CN1875046A - Acyloxy acetic acid polymer and method for producing same - Google Patents
Acyloxy acetic acid polymer and method for producing same Download PDFInfo
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- CN1875046A CN1875046A CN 200480031690 CN200480031690A CN1875046A CN 1875046 A CN1875046 A CN 1875046A CN 200480031690 CN200480031690 CN 200480031690 CN 200480031690 A CN200480031690 A CN 200480031690A CN 1875046 A CN1875046 A CN 1875046A
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Abstract
Disclosed is an acyloxy acetic acid polymer which enables to economically synthesize an acyloxy acetic acid, a glycolic acid, esters thereof or glycolides more simply under milder conditions. The acyloxy acetic acid polymer can be used as a biodegradable polymer. The acyloxy acetic acid polymer is represented by the general formula (1) below. In the preferred embodiment of the present invention, the acyloxy acetic acid polymer is obtained by reacting a formaldehyde compound, carbon monoxide, and an organic carboxylic acid or its derivative in the presence of an acid catalyst. (In the general formula (1), R<1> and R<2> independently represent a hydrogen atom or a lower alkyl group which may be branched, and n represents an integer of not less than 5).
Description
Technical field
The present invention relates to a kind of new acyloxy acetic acid polymer and manufacture method thereof.
Background technology
The high acetoxyacetic acid of utility value in the acyloxy acetic acid when various chemical preparationss such as manufacturing agricultural chemicals and surface treatment agent, is used as synthesis material and uses, and is important compound in chemical industry.In addition, oxyacetic acid as industrial intermediate, also as polymer raw material and additive, is important compound except direct purposes such as chemical.As the synthetic method of these compounds, known have a following method.
For acetoxyacetic acid, have in benzene thereby hydroxyl ethyl acetate and acetate heated, removes the water of generation and ethyl acetate synthetic method (for example with reference to non-patent literature 1) with a spot of sulfuric acid and under alkaline metal iodide, metal oxide (or metal acetate), three kinds of compositions coexistences of iodine, make method (for example with reference to patent documentation 1) that acetate and oxygen reacts etc. under High Temperature High Pressure.
In the former method, the hydroxyl ethyl acetate of raw material is pungency, flammable material, be not easy to handle, and the price height.In the latter's method, do not make three kinds of composition coexistences just can not bring into play catalytic capability, so 1 weight %), have that the lock out operation of catalyzer and resultant becomes complicated, cost is high and as the low (yield of the acetoxyacetic acid among the embodiment: problem such as of the yield of the acetoxyacetic acid of resultant.
Proposed with fatty aldehyde and carbon monoxide to use SiO as catalyzer
2/ Al
2O
3Mol ratio is at least the mordenite more than 100, and it is reacted in reaction medium, obtains the method (for example with reference to patent documentation 2) of alpha-hydroxy carboxylic acid derivatives, simultaneously, has reported as hydroxycarboxylic acid, acetoxyacetic acid and can synthesize.But, in the method,, need 170～200 ℃ high temperature in order to obtain the high yield of acetoxyacetic acid.When using the high gas of the such toxicity of carbon monoxide, the preferred reaction conditions gentleness.In addition, SiO
2/ Al
2O
3The mordenite of the high silicon-type that mol ratio is high is compared with common mordenite, and price is very high.
In addition, have been proposed in the reaction medium, carry the metal oxide hold sulfate radical (carry the zirconium white of holding sulfate radical, carry the titanium dioxide of holding sulfate radical and carry the stannic oxide of holding sulfate radical) in the presence of, make carbon monoxide, acetate and/or diacetyl oxide and formaldehyde reaction, the method of synthesis of acetic acid guanidine-acetic acid, but to separating not report (for example with reference to patent documentation 3) of object particularly.
For oxyacetic acid and ester body thereof, mineral acids such as the sulfuric acid of use, phosphoric acid, hydrochloric acid are arranged as catalyzer, formaldehyde, water and carbon monoxide are under high pressure reacted, the method (for example with reference to patent documentation 4) of oxyacetic acid is made on one step ground, with make formaldehyde, water and carbon monoxide in hydrogen fluoride, under normal pressure, react, the method (for example with reference to patent documentation 5) of oxyacetic acid etc. is made on a step ground.In these methods, existence needs problems such as complicated operations in order to separate oxyacetic acid from reaction solution, in the industrial excellent method of can not saying so.
In addition, reported in the presence of acid catalyst,, in reactive system, only generated few condensation dimer (for example with reference to patent documentation 6) by the reaction of manthanoate, formaldehyde and carbon monoxide.In this report, the dimer of generation is not carried out dimeric separation by direct hydrolysis or alcoholysis.
Non-patent literature 1:Beilstein, 3,233
Patent documentation 1: the spy opens clear 56-63941 communique
Patent documentation 2: the spy opens flat 11-147042 communique
Patent documentation 3: the spy opens the 2001-335538 communique
Patent documentation 4: special public clear 53-44454 communique
Patent documentation 5: the spy opens clear 51-13719 communique
Patent documentation 6: the spy opens clear 56-122321 communique
Summary of the invention
The present invention makes in view of above-mentioned practical situation, its purpose is, provide a kind of can be under the condition of simpler and easy, milder, synthetic economically acyloxy acetic acid, oxyacetic acid and ester class and glycollide, and can be as the acyloxy acetic acid polymer (acyloxy acetic acid polymer) and the manufacture method thereof of Biodegradable polymer use.
The result that the inventor furthers investigate repeatedly, found a kind ofly can synthesize acyloxy acetic acid (acyloxy acetic acid) and oxyacetic acid, can synthesize acyloxy acetic acid ester and glycolic acid esters, can synthesize the new acyloxy acetic acid polymer and the manufacture method thereof of glycollide, thereby finished the present invention by thermal degradation by alcoholysis by hydrolysis.
That is, a first aspect of the present invention is a kind of acyloxy acetic acid polymer, it is characterized in that: represent with following general formula (1).
[Chemical formula 1]
(in the general formula (1), each R
1And R
2Represent hydrogen atom or can the ramose low alkyl group respectively independently, n represents the integer more than 5.)
Then, a second aspect of the present invention is the manufacture method with the acyloxy acetic acid polymer of above-mentioned general formula (1) expression, it is characterized in that: in the presence of acid catalyst, make formolation compound, carbon monoxide, the reaction of organic carboxyl acid or derivatives thereof, obtain the acyloxy acetic acid derivative, then, the acyloxy acetic acid derivative that obtains is carried out condensation.
Acyloxy acetic acid polymer of the present invention can generate acyloxy acetic acid and oxyacetic acid by hydrolysis, can generate acyloxy acetic acid ester and glycolic acid esters by alcoholysis, in addition, can generate glycollide by thermal degradation, in addition, also can use as Biodegradable polymer.
Embodiment
Below explain the present invention.Acyloxy acetic acid polymer of the present invention is represented by above-mentioned general formula (1).In above-mentioned general formula (1), each R
1And R
2Be preferably the low alkyl group of hydrogen atom or C1～C6, more preferably the alkyl of hydrogen atom or C1～C4 is preferably hydrogen atom (compound of this moment is the acetoxyacetic acid polymkeric substance) especially.In addition, polymerization degree n is preferably more than 5, more preferably more than 10, be preferably more than 25 especially.If n is more than 5, then have easily from the isolating advantage of reactive system, if be more than 10, then because solidify separation easily, so processing becomes easier.The upper limit of polymerization degree n is generally 10000.
Acyloxy acetic acid polymer of the present invention, acetoxyacetic acid polymkeric substance for example, after basic hydrolysis, as by the quantitative value of high-speed liquid chromatography, oxyacetic acid content is generally 110～130 weight %, acetoxyl group content is generally 0.1～15 weight %.In addition, its fusing point is generally more than 120 ℃.Weight-average molecular weight is generally 500～580000.In this polymkeric substance, contain diglycollic acid as impurity, its amount is preferably below the 1 weight %, more preferably below the 0.1 weight %.
Acyloxy acetic acid polymer of the present invention preferably carries out condensation with the acyloxy acetic acid derivative and obtains.As said acyloxy acetic acid derivative here, can enumerate acyloxy acetic acid, oxyacetic acid, acyloxy acetic acid oligopolymer, glycolic acid oligomers, their ester etc.
In addition, acyloxy acetic acid polymer of the present invention preferably will make formolation compound, carbon monoxide, organic carboxyl acid or derivatives thereof react in the presence of acid catalyst and the acyloxy acetic acid derivative as described above that obtains carries out condensation and obtains.Especially, preferred: as in the presence of acid catalyst, the acyloxy acetic acid derivative that organic carboxyl acid, aldehyde cpd, reaction of carbon monoxide are obtained not to be separated, directly make its condensation, generate acyloxy acetic acid polymer of the present invention and separate.Following chemical formula is an example of above-mentioned series reaction.
[Chemical formula 2]
As above-mentioned acid catalyst, can enumerate: mineral acids such as hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, hydrofluoric acid, perchloric acid, nitric acid, sulfuric acid, phosphofluoric acid, fluosulfonic acid, chlorsulfonic acid, organic acids such as trifluoroacetic acid, methylsulfonic acid, Phenylsulfonic acid, tosic acid, trifluoromethanesulfonic acid, heteropolyacids such as silicotungstic acid, phospho-wolframic acid, phospho-molybdic acid, Lewis acids such as boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, solid acids such as storng-acid cation exchange resin, clay mineral, zeolite, solid shapeization acid, inorganic oxide, inorganic salt, composite oxides.
As storng-acid cation exchange resin, can enumerate the functional group and be sulfonic AMBERLYST 15 (Luo Men-Haars Co., Ltd (Rohm and Haas Company) production), Diaion PK228 styrene diethylene benzene copoly mers such as (Mitsubishi Chemical Ind's productions), Nafion tetrafluoroethylene base polymers such as (E.I.Du Pont Company's productions) etc.In addition, as clay mineral and zeolite, can enumerate montmorillonite, kaolinite, wilkinite, halloysite (halloysite), terre verte (smectite), illite, vermiculite, chlorite, sepiolite, attapulgite, polygorskite, mordenite etc., especially preferably exchange the material that obtains with hydrogen ion with the material of acid treatment such as hydrofluoric acid or the metal ion that can as H type zeolite, exchange.As solid shapeization acid, can enumerate acid such as making heteropolyacid and carry the material that is held in the carriers such as gac, silicon-dioxide.If consider the separation circuit of end product, preferred undissolved solid acid in reactive system then, preferred especially storng-acid cation exchange resin (sulfonic acid ion exchange resin).
In the present invention, above-mentioned sulfonic acid ion exchange resin, preferably the back use is cleaned in acid in advance.Clean by acid, can easily remove the sulfate radical that contains as impurity in the sulfonic acid ion exchange resin, thus the acyloxy acetic acid polymer of the mixed volume of the sulfate radical that can be reduced.
Above-mentioned acid is cleaned, and for example uses the organic carboxyl acid described later as raw material to carry out.The usage quantity of acid in the weight ratio with respect to sulfonic acid ion exchange resin, is generally 1～10 times, is preferably 2～5 times.In addition, the temperature that acid is cleaned is generally 10～150 ℃, and the time is 0.5～10 hour.Acid is cleaned usually in proper container, is under agitation carried out.Clean by such acid, can remove the free sulfate radical that exists in the sulfonic acid ion exchange resin, thereby can produce the acyloxy acetic acid polymer of the mixed volume reduction of sulfate radical.
As the aldehyde cpd of raw material, except formalin (formalin), gaseous formaldehyde, so long as Paraformaldehyde 96, trioxane, methylal etc. generate the compound of formaldehyde under reaction conditions, just there is no particular limitation.These compounds can use more than 2 kinds simultaneously.In addition, as organic carboxyl acid, except acetate, propionic acid, butyric acid etc., also can be the carboxylic acid that propynoic acid etc. has unsaturated link(age).In addition, as the derivative of organic carboxyl acid, can be the ester body, also can be acid anhydride.In addition, after producing above-mentioned acyloxy acetic acid derivative or acyloxy acetic acid polymer of the present invention, they derivatives as organic carboxyl acid can be used as its condenses.Above-mentioned organic carboxyl acid also has the effect as reaction solvent except participating in reaction.Its usage quantity, the mole number (when generating the compound of formaldehyde under reaction conditions, getting the mole number that is scaled formaldehyde) with respect to the formaldehyde of raw material from waiting mole to 100 times of moles, is preferably 1～5 times of mole usually.The usage quantity of organic carboxyl acid derivative too.
Except above-mentioned organic carboxyl acid, can add reaction solvent.As the solvent species that uses this moment, no matter polarity, nonpolar can be used, but have certain polar solvent by use, can obtain the acyloxy acetic acid compound with high yield.As reaction medium, can enumerate for example halogenation such as chloroform, methylene dichloride aliphatic hydrocarbon, halogenated aromatic hydrocarbon such as chlorobenzene, aliphatic hydrocarbons such as hexane, hexanaphthene, methylcyclohexane, aromatic hydrocarbonss such as benzene etc.
Carbon monoxide not only can use high-purity carbon monooxide, and can use the carbon monoxide of rare gas elementes such as sneaking into nitrogen, argon, hydrogen and/or carbonic acid gas etc.
Reaction pressure is generally 10～200kg/cm
2, be preferably 50～100kg/cm
2Temperature of reaction is generally 80～200 ℃, is preferably 100～150 ℃.
Reaction finishes the back, by the solid acid catalyst that from reactive system, is removed such as filtering, the catalyst recirculation that can be used as next batch is used.Can reduce the catalyzer cost thus.
In addition, the condensation of acyloxy acetic acid derivative is to add thermal condensation, because can reach highly condensed, so preferred.Temperature of reaction is generally 100～250 ℃, is preferably 140～200 ℃.Reaction pressure can be a normal pressure, but is generally 650～10torr, is preferably 200～10torr.Under reduced pressure remove acetate and the water that produces as byproduct on one side, Yi Bian carry out condensation reaction.
As the acyloxy acetic acid polymer of target, after condensation reaction, by removing volatile matter, can be used as solids constituent from, in addition, in condensation reaction solution, add the solvent of polymkeric substance indissoluble such as water after, make it to separate out by cooling, can separate with usual method, for example centrifugation etc.
Especially, use the above-mentioned series reaction of solid acid catalyst, for example can use the producing apparatus of the reactor that comprises formalin thickener, holding solid acid catalyst, acetate thickener, condensation reactor, followingly semi-continuously carry out.
At first, will be dissolved in the organic carboxyl acid by the spissated formolation compound of formalin thickener, and supply response device continuously, and at this moment, supply with carbon monoxide continuously and react.Then, only take out and contain the reaction solution of acyloxy acetic acid derivative and supply with the acetate thickener, the carbon monoxide that will produce and in reactor, circulate respectively by concentrating the organic carboxyl acid that is recovered at this decompress(ion).The concentrated solution of the acyloxy acetic acid derivative that will take out from the acetate thickener is supplied with condensation reactor, under reduced pressure adds thermal condensation, obtains acyloxy acetic acid polymer.Then, take out condensation reaction solution, decompression dehydration reclaims acyloxy acetic acid polymer.
In above-mentioned manufacture method, moisture concentration in the reactor is different because of the difference of the moisture concentration in the concentrating degree in the formalin thickener, the organic carboxyl acid that is recovered, the amount of recycling etc., preferably controls these conditions, it is maintained certain scope.Moisture concentration in the reactor is generally 0～20 weight %, is preferably 1～5 weight %.In addition, the moisture concentration in the controlling reactor easily can use acid anhydrides such as diacetyl oxide as organic carboxyl acid.
The sulfate radical content of the acyloxy acetic acid polymer in the optimal way of the present invention is generally below the 3000ppm, is preferably below the 500ppm.The sulfate radical content of acyloxy acetic acid polymer contains sulfate radical as impurity, the defective that exists its purposes to be restricted in the useful compound such as the acyloxy acetic acid that obtains by hydrolysis, alcoholysis, thermal degradation etc., oxyacetic acid, glycollide for a long time.
Acyloxy acetic acid polymer of the present invention can synthesize acyloxy acetic acid and oxyacetic acid by hydrolysis, can synthesize acyloxy acetic acid ester and glycolic acid esters by alcoholysis, in addition, can synthesize glycollide by thermal degradation.For example, the situation of glycolic acid esters in the presence of acid catalyst as described above, adds for example methyl alcohol of 10 times of amounts, makes it and the acetoxyacetic acid polymer reaction, can easily obtain hydroxy methyl acetate thus.
The analytical procedure of the acyloxy acetic acid polymer that obtains among the present invention is as follows.
About fusing point, " DSC6200 type " differential scanning calorimeter that uses Seiko Instruments Inc. to produce, in aluminum pot (aluminium pan), pack into the sample of about 3g, under nitrogen 50ml/min atmosphere, speed with 10 ℃/min is warmed up to 30～260 ℃, and the temperature of endotherm(ic)peak is obtained as fusing point.
Weight-average molecular weight, is measured with the gpc analysis device as solvent with hexafluoroisopropanol.Condition determination is set at 40 ℃ of column temperatures, flow velocity 1ml/min, and standard P MMA (polymethylmethacrylate) is used in the making of inspection amount line.
Embodiment
Next, illustrate in greater detail the present invention, but the present invention is not limited by following embodiment in the scope that does not exceed its main points with embodiment.
Embodiment 1
In autoclave, add the 80 weight % Paraformaldehyde 96s of 90.9g acetate, 22.5g, as the 15g Zeo-karb (" AMBERLYST15dry " that Luo Men-Haars Co., Ltd produces) of catalyzer, behind the carbon monoxide purging, be warmed up to 120 ℃, import carbon monoxide up to 80kg/cm
2, under the stirring of 1200rpm, make its reaction 3 hours.
After reaction finishes,, after the nitrogen displacement, reaction soln and catalyzer are filtered separately the catalyzer that goes out with the acetate cleaning and filtering with the carbon monoxide decompress(ion).Respectively this reaction filtrate and catalyzer scavenging solution are sampled, use basic hydrolysis, the result who uses high-speed liquid chromatography (" LC-10A " that Shimadzu Seisakusho Ltd. produces) to analyze shows that the oxyacetic acid yield of (formaldehydebase) is 95 moles of % at the bottom of the carboxaldehyde radicals of adding.In addition, this filtrate is shown with the result of high-speed liquid phase chromatogram analysis directly that at the bottom of the carboxaldehyde radicals that adds, oxyacetic acid is 8 moles of %, acetoxyacetic acid is 61 moles of %, and the acetoxyacetic acid oligopolymer is 26 moles of %.
Add above-mentioned filtrate in having the there-necked flask of stirrer, under the decompression of 100torr, be heated to 140 ℃ in oil bath, the limit distillation is removed the acetate He Shui, the limit that produce as by product and is carried out condensation reaction.140 ℃ reaction is after 4 hours down in interior temperature, and the 50g pure water is added in slowly cooling when interior temperature becomes 90 ℃, further be cooled to room temperature.After the acetoxyacetic acid polymkeric substance that generates filtered,, obtain the acetoxyacetic acid polymkeric substance of 34.2g 60 ℃ of following warm air dryings 24 hours.In the acetoxyacetic acid polymkeric substance that obtains, oxyacetic acid content is 111 weight %, acetoxyl group content be 9.8 weight % (with after the basic hydrolysis, quantitative with high-speed liquid chromatography), be below the 0.1 weight % as the content of the diglycollic acid of impurity.Yield at the bottom of the carboxaldehyde radicals that adds is 83.2 moles of %.
The fusing point of above-mentioned acetoxyacetic acid polymkeric substance, the result who utilizes DSC to measure is 125 ℃, weight-average molecular weight, using hexafluoroisopropanol is 4000 (PMMA conversions) as the result of the GPC mensuration of solvent, the polymerization degree n of calculating according to this value is 68.In addition, for the filtrate behind the acetoxyacetic acid polymer filtration, similarly operate, the result of analysis shows, at the bottom of the carboxaldehyde radicals that adds, contains the oxyacetic acid of 10.5 moles of %, in addition, has observed the peak of impurity such as diglycollic acid.
Embodiment 2
In embodiment 1, except will be among the embodiment 1 use ion exchange resin that after-filtration tells directly with the state of wet (wet) as catalyzer use, acetate uses the refining acetate that obtains of acetic acid solution distillation that distillation is removed and reclaimed during condensation reaction among the embodiment 1, react similarly to Example 1.The moisture of distillation purified product is 0.1 weight % (Ka Er-Fischer (Karl-Fischer) method), in the analysis that utilizes gas-chromatography, does not have the peak of special survey to acetate impurity in addition.Reaction filters out catalyzer after finishing, and the result who analyzes similarly to Example 1 shows that the oxyacetic acid yield at the bottom of the carboxaldehyde radicals of adding is 92 moles of %, confirms that catalyzer can repeatedly use.
Embodiment 3
In embodiment 1, except using " Nafion " that E.I.Du Pont Company produces, and reaction pressure (carbon monoxide pressure of tension) is changed into 100kg/cm as ion exchange resin
2, temperature of reaction changes into beyond 130 ℃, react similarly to Example 1.After reaction finishes, after reaction mixture and catalyzer filtration separately, carry out same analysis with embodiment 1, the result shows that the oxyacetic acid yield at the bottom of the carboxaldehyde radicals of adding is 95 moles of %.
In having the there-necked flask of stirrer, add above-mentioned filtrate, under the decompression of 50torr, in oil bath, be heated to 200 ℃, carry out 4 hours condensation reaction.After the reaction, when reaction solution is cooled off, directly solidify.With pulverizer this solid is pulverized, obtained the powder goods of acetoxyacetic acid polymkeric substance.The result that these goods are analyzed shows, oxyacetic acid content is 129 weight %, acetoxyl group content be 1.0 weight % (with after the basic hydrolysis, quantitative with high-speed liquid chromatography), be 0.6 weight % as the content of the diglycollic acid of impurity, the yield at the bottom of the carboxaldehyde radicals of adding is 89 moles of %.In addition, fusing point is 205 ℃ with the result that DSC measures, and weight-average molecular weight is 11000 (PMMA conversions) by the result that the GPC that uses hexafluoroisopropanol as solvent measures, and the polymerization degree n of calculating according to this value is 189.
Reference example 1
Use the above-mentioned acetoxyacetic acid polymkeric substance that obtains, carry out esterification reaction of organic acid.That is, in the autoclave (capacity 80ml) of hastelloy system, add the acetoxyacetic acid polymkeric substance that obtains among the 1g embodiment 3,10g methyl alcohol, 0.26g 96 weight % sulfuric acid, add magnetic stick, replace with nitrogen as catalyzer.With these autoclave sealed cans, after reacting 3 hours under 100 ℃, cooling back, the result who reaction solution is analyzed with high-speed liquid chromatography show, as benchmark, generates hydroxy methyl acetate with the yield of 92 moles of % with the oxyacetic acid in the acetoxyacetic acid polymkeric substance that uses.
Embodiment 4
In the glass container, add 150g Zeo-karb (" AMBERLYST 36wet " that Luo Men-Haars Co., Ltd produces), add 750g acetate again, after the nitrogen displacement, stirred 5 hours down at 100 ℃ as cleaning solvent.After being cooled to room temperature, Zeo-karb and cleaning solvent are filtered separately, reuse 750g acetate, under condition same as described above, carry out the cleaning of Zeo-karb.The acetic acid solvent that uses in heated wash is taken a sample, after microwave decomposition, with chromatography of ions carrier for evaporating dry solidification, the sulfate concentration of dilution back in the ion chromatography solvent.Sulfate concentration in the primary cleaning solvent is 170ppm, and the sulfate concentration in secondary cleaning solvent is 55ppm.
Then, use Zeo-karb after above-mentioned acid is cleaned, react according to embodiment 1 as catalyzer.That is, in embodiment 1, except the 92 weight % Paraformaldehyde 96s that use 19.6g as formaldehyde, use 30.8g (drying schedule is about 15g) Zeo-karb, reaction pressure changed into 70kg/cm
2In addition, react similarly to Example 1.Reaction filters out catalyzer after finishing, and the result who analyzes similarly to Example 1 shows that the oxyacetic acid yield at the bottom of the carboxaldehyde radicals of adding is 92 moles of %.To the reaction solution (filtrate) that leaches catalyzer, with the above-mentioned sulfate concentration of similarly measuring, the result is 140ppm.In addition, this filtrate is shown with the result of high-speed liquid phase chromatogram analysis directly that at the bottom of the carboxaldehyde radicals that adds, oxyacetic acid is 6 moles of %, acetoxyacetic acid is 60 moles of %, and the acetoxyacetic acid oligopolymer is 26 moles of %.
Add above-mentioned filtrate in having the there-necked flask of stirrer, under the decompression of 100torr, be heated to 160 ℃ in oil bath, the limit distillation is removed the acetate He Shui, the limit that produce as by product and is carried out condensation reaction.160 ℃ reaction is after 4 hours down in interior temperature, and the 50g pure water is added in slowly cooling when interior temperature becomes 90 ℃, further be cooled to room temperature.After the acetoxyacetic acid polymkeric substance that generates filtered,, obtain the acetoxyacetic acid polymkeric substance of 33.0g 60 ℃ of following warm air dryings 24 hours.In the acetoxyacetic acid polymkeric substance that obtains, oxyacetic acid content is 118 weight %, acetoxyl group content be 9.8 weight % (with after the basic hydrolysis, quantitative with high-speed liquid chromatography), be below the 0.1 weight % as the content of the diglycollic acid of impurity.Yield at the bottom of the carboxaldehyde radicals that adds is 85.4 moles of %.In addition, the sulfate radical content of acetoxyacetic acid polymkeric substance is 470ppm.
The fusing point of above-mentioned acetoxyacetic acid polymkeric substance, the result who measures with DSC is 170 ℃, and weight-average molecular weight is 6500 (PMMA conversions) by the result that the GPC that uses hexafluoroisopropanol as solvent measures, and the polymerization degree n of calculating according to this value is 111.In addition, to the filtrate behind the filtration acetoxyacetic acid polymkeric substance, operation similarly, the result of analysis shows, at the bottom of the carboxaldehyde radicals that adds, contains the oxyacetic acid of 6.5 moles of %, in addition, has observed the peak of impurity such as diglycollic acid.
Claims (6)
1. acyloxy acetic acid polymer is characterized in that: represent with following general formula (1):
In the general formula (1), each R
1And R
2Represent hydrogen atom or can the ramose low alkyl group respectively independently, n represents the integer more than 5.
2. acyloxy acetic acid polymer as claimed in claim 1 is characterized in that: the condensation of acyloxy acetic acid derivative is obtained.
3. acyloxy acetic acid polymer as claimed in claim 2 is characterized in that: condensation is to add thermal condensation.
4. as each described acyloxy acetic acid polymer in the claim 2～3, it is characterized in that: the acyloxy acetic acid derivative is in the presence of acid catalyst, makes formolation compound, carbon monoxide, the reaction of organic carboxyl acid or derivatives thereof and the material that obtains.
5. manufacture method with the acyloxy acetic acid polymer of described general formula (1) expression, it is characterized in that: in the presence of acid catalyst, make formolation compound, carbon monoxide, the reaction of organic carboxyl acid or derivatives thereof, obtain the acyloxy acetic acid derivative, then, the acyloxy acetic acid derivative that obtains is carried out condensation.
6. manufacture method as claimed in claim 5 is characterized in that: as acid catalyst, use the sulfonic acid ion exchange resin that cleans with acid in advance.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003369044 | 2003-10-29 | ||
| JP369044/2003 | 2003-10-29 | ||
| JP064111/2004 | 2004-03-08 | ||
| JP125777/2004 | 2004-04-21 |
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| Publication Number | Publication Date |
|---|---|
| CN1875046A true CN1875046A (en) | 2006-12-06 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220414A (en) * | 2012-03-27 | 2014-12-17 | 伊士曼化工公司 | Hydrocarboxylation of formaldehyde in the presence of higher order carboxylic acid and heterogeneous catalyst |
| CN111646895A (en) * | 2020-07-09 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Preparation method of glycolic acid or glycolate |
-
2004
- 2004-10-26 CN CN 200480031690 patent/CN1875046A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220414A (en) * | 2012-03-27 | 2014-12-17 | 伊士曼化工公司 | Hydrocarboxylation of formaldehyde in the presence of higher order carboxylic acid and heterogeneous catalyst |
| CN104220414B (en) * | 2012-03-27 | 2016-09-21 | 伊士曼化工公司 | The hydrocarboxylation of the formaldehyde in the presence of high carboxylic acid and heterogeneous catalyst |
| CN111646895A (en) * | 2020-07-09 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Preparation method of glycolic acid or glycolate |
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