CN1161693A - Synthetic lubricating oil - Google Patents

Synthetic lubricating oil Download PDF

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CN1161693A
CN1161693A CN 95195775 CN95195775A CN1161693A CN 1161693 A CN1161693 A CN 1161693A CN 95195775 CN95195775 CN 95195775 CN 95195775 A CN95195775 A CN 95195775A CN 1161693 A CN1161693 A CN 1161693A
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cyclic
ketal
acetal
expression
oil
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萩原敏也
中川庄次
小林通一郎
富博靖
平幸治
酒井章充
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Kao Corp
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Kao Corp
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Abstract

The present invention relates to a synthetic lubricating oil comprising cyclic ketals or cyclic acetals obtained by a reaction between one or more polyhydric alcohols having an even number of hydroxyl groups of not less than 4 and not more than 10 and one or more specific carbonyl compounds, or one or more ketals or acetals which are reactive derivatives of said carbonyl compounds; a working fluid composition for a refrigerating machine comprising a hydrofluorocarbon and a refrigeration oil containing the cyclic ketals or cyclic acetals; and novel compounds of the above cyclic acetals and a production method thereof. The present invention provides a synthetic lubricating oil which shows a good thermal stability, a good oxidation resistance, no carboxylic acid formation due to hydrolysis and a low hygroscopicity and is inexpensive as well. Also, a working fluid composition for a refrigerating machine which shows a good insulating property, favorable hygroscopicity, and no carboxylic acid formation due to hydrolysis as well as being inexpensive can be provided.

Description

Ucon oil
Technical field
The cyclic ketal or the cyclic acetal compound that the present invention relates to so that ad hoc structure to be arranged are the ucon oil of base oil.In addition, also relate to the refrigerator working fluid compositions that has used this ucon oil.
And then, the invention still further relates to and can be used as preparation polar oil, organic solvent, lubricant, ucon oil, refrigerator wet goods, or as cyclic acetal class of the intermediate of tensio-active agent, organic solvent, polar oil, ucon oil, refrigerator wet goods and preparation method thereof.
Background technology
In recent years, be accompanied by the high performance, miniaturization of the prolongation of oil change interval, energy-conservation demand or mechanism etc., it is harsh more that the performance that requires lubricating oil to possess also becomes, and especially the lubricating oil to thermostability and oxidative stability excellence has tight demand.In addition, the depletion of the ozone layer that freonll-11 causes, the Global warming that carbonic acid gas, methane gas cause, the devastation that sulfurous gas or NOx cause in the waste gas, the soil that the chemical substance leakage causes, lake pollution etc., some global problem of environmental pollution become urgent day by day like this, have also required Corresponding Countermeasures aspect lubricating oil.
In order satisfy to improve the requirement of thermostability, oxidative stability, having developed ester classes such as ethers or aliphatic diester such as polyalkylene glycol or the ester that is obstructed, and being used for machine oil, working medium, consistent lubricant base oil, gear oil, rolling oil, precision optical machinery wet goods.
Yet ethers such as polyalkylene glycol are because to compare polarity too high with the mineral oil that always uses, thereby have 1. water absorbability greatly, 2. not dissolve the shortcomings of always using such as additive.As compare the not too high ether of polarity with this polyalkylene glycol, there is special fair 1-29240 communique described from alkylogen and how pure synthetic ether, but residual minim halogen in the ether that is generated, the possibility that has the thermostability of making, oxidative stability to worsen.
In addition, aspect ester, also have and can hydrolysis generate carboxylic acid and the such problem of corroding metal, or owing to the excellent frictional coefficient that makes of adsorptivity to metal reduces such strong point, but the such shortcoming of effect of infringement oiliness improver or extreme pressure agent etc. is also arranged conversely.
Therefore, need that such polarity is not too high, thermostability, oxidative stability excellence, can not produce carboxylic acid, ucon oil that water absorbability is low because of hydrolysis etc.
On the other hand, from the viewpoint of global environment, in order to protect ozonosphere, the Refrigerant 12 that uses in refrigerator chamber or the motorcar air conditioner (CFC-12) is subjected to legal restrictions in the use, and decision bans use of at the bottom of nineteen ninety-five.Subsequently, the use of the chlorodifluoromethane (HCFC-22) that uses in the room air conditioner etc. also has legal restrictions.Therefore,, developed the hydrogen fluorohydrocarbon that does not damage the ozone layer as the surrogate of this CFC-12 or HCFC-22, for example, 1,1,1,2-Tetrafluoroethane (HFC-134a) or methylene fluoride (HFC-32) or pentafluoride ethane (HFC-125).
But, because the polarity of hydrogen fluorohydrocarbon is than CFC-12 or HCFC-22 height, if thereby use on the prior art the general naphthalene that uses be mineral oil or lubricating oil such as poly-alpha-olefin, alkylbenzene as refrigerator oil, then two separate can take place in the poor compatibility of these lubricating oil and hydrogen fluorohydrocarbon at low temperatures.If the generation two separate, then oil reflux to worsen, and adheres to one deck heavy oil film near as the condenser of heat exchanger or vaporizer and hinder heat transfer, and becomes insufficient lubrication or cause the reason of significant drawbacks such as foaming when starting.Therefore, the refrigerator oil of prior art can not be used as the refrigerator oil under these new refrigerant atmosphere.Thereby lubricating oil that need be compatible good with the hydrogen fluorohydrocarbon.
And, with regard to oilness, in CFC-12 or HCFC-22, the part decomposition also can take place and generate hydrogenchloride, this hydrogenchloride and friction surface reaction form the muriate epithelium, have and improve the such effect of oilness.Yet, owing in not containing the hydrogen fluorohydrocarbon of chlorine atom, can not expect such effect, thereby in the refrigerator oil that uses with the hydrogen fluorohydrocarbon, need the oilness lubricating oil more excellent more than prior art product.
In addition, as the refrigerator oil that uses with the hydrogen fluorohydrocarbon, also must under coexisting, good thermostability be arranged with the hydrogen fluorohydrocarbon.
And then, in compression-type refrigerating machines such as refrigerator or room air conditioner, owing to exist the organic materials that insulating material or enameled wire etc. are used for motor, thereby as the working medium of forming by hydrogen fluorohydrocarbon and refrigerator oil, must these organic materialss not produced detrimentally affect, its electrical insulating property also must be good.
As can with the hydrogen fluorohydrocarbon as 1,1,1, the shared refrigerator oil of 2-Tetrafluoroethane (HFC-134a), at United States Patent (USP) the 4th, 755, No. 316 specification sheetss (the flat 2-502385 communique of special table) or spy open flat 3-14894 communique (No. the 377122nd, European patent), spy and open in the flat 2-182780 communique (WO90/05172 number) etc. and disclose the polyalkylene glycols compound.
The polyalkylene glycols compound since polarity than naphthalene class mineral innage, thereby with the low temperature intermiscibility of HFC-134a be good really.Yet as United States Patent (USP) the 4th, 755, described in No. 316 specification sheetss, the polyalkylene glycols compound has two such problems that are separated takes place when temperature rises on the contrary.And, for the polyalkylene glycols compound, in addition also have several problems.The problem that first electrical insulating property difference is such.This is a very large problem, can not be used for use in refrigerator refrigerator or the idle call refrigerator of built-in motor in compressor.Therefore, the someone proposes the automative air conditioning purposes that this compounds can be used for not having a kind of like this worry.Another problem is that water absorbability is big.Moisture in the polyalkylene glycols compound can make the thermostability under the HFC-134a coexistence worsen, and perhaps makes organic materials generation hydrolysis such as PET film.By reducing the ehter bond number of per unit weight, can improve electrical insulating property and reduce water absorbability, but worsen with the intermiscibility of hydrogen fluorohydrocarbon.Therefore, the such ether compound of polyalkylene glycol can not have both and the intermiscibility of hydrogen fluorohydrocarbon and electrical insulating property, hygroscopic characteristic simultaneously.
In order to improve the problem of the polyalkylene glycols compound of some electrical insulating properties, water absorbability etc. like this, ester compound or carbonats compound have been developed.For example, as can be with 1,1,1, the shared refrigerator oil of 2-Tetrafluoroethane (HFC-134a), United States Patent (USP) the 4th, 851, No. 144 specification sheetss (spy opens flat 2-276894 communique) or the special mixing oil that discloses polyalkylene glycol compounds and ester oil in the flat 2-158693 communique of opening, the special flat 3-505602 communique (WO90/12849 number), spy shown opened flat 3-128991 communique, spy and opened that flat 3-128992 communique, spy are opened flat 3-88892 communique, the spy opens in the flat 3-179091 communique and discloses ester oil.In addition, the spy opens flat 2-132178 communique, the spy opens in flat 3-149295 communique, the 421st, No. 298 specification sheets of European patent and discloses carbonic acid ester oil.
The intermiscibility excellence of ester compound or carbonats compound and hydrogen fluorohydrocarbon, the thermostability under the coexistence of hydrogen fluorohydrocarbon also is excellent.Compare with the polyalkylene glycols compound, electrical insulating property is extremely excellent, and suction temperature also is quite low.Yet, compare with CFC-12-mineral oil system prior art working medium, the polarity of freonll-11 and oil has all improved in hydrogen fluorohydrocarbon-ester oil system or hydrogen fluorohydrocarbon-carbonic ether oil body system, and is also moisture easily.Therefore, hydrolysis can take place and generate carboxylic acid in ester, and the carboxylic acid that is generated can corroding metal, thereby has and cause abrasive problem.In addition, hydrolysis can take place and generate non-condensability carbonic acid gas in carbonic acid ester oil, thereby also can produce the such problem of refrigeration capacity decline that makes.
Particularly, because the refrigeration agent can of room air conditioner is normally carried out at the scene, this point is different with the situation of the refrigerator that carries out can in factory, thereby may prevent sneaking into of moisture hardly, make that hydrogen fluorohydrocarbon-ester oil system or the reliability that the hydrogen fluorohydrocarbon-the carbonic ether oil body ties up in the room air conditioner are worrying.
In addition, the polyether compound as the electrical insulating property problem that can improve polyalkylene glycol discloses the polyvinyl ether compounds in the WO93/24435 communique.This polyvinyl ether compounds obtains by making ethene ethers monomer polymerization, hydrogenation, and according to open, the intermiscibility of this compound and hydrogen fluorohydrocarbon is good, also is good aspect electrical insulating property.Yet the polyvinyl ether compounds is to use the polymerization synthetic, and resultant has the molecular weight distribution chromatic dispersion, thereby a part of high molecular weight material might become the reason that kapillary stops up, and might make itself and the intermiscibility deterioration of hydrogen fluorohydrocarbon.In addition, its post-treating method is numerous and diverse, has used unsettled ethene ethers monomer again in raw material, thereby it is hard to tell that one reaches high yield surely.Especially (about the polymerization degree 6) has the such shortcoming of yield decline under the situation of low polymerization degree.And ethene ethers monomer is different because of structure, is difficult to obtain raw material sometimes, thereby the price that becomes is high.
On the other hand, the spy opens flat 4-320498 communique, the spy opens flat 6-57243 communique and described the example that uses cyclic ketal, cyclic acetal in refrigerator working medium.The former has described the ketal or the acetal that obtain from monohydroxy-alcohol or dibasic alcohol and ketone or aldehyde and has been used to prepare ester class or polyalkylene glycols ucon oil, and the latter is ester or the carbonic acid ester derivative that intramolecularly contains ketal or acetal radical, glycerine, three (methylol) ethane, three (methylol) propane, tetramethylolmethane.The former acetal, ketal have that molecular weight is little, boiling point, the low such shortcoming of flash-point, and the latter's acetal, ketal be because two above steps of experience thereby the high such shortcoming of price is arranged during preparation, and some of them have and are difficult to reach highly purified shortcoming.In addition, the latter is as acetal, the concrete disclosed compound of ketal, and intramolecularly contains 2 above ehter bonds, thereby has and can not fully improve the such problem of electrical insulating property.
Like this, Kai Fa hydrogen fluorohydrocarbon-polyalkylene glycol system has the problem of water absorbability, electrical insulating property aspect up to now, hydrogen fluorohydrocarbon-ester system, hydrogen fluorohydrocarbon-carbonic ether system have the problem of hydrolytic resistance aspect, and, any one system is compared with the CFC-12-mineral oil system that has earlier, all have moisture easily, cause that thermostability descends or problems such as organic materials deterioration, metallic corrosion or abrasion, be unsafty as refrigerator working medium.In addition, the polyvinyl ether compounds contains some high-molecular weight compounds owing to having molecular weight distribution, and this has the shortcoming that intermiscibility is reduced, and because raw material type is restricted, the such shortcoming of the cost of increase is arranged also.And then Bao Gao ketal or acetal have all that molecular weight is low, the high such shortcoming of price up to now.
, cyclic acetal in the past mainly uses acetone as ketone, in most cases is used as the protecting group in sugar or the synthetic field of many alcohol.Recently, from formaldehyde and ethylene glycol synthetic 1, the 3-dioxolane goes on the market as organic solvent.
On the other hand, as from Sorbitol Powder and phenyl aldehyde synthetic cyclic acetal, dibenzylidene sorbitol is known to be a kind of gelating agent, then is used as a kind of polymer raw material from unsaturated aldehyde and Sorbitol Powder synthetic cyclic acetal.
In addition, be known from Sorbitol Powder and acetone, formaldehyde, acetaldehyde or butyraldehyde synthetic cyclic acetal class, then be unknown but the cyclic acetal than this longer straight or branched is arranged.And, also be unknown from Sorbitol Powder and isobutyric aldehyde synthetic cyclic acetal.
With regard to the purposes of cyclic acetal class, except that the above organic solvent or the solvent of printing ink, coating etc. or additive and gelating agent, polymer raw material, also know the absorption agent (spy opens clear 59-25892 communique) that can be used as absorption refrigerating machine, the dewatering agent (spy opens flat 4-320498 communique, the spy opens flat 6-57243 communique) of refrigerator oil etc.
Up to now; be in order to protect hexavalent alcohol some compounds or carry out structure and identify the cyclic ketal that just synthesizes itself and acetone as Sorbitol Powder or mannitol so always; but this cyclic ketal has high-melting-point, is difficult to use near the such ask for something of polar oil, ucon oil or refrigerator oil is liquid proterties room temperature purposes.Although have the cyclic ketal of unsaturated link(age) to have the feature such on the alkyl chain, the such shortcoming of less stable also arranged than low melting point.In addition, the cyclic ketal with aromatic nucleus such as phenyl has the such feature of the gelation of generation, is not suitable for polar oil, ucon oil or refrigerator wet goods purposes.On the other hand, make the few pure synthetic cyclic acetal class viscosity of first numbers such as spent glycol lower, also be not suitable for the such purposes of ucon oil or refrigerator oil.
Disclosure of the Invention
Therefore, the purpose of this invention is to provide thermostability, oxidative stability excellence, do not produce carboxylic acid, the low and cheap ucon oil of water absorbability, perhaps provide with excellent performances such as the intermiscibility of hydrogen fluorohydrocarbon, electrical insulating property, water absorbability, do not produce carboxylic acid and cheap refrigerator working medium composition because of hydrolysis etc. because of hydrolysis etc.
In addition, another object of the present invention provides the novel cyclic acetals that is particularly suitable for ucon oil or the more such purposes of refrigerator oil.Another purpose of the present invention provides the preparation method who obtains this novel cyclic acetals with simple method with high yield.
The artificial result who solves above-mentioned problem and further investigate repeatedly such as present inventor, notice ether compound with the structure that does not produce carboxylic acid or carbonic acid gas, discovery has the ketal of ad hoc structure or acetal compound to have high electrical insulating property, and successfully make it to have both have earlier ether compound that can not have both with the intermiscibility hydrogen fluorohydrocarbon and electrical insulating property, water absorbability, finish the present invention finally.
That is, main points of the present invention relate to
(1) ucon oil, it is characterized in that containing and (comprise a kind of from more than one, down with) more than 4 yuan～(comprise 4 yuan and 10 yuan below 10 yuan, down with), first number is cyclic ketal or the cyclic acetal that carbonyl compound shown in even polyvalent alcohol and more than one general formulas (I) or its active derivative ketal or acetal obtain
Figure A9519577500111
R in the formula 1Straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～18 carbon atom, R 2Straight chain, side chain or the cyclic alkyl of 1～18 carbon atom of expression, perhaps R 1And R 2Lump together the alkylidene group of 2～36 carbon atoms of expression;
(2) ucon oil, it is characterized in that containing from more than one more than 4 yuan～below 8 yuan, first number is cyclic ketal or the cyclic acetal that carbonyl compound shown in even polyvalent alcohol and more than one general formulas (II) or its active derivative ketal or acetal obtain,
Figure A9519577500121
R in the formula 3Expression hydrogen atom or 1～12 carbon atom straight chain, side chain or cyclic alkyl, R 4Straight chain, side chain or the cyclic alkyl of 1～12 carbon atom of expression, perhaps R 3And R 4Lump together the alkylidene group of 2～13 carbon atoms of expression, R 3And R 4The total carbonatoms be 1～13;
(3) above-mentioned (1) or (2) described ucon oil, wherein polyvalent alcohol does not have ehter bond;
(4) above-mentioned (1) or (2) described ucon oil, wherein polyvalent alcohol has an ehter bond;
(5) above-mentioned (3) or (4) described ucon oil, wherein cyclic ketal or cyclic acetal contain 1,3-dioxolane structure and/or 1,3-diox structure;
(6) any one described ucon oil in above-mentioned (3)～(5) is characterized in that containing the cyclic ketal or the cyclic acetal that obtain from the radical of saturated aliphatic alcohol of 4 yuan or 6 yuan, 4～25 carbon atoms and carbonyl compound shown in more than one general formulas (II) or its active derivative ketal or acetal;
(7) ucon oil, it is characterized in that containing more than one formulas (IIIa), (IIIb), (IVa) or (IVb) shown in cyclic ketal or cyclic acetal,
Figure A9519577500122
R in the formula 3Straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～12 carbon atom, R 4Straight chain, side chain or the cyclic alkyl of 1～12 carbon atom of expression, perhaps R 3And R 4Lump together the alkylidene group of 2～13 carbon atoms of expression, R 3And R 4The total carbonatoms be 1～13;
(8) ucon oil, it is characterized in that containing more than one formula V or (VI) shown in cyclic ketal or cyclic acetal, R in the formula 3Straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～12 carbon atom, R 4Straight chain, side chain or the cyclic alkyl of 1～12 carbon atom of expression, perhaps R 3And R 4Lump together the alkylidene group of 2～13 carbon atoms of expression, R 3And R 4The total carbonatoms be 1～13;
(9) refrigerator working fluid compositions, the refrigerator oil of any one described cyclic ketal or cyclic acetal and hydrogen fluorohydrocarbon in above-mentioned comprising containing (2)～(8);
(10) above-mentioned (9) described refrigerator working fluid compositions wherein contains hydrogen fluorohydrocarbon and refrigerator oil with hydrogen fluorohydrocarbon/refrigerator oil=50/1～1/20 (weight ratio);
(11) following general formula (i) or (ii) shown in the cyclic acetal class,
Figure A9519577500151
R in the formula 5The expression hydrogen atom, in this case, R 6The branched-chain alkyl of 3 carbon atoms of expression, or the straight or branched alkyl of 4～21 carbon atoms; Perhaps R 5The straight or branched alkyl of 1～21 carbon atom of expression, in this case, R 6The straight or branched alkyl of 2～21 carbon atoms of expression;
(12) above-mentioned (11) described cyclic acetal class, wherein R 5Be hydrogen atom and R 6Be the branched-chain alkyl of 3 carbon atoms or the straight or branched alkyl of 4～12 carbon atoms, perhaps R 5Be the straight or branched alkyl of 1～12 carbon atom and R 6It is the straight or branched alkyl of 2～12 carbon atoms;
(13) above-mentioned (11) described cyclic acetal class, wherein R 5Be hydrogen atom and R 6Be the branched-chain alkyl of 3～12 carbon atoms, perhaps R 5Be the straight or branched alkyl of 1～12 carbon atom and R 6It is the straight or branched alkyl of 2～12 carbon atoms;
(14) any one described cyclic acetal class in above-mentioned (11)～(13), wherein 6 yuan of pure residues are from sorbitol derived;
(15) general formula (i) or (ii) shown in the preparation method of above-mentioned (11) described cyclic acetal class, it is characterized in that the carbonyl compound shown in hexavalent alcohol shown in following formula (iii) and general formula are (iv) or its active derivative (ketal or acetal) react in the presence of acid catalyst
Figure A9519577500161
R in the formula 5The expression hydrogen atom, in this case, R 6The branched-chain alkyl of 3 carbon atoms of expression, or the straight or branched alkyl of 4～21 carbon atoms; Perhaps R 5The straight or branched alkyl of 1～21 carbon atom of expression, in this case, R 6The straight or branched alkyl of 2～21 carbon atoms of expression;
(16) above-mentioned (15) described preparation method, wherein 6 yuan of alcohol are Sorbitol Powders.
The best example of invention
The present invention includes and relate to ucon oil and the refrigerator working fluid compositions that contains specific cyclic ketal or cyclic acetal and relate to the novel cpd that ad hoc structure is arranged in these cyclic ketals or the cyclic acetal.In this specification sheets, for simplicity, claim the former be first the invention, the latter be second the invention, below respectively the explanation each the invention.First invention at first is described.
The polyvalent alcohol that uses is that 4～10 yuan, first number are the even polyvalent alcohol in first invention.First number at polyvalent alcohol is under the situation of odd number, inevitable remaining unreacted hydroxyl and viscosity is increased, thereby bad.And under the situation that is used for refrigerator working medium, if remaining hydroxyl, then the intermiscibility with the hydrogen fluorohydrocarbon worsens, thereby bad.By making unreacted hydroxyl generation alkylated reaction form ether structure, can improve viscosity or with the intermiscibility of hydrogen fluorohydrocarbon, but since in preparation process reactions steps increase, thereby bad.And, therefore be difficult to obtain highly purified product.Specifically, tetrahydroxybutane is arranged, two Polyglycerine, pectinose, ribose, Sorbitol Powder, mannitol, melampyrum, iditol, talitol, allitol, 4,7-dioxadecane-1,2,9, the 10-tetrol, 5-methyl-4,7-dioxadecane-1,2,9, the 10-tetrol, 4,7,10-trioxa tridecane-1,2,12, the 13-tetrol, 1,6-dimethoxy hexane-2,3,4, the 5-tetrol, 3,4-diethoxy hexane-1,2,5, polyvalent alcohols such as 6-tetrol, or tetramethylolmethane, dimerization three (methylol) ethane, dimerization three (methylol) propane, dipentaerythritol, tripentaerythritol, 2,9-diethyl-2,9-two (methylol)-4,7-dioxadecane-1, the 10-glycol, 2,12-diethyl-2,12-two (methylol)-5,8-dimethyl-4,7,10-trioxa tridecane-1, hindered alcohols such as 13-glycol.Wherein, 4,7-dioxadecane-1,2,9,10-tetrol, 5-methyl-4,7-dioxadecane-1,2,9,10-tetrol, 4,7,10-trioxa tridecane-1,2,12,13-tetrol, 1,6-dimethoxy hexane-2,3,4,5-tetrol, 3,4-diethoxy hexane-1,2,5,6-tetrol, 2,9-diethyl-2,9-two (methylol)-4,7-dioxadecane-1,10-glycol, 2,12-diethyl-2,12-two (methylol)-5,8-dimethyl-4,7,10-trioxa tridecane-1, some have the polyvalent alcohol of 2 above ehter bonds to the 13-glycol like this; Since industrial be not easy to obtain and also preparation process in need many steps, so thereby cost height is bad.
First number of the polyvalent alcohol that uses in first invention is 4 yuan, 6 yuan, 8 yuan or 10 yuan, but is preferably 4 yuan, 6 yuan or 8 yuan, is more preferably 4 yuan or 6 yuan.If greater than 10 yuan, the viscosity of then resulting cyclic ketal or cyclic acetal can be too high.And if less than 4 yuan, then molecular weight is too low, thereby make boiling point, flash-point is on the low side, thus bad.
The polyvalent alcohol that uses in first invention has 4～25 carbon atoms, better 4～20 carbon atoms is arranged.If surpass 25 carbon atoms, the viscosity of then resulting cyclic ketal or cyclic acetal can be too high.And if be less than 4 carbon atoms, then molecular weight can be too low, thereby make boiling point, flash-point is on the low side, thereby bad.
In addition, the polyvalent alcohol that uses in first invention is a radical of saturated aliphatic alcohol.If it is unsaturated link(age) is arranged, then bad because thermostability worsens.
And then, the polyvalent alcohol that uses in first invention, if from having the such viewpoint of excellent electric insulating, then preferably intramolecularly does not have ehter bond.Even and have ehter bond, also be an ehter bond preferably.If have more than two,, thereby under the situation that the cyclic ketal or the cyclic acetal of first invention is used for electric insulation oil or refrigerator working medium etc., be bad then because electrical insulating property worsens.The specific examples that intramolecularly does not have the polyvalent alcohol of ehter bond is tetrahydroxybutane, Sorbitol Powder, mannitol, melampyrum, iditol, talitol, allitol, tetramethylolmethane etc., and the specific examples that the polyvalent alcohol of an ehter bond is arranged is two Polyglycerine, dimerization three (methylol) propane, dimerization three (methylol) ethane etc.
And, being used under the situation of refrigerator working medium at first cyclic ketal or the cyclic acetal of inventing, first number of polyvalent alcohol is preferably 4 yuan, 6 yuan or 8 yuan, is more preferably 4 yuan or 6 yuan.If first number of polyvalent alcohol is greater than 8 yuan, then viscosity can be too high, and can worsen with the intermiscibility of hydrogen fluorohydrocarbon.And if first number of polyvalent alcohol is less than 4 yuan, then molecular weight is too low, thereby makes boiling point, flash-point is on the low side, thereby bad.In addition, carbonatoms be preferably 4～20, be more preferably 4～15, especially good be 4～10.If carbonatoms is greater than 20, then the intermiscibility with the hydrogen fluorohydrocarbon worsens, thereby bad.And if carbonatoms is less than 4, then molecular weight can be too low, thereby make boiling point, flash-point is on the low side, and is also bad.And under the situation of using the high alcohol of the such symmetry of tetramethylolmethane, the fusing point of resulting cyclic ketal or cyclic acetal is higher, thereby, should not be as refrigerator working medium purposes.
The carbonyl compound that uses in first invention is ketone or the aldehyde shown in the general formula (I).
Figure A9519577500181
The carbonatoms of ketone or aldehyde shown in the general formula (I) is 2～37, is preferably 2～25, is more preferably 2～17.Carbonatoms is if surpass 37, and the viscosity of then resulting cyclic ketal or cyclic acetal can be too high, thereby bad.
R 1Straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～18 carbon atom, be preferably straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～12 carbon atom, be more preferably straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～8 carbon atom.R 2Straight chain, side chain or the cyclic alkyl of 1～18 carbon atom of expression are preferably straight chain, side chain or the cyclic alkyl of representing 1～12 carbon atom, are more preferably straight chain, side chain or the cyclic alkyl of 1～8 carbon atom of expression.Perhaps, R 1And R 2Lump together 2～36 carbon atoms of expression, be preferably 2～24 carbon atoms, be more preferably the alkylidene group of 2～16 carbon atoms.And, R 1And R 2Can be the same or different.
R 1Or R 2Carbonatoms if surpass 18, the viscosity of then resulting cyclic ketal or cyclic acetal can be too high, thereby bad.And, R 1And R 2The carbonatoms of alkylidene group that lumps together formation is if surpass 36, and the viscosity of then resulting cyclic ketal or cyclic acetal can be too high and bad.
Specifically, as R 1And R 2Be the ketone of alkyl, can enumerate acetone, methyl ethyl ketone, methyl propyl ketone, metacetone, methyl isopropyl Ketone, methyl butyl ketone, ethyl propyl ketone, methyl sec-butyl ketone, methyl iso-butyl ketone (MIBK), the ethyl nezukone, methyl tertbutyl ketone, Methyl amyl ketone, ethyl butyl ketone, diisopropyl ketone, methyl isoamyl ketone, butyrone, sec.-propyl propyl group ketone, methyl neo-pentyl ketone, ethyl tert-butyl ketone, methyl hexyl ketone, ethyl pentyl group ketone, 6-methyl-2-heptanone, 4-methyl-3-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, methylcyclohexyl ketone, methyl heptyl ketone, ethyl hexyl ketone, dibutyl ketone, diisobutyl ketone, Methyl Octyl ketone, methyl nonyl ketone, diamyl ketone, methyl decyl ketone, methyl undecyl ketone, dihexyl ketone, 5-(2 ', 2 ', 5 '-trimethylcyclohexyl)-2 pentanone, 6,10-dimethyl-2-11 (alkane) ketone, methyl tridecyl ketone, diheptyl ketone, methyl tetradecyl ketone, nonylone, methyl pentadecyl ketone, diisooctyl ketone, methyl hexadecyl ketone, 6,10,14-trimethylammonium-2-15 (alkane) ketone, n-dinonyl ketone, methyl heptadecyl ketone, methyl octadecyl ketone, didecyl ketone etc.
In addition, as R 1And R 2Lump together the ketone that forms alkylidene group, can enumerate cyclopropanone, cyclobutanone, cyclopentanone, pimelinketone, 2-methyl-cyclopentanone, 3-methyl-cyclopentanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, suberone, 2,4-dimethylcyclohexanon, 2,6-dimethylcyclohexanon, cyclooctanone, 2-ethyl cyclohexanone, 3-ethyl cyclohexanone, 4-ethyl cyclohexanone, 3,5,5-trimethylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-sec.-propyl-4-methylcyclohexanone, ring decanone, cyclododecanone etc.
And then, as R1 is the aldehyde of hydrogen atom, can enumerate acetaldehyde, propionic aldehyde, butyraldehyde, isobutyric aldehyde, valeral, isovaleric aldehyde, 2 methyl butyraldehyde, hexanal, 2 methyl pentanal, the 3-methyl pentanal, the 4-methyl pentanal, 2-ethyl butyraldehyde, 2, the 3-dimethyl butyraldehyde, 3, the 3-dimethyl butyraldehyde, Cyclopentylacetaldehyde, enanthaldehyde, 2 methyl hexyl aldehyde, 3-methyl hexanal, 4-methyl hexanal, 5-methyl hexanal, 2-ethyl valeral, cyclohexyl acetaldehyde, octanal, 2-methyl enanthaldehyde, the 2-ethyl hexanal, 2-propyl group valeral, 2,4,4-trimethylammonium valeral, aldehyde C-9,3,5,5-trimethylammonium hexanal, capraldehyde, isodecyl aldehyde, 3,7-dimethyl octanal, 2-sec.-propyl-5-methyl hexanal, 11 (alkane) aldehyde, 12 (alkane) aldehyde, 13 (alkane) aldehyde, different 13 (alkane) aldehyde, 16 (alkane) aldehyde, different 18 (alkane) aldehyde, 18 (alkane) aldehyde, 2-methyl 18 (alkane) aldehyde etc.
And be used for refrigerator working medium with under the situation of base oil at the cyclic ketal or the cyclic acetal of first invention, be preferably ketone or the aldehyde shown in the general formula (II) in the general formula (I).
Figure A9519577500191
The carbonatoms of ketone or aldehyde shown in the general formula (II) is 2～25, is preferably 2～17, is more preferably 2～11.Carbonatoms is if surpass 25, and the intermiscibility of then resulting cyclic ketal or cyclic acetal and hydrogen fluorohydrocarbon worsens, thereby bad.
R 3Straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～12 carbon atom are preferably straight chain, side chain or the cyclic alkyl of hydrogen atom or 1～8 carbon atom, are more preferably straight chain, side chain or the cyclic alkyl of hydrogen atom or 1～5 carbon atom.R 4Straight chain, side chain or the cyclic alkyl of 1～12 carbon atom of expression are preferably straight chain, side chain or the cyclic alkyl of 1～8 carbon atom, are more preferably straight chain, side chain or the cyclic alkyl of 1～5 carbon atom.Perhaps, R 3And R 4The alkylidene group that lumps together 2～13 carbon atoms of expression is preferably the alkylidene group of 4～10 carbon atoms, is more preferably the alkylidene group of 4～5 carbon atoms.R 3And R 4The total carbonatoms be 1～13, be preferably 1～10, be more preferably 1～5.
R 3Or R 4Carbonatoms if surpass 12, the intermiscibility deterioration of then resulting cyclic ketal or cyclic acetal and hydrogen fluorohydrocarbon, thereby bad.In addition, R 3And R 4The carbonatoms of alkylidene group that lumps together formation is if surpass 13, the intermiscibility deterioration of then resulting cyclic ketal or cyclic acetal and hydrogen fluorohydrocarbon, thereby bad.And, R 3And R 4The total carbonatoms if surpass 13, the intermiscibility deterioration of then resulting cyclic ketal or cyclic acetal and hydrogen fluorohydrocarbon, thereby bad.
And then, from the intermiscibility of resulting cyclic ketal or cyclic acetal and hydrogen fluorohydrocarbon, R 3, R 4Alkyl have linear chain structure with it not as having side chain or ring texture, and R 3And R 4Lump together, be not so good as not form with its formation alkylidene group.
The general formula (I) that uses in first invention, the ketone shown in (II) can easily react (Wacker method) by lipid acid high temperature decarboxylation dimerization reaction or olefin catalytic oxidation or secondary alcohol oxydehydrogenation or cycloalkanes oxidation etc. obtain.Under the situation of Wacker method, resulting ketone can be refined into pure product by rectifying separation.And the general formula (I) that uses in first invention, the aldehyde shown in (II) can be easily reduce or the direct hydrogenation of lipid acid obtains by the Rosenmund such as the hydroformylation reaction (oxo synthesis) of Fatty Alcohol(C12-C14 and C12-C18) dehydrogenation reaction, alkene, fat acyl chloride.Under the situation of oxo synthesis, generate linear chain aldehyde and branched chain aldehyde, but the both can be refined into pure product by rectifying separation.
In addition, as the active derivative of the carbonyl compound that uses in first invention, have from the lower alcohol of the above ketone, aldehyde and 1～6 carbon atom and pass through the easy synthetic ketal of acid catalysis, acetal.Specific examples as the lower alcohol of 1～6 carbon atom, can enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, primary isoamyl alcohol, neopentyl alcohol, 1-methyl butanol, 1,1-dimethyl propyl alcohol, 1-ethyl propyl alcohol, hexanol, isohexyl alcohol, 2-ethyl butanol, 1-methyl amyl alcohol, 1,3-dimethyl butyrate alcohol, 1-ethyl butanol etc.
Cyclic ketal, the cyclic acetal of first invention can obtain by the following stated method.The reaction of polyvalent alcohol and above-mentioned ketone is a ketal reaction, this reaction is carried out as catalyzer with acid catalysts such as tosic acid, methylsulfonic acid, sulfuric acid, for polyvalent alcohol, catalyst levels is 0.1～10% (mole), is preferably 1.0～7.0% (moles), is more preferably 1.0～5.0% (moles).This reaction is without solvent, or in inert solvents such as dimethylbenzene, toluene, benzene, octane, octane-iso, heptane, hexane, hexanaphthene, pentane, petroleum naphtha (ligroin), sherwood oil or in its mixing solutions, because of the boiling point of use ketone different, 40～130 ℃, 60～100 ℃ temperature is carried out more fortunately, better is the water of removing generation while carrying out.Different because of situation, it also is effective under reduced pressure reacting sometimes.If temperature is lower than this, then reaction can not be carried out; And it is, painted intensive side reaction can take place then, thereby also bad if than this height.Can lead under the condition of nitrogen gas, carry out under the nitrogen atmosphere and under the inferior any condition of dry air atmosphere.Reaction times is different because of various conditions, is preferably 5～200 hours usually.In the resulting cyclic ketal and after filter, pre-treatment such as washing, then, can make with extra care by operations such as clay treatment, crystallization, evaporations.
In addition, the reaction of polyvalent alcohol and above-mentioned aldehyde is an acetalation, this reaction is to use acid catalysts such as tosic acid, methylsulfonic acid, sulfuric acid to carry out as catalyzer, and for polyvalent alcohol, catalyst levels is 0.01～5.0% (mole), be more preferably 0.1～2.0% (mole).This method is without solvent, or in inert solvents such as dimethylbenzene, toluene, benzene, octane, octane-iso, heptane, hexane, hexanaphthene, pentane, butane, petroleum naphtha, sherwood oil or its mixed solvent, because of the boiling point of use aldehyde different, 20～130 ℃, 40～100 ℃ temperature is carried out more fortunately, is preferably the water of removing generation while carrying out.Different because of situation, it also is effective under reduced pressure reacting sometimes.If temperature is low, then reaction can not be carried out; And if painted intensive side reaction then takes place the temperature height.In addition, also can carry out under the logical nitrogen condition, under the nitrogen atmosphere and under the inferior any condition of dry air atmosphere.Reaction times is different because of various conditions, is preferably 1～30 hour usually.In the resulting cyclic acetal and after filter, pre-treatment such as washing, can use operations such as clay treatment, crystallization, distillation to make with extra care then.
In addition, the reaction of the active derivative ketal of polyvalent alcohol and ketone is transketalisation reaction (transketalization), this reaction is to use acid catalysts such as tosic acid, methylsulfonic acid, sulfuric acid to carry out as catalyzer, for polyvalent alcohol, catalyst levels is 0.1～10% (mole), is preferably 1.0～7.0% (moles), is more preferably 1.0～5.0% (moles).This reaction is without solvent, or in inert solvents such as dimethylbenzene, toluene, benzene, octane, octane-iso, heptane, hexane, hexanaphthene, pentane, petroleum naphtha, sherwood oil or in its mixed solvent, because of the boiling point of employed ketal and the lower alcohol that generated different, 40～150 ℃, 70～130 ℃ temperature is carried out more fortunately, better is the lower alcohol of removing generation while carrying out.Different because of situation, it also is effective under reduced pressure reacting sometimes.If temperature is lower than this, then reaction can not be carried out; If than this height, painted intensive side reaction then can take place, thereby bad.In addition, also can carry out under the logical nitrogen condition, under the nitrogen atmosphere and under the inferior any condition of dry air atmosphere.Reaction times is different because of various conditions, is preferably 5～200 hours usually.In the cyclic ketal that obtains and after filter, pre-treatment such as washing, can use operations such as clay treatment, crystallization, distillation to make with extra care then.
In addition, the reaction of the active derivative acetal of polyvalent alcohol and aldehyde is to change acetalation (transacetalization), this reaction is carried out as catalyzer with acid catalysts such as tosic acid, methylsulfonic acid, sulfuric acid, for polyvalent alcohol, catalyst levels is 0.01～5.0% (mole), be preferably 0.1～2.0% (mole).This method is without solvent, or in inert solvents such as dimethylbenzene, toluene, benzene, octane, octane-iso, heptane, hexane, hexanaphthene, pentane, butane, petroleum naphtha, sherwood oil or its mixed solvent, because of the boiling point of employed acetal and the lower alcohol that generated different, 20～150 ℃, 50～130 ℃ temperature is carried out more fortunately, is preferably the lower alcohol of removing generation while carrying out.Different because of situation, it also is effective under reduced pressure reacting sometimes.If temperature is low, then reaction can not be carried out, and if painted intensive side reaction then can take place the temperature height.In addition, also can carry out under the logical nitrogen condition, under the nitrogen atmosphere and under the inferior any condition of dry air atmosphere.Reaction times is different because of various conditions, is preferably 1～30 hour usually.In the cyclic acetal that obtains and after filter, pre-treatment such as washing, can use operations such as clay treatment, crystallization, distillation to make with extra care then.
With the ratio of the active derivative acetal (hereinafter to be referred as carbonyl compound) of the active derivative ketal of the ketone of polyol reaction or ketone or aldehyde or aldehyde, be per 1 mole of polyvalent alcohol A/2 mole carbonyl compound (A is first number of polyvalent alcohol).For improving speed of response, also can adopt with carbonyl compound and react, the method for removing superfluous carbonyl compound again after reaction finishes than A/2 mole surplus.
The cyclic ketal or the cyclic acetal of first invention can make more than one polyvalent alcohol, obtain with more than one ketone or the active derivative ketal of ketone or the active derivative aldolization of aldehyde or aldehyde.In addition, cyclic ketal that obtains separately or cyclic acetal also can mix use.For example, from 1 mole of Sorbitol Powder and 3 moles of cyclic ketal (40 ℃ of viscosity 63.1mm that methyl ethyl ketone obtains 2/ s) and from 1 mole of two Polyglycerine and 2 moles of cyclic ketal (40 ℃ of viscosity 7.69mm that methyl ethyl ketone obtains 2/ s) can synthesize respectively, then both are mixed, adjust to desirable viscosity.As specific examples, the 1 mole of cyclic ketal that obtains from 1 mole of Sorbitol Powder and 3 moles of methyl ethyl ketones mixes with the 1 mole of cyclic ketal that obtains from 1 mole of two Polyglycerine and 2 moles of methyl ethyl ketones, can obtain VG22 lubricating oil.Perhaps, make 1 mole of Sorbitol Powder and 1 mole of two Polyglycerine and 5 moles of methylethyl reactive ketones, can obtain said mixture.In addition, make 1 mole of Sorbitol Powder and two kinds of ketone or aldehyde, for example 2 mole 3,5,5-trimethylammonium hexanal, 1 mole of methylethyl reactive ketone also can obtain the cyclic ketal or the cyclic acetal of first invention.
And, the unreacted hydroxyl that exists in resulting cyclic ketal, the cyclic acetal is few more good more, such unreacted hydroxyl is in mean value, for the hydroxyl value of raw polyol, will be below 20%, more fortunately below 10%, be more preferably below 5%, especially good be below 3%.If there is the unreacted hydroxyl above 20% remaining, then viscosity can be too high, and boiling point or flash-point also can be too low, thereby bad.Be used at this cyclic ketal or cyclic acetal under the situation of base oil of refrigerator working medium, the unreacted hydroxyl is few especially more good more, below 10%, more fortunately below 5%, be more preferably below 3%, especially good be below 2%, preferably below 1%.If there is the unreacted hydroxyl above 10% remaining, then intermiscibility or the electrical insulating property with the hydrogen fluorohydrocarbon can worsen, thereby bad.
In addition, under the situation of the cyclic ketal of first invention or the cyclic acetal base oil that is used for electric insulation oil or refrigerator working medium, polyvalent alcohol does not have the structure person of ehter bond, and its electrical insulating property is higher, thereby better.Therefore, the cyclic ketal or the cyclic acetal that obtain from polyvalent alcohols such as hexavalent alcohol such as Sorbitol Powder, mannitol, melampyrum, iditol, talitol, allitol or tetrahydroxybutanes, the cyclic ketal or the cyclic acetal that obtain than the alcohol that has an ehter bond from two Polyglycerine or dimerization three (methylol) propane etc. are good.
And then, under the situation of the cyclic ketal of first invention or the cyclic acetal base oil that is used for electric insulation oil or refrigerator working medium, contain 1,3-dioxolane structure and/or 1,3-diox structure person, because the electrical insulating property height, thereby better.And, wherein especially contain 1,3-dioxolane structure person is good especially.Therefore, better adopt tetrahydroxybutane, two Polyglycerine, Sorbitol Powder, mannitol, melampyrum, iditol, talitol, allitol etc. that the alcohol of hydroxyl is arranged on the ortho position.And, under the situation of using hexavalent alcohol such as Sorbitol Powder, mannitol, melampyrum, iditol, talitol, allitol, can obtain cyclic ketal or the cyclic acetal shown in formula III a and the formula III b, but have 31, the formula III a compound of 3-dioxolane structure is better high because of its electrical insulating property.And under the situation of using tetrahydroxybutane, can obtain cyclic ketal or the cyclic acetal shown in formula IVa or the formula IVb, but have 21, the formula IVa compound of 3-dioxolane structure is better high because of its electrical insulating property.Hexavalent alcohol such as Sorbitol Powder, mannitol, melampyrum, iditol, talitol, allitol or tetrahydroxybutane if with ketone or ketal reaction, the easy cyclic ketal of production IIIa, formula IVa then, and if with aldehyde or aldolization, the then easy cyclic acetal of production IIIb, formula IVb.Therefore, for these alcohol, be preferably and use ketone or ketal to react.
Moreover, under the situation of the cyclic ketal of first invention or the cyclic acetal base oil that is used for refrigerator working medium, first number of polyvalent alcohol is among the even number person, the cyclic ketal or the cyclic acetal that obtain from hexavalent alcohol shown in the formula (III), or the cyclic ketal or the cyclic acetal that obtain from tetravalent alcohols such as tetrahydroxybutane, two Polyglycerine, dimerization three (methylol) propane shown in the formula (IV)～(VI), from the viewpoint that averages out with various physical propertiess such as the intermiscibility of hydrogen fluorohydrocarbon or electrical insulating property, fusing point, viscosity, be good especially.Even be tetravalent alcohol equally, the cyclic ketal that obtains from the good tetramethylolmethane of symmetry shown in formula (VIIa) or the formula (VIIb) at room temperature all is solid state because of it, thereby also bad.In the compound shown in the formula (III)～(VI), be preferably 1, compound shown in (IIIa) of 3-dioxolane structure, (IIIb), (IVa), (V), wherein especially only to have 1, compound shown in (IIIa) of 3-dioxolane structure, (IVa), (V) wherein is more preferably (IIIa), the compound shown in (IVa) that polyol moiety does not have ehter bond for well.
The cyclic ketal of first invention or the fusing point of cyclic acetal more fortunately below 10 ℃, be more preferably below-10 ℃, good especially be below-30 ℃.As (VIIa), (VIIb) though fusing point bad when surpassing 10 ℃ cyclic ketal or cyclic acetal and using as lubricating oil separately, can be by mixing with low-melting first other cyclic ketal of inventing or cyclic acetal or other lubricating oil and limiting its addition and use.
Figure A9519577500251
The cyclic ketal or the cyclic acetal that use in first invention, its viscosity of 100 ℃ is 1mm more fortunately 2More than/the s～100mm 2Below/the s, be more preferably at 1mm 2More than/the s～50mm 2Below/the s, especially good is at 1mm 2More than/the s～30mm 2Below/the s.
In addition, under the situation of the base oil that cyclic ketal that uses in first invention or cyclic acetal are used for refrigerator working medium, low more good more with two phase separation temperatures of hydrogen fluorohydrocarbon, wish below 10 ℃, more fortunately below 0 ℃, be more preferably below-10 ℃, especially good is below-30 ℃.
The cyclic ketal or the cyclic acetal of first invention can mix use with other lubricating oil.As other lubricating oil, can enumerate hydrocarbon synthesis oil such as mineral oil or polybutene, poly-alpha-olefin, alkylbenzene, aliphatics dibasic acid esters or neo-pentyl polyol ester, polyalkylene glycol, polyphenylene ether, carbonic ether, phosphoric acid ester, silicon ester, silicone oil, PFPE etc., specific examples can be consulted new edition " lubricated physical chemistry " (good fortune study) or " basis of lubricating oil and application " (Corona company) etc.
The cyclic ketal of first invention or the mixture ratio of cyclic acetal and other lubricating oil, the content that it is desirable to cyclic ketal in the compoundoil or cyclic acetal is more than 0.1% (weight), more fortunately more than 1.0% (weight), be more preferably in 5.0% (weight), good especially is more than 10% (weight).If content is lower than 0.1% (weight), then improves the effect of oilness or prevent ester or the effect of hydrolysis such as carbonic ether can not be given full play to.And, under the situation of the cyclic ketal of first invention or the cyclic acetal base oil that is used for refrigerator working medium, other lubricating oil of blended with the intermiscibility excellence person of hydrogen fluorohydrocarbon for well, be preferably neo-pentyl polyol ester or polyalkylene glycol, carbonic ether etc.Yet, under the very excellent situation of the cyclic ketal of first invention or the intermiscibility of cyclic acetal and hydrogen fluorohydrocarbon, also can be in two phase separation temperatures be no more than 10 ℃ scope with such as at two phase separation temperatures below-30 ℃, more fortunately-50 ℃ under the situation below with the bad lubricating oil of the intermiscibility of hydrogen fluorohydrocarbon for example alkylbenzene or mineral oil.
The cyclic ketal of first invention or cyclic acetal be because also excellent with the intermiscibility excellence of hydrogen fluorohydrocarbon, electrical insulating property, thereby the mixture that can be used as with the hydrogen fluorohydrocarbon is used for refrigerator working medium.And, because the electrical insulating property excellence, thereby can be used for electric insulation oil.In addition, because intramolecularly has ring structure, thereby can be used for traction (traction oils).And then, because oilness or excellent heat resistance, thereby can be used for machine oil or turbine oil, gear oil, hydraulic efficiency oil, bearing oil, metalworking fluid, compressor oil, consistent lubricant base oil etc.Moreover, because the oilness excellence, thereby can be used as low-sulfur light oil additive.And, because intramolecularly also contains many Sauerstoffatoms, thereby also can be used as the such fuel oil additive of octane value synergism agent (octane value booster).
Cyclic ketal or cyclic acetal in first invention are used under the situation of refrigerator working medium, the mixture ratio of the refrigerator oil that contains cyclic ketal or cyclic acetal that uses among hydrogen fluorohydrocarbon and the present invention in the refrigerator working fluid compositions of the present invention, normally hydrogen fluorohydrocarbon/refrigerator oil=50/1～1/20 (weight ratio), be preferably 10/1～1/5 (weight ratio).The ratio of hydrogen fluorohydrocarbon is if be higher than hydrogen fluorohydrocarbon/refrigerator oil=50/1, and then the viscosity of hydrogen fluorohydrocarbon-refrigerator oil mixing solutions can descend, thus the possibility that has the oilness of making to worsen, thereby bad.And the ratio of hydrogen fluorohydrocarbon then has the insufficient possibility of refrigerating capacity if be lower than hydrogen fluorohydrocarbon/refrigerator oil=1/20, thereby also bad.
Operable hydrogen fluorohydrocarbon in first invention means methylene fluoride (HFC-32), 1,1-C2H4F2 C2H4F2 (HFC-152a), 1,1,1-Halothane (HFC-143a), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1,1,2,2-Tetrafluoroethane (HFC-134), pentafluoride ethane (HFC-125) etc., especially good is 1,1,1,2-Tetrafluoroethane, methylene fluoride, pentafluoride ethane, 1,1, the 1-Halothane.These hydrogen fluorohydrocarbons can use separately, also can mix use by the hydrogen fluorohydrocarbon more than 2 kinds or 3 kinds.
In the cyclic ketal or cyclic acetal of first invention, also can add lubricating oil additives such as normally used oxidation inhibitor, extreme pressure agent, oiliness improver, defoamer, washing composition dispersion agent, viscosity index improver, rust-preventive agent, non-emulsifying agent in case of necessity.For example, can be used as that oxidation inhibitor uses, have 2, the 6-DI-tert-butylphenol compounds, 2,6-di-t-butyl-4-toluene phenol, 4,4 '-methylene radical two (2, the 6-DI-tert-butylphenol compounds) phenol oxidation inhibitor such as, or P, P-dioctyl phenyl amine, one octyldiphenylamine, thiodiphenylamine, 3,7-dioctyl thiodiphenylamine, phenyl-1-naphthylamine, phenyl-2-naphthylamines, alkyl phenyl-naphthalidine, alkyl phenyl-amine antioxidants such as 2-naphthylamines, or alkyl disulfide, thiodipropionate, sulfur type antioxidants such as benzothiazole, or zinc dialkyl dithiophosphate, diaryl zinc dithiophosphate etc.Its addition for the lubricating oil of cyclic ketal that contains first invention or cyclic acetal, is 0.05～2.0% (weight).
Can be used as extreme pressure agent, oiliness improver uses, such as zinc dialkyl dithiophosphate, zn cpdss such as diaryl zinc dithiophosphate, or thiodipropionate, dialkyl sulfide, dibenzyl sulfide, dialkyl polysulfide, alkyl sulfhydryl, dibenzothiophene, 2,2 '-dithio two sulphur compounds such as (benzothiazoles), tri aromatic ester of phosphic acid or tricresyl phosphite aromatic ester, phosphorus compounds such as tricresyl phosphite alkane ester or tricresyl phosphate alkane ester, chlorine compounds such as chloroparaffin, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum compounds such as molybdenumdisulphide, the perfluoroalkyl polyethers, the trifluorochloroethylene polymkeric substance, fluorine cpd such as fluorographite, silicon compounds such as fatty acid modified polysiloxane, graphite etc.Its addition for the lubricating oil of cyclic ketal that contains first invention or cyclic acetal, is 0.05～10% (weight).
Can be used as that defoamer uses, organosilicon acid esters classes such as silicone oil such as dimethyl polysiloxane or silicic acid diethyl ester etc. are arranged.Its addition for the lubricating oil of cyclic ketal that contains first invention or cyclic acetal, is 0.0005～1% (weight).
Can be used as that the washing composition dispersion agent uses, have sulfonate, phenates, salicylate, phosphoric acid salt, polybutylene-based succinimide, polybutylene-based succinate etc.Its addition for the lubricating oil of cyclic ketal that contains first invention or cyclic acetal, is 0.05～10% (weight).
Cyclic ketal or cyclic acetal in first invention are used under the situation of refrigerator working medium; as additive; can add the benzotriazole and/or the benzotriazole derivatives that are used for the protective money metal surface; also can add the tri aromatic ester of phosphic acid and/or the tricresyl phosphite aromatic ester that are used to improve oilness, also can add be used to improve thermostability, the phenol compound of catching the free radical ability is arranged or metal passivator of sequestering power etc. is arranged.
Can be used for the tri aromatic ester of phosphic acid or the tricresyl phosphite aromatic ester of first invention, 18～70 carbon atoms are arranged, be more preferably 18～50 carbon atoms.Specifically, can enumerate triphenylphosphate, tricresyl phosphate (oxybenzene ester), tricresyl phosphate (diformazan phenyl ester), phosphoric acid (oxybenzene ester) diphenyl ester, phosphoric acid (diformazan phenyl ester) diphenyl ester, tricresyl phosphate (tribromophenyl), tricresyl phosphate (dibromo phenyl ester), tricresyl phosphate (2,4-di-t-butyl phenyl ester), tricresyl phosphate tri aromatic ester of phosphic acid such as (nonyl phenyl esters), or triphenyl phosphite, tricresyl phosphite (oxybenzene ester), tricresyl phosphite (diformazan phenyl ester), phosphorous acid (oxybenzene ester) diphenyl ester, phosphorous acid (diformazan phenyl ester) diphenyl ester, tricresyl phosphite (2,4-tertiary butyl phenyl ester), tricresyl phosphite (nonyl phenyl ester), tricresyl phosphite (tribromophenyl), tricresyl phosphite tricresyl phosphite aromatic ester such as (dibromo phenyl esters), be preferably triphenylphosphate, tricresyl phosphate (oxybenzene ester), tricresyl phosphate (diformazan phenyl ester), tricresyl phosphate (2,4-di-t-butyl phenyl ester), triphenyl phosphite, tricresyl phosphite (oxybenzene ester), tricresyl phosphite (diformazan phenyl ester), tricresyl phosphite (2,4-di-t-butyl phenyl ester).The addition of tri aromatic ester of phosphic acid and/or tricresyl phosphite aromatic ester, for the cyclic ketal or the lubricating oil of cyclic acetal that contain first invention, 0.1～5.0% (weight) normally.Be preferably 0.5～2.0% (weight).
Can be used for first the invention benzotriazole and/or the addition of benzotriazole derivatives, for the lubricating oil that contains cyclic ketal of the present invention or cyclic acetal, normally 0.001～0.1% (weight), be preferably 0.003～0.03% (weight).And, can be used for benzotriazole of the present invention, benzotriazole derivatives has 6～50 carbon atoms, has been preferably 6～30 carbon atoms.Specifically, can enumerate benzotriazole, 5-methyl isophthalic acid H benzotriazole, 1-(dioctyl amino methyl) benzotriazole, 1-(dioctyl amino methyl)-5-Methylbenzotriazole, 2-(5 '-methyl-2 '-hydroxy phenyl) benzotriazole, 2-[2 '-hydroxyl-3 ', 5 '-two (α, α-Er Jiajibianji) phenyl]-the 2H-benzotriazole, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxy phenyl)-the 5-chlorobenzotriazole, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-the 5-chlorobenzotriazole, 2-(3 ', 5 '-two tert-pentyls-2 '-hydroxy phenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-[2 '-hydroxyl-3 '-(3 "; 4 " 5 "; 6 "-tetrahydric phthalimide ylmethyl)-5 '-aminomethyl phenyl] benzotriazole etc., be preferably benzotriazole, 5-methyl isophthalic acid H-benzotriazole etc.
The addition of metal passivator that can be used for first invention, for the lubricating oil that contains cyclic ketal of the present invention or cyclic acetal, normally 0.001～2.0% (weight), be preferably 0.003～0.5% (weight).Can be used for metal passivator of the present invention and be preferably sequestering power, and 5～50 carbon atoms are arranged, better 5～20 carbon atoms are arranged.Specifically, can enumerate N, N '-two salicylidene-1, the 2-diaminoethanes, N, N '-two salicylidene-1, the 2-diaminopropanes, N-salicylidene-N '-dimethyl-1, the 2-diaminoethanes, N, N '-two salicylidene hydrazine, N, N '-two (α, 5-dimethyl salicylidene)-1, the 2-diaminoethanes, N, N '-two (α, 5-dimethyl salicylidene)-1, the 3-propylene diamine, N, N '-two (α, 5-dimethyl salicylidene)-1, the 6-hexanediamine, N, N '-two (α, 5-dimethyl salicylidene)-1, the 10-decamethylene diamine, N, N '-two (α, 5-dimethyl salicylidene) ethylidene tetramine, salicylaldoxime, 2-hydroxy-5-methyl base phenyl methyl ketone oxime, methyl ethyl diketone, methyl aceto acetate, etheric acid-2-ethylhexyl, dimethyl malonate, diethyl malonate, propanedioic acid 2-ethylhexyl, anthranilic acid, nitrilotriacetic acid(NTA), dihydroxyethylglycin, Oxyethylethylenediaminetriacetic acid, the hydroxyethyl imido oxalic acid, quadrol, 3-sulfydryl-1, the 2-propylene glycol, alizarin, quinizarin, mercaptobenzothiazole etc., be preferably N, N '-two salicylidenes-1, N, N '-two salicylidenes-1, methyl ethyl diketone, methyl aceto acetate, alizarin, quinizarin etc.
Can be used for first addition invention, that the phenol compound of free radical capture ability is arranged, for the lubricating oil that contains cyclic ketal of the present invention or cyclic acetal, normally 0.05～2.0% (weight), be preferably 0.05～0.5% (weight).Can be used for phenol compound of the present invention 6～100 carbon atoms are arranged, be preferably 10～80 carbon atoms.Specifically, can enumerate 2, the 6-DI-tert-butylphenol compounds, 2, the 6-di-tert-butyl-4-methy phenol, 4,4 '-methylene radical two (2, the 6-DI-tert-butylphenol compounds), 4 ', the inclined to one side butylidene two of 4-(3 methy 6 tert butyl phenol), 2,2-methylene radical two (4-ethyl-6-tert.-butyl phenol), 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), 4,4 '-inclined to one side isopropylidene biphenol, 2,4-dimethyl-6-tert.-butyl phenol, four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2,2 '-dihydroxyl-3,3 '-two (Alpha-Methyl cyclohexyl)-5,5 '-dimethyl-ditan, 2,2 '-inclined to one side isobutylidene two (4, the 6-xylenol), two [3,3-two (4 '-hydroxyl-3 '-tert-butyl-phenyl) the butyric acid glycol ester, 2,6-two (2 '-hydroxyl-3 '-tertiary butyl-5 '-methyl-benzyl)-the 4-methylphenol, 1,1 '-two (4-hydroxy phenyl) hexanaphthene, 2,5-two amyl hydroquinone, 2, the 5-di-tert-butyl hydroquinone, 1, the 4-dihydroxyanthraquinone, 3-tertiary butyl-4-hydroxy phenylmethylether, 2, the 4-dibenzoyl resorcinol, the 4-tert-butyl catechol, 2,6-di-t-butyl-4-ethylphenol, 2-hydroxyl-4-methoxyl group benzoyl benzene, 2,4-dihydroxyl benzoyl benzene, 2,2 '-dihydroxyl-4-methoxyl group benzoyl benzene, 2,4,5-trihydroxy-benzoyl benzene, alpha-tocopherol, terephthalic acid two [2-(2-hydroxy-5-methyl base-3-tertiary butyl benzyl)-4-methyl-6-tert butyl phenyl ester], triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester], 1,6-hexylene glycol two [3-(3,5-di-t-butyl-4-hydroxyl phenol) propionic ester], 3,9-two [2-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5.5] undecane etc., be preferably 2, the 6-DI-tert-butylphenol compounds, 2,6 di tert butyl 4 methyl phenol, 4,4 '-methylene radical two (2, the 6-DI-tert-butylphenol compounds), 4,4 '-inclined to one side butylidene two (3 methy 6 tert butyl phenol), 2,2 '-methylene radical two (4-ethyl-6-tert.-butyl phenol), 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), 4,4 '-inclined to one side isopropylidene biphenol, 2,4-dimethyl-6-tert.-butyl phenol, four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2,6-di-t-butyl-4-ethylphenol, 2,6-two (2 '-hydroxyl-3 '-tertiary butyl-5 '-methyl-benzyl)-the 4-methylphenol, terephthalic acid two [2-(2-hydroxy-5-methyl base-3-tertiary butyl benzyl)-4-methyl-6-tert butyl phenyl ester], triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester, 1,6-hexylene glycol two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] etc.
In addition, also can be added with machine tin compound, boron compound etc. and can make the stable additive of freon refrigerant.Its addition for the lubricating oil of cyclic ketal that contains first invention or cyclic acetal, is 0.001～10% (weight).
Below explanation second invention.
In the cyclic ketal and cyclic acetal of first invention, compound shown in formula (IIIa), the formula (IIIb) is a novel cpd, below with relate to the cyclic acetal class that comprises these compounds (general formula (i) or (ii) shown in compound) invention be illustrated as second invention.In second invention, the described cyclic ketal of first invention, cyclic acetal are generically and collectively referred to as " cyclic acetal class ".
Figure A9519577500321
R in the formula 5The expression hydrogen atom, in this case, R 6The branched-chain alkyl of 3 carbon atoms of expression or the straight or branched alkyl of 4～21 carbon atoms; Perhaps R 5The straight or branched alkyl of 1～21 carbon atom of expression, in this case, R 6The straight or branched alkyl of 2～21 carbon atoms of expression.
At general formula (i) or in the compound (ii), as the hexavalent alcohol that can provide the hexavalent alcohol residue, the hexavalent alcohol shown in can being listed below particularly.That is, the hexitol that obtains with hexose reduction is as Sorbitol Powder, mannitol, melampyrum, iditol, talitol, allitol etc.
Wherein, from the viewpoint of availability or price, best is Sorbitol Powder.
General formula (i) or (ii) in, at R 5Under the situation for hydrogen atom, R 6It is the branched-chain alkyl of 3 carbon atoms, the perhaps side chain of 4～21 carbon atoms or branched-chain alkyl, be preferably the side chain saturated alkyl of 3 carbon atoms or the straight or branched saturated alkyl of 4～12 carbon atoms, be more preferably the side chain saturated alkyl of 3～12 carbon atoms.
R 63 shown carbon atom branched-chain alkyls are meant sec.-propyl particularly.
And, can be listed below particularly as the straight or branched alkyl of 4～21 carbon atoms.
That is,, can enumerate butyl, amyl group, hexyl, heptyl, octyl group, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, nonadecyl, heneicosyl etc. as straight chained alkyl.
As the alkyl of Alpha-Methyl side chain, can enumerate 1-methyl-propyl, 1-methyl butyl, 1-methyl amyl, 1-methyl hexyl, 1-methylheptyl, 1-Methyl Octyl, 1-methyl nonyl, 1-methyl decyl, 1-methyl undecyl, 1-methyl octadecyl etc.
As the alkyl of α-side chain, can enumerate 1-ethyl propyl, 1-ethyl-butyl, 1-ethyl pentyl group, 1-propyl group butyl, 1-ethylhexyl, 1-propyl group amyl group, 1-ethyl heptyl, 1-propyl group hexyl, 1-butyl amyl group, 1-amyl group hexyl, 1-hexyl heptyl, 1-octyl group nonyl, 1-hexyl undecyl, 1-decyl undecyl etc.
As existing α-side chain and the α-higly branched chain alkyl of the side chain except that α-side chain more than, can enumerate 1,2-dimethyl propyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1-ethyl-2-methyl-propyl, di-isopropyl methyl, 1,4-dimethyl amyl group, 1-sec.-propyl butyl, 1,3,3-trimethylammonium butyl, 1,5-dimethyl hexyl, 1-ethyl-2-methyl amyl, 1-butyl-2-methyl-propyl, 1-ethyl-3-methyl amyl, diisobutyl methyl, 1,5,9-trimethylammonium decyl etc.
As β-branched-chain alkyl, can enumerate 2-methyl-propyl, 2-methyl butyl, 2-methyl amyl, 2-ethyl-butyl, 2-methyl hexyl, 2-ethyl pentyl group, 2-methylheptyl, 2-ethylhexyl, 2-propyl group amyl group etc.
As existing β-side chain and the β-higly branched chain alkyl of the side chain except that α-side chain and β-side chain more than, can enumerate 2,3-dimethylbutyl, 2,4,4-tri-methyl-amyl, 2-sec.-propyl-5-methyl hexyl etc.
As other branched-chain alkyl that exists the side chain except that α-side chain and β-side chain more than, can enumerate 3-methyl butyl, 3-methyl amyl, 4-methyl amyl, 3,3-dimethylbutyl, 3-methyl hexyl, 4-methyl hexyl, 5-methyl hexyl, 3,5,5-trimethylammonium hexyl, isodecyl, 3,7-dimethyl octyl group, different heptadecyl etc.
As there not being the alkyl that tertiary carbon atom is arranged on hydrogen atom and the alpha-position on the alpha-position, can enumerate 1,1-dimethyl ethyl, 1-methyl cyclopropyl, 1,1-dimethyl propyl, 1-methyl cyclobutyl, 1,1-dimethylbutyl, 1,1,2-trimethylammonium propyl group, 1-methylcyclopentyl, 1,1-dimethyl amyl group, 1-methyl isophthalic acid-ethyl-butyl, 1,1-diethyl propyl group, 1,1-diethyl butyl etc.
As there not being the alkyl that tertiary carbon atom is arranged on hydrogen atom and the β-position on β-position, can enumerate 2,2-dimethyl propyl, 2,2-dimethylbutyl, 1,2,2-trimethylammonium propyl group, 1-ethyl-2,2-dimethyl propyl, 2,2-dimethyl amyl group, 2,3-dimethyl-2-sec.-propyl butyl etc.
As there not being the alkyl that tertiary carbon atom is all arranged on hydrogen atom and alpha-position, the β-position on alpha-position, the β-position, can enumerate 1,1,2,2-tetramethyl-propyl group, 1,1,2,2-tetramethyl butyl, 1,1,2,2-tetramethyl-hexyl etc.
In addition, at general formula (i) or (ii), at R 5Be under the situation of straight or branched alkyl of 1～21 carbon atom, R 6It is the straight or branched alkyl of 2～21 carbon atoms.Be more preferably R 5Be the straight or branched saturated alkyl of 1～12 carbon atom, and in this case, R 6Be preferably the straight or branched saturated alkyl of 2～12 carbon atoms.
In these cases, as R 5Shown in the straight or branched alkyl of 1～21 carbon atom, specifically, except that the concrete example of the straight or branched alkyl of above-mentioned 4～21 carbon atoms, can also enumerate methyl, ethyl, propyl group, sec.-propyl.
Therefore, as R 6Shown in the straight or branched alkyl of 2～21 carbon atoms, specifically, except that the concrete example of the straight or branched alkyl of above-mentioned 4～21 carbon atoms, can also enumerate ethyl, propyl group, sec.-propyl.
As above general formula (i) or cyclic acetal class (ii), the specific examples that can be listed below (compound title and structural formula), but be not limited to these.
(1) 1.2: 3.4: 5.6-three-O-(the inclined to one side propylidene of 2-methyl) Sorbitol Powder
(2) 1.3: 2.4: 5.6-three-O-(the inclined to one side propylidene of 2-methyl) Sorbitol Powder
(3) 1.2: 3.4: 5.6-three-O-(3,5, the inclined to one side hexylidene of 5-trimethylammonium) Sorbitol Powder
(4) 1.3: 2.4: 5.6-three-O-(3,5, the inclined to one side hexylidene of 5-trimethylammonium) Sorbitol Powder
(5) 1.2: 3.4: 5.6-three-O-(the inclined to one side propylidene of 1-methyl) Sorbitol Powder
Figure A9519577500361
(6) 1.3: 2.4: 5.6-three-O-(the inclined to one side propylidene of 1-methyl) Sorbitol Powder
Figure A9519577500362
(7) 1.2: 3.4: 5.6-three-O-(1, the inclined to one side butylidene of 3-dimethyl) Sorbitol Powder
(8) 1.3: 2.4: 5.6-three-O-(1, the inclined to one side butylidene of 3-dimethyl) Sorbitol Powder
Figure A9519577500371
(9) 1.2: 3.4: 5.6-three-O-(hexylidene partially) Sorbitol Powder
(10) 1.3: 2.4: 5.6-three-O-(hexylidene partially) Sorbitol Powder
Figure A9519577500373
(11) 1.2: 3.4: 5.6-three-O-(inferior partially isooctadecane base) Sorbitol Powder
Figure A9519577500381
(12) 1.3: 2.4: 5.6-three-O-(inferior partially isooctadecane base) Sorbitol Powder
(13) 1.2: 3.4: 5.6-three-O-(the inclined to one side hexylidene of 2-ethyl) Sorbitol Powder
Figure A9519577500383
(14) 1.3: 2.4: 5.6-three-O-(the inclined to one side hexylidene of 2-ethyl) Sorbitol Powder
Figure A9519577500391
(15) 1.2: 3.4: 5.6-three-O-(the inferior partially octadecyl of 1-heptadecyl) Sorbitol Powder
Figure A9519577500392
(16) 1.3: 2.4: 5.6-three-O-(the inferior partially octadecyl of 1-heptadecyl) Sorbitol Powder
(17) 1.2: 3.4: 5.6-three-O-(the inclined to one side propylidene of 1-methyl) mannitol
(18) 1.3: 2.4: 5.6-three-O-(the inclined to one side propylidene of 1-methyl) mannitol
Figure A9519577500403
Above cyclic acetal class can suitably prepare with the preparation method of second invention, but is not limited thereto.
In addition, the cyclic acetal class of second invention both can be used as polar oil, organic solvent, lubricant, ucon oil, refrigerator oil, also the preparation intermediate of useful as surfactants, organic solvent, polar oil, ucon oil, refrigerator wet goods.
The cyclic acetal class preparation method of second invention below is described.
Preparation method of the present invention is characterized in that making in the presence of acid catalyst hexavalent alcohol and carbonyl compound (ketone or aldehyde) or its active derivative (ketal or acetal) to react.The reaction formula of this reaction is as follows. R in the formula 5And R 6Represent implication same as described above; And, R 7The straight or branched alkyl of 1～6 carbon atom of expression.
Promptly, use acid catalyst, make carbonyl compound or its active derivative generation dehydration reaction or dealcoholizations such as hexavalent alcohol such as the Sorbitol Powder of formula shown in (iii) or mannitol and general formula ketone shown in (iv) or aldehyde, obtain general formula (i) or cyclic acetal class (ii).With under the situation of ketone, mainly obtain general formula (i); And, can obtain general formula (I) and mixture (ii) with under the situation of aldehyde.α-branched-chain alkyl person is arranged in aldehyde, and the content of general formula (i) is more.And if carry out the short period of time reaction, then general formula content (ii) increases.
As operable hexavalent alcohol, can enumerate above-mentioned formula those shown in (iii), specifically, can enumerate the hexitol that obtains with the hexose reduction, i.e. Sorbitol Powder, mannitol, melampyrum, iditol, talitol, allitol etc.Wherein, from the viewpoint of availability or price, Sorbitol Powder is best.
Operable carbonyl compound has ketone or aldehyde in the method for second invention, and ketone wherein can be easily obtains by means of lipid acid high temperature decarboxylation dimerization reaction or olefin catalytic oxidation reaction (Wacker method) or methods such as secondary alcohol oxidation, dehydrogenation or cycloalkanes oxidation.Under the situation of Wacker method, resulting ketone has distribution, but can utilize rectification method separation and purification Cheng Chunpin.The specific examples of ketone can be listed below, but not necessarily is limited to these.
For example, as methyl alkyl ketone, can enumerate methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, Methyl amyl ketone, methyl hexyl ketone, methyl heptyl ketone, Methyl Octyl ketone, methyl nonyl ketone, methyl undecyl ketone, methyl heptadecyl ketone etc.
As dialkyl ketone, can enumerate metacetone, ethyl propyl ketone, ethyl butyl ketone, butyrone, ethyl pentyl group ketone, ethyl hexyl ketone, dibutyl ketone, diamyl ketone, dihexyl ketone, two (undecyl) ketone, two (heptadecyl) ketone etc.
As higly branched chain ketone, can enumerate methyl isopropyl Ketone, methyl sec-butyl ketone, methyl iso-butyl ketone (MIBK), ethyl nezukone, methyl tertbutyl ketone, diisopropyl ketone, methyl isoamyl ketone, sec.-propyl propyl group ketone, methyl neo-pentyl ketone, ethyl tert-butyl ketone, 6-methyl-2-heptanone, 4-methyl-3-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, diisobutyl ketone, 6,10-dimethyl-methyln nonyl ketone etc.
In addition, operable aldehyde, can be easily by means of obtaining such as methods such as the Rosenmund reduction of the hydroformylation reaction (oxo synthesis) of Fatty Alcohol(C12-C14 and C12-C18) dehydrogenation reaction, alkene, fat acyl chloride or the direct hydrogenation of lipid acid.Under the situation of oxo synthesis, can generate linear chain aldehyde and branched chain aldehyde, but can use rectification method separation and purification Cheng Chunpin.Respectively the specific examples of this alkyl aldehydes can be listed below, but not necessarily is limited to these.
For example, as straight chained alkyl aldehyde, can enumerate valeral, hexanal, enanthaldehyde, octanal, capraldehyde, 12 (alkane) aldehyde, 14 (alkane) aldehyde, 18 (alkane) aldehyde, Shan Yu aldehyde etc.
As α-branched-chain alkyl aldehyde, can enumerate isobutyric aldehyde, 2 methyl butyraldehyde, 2 methyl pentanal, 2-ethyl butyraldehyde, 2 methyl hexyl aldehyde, 2-ethyl valeral, 2-methyl enanthaldehyde, 2-ethyl hexanal, 2-propyl group valeral etc.
As the α that also has an above side chain the α-side chain on α-side chain-higly branched chain alkyl, can enumerate 2,3-dimethyl butyraldehyde, 2,4,4-trimethylammonium valeral, 2-sec.-propyl-5-methyl hexanal etc.
As other branched-chain alkyl aldehyde that exists the side chain except that α-side chain more than, can enumerate isovaleric aldehyde, 3-methyl pentanal, 4-methyl pentanal, 3,3-dimethyl butyraldehyde, 3-methyl hexanal, 4-methyl hexanal, 5-methyl hexanal, 3,5,5-trimethylammonium hexanal, isodecyl aldehyde, 3,7-dimethyl octanal, different 18 (alkane) aldehyde etc.
In addition, as the active derivative of operable carbonyl compound in second invention, be to utilize the acid catalyst can be easily from ketal and acetal shown in the lower alcohol synthetic general formula (iv ') of the above ketone, aldehyde and 1～6 carbon atom.As the specific examples that can provide the lower alcohol R7 residue, 1～6 carbon atom, can enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, primary isoamyl alcohol, neopentyl alcohol, 1-methyl butanol, 1,1-dimethyl propyl alcohol, 1-ethyl propyl alcohol, hexanol, isohexyl alcohol, 2-ethyl butanol, 1-methyl amyl alcohol, 1,3-dimethyl butyrate alcohol, 1-ethyl butanol etc.
In second invention, formula (iii) shown in the reaction of hexavalent alcohol and ketone be ketal reaction, ketone and formula (iii) shown in the mol ratio of hexavalent alcohol be 1.5～15, be preferably 2.7～7.5.This reaction is carried out as catalyzer with acid catalysts such as tosic acid, methylsulfonic acid, sulfuric acid, with respect to formula (iii) shown in for the hexavalent alcohol, catalyst levels is 0.1～10% (mole), be preferably 1.0～5% (moles).
This reaction is without solvent, or in inert solvents such as dimethylbenzene, toluene, benzene, octane, octane-iso, heptane, hexane, hexanaphthene, pentane, petroleum naphtha, sherwood oil or in its mixed solvent, because of the boiling point of use ketone different, 30～130 ℃, 60～100 ℃ temperature is carried out more fortunately, is preferably the water of removing generation while carrying out.Carry out if temperature in these scopes, then helps reaction, this is because the painted tendency that has minimizing to cause because of side reaction.In addition, also can carry out under the logical nitrogen condition, under the nitrogen atmosphere and under the inferior any condition of dry air atmosphere.Reaction times is different because of various conditions, is preferably 5～200 hours usually.Resulting cyclic ketal (i) or (ii) filter after the neutralization, pre-treatment such as washing, can use operations such as adsorption treatment, crystallization, distillation to make with extra care then.
In addition, formula (iii) shown in the reaction of hexavalent alcohol and aldehyde be acetalation, aldehyde and formula (iii) shown in the mol ratio of hexavalent alcohol be 1.5～6, be preferably 2.7～3.8.This reaction uses acid catalysts such as tosic acid, methylsulfonic acid, sulfuric acid to carry out as catalyzer, with respect to formula (iii) shown in for the hexavalent alcohol, catalyst levels is 0.01～5% (mole), be preferably 0.1～2% (mole).
This reaction is without solvent, or in inert solvents such as dimethylbenzene, toluene, benzene, octane, octane-iso, heptane, hexane, hexanaphthene, pentane, butane, petroleum naphtha, sherwood oil or its mixed solvent, because of the boiling point of use aldehyde different, 20～130 ℃, 40～100 ℃ temperature is carried out more fortunately, is preferably the water of removing generation while carrying out.Carry out if temperature in these scopes, then helps reaction, this is because the painted trend that has minimizing to cause because of side reaction.And can carry out under the logical nitrogen condition, under the nitrogen atmosphere and under the inferior any condition of dry air atmosphere.Reaction times is different because of various conditions, is preferably 1～30 hour usually.Resulting cyclic acetal (i) or (ii) filter after the neutralization, pre-treatment such as washing, can use operations such as adsorption treatment, crystallization, distillation to make with extra care then.
In addition, formula (iii) shown in the reaction of active derivative ketal (iv ') of hexavalent alcohol and ketone be the transketalisation reaction, ketal (iv ') and formula (iii) shown in the mol ratio of hexavalent alcohol be 1.5～15, be preferably 2.7～7.5.This reaction uses acid catalysts such as tosic acid, methylsulfonic acid, sulfuric acid to carry out as catalyzer, with respect to formula (iii) shown in for the hexavalent alcohol, catalyst levels is 0.1～10% (mole), be preferably 1.0～5% (moles).
This reaction is without solvent, or in inert solvents such as dimethylbenzene, toluene, benzene, octane, octane-iso, heptane, hexane, hexanaphthene, pentane, petroleum naphtha, sherwood oil or in its mixed solvent, because of the boiling point of employed ketal (iv ') and the lower alcohol that generated different, 40～150 ℃, 70～130 ℃ temperature is carried out more fortunately, be preferably and remove the lower alcohol that is generated while carrying out.Carry out if temperature in these scopes, then helps reaction, this is because the minimizing trend painted because of side reaction causes is arranged.In addition, also can carry out under the logical nitrogen condition, under the nitrogen atmosphere and under the inferior any condition of dry air atmosphere.Reaction times is different because of various conditions, is preferably 5～200 hours usually.The cyclic ketal that obtains (i) or (ii) filter after the neutralization, pre-treatment such as washing, can use operations such as adsorption treatment, crystallization, distillation to make with extra care then.
And then, formula (iii) shown in the reaction of active derivative acetal (iv ') of hexavalent alcohol and aldehyde be to change acetalation, acetal (iv ') and formula (iii) shown in the mol ratio of hexavalent alcohol be 1.5～6, be preferably 2.7～3.8.This reaction uses acid catalysts such as tosic acid, methylsulfonic acid, sulfuric acid to carry out as catalyzer, with respect to formula (iii) shown in for the hexavalent alcohol, catalyst levels is 0.01～5% (mole), better is 0.1～2% (mole).
This reaction is without solvent, or in inert solvents such as dimethylbenzene, toluene, benzene, octane, octane-iso, heptane, hexane, hexanaphthene, pentane, butane, petroleum naphtha, sherwood oil or its mixed solvent, because of the boiling point of employed acetal (iv ') and the lower alcohol that generated different, 20～150 ℃, 50～130 ℃ temperature is carried out more fortunately, be preferably and remove the lower alcohol that is generated while carrying out.Carry out if temperature in these scopes, then helps reaction, this is because the minimizing trend painted because of side reaction causes is arranged.In addition, also can carry out under the logical nitrogen condition, under the nitrogen atmosphere and under the inferior any condition of dry air atmosphere.Reaction times is different because of various conditions, is preferably 1～30 hour usually.Resulting cyclic acetal (i) or (ii) filter after the neutralization, pre-treatment such as washing, can use operations such as adsorption treatment, crystallization, distillation to make with extra care then.
Preparation method according to second invention, under the situation of using aldehyde as previously mentioned, can obtain general formula (i) and mixture (ii), but as making both isolating methods, can carry out with the refining means of common Separation of Organic Compounds, for example, can separate with rectifying, column chromatography, tlc, Steppecd crystallization, preparation HPLC (liquid chromatography), preparation type vapor-phase chromatography etc.Yet both are because physical properties etc. is approximate, thereby can both not separated, and former state is used as ucon oil, refrigerator wet goods.
Preparation method according to second invention can obtain above-mentioned cyclic acetal class with the yield higher than simple method.
Preparation example of the present invention, embodiment, synthesis example and test example below are described, but the present invention is not subjected to any restriction of these examples.Be noted that preparation example and embodiment are that first invention is related, synthesis example and test example then are that second invention is related.
Preparation example 1
The dehydrating tube of agitator, thermometer, logical nitrogen pipe and band condenser is installed on 3 liters of 4 mouthfuls of flasks.In described flask, add D-Sorbitol Powder 336.8g (1.85mol), methyl ethyl ketone 800.0g (11.1mol), tosic acid-hydrate 17.6g (0.092mol) and hexane 200ml.Under nitrogen atmosphere, carry out reacting in 8 hours in 69～79 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 19.6g (0.185mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 200g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud,, under reduced pressure remove hexane and superfluous methyl ethyl ketone with rotatory evaporator with saturated aqueous common salt 200g washing.Further underpressure distillation obtains cyclic ketal A 1(hydroxyl value 12.9mgKOH/g, vapor-phase chromatography purity 97.3%).Then, a part of cyclic ketal A 1Further refining with column chromatography, obtain cyclic ketal A 2(hydroxyl value 0.0mgKOH/g, vapor-phase chromatography purity 99.8%).
Preparation example 2
On 3 liters of 4 mouthfuls of flasks, agitator, thermometer, calcium chloride tube are installed and are had the dehydrating tube of condenser.In described flask, add the sherwood oil 400ml of 30～60 ℃ of D-Sorbitol Powder 450.0g (2.47mol), isobutyric aldehyde 588.0g (8.15mol), tosic acid-hydrate 4.7g (0.025mol) and boiling points.Under the dry air atmosphere, carry out reacting in 15 hours in 40～65 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 5.24g (0.049mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud, with saturated aqueous common salt 100g washing, under reduced pressure remove sherwood oil and superfluous isobutyric aldehyde with rotatory evaporator, further underpressure distillation obtains cyclic acetal B (hydroxyl value 6.0mgKOH/g, vapor-phase chromatography purity 99.0%).
Preparation example 3
On 3 liters of 4 mouthfuls of flasks, agitator, thermometer, calcium chloride tube are installed, had the dehydrating tube of condenser.In described flask, add D-Sorbitol Powder 450.0g (2.47mol), butyraldehyde-n 588.0g (8.15mol), tosic acid-hydrate 4.7g (0.025mol) and hexane 400ml.Under the dry air atmosphere, carry out reacting in 5 hours in 62～83 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 5.24g (0.049mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud, with saturated aqueous common salt 100g washing, under reduced pressure remove hexane and superfluous butyraldehyde-n with rotatory evaporator, further underpressure distillation obtains cyclic acetal C 1(hydroxyl value 13.1mgKOH/g, vapor-phase chromatography purity 97.8%).Then, a part of cyclic acetal C 1Further refining with column chromatography, obtain cyclic acetal C 2(hydroxyl value 4.1mg KOH/g, vapor-phase chromatography purity 99.3%).
Preparation example 4
The dehydrating tube of agitator, thermometer, calcium chloride tube, band condenser is installed on 3 liters of 4 mouthfuls of flasks.In described flask, add D-Sorbitol Powder 363.8g (2.00mol), methyl iso-butyl ketone (MIBK) 1200g (12.0mol), tosic acid-hydrate 18.99g (0.100mol) and hexane 300ml.Under the dry air atmosphere, carry out reacting in 23 hours in 93～98 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 21.16g (0.200mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 200g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud,, under reduced pressure remove hexane and superfluous methyl iso-butyl ketone (MIBK), further remove low boiling point component with distillation under vacuum with rotatory evaporator with saturated aqueous common salt 200g washing.The thick ketal 657.6g that obtains filters by atlapulgite, obtains cyclic ketal D 1(hydroxyl value 34.3mgKOH/g, vapor-phase chromatography purity 93.1%).Part cyclic ketal D 1Further refining with column chromatography, obtain cyclic ketal D 2(hydroxyl value 0.0mgKOH/g, vapor-phase chromatography purity 99.6%).
Preparation example 5
The dehydrating tube of agitator, thermometer, calcium chloride tube, band condenser is installed on 3 liters of 4 mouthfuls of flasks.In described flask, add D-Sorbitol Powder 170.8g (0.937mol), 3,5,5-trimethylammonium hexanal 400.0g (2.81mol), tosic acid-hydrate 1.78g (0.0094mol) and hexane 400ml.Under the dry air atmosphere, carry out reacting in 8 hours in 79～81 ℃ at normal pressure, water is steamed.Reaction is cooled to 70 ℃ after finishing, and adds yellow soda ash 1.99g (0.019mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 70 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud,, under reduced pressure remove hexane, further remove low boiling point component with distillation under vacuum with rotatory evaporator with saturated aqueous common salt 100g washing.In the thick acetal 500.9g that obtains, add hexane 500ml, filter, under reduced pressure remove hexane with rotatory evaporator then, obtain cyclic acetal E (hydroxyl value 27.2mgKOH/g, vapor-phase chromatography purity 93.2%) by atlapulgite.
Preparation example 6
Agitator, thermometer, logical nitrogen pipe are installed on 1 liter of 4 mouthfuls of flask and are had the dehydrating tube of condenser.In described flask, add two Polyglycerine 166.0g (1.00mol), methyl ethyl ketone 288.0g (4.00mol), tosic acid-hydrate 3.80g (0.020mol) and hexane 100ml.Under nitrogen atmosphere, carry out reacting in 15 hours in 66～81 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 4.24g (0.040mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud, water 100g washing is under reduced pressure removed hexane and superfluous methyl ethyl ketone with rotatory evaporator, further removes low boiling point component with distillation under vacuum.In resulting thick ketal 223.0g, add activated alumina 0.6g, stirred 30 minutes at 50 ℃.After filtering, obtain cyclic ketal F 1(hydroxyl value 15.7mgKOH/g, vapor-phase chromatography purity 96.7%).Then, a part of cyclic ketal F 1Further refining with column chromatography, obtain cyclic ketal F 2(hydroxyl value 0.0mgKOH/g, vapor-phase chromatography purity 99.7%).
Preparation example 7
The dehydrating tube of agitator, thermometer, logical nitrogen pipe and band condenser is installed on 1 liter of 4 mouthfuls of flask.In described flask, add two Polyglycerine 100.0g (0.602mol), methyl iso-butyl ketone (MIBK) 180.8g (1.81mol), tosic acid-hydrate 2.29g (0.012mol) and toluene 300ml.Under nitrogen atmosphere, carry out reacting in 55 hours in 110～119 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 2.54g (0.024mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud,, under reduced pressure remove toluene and superfluous methyl iso-butyl ketone (MIBK), further carry out underpressure distillation, obtain cyclic ketal G with rotatory evaporator with saturated aqueous common salt 50g washing 1(hydroxyl value 26.2mgKOH/g, vapor-phase chromatography purity 95.1%).Then, a part of cyclic ketal G 1Further refining with column chromatography, obtain cyclic ketal G 2(hydroxyl value 1.6mgKOH/g, vapor-phase chromatography purity 99.5%).
Preparation example 8
The dehydrating tube of agitator, thermometer, calcium chloride tube and band condenser is installed on 3 liters of 4 mouthfuls of flasks.In described flask, add two Polyglycerine 332.4g (2.00mol), diisobutyl ketone 853.4g (6.00mol), tosic acid-hydrate 7.61g (0.040mol) and hexane 500ml.Under the dry air air-flow, carry out reacting in 123 hours in 96～97 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 8.48g (0.080mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud, with saturated aqueous common salt 100g washing, under reduced pressure remove hexane with rotatory evaporator, further diisobutyl ketone is removed in underpressure distillation.In resulting thick ketal 666.7g, add hexane 400ml, filter, under reduced pressure remove hexane with rotatory evaporator then, obtain cyclic ketal H (hydroxyl value 4.0mgKOH/g, vapor-phase chromatography purity 98.0%) by atlapulgite.
Preparation example 9
The dehydrating tube of agitator, thermometer, logical nitrogen pipe and band condenser is installed on 1 liter of 4 mouthfuls of flask.In described flask, add two Polyglycerine 166.0g (1.00mol), 3,5,5-trimethylammonium hexanal 289.7g (2.04mol), tosic acid-hydrate 1.90g (0.010mol) and hexane 150ml.Under nitrogen gas stream, carry out reacting in 8 hours in 75～92 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 2.12g (0.020mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud,, under reduced pressure remove hexane, further remove low boiling point component with distillation under vacuum with rotatory evaporator with saturated aqueous common salt 100g washing.In resultant thick acetal 405.5g, add activated alumina 1.2g, stirred 30 minutes at 50 ℃.After filtering, obtain cyclic acetal I 1(hydroxyl value 23.1mgKOH/g, vapor-phase chromatography purity 94.3%).Then, a part of cyclic acetal I1 is further refining with column chromatography, obtains cyclic acetal I 2(hydroxyl value 2.7mgKOH/g, vapor-phase chromatography purity 99.1%).
Preparation example 10
The dehydrating tube of agitator, thermometer, logical nitrogen pipe and band condenser is installed on 1 liter of 4 mouthfuls of flask.In described flask, add two Polyglycerine 100.0g (0.602mol), 6-hendecanone 205.g (1.20mol), tosic acid-hydrate 2.29g (0.012mol) and toluene 300ml.Under nitrogen gas stream, carry out reacting in 48 hours in 122～124 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 2.54g (0.024mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud,, under reduced pressure remove toluene, further carry out underpressure distillation, obtain cyclic ketal J with rotatory evaporator with saturated aqueous common salt 50g washing 1(hydroxyl value 13.2mgKOH/g, vapor-phase chromatography purity 96.5%).Then, a part of cyclic ketal J 1Further refining with column chromatography, obtain cyclic ketal J 2(hydroxyl value 0.9mgKOH/g, vapor-phase chromatography purity 99.0%).
Preparation example 11
The dehydrating tube of agitator, thermometer, logical nitrogen pipe and band condenser is installed on 1 liter of 4 mouthfuls of flask.In described flask, add meso tetrahydroxybutane 122.0g (1.00mol), methyl ethyl ketone 288.0g (4.00mol), tosic acid-hydrate 3.80g (0.020mol) and hexane 100ml.Under nitrogen atmosphere, carry out reacting in 15 hours in 63～78 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 4.24g (0.040mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud, water 100g washing is under reduced pressure removed hexane and superfluous methyl ethyl ketone with rotatory evaporator, further carries out underpressure distillation, obtains cyclic ketal K (hydroxyl value 1.0mgKOH/g, vapor-phase chromatography purity 99.4%).
Preparation example 12
The dehydrating tube of agitator, thermometer, calcium chloride tube and band condenser is installed on 3 liters of 4 mouthfuls of flasks.In described flask, add meso tetrahydroxybutane 270.0g (2.21mol), 3,5,5-trimethylammonium hexanal 629.0g (4.42mol), tosic acid-hydrate 4.21g (0.022mol) and hexane 600ml.Under the dry air atmosphere, carry out reacting in 7 hours in 76～83 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 4.68g (0.040mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud,, under reduced pressure remove hexane, further remove low boiling point component with distillation under vacuum with rotatory evaporator with saturated aqueous common salt 100g washing.In resulting thick acetal 781.8g, add hexane 400ml, filter, under reduced pressure remove hexane with rotatory evaporator then, obtain cyclic acetal L by atlapulgite 1(hydroxyl value 20.2mgKOH/g, vapor-phase chromatography purity 95.3%).Then, a part of cyclic acetal L 1Further refining with column chromatography, obtain cyclic acetal L2 (hydroxyl value 5.1mgKOH/g, vapor-phase chromatography purity 98.0%).
Preparation example 13
The dehydrating tube of agitator, thermometer, logical nitrogen pipe and band condenser is installed on 3 liters of 4 mouthfuls of flasks.In described flask, add D-mannitol 336.8g (1.85mol), methyl ethyl ketone 800.0g (11.1mol), tosic acid-hydrate 17.6g (0.092mol) and hexane 200ml.Under nitrogen atmosphere, carry out reacting in 10 hours in 68～76 ℃ at normal pressure, water is steamed.Reaction is cooled to 60 ℃ after finishing, and adds yellow soda ash 19.6g (0.185mol, 2 times of equivalents of tosic acid) and neutralizes, and stirs 30 minutes at 60 ℃.Add water 200g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud,, under reduced pressure remove hexane and superfluous methyl ethyl ketone with rotatory evaporator with saturated aqueous common salt 200g washing.Further underpressure distillation, refining with column chromatography, obtain cyclic ketal M (hydroxyl value 0.2mgKOH/g, vapor-phase chromatography purity 99.6%).
Preparation example 14
The dehydrating tube of agitator, thermometer and band condenser is installed on 3 liters of 4 mouthfuls of flasks.In described flask, add three (methylol) propane 500g (3.73mol), 2,2-Propanal dimethyl acetal 777g (7.46mol) and tosic acid-hydrate 14.17g (0.075mol).Under nitrogen atmosphere, carry out reacting in 2 hours in 60～70 ℃ at normal pressure, methyl alcohol is steamed.After reaction finishes, carry out the aftertreatment same, further carry out underpressure distillation, obtain 1,3-two oxa-s-5-ethyl-2,2-dimethyl-5-hexahydrobenzyl alcohol (Na) 584.9g (yield 90%, hydroxyl value 322.6mgKOH/g) with preparation example 13.
On 2 liters of 4 mouthfuls of flasks, agitator, thermometer, condenser and dropping funnel are installed, are carried out nitrogen replacement.In described flask, add sodium hydride (content 60%, oily) 20.0g (0.5mol), 1,2-glycol dimethyl ether 450ml and dimethyl sulfoxide (DMSO) 150ml.Under nitrogen atmosphere, in room temperature, drip the above-mentioned compound that obtains (Na) 87.1g (0.5mol) with 15 fens clock times, further stirred 1 hour, add ethylene glycol bisthioglycolate p-toluenesulfonic esters (Tokyo changes into corporate system) powder 77.0g (0.208mol) with 30 fens clock times subsequently.Under nitrogen atmosphere, spend the night, add water 750ml, Anaesthetie Ether 500ml then 70 ℃ of stirrings, layering, water layer extracts 2 times with Anaesthetie Ether 300ml.Merge organic layer, with 5% aqueous sodium carbonate 300ml washing 3 times, with the mixture drying of anhydrous sodium sulphate and anhydrous sodium carbonate.Except that desolvating, obtain oily mater 115.3g with rotatory evaporator.Further use silica gel column chromatography (is to launch solvent with the hexane/ethyl acetate) that it is refining, obtain ethylene glycol bisthioglycolate [1,3-two oxa-s-5-ethyl-2,2-dimethyl-5-cyclohexyl] methyl ether (Nb) 51g (column chromatography purity 99%, hydroxyl value 0.0mgKOH/g).
On 1 liter of 4 mouthfuls of flask, agitator, thermometer and condenser are installed.In described flask, add the above-mentioned compound that obtains (Nb) 50g (0.13mol), ethanol 500ml and 1N hydrochloric acid 50ml.Under nitrogen atmosphere, 80～100 ℃ of backflows, carry out reaction in 5 hours, cool to room temperature neutralizes with 1N sodium hydroxide then.Under reduced pressure steam solvent fully, resulting residue is dissolved in the water, carries out removing moisture after the electrodialysis, obtains 2,9-diethyl-2,9-two (methylol)-4,7-dioxadecane-1,10-glycol (Nc) 37.6g.
The dehydrating tube of agitator, thermometer and band condenser is installed on 4 mouthfuls of flasks of 300ml.In described flask, add the above-mentioned compound that obtains (Nc) 37g (0.13mol), methyl ethyl ketone 28.1g (0.39mol), tosic acid-hydrate 0.49g (0.0026mol) and hexane 50g.Under nitrogen atmosphere, carry out reacting in 8 hours in 60～70 ℃ at normal pressure, water is steamed.After reaction finishes, carry out the aftertreatment same, remove with rotatory evaporator and desolvate, obtain oily mater 52.3g with preparation example 13.Further use silica gel column chromatography (is to launch solvent with the hexane/ethyl acetate) that it is refining, obtain ethylene glycol bisthioglycolate [1,3-two oxa-s-2,5-diethyl-2-methyl-5-cyclohexyl] methyl ether (cyclic ketal N) 45g (column chromatography purity 98.5%, hydroxyl value 0.0mgKOH/g).
Preparation example 15
In 3 liters reaction vessel, add three (methylol) propane 292.1g (2.18mol), acetone 474.0g (8.17mol), tosic acid-hydrate 6.0g (0.0315mol) and hexane 900ml, refluxed 24 hours, the water that produces is rejected to outside the system.Reactant with in the aqueous sodium hydroxide solution and after, under reduced pressure distillation has been synthesized 5-methylol-5-ethyl-2,2-dimethyl-1,3-diox.
Then, in the stainless steel autoclave of 500ml (being equipped with agitator, liquid ingress pipe, gas outlet pipe, thermometer), add above-mentioned 5-methylol-5-ethyl-2,2-dimethyl-1,3-diox 17.4g (0.1mol), 28% (weight) methanol solution of sodium methylate 0.19g (0.001mol) and toluene 5ml, under 110 ℃ of heating, slowly reduced pressure (0.4mmHg) from normal pressure, low boiling point component is steamed from gas outlet pipe with 1 hour time.After airtight, at 110 ℃, with 8 hour time propylene oxide 58.0g (1.0mol) from the liquid ingress pipe imports autoclave.After the cooling, in reactant, add 28% (weight) methanol solution of sodium methylate 21.2g (0.11mol) and toluene 150ml, under 110 ℃ of heating, slowly reduced pressure (0.4mmHg) from normal pressure, low boiling point component is steamed from gas outlet pipe with 2 hour time.
After the cooling, add methyl-iodide 15.6g (0.11mol), airtight, 60 ℃ of heating 3 hours, further 90 ℃ of heating 5 hours.2.8g Kyoward600 (alkali sorbent material, consonance chemical industrial company system) is added in the cooling back, stirs 1 hour after-filtration, obtains being used for the relatively oily fa of product (vapor-phase chromatography purity 78%).Part fa is further refining with column chromatography, obtains being used for the relatively oily f of product (vapor-phase chromatography purity 85%).
Embodiment 1
Measure preparation example cyclic ketal that obtain, that be used for the present invention's product or cyclic acetal A 1The ratio of the hydroxyl value of～N (JISK-0070) and hydroxyl value that obtain from this hydroxyl value, unreacted hydroxyl and raw polyol, the kinetic viscosity (JISH-2283) of 40 ℃ and 100 ℃, yield point (JISK-2269).It the results are shown in table 1.In addition, also measured and be used for relatively 40 ℃ and 100 ℃ kinetic viscosity (JISK-2283), the yield point (JISK-2269) of the oily a～f of product.The results are shown in Table 2 for it.
Table 1
The cyclic ketal acetal 40 ℃ of viscosity (mm 2/s) 100 ℃ of viscosity (mm 2/s) Yield point (℃)
Raw alcohol The raw material keto-aldehyde Hydroxyl value (mgKOH/g) Unreacted hydroxyl (%)
?A 1 Sorbitol Powder Methyl ethyl ketone ????12.9 ????1.3 ????66.9 ????4.62 ????-32.5
?A 2 Sorbitol Powder Methyl ethyl ketone ????0.0 ????0.0 ????63.1 ????4.54 ????-32.5
?B Sorbitol Powder Isobutyl-aldehyde ????6.0 ????0.61 ????167.8 ????5.81 ????-25.0
?C 1 Sorbitol Powder Normal-butyl aldehyde ????13.1 ????1.3 ????68.2 ????5.49 ????-37.5
?C 2 Sorbitol Powder Normal-butyl aldehyde ????4.1 ????0.42 ????65.6 ????5.42 ????-37.5
?D 1 Sorbitol Powder Methyl iso-butyl ketone (MIBK) ????34.3 ????4.2 ????62.3 ????5.61 ????-27.5
?D2 Sorbitol Powder Methyl iso-butyl ketone (MIBK) ????0.0 ????0.0 ????53.9 ????5.36 ????-27.5
?E Sorbitol Powder 3,5,5-trimethylammonium hexanal ????27.2 ????4.3 ????394.6 ????15.5 ????-20.0＞
?F 1 Two Polyglycerine Methyl ethyl ketone ????15.7 ????1.9 ????7.69 ????1.97 ????-45.0＞
?F 2 Two Polyglycerine Methyl ethyl ketone ????0.0 ????0.0 ????6.82 ????1.87 ????-45.0＞
?G 1 Two Polyglycerine Methyl iso-butyl ketone (MIBK) ????26.2 ????3.8 ????9.08 ????2.35 ????-20.0＞
?G 2 Two Polyglycerine Methyl iso-butyl ketone (MIBK) ????1.6 ????0.24 ????7.83 ????2.16 ????-20.0＞
Table 1 (continuing)
Figure A9519577500551
Table 2
Figure A9519577500561
Embodiment 2
Preparation example cyclic ketal that obtain, that be used for the present invention's product or cyclic acetal A have been investigated 1～D 2, F 1～I 2, K, M, N and 1,1,1,2-Tetrafluoroethane (HFC-134a), or 1,1,1, the mix refrigerant of 2-Tetrafluoroethane and methylene fluoride (HFC-32), or 1,1,1, the intermiscibility of the mix refrigerant of 2-Tetrafluoroethane and methylene fluoride and pentafluoride ethane (HFC-125).
Measured shown in the table 3, cyclic ketal or cyclic acetal A 1～D 2, F 1～I 2, K, M, N and 1,1,1,2-Tetrafluoroethane (HFC-134a) or 1,1,1, the mix refrigerant or 1 of 2-Tetrafluoroethane and methylene fluoride (HFC-32), 1,1, the composition of the mix refrigerant of 2-Tetrafluoroethane and methylene fluoride and pentafluoride ethane (HFC-125) is the present invention's product 1～20, with be used for the relatively oily a (naphthenic oil) and 1 of product, 1,1, the composition of 2-Tetrafluoroethane i.e. product 1 two phase separation temperatures at low temperatures relatively.The results are shown in Table 3.
As can be seen from Table 3, product of the present invention and hydrogen fluorohydrocarbon intermiscibility at low temperatures are excellent.In the present invention's product, cyclic ketal or cyclic acetal A 1, A 2, B, D 1, D 2, F 1, F 2, G 2, K, M composition be excellent especially.In addition, cyclic ketal A 1With A 2(the present invention's product 1 and 2), D 1With D 2(the present invention's product 6 and 7), cyclic acetal I 1With I 2(the present invention's product 11 and 17) compare, and as can be seen, the unreacted hydroxyl is few more, and are just good more with the intermiscibility of hydrogen fluorohydrocarbon.
Table 3
Form Two phase separation temperatures (℃)
Oil is planted The hydrogen fluorohydrocarbon Oil concentration (volume %)
????1 ????6 ????10 ????20 ????30 ????40 ????50
The present invention's product ??1 Cyclic ketal A 1 ??HFC134a ???-67 ???-55 ???-60 ???-67 ???-66 ???-68 ????-69
??2 Cyclic ketal A 2 ??HFC134a ???-70＞ ???-70＞ ???-70＞ ???-70＞ ????-70＞
??3 Cyclic ketal A 2 HFC134a/HFC32 (70/30 weight ratio) ???-70＞ ???-70＞ ???-57 ???-53 ???-54 ????-57
??4 Cyclic acetal B ??HFC134a ???-70＞ ???-62 ???-44 ???-39 ???-39 ????-42
??5 Cyclic acetal C 1 ??HFC134a ????9 ????13 ????14 ????15 ????15
??6 Cyclic ketal D 1 ??HFC134a ???-4 ????2 ????6 ????5.5 ????5
??7 Cyclic ketal D 2 ??HFC134a ???-17 ???-1 ????5 ????4.5 ????2
??8 Cyclic ketal F 1 ??HFC134a ???-70＞ ???-70＞ ???-70＞ ???-70＞ ???-70＞ ???-70＞ ???-70＞
??9 Cyclic ketal F 1 HFC134a/HFC32 (70/30 weight ratio) ???-70＞ ???-70＞ ???-70＞ ???-70＞ ???-70＞
??10 Cyclic ketal H ??HFC134a ???-10 ????13 ????16 ????13 ????4
??11 Cyclic acetal I 1 ?HFC134a ???-13 ????10 ????14 ????11 ???-2
Relatively product 1 A (naphthenic oil) HFC134a ????20＜ ????20＜ ????20＜ ????20＜ ????20＜ ????20＜
Table 3 (continuing)
Form Two phase separation temperatures (℃)
Oil is planted The hydrogen fluorohydrocarbon Oil concentration (volume %)
The present invention's product ???1 ???6 ???10 ???20 ???30 ???40 ???50
??12 Cyclic ketal A 2 HFC134a/HFC32/HFC125 (52/23/25 weight ratio) ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞
??13 Cyclic ketal F 2 ??HFC134a ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞
??14 Cyclic ketal F 2 HFC134a/HFC32 (70/30 weight ratio) ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞
??15 Cyclic acetal F 2 HFC134a/HFC32/HFC125 (52/23/25 weight ratio) ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞
??16 Cyclic ketal G 2 ??HFC134a ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞
??17 Cyclic ketal I 2 ??HFC134a ??-19 ???9 ???12 ???9 ???3
??18 Cyclic ketal K ??HFC134a ??-27 ??-20 ??-17 ??-15 ??-15
??19 Cyclic ketal M ??HFC134a ??-46 ??-38 ??-30 ??-27 ??-28
??20 Cyclic ketal N ??HFC134a ??-70＞ ??-70＞ ??-70＞ ??-70＞ ??-70＞
Embodiment 3
Investigate preparation example cyclic ketal A that obtain, that be used for the present invention's product 2With 1,1,1, the composition of 2-Tetrafluoroethane (HFC-134a) is the present invention's product 2 intermiscibilities at high temperature.To volume is 372cm 3, be equipped with in the autoclave of sight glass and add 60.0g cyclic ketal A 2And 240.0gHFC-134a, agitation as appropriate limit, limit is heated to 100 ℃ from room temperature, observes the separate stage of mixing solutions with appearance method.
The present invention's product 2 (oil concentration 20% (weight)) ℃ all are uniform dissolution from room temperature to 100, do not observe separate stage.Get 20.0g cyclic ketal A equally 2With 380.0g HFC-134a, investigate its separate stage, also demonstrating the present invention's product 2 (oil concentration 5% (weight)) ℃ all is uniform dissolution from room temperature to 100, does not observe separate stage.
Equally, the present invention's product 2 of oil concentration 10% (weight), 30% (weight), 40% (weight), 50% (weight) also demonstrate from room temperature to 100 ℃ all be uniform dissolution, do not observe separate stage.
Embodiment 4
Investigate preparation example cyclic ketal A that obtain, that be used for the present invention's product 1, A 2, B, C 2, D 1, D 2, F 2, I 1, J 2, K, L 1, M, N and be used for the oily b (polyalkylene glycol) of product relatively, the electrical insulating property of f.In addition, equally also investigated cyclic ketal A 2Be used for the relatively electrical insulating property of the mixture of the oily b of product (50: 50 (weight ratio)).
Mensuration is undertaken by JISC-2101, promptly measures 25 ℃ volume specific resistance.The results are shown in Table 4.
Table 4
Oil is planted Volume specific resistance (Ω cm)
The oil that is used for the present invention's product Cyclic ketal A 1Cyclic ketal A 2Cyclic ketal D 1Cyclic ketal D 2Cyclic ketal A 2+ be used for the relatively oily b of product (50: 50 weight ratios) cyclic acetal B cyclic acetal C 2Cyclic ketal F 2Cyclic acetal I 2Cyclic ketal J 2Cyclic ketal K cyclic acetal L 2Cyclic ketal M cyclic ketal N ????1.7×10 15????9.4×10 15????4.7×10 14????5.8×10 15????1.5×10 13????3.6×10 14????1.7×10 13????2.1×10 15????1.8×10 14????1.3×10 14????8.9×10 15????7.8×10 15????3.9×10 15????5.4×10 12
The oil that is used for comparative example B (polyalkylene glycol) ????7.8×10 11
??f ????8.3×10 11
As can be seen from Table 4, the volume specific resistance height of the present invention's product, electrical insulating property all is better than comparative example b, f.In addition, the cyclic ketal or the cyclic acetal that use in the present invention's product mix with polyalkylene glycol, also can improve the electrical insulating property of polyalkylene glycol.And, cyclic ketal A 1With A 2, D 1With D 2Relatively, show that also the few more person's electrical insulating property of unreacted hydroxyl is good more.And then, cyclic ketal A 2With cyclic acetal B, C 2Relatively, also show the cyclic ketal A that obtains from ketone 2Than the cyclic acetal B, the C that obtain from aldehyde 2Better electrical insulating property is arranged.Analyze and gc analysis by NMR (nucleus magnetic resonance), show cyclic ketal A 2Be the IIIa structure all, and the IIIa of cyclic acetal B, C structure/IIIb texture ratio is respectively 56/44,36/66.Therefore, have 1,3-dioxolane structure person, electrical insulating property is more excellent.On the other hand, polyol moiety has the cyclic ketal N of 2 ehter bonds, 1 ehter bond is arranged or do not have the cyclic ketal of ehter bond or cyclic acetal A～M to compare with polyol moiety, and electrical insulating property is relatively poor.
Embodiment 5
That preparation example obtains in order to investigate, as to be used for the present invention's product cyclic ketal or cyclic acetal A 1, A 2, B, D 2, F 1, G 2, K, M and 1,1,1,2-Tetrafluoroethane (HFC-134a) or 1,1,1, the mix refrigerant of 2-Tetrafluoroethane and methylene fluoride or 1,1,1, the composition of the mix refrigerant of 2-Tetrafluoroethane and methylene fluoride and pentafluoride ethane is the thermostability of the present invention's product 1,2,3,4,7,8,12,16,18,19, carries out the tube sealing test under condition shown below.
That is, make moisture concentration reach 10ppm is following, acid number reaches the following preparation of 0.03 (mgKOH/g) lubricating oil 10g and hydrogen fluorohydrocarbon 5g in advance and pack into together in the Glass tubing, add iron, copper, aluminium as catalyzer, tube sealing.Carry out test in 14 days at 175 ℃, investigate the outward appearance of hydrogen fluorohydrocarbon and the composition of oil then and have or not precipitate, open tube sealing, remove the dehydrogenation fluorohydrocarbon, measure the acid number of oil then.The results are shown in Table 5.
As can be seen from Table 5, the present invention's product all are that outward appearance well, does not have precipitate yet and acid number does not rise yet, good thermal stability.
Table 5
Physical properties after the test
Outward appearance Have or not precipitate The acid number (mgKOH/g) of oil
The present invention's product ??1 No change Do not have ??????0.03＞
??2 No change Do not have ??????0.03＞
??3 No change Do not have ??????0.03＞
??4 No change Do not have ??????0.03＞
??7 No change Do not have ??????0.03＞
??8 No change Do not have ??????0.03＞
??12 No change Do not have ??????0.03＞
??16 No change Do not have ??????0.03＞
??18 No change Do not have ??????0.03＞
??19 No change Do not have ??????0.03＞
Embodiment 6
That preparation example obtains in order to investigate, as to be used for the present invention's product cyclic ketal or cyclic acetal A 1, A 2, B, D 2, F 1, G 2, K, M and 1,1,1,2-Tetrafluoroethane (HFC-134a) or 1,1,1, the mix refrigerant of 2-Tetrafluoroethane and methylene fluoride or 1,1,1, the composition of the mix refrigerant of 2-Tetrafluoroethane and methylene fluoride and pentafluoride ethane is the present invention's product 1,2,3,4,7,8,12,16,18,19 and is used for relatively oily c, the d (ester) and 1 of product, 1,1, the composition of 2-Tetrafluoroethane (HFC-1 34a) i.e. is the thermostability of product 2,3 in the presence of water relatively, carries out the tube sealing test under condition shown below.In addition, for cyclic ketal A1 and be used for the relatively mixture of the oily c of product (50: 50 weight ratios) and 1,1,1, the composition of 2-Tetrafluoroethane (HFC-134a) is the present invention's product 21, has also carried out same test.
That is, make water concentration reach the lubricating oil 10g that 3000ppm, acid number reach the following preparation of 0.03 (mgKOH/g) in advance, pack in the Glass tubing, add iron, copper, aluminium as catalyzer, tube sealing with hydrogen fluorohydrocarbon 5g.175 ℃ carry out test in 14 days after, observe the outward appearance of hydrogen fluorohydrocarbon and the composition of oil and have or not precipitate, open tube sealing, remove the acid number of measuring oil behind the dehydrogenation fluorohydrocarbon.The results are shown in Table 6.
As can be seen from Table 6, the present invention's product all are that outward appearance is good, also do not have precipitate and acid number does not rise yet, and the thermostability in the presence of water is good.In addition, shown in the present invention's product 21, in ester, add cyclic ketal of the present invention or cyclic acetal, can prevent the hydrolysis of ester.
Table 6
Physical properties after the test
Outward appearance Have or not precipitate The acid number (mgKOH/g) of oil
The present invention's product ??1 No change Do not have ??????0.03＞
??2 No change Do not have ??????0.03＞
??3 No change Do not have ??????0.03＞
??4 No change Do not have ??????0.03＞
??7 No change Do not have ??????0.03＞
??8 No change Do not have ??????0.03＞
??12 No change Do not have ??????0.03＞
??16 No change Do not have ??????0.03＞
??18 No change Do not have ??????0.03＞
??19 No change Do not have ??????0.03＞
??21 No change Do not have ??????0.03＞
Product relatively ??2 No change Do not have ??????6.7
??3 No change Do not have ??????4.4
Embodiment 7
Cyclic ketal that obtains for preparation example, be used for the present invention's product or cyclic acetal A 1, B and 1,1,1, the composition of 2-Tetrafluoroethane (HFC-134a) is the present invention 1,4, and is used for relatively oily d, the e (ester) and 1,1,1 of product, the composition of 2-Tetrafluoroethane (HFC-134a) i.e. product 3,4 relatively, have investigated wear resistant with the Falex test.
Oily 100ml is warmed to 80 ℃, feeds 1,1,1 with the speed of 10L per hour, 2-Tetrafluoroethane (HFC-134a) with the load running of 150 (1b) 4 hours, is measured the wear loss of running back V slide block (block) and pin (pin).The results are shown in Table 7.
As can be seen from Table 7, the present invention's product all are that wear loss is few, wear resistant is excellent.
Table 7
Wear loss (mg)
The present invention's product 1 the present invention's product 4 ?????3.7 ?????1.5
Product 3 product 4 relatively relatively ?????16.4 ?????8.1
Embodiment 8
Investigated preparation example cyclic ketal A that obtain, that be used for the present invention's product 2With the oily b (polyalkylene glycol) that is used for product relatively, the water absorbability of c (ester).
In the Glass tubing of internal diameter 18mm, the about 10ml of volume, add oily 2g moisture concentration is reached prepare below the 50ppm, place in 25 ℃, the thermostatic bath of humidity 80%.After placing certain hour, measure the moisture concentration of oil with Karl Fischer method (JISK-2275).The results are shown in Table 8.
As can be seen from Table 8, be used for the cyclic ketal of the present invention's product or the water absorbability of cyclic acetal and be significantly less than polyalkylene glycol, but approximately identical with ester.
Table 8
Moisture concentration (ppm)
0 day 1 day 3 days 6 days 9 days
Be used for oily A of the present invention 2 ???45 ????1,965 ????2,575 ????2,588 ????2,697
Be used for the relatively oily b of product ???47 ????13,400 ????17,600 ????19,100 ????19,800
Be used for the relatively oily c of product ???23 ????1,352 ????1,742 ????1,780 ????1,779
Embodiment 9
The cyclic ketal A that obtains for preparation example, be used for the present invention's product 1, A 2Be used for the relatively oily e (ester) of product, carry out compressor test with commercially available rotary compressor.
Inject the oily 170g, 1,1,1 moisture concentration is reached prepare below the 20ppm in rotary compressor, 2-Tetrafluoroethane (HFC-134a) 60g carries out 500 hours continuous operation 140 ℃ of compression case temperature.
After 500 hours finish, cyclic ketal A 1, A 2The oily e of product compares with being used for relatively, painted less, hydroxyl value also not change, and also do not find the existence of resolvent or polymkeric substance in gas chromatographic analysis or gel osmoticing chromatogram analysis, shows that the stability of oil is good.In addition, as shown in table 9, with regard to the abrasion of slide unit, cyclic ketal A 1, A 2The oily e of product compares with being used for relatively, wear away little, thereby oilness excellence.And, with regard to the mud attachment state of discharge section, cyclic ketal A 1, A 2Also the oily e of product lacks than being used for relatively, thereby is good.
Table 9
The impeller tip abrasion Adhesion on the impeller side
Be used for oily A of the present invention 1 ????5μm Do not have
Be used for oily A of the present invention 2 ????5μm Do not have
Be used for the relatively oily e of product ????20μm Have
Embodiment 10
The cyclic ketal A that obtains for preparation example, be used for the present invention's product 2, investigate its oilness with the Falez test.
In low-sulfur light oil (S=0.04%), add cyclic ketal A 2, make it to reach 50ppm, under 25 ℃ atmosphere,, measure the wear loss of running back V slide block (block) and pin (pin) with the load running of 150 (1b) 3 hours.The results are shown in Table 10.
As can be seen from Table 10, added cyclic ketal A 2The present invention's product 22 with do not add A 2Relatively product 5 compare, wear loss is little, and compares with the light oil (relatively product 6) of sulphur concentration 0.2%, wear loss is also still little, shows the oilness excellence.
Table 10
Wear loss (mg)
The present invention's product 22 Low-sulfur light oil (S=0.04%)+cyclic ketal A 2?50ppm ????20.0
Relatively product 5 Low-sulfur light oil (S=0.04%) ????38.0
Relatively product 6 Light oil (0.2%) ????24.8
Embodiment 11
The cyclic ketal A that obtains for preparation example, be used for the present invention's product 2, (Soda ' spendulum) its oilness is investigated in test with the pendulum of field once.
In low-sulfur light oil (S=0.04%), add cyclic ketal A 2, make it to reach 50ppm, measure 25 ℃ frictional coefficient.The results are shown in Table 11.
As can be seen from Table 11, added cyclic ketal A 2The frictional coefficient of the present invention's product 22 littler than the relatively product 5 that do not add, and lower than the frictional coefficient of the light oil (relatively product 6) of sulphur concentration 0.2%, show the oilness excellence.
Table 11
Frictional coefficient
The present invention's product 22 ????0.164
Relatively product 5 ????0.328
Relatively product 6 ????0.304
Embodiment 12
That preparation example obtains in order to investigate, as to be used for the present invention's product cyclic ketal A 2, D 2, F 2, I 2, K, L 2, M and be used for the relatively electrical insulating property of the oily b (polyalkylene glycol) of product, measure 25 ℃ ratio specific inductivity according to JISC-2101.The results are shown in Table 12.
As can be seen from Table 12, the ratio specific inductivity of the present invention's product is low, all has excellent electric insulating.
In addition, with the cyclic ketal F that contains an ehter bond 2, cyclic acetal I 2Compare, not the cyclic ketal A of ether-containing key 2, D 2, K, M, cyclic acetal L 2The ratio specific inductivity low, show the electrical insulating property excellence.
Table 12
Oil is planted Compare specific inductivity
The oil that is used for the present invention's product Cyclic ketal A 2 ????2.92
Cyclic ketal D 2 ????2.78
Cyclic ketal F 2 ????3.47
Cyclic acetal I 2 ????3.22
Cyclic ketal K ????2.65
Cyclic acetal L 2 ????2.50
Cyclic ketal M ????2.89
Be used for the relatively oil of product B (polyalkylene glycol) ????5.31
Synthesis example 11.2: 3.4: 5.6-three-O-(the inclined to one side propylidene of 2-methyl) Sorbitol Powder (1) and 1.3: 2.4: the mixture of 5.6-three-O-(the inclined to one side propylidene of 2-methyl) Sorbitol Powder (2) synthetic
Be equipped with in 3 liters of reaction vessels of thermometer, reflux exchanger, Dean-Stark trap, calcium chloride tube and agitator, add D-Sorbitol Powder 450g (2.470mol), isobutyl-aldehyde 588g (8.154mol), tosic acid-hydrate 4.70g (0.0247mol) and sherwood oil (30～60 ℃ of boiling points) 400ml.Warming while stirring is carried out reaction in 15 hours at 40～65 ℃, steams the water of calculated amount.Reaction finishes postcooling to 60 ℃, adds yellow soda ash 5.24g (0.0494mol), 60 ℃ stir 30 minutes after, add water 100g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud,, obtain the mixture 868.03g of thick title compound (1), (2) with saturated aqueous common salt 100g washing, evaporation.This mixture underpressure distillation obtains the mixture 800.17g of title compound (1), (2).
Yield 94.0%, 137～149 ℃/0.3～0.6mmHg of boiling point, vapor-phase chromatography purity 99.0% (the mixture ratio of title compound (1)/(2) is 88/12 (weight ratio)), hydroxyl value 6.0mgKOH/g (theoretical value 0).
The spectrum of the mixture of title compound (1), (2)
IR (NEAT, cm -1): 2972,2936,2884 (C-H is flexible), 1476,1406,1368 (C-H angles), 1194,1106,1038 (C-O-C is flexible), 722 (CH 2Wave)
1HNMR(CDCl 3，δppm)：
0.58～1.49 (18H, multiplet ,-CH 3)
1.53～2.13 (3H, multiplet ,-CH (CH 3) 2)
3.32～3.70,4.50～4.97 (3H, multiplet, (O-) 2CH-)
3.70～4.50 (8H, multiplet ,-CH 2CHCHCHCHCH 2-)
Mixture 1.0g from title compound (1), (2), with preparation type silica gel thin-layer chromatography, as launching solvent, obtain title compound (1) 0.63g of Rf value 0.6～0.7 part and title compound (2) 0.09g of Rf value 0.5 part with hexane/ethyl acetate=9/1 respectively.
Title compound (1) 13CNMR (CDCl 3, δ ppm): 107.7～109.1 expression five-ring ethylidene ether structures.
Title compound (2) 13CNMR (CDCl 3, δ ppm): 107.7～109.1,104.9 represent five-ring acetal, six-ring ethylidene ether structure (107.7～109.1 peak is 1 to 2 with the strength ratio at 104.9 peak) respectively.
Synthesis example 21.2: 3.4: 5.6-three-O-(3,5, the inclined to one side hexylidene of 5-trimethylammonium) Sorbitol Powder (3) and 1.3: 2.4: the mixture of 5.6-three-O-(3,5, the inclined to one side hexylidene of 5-trimethylammonium) Sorbitol Powder (4) synthetic
Be equipped with in 3 liters of reaction vessels of thermometer, reflux exchanger, Dean-Stark trap, calcium chloride tube and agitator, add D-Sorbitol Powder 170.76g (0.937mol), 3,5,5-trimethylammonium hexanal 400g (2.812mol), tosic acid-hydrate 1.78g (0.00936mol) and hexane 400ml.Warming while stirring is carried out reaction in 8 hours at 79～81 ℃, steams the water of calculated amount.Reaction finishes postcooling to 70 ℃, add yellow soda ash 1.99g (0.0188mol) and neutralize, 70 ℃ stir 30 minutes after, add water 100g, stirred standing demix 30 minutes at 60 ℃.Remove after the sub-cloud,, obtain the mixture 529.51g of thick title compound (3), (4) with saturated aqueous common salt 100g washing, evaporation.This mixture underpressure distillation (boiling point 27～85 ℃/0.5～0.9mmHg), remove singlings, resulting residue 500.87g is dissolved among the hexane 500ml, carry out pressure filtration (PTFE by atlapulgite 25.04g (with respect to residue 5% weight), 0.2 μ m), use hexane wash, the hexane in the hexane solution is evaporated fully, obtain the mixture 501.14g of title compound (3), (4).
Yield 96.4%, vapor-phase chromatography purity 93.2% (ratio of mixture of title compound (3)/(4) is 31/69 (weight)), hydroxyl value 27.2mgKOH/g (theoretical value 0).
IR (NEAT, cm -1): 2960,2908,2876 (C-H is flexible), 1476,1414,1396,1368 (C-H angles), 1132,1098,1042 (C-O-C is flexible), 714 (CH 2Wave)
1HNMR(CDCl 3，δppm)：
0.77～1.40 (42H, multiplet ,-CH (CH 3) CH 2C (CH 3) 3)
1.40～2.49 (9H, multiplet ,-CH 2CH (CH 3) CH 2C (CH 3) 3)
3.88～3.68,4.48～5.15 (3H, multiplet, (O-) 2CH-)
3.68～4.42 (8H, multiplet ,-CH 2CHCHCHCHCH 2-)
Synthesis example 31.3: 2.4: 5.6-three-O-(the inclined to one side propylidene of 1-methyl) Sorbitol Powder (5) synthetic
Be equipped with in 3 liters of reactors of thermometer, reflux exchanger, Dean-Stark trap, logical nitrogen pipe and agitator, added D-Sorbitol Powder 336.84g (1.849mol), methyl ethyl ketone 800g (11.094mol), tosic acid-hydrate 17.58g (0.092mol) and hexane 200ml.Warming while stirring is carried out reaction in 8 hours at 69～79 ℃, steams the water of calculated amount.Reaction finishes postcooling to 60 ℃, adds yellow soda ash 19.6g (0.185mol) and neutralizes, and adds water 200g at 60 ℃ after stirring 30 minutes, stirs standing demix 30 minutes at 60 ℃.After removing sub-cloud, with saturated aqueous common salt 200g washing, evaporation obtains thick title compound (5) 643.75g.This thing underpressure distillation obtains title compound (5) 606.71g.
Yield 95.3%, 136～140 ℃/0.6mmHg of boiling point, vapor-phase chromatography purity 97.3%, hydroxyl value 12.9mgKOH/g (theoretical value 0).
Synthesis example 4
1.2: 3.4: 5.6-three-O-(the inclined to one side propylidene of 1-methyl) Sorbitol Powder (5) synthetic
Be equipped with in 2 liters of reaction vessels of thermometer, reflux exchanger, Dean-Stark trap and agitator, added D-Sorbitol Powder 168.4g (0.93mol), methyl ethyl ketone 400g (5.6mol), tosic acid-hydrate 8.8g (0.046mol) and hexane 100g.Warming while stirring under nitrogen atmosphere is carried out reaction in 7 hours at 65～72 ℃, steams the water of calculated amount.Reaction finishes postcooling to 60 ℃, adds yellow soda ash 9.8g (0.09mol) and neutralizes, and adds water 100g at 60 ℃ after stirring 30 minutes, stirs standing demix 30 minutes at 60 ℃.After removing sub-cloud, to neutral, use anhydrous sodium sulfate drying then, filter and steam hexane, obtain thick title compound (5) 293.5g with the saturated common salt water washing.
Thick yield 92.2%, hydroxyl value 18.0mgKOH/g (theoretical value 0).
This thing 100g is dissolved among the hexane 100ml, and is refining with silica gel column chromatography.Collection is with the fraction of hexane/ethyl acetate=8/2 stripping, and evaporation obtains title compound (5) 95g.
Vapor-phase chromatography purity 99.7%, hydroxyl value 0mgKOH/g (theoretical value 0).
IR (NEAT, cm -1): 2980,2938,2890 (C-H is flexible), 1470,1380 (C-H angles), 1242,1194,1140,1080 (C-O-C is flexible), 717 (CH 2Wave)
1HNMR(CDCl 3，δppm)：
0.72～1.10 (9H, multiplet ,-CH 2CH 3)
1.10～1.48 (9H, multiplet, (O-) 2C (CH 3)-)
1.48～1.90 (6H, multiplet ,-CH 2CH 3)
3.71～4.31 (8H, multiplet ,-CH 2CHCHCHCHCH 2-)
Synthesis example 5
1.2: 3.4: 5.6-three-O-(1, the inclined to one side butylidene of 3-dimethyl) Sorbitol Powder (7) synthetic:
Be equipped with in 3 liters of reaction vessels of thermometer, reflux exchanger, Dean-Stark trap, calcium chloride tube and agitator, added D-Sorbitol Powder 363.76g (1.997mol), methyl iso-butyl ketone (MIBK) 1200g (11.981mol), tosic acid-hydrate 18.99g (0.0998mol and hexane 300ml.Warming while stirring is carried out reaction in 23 hours at 93～98 ℃, steams the water of calculated amount.Reaction finishes postcooling to 60 ℃, adds yellow soda ash 21.16g (0.1996mol) and neutralizes, and adds water 200g at 60 ℃ after stirring 30 minutes, stirs standing demix 30 minutes at 60 ℃.After removing sub-cloud, with saturated aqueous common salt 200g washing, evaporation obtains thick title compound (7) 736.65g.(boiling point 30.5～141 ℃/2～0.7mmHg) removes singlings, and the residue 657.62g that obtains obtains title compound (7) 637.44g by atlapulgite (with respect to residue 5% weight) pressure filtration (PTFE, 0.2 μ m) in this thing underpressure distillation.
Yield 74.5%, vapor-phase chromatography purity 93.1%, hydroxyl value 34.3mgKOH/g (theoretical value 0).
Synthesis example 6
1.2: 3.4: 5.6-three-O-(1, the inclined to one side butylidene of 3-dimethyl) Sorbitol Powder (7) synthetic:
Be equipped with in 1 liter of reaction vessel of thermometer, reflux exchanger, Dean-Stark trap, logical nitrogen pipe and agitator, added D-Sorbitol Powder 127.5g (0.7mol), methyl iso-butyl ketone (MIBK) 420.7g (4.2mol), tosic acid-hydrate 6.7g (0.035mol) and toluene 100g.Under nitrogen gas stream, warming while stirring is carried out decompression dehydration reaction in 8 hours at 92 ℃.Reaction finishes postcooling to 60 ℃, add yellow soda ash 10.6g (0.1mol) and neutralize, 60 ℃ stir 30 minutes after, add water 60g, stirred standing demix 30 minutes at 60 ℃.After removing sub-cloud, arrive neutral with the saturated common salt water washing.Steam toluene, obtain thick title compound (7) 247.2g.
Thick yield 82.4%, hydroxyl value 33.2mgKOH/g (theoretical value 0).
This thing 100g is dissolved among the hexane 100ml, and is refining with silica gel column chromatography.Collection is with the fraction of hexane/ethyl acetate=8/2 stripping, and evaporation obtains title compound (7) 90g.
Vapor-phase chromatography purity 99.4%, hydroxyl value 0mgKOH/g (theoretical value 0).
IR (NEAT, cm -1): 2984,2956,2876 (C-H is flexible), 1470,1378 (C-H angles), 1242,1186,1148,1096 (C-O-C is flexible), 718 (CH 2Wave)
1HNMR(CDCl 3，δppm)：
0.78～1.10 (18H, multiplet ,-CH 2CH (CH 3) 2)
1.22～1.47 (9H, multiplet, (O-) 2C (CH 3)-)
1.47～1.68 (6H, multiplet ,-CH 2CH (CH 3) 2)
1.68～2.03 (3H, multiplet ,-CH 2CH (CH 3) 2)
3.71～4.38 (8H, multiplet ,-CH 2CHCHCHCHCH 2-)
Synthesis example 7
1.2: 3.4: 5.6-three-O-(the inclined to one side propylidene of 1-methyl) mannitol (17) synthetic:
Be equipped with in 3 liters of reaction vessels of thermometer, reflux exchanger, Dean-Stark trap and agitator, added D-mannitol 336.84g (1.849mol), methyl ethyl ketone 800.0g (11.094mol), tosic acid-hydrate 17.58g (0.092mol) and hexane 200ml.Under nitrogen atmosphere, warming while stirring is carried out reaction in 10 hours at 68～76 ℃, steams the water of calculated amount.Reaction finishes postcooling to 60 ℃, adds yellow soda ash 19.6g (0.185mol) and neutralizes, and adds water 200g after 60 ℃ are stirred 30 minutes, at 60 ℃ of stirrings 30 minutes, standing demix.After removing sub-cloud, with saturated aqueous common salt 200g washing, evaporation obtains thick title compound (17) 639.06g.It is refining that part is carried out in this thing underpressure distillation, obtains title compound (17) 605.76g (yield 95.1%).
136～140 ℃/0.3mmHg of boiling point, vapor-phase chromatography purity 94.2%, hydroxyl value 12.7mgKOH/g (theoretical value 0).
40 ℃ kinetic viscosity 37.65mm 2/ s, 100 ℃ kinetic viscosity 3.726mm 2/ s.
This thing 150g is dissolved among the hexane 150ml, and is refining with silica gel column chromatography.Collection is with the fraction of hexane/ethyl acetate=8/2 stripping, and evaporation obtains title compound (17) 135g.
Vapor-phase chromatography purity 99.6%, hydroxyl value 0.2mgKOH/g (theoretical value 0).
IR (NEAT, cm -1): 2986,2944,2890 (C-H is flexible), 1467,1377 (C-H angles), 1242,1191,1137,1077 (C-O-C is flexible), 708 (CH 2Wave)
1HNMR(CDCl 3，δppm)：
0.72～1.13 (9H, multiplet ,-CH 2CH 3)
1.13～1.50 (9H, multiplet, (O-) 2C (CH 3)-)
1.50～1.90 (6H, multiplet ,-CH 2CH 3)
3.88～4.37 (8H, multiplet ,-CH 2CHCHCHCHCH 2-)
Test example 1
Measure 40 ℃ of cyclic acetal class of the present invention that synthesis example obtains and 100 ℃ of kinetic viscosities (JISK-2283), yield point (JISK-2269).The results are shown in Table 13 for it.
Table 13
Compound 40 ℃ of viscosity (mm 2/s) 100 ℃ of viscosity (mm 2/s) Yield point (℃)
The mixture of The compounds of this invention (1) and (2) (synthetic) with synthesis example 1 ????167.8 ????5.81 ????-25.0
The mixture of The compounds of this invention (3) and (4) (synthetic) with synthesis example 2 ????394.6 ????15.5 ????＜-20.0
The compounds of this invention (5) (synthetic) with synthesis example 4 ????63.1 ????4.54 ????-32.5
The compounds of this invention (7) (synthetic) with synthesis example 6 ????53.9 ????5.36 ????-27.5
The compounds of this invention (17) (synthetic) with synthesis example 7 ????35.2 ????3.63 ????-45.0
Product 1 (naphthenic oil: SUNISO 4GS, Japanese SUN oil company system) relatively ????55.5 ????5.87 ????-40.0
Product 2 (polyalkylene glycol: Newpol LB-285, Sanyo change into industrial's system) relatively ????60.3 ????11.4 ????-40.0
Product 3 (three (methylol) propane/2-methylhexanoic acid, 2-ethyl valeric acid, 3,5,5 Trimethylhexanoic acid ester) relatively ????31.4 ????5.31 ????＜-45.0
Product 4 (tetramethylolmethane/2 ethyl hexanoic acid, 3,5,5 Trimethylhexanoic acid ester) relatively ????62.2 ????7.99 ????＜45.0
Test example 2
Measure synthesis example and obtained cyclic acetal class of the present invention and product and 1,1,1 relatively, the intermiscibility of 2-Tetrafluoroethane (HFC-134a).That is, when the mensuration oil concentration respectively is 10% (volume), 20% (volume), 30% (volume), 40% (volume), 50% (volume), to 1,1,1, two phase separation temperatures under the low temperature of 2-Tetrafluoroethane.It the results are shown in table 14.
Table 14
Compound The low ternperature separation process temperature (℃)
10% (volume) 20% (volume) 30% (volume) 40% (volume) 50% (volume)
The mixture of The compounds of this invention (1) and (2) (synthetic) with synthesis example 1 ????-62 ????-44 ????-39 ????-39 ????-42
The compounds of this invention (5) (synthetic) with synthesis example 4 ????＜-70 ????＜-70 ????＜-70 ????＜-70 ????＜-70
The compounds of this invention (7) (synthetic) with synthesis example 6 ????-17 ????-1 ????5 ????4.5 ????2
The compounds of this invention (17) (synthetic) with synthesis example 7 ????-46 ????-38 ????-30 ????-27 ????-28
Product 1 (naphthenic oil: SUNISO 4GS, Japanese SUN oil company system) relatively ????＞20 ????＞20 ????＞20 ????＞20 ????＞20
As can be seen from Table 14, frequently product are excellent for the intermiscibility of the present invention's product.
Test example 3
Measure cyclic acetal class of the present invention that synthesis example obtains and 25 ℃ of volume specific resistances of product (according to JISC-2101 mensuration) relatively.The results are shown in Table 15 for it.
Table 15
Compound Volume specific resistance (Ω .cm)
The mixture of The compounds of this invention (1) and (2) (synthetic) with synthesis example 1 ????3.6×10 14
The compounds of this invention (5) (synthetic) with synthesis example 4 ????9.4×10 15
The compounds of this invention (7) (synthetic) with synthesis example 6 ????5.8×10 15
The compounds of this invention (17) (synthetic) with synthesis example 7 ????3.9×10 15
Product 2 (polyalkylene glycol: Newpol LB-285, Sanyo change into industrial's system) relatively ????7.8×10 11
As can be seen from Table 15, the volume specific resistance of the present invention's product is better than relatively product.
Test example 4
For the cyclic acetal class of the present invention and 1,1,1 that synthesis example obtains, the composition of 2-Tetrafluoroethane (HFC-134a) and the ester and 1,1,1 of product as a comparison, the composition of 2-Tetrafluoroethane (HFC-134a) is investigated its wear resistant with the Falex test.
Oil 100ml is warmed to 80 ℃, and per hour 101 to feed 1,1,1,2-Tetrafluoroethane (HFC-134a) turned round 4 hours under the load of 150 (1b), measured the wear loss of running back V slide block (block) and pin (pin).The results are shown in Table 16 for it.
As can be seen from Table 16, the wear loss of the present invention's product is all very little, shows the wear resistant excellence.
Table 16
Compound Wear loss (mg)
The mixture of The compounds of this invention (1) and (2) (synthetic) with synthesis example 1 ?????1.5
The compounds of this invention (5) (synthetic) with synthesis example 3 ?????3.7
Product 3 (three (methylol) propane/2 methyl caproic acid, 2-ethyl valeric acid, 3,5,5 Trimethylhexanoic acid ester) relatively ?????16.4
Product 4 (tetramethylolmethane/2 ethyl hexanoic acid, 3,5,5 Trimethylhexanoic acid ester) relatively ?????8.1
The possibility of utilizing on the industry
The invention provides heat endurance, oxidation stability excellence, do not produce carboxylic acid, the low and cheap synthetic lubricant fluid of hygroscopicity because of hydrolysis. In addition, such synthetic lubricant fluid and the preparation of hydrogen fluorohydrocarbon can provide electrical insulating property, hygroscopicity excellence, not produce carboxylic acid and cheap refrigerator working fluid compositions because of hydrolysis. And then, according to the present invention, can be used as the novel cyclic acetals of synthetic lubricant fluid, be that the raw material from cheapness obtains with high yield, high-purity with easy method.

Claims (16)

1. ucon oil, it is characterized in that containing cyclic ketal or cyclic acetal, described cyclic ketal or cyclic acetal from one or more more than 4 yuan～(comprise 4 yuan and 10 yuan) below 10 yuan, first number is carbonyl compound shown in even polyvalent alcohol and one or more general formulas (I) or its active derivative ketal or acetal obtain R in the formula 1Straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～18 carbon atom, R 2Straight chain, side chain or the cyclic alkyl of 1～18 carbon atom of expression; Or R 1And R 2Lump together the alkylidene group of 2～36 carbon atoms of expression.
2. ucon oil, it is characterized in that containing cyclic ketal or cyclic acetal, described cyclic ketal or cyclic acetal from one or more more than 4 yuan～(comprise 4 yuan and 8 yuan) below 8 yuan, first number is carbonyl compound shown in even polyvalent alcohol and one or more general formulas (II) or its active derivative ketal or acetal obtain R in the formula 3Straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～12 carbon atom, R 4Straight chain, side chain or the cyclic alkyl of 1～12 carbon atom of expression; Or R 3And R 4Lump together the alkylidene group of 2～13 carbon atoms of expression; R 3And R 4The total carbonatoms be 1～13.
3. claim 1 or 2 described ucon oils, wherein polyvalent alcohol does not have ehter bond.
4. claim 1 or 2 described ucon oils, wherein polyvalent alcohol has an ehter bond.
5. claim 3 or 4 described ucon oils, wherein cyclic ketal or cyclic acetal contain 1,3-dioxolane structure and/or 1,3-diox structure.
6. any one described ucon oil in the claim 3～5, it is characterized in that containing cyclic ketal or cyclic acetal, described cyclic ketal or cyclic acetal are to obtain from the radical of saturated aliphatic of 4 yuan or 6 yuan, 4～25 carbon atoms alcohol and carbonyl compound shown in one or more general formulas (II) or its active derivative ketal or acetal.
7. ucon oil, it is characterized in that containing one or more formulas (IIIa), (IIIb), (IVa) or (IVb) shown in cyclic ketal or cyclic acetal,
Figure A9519577500031
R in the formula 3Straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～12 carbon atom, R 4Straight chain, side chain or the cyclic alkyl of 1～12 carbon atom of expression; Or R 3And R 4Lump together the alkylidene group of 2～13 carbon atoms of expression; R 3And R 4The total carbonatoms be 1～13.
8. ucon oil, it is characterized in that containing one or more formula V or (VI) shown in cyclic ketal or cyclic acetal,
Figure A9519577500041
R in the formula 3Straight chain, side chain or the cyclic alkyl of expression hydrogen atom or 1～12 carbon atom, R 4Straight chain, side chain or the cyclic alkyl of 1～12 carbon atom of expression; Or R 3And R 4Lump together the alkylidene group of 2～13 carbon atoms of expression; R 3And R 4The total carbonatoms be 1～13.
9. refrigerator working fluid compositions wherein contains refrigerator oil and hydrogen fluorohydrocarbon that right requires any one described cyclic ketal among the 2-8 or cyclic acetal.
10. the described refrigerator working fluid compositions of claim 9 wherein contains hydrogen fluorohydrocarbon and refrigerator oil with hydrogen fluorohydrocarbon/refrigerator oil=50/1～1/20 (weight ratio).
11. following general formula (i) or (ii) shown in the cyclic acetal class, R in the formula 5The expression hydrogen atom, in this case, R 6The branched-chain alkyl of 3 carbon atoms of expression or the straight or branched alkyl of 4-21 carbon atom; Perhaps R 5The straight or branched alkyl of 1～21 carbon atom of expression, in this case, R 6The straight or branched alkyl of 2～21 carbon atoms of expression.
12. the described cyclic acetal class of claim 11, wherein R 5R during for hydrogen atom 6Be the branched-chain alkyl of 3 carbon atoms or the straight or branched alkyl of 4～12 carbon atoms, perhaps R 5R when being the straight or branched alkyl of 1～12 carbon atom 6It is the straight or branched alkyl of 2～12 carbon atoms.
13. the described cyclic acetal class of claim 11, wherein R 5R during for hydrogen atom 6Be the branched-chain alkyl of 3～12 carbon atoms, perhaps R 5R when being the straight or branched alkyl of 1～12 carbon atom 6It is the straight or branched alkyl of 2～12 carbon atoms.
14. any one described cyclic acetal class in the claim 11～13, wherein the hexavalent alcohol residue produces from Sorbitol Powder.
15. general formula (i) or (ii) shown in the preparation method of the described cyclic acetal class of claim 11, it is characterized in that making as shown in the formula hexavalent alcohol shown in (iii) and general formula (iv) shown in carbonyl compound or its active derivative (ketal or acetal) in the presence of acid catalyst, react
Figure A9519577500052
R in the formula 5The expression hydrogen atom, in this case, R 6The branched-chain alkyl of 3 carbon atoms of expression or the straight or branched alkyl of 4～21 carbon atoms; Perhaps R 5The straight or branched alkyl of 1～21 carbon atom of expression, in this case, R 6The straight or branched alkyl of 2～21 carbon atoms of expression.
16. the described preparation method of claim 15, wherein hexavalent alcohol is a Sorbitol Powder.
CN 95195775 1994-08-29 1995-02-27 Synthetic lubricating oil Pending CN1161693A (en)

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JP292431/96 1994-10-31
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101955837B (en) * 2004-02-25 2012-10-10 出光兴产株式会社 Alkyl acetal compound, process for producing the same, and lubricating oil composition
CN111925856A (en) * 2020-07-15 2020-11-13 珠海凌达压缩机有限公司 Refrigerating oil composition, application thereof and compressor
CN113891771A (en) * 2019-09-09 2022-01-04 花王株式会社 Binder composition for mold making
CN113891771B (en) * 2019-09-09 2024-05-10 花王株式会社 Adhesive composition for casting mold

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101955837B (en) * 2004-02-25 2012-10-10 出光兴产株式会社 Alkyl acetal compound, process for producing the same, and lubricating oil composition
CN113891771A (en) * 2019-09-09 2022-01-04 花王株式会社 Binder composition for mold making
CN113891771B (en) * 2019-09-09 2024-05-10 花王株式会社 Adhesive composition for casting mold
CN111925856A (en) * 2020-07-15 2020-11-13 珠海凌达压缩机有限公司 Refrigerating oil composition, application thereof and compressor

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