Novel halogen-containing polyether, production and use thereof

[Detailed Description of the Invention]

The present invention relates to new halogen polyether, and its process and use. New halogen-containing-polyether (I) of the present invention, (a) Formula: -(CH₂CF₂CF₂O)- The repetition unit come out of and shown, (b) Formula: -(CHClCF₂CF₂O)- The repetition unit come out of and shown, (c) Formula: -(CCl₂CF₂CF₂O)- The repetition unit come out of and shown, (d) Formula: -(CHFCF₂CF₂O)- The repetition unit come out of and shown, (e) Formula: -(CFClCF₂CF₂O)- the repetition unit come out of and shown -- and (f) Formula: -(CF₂CF₂CF₂O)- It is a compound which comprises at least one sort of 2~200 repetition units chosen from the group which comes out and comprises the repetition unit shown, includes repetition unit (b), (c), and (e) in at least one sum total, and contains a repetition unit (a), (c), (d), and (f) in at least one sum total. In halogen-containing-polyether (I) of the present invention, arrangement in the molecule of each repetition unit is arbitrary. Halogen containing polyether of the present invention is formula:, for example. - (CH)₂CF₂CF₂O)- It can manufacture easily by chlorinating and fluorinating fluorine-containing polyether () which comes out and comprises 2~200 repetition units shown, i.e., a repetition unit, (a). Chlorination can be preferably performed to polyether () by making gaseous chlorine react under a 200~500-nm ultraviolet exposure. Although it is dependent on the degree of polymerization of polyether () of materials, the reaction temperature should just choose the viscosity in which required churning is possible, and temperature which changes, when advancing a reaction smoothly. Since the pour point of output generally falls as chlorination advances, reaction temperature can be reduced according to it. Usually, the reaction temperature of 30~200degreeC, preferably 50~150 degreeC is adopted. Although gaseous chlorine is blown into reaction liquid, it may circulate a gas phase portion, and it may dilute and use it with suitable inactive gas (for example, nitrogen, argon, etc.). The Pyrex glass is industrially enough, although it may be a container in which the exterior or an inside to light irradiation is possible as a reaction vessel and quartz etc. are preferred as optical penetration material. Halogen-containing-polyether () obtained by chlorination is a compound which comprises at least one sort of 2~200 repetition units chosen from the group which changes, and includes repetition unit (b) and (c) in at least one sum total from repetition unit (a), (b), and (c). Halogen-containing-polyether (I) of the present invention can be manufactured by further fluorinating polyether (). Fluorination can be performed by making fluoride gas react to polyether () in room temperature~300degreeC, preferably 50~200 degreeC. Fluoride gas may be diluted with suitable inactive gas (for example, nitrogen, argon, etc.), and may be used. as a reaction form -- both a circulation type and a Batches type -- although -- it may be adopted. Although polyether (I) of the present invention can manufacture line intermediary polyether () for chlorination first as mentioned above and it can manufacture by further fluorinating it, an order of chlorination and fluorination may be made reverse and the order is not essential. namely (a) Formula: -(CH₂CF₂CF₂O)- The repetition unit come out of and shown, (d) Formula: -(CHFCF₂CF₂O)- the repetition unit come out of and shown -- and (f) Formula: -(CF₂CF₂CF₂O)- At least one sort of 2~200 repetition units chosen from the group which comes out and comprises the repetition unit shown can be comprised, polyether () which includes repetition unit (d) and (f) in at least one sum total can be obtained, this can be chlorinated, and polyether (I) can be manufactured. Polyether () is also a new molecular entity and it can manufacture by carrying out ring opening polymerization of the 2, 2, 3, and 3-tetrafluoro oxetane. The process is explained below. When performing the above-mentioned ring opening polymerization, generally a polymerization initiator is used. As a polymerization initiator, the thing which produces active halogen negative ion in an aprotic solvent, or a compound as the strong Lewis acidity shown is preferably used like alkali metal halide. Although limitation in particular is not carried out, as for the amount of initiators to be used, to the amount of 2, 2, 3, and 3-tetrafluoro oxetane, 0.001~30-mol%, preferably 0.01~10-mol% may usually be adopted. Although the alkali metal halide in particular as the above-mentioned polymerization initiator is not limited, potassium fluoride, cesium fluoride, potassium iodide, potassium bromide, etc. are used preferably, for example. Generally the output at the time of using alkali metal halide as an initiator is formula:A (CH).₂CF₂CF₂O)nCH₂CF₂COF (1) It is a compound shown by [F, Br or I, and n express the integer of 0~200 among a formula, as for A]. The acid fluoride end group of this compound can be easily led to acid, alkali salt, ester, or amide corresponding with the reaction method of common knowledge, such as hydrolysis and etherification, etc. the alkaline metal fluoride as the above-mentioned polymerization initiator -- simultaneously -- for example formula: -- RfCOF -- or<img file="JPH0160170B2_D0001.tif" />When it comes out and a Acyl fluoride compound as shown is used, A of the above-mentioned (1) formula is formula:RfCF, respectively.₂O- or<img file="JPH0160170B2_D0002.tif" />However, Rf the perfluoroalkyl machine of carbon number 1~10 and Rf' the perfluoroalkyl machine or formula of carbon number 1~10:<img file="JPH0160170B2_D0003.tif" />It comes out and the basis and t which are shown express the integer of 0~50. Formula:-CH expressed₂CF₂CF₂The compound which has a repetition unit shown by O- is compoundable. FCH produced by Ring opening(ing) 2, 2, 3, and 3-tetrafluoro oxetane₂CF₂When the Acyl fluoride as for which COF becomes is used simultaneously with cesium fluoride, the polymerization thing of the same structure as the case where it polymerizes using alkaline metal fluoride independently is obtained. This method is an effective method when making low-molecular-like oligomer profitably like, controlling molecular weight distribution. After after [ the end of a polymerization reaction ] distillation recovery is carried out, the low-molecular quantity output with comparatively high volatility contained in polymerization output may be re-used as a polymerization initiator by using it simultaneously with alkaline metal fluoride again, so that above-mentioned explanation may also show. This can be made to react to 2, 2, 3, and 3-tetrafluoro oxetane like the above using fluorine-containing EPO Xide which does not use a Acyl fluoride compound from the beginning, for example, reacts to alkaline metal fluoride beforehand, and produces Acyl fluoride. For example, it is a formula by making hexafluoro propylene oxide react using cesium fluoride in a Aproits solvent:<img file="JPH0160170B2_D0004.tif" />The becoming compound [in which t expresses the integer of 0~50 among a formula] is compounded, 2, 2, 3, and 3-tetrafluoro oxetane can be taught into the system, and the same compound as the case where the above-mentioned Acyl fluoride is used independently as a result can also be compounded. What hexafluoro propylene oxide is taught for to the system which carried out ring opening polymerization of the 2, 2, 3, and 3-tetrafluoro oxetane using the alkali-metal-halide initiator, or alkaline metal fluoride and the coexistence initiator of Acyl fluoride beforehand on the contrary, for example<img file="JPH0160170B2_D0005.tif" />the inside of [type, and A -- (1) type -- the same -- x expresses the integer of 2~200 and y expresses the integer of 0~50. ] Composition of the becoming compound can also be performed. The epoxy compound in which ring opening polymerization is possible at the same initiator system like for example, 2, 2, 3, and 3-tetrafluoro oxetane and hexafluoro propylene oxide is alternation theoretically so that I may be understood also from the above-mentioned explanation, or a block copolymerization thing can be given at random -- moreover It is FOCCF when 2 organic-functions Acyl fluoride like for example, oxalic acid fluoride (FOC-COF) is used as a polymerization initiator of 2, 2, 3, and 3-tetrafluoro oxetane simultaneously with alkaline metal fluoride.₂CH₂(OCF₂CF₂CH₂)zOCF₂CF₂O(CH₂CF₂CF₂O)w-CH₂CF₂COF(3) The bifunctional polymerization thing whose end expressed with [z and w express the integer of 0~200 among a formula, respectively] is Acyl fluoride, respectively is obtained. Generally, it acts with alkaline metal fluoride in an aprotic solvent, and is ~COF+MF~CF.₂O^-M⁺(4) M is an alkaline metal kind among [type. All Acyl fluoride compounds that carry out the amount formation of balances of the Fluoro alkoxy anion as shown by] (4) formula serve as a ring-opening-polymerization initiator of 2, 2, 3, and 3-tetrafluoro oxetane under alkaline metal fluoride coexistence, and are ~CF.₂O - It can be said that the end of a ring-opening-polymerization object can be formed in the form of an alkoxy group. As a Lewis acidity initiator, it is antimony pentafluoride (SbF).₅It is used preferably. It usually carries out by the liquid phase and Ring opening reaction of 2, 2, 3, and 3-tetrafluoro oxetane is as a reaction solvent, Except a Lewis acid initiator, the polyethylene-glycols dimethyl ether like an aprotic solvent, for example, a jig lime, Tori Gleim, or tetraglyme is used preferably. Acetonitrile and CH₃OCH₂CH₂OCH₃or [ that a reaction is slow when (Gleim) is used as a solvent ] -- or although it does not react at all, it may be made to react smoothly by using a little macrocyclic polyether compounds like 18-crown ether 6 Since the boiling point of acetonitrile or Gleim is low, they are advantageous at the object output and the point which can carry out distillation separation easily at the time of the end of a reaction. Especially in the case of a Lewis acid initiator, although a solvent is not needed, the dimer or trimer of hexafluoropropylene may be used as a solvent. Although reaction temperature may change with the kinds and solvents of an initiator, the temperature of -80~100 degreeC is usually used, and preferably the reaction temperature of -30~50 degreeC may be adopted. A reaction product is recoverable by the usual method. For example, after solid output's washing and removing a solvent and an initiator residual substance, a volatile output is recoverable by carrying out Rectification separation by filtering again. A reaction product is formula:A (CH) as mentioned above.₂CF₂CF₂O)nCH₂CF₂COF It has the becoming structure, and although the Acyl fluoride of an end has high reaction activity and is chemically valuable in itself as everyone knows, an un-active thing is required depending on a use. For example, the above-mentioned Acyl fluoride compound is antimony pentafluoride (SbF).₅It is a formula by heating in the dimer of There for the amounts of catalysts, and hexafluoropropylene, or a trimer beyond room temperature: X(CH₂CF₂CF₂O)nCH₂CF₃It comes out and can change into the compound shown. Thus, the polyether which changed the end into inactivity chemically can be adapted for the above demands. Chlorination and fluorination under ultraviolet-rays existence are faced, and an end is -OCH.₂CF₂COOH or -OCH₂-CF₂An end is -OCXYCF when polyether () which is COF is used.₃Or -OCXYCF₂- The inside of Cl[type, and X and Y are the above and the meaning. The inside of a -OCXYCOF or -OCXYCOCl[type, and X and Y are [ the output which is], and / an end ] the above and the meaning. The output which is] exists. When introduction of chlorine or fluoride is stopped, and nitrogen gas replaces the inside of the system of reaction and also an ultraviolet exposure is continued, all the ends are -OCXYCF(s).₃Or -OCXYCF₂It is changed into Cl. After hydrolyzing with water, when fluoride is circulated, it is -OCXYCF easily about an end.₃It can be alike and can change. The main chain of new halogen-containing-polyether (I) of the present invention is thermally and chemical very stable, and it can apply it to various uses according to the quality. [ especially / usual perfluoro polyether ], the oil of a chloro Fluoro hydrocarbon system is excelled and polyether (I)s of the present invention are chemical and a thing in which the lubricity endures perfluoro polyether, although thermal stability is a little inferior. It can be used as a solvent, a heat carrier, lubricating oil, vacuum pump oil, etc. as oil with heat resistance and chemical resistance using this characteristic. What does not carry out end stabilization can be used as the intermediate for manufacturing a chlorinated fluorine compound, and materials of a fluorochemical surfactant. Next, a reference example and an example are shown and the present invention is explained concretely. Reference example 1 It was which teaches 50 ml of often dry jig limes, cesium fluoride 0.15g, 2, 2 and 3, and 50 g of 3-tetrafluoro oxetane to a 200-ml glass tube with a rotor flow valve, and it maintains at room temperature under churning for 15 hours. The reaction mixture was put into 1000 ml of water, the glass filter separated the solid material which deposited, and after washing with methanol, a line intermediary and white powder 45g were obtained for vacuum drying. Melting point: 78degreeC. Decomposition temperature: 316degreeC. Ultimate analysis: [Table]

NMR:delta(ppm) =4.62 (CH)₂(Internal standard: TMS). delta(ppm) =-7.2 (-CF)₂O-, -41.4 (CH)₂CF₂(External standard: TFA) it (the lower field side is made into + from a standard). . IR chart of this compound is shown in Drawing 1. From these results, output is -CH.₂CF₂CF₂It has checked that it was polymer which has a frame of O-. An average molecular weight is 1.5x10 from GPC.⁴It came out and a certain thing became clear. Reference example 2 Dry nitrogen gas fully replaces the flask of 1 which connected the dry ice capacitor and the dropping funnel, It was which prepares 200 ml of dry jig limes, and cesium fluoride 4.2g, and adds 166 g of perfluoro 2-propoxy propionic acid fluoride under churning in an ice bath, and it maintains for 30 minutes. 650 g of 2, 2, 3, and 3-tetrafluoro oxetane was dropped over 5 hours. It was which exchanges an ice bath to 25 degreeC bathing, and maintains it after the end of dropping for 15 hours. Uniformly, distillation under reduced pressure of the No sauce was carried out, and liquefied thing 725g (60~200 degreeC/1mmHg) was obtained. This is a result of GC/MS, NMR, and IR analysis,<img file="JPH0160170B2_D0006.tif" />(a is an integer of 1~10) It became clear that it is Of a mixture. Reference example 3 Dry nitrogen gas fully replaces the 300-ml flask which connected the dry ice capacitor and the dropping funnel, It was which prepares 50 ml of dry jig limes, and cesium fluoride 0.2g, and adds the bottom of churning, and 26.0 g of 2, 2, and 3-trifluoro propionic acid Florido in an ice bath, and it maintains for 30 minutes. 130 g of 2, 2, 3, and 3-tetrafluoro oxetane was dropped over 3 hours. It was which exchanges an ice bath to bathing and maintains it after the end of dropping for 12 hours. Methanol 30g was dropped, the reaction mixture was put into water 2 after It was maintained for 30 minutes, and it fully agitated, and separated low-layer solution by the separating funnel (150g of yields). This is F (CH) as a result of analysis.₂CF₂CF₂O)bCH₂CF₂COOCH₃(b is an integer of 0~9) It became clear that it is Of a mixture. Reference example 4 6 fluoridation propylene dimer [(CF)₃)₂CFCF=CF-CF₃30 weight sections (CF)₃)₂C=CFCF₂CF₃It was which prepares mixture]150g and antimony pentafluoride 0.3g with 70 weight sections, and trickles slowly 65 g of 2, 2, 3, and 3-tetrafluoro oxetane under churning, and it maintains by -50~0 degreeC for 5 hours. It decompressed, the low-boiling fraction was removed and 50 g of wax-like output was obtained. Melting point 52degreeC. This is -CH as a result of analysis.₂CF₂CF₂It became clear that it had the structure of O-. Reference example 5 It was which teaches 100 ml of often dry jig limes and potassium fluoride 1.0g to a 500-ml glass flask, and trickles slowly 130 g of 2, 2, 3, and 3-tetrafluoro oxetane under churning and in an ice bath, and it maintains for 15 hours. A Line intermediary and 120 g of polymer were obtained for the same post-processing as reference example 1. This is -CH as a result of analysis.₂CF₂CF₂It became clear that it had the structure of O-. An average molecular weight is 1.0x10 from GPC.⁴Was. Reference example 6 It was which teaches 50 ml of dry jig limes, and 15 g of potassium iodide, and trickles 32.5 g of 3-tetrafluoro oxetane slowly under [ 2, 2, and 3 ] churning, and it maintains for 24 hours. Methanol 10g was dropped, and after It was maintained for 30 minutes, it often washed with water and obtained 30 g of oily output. This is I (CH) as a result of analysis.₂CF₂CF₂O)cCH₂CF₂COOCH₃(c is an integer of 0~5) It became clear that it is Of a mixture. Reference example 7 30 ml of dry jig limes and cesium fluoride 1.2g were taught to the 100-ml flask which connected the dry ice capacitor and the dropping funnel, and it agitated in bath cooled to -30 degreeC. Subsequently, 10 g of perfluoro propionic acid fluorides were taught by the shape of gas, bath temperature was raised to 0 degreeC after the end after It was maintained as it is for 30 minutes, and cotton intermediary dropping of 50 g of the 2, 2, 3, and 3-tetrafluoro oxetane was carried out in 20 hours. After having put in methanol 50g after raising bath temperature to 20 degreeC gradually after the end of dropping and also continuing churning for 5 hours, agitating and also washing with a lot of water, 47 g of oil-like output was obtained. Output is CF as a result of NMR, IR, and GC-MS analyzing.₃CF₂CF₂O(CH₂CF₂CF₂O)dCH₂CF₂COOCH₃(d is an integer of 1~8) It was which that it is Of a mixture divides. Reference example 8 10 ml of dry jig limes, cesium fluoride 1.2g, 2 and 2, and 2.0 g of 3-trifluoro propionic acid fluorides were added to the 30-ml flask which connected the dry ice capacitor and the dropping funnel, and it agitated in bathing for 1 hour. Subsequently, cotton intermediary dropping of 10.0 g of the 3-tetrafluoro oxetane was carried out under [ 2, 2, and 3 ] churning in 3 hours. Churning was continued after the end of dropping for 15 hours. Subsequently, the reaction was continued for 5 hours, after exchanging bathing to the ice bath and blowing hexafluoro propylene oxide into a system by a 10ml/minute flow for 2 hours. Reaction liquid was processed and washed with methanol and oil-like thing 18.0g was obtained. By analysis, it is output,<img file="JPH0160170B2_D0007.tif" />It was which it divides that (e is an integer of 2~9 and f is a mixture of integer) of 0~3. Example 1 To a 100-ml silica tube with a rotor flow valve, it is formula:F (CH).₂CF₂CF₂O)nCH₂CF₃(Average [ of n ] =5) It came out, poly Fluoro ether 1.76g and 0.55 g of chlorine which are shown were taught, and it irradiated with ultraviolet rays for 15 hours using the high-pressure ultraviolet exposure device. After the end of irradiation, it deaerated and obtained 2.00 g of oily matters. A reaction product is from IR and NMR analysis (CH).₂CF₂CF₂O)x-(CHClCF₂CF₂O)y It was which it divides that it is a compound which comes out and includes the repeat unit shown. Example 2 To the reaction pipe made from 100-ml silica with a blowing-in pipe, it is formula:F (CH).₂CF₂CF₂O)nCH₂CF₃(Average [ of n ] =5) It came out and poly Fluoro ether 35.0g shown was prepared, and it irradiated with ultraviolet rays with the high-pressure mercury lamp, blowing gaseous chlorine into this at the 50ml/minute flow velocity, and making it circulate from a pipe. When the part was taken out and it analyzed by GLC, IR, and NMR 6 hours afterward, this compound is mainly F (CHClCF).₂CF₂O)nCHClCF₃It was which coming out and having the structure shown divides. The reaction was continued, the reaction was stopped 14 hours afterward, and 52.1 g of output was obtained. It is F (CCl) when NMR, IR, and ultimate analysis analyzed this compound.₂CF₂CF₂O)nCCl₂CF₃(Average [ of n ] =5) It was out of which it comes and which a certain thing divides. Example 3 To the 100-ml flask made from Pyrex, it is formula:F (CH).₂CF₂CF₂O)nCH₂CF₂COOH (Average [ of n ] =25) It came out, white powdered poly Fluoro ether 50.0g shown was prepared, the flask was heated to 100~150 degreeC in fluoride oil, and gaseous chlorine was blown in a minute in 100ml /from the plug pipe under high-pressure mercury lamp irradiation, agitating with a magnetic stirrer. One week afterward, with nitrogen, the inside of a flask was replaced, and it cooled, and obtained 75.0 g of wax-like output. It is F (CCl) as a result of analysis.₂CF₂CF₂O)nCCl₂CF₂Cl (Average [ of n ] =25) It was out of which it comes and which that it is a compound shown divides. IR chart of this compound is shown in Drawing 2. Example 4 To a condensator and the 100-ml flask made from Pyrex with a plug pipe, it is formula:CH.₂FCF₂CF₂OCH₂CF₂CF₂OCH₂-CF₃It came out and liquefied compound 50.0g shown was prepared, and gaseous chlorine was blown in a minute in 100ml /from the plug pipe under high-pressure mercury lamp irradiation, agitating with a magnetic stirrer. Internal temperature rose to 90degreeC with the heat of the mercury lamp. It is formula:CCl, when nitrogen replaced 24 hours afterward and the reaction product was analyzed.₂FCF₂CF₂OCCl₂CF₂CF₂O-CCl₂CF₃It was out of which it comes and which that it is a compound shown divides. 72.0g of yields. IR chart of this compound is shown in Drawing 3. Example 5 To the same device as Example 4, it is formula:F (CH).₂CF₂CF₂O)nCH₂CF₃(Average [ of n ] =5) It came out, poly Fluoro ether 50.0g shown was prepared, and gaseous chlorine was blown into this at the 50ml/minute flow velocity for 3 hours. When blowing in of gaseous chlorine is stopped, output is taken out and it analyzes, a chlorination percentage is 20%, and it is Oh. Fluoride / nitrogen (capacity ratios 70/30) mixed gas was circulated at room temperature in a minute in 50ml /, taking 10 g from this sample, teaching the reaction pipe made from stainless steel (reading is impossible), and agitating with a magnetic stirrer. It is formula:F (CClxFyCF) when output was analyzed 12 hours afterward.₂CF₂O)nCClxFyCF₃It was which it divides that it is a compound shown by (average [ of n ] =5, x:y=1:4). Example 6 The reaction machine made from 20 stainless steel with a stirrer is maintained at 100 degreeC, and it is formula:F (CH).₂CF₂CF₂O)nCH₂CF₃(Average [ of n ] =20) It comes out, 10 kg of the poly Fluoro ether shown is prepared, fluoride gas is taught to this at the flow velocity for 5/, and it is I got it about a fluorination reaction. The preparation of fluoride gas is suspended in 40 hours, nitrogen fully replaces, output is extracted, and it is formula:F (CF).₂CF₂CF₂O-)_x-(CHFCF₂CF₂O)-_yCF₂CF₂COF (x:y=2:1) It came out and obtained 12 kg of the poly Fluoro ether shown. This poly Fluoro ether was taught to the reaction machine made from 20 pyrex glass, and it maintained at 100 degreeC, and blew chlorine from the blowing-in pipe at the flow velocity for 5/under irradiation with the mercury lamp (1 kW) for 48 hours. After-end nitrogen replaces, output is extracted and it is formula:F (CF).₂CF₂CF₂O-)_x-(CClFCF₂CF₂O)-_yCF₂CF₂COF (x:y=2:1) It came out and obtained 12.5 kg of the poly Fluoro ether shown. This poly Fluoro ether is returned to the first stainless steel reaction machine, after adding and agitating water 100g, temperature was raised to 150 degreeC and fluoride gas was again circulated at the flow velocity for 2/for 12 hours. After the end of a reaction, after nitrogen replaces, output is extracted, and it is formula:F (CF).₂CF₂CF₂O-)_x-(CClFCF₂CF₂O)-_yCF₂CF₃It came out and obtained 12.0 kg of polyether shown. IR of a reaction product is shown in Drawing 4. Example 7 It is I got it about operation of the plasma generator for an examination which lubricates the oil obtained in Example 6 and uses the mixed gas of chlorofluocarbon 14 and water oxygen after a solvent washes the oil rotation pump after direct connection strictly. Abnormalities were not observed in a motor current value even after operation for 30 days. As a result of extracting and investigating oil, viscosity is 85cst in 40 degreeC, and a remarkable change was not accepted compared with 83cst of the oil before pouring. As for IR of the oil after use, and the analysis result of NMR, change was accepted by neither as compared with use before.

[Brief Description of the Drawings]

Drawing 1 is IR chart of the polymer obtained by reference example 1. Drawing 2 is IR chart of the polyether obtained in Example 3. Drawing 3 is IR chart of the polyether obtained in Example 4. Drawing 4 is IR chart of the polyether obtained in Example 6.