RU2267498C1 - Linear statistical tetrafluoroethylene terpolymer with functional perfluorinated co-monomers and method for its preparing - Google Patents

Abstract

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a linear statistical tetrafluoroethylene terpolymer with functional perfluorinated co-monomers of the general structural formula:

wherein M means hydrogen or alkaline metal ion; a = 5-19.5 mole%; b = 80-91 mole%; c = 0.5-5 mole%;

. Terpolymer shoes endothermic peak in the temperature interval 70-75°C on the crystalline melting curve measured by scanning differential calorimeter. Terpolymer has mean-weighted molecular mass (2-8) x 10⁵ Da and the ratio of mean-weighted molecular mass to average molecular mass = 1.2-1.35. Also, invention relates to a method for preparing terpolymer. Invention provides preparing terpolymer that is able after hydrolysis to form concentrated solutions (above 5 wt.-%) in available solvents and under mild conditions, and to enhance the strength and to reduce electric resistance of membranes made of the claimed terpolymer.

EFFECT: improved preparing method, valuable properties of terpolymer.

4 cl, 2 tbl, 3 dwg, 37 ex

Description

The present invention relates to new chemical compounds, namely to a linear statistical tetrafluoroethylene (TFE) terpolymer with functional perfluorinated comonomers having the general structural formula

where M is a hydrogen or alkali metal ion;

a = 5-19.5 mol.%;

b = 80-91 mol%;

c = 0.5-5 mol.%;

_w) к среднечисленной молекулярной массе (

_n), равное 1,2-1,35.characterized by an endothermic peak in the temperature range of 70-75 ° C on the crystalline melting curve, measured using a scanning differential calorimeter, and having a weight average molecular weight (2-8) · 10 ⁵ and a ratio of weight average molecular weight (

_w ) to number average molecular weight (

_n ) equal to 1.2-1.35.

The specified terpolymer can be used in the manufacture of cation exchange membranes (KOM) used in fuel cells, in the electrolysis of water and aqueous solutions of alkali metal salts, for example, in chlor-alkali electrolysis, as well as in the manufacture of membrane-electrode blocks of electrochemical devices, gas separation membranes, for example gas separation hollow fibers, acid catalysts, etc.

The present invention also relates to a method for producing the above new linear statistical TFE terpolymer with functional perfluorinated comonomers.

Known [US patent No. 3282875, NKI 260-29.6, publ. 11/01/66] copolymer of TFE and functional perfluorinated comonomer of the general structural formula

where M is fluorine, a hydroxyl radical or a radical of the formula —OMe (where Me is an alkali metal ion or quaternary ammonium radical);

a = 95-99.8 mol%;

b = 0.2-5 mol.%.

The copolymer contains 0.2-5 mol.% (9-23 wt.%) Of the functional perfluorinated comonomer of the indicated structural formula — perfluorovinyl ether with the functional group —SO ₂ M (HGE), where M is indicated above.

Such a copolymer can be used to obtain chemically stable and thermostable coatings, as ion exchange resins, and for the manufacture of acid catalysts. Any physico-mechanical or electrochemical characteristics of these copolymers in US patent No. 3282875 are not given.

The disadvantages of these copolymers are:

1. The low content of HSE in the copolymer (up to 5 mol.%), And therefore, too high equivalent mass (EM) of the resulting copolymer (> 2000), which limits its application. Such a copolymer, for example, cannot be used for the manufacture of KOM used in chlor-alkali electrolysis and in fuel cells, due to too high electrical resistance (the TFE-HPS copolymer used in electrolysis processes must have an EM in the range of 800-1400).

2. Too high melting temperature (T _PL ), and therefore, too high temperature range for processing the resulting copolymer by extrusion or pressing.

So, according to our data, when the content of HHE is 3.3 mol.%, The copolymer has T _pl. = 315 ° C, and accordingly the temperature range for the processing of the copolymer is 315-325 ° C (see our control example 20). However, at the indicated temperatures, the process of destruction of the functional groups —SO ₂ F, —SO ₃ H, —SO ₃ Me begins [Plastics, 1980, No. 12, pp. 23-25], and, therefore, the properties obtained from such a copolymer are worsened products. When the content of VGE is less than 3 mol%, the copolymer is practically not processed from the melt (the copolymer does not melt, the processing temperature range is higher than the decomposition temperature of the copolymer).

The copolymers described in US Pat. No. 3,228,275, namely, double copolymers of TFE with HFCE of the above structural formula, can be obtained by copolymerizing TFE with HFCE in a fluorine-containing solvent (perfluorodimethylcyclobutane) when the HFCE has -SO ₂ F functional groups (perfluorine - [2- (Fluorosulfonylethoxy) propyl vinyl ether]), or in an aqueous medium when the HHPE contains —SO ₃ H or —SO ₃ Me groups. Free-radical initiators are used: N ₂ F ₂ (difluorodiazide) - when carrying out the process in a fluorine-containing solvent and ammonium persulfate - when carrying out the process in an aqueous medium.

The copolymerization process is carried out with a single loading of monomers (without recharge) or with TFE replenishment during the process to maintain a constant pressure at a temperature of not more than 110 ° C, preferably 68-85 ° C. The comonomers are introduced into the reaction medium in a mass ratio of TFE-HSE equal to (1-2.4): 1, which corresponds to the composition of the loading mixture of 82-90.9 mol.% TFE and 18-9.1 mol.% HSE.

The disadvantages of the described method are:

1. The inability to obtain a copolymer with an HSE content of more than 5 mol.% (With EM less than 2000) due to the too high TFE content in the reaction medium (TFE content is 82-91.6 mol%) despite the fact that, as is known, polymerization activity TFE is 15-20 times higher than the polymerization activity of VGE.

2. The heterogeneity of the composition of the resulting copolymer, due to the fact that the process proceeds at relatively high temperatures (70-85 ° C), at which there is a tendency to the formation of a TFE homopolymer. In the case of the copolymerization process without feeding TFE with a constant pressure drop, the ratio of comonomers constantly changes, which also leads to heterogeneity of the composition of the obtained copolymer.

3. Low molecular weight (MM) of the resulting copolymer, which is associated with a relatively high copolymerization temperature (68-85 ° C) and the absence of TFE replenishment during the process in a solvent environment.

степени кристалличности, плотности и т.д., так как регулирование свойств возможно только за счет изменения концентрации мономеров и инициатора, что недостаточно для получения сополимера с заданным оптимальным комплексом свойств.4. The difficulty of controlling the properties of the obtained copolymer according to MM, ratio

crystallinity, density, etc., since the regulation of properties is possible only by changing the concentration of monomers and initiator, which is not enough to obtain a copolymer with a given optimal set of properties.

Also known [US patent No. 5281680, MKI ⁵ C 08 F 12/30, publ. 25.01.94] double copolymer of TFE with a functional perfluorinated comonomer having the General structural formula

where the molar ratio a / b is from 2: 1 to 5.6: 1. The copolymer has a fairly high MM — the melt index (MF) at 270 ° C (load 1.2 kg, capillary 8 mm long and 2.09 mm in diameter) is less than 30 g / 10 min. After hydrolysis, the copolymer has an EM of 670-1088. The copolymer has no endothermic peaks in the crystalline melting curve (see our control example 21 in table 2). Such a copolymer is used in the form of a film (membrane) in electrolytic cells, such as chlor-alkali or fuel.

The disadvantages of the copolymer according to US patent No. 5281680 are:

1. Significant moisture loss made of KOM copolymer during operation, leading to a deterioration in the electrochemical characteristics of the membranes, which is apparently due to the non-optimal supramolecular structure of such copolymers. So, after 3000 hours of operation of a fuel cell (TE) with a KOM thickness (δ) of 125 μm from a copolymer with EM 1000 that does not have an endothermic peak in the crystalline melting curve, the membrane humidity decreased from 22 to 19.5%, the specific volume electric resistance ( ρ _v ) increased from 14 to 16 Ohm · cm, the voltage on the FC decreased from 0.83-0.84 to 0.81-0.82 V (see our control example 21 in table 2, control example 34 )

которое характеризует молекулярно-массовое распределение (см. наш контр. пример 21 в табл.2 и контр. пример 36).2. The limited scope of the copolymer associated with the impossibility of obtaining concentrated solutions from it (> 5 wt.%) In available solvents (methanol, ethanol, dimethylformamide, etc.), necessary for the manufacture of cost-effective (with a low consumption of expensive perfluorinated ion-exchange copolymers) thin reinforced or unreinforced films (membranes) with a thickness of ≤80 μm by irrigation or impregnation, as well as hollow gas separation fibers with a wall thickness of 30-40 μm. This is probably due to too high MM copolymer and too low ratio

which characterizes the molecular weight distribution (see our count. example 21 in table 2 and count. example 36).

3. The insufficiently high strength of the films (membranes) obtained from the copolymer in the wet state, as well as their relatively high electrical resistance. Thus, according to our data, the strength of a wet hydrolyzed film with a thickness of 125 μm from a copolymer with EM 1000 is 18.0 MPa, and ρ _v 14 Ohm · cm (see our control example 21 in Table 2), while the strength is similar films from the claimed terpolymer with EM 1000 is 22.9-25.2 MPa, ρ _v 10.4-11.2 Ohm · cm (see our examples 4-6 in table 2).

As is known, the strength of a film made of an ion-exchange copolymer and its electrical resistance (among other properties) substantially depend on the EM of the copolymer (the higher the EM, the higher the strength and ρ _v ), and therefore, the strength and ρ _{v are} compared for copolymers having the same EM.

The copolymer according to US patent No. 5281680 is obtained by copolymerization of TFE and HESE of the above formula in a non-aqueous medium (in a fluorinated solvent or in the mass of monomers) in the presence of a soluble initiator, preferably perfluoropropionyl peroxide (PFPP), at a temperature of from 35 to 60 ° C, preferably 45 ° C, and a pressure of 280-1100 kPa (2.8-11 kg / cm ² ). In the copolymerization process, the pressure is maintained by continuously feeding TFE. At the end of the process, unreacted TFE is blown away, and the HHPE is removed by distillation. The content of comonomers in the reaction medium is selected so that the molar ratio of TFE and HSE in the resulting copolymer is respectively (2.1-5.6): 1. The relatively low molar ratio of TFE to HSE and the relatively low copolymerization temperatures make it possible to obtain a copolymer with a sufficiently high MM (specific MM values are not given in the description of US Patent No. 5281680), while the EM of the copolymer is 670-1088.

The disadvantages of the described method are:

1. The impossibility of obtaining in this way copolymers having the optimal molecular weight, supramolecular structure and molecular weight distribution from the point of view of extrusion and dissolution of the copolymers, since the properties of the resulting copolymers are regulated during the synthesis only by changing the concentration of reagents, which is insufficient to obtain copolymers with given optimal set of properties.

2. Use as an initiator PFPP, which introduces into the copolymer unstable end groups C ₂ F ₅ COO-, formed during the decay of the initiator. These end groups decompose at 220-240 ° C, i.e. at temperatures close to the processing temperature of the copolymers, which affects the quality of the copolymer and the products obtained from it. The thermal stability of such a copolymer at 270 ° C is 0.20 (see our control example 21 in Table 2).

3. The presence in the copolymer of impurities of oligomers that are not removed by distillation of unreacted VGE even under vacuum. During hydrolysis (conversion of non-ion-exchange groups of -SO ₂ F copolymer into the ion-exchange form -SO ₃ М, where М-Н, alkali metal), these oligomeric impurities are washed out of the films (membranes), which leads to a decrease in their mechanical strength, for example, from 22 to 18 MPa (see our count. Example 21 in table 2 and count. Example 34).

Known [US Pat. US No. 4330654, MKI ³ C 08 F 214/02, 214/18, publ. 18.05.82] TFE terpolymers with perfluorinated vinyl ether containing a -SO ₂ F functional group and chlorinated fluorinated vinyl esters, preferably TFE terpolymers with short chain fluorinated vinyl esters having the general structural formula:

where n = 2, 3.

The values of x, y and z are chosen in such a way as to obtain terpolymers having a given EM.

In particular, in specific examples of the description of the invention, copolymers with EM 894-1725 are prepared, the molar ratio x: y: z in the copolymer being (4.5-14): 1: (0.02-0.07).

The introduction of a chlorine-containing monomer improves the processability of the terpolymer (it is pressed into a transparent thin film at a temperature of 260 ° C), and also provides the possibility of further crosslinking of the terpolymer.

These terpolymers after hydrolysis (in the form of a film) are used as KOM in chlor-alkali electrolysis processes and other membrane separation processes, as well as solid acid catalysts.

The disadvantages of these terpolymers are:

1. The presence in the terpolymer of impurities that reduce its thermal and chemical stability, which is associated with the contamination of the terpolymer by cyclization products of the short-chain monomer FSO ₂ (CF ₂ ) ₂ OCF = CF ₂ , which are known [see U.S. Patent No. 4,329,435, MKI ³ B 01 J 47/12, publ. 1982], are formed in the process of copolymerization.

2. The relatively high processing temperature of terpolymers even with low EM (about 894-1000). The terpolymers are pressed into a film at 260 ° C, and accordingly, a temperature of at least 280 ° C will be required to process such a polymer by extrusion. This is due to the fact that the short side chains of the terpolymer are inactive and do not provide sufficient internal plasticization to reduce the viscosity of the terpolymer melt.

3. The relatively high ρ _{v of the} resulting terpolymer. So, with EM 894 ρ _{v the} terpolymer is 58 Ohm · cm, and with EM 1240 279 Ohm · cm, which determines a rather high energy consumption when using KOM of such terpolymers in chlor-alkali electrolysis. It is known [US patent No. 4478695, MKI ³ With 25 In 1/34, publ. 23.10.84 g.] That the energy consumption when using KOM of such copolymers is 2345-2500 kW · h / t NaOH when receiving 15% NaOH.

The terpolymers according to US Pat. No. 4,330,654 are obtained by copolymerizing TFE with functional perforated monomers of the structural formula CF ₂ = CFO- (CF ₂ ) ₂ SO ₂ F and CF ₂ = CFO- (CF ₂ ) _n Cl, where n = 2, 3, in aqueous medium in the presence of potassium persulfate (initiator), sodium bisulfite (reducing agent) and potassium perfluorooctanoate (surfactant, surfactant) at a temperature of 20-50 ° C and a pressure of 0.38-0.42 MPa. In the copolymerization process, the TFE reaction medium is not fed. Unreacted monomers are removed by heating and evacuation. The terpolymer is coagulated by freezing, after which it is washed and dried in vacuo.

The specified method of obtaining terpolymers has the following disadvantages:

1. Use in the copolymerization of potassium persulfate, as well as sodium bisulfate, which leads to insufficient thermal stability of the resulting terpolymer. This is due to the fact that during copolymerization in an aqueous medium in the presence of potassium persulfate, unstable end groups are formed in the copolymer which decompose at the processing temperature of the copolymer, as a result of which the appearance and quality of products made from such a terpolymer deteriorate [IUD, vol. A XXV, No. 10, 1983, p.2144].

2. The heterogeneity in the composition of the resulting terpolymer, which is associated with the lack of feeding the TFE reaction medium in the copolymerization process.

3. The impossibility of obtaining in this way terpolymers with optimal molecular weight characteristics and a supramolecular structure, necessary when processing terpolymers by extrusion and to obtain concentrated solutions in accessible solvents. This is due to the fact that the method does not contain techniques that allow you to adjust these properties.

Also known [French application No. 2388012, IPC C 08 J 5/22, publ. 17.11.78] TFE terpolymer with perfluorinated vinyl ether containing functional sulfonyl fluoride groups (-SO ₂ F) and perfluorinated vinyl ether containing carboxyl or nitrile groups, in particular TFE terpolymer with perfluoro- (3,6-dioxa-4- methyloctene) sulfonyl fluoride of the structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F (i.e., HSE) and perfluoro- (4,7-dioxa-2,5-dimethyl-8-nonene) nitrile of structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) CN or perfluoro- (4,7-dioxa-5-methyl-8-nonate) methylate of structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOCH ₃ , General structural formulas s:

where Y is COOSN ₃ , CN; X is F, CF ₃ ;

r is 0-10;

q = 3-15;

p = 1-10.

The terpolymers have such a monomer ratio that their EM after hydrolysis does not exceed 2000, preferably 1500. Such terpolymers after hydrolysis contain both sulfo and carboxy ion exchange groups. The presence of the indicated ion-exchange groups in the terpolymer makes it possible to use such terpolymer in the manufacture of KOM, which work quite efficiently in the process of chlor-alkali electrolysis, since carboxyl groups having low swelling in water reduce the migration of OH-ions through KOM, which leads to an increase in the yield by current upon receipt of a 30-40% alkali compared to KOM made from a double TFE-HPS copolymer, while a rather high current efficiency (60-70%) is maintained for a relatively long time The first time, 12 days (see example 4 of the description to the application of France No. 2388012).

However, such a terpolymer has the following disadvantages:

1. Significant moisture loss made of KOM terpolymer during long-term operation, which leads to a deterioration in the electrochemical characteristics of the membranes. This, apparently, is associated with the non-optimal supramolecular structure of the terpolymer. So, after 3000 hours of operation of a FC with a COM made of TFE terpolymer with an EM 1000 (according to example 22 counter.), The membrane humidity decreased from 20 to 18%, ρ _v increased from 15.9 to 16.7 Ohm · cm, while the voltage on the FC decreased from 0.74-0.76 V to 0.71-0.73 V (see our control example 35).

2. The insufficiently high strength obtained from terpolymer membranes in the wet state, as well as their relatively high electrical resistance. Thus, according to our data, the tensile strength of a film 125 μm thick from a copolymer with EM 1000 at a moisture content of 21% (measured after boiling in water for 30 min) is only 18 MPa, and ρ _v 15.9 Ohm · cm (see our control example 22 in table 2).

3. The limited scope of terpolymer, due to the fact that such terpolymer is inappropriate to use when producing KOM for TE and electrolysis of water due to the low electrochemical characteristics of such KOM during operation, due to the sulfo group contained in the terpolymer is effective in neutral or acidic medium, whereas for the efficient operation of the carboxyl groups of the terpolymer an alkaline medium is required. As a result of this, the total electrochemical characteristics of the cell using such KOM will be lower than the characteristics of KOM containing only one functional group — only sulfo groups or only carboxyl groups.

4. The difficulty in obtaining concentrated solutions (above 5 wt.%) From the indicated terpolymer with EM> 700 in available solvents, since the presence of sulfo and carboxyl groups in terpolymer simultaneously worsens its solubility, since it is known that copolymers with sulfo groups dissolve well only in strongly polar solvents, whereas copolymers with carboxyl groups are better soluble in weakly polar solvents.

The closest set of essential features to the claimed method is a method for producing TFE terpolymer with functional perfluorinated comonomers according to French application No. 2388012, comprising copolymerizing TFE with a sulfonated vinyl ether having the structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F (HESE), and the third modifying comonomer, a carboxyl-containing vinyl ether of the formula CF ₂ = CFOFP ₂ CF (CF ₃ ) OCF ₂ CF ₂ СООСН ₃ or the formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) CN in the mass of monomers (in a liquid medium) at a temperature of 50 ° C and autogenously pressure in the presence of a perfluorinated organic peroxide (PFPP). The reaction medium TFE in the copolymerization process is not carried out. The loading mixture contains 72 mol.% TFE, 20 mol.% HESE and 8 mol.% Modifying carboxyl-containing monomer.

The disadvantages of this method are:

1. The heterogeneity of the composition of the resulting terpolymer associated with the lack of replenishment of TFE during the copolymerization process and, accordingly, with a variable ratio of comonomers in the reaction medium, which leads to a deterioration in the physicomechanical and electrochemical characteristics of products obtained from such terpolymer, including KOM.

степень кристалличности и плотность, оказывающих существенное влияние на свойства изготовленных из терполимера КОМ, такие как прочность, влажность, электрохимические характеристики. Это связано с тем, что процесс осуществляется при аутогенном давлении, при котором невозможно обеспечить поддержание необходимого определенного соотношения мономеров в реакционной среде и нет каких-либо специальных приемов, позволяющих регулировать указанные свойства.2. The difficulty of regulation during the synthesis of terpolymer properties, such as supramolecular structure, ratio

the degree of crystallinity and density, which significantly affect the properties made of KOM terpolymer, such as strength, humidity, electrochemical characteristics. This is due to the fact that the process is carried out at autogenous pressure, at which it is impossible to maintain the required specific ratio of monomers in the reaction medium and there are no special techniques to regulate these properties.

3. The use in the synthesis process of the initiator (PFPP), which introduces into the terpolymer the unstable end groups C ₂ F ₅ COO-, formed during the decomposition of the specified peroxide. These end groups decompose at a temperature of 220-240 ° C, i.e. at a temperature close to the processing temperature, which affects the quality of terpolymer and products obtained from it. For example, the thermal stability of such a terpolymer at 270 ° C is 0.23% (see our control example 22 in Table 2).

The technical result, which is achieved by the claimed TFE terpolymer with functional perfluorinated comonomers, is to increase the strength and decrease the electrical resistance of KOM made from the claimed terpolymer, as well as to reduce the moisture loss of such KOM during their long-term operation and, accordingly, to improve their electrochemical characteristics, and , in addition, in the ability of the claimed terpolymer after hydrolysis to form concentrated solutions (> 5 wt.%) in available solutions celeration (ethanol, isopropanol, dimethylformamide), allowing to obtain an economically advantageous thin (<100 microns) membrane, unreinforced and reinforced watering or impregnation method, and a thin gas separation hollow fiber.

The specified technical result is achieved due to the fact that the inventors synthesized a linear statistical TFE terpolymer with functional perfluorinated comonomers of the general structural formula:

where M is a hydrogen or alkali metal ion;

a = 5-19.5 mol.%;

b = 80-91 mol%;

c = 0.5-5 mol.%;

равное 1,2-1,35.characterized by an endothermic peak in the temperature range of 70-75 ° C on the crystalline melting curve, measured using a scanning differential calorimeter, and having a weight average molecular weight (2-8) · 10 ⁵ and the ratio

equal to 1.2-1.35.

The technical result, which provides the claimed method for producing TFE terpolymers with functional perfluorinated comonomers, consists in the possibility of controlling the properties of the resulting terpolymer in the synthesis process, as well as in the possibility of obtaining terpolymer suitable for the manufacture of KOH with increased strength, low moisture loss, low ρ _v and improved electrochemical properties during long-term operation, as well as suitable for the preparation of concentrated solutions (> 5 wt.% ) in available organic solvents.

The specified technical result is achieved due to the fact that in the method for producing TFE terpolymer with 9-20 mol% functional perfluorinated comonomers, including copolymerization of TFE with perfluorinated sulfonated vinyl ether having the structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, and the third modifying comonomer in a liquid medium in the presence of a perhalogenated organic peroxide at elevated temperature and pressure, as a third modifying comonomer employed perfluorinated vinyl ether, have s structural formula CF ₂ = CFOCF ₂ CF (CF ₃₎ OCF ₂ CF ₂ SO ₃ M (TNI), where M - hydrogen ion or an alkali metal, and use the loading monomer mixture comprising 35-65 mol% TFE, 19. 2-63.2 mol% of perfluorinated sulfonated vinyl ester having the structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, and 1.8-18.0 mol% of a third modifying comonomer having structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ M, where M is indicated above, moreover, during the copolymerization, the reaction medium is fed with tetrafluoroethylene, providing a constant pressure drop during oosta with an average rate of (2.3-18) · 10 ^-3 MPa / h, and perfluorocyclohexanoyl peroxide or α-chloroperfluoropropionyl peroxide is used as a perhalogenated organic peroxide.

When carrying out the process in an aqueous medium, α-chloroperfluoropropionyl peroxide is used and the copolymerization is carried out at a temperature of 25-30 ° C and an initial pressure of 0.40-0.45 MPa with a drop to a final pressure of 0.35-0.40 MPa.

When carrying out the process in a fluorine-containing organic solvent, perfluorocyclohexanoyl peroxide is used as the initiator and the copolymerization is carried out at a temperature of 30-35 ° C and an initial pressure of 0.25-0.50 MPa with a drop to a final pressure of 0.21-0.42 MPa.

The authors of the present invention, when conducting research in the field of synthesis of perfluorinated TFE copolymers containing functional sulfonyl fluoride groups (-SO ₂ F), capable of being converted into ion-exchange groups, it was unexpectedly found that if a third modifying fluorinated comonomer containing functional group in the ionic form —SO ₃ M, then the indicated comonomer allows one to arrange in the terpolymer the spatial arrangement of side chains of HGE containing —SO ₂ F groups, a certain ordered supramolecular structure is influenced, which affects the degree of crystallinity, the melting temperature, and the density of the resulting terpolymer. The presence of such a supramolecular structure is confirmed by the appearance of an endothermic peak on the crystalline melting curve of the terpolymer in the region of 70-75 ° C (see Figs. 1 and 2 and examples 1-12 in Table 2), while for double TFE-HPS copolymers ( not containing monomer with -SO ₃ M groups) in the indicated temperature range on the crystalline melting curve there is no such peak (see Fig. 3 and control examples 21 and 22 in Table 2). The authors also found that the supramolecular structure formed during the synthesis of the inventive terpolymer is a precursor to the future channel-cluster structure of the hydrolyzed terpolymer, and therefore, at the stage of synthesis, the indicated terpolymer structure formed after hydrolysis can be regulated and accordingly affect the physicomechanical and electrochemical terpolymer properties.

As already mentioned above, KOM lose water during operation during electrolysis, which leads to a deterioration in their electrochemical characteristics. The presence in the inventive terpolymer of a modifying comonomer with an ion-exchange group (-SO ₃ M) allows you to create a more uniform channel-cluster structure during hydrolysis of terpolymer. COM from such a hydrolyzed terpolymer have initially lower electrical resistance, they lose less moisture during long-term operation and have increased wet strength.

As mentioned previously, it is known to use a monomer with an ion-exchange group of the formula CF ₂ = CFOCF (CF ₃ ) OCF ₂ CF ₂ SO ₃ M (where M is indicated above) in the preparation of double copolymers with TFE when its content in the copolymer is not more than 5 mol% (see US patent No. 3282875). In particular, a TFE copolymer is described containing 14 wt.% (3.3 mol.%) Of a monomer with a functional group in ionic form. Such a copolymer immediately after synthesis is ion exchange; it has an EM 3300. The specified double copolymer cannot be processed by extrusion from the melt due to the high processing temperature at which the destruction of ion-exchange groups occurs. It is also not able to form solutions in available solvents due to too high EM. Such a copolymer is not suitable for the manufacture of KOM used in fuel cells, in the electrolysis of water, in chlor-alkali electrolysis due to too high electrical resistance and low swelling in water.

и оптимальную надмолекулярную структуру, хорошо экструдируется при температурах 240-270°С, в том числе в тонкие пленки и трубки, а также хорошо растворяется после гидролиза в доступных органических растворителях.In the claimed terpolymer, the total content of monomers with functional groups is 9-20 mol.%, Of which the monomer with a functional group in non-ionic form (-SO ₂ F) is 8.5-15 mol.%, And the monomer with a functional group in ionic form (-SO ₃ M) 0.5-5 mol.%. As a result, the claimed terpolymer having

and the optimal supramolecular structure, it is well extruded at temperatures of 240-270 ° C, including into thin films and tubes, and also dissolves well after hydrolysis in available organic solvents.

If the content of the monomer with —SO ₃ M groups in the terpolymer is less than 0.5 mol%, then it practically does not affect the properties of the resulting terpolymer (see control example 13, table 2). In the case when the content of the monomer with —SO ₃ M groups in the terpolymer is more than 5 mol%, the optimal supramolecular structure is not formed, while the terpolymer does not have the necessary molecular weight characteristics, and ρ _{v of} hydrolyzed terpolymer films (with EM 1000 ) has increased values (see control. Example 14, table 2).

что затрудняет его переработку методом экструзии, так как Т_пл. терполимера близка к температуре разложения функциональных групп (см. контр. пример 16, табл.2). Кроме того, такой гидролизованный терполимер имеет высокое ρ_v (>3000 Ом·см) и из него невозможно получить концентрированные растворы.In the case when in the terpolymer the ratio b / a + c is more than 10, the EM of the terpolymer, its melting point and

which complicates its processing by extrusion, as T _pl. terpolymer is close to the temperature of decomposition of functional groups (see control. example 16, table 2). In addition, such a hydrolyzed terpolymer has a high ρ _v (> 3000 Ohm · cm) and it is impossible to obtain concentrated solutions from it.

и соответственно получаемые из такого терполимера пленки (мембраны) имеют очень низкую механическую прочность (см. контр. пример 15, табл.2).If the ratio b / a + c in the terpolymer is less than 4, then the resulting terpolymer has too low EM, low

and accordingly the films (membranes) obtained from such a terpolymer have very low mechanical strength (see control example 15, table 2).

является оптимальным с точки зрения как экструдирования из расплава, так и растворения терполимера (после гидролиза) в доступных органических растворителях с получением концентрированных растворов (>5 мас.%). Если

терполимера будет ниже 2·10⁵, то ухудшаются его физико-механические свойства и соответственно физико-механические свойства КОМ на его основе. При увеличении

терполимера до более 8·10⁵ ухудшается его растворимость в среде доступных органических растворителей, а также затрудняется его перерабатываемость методом экструзии, в частности из терполимера с такой

невозможно получать пленки толщиной менее 100 мкм. При отношении

меньшем чем 1,2, терполимер хуже растворяется в органических растворителях и труднее экструдируется, а если

больше 1,35, то ухудшаются физико-механические свойства полученных из терполимера изделий.The combination of the claimed terpolymer properties such as an ordered supramolecular structure,

is optimal in terms of both melt extrusion and dissolution of terpolymer (after hydrolysis) in available organic solvents to obtain concentrated solutions (> 5 wt.%). If

terpolymer will be below 2 · 10 ⁵ , then its physical and mechanical properties and, accordingly, the physical and mechanical properties of KOM based on it will deteriorate. With increasing

terpolymer to more than 8 · 10 ⁵ deteriorates its solubility in the environment of available organic solvents, and also makes it difficult to process it by extrusion, in particular from terpolymer with such

it is impossible to obtain films with a thickness of less than 100 microns. With respect

less than 1.2, terpolymer dissolves worse in organic solvents and is more difficult to extrude, and if

more than 1.35, the physical and mechanical properties of terpolymer-derived products are impaired.

ПТР=7-84 г/10 мин (при 270°С), Т_пл.=220-260°С, прочность при разрыве 23,5-30 МПа, степень кристалличности 8,0-16,5%, плотность 2,076-2,087 г/см³ и термостабильность 0,01-0,033% (при 270°С), при этом терполимеры однородны по составу и имеют эндотермический пик в температурном интервале 70-75°С на кривой кристаллического плавления.According to the claimed method, depending on the purpose, terpolymers can be obtained with a content of 9-20 mol.% Functional perfluorinated comonomers having after hydrolysis EM = 850-1445 and having the following optimal complex of physical and physico-mechanical characteristics:

MF = 7-84 g / 10 min (at 270 ° C), T _pl. = 220-260 ° C, tensile strength 23.5-30 MPa, crystallinity 8.0-16.5%, density 2.076-2.087 g / cm ³ and thermal stability 0.01-0.033% (at 270 ° C) while terpolymers are uniform in composition and have an endothermic peak in the temperature range of 70-75 ° C on the crystalline melting curve.

Figure 1 shows the crystalline melting curve of a terpolymer containing 86.8 mol.% TFE, 12.7 mol.% HCE and 0.5 mol.% VSI, having an endothermic peak with a temperature of 70.23 ° C (enthalpy 37.83 J / g); figure 2 presents the crystalline melting curve of a terpolymer containing 84.7 mol.% TFE, 11.7 mol.% VGE and 3.5 mol.% VSI, having an endothermic peak with a temperature of 73.48 ° C (enthalpy 19.91 J / g); and figure 3 presents the crystalline melting curve of a terpolymer containing 84.5 mol.% TFE and 15.5 mol.% HHES, on which there is no endothermic peak.

The indicated optimal set of properties is ensured by the synthesis conditions of the terpolymer, in particular, using the loading mixture containing TFE, VGE and modifying comonomer with functional groups -SO ₃ M in the above ratio, and replenishing the TFE reaction medium with a constant pressure drop during the process according to the claimed method with a given average speed, which allows to maintain a constant predetermined ratio of comonomers in the reaction medium during the entire copolymerization process, as well as lzovaniem as initiator perftorgeksanoilperoksida or α-hlorperftorpropionilperoksida.

The copolymerization process is carried out with a constant decrease in pressure in the reaction medium: from the initial 0.25-0.5 MPa to the final 0.21-0.42 MPa, respectively. The initial pressure is set depending on the type of reaction medium (water or an organic solvent), the type of initiator used and the given composition of the synthesized terpolymer. The pressure in the copolymerization process is regulated by feeding the reaction medium with the calculated amount of TFE so as to ensure a decrease in pressure in the reaction medium during the process with an average rate of (2.3-18) · 10 ^-3 MPa / h. The composition of the loading mixture, the required amount of TFE fed, and the specific rate of pressure reduction in the reaction medium to ensure a given constant ratio of comonomers in the reaction medium upon receipt of the terpolymer of the given EM were calculated by the inventors in accordance with the curves of the dependence of the terpolymer composition and process speed on the composition of the loading mixture obtained by them.

и снижается

(см. пример 4 и контр. примеры 17 и 19 в табл.1 и 2). При средней скорости снижения давления в реакционной среде более 18·10^-3 МПа/ч при одинаковом составе загрузочной смеси, тех же условиях сополимеризации и при одном и том же времени сополимеризации уменьшается ЭМ терполимера, уменьшается

увеличивается

(см. пример 12 и контр. пример 18 в табл.1 и 2).If the average rate of pressure decrease in the reaction medium is less than 2.3 · 10 ^-3 MPa / h or the process is carried out at constant pressure, it is difficult to control the properties of the resulting terpolymer: with the same composition of the loading mixture, the same copolymerization conditions and at the same time copolymerization increases the terpolymer EM, increases

and declining

(see example 4 and counter. examples 17 and 19 in tables 1 and 2). At an average rate of pressure drop in the reaction medium of more than 18 · 10 ^-3 MPa / h with the same composition of the loading mixture, the same copolymerization conditions and at the same copolymerization time, the terpolymer EM decreases, decreases

is increasing

(see example 12 and counter. example 18 in tables 1 and 2).

In accordance with the claimed method of producing a TFE terpolymer with 9-20 mol.% Functional perfluorinated comonomers, the copolymerization process can be carried out in an aqueous medium or in an environment of a fluorine-containing organic solvent, such as perfluorocyclobutane (PFCB), perfluorodimethylcyclobutane, 1,1,2-trichloro-1 , 2,2-trifluoroethane (freon-113, X-113), etc.

Used in the copolymerization of the monomers of VGE and VSI can be obtained in accordance with US patent No. 3282875. In the conditions of the proposed method, the monomers of VGE and VVI are not homopolymerized and not copolymerized with each other.

As a perhalogenated initiator, α-chloro-perfluoropropionyl peroxide (α-HFPPP) or perfluorocyclohexanoyl peroxide (PFSPP) in the amount of 0.05-0.15% by weight of loaded monomers can be used. The use of such peroxides allows the copolymerization process to be carried out at low temperatures (25-35 ° C), which reduces the danger of the process and promotes the formation of terpolymers with a given set of properties.

When copolymerization is carried out in an organic solvent, the calculated amounts of solvent, HESE, modifying monomer (HSI) and PFSPH are loaded into the reactor in the form of a 10% solution in a fluorine-containing solvent. Then the reactor is purged with nitrogen, cooled to a temperature of -20 ° C, vacuum and with stirring load the specified amount of TFE. Then the reactor is heated to the desired temperature, while the set initial pressure is set in the reactor. The pressure in the copolymerization process is reduced at a predetermined average rate, which is controlled by feeding the calculated amount of TFE with a decrease in pressure in the reactor of 0.01 MPa. The time of the copolymerization process is determined by the specified values of the initial pressure of TFE, EM of the resulting terpolymer, the degree of conversion of comonomers with functional groups and is 4-20 hours.

At the end of the copolymerization process, the reactor is cooled, vacuumized to remove unreacted TFE, and the finished terpolymer is discharged in the form of a dispersion in a mixture of solvent and unreacted monomers. The terpolymer is isolated from the dispersion by distillation of the solvent and unreacted HCEE monomer, the terpolymer obtained is washed with water to remove unreacted HCE and HFC-113, and dried in vacuum at a temperature of 60-80 ° C.

When carrying out the copolymerization process in an aqueous medium, a predetermined amount of demineralized water, VGE, VSI and α-HFPPP is loaded into the reactor in the form of a 5% solution in Freon-113. Then, TFE is fed into the reactor in an amount providing a predetermined initial pressure of the copolymerization process, and heated to a predetermined temperature. The pressure in the copolymerization process is reduced at a given average rate, feeding TFE with a decrease in pressure in the reactor of 0.01 MPa. At the end of the copolymerization, the reactor is cooled, vacuumized to remove TFE, and a mixture of the obtained terpolymer in the form of an aqueous dispersion and unreacted monomers is unloaded from the reactor. The aqueous dispersion of terpolymer is separated from unreacted monomers and the aqueous dispersion is coagulated with vigorous stirring to isolate the terpolymer. The terpolymer is separated from the aqueous phase, washed several times with distilled water, HFC-113, filtered and dried in vacuum at a temperature of 60-80 ° C.

The properties of the obtained copolymers were determined as follows:

1. The presence of an endothermic peak on the polymer crystalline melting curve and its temperature were determined by differential scanning calorimetry (DSC) using a DuPont model 9900 Thermal Analysis instrument.

2. The content of HHPE and HHI monomers was determined by IR spectroscopy on a Perkin-Elmer spectrometer, model 1760. The presence of an absorption band in the region of 1460 cm ^-1 characterizes the presence of -SO ₂ F groups. The presence of an absorption band in the region of 1060 cm ^-1 symmetric stretching vibrations of S — O bonds in the —SO ₃ M or —SO ₃ N. group

3. The melt flow rate (MFR) was determined according to GOST 11645-73 on an IIIRT-AM extrusion plastomer at a temperature of 270 ± 0.5 ° C, a load of 2.16 kg, on a capillary with a diameter of 2.09 ± 0.005 mm with a sample exposure time in the extrusion chamber under load for 5 minutes

4. The tensile strength was determined according to GOST 11262-80 on samples with a thickness of 1.5 ± 0.2 mm, made by pressing the copolymer powder at a temperature of 220-270 ° C and a pressure of 20 ± 2.5 MPa.

5. The equivalent mass was determined by calculation using the total exchange capacity, which was determined according to GOST 17552-72 on film samples 0.2 ± 0.05 mm thick obtained by pressing a copolymer sample at a temperature of 220 ± 2 ° C and a pressure of 20 ± 2.5 MPa

определяли расчетным путем.6. The number average and mass average molecular weights were determined by thin layer and liquid chromatography of a 1-5% solution of the polymer in isopropyl alcohol or dimethylacetamide. Attitude

determined by calculation.

7. The degree of crystallinity was determined by X-ray diffraction using a small-angle scattering chamber KRM-1.

8. The density was determined according to GOST 15139-69 by hydrostatic weighing.

9. Thermostability was determined by the loss of mass of the polymer powder when holding it at a temperature of 270 ± 5 ° C for 5 hours.

10. Humidity was determined according to GOST 17554-72.

11. ρ _{v was} determined according to TU 301-05-12-89.

12. The melting temperature (T _pl. ) Was determined on a Dupont model 9900 Thermal Analysis system instrument.

The following examples illustrate the present invention.

Example 1

In a 1.3-liter stainless steel reactor equipped with a jacket, an anchor stirrer, a manometer and a thermometer, 670 g of Freon-113, 325.6 g of HESE of the formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ are charged F, 9.4 g of the AFR of the formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ F and 0.52 g of PFSPHP in the form of a 10% solution in Freon-113. Then the reactor is purged with nitrogen, cooled to a temperature of -20 ° C, vacuum to a residual pressure of 10 mm Hg and with stirring, 52.6 g of TFE are introduced into it. Then the reactor is heated to a temperature of 30 ° C, while the initial pressure in the reactor is set at 0.25 MPa, and 52.3 g of TFE are fed into it gradually as the pressure drops by 0.01 MPa for 17 hours, providing a constant pressure drop in during the copolymerization process with an average rate of 2.3 · 10 ^-3 MPa / h to a final pressure of 0.21 MPa. After the copolymerization process is completed, the reactor is cooled to 0 ° C and the unreacted TFE is blown off. After that, the obtained dispersion of TFE terpolymer with VGE and VVI in a mixture of HFC-113 and unreacted VGE and VVI is discharged from the reactor, chladon-113 and VVGE are distilled off. The resulting terpolymer is washed with water to remove unreacted VSI, then with Freon-113 and dried under vacuum at a temperature of 80 ° C. Obtain 110 g of TFE terpolymer powder with 19.5 mol.% VGE and 0.5 mol.% VSI.

The process parameters and properties of the copolymers of example 1 and all of the following examples are shown in tables 1 and 2, respectively.

Example 2

In a 1.3-liter stainless steel reactor equipped with a jacket, anchor stirrer, pressure gauge and thermometer, 400 ml of distilled water, 300 g of HESE of the formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, 100 are charged g of ALL formula of CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ Li and 0.55 g of α-HFPPP in the form of a 5% solution in HFC-113, purged with nitrogen, vacuum to a residual pressure of 10 mm RT .art. and with stirring, 62.0 g of TFE are introduced into it. Then the reactor is heated to a temperature of 25 ° C, while the initial pressure in the reactor is set at 0.4 MPa, and 62.5 g of TFE is fed into it gradually as the pressure drops by 0.01 MPa for 20 hours, providing a constant pressure drop in during the copolymerization process with an average rate of 2.3 · 10 ^-3 MPa / h, the final pressure in the reactor of 0.35 MPa. After the copolymerization process is completed, the reactor is cooled to a temperature of 10 ° C and vacuumized to remove TFE. After that, the vacuum is turned off and the resulting dispersion of TFE terpolymer with HHPE and HSS in a mixture of water and unreacted HHPS and HSP coagulate with vigorous stirring. The terpolymer powder is separated from the aqueous phase, washed with distilled water, HFC-113 and dried under vacuum at a temperature of 80 ° C. 130 g of TFE terpolymer powder are obtained with 15.0 mol% of HCE and 5.0 mol% of HFI.

Examples 3-12 and 13-19 (control)

The copolymerization process is carried out analogously to example 1 or 2, but the process parameters vary. In examples 1, 3-5, 9-12 and 13, 16-19 (control), the process is carried out in a HFC-113 medium in the presence of PFSPP, in example 8 in a perfluorocyclobutane medium in the presence of PFSPP. In examples 2, 6, 7 and 14-15 (control), the process is carried out in an aqueous medium in the presence of α-HFPPP. In example 19 (control.) Spend replenishment of TFE, maintaining a constant pressure of 0.29 MPa.

Example 20 (counter. US patent No. 3282875)

In a steel ampoule with a capacity of 0.33 l, 200 ml of distilled water, 30 g of the SCI of the formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ Na and 1 g of ammonium persulfate [(NH ₄ ) ₂ S ₂ O ₈ are loaded ]. The ampoule is purged with nitrogen, vacuum and served 30 g of TFE. The ampoule is placed in a "rocking chair" with a number of swings of 100-110 per min and heated to a temperature of 70 ° C. The process is carried out at autogenous pressure for 2 hours. Then the ampoule is cooled to room temperature, the unreacted TFE is blown off and the copolymer dispersion is discharged. The resulting dispersion is coagulated with vigorous stirring, the copolymer is filtered off, washed several times with water and dried at a temperature of 80 ° C in vacuum. Get 15 g of a copolymer containing 3.3 mol.% VSI.

Example 21 (counter. US patent No. 5281680)

The copolymerization process is carried out analogously to example 1, using a bootable mixture containing 52.0 mol.% TFE and 48.0 mol.% VGE, and PFPP as an initiator. The process is carried out at a temperature of 45 ° C and a pressure of 0.39 MPa, maintaining the pressure by constant replenishment of the TFE reaction medium for 3 hours. Received 25 g of a copolymer.

Example 22 (counter. On the application of France No. 2388012)

In a steel ampoule with a capacity of 0.33 l, 25.4 g of HESE, 8.1 g of perfluoro (4.7-dioxa-2,5-dimethyl-8-nonen) nitrile and 15 ml of a 0.05% PFPP solution in freon-113. The ampoule is cooled to 0 ° C, vacuumized and 20 g of TFE are fed into it, after which the ampoule is placed in a “rocking chair” with a number of swings of 100-110 per minute. The feed mixture contains 72.0 mol.% TFE, 20.0 mol.% HHE and 8.0 mol.% Perfluoro (4,7-dioxa-2,5-dimethyl-8-nonene) nitrile. The ampoule is heated to a temperature of 50 ° C, while a pressure of 1.4 MPa is set. Next, the process is carried out at a temperature of 50 ° C and autogenous pressure for 3 hours. The final pressure of the process is 1.2 MPa. After the end of the process, the ampoule is cooled and the unreacted TFE is blown off. The dispersion of the resulting terpolymer in Freon-113 is discharged from the ampoule and the Freon-113 and unregulated monomers are distilled off. The resulting terpolymer powder is washed with water, HFC-113 and dried in vacuum at a temperature of 80 ° C. Get 5 g of terpolymer containing 12.4 mol.% VGE and 2.6 mol.% Perfluoro (4,7-dioxa-2,5-dimethyl-8-nonene) nitrile.

Example 23

отношение

используют для получения раствора с концентрацией 7 мас.%. Перед растворением порошок терполимера с размером частиц 100-500 мкм гидролизуют 10%-ным водным раствором гидроокиси калия при температуре 95°С в течение 14 часов, а затем обрабатывают 5%-ным водным раствором соляной кислоты в течение 10 часов, промывают водой и сушат в термостате при 60-70°С. После гидролиза терполимер содержит группы -SO₃Н и имеет ЭМ 1000.A functional polymer -SO ₂ F and -SO ₃ H obtained in Example 4 with an IRR content of 5 mol% (endothermic peak with a maximum temperature of 75 ° C on the crystalline melting curve,

the attitude

used to obtain a solution with a concentration of 7 wt.%. Before dissolving, a terpolymer powder with a particle size of 100-500 μm is hydrolyzed with a 10% aqueous solution of potassium hydroxide at 95 ° C for 14 hours, and then treated with a 5% aqueous solution of hydrochloric acid for 10 hours, washed with water and dried in the thermostat at 60-70 ° C. After hydrolysis, the terpolymer contains —SO ₃ H groups and has an EM of 1000.

A 500 ml round bottom flask equipped with a stirrer, thermometer and reflux condenser was charged with 14 g of the powder of the indicated hydrolyzed terpolymer and 186 g of isopropyl alcohol (isopropanol), the stirrer was turned on, and the terpolymer was dissolved at 70 ° C for 1 h. The terpolymer completely dissolved at specified conditions. Then, the resulting solution was cooled to room temperature and filtered through a nylon filter. After filtration, the solution has a concentration of 7 wt.%.

Example 24

отношение

используют при получении мембран для электролиза воды. Из указанного терполимера на лабораторном экструдере при температуре 270°С получают экструзионную пленку толщиной 125 мкм. Пленка имеет прочность при разрыве 28,5 МПа. Полученную пленку гидролизуют 15%-ным водным раствором гидроокиси калия при 90°С в течение 12 часов, а затем обрабатывают 5%-ным водным раствором соляной кислоты при 95°С в течение 4 часов. После гидролиза полученная КОМ имеет функциональные группы -SO₃Н, ЭМ 1000, прочность при разрыве 27,5 МПа, влажность 33%, ρ_v 12 Ом·см. КОМ была использована при изготовлении мембранно-электродного блока (МЭБ) для электролиза воды.A functional polymer -SO ₂ F and -SO ₃ K, obtained according to example 7, with a content of VSI 3 mol.% (Endothermic peak with a maximum temperature of 73 ° C on the crystalline melting curve,

the attitude

used in the preparation of membranes for electrolysis of water. From the indicated terpolymer on a laboratory extruder at a temperature of 270 ° C., an extrusion film of a thickness of 125 μm is obtained. The film has a tensile strength of 28.5 MPa. The resulting film is hydrolyzed with a 15% aqueous solution of potassium hydroxide at 90 ° C for 12 hours, and then treated with a 5% aqueous solution of hydrochloric acid at 95 ° C for 4 hours. After hydrolysis, the resulting KOM has functional groups —SO ₃ H, EM 1000, tensile strength 27.5 MPa, humidity 33%, ρ _v 12 Ohm · cm. COM was used in the manufacture of the membrane-electrode block (OIE) for electrolysis of water.

To obtain the electrode material in a glass container, 0.92 g of an electrocatalyst — platinum black (particle size 0.06 μm) is mixed with 2.2 g of a 7% solution of terpolymer according to Example 23 (EM 1000, —SO ₃ H group). The resulting viscous mass is applied to one of the surfaces of the above KOM (in the form of an air-dry film with a diameter of 100 mm) by pouring a mixture of such a thickness that, after removal of the solvent, the layer of electrode material has a thickness of 10 μm. Then KOM is placed in a thermostat and heat treated with a stepwise rise in temperature: holding at 20-22 ° C for 10 min, at 60 ° C for 40 min, at 80 ° C for 20 min and at 90 ° C for 20 min . After this, the KOM is removed from the thermostat, cooled to room temperature, and the same electrode material is applied on its other surface in the same way, placed in a thermostat and heat treated in the manner described above. The obtained OIE is tested during electrolysis of water.

A current collector made of porous titanium with down conductors is pressed onto the OIE on both sides, the assembly obtained is compacted using a plate coupler, immersed in a vessel with distilled water, and an electric current of 0.5 A / cm ^{2 is} supplied at 90 ° C for 1 hour. Then the assembly is installed in the cell for electrolysis of deionized water. The voltage on the cell was 1.61 V at a current density of 1 A / cm ² and a temperature of 100 ° C. The cell worked stably for 3500 hours without changing the indicators. Then the process was stopped and the OIE was removed from the cell. A visual inspection of the OIE did not show any changes. KOM after operation had the following characteristics:

Humidity 33% Tensile strength 27.5 MPa ρ _v 12 Ohm cm

Example 25

путем экструзии на лабораторном экструдере при температуре 265°С получают пленку толщиной 125 мкм. Пленка в сухом состоянии имеет прочность при разрыве 27 МПа. Полученную пленку гидролизуют 15%-ным водным раствором гидроокиси калия при 90°С в течение 10 часов, а затем обрабатывают 5%-ным раствором соляной кислоты при 95°С в течение 4 часов. После гидролиза полученная КОМ имеет функциональные группы -SO₃Н (ЭМ=1000), влажность 35%, ρ_v 11,2 Ом·см, прочность при разрыве 25,2 МПа. КОМ используют при изготовлении МЭБ для ТЭ.From a terpolymer with functional groups —SO ₂ F and —SO ₃ H, obtained according to Example 6, with an IRR content of 5.0 mol% (endothermic peak with a temperature of 75 ° C on the crystalline melting curve,

by extrusion on a laboratory extruder at a temperature of 265 ° C, a film with a thickness of 125 μm is obtained. The film in a dry state has a tensile strength of 27 MPa. The resulting film is hydrolyzed with a 15% aqueous solution of potassium hydroxide at 90 ° C for 10 hours, and then treated with a 5% solution of hydrochloric acid at 95 ° C for 4 hours. After hydrolysis, the obtained KOM has functional groups —SO ₃ N (EM = 1000), humidity 35%, ρ _v 11.2 Ohm · cm, tensile strength 25.2 MPa. COM is used in the manufacture of the OIE for fuel cells.

To obtain the electrode material in a glass container, 0.9 g of an electrocatalyst - platinum black (particle size - 0.09 μm) is mixed with 0.03 g of an electrically conductive inactive material - carbon black with a particle size of 0.01 μm, after which they are added to the resulting mixture 3 g of a 7% solution of terpolymer (EM 1000, group -SO ₃ H) according to example 23.

The resulting viscous mass is applied to one of the surfaces obtained as indicated above by KOM (air-dry film with a diameter of 100 mm) by spreading the mixture with a layer of such a thickness that, after drying, the layer of electrode material has a thickness of 6 μm. Then the membrane is placed in a thermostat and treated with the next stepwise rise in temperature: it is kept at 20-22 ° С for 10 minutes, at 60 ° С - 40 minutes, at 80 ° С - 20 minutes, at 90 ° С - 20 minutes. After that, the KOM is removed from the thermostat, cooled to room temperature, and the same electrode material is applied on its other surface in the same way, then it is again placed in the thermostat and heat treated in the manner described above. The fabricated OIE is tested in a fuel cell as follows. A carbon cloth impregnated with polytetrafluoroethylene dispersion (TU 6-05-1246-81) is placed on both surfaces of the electrode layers of the obtained OIE and compressed. Then, carbon collectors of current are applied to both surfaces of the OIE and the assembly is installed in the fuel cell. OIE studies are carried out at 80 ° C when gas is supplied to the fuel cell: hydrogen - to the anode chamber at a pressure of 0.1 MPa and oxygen - to the cathode chamber at a pressure of 0.12 MPa. The following initial characteristics of the fuel cell were obtained:

Cell voltage 0.87-0.88 V Current density 700 mA / cm ²

The fuel cell worked stably for 3500 hours at a cell voltage of 0.87 V, after which the process was stopped and the OIE was removed from the cell. Visual inspection of the OIE did not observe any changes. COM after testing had the following characteristics:

Humidity 35% Tensile strength 25 MPa ρ _v 11.2 ohm cm

Example 26

путем экструзии на лабораторном экструдере при температуре 255°С изготавливают пленку толщиной 220 мкм (пленка №1). Затем из терполимера с функциональными группами -SO₂F и -SO₃Na, полученного по примеру 12, с содержанием ВСИ 4,0 мол.% (эндотермический пик с температурой 73,5°С на кривой кристаллического плавления,

путем экструзии на лабораторном экструдере при температуре 270°С изготавливают пленку толщиной 30 мкм (пленка №2). Экструзионные пленки №1 и 2 соединяют вакуумным ламинированием при 260°С. Полученную комбинированную пленку толщиной 250 мкм гидролизуют 15%-ным водным раствором гидроокиси натрия при температуре 95-98°С в течение 12 часов. После гидролиза полученная комбинированная КОМ имеет функциональные группы -SO₃Na (пленка №1 имеет ЭМ терполимера 1100, пленка №2 1445). КОМ используют при изготовлении МЭБ для электролиза раствора хлористого натрия (NaCl) с концентрацией 230 г/л. Для получения электродного материала в стеклянной емкости смешивают 3·10^-2 г электрокатализатора - платиновой черни (диаметр частиц 0,09 мкм) с 10 г хладона-113, после чего к смеси добавляют 1 г 7%-ного раствора терполимера с ЭМ=1000, группы -SO₃Н в изопропаноле (по примеру 23). Полученную вязкую массу наносят на одну из поверхностей комбинированной КОМ (в виде воздушно-сухой пленки диаметром 5 см) методом намазывания смеси такой толщины, чтобы после высушивания слой электродного материала имел толщину 4,5 мкм. Затем КОМ помещают в термостат и обрабатывают при следующем ступенчатом подъеме температуры: выдерживают при 20 - 22°С в течение 10 мин, при 60°С - 40 мин, при 80°С - 20 мин, при 90°С - 20 мин. После этого мембрану вынимают из термостата, охлаждают до комнатной температуры и аналогичным образом на другую ее поверхность наносят тот же самый электродный материал, затем снова помещают в термостат и термообрабатывают указанным выше способом.From a terpolymer with functional groups —SO ₂ F and —SO ₃ Na, obtained according to Example 8, with an IRR content of 0.5 mol% (endothermic peak with a temperature of 70 ° C on the crystalline melting curve,

by extrusion on a laboratory extruder at a temperature of 255 ° C, a film with a thickness of 220 μm is made (film No. 1). Then, from a terpolymer with functional groups —SO ₂ F and —SO ₃ Na, obtained according to Example 12, with an ALL content of 4.0 mol% (endothermic peak with a temperature of 73.5 ° C on the crystalline melting curve,

by extrusion on a laboratory extruder at a temperature of 270 ° C, a film 30 microns thick is made (film No. 2). Extrusion films No. 1 and 2 are connected by vacuum lamination at 260 ° C. The resulting combined film with a thickness of 250 μm is hydrolyzed with a 15% aqueous solution of sodium hydroxide at a temperature of 95-98 ° C for 12 hours. After hydrolysis, the resulting combined KOM has functional groups —SO ₃ Na (film No. 1 has an EM terpolymer 1100, film No. 2 1445). COM is used in the manufacture of OIE for the electrolysis of a solution of sodium chloride (NaCl) with a concentration of 230 g / l. To obtain the electrode material in a glass container, 3 · 10 ^-2 g of electrocatalyst - platinum black (particle diameter 0.09 μm) are mixed with 10 g of Freon-113, after which 1 g of a 7% solution of terpolymer with EM = 1000 is added to the mixture , —SO ₃ H groups in isopropanol (as in Example 23). The resulting viscous mass is applied to one of the surfaces of the combined KOM (in the form of an air-dry film with a diameter of 5 cm) by spreading a mixture of such a thickness that, after drying, the layer of electrode material has a thickness of 4.5 μm. Then the KOM is placed in a thermostat and processed at the next stepwise rise in temperature: it is held at 20 - 22 ° C for 10 minutes, at 60 ° C - 40 minutes, at 80 ° C - 20 minutes, at 90 ° C - 20 minutes. After that, the membrane is removed from the thermostat, cooled to room temperature and the same electrode material is applied to its other surface in the same way, then it is again placed in the thermostat and heat treated in the manner described above.

The fabricated OIE is tested in an electrolytic cell to produce chlorine and alkali as follows. 0.45 mm thick carbon fabric is placed on both surfaces of the electrode layers of the obtained OIE, which will act as a current collector, and is compressed. Then the OIE is installed in the electrolytic cell so that the KOM side having EM 1445 faces the cathode.

OIE studies are carried out at 90 ° C and a current density of 3 kA / m ² when an aqueous solution of sodium chloride with a concentration of 230 g / l is fed into the anode chamber. The following characteristics are obtained:

NaOH concentration 24% Current output 91% Cell voltage 3.12V

The electrolytic cell operated stably at a voltage of 3.12 V for 3000 hours, the power consumption was 2300 kW / h, after which the process was stopped and the OIE was removed from the cell. Visual inspection of the OIE did not observe any changes.

Example 27

отношение

на лабораторном экструдере при температуре 270°С изготавливают трубки с внутренним диаметром 500 мкм и толщиной стенки 90 мкм. Изготовленные трубки гидролизуют 15%-ным водным раствором гидроокиси калия. После гидролиза терполимер имеет функциональные группы -SO₃К (ЭМ 1280). Полученные трубки используют для осушки влажного атмосферного воздуха (относительная влажность воздуха 98%) при температуре окружающей среды 22-24°С. Относительная влажность атмосферного высушенного воздуха составляет 9%.From a terpolymer with functional groups —SO ₂ F and —SO ₃ K, obtained according to Example 11, with an IRR content of 2.5 mol% (endothermic peak with a maximum temperature of 72 ° C on the crystalline melting curve,

the attitude

tubes with an inner diameter of 500 μm and a wall thickness of 90 μm are manufactured on a laboratory extruder at a temperature of 270 ° C. The tubes made are hydrolyzed with a 15% aqueous potassium hydroxide solution. After hydrolysis, the terpolymer has functional groups —SO ₃ K (EM 1280). The obtained tubes are used for drying humid atmospheric air (relative humidity 98%) at an ambient temperature of 22-24 ° C. The relative humidity of the atmospheric dried air is 9%.

Example 28

используют для получения раствора с концентрацией 20 мас.%. Перед растворением сополимер гидролизуют 10%-ным водным раствором гидроокиси лития (LiOH) при температуре 95°С в течение 12 часов, после чего гидролизованный терполимер отмывают водой от гидроокиси лития и сушат в термостате при температуре 60-70°С. После гидролиза терполимер содержит группы -SO₃Li и имеет ЭМ 950. В круглодонную колбу объемом 200 мл, снабженную мешалкой, термометром и обратным холодильником, загружают 20 г порошка указанного гидролизованного терполимера с размером частиц 100-500 мкм, 80 г диметилформамида и растворяют терполимер при температуре 120°С в течение 2 часов. Терполимер полностью растворился в указанных условиях. Затем раствор охлаждают до комнатной температуры и фильтруют через капроновый фильтр. После фильтрации раствор имеет концентрацию 20 мас.%.A functional polymer -SO ₂ F and -SO ₃ H obtained in Example 3 with an IRR content of 5 mol% (endothermic peak with a maximum temperature of 75 ° C on the crystalline melting curve,

used to obtain a solution with a concentration of 20 wt.%. Before dissolution, the copolymer is hydrolyzed with a 10% aqueous solution of lithium hydroxide (LiOH) at a temperature of 95 ° C for 12 hours, after which the hydrolyzed terpolymer is washed with water from lithium hydroxide and dried in a thermostat at a temperature of 60-70 ° C. After hydrolysis, the terpolymer contains —SO ₃ Li groups and has an EM of 950. In a 200 ml round bottom flask equipped with a stirrer, thermometer and reflux condenser, 20 g of the powder of the indicated hydrolyzed terpolymer with a particle size of 100-500 μm, 80 g of dimethylformamide are dissolved and the terpolymer is dissolved at a temperature of 120 ° C for 2 hours. The terpolymer is completely dissolved under the indicated conditions. Then the solution is cooled to room temperature and filtered through a nylon filter. After filtration, the solution has a concentration of 20 wt.%.

The resulting solution is used in the manufacture of a film for air humidity sensors. The film is obtained by pouring the solution onto glass with a layer of such a thickness that, after drying, a film with a thickness of 40 μm and a size of 50 × 50 mm is formed. The glass with the solution deposited on it is placed in a thermostat and the solvent is evaporated with a gradual increase in temperature with exposure at 22 ° C for 10 minutes, at 80 ° C for 20 minutes, at 140 ° C for 20 minutes. After that, the glass with the ion-exchange film formed on it is used as a sensitive air humidity sensor, operating on the principle of changes in resistance when the moisture content of the film changes. A device with the specified humidity sensor responds to changes in air humidity within 20-100%.

Example 29

используют для получения раствора с концентрацией 15 мас.%. Перед растворением порошок гидролизуют 10%-ным водным раствором гидроокиси лития (LiOH) при температуре 95°С в течение 12 часов, после чего гидролизованный порошок отмывают водой от гидроокиси лития и сушат в термостате при температуре 50-60°С. После гидролиза сополимер содержит группы -SO₃Li и имеет ЭМ 1000. В круглодонную колбу объемом 500 мл, снабженную мешалкой, термометром и обратным холодильником, загружают 30 г порошка указанного гидролизованного терполимера с размером частиц 100-400 мкм и 170 г изопропанола, включают мешалку и растворяют терполимер при температуре 70°С в течение 1 часа. Терполимер полностью растворяется при указанных условиях. Затем полученный раствор охлаждают до комнатной температуры и фильтруют через капроновый фильтр. После фильтрации раствор имеет концентрацию 15 мас.%. Полученный раствор используют для изготовления газоразделительного полого волокна. Полое волокно получают на лабораторной установке мокрым способом в осадительной ванне, содержащей 80 мас.% воды и 20 мас.% изопропанола. Внутренний диаметр волокна составляет 80 мкм, толщина стенки 40 мкм. Полученное полое волокно используют в газоразделительном устройстве для выделения аммиака из смеси аммиака и водорода. Газовую смесь, состоящую из 50 об.% аммиака и 50 об.% водорода, подают внутрь полого волокна, предварительно увлажняя водяным паром, под давлением 100 кПа и при температуре 22°С. На основе анализа состава газовой смеси с внешней стороны волокна вычисляют коэффициенты проницаемости составляющих смесь газов, которые для аммиака и водорода равны 3,92·10^-11 и 1,85·10^-15 моль·м/м²·с·Па соответственно, и коэффициент селективности, равный 2,12·10⁴ в пользу аммиака. После очистки смесь содержит 99,8 об.% аммиака и 0,2 об.% водорода.A copolymer with functional groups —SO ₂ F and —SO ₃ Li according to Example 5 with an IRR content of 3.5 mol% (endothermic peak with a maximum temperature of 73 ° C on the crystalline melting curve,

used to obtain a solution with a concentration of 15 wt.%. Before dissolving, the powder is hydrolyzed with a 10% aqueous solution of lithium hydroxide (LiOH) at a temperature of 95 ° C for 12 hours, after which the hydrolyzed powder is washed with water from lithium hydroxide and dried in an oven at a temperature of 50-60 ° C. After hydrolysis, the copolymer contains —SO ₃ Li groups and has an EM of 1000. Into a 500 ml round bottom flask equipped with a stirrer, thermometer, and reflux condenser, 30 g of the powder of the indicated hydrolyzed terpolymer with a particle size of 100-400 μm and 170 g of isopropanol are added, and the mixer is included and dissolve the terpolymer at a temperature of 70 ° C for 1 hour. The terpolymer completely dissolves under the indicated conditions. Then, the resulting solution was cooled to room temperature and filtered through a nylon filter. After filtration, the solution has a concentration of 15 wt.%. The resulting solution is used for the manufacture of gas separation hollow fiber. Hollow fiber is obtained in a laboratory setup by the wet method in a precipitation bath containing 80 wt.% Water and 20 wt.% Isopropanol. The inner diameter of the fiber is 80 microns, the wall thickness is 40 microns. The obtained hollow fiber is used in a gas separation device for separating ammonia from a mixture of ammonia and hydrogen. The gas mixture, consisting of 50 vol.% Ammonia and 50 vol.% Hydrogen, is fed into the hollow fiber, previously moistened with water vapor, at a pressure of 100 kPa and at a temperature of 22 ° C. Based on the analysis of the composition of the gas mixture from the outer side of the fiber, the permeability coefficients of the gases constituting the mixture are calculated, which for ammonia and hydrogen are 3.92 · 10 ^-11 and 1.85 · 10 ^-15 mol · m / m ² · s · Pa, respectively, and a selectivity of 2.12 · 10 ⁴ in favor of ammonia. After purification, the mixture contains 99.8 vol.% Ammonia and 0.2 vol.% Hydrogen.

Example 30

отношение

Перед растворением терполимер в виде порошка гидролизуют 10%-ным водным раствором гидроокиси натрия при температуре 95°С в течение 16 часов, а затем 10%-ным водным раствором соляной кислоты при температуре 95°С в течение 12 часов. Гидролизованный терполимер отмывают водой и сушат в термостате при температуре 50-60°С. После гидролиза терполимер содержит группы -SO₃Н и имеет ЭМ 1200. 30 г порошка гидролизованного терполимера растворяют при температуре 70°С в 170 г этилового спирта и после фильтрации получают раствор с концентрацией 15 мас.%. Полученный раствор используют при изготовлении ионообменной мембраны в форме пленки. Мембрану в форме пленки получают поливом на стекло указанного раствора слоем такой толщины, чтобы после удаления растворителя образовалась пленка толщиной 80 мкм. Стекло с налитым на него раствором помещают в термостат и испаряют растворитель при постепенном подъеме температуры с выдержкой при 22°С в течение 10 мин и при 80°С в течение 40 мин. После удаления растворителя мембрана (пленка) имела толщину 80 мкм, предел прочности при растяжении 25 МПа, ρ_v 11 Ом·см, влажность 35%. Полученную пленку используют в качестве мембраны при изготовлении МЭБ для электролиза воды. Для получения электродного материала в стеклянной емкости смешивают 0,92 г катализатора - платиновой черни (размер частиц 0,06 мкм) с 2,2 г 7%-ного раствора терполимера по примеру 23 (ЭМ 1000, группы -SO₃Н) в изопропаноле, наносят на одну из поверхностей полученной, как указано выше, высушенной мембраны (в виде воздушно-сухой пленки диаметром 100 мм) методом полива смесь такой толщины, чтобы после удаления растворителя слой электродного материала имел толщину 10 мкм. Затем пленку помещают в термостат и термообрабатывают при ступенчатом подъеме температуры: выдержка при 40°С в течение 15 мин, при 70°С - в течение 40 мин. После этого мембрану вынимают из термостата, охлаждают до комнатной температуры и аналогичным образом на другую ее поверхность наносят тот же самый электродный материал, помещают в термостат и термообрабатывают указанным выше способом. Полученный МЭБ испытывают при электролизе воды, К МЭБ с обеих сторон прижимают коллектор тока из пористого титана с токоотводами, уплотняют полученную сборку с помощью стяжки плит, погружают в сосуд с дистиллированной водой и подают электрический ток силой 0,5 А/см² при 90°С в течение 1 часа. Затем сборку устанавливают в ячейку для электролиза деионизованной воды. Напряжение на блоке составило 1,62 В при плотности тока 1 А/см² и температуре 100°С.A solution of a terpolymer with a concentration of 15 wt.% Is obtained, using the terpolymer of Example 10 to prepare the solution, having the functional groups —SO ₂ F and —SO ₃ H and an ALL content of 4.0 mol.% (Endothermic peak with a maximum temperature of 74 ° C on the curve crystalline melting

the attitude

Before dissolving, the terpolymer in the form of a powder is hydrolyzed with a 10% aqueous solution of sodium hydroxide at a temperature of 95 ° C for 16 hours, and then with a 10% aqueous solution of hydrochloric acid at a temperature of 95 ° C for 12 hours. The hydrolyzed terpolymer is washed with water and dried in a thermostat at a temperature of 50-60 ° C. After hydrolysis, the terpolymer contains —SO ₃ H groups and has an EM of 1200. 30 g of hydrolyzed terpolymer powder is dissolved at 70 ° C. in 170 g of ethanol and after filtration a solution with a concentration of 15 wt.% Is obtained. The resulting solution is used in the manufacture of an ion-exchange membrane in the form of a film. A membrane in the form of a film is obtained by pouring a solution of such a thickness onto the glass of the indicated solution so that after removal of the solvent a film with a thickness of 80 μm is formed. The glass with the solution poured on it is placed in a thermostat and the solvent is evaporated with a gradual increase in temperature with exposure at 22 ° C for 10 min and at 80 ° C for 40 min. After removal of the solvent, the membrane (film) had a thickness of 80 μm, tensile strength 25 MPa, ρ _v 11 Ohm · cm, humidity 35%. The resulting film is used as a membrane in the manufacture of the OIE for the electrolysis of water. To obtain the electrode material in a glass container, 0.92 g of a platinum black catalyst (particle size 0.06 μm) is mixed with 2.2 g of a 7% solution of terpolymer according to Example 23 (EM 1000, -SO ₃ H groups) in isopropanol is applied onto one of the surfaces of the dried membrane obtained as described above (in the form of an air-dry film with a diameter of 100 mm) by spraying a mixture of such a thickness that, after removal of the solvent, the layer of electrode material has a thickness of 10 μm. Then the film is placed in a thermostat and heat treated with a stepwise rise in temperature: holding at 40 ° C for 15 minutes, at 70 ° C for 40 minutes. After that, the membrane is removed from the thermostat, cooled to room temperature, and the same electrode material is applied on its other surface in the same way, placed in a thermostat and heat treated in the manner described above. The obtained OIE is tested during electrolysis of water, A current collector made of porous titanium with down conductors is pressed onto the OIE on both sides, the assembly obtained is sealed with a coupler plate, immersed in a vessel with distilled water, and an electric current of 0.5 A / cm ^{2 is} supplied at 90 ° C for 1 hour. Then the assembly is installed in the cell for electrolysis of deionized water. The voltage on the block was 1.62 V at a current density of 1 A / cm ² and a temperature of 100 ° C.

The cell worked stably for 3500 hours without changing the indicators. Then the process was stopped, the OIE was removed from the cell. During a visual inspection of the OIE, no changes in the COM were observed. KOM after operation had the following characteristics:

Humidity 35% Tensile strength 25 MPa ρ _v 10 ohm cm

Example 31

отношение

Перед растворением терполимер в виде порошка гидролизуют 10%-ным водным раствором гидроокиси лития при температуре 95°С в течение 16 часов, а затем 10%-ным водным раствором соляной кислоты при температуре 95°С в течение 16 часов. Гидролизованный терполимер отмывают водой и сушат в термостате при температуре 50-60°С. После гидролиза терполимер содержит функциональные группы -SO₃Н и имеет ЭМ 1150. 10 г порошка гидролизованного терполимера растворяют при температуре 70°С в 90 г изопропанола в течение 2 часов и после фильтрации получают раствор с концентрацией 10 мас.%. Полученный раствор используют для изготовления ионоселективной мембраны для отделения пентена от пентана. Мембрану в форме пленки получают поливом на стекло указанного раствора слоем такой толщины, чтобы после высушивания образовалась пленка толщиной 50 мкм. Стекло с налитым на него раствором помещают в термостат и испаряют растворитель при постепенном подъеме температуры с выдержкой при 22°С в течение 20 мин и при 80°С в течение 30 мин. После удаления растворителя мембрана (пленка) имеет толщину 50 мкм. Полученную мембрану помещают в 1 молярный раствор азотнокислого серебра (AgNO₃) и выдерживают в нем в течение 12 ч при температуре 20-22°С. После чего мембрану с функциональными группами -SO₃Ag отмывают водой от остатков раствора азотнокислого серебра и используют для разделения смеси пентена и пентана в соотношении 1:1. Смесь пентена и пентана подают в камеру высокого давления. Перепад парциального давления на мембране составил 10 кПа. На основе анализа состава и количества пентена в принимающей камере коэффициент селективности составил 40 в пользу пентена, проницаемость пентена равна 7,13·10^-9 моль·см^-2·с^-1, а пентана 1,79·10^-10 моль·см^-2·с^-1. Производительность установки составила 70 мл/мин.A solution of terpolymer with a concentration of 10 wt.% Is obtained, using the terpolymer obtained in Example 9 to prepare the solution, having —SO ₂ F and —SO ₃ Li functional groups, an IRR content of 1.0 mol% (endothermic peak with a maximum temperature of 71 ° C) on the crystalline melting curve

the attitude

Before dissolving, the terpolymer in the form of a powder is hydrolyzed with a 10% aqueous solution of lithium hydroxide at a temperature of 95 ° C for 16 hours, and then with a 10% aqueous solution of hydrochloric acid at a temperature of 95 ° C for 16 hours. The hydrolyzed terpolymer is washed with water and dried in a thermostat at a temperature of 50-60 ° C. After hydrolysis, the terpolymer contains functional groups —SO ₃ H and has an EM of 1150. 10 g of the hydrolyzed terpolymer powder is dissolved at 70 ° C. in 90 g of isopropanol for 2 hours and after filtration a solution with a concentration of 10 wt.% Is obtained. The resulting solution is used to make an ion-selective membrane for separating pentene from pentane. A membrane in the form of a film is obtained by pouring a solution of such a thickness onto the glass of the indicated solution so that a film with a thickness of 50 μm is formed after drying. The glass with the solution poured on it is placed in a thermostat and the solvent is evaporated with a gradual increase in temperature with exposure at 22 ° C for 20 min and at 80 ° C for 30 min. After removal of the solvent, the membrane (film) has a thickness of 50 μm. The resulting membrane is placed in 1 molar solution of silver nitrate (AgNO ₃ ) and incubated in it for 12 hours at a temperature of 20-22 ° C. After that, a membrane with functional groups —SO ₃ Ag is washed with water from the residues of silver nitrate solution and is used to separate a mixture of pentene and pentane in a 1: 1 ratio. A mixture of pentene and pentane is fed into a high pressure chamber. The differential pressure of the membrane was 10 kPa. Based on the analysis of the composition and amount of pentene in the receiving chamber, the selectivity coefficient was 40 in favor of pentene, the permeability of pentene is 7.13 · 10 ^-9 mol · cm ^-2 · s ^-1 , and pentane 1.79 · 10 ^-10 mol · cm ^-2 s ^-1 . The plant productivity was 70 ml / min.

Example 32

используют для получения раствора концентрацией 3 мас.%.A copolymer with functional groups —SO ₂ F and —SO ₃ Li according to Example 2 with an IRR content of 5.0 mol% (endothermic peak with a temperature of 75 ° C on the crystalline melting curve,

used to obtain a solution of a concentration of 3 wt.%.

A 500 ml round-bottom flask equipped with a stirrer, thermometer and reflux condenser was charged with 6 g of powder of the indicated terpolymer (not hydrolyzed) with a particle size of 100 - 200 μm and 194 g of dimethylformamide, the stirrer was turned on and the terpolymer was dissolved at a temperature of 140 ° C for 2 hours. The copolymer is completely dissolved under the indicated conditions. Then, the resulting solution was cooled to room temperature and filtered through a nylon filter. After filtration, the solution has a concentration of 3 wt.%. The resulting solution is used to impregnate a porous film of polytetrafluoroethylene (PTFE) with a thickness of 400 μm with a porosity of 25-30%. A disk with a diameter of 100 mm and an area of 78.5 cm ^{2 is} cut from a PTFE film and placed in a Buchner funnel attached to a Bunsen flask. The device is connected to a water-jet pump (vacuum 150-200 mm Hg). 100 ml of the above 3% solution of terpolymer in dimethylformamide are poured into the funnel and the pump is turned on. After the solution passes through a sample of a porous PTFE film, the pump is turned off, the impregnated PTFE film is removed and dried in a thermostat with a stepwise rise in temperature from 20 to 150 ° С (20 ° С-20 min, 140 ° С - 40 min, 150 ° С - 40 min). The obtained terpolymer-impregnated film is used as a filter for cleaning mechanical gallium metal melt (at 70 ° C). Filtration rate 280 g / h / cm ² .

Example 33

после синтеза, без гидролиза в виде порошка с размером частиц 100-200 мкм используют в качестве суперкислого катализатора в реакции этерификации акриловой кислоты этанолом. Смесь акриловой кислоты с этанолом в соотношении 1:1,2 пропускают над порошком указанного терполимера при температуре 95°С. Продолжительность контакта с катализатором составляет 5 сек. Выход этилового эфира акриловой кислоты составляет 96%.A copolymer with functional groups —SO ₂ F and —SO ₃ H according to Example 3 with an IRR content of 5 mol% (endothermic peak with a maximum temperature of 75 ° C on the crystalline melting curve,

after synthesis, without hydrolysis in the form of a powder with a particle size of 100-200 microns, they are used as a super acid catalyst in the reaction of esterification of acrylic acid with ethanol. A mixture of acrylic acid with ethanol in a ratio of 1: 1.2 is passed over the powder of the indicated terpolymer at a temperature of 95 ° C. The duration of contact with the catalyst is 5 seconds. The yield of ethyl acrylic acid is 96%.

Example 34 (counter. US Pat. No. 5,281,680).

методом экструзии на лабораторном экструдере при температуре 280°С получают пленку толщиной 125 мкм. Пленка в сухом состоянии имеет прочность при разрыве 22 МПа. Полученную пленку гидролизуют 15%-ным водным раствором гидроокиси калия при 90°С в течение 10 часов, а затем обрабатывают 5%-ным раствором соляной кислоты при 95°С в течение 4 часов. После обработки полученная КОМ имеет функциональные группы -SO₃Н (ЭМ=1000), прочность при разрыве 18 МПа, влажность 22%, ρ_v 14 Ом·см. КОМ используют для приготовления МЭБ для ТЭ. Получение МЭБ и установку его в ТЭ проводят аналогично примеру 25.From a copolymer of TFE with VGE with functional groups —SO ₂ F, obtained according to Example 21 count., S

by extrusion on a laboratory extruder at a temperature of 280 ° C, a film with a thickness of 125 μm is obtained. The film in the dry state has a tensile strength of 22 MPa. The resulting film is hydrolyzed with a 15% aqueous solution of potassium hydroxide at 90 ° C for 10 hours, and then treated with a 5% solution of hydrochloric acid at 95 ° C for 4 hours. After processing, the resulting KOM has functional groups —SO ₃ N (EM = 1000), tensile strength 18 MPa, humidity 22%, ρ _v 14 Ohm · cm. COM is used to prepare the OIE for fuel cells. Obtaining the OIE and installing it in the fuel cell is carried out analogously to example 25.

The following characteristics of the fuel cell are obtained:

Voltage 0.83-0.84 V Current density 700 mA / cm

After 3000 hours of operation of the fuel cell, the voltage drops to 0.81-0.82 V, after which the process was stopped and the OIE was removed from the cell. On visual inspection of the OIE, no significant changes were observed. COM after testing has the following characteristics:

Humidity 19.5 wt.% Tensile strength 18 MPa ρ _v 16 ohm cm

Example 35 (counter. On the application of France 2388012)

и

методом экструзии на лабораторном экструдере при температуре 260°С получают пленку толщиной 125 мкм. Пленка имеет прочность при разрыве 20 МПа. Далее пленку гидролизуют аналогично контрольному примеру 34. После гидролиза полученная КОМ имеет функциональные группы -SO₃Н и -СООН (ЭМ=1000), прочность при разрыве 18 МПа, влажность 21%, ρ_v 15,9 Ом·см. КОМ используют для изготовления МЭБ для ТЭ. Получение МЭБ и установку его в ТЭ проводят аналогично примеру 25.From a terpolymer with functional groups —SO ₂ F and —CN obtained in Control Example 22, c

and

by extrusion on a laboratory extruder at a temperature of 260 ° C, a film with a thickness of 125 μm is obtained. The film has a tensile strength of 20 MPa. Further, the film is hydrolyzed in the same way as in control example 34. After hydrolysis, the obtained KOM has functional groups —SO ₃ H and —COOH (EM = 1000), tensile strength 18 MPa, humidity 21%, ρ _v 15.9 Ohm · cm. COM is used for the manufacture of OIE for fuel cells. Obtaining the OIE and installing it in the fuel cell is carried out analogously to example 25.

TE has the following characteristics:

Voltage 0.74-0.76 V Current density 700 mA / cm ²

After 3000 hours of operation of the fuel cell, the voltage drops to 0.71-0.73 V, after which the process was stopped and the OIE was removed from the cell. A visual inspection of the OIE revealed no changes.

COM after testing has the following characteristics:

Humidity eighteen% Tensile strength 18 MPa ρ _v 16.7 ohm cm

Example 36 (counter. US patent 5281680)

и

используют для получения 20%-ного раствора в диметилформамиде аналогично примеру 28. Перед растворением порошок сополимера с размером частиц ≤500 мкм гидролизуют 10%-ным водным раствором гидроокиси лития при температуре 95°С в течение 12 часов, после чего гидролизованный сополимер отмывают водой и сушат в термостате при температуре 60-70°С. После гидролиза сополимер содержит группы -SO₃Li и имеет ЭМ 1000. В круглодонную колбу объемом 200 мл, снабженную мешалкой, термометром и обратным холодильником, загружают 20 г порошка указанного гидролизованного сополимера, 80 мл диметилформамида и растворяют сополимер при 140°С в течение 2 часов. Сополимер частично растворился в диметилформамиде. Смесь образовавшегося раствора и нерастворившегося сополимера охлаждают и отфильтровывают через капроновый фильтр. После фильтрации раствор сополимера имеет концентрацию 2,5 мас.%, а осадок нерастворившегося сополимера составляет 17,5 г.A copolymer of TFE with HESE with functional groups —SO ₂ F, obtained according to control example 21, s

and

used to obtain a 20% solution in dimethylformamide analogously to example 28. Before dissolving, the copolymer powder with a particle size of ≤500 μm is hydrolyzed with a 10% aqueous lithium hydroxide solution at 95 ° C for 12 hours, after which the hydrolyzed copolymer is washed with water and dried in a thermostat at a temperature of 60-70 ° C. After hydrolysis, the copolymer contains —SO ₃ Li groups and has an EM of 1000. In a 200 ml round bottom flask equipped with a stirrer, thermometer and reflux condenser, 20 g of the powder of the indicated hydrolyzed copolymer, 80 ml of dimethylformamide are charged and the copolymer is dissolved at 140 ° C for 2 hours. The copolymer partially dissolved in dimethylformamide. The mixture of the resulting solution and the insoluble copolymer is cooled and filtered through a nylon filter. After filtration, the copolymer solution has a concentration of 2.5 wt.%, And the precipitate of insoluble copolymer is 17.5 g.

Example 37 (counter. On the application of France No. 2388012)

используют для приготовления 20%-ного раствора в диметилформамиде аналогично примеру 28. После гидролиза сополимер имеет функциональные группы -SO₃Li (ЭМ=1000). Сополимер растворяют в диметилформамиде аналогично примеру 28. После фильтрации полученный раствор сополимера имеет концентрацию 1 мас.%, а осадок нерастворившегося сополимера составляет 19 г.The copolymer with functional groups —SO ₂ F and —CN obtained in Control Example 22, c

used to prepare a 20% solution in dimethylformamide analogously to example 28. After hydrolysis, the copolymer has functional groups —SO ₃ Li (EM = 1000). The copolymer is dissolved in dimethylformamide as in Example 28. After filtration, the resulting copolymer solution has a concentration of 1 wt.%, And the precipitate of the insoluble copolymer is 19 g.

As can be seen from the above data, the claimed TFE terpolymer with VGE and VVI, suitable for the manufacture of KOM and gas separation membranes, after synthesis, contains both units of a perfluorinated monomer with functional groups in non-ionic form —SO ₂ F (VGE) and the third modifying perfluorinated comonomer (VSI) with functional groups in the ionic form —SO ₃ M (where M is indicated above), while the known TFE copolymers with functional perfluorinated comonomers suitable for the manufacture of KOM and gas separation membranes contain, after synthesis, units of comonomers with functional groups in only one form, preferably non-ionic —SO ₂ F, —CN or —CF ₂ Cl [US patent No. 5281680, French application 2388012, US patent 4330654].

является более равномерной и упорядоченной, что позволяет изготавливать из него экструзией или поливом из раствора пленки с повышенной прочностью и более низким электрическим сопротивлением, чем из известных ионообменных фторсодержащих сополимеров. Так, прочность пленки из гидролизованного заявляемого терполимера с ЭМ 1000 толщиной 125 мкм составляет 25,2 МПа, a ρ_v 11,2 Ом·см (см. пр. 6, табл.2). Прочность же гидролизованной пленки из известного ионообменного сополимера ТФЭ с ВСГЭ с той же ЭМ и той же толщины составляет всего 18 МПа, а ρ_v 14 Ом·см (см. наш контр. пр. 21, табл.2).The presence in the terpolymer of VSI in the amount of 0.5-5 mol.% Introduced during the synthesis allows creating a certain supramolecular structure of the terpolymer, which is characterized by the presence of an endothermic peak in the temperature range 70-75 ° C on the crystalline melting curve, while the known the dual TFE-HPSE copolymers and TFE-HPSE terpolymers and the third modifying comonomer do not have an endothermic peak in the temperature range 70-75 ° C on the crystalline melting curve (see examples 1-12 and control examples 21 and 22 in table 2). The specified structure of the claimed terpolymer is a precursor to the channel-cluster structure of terpolymer formed during its hydrolysis. This structure of the claimed terpolymer having MM in the range of (2 - 8) · 10 ⁵ and the ratio

It is more uniform and ordered, which allows it to be made from it by extrusion or pouring from a solution of a film with increased strength and lower electrical resistance than from known ion-exchange fluorine-containing copolymers. So, the strength of the film of the hydrolyzed inventive terpolymer with EM 1000 with a thickness of 125 μm is 25.2 MPa, and ρ _v 11.2 Ohm · cm (see pr. 6, table 2). The strength of the hydrolyzed film from the known ion-exchange copolymer of TFE with VGE with the same EM and the same thickness is only 18 MPa and ρ _v 14 Ohm · cm (see our counter. Pr. 21, Table 2).

A more uniform channel-cluster structure of the claimed terpolymer after hydrolysis provides the necessary diffusion of the organic solvent (s) into the terpolymer macromolecule, which facilitates the dissolution of terpolymer and its transition to a stable solution with a concentration of 7-20 wt.% Under mild conditions and in accessible solvents (ethanol, isopropanol , dimethylformamide, etc.), while the known ion-exchange fluorine-containing polymers with the same EM, for example with EM ~ 1000, either dissolve in general under the indicated conditions, or give solutions with a concentration of less than 5 wt.% (see our examples 23, 28-31 and control. examples 36 and 37). A high concentration of solutions from the claimed terpolymer allows one to obtain economically profitable thin (<100 μm) KOM from them with increased strength by the method of irrigation (see example 30) or by impregnation in 1-2 applications (1-2 layers) and strong hollow gas separation fibers with a thickness walls 30-40 microns, for example, for the allocation of ammonia (see example 29).

The non-hydrolyzed inventive terpolymer containing 0.5-5 mol.% BCI with functional groups —SO ₃ M is also relatively easily soluble in conventional solvents to obtain solutions with a concentration of 3-5 wt.%, Which can be successfully used to impregnate various materials to impart them wettability, for example, upon receipt of filters from porous PTFE, designed to filter the molten metal gallium (see example 32). The inventive terpolymer can also be used for extrusion of tubes with a wall thickness of 90 μm, which are suitable for drying moist gases, such as air (see example 27), for the manufacture by irrigation of ion-selective membranes to separate pentene from pentane (see example 31) , as a super acid catalyst (see Example 33), etc.

COM from the claimed terpolymer with EM 850-1445 have a significantly lower initial electrical resistance, as well as lower moisture losses during long-term operation, for example, in fuel cells, chlor-alkali electrolysis cells or during electrolysis of water, and, accordingly, retain their electrochemical characteristics for a longer time Compared with KOM from known ion-exchange fluoropolymers. So, after operating for 3500 hours a fuel cell with KOM from the claimed terpolymer with EM 1000 with a thickness of 125 μm, the electrical resistance and humidity of KOM practically did not change, while the voltage on the fuel cell remained at the same level of 0.87-0.88 V (cm . Our example 25), while after 3000 hours of operation of a fuel cell with a KOM having EM 1000 and the same thickness, but made of the known ion-exchange copolymer according to US Pat. USA No. 5281680, KOM humidity decreased from 22 to 19.5%, ρ _v increased from 14 to 16 Ohm · cm, and the voltage on the fuel cell decreased from 0.83-0.84 V to 0.81-0.82 V (see our count. example 34).

Т_пл. ПТР, плотность, степень кристалличности) за счет изменения содержания ВСИ и поддержания постоянным заданного соотношения мономеров в реакционной среде в процессе синтеза путем регулирования средней скорости снижения давления реакционной среды подпиткой заданным количеством ТФЭ. По способу-прототипу регулирование свойств получаемых терполимеров ТФЭ с ВСГЭ и мономером с карбоксильными или нитрильными группами возможно только за счет изменения концентрации реагентов, при этом не соблюдается постоянное соотношение мономеров в реакционной среде, что не позволяет получать терполимеры с заданным оптимальным комплексом свойств. Заявляемый способ позволяет получать терполимеры ТФЭ с ВСГЭ и ВСИ со следующим оптимальным комплексом свойств: с эндотермическим пиком в интервале температур 70-75°С на кривой кристаллического плавления,

Т_пл.=220-260°С, ПТР=7-84 г/10 мин (при 270°С), ЭМ=850-1445, степенью кристалличности 8,0-16,5%, плотностью 2,076-2,087 г/см³ и термостабильностью 0,01-0,035%. Комплекс свойств обеспечивает возможность использования таких терполимеров, как уже указывалось выше, для изготовления методом экструзии или полива из раствора тонких пленок с повышенной прочностью, низким электрическим сопротивлением и низкой потерей влажности при длительной эксплуатации, которые могут использоваться как КОМ, например, при электролизе воды (см. пример 24), в топливных элементах (см. пример 25), в хлорщелочных электролизерах (см. пример 26). Из концентрированных растворов заявляемого терполимера можно получать прочные газоразделительные полые волокна с тонкими стенками, используемые, например, для выделения аммиака (см. пример 29), пленки для датчиков влажности воздуха (см. пример 28), ионоселективные мембраны (см. пример 31) и т.д., а также использовать такие растворы для пропитки различных субстратов. Заявляемый способ позволяет проводить процесс сополимеризации в мягких условиях при температурах 25-35°С и синтезировать терполимеры с повышенной термостабильностью за счет использования в процессе таких фторированных пероксидов, как перфторциклогексаноилпероксид и α-хлорперфторпропионилпероксид, которые не вводят в образующийся терполимер нестойких концевых групп.As can be seen from the above data, the claimed method in comparison with the known method of the prototype (French application No. 2388012) makes it quite easy in the synthesis process to control the properties of the obtained TFE terpolymers with VGE and VSI (supramolecular structure, MM,

T _pl. MFR, density, crystallinity) by changing the content of the IRR and keeping the ratio of monomers in the reaction medium constant during the synthesis process by adjusting the average rate of pressure drop in the reaction medium by feeding a given amount of TFE. According to the prototype method, the regulation of the properties of the obtained TFE terpolymers with VGE and the monomer with carboxyl or nitrile groups is possible only by changing the concentration of reagents, while the constant ratio of monomers in the reaction medium is not observed, which does not allow to obtain terpolymers with a given optimal set of properties. The inventive method allows to obtain terpolymers of TFE with VGE and VSI with the following optimal set of properties: with an endothermic peak in the temperature range of 70-75 ° C on the crystalline melting curve,

T _pl. = 220-260 ° C, PTR = 7-84 g / 10 min (at 270 ° C), EM = 850-1445, crystallinity 8.0-16.5%, density 2.076-2.087 g / cm ³ and thermal stability 0.01-0.035%. The set of properties makes it possible to use such terpolymers, as already mentioned above, for the manufacture by extrusion or irrigation of thin films of a solution with increased strength, low electrical resistance, and low moisture loss during prolonged use, which can be used as KOM, for example, in the electrolysis of water ( see example 24), in fuel cells (see example 25), in chlor-alkali electrolyzers (see example 26). From concentrated solutions of the inventive terpolymer, it is possible to obtain strong gas-separation hollow fibers with thin walls, used, for example, for the separation of ammonia (see example 29), films for air humidity sensors (see example 28), ion-selective membranes (see example 31) and etc., and also use such solutions for the impregnation of various substrates. The inventive method allows the copolymerization process under mild conditions at temperatures of 25-35 ° C and the synthesis of terpolymers with increased thermal stability due to the use of fluorinated peroxides such as perfluorocyclohexanoyl peroxide and α-chloroperfluoropropionyl peroxide in the process, which do not introduce unstable end groups into the resulting terpolymer.

Table 1
Synthesis conditions for TFE copolymers with functional perfluorinated comonomers Example No. Wednesday The composition of the boot mixture, mol.% Functional Group TFE HESE All one 2 3 four 5 6 one X-113 35.0 63,2 1.8 -SO ₃ K 2 water 35.0 48.5 16.5 -SO ₃ Li 3 X-113 40,0 42.0 18.0 -SO ₃ N four X-113 45.0 37.0 18.0 -SO ₃ N 5 X-113 45.0 41,4 13.6 -SO ₃ Li 6 water 45.0 37.0 18.0 -SO ₃ N 7 water 50,0 38.6 11,4 -SO ₃ K 8 PFZB 50,0 48.0 2.0 -SO ₃ Na 9 X-113 53.0 43,2 3.8 -SO ₃ Li 10 X-113 55.0 29.6 15.4 -SO ₃ N eleven X-113 60.0 30.6 9,4 -SO ₃ K 12 X-113 65.0 19,2 15.8 -SO ₃ Na 13 counter. X-113 45.0 54.0 1,0 -SO ₃ N 14 count. water 45.0 33.0 22.0 -SO ₃ N 15 count. water 27.0 62.0 11.0 -SO ₃ Na 16 counter. X-113 70.5 27.7 1.8 -SO ₃ N 17 counter. X-113 45.0 37.0 18.0 -SO ₃ N 18 counter. X-113 65.0 19,2 15.8 -SO ₃ Na 19 counter. X-113 45.0 37.0 18.0 -SO ₃ N 20 count. according to US Pat. US 3282875 water 82,4 - 17.6 -SO ₃ Na 21 counter according to US Pat. US 5281680 X-113 52.0 48.0 - - 22 count. at the request of Fr. 2388012 X-113 72.0 20,0 8.0 * -CN * * The third modifying comonomer of the formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) CN [(perfluoro (4,7-dioxa-2,5-dimethyl-8-nonene) nitrile].

Continuation of table 1
Synthesis conditions for TFE copolymers with functional perfluorinated comonomers Example No. Initiator Temperature ° C Pressure, MPa Pressure reduction rate, · 10 ^-3 MPa / h Initial Final one 7 8 9 10 eleven one PFTSGP thirty 0.25 0.21 2,3 2 α-HFPFP 25 0.40 0.35 2,3 3 PFTSGP 35 0.32 0.27 2,8 four PFTSGP thirty 0.29 0.25 3.2 5 PFTSGP thirty 0.29 0.25 3.2 6 α-HFPFP thirty 0.45 0.40 3.2 7 α-HFPFP 25 0.40 0.35 5,0 8 PFTSGP thirty 0.32 0.27 5,0 9 PFTSGP thirty 0.33 0.28 6.0 10 PFTSGP 32 0.35 0.29 8.0 eleven PFTSGP thirty 0.38 0.32 9.5 12 PFTSGP 35 0.50 0.42 eighteen 13 counter. PFTSGP thirty 0.29 0.25 3.2 14 count. α-HFPFP 25 0.40 0.34 3.2 15 count. α-HFPFP 25 0.35 0.30 1.8 16 counter. PFTSGP thirty 0.50 0.42 24.0 17 counter. PFTSGP thirty 0.29 0.27 1,6 18 counter. PFTSGP 35 0.50 0.40 20,4 19 counter. PFTSGP thirty 0.29 0.29 0 20 count. according to US Pat. US 3282875 (NH ₄ ) ₂ S ₂ O ₈ 70 6.7 5.7 not identified 21 counter according to US Pat. US 5281680 PFPP 45.0 0.39 0.39 0 22 count. at the request of Fr. 2388012 PFPP 50,0 1.4 1,2 not identified

table 2
Properties of copolymers and hydrolyzed films based on them Example No. The content of monomer units in terpolymer, mol.% EM The degree of crystallinity,% T _pl. ° C Density, g / cm ³ Thermostability (270 ° C),% TFE (b) HESE (a) All (s)

one 2 3 four 5 6 7 8 9 10 one 80 19.5 0.5 4.0 850 8.0 220 2,076 0.02 2 80 15.0 5,0 4.0 850 8.5 240 2,078 0,023 3 83.5 11.5 5,0 5.06 950 9.0 230 2,077 0,03 four 84.7 10.3 5,0 5.53 1000 10 240 2,078 0.01 5 84.7 11.8 3,5 5.53 1000 eleven 235 2,077 0,021 6 84.7 10.3 5,0 5.53 1000 11.3 250 2,084 0.016 7 86.8 10,2 3.0 6.57 1100 11.5 260 2,084 0.016 8 86.8 12.7 0.5 6.57 1100 11.0 245 2,083 0,022 9 87.6 11,4 1,0 7.06 1150 11.5 255 2,084 0,033 10 88.3 7.7 4.0 7.54 1200 11.9 255 2,083 0,021 eleven 89.3 8.2 2,5 8.35 1280 12.0 260 2,085 0.01 12 91 5,0 4.0 10.0 1445 16.5 260 2,087 0.01 13 counter. 84.7 15.0 0.3 5.53 1000 10.0 260 2,081 0.04 14 count. 84.7 9.3 6.0 5.53 1000 10,2 240 2,077 0.024 150 count. 76 19.5 4,5 3.16 760 5,0 180 2.07 0.05 16 counter. 92.3 7.2 0.5 12.0 1644 twenty 290 2,089 0.01 17 counter. 85.8 9.2 5,0 6.02 1050 10.6 245 2,082 0.02 18 counter. 89.8 6.2 4.0 8.8 1320 13.8 255 2,083 0,023 19 counter. 87.6 8.2 4.2 7.06 1150 10.9 240 2,082 0.024 20 count. according to US Pat. US 3282875 96.7 - 3.3 29.3 b / s 3300 22 315 2.09 0.4 21 counter according to US Pat. US 5281680 84.5 15,5 - 5.45 b / a 1000 12.7 270 2,079 0.20 22 count. by application of France 2388012 85 12,4 2.6 (carboxyl comonomer) 5.66 1000 9,4 240 2,076 0.23

Continuation of table 2
Properties of copolymers and hydrolyzed films based on them Example No. Tensile strength, MPa MFI (270 ° C, p = 2.16 kg), g / 10 min

×10⁵

× 10 ⁵

The temperature of the endothermic peak, ° C Properties of extrusion films after hydrolysis (δ = 125 μm, -SO ₃ N) Tensile strength, MPa Humidity% ρ _v , Ohm · cm one eleven 12 13 fourteen fifteen 16 17 eighteen one 23.5 74 2.0 1.25 70 22.5 42 9.1 2 26.0 22 7.5 1.35 75 24.2 38 9.6 3 24.3 84 4.0 1.31 75 23.1 38 9.8 four 25.1 58 5.8 1.35 75 24.0 37 10,4 5 25.0 63 6.2 1.28 73 22.9 36 10.8 6 27.0 thirty 8.0 1.32 75 25,2 35 11.2 7 28.5 8.0 8.0 1.28 73 27.5 33 12 8 26.5 55 5.5 1.35 70 24.7 32 12.1 9 26 55 6.0 1.33 71 24.0 31,2 13.0 10 27 fifty 4.8 1.27 74 24.3 30,2 13.3 eleven 28 12 6.5 1,2 72 25,4 25.6 14.5 12 thirty 7.0 6.0 1.34 73.5 27.5 19.0 18.3 13 counter. 23 7.0 8.2 1.17 - 19.0 25 13.0 14 count. 24 60 8.0 1.37 76 20.9 27 12.6 15 count. 10.0 > 100 2.0 1.4 74 8.0 49 9.0 16 counter. 33 1,6 8.5 1.39 75 31.6 12.5 > 500 17 counter. 25.8 31 6.2 1.32 75 24.4 35 10.8 18 counter. 27.0 eleven 5.5 1.4 74 25.0 twenty 16.1 19 counter. 25 57 6.6 1.31 74 22.7 26 13.5 20 count. according to US Pat. US 3282875 thirty does not flow not determined not determined 21 counter according to US Pat. US 5281680 22 5.1 8.6 1.15 - 18.0 22 14.0 22 count. by application of France 2388012 twenty 80 6.0 1.41 - 18.0 21 15.9

Claims (4)

1. A linear statistical tetrafluoroethylene terpolymer with functional perfluorinated comonomers of the general structural formula

where M is a hydrogen or alkali metal ion; a = 5-19.5 mol.%; b = 80-91 mol%; c = 0.5-5 mol.%;

characterized by an endothermic peak in the temperature range of 70-75 ° C on the crystalline melting curve, measured using a scanning differential calorimeter, and having a weight average molecular weight (2 ÷ 8) · 10 ⁵ and a weight average molecular weight to number average molecular weight of 1.2 -1.35. 2. A method of obtaining a tetrafluoroethylene terpolymer with 9-20 mol% functional perfluorinated comonomers, comprising copolymerizing tetrafluoroethylene with a perfluorinated sulfonated vinyl ether having the structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F and a third modifying comonomer in a liquid medium in the presence of a perhalogenated organic peroxide at elevated temperature and pressure, characterized in that the third modifying comonomer uses perfluorinated vinyl ether having structural w formula CF ₂ = CFOCF ₂ CF (CF ₃₎ OCF ₂ CF ₂ SO ₃ M, where M - hydrogen ion or an alkali metal, and use the loading monomer mixture comprising 35-65 mol% of tetrafluoroethylene, 19,2-63,. 2 mol% of perfluorinated sulfonated vinyl ether having the structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₂ F, and 1.8-18.0 mol% of perfluorinated vinyl ether having the structural formula CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ M, where M is as described above, and during the copolymerization, the reaction medium is fed with tetrafluoroethylene, providing a constant pressure drop during copolymerization process with an average rate of (2.3 ÷ 18) · 10 ^-3 MPa / h, and perfluorocyclohexanoyl peroxide or α-chloroperfluoropropionyl peroxide is used as a perhalogenated organic peroxide. 3. The method of producing tetrafluoroethylene terpolymer according to claim 2, characterized in that the copolymerization process is carried out in an aqueous medium in the presence of α-chloroperfluoro-propionyl peroxide at a temperature of 25-30 ° C and an initial pressure of 0.40-0.45 MPa with a drop to the final pressure 0.35-0.40 MPa. 4. The method of producing tetrafluoroethylene terpolymer according to claim 2, characterized in that the copolymerization process is carried out in a fluorine-containing organic solvent in the presence of perfluorocyclohexanoyl peroxide at a temperature of 30-35 ° C and an initial pressure of 0.25-0.50 MPa with a drop to a final pressure of 0 , 21-0.42 MPa.

Images