The method of producing perspire, the composition comprising forsport, its use as a solvent dye, an optical disk with a recording layer on the basis of perspire

 

(57) Abstract:

The invention relates to a method of producing perspire formula H(CFR1CF2)nCH2OH (I) wherein R1is F or CF3when n=1, and R1is F, when n=2, including the interaction of methanol with tetrafluoroethylene or HEXAFLUOROPROPYLENE in the presence of a source of free radicals. The resulting reaction mixture is subjected to distillation or in the presence of a base, or after exposure of this mixture to the base. Forsport formula I, obtained by distillation, is the residue from evaporation is not more than 50 m D. as a source of free radicals using peroxide initiator reaction, UV radiation or heat. The composition is forsport formula I with residue from evaporation is not more than 50 m D. the Composition is used as a solvent of the dye in the manufacture of recording media information for laser writing and/or reading. Using perspire formula I create an optical disk for laser writing and/or reading. Technical result - receiving perspire, suitable for the manufacture of laser media information recording and/or reading. 4 C. and 16 h.p. f-crystals, 13 tab., 2 Il.


H(CFR1CF2)nCH2OH (I)

where R1is F or CF3when n=1, and R1represents F, when n= 2, which is essentially free from impurities, and to use the specified perspire for the production of recording medium information including a substrate and created on it recording (recording) layer adapted for laser writing and/or reading.

Prior

Regarding the technology of H(CF2CF2)nCH2OH (n=1, 2) it should be noted that in the Japanese did not pass the examination patent publication 154707/1979 and U.S. patent 2559628, describes that the mixture of telomeres, i.e., N(CF2CF2)nCH2HE (the maximum value n= 12) can be obtained by the interaction of methanol with tetrafluoroethylene in the presence of tert-butylacrylamide.

However, even if telomeric mixture obtained by this method, purified by distillation, formed after evaporation the residue of the order of several hundred hours /million cannot be removed, and as a result, when this mixture is used as solvent in the manufacture of recording media information, comprising a substrate and VD-R, the inevitable downside is the lack of quality media for recording information due to the influence of this residue formed after evaporation.

The subject of this invention is the provision of perspire General formula I

H(CFR1CF2)nCH2OH (I)

where n and R1have the above specified values,

which is essentially free from impurities, such as residue after evaporation and substances that absorb UV radiation, the method of obtaining the specified perspire, the use of this perspire as a solvent for the manufacture of the recording medium information including a substrate and created for him a recording layer adapted for laser writing and/or reading.

Description of the invention

The invention relates to the following items 1-20.

1. The method of producing perspire the following formula I

H(CFR1CF2)nCH2OH (I)

where R1represents F or CF3when n=1, and R1represents F, when n=2,

including the interaction of methanol with tetrafluoroethylene or HEXAFLUOROPROPYLENE in the presence of a source of free radical is of the specified reaction mixture with a base.

2. The method of producing perspire under item 1, in which the base is a substance that has a value b not more than 2.

3. The method of producing perspire under item 1, in which the base is an alkoxide of an alkali metal or a hydroxide of an alkali metal.

4. The method of producing perspire under item 1, in which the base is at least one substance selected from the group comprising alkoxides of sodium, sodium hydroxide and potassium hydroxide.

5. The method of producing perspire under item 1, in which forsport formula I

H(CFR1CF2)nCH2OH (I)

where R1and n are as defined above values,

which is obtained by distillation, is the residue after evaporation is not more than 50 hours/million

6. The method of producing perspire under item 5, in which forsport formula I

H(CFR1CF2)nCH2OH (I)

where R1and n are as defined above values,

which is obtained by distillation, is the residue after evaporation is not more than 25 hours/million

7. The method of producing perspire under item 5, in which forsport formula I

H(CFR1CF2)nCH2OH (I)

where R1and n are as defined above values,

9. The method of producing perspire under item 8, in which the source of free radicals is the reaction initiator having a half-life at the reaction temperature for about 10 hours.

10. The method of producing perspire under item 8, in which the source of free radicals is a peroxide.

11. The method of producing perspire under item 8, in which the source of free radicals is a di-tert-butylperoxide, tert-butyl peroxy isopropyl carbonate or tert-butyl peroxy-2-ethylhexanoate.

12. The method of producing perspire under item 1, which together with the source of free radicals is used, the acid acceptor.

13. Forsport formula I

H(CFR1CF2)nCH2OH (I)

where R1represents F or CF3when n=1, R1represents F, when n=2,

which is the residue from evaporation is not more than 50 hours/million

14. Forsport under item 13, the residue from evaporation is not more than 25 hours/million

15. Forsport under item 13, the remainder of the issue is anole is not more than 0.2 abs.

17. Forsport under item 13, the absorbance (205 nm) in which methanol is not more than 0.1 abs.

18. Forsport on p. 17, the absorbance (205 nm) in which methanol is not more than -0,2 abs.

19. The use of perspire on p. 13 for the manufacture of recording media information, comprising a substrate and created for him a recording layer adapted for laser writing and/or reading.

20. The recording medium information including a substrate and created for him a recording layer adapted for laser writing and/or reading and fabricated using perspire formula I

H(CFR1CF2)nCH2OH (I)

where R1represents F or CF3when n=1, R1represents F, when n=2,

obtained by the method under item 1, or perspire formula I

H(CFR1CF2)nCH2OH (I)

where R1represents F or CF3when n=1, R1represents F, when n=2, under item 13.

In the method of receiving according to this invention, methanol is used in excess relative to the tetrafluoroethylene or hexaferrite. The reaction temperature is about 40-140oC, the reaction time is about 3-12 hours, gallerier, the autoclave. The reaction system is preferably purged with an inert gas using nitrogen, argon or a similar gas.

After completion of the reaction, excess methanol optionally distilled off and the residue is optionally subjected to distillation in the presence of a base. In addition, in the case when the reaction mixture contains as an impurity N(CF2CF2)nCH2HE (n3) or H(CF(CF3CF2)nCH2OH (n2), the admixture is preferably removed in advance by distillation. The reaction mixture containing forsport formula

H(CFR1CF2)nCH2OH (I)

where n and R1have the meanings given above,

subjected to distillation or in the presence of a base, or after contacting the reaction mixture with a base.

The base is added to this reaction mixture or contact with it, preferably represents a base value b not more than 2, and thus includes alkoxides of alkali metals such as sodium methoxide, ethoxide sodium, proposed sodium tert-piperonyl potassium, atoxic lithium and others , hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., figurine hydria is about 0.05-1.0 mol, preferably approximately 0.1 to 0.5 mol per 1 kg of the reaction mixture from which remove the methanol.

The acid acceptor includes, but is not limited to, carbonates and bicarbonates of alkali metals or alkaline earth metals such as calcium carbonate, magnesium carbonate, barium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc., calcium oxide, calcium hydroxide and soda lime. The preferred acid acceptor is a substance that is able to capture the acid formed during the reaction, for example HF, not giving a reaction system high basicity.

The amount of acid acceptor is not specifically limited, and may be about 0,001-0,1 mol based on 1 mol of tetrafluoroethylene or hexaferrite.

As the source or generator of free radicals can be used, at least one representative of the group, including the initiator of the reaction, UV radiation and heat. When the source of free radicals is a UV-radiation, can be used UV light from a mercury lamp, for example, medium pressure or high pressure. When the source of free radicals is heating, the temperature of the can is, eroxide, and it is preferable to use the initiator with a half-life at the reaction temperature for about 10 hours.

The preferred source of free radicals includes terbutyl D (di-tert-butylperoxide), terbutyl About (tert-butyl peroxy-2-ethylhexanoate) and parboil I (tert-butyl peroxy isopropyl carbonate). The amount of initiator, the reaction should generally be about from 0.005 to 0.1 mol per 1 mol of tetrafluorethylene or hexaferrite.

The amount of residue after evaporation of perspire obtained according to this invention, is 50 hours/million (M. D.) or less, preferably 25 memorial plaques or less, preferably 10 m days or less.

The amount of residue after evaporation can be determined as follows. Forsport is evaporated at 40oC /5 mm RT. century, the residue is weighed and expressed in mass fractions of "parts per million" (M. D.) based on forsport, such as F2CF2CH2HE.

UV absorption perspire formula I obtained according to this invention, in methanol at 205 nm is not more than 0.1 abs, preferably-0.1 abs or less, preferably -0,2 abs or less. UV-absorbance in methanol can be measured using

That forsport of the present invention is essentially free from impurities" means that (i) the residue after evaporation of perspire is not more than 50 M. D. , preferably not more than 25 M. D., preferably not more than 10 memorial plaques, and/or (ii) the UV absorbance (205 nm) in methanol is not more than 0.1 abs, preferably not more than-0.1 abs, preferably not more than -0,2 abs.

The recording medium information including a substrate and created for him a recording layer adapted for laser writing and/or reading, can be made by dissolving the dye in a solvent containing forsport General formula I according to the invention, preferably in a solvent fluoride row containing the specified forsport, with the subsequent implementation of the standard number of operations using the obtained dye solution, including coverage of the substrate with this solution and drying the coated substrate to provide a recording layer containing the dye. The above dye include cyanine dyes, phthalocyanine dyes, prelievi dyes, thiapyrilium dyes, squarewave dyes, asplenietea dyes, indophenol dyes, indianeconomy dyes based on metal complexes. Raw material for the substrate include plastics, such as polycarbonates, poly(methyl methacrylate), Apeksimova, amorphous polyolefins, polyesters, poly(vinyl chloride), and so on, glass and ceramics. With the aim of improving the surface smoothness and adhesion or prevent decomposition of the recording layer between a recording layer and a substrate can be provided with a primer coating or gasket and/or the recording layer can be formed in the protective layer.

According to the invention can be easily obtained essentially free from impurities F2CF2CH2HE, N(CF2CF2)2CH2HE F(CF3)CF2CH2HE that is suitable for use in the manufacture of the recording medium information including a substrate and created for him a recording layer adapted for laser writing and/or reading optical discs, such as CD-R, DVD-R and so on) or the photosensitive material film.

The best way of carrying out the invention

The following examples illustrate the invention in more detail.

EXAMPLE 1

In the autoclave add methanol (2 l), di-tert-butylperoxide (45 g) and calcium carbonate (30 g). After purging with nitrogen the funding of temperature and pressure level, respectively 125oC and 0.8 MPa.

After cooling, the reaction mixture is distilled to remove methanol and then H(CF2CF2)nCH2OH (n is an integer of 2 or more), getting faction F2CF2CH2HE (1.2 l). The residue after evaporation of the fractions HCF2CF2CH2OH is approximately 600 M. D., and the absorbance (205 nm) is 2.0 abs. Analysis of capillary GC/MS shows the presence as an impurity in various aldehydes, such as SNO, HCF2CF2CHO, HCF2CHFCHO, HCF2CF2CF2CF2CHO, HCF2COOCH2CH=CHCHO, HCF2CH2COOCH=CHCHO, HCF2CF2CH(OH)OCH2SNO.

Re-distillation of the specified faction almost does not cause any change of any of the quantities specified impurities, residue from evaporation and absorbance (205 nm).

To the resulting higher fraction HCF2CF2CH2OH (1 l) was added 28% sodium methoxide in methanol (30 g) and the mixture is distilled by heating, receiving HCF2CF2CH2OH that is essentially free from impurities. The distillation residue thus obtained HCF2CF2CH2OH amounted to no more than 10 M. D., his absorbance (205 nm) was less than -0,2 abs. The amount of the above-mentioned ALD the DB-1301

The film thickness of 1.00 μm

Column size 60 m x 0,247 mm

2) Conditions analysis:

The carrier 200 kPa

The air 40 kPa

H250 kPa

Temperature 50oWith in 5 minutes - 220oC for 15 minutes (temperature rising at a rate of 15oC/min).

Injection 200oC.

EXAMPLE 2

Fraction H(CF2CF2)nCH2OH (n2) fractional distillation for separation of fractions N(CF2CF2)2CH2HE. This fraction is added sodium methoxide, as shown in example 1, and the mixture is distilled, collecting the fraction H(CF2CF2)2CH2OH, showing the residue from evaporation is not more than 25 M. D.

EXAMPLE 3

The reaction and purification procedure using distillation was carried out according to the method of example 1, except that used HEXAFLUOROPROPYLENE instead of tetrafluoroethylene. The result is F(CF3)CF2CH2HE, with the residue from evaporation is not more than 25 M. D., UV-absorbance (205 nm) of not more than 0.1 abs.

EXAMPLE 4

Fraction HCF2CF2CH2OH to distillation in the presence of a base obtained in example 1 was passed through a column of sodium lime to remove HF. The result is 2OH low purity distilled, got HCF2CF2CH2OH, give the residue from evaporation is not more than 50 M. D., the significance of UV absorbance (205 nm) of not more than 0.1 abs.

COMPARATIVE TEST

The test was performed in the same conditions as in examples 19 and 20 of U.S. patent 4346250.

In a glass autoclave (internal volume of 2000 ml equipped with a stirrer, stainless steel, download methanol (800 g, 25 mol) and peroxide di-tert-butyl (terbutyl D, 20 g), after closing the autoclave was reduced internal pressure under stirring until until the methanol is not to boil. Then added tetrafluoroethylene (TPV) to achieve atmospheric pressure and under heat raised the temperature to 125oC. the Reaction was initiated by introducing into the autoclave TPV to a pressure of 0.8 MPa (about 8 kg/cm2). When the pressure was decreased to 0.7 MPa (about 7 kg/cm2) was immediately added TPV to increase the pressure up to 0.8 MPa (about 8 kg/cm2). This cycle reactions were repeated, each cycle was introduced the same number of TPV (about 3 g) and at the same time received the same number of telomeres. At the 30th cycle after initiation of the reaction in the autoclave under the pressure of the solution was added methanol (10 ml) containing KOH (0.56 g), or CH3ASO (0,54 is initsiirovaniya reaction are listed in table I at the end of the description.

As shown in table I, the reaction rate is restored by adding KOH or CH3The ASO.

Upon completion of the reaction, the autoclave was cooled to room temperature. TPV was released to collect the reaction mixture. Methanol was removed from the reaction mixtures by distillation, getting 210 g and 215 g of a mixture of telomeres, respectively. the pH and the content of HF in both mixtures telomeres were: pH 3.5 and HF 0.95 g (0,048 mol). Therefore, the entire CON and CH3OPA added in the reaction is consumed in the neutralization.

Subsequently, N(CH2CF2)nCH2HE, in which n represents an integer equal to 2 or more, separated, getting faction HCH2CF2CH2OH (150 g in both cases). The residue from evaporation and absorption (205 nm) fractions HCH2CF2CH2OH are shown in table II.

Analysis of the fractions by capillary GC/mass spectrometry showed that both fractions contained a large number of aldehydes, such as formaldehyde, HCF2CF2CHO, HCF2CHFCHO, HCF2CF2CF2CF2CHO, HCF2COOCH2CH=CHCHO, HCF2CH2COOCH=CHCHO and HCF2CF2CH(OH)OCH2CHO.

Re-distillation of the indicated fractions were caused only insignificant

The reasons for the residue from evaporation cannot be removed from perspire repeated distillations

The reaction mixture contains a large number of organic compounds such as formaldehyde (NSNO), residual initiator in the reaction and decomposition products other than source material (methanol), and the reaction products [N (CFRlCF2)nCH2HE] , where R1is F, when n=1, R1is F or CF3when n=2.

Aldehyde compounds, including (3) HCF2CHFCHO, (5) HCF2COOCH2CH= CHCHO, (6) HCF2CH2COOCH=CHCHO and (7) HCF2CF2CH(OH)OCH2CHO, formed in the reaction mixture under the action of radicals or oxidative conditions. Although the high-boiling aldehyde compounds (having a longer retention time in GC) can be removed, aldehyde compounds (3), (5) and (6) is difficult to remove because of the proximity of their boiling points to HCF2CF2CH2OH and a large number of azeotropes.

Seems aldehyde components (3), (5) and (6) do not cause problems when used for the production of a CD-R, as the aldehyde component (3), (5) and (6) evaporated together with the HCF2CF2CH2HE did not remain in the CD-R. However, the components (3), (5) and (6) contained in CFT the components remains in the CD-R in the form of high-boiling compounds and affects the recording properties of CD-R discs.

When carrying out distillation after transformation components (3), (5) and (6) in the high-boiling compounds by thermal decomposition HCF2CF2CH2During the distillation are formed inseparable components (3), (5) and (6). Therefore, the content of aldehydic components (3), (5) and (6) in the distillate cannot be reduced (see table III). In conclusion, using distillation in the absence of a basis is practically impossible to reduce the residue from evaporation of up to 50m doctor

Impurities in perspire:

(I) HCF2CF2CHO

(2) CH3HE

(3) THE HCF2CHFCHO

(4) THE HCF2CF2CF2CF2CHO

(5) THE HCF2COOCH2CH=CHCHO

(6) THE HCF2CH2COOCH=CHCHO

(7) THE HCF2CF2CH(OH)OCH2SNO

(8) THE HCF2CF2CH2OCH2OCH2CF2CF2H

(9) others, such as high-boiling compounds.

Experimental data (1)

Comparative data using perspire (HCF2CF2CH2OH: DFT) with varying amounts of residue from evaporation

[Sample forsport]

As shown in table 1, were used samples HCF2CF2CH2OH (DFT 1-6) with six levels of residue from evaporation.

[Conditions of proizvodi2HE (DFT 1-DFT 6):

Matrix

The height of the grooves ~200 nm

The width of the grooves ~450 nm

The composition of sample solutions of cyanine dye:

Concentration: the solids content of 40 g/(DFT)

Solids content: dye: S04/L04 (70/30) (product of NIPPON KANKO SHIKISO).

Production procedure:

Temperature 220,5oWITH

Humidity 452,5%

Treatment: standard (variable with the scale on the fifth level)

Drying 40oWith x 1 min.

Reflective layer: silver, 80 nm thick

Protective layer: type DSM 5100 (Lac)

Production of CD-R drives:

the apparatus is thoroughly washed and dried before sending samples

the dye solution used during the day, when the solution is prepared,

after the process of production of a CD-R is stable, the production of CD-R continue until, until you get 100 records CD-R discs in good condition.

Disks store indoors.

[Test recorded CD-R disc]

Three sets of disks, each consisting of 5 disks, selected randomly from disks made using samples of the DFT. On the selected disks made a record under the following conditions. As for each disk, CPOB (chastie acceleration at a temperature of 65oC and humidity of 85% for 7 days and 14 days, (iii) after the test on the impact acceleration at a temperature of 80oC and humidity of 85% for 7 days and 14 days. The results are shown in tables 2, 3 and 4, with each table corresponds to a test on the impact acceleration (ii), (iii) and (iv).

Terms of recording:

recorder: Plextor Plexwriter 6/28

write speed: four-speed

the recording 72 min

Residues from the evaporation of each sample DFT are summarized in table 5. Speed increase CPOB per hour for CD-R manufactured using each of the samples of the DFT given in table 6.

The speed increase CPOB in 1 hour in table 6 was transferred to a logarithmic value, it is shown in table 7.

The data of table 7 are plotted on a graph according to the Arrhenius equation, where on the x-axis presents the inverse of absolute temperature (1/T), and on the y-axis presents the logarithmic value of the speed increase CPOB in 1 hour (Fig.1).

In Fig.1, the rate of increase CPOB in CPOB 1 hour at 25oWith (1/T=3/35K-03) extrapolate by calculating an approximate straight line by the least squares method using the data at t is, necessary for increasing values CPOB for each CD-R up to 200 calculated on the basis of speed increase CPOB in 1 hour, as shown in table 8, and are presented as the longevity of CD-R at 25oIn table 9. Fig.2 is a graph on which the x-axis presents the residue from evaporation of the DFT, and on the y-axis presents the longevity of CD-R at 25oC.

These results, shown in Fig.2, show that to obtain a CD-R with practical durability suitable is preferably not more than 25 M. D. residue from evaporation of TFP and that more than 50 memorial plaques residue from evaporation greatly reduce the longevity of CD-R's.

Additional examples 5-41

Summary of examples 1-4 description (see tab.10).

EXAMPLE 5

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was added 95% sodium ethylate (11 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation resulting HCF2CF2CH2OH amounted to no more than 10 M. D., and absorption (absorption) (205 nm) was less than -0,2 abs.

EXAMPLE 6

Fraction HCF2C the functions HCF2CF2CH2HE (1 liter) was added 25% propilot sodium in the solution of propanol (51 g, about 0.16 mol) and the mixture was distilled by heating. The residue from evaporation resulting HCF2CF2CH2HE was no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 7

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was added to 97% tert-butyl potassium (18 g, about 0.16 mol) and the mixture was distilled by heating. The residue from evaporation resulting HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was no more than -0,2 abs.

EXAMPLE 8

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was added 10% lithium ethylate in ethanol (81 g, about 0.16 mol) and the mixture was distilled by heating. The residue from evaporation resulting HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 9

Fraction HCF2CF22CF2CH2OH (1 liter) was added 25% aqueous sodium hydroxide solution (25 g, about 0.16 mol) and the mixture was distilled by heating. The residue after evaporation resulting HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 10

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was added 25% aqueous solution of potassium hydroxide (35 g, about 0.16 mol) and the mixture was distilled by heating. The residue from evaporation resulting HCF2CF2CH2HE was no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 11

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was added 25% aqueous solution of lithium hydroxide (15 g, about 0.16 mol) and the mixture was distilled by heating. The residue from evaporation resulting HCF2CF2CH2HE was no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 12

Tracciare 1. Fraction HCF2CF2CH2OH (1 liter) was passed through the tube, which was filled with calcium hydroxide (50 g, about to 0.68 mol) to remove HF. Purity HCF2CF2CH2OH, determined by gas chromatography was reduced from 99,968% to 99,523% when processing in the receiver with Ca(OH)2. Fraction HCF2CF2CH2OH low purity distilled by heating. The residue from evaporation resulting HCF2CF2CH2OH amounted to no more than 25 M. D., and absorbance (205 nm) was not more than 0.1 abs.

EXAMPLE 13

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was passed through a tube filled with aluminum hydroxide (50 g, about 0.64 mol), to remove HF. Purity HCF2CF2CH2IT is determined by gas chromatography was reduced from 99,968% to 99,523% when processing in the receiver with A1(OH)3. Fraction HCF2CF2CH2OH low purity distilled by heating. The residue from evaporation resulting HCF2CF2CH2OH amounted to no more than 25 M. D., and absorbance (205 nm) was not more than 0.1 abs.

N the way as in example 1. Fraction HCF2CF2CH2OH (1 liter) was passed through a tube filled with octahydrate of barium hydroxide (150 g, about 0.48 mol), to remove HF. Purity HCF2CF2CH2OH, determined by gas chromatography was reduced from 99,972% to 99,511% when processing in the receiver with BA(OH)36N2O. Fraction HCF2CF2CH2OH low purity distilled by heating. The residue from evaporation resulting HCF2CF2CH2OH amounted to no more than 25 M. D., and absorbance (205 nm) was not more than 0.1 abs.

EXAMPLE 15

Fraction HCF2CF2CH2HE before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was passed through a tube filled with magnesium hydroxide (50 g, about 0.86 mol), to remove HF. Purity HCF2CF2CH2OH, determined by gas chromatography was reduced from 99,975% to 99,535% when processing in the receiver with SB(OH)2. Fraction HCF2CF2CH2OH low purity distilled by heating. The residue from evaporation resulting HCF2CF2CH2OH amounted to no more than 25 M. D., and absorbance (205 nm) sostav the Ali methanol (2 liters) and calcium carbonate (30 g). After replacement with nitrogen was loaded with TPV initial velocity of 600 g/H. the Reaction was carried out under irradiation of UV light using a mercury lamp high pressure for 48 hours at a temperature of 125oC and a pressure of 0.8 MPa. The reaction mixture was cooled and distilled to remove the methanol, then distilled addition to separate faction HCF2CF2CH2OH from H(CF2CF2)nCH2HE (n is an integer equal to 2 or more). Any resulting fraction HCF2CF2CH2OH had the residue from evaporation of about 400 hours/million and the absorbance (205 nm) 1.5 abs.

Analysis of this fraction by capillary GC/mass spectrometry showed that the fraction contains a large number of aldehydes. Re-distillation of the specified faction, led to a small change of the balance of evaporation and absorption (205 nm).

To the thus obtained fraction HCF2CF2CH2OH (0.2 liters) was added 28% of N3(6 g, 0.03 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 17

The reaction and distillation spend propylen, getting 0,22 liter fractions HCF(CF3CF2CH2OH. The residue from evaporation of the resulting fractions HCF2CF2CH2HE was 450 M. D., and absorbance (205 nm) was 1.6 abs.

To the thus obtained fraction HCF2CF2CH2OH (0.2 liters) was added 28% of N3(6 g, 0.03 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 25 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 18

The reaction was carried out for 72 hours in the same manner as in example 16, except that instead of the mercury lamp high pressure used mercury lamp, low pressure. The reaction mixture was distilled, collecting the fraction HCF2CF2CH2HE (0,23 liters). The residue from evaporation of the resulting fractions HCF2CF2CH2OH was 400 M. D., and absorbance (205 nm) was 1.5 abs.

To the thus obtained fraction HCF2CF2CH2OH (0.2 liters) was added 28% NaOCH3(6 g, about 0.03 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to not more than 10 m tra) and calcium carbonate (30 g). After replacement with nitrogen was loaded with TPV initial velocity of 600 g/H. the Reaction was conducted for 48 hours at a temperature of 280oC and a pressure of 1.0 MPa. The reaction mixture was cooled and distilled to remove methanol and then further distilled to separate a fraction HCF2CF2CH2OH (0.35 litres) of H(CF2CF2)nCH20H (n is an integer equal to 2 or more). Any resulting fraction HCF2CF2CH2OH had the residue from evaporation of about 500 m. D. and absorbance (205 nm) 2.0 abs. Analysis of this fraction by capillary mass spectrometry-GC showed that the fraction contains a large number of aldehydes. Repeated distillation resulted in a small change of the balance of evaporation and absorption (205 nm).

To the thus obtained fraction HCF2CF2CH2OH (0.2 liters) was added 28% of N3(6 g, about 0.03 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 20

The reaction and distillation was performed in the same manner as in example 19, except that instead of tetrafluoroethylene is obtained when this fraction HCF2CF2CH2OH was $ 550 memorial plaques, and the absorbance (205 nm) was 2.1 abs.

To the thus obtained fraction HCF2CF2CH2OH (0.2 liters) was added 28% of N3(6 g, about 0.03 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2HE was not more than 25 M. D., and absorbance (205 nm) was less than-0.1 abs.

EXAMPLE 21

To the autoclave was added methanol (2 liters), perventing acid (75 g) and calcium carbonate (30 g). After replacement with nitrogen was loaded with TPV initial velocity of 600 g/H. the Reaction was conducted for 6 hours at a temperature of 75oC and a pressure of 0.8 MPa. The reaction mixture was cooled and distilled to remove methanol, and then was then distilled to separate a fraction HCF2CF2CH2OH (0.6-liter) from H(CF2CF2)nCH2HE (n is an integer equal to 2 or more). Any resulting fraction HCF2CF2CH2OH had the residue from evaporation of about 600 M. D. and absorbance (205 nm) 2.0 abs. Analysis of this fraction by capillary mass spectrometry-GC showed that the fraction contains a large number of aldehydes. Repeated distillation resulted in a small change in H2HE (0.5 liter) was added 28% of N3(15 g, about 0.08 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH20H amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 22

The reaction and distillation was performed in the same manner as in example 21, except that instead of perbenzoic acid used AIBN (50 g), receiving 0.6-liter fractions HCF2CF2CH2HE. The residue from evaporation of the resulting fractions HCF2CF2CH2HE was 600 M. D., and absorbance (205 nm) was 1.8 abs.

To the thus obtained fraction HCF2CF2CH2HE (0.5 liter) was added 28% of N3(15 g, about 0.08 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 23

The reaction was carried out for 72 hours in the same manner as in example 16, except that instead of the mercury lamp high pressure and tetrafluoroethylene used the lamp infrared radiation and a mixture of tetrafluoroethylene/ozone (200/1 in molar with the tra). The residue from evaporation of the resulting fractions HCF2CF2CH2HE was 400 M. D., and absorbance (205 nm) was 1.5 abs.

To the thus obtained fraction HCF2CF2CH2OH (0.2 liters) was added 28% of N3(6 g, about 0.03 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2HE was no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 24

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2HE (1 liter) was slowly added NaH (3.6 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 25

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was slowly added NaH 15% solution of utility in hexane (64 g, about 0.15 mol) and the mixture was distilled by heating. The remainder of the issue is) was not more than -0,2 abs.

EXAMPLE 26

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2HE (1 liter) was slowly added NaH, 97% diisopropylamide lithium-ion (16.5 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 27

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was gradually added sodium amide (5.9 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 28

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was gradually added (C6H5)3Spa (40 g, about 0.15 mol) and the mixture was distilled by heating. The remainder of cypriani the head amounted to no more than -0,2 abs.

EXAMPLE 29

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was gradually added (C6H5)3Sopa (14.4 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 30

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was gradually added Na (3.5 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 31

Fraction HCF2CF2CH2OH before distillation in the presence of a base received in the same manner as in example 1. Fraction HCF2CF2CH2OH (1 liter) was gradually added MD (3.6 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2 IS A 32

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the acid acceptor used MgSO3(30 g), receiving a 1.2 liter fractions HCF2CF2CH2OH. The residue from evaporation of the resulting fractions HCF2CF2CH2OH was $ 600 M. D., and absorbance (205 nm) was 2.0 abs.

To the thus obtained fraction HCF2CF2CH2OH (1 liter) was added 28% of N3(30 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 33

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the acid acceptor used PA2CO3(30 g), receiving a 1.2 liter fractions HCF2CF2CH2HE. The residue from evaporation of the resulting fractions HCF2CF2CH2OH was $ 600 M. D., and absorbance (205 nm) was 2.0 abs.

To the thus obtained fraction F2CF2CH2HE (1 liter) was added 28% NaOCH3(30 g, about 0.15 UB>2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 34

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the acid acceptor used FOR2CO3(30 g), receiving a 1.2 liter fractions HCF2CF2CH2OH. The residue from evaporation of the resulting fractions HCF2CF2CH2OH was $ 600 M. D., and absorbance (205 nm) was 2.0 abs.

To the thus obtained fraction HCF2CF2CH2OH (1 liter) was added 28% of N3(30 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions F2CF2CH2HE was no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 35

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the acid acceptor used Panso3(30 g), receiving a 1.2 liter fractions HCF2CF2CH2OH. The residue from evaporation of the resulting fractions HCF2CF2CH2HE was 600 M. D., and absorbance (205 nm) was 2.0 abs.

It received the offer was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 36

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the acid acceptor used knso3(30 g), receiving a 1.2 liter fractions HCF2CF2CH2OH. The residue from evaporation of the resulting fractions HCF2CF2CH2OH was $ 600 M. D., and absorbance (205 nm) was 2.0 abs.

To the thus obtained fraction HCF2CF2CH2OH (1 liter) was added 28% NaOCH3(30 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 37

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the acid acceptor used Cao (30 g), receiving a 1.2 liter fractions HCF2CF2CH2OH. The residue from evaporation of the resulting fractions HCF2CF2CH2OH was $ 600 M. D., and absorbed what was added 28% of N3(30 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 38

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the acid acceptor used VASO3(30 g), receiving a 1.2 liter fractions HCF2CF2CH2OH. The residue from evaporation of the resulting fractions HCF2CF2CH2OH was $ 600 M. D., and absorbance (205 nm) was 2.0 abs.

To the thus obtained fraction HCF2CF2CH2OH (1 liter) was added 28% of N3(30 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 39

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the acid acceptor used KYOWORD 200V (A12O3HN2About 30 g), receiving a 1.2 liter fractions HCF2CF2CH2HE. The remainder of villalo 2.0 abs.

To the thus obtained fraction HCF2CF2CH2OH (1 liter) was added 28% of N3(30 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 40

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the acid acceptor used KYOWORD 500 (Mg6Al2(OH)16CO34H2About 30 g), receiving a 1.2 liter fractions HCF2CF2CH2OH. The residue from evaporation of the resulting fractions HCF2CF2CH2OH was $ 600 M. D., and absorbance (205 nm) was 2.0 abs.

To the thus obtained fraction HCF2CF2CH2OH (1 liter) was added 28% of N3(30 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

EXAMPLE 41

The reaction and distillation was performed in the same manner as in example 1, except that instead of caso3as the fraction of the HCF2CF2CH2OH. The residue from evaporation of the resulting fractions HCF2CF2CH2OH was $ 600 M. D., and absorbance (205 nm) was 2.0 abs.

To the thus obtained fraction HCF2CF2CH2OH (1 liter) was added 28% of N3(30 g, about 0.15 mol) and the mixture was distilled by heating. The residue from evaporation of the resulting fractions HCF2CF2CH2OH amounted to no more than 10 M. D., and absorbance (205 nm) was less than -0,2 abs.

1. The method of producing perspire formula I

H(CFR1CF2)nCH2OH (I),

where R1is F or CF3when n=1, and R1is F, when n= 2,

including the interaction of methanol with tetrafluoroethylene or HEXAFLUOROPROPYLENE in the presence of a source of free radicals, according to which the reaction mixture is subjected to distillation or in the presence of a base, or after a specified contact of the reaction mixture with a base.

2. The method of producing perspire under item 1, characterized in that the base is a substance with a pKb value of not more than 2.

3. The method of producing perspire under item 1, characterized in that the base is an alkoxide of an alkaline IU the base is, at least one substance selected from the group comprising alkoxides of sodium, sodium hydroxide and potassium hydroxide.

5. The method of producing perspire under item 1, characterized in that forsport formula I

H(CFR1CF2)nCH2OH (I),

where R1and n have the meanings given above,

obtained by distillation, is the residue from evaporation is not more than 50 memorial plaques

6. The method of producing perspire under item 5, characterized in that forsport formula I

H(CFR1CF2)nCH2OH (I),

where R1and n have the meanings given above,

obtained by distillation, is the residue from evaporation is not more than 25 M. D.

7. The method of producing perspire under item 5, characterized in that forsport formula I

H(CFR1CF2)nCH2OH (I),

where R1and n have the meanings given above,

obtained by distillation, is the residue from evaporation is not more than 10 meters D.

8. The method of producing perspire under item 1, characterized in that the source of free radicals is at least one representative selected from the group comprising a reaction initiator, UV and heat.

9. The method of producing perspira on what Espada at the reaction temperature for about 10 hours

10. The method of producing perspire under item 8, wherein the source of free radicals is hydrogen peroxide.

11. The method of producing perspire under item 8, wherein the source of free radicals is di-tert-butylperoxide, tert-butyl peroxy isopropyl carbonate or tert-butyl peroxy-2-ethylhexanoate.

12. The method of producing perspire under item 1, characterized in that together with the source of free radicals is used, the acid acceptor.

13. The composition comprising forsport, characterized in that it contains forsport formula I

H(CFR1CF2)nCH2OH (I),

in which R1is F or CF3when n=1, R1is F, when n=2,

in which the residue from evaporation is not more than 50 memorial plaques

14. The composition according to p. 13, characterized in that the residue from evaporation of perspire is not more than 25 M. D.

15. The composition according to p. 13, characterized in that the residue from evaporation of perspire is no more than 10 M. D.

16. The composition according to p. 13, characterized in that the absorption perspire (190-300 nm) in methanol is not more than 0.2 abs.

17. The composition according to p. 13, characterized in that the absorption perspire (205 nm) in methanol is nlay not more -0,2 abs.

19. Applying a composition comprising forsport on p. 13, as a solvent of the dye in the manufacture of the recording medium information including a substrate and created for him a recording layer adapted for laser writing and/or reading.

20. An optical disk comprising a substrate and created for him a recording layer adapted for laser writing and/or reading obtained with the use of perspire formula I

H(CFR1CF2)nCH2OH (I),

where R1is F or CF3when n=1, R1represents F, when n=2,

obtained by the method under item 1, or the composition under item 13.

Priorities for items:

28.12.1998 on PP.1-12;

25.02.1999 on PP.13-20.

 

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