CN110229255B - Method for producing vinylidene fluoride polymer - Google Patents
Method for producing vinylidene fluoride polymer Download PDFInfo
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- CN110229255B CN110229255B CN201910069020.7A CN201910069020A CN110229255B CN 110229255 B CN110229255 B CN 110229255B CN 201910069020 A CN201910069020 A CN 201910069020A CN 110229255 B CN110229255 B CN 110229255B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
- C08F14/22—Vinylidene fluoride
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
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Abstract
The invention provides a method for producing vinylidene fluoride polymer. The present application realizes a method for producing a vinylidene fluoride polymer in a shorter time and in a simpler manner. By mixing water and vinylidene fluoride-containing monomer at initial polymerization temperature to obtain vinylidene fluoride-containing monomer with density of 0.580g/cm 3 ～0.660g/cm 3 The vinylidene fluoride-containing monomer of the amount of (b) is supplied to a reactor, and suspension polymerization is performed in water under a condition that vinylidene fluoride is brought into a supercritical state to produce a vinylidene fluoride polymer.
Description
Technical Field
The present invention relates to a method for producing a vinylidene fluoride polymer.
Background
Vinylidene fluoride polymers are generally excellent in chemical resistance, weather resistance, stain resistance and the like, and are used in various applications such as various films, molding materials, coatings, adhesives and the like.
As a method for producing a vinylidene fluoride polymer, for example, a method for producing a vinylidene fluoride copolymer at a polymerization temperature of about 30 ℃ using a comonomer having a carboxyl group is known (for example, see patent document 1). Further, as a method for producing a vinylidene fluoride polymer, a method is known in which vinylidene fluoride is supplied at a temperature of 50 ℃ or higher in the initial stage of polymerization in a state of being lower than the critical pressure of vinylidene fluoride, and is additionally supplied at a pressure of not lower than the critical pressure during the polymerization to produce a vinylidene fluoride homopolymer (for example, see patent document 2). Further, as a method for producing a vinylidene fluoride polymer, a method for producing a vinylidene fluoride homopolymer by suspension polymerization of vinylidene fluoride at a temperature and a pressure (for example, 60 ℃ c., 55 bar to 200 bar) at which vinylidene fluoride is in a supercritical state is known (for example, see patent document 3).
Documents of the prior art
Patent literature
Patent document 1: japanese laid-open patent publication No. 6-172452 (published on 21/6/1994)
Patent document 2: international publication WO2006/061988 (published on 6/15/2006)
Patent document 3: japanese laid-open patent publication No. Sho 59-174605 (published 10/3/1984)
Disclosure of Invention
Problems to be solved by the invention
However, the production method described in patent document 1 has a long polymerization time, and there is still room for improvement from the viewpoint of productivity.
In the production method described in patent document 2, it is necessary to additionally supply the monomer during the polymerization reaction. Therefore, there is still room for improvement from the viewpoint of simplification of the manufacturing operation and the manufacturing apparatus.
In addition, the manufacturing method described in patent document 3 requires a manufacturing apparatus having high pressure resistance. Therefore, there is still room for improvement from the viewpoint of simplification of the manufacturing apparatus.
An object of one embodiment of the present invention is to provide a method for producing a vinylidene fluoride polymer in a shorter time and in a simpler manner.
Technical scheme
A method for producing a vinylidene fluoride polymer according to an aspect of the present invention comprises: a step of subjecting a vinylidene fluoride-containing monomer to suspension polymerization in water under conditions such that the vinylidene fluoride is in a supercritical state, wherein the density of the monomer at the polymerization initiation temperature of the suspension polymerization is 0.580g/cm 3 Above and 0.660g/cm 3 The following amount of the monomer was supplied to the reactor, and suspension polymerization was carried out under the condition of being brought into the supercritical state.
Advantageous effects
According to the present invention, a vinylidene fluoride polymer can be produced in a shorter time and more easily.
Detailed Description
Hereinafter, an embodiment of the present invention will be described in detail.
The method for producing a vinylidene fluoride polymer according to the present embodiment produces a vinylidene fluoride polymer by subjecting a vinylidene fluoride-containing monomer (hereinafter, also referred to as "vinylidene fluoride-containing monomer") to suspension polymerization in water under conditions such that vinylidene fluoride is in a supercritical state.
The vinylidene fluoride polymer is a polymer obtained by polymerizing a vinylidene fluoride-containing monomer, and includes a homopolymer of vinylidene fluoride (critical temperature Tc of 30.1 ℃ and critical pressure Pcr of 4.38MPa) and a copolymer of vinylidene fluoride and a monomer other than vinylidene fluoride that is polymerizable. The vinylidene fluoride copolymer contains a structural unit derived from vinylidene fluoride and a structural unit derived from a monomer other than vinylidene fluoride.
In other examples of monomers, include: fluorine-containing monomers (e.g., fluorinated ethylene, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether), ethylene, unsaturated dibasic acid derivatives (e.g., monomethyl maleate, dimethyl maleate), vinyl acetate, (meth) acrylamide, (meth) dimethylacrylamide, allyl glycidyl ether, alkyl (meth) acrylate compounds (e.g., (meth) methyl acrylate), carboxyl group-containing acrylate compounds, (e.g., (meth) acrylic acid, 2-carboxyethyl acrylate, (meth) acryloyloxypropyl succinate, (meth) acryloyloxyethyl succinate), 2-hydroxyethyl acrylate, and hydroxypropyl acrylate. Among them, one or more compounds selected from the group consisting of hexafluoropropylene, monomethyl maleate, (meth) acrylic acid, 2-carboxyethyl acrylate, (meth) acryloyloxypropyl succinate, and (meth) acryloyloxyethyl succinate are preferable.
The vinylidene fluoride content in the vinylidene fluoride-containing monomer of the present embodiment may be an amount of vinylidene fluoride as a main component, and may be 50 mass% or more, for example. The content of vinylidene fluoride in the vinylidene fluoride-containing monomer may be appropriately determined depending on the properties required for the vinylidene fluoride polymer to be produced. For example, from the viewpoint of sufficiently exhibiting the function of the structure derived from vinylidene fluoride in the vinylidene fluoride polymer, the content is preferably 80% by mass or more, more preferably 85% by mass or more, and particularly preferably 90% by mass or more. The content may be 100% by mass, but when the vinylidene fluoride polymer is a copolymer, for example, 99.9% by mass or less, more preferably 99% by mass or less is preferable in order to exhibit properties as a copolymer.
The production method of the present embodiment can be carried out in the same manner as a known method for producing a vinylidene fluoride polymer by suspension polymerization of vinylidene fluoride-containing monomer in water under conditions in which vinylidene fluoride is in a supercritical state, except for the supply amount of the vinylidene fluoride-containing monomer.
In the production method of the present embodiment, a specific amount of vinylidene fluoride-containing monomer and water are supplied to a reactor, and suspension polymerization is performed under conditions in which vinylidene fluoride is in a supercritical state. The vinylidene fluoride-containing monomer of the present embodiment is supplied to the reactor in such an amount that the density of the vinylidene fluoride-containing monomer at the polymerization initiation temperature of suspension polymerization is 0.580g/cm 3 Above and 0.660g/cm 3 The following amounts. When the amount of the vinylidene fluoride-containing monomer is in the above range, polymerization can be carried out in a short time while preventing the pressure in the reaction system from becoming too high. In addition, the vinylidene fluoride-containing monomer is preferably supplied in an amount within the above range from the viewpoint of achieving high productivity without additionally supplying the vinylidene fluoride-containing monomer and from the viewpoint of sufficiently improving the bulk density of the resulting vinylidene fluoride polymer. On the other hand, if the supply amount of the vinylidene fluoride-containing monomer is less than the above range, the bulk density of the powder of the produced vinylidene fluoride polymer may be decreased, and the productivity of the vinylidene fluoride polymer may be lowered. When the supply amount of the vinylidene fluoride-containing monomer is larger than the above range, the pressure in the suspension polymerization increases, and a specific production facility having high pressure resistance is required, which is not preferable.
Here, the polymerization initiation temperature is a temperature set as a start temperature of suspension polymerization. The starting temperature is a polymerization temperature when the suspension polymerization is carried out at a constant polymerization temperature. In the case where the polymerization temperature of the suspension polymerization is changed (for example, increased) in multiple stages, the above-mentioned starting temperature is the temperature of the first stage (i.e., the initial temperature of the polymerization) of the polymerization temperature. As described above, in the present embodiment, the start temperature of the suspension polymerization is usually adjusted to the polymerization initiation temperature.
The density of the vinylidene fluoride-containing monomer at the initial polymerization temperature is calculated by the following formula.
Dv＝Mv/(Vc-Vw)
In the above formula, Dv is the density (g/cm) of the vinylidene fluoride-containing monomer at the initial polymerization temperature 3 ) Mv is the feed amount (g) of the vinylidene fluoride-containing monomer, and Vc is the internal volume (cm) of the reactor 3 )，Vw is the volume of water (cm) in the reactor at the initial temperature of polymerization 3 ). Vc can be determined as the volume of water when the reactor equipped with a device for suspension polymerization such as a stirrer is filled with water. The content of the reactor can be measured at room temperature. Vw can be determined by dividing the amount of water supplied (g) by the density of water at the initial temperature of polymerization (g/cm) 3 ) And then the result is obtained.
If the amount of vinylidene fluoride-containing monomer to be supplied is too large, the pressure of the reaction system in the suspension polymerization increases, and a reactor having higher pressure resistance may be required. If the amount of the above-mentioned raw material is too small, the bulk density of the obtained vinylidene fluoride polymer powder may be lowered, and the powder may be deteriorated in handling property in the post-treatment, thereby lowering productivity. From the viewpoint of improving productivity, the above-mentioned supply amount is preferably such that the density of the vinylidene fluoride-containing monomer at the initial polymerization temperature is 0.580g/cm 3 More preferably, the density is 0.600g/cm 3 The above amount. In addition, from the viewpoint of suppressing the excessive rise of the pressure of the reaction system during suspension polymerization, the above supply amount is preferably such that the density of the vinylidene fluoride-containing monomer at the initial polymerization temperature is 0.660g/cm 3 The amount of (A) is more preferably 0.640g/cm 3 The following amounts.
In the production method of the present embodiment, the amount of water supplied to the reactor may be appropriately determined within a range in which suspension polymerization of the vinylidene fluoride-containing monomer can be sufficiently performed, and within a range in which the density of the vinylidene fluoride-containing monomer can be achieved. From such a viewpoint, the amount of water supplied to the reactor is preferably 2.6 times or more, and more preferably 3.0 times or more, based on the amount of the vinylidene fluoride-containing monomer supplied to the reactor. From the above viewpoint, the amount of water supplied is preferably 4 times or less, more preferably 3.6 times or less, based on the amount of vinylidene fluoride-containing monomer supplied to the reactor.
In the production method of the present embodiment, the polymerization initiation temperature may be appropriately determined within a temperature range sufficient to bring the vinylidene fluoride in the reactor into a supercritical state. Within this range, when the polymerization initiation temperature is too low, the reaction time of the suspension polymerization becomes long, and thus the productivity of the vinylidene fluoride polymer may be low, and when the polymerization initiation temperature is too high, the pressure of the reaction system of the suspension polymerization may be high, and a reactor having higher pressure resistance may be required. The polymerization initiation temperature is preferably 35 ℃ or higher, and more preferably 38 ℃ or higher, from the viewpoint of improving the productivity of the vinylidene fluoride polymer. From the viewpoint of suppressing the pressure rise in the reaction system, the polymerization initiation temperature is preferably 55 ℃ or lower, and more preferably 52 ℃ or lower.
In the production method of the present embodiment, other components than the above-mentioned water and vinylidene fluoride-containing monomer may be further used. Examples of such other components include a chain transfer agent, a polymerization initiator, and a suspending agent.
The chain transfer agent is used for the purpose of adjusting the molecular weight of the resulting polymer. The chain transfer agent may be one or more. The chain transfer agent may be appropriately selected from known compounds that can be used to adjust the molecular weight of the vinylidene fluoride-containing monomer. Examples of the chain transfer agent include ethyl acetate, propyl acetate, acetone, and diethyl carbonate. For example, the amount of the chain transfer agent is, for example, 5 parts by mass or less with respect to 100 parts by mass of the vinylidene fluoride-containing monomer.
The polymerization initiator may be one or more, and examples thereof include diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and tert-butyl peroxypivalate (perbutyl peroxibivalate). The amount of the polymerization initiator is, for example, 0.001 to 2 parts by mass per 100 parts by mass of the vinylidene fluoride-containing monomer.
The suspending agent is used for the purpose of improving dispersibility of the vinylidene fluoride-containing monomer in water. The suspending agent can be one or more than one. Examples of the suspending agent include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, partially saponified polyvinyl acetate, and acrylic polymer. The amount of the suspending agent is, for example, 0.01 to 2 parts by mass per 100 parts by mass of the vinylidene fluoride-containing monomer.
The manufacturing method of the present embodiment can be performed as follows: water, vinylidene fluoride-containing monomer, and other components added as needed are supplied to the reactor, and the temperature in the reactor is heated to the polymerization initiation temperature and maintained at the polymerization initiation temperature. The actual temperature in the reactor at this time is usually maintained within. + -. 1 ℃ relative to the initial polymerization temperature.
The reactor may be appropriately selected from known reactors within a range of conditions capable of achieving the suspension polymerization of the present embodiment. In the example of a reactor, an autoclave (autoclave) is included.
In the production method of the present embodiment, the pressure in the reactor is increased to the polymerization initiation temperature to sufficiently exceed the critical pressure (4.38MPa) of vinylidene fluoride, and is usually the maximum value in the polymerization reaction. Thus, vinylidene fluoride in the vinylidene fluoride-containing monomer is mainly used in the polymerization reaction in the state of a supercritical fluid. The pressure within the reaction system generally decreases as the vinylidene fluoride-containing monomer is used for polymerization.
When the pressure in the reactor at the time of heating the reaction system to the polymerization initiation temperature is too high, a vessel having high pressure resistance may be required, and when the pressure is too low, the polymerization reaction time may be prolonged, and the productivity may be lowered. The pressure in the reactor at the time when the reaction system is heated to the initial polymerization temperature is preferably 5MPa or more, and more preferably 5.5MPa or more, from the viewpoint of shortening the reaction time. In addition, the pressure is preferably 8MPa or less, and more preferably 7.5MPa or less, from the viewpoint of reducing the cost of the reactor, for example. The pressure may be adjusted depending on various factors such as the amount of vinylidene fluoride-containing monomer to be fed, the initial polymerization temperature, and the monomer density.
In the production method of the present embodiment, the reaction system may be heated a plurality of times to raise the temperature in the reaction system a plurality of times, if necessary. The temperature in the reaction system under heating during such polymerization reaction may be a temperature exceeding the polymerization initiation temperature, for example, in the range of 50 to 60 ℃ or in the range of 50 to 80 ℃. The above-mentioned multiple heating is preferable from the viewpoint of suppressing a decrease in pressure and a decrease in reaction rate associated with consumption of the monomer and improving reaction efficiency.
The end point of the suspension polymerization is appropriately selected in consideration of the balance between the reduction in the amount of the unreacted monomer and the prolongation of the polymerization time (i.e., the productivity of the product polymer). For example, the end point of the suspension polymerization can be determined by sampling the reaction product, and by the temperature rise in the reaction system and the pressure fluctuation caused thereby.
In the production method of the present embodiment, the vinylidene fluoride polymer is obtained as a powder. The powder is obtained by dehydrating, washing with water, and drying the polymer slurry after the suspension polymerization is completed.
According to the production method of the present embodiment, the reaction efficiency can be improved and the polymerization time can be shortened. Specifically, the polymerization time from the time point when the raw material is supplied to the reactor and the polymerization initiation temperature is reached to the end of polymerization may be, for example, about 20 hours or less, or may be 15 hours or less.
If the bulk density of the vinylidene fluoride polymer powder is too low, the handling difficulty in the post-treatment may increase. Further, when the pressure of the reaction system in the suspension polymerization rises excessively, the bulk density tends to be high. Therefore, from the viewpoint of suppressing an excessive rise in the pressure of the reaction system, an excessively high bulk density may not be preferable. From the viewpoint of handling properties of the post-treatment, the bulk density is preferably 0.30g/cm, for example 3 Above, more preferably 0.33g/cm 3 The above. From the viewpoint of achieving a preferable range of the pressure in the reaction system, the bulk density is, for example, 0.50g/cm 3 The following. From the viewpoint of obtaining a powder having a preferable particle shape and from the viewpoint of suppressing accidental breakage of the powder, it is preferable that the bulk density is within the above range.
In the case of producing a vinylidene fluoride copolymer by conventional suspension polymerization, for example, in the case of producing a copolymer of vinylidene fluoride and a non-fluorine-based monomer having a polar functional group, there are problems, in particular, as follows: the bulk density of the polymer powder produced is liable to decrease, and accidental breakage of the powder is liable to occur in the post-treatment step. However, according to the production method of the present embodiment, in the production of the vinylidene fluoride copolymer, the bulk density of the powder to be a finished product can be easily controlled to be within a desired range. Therefore, the occurrence of such a problem can be prevented.
The bulk density of the polymer powder is a value calculated for the antistatic powder sample based on the measurement method of JIS K6721-3.3 "bulk specific gravity" with respect to the equipment and the calculation method.
The inherent viscosity (inherent viscosity at 30 ℃ of a solution prepared by dissolving 4g of the resin in 1 liter of N, N-dimethylformamide) of the vinylidene fluoride polymer obtained by the production method of the present embodiment is 0.5dL/g or more, and particularly preferably in the range of 0.8dL/g to 4.0dL/g, from the viewpoint of physical properties and the like suitable for various applications.
In the production method of the present embodiment, it is not necessary to add the vinylidene fluoride-containing monomer in the middle of the suspension polymerization. Therefore, there is a tendency that the composition of the monomer used for suspension polymerization is stable. From the viewpoint of producing a homogeneous vinylidene fluoride polymer, this is preferable, and particularly preferable from the viewpoint of producing a homogeneous vinylidene fluoride polymer as a copolymer.
The vinylidene fluoride polymer obtained by the above-mentioned production method can be produced with higher productivity than conventional production methods, and is preferably used as a raw material resin for forming various molded articles.
The present invention will be further specifically described below by way of examples and comparative examples.
[ examples ]
The bulk densities of the vinylidene fluoride polymer powders obtained in examples and comparative examples were measured by the following methods.
[ bulk Density ]
The bulk density of the vinylidene fluoride polymer powder was measured by a method of measuring "bulk specific gravity" in accordance with JIS K6721-3.3. Specifically, 2mL of a 5% ethanol solution of a surfactant was added to 100g of the powder sample, and the mixture was sufficiently stirred with a spatula (spatula) and then left for 10 minutes. 120mL of the antistatic powder sample was put into a funnel with a baffle (damper) inserted therein of a bulk specific gravity measuring apparatus, and then the baffle was rapidly withdrawn to drop the sample into a receiver. After the sample overflowing from the receiver was scraped off with a glass rod, the mass of the receiver with the sample placed therein was accurately weighed to 0.1g, and the bulk density was calculated by the following equation.
S＝(C-A)/B
S: bulk Density (g/cm) 3 )
A: mass of receiver (g)
B: inner volume (cm) of the receiver 3 )
C: the mass (g) of the receiver into which the sample is placed
(example 1)
Inward volume 1940cm 3 In the autoclave (2), 430g of vinylidene fluoride (VDF) as a vinylidene fluoride-containing monomer was charged together with 1230g of ion-exchanged water (2.86 times the amount of the vinylidene fluoride-containing monomer), 0.22g of a suspending agent (methylcellulose), 13.0g of a chain transfer agent (ethyl acetate), and 0.86g of a polymerization initiator (di-n-propyl peroxydicarbonate), and the temperature was raised to 40 ℃ as a polymerization initiation temperature for 1.5 hours, and then maintained at 40 ℃ for 13.5 hours. The maximum ultimate pressure during this period was 6.0 MPa.
The density of the vinylidene fluoride-containing monomer in this example was 0.614g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated from the value is 700cm 3 . The density of the vinylidene fluoride-containing monomer was 0.9922g/cm, which is the density of water at 40 ℃ 3 The calculation is based on the following formula.
Dv＝Mv/(Vc-Vw)
And Dv: density (g/cm) of vinylidene fluoride-containing monomer at polymerization initiation temperature 3 )
Mv: supply amount (g) of vinylidene fluoride-containing monomer
Vc: internal volume (cm) of reactor (autoclave) 3 )
Vw: volume of water (cm) in the reactor at the initial temperature of polymerization 3 ) (supply mass of water (g)/density of water (g/cm) 3 ))
Suspension polymerization was completed after 13.5 hours from the completion of the temperature increase to 40 ℃. The pressure at the end of the polymerization was 1.0 MPa. After completion of the polymerization, the obtained polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a homopolymer powder of vinylidene fluoride. The yield of the polymer was 94.0% by calculation based on the amount of vinylidene fluoride-containing monomer supplied. Further, the bulk density of the obtained polymer powder was 0.351g/cm 3 The inherent viscosity was 1.04 dL/g.
(example 2)
Inward volume 1940cm 3 In the autoclave (2), 420g of vinylidene fluoride (VDF) as a vinylidene fluoride-containing monomer was charged together with 1280g of ion-exchange water (3.05 times the amount of the vinylidene fluoride-containing monomer), 0.12g of a suspending agent (methylcellulose), 8.0g of a chain transfer agent (diethyl carbonate), and 0.80g of a polymerization initiator (diisopropyl peroxydicarbonate), and the temperature was raised to 40 ℃ over 1.5 hours, and then maintained at 40 ℃ for 14.5 hours. The maximum ultimate pressure during this period was 6.5 MPa. In addition, the density of the vinylidene fluoride-containing monomer in the present example was 0.646g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated from the value was 650cm 3 . The density of the vinylidene fluoride-containing monomer was calculated in the same manner as in example 1.
Suspension polymerization was completed after 14.5 hours from the completion of the temperature increase to 40 ℃. The pressure at the end of the polymerization was 0.5 MPa. After completion of the polymerization, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a homopolymer powder of vinylidene fluoride. The yield of the polymer was 96.0% by calculation based on the amount of vinylidene fluoride-containing monomer supplied. Further, the bulk density of the obtained polymer powder was 0.370g/cm 3 The inherent viscosity was 1.08 dL/g.
(example 3)
Inward volume 1940cm 3 The autoclave (2) was charged with 1260g of ion-exchanged water (3.20 times the amount of vinylidene fluoride-containing monomer fed), 0.59g of a suspending agent (methylcellulose), 1.0g of a chain transfer agent (ethyl acetate), and 1.97g of a polymerization initiator (diisopropyl peroxydicarbonate) to obtain a mixture containing vinylidene fluoride390g of vinylidene fluoride (VDF) and 3.9g of monomethyl maleate (MMM) as ethylene monomers were heated to 40 ℃ over 1.5 hours, and then maintained at 40 ℃ for 13.8 hours. The maximum ultimate pressure during this time was 6.1 MPa. In addition, the vinylidene fluoride-containing monomer in this example had a density of 0.588g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated according to the value is 670cm 3 . The density of the vinylidene fluoride-containing monomer was calculated in the same manner as in example 1.
Suspension polymerization was completed after 13.8 hours from the completion of the temperature increase to 40 ℃. The pressure at the end of the polymerization was 1.2 MPa. After the polymerization was completed, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a copolymer powder of vinylidene fluoride and monomethyl maleate. The yield of the polymer was 94.0% by calculation based on the amount of vinylidene fluoride-containing monomer supplied. Further, the bulk density of the obtained polymer powder was 0.334g/cm 3 The inherent viscosity was 1.51 dL/g.
(example 4)
Inward volume 1940cm 3 In the autoclave (2), with 1320g of ion-exchanged water (3.32 times the amount of the vinylidene fluoride-containing monomer), 0.60g of a suspending agent (methylcellulose), 4.8g of a chain transfer agent (ethyl acetate), and 2.20g of a polymerization initiator (diisopropyl peroxydicarbonate), 393g of vinylidene fluoride (VDF) and 4.0g of monomethyl maleate (MMM) as the vinylidene fluoride-containing monomer were charged, and after the temperature was raised to 40 ℃ over 1.5 hours, the mixture was maintained at 40 ℃ for 15.1 hours. The maximum ultimate pressure during this period was 6.9 MPa. In addition, the density of the vinylidene fluoride-containing monomer in this example was 0.651g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated from the value was 610cm 3 . The density of the vinylidene fluoride-containing monomer was calculated in the same manner as in example 1.
After 15.1 hours from the completion of the temperature increase to 40 ℃, the suspension polymerization was completed. The pressure at the end of the polymerization was 1.2 MPa. After the polymerization was completed, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a copolymer powder of vinylidene fluoride and monomethyl maleate. Calculated according to the supply amount of the vinylidene fluoride monomerThe yield of the polymer obtained was 95.2%. Further, the bulk density of the obtained polymer powder was 0.368g/cm 3 The inherent viscosity was 1.16 dL/g.
(example 5)
Inward volume 1940cm 3 The autoclave (2) was charged with 365g of vinylidene fluoride (VDF), 32g of Hexafluoropropylene (HFP) and 2.0g of monomethyl maleate (MMM) as vinylidene fluoride-containing monomers, together with 1280g of ion-exchange water (3.21 times the amount of vinylidene fluoride-containing monomer), 0.60g of a suspending agent (methylcellulose) and 1.24g of a polymerization initiator (diisopropyl peroxydicarbonate), and the temperature was raised to 45 ℃ over 1.5 hours and then maintained at 45 ℃ for 14.3 hours. The maximum ultimate pressure during this period was 6.7 MPa. In addition, the density of the vinylidene fluoride monomer in the embodiment is 0.616g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated from this value was 647cm 3 . The density of vinylidene fluoride-containing monomer was 0.9902g/cm, as in example 1, and the density of water at 45 ℃ 3 And calculated.
Suspension polymerization was completed after 14.3 hours from the completion of the temperature increase to 45 ℃. The pressure at the end of the polymerization was 0.5 MPa. After completion of the polymerization, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a copolymer powder of vinylidene fluoride, hexafluoropropylene and monomethyl maleate. The yield of the polymer was 97.0% by calculation based on the amount of vinylidene fluoride-containing monomer supplied. Further, the bulk density of the obtained polymer powder was 0.373g/cm 3 The inherent viscosity was 2.51 dL/g.
(example 6)
Inward volume 1940cm 3 In the autoclave (2), 1230g of ion exchange water (2.86 times the amount of vinylidene fluoride-containing monomer supplied), 0.22g of a suspending agent (methylcellulose), and 1.2g of a polymerization initiator (diisopropyl peroxydicarbonate) were charged with 413g of vinylidene fluoride (VDF) and 17g of Chlorotrifluoroethylene (CTFE) as vinylidene fluoride-containing monomers, and the mixture was heated to 40 ℃ over 1.5 hours and then maintained at 40 ℃ for 8.3 hours. The maximum ultimate pressure during this period was 5.9 MPa. In addition, the vinylidene fluoride-containing monomer in the present example had a density of 0.614g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated from the value is 700cm 3 . The density of vinylidene fluoride-containing monomer was 0.9922g/cm, as in example 1, and the density of water at 40 ℃ 3 And calculated.
After 8.3 hours from the completion of the temperature increase to 40 ℃, the suspension polymerization was completed. The pressure at the end of the polymerization was 0.9 MPa. After the polymerization was completed, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a copolymer powder of vinylidene fluoride and chlorotrifluoroethylene. The yield of the polymer was 89.0% by calculation based on the amount of vinylidene fluoride-containing monomer supplied. Further, the bulk density of the obtained polymer powder was 0.342g/cm 3 The inherent viscosity was 2.64 dL/g.
(example 7)
Inward volume 1940cm 3 In the autoclave (2), 400g of vinylidene fluoride (VDF) and 2g of Methyl Acrylate (MA), which are vinylidene fluoride-containing monomers, were charged together with 1280g of ion-exchange water (3.18 times the amount of vinylidene fluoride-containing monomers), 0.20g of a suspending agent (methylcellulose), 2.0g of a chain transfer agent (ethyl acetate) and 2.4g of a polymerization initiator (diisopropyl peroxydicarbonate), and the temperature was raised to 45 ℃ over 1.5 hours, and then maintained at 45 ℃ for 6.5 hours. The maximum ultimate pressure during this period was 7.1 MPa. In addition, the vinylidene fluoride-containing monomer in the present example had a density of 0.621g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated from the value was 647cm 3 . The density of vinylidene fluoride-containing monomer was 0.9902g/cm, as in example 1, and the density of water at 45 ℃ 3 And calculated.
After 6.5 hours from the completion of the temperature increase to 45 ℃, the suspension polymerization was completed. The pressure at the end of the polymerization was 1.5 MPa. After the polymerization was completed, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a copolymer powder of vinylidene fluoride and methyl acrylate. The yield of the polymer was 91% by calculation based on the amount of vinylidene fluoride-containing monomer supplied. Further, the bulk density of the obtained polymer powder was 0.383g/cm 3 Logarithmic viscosity of specific gravityThe degree was 1.46 dL/g.
(example 8)
Inward volume 1940cm 3 The autoclave (2) was charged with 328g of vinylidene fluoride (VDF) and 72g of Hexafluoropropylene (HFP) as vinylidene fluoride-containing monomers, together with 1280g of ion-exchange water (3.2 times the amount of vinylidene fluoride-containing monomer), 0.20g of a suspending agent (methylcellulose), 2.0g of a chain transfer agent (diethyl carbonate) and 1.0g of a polymerization initiator (diisopropyl peroxydicarbonate), heated to 50 ℃ over 1.5 hours, and then maintained at 50 ℃ for 5.0 hours. The maximum ultimate pressure during this period was 6.1 MPa. In addition, the density of the vinylidene fluoride-containing monomer in the present example was 0.621g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated from the value was 645cm 3 . The density of the vinylidene fluoride-containing monomer was 0.9881g/cm as the density of water at 50 ℃ in the same manner as in example 1 3 And calculated.
After 5.0 hours from the completion of the temperature increase to 50 ℃, the suspension polymerization was completed. The pressure at the end of the polymerization was 1.5 MPa. After completion of the polymerization, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a copolymer powder of vinylidene fluoride and hexafluoropropylene. The yield of the polymer was 87% by calculation based on the amount of vinylidene fluoride-containing monomer supplied. Further, the bulk density of the obtained polymer powder was 0.331g/cm 3 The inherent viscosity was 1.30 dL/g.
Comparative example 1
Inward volume 1940cm 3 In the autoclave (2), 430g of vinylidene fluoride (VDF) as a vinylidene fluoride-containing monomer was charged together with 1100g of ion-exchanged water (2.56 times the amount of the vinylidene fluoride-containing monomer), 0.22g of a suspending agent (methylcellulose), 10.5g of a chain transfer agent (ethyl acetate), and 2.58g of a polymerization initiator (di-n-propyl peroxydicarbonate), and the temperature was raised to 26 ℃ over 1 hour and then maintained at 26 ℃ for 22.7 hours. The maximum ultimate pressure during this period was 3.9 MPa.
In the comparative example, the density of vinylidene fluoride-containing monomer was 0.9968g/cm, as in example 1, when the density of water at 26 ℃ 3 When calculated, it was 0.514g/cm 3 . In addition, the volume of the vinylidene fluoride-containing monomer calculated from this value was 836cm 3 . At the above temperature and pressure, vinylidene fluoride does not become a supercritical state, and the density of the vinylidene fluoride-containing monomer determined from the literature value is 0.57g/cm 3 。
Suspension polymerization was completed after 22.7 hours from the completion of the temperature increase to 26 ℃. The pressure at the end of the polymerization was 1.4 MPa. After completion of the polymerization, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a homopolymer powder of vinylidene fluoride. The yield of the polymer was 86.8% as calculated from the feed of vinylidene fluoride-containing monomer. Further, the bulk density of the obtained polymer powder was 0.429g/cm 3 The inherent viscosity was 1.02 dL/g.
Comparative example 2
Inward volume 1940cm 3 In the autoclave (2), 420g of vinylidene fluoride (VDF) and 4.2g of monomethyl maleate (MMM) as vinylidene fluoride-containing monomers were charged together with 1090g of ion-exchange water (2.57 times the amount of vinylidene fluoride-containing monomers supplied), 0.64g of a suspending agent (methylcellulose), 2.1g of a chain transfer agent (ethyl acetate), and 4.25g of a polymerization initiator (diisopropyl peroxydicarbonate), and the temperature was raised to 26 ℃ over 1 hour and then maintained at 26 ℃ for 40.7 hours. The maximum ultimate pressure during this period was 4.0 MPa.
In addition, the density of the vinylidene fluoride-containing monomer in this comparative example was calculated to be 0.501g/cm in the same manner as in comparative example 1 3 . Further, the volume of the vinylidene fluoride-containing monomer calculated from the value was 847cm 3 . The density of the vinylidene fluoride-containing monomer obtained from the literature value was the same as that of comparative example 1.
After 40.7 hours from the completion of the temperature increase to 26 ℃, the suspension polymerization was completed. The pressure at the end of the polymerization was 1.5 MPa. After the polymerization was completed, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a copolymer powder of vinylidene fluoride and monomethyl maleate. The yield of the polymer calculated from the amount of the vinylidene fluoride-containing monomer fed was 90.9%. In addition, the bulk density of the obtained polymer powder was 0.447g/cm 3 The inherent viscosity was 1.19 dL/g.
Comparative example 3
Inward volume 1940cm 3 In the autoclave (2), 420g of vinylidene fluoride (VDF) as a vinylidene fluoride-containing monomer was charged together with 1070g of ion-exchange water (2.55 times the amount of the vinylidene fluoride-containing monomer), 0.22g of a suspending agent (methylcellulose), 5.9g of a chain transfer agent (ethyl acetate), and 1.26g of a polymerization initiator (di-n-propyl peroxydicarbonate), and the temperature was raised to 40 ℃ over 1.5 hours and then maintained at 40 ℃ for 10.2 hours. The maximum ultimate pressure during this period was 5.5 MPa. In addition, the density of the vinylidene fluoride-containing monomer in this comparative example was 0.487g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated according to the value is 862cm 3 . The density of the vinylidene fluoride-containing monomer was calculated in the same manner as in example 1.
Suspension polymerization was completed after 10.2 hours from the completion of the temperature increase to 40 ℃. The pressure at the end of the polymerization was 1.5 MPa. After completion of the polymerization, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a homopolymer powder of vinylidene fluoride. The yield of the polymer was 86.9% as calculated from the feed of vinylidene fluoride-containing monomer. Further, the bulk density of the obtained polymer powder was 0.280g/cm 3 The inherent viscosity was 1.06 dL/g.
Comparative example 4
Inward volume 1940cm 3 In the autoclave (2), 430g of vinylidene fluoride (VDF) and 4.3g of monomethyl maleate (MMM) as vinylidene fluoride-containing monomers were charged together with 1110g of ion-exchanged water (2.56 times the amount of vinylidene fluoride-containing monomers supplied), 0.64g of a suspending agent (methylcellulose), 1.3g of a chain transfer agent (ethyl acetate) and 1.95g of a polymerization initiator (diisopropyl peroxydicarbonate), and the temperature was raised to 50 ℃ over 1.5 hours and then maintained at 50 ℃ for 6.3 hours. The maximum ultimate pressure during this period was 7.2 MPa. In addition, the density of the vinylidene fluoride monomer in this comparative example was 0.532g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated according to the value is 817cm 3 . The density of the vinylidene fluoride-containing monomer was adjusted to 50 ℃ in the same manner as in example 1The density was set at 0.98805g/cm 3 And calculated.
After 7.8 hours from the completion of the temperature increase to 50 ℃, the suspension polymerization was completed. The pressure at the end of the polymerization was 1.5 MPa. After the polymerization was completed, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a copolymer powder of vinylidene fluoride and monomethyl maleate. The yield of the polymer calculated from the amount of the vinylidene fluoride-containing monomer fed was 91.5%. Further, the bulk density of the obtained polymer powder was 0.297g/cm 3 The inherent viscosity was 1.25 dL/g.
Comparative example 5
Inward volume 1940cm 3 In the autoclave (2), 395g of vinylidene fluoride (VDF) and 4.0g of monomethyl maleate (MMM) as vinylidene fluoride-containing monomers were charged together with 1350g of ion-exchanged water (3.38 times the amount of vinylidene fluoride-containing monomers supplied), 0.60g of a suspending agent (methylcellulose), 4.8g of a chain transfer agent (ethyl acetate), and 2.20g of a polymerization initiator (diisopropyl peroxydicarbonate), and the temperature was raised to 40 ℃ over 1.5 hours, and then maintained at 40 ℃ for 14.2 hours. The maximum ultimate pressure during this period was 7.7 MPa. In addition, the density of the vinylidene fluoride-containing monomer in this comparative example was 0.689g/cm 3 The volume of the vinylidene fluoride-containing monomer calculated according to the value is 579cm 3 . The density of the vinylidene fluoride-containing monomer was calculated in the same manner as in example 1.
Suspension polymerization was completed after 14.2 hours from the completion of the temperature increase to 40 ℃. The pressure at the end of the polymerization was 1.2 MPa. After the polymerization was completed, the polymer slurry was dehydrated and washed with water, and further dried at 80 ℃ for 20 hours to obtain a copolymer powder of vinylidene fluoride and monomethyl maleate. The yield of the polymer was 94.5% as calculated from the feed of vinylidene fluoride-containing monomer. Further, the bulk density of the obtained polymer powder was 0.390g/cm 3 The inherent viscosity was 1.19 dL/g.
In any of the examples and comparative examples, the maximum limiting temperature was the same as the polymerization initiation temperature, and the maximum limiting pressure was the pressure in the reaction system at the polymerization initiation temperature.
The polymerization conditions, the yields and the bulk densities of the vinylidene fluoride polymers obtained in the above examples are shown in tables 1 and 2. The polymerization conditions, the yields of the vinylidene fluoride polymers obtained, and the bulk densities in the comparative examples are shown in table 3.
[ Table 1]
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Inner volume (cm) of reaction vessel 3 ) | 1940 | 1940 | 1940 | 1940 | 1940 |
| Amount of Water supplied (g) | 1230 | 1280 | 1260 | 1320 | 1280 |
| Amount of chain transfer agent supplied (g) | 13.0 | 8.0 | 1.0 | 4.8 | 0 |
| Amount (g) of polymerization initiator supplied | 0.86 | 0.80 | 1.97 | 2.20 | 1.24 |
| Amount of suspending agent supplied (g) | 0.22 | 0.12 | 0.59 | 0.60 | 0.60 |
| VDF supply amount (g) | 430 | 420 | 390 | 393 | 365 |
| MMM supply (g) | 0 | 0 | 3.9 | 4.0 | 2.0 |
| HFP supply amount (g) | 0 | 0 | 0 | 0 | 32 |
| Supply ratio (water/monomer) | 2.86 | 3.05 | 3.20 | 3.32 | 3.21 |
| Monomer Density (g/cm) 3 ) | 0.614 | 0.646 | 0.588 | 0.651 | 0.616 |
| Monomer volume (cm) 3 ) | 700 | 650 | 670 | 610 | 647 |
| Maximum limit temperature (. degree. C.) | 40 | 40 | 40 | 40 | 45 |
| Maximum ultimate pressure (MPa) | 6.0 | 6.5 | 6.1 | 6.9 | 6.7 |
| Polymerization time (h) | 13.5 | 14.5 | 13.8 | 15.1 | 14.3 |
| Yield (%) | 94.0 | 96.0 | 94.0 | 95.2 | 97.0 |
| Bulk Density (g/cm) 3 ) | 0.351 | 0.370 | 0.334 | 0.368 | 0.373 |
| Inherent viscosity (dL/g) | 1.04 | 1.08 | 1.51 | 1.16 | 2.51 |
[ Table 2]
| Example 6 | Example 7 | Example 8 | |
| Inner volume (cm) of reaction vessel 3 ) | 1940 | 1940 | 1940 |
| Amount of Water supplied (g) | 1230 | 1280 | 1280 |
| Amount of chain transfer agent supplied (g) | 0 | 2.0 | 2.0 |
| Amount (g) of polymerization initiator supplied | 1.20 | 2.40 | 1.00 |
| Amount of suspending agent supplied (g) | 0.22 | 0.20 | 0.20 |
| VDF supply amount (g) | 413 | 400 | 328 |
| MMM supply (g) | 0 | 0 | 0 |
| HFP supply amount (g) | 0 | 0 | 72 |
| CTFE supply amount (g) | 17 | 0 | 0 |
| MA supply amount (g) | 0 | 2.0 | 0 |
| Supply ratio (water/monomer) | 2.86 | 3.18 | 3.2 |
| Monomer Density (g/cm) 3 ) | 0.614 | 0.621 | 0.621 |
| Monomer volume (cm) 3 ) | 700 | 647 | 645 |
| Maximum limit temperature (. degree. C.) | 40 | 45 | 50 |
| Maximum ultimate pressure (MPa) | 5.9 | 7.1 | 6.1 |
| Polymerization time (h) | 8.3 | 6.5 | 5.0 |
| Yield (%) | 89.0 | 91.0 | 87.0 |
| Bulk Density (g/cm) 3 ) | 0.342 | 0.383 | 0.331 |
| Inherent viscosity (dL/g) | 2.64 | 1.46 | 1.30 |
[ Table 3]
From the results shown in tables 1 and 2, it is understood that, in examples 1 to 8 in which the density of the vinylidene fluoride-containing monomer at the time point of reaching the maximum limiting temperature is within the predetermined range, a polymer having an appropriate bulk density is obtained with good yield.
In contrast, as shown in table 3, in comparative example 1 and comparative example 2 in which the maximum limit temperature of the heating process was 26 ℃, vinylidene fluoride did not reach the supercritical state, although the polymerization time was prolonged, the yield was poor as compared with the above examples, and the bulk density of the obtained polymer was large.
In comparative examples 3 and 4 in which the density of the vinylidene fluoride-containing monomer at the time point when the maximum limit temperature is reached is less than the predetermined range, the bulk density of the obtained polymer is smaller than that of the above examples. In comparative example 5 in which the density of the vinylidene fluoride-containing monomer at the time point when the maximum limit temperature was reached was larger than the predetermined range, the pressure in the reactor was excessively increased in the heating step as compared with the above examples, and the bulk density of the obtained polymer was high.
Claims (5)
1. A method for producing a vinylidene fluoride polymer, characterized by comprising:
a step of subjecting a vinylidene fluoride-containing monomer to suspension polymerization in water under conditions such that the vinylidene fluoride is in a supercritical state,
the density of water and the monomer at the polymerization initiation temperature of the suspension polymerization was made to be 0.580g/cm 3 Above and 0.640g/cm 3 The following amount of the monomer was fed to the reactor,
suspension polymerization is carried out while maintaining the polymerization initiation temperature under the condition of being brought into the supercritical state,
the polymerization initiation temperature is 35 ℃ or higher and 55 ℃ or lower,
the monomer does not need to be added in the middle of suspension polymerization.
2. The method for producing a vinylidene fluoride polymer according to claim 1, wherein the monomer further comprises a monomer other than vinylidene fluoride that is polymerizable.
3. The method for producing a vinylidene fluoride polymer according to claim 2, wherein the other monomer is at least one compound selected from the group consisting of a fluorine-containing monomer, an unsaturated dibasic acid derivative, an alkyl (meth) acrylate compound and a carboxyl group-containing acrylate compound.
4. A method for producing a vinylidene fluoride polymer as defined in any one of claims 1 to 3, wherein the monomer contains 80 mass% or more of vinylidene fluoride.
5. A method for producing a vinylidene fluoride polymer as defined in any one of claims 1 to 3, wherein the water is supplied to the reactor in a mass ratio of 2.6 times or more the monomer.
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