.55 parts.

Polymerization was carried out twice with 484 parts, 0.475 parts, and 0.468 parts.

 10 g of each obtained emulsion polymerization reaction liquid was collected, and this was added to tetrahydrofuran (20

46.5% water solubility at ° C, δ value of solubility parameter 18.6ΜΡa ^1/2 ) 8

Fourteen kinds of 95 g (about 110 m 1) of a homogeneous solution (polymer content 2.4%) dissolved in 5 g were prepared. These homogeneous solutions were measured at 25 ° C using a tuning fork vibrating viscometer (CJV5000, manufactured by A & D).

'' 1250 parts of each emulsion polymerization reaction solution was added to 2500 parts of a 10% aqueous sodium chloride solution at 60 ° C to precipitate a polymer, and the polymer precipitated was collected by filtration, and 3500 parts of deionized water was collected. After two washes in 80. It was dried under hot air of C for 90 minutes. According to JIS-K6300, the mu-viscosity (ML _{1 + 4} , 100 ° C) of the obtained 14 types of polymers was measured according to JIS-K6300 (Moon VIS VIS COMET manufactured by Shimadzu Corporation). It was measured at 100 ° C using ER SMV-202).

 Assuming that the measured solution viscosity is x (mP a · s) and the Mooney viscosity is y, the following correlation was found between x and y. FIG. 8 shows this relational expression. y = 16.2 3 X-1 7.70

 (Correlation coefficient 0.99 7 9)

 Example 13

 30 parts of acrylonitrile, 70 parts of butadiene, 0.358 parts, 0.340 parts, 0.340 parts, 0.313 parts, 0.21 part, 0.239 parts, 0.223 parts of dodecyl mercaptan Polymerization was carried out twice in the same manner as in Example 12 except that the amount was changed to 0.22 parts. Thereafter, as in Example 12, when the measured solution viscosity was X (mPas) and the Mooney viscosity was y, it was found that there was the following correlation between X and y. . This relation is shown in FIG.

y = 1 4.5 6-2 7.76

 (Correlation coefficient 98 3)

 Example 14

 20 parts of acrylonitrile, 80 parts of butadiene, 0.253 parts of dodecyl mercaptan, 0.243 parts, 0.234 parts, 0.234 parts, 0.224 parts, 0.216 parts, 0.211 parts, Polymerization was performed twice in the same manner as in Example 12 except that the amount was 0.26 parts. Then, as in Example 12, when the measured solution viscosity was X (mPa-s) and the Muney viscosity was y, it was found that the following correlations exist between X and y. . This relation is shown in FIG.

y = 1 1.22-9.3 52

 (Correlation coefficient 0.983)

Claims

The scope of the claims

1. a step of measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the polymerization reaction solution using a vibrating viscometer;

 Calculating the value of the viscosity of the polymer contained in the homogeneous solution from the value of the measured solution viscosity.

 A method for measuring the viscosity of a polymer.

2. The method according to claim 1, wherein a tuning fork type viscometer is used.

3. The method according to claim 1, wherein an emulsion polymerization reaction liquid is used as the polymerization reaction liquid.

4. The method according to claim 3, wherein an emulsion polymerization reaction solution of a copolymer composed of unsaturated 2'-tolyl and a conjugated diene is used.

5. The method for measuring the Mooney viscosity of a polymer according to claim 1, wherein a solvent having a water solubility of 5% by weight or more at 5.2 ° C. is used.

6. The method for measuring Mooney viscosity of a polymer according to claim 5, wherein a ketone or a cyclic ether solvent is used as the solvent.

7. The method according to claim 1, wherein a homogeneous solution having a polymer content of 0.5 to 6% by weight is used.

8. A concentration measuring means for measuring the solid content concentration of the polymerization reaction solution, and an amount of the polymerization reaction solution or a solvent containing a predetermined amount of the polymer based on the value of the solid content concentration measured by the concentration measuring means. An amount determining means for determining the amount; Adding a predetermined amount of solvent to the amount of polymerization reaction solution determined by the amount determination means, or adding the determined amount of solvent to a predetermined amount of polymerization reaction solution to prepare a uniform solution Preparation means;

 A vibrating viscometer for measuring the solution viscosity of the uniform solution prepared by the uniform solution preparation means,

 A viscosity calculating means for calculating a viscosity of the polymer contained in the homogeneous solution from a value of the solution viscosity measured by the viscometer.

 A device for measuring the Mooney viscosity of a polymer.

9. The apparatus for measuring Mooney viscosity of a polymer according to claim 8, further comprising a sampling means for sampling a predetermined amount of a polymerization reaction solution for measuring a solid content concentration. -

10. A step of obtaining an emulsion polymerization reaction solution by an emulsion polymerization reaction, and a step of measuring the solution viscosity of a uniform solution prepared by adding a solvent to the emulsion polymerization reaction solution using a vibrating viscometer,

 From the value of the measured solution viscosity, a step of calculating the value of Mooney viscosity of the polymer contained in the homogeneous solution,

 Changing the polymerization reaction factor in accordance with the calculated value of the Mooney viscosity of the polymer.

 A method for producing a polymer.

11. A step of obtaining an emulsion polymerization reaction solution by an emulsion polymerization reaction, and a step of measuring the solution viscosity of a uniform solution prepared by adding a solvent to the emulsion polymerization reaction solution, using a vibrating viscometer,

 Changing a polymerization reaction factor in accordance with the value of the measured solution viscosity.

 A method for producing a polymer.

12. The method according to claim 10 or 11, wherein a tuning fork type viscometer is used. A method for producing a polymer.

1 3. The polymerization reaction factor is a raw material supply element,? At least one member selected from the group consisting of

 The raw material supply element is at least one selected from the presence or absence of additional input, the timing of additional input, and the additional input amount of a monomer, a polymerization initiator, a molecular weight modifier and other polymerization auxiliary materials,

 The emulsion polymerization element is at least one selected from a flow rate of a refrigerant or a heat medium for controlling a reaction temperature, a reaction pressure, a stirring speed of a polymerization reaction tank, and a stirring method of a polymerization reaction tank,

 The method for producing a polymer according to claim 10, wherein the polymerization terminating element is at least one selected from charging of a polymerization terminator, cooling in the polymerization reaction vessel, and reduced pressure in the polymerization reaction vessel.

14. A raw material supply step of supplying a raw material comprising a monomer, a polymerization initiator, a molecular weight modifier, and other polymerization auxiliary materials to a polymerization reaction tank;

 A method for producing a polymer, comprising: an emulsion polymerization step of polymerizing monomers in the polymerization reaction tank to obtain an 'emulsion polymerization reaction solution'; and a polymerization termination step of terminating the emulsion polymerization at a predetermined viscosity. And

 Measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the emulsion polymerization reaction solution collected from the polymerization reaction tank using a vibrating viscometer;

 Calculating a value of the viscosity of the polymer contained in the homogeneous solution from the value of the measured solution viscosity; and

 The calculated value of the viscosity of the polymer is transmitted to at least one step selected from the raw material supply step, the emulsification polymerization step, and the polymerization termination step, and the polymerization reaction in each step is performed. And a factor changing step of changing a factor.

 A method for producing a polymer.

1 5. Monomer, polymerization initiator, molecular weight modifier, and other polymerization auxiliary materials A raw material supply step of supplying a raw material comprising

 A method for producing a polymer, comprising: an emulsion polymerization step of polymerizing monomers in the polymerization reaction tank to obtain an emulsion polymerization reaction solution; and a polymerization termination step of terminating the emulsion polymerization at a predetermined Mooney viscosity.

 A step of measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the emulsion polymerization reaction solution collected from the polymerization reaction tank, using a vibrating viscometer,

 A factor changing step of transmitting the measured solution viscosity value to at least one step selected from the raw material supply step, the emulsion polymerization step, and the polymerization termination step, thereby changing a polymerization reaction factor in each step. And having

 A method for producing a polymer.

16. The calculated value of the viscosity of the polymer is transmitted to the raw material supply step, and at least one selected from the presence or absence of additional input of each raw material, the timing of additional input, and the additional input amount. 15. The method for producing a polymer according to claim 14, wherein

17. The value of the measured solution viscosity is transmitted to the raw material supply step, and at least one selected from the presence / absence of additional input of each raw material, the timing of additional input, and the additional input amount is changed. 15. The method for producing a polymer according to 15.

18. The calculated value of the Mooney viscosity of the polymer is transmitted to the polymerization stopping step, and is selected from the addition of a polymerization terminator, cooling in the polymerization reaction tank, and reduced pressure in the polymerization reaction tank. 15. The method for producing a polymer according to claim 14, wherein the polymerization reaction is stopped by at least one method.

19. The measured value of the solution viscosity is transmitted to the polymerization termination step, and at least one method is selected from the addition of a polymerization terminator, the cooling in the polymerization reactor, and the reduced pressure in the polymerization reactor. The method for producing a polymer according to claim 15, wherein the polymerization reaction is stopped by the method.

20. The method for producing a polymer according to claim 14 or 15, wherein an unsaturated etryl and a conjugated diene are used as monomers.

21. A polymerization reaction tank for obtaining an emulsion polymerization reaction liquid by an emulsion polymerization reaction, and a viscous viscosity for measuring the solution viscosity of a homogeneous solution prepared by adding a solvent to the emulsion polymerization reaction liquid collected from the polymerization reaction tank. And

 From the value of the solution viscosity measured by the viscometer, a Muney viscosity calculating means for calculating a Muie viscosity value of the polymer contained in the homogeneous solution,

 A factor changing means for changing a polymerization reaction factor in accordance with a value of the viscosity of the polymer calculated by the viscosity calculating means.

 Polymer production equipment.