CN102798676B - Method for indirect detection of purity of amino-terminated polyether - Google Patents
Method for indirect detection of purity of amino-terminated polyether Download PDFInfo
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Abstract
The invention discloses a method for indirect detection of purity of an amino-terminated polyether. The method utilizes a mixture of an amino-terminated polyether and a hydroxyl-terminated polyether corresponding to the amino-terminated polyether as a substrate needing to be detected. The method comprises the following steps that 1, the amino-terminated polyether and the hydroxyl-terminated polyether are mixed according to a mass ratio of 1: 1 into a standard substance; and the standard substance undergoes an acylation reaction to produce an amide-containing standard substance reaction solution; 2, the substrate needing to be detected undergoes an acylation reaction to produce an amide-containing detected-substrate reaction solution; 3, benzoyl chloride in the amide-containing standard substance reaction solution is removed and then liquid chromatogram analysis of the amide-containing standard substance reaction solution without benzoyl chloride is carried out, wherein the quotient of a hydroxyl-terminated polyether derivative peak area divided by an amino-terminated polyether derivative peak area is represented by J; and 4, benzoyl chloride in the amide-containing detected-substrate reaction solution is removed and then liquid chromatogram analysis of the amide-containing detected-substrate reaction solution without benzoyl chloride is carried out so that the amino-terminated polyether derivative peak area S1 and the hydroxyl-terminated polyether derivative peak area S2 are obtained, wherein amino-terminated polyether purity is equal to S1/(S1+S2/J).
Description
Technical field
The present invention relates to a kind of indirectly testing method of polymer end amino-polyether purity.
Background technology
Amine terminated polyether is that a class has soft polyether skeleton, terminal polymkeric substance with amino or amido end-blocking, at present, amine terminated polyether is mainly used in surfactant, oil dope, polyurethane and epoxy curing agent, is used widely in fields such as building, water conservancy, traffic, machineries.
The amine terminated polyether major part all is that the terminal hydroxyl to corresponding end hydroxy polyether carries out chemical modification and obtains.Utilize end hydroxy polyether to prepare that amine terminated polyether is general to adopt following method: to be catalyzer with the Raney's nickel, under the hydrogen high pressure, be raw material with end hydroxy polyether and ammonia, react under the High Temperature High Pressure, reaction finishes, excessive hydrogen all separates with gas with ammonia, Raney's nickel is dispersed fine in water, and water and amine terminated polyether and end hydroxy polyether are all immiscible, can Raney's nickel be removed by separatory, may comprise the end hydroxy polyether of certain content in the product (amine terminated polyether) of final gained.How to determine the purity (being the mass content of amine terminated polyether) of amine terminated polyether in the product of final gained, the detection method that adopts of people is to adopt Potential Titration Analysis to determine total amine value at present; Because amine terminated polyether is weak base, does not have tangible mutation process in titration process, thereby cause endpoint to be difficult for, that is, can't obtain the content of amine terminated polyether accurately.
Summary of the invention
The technical problem to be solved in the present invention provides the indirectly testing method of the high amine terminated polyether purity of a kind of accuracy of detection.
In order to solve the problems of the technologies described above, the invention provides a kind of indirectly testing method of amine terminated polyether purity,, may further comprise the steps as substrate to be measured with the potpourri of amine terminated polyether and the end hydroxy polyether corresponding with it:
1), takes by weighing with the amine terminated polyether in the substrate to be measured and take by weighing with the end hydroxy polyether in the substrate to be measured (namely, the amine terminated polyether that takes by weighing is with the amine terminated polyether in the substrate to be measured, the end hydroxy polyether that takes by weighing is with the end hydroxy polyether in the substrate to be measured), amine terminated polyether and end hydroxy polyether are mixed, as reference material according to the mass ratio of 1:1;
In reference material, add chlorobenzoyl chloride as acylating reagent, under the effect of organic catalyst, carry out acylation reaction, the mol ratio of reference material and chlorobenzoyl chloride is 1:3 ~ 6, the mass ratio of organic catalyst and reference material is 1:50 ~ 20, temperature of reaction is 40 ~ 80 ℃, reacted 4 ~ 8 hours, and obtained containing the reference material reactant liquor of acid amides;
2), in substrate to be measured, add chlorobenzoyl chloride as acylating reagent, under the effect of organic catalyst, carry out acylation reaction, the mol ratio of substrate to be measured and chlorobenzoyl chloride is with the mol ratio of reference material in the step 1) and chlorobenzoyl chloride, organic catalyst is with the organic catalyst in the step 1), the mass ratio of organic catalyst and substrate to be measured is with the mass ratio of organic catalyst in the step 1) and reference material, temperature of reaction is with the temperature of reaction of step 1), and the reaction time is with the reaction time of step 1); Obtain containing the substrate reactions liquid to be measured of acid amides;
3), remove excessive chlorobenzoyl chloride in the reference material reactant liquor that contains acid amides of step 1) gained with saturated sodium bicarbonate solution, leave standstill separatory, get oil phase and carry out liquid-phase chromatographic analysis, used liquid chromatography is equipped with UV-detector, choosing 254nm is absorbing wavelength, be 9:1 with volume ratio 8.8 ~ 9.2:1(the best) the mixed liquor of methyl alcohol and water be the phase that flows, the flow flow velocity of phase of control is 0.48 ~ 0.52 mL/min (best be 0.5mL/min), obtains respectively from the amine terminated polyether derivant of reference material with from retention time and the peak area of end hydroxy polyether derivant in liquid chromatography of reference material;
Setting is from the end hydroxy polyether derivative peak area ÷ of the reference material amine terminated polyether derivative peak area=J from reference material;
4), remove step 2 with saturated sodium bicarbonate solution) excessive chlorobenzoyl chloride in the substrate reactions liquid to be measured that contains acid amides of gained, leave standstill separatory, get oil phase and carry out liquid-phase chromatographic analysis, the flow velocity of used liquid chromatography, UV-detector, absorbing wavelength, the phase that flows, the phase that flows is with the corresponding process parameters in the step 3); Under the retention time from the amine terminated polyether derivant of reference material with step 3), obtain the peak area S1 from the amine terminated polyether derivant of substrate to be measured; Under the retention time from the end hydroxy polyether derivant of reference material with step 3), obtain the peak area S2 from the end hydroxy polyether derivant of substrate to be measured;
Quality percentage composition=S1/(S1+ S2/ the J of amine terminated polyether in substrate to be measured), that is, and amine terminated polyether purity=S1/(S1+ S2/ J).
Improvement as the indirectly testing method of amine terminated polyether purity of the present invention:
Amine terminated polyether is the amino PPOX ether of end, and the end hydroxy polyether corresponding with it is terminal hydroxy group PPOX ether.
Amine terminated polyether is the amino polyoxyethylene ether of end, and the end hydroxy polyether corresponding with it is terminal hydroxy group polyoxyethylene ether.
Further improvement as the indirectly testing method of amine terminated polyether purity of the present invention: organic catalyst is N, dinethylformamide (DMF), pyridine or triethylamine.
In step 1) of the present invention and step 2) in: since amine terminated polyether with have only the group at two ends different with the difference of its corresponding end hydroxy polyether; Their molecular weight only differs from 2, and the molecular weight of amine terminated polyether big have 8000, minimum also has 200, so can ignore the difference of the molecular weight of amine terminated polyether and the end hydroxy polyether corresponding with it substantially.Therefore as long as know the quality of reference material/substrate to be measured of adding and the type (being the mean molecular weight of amine terminated polyether) of amine terminated polyether, just can know the integral molar quantity of reference material/substrate to be measured (being amine terminated polyether and the end hydroxy polyether sum corresponding with it).
In step 3) of the present invention, remove excessive chlorobenzoyl chloride in the reference material reactant liquor that contains acid amides with saturated sodium bicarbonate solution, be conventional method, for example can adopt following method:
At first, according to the theoretical value of the chlorobenzoyl chloride of the reference material adapted 2mol of every mol, again according to step 2) in reference material and the mol ratio of chlorobenzoyl chloride, can learn step 2) amount of unnecessary chlorobenzoyl chloride after finishing; Again according to the theoretical amount ratio of saturated sodium bicarbonate solution and chlorobenzoyl chloride, suitably increase the actual use amount (for example be set to theoretical value 5 ~ 12 times) of saturated sodium bicarbonate solution again, just can finish easily with saturated sodium bicarbonate solution and remove excessive chlorobenzoyl chloride in the reference material reactant liquor that contains acid amides.
In like manner, in step 4) of the present invention, also can finish easily with saturated sodium bicarbonate solution and remove excessive chlorobenzoyl chloride in the substrate reactions liquid to be measured that contains acid amides.
The design concept of step 3) of the present invention and step 4) is specific as follows:
Since amine terminated polyether with have only the group at two ends different with the difference of its corresponding end hydroxy polyether, their molecular weight only differs from 2, and the molecular weight of amine terminated polyether big have 8000, minimum also has 200, so can ignore the difference of the molecular weight of amine terminated polyether and the end hydroxy polyether corresponding with it substantially.Thereby suppose that amine terminated polyether and the end hydroxy polyether corresponding with it are identical in quality, the quality of both derivants of back (being the amine terminated polyether derivant and end hydroxy polyether derivant of gained after the acylation reaction) of then deriving is also consistent.
In the step 3), set the amine terminated polyether derivative peak area=J from reference material from the end hydroxy polyether derivative peak area ÷ of reference material;
In the step 4), under with the retention time of step 3) from the amine terminated polyether derivant of reference material, obtain the peak area S1 from the amine terminated polyether derivant of substrate to be measured; Under with the retention time of step 3) from the end hydroxy polyether derivant of reference material, obtain the peak area S2 from the end hydroxy polyether derivant of substrate to be measured.Peak area representation quality in the chromatogram.Amine terminated polyether derivative molecular amount is M1, and end hydroxy polyether derivative molecular amount is M2, and the amine terminated polyether molecular weight is m1, and the end hydroxy polyether molecular weight is m2.
The amine terminated polyether derivant: end hydroxy polyether derivant (mol ratio)=(S1/M1): (S2/(M2*J))=amine terminated polyether: end hydroxy polyether (mol ratio),
Amine terminated polyether: end hydroxy polyether (mass ratio)=(m1*S1/M1): (m2*S2/(M2*J)),
The quality percentage composition of amine terminated polyether=(m1*S1/M1)/(m1*S1/M1+ m2*S2/(M2*J)),
Because we suppose that amine terminated polyether is identical with the end hydroxy polyether molecular weight and both molecular weight of derivant are identical, therefore obtain the quality percentage composition=S1/(S1+ S2/ J of amine terminated polyether).
In invention process of the present invention, the inventor also finds:
1, with the 9:1(volume ratio) the mixed liquor of methyl alcohol and water mutually extremely important as flowing; If make 8:2 into, the content of water has increased, and the phase eluting power that causes flowing reduces, the peak broadens short in the chromatogram that can cause obtaining at last, and the appearance time change is late, can cause two adjacent peaks well not separate, thereby brings difficulty to calculating peak area.
2, in step 1) and step 2) in, if chlorobenzoyl chloride is inexcessive, can cause amine terminated polyether and end hydroxy polyether in reference material/substrate to be measured not to have complete reaction, this can cause the reduction greatly of last accuracy of detection.
3, the lower limit of the consumption of organic catalyst " mass ratio of organic catalyst and reference material is 1:50 ~ 20 " that set less than the present invention can cause reaction not exclusively, thereby cause the reduction greatly of last accuracy of detection.
The higher limit of " mass ratio of organic catalyst and reference material is 1:50 ~ 20 " that the consumption of organic catalyst sets greater than the present invention not only can cause the increase of cost, also can increase the weight of the burden of aftertreatment.
Compare with potentiometric titration, the HPLC method has detection speed advantage fast, highly sensitive and simple to operate, but because amine terminated polyether does not have the not easy-to-use HPLC of uv absorption directly to detect, so the present invention forms acid amides with the amine terminated polyether derivatization earlier, thereby make molecule have uv absorption, so that carry out liquid-phase chromatographic analysis.
The indirectly testing method of amine terminated polyether purity of the present invention has replaced muting sensitivity, potentiometric titration that accuracy is low with high sensitivity, liquid phase chromatography that accuracy is high; Therefore method of testing of the present invention has simple, the characteristic of accurate as a result of method.
Embodiment
In following examples, amine terminated polyether is the amino PPOX ether of end, and being specially amine terminated polyether D-2000 is example; The end hydroxy polyether corresponding with it is terminal hydroxy group PPOX ether, and being specially end hydroxy polyether PPG-2000 is example.
The derivative reaction process is shown below:
The indirectly testing method of embodiment 1, a kind of amine terminated polyether D-2000 purity, carry out following steps successively:
1) the about 0.00375mol of amine terminated polyether D-2000(that, in having the 50mL there-necked flask of paddle and thermometer, adds 7.5g) and the about 0.00375mol of end hydroxy polyether PPG-2000(of 7.5g), namely, amine terminated polyether D-2000 and end hydroxy polyether PPG-2000 are mixed according to the mass ratio of 1:1, as reference material;
Add 0.5gN in reference material, dinethylformamide is warming up to 70 ℃, slowly splashes into 3.16g chlorobenzoyl chloride (0.0225mol drips 15 ~ 20 of the about per minutes of speed), keeps thermotonus to finish reaction in 5 hours, obtains containing the reference material reactant liquor of acid amides.
2), in having the 50mL there-necked flask of paddle and thermometer, add the about 0.0075mol of 15g amine terminated polyether D-2000() as substrate to be measured, add 0.5gN again, dinethylformamide, be warming up to 70 ℃, slowly splash into 3.16g chlorobenzoyl chloride (0.0225mol), keep thermotonus to finish reaction in 5 hours, obtain containing the substrate reactions liquid to be measured of acid amides.
3), with above-mentioned steps 1) the reference material reactant liquor that contains acid amides of gained is with the saturated sodium bicarbonate solution washing of 25 mL (namely stirring the back standing demix); Gained oil phase (being positioned at the upper strata) is 2 saturated sodium bicarbonate solution (being new saturated sodium bicarbonate solution) washings of 25 above-mentioned mL repeatedly again; Thereby guarantee in the reference material reactant liquor that contains acid amides of step 1) gained that residual excessive benzene formyl chloride is hydrolyzed that to form Sodium Benzoate water-soluble, that is, guarantee not contain chlorobenzoyl chloride in the oil phase of 3 washing back gained.
The oil phase of above-mentioned 3 washing back gained is detected, used liquid chromatograph (select for use C18 as filling material as packed column, the C18 reversed-phase column, column length 250 mm, column diameter 4.6 mm, particle diameter is 5.0 microns in the post) be equipped with UV-detector (choosing 254nm is absorbing wavelength), be mobile phase with the mixed liquor of the methyl alcohol of volume ratio 9:1 and water, under flow velocity 0.5mL/min; The peak area that obtains from the amine terminated polyether D-2000 derivant of reference material is 0.581; Its retention time is 6.3min; The peak area that also obtains accordingly from the end hydroxy polyether PPG-2000 derivant of reference material is 0.419; Its retention time is 6.9min.
J=0.419/0.581=0.721。
4), with above-mentioned steps 2) the substrate reactions liquid to be measured that contains acid amides of gained is with the saturated sodium bicarbonate solution washing of 25 mL (namely stirring the back standing demix); Gained oil phase (being positioned at the upper strata) is 2 saturated sodium bicarbonate solution washings of 25 above-mentioned mL repeatedly again; Thereby guarantee step 2) residual excessive benzene formyl chloride is hydrolyzed that to form Sodium Benzoate water-soluble in the substrate reactions liquid to be measured that contains acid amides of gained, that is, guarantee not contain chlorobenzoyl chloride in the oil phase of 3 washing back gained.
The oil phase of above-mentioned 3 washing back gained is detected, used liquid chromatograph with step 3) is equipped with the UV-detector (choosing 254nm is absorbing wavelength) with step 3), mixed liquor with the methyl alcohol of volume ratio 9:1 and water is the phase that flows, under flow velocity 0.5mL/min; When retention time is 6.3min, the peak area S1 that obtains from the amine terminated polyether D-2000 derivant of substrate to be measured is 0.999, when retention time was 6.9min, the peak area S2 that obtains from the end hydroxy polyether PPG-2000 derivant of substrate to be measured was 0.001.
Therefore, amine terminated polyether is at the quality percentage composition=S1/(S1+ S2/ J of substrate to be measured)=0.999/(0.999+0.001/0.721)=99.96%.Accuracy is 99.96%.
The indirectly testing method of embodiment 2, a kind of amine terminated polyether D-2000 purity, carry out following steps successively:
1) the about 0.00375mol of amine terminated polyether D-2000(that, in having the 50mL there-necked flask of paddle and thermometer, adds 7.5g) and the about 0.00375mol of end hydroxy polyether PPG-2000(of 7.5g), namely, amine terminated polyether D-2000 and end hydroxy polyether PPG-2000 are mixed according to the mass ratio of 1:1, as reference material;
In reference material, add the 0.3g pyridine, be warming up to 80 ℃, slowly splash into 4.22g chlorobenzoyl chloride (0.03mol), keep thermotonus to finish reaction in 8 hours, obtain containing the reference material reactant liquor of acid amides.
2), in having the 50mL there-necked flask of paddle and thermometer, add 12g amine terminated polyether D-2000 and 3g end hydroxy polyether PPG-2000 as substrate to be measured, add the 0.3g pyridine again, be warming up to 80 ℃, slowly splash into 4.22g chlorobenzoyl chloride (0.03mol), keep thermotonus to finish reaction in 8 hours, obtain containing the substrate reactions liquid to be measured of acid amides.
3), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 50ml into; All the other are equal to the step 3) of embodiment 1; The peak area that obtains from the amine terminated polyether D-2000 derivant of reference material is 0.582; Its retention time is 6.3min; The peak area that also obtains accordingly from the end hydroxy polyether PPG-2000 derivant of reference material is 0.418; Its retention time is 6.9min.
J=0.418/0.582=0.718。
4), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 50ml into; The step 4) that is equal to embodiment 1; When retention time is 6.3min, the peak area S1 that obtains from the amine terminated polyether D-2000 derivant of substrate to be measured is 0.849, when retention time was 6.9min, the peak area S2 that obtains from the end hydroxy polyether PPG-2000 derivant of substrate to be measured was 0.151.
Therefore, amine terminated polyether is at the quality percentage composition=S1/(S1+ S2/ J of substrate to be measured)=80.1%.That is, accuracy is 99.9%.
The indirectly testing method of embodiment 3, a kind of amine terminated polyether D-2000 purity, carry out following steps successively:
1) the about 0.0025mol of amine terminated polyether D-2000(that, in having the 50mL there-necked flask of paddle and thermometer, adds 5g) and the about 0.0025mol of end hydroxy polyether PPG-2000(of 5g), namely, amine terminated polyether D-2000 and end hydroxy polyether PPG-2000 are mixed according to the mass ratio of 1:1, as reference material;
In reference material, add 0.2gDMF, be warming up to 40 ℃, slowly splash into 2.11g chlorobenzoyl chloride (0.015mol), keep thermotonus to finish reaction in 4 hours, obtain containing the reference material reactant liquor of acid amides.
2), in having the 50mL there-necked flask of paddle and thermometer, add 14.25g amine terminated polyether D-2000 and 0.75g end hydroxy polyether PPG-2000 as substrate to be measured, add 0.3gDMF again, be warming up to 40 ℃, slowly splash into 3.16g chlorobenzoyl chloride (0.0225mol), keep thermotonus to finish reaction in 4 hours, obtain containing the substrate reactions liquid to be measured of acid amides.
3), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 20ml into, all the other steps are equal to the step 3) of embodiment 1; The peak area that obtains from the amine terminated polyether D-2000 derivant of reference material is 0.581; Its retention time is 6.3min; The peak area that also obtains accordingly from the end hydroxy polyether PPG-2000 derivant of reference material is 0.419; Its retention time is 6.9min.
Therefore, J=0.721.
4), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 30ml into, all the other steps are equal to the step 4) of embodiment 1; When retention time is 6.3min, the peak area S1 that obtains from the amine terminated polyether D-2000 derivant of substrate to be measured is 0.957, when retention time was 6.9min, the peak area S2 that obtains from the end hydroxy polyether PPG-2000 derivant of substrate to be measured was 0.043.
Therefore, amine terminated polyether is at the quality percentage composition=S1/(S1+ S2/ J of substrate to be measured)=0.957/(0.957+ 0.043/ 0.721)=94.1%.That is, accuracy is 99.1%.
The indirectly testing method of embodiment 4, a kind of amine terminated polyether D-2000 purity, carry out following steps successively:
1) the about 0.00375mol of amine terminated polyether D-2000(that, in having the 50mL there-necked flask of paddle and thermometer, adds 7.5g) and the about 0.00375mol of end hydroxy polyether PPG-2000(of 7.5g), namely, amine terminated polyether D-2000 and end hydroxy polyether PPG-2000 are mixed according to the mass ratio of 1:1, as reference material;
In reference material, add the 0.375g pyridine, be warming up to 60 ℃, slowly splash into 4.22g chlorobenzoyl chloride (0.03mol), keep thermotonus to finish reaction in 5 hours, obtain containing the reference material reactant liquor of acid amides.
2), in having the 50mL there-necked flask of paddle and thermometer, add 13.5g amine terminated polyether D-2000 and 1.5g end hydroxy polyether PPG-2000 as substrate to be measured, add the 0.375g pyridine again, be warming up to 60 ℃, slowly splash into 4.22g chlorobenzoyl chloride (0.03mol), keep thermotonus to finish reaction in 5 hours, obtain containing the substrate reactions liquid to be measured of acid amides.
3), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 50ml into, all the other steps are equal to the step 3) of embodiment 1; The peak area that obtains from the amine terminated polyether D-2000 derivant of reference material is 0.581; Its retention time is 6.3min; The peak area that also obtains accordingly from the end hydroxy polyether PPG-2000 derivant of reference material is 0.419; Its retention time is 6.9min.
J=0.721。
4), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 50ml into, all the other steps are equal to the step 4) of embodiment 1; When retention time is 6.3min, the peak area S1 that obtains from the amine terminated polyether D-2000 derivant of substrate to be measured is 0.922, when retention time was 6.9min, the peak area S2 that obtains from the end hydroxy polyether PPG-2000 derivant of substrate to be measured was 0.078.
Therefore, amine terminated polyether is at the quality percentage composition=S1/(S1+ S2/ J of substrate to be measured)=0.922/(0.922+ 0.078/ 0.721)=89.5%.That is, accuracy is 99.4%.
The indirectly testing method of embodiment 5, a kind of amine terminated polyether D-2000 purity, carry out following steps successively:
1) the amine terminated polyether D-2000(0.00375mol that, in having the 50mL there-necked flask of paddle and thermometer, adds 7.5g) and the end hydroxy polyether PPG-2000(0.00375mol of 7.5g), namely, amine terminated polyether D-2000 and end hydroxy polyether PPG-2000 are mixed according to the mass ratio of 1:1, as reference material;
In reference material, add the 0.5g triethylamine, be warming up to 80 ℃, slowly splash into 5.275g chlorobenzoyl chloride (0.0375mol), keep thermotonus to finish reaction in 6 hours, obtain containing the reference material reactant liquor of acid amides.
2), in having the 50mL there-necked flask of paddle and thermometer, add 12.75g amine terminated polyether D-2000 and 2.25g end hydroxy polyether PPG-2000 as substrate to be measured, add the 0.5g triethylamine again, be warming up to 80 ℃, slowly splash into 5.275g chlorobenzoyl chloride (0.0375mol), keep thermotonus to finish reaction in 6 hours, obtain containing the substrate reactions liquid to be measured of acid amides.
3), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 70ml into, all the other steps are equal to the step 3) of embodiment 1; The peak area that obtains from the amine terminated polyether D-2000 derivant of reference material is 0.580; Its retention time is 6.3min; The peak area that also obtains accordingly from the end hydroxy polyether PPG-2000 derivant of reference material is 0.420; Its retention time is 6.9min.
J=0.724。
4), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 70ml into, all the other steps are equal to the step 4) of embodiment 1; When retention time is 6.3min, the peak area S1 that obtains from the amine terminated polyether D-2000 derivant of substrate to be measured is 0.891, when retention time was 6.9min, the peak area S2 that obtains from the end hydroxy polyether PPG-2000 derivant of substrate to be measured was 0.109.
Therefore, amine terminated polyether is at the quality percentage composition=S1/(S1+ S2/ J of substrate to be measured)=0.891/(0.891+ 0.109/ 0.724)=85.5%.That is, accuracy is 99.4%.
The indirectly testing method of embodiment 6, a kind of amine terminated polyether D-2000 purity, carry out following steps successively:
1) the amine terminated polyether D-2000(0.00375mol that, in having the 50mL there-necked flask of paddle and thermometer, adds 7.5g) and the end hydroxy polyether PPG-2000(0.00375mol of 7.5g), namely, amine terminated polyether D-2000 and end hydroxy polyether PPG-2000 are mixed according to the mass ratio of 1:1, as reference material;
In reference material, add 0.75gDMF, be warming up to 40 ℃, slowly splash into 6.33g chlorobenzoyl chloride (0.045mol), keep thermotonus to finish reaction in 7 hours, obtain containing the reference material reactant liquor of acid amides.
2), in having the 50mL there-necked flask of paddle and thermometer, add 11.25g amine terminated polyether D-2000 and 3.75g end hydroxy polyether PPG-2000 as substrate to be measured, add 0.75gDMF again, be warming up to 40 ℃, slowly splash into 6.33g chlorobenzoyl chloride (0.045mol), keep thermotonus to finish reaction in 7 hours, obtain containing the substrate reactions liquid to be measured of acid amides.
3), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 90ml into, all the other steps are equal to the step 3) of embodiment 1; The peak area that obtains from the amine terminated polyether D-2000 derivant of reference material is 0.581; Its retention time is 6.3min; The peak area that also obtains accordingly from the end hydroxy polyether PPG-2000 derivant of reference material is 0.419; Its retention time is 6.9min.
J=0.721。
4), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 90ml into, all the other steps are equal to the step 4) of embodiment 1; When retention time is 6.3min, the peak area S1 that obtains from the amine terminated polyether D-2000 derivant of substrate to be measured is 0.811, when retention time was 6.9min, the peak area S2 that obtains from the end hydroxy polyether PPG-2000 derivant of substrate to be measured was 0.189.
Therefore, amine terminated polyether is at the quality percentage composition=S1/(S1+ S2/ J of substrate to be measured)=0.811/(0.811+ 0.189/ 0.721)=75.6%.That is, accuracy is 99.2%.
The indirectly testing method of embodiment 7, a kind of amine terminated polyether D-2000 purity, carry out following steps successively:
1) the amine terminated polyether D-2000(0.00375mol that, in having the 50mL there-necked flask of paddle and thermometer, adds 7.5g) and the end hydroxy polyether PPG-2000(0.00375mol of 7.5g), namely, amine terminated polyether D-2000 and end hydroxy polyether PPG-2000 are mixed according to the mass ratio of 1:1, as reference material;
In reference material, add the 0.3g pyridine, be warming up to 60 ℃, slowly splash into 3.16g chlorobenzoyl chloride (0.0225mol), keep thermotonus to finish reaction in 8 hours, obtain containing the reference material reactant liquor of acid amides.
2), in having the 50mL there-necked flask of paddle and thermometer, add 10.5g amine terminated polyether D-2000 and 4.5g end hydroxy polyether PPG-2000 as substrate to be measured, add the 0.3g pyridine again, be warming up to 60 ℃, slowly splash into 3.16g chlorobenzoyl chloride (0.0225mol), keep thermotonus to finish reaction in 8 hours, obtain containing the substrate reactions liquid to be measured of acid amides.
3), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 25ml into, all the other steps are equal to the step 3) of embodiment 1; The peak area that obtains from the amine terminated polyether D-2000 derivant of reference material is 0.582; Its retention time is 6.3min; The peak area that also obtains accordingly from the end hydroxy polyether PPG-2000 derivant of reference material is 0.418; Its retention time is 6.9min.
J=0.718。
4), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 25ml into, all the other steps are equal to the step 4) of embodiment 1; When retention time is 6.3min, the peak area S1 that obtains from the amine terminated polyether D-2000 derivant of substrate to be measured is 0.763, when retention time was 6.9min, the peak area S2 that obtains from the end hydroxy polyether PPG-2000 derivant of substrate to be measured was 0.237.
Therefore, amine terminated polyether is at the quality percentage composition=S1/(S1+ S2/ J of substrate to be measured)=0.763/(0.763+ 0.237/ 0.718)=69.8%.That is, accuracy is 99.7%.
The indirectly testing method of embodiment 8, a kind of amine terminated polyether D-2000 purity, carry out following steps successively:
1) the amine terminated polyether D-2000(0.00375mol that, in having the 50mL there-necked flask of paddle and thermometer, adds 7.5g) and the end hydroxy polyether PPG-2000(0.00375mol of 7.5g), namely, amine terminated polyether D-2000 and end hydroxy polyether PPG-2000 are mixed according to the mass ratio of 1:1, as reference material;
In reference material, add the 0.375g triethylamine, be warming up to 80 ℃, slowly splash into 4.22g chlorobenzoyl chloride (0.03mol), keep thermotonus to finish reaction in 4 hours, obtain containing the reference material reactant liquor of acid amides.
2), in having the 50mL there-necked flask of paddle and thermometer, add 9.75g amine terminated polyether D-2000 and 5.25g end hydroxy polyether PPG-2000 as substrate to be measured, add the 0.375g triethylamine again, be warming up to 80 ℃, slowly splash into 4.22g chlorobenzoyl chloride (0.03mol), keep thermotonus to finish reaction in 4 hours, obtain containing the substrate reactions liquid to be measured of acid amides.
3), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 50ml into, all the other steps are equal to the step 3) of embodiment 1; The peak area that obtains from the amine terminated polyether D-2000 derivant of reference material is 0.582; Its retention time is 6.3min; The peak area that also obtains accordingly from the end hydroxy polyether PPG-2000 derivant of reference material is 0.418; Its retention time is 6.9min.
J=0.718。
4), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 50ml into, all the other steps are equal to the step 4) of embodiment 1; When retention time is 6.3min, the peak area S1 that obtains from the amine terminated polyether D-2000 derivant of substrate to be measured is 0.726, when retention time was 6.9min, the peak area S2 that obtains from the end hydroxy polyether PPG-2000 derivant of substrate to be measured was 0.274.
Therefore, amine terminated polyether is at the quality percentage composition=S1/(S1+ S2/ J of substrate to be measured)=0.726/(0.726+ 0.274/ 0.718)=65.5%.That is, accuracy is 99.2%.
The indirectly testing method of embodiment 9, a kind of amine terminated polyether D-2000 purity, carry out following steps successively:
1) the amine terminated polyether D-2000(0.00375mol that, in having the 50mL there-necked flask of paddle and thermometer, adds 7.5g) and the end hydroxy polyether PPG-2000(0.00375mol of 7.5g), namely, amine terminated polyether D-2000 and end hydroxy polyether PPG-2000 are mixed according to the mass ratio of 1:1, as reference material;
In reference material, add 0.5gDMF, be warming up to 80 ℃, slowly splash into 5.275g chlorobenzoyl chloride (0.0375mol), keep thermotonus to finish reaction in 5 hours, obtain containing the reference material reactant liquor of acid amides.
2), in having the 50mL there-necked flask of paddle and thermometer, add 9g amine terminated polyether D-2000 and 6g end hydroxy polyether PPG-2000 as substrate to be measured, add 0.5gDMF again, be warming up to 80 ℃, slowly splash into 5.275g chlorobenzoyl chloride (0.0375mol), keep thermotonus to finish reaction in 5 hours, obtain containing the substrate reactions liquid to be measured of acid amides.
3), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 70ml into, all the other steps are equal to the step 3) of embodiment 1; The peak area that obtains from the amine terminated polyether D-2000 derivant of reference material is 0.581; Its retention time is 6.3min; The peak area that also obtains accordingly from the end hydroxy polyether PPG-2000 derivant of reference material is 0.419; Its retention time is 6.9min.
J=0.721。
4), when washing at every turn, the consumption of saturated sodium bicarbonate solution makes 70ml into, all the other steps are equal to the step 4) of embodiment 1; When retention time is 6.3min, the peak area S1 that obtains from the amine terminated polyether D-2000 derivant of substrate to be measured is 0.677, when retention time was 6.9min, the peak area S2 that obtains from the end hydroxy polyether PPG-2000 derivant of substrate to be measured was 0.323.
Therefore, amine terminated polyether is at the quality percentage composition=S1/(S1+ S2/ J of substrate to be measured)=0.677/(0.677+ 0.323/ 0.721)=60.2%.That is, accuracy is 99.7%.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (2)
1. the indirectly testing method of amine terminated polyether purity is characterized in that:, may further comprise the steps as substrate to be measured with the potpourri of amine terminated polyether and the end hydroxy polyether corresponding with it:
1), take by weighing with the amine terminated polyether in the substrate to be measured and take by weighing with the end hydroxy polyether in the substrate to be measured, described amine terminated polyether and end hydroxy polyether are mixed, as reference material according to the mass ratio of 1:1;
In reference material, add chlorobenzoyl chloride as acylating reagent, under the effect of organic catalyst, carry out acylation reaction, the mol ratio of reference material and chlorobenzoyl chloride is 1:3 ~ 6, the mass ratio of organic catalyst and reference material is 1:50 ~ 20, temperature of reaction is 40 ~ 80 ℃, reacted 4 ~ 8 hours, and obtained containing the reference material reactant liquor of acid amides;
2), in substrate to be measured, add chlorobenzoyl chloride as acylating reagent, under the effect of organic catalyst, carry out acylation reaction, the mol ratio of substrate to be measured and chlorobenzoyl chloride is with the mol ratio of reference material in the step 1) and chlorobenzoyl chloride, organic catalyst is with the organic catalyst in the step 1), the mass ratio of organic catalyst and substrate to be measured is with the mass ratio of organic catalyst in the step 1) and reference material, temperature of reaction is with the temperature of reaction of step 1), and the reaction time is with the reaction time of step 1); Obtain containing the substrate reactions liquid to be measured of acid amides;
3), remove excessive chlorobenzoyl chloride in the reference material reactant liquor that contains acid amides of step 1) gained with saturated sodium bicarbonate solution, leave standstill separatory, get oil phase and carry out liquid-phase chromatographic analysis, used liquid chromatography is equipped with UV-detector, choosing 254nm is absorbing wavelength, mixed liquor with the methyl alcohol of volume ratio 8.8 ~ 9.2:1 and water is the phase that flows, the flow flow velocity of phase of control is 0.48 ~ 0.52mL/min, obtains respectively from the amine terminated polyether derivant of reference material with from retention time and the peak area of end hydroxy polyether derivant in liquid chromatography of reference material;
Setting is from the end hydroxy polyether derivative peak area ÷ of the reference material amine terminated polyether derivative peak area=J from reference material;
4), remove step 2 with saturated sodium bicarbonate solution) excessive chlorobenzoyl chloride in the substrate reactions liquid to be measured that contains acid amides of gained, leave standstill separatory, get oil phase and carry out liquid-phase chromatographic analysis, the flow velocity of used liquid chromatography, UV-detector, absorbing wavelength, the phase that flows, the phase that flows is with the corresponding process parameters in the step 3); Under the retention time from the amine terminated polyether derivant of reference material with step 3), obtain the peak area S1 from the amine terminated polyether derivant of substrate to be measured; Under the retention time from the end hydroxy polyether derivant of reference material with step 3), obtain the peak area S2 from the end hydroxy polyether derivant of substrate to be measured;
Quality percentage composition=S1/(S1+ S2/ the J of amine terminated polyether in substrate to be measured);
Described organic catalyst is N, dinethylformamide, pyridine or triethylamine.
2. the indirectly testing method of amine terminated polyether purity according to claim 1 is characterized in that:
Described amine terminated polyether is the amino PPOX ether of end, and the end hydroxy polyether corresponding with it is terminal hydroxy group PPOX ether;
Described amine terminated polyether is the amino polyoxyethylene ether of end, and the end hydroxy polyether corresponding with it is terminal hydroxy group polyoxyethylene ether.
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| WO2011144644A1 (en) * | 2010-05-21 | 2011-11-24 | Evonik Degussa Gmbh | Hydrophilic polyisocyanates |
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| WO2011144644A1 (en) * | 2010-05-21 | 2011-11-24 | Evonik Degussa Gmbh | Hydrophilic polyisocyanates |
| CN102389802A (en) * | 2011-09-20 | 2012-03-28 | 中国石油化工集团公司 | Amine-terminated polyether synthetic catalyst and preparation method thereof |
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