A kind of polycarboxylic acids and preparation method thereof prepared by citric acid and its sodium salt
Technical field
The present invention relates to polymer preparation field, more particularly, to a kind of polycarboxylic acids prepared by citric acid and its sodium salt and
Preparation method.
Background technique
Polycarboxylic acids is in cement water reducing agent, cement grinding aid, the non-ironing crosslinking agent of fabric, industrial water system antisludging agent, surface
Activating agent, dispersing agent, super plasticizer, detergent etc. have a wide range of applications.The demand of polycarboxylic acids product is also increasingly
Greatly.And the preparation of polycarboxylic acids at present is mostly used the monomers such as vinyl carboxylic acid and carries out addition polymerization or use amino carboxylic acid, hydroxyl carboxylic
The monomers such as acid carry out condensation polymerization and obtain.These preparation methods are further divided into many kinds, cause ethylene for example, by using initiator
Conventional radical polymerization, ionic polymerization and its corresponding more monomer copolymerizable methods of base monomer are condensed using between functional group
The methods of the graft polymerization of progress is reacted between the condensation polymerization and macromole evocating agent or macromolecular functional group of reaction.Closely
Come, also occurs preparing polycarboxylic acids using the methods of microwave heating or auxiliary, light initiating polymerizing reaction.
Above method is although simple and easy, but the chemicals used is more, such as needs initiator, organic solvent
Deng;Sometimes the condition that polymerization reaction carries out is mild not enough, such as requires heat to the operations such as higher temperature, preparation high vacuum
Deng it is environmentally protective not enough in practical application that these result in these polymerizations.
The method of electrochemistry preparation is used for chemical synthesis etc. very early, especially in metal surface coating and organic point
Using relatively broad in the preparation of son.And applying in terms of polymer preparation is more successfully that (conjugated type is high for conducting polymer
Molecule) such as polyaniline electrochemistry preparation.The polymer such as polyaniline when prepared by electrochemistry more be deposited on electrode surface and formed
Covering is often hindered further polymerization reaction, so that further increasing for monomer conversion is restricted.Separately
Outside, primary group of free radicals is gone out using electrochemical electrolysis decomposition of initiator, the report for further causing vinyl monomer polymerization is also more normal
See.The greenization of these electrochemical preparing methods and polymerization reaction, environmental protection have a certain gap.
Kolbe cell reaction is that one kind of larger organic compound is prepared by free radical coupling after carboxylate electrolytic decarbodylation
Organic electrochemistry reaction, can carry out in aqueous solution, can avoid using not environmentally friendly enough organic solvent.This reaction is commonly used in having
The synthesis of machine small molecule has not been reported the preparation for polymer.And the present invention will to prepare molecular weight biggish using this reaction
Polycarboxylate polymer.
Citric acid and sodium citrate salt are a kind of common nontoxic organic compounds that can be used for food, can be made with it
Polycarboxylate/polycarboxylate polymer is prepared for raw material.This is a kind of more environmentally protective synthetic route.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind by citric acid and its
The polycarboxylic acids and preparation method thereof of sodium salt preparation.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of the polycarboxylic acids prepared by citric acid and its sodium salt, which comprises the following steps:
(1) it raw material will be prepared is added in reactor and obtain reaction solution, reaction solution constant temperature is flowed back;
(2) metal electrode is immersed in reaction solution, forms electrochemical reactor system;
(3) electrochemical polymerization reaction is carried out using DC power supply, sets voltage as 3~10V;
(4) it is acidity with the acid-base property that acid-base property regulator adjusts reaction solution, dialysis treatment then is carried out to reaction solution, is steamed
Hair removes solvent water process, finally reaction solution is dried to get the polycarboxylic acids is arrived;
The mixture for preparing raw material and being selected from aqueous citric acid solution or sodium citrate aqueous solution or both.
The mass concentration 5~70% of the aqueous citric acid solution;The mass concentration of the sodium citrate aqueous solution be 5~
70%.
Preferably, the mass concentration of the aqueous citric acid solution is 20%;The mass concentration of the sodium citrate aqueous solution
It is 20%.
The sodium citrate or citric acid that the mass concentration of aqueous citric acid solution or sodium citrate aqueous solution is dissolved with 100g water
Mass Calculation.
Wherein, the thermostat temperature of reaction solution is 25~120 DEG C in the step (1);
Metal electrode is two platinum plate electrodes in the step (2), and two platinum plate electrode fronts are staggered relatively;It was reacting
It is remained under liquid level of solution in journey.
The platinum plate electrode work area is 1~4cm2, spacing is 1~3cm;
Preferably, the platinum plate electrode work area is 1.0cm2, two platinum plate electrode spacing are 1.0cm.
Voltage is set in the step (3) as 3.0V, and the reaction time is 24~168h.
It is 5-7 that reaction solution, which is acid corresponding pH value, in the step (4);The retention of dialysis membrane used in the dialysis treatment
Molecular weight is 1000 or more;To the reaction solution after the dialysis treatment using rotary evaporation remove aqueous solvent, then carry out 50~
Dry 24~the 48h of 60 DEG C of constant-temperature vacuums obtains the polycarboxylic acids.
Preferably, the reaction solution of evaporation of solvent water is dried in vacuo 24 hours under 50 DEG C of constant temperature, can be prepared into
To polycarboxylic acid polymer.
The acid-base property regulator is selected from sodium hydroxide solution or sulfuric acid solution;The concentration of the sodium hydroxide solution is 1
~5mol/L;The concentration of the sulfuric acid solution is 1~2.5mol/L.
The concentration of the sodium hydroxide solution is 5mol/L;The concentration of the sulfuric acid solution is 2.5mol/L.
A kind of polycarboxylic acids is prepared by this method, the number-average molecular weight of the polycarboxylic acids is 6000-10000, weight
Average molecular weight is 12000~17000, and structural formula is as follows:
Poly- citric acid is prepared using electrochemical method for synthesizing, used theoretical foundation is Kolbe electrolysis, and carboxylic acid is in electrode
Redox reaction occurs for anode, and decarboxylize forms hydrocarbon, reaction process such as following formula:
R-COOH→R-R+CO2+2e-
Kolbe is electrolysed the preparation for being usually used in the small organic molecules such as the alkane such as octadecane of longer carbon chain, and has no this side
Method is used for the report of water soluble polymer preparation.Kolbe electrolytic method is used for the high molecular preparation of polycarboxylic acids by the present invention, former
The key point of reason is the citric acid for using carboxylic group there are three tools in each molecule, two between two citric acid molecules
Carboxyl can carry out the water soluble molecules that coupling becomes new with 4 carboxyls after decarboxylic reaction occurs, and the carboxyl in this molecule can
To continue that Kolbe cell reaction occurs, thus Kolbe cell reaction can be repeated to generate the poly- carboxylic of high molecular weight
Acid.According to above-mentioned principle, part citric acid molecule can also be made to slough three carboxyls in the polymerization using electrolysis method and be formed
Molecule residues with branched structure are further coupled with after the other three citric acid molecule decarboxylation, to form over-expense
The polycarboxylic acid structure of change.
During the preparation process, committed step is the control of temperature, the regulation of pH value, the control of concentration and voltage
Control.The raising of temperature, the raising of voltage, the increase of concentration will lead to reaction speed quickening, and reaction speed is too fast to be reduced
The stability of reaction, and same, temperature is too low, brownout and concentration is too low will lead to reaction speed reduction, and too low is anti-
Answer what speed will lead to product to be difficult to separating-purifying.
Compared with prior art, the polycarboxylic acids that the present invention is prepared uses citric acid or sodium citrate to prepare as raw material,
The raw material used is cheap and easy to get, nontoxic.Product polycarboxylic acids can have dissaving structure, have hydroxyl base in polymer molecule
Group and carboxylic group, convenient for being further converted to other structures polymer.Further, it is provided by the invention it is a kind of with citric acid and
Chemical initiator is not used in the preparation process for the polycarboxylic acids that its sodium salt is prepared as raw material, it may be convenient to control polymerizate
Molecular weight, can " step " prepare the polycarboxylic acid polymer with dissaving structure.Method and step letter of the present invention
Single, it is a kind of method for producing polymer of green that operation control, which is easy,.
Detailed description of the invention
Fig. 1 is the polymerization process schematic diagram of polycarboxylic acids preparation.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
A kind of polycarboxylic acids for using citric acid and its sodium salt to prepare as raw material, i.e., pass through electrochemistry by raw material of sodium citrate
It polymerize obtained polycarboxylic acids, reaction process is as shown in Figure 1, each lemon acid monomers contain three carboxyls, when two citric acids
Molecule aoxidizes two molecule residues with free radical of decarboxylize generation in anode respectively and releases two under the voltage of 3V
The carbon dioxide of a molecule, two molecule residues with free radical can be coupled as one containing there are four the citric acids of carboxyl
The dimer molecule of residue, the carboxyl in carboxyl and citric acid on dimer molecule can continue that electrolysis-idol as above occurs
Connection reaction, so circulation are until generate the polymer of macromolecular.Preparation method specifically comprises the following steps:
(1) sodium citrate 10.0g is weighed, is dissolved in 50.0mL distilled water, three mouthfuls of round bottoms with reflux condensing tube are poured into
In flask;
(2) 1.0cm is placed respectively in another two mouthfuls of above-mentioned three neck round bottom flask2Platinum plate electrode, two electrode fronts are opposite,
Distance 1cm, this to platinum plate electrode immerse sodium citrate aqueous solution in, remain at during the reaction liquid level of solution it
Under;Two electrodes are separately connected DC power supply positive and negative anodes, set voltage as 3.0V.Three neck round bottom flask is placed in constant temperature oil bath
In, oil bath temperature is set as 110 DEG C.It opens power supply and carries out reaction 24 hours.
(3) after reaction, pH value is adjusted to 6, using the half of molecular weight cut-off value 1000 with 2.5mol/L sulfuric acid solution
Permeable membrane dialyses to reaction solution, isolates polymerizate and is dried in vacuo for 24 hours at 50 DEG C, obtains polycarboxylic acids product 1.0g.
(4) molecule of size exclusion chromatograph (SEC) method (using polyethylene glycol as standard specimen, water is mobile phase) measurement product is used
Amount and molecular weight distribution.Product number-average molecular weight is 8000, weight average molecular weight 12000.
In order to prove the formation of carboxylic acid polyalcohol, the present embodiment has obtained monomer sodium citrate and carboxylic acid before and after polymerization reaction
The infrared spectrogram of polymer.It is shown in the infrared spectrogram of monomer and polymer and contains carboxylic acid group (- COOH/- in molecule
COO-, 1580-1570cm-1cm-1), hydroxyl group (- OH, 3449,3444,3265-3200,1144cm-1), secondary carbon (- CH2,
2960-2820、1395-1380cm-1), quaternary carbon (1280-1260cm-1).Polymer contained group compared with monomer
Type is the same, and only infrared absorption peak specific location has offset, and the power at peak is slightly changed.
According further to size exclusion chromatograph (SEC) measurement molecular weight as a result, the molecular weight distribution of polymer is arrived 3000
Between 20000, and between the molecular size range of monomer about 200-600 (there are caused by association phenomenon between molecules in solution).More than
Test result proves that monomer is successfully polymerize to have obtained polymer.
From the molecular structural formula of polycarboxylic acids it is found that having hydroxyl group and carboxylic group in product polycarboxylic acids molecule, it is convenient for
It is further converted to other structures polymer;Preparation process does not use chemical initiator, it may be convenient to control polymerizate
Molecular weight, can " step " prepare the polycarboxylic acid polymer with dissaving structure;Preparation method is simple, and operation control is held
It easily, is a kind of method for producing polymer of green.
Embodiment 2
A kind of polycarboxylic acids for using citric acid and its sodium salt to prepare as raw material, i.e., pass through electrochemistry by raw material of sodium citrate
It polymerize obtained polycarboxylic acids, preparation method specifically comprises the following steps:
(1) sodium citrate 5.0g is weighed, is dissolved in 100.0mL distilled water, three mouthfuls of round bottoms with reflux condensing tube are poured into
In flask;
(2) 1.0cm is placed respectively in another two mouthfuls of above-mentioned three neck round bottom flask2Platinum plate electrode, two electrode fronts are opposite,
Distance 1cm immerses this in citric acid/sodium citrate aqueous solution to platinum plate electrode, remains at solution during the reaction
Under liquid level;Two electrodes are separately connected DC power supply positive and negative anodes, set voltage as 3.0V.Three neck round bottom flask is placed in constant temperature
In oil bath, oil bath temperature is set as 110 DEG C.It opens power supply and carries out reaction 168 hours.
(3) after reaction, pH value is adjusted to 5, using the half of molecular weight cut-off value 1000 with 2.5mol/L sulfuric acid solution
Permeable membrane dialyses to reaction solution, isolates polymerizate and is dried in vacuo for 24 hours at 50 DEG C, obtains polycarboxylic acids product 0.3g.
(4) molecule of size exclusion chromatograph (SEC) method (using polyethylene glycol as standard specimen, water is mobile phase) measurement product is used
Amount and molecular weight distribution.Product number-average molecular weight is 9000, weight average molecular weight 14000.
Embodiment 3
A kind of polycarboxylic acids for using citric acid and its sodium salt to prepare as raw material, i.e., pass through electrochemistry by raw material of sodium citrate
It polymerize obtained polycarboxylic acids, preparation method specifically comprises the following steps:
(1) sodium citrate 35.0g is weighed, is dissolved in 50.0mL distilled water, three mouthfuls of round bottoms with reflux condensing tube are poured into
In flask;
(2) 1.0cm is placed respectively in another two mouthfuls of above-mentioned three neck round bottom flask2Platinum plate electrode, two electrode fronts are opposite,
Distance 1cm immerses this in citric acid/sodium citrate aqueous solution to platinum plate electrode, remains at solution during the reaction
Under liquid level;Two electrodes are separately connected DC power supply positive and negative anodes, set voltage as 3.0V.Three neck round bottom flask is placed in constant temperature
In oil bath, oil bath temperature is set as 110 DEG C.It opens power supply and carries out reaction 72 hours.
(3) after reaction, pH value is adjusted to 7, using the half of molecular weight cut-off value 1000 with 2.5mol/L sulfuric acid solution
Permeable membrane dialyses to reaction solution, isolates polymerizate and is dried in vacuo for 24 hours at 50 DEG C, obtains polycarboxylic acids product 1.5g.
(4) molecule of size exclusion chromatograph (SEC) method (using polyethylene glycol as standard specimen, water is mobile phase) measurement product is used
Amount and molecular weight distribution.Product number-average molecular weight is 10000, weight average molecular weight 17000.
Embodiment 4
A kind of polycarboxylic acids for using citric acid and its sodium salt to prepare as raw material, i.e., it is poly- by electrochemistry by raw material of citric acid
Obtained polycarboxylic acids is closed, preparation method specifically comprises the following steps:
(1) citric acid 10.0g is weighed, is dissolved in 50.0mL distilled water, three mouthfuls of round bottoms with reflux condensing tube is poured into and burns
In bottle;
(2) 1.0cm is placed respectively in another two mouthfuls of above-mentioned three neck round bottom flask2Platinum plate electrode, two electrode fronts are opposite,
Distance 1cm immerses this in citric acid/sodium citrate aqueous solution to platinum plate electrode, remains at solution during the reaction
Under liquid level;Two electrodes are separately connected DC power supply positive and negative anodes, set voltage as 3.0V.Three neck round bottom flask is placed in constant temperature
In oil bath, oil bath temperature is set as 110 DEG C.It opens power supply and carries out reaction 48 hours.
(3) after reaction, pH value is adjusted to 6, using molecular weight cut-off value 1000 with 5mol/L sodium hydroxide solution
Semi-permeable membrane dialyses to reaction solution, isolates polymerizate and is dried in vacuo for 24 hours at 50 DEG C, obtains polycarboxylic acids product
1.8g。
(4) molecule of size exclusion chromatograph (SEC) method (using polyethylene glycol as standard specimen, water is mobile phase) measurement product is used
Amount and molecular weight distribution.Product number-average molecular weight is 7000, weight average molecular weight 13000.
Embodiment 5
A kind of polycarboxylic acids for using citric acid and its sodium salt to prepare as raw material, i.e., it is poly- by electrochemistry by raw material of citric acid
Obtained polycarboxylic acids is closed, preparation method specifically comprises the following steps:
(1) citric acid 2.5g is weighed, is dissolved in 50.0mL distilled water, the three neck round bottom flask with reflux condensing tube is poured into
In;
(2) 1.0cm is placed respectively in another two mouthfuls of above-mentioned three neck round bottom flask2Platinum plate electrode, two electrode fronts are opposite,
Distance 1cm immerses this in citric acid/sodium citrate aqueous solution to platinum plate electrode, remains at solution during the reaction
Under liquid level;Two electrodes are separately connected DC power supply positive and negative anodes, set voltage as 10V.Three neck round bottom flask is placed in constant temperature
In oil bath, oil bath temperature is set as 25 DEG C.It opens power supply and carries out reaction 72 hours.
(3) after reaction, pH value is adjusted to 6, using molecular weight cut-off value 1000 with 5mol/L sodium hydroxide solution
Semi-permeable membrane dialyses to reaction solution, isolates polymerizate and is dried in vacuo 48h at 60 DEG C, obtains polycarboxylic acids product
0.4g。
(4) molecule of size exclusion chromatograph (SEC) method (using polyethylene glycol as standard specimen, water is mobile phase) measurement product is used
Amount and molecular weight distribution.Product number-average molecular weight is 6000, weight average molecular weight 10000.
Embodiment 6
A kind of polycarboxylic acids for using citric acid and its sodium salt to prepare as raw material, i.e., it is poly- by electrochemistry by raw material of citric acid
Obtained polycarboxylic acids is closed, preparation method specifically comprises the following steps:
(1) citric acid 10g is weighed, is dissolved in 50.0mL distilled water, the three neck round bottom flask with reflux condensing tube is poured into
In;
(2) 1.0cm is placed respectively in another two mouthfuls of above-mentioned three neck round bottom flask2Platinum plate electrode, two electrode fronts are opposite,
Distance 1cm immerses this in citric acid/sodium citrate aqueous solution to platinum plate electrode, remains at solution during the reaction
Under liquid level;Two electrodes are separately connected DC power supply positive and negative anodes, set voltage as 5V.Three neck round bottom flask is placed in thermostatical oil
In bath, oil bath temperature is set as 120 DEG C.It opens power supply and carries out reaction 24 hours.
(3) after reaction, pH value is adjusted to 6, using molecular weight cut-off value 1000 with 1mol/L sodium hydroxide solution
Semi-permeable membrane dialyses to reaction solution, isolates polymerizate and is dried in vacuo for 24 hours at 50 DEG C, obtains polycarboxylic acids product
0.5g。
(4) molecule of size exclusion chromatograph (SEC) method (using polyethylene glycol as standard specimen, water is mobile phase) measurement product is used
Amount and molecular weight distribution.Product number-average molecular weight is 7500, weight average molecular weight 11000.
Embodiment 7
A kind of polycarboxylic acids for using citric acid and its sodium salt to prepare as raw material, i.e., pass through electrochemistry by raw material of sodium citrate
It polymerize obtained polycarboxylic acids, preparation method specifically comprises the following steps:
(1) sodium citrate 35.0g is weighed, is dissolved in 50.0mL distilled water, three mouthfuls of round bottoms with reflux condensing tube are poured into
In flask;
(2) 1.0cm is placed respectively in another two mouthfuls of above-mentioned three neck round bottom flask2Platinum plate electrode, two electrode fronts are opposite,
Distance 1cm immerses this in citric acid/sodium citrate aqueous solution to platinum plate electrode, remains at solution during the reaction
Under liquid level;Two electrodes are separately connected DC power supply positive and negative anodes, set voltage as 3.0V.Three neck round bottom flask is placed in constant temperature
In oil bath, oil bath temperature is set as 110 DEG C.It opens power supply and carries out reaction 72 hours.
(3) after reaction, pH value is adjusted to 7, using the semi-transparent of molecular weight cut-off value 1000 with 1mol/L sulfuric acid solution
Film dialyses to reaction solution, isolates polymerizate and is dried in vacuo for 24 hours at 50 DEG C, obtains polycarboxylic acids product 1.1g.
(4) molecule of size exclusion chromatograph (SEC) method (using polyethylene glycol as standard specimen, water is mobile phase) measurement product is used
Amount and molecular weight distribution.Product number-average molecular weight is 9500, weight average molecular weight 16000.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.