RU2139889C1 - Polyvinyl ether (variants), method of preparation thereof and lubricating oil based thereon for rifrigerators - Google Patents

Abstract

FIELD: chemical industry. SUBSTANCE: polyvinyl ehter having end groups and molecular weight of 300-1200 is prepared by polymerization of vinyl ether in the presence of initiator, e.g. water, alcohol, phenol, acetal and Brensted acid catalyst or organometallic compounds. Polyvinyl ether is used as lubricating oil for compressor type refrigerators. Polyvinyl ether based lubricating oil is nicely miscible with freons, has superb stability and lubricating properties. EFFECT: improved quality of lubricating oil. 29 cl, 43 ex, 53 dwg, 3 tbl

Description

 The present invention relates to a new lubricating oil for compression-type refrigerators, a new method for producing polyvinyl ethers and ethers, and a new polyvinyl ether. In particular, the present invention relates to (I) a lubricating oil for compression refrigerators, which comprises as its main component polyvinyl ether having excellent compatibility with hydrogen-containing flons (freons ["flon" means generally chlorofluorocarbon (CFC), hydrofluorocarbon (HFC) and hydrofluorocarbon (HCFC)], such as 1,1,1,2-tetrafluoroethane (hereinafter referred to as flon-134a) and the like, which can be used as a refrigerant, instead of compounds that cause environmental pollution, such like dichlorofluoride tan (hereinafter referred to as flon-12), etc., and having excellent lubricating properties, (2) a method for efficiently and industrially producing polyvinyl ether, having a wide range of applications as a solvent, lubricating oil, glue, resin, etc. p. (3) a method for efficient and industrially profitable production of a useful ether having a wide range of applications as a solvent, lubricating oil, etc., by hydrogenation of acetal or ketal, and (4) a new polyvinyl ether suitable for use as a lubricating oil for compression refrigerators, electrical insulating (transformer) oil, organic solvent, surfactant, etc.

 Compression-type refrigerators typically consist of a compressor, condenser, control (throttle) valve and evaporator and are designed in which a mixture of refrigerant and lubricating oil circulates in a closed system. Depending on the type of equipment in a compression type refrigerator, the temperature is usually high in the compressor and low in the refrigerator, and it is usually necessary that the refrigerant and lubricating oil circulate in the phase separation system over a wide temperature range. If phase separation occurs during the operation of the refrigerator, this has a significant detrimental effect on the service life and performance of the device. For example, when the phase separation of the refrigerant and the lubricating oil occurs in the compressor area, the lubrication of the moving parts deteriorates and scoring forms, which significantly reduces the service life of the apparatus. When phase separation occurs in the evaporator, the heat transfer efficiency is reduced due to the presence of high viscosity lubricating oil.

Since lubricating oil for a refrigerator is used to lubricate moving parts in refrigerators, its lubricating properties are naturally important. In particular, since the temperature in the compressor is high, viscosity is important to maintain the oil film required for lubrication. The required viscosity varies depending on the type of compressor used and the operating conditions, and it is usually preferred that the viscosity (kinematic viscosity) of the lubricating oil before mixing with the refrigerant is 5-1000 cc at 40 ^° C. With a viscosity lower than the specified range, the oil film becomes thin, which leads to insufficient lubrication, and when the viscosity is higher than in the specified range, the heat transfer efficiency decreases.

Electric refrigerators have an electric motor and compressor, enclosed in one case, and therefore it is necessary that the lubricating oil for their lubrication has a high electrical insulating ability. Typically, a volumetric intrinsic resistance of 10 ¹² Ω • cm or more is required at 80 ^° C. If the resistance is lower than the indicated value, the possibility of electric leakage is increased.

 So far, mainly flon-12 has been used as a refrigerant for compression type refrigerators, and various types of mineral and synthetic oils meeting the above requirements have been used as lubricating oil. However, chlorofluorocarbons (CFCs), including flon-12, have a more strictly limited use worldwide because they introduce pollution into the environment, leading to the destruction of the ozone layer. For this reason, hydrogen-containing flons, such as hydrofluorocarbons (HFC) and hydrochlorofluorocarbons (HCFC), are attracting attention as new types of refrigerant. Hydrogen-containing fluorocarbons, in particular hydrofluorocarbons (HFCs) of the flon-134a type, are preferred as refrigerant for compression type refrigerators, because they have little chance of destroying the ozone layer and can replace flon-12 with a slight change in the design of the refrigerators used so far.

 Naturally, when using the hydrogen-containing flon described above, such as flon-134a, flon-32a, flon-125, flon-22, etc., as a refrigerant for refrigerators of the compression type, instead of flon-12, a lubricant having good compatibility with a hydrogen-containing flon, such as flon-134a, flon-32, flon-125, flon-22, etc., and good lubricity that meets the requirements described above. However, since the lubricating oils used so far in combination with flon-12 do not have good compatibility with a hydrogen-containing flon, such as flon-134a, flon-32, flon-125, etc., a new lubricating oil is necessary suitable for these compounds. It is advisable that when using a new lubricating oil, large changes in the design of the apparatus are not needed. It is undesirable that it was necessary to make significant changes in the design of existing machines due to the new lubricating oil.

It is known to use, for example, polyoxyalkylene glycols as a lubricating oil having compatibility with flon-134a. Such lubricating oils are disclosed, for example, in the search report N 17463 (October 1978), the description of US patent N 4755316, Japanese patent application laid N N 1989 - 256094, N 1989-259093, N 1989-259094, N 1989-271491, N 1990-43290, N 1990-84491, NN 1990-132176-132178, N 1990-132179, N 1990-173195, NN 1990-180986-180987, NN 1990-182780 -182781, N 1990-242888, N 1990-258895 N 1990-269195; N 1990-272097; N 1990-305893; N 1991-28296; N 1991-33193; NN 1991-103496 - 103497; N 1991-50297; N 1991-52995; NN 1991-70794 - 70795; N 1991-79696, N 1991-106992, N 1991-109492, N 1991-121195, N 1991-205492, N 1991-231992, N 1991-231994, 1992-15295, N 1992-39394 and NN 1992-43991 - 41592 However, polyoxyalkylene glycol lubricating oils usually have a low volumetric intrinsic resistance and, in addition to On the other hand, in the above descriptions, not a single example is satisfied that satisfies a value of 10 ¹² Ohm • cm or more at 80 ^o C.

 In addition to lubricants from polyoxyalkylene glycols as compounds compatible with flon-134a, ester lubricants are disclosed in the laid-out description to UK patent N 2216541, N 6979 (1990), Japanese Patent Application Laid-Open N 1990-276894, N 1991-128992 , N 1991-88892, N 1991-179091, N 1991-252497, N 1991-275799, N 1991-4294, N 1992-20597 and the description of US patent N 5021179. However, lubricating oils from esters do not have sufficient compatibility because for phase separation at high viscosity lubricating oils at lower temperatures, even if they show good with compatibility at higher temperatures.

Thus, it turns out that at present the lubricant oil for compression refrigerators has not yet been disclosed, which has excellent compatibility with the -134a flon, excellent stability and lubricating properties, and a volumetric intrinsic resistance at 80 ^° C. of 10 ¹² Ω · cm or more . The creation of such a lubricant is highly desirable.

 Important compounds having a wide range of applications as solvents, lubricants, adhesives, resins, etc., are polyvinyl ethers, the production methods of which are known as polymerization methods, radical, cationic or radiation, monomers, which are simple vinyl ether ( "Gosei Kobunshi III", publication by Asakura Shoten edited by Shunsuke Murahashi, Minoru Imotu and Hisashi Jani). However, these traditional methods are not always satisfactory due to the fact that it is not easy to obtain a compound having the desired degree of polymerization, that the process is complicated, that it is difficult to control the reaction, that a large amount of solvent, etc. is required. Therefore, it is highly desirable to develop a method for producing a simple polyvinyl ether without the above problems.

 Known ("Sikken Kagaku Koza, v.20, 4th edition, Maruzen publication) methods for producing a simple ether, having a wide scope as a solvent and lubricant, from acetals or ketals, such as, for example, the method using acid and hydride alkali metal method using a silicon reagent and a method using diborane or the like

 However, stoichiometric amounts of very expensive materials, such as alkali metal hydride, diborane and silicon reagent, are used as hydrogenation reagent in these reactions, and therefore, these methods are not preferred for industrial production.

 A known method of combining an acid catalyst and catalytic hydrogenation. W.Z. Howard (I. Org. Chem., Vol. 26, p. 1026, 1961) described the preparation of an ether by catalytic hydrocracking of a ketal using a catalyst in which rhodium is supported on alumina in the presence of hydrochloric acid.

 U.S. Pat. No. 4,088,700 describes a process for producing an ether by catalytic hydrocracking of 1,3-dioxoranes which are cyclic acetals using a platinum or rhodium catalyst in the presence of a Lewis acid such as boron trifluoride, aluminum trichloride, etc. However, since hydrochloric acid, boron trifluoride, aluminum trichloride or the like are used in these production methods, there is a problem of corrosion of the equipment when using its usual type, and the necessary Social processing makes these methods unattractive.

 Japanese Patent Application Laid-Open N 1983-4739 and N 1983-177929 disclose an acid-free process for producing an ether by hydrocracking acetals using a palladium catalyst supported on coal. There is no corrosion problem caused by the use of acid, but the degree of conversion of acetal as a raw material is not satisfactory.

 Thus, there is still no way to obtain ether from acetal or ketal having sufficient reactivity, which (method) provides good selectivity and does not cause corrosion of equipment, and therefore the development of such a method is highly desirable.

 On the other hand, for applications as lubricating oils, electrical insulating oils and solvents, fluidity is necessary and therefore a polymer having a low degree of polymerization is desirable. As for the well-known polyalkyl vinyl ethers, examples of the synthesis of their various types are described in "Jikhen Kagaku", volume 18, "Reaction of organic compounds 11 (A)", publication of the Chemical Society of Japan (publication Maruzen). In the case of alkyl vinyl ethers having a low molecular weight and an alkyl group of 3 or less carbon atoms, from the above examples, the lowest molecular weight of the polymer is, for example, 2545 for the methyl vinyl ether polymer, 4000 for the ethyl vinyl ether polymer, 4830 for the n-propyl vinyl ether polymer and 4580 for an isopropyl vinyl ether polymer. A polymer of methyl vinyl ether having a molecular weight of 3000 is described in Macromolecules, Volume 17, p. 2228 (1984), and a polymer of ethyl vinyl ether having a molecular weight of 2600 is described in Macromolecules, Volume 18, p. 2 (1985). However, the indicated molecular weight values suggest that these polymers have very low fluidity and are semi-solid at room temperature.

 In the case of compounds having an alkyl group with 4 or more carbon atoms, an example is found in which a dimer is isolated and an example in which a polymer having a molecular weight of 600 is obtained. For polymers of vinyl vinyl ethers having an alkyl group with 4 or more carbon atoms , do not meet the necessary requirements, because they are not compatible with hydrofluorocarbons, such as flon-134a.

 As described above, a polymer of an alkyl vinyl ether and an alkyl group having 3 or less carbon atoms, which has a molecular weight of 1200 or lower, is not yet known.

 The end groups of these polymers are olefins in the case of acid catalysts and acetals, when alcohol is present, and in the presence of water, acetal and aldehyde end groups are also formed. Olefin at the end of the chain sometimes causes staining and viscosity increase in the presence of acid, and the aldehyde end group also sometimes causes staining. Acetals decompose in the presence of acid into olefins and alcohols. Olefins react with each other, causing staining and increasing viscosity, and when water is additionally present, aldehydes are formed, which also sometimes cause staining. But polyvinyl ether, which does not have structures such as acetals, aldehydes and olefins that cause degradation at the ends of the molecule and has excellent stability, is still not known.

Under the conditions described above, the present invention was developed with the aim of creating (1) a lubricating oil for compression type refrigerators having excellent compatibility with hydrogen-containing flons (freons), such as flon-134a, flon-32, flon-125, etc. . which can replace the flon-12 refrigerant and other flons, which are highly decomposed and, in particular, cause environmental pollution, over the entire operating temperature range, which has excellent stability and lubricating properties and has a volume intrinsic electrical resistance of 10 ¹² Ohm • cm or more at 80 ^o C), (2) an industrially advantageous method for producing a simple polyvinyl ether having a high degree of polymerization using a simple, reliable, safe and efficient process, (3) an eff active production of ether by hydrogenation of acetal or ketal using a catalyst having sufficient reactivity and excellent selectivity and non-corrosive equipment, and (4) a new polyvinyl ether for preferred use, in particular, as a lubricating oil for the compression refrigerators described above type.

 As a result of intensive research conducted by these inventors in order to achieve the goals described above, it was discovered (1) that the first of these goals can be achieved with a lubricating oil containing polyvinyl ether having a specific structure as its main component), (2) that the second goal can be achieved by adding dropwise a simple vinyl ether monomer to a particular initiator in the presence of a catalyst and polymerizing the monomer, (3) that the third goal can can be achieved by using a solid catalyst having acidic properties and hydrogenating ability as said catalyst and (4) that the fourth goal can be achieved using (a) a simple polyvinyl ether, which is a homopolymer or copolymer of an alkyl vinyl ether having an alkyl group with 1-3 carbon atoms, has a mass-average molecular weight and a range of 300-1200 and has end groups of a specific structure and (o) a specific vinyl vinyl ether polymer specific uctury, which does not contain either an unsaturated bond or acetal and aldehyde structures and has a mass-average molecular weight in a certain range. The present invention has been made based on the aforementioned discovery.

где R⁴², R⁴³ и R⁴⁴ - каждый атом водорода или углеводородная группа, имеющая 1-8 атомов углерода, и могут быть одинаковыми или отличающимися друг от друга, R⁴⁵ - двухвалентная углеводородная группа, имеющая 2-10 атомов углерода, R⁴⁶ - углеводородная группа, имеющая 1-10 атомов углерода, V - число, среднее значение которого находится в диапазоне 0-10, и R⁴⁵ O могут быть одинаковыми или отличающимися друг от друга, когда имеется несколько групп R⁴⁵O.Thus, the lubricating oil for refrigerators of the compression type, which is created in accordance with the first objective of the present invention, contains as its main component a simple polyvinyl ether having constituent units expressed by the general formula (XXII):

where R ⁴² , R ⁴³ and R ⁴⁴ are each hydrogen atom or a hydrocarbon group having 1-8 carbon atoms, and may be the same or different from each other, R ⁴⁵ is a divalent hydrocarbon group having 2-10 carbon atoms, R ⁴⁶ a hydrocarbon group having 1-10 carbon atoms, V is a number whose average value is in the range of 0-10, and R ⁴⁵ O may be the same or different from each other when there are several R ⁴⁵ O groups.

где R¹⁹, R²⁰ и R²¹ - каждый атом водорода или углеводородная группа, имеющая 1-8 атомов углерода, и могут быть одинаковыми или отличающимися друг от друга, R²² - двухвалентная углеводородная группа, имеющая 2-10 атомов углерода, R²³ - углеводородная группа, имеющая 1-10 атомов углерода, q - число, среднее значение которого находится в диапазоне 0-10, и R²²O могут быть одинаковыми или отличающимися друг от друга, когда имеется несколько групп R²²O, который (способ) создан в соответствии со второй целью настоящего изобретения, включает в себя полимеризацию представляющего собой простой виниловый эфир мономера, имеющего общую формулу (IX):

где R¹⁹-R²³ и q - такие, как указанные ранее, путем использования сочетания кислоты Брэнстеда (апротонной кислоты), кислоты Льюиса или металлоорганического соединения с водой, спиртом, фенолом, ацеталием или аддуктом простого винилового эфира и карбоновой кислоты в качестве инициатора.A method of producing a simple polyvinyl ether containing constituent units expressed by the general formula (X):

where R ¹⁹ , R ²⁰ and R ²¹ are each hydrogen atom or a hydrocarbon group having 1-8 carbon atoms, and may be the same or different from each other, R ²² is a divalent hydrocarbon group having 2-10 carbon atoms, R ²³ - a hydrocarbon group having 1-10 carbon atoms, q is a number whose average value is in the range 0-10, and R ²² O can be the same or different from each other when there are several groups of R ²² O, which (method) created in accordance with the second objective of the present invention, includes the polymerization of pre resents a vinyl ether monomer having the general formula (IX):

where R ¹⁹ -R ²³ and q are as previously described by using a combination of Branstead acid (aprotic acid), Lewis acid or an organometallic compound with water, alcohol, phenol, acetal or an adduct of vinyl ether and carboxylic acid as an initiator.

или общей формулой (XVI):

где R³³ и R³⁴ - каждый углеводородная группа или углеводородная группа, содержащая атомы кислорода простого эфира в основной цепи, в боковой цепи или и той и другой цепях, и могут быть одинаковыми или отличающимися друг от друга, а R³⁵, R³⁶ и R³⁷ - каждый атом водорода, углеводородная группа или углеводородная группа, содержащая атомы эфирного кислорода в основной цепи, в боковой цепи или в той и другой цепях, и могут быть одинаковыми или разными, который (способ) создан в соответствии с третьей целью настоящего изобретения, включает в себя введение ацеталя или кеталя, выраженного общей формулой (XIV):

где R³³, R³⁴, R³⁵, R³⁶ и R³⁷ - такие же, как указанные выше, в химическое взаимодействие с водородом в присутствии твердого катализатора, имеющего кислотные свойства и гидрирующую способность.A method for producing an ether expressed by the general formula (XV):

or general formula (XVI):

where R ³³ and R ³⁴ are each hydrocarbon group or hydrocarbon group containing ether oxygen atoms in the main chain, in the side chain, or both, and may be the same or different from each other, and R ³⁵ , R ³⁶ and R ³⁷ is each hydrogen atom, hydrocarbon group or hydrocarbon group containing ether oxygen atoms in the main chain, in the side chain or in both chains, and may be the same or different, which (method) is created in accordance with the third objective of the present invention includes introduction acetal or ketal expressed by the general formula (XIV):

where R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are the same as above, in the chemical interaction with hydrogen in the presence of a solid catalyst having acidic properties and hydrogenation ability.

где R¹ - алкильная группа, имеющая 1-3 атома углерода, и имеющий среднемассовую молекулярную массу 300-1200 и одну концевую группировку, имеющую структуру, выраженную общей формулой: (II):

или общей формулой (III):
-CH=CHOR^a (III),
где R¹ - такой же, как указанный выше, R² - углеводородная группа, имеющая 1 - 8 атомов углерода, и R^a - один из радикалов R¹ и R², а простой поливиниловый эфир, также созданный в соответствии с четвертой целью настоящего изобретения, содержит составляющие звенья, выраженные общей формулой (IV):

где R³, R⁴ и R⁵ - каждый атом водорода или алкильная группа, имеющая 1 - 4 атома углерода, и могут быть одинаковыми или отличающимися друг от друга, R⁶ - алкиленовая группа, имеющая 2 - 4 углеродных атома, R⁷ - алкильная группа, имеющая 1 - 10 углеродных атомов, k - число, среднее значение которого находится в диапазоне 1 - 10, R³ и R⁷ могут быть одинаковыми или разными в разных составляющих звеньях и R⁶ могут быть одинаковыми или отличающимися друг от друга, когда составляющее звено содержит несколько радикалов R⁶, причем упомянутый поливиниловый эфир не содержит ни ненасыщенной связи, ни ацетальной и альдегидной структур в молекуле и имеет среднемассовую молекулярную массу 300 - 3000.The polyvinyl ether created in accordance with the fourth objective of the present invention contains a homopolymer or copolymer of alkyl vinyl ether containing constituent units expressed by the general formula (I) or (I '):

where R ¹ is an alkyl group having 1-3 carbon atoms and having a weight average molecular weight of 300-1200 and one end moiety having a structure expressed by the general formula: (II):

or general formula (III):
-CH = CHOR ^a (III),
where R ¹ is the same as above, R ² is a hydrocarbon group having 1 to 8 carbon atoms, and R ^a is one of the radicals R ¹ and R ² , and polyvinyl ether, also created in accordance with the fourth purpose of this the invention contains constituent units expressed by the general formula (IV):

where R ³ , R ⁴ and R ⁵ are each hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different from each other, R ⁶ is an alkylene group having 2 to 4 carbon atoms, R ⁷ is an alkyl group having 1 to 10 carbon atoms, k is a number whose average value is in the range of 1 to 10, R ³ and R ⁷ may be the same or different in different constituent units, and R ⁶ may be the same or different from each other, when the constituting unit contains a plurality of radicals R ^6, wherein said polyvinyl ester is not sod rzhit no unsaturated bond or acetal and aldehyde structures in the molecule and has a weight average molecular weight of 300 - 3000.

The following is a brief description of the drawings, in which: Figures 1, 4, 7, 8, 11, 12, 15, 18, 21, 24, 27, 30, 33, 36, 37, 40, 43, 46, and 49 — Absorption Spectra in the infrared region of the polyvinyl esters obtained in examples 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 and 25A, respectively,
figures 2, 5, 9, 13, 16, 19, 22, 25, 28, 31, 34, 38, 41, 44, 47 and 50 — NMR ¹³ C Spectra of polyvinyl ethers obtained in Examples 8, 9, 11 , 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, and 25A, respectively,
figures 3, 6, 10, 14, 17, 20, 23, 26, 29, 32, 35, 39, 42, 45, 48 and 51 - NMR ¹ H-spectra of polyvinyl ether obtained in examples 8, 9, 11, 13 , 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, and 25A, respectively, and
figures 52 and 53 are NMR ¹ H-spectra of the acetal oligomer obtained in Example 37 (1) and the ether obtained in Example 37 (2), respectively.

 A description is first made of a lubricating oil for compression type refrigerators in accordance with a third objective of the present invention.

где R⁴², R⁴³ и R⁴⁴ - каждый атом водорода или углеводородная группа, имеющая 1 - 8 атомов углерода, и могут быть одинаковыми или отличающимися друг от друга, R⁴⁵ - двухвалентная углеводородная группа, имеющая 2 - 10 атомов углерода, R⁴⁶ - углеводородная группа, имеющая 1 - 10 атомов углерода, V - число, среднее значение которого находится в диапазоне 0 - 10, R⁴² - R⁴⁶ могут быть одинаковыми или отличающимися друг от друга в разных составляющих звеньях и R⁴⁵O могут быть одинаковыми или разными, когда имеется несколько R⁴⁵O.The lubricating oil for compression refrigerators in accordance with the present invention contains, as a main component, polyvinyl ether having constituent units expressed by the general formula (XXII):

where R ⁴² , R ⁴³ and R ⁴⁴ are each hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other, R ⁴⁵ is a divalent hydrocarbon group having 2 to 10 carbon atoms, R ⁴⁶ a hydrocarbon group having 1 to 10 carbon atoms, V is a number whose average value is in the range of 0 to 10, R ⁴² to R ⁴⁶ may be the same or different from each other in different constituent units, and R ⁴⁵ O may be the same or different when there are several R ⁴⁵ O.

In the formula (XXII), R ⁴² , R ⁴³ and R ⁴⁴ represents each hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other. Specific examples of the hydrocarbon group described above are an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl groups, various types of pentyl groups, various types of hexyl groups, various types of heptyl groups and various kinds of octyl group, cycloalkyl group such as cyclopentyl, cyclohexyl, various types of methylcyclohexyl, ethylcyclohexyl, dimethylcyclohexyl groups and the like, an aryl group such as phen an alkyl group, various types of methylphenyl, ethylphenyl and dimethylphenyl groups, or an arylalkyl group such as a benzyl group, various types of phenylethyl group and various types of methylbenzyl group. R ⁴² , R ⁴³ and R ⁴⁴ are preferably a hydrogen atom or an aliphatic hydrocarbon group having 5 or less carbon atoms (respectively), and more preferably a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms, respectively.

R ⁴⁵ in the formula (XXII) is a divalent hydrocarbon group having 2 to 10 carbon atoms, which is, for example, a divalent aliphatic group, such as ethylene, phenylethylene, 1,2-propylene, 2-phenyl-1,2- propylene, 1,3-propylene groups and various types of butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene groups, an alicyclic group having two bonding positions on an alicyclic hydrocarbon such as cyclohexane, methylcyclohexane, ethylcyclohexane, d cyclohexane, propylcyclohexane and the like, a divalent aromatic hydrocarbon; such as various types of phenylene, methylene, ethylphenylene, dimethylphenylene, naphthylene, etc. groups, an alkyl aromatic group having one monovalent binding position on each part of the alkyl group and the aromatic part of the alkyl aromatic hydrocarbon such as toluene, xylene, ethylbenzene and the like. or an alkyl aromatic group having binding positions on parts of the alkyl groups of a polyalkyl aromatic hydrocarbon, such as xylene, diethylbenzene and the like.

Particularly preferred of these is an aliphatic group having 2 to 4 carbon atoms. Several R ⁴⁵ O moieties may be the same or different from each other.

 In the formula (XXII), k represents the number of repetitions, the average value of k being in the range of 0-10, and preferably in the range of 0-5.

In formula (XXII), R ⁴⁶ is a hydrocarbon group having 1 to 10 carbon atoms, and an example of such a group is an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert -butyl groups, various types of pentyl, hexyl, heptyl groups, octyl, nonyl and decyl groups, cycloalkyl groups such as cyclopentyl, cyclohexyl groups and various types of methylcyclohexyl, propylcyclohexyl, dimethylcyclohexyl groups and the like, an aryl group such ac phenyl group, various types of methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl, trimethylphenyl, butylphenyl, naphthyl, etc. or an arylalkyl group, such as a benzyl group, various kinds of phenylethyl, methylbenzyl, phenylpropyl and butylphenyl groups. Of these, hydrocarbons having 8 or less carbon atoms are preferred. When V = 0, an alkyl group having 1 to 6 atoms is particularly preferred, and when V = 1 or more, an alkyl group having 1 to 4 carbon atoms is particularly preferred.

The number of repetitions in the polyvinyl ether expressed by the formula (XXII), which corresponds to the degree of polymerization, can be appropriately selected in accordance with the desired kinematic viscosity, which is usually in the range of 5 to 1000 cc at 40 ^o C, and preferably in the range of 5 to 800 cc at 40 ^o C.

 The polyvinyl ester can be obtained by polymerization of the corresponding vinyl ester monomer, and the polyvinyl ether production method described below, which is the second objective of the present invention, can be carried out as a polymerization method.

 The end groups of the resulting polyvinyl ether can be converted to the desired structure using the method disclosed in the embodiments of the present invention, or using traditional methods. The group to be converted is a saturated hydrocarbon, ether, alcohol, ketone, amide, imide, nitrile or the like.

где R⁴⁷, R⁴⁸, и R⁴⁹ - каждый атом водорода или углеводородная группа, имеющая 1 - 8 атомов углерода и могут быть одинаковыми или разными, R⁵⁰ - двухвалентная углеводородная группа, имеющая 2 - 20 атомов углерода, R⁵¹ - углеводородная группа, имеющая 1 - 10 атомов углерода, a - число, среднее значение которого находится в диапазоне 0 - 10, и R⁵⁰O могут быть одинаковыми или разными, когда имеется несколько групп R⁵⁰O, а другое концевое звено выражено формулой (XXIV):

где R⁵², R⁵³ и R⁵⁴ - каждый атом водорода или углеводородная группа, имеющая 1 - 8 атомов углерода, и могут быть одинаковыми или отличающимися друг от друга, R⁵⁵ - двухвалентная углеводородная группа, имеющая 2 - 10 атомов углерода, R⁵⁶ - углеводородная группа, имеющая 1 - 10 атомов углерода, b - число, среднее значение которого находится в диапазоне 0 - 10, и R⁵⁰O могут быть одинаковыми или разными, когда имеется несколько групп R⁵⁰O.As the simple polyvinyl ether, which is the main component of the lubricating oil in accordance with the present invention, it is preferable to use compounds having the following end structures;
(1) A structure in which one end link is expressed by formula (XXIII):

where R ⁴⁷ , R ⁴⁸ , and R ⁴⁹ are each hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms and may be the same or different, R ⁵⁰ is a divalent hydrocarbon group having 2 to 20 carbon atoms, R ⁵¹ is a hydrocarbon group having 1 to 10 carbon atoms, a is a number whose average value is in the range 0 to 10, and R ⁵⁰ O can be the same or different when there are several R ⁵⁰ O groups, and the other end link is expressed by the formula (XXIV):

where R ⁵² , R ⁵³ and R ⁵⁴ are each hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other, R ⁵⁵ is a divalent hydrocarbon group having 2 to 10 carbon atoms, R ⁵⁶ - a hydrocarbon group having 1 to 10 carbon atoms, b is a number whose average value is in the range of 0 to 10, and R ⁵⁰ O may be the same or different when there are several groups of R ⁵⁰ O.

где R⁵⁷, R⁵⁸ и R⁵⁹ - каждый атом водорода или углеводородная группа, имеющая 1 - 8 атомов углерода, и могут быть одинаковыми или разными, R⁶⁰ и R⁶² - соответственно двухвалентная углеводородная группа, имеющая 2 - 10 атомов углерода, группа, имеющая 1 - 8 атомов углерода, и могут быть одинаковыми или разными, R⁶¹ и R⁶³ - каждый углеводородная группа, имеющая 1 - 10 атомов углерода, и могут быть одинаковыми или разными, c и d каждый - число, среднее значение которого находится в диапазоне 0 - 10, и могут быть одинаковыми или отличающимися друг от друга, R⁶⁰O могут быть одинаковыми или отличающимися друг от друга, когда имеется несколько групп R⁶⁰O, и R⁶²O могут быть одинаковыми или разными, когда имеется несколько групп R⁶²O.(2) A structure in which one end link is expressed by formula (XXIII) and the other by formula (XXV):

where R ⁵⁷ , R ⁵⁸ and R ⁵⁹ are each hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different, R ⁶⁰ and R ⁶² are respectively a divalent hydrocarbon group having 2 to 10 carbon atoms, a group having 1 to 8 carbon atoms, and may be the same or different, R ⁶¹ and R ⁶³ are each hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different, c and d each is a number whose average value is in the range of 0 - 10, and may be the same or different from each other, R ⁶⁰ O may be dinakovymi or different from each other when there are multiple R ⁶⁰ O groups, and R ⁶² O may be the same or different when there are several groups of R ⁶² O.

где R⁶⁴, R⁶⁵ и R⁶⁶ каждый - атом водорода или углеводородная группа, имеющая 1 - 8 атомов углерода, и могут быть одинаковыми или разными.(3) A structure in which one end link is expressed by formula (XXIII) and the other contains an unsaturated double bond, and
(4) A structure in which one end link is expressed by formula (XXIII) and the other by formula (XXVI):

where R ⁶⁴ , R ⁶⁵ and R ⁶⁶ each is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different.

 Polyvinyl ether can be a mixture of two or more compounds having terminal structures selected from the group consisting of structures (1) to (4). Preferred examples of such a mixture are mixtures of a compound having structure (1) and a compound having structure (4) and a mixture of a compound having structure (2) and a compound having structure (3).

The lubricating oil in accordance with the present invention contains the polyvinyl ether described above as a main component. Since the kinematic viscosity of the lubricating oil before mixing with the refrigerant is preferably in the range of 5-1000 cc at 40 ^° C cc at 40 ^° C, the starting materials, initiator and conditions described above are selected so as to obtain a polyvinyl ester having a kinematic viscosity in the specified range . The average molecular weight of this polymer is usually in the range of 150-2000, and preferably in the range of 150-4000. When the kinematic viscosity of the polymer is outside the specified range, it can be adjusted to a value in the specified range by mixing with another polymer having a suitable kinematic viscosity.

 In the lubricating oil for refrigerators in accordance with the present invention, the polyvinyl ether expressed by the formula (XXII) described above can be used alone or in combination of two or more kinds. It can also be used by mixing with other types of lubricating oils.

 Various types of additives used in conventional lubricating oils can be added to the lubricant for refrigerators in accordance with the present invention, such as additives to increase resistance to stress, chlorine scavengers, antioxidants, metal deactivators, antifoam agents, detergents and dispersants , viscosity reducing agents, oil control agents, antiwear additives, extreme pressure additives, anti-rust additives, for corrosion retardants, additives that lower the pour point of oil, etc.

 Examples of the load resistance additives described above are sulfur-containing organic compounds such as monosulfides, polysulfides, sulfoxides, sulfones, thiosulfinates, sulfonated oils and esters, thiocarbonates, thiophenes, thiazoles, methanesulfonic acid esters and the like. Phosphoric acid esters, such as phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid esters (tricresyl phosphate) and the like, phosphoric acid esters, such as monoesters, diesters and phosphoric acid esters and the like, thiophosphoric esters such as thiophosphoric acid esters, fatty acid esters, such as higher fatty acid esters, hydroxylaryl fatty acid esters, polyhydric alcohol esters containing carboxylic acids, acrylic acid esters and the like, organic chlorine additives, such such as chlorinated hydrocarbons, chlorine derivatives of carboxylic acids, etc., organic fluorine-containing additives, such as fluorinated aliphatic carboxylic acids, fluoroethylene resins, fluoroalkyl polysiloxanes, fluorinated graphite, etc., alcohol additives, such as higher alcohols and the like. , additives, metal compound content, such as salts of naphthenic acid (lead naphthenate), salts of fatty acids (lead salts of fatty acids), salts of thiophosphates (zinc dialkyldithiophosphates), salts of thiocarbamic acid, organomolybdenum Connections, organotin compounds, organogermanium compounds, boric acid esters and the like

 Examples of a chlorine scavenger are compounds having a simple glycidic ether group, epoxy fatty acid monoesters, epoxidized fats and oils, compounds having an epoxycycloalkyl group, and the like. Examples of antioxidants are phenols (2,6-di-tert-butyl-para-cresol), aromatic amines (α-naphthylamine) and the like. Examples of metal deactivators are benzotriazole derivatives and the like. Examples of antifoam additives are silicone oil (dimethylpolysiloxane), polymethacrylates, and the like. Examples of detergent-dispersing agents are sulfonates, phenolates, succinimides, etc. Examples of additives that lower the temperature dependence of the viscosity of an oil are polymethacrylates, polyisobutylene, ethylene and propylene copolymers, hydrogenated styrene and diene copolymers, and the like.

 The lubricating oil according to the present invention is used as a lubricating oil for compression type refrigerators due to its excellent compatibility with refrigerants and excellent lubricating properties. In contrast to traditional lubricating oils, the lubricating oil in accordance with the present invention has excellent compatibility with hydrogen-containing flons, such as flon-134a, and the like, which more specifically is, in addition to the above-described flon-134a, 1,1-dichloro- 2,2,2-trifluoroethane (flon-123), 1-chloro-1,1-difluoroethane (flon-142 b) 1,1-difluoroethane (flon-152a), chlorodifluoromethane (flon-22), trifluoromethane (flon- 23), difluoromethane (flon-32), pentafluoroethane (flon-125), etc.

 The lubricating oil in accordance with the present invention can be used in a mixture with other lubricating oil for compression type refrigerators in order to improve compatibility with the refrigerant.

 The following describes a method for producing a simple polyvinyl ether.

В представленной выше формуле R¹⁹, R²⁰ и R²¹ каждый - атом водорода или углеводород, имеющий 1-8 атомов углерода, и могут быть одинаковыми или разными. Примерами углеводородной группы являются те группы, которые представлены в примерах при описывании радикалов R⁴²-R⁴⁴ (XXII). R¹⁹, R²⁰ и R²¹ каждый - предпочтительно атом водорода или алифатическая углеводородная группа, имеющая 5 или менее атомов углерода, а более предпочтительно атом водорода или углеводородная группа имеющая 3 или менее атомов углерода.In the method for producing polyvinyl ester, the compound expressed by formula (IX) is used as the starting vinyl ester monomer:

In the above formula, R ¹⁹ , R ²⁰ and R ²¹ each is a hydrogen atom or a hydrocarbon having 1-8 carbon atoms, and may be the same or different. Examples of the hydrocarbon group are those groups that are presented in the examples when describing the radicals R ⁴² -R ⁴⁴ (XXII). R ¹⁹ , R ²⁰ and R ^{21 are} each preferably a hydrogen atom or an aliphatic hydrocarbon group having 5 or less carbon atoms, and more preferably a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms.

In the formula (IX), R ²² represents a divalent hydrocarbon group having 2-10 carbon atoms, and examples of the divalent hydrocarbon group are those groups that are presented as examples when describing the radical R ⁴⁵ in the formula (XXII). R ²² is preferably an aliphatic group having 2-4 carbon atoms, and R ²² O may be the same or different.

 In formula (IX), q is the number of repetitions, and the average value of q is in the range of 0-10, and preferably in the range of 0-5.

R ²³ in the formula (IX) is a hydrocarbon group having 1-10 carbon atoms, and its examples are the same groups that are presented as examples when describing the radical R ⁴⁶ in the formula (XXII). R ²³ is preferably a hydrocarbon group having 8 or less carbon atoms. When q = 0, an alkyl group having 1-6 carbon atoms is particularly preferred, and when q = 1 or more, an alkyl group having 1-4 carbon atoms is particularly preferred.

 Examples of the monomer, which is a simple vinyl ether, expressed by the formula (IX) are vinyl methyl, vinyl ethyl, vinyl n-propyl, vinyl isopropyl, vinyl n-butyl, vinyl isobutyl, vinyl-sec-butyl, vinyl-tert-butyl, vinyl n-pentyl, vinyl-n-hexyl, vinyl-2-methoxyethyl, vinyl-2-ethoxyethyl, vinyl-2-methoxy-1-methylethyl, vinyl-2-methoxypropyl, vinyl-3,6-dioxaheptyl, vinyl-3, 6,9-trioxadecyl, vinyl-1,4-dimethyl-3,6-dioxaheptyl, vinyl-1,4,7-trimethyl-3,6,9-trioxadecyl esters, 1-methox ipropen, 1-ethoxypropene, 1-n-propoxypropene, 1-isopropoxypropene, 1-n-butoxypropene, 1-isobutoxypropene, 1-sec-butoxypropene, 1-tert-butoxypropene, 1-methoxypropene, 2-ethoxypropene, 2-n- propoxypropene, 2-isopropoxypropene, 2-n-butoxypropene, 2-isobutoxypropene, 2-sec-butoxypropene, 2-tert-butoxypropene, 1-methoxy-1-butene, 1-ethoxy-1-butene, 1-n-propoxy- 1-butene, 1-isopropoxy-1-butene, 1-n-butoxy-1-butene, 1-isobutoxy-1-butene, 1-sec-butoxy-1-butene, 1-tert-butoxy-1-butene, 2-methoxy-1-butene, 2-ethoxy-1-butene, 2-n-propoxy-1-butene, 2-isopropoxy-1-butene, 2-n-butoxy-1-butene, 2- zobutoxy-1-butene, 2-sec-butoxy-1-butene, 2-tert-butoxy-1-butene, 2-methoxy-2-butene, 2-ethoxy-2-butene, 2-n-propoxy-2- butene, 2-isopropoxy-2-butene, 2-n-butoxy-2-butene, 2-isobutoxy-2-butene, 2-sec-butoxy-2-butene, 2-tert-butoxy-2-butene, etc. P. These vinyl esters can be obtained in any conventional manner.

 In the method according to the invention, a combination of Bransted acid (aprotic acid), Lewis acid or an organometallic compound and water, alcohol, phenol, acetal or a vinyl ether and carboxylic acid addition product can be used as initiator.

 Examples of aprotic acid are hydrofluoric, hydrochloric, hydrobromic, nitric, sulfuric, trichloroacetic, trifluoroacetic acids and the like. Examples of Lewis acids are boron trifluoride, aluminum trichloride, aluminum tribromide, tin tetrachloride, zinc dichloride, iron chloride (3), and the like. Of these Lewis acids, boron trifluoride and its complexes are particularly preferred. Examples of the organometallic compound are diethylaluminium chloride, ethylaluminium chloride, diethylzinc, etc.

 A suitable compound may be selected from water, alcohol, phenol, acetal, or a vinyl ether adduct with a carboxylic acid and used in combination with aprotic acid (Bransted acid), Lewis acid, or an organometallic compound.

 Examples of the above-mentioned alcohol are saturated aliphatic alcohols having 1-10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, various kinds of pantanol, hexanol and octanol, etc. . alcohols containing oxygen bound as an ether bond, such as ethylene glycol monoalkyl ethers, ethylene glycol monoaryl ethers, propylene glycol monoalkyl ethers, propylene glycol monoaryl ethers, polyethylene glycol monoalkyl ethers, polyethylene glycol monoaryl ethers, polyethylene glycol ethers -2-propanol, 1-ethoxy-3-methoxy-2-propanol, 1,3-diethoxy-2-propanol and the like. and the like compounds. Of these compounds, aliphatic alcohols having 3 or less carbon atoms are preferred, and methanol and ethanol are particularly preferred. As an alcohol containing oxygen bound as an ether bond, compounds of this structure having 14 or less carbon atoms are preferred.

 Examples of phenol are phenol, various types of cresol and the like.

Examples of acetal are acetaldehyde dimethyl acetal, acetaldehyde diethyl acetal, acetaldehyde methyl ethyl acetal, acetaldehyde di-n-propyl acetal, methyl n-propyl acetal, acetaldehyde, acetaldehyde diisopropyl acetal, acetone di-propyl acetaldehyde, methyl isopropyl acetal acetaldehyde, ethyl isopropyl acetal acetaldehyde, acetaldehyde n-butyl acetal, acetaldehyde methyl n-butyl acetal, acetaldehyde ethyl n-butyl acetal, acetaldehyde n-propyl n-butyl acetal, isopropyl n-butyl acetaldehyde acetaldehyde, acetaldehyde diisobutyl acetal, acetaldehyde methyl isobutyl acetal, acetaldehyde ethyl isobutyl acetal, acetaldehyde n-propyl isobutyl acetaldehyde, acetaldehyde acetaldehyde di-sec-butyl acetaldehyde acetaldehyde acetaldehyde acetaldehyde acetaldehyde , isopropyl-sec-butyl acetaldehyde, n-butyl sec-butyl acetaldehyde, isobutyl sec-butyl acetaldehyde, di-tr acetaldehyde t-butyl acetal, acetaldehyde methyl tert-butyl acetate, acetaldehyde ethyl tert-butyl acetal, acetaldehyde n-propyl tert-butyl acetaldehyde, acetaldehyde n-butyl tert-butyl acetaldehyde, isobutyl tert-butyl acetaldehyde , sec-butyl tert-butyl acetaldehyde, di (β-methoxyethyl) acetaldehyde acetal, (β-methoxyisopropyl) acetaldehyde acetal, propionaldehyde dimethyl acetal, propionaldehyde diethyl acetal, propionaldehyde methyl ethyl acetal, propional di-n-propyl acetal dehydide, propionaldehyde methyl-n-propylacetal, propionaldehyde ethyl-n-propylacetal, propionaldehyde diisopropylacetal, propionaldehyde methylisopropylacetal propinaldehyde ethylisopropylacetal propionaldehyde n-propylisopropylacetalide, di-n-butyl-acetaldehyde propionaldehyde , n-propyl-n-butylacetal propionaldehyde, isopropyl-n-butylacetal propionaldehyde, diisobutyl acetal propionaldehyde, methyl isobutyl acetal propionaldehyde, ethyl isobut ilatsetal propionaldehyde, n-propionaldehyde propilizobutilatsetal, izopropilizobutilatsetal propionaldehyde, n-butilizobutilatsetal propionaldehyde di-vtorbutilatsetal propionaldehyde, methyl vtorbutilatsetal propionaldehyde, ethyl vtorbutilatsetal propionaldehyde, n-propyl vtorbutilatsetal propionaldehyde, iso-vtorbutilatsetal propionaldehyde, n -butyl-sec-butylacetal of propionaldehyde, isobutyl-sec-butylacetal of propionaldehyde, di-tert-butylacetal of propionaldehyde, methyl tert-butylacetal propionalalde guide, propionaldehyde ethyl tert-butyl acetal, propionaldehyde n-propyl-tert-butyl acetaldehyde, propionaldehyde isopropyl tert-butyl acetaldehyde, propionaldehyde n-butyl tert-butyl acetaldehyde, propionaldehyde isobutyl tert-butyl acetal, di-tert-butyl acetaldehyde β-methoxyethyl) propionaldehyde acetal, di (β-methoxyisopropyl) propionaldehyde acetal, n-butyraldehyde dimethyl acetal, n-butyraldehyde diethyl acetal, n-butyraldehyde methyl ethyl acetal, n-butyraldehyde di-n-propyl acetal n-butyl acetal n-methyl acetal ide, ethyl-n-propilatsetal n-butyraldehyde, n-butyraldehyde diizopropilatsetal, metilizopropilatsetal n-butyraldehyde, n-butyraldehyde etilizopropilatsetal,
n-butyl aldehyde n-propylisopropylacetal, n-butyraldehyde di-n-butyl acetal, n-butyraldehyde methyl n-butyl acetal, n-butyraldehyde ethyl n-butyl acetal, n-butyl n-butyl acetal n-butyl acetal n-butyl acetal n-butyraldehyde, diisobutyl acetal n-butyraldehyde, methyl isobutyl acetal n-butyraldehyde, ethyl isobutyl acetal and-butyraldehyde, n-propyl isobutyl acetal, n-butyraldehyde, isopropyl-isobutylacetal n-butyraldehyde-butyldehyde-butyldehyde-butylidehyde methyl sec-buti n-butyraldehyde acetal, ethyl-sec-butyl acetal, n-butyraldehyde, n-propyl-sec-butyl acetal n-butyraldehyde, isopropyl sec-butyl acetal n-butyraldehyde, n-butyl sec-butyl acetal n-butyraldehyde, from n-butyraldehyde butyl acetal, n-butyraldehyde di-tert-butyl acetal, n-butyraldehyde methyl tert-butyl acetal, n-butyraldehyde ethyl t-butyl acetal, n-propyl tert-butyl acetal n-butyraldehyde, isopropyl n-butyraldehyde butyraldehyde, n-butyl tert-butyl acetal n-butyraldehyde isobutyl tert-butyl acetal n-butyl aldehyde, sec-butyl tert-butyl acetal, n-butyraldehyde di (β-methoxyethyl) -atsetal n-butyraldehyde di (β -metoksiizopropil) n-butyraldehyde acetal, etc.

 Examples of the carboxylic acid used to form the adduct with vinyl ether are acetic, propionic, n-butyric, isobutyric, n-valerianic, isovalerianic, 2-methylbutyric, trimethylacetic, n-caproic, 2,2-dimethylbutyric, 2-methylvalerianic 3 methylvalerianic, 4-methylvalerianic, enanthic, 2-methylcaproic, caprylic, 2-ethylcaproic, 2-n-propylvalerianic, n-nonanoic, 3,5,5-trimethylcaproic, undecanoic acid, etc.

Vinyl ether may be the same as or used for polymerization, and specific examples are the same compounds that are indicated as examples in the description of vinyl ether monomers expressed by formula (IX). The vinyl ester and carboxylic acid adduct can be obtained by mixing these compounds and carrying out the reaction at a temperature of about 0-100 ^° C. The adduct can be used for the reaction after isolation by distillation or as such without isolation.

 Hydrogen is attached to the initiated end of the polymer chain when water, alcohol or phenol is used, and a group formed by cleavage of one of the alkoxy groups from the acetal used when acetal is used. When using a vinyl ester adduct with a carboxylic acid, a group formed by cleaving an alkyl carboxy group derived from a carboxylic acid from a vinyl ester adduct and a carboxylic acid is attached.

 On the other hand, acetal, olefin or aldehyde is formed at the dangling end of the polymer chain when water, alcohol, phenol or acetal is used. And when a vinyl ester adduct with a carboxylic acid is used, a semi-acetal ester derived from the carboxylic acid is formed. When this hemiacetal ester is hydrolyzed in the presence of an acid, an aldehyde is formed.

The polymerization temperature of the vinyl ester monomer expressed by the formula (IX) is usually in the range of 80-150 ^° C, and preferably 0-100 ^° C, although it can be changed depending on the type of the starting materials and the initiator. The polymerization reaction is concluded in a time of from about 10 seconds to 10 hours.

 To control the molecular weight during the polymerization reaction, it can be reduced by increasing the amount of water, alcohol, phenol, acetal, or the adduct of vinyl ether with a carboxylic acid relative to the amount of vinyl ester monomer expressed by formula (IX), as well as by increasing the amount of Branstead acid or Lewis acid.

 The polymerization can be carried out without a solvent, but a solvent inert under the conditions of the reaction can be used. The type of solvent is not particularly limited. Preferred examples of the solvent are hydrocarbon solvents are hydrocarbon solvents such as hexane, benzene, toluene and the like. and ethereal solvents such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and the like. The polymerization reaction can be completed by adding alkali.

где R¹⁹-R²³ и q - такие же, как указано выше.By the methods described above, polyvinyl ether is prepared having a constituent unit expressed by the formula (X):

where R ¹⁹ -R ²³ and q are the same as described above.

 Of the methods for producing polyvinyl ether, the two methods described below are preferred.

В ацетале формулы (XI), используемом в описанном выше способе, R²⁴, R²⁵ и R²⁶ - каждый - атом водорода или углеводородная группа, имеющая 1-8 атомов углерода, и могут быть одинаковыми или разными. Примерами углеводородной группы являются те же самые группы, которые представлены в качестве примеров при описании радикалов R⁴² и R⁴⁴ в формуле (XXII). R²⁷ и R²⁹ представляют собой каждый двухвалентную углеводородную группу, имеющую 2 - 10 атомов углерода, и могут быть одинаковыми или отличающимися друг от друга. Примерами двухвалентной углеводородной группы являются те же самые группы, что представлены в качестве примеров при описании R⁴⁵ в формуле (XXII). Несколько групп R²⁷O и R²⁹O могут быть соответственно одинаковыми или разными. Далее, r и s каждый - число повторений, среднее значение которого находится в диапазоне 1 - 10, предпочтительно 0 - 5, и могут быть одинаковыми или разными, R²⁸ и R³⁰ каждый - углеводородная группа, имеющая 1 - 10 атомов углерода, и могут быть одинаковыми или разными. Примерами углеводородной группы, имеющей 1 - 10 углеродных атомов, являются те же самые группы, что представлены в качестве примеров при описании R⁴⁶ в формуле (XXII). В качестве R²⁸ особо предпочтительными являются алкильная группа, имеющая 1 - 6 атомов углерода, когда r = 0, и алкильная группа, имеющая 1 - 4 атома углерода, когда r = 1 или более. В качестве R³⁰ особо предпочтительными являются алкильная группа, имеющая 1 - 6 атомов углерода, когда s = 0, и алкильная группа, имеющая 1 - 4 атома углерода, когда s = 1, или более.The first of the preferred methods is a method for the polymerization of a vinyl ester monomer in the presence of a Lewis acid as a catalyst and acetal expressed by the formula (XI):

In the acetal of formula (XI) used in the above method, R ²⁴ , R ²⁵ and R ²⁶ are each a hydrogen atom or a hydrocarbon group having 1-8 carbon atoms, and may be the same or different. Examples of the hydrocarbon group are the same groups that are presented as examples in the description of the radicals R ⁴² and R ⁴⁴ in the formula (XXII). R ²⁷ and R ²⁹ represent each divalent hydrocarbon group having 2 to 10 carbon atoms, and may be the same or different from each other. Examples of a divalent hydrocarbon group are the same groups that are presented as examples in the description of R ⁴⁵ in the formula (XXII). Several groups of R ²⁷ O and R ²⁹ O may be the same or different, respectively. Further, r and s each is the number of repetitions, the average value of which is in the range of 1-10, preferably 0-5, and may be the same or different, R ²⁸ and R ³⁰ each is a hydrocarbon group having 1-10 carbon atoms, and may be the same or different. Examples of a hydrocarbon group having 1 to 10 carbon atoms are the same groups that are presented as examples in the description of R ⁴⁶ in the formula (XXII). As R ²⁸ , an alkyl group having 1 to 6 carbon atoms when r = 0 and an alkyl group having 1 to 4 carbon atoms when r = 1 or more are particularly preferred. As R ³⁰ , an alkyl group having 1 to 6 carbon atoms when s = 0 and an alkyl group having 1 to 4 carbon atoms when s = 1 or more are particularly preferred.

 Examples of acetal expressed by formula (XI) are the same compounds that are presented as examples in the above description of acetals.

где R¹⁹-R²³, R³¹, R³², q и t - такие же, как указанные выше, путем добавления винилэфирного мономера, выраженного формулой (IX), к спирту, выраженному формулой (XII):
R³² (OR³¹)_tOH (XII)
в присутствии кислоты Льюиса в качестве катализатора, после чего к ацеталю добавляют еще винилэфирный мономер, выраженный формулой (IX), и полимеризуют.A second preferred method is a method in which an acetal having the formula (XIII) is prepared:

where R ¹⁹ -R ²³ , R ³¹ , R ³² , q and t are the same as above by adding the vinyl ester monomer expressed by formula (IX) to the alcohol expressed by formula (XII):
R ³² (OR ³¹ ) _t OH (XII)
in the presence of a Lewis acid as a catalyst, after which another vinyl ester monomer of the formula (IX) is added to the acetal and polymerized.

In the alcohol expressed by the formula (XII), R ³¹ is a divalent hydrocarbon group having 2 to 10 carbon atoms, examples of which are the same groups that are presented as examples when describing the radical R ⁴⁵ in the formula (XXII) Several R ³¹ O groups may be the same or different. Further, t is the number of repetitions, the average value of which is in the range 0 - 10, and preferably in the range 0 - 5. R ³² is a hydrocarbon group having 1 to 10 carbon atoms, examples of which are the same groups that are presented as examples when describing R ⁴⁶ in the formula (XXII). As R ³² , an alkyl group having 1 to 6 carbon atoms when t = 0 and an alkyl group having 1 to 4 carbon atoms when t = 1 or more are particularly preferred.

 Examples of the alcohol expressed by the formula (XII) are the same alcohols that are presented as examples in the description of the alcohols mentioned above.

 Examples of the Lewis acid used as a catalyst in the first and second preferred methods are the same acids that are presented as examples in the above description of the Lewis acids used as a catalyst. Of these compounds, boron trifluoride and its complexes are particularly preferred.

The polymerization of the vinyl ester monomer in the first and second preferred methods can be carried out at a temperature usually in the range of - 80 - +150 ^o C, and preferably in the range of 0 - 100 ^o C, but it can be changed depending on the type of starting materials and initiator. When using acetal, heat is generated from polymerization without an induction period, and when using alcohol, heat is released from polymerization without an induction period after the formation of acetal. Thus, temperature control during the reaction can be easily done by adding a vinyl ester monomer at a rate that balances the ability of the apparatus to generate heat. The polymerization is usually completed after a period of time from 10 seconds to 10 hours after the start of the reaction.

 After the polymerization is carried out as described above, the desired polyvinyl ether can be obtained by separation and purification by any conventional method as required.

В формуле (XIV) R³³ и R³⁴ каждый - углеводородная группа, такая, как метильная, этильная, н-пропильная, изопропильная, группы и т.п. или углеводородная группа: содержащая атомы эфирного кислорода в основной цепи, в боковой цепи или и в той, и в другой цепях, такая, как группы, выраженные формулами:

где R - углеводородная группа, имеющая 1 - 10 атомов углерода, и W - целое число от 1 до 500. R³³ и R³⁴ могут быть одинаковыми или разными. R³⁵, R³⁶ и R³⁷ каждый - атом водорода, углеводородная группа или углеводородная группа, содержащая атомы эфирного кислорода в основной, боковой или той и другой цепях. Примерами углеводородной группы или углеводородной группы, содержащей атомы эфирного кислорода, являются те же самые группы, что указаны в качестве примеров при описании радикалов R³³ и R³⁴, группы, выраженные формулой:

где R - углеводородная группа, имеющая 1 - 10 атомов углерода, и W - целое число от 1 до 500, и тому подобные группы,
R³⁵, R³⁶ и R³⁷ могут быть одинаковыми или отличающимися друг от друга.In the method for producing ether, an acetal or a ketal of formula (XIV) is used as a starting material:

In the formula (XIV), R ³³ and R ^{34 are} each a hydrocarbon group, such as methyl, ethyl, n-propyl, isopropyl, groups and the like. or a hydrocarbon group: containing ether oxygen atoms in the main chain, in the side chain, or in both chains, such as groups expressed by the formulas:

where R is a hydrocarbon group having 1 to 10 carbon atoms, and W is an integer from 1 to 500. R ³³ and R ³⁴ may be the same or different. R ³⁵ , R ³⁶ and R ³⁷ each is a hydrogen atom, a hydrocarbon group or a hydrocarbon group containing ether oxygen atoms in the main, side or one and the other chains. Examples of a hydrocarbon group or a hydrocarbon group containing ether oxygen atoms are the same groups that are indicated as examples when describing the radicals R ³³ and R ³⁴ , groups expressed by the formula:

where R is a hydrocarbon group having 1 to 10 carbon atoms, and W is an integer from 1 to 500, and the like groups,
R ³⁵ , R ³⁶ and R ³⁷ may be the same or different from each other.

или

где R³³, R³⁴, R³⁵, R³⁶ и R³⁷ - такие же, как указанные выше, получают путем проведения реакции между ацеталем или кеталем, выраженными формулой (XIV) и водородом в присутствии твердого катализатора, обладающего кислотными свойствами и гидрирующей способностью.In accordance with the present invention, an ether expressed by the formula (XV):

or

where R ³³ , R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are the same as those described above, obtained by reaction between acetal or ketal expressed by formula (XIV) and hydrogen in the presence of a solid catalyst having acidic properties and hydrogenation ability .

где R³⁸ и R³⁹ каждый - углеводородная группа, имеющая 1-20 атомов углерода, или углеводородная группа, содержащая атомы кислорода простого эфира и могут быть одинаковыми или разными, R³⁸ - одинаковый с составляющими звеньями или отличающийся от них и - целое число от 1 до 500. В данном случае получают в качестве упомянутого простого эфира соединение, выраженное формулой (XVIII):

где R³⁸, R³⁹ и U - такие же, как указанные выше.As acetal or ketal of formula (XIV), a compound expressed by formula (XVII) is preferred:

where R ³⁸ and R ³⁹ each is a hydrocarbon group having 1-20 carbon atoms, or a hydrocarbon group containing ether oxygen atoms and can be the same or different, R ³⁸ is the same with or different from the constituent units and is an integer from 1 to 500. In this case, a compound expressed by the formula (XVIII) is obtained as said ether:

where R ³⁸ , R ³⁹ and U are the same as above.

где R³⁸ и U - такие же, как указанные выше, и в данном случае полученным соединением является соединение, выраженное описанной выше формулой (XVIII), или смесь соединения, выраженного формулой (XVIII), и соединения, выраженного формулой (XIX).In the compound expressed by formula (XVII), sometimes contains a compound expressed by formula: (XXVII):

where R ³⁸ and U are the same as above, and in this case, the obtained compound is a compound expressed by the above formula (XVIII), or a mixture of a compound expressed by the formula (XVIII) and a compound expressed by the formula (XIX).

As the acetal and ketal expressed by the formula (XIV), it is also good to use the compound expressed by the formula (XX):
R ⁴⁰ CH (OR ⁴¹ ) ₂ (XX)
where R ⁴⁰ and R ⁴¹ each is a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different. In this case, as a simple ether get the compound expressed by formula (XXI):
R ⁴⁰ CH ₂ OR ⁴¹ (XXI),
where R ⁴⁰ and R ⁴¹ are the same as above.

 The process according to the invention uses a solid catalyst having acidic properties and hydrogenating ability. As a solid catalyst having acidic properties and a hydrogenating ability, a combination of two types of catalyst is used, which are a hydrogenation catalyst and a solid acid catalyst, or a solid acid catalyst having a hydrogenating ability.

 The hydrogenation catalyst is not particularly limited, and various types of commonly used hydrogenation catalyst can be used. Examples of a particularly effective catalyst are (1) metals, such as nickel, palladium, rhodium and ruthenium in the singular or as a main component, (2) a catalyst having as a component a metal catalyst from group (1) supported on activated carbon , alumina, diatomaceous earth (kieselguhr) or the like. and (3) Raney catalysts: such as Raney nickel and Raney cobalt.

 The solid acid catalyst is not particularly limited, and various types of commonly used solid acid catalyst can be used. For example, activated clay, acid clay, various types of zeolite, ion exchange resins, silica, alumina and heteropoly acids are particularly effective.

 The solid acid catalyst having a hydrogenating ability is not particularly limited, and various kinds of commonly used solid acid catalyst having a hydrogenating ability can be used. For example, catalysts are particularly effective in which nickel, palladium, platinum, ruthenium or the like are coated on various types of zeolite.

 The following amounts of catalyst are preferably used to carry out the process of the present invention. When using a combined catalyst, the amount of hydrogenation catalyst is 0.1 to 50 wt.% And the amount of solid catalyst is 0.1 to 50 wt. % of the amount of reacting materials, respectively. When using a solid acid catalyst having a hydrogenating ability, its amount is 0.1 to 50 wt.% Of the amount of reacting materials. When the amount is less than 0.1 wt.%, The reaction time is insufficient, and when the amount exceeds 50 wt.%, An excessively large amount of catalyst with respect to the reacting materials causes a problem in reducing productivity.

 In accordance with the present invention, acetal or ketal of formula (XIV) is reacted with hydrogen in the presence of the catalyst described above. It is preferred that hydrogen gas and acetal or ketal are brought into contact with each other in a molar ratio of 1:10 to 200: 1. When the molar ratio is less than the value in the indicated range, the reaction time is insufficient, and when it exceeds the values in the indicated range, the problem of reducing productivity arises.

The preferred reaction conditions carried out in accordance with the method of the present invention are the following: the reaction temperature is 10 - 250 ^o C, the partial pressure of hydrogen is 1 - 200 kg / cm ² the reaction time in the case of a periodic reaction is 0.1 to 10 hours , and in the case of a flow system, the hourly space-mass velocity (WHSV) of the reacting liquid is 0.01 to 100 / hour, and the hourly space velocity (GHSV) of hydrogen gas is 100 to 10000 / hour.

 The reaction can be carried out without a solvent, but a solvent can be used provided that it is stable under the reaction conditions. Examples of suitable solvents are hydrocarbon solvents such as hexane, pentane and octane.

By the reaction described above, the formula (XIV) of the group - OR ³³ or - OR ^{34 is} cleaved from the acetal or ketal and replaced with hydrogen, thereby forming an ether expressed by the formula (XV) or the formula (XVI). This reaction clearly shows that even when any of the radicals R ³³ -R ³⁷ represents a hydrocarbon group containing ether oxygen atoms, hydrogen does not react with ether oxygen, but only with oxygen in the part of acetal or ketal.

 After completion, the reaction product can be separated from the catalyst by conventional filtration or decantation. The separated catalyst can be used again without much processing.

 The reaction product can be isolated by methods such as distillation, extraction, washing and drying, if necessary.

 A new compound, polyvinyl ether, is described below as a second object of the present invention.

 In accordance with the present invention, two types of compounds are provided as the new polyvinyl ether.

 The first of the new compounds contains a homopolymer or copolymer of a simple vinyl vinyl ether having an alkyl group with 1-3 carbon atoms. It is necessary that the weight average molecular weight of the polymer is in the range of 300 to 1200, and preferably in the range of 400 to 1000. The ratio of the weight average molecular weight to number average molecular weight is usually in the range of 1.05 - 1.50, and preferably in the range of 1.06 - 1.40.

 The polyvinyl ether in accordance with the present invention can be obtained by polymerization of the corresponding monomer - simple vinyl ether. Examples of the vinyl ester monomer are vinyl methyl, vinyl ethyl, vinyl n-propyl, vinyl isopropyl ethers, 1-methoxy1-propene, 1-ethoxy-1-propene and 1-propoxy-1-propene. The vinyl ester monomer may be used singularly or as a combination of two or more kinds.

 As a method for polymerizing a vinyl ether monomer, a method for producing a polyvinyl ether can be carried out, which is an object of the present invention. In accordance with this method, the polyvinyl ether of the present invention is prepared by polymerizing a vinyl ester monomer using a combination of aprotic acid, Lewis acid or an organometallic compound with alcohol or acetal as an initiator. Suitable aprotic acid, Lewis acid, organometallic compound and acetal are the compounds shown as examples in the description of the method for producing polyvinyl ether in accordance with the second objective of the present invention.

 Examples of the alcohol are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, various types of pentanol and hexanol, etc. Of these compounds, alcohols having 3 or less carbon atoms are preferred. In particular, methanol and ethanol are preferred.

где R¹ - алкильная группа, имеющая 1-3 атома углерода, причем одна концевая группа имеет структуру, выраженную формулой (II):

или формулой (III)
-CH=CHOR^a
где R¹ - такой же, как указанный выше, R² - углеводородная группа, имеющая 1-8 атомов углерода, и R^a - любой из радикалов R¹ и R².Thus obtained polyvinyl ether in accordance with the present invention contains a homopolymer or copolymer of alkyl vinyl ether containing one or more kinds of constituent units, expressed by the formula (I) or (I '):

where R ¹ is an alkyl group having 1-3 carbon atoms, and one end group has a structure expressed by formula (II):

or formula (III)
-CH = CHOR ^a
where R ¹ is the same as above, R ² is a hydrocarbon group having 1-8 carbon atoms, and R ^a is any of the radicals R ¹ and R ² .

In formula (II), R ^{2 is} derived from a residual group formed by cleavage of a hydroxyl group from an alcohol, or from a residual group formed by cleavage of an oxygen atom from an alkoxy group in acetal, which, like alcohol, is used to initiate polymerization.

 When using alcohol, hydrogen is attached to the initiated end of the polymer chain, and when using acetal, the residual group formed by cleavage of one of the alkoxy groups from acetal. An acetal group expressed by the above formula (II) or an olefin group expressed by the above formula (III) is attached to the dangling end.

 The alkyl vinyl ether homopolymer or copolymer may contain a dangling end group expressed solely by formula (II), only formula (III), or having a structure mixed from the two.

The polymerization can be carried out at a temperature in the range of - 80 - 150 ^o C, preferably 0 - 100 ^o C, and it can be changed depending on the type of starting materials and initiator. The polymerization reaction is usually completed after a period of time from 10 seconds to 10 hours after the start of the reaction.

 To control the molecular weight during the polymerization reaction, the molecular weight of the polymer is reduced by increasing the amount of alcohol or acetal.

 The polymerization can be carried out without a solvent, but a solvent can be used if it is stable under the reaction conditions. The solvent is not particularly limited. Preferred examples of the solvent are hydrocarbon solvents such as hexane, benzene, and toluene and ether solvents such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran. The polymerization reaction can be completed by adding alkali.

В представленной выше формуле (IV) R³, R⁴ и R⁵ каждый представляет собой атом водорода или алкильную группу, имеющую 1-4 атома углерода. Примерами алкильной группы являются метильная, этильная, н-пропильная, изопропильная, н-бутильная, изобутильная, втор-бутильная и трет-бутильная группы, R³, R⁴ и R⁵ могут быть одинаковыми или разными. Из водорода и указанных выше групп предпочтительными являются водород и метильная и этильная группы, причем является предпочтительным, чтобы по крайней мере один из радикалов R³, R⁴ и R⁵ был атомом водорода.The second polyvinyl ether in accordance with the present invention contains constituent units expressed by formula (I):

In the above formula (IV), R ³ , R ⁴ and R ⁵ each represents a hydrogen atom or an alkyl group having 1-4 carbon atoms. Examples of the alkyl group are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups, R ³ , R ⁴ and R ⁵ may be the same or different. Of the hydrogen and the above groups, hydrogen and methyl and ethyl groups are preferred, with it being preferred that at least one of the radicals R ³ , R ⁴ and R ⁵ be a hydrogen atom.

R ⁶ in the formula (IV) is an alkylene group having 2-4 carbon atoms, and more specifically, an ethylene, trimethylene, methylene, tetramethylene, 1,1-dimethylethylene or 1,2-dimethylethylene group. Of these, alkylene groups having 2 or 3 carbon atoms are particularly preferred. In formula (IV), k is the number of repetitions of the group R ⁶ O, the average value of which is in the range of 0-10, and preferably 0-5.

R ⁷ in the formula (IV) is an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group are alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl group, various kinds of pentyl, hexyl and octyl groups, cycloalkyl groups, such as cyclopentyl, cyclohexyl groups, various types of methylcyclohexyl, ethylcyclohexyl, and dimethylcyclohexyl groups, and the like. groups. Of these, alkyl groups having 8 or less carbon atoms are preferred. When k = 0, alkyl groups having 1-6 carbon atoms are particularly preferred, and when k = 1 or more, alkyl groups having 1-4 carbon atoms are particularly preferred.

R ³ -R ⁷ may be the same or different in the series of constituent units, and when the constituent unit contains several R ⁶ O groups, they may be the same or different from each other.

где R⁸, R⁹ и R¹⁰ каждый - атом водорода или алкильная группа, имеющая 1-4 атома углерода, и могут быть одинаковыми или разными, R¹¹ - алкиленовая группа, имеющая 2-4 атома углерода, R¹² - алкильная группа, имеющая 1-10 атомов углерода, m - число, среднее значение которого находится в диапазоне 0-10, и несколько групп R¹¹O могут быть одинаковыми или разными, а другой конец цепи выражен формулой (VI):

где R¹³, R¹⁴ и R¹⁵ каждый - атом водорода или алкильная группа, имеющая 1-4 атома углерода, и могут быть одинаковыми или разными, R¹⁶ - алкильная группа, имеющая 2-4 атома углерода, R¹⁷ - алкильная группа, имеющая 1-10 атомов углерода, n - число, среднее значение которого находится в диапазоне 0-10, и несколько групп R¹⁶O могут быть одинаковыми или отличающимися друг от друга.It is necessary that the polyvinyl ether in accordance with the present invention does not contain an unsaturated bond and acetal and aldehyde structures in the molecule. Polyvinyl ether usually has a structure in which one end of the chain is expressed by formula (V):

where R ⁸ , R ⁹ and R ¹⁰ each is a hydrogen atom or an alkyl group having 1-4 carbon atoms, and may be the same or different, R ¹¹ is an alkylene group having 2-4 carbon atoms, R ¹² is an alkyl group, having 1-10 carbon atoms, m is a number whose average value is in the range of 0-10, and several R ¹¹ O groups can be the same or different, and the other end of the chain is expressed by formula (VI):

where R ¹³ , R ¹⁴ and R ¹⁵ each is a hydrogen atom or an alkyl group having 1-4 carbon atoms, and may be the same or different, R ¹⁶ is an alkyl group having 2-4 carbon atoms, R ¹⁷ is an alkyl group, having 1-10 carbon atoms, n is a number whose average value is in the range 0-10, and several R ¹⁶ O groups may be the same or different from each other.

In the above formula (V), R ⁸ , R ⁹ and R ^{10 are} each a hydrogen atom or an alkyl group having 1-4 carbon atoms. Examples of the alkyl group are the same groups that are presented as examples in the description of the radicals R ³ -R ⁵ in the formula (IV). R ⁸ , R ⁹ and R ¹⁰ may be the same or different. Of these, a hydrogen atom and methyl and ethyl groups are preferred, and it is preferred that at least one of the radicals R ⁸ , R ⁹ and R ¹⁰ be a hydrogen atom.

R ¹¹ in the formula (V) is an alkylene group having 2-4 carbon atoms. Examples of alkylene groups are the same groups that are presented as examples in the description of R ⁶ in the formula (IV). Of these, alkylene groups having 2 or 3 carbon atoms are particularly preferred. In the formula (V), m is the number of repetitions of the group R ¹¹ O, the average value of which is in the range of 0-10, and preferably 0-5. In the presence of several R ¹¹ O groups, they may be the same or different.

R ¹² in the formula (V) is an alkyl group having 1-10 carbon atoms. Examples of the alkyl group are the same groups that are presented as examples in the description of R ⁷ in the formula (IV). Of these, alkyl groups having 8 or less carbon atoms are preferred. When m = 0, alkyl groups having 1-6 carbon atoms are particularly preferred, and when m = 1 or more, alkyl groups having 1-4 carbon atoms are especially significant.

In the above formula (VI), R ¹³ , R ¹⁴ and R ¹⁵ each represents a hydrogen atom or an alkyl group having 1-4 carbon atoms. Examples of the alkyl group are the same groups that are presented as examples in the description of R ³ -R ⁵ in the formula (IV), R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different. Of these, hydrogen atoms and methyl and ethyl groups are preferred, with at least one of the radicals R ¹³ , R ¹⁴ and R ¹⁵ being a hydrogen atom.

R ¹⁶ in the formula (VI) represents an alkylene group having 2-4 carbon atoms. Examples of alkylene groups are the same groups that are presented as examples in the description of R ⁶ in the formula (IV). Of these, alkylene groups having 2 or 3 carbon atoms are particularly preferred. In formula (VI), n is the number of repetitions of the group R ¹⁶ O, the average value of which is in the range of 0-10, and preferably 0-5. In the presence of several R ¹⁶ O groups, they may be the same or different.

R ¹⁷ in the formula (VI) represents an alkyl group having 1-10 carbon atoms. Examples of the alkyl group are the same groups that are presented as examples in the description of R ⁷ in the formula (IV). Of these, alkyl groups having 8 or less carbon atoms are preferred. When n = 0, alkyl groups having 1-6 carbon atoms are particularly preferred, and when n = 1 or more, alkyl groups having 1-4 carbon atoms are particularly preferred.

 The polyvinyl ether in accordance with the present invention has a weight average molecular weight in the range of 300-3000, preferably 400-2000, and more preferably 400-1000, and the degree of polymerization is preferably in the range of 5-10. The ratio of the weight average molecular weight to number average molecular weight is in the range of 1.05-2.00, and 1.06-1.90 is preferred.

где R¹⁸ - алкильная группа, имеющая 1-4 атома углерода, и может быть одинаковым с остальными составляющими звеньями или отличающимися от них, не содержит ненасыщенной связи и ацетальной и альдегидной структур и имеет среднемассовую молекулярную массу в диапазоне 300-3000. Из них предпочтительными являются соединения, имеющие составляющие звенья, выраженные формулой (VIII):

где R¹⁸ - такой, указанный выше, и p - степень полимеризации, и среднемассовую молекулярную массу в диапазоне 300-3000, предпочтительно 400-1000.Preferred compounds in the series of polyvinyl esters in accordance with the present invention are compounds that have constituent units expressed by formula (VII):

where R ¹⁸ is an alkyl group having 1-4 carbon atoms, and may be the same with the other constituent units or different from them, does not contain an unsaturated bond and acetal and aldehyde structures and has a weight average molecular weight in the range of 300-3000. Of these, preferred are compounds having constituent units expressed by formula (VIII):

where R ¹⁸ is the one indicated above and p is the degree of polymerization and the weight average molecular weight in the range of 300-3000, preferably 400-1000.

 The polyvinyl ether in accordance with the present invention can be obtained (a) by polymerizing a suitable vinyl ester monomer and (b) by treating olefins, acetals and aldehydes in a polymerization product.

(a) Polymerization Method
As the polymerization method, a method for producing a polyvinyl ether can be carried out, which is the second objective of the present invention described above.

(b) Processing Method
In this method, unsaturated bonds, acetals and aldehydes in the polymerization product are converted to saturated bonds and ethers.

(1) Unsaturated bonds
Unsaturated bonds formed at the end of the polymer chain by polymerization can be converted to saturated bonds under traditional conditions, such as a reaction temperature of 20-200 ^° C, a hydrogen pressure of 1-100 kg / cm ² , and in the presence of a hydrogenation catalyst. As the hydrogenation catalyst, platinum, rhodium, ruthenium, nickel, cobalt catalysts and the like are preferred.

(2) Aldehydes
Aldehydes formed by the hydrolysis of acetals or esters derived from carboxylic acids and semi-acetals can be converted to alcohols via a hydrogenation reaction and then further converted to ethers via Williamson synthesis. In particular, plate, palladium, ruthenium and nickel catalysts are particularly preferred as the hydrogenation catalyst, and the reaction can be carried out at a temperature of 20-200 ^° C and a hydrogen pressure of 1-100 kg / cm ² . The ether conversion reaction is usually carried out by a process in which a hydroxyl group is reacted with an alkali metal such as sodium metal, an alkali metal hydride such as sodium hydride, an alkali metal hydroxide such as sodium hydroxide or derived from a lower alcohol with an alkali metal salt such as sodium methoxide to obtain an alkali metal salt of the polymerization product, after which the product is reacted with halogenated or sulfonic acid ester, respectively having 1-10 carbon atoms, or a method in which the hydroxyl group in the polymerization product is converted to sulfonic acid esters or halides, after which the product is reacted with an aliphatic alcohol having 1-10 carbon atoms or an alkali metal salt thereof.

(3) Acetal
The acetal formed at the end of the polymerization chain forms, by reaction with water in the presence of an acid catalyst, such as hydrochloric acid, sulfuric acid and sulfonic acid, aldehydes, which can be converted into ethers by the methods described above. Examples of the method for directly converting acetals to ethers are a method using LiAlH ₄ -BF ₃ , LiAlH ₄ -AlCl ₃ , B ₂ H ₆ , NaB (CN) H ₃ -HCl or (CH ₃ O) AlH ₂ , a method using silicon reagents and the like, which are described in Jikken Kagaku Koza, 4th edition, volume 20, p. 202 (published by Maruzen), and a method for carrying out a reaction in a hydrogen medium in the presence of a catalytic system in the form of a combination of platinum oxide and hydrochloric acid, which (method) is described in Jan T. Karrison and Shuyen Harrison, Compendium of Organic Synthetic Methods, p. 317 (1971).

 In addition, acetals can be effectively converted to ethers by the ether preparation process, which is the third objective of the present invention and includes hydrogenation in the presence of a solid catalyst having acidic properties and hydrogenating ability. Solid catalysts and reaction conditions described in connection with the preparation of an ether can be used as a solid catalyst having acidic and hydrogenating properties and reaction conditions used for the reaction.

 Lubricating oil for compression refrigerators in accordance with the present invention has excellent refrigerant compatibility, stability, electrical insulating ability and lubricating properties. Therefore, it is particularly suitable as a lubricating oil for compression refrigerators in which flon-134a is used as a refrigerant.

 By the method for producing polyvinyl ether in accordance with the present invention, it is possible, using simple processes, to reliably, safely, efficiently and industrially obtain polyvinyl ether with the degree of polymerization required therein, having a wide range of applications, for example, as a solvent, lubricating oil, adhesive or resin .

 By the method of producing ether, ether can be obtained from acetal or ketal with a high degree of conversion and high selectivity, and since there is no corrosion problem, equipment used for conventional production can be used. According to the method of the present invention, only acetals and ketals are hydrogenated, and even when the starting acetal or ketal contains hydrocarbon groups having ether oxygen atoms, part of the ether oxygen remains intact and the acetal bond is converted to a simple ether bond.

Further, the polyvinyl ether in accordance with the present invention contains a homopolymer or copolymer of a simple vinyl vinyl ether having an alkyl group with 1-3 carbon atoms, and has a relatively low molecular weight and narrower distribution thereof, and the homopolymer or copolymer of vinyl monomer does not have in the molecule neither unsaturated bonds, nor acetal and aldehyde structures. Polyvinyl ether has excellent compatibility, in particular with hydrogen-containing flons, such as flon-134a, excellent stability and lubricating properties, and a volumetric intrinsic electrical resistance at 80 ^° C. of 10 ¹² Ω · cm or more and is very suitable for use in as lubricating oil for compressors.

 Polyvinyl ether is also suitable for use as an electrically insulating agent, an organic solvent, a surfactant, and the like.

 Further, the present invention is described in more detail with reference to examples. However, the invention is not limited to the described examples.

 Methods for measuring kinematic viscosity, average molecular weight, compatibility with flon, and intrinsic volumetric electrical resistance and a test method for hydrolysis of polyvinyl ether are described below.

(1) Kinematic viscosity
Kinematic viscosity was measured in accordance with the method of Japanese industrial standard K-2283 (1983) using a glass capillary viscometer.

(2) Average molecular weight (examples 8-25 and 25A)
Using the device and the conditions described below, the mass average and number average molecular weights were measured and the dispersion (the ratio of the mass average molecular weight to the number average molecular weight) was determined from the measurement results
Device: product "Nippon Banco Kogio Co., Ltd." 880-PU (pump)
Shodeks RI SE-61 (detector)
Column: TSK H8 + G 2000 H8 + G 1000 H8
Temperature: room
Solvent: THF (tetrahydrofuran)
Elution Rate: 1.4 ml / min
Standard substance: polyethylene glycol
(3) Compatibility Test
(a) flon-134a.

The sample was loaded into a pressure-resistant glass ampoule in a predetermined amount, set to be 5 wt.% Or 10 wt.% From -134a flon (1,1,1,2-tetrafluoroethane), and the ampoule was connected to a vacuum line and with the line for gaseous flon-134a. The ampoule was degassed in vacuo at room temperature, cooled with liquid nitrogen, and then a predetermined amount of flon-134 was introduced into it. After this, the ampoule was sealed and the temperature of the onset of phase separation was measured as follows. To measure compatibility at low temperatures, the sample was slowly cooled to room temperature to -60 ^o C in a thermostat, and to measure compatibility at high temperatures, the sample was slowly heated from room temperature to +80 ^o C. It is preferred that the phase separation temperature be lower at low temperatures, but higher in high temperatures.

(b) Flon-32
The sample was loaded into a pressure-resistant glass ampoule in a predetermined amount, set so that it was 10 wt.% Or 20 wt.% Of flon-32 (difluoromethane), and the ampoule was connected to a vacuum line and to a line of gaseous flon-32. The ampoule was degassed in vacuo at room temperature, cooled with liquid nitrogen, and then a predetermined amount of flon-32 was introduced into it. After this, the ampoule was sealed and the temperature of the onset of phase separation was measured as follows. To measure compatibility at low temperatures, the sample was slowly cooled to room temperature in a thermostat, and to measure compatibility at high temperatures, the sample was slowly heated from room temperature to +40 ^o C. It is preferable that the phase separation temperature be lower at low temperatures, but higher at high temperatures.

(4) Volume intrinsic electrical resistance
The sample was dried under reduced pressure (0.3-0.8 mm Hg) at 100 ^o C for 1 hour and then immersed in a vessel for measuring the volumetric intrinsic resistance of the liquid, which was placed in a thermostat at 80 ^o C. After holding the sample in a thermostat at 80 ^o C for 40 minutes, the volumetric intrinsic resistance was measured at an applied voltage of 250 V using an ultrahigh specific resistance meter of type P8340 (trademark) manufactured by f. Advantest Co.

(5) Hydrolysis Test
75 g of a sample of 25 g of water and a piece of copper (13 x 50 mm) were placed in a pressure-resistant flask with a capacity of 250 ml and the medium in the flask was replaced with nitrogen. The sample was kept in a rotating thermostat at a temperature of 102 ^o C for 192 hours. After completion of the test, the appearance of the sample and the condition of the piece of copper were visually examined, and the total acid number was measured.

Preparation Example 1
100 g (with water) of Raney Nickel (M300T, manufactured by Kawaken Fine Chemical Co., Ltd.) was charged into a flask and 100 g of absolute ethanol was added to it with sufficient stirring. The mixture was sedimented to precipitate Raney nickel, after which the supernatant was removed by decantation. The remaining Raney nickel in the flask was treated as described above, another 5 times. Obtained in this preparation example, Raney nickel was used in the examples, moistened with ethanol.

Preparation Example 2
20 g of zeolite (HSZ330HUA, manufactured by Toso Co., Ltd.) were placed in a pear-shaped flask with a capacity of 100 ml, then the flask was immersed in an oil bath at 150 ^° C and air was pumped out of it by means of an oil rotary vacuum pump for 1 hour. At room temperature, atmospheric pressure was restored in the flask by introducing dry nitrogen.The zeolites used in the examples are those obtained in this preparation example.

Preparation Example 3
20 g of activated clay (product of Wako jan-yaku Co., Ltd.) was placed in a 100 ml pear-shaped flask. The flask was then immersed in an oil bath at 150 ^° C and air was pumped out of it by means of an oil rotary vacuum pump for 1 hour. After cooling to room temperature, atmospheric pressure was restored in the flask by introducing dry nitrogen.The activated clays used in the examples are those obtained in this preparation example.

Example 1
In a 5 liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer, 600 g of ethyl vinyl ether, 72 g of methanol and 2400 g of hexane were charged and cooled with water with stirring. When the temperature reached 5 ^° C., a solution prepared by dissolving 3.6 g of boron trifluoride diethyl etherate in 20 g of tetrahydrofuran was added, and the mixture was stirred for 1 hour. During this period, the reaction began and the temperature of the reaction liquid increased, and the reverse flow of ethyl vinyl ether in the refrigerator was observed. The reaction mixture was transferred to a washing vessel and washed with 1500 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times, and then 1500 ml of water 3 times. The product was concentrated using a rotary evaporator and dried under reduced pressure (0.2 mm Hg) at 50 ^° C. for 1 hour, resulting in 468 g of a crude (crude) product.

400 g of a crude product obtained as described above, 500 g of acetone, 800 g of water and 10 g of concentrated hydrochloric acid (35 wt.%) Were charged into a 5-liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer, and the mixture was stirred at 50-60 ^o C for 3 hours. After neutralization of hydrochloric acid with sodium bicarbonate, acetone and the like were removed. under reduced pressure using a rotary evaporator and the remaining product was poured into 400 ml of hexane. After removal of the aqueous phase, the product was washed with 400 ml of water once. The hexane phase was transferred to an autoclave and hydrogenated using 0.8 g of platinum oxide as a catalyst at a hydrogen pressure of 20 kg / cm ² and 50 ^° C. for 1 hour. After removing platinum oxide by filtration, the product was transferred to a 2 liter glass flask, 40 g of methanol and 8 g of sodium borohydride were added and stirred for 1 hour at room temperature. The product was slightly acidified with an aqueous solution of acetic acid, after which the acetic acid was neutralized with sodium bicarbonate. The product was washed once with 400 ml of water and the solvent and water were removed under reduced pressure using a rotary evaporator.

 The resulting residual product was dissolved in 300 ml of tetrahydrofuran and reacted with 12 g of sodium hydride for 1 hour. During this reaction, evolution of hydrogen gas was observed. Then, 120 g of methyl iodide was added dropwise to the reaction mixture over 30 minutes. During this period, heat was observed. After dropwise addition of methyl iodide, the reaction mixture was stirred for another 1 hour. Using a rotary evaporator, the solvent and unreacted materials were removed under reduced pressure. The residue was transferred to a 2 liter washing vessel and, after dissolving in 400 ml of hexane, washed with 400 ml of water 5 times. Then, adding 40 g of ion exchange resin, the product was stirred for 3 hours. The ion-exchange resin was removed from the product by filtration and hexane under reduced pressure by means of a rotary evaporator. The yield of polyvinyl ether obtained in the manner described was 200 g.

Были измерены кинематическая вязкость, совместимость с флоном, объемное собственное электрическое сопротивление и стойкость к гидролизу полимера простого этилвинилового эфира.A nuclear magnetic resonance spectrum (hereinafter referred to as NMR) and an infrared spectrum (hereinafter referred to as IR) of the product were obtained, which confirmed that one of the terminal structures of the polymer was structure (A) and the other (B):

Kinematic viscosity, flon compatibility, intrinsic electrical resistance, and hydrolysis resistance of the ethyl vinyl ether polymer were measured.

 The results are shown in table. 1 (see end of description).

Example 2
600 g of ethyl vinyl ether, 60 g of methanol and 2400 g of hexane were charged into a 5-liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer, and cooled with stirring with water. When the temperature reached 5 ^° C., a solution prepared by dissolving 3.6 g of boron trifluoride diethyl etherate in 20 g of tetrahydrofuran was added, and the mixture was stirred for 1 hour. During this period, the reaction began and the reaction temperature increased, and in the refrigerator, the reverse flow of ethyl vinyl ether was observed. The reaction mixture was transferred to a washing vessel and washed with 1500 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times, and then 1500 ml of water 3 times. The product was concentrated using a rotary evaporator and dried under reduced pressure (0.2 mm Hg) at 50 ^° C. for 1 hour, resulting in 452 g of a crude product.

400 g of the crude product obtained as described above, 500 g of acetone, 800 g and 10 g of concentrated hydrochloric acid (35 wt.%) Were charged into a 5-liter glass flask equipped with a dropping funnel, refrigerator and stirrer and stirred at 50 -60 ^o C for 3 hours. After neutralization of hydrochloric acid with sodium bicarbonate, acetone and the like were removed under reduced pressure using a rotary evaporator, and the remaining product was poured into 400 ml of hexane. After removal of the aqueous phase, the product was washed once with 400 ml of water. The hexane phase was transferred to an autoclave and hydrogenated using 0.8 g of platinum oxide as a catalyst at a hydrogen pressure of 20 kg / cm ² and 50 ^° C. for 1 hour. After removal of the platinum oxide catalyst by filtration, the product was transferred to a 2 liter glass flask, 40 g of methanol and 8 g of sodium borohydride were added and stirred for 1 hour at room temperature. The product was slightly acidified with an aqueous solution of acetic acid, after which the acetic acid was neutralized with sodium bicarbonate. The product was washed once with 400 ml of water, and the solvent and water were removed under reduced pressure using a rotary evaporator.

 The residual product obtained as described above was dissolved in 300 ml of tetrahydrofuran and the reaction was carried out with 12 g of sodium hydride for 1 hour. During this reaction, evolution of hydrogen gas was observed. Then, 120 g of methyl iodide was added dropwise to the reaction mixture over 30 minutes. During this period, heat was observed. After dropwise addition of methyl iodide, the reaction mixture was stirred for another 1 hour. Using a rotary evaporator, the solvent and unreacted materials were removed under reduced pressure. The residue was transferred to a 2 liter washing vessel and, after dissolving in 400 ml of hexane, washed with 400 ml of water 5 times. Then, adding 40 g of ion exchange resin, the product was stirred for 3 hours. After removing the ion-exchange resin from the product by filtration, hexane was removed under reduced pressure using a rotary evaporator. The yield of the resulting polyvinyl ether was 208 g. The NMR and IR spectra of the product were obtained, which showed that one of the terminal structures of the polymer was structure (A) and the other (B).

 Kinematic viscosity, flon compatibility, intrinsic resistance and hydrolysis resistance of the ethyl vinyl ether polymer were measured. The results are shown in table 1.

Example 3
500 g of hexane was charged into a 5-liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer, a solution prepared by dissolving 12 g of boron diethyl trifluoride in 24 g of tetrahydrofuran was added, and the mixture was cooled to 5 ^° C in an ice water bath . 2000 g of ethyl vinyl ether and 120 g of methanol were charged into a dropping funnel and the mixture was allowed to drip for 1 hour 30 minutes. During this period, the reaction began and the temperature of the reaction mixture increased. The temperature was maintained at about 30.degree ^. C. by cooling with an ice water bath. After completion of the dripping, stirring was continued for another 30 minutes. The reaction mixture was transferred to a washing vessel and washed with 1500 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times, and then 1500 ml of water 3 times. The solvent and unreacted materials were removed under reduced pressure by means of a rotary evaporator, resulting in 1806 g of a crude product.

Были измерены кинематическая вязкость, совместимость с флоном, объемное собственное сопротивление и стойкость к гидролизу. Результаты показаны в таблице 1.In a 2 liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer, 400 g of the crude product obtained as described above and 300 g of tetrahydrofuran were charged and then 15 g of lithium aluminum hydride was added, followed by stirring for 30 minutes. 196 g of boron trifluoride diethyl etherate was charged into a dropping funnel and allowed to drip for 1 hour. Heat was observed during the dripping, and the temperature was maintained at 10-20 ^° C. by cooling in an ice water bath. After the completion of the dripping, the reaction mixture was stirred for another 30 minutes, after which it was neutralized by adding sodium hydroxide. The resulting precipitate was removed by filtration, and the liquid phase was treated in a rotary evaporator to remove the formed alcohol, solvent and water under reduced pressure. The remaining product was transferred to a 2 liter washing vessel and dissolved in 500 ml of hexane. The solution was washed with 200 ml of a 5% (by weight) aqueous sodium hydroxide solution 10 times and then 200 ml of water 3 times. 100 g of ion exchange resin was added to the solution, and the mixture was stirred for 3 hours. After removal of the ion exchange resin by filtration, hexane was removed under reduced pressure using a rotary evaporator. The yield of ethyl vinyl ether polymer was 235 g. The NMR and IR spectra of the product showed that one of the end structures of the polymer was structure (A), and the other a mixture of structures (B) and (C):

Kinematic viscosity, flon compatibility, intrinsic volume resistance, and hydrolysis resistance were measured. The results are shown in table 1.

Example 4
1000 g of toluene, 500 g of acetaldehyde diethyl acetal and 5.0 g of boron trifluoride diethyl etherate were charged into a 5 liter glass flask equipped with a dropping funnel, refrigerator and stirrer. 2500 g of ethyl vinyl ether was charged into a dropping funnel and allowed to drip for 1 hour 30 minutes. During this period, the reaction began, and the temperature of the reaction mixture increased. The temperature was maintained at about 25 ^° C. cooling in an ice water bath. After dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 1000 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 1000 ml of water 3 times. Using a rotary evaporator under reduced pressure, the solvent and unreacted raw materials, resulting in 2833 g of a crude product.

600 g of crude product, 600 g of hexane, 60 g of Raney nickel and 60 g of zeolite were charged into an autoclave. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, the pressure of which was regulated to 20 kg / cm ² , and after stirring for about 30 seconds it was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. The reaction was carried out at 130 ^o C for 1 hour. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 100 ml of hexane twice. The wash and reaction liquid were combined with each other and filtered through filter paper. The combined liquid was then transferred to a washing vessel and washed with 500 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 500 ml of distilled water 5 times. By means of a rotary evaporator, hexane, water and the like were removed under reduced pressure. The yield was 468 g.

 NMR-IR spectra of the product showed that one of the terminal structures of the polymer was structure (A), and the other was a mixture of (C) and (D), in which (C) was the main structure, in (D) it was secondary.

Были измерены кинематическая вязкость, совместимость с флоном, объемное собственное сопротивление и стойкость к гидролизу полимера этилвинилового эфира. Результаты показаны в таблице 1.

Kinematic viscosity, flon compatibility, intrinsic resistance and hydrolysis resistance of the ethyl vinyl ether polymer were measured. The results are shown in table 1.

Example 5
Using the catalyst trapped by decantation in Example 4, a reaction was carried out with 600 g of the crude product obtained in Example 4, as in Example 4. The yield was 501 g. This showed that the catalyst could be reused.

 The NMR and IR spectra of the product showed that one of the terminal structures of the polymer was structure (A), and the other was a mixture of (C) and (D), in which (C) was the main structure and (D) was secondary.

 Kinematic viscosity, flon compatibility, intrinsic resistance and hydrolysis resistance of the ethyl vinyl ether polymer were measured.

Example 6
A 1 liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 250 g of toluene, 36.82 g of isopropyl alcohol and 4.35 g of boron trifluoride diethyl ether. 500 g of isopropyl vinyl ether was charged into a dropping funnel, which was added dropwise in 30 minutes. During this period, the reaction began, and the temperature of the reaction solution increased. The temperature was maintained at about 30 ^° C. by cooling in an ice water bath. After dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 130 ml of a 3% by weight aqueous solution of sodium hydroxide 3 times and then with 200 ml of water 3 times. The solvent and unreacted raw materials were removed using a rotary evaporator under reduced pressure, resulting in 475.3 g of a crude product.

380 g of crude product, 100 g of hexane, 45 g of Raney nickel and 45 g of zeolite were charged into an autoclave. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 20 kg / cm ² . after stirring for about 30 seconds, the pressure was released. Hydrogen was reintroduced into the autoclave, providing a pressure of 20 kg / cm ² , and after stirring for about 30 seconds, the pressure was released. Repeating this operation once again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. The reaction was carried out at 130 ^° C. for 1 hour. The reaction proceeded during and after an increase in temperature, and a pressure drop was observed. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour, and the reaction liquid was separated by decantation. The catalyst was washed with 100 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. The catalyst could be reused. The combined liquid was then transferred to a washing vessel and washed with 200 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 200 ml of distilled water 5 times. Hexane, water, etc., were removed under reduced pressure using a rotary evaporator.

 The yield was 287 g.

 NMR and IR spectra showed that one of the terminal structures was structure (E), and the other was a mixture of (F) and (D), in which (F) was the main structure, and (D) was the secondary structure.

Были измерены кинематическая вязкость, совместимость с флоном, объемное собственное сопротивление и стойкость к гидролизу полимера изопропилвинилового эфира. Результаты показаны в таблице 1.

Kinematic viscosity, flon compatibility, intrinsic resistance and hydrolysis resistance of isopropyl vinyl ether polymer were measured. The results are shown in table 1.

Example 7
200 g of toluene, 5.5 g of methanol and 1.2 g of boron trifluoride diethyl etherate were charged into a 1 liter autoclave and the atmosphere in the autoclave was replaced with nitrogen. While stirring the contents of the autoclave, 200 g of methyl vinyl ether was added thereto over 4 hours. During this period, the reaction began and heat was released. The reaction was carried out while maintaining the temperature in the autoclave at about 5 ^° C. by cooling the autoclave in an ice water bath. After the completion of the addition of methyl vinyl ether under pressure, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 100 ml of a 5% - (by weight) aqueous solution of sodium hydroxide 3 times and then with 100 ml of water 3 times. The solvent and unreacted starting materials were removed by rotary evaporation, resulting in 165 g of a crude product.

165 g of crude product, 200 g of hexane, 15 g of Raney nickel and 15 g of zeolite were charged into an autoclave. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave with a hydrogen pressure of 20 kg / cm ² and after stirring for about 30 seconds, the hydrogen pressure was relieved. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. The reaction was carried out at 130 ^o C for 1 hour. The reaction proceeded during and after an increase in temperature, and a pressure drop was observed. The pressure increase with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby maintaining the hydrogen pressure during the reaction at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 50 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. Hexane was removed under reduced pressure using a rotary evaporator, and 300 g of chloroform was added. Then the liquid was transferred into a washing vessel and washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 100 ml of distilled water 5 times. Using a rotary evaporator, chloroform, water and the like were removed under reduced pressure.

 The yield was 150 g.

 The NMR and IR spectra of the product confirmed that one of the terminal structures of the polymer was structure (G), and the other was a mixture of (B) and (D), in which (B) was the main structure and (D) was the secondary structure.

Были измерены кинематическая вязкость, совместимость с флоном, объемное собственное сопротивление и стойкость к гидролизу полимера метилвинилового эфира. Результаты показаны в таблице 1.

Kinematic viscosity, flon compatibility, intrinsic resistance and hydrolysis resistance of the methyl vinyl ether polymer were measured. The results are shown in table 1.

Example 7A
In a 5 liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer, 1000 g of toluene, 500 g of acetaldehyde diethyl acetal and 5.0 boron trifluoride diethyl etherate were charged. 2500 g of ethyl vinyl ether was charged into a dropping funnel and dispensed dropwise in 2 hours 30 minutes. During this period, the reaction began, and the temperature of the reaction solution increased. By cooling in an ice water bath, the temperature was maintained at about 25 ^° C. After completion of the dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 1000 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 1000 ml of water 3 times. The solvent and unreacted materials were removed using a rotary evaporator under reduced pressure, resulting in 2833 g of a crude product.

 NMR and IR spectra showed that one of the terminal structures of the polymer was structure (A), and the other was a mixture of (H) and (I), in which the ratio (H) / (I) was 1 / 4.5.

Пример 7B
В двухлитровый автоклав, изготовленный из SUS-316L, загружали 700 г полимера этилвинилового эфира, полученного в примере 7A, 35 г никеля Ренея, 35 г цеолита и 1,5 г воды. Вводили в автоклав водород, давление которого регулировали до 10 кг/см². После перемешивания в течение примерно 30 секунд давление сбрасывали. Вновь вводили в автоклав водород, обеспечивая его давление 10 кг/см², и после перемешивания в течение примерно 30 секунд давление водорода сбрасывали. Повторив эту операцию еще раз, давление водорода повышали до 35 кг/см² и повышали температуру до 140^oC за 30 минут при перемешивании. При 140^oC реакцию проводили в течение 2 часов. Реакция протекала во время и после повышения температуры, и при этом происходило падение давления. Рост давления с повышением температуры и понижение давления в результате реакции подходящим образом компенсировали путем понижения или повышения давления, обеспечивая тем самым поддержание давления водорода во время реакции на уровне 35 кг/см². После окончания реакции реакционную смесь охлаждали до комнатной температуры, и снижали давление до атмосферного. Продукт реакции фильтровали через фильтровальную бумагу. Затем продукт реакции переносили в 2-литровый промывной сосуд, разбавляли 300 г гексана и промывали 250 мл 5%-ного (по массе) водного раствора гидроксида натрия 3 раза и затем 250 мл дистиллированной воды 5 раз. С помощью роторного испарителя удаляли под пониженным давлением гексан, воду и т.п. Выход составлял 550 г. ЯМР и ИК-спектры продукта показали, что одной из концевых структур полимера была структура (A), а другой - смесь (C) и (D).

Example 7B
In a two-liter autoclave made from SUS-316L, 700 g of the ethyl vinyl ether polymer obtained in Example 7A, 35 g of Raney nickel, 35 g of zeolite and 1.5 g of water were charged. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 10 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Hydrogen was reintroduced into the autoclave, providing a pressure of 10 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 35 kg / cm ² and the temperature was raised to 140 ^o C for 30 minutes with stirring. At 140 ^° C., the reaction was carried out for 2 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the decrease in pressure as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 35 kg / cm ² . After the reaction, the reaction mixture was cooled to room temperature, and the pressure was reduced to atmospheric. The reaction product was filtered through filter paper. Then the reaction product was transferred to a 2-liter washing vessel, diluted with 300 g of hexane and washed with 250 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 250 ml of distilled water 5 times. Hexane, water, etc., were removed under reduced pressure using a rotary evaporator. The yield was 550 g. NMR and IR spectra of the product showed that one of the terminal structures of the polymer was structure (A), and the other a mixture of (C) and (D).

Example 7C
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 50 g of toluene, 17.7 g of acetaldehyde diethyl acetal and 1.5 boron trifluoride diethyl etherate. 43 g of ethyl vinyl ether was charged into a dropping funnel, which was dropped in 50 minutes. The heat of the reaction increased the temperature of the reaction solution and kept it at about 30 ^° C. by cooling with an ice water bath. After dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a wash and washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 150 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure, resulting in 120 g of a crude product. The crude product had a kinematic viscosity of 48.8 cc at 40 ^° C. NMR and IR spectra showed that one of the end structures of the polymer was a mixture of (A) and (E), and the other a mixture of (H), (I) and structures in which the hydroxyethyl groups in (H) and (I) are substituted with an oxyisopropyl group, respectively.

Example 7D
In a 1 L autoclave made of SUS-316L, 110 g of a copolymer of ethyl vinyl ether and isopropyl vinyl ether obtained in Example 7C, 300 g of hexane, 5.5 g of Raney nickel and 5.5 g of zeolite were charged. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing a pressure of 29 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 140 ^o C for 30 minutes with stirring. At 140 ^° C., the reaction was carried out for 2 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The reaction product was filtered through filter paper. After this, the reaction product was transferred to a washing vessel and washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 150 distilled water 5 times. Using a rotary evaporator, hexane, water and the like were removed under reduced pressure. The yield was 97 g. NMR and IR spectra showed that one of the terminal structures of the polymer was a mixture of (A) and (E), and the other was a mixture of (C), (F) and (D), in which (C) and (F) were the primary structures, and (D) the secondary structures.

Example 7E
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 80 g of toluene, 40 g of propionaldehyde diethyl acetal and 0.4 g of boron trifluoride diethyl etherate. 116 g of 1-ethoxy-1-propene were charged into a dropping funnel, and it was released dropwise in 60 minutes. The heat from the reaction raised the temperature of the reaction solution and was maintained at about 30 ^° C. by cooling with an ice water bath. After dripping, the solution was stirred for another 40 minutes. The reaction mixture was transferred to a washing vessel and washed with 150 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 200 ml of water 3 times. The solvent and unreacted starting materials were removed using a rotary evaporator under reduced pressure, resulting in 140 g of a crude product. This product had a kinematic viscosity of 34.4 cc at 40 ^o C.

A 1 liter autoclave made from SUS-316L was charged with 120 g of the above crude product, 300 g of hexane, 6 g of Raney nickel and 6 zeolite. Hydrogen was introduced into the autoclave, the pressure of which was brought to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again, hydrogen was introduced into the autoclave, providing a pressure of 20 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. At 130 ^° C., the reaction was carried out for 2 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 50 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. The combined liquid was then transferred to a one-liter washing vessel and washed with 150 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 200 ml of distilled water 5 times. Hexane, water, etc., were removed under reduced pressure using a rotary evaporator. The yield was 95 g NMR and the IR spectra of the product showed that one of the terminal structures of the polymer was structure (J), and the other was a mixture of (K) and (L), in which (K) was the main structure and (L) secondary.

Пример 7F
В 5-литровую стеклянную колбу, оборудованную капельной воронкой, холодильником и мешалкой, загружали 1000 г толуола, 304 г этанола и 7,8 г диэтилэфирата трифторида бора. В капельную воронку загружали 3284 г этилвинилового эфира, который выпускали затем по каплям за 4 часа 30 минут. В течение этого периода тепло реакции повышало температуру реакционного раствора, и путем охлаждения с помощью ванны с ледяной водой температуру поддерживали на уровне примерно 25^oC. После окончания капания раствор перемешивали еще 5 минут. Реакционную смесь переносили в промывочный сосуд и промывали 1100 мл 5%-ного (по массе) водного раствора гидроксида натрия 3 раза и затем 1100 мл воды 3 раза. Посредством роторного испарителя удаляли под пониженным давлением растворитель и непрореагировавшие исходные материалы, получив в результате 3397 г неочищенного продукта.

Example 7F
In a 5-liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer, 1000 g of toluene, 304 g of ethanol and 7.8 g of boron trifluoride diethyl ether were charged. 3284 g of ethyl vinyl ether was charged into a dropping funnel, which was then released dropwise in 4 hours 30 minutes. During this period, the heat of reaction increased the temperature of the reaction solution, and by cooling with an ice water bath, the temperature was maintained at about 25 ^° C. After the completion of the dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 1100 ml of a 5% (by weight) aqueous sodium hydroxide solution 3 times and then 1100 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure, resulting in 3397 g of a crude product.

A 2 liter autoclave made from SUS-316L was charged with 600 g of the obtained crude product, 600 g of hexane, 18 g of Raney nickel and 18 g of zeolite. Hydrogen was introduced into the autoclave, the pressure of which was brought to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing it with a pressure of 20 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 140 ^o C for 30 minutes with stirring. At 140 ^° C., the reaction was carried out for 2 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 100 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. Then, the combined liquid was transferred to a washing vessel and washed with 500 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 500 ml of distilled water 5 times. Hexane, water, etc., were removed under reduced pressure using a rotary evaporator. The yield was 492 g. NMR and IR spectra of the product showed that one of the terminal structures of the polymer was structure (A), and the other a mixture of (C) and (D), in which (C) was the main structure, and (D) - secondary.

Example 7G
1000 g of toluene, 500 g of acetaldehyde diethyl acetal and 5.0 g of boron trifluoride diethyl etherate were charged into a 5 liter glass flask equipped with a dropping funnel, refrigerator and stirrer. 2700 g of ethyl vinyl ether was charged into a dropping funnel, which was released dropwise from there in 3 hours.

The heat of reaction increased the temperature of the reaction solution, and by cooling the solution in an ice water bath, the temperature was maintained at about 25 ^° C. After the completion of the dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 1000 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 1000 ml of water 3 times. The solvent and unreacted starting materials were removed under reduced pressure using a rotary evaporator, resulting in 3040 g of a crude product. This product had a kinematic viscosity of 42.1 cc at 40 ^o C.

A 2 liter autoclave made from SUS-316L was charged with 600 g of the obtained crude product, 600 g of hexane, 18 g of Raney nickel and 18 g of zeolite. Hydrogen was introduced into the autoclave, the pressure of which was brought to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing it with a pressure of 20 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 140 ^o C for 30 minutes with stirring. The reaction was carried out at 140 ^° C. for 2 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 100 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. The combined liquid was then transferred to a washing vessel and washed with 500 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 500 ml of distilled water 5 times. By means of a rotary evaporator, hexane, water and the like were removed under reduced pressure. The yield was 495 g. The polymer had the same end structures as in Example 4.

Example 7H
1000 g of toluene, 450 g of acetaldehyde diethyl acetal and 4.5 g of boron trifluoride diethyl etherate were charged into a 5 liter glass flask equipped with a dropping funnel, refrigerator and stirrer. 3200 g of ethyl vinyl ether were charged into a dropping funnel and released dropwise in 4 hours 10 minutes. The heat of reaction increased the temperature of the reaction solution, and by cooling the solution in an ice water bath, the temperature was maintained at about 25 ^° C. After the completion of the dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 1000 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 1000 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure, resulting in 3466 g of a crude product. This product had a kinematic viscosity of 76.1 cc at 40 ^o C.

A 2 liter autoclave made from SUS-316L was charged with 600 g of the obtained crude product, 600 g of hexane, 18 g of Raney nickel and 18 g of zeolite. Hydrogen was introduced into the autoclave, the pressure of which was brought to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing it with a pressure of 20 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 140 ^o C for 30 minutes with stirring. The reaction was carried out at 140 ^° C. for 2 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 100 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. Then, the combined liquid was transferred to a washing vessel and washed with 500 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 500 ml of distilled water 5 times. Hexane, water, etc., were removed under reduced pressure using a rotary evaporator. The yield was 498 g. The polymer had end structures the same as in Example 4.

 Kinematic viscosity, flon compatibility (flon-134a), intrinsic resistance, and hydrolysis resistance of the polymers obtained in Examples 7A-7H were measured. The results are shown in table IA (see end of description). The compatibility of the polymers obtained in examples 7G and 7H with flon - 32 was also measured, and the results are shown in table IB (see the end of the description).

Comparative Example 1
Kinematic viscosity, flon compatibility, intrinsic resistance and hydrolysis resistance of market paraffin mineral oil (VG 32) were measured. The results are shown in table 1A.

Reference Example 2
Kinematic viscosity, flon compatibility, intrinsic resistance, and hydrolysis resistance of Unilab MV11 polypropylene glycol (product of F. Nippon Yushi Co., Ltd.) were measured. The results are shown in Table 1A.

Reference Example 3
1091 g of pentaerythritol and 3909 g of n-hexanoic acid were charged into a 5 liter glass flask equipped with a Dean and Stark tube, refrigerator and stirrer, and the mixture was heated with stirring. When the temperature of the solution reached 200 ^° C., it was kept constant for 3 hours. Then the temperature was raised to 220 ^o C and kept at this level for 10 hours. During this period, the reaction began and water formed. After completion of the reaction, the reaction solution was cooled to 150 ^° C and the majority of unreacted hexanoic acid was recovered under reduced pressure. The remaining solution was transferred to a washing vessel and, after dissolving in 2 liters of hexane, washed with 1500 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times and 1500 ml of water 3 times. Then 800 g of ion exchange resin was added and the mixture was stirred for 3 hours. The ion-exchange resin was removed by filtration and hexane was removed under reduced pressure using a rotary evaporator. The yield of polyhydric alcohol ester was 3390 g.

 Kinematic viscosity, compatibility with the flon, intrinsic volume resistance, and hydrolysis resistance of the polymer obtained above were measured. The results are presented in table 1A.

Example 8
In a 5 liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer, 1000 g of toluene, 234 g of ethanol and 6.0 g of boron trifluoride diethyl ether were charged. 2526 g of ethyl vinyl ether was charged into a dropping funnel, which was released dropwise from there in 3 hours 20 minutes. During this period, the heat of reaction increased the temperature of the reaction solution, and by cooling the solution with an ice water bath, the temperature was maintained at about 25 ^° C. Until the amount of monomer reached an equivalent amount of ethanol, the monomer was slowly released dropwise. because there was an induction period of heat generation. After dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 870 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 870 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure to obtain 2622 g of an ethyl vinyl ether polymer. The product was a light yellow color.

 The kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon and intrinsic resistance of the ethyl vinyl ether polymer obtained as described above were measured. The results are presented in table 2.

In figures 1, 2 and 3, respectively, the infrared absorption spectrum, ¹³ C NMR spectrum and ¹ H NMR spectrum are shown.

In FIG. 2 peaks at 101 ppm, 129 ppm and 134 ppm refer to the carbon atom underlined in the following formulas, respectively:
-CH ₂ -CH (OC ₂ H ₅ ) ₂
-CH = CH-OC ₂ H ₅
-CH = CH-OC ₂ H ₅
In FIG. 3 peaks at 4.7 ppm 5.35 ppm and 5.6 ppm refer to the hydrogen atom, underlined in the following formulas, respectively:
-CH ₂ -CH (OC ₂ H ₅ ) ₂
-CH = CH-OC ₂ H ₅
-CH = CH-OC ₂ H ₅
Thus, the terminal structure of the compound was a mixture of the structures of formula (II) and formula (III) and the mass ratio of the molecule obtained from the ratio of proton (II) :( III) = 5.1: 1.

Example 9
1000 g of toluene, 195 g of ethanol and 5.0 g of boron trifluoride diethyl etherate were charged into a 5-liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer. 3005 g of ethyl vinyl ether was charged into a dropping funnel and dispensed dropwise in 3 hours 50 minutes. During this period, the heat of reaction increased the temperature of the reaction solution, and by cooling the solution with an ice water bath, the temperature was maintained at about 25 ^° C. Until the amount of monomer reached an equivalent amount of ethanol, the monomer was slowly released dropwise. because there was an induction period of heat release. After dripping, the solution was stirred for another 5 minutes. Then the reaction mixture was transferred to a washing vessel and washed with 1000 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 1000 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure to obtain 3008 g of an ethyl vinyl ether polymer. The product was a light yellow color.

 The kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon, and intrinsic resistance of the ethyl vinyl ether polymer obtained as described above were measured. The results are presented in table 2.

Figures 4, 5 and 6 show infrared absorption spectra, ¹³ C NMR, and ¹ H NMR, respectively. The terminal structure of the compound was a mixture of structures of formula (II) and formula (III), and the mass ratio of the molecule obtained by the same method as in Example 8, was: (II) :( III): = 3.9: 1.

Example 10
1000 g of toluene, 450 g of acetaldehyde diethyl acetal and 4.5 g of boron trifluoride diethyl etherate were charged into a 5 liter glass flask equipped with a dropping funnel, refrigerator and stirrer. 3200 g of ethyl vinyl ether was charged into a dropping funnel, after which it was dispensed dropwise in 4 hours 10 minutes. During this period, the temperature of the reaction solution increased as a result of the reaction heat, and by cooling the solution with an ice water bath, the temperature was maintained at about 25 ^° C. After the completion of the dripping, the solution was stirred for another 5 minutes. Then the reaction mixture was transferred to a washing vessel and washed with 1000 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 1000 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure, resulting in 3466 g of a polymer of ethyl vinyl ether. The product was a light yellow color.

 The kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon, and intrinsic resistance of the ethyl vinyl ether polymer obtained as described above were measured. The results are presented in table. 2 (see the end of the description).

 The infrared absorption spectrum is shown in FIG. 7.

Example 11
1000 g of toluene, 195 g of ethanol and 4.5 g of boron trifluoride diethyl etherate were charged into a 5-liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer. 3875 g of ethyl vinyl ether was charged into a dropping funnel, after which it was dispensed dropwise in 4 hours 40 minutes. During this period, the temperature of the reaction solution increased as a result of the heat of reaction, and by cooling the solution with an ice water bath, the temperature was maintained at about 25 ^° C. Until the amount of monomer reached an equivalent amount of ethanol, the monomer was released dropwise slowly, because there was an induction period of heat release. After dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 1000 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 1000 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure to obtain 3867 g of an ethyl vinyl ether polymer. The product was a light yellow color.

 The kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon, and intrinsic resistance of the ethyl vinyl ether polymer obtained as described above were measured. The results are presented in table 2.

In figures 8, 9 and 10 shows the spectra, respectively, of infrared absorption, ¹³ C NMR and ¹ H. NMR.

 The mass ratio of the molecule of formula (II) and formula (III), obtained in the same manner as in example 8, was: (II) :( III) = 2.9: 1.

Example 12
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 125 g of toluene, 19.4 g of isopropyl alcohol and 2.3 g of boron trifluoride diethyl etherate. 250 g of isopropyl vinyl ether was charged into a dropping funnel, and then it was dispensed dropwise in 30 minutes. During this period, the temperature of the reaction solution increased as a result of the reaction heat, and by cooling the solution with an ice water bath, the temperature was maintained at about 25 ^° C. After the completion of the dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 80 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 80 ml of water 3 times. The solvent and unreacted starting materials were removed using a rotary evaporator under reduced pressure to obtain 238 g of an isopropyl vinyl ether polymer. The product was a light yellow color.

 Kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon and intrinsic resistance of the isopropyl vinyl ether polymer obtained as described above were measured. The results are presented in table 2.

 In FIG. 11 shows an infrared absorption spectrum.

Example 13
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 125 g of toluene, 17.4 isopropyl alcohol and 2.1 boron trifluoride diethyl etherate. 250 g of isopropyl vinyl ether was charged into a dropping funnel and dispensed dropwise over 30 minutes. During this period, the temperature of the reaction solution increased as a result of the reaction heat, and by cooling the solution with an ice water bath, the temperature of the solution was maintained at about 25 ^° C. After the completion of the dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 80 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 80 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure to obtain 236 g of an isopropyl vinyl ether polymer. The product was a light yellow color.

 Kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon and intrinsic resistance of the isopropyl vinyl ether polymer obtained as described above were measured. The results are presented in table 2.

In figures 12, 13 and 14 shows the spectra, respectively, of infrared absorption, ¹³ C NMR and ¹ H. NMR.

 The mass ratio of the molecules of formula (II) and formula (III), obtained by the same method as in example 8, was: (II) :( III) = 3.8: 1.

Example 14
A 200 ml stainless steel autoclave equipped with a stirrer was charged with 40 g of toluene, 2.5 g of methanol and 0.18 g of boron trifluoride diethyl etherate. After the autoclave was closed, the atmosphere in it was replaced with nitrogen. 47 g of methyl vinyl ether was added to the autoclave from a balloon under compound pressure for 5 hours. During this period, the temperature of the reaction solution increased as a result of the heat of reaction, and the temperature was maintained at about 25 ^° C. by cooling the solution with an ice water bath. After the addition was complete, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 50 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 100 ml of water 3 times. The solvent and unreacted starting materials were removed under reduced pressure using a rotary evaporator, yielding 42 g of a methyl vinyl ether polymer. The product was a light yellow color.

 The kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon and intrinsic resistance of the methyl vinyl ether polymer obtained as described above were measured.

 The results are presented in table 2.

In figures 15, 16 and 17 shows the spectra of infrared absorption, NMR ¹³ C and NMR ¹ H. : (III) = 8.9: 1.

Example 15
The average molecular weights and the molecular weight dispersion were measured in the copolymer of ethyl vinyl ether and isopropyl vinyl ether obtained in the above Example 7C. The measurement results are shown in table 2 together with the results of measurements of kinematic viscosity, compatibility with the flon and volume intrinsic resistance.

Absorption spectra in the infrared region, ¹³ C NMR and ¹ H NMR are shown in figures 18, 19 and 20, respectively.

 The mass ratio of the molecule of formula (II) and formula (III) obtained by the same method as in example 8 was: (II) :( III) = 3.1: 1.

Example 16
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 50 g of toluene, 4.6 g of ethyl alcohol and 0.2 boron trifluoride diethyl etherate. 86 g of 1-ethoxy-1-propene were charged into a dropping funnel, and then it was dispensed dropwise in 50 minutes. During this period, the temperature of the reaction solution increased as a result of the heat of reaction, and the temperature was maintained at about 30 ^° C by cooling the solution with an ice water bath. After completion of the dripping, the solution was stirred for another 30 minutes. Then the reaction mixture was transferred to a washing vessel and washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 150 ml of water 3 times. The solvent and unreacted starting materials were removed under reduced pressure using a rotary evaporator, resulting in 84 g of 1-ethoxy-1-propene polymer.

 Kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon and intrinsic resistance of the 1-ethoxy-1-propene polymer obtained as described above were measured. The results are presented in table. 2.

Absorption spectra in the infrared region, ¹³ C NMR and ¹ H NMR are shown in figures 21, 22 and 23, respectively.

Example 17
In a 5-liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer, 1000 g of toluene, 304 g of ethanol and 7.8 g of boron trifluoride diethyl ether were charged. 3284 g of ethyl vinyl ether was charged into a dropping funnel and released dropwise in 4 hours 30 minutes. The heat of reaction increased the temperature of the solution, and by cooling with an ice water bath, the temperature was maintained at about 25 ^° C. After the completion of the dripping, the solution was stirred for another 5 minutes. Then the reaction mixture was transferred to a washing vessel and washed with 1100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 1100 ml of water 3 times. The solvent and unreacted materials were removed under reduced pressure using a rotary evaporator, resulting in 3397 g of a crude product. ¹ H NMR and ¹³ C NMR spectra of the crude product were obtained. NMR ¹ H-spectrum had peaks at 4.7 ppm, 5.35 ppm and 5.6 ppm, and ¹³ C NMR at 101 ppm, 129 ppm and 134 ppm

The crude product had a kinematic viscosity of 17.8 cc at 40 ^° C.

 By further processing the crude product in the same manner as in Example 7F, 492 g of an ethyl vinyl ether polymer was obtained.

 The average molecular weights and molecular dispersion of the molecular weight of the ethyl vinyl ether polymer obtained as described above were changed. The measurement results are presented in table 3 together with the results of measurements of kinematic viscosity, compatibility with the flon and volume intrinsic resistance.

The infrared absorption spectra, ¹³ C NMR and ¹ H NMR are shown in figures 24, 25 and 26, respectively.

In the ¹ H NMR spectrum of this polymer, the peaks of 4.7 5.35 and 5.6 ppm, which were in the spectrum of the crude product described above, were not found. The ¹³ C NMR spectrum of this polymer peaks at 101, 129, and 134 ppm. also absent. In addition, in the region of 9.7 ppm. ¹ H NMR ^of the spectrum usually found a peak related to the hydrogen of the aldehyde, and in the region of 200 ppm in the ¹³ C NMR spectrum, there was usually a peak related to the carbon of the aldehyde. None of these peaks were found in the spectra of the polymer obtained as described above. Therefore, we can assume that the obtained polymer does not contain unsaturated bonds and acetal and aldehyde structures.

Example 18
The average molecular weights and molecular weight dispersion of the polymer of ethyl vinyl ether obtained in Example 7G described above were measured. The measurement results are presented in table 3 together with the results of measurements of kinematic viscosity, compatibility with the flon and volume intrinsic resistance.

The infrared absorption spectra, ¹³ C NMR and ¹ H NMR are shown in figures 27, 28 and 29, respectively.

 For the same reason as in Example 17, the polymer obtained above did not contain either an unsaturated bond or acetal and aldehyde structures.

Example 19
The average molecular weights and molecular weight dispersion of the polymer of ethyl vinyl ether obtained in Example 7H described above were measured. The measurement results are presented in table 3 together with the results of measurements of kinematic viscosity, compatibility with the flon and volume intrinsic resistance.

The infrared absorption spectra, ¹³ C NMR and ¹ H NMR are shown in figures 30, 31 and 32, respectively.

 For the same reason as in Example 17, the polymer obtained above did not contain either an unsaturated bond or acetal and aldehyde structures.

Example 20
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 95 g of toluene, 14.7 g of isopropyl alcohol and 1.8 g of boron trifluoride diethyl etherate. 190 g of isopropyl vinyl ether was charged into a dropping funnel and released dropwise in 30 minutes. The heat of reaction increased the temperature of the reaction solution, and by cooling with an ice-water bath, the temperature was maintained at about 25 ^° C. After completion of the dripping, the solution was stirred for another 5 minutes. Then the reaction mixture was transferred to a washing vessel and washed with 70 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 70 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted materials were removed under reduced pressure, resulting in 179 g of a crude product. This product had a kinematic viscosity of 27.0 cc at 40 ^° C. A 1 L autoclave made of SUS-316L was charged with 171 g of the obtained crude product, 130 g of hexane, 20 g of Raney nickel and 20 g of zeolite. Hydrogen was introduced into the autoclave, the pressure of which was brought to 20 kg / cm ³ . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing it with a pressure of 20 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. At 130 ^° C., a reaction was carried out for 1 hour. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After the reaction, the reaction mixture was cooled to room temperature, and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 100 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. The combined liquid was then transferred to a 2-liter washing vessel and washed with 50 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 50 ml of distilled water 5 times. Using a rotary evaporator, hexane, water and the like were removed under reduced pressure. The yield was 131 g.

 Kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon, intrinsic resistance, and hydrolysis resistance of the isopropyl vinyl ether polymer obtained above were measured. The results are presented in table. 3 (see the end of the description).

The infrared absorption spectra, ¹³ C NMR and ¹ H NMR are shown in figures 33, 34 and 35, respectively.

 For the same reason as in Example 17, the polymer obtained as described above did not contain either an unsaturated bond or acetal and aldehyde structures.

Example 21
The average molecular weights and the molecular weight dispersion of the isopropyl vinyl ether polymer obtained in the above Example 6 were measured. The measurement results are presented in table 3 together with the results of measurements of kinematic viscosity, compatibility with the flon and volume intrinsic resistance.

 The infrared absorption spectrum is shown in FIG. 36.

 For the same reason as in Example 17, the polymer obtained as described above did not contain either an unsaturated bond or acetal and aldehyde structures.

Example 22
A 200 ml stainless steel autoclave equipped with a stirrer was charged with 40 g of toluene, 6.4 methanol and 0.45 g of boron trifluoride diethyl etherate. The autoclave was tightly closed and the atmosphere in the autoclave was replaced with nitrogen. 107 g of methyl vinyl ether was added to the autoclave from a bomb under compound pressure for 5 hours. The heat of reaction increased the temperature of the reaction solution, and by cooling the solution with an ice water bath, the temperature was maintained at about 25 ^° C. After the addition was complete, the solution was stirred for another 10 minutes. Then the reaction mixture was transferred to a washing vessel and washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 150 ml of water 3 times. The solvent and unreacted starting materials were removed under reduced pressure using a rotary evaporator, resulting in 95 g of a crude product. This product had a kinematic viscosity of 56.9 cc at 40 ^o C.

A one liter autoclave made from SUS-316L was charged with 90 g of the obtained crude product, 300 g of hexane, 4.5 g of Raney nickel and 4.5 g of zeolite. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing it with a pressure of 20 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. At 130 ^° C., the reaction was carried out for 1 hour. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 30 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. After hexane was removed using a rotary evaporator under reduced pressure, 100 ml of toluene was added to the residual product, and then the product was transferred to a washing vessel and washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 150 ml of distilled water 5 times. Using a rotary evaporator, toluene, water and the like were removed under reduced pressure. The yield was 80.5 g.

 Kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon, intrinsic resistance, and hydrolysis resistance of the methyl vinyl ether polymer obtained above were measured. The results are presented in table 3.

Absorption spectra in the infrared region, ¹³ C NMR and ¹ H NMR are shown in figures 37, 38 and 39, respectively.

 For the same reason as in Example 17, the polymer obtained above did not contain either an unsaturated bond or acetal and aldehyde structures.

Example 23
The average molecular weights and the molecular dispersion of the molecular weight of the ethyl vinyl isopropyl ester copolymer obtained in the above Example 7D were measured. The measurement results are presented in table 3 together with the results of measurements of kinematic viscosity, compatibility with the flon and volume intrinsic resistance.

The infrared absorption spectra, ¹³ C NMR and ¹ H NMR are shown in figures 40, 41 and 42, respectively.

 For the same reason as in Example 17, the polymer obtained above did not contain either an unsaturated bond or acetal and aldehyde structures.

Example 24
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 50 g of toluene, 11 g of isobutyl alcohol and 0.5 boron trifluoride diethyl etherate.

100 g of isobutyl vinyl ether was charged into a dropping funnel, and then it was dropped therefrom in 55 minutes. The heat of reaction increased the temperature of the reaction solution, and by cooling the solution with an ice water bath, the temperature was maintained at about 30 ^° C. After the completion of the dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 150 ml of water 3 times. By means of a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure to obtain 107 g of a crude product. This product had a kinematic viscosity of 52.4 cc at 40 ^o C.

A one liter autoclave made from SUS-316L was charged with 90 g of the obtained crude product, 300 g of hexane, 4.8 g of Raney nickel and 4.8 g of zeolite. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing a pressure of 20 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 140 ^o C for 30 minutes with stirring. At 140 ^° C., the reaction was carried out for 2 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The pressure increase with increasing temperature with the pressure drop as a result of the reaction was suitably compensated by lowering or increasing the pressure, thereby maintaining the hydrogen pressure during the reaction at a level of 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 30 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. The combined liquid was then transferred to a 1 liter washing vessel and washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then with 150 ml of distilled water 5 times. Using a rotary evaporator, hexane, water and the like were removed under increased pressure. The yield was 80.5 g.

 The kinematic viscosity, average molecular weights, molecular weight dispersion, compatibility with the flon, intrinsic resistance, and hydrolysis resistance of the isobutyl vinyl ether polymer obtained as described above were measured. The results are presented in table 3.

The infrared absorption spectra, ¹³ C NMR and ¹ H NMR are shown in figures 43, 44 and 45, respectively.

 For the same reason as in Example 17, the polymer obtained above did not contain either an unsaturated bond or acetal and aldehyde structures.

Example 25
The average molecular weights and the molecular weight dispersion of the 1-ethoxy-1-propene polymer obtained in the above Example 7E were measured. The measurement results are presented in table 3 together with the results of measurements of kinematic viscosity, compatibility in the flon and volume intrinsic resistance.

The infrared absorption spectra, ¹⁵ C NMR and ¹ H NMR are shown in figures 46, 47 and 48, respectively.

 For the same reason as in Example 17, the polymer obtained above did not contain either an unsaturated bond or an acetal and aldehyde structure.

Example 25A
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 100 g of toluene, 21.3 acetaldehyde dimethoxyethyl acetal and 0.45 g of boron trifluoride diethyl etherate. 112 g of methoxyethyl vinyl ether was charged into a dropping funnel and dispensed dropwise in 50 minutes. The heat of reaction increased the temperature of the reaction solution, and by cooling the solution with an ice water bath, the temperature was maintained at about 25 ^° C. After the completion of the dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and 200 ml of chloroform was added thereto. The product was washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 150 ml of water 3 times. The solvent and unreacted starting materials were removed using a rotary evaporator under reduced pressure to obtain 129 g of a crude product. The crude product had a kinematic viscosity of 33.3 cc at 40 ^° C.

Into a one liter autoclave made from SUS-316L, 110 g of crude product, 300 g of hexane, 5.5 Raney nickel, 5.5 g zeolite were charged. Hydrogen was introduced into the autoclave, the pressure of which was up to 20 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing it with a pressure of 20 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 50 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. At 130 ^° C., the reaction was carried out for 2 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 50 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The catalyst was precipitated by settling for 1 hour and the reaction liquid was separated by decantation. The catalyst was washed with 30 ml of hexane twice. The wash liquid was combined with the reaction liquid and filtered through filter paper. Using a rotary evaporator, hexane was removed from the combined liquid under reduced pressure, and 200 ml of chloroform was added to the remaining product. The product was then transferred to a washing vessel and washed with 100 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 150 ml of distilled water 5 times. Using a rotary evaporator, solvent, water, and the like were removed under reduced pressure. The yield was 94 g.

 The kinematic viscosity, compatibility with the flon and the hydrolysis resistance of the methoxyethyl vinyl ether polymer obtained above were measured. The results are presented in table 3.

The infrared absorption spectra, ¹³ C NMR and ¹ H NMR are shown in figures 49, 50 and 51, respectively.

 For the same reason as in Example 17, the polymer obtained above did not contain either an unsaturated bond or acetal and aldehyde structures.

Example 26
1000 g of toluene, 195 g of ethanol and 5.0 g of boron trifluoride diethyl etherate were charged into a 5-liter glass flask equipped with a dropping funnel, a refrigerator and a stirrer. The temperature of the solution was 14 ^° C. 102 g of ethyl vinyl ether was added to the solution. The heat of reaction increased the temperature of the reaction solution, and the reaction solution was stirred while cooling with an ice water bath. (3 minutes after the addition, the temperature of the solution reached a maximum of 21 ^° C. The reaction was carried out with cooling by means of a bath of ice water in all subsequent stages). After lowering the temperature to 15 ^° C., 102 g of ethyl vinyl ether was again added. Again, heat was generated and the temperature rose. By lowering the temperature to 15 ^° C., another 102 g of ethyl vinyl ether was added. Again, heat was observed, and the temperature of the solution rose again. While the solution was lowering the temperature, ethyl vinyl ether was added dropwise, and heat was immediately generated in response to this addition. After that, 2700 g of ethyl vinyl ether was added dropwise into the solution at an approximately constant speed (about 20 cm ³ per minute) so that the temperature of the reaction solution was constantly kept at about 25 ^° C. After the completion of the dripping, the reaction mixture was transferred to a washing vessel and washed 1000 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times and then 1000 ml of water 3 times. Using a rotary evaporator, the solvent and low boiling components were removed under reduced pressure, resulting in 3040 g of product. The product was a light yellow color.

The product had a kinematic viscosity of 44.3 ss at 40 ^o C and 5.90 ss at 100 ^o C.

Example 27
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 36 g of acetaldehyde diethyl acetal, 80 g of toluene and 0.36 g of boron trifluoride diethyl etherate. The temperature of the solution was 15 ^° C. When ethyl vinyl ether was added dropwise to the solution, heat was generated immediately in response to this, and 256 g of ethyl vinyl ether was added dropwise at an approximately constant speed (about 5 cm ³ per minute) so that the temperature the reaction solution was kept constant at 25 ^o C while cooling the solution through a bath of ice water. After completion of the dripping, the reaction mixture was transferred to a washing vessel and washed with 100 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times and then with 100 ml of water 3 times. Using a rotary evaporator, the solvent and low boiling components were removed under reduced pressure to obtain 277 g of product. The product was a light yellow color.

The product had a kinematic viscosity of 130.7 cc at 40 ^° C and 11.8 cc at 100 ^° C.

Example 28
A 500 ml glass flask equipped with a dropping funnel, refrigerator and stirrer was charged with 18 g of acetaldehyde diethyl acetal, 80 g of toluene, and 0.18 g of boron trifluoride diethyl etherate. The temperature of the solution was 15 ^° C. When ethyl vinyl ether was added dropwise to the solution, heat was generated immediately in response to this, and 256 g of ethyl vinyl ether was added dropwise at an approximately constant speed (about 5 cm ³ per minute) so that the temperature the reaction solution was kept constant at 25 ^o C while cooling the solution through a bath of ice water. After the completion of the dripping, the reaction mixture was transferred to a washing vessel and washed with 100 ml of a 3% aqueous sodium hydroxide solution 3 times and 100 ml of water 3 times. Using a rotary evaporator, the solvent and low boiling components were removed under reduced pressure to obtain 261 g of product. The product was a light yellow color. The product had a kinematic viscosity of 993.1 cc at 40 ^° C and 44.7 cc at 100 ^° C.

Example 29
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 9 g of acetaldehyde diethyl acetal, 80 g of toluene and 0.09 g of boron trifluoride diethyl etherate. The temperature of the solution was 15 ^° C. When ethyl vinyl ether was added dropwise to the solution, heat was generated immediately in response to this, and 256 g of ethyl vinyl ether was added dropwise at an approximately constant rate (about 5 cm ³ per minute) so that the temperature the reaction solution was kept constant at 25 ^o C while cooling the solution through a bath of ice water. After completion of the dripping, the reaction mixture was transferred to a washing vessel and washed with 100 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times and then with 100 ml of water 3 times. Using a rotary evaporator, the solvent and low boiling components were removed under reduced pressure and 255 g of product was obtained. The product was a light yellow color.

The product had a kinematic viscosity of 9356 cc at 40 ^o C and 225.5 cc at 100 ^o C.

Example 30
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 4 g of acetaldehyde diethyl acetal, 80 g of toluene and 0.04 g of boron trifluoride diethyl etherate. The temperature of the solution was 15 ^° C. When ethyl vinyl ether was added dropwise to the solution, heat was generated immediately in response to this, and 256 g of ethyl vinyl ether was added dropwise at an approximately constant speed (about 5 cm ³ per minute) so that the temperature the reaction solution was kept constant at 25 ^o C while cooling the solution through a bath of ice water. After completion of the dripping, the reaction mixture was transferred to a washing vessel and washed with 100 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times and then with 100 ml of water 3 times. Using a rotary evaporator, the solvent and low boiling components were removed under reduced pressure, resulting in 252 g of product. The product was a light yellow color.

 The product had a weight average molecular weight of 2079 and a number average molecular weight of 6750.

Average molecular weights were obtained by GPC (gel permeation chromatography) under the following conditions (these conditions were used only in this example):
Device: product f. Nippon Banco Co., Ltd. (pump)
Shodeks RI SE-61 (detector)
Column: TSK HM + GMH6x2 + G2000H8
Temperature: room
Solvent: THF
Elution Rate: 1.4 ml / min
Standard substance: polystyrene
Example 31
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 16 g of acetaldehyde diethyl acetal, 80 g of toluene and 0.16 g of boron trifluoride diethyl etherate. The temperature of the solution was 15 ^° C. When ethyl vinyl ether was added dropwise to the solution, heat was generated immediately in response to this, and 256 g of ethyl vinyl ether was added dropwise at an approximately constant rate (about 5 cm ³ per minute) so that the temperature the solution was kept constant at 25 ^o C while cooling the solution through a bath of ice water. After completion of the dripping, the reaction mixture was transferred to a washing vessel and washed with 100 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times and then with 100 ml of water 3 times. Using a rotary evaporator, the solvent and low boiling components were removed under reduced pressure, and 262 g of product was obtained. The product was a light yellow color.

The product had a kinematic viscosity of 1746 cc at 40 ^o C and 64.6 cc at 100 ^o C.

Example 32
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 15 g of acetaldehyde diethyl acetal, 80 g of toluene and 0.15 g of boron trifluoride diethyl etherate. The temperature of the solution was 15 ^° C. When ethyl vinyl ether was added dropwise to the solution, heat was generated immediately in response to this, and 256 g of ethyl vinyl ether was added dropwise at an approximately constant speed (about 5 cm ³ per minute) so that the temperature the reaction solution was kept constant at 25 ^o C while cooling the solution through a bath of ice water. After the completion of the dripping, the reaction mixture was transferred to a washing vessel and washed with 100 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times and 100 ml of water 3 times. Using a rotary evaporator, the solvent and low boiling components were removed under reduced pressure, resulting in 260 g of product. The product was a light yellow color.

The product had a kinematic viscosity of 1903 cc at 40 ^° C and 68.1 cc at 100 ^° C.

Example 33
In a 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer, 4 g of diethyl acetaldehyde, 30 g of toluene and 0.4 g of FeCl ₃ · 6H ₂ O were charged. The temperature of the solution was 10 ^° C. Ethyl vinyl ether was added dropwise to the solution. heat was released immediately in response to this, and 30 g of ethyl vinyl ether was added dropwise at an approximately constant speed so that the temperature of the reaction solution was kept constant at 10 ^° C. while cooling the solution by means of a bath of ice water. After the completion of the dripping, the reaction mixture was transferred to a washing vessel and washed with 15 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times and then 15 ml of water 3 times. Using a rotary evaporator, the solvent and low boiling components were removed under reduced pressure, and 30.6 g of product was obtained. The product was a dark yellow color.

The product had a kinematic viscosity of 21.86 ss at 40 ^o C and 3.94 ss at 100 ^o C.

Example 34
A 500 ml glass flask equipped with a dropping funnel, a refrigerator and a stirrer was charged with 3 g of acetaldehyde diethyl acetal, 30 g of toluene and 0.18 g of FeCl ₃ . The temperature of the solution was 15 ^° C. When ethyl vinyl ether was added dropwise to the solution, heat was released immediately in response to this, and 30 g of ethyl vinyl ether was added dropwise at an approximately constant rate so that the temperature of the solution was kept constant at 30 ^° C. while cooling the solution through a bath of ice water. After the completion of the dripping, the reaction mixture was transferred to a washing vessel and washed with 15 ml of a 3% (by weight) aqueous solution of sodium hydroxide 3 times and then 15 ml of water 3 times. Using a rotary evaporator, the solvent and low boiling components were removed under reduced pressure, and 29.4 g of product was obtained. The product was a dark yellow color.

The product had a kinematic viscosity of 326.7 ss at 40 ^o C and 25.69 ss at 100 ^o C.

Example 35
In a one liter autoclave made from SUS-316L, 100 g of acetaldehyde diethyl acetal, 100 g of n-heptane, 3.0 g of Raney nickel and 3.0 g of zeolite were charged. Hydrogen was introduced into the autoclave, the pressure of which was brought to 10 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing a pressure of 10 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Then the hydrogen pressure was increased to 30 kg / cm ² and the temperature was increased to 130 ^o C for 30 minutes with stirring. At 130 ^° C., the reaction was carried out for 2 hours 30 minutes. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 30 kg / cm ² . After the reaction, the reaction mixture was cooled to 20 ^o C and reduced the pressure to atmospheric. By gas chromatography, quantitative and qualitative analyzes of the reaction product were carried out. The degree of conversion of acetaldehyde diethyl acetal was 94.9%, and the selectivity of diethyl ether was 68.3%.

Example 36
In a one liter autoclave made from SUS-316L, 100 g of propionaldehyde diethyl acetal, 100 g of n-octane, 6.0 g of Raney nickel and 6.0 g of zeolite were charged. Hydrogen was introduced into the autoclave, the pressure of which was brought to 10 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing a pressure of 10 kg / cm, and after stirring for about 30 seconds, the hydrogen pressure was released. Then the hydrogen pressure was increased to 30 kg / cm ² and the temperature was increased to 130 ^o C for 30 minutes with stirring. At 130 ^° C., the reaction was carried out for 1 hour 30 minutes. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 30 kg / cm ² . After the reaction, the reaction mixture was cooled to 20 ^o C and reduced the pressure to atmospheric. By gas chromatography, quantitative and qualitative analyzes of the reaction product were carried out. The degree of conversion of propionaldehyde diethyl acetal was 97.0%, and the selectivity of ethyl n-propyl ether was 72.0%.

.Example 37
(1) Receiving material
1000 g of toluene, 500 g of acetaldehyde diethyl acetal and 5.0 g of boron trifluoride diethyl etherate were charged into a 5 liter glass flask equipped with a dropping funnel, refrigerator and stirrer. 2500 g of ethyl vinyl ether was charged into a dropping funnel and then released dropwise in 2 hours 30 minutes. During this period, the reaction began and the temperature of the reaction solution increased. The temperature was maintained at about 25 ^° C. by cooling the reaction solution with an ice water bath. After dripping, the solution was stirred for another 5 minutes. The reaction mixture was transferred to a washing vessel and washed with 1000 ml of a 5% (by weight) aqueous solution of sodium hydroxide 3 times and then 1000 ml of water 3 times. Using a rotary evaporator, the solvent and unreacted starting materials were removed under reduced pressure, resulting in 2833 g of product. NMR ^{1 The} H-spectrum of this product is shown in FIG. 52. As this spectrum showed, the product had the structure of the formulas (A ′) and (B ′) below. The product had a kinematic viscosity of 5.18 cc at 100 ^° C and 38.12 cc at 40 ^° C

.

 The mass ratio of the molecule was: (A ') :( B') = 4.5: 1, and the average value was 5.6.

(2) In a one liter autoclave made from SUS-316L, 200 g of an oligomer prepared as described above in paragraph (1), 6.0 g of Raney nickel and 6.0 g of zeolite were charged. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 10 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave, providing a pressure of 10 kg / cm ² , and after stirring for about 30 seconds, the hydrogen pressure was released. Repeating this operation again, the hydrogen pressure was increased to 25 kg / cm ² and the temperature was raised to 140 ^o C for 30 minutes with stirring. At 140 ^° C., the reaction was carried out for 2 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 25 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. 100 ml of hexane was added to the reaction mixture. The catalyst was precipitated by settling for 30 minutes and the reaction solution was separated by decantation. The hexane solution was combined with the reaction solution and filtered through filter paper. The catalyst was reused in Example 39. Hexane, water, and the like were removed under reduced pressure using a rotary evaporator. The yield was 162 g.

где E_t - этильная группа. Степень превращения составляла 100%. Кинематическая вязкость была 4,90 сс при 100^oC и 29,50 сс при 40^oC. Олигомер зтилвинилового эфира, имеющий представленную выше формулу (B'), тоже был превращен в простой эфир, имеющий представленную выше формулу (C'). ¹ H NMR — The spectrum of this product is shown in FIG. 53. As this spectrum showed, the starting acetal was converted to ether represented by the formula (C '):

where E _t is an ethyl group. The degree of conversion was 100%. The kinematic viscosity was 4.90 cc at 100 ^° C and 29.50 cc at 40 ^° C. The vinyl ether oligomer having the above formula (B ′) was also converted to an ether having the above formula (C ′).

Example 38
In a one liter autoclave made from SUS-316L, 200 g of the oligomer obtained in Example 37 (1) described above, 20 r of Raney nickel and 20 g of zeolite were charged. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 7 kg / cm ² . After stirring for 30 seconds, the pressure was released. Repeating this operation again, the hydrogen pressure was adjusted to 7 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. At 130 ^° C., the reaction was carried out for 2 hours 30 minutes. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred.

The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 7 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The reaction mixture was filtered and, using a rotary evaporator, water and the like were removed from the filtered solution under reduced pressure. The yield was 160 g. As a result of this procedure, the same ether was obtained from the starting acetal as in Example 37 (2), the degree of conversion being 100%. The kinematic viscosity was 4.77 ss at 100 ^o C and 30.27 ss at 40 ^o C.

Example 39
In the autoclave used in example 37 (2), in which the catalyst remained, 200 g of the oligomer obtained in example 37 (1) was loaded, the reaction was carried out in the same way as in example 37 (2). The yield was 164 g. As a result of this procedure, the ether was obtained from the starting acetal as in Example 37 (2), and the degree of conversion was 100%. The kinematic viscosity was 4.93 ss at 100 ^o C and 29.13 ss at 40 ^o C.

Example 40
(1) Receiving material
The reaction was carried out as in example 37 (1) except that the amount of acetaldehyde was 450 g, the amount of boron trifluoride etherate was 4.5 g and the amount of ethyl vinyl ether was 2800 g. The yield was 3175 g. The product had the same structure , as well as the product obtained in example 37 (1). The kinematic viscosity was 6.79 ss at 100 ^o C and 59.68 ss at 40 ^o C. The ratio of the mass numbers of the molecule was: (A ') :( B') = 8: 1, and the average value was 6.8.

(2) In a one liter autoclave made from SUS-316L, 200 g of the oligomer obtained in the above paragraph (1), 10 g of Raney nickel and 15 g of activated clay were charged. Hydrogen was introduced into the autoclave, the pressure of which was regulated to 10 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Hydrogen was reintroduced into the autoclave and its pressure was adjusted to 10 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Repeating this operation again, the hydrogen pressure was increased to 3 kg / cm ² and the temperature was raised to 150 ^o C for 40 minutes with stirring. At 150 ^° C., the reaction was carried out for 1 hour. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby maintaining the hydrogen pressure during the reaction at 30 kg / cm ² . After the completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was removed to atmospheric. The reaction mixture was filtered, and water and the like were removed from the solution using a rotary evaporator. The yield was 158 g. As a result of this procedure, the ether was obtained from the starting acetal as in Example 37 (2), and the degree of conversion was 100%. The kinematic viscosity was 7.06 cc at 100 ^o C and 57.32 cc at 40 ^o C.

Example 41
In a one liter autoclave made from SUS-316L, 200 g of the oligomer obtained in Example 37 (1) described above, 10 g of zeolite and 5.0 g of Pd / C (carrying 5% Pd, product of Wako Jan-yaku f.) Were charged. Co., Ltd. "). Hydrogen was introduced into the autoclave, the pressure of which was regulated to 7 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Hydrogen was reintroduced into the autoclave and its pressure was adjusted to 7 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Repeating this operation again, the hydrogen pressure was adjusted to 7 kg / cm ² and the temperature was raised to 120 ^o C for 30 minutes with stirring. At 120 ^° C., the reaction was transported for 7 hours. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 7 kg / cm ² . After the completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was removed to atmospheric. The reaction mixture was filtered and, using a rotary evaporator, water and the like were removed from the filtered solution under reduced pressure. The yield was 167.2 g. As a result of this procedure, the same ether was obtained from the starting acetal as in Example 37 (2), the degree of conversion being 100%. The kinematic viscosity was 5.28 ss at 100 ^o C and 32.93 ss at 40 ^o C.

Example 42
In a 1 L autoclave made of SUS-316L, 200 g of an oligomer prepared as described above in paragraph (1), 20 g of zeolite and 20 g of Ru / C (bearing 5% Ru, product of F. Waco Jan -yako Co., Ltd. ") Hydrogen was introduced into the autoclave, the pressure of which was regulated to 30 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave and its pressure was adjusted to 30 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Repeating this operation again, the hydrogen pressure was adjusted to 30 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. At 130 ^° C., the reaction was carried out for 1 hour. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 30 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The reaction mixture was filtered and, using a rotary evaporator, water and the like were removed from the filtered solution under reduced pressure. The yield was 156 g. As a result of this procedure, the same ether was obtained from the starting acetal as in Example 37 (2), and the degree of conversion was 100%. The kinematic viscosity was 5.18 ss at 100 ^o C and 31.53 ss at 40 ^o C.

Example 43
A 2 liter autoclave made of SUS-316L was charged with 15 g of Ni diatomaceous earth and 350 g of hexane. After replacing the atmosphere in the autoclave with hydrogen, the hydrogen pressure was brought to 30 kg / cm ^o C. The temperature was raised to 150 ^o C for 30 minutes with stirring and the catalyst was activated for 30 minutes. After cooling the autoclave, 300 g of the oligomer obtained in Example 37 (1) described above and 15 g of zeolite were charged. Hydrogen was introduced into the autoclave and its pressure was adjusted to 30 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Again hydrogen was introduced into the autoclave and the pressure of hydrogen in the autoclave was adjusted to 30 kg / cm ² . After stirring for about 30 seconds, the pressure was released. Repeating this operation again, the hydrogen pressure was adjusted to 30 kg / cm ² and the temperature was raised to 130 ^o C for 30 minutes with stirring. At 130 ^° C., the reaction was carried out for 1 hour. The reaction proceeded during and after an increase in temperature, and a pressure drop occurred. The increase in pressure with increasing temperature and the pressure drop as a result of the reaction were suitably compensated by lowering or increasing the pressure, thereby ensuring that the hydrogen pressure during the reaction was maintained at 30 kg / cm ² . After completion of the reaction, the reaction mixture was cooled to room temperature and the pressure was reduced to atmospheric. The reaction mixture was filtered and, using a rotary evaporator, water and the like were removed from the filtered solution under reduced pressure. The yield was 240 g.

The degree of conversion of the starting acetal was 100%, as in Example 37. The kinematic viscosity was 5.38 ss at 100 ^o C and 33.12 ss at 40 ^o C.

Claims (27)

1. A simple polyvinyl ether, which is a homo - or copolymer of a simple vinyl vinyl ether of the General formula I

where R ₁ is H or CH ₃ ;
R ₂ is alkyl C ₁ - C ₃ ,
having a weight average molecular weight of 300 to 1200, with one end of the chain having a structure expressed by general formula II

or formula III
-CH = CHOR _a ,
where R ₂ is the same as above
R ₃ is a hydrocarbon group having 1 to 8 carbon atoms;
R _a is one of the radicals R ₂ and R ₃ .  2. The simple polyvinyl ether according to claim 1, characterized in that the constituent units, expressed by the general formula I, contain one kind of constituent unit.  3. The polyvinyl ether according to claim 1, characterized in that the component units, expressed by the general formula I, contain two or more kinds of component parts.  4. The simple polyvinyl ether according to claim 1, characterized in that the ratio of the weight average molecular weight to number average molecular weight is in the range of 1.05 to 1.50. 5. A simple polyvinyl ether, representing a homo - or copolymer of a simple vinyl vinyl ether of the General formula IV

where R ₄ , R ₅ and R ₆ are each hydrogen atom or an alkyl group C ₁ - C ₄ and may be the same or different;
R ₇ is an alkylene group C ₂ - C ₄ ;
R ₈ is an alkyl group C ₁ - C ₁₀ ;
x is a number whose average value is in the range of 1-10;
R ₇ O may be the same or different when the constituent unit contains several R ₇ O, with a weight average molecular weight of 300 to 3000. 6. The simple polyvinyl ether according to claim 5, characterized in that one end of the chain is expressed by the General formula

where R ₄ - R _{8 are as} defined above;
m is a number whose average value is in the range 0 - 10,
several groups of R ₇ O may be the same or different,
and the other end of the chain is expressed by the general formula

where R ₄ - R _{8 are as} defined above;
n is a number whose average value is in the range 0 - 10;
several R ₇ O moieties may be the same or different. 7. The polyvinyl ether according to claim 5 of general formula IV, characterized in that R ₈ is an alkyl group C ₁ - C ₄ and in the series of constituent units may be the same or different and has the structural formula

8. The polyvinyl ether according to claim 5 of general formula IV, in which R ₄ = R ₅ = R ₆ - are hydrogen, x = 0, R ₈ is an alkyl group C ₁ - C ₄ , structural formula

where p is the degree of polymerization.  9. The simple polyvinyl ether according to claim 5 of the general formula IV, characterized in that it has a weight average molecular weight of 400-1000.  10. The polyvinyl ether according to claim 5 of general formula IV, characterized in that the ratio of the weight average molecular weight to number average molecular weight is in the range of 1.05 - 2.00. 11. A method of obtaining a simple polyvinyl ether of General formula V

where R ₉ , R ₁₀ and R ₁₁ are each hydrogen atom or a hydrocarbon group with C ₁ - C ₈ and may be the same or different;
R ₁₂ is a divalent hydrocarbon group with C ₂ - C ₁₀ ;
R ₁₃ is a hydrocarbon group with C ₁ - C ₁₀ ;
q is a number whose average value is in the range 0 - 10;
R ₁₂ may be the same or different when there are several groups of R ₁₂ O,
characterized in that the polymerization of the vinyl ether monomer of the general formula VI is carried out

where R ₉ - R ₁₃ and q are indicated above,
in the presence of aprotic acid, Lewis acid, or an organometallic compound and an initiator selected from the group consisting of water, alcohol, phenol, acetal, or the adduct of vinyl ether and carboxylic acid. 12. The method according to claim 11, characterized in that the polymerization of a simple vinyl ether of General formula VI is carried out in the presence of Lewis acid and acetal of General formula VII

where R ₁₄ , R ₁₅ and R ₁₆ are each hydrogen atom or a hydrocarbon group with C ₁ - C ₈ and may be the same or different;
R ₁₇ and R ₁₈ are each divalent hydrocarbon group with C ₂ - C ₁₀ and may be the same or different;
R ₁₉ and R ₂₀ are each C ₁ - C ₁₀ hydrocarbon group and may be the same or different;
s and r - each number whose average value is in the range 0 - 10;
R ₁₇ O may be the same or different when there are several groups of R ₁₇ O;
R ₁₉ O may be the same or different when there are several groups of R ₁₉ O. 13. The method according to claim 11, characterized in that the acetal of general formula VIII is first obtained

where R ₉ - R ₁₃ and q have the meanings in accordance with paragraph 10;
R ₂₁ is a divalent hydrocarbon group with C ₂ - C ₁₀ ;
R ₂₂ is a hydrocarbon group with C ₁ - C ₁₀ ;
t is a number whose average value is in the range 0 - 10;
R ₂₁ O - may be the same or different when there are several groups of R ₂₁ O,
by adding a vinyl ether of general formula VI to an alcohol of general formula
R ₂₂ (OR ₂₁ ) _t OH,
where R ₂₂ , R ₂₁ and t have the meanings corresponding to the general formula VIII,
in the presence of a Lewis acid as a catalyst, then a new portion of the vinyl ether of general formula VI is added to the obtained acetal and polymerization is carried out. 14. The method according to p. 12 or 13, characterized in that the polymerization is carried out at 0 - 100 ^o C.  15. The method according to p. 12 or 13, characterized in that as the Lewis acid use boron trifluoride or its complex. 16. Lubricating oil for compressor-type refrigerators, including, as a main component, polyvinyl ether of the general formula IX

where R ₉ - R ₁₃ and q have the meanings corresponding to the general formula V according to claim 11. 17. Lubricating oil according to clause 16, characterized in that one end chain link of a simple polyvinyl ether is expressed by the general formula X

where R ₂₃ , R ₂₄ , R ₂₅ is each hydrogen atom or a hydrocarbon group with C ₁ - C ₈ and may be the same or different;
R ₂₆ is a divalent hydrocarbon group with C ₂ - C ₂₀ ;
R ₂₇ is a hydrocarbon group with C ₁ - C ₁₀ ;
and - a number whose average value is in the range 0 - 10;
R ₂₆ O may be the same or different when there are several groups of R ₂₆ O,
and the other end link is expressed by the general formula XI

where R ₂₈ , R ₂₉ and R ₃₀ are each hydrogen atom or a hydrocarbon group with C ₁ - C ₈ and may be the same or different;
R ₃₁ is a divalent hydrocarbon group with C ₂ - C ₁₀ ;
R ₃₂ is a hydrocarbon group with C ₁ - C ₁₀ ;
b is a number whose average value is in the range 0 - 10;
R ₃₁ O - may be the same or different when there are several groups of R ₃₁ O. 18. Lubricating oil according to claim 17, characterized in that one end chain link of a simple polyvinyl ether is expressed by the general formula X, and the other by the general formula XII

where R ₃₃ , R ₃₄ , R ₃₅ is each hydrogen atom or a hydrocarbon group with C ₁ - C ₈ and may be the same or different;
R ₃₆ and R ₃₈ are each divalent hydrocarbon group with C ₂ - C ₁₀ and may be the same or different;
R ₃₇ and R ₃₉ - each hydrocarbon group with C ₁ - C ₁₀ and may be the same or different;
c and d - a number whose average value is in the range 0 - 10, and can be the same or different;
R ₃₆ O may be the same or different when there are several groups of R ₃₆ O.  19. The lubricating oil according to p. 18, characterized in that one end link of a simple polyvinyl ether is expressed by the general formula XI, and the other end link has a structure containing an olefinically unsaturated bond. 20. Lubricating oil according to clause 16, characterized in that one end link of a simple polyvinyl ether is expressed by the general formula XIII

where R ₄₀ , R ₄₁ and R ₄₂ are each hydrogen atom or a hydrocarbon group with C ₁ - C ₈ and may be the same or different.  21. The lubricating oil according to clause 16, wherein the polyvinyl ether is a mixture of two or more compounds selected from the group comprising a compound having a structure in which one end unit is expressed by general formula X and the other by general formula XI , a compound having a structure in which one end unit is expressed by general formula XI, and the other is represented by general formula XII, a compound having a structure in which one end unit is expressed by general formula XI, and the other end unit contains an olefinically unsaturated bond.  22. The lubricating oil according to clause 16, wherein the polyvinyl ether is a mixture of compounds having a structure in which one end unit is expressed by general formula XI, and the other is represented by general formula X, with a compound having a structure in which one the end link is expressed by the general formula XI, and the other by the general formula XIII.  23. The lubricating oil according to clause 16, wherein the polyvinyl ether is a mixture of a compound having a structure in which one end unit is expressed by general formula XI, and the other is represented by general formula X, with a compound having a structure in which one the end link is expressed by the general formula XI, and the other end link contains an olefinically unsaturated bond. 24. Lubricating oil according to PP.16 - 23, characterized in that the kinematic viscosity at 40 ^o With is in the range of 5 - 1000 ss.  25. Lubricating oil according to claim 20, characterized in that in the compressor refrigerator, hydrofluorocarbon is used as a refrigerant.  26. Lubricating oil according to clause 16, characterized in that in the compressor refrigerator, hydrochlorofluorocarbon is used as a refrigerant.  27. Lubricating oil according to clause 16, characterized in that 1,1,1,2-tetrachloroethane is used as a refrigerant in the compressor refrigerator.  28. Lubricating oil according to clause 16, characterized in that in the compressor refrigerator, difluoromethane is used as the refrigerant. Priority on points:
05/25/93 according to claims 1 to 10;
06/04/92 according to claims 11-29.

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