HPLC (High Performance Liquid Chromatography) analysis method for analyzing HPLC standard substance and polyether polyol reaction byproducts

Abstract

The invention belongs to the field of organic synthesis and the technical field of analytical chemistry, and particularly relates to a high performance liquid chromatography standard substance and preparation thereof, the standard substance is applied to a byproduct analysis process of a reaction for synthesizing polyether polyol by taking epoxybutane as a monomer, the structural formula of the standard substance is # imgabs0 #, and n is a positive integer in a range of 2-20. In addition, the invention also relates to a high performance liquid chromatography for analyzing by-products of a reaction for synthesizing polyether polyol by taking epoxybutane as a monomer, which is established based on the standard substance. The method provided by the invention solves the problem that no epoxybutane auto-polymer standard substance exists in the market at present, so that qualitative and quantitative analysis of by-products in a reaction for synthesizing polyether polyol by taking epoxybutane as a monomer cannot be realized.

Description

Technical Field

[0001] The present invention relates to the fields of organic synthesis and analytical chemistry, and particularly to a standard product of by-products of epoxy butane self-polymerization, a preparation method thereof, and a high performance liquid chromatography analysis method for analyzing by-products of epoxy butane polymerization reaction established by using the standard product. Background Art

[0002] Polyether polyol, abbreviated as polyether, is a new type of synthetic lubricating oil base oil developed in the late 1970s and early 1980s. There are many types of it, mainly distinguished by monomers. The monomers for synthesizing polyether that have been developed currently include ethylene oxide, propylene oxide, epoxy butane, and tetrahydrofuran, etc. Polyether can be used not only as the base oil of a new type of synthetic lubricating oil, but also as an important raw material for producing polyurethane, and has various functions such as defoaming, demulsifying, dispersing, penetrating, and emulsifying. Due to the limitation of epoxy butane production technology, the polyethers we commonly see currently are mainly polyether polyols synthesized with ethylene oxide or propylene oxide as monomer raw materials. The polyether synthesized with epoxy butane as the monomer accounts for a small market share. However, due to its own characteristics, the solubility of epoxy butane polymer in water is lower than that of polyethylene oxide and polypropylene oxide with the same chain segment length, and its uses are constantly expanding, having broad development prospects.

[0003] However, in the process of synthesizing polyether polyol with epoxy butane as the monomer, under the action of a catalyst, while epoxy butane opens the ring and undergoes a polymerization reaction with an initiator, there is also a tendency of self-polymerization reaction to generate epoxide self-polymers. Given that the research on the process of synthesizing polyether polyol with epoxy butane as the monomer is less, there is currently no analytical means and method for determining the content of by-products. At the same time, in the traditional process of preparing standard products of epoxide self-polymers, water is used as the initiator, resulting in too fast reaction speed, higher heat release, and the risk of explosion.

[0004] As a test method for qualitative and quantitative analysis of organic substances, high performance liquid chromatography (HPLC) has the advantages of strong selectivity, high accuracy, quantifiable and quantitative analysis, etc. However, accurate quantitative analysis by HPLC method depends on HPLC standard products, and HPLC standard products not only require a high-purity chemical substance, but also require ensuring the consistency and quality of the product during the manufacturing process to ensure the effectiveness and credibility of the analysis results. However, there is currently no high performance liquid chromatography analysis standard product for epoxy butane self-polymerization by-products in the market. Therefore, there is currently no established high performance liquid chromatography analysis method for analyzing the content of epoxy butane self-polymerization by-products in the product of synthesizing polyether polyol with epoxy butane as the monomer by high performance liquid chromatography. Summary of the Invention

[0005] In order to solve the technical problem that there is no commercially available high-performance liquid chromatography (HPLC) standard for analyzing the by-products of the self-polymerization of epoxybutane, the first object of the present invention is to provide a standard for the by-products of the self-polymerization of epoxybutane.

[0006] To achieve the above object, the present invention adopts the following technical solutions.

[0007] An HPLC standard is used for analyzing the by-products of the reaction of synthesizing polyether polyol with epoxybutane as the monomer, and its structural formula is:

[0008]

[0009] Wherein, n is a positive integer from 2 to 30.

[0010] The preparation method of the HPLC standard is as follows:

[0011] (1) Mix the catalyst, butanediol and the first part of epoxybutane, and carry out an induction reaction at 150 - 180°C under an inert protective gas atmosphere and a stirring rate of 500 - 600 r / min. After 30 min of reaction, add the second part of epoxybutane to the reaction system and continue the reaction until the end of the reaction;

[0012] (2) Subject the reaction product obtained in step (1) to molecular distillation and vacuum distillation to obtain an HPLC standard with a purity of not less than 98%.

[0013] Preferably, in the preparation method, the mass ratio of the first part of epoxybutane to the second part of epoxybutane is 1:5 - 30.

[0014] Preferably, in the preparation method, the molecular distillation and vacuum distillation process is as follows: first, under the conditions of a temperature of 90 - 100°C and a vacuum degree of 0.001 - 0.01 kPa, use molecular distillation to remove the initiator residue and a small part of low-molecular-weight impurities in the product; then, under the conditions of a temperature of 100 - 300°C and a pressure of 2.67 kPa, use vacuum distillation to remove the low-adduct-number products present in the product.

[0015] In the above preparation method, butanediol is used instead of conventional water as the initiator, thereby effectively avoiding the danger of explosion caused by too fast reaction speed and rapid heat release during the reaction process.

[0016] The present invention also relates to an HPLC analysis method established using the above HPLC standard and its application in the analysis of the by-products of the reaction of synthesizing polyether polyol with epoxybutane as the monomer. The HPLC analysis method includes the following steps:

[0017] 1) Prepare a series of standard solutions with concentration gradients of 0.01 g / L, 0.05 g / L, 0.1 g / L, 0.25 g / L, 0.5 g / L, and 1 g / L respectively using the high-performance liquid chromatography reference standards described in claims 1 to 3;

[0018] 2) Use high-performance liquid chromatography to measure the peak areas of the series of standard solutions respectively, and plot the peak area - mass standard curve;

[0019] 3) Prepare the reaction product of the reaction for synthesizing polyether polyol with epoxy butane as the monomer into a sample solution, and use high-performance liquid chromatography to measure the peak area of the by-products in the sample solution;

[0020] 4) According to the external standard method, use the peak area - mass standard curve obtained in step 2) to record the peak area of the by-products in the sample solution, and obtain the content value of the by-product components in the sample.

[0021] In the above high-performance liquid chromatography analysis method, the preferred detection conditions are:

[0022] Mobile phase: Use water as mobile phase A and methanol solution as mobile phase B; the mobile phase A and mobile phase B flow in pump A and pump B respectively; gradient elution is adopted, and the gradient elution program is as follows:

[0023] Time (min) Pump A Pump B 0 - 4 min 10％ 90％ 4 - 12 min 10-0％ 90-100％ 12 - 27 min 0％ 100％ 27 - 30 min 10％ 90％ 30 - 41 min 10％ 90％

[0024] The chromatographic column is Agilent ZORBAX SB-C18 chromatographic column; specifications: 4.6×250 mm, 5 μm;

[0025] The detector uses an ELSD6000 evaporative light scattering detector;

[0026] The column temperature of the chromatographic column is 25 - 35 °C;

[0027] The flow rate range is 0.5 ml / min - 1.0 ml / min.

[0028] Preferably, the column temperature of the chromatographic column is 25 °C.

[0029] Preferably, the flow rates of mobile phase A and mobile phase B are 0.8 ml / min.

[0030] Preferably, mobile phase A and mobile phase B are injected simultaneously, and the injection volume is 20 μL for both.

[0031] Preferably, the concentration gradient range of the standard solution is 0.05 g / L - 1 g / L.

[0032] Preferably, the specific process for obtaining the content value of the by-product component in the sample is as follows: First, take the logarithm of the peak area A of the high-performance liquid chromatography standard product and the mass m of the high-performance liquid chromatography standard product in the solution. With lgA as the y-axis and lgm as the x-axis, draw a standard curve; then, based on the established standard curve, obtain the mass m of the epoxybutane self-polymerization by-product in the sample. 1 , then the content ω of the epoxybutane self-polymerization by-product in the sample, expressed as a mass fraction, is calculated according to the formula:

[0033]

[0034] In the formula: m1 - the mass (g) of the epoxybutane self-polymerization by-product in the sample; m 0 - the total mass (g) of the sample weighed.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] (1) The present invention provides a standard product of epoxybutane self-polymerization by-product and a preparation method thereof, which solves the technical problem of lacking a standard product of epoxybutane self-polymer in the process of analyzing polyether polyol products synthesized with epoxybutane as a monomer by high-performance liquid chromatography. At the same time, in the process of preparing the epoxybutane self-polymer standard product, butanediol is used instead of conventional water as an initiator, thereby effectively avoiding the danger of explosion caused by too fast reaction speed and rapid heat release during the reaction process.

[0037] (2) By preparing the epoxybutane self-polymerization by-product standard product, the present invention further establishes an analytical method for analyzing the epoxybutane self-polymerization by-product in the products of polyether polyols synthesized with epoxybutane as a monomer based on this standard product by high-performance liquid chromatography, which solves the industry problem of unable to quantitatively analyze the epoxybutane self-polymerization by-product in the prior art.

[0038] (3) The high-performance liquid chromatography analysis method provided by the present invention can be used for the on-line control analysis of the epoxybutane polymerization reaction process and the production end point, and has the advantages of simple operation method and accurate and reliable analysis data. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is the gas chromatography-mass spectrometry combined diagram of the HPLC standard product with an adduct number of 2 obtained from 1,4-butanediol and 1,2-epoxybutane in Example 1.

[0040] Figure 2 It is the molecular mass test result of the high-resolution mass spectrometer of the HPLC standard product with an adduct number of 15 obtained from 1,4-butanediol and 1,2-epoxybutane in Example 2.

[0041] Figure 3It is a comparison chart of chromatogram effects under different elution flow rates and elution temperature conditions during the analysis of the HPLC reference standard of the present invention using an HPLC instrument.

[0042] Figure 4 It is a by-product of butylene oxide homopolymer in polybutoxylated alcohol ether (ABO n , with the addition number n = 2, 3) and an HPLC comparison chart with the HPLC reference standard of the present invention (with the addition number n = 15).

[0043] Figure 5 It is a standard curve drawn based on the HPLC determination results of the HPLC reference standard of the present invention.

[0044] Figure 6 They are respectively the HPLC reference standard of the present invention, ABO 2 the content of by-products in the sample (7%) and the HPLC analysis chromatogram comparison after spiking 7% of ABO 2 Detailed implementation manners

[0045] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the technical content of the present invention will be described in detail below by way of specific embodiments in combination with the accompanying drawings. Obviously, the embodiments and the accompanying drawings described below are only some of the best embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other variations or equivalent embodiments can be obtained based on the best embodiments.

[0046]

Example 1

[0047] Synthesis of HPLC Standard (PBG, n = 2) and Analysis of Product Structure

[0048] ​1,4-butanediol (54 g) and potassium hydroxide with a mass fraction of 0.2% (0.4786 g) were dissolved uniformly by heating (40 °C) and stirring, and then inhaled into a high-temperature and high-pressure reactor by vacuum pumping. The reactor was purged with nitrogen and the evacuation pipeline three times. The temperature of the reactor was raised to 160 °C, and the mechanical stirrer switch of the reactor was turned on. The stirring speed was controlled at 600 r / min, and the condensate pipeline switch was turned on. When the temperature reached 160 °C, 10 g of 1,2-epoxybutane was introduced for an induction reaction. When the system pressure ≤ 0.03 MPa, the remaining 94.52 g of 1,2-epoxybutane was added to the reactor. The remaining 94.52 g of 1,2-epoxybutane was added to the reactor through a 1,2-epoxybutane storage tank, and the pressure of the 1,2-epoxybutane storage tank was maintained at 0.18 MPa. When the pressure of the reactor decreased to 0.03 MPa and did not change within 30 min, the reaction temperature was lowered to 50 °C, and the product was discharged by nitrogen blowing to obtain an epoxybutane homopolymer (PBG, degree of polymerization n = 2). The obtained PBG product was first subjected to molecular distillation at a temperature of 90 - 100 °C and a vacuum degree of 0.001 - 0.01 kPa to remove the initiator residue and a small part of low-molecular-weight impurities in the product, and then subjected to vacuum distillation at a temperature of 100 - 300 °C and a pressure of 2.67 kPa to remove the low-degree-of-polymerization products present in the product, obtaining a PBG (degree of polymerization n = 2) HPLC standard with a purity of not less than 98%.

[0049] The molecular weight and content of the obtained PBG (degree of polymerization n = 2) HPLC standard were determined by gas chromatography-mass spectrometry (GC-MS) and the product structure was analyzed. The results are shown in Figure 1 .

[0050] It can be seen from Figure 1 that the mass-to-charge ratio of 162 at t = 7.159 min indicates the product of butanediol adding one epoxybutane (BO), and the content ratio is 5.9%; the mass-to-charge ratio of 234 at t = 9.432 min indicates the product of butanediol adding two BOs, and the content ratio is 15.47%; the mass-to-charge ratio of 306 at t = 11.048 min indicates the product of adding three BOs, and the content ratio is 26.87%; the mass-to-charge ratio of 378 at t = 12.366 min indicates the product of adding four BOs, and the content ratio is 27.97%; the mass-to-charge ratio of 450 at t = 13.990 min indicates the product of adding five BOs, and the content ratio is 18.36%. The test results show that the PBG (degree of polymerization n = 2) HPLC standard was successfully synthesized by the method of Example 1.

[0051]

Example 2

[0052] Synthesis of HPLC Standard (PBG, n = 15) and Analysis of Product Structure

[0053] 1,4-butanediol (30 g) and potassium hydroxide with a mass fraction of 0.2% (0.6732 g) were dissolved evenly by heating (40 °C) and stirring, and then inhaled into a high-temperature and high-pressure reactor by vacuum pumping. The reactor was purged with nitrogen and the evacuation pipeline three times. The temperature of the reactor was raised to 160 °C, and the mechanical stirrer switch of the reactor was turned on. The stirring speed was controlled at 600 r / min, and the condensate pipeline switch was turned on. When the temperature reached 160 °C, 20 g of 1,2-epoxybutane was introduced for an induction reaction. When the system pressure ≤ 0.03 MPa, the remaining 339 g of 1,2-epoxybutane was added to the reactor through the 1,2-epoxybutane storage tank, and the pressure of the 1,2-epoxybutane storage tank was maintained at 0.14 MPa. When the pressure of the reactor decreased to 0.03 MPa and did not change within 30 min, the reaction temperature was lowered to 50 °C, and the product was discharged by nitrogen blowing to obtain an epoxybutane homopolymer (PBG, degree of polymerization n = 15). The obtained PBG product was first subjected to molecular distillation to remove the initiator residue and a small part of low-molecular-weight impurities in the product under the conditions of a temperature of 90 - 100 °C and a vacuum degree of 0.001 - 0.01 kPa, and then the low-degree-of-polymerization products present in the product were removed by vacuum distillation under the conditions of a temperature of 100 - 300 °C and a pressure of 2.67 kPa to obtain a PBG (degree of polymerization n = 15) HPLC standard with a purity not less than 98%.

[0054] The molecular weight and content of the obtained PBG (degree of polymerization n = 2) HPLC standard were measured by a high-resolution mass spectrometer, and the product structure was analyzed. The results are shown in Figure 2 .

[0055] As Figure 2 shown, by comparing and subtracting the adjacent peak values of the molecular ion peak, the m / z differences were found to be 28, 56, and 72. The BO group increased the -CH2-CH3 group for the structural change. The ion peak of the ethyl group is 28, and the differences of 28 and 56 indicate the successful introduction of the BO group, that is, the successful synthesis. At the same time, the molecular mass corresponding to the molecular ion peak is 1170, which is the peak value of the molecular mass of the product of the addition of butanediol and 15 epoxybutanes. The test results show that the PBG (degree of polymerization n = 15) HPLC standard was successfully synthesized by the method of Example 2.

[0056]

Example 3

[0057] Determination of HPLC Analysis Method Procedure for HPLC Standard

[0058] Taking the PBG (degree of polymerization n = 15) HPLC standard synthesized in Example 2 as an example, the establishment process of the HPLC analysis method program for the HPLC standard prepared by the present invention is described in detail.

[0059] The HPLC standard product prepared by the present invention was chromatographically analyzed using an Agilent high performance liquid chromatograph (product model 1260 Infinity III). The detection conditions were as follows: the chromatographic column was an Agilent ZORBAX SB-C18 chromatographic column (specification: 4.6×250 mm, 5 μm); the detector used was an ELSD 6000 evaporative light scattering detector; the mobile phase: water was used as mobile phase A, and methanol solution was used as mobile phase B; the mobile phase A and mobile phase B flowed in pump A and pump B respectively, and the selected flow rate conditions were: 0.5 mL / min, 0.8 mL / min, and 1.0 mL / min; the single factor variable method was used for research, and the column temperature was set at: 25 °C, 30 °C, and 35 °C. During the HPLC determination process, gradient elution was adopted, and the gradient elution program was:

[0060] Time (min) Pump A Pump B 0 - 4 min 10％ 90％ 4 - 12 min 10-0％ 90-100％ 12 - 27 min 0％ 100％ 27 - 30 min 10％ 90％ 30 - 41 min 10％ 90％

[0061] Among them, mobile phase A was in pump A, and mobile phase B was in pump B; at the same time, the injection volume was 20 μL.

[0062] The HPLC analysis and test results are shown in Figure 3 , in the figure: FL represents the flow rate, and CT represents the column temperature. It can be seen from Figure 3 that as the flow rate increases, the elution speed accelerates, resulting in a shorter elution in the chromatographic column, so the retention time gradually moves forward; under the condition of the same flow rate, the chromatogram of this high performance liquid chromatography standard product moves forward with the increase of the column temperature, but at 1.0 min / L and 35 °C, the retention time of the separation shows a backward shift phenomenon. It may be that under this condition, the adsorbed substances eluted out act together, resulting in a gradual lag in the separation of each mixture. Under the separation conditions of 0.8 mL / min and 25 °C, the separation effect of the HPLC standard product shows a standard sharp peak (no peak overlap) and normal distribution, and at the same time, the retention time is appropriate. Therefore, after comparison, it was finally decided that 0.8 mL / min and 25 °C were used as the optimal elution conditions.

[0063]

Example 4

[0064] Verification of HPLC Analysis Method for HPLC Standard

[0065] The purpose of the HPLC standard product provided by the present invention is to be applied to the by-product analysis of the reaction of synthesizing polyether polyol with epoxy butane as the monomer. Theoretically, for any polymerization / addition reaction carried out with epoxy butane as the monomer under the action of an initiator, the retention time of the by-product epoxy butane self-polymer in the HPLC chromatogram should be exactly the same as that of the epoxy butane self-polymer HPLC standard product (PBG) provided by the present invention in the HPLC chromatogram. For this reason, we synthesized polybutoxylated alcohol ether ABO by the polymerization reaction of dodecanol and 1,2-epoxy butanen (Degree of adduct n = 2, 3) as an example, under the optimal elution program, a qualitative comparative analysis of this high-performance liquid chromatography analysis method was carried out with the HPLC standard product (PBG, degree of adduct n = 15) synthesized in Example 2 to verify the high-performance liquid chromatography analysis method established based on the HPLC standard product of the present invention. ABO n The preparation method of (Degree of adduct n = 2, 3) can be found in the patent: A polyoxybutylene alcohol ether and its preparation method and application (Publication number: CN118221925A).

[0066] Figure 4 is polybutoxylated alcohol ether (ABO n , degree of adduct n = 2, 3) and the HPLC comparison chart of the HPLC standard product (degree of adduct n = 15) of the present invention. In the figure: above (a) is the HPLC chromatogram of the HPLC standard product (degree of adduct n = 15) of the present invention, and below is ABO n (Degree of adduct n = 2) sample chromatogram; above (b) is the HPLC chromatogram of the HPLC standard product (degree of adduct n = 15) of the present invention, and below is ABO n (Degree of adduct n = 3) sample chromatogram; in the chromatograms below (a) and (b), the by-products of ABO corresponding to the HPLC standard product chromatogram of the present invention are marked with a yellow background, and the main component of polybutoxylated alcohol ether in ABO n is marked with a blue background. From n it can be seen that the retention time of the chromatogram of the PBG (degree of adduct n = 15) HPLC standard product has completely covered the retention time of the by-products in ABO Figure 4 , and the HPLC standard product (PBG, degree of adduct n = 15) of the present invention can completely correspond to the by-products in ABO n . At the same time, it can also be seen that as the BO degree of adduct (n = 2, 3) in this HPLC standard product increases, the molecular weight increases, and the elution time extends, so n the retention time of the by-products (yellow background) in moves backward. Figure 4 In summary,

[0067] the test results show that the retention time of the chromatogram of the butylene oxide self-polymer HPLC standard product (PBG) provided by the present invention has completely covered the retention time of the by-products in ABO Figure 4 , indicating that the molecular weight of the by-products in ABO n is within the range of this HPLC standard product, proving that the HPLC standard product provided by the present invention can be used as a standard product for high-performance liquid chromatography analysis of the content of butylene oxide self-polymer by-products in polyether polyol products synthesized with butylene oxide as a monomer. n

[0068]

Example 5

[0069] Drawing of Standard Curve of HPLC Standard and Verification of Content Determination Method

[0070] Prepare a standard stock solution using butylene oxide self-polymer HPLC standard (PBG) as the standard: Weigh 0.1 g of this substance (accurate to 0.01 g), dissolve it with the mobile phase and make up the volume to 100 mL. Then use this standard stock solution to prepare standard solutions of various concentrations: Pipette 1.0 mL, 5.0 mL, 10.0 mL, 25.0 mL, and 50.0 mL of the standard stock solution into 100-mL volumetric flasks respectively, dilute and make up the volume to 10 mL with the mobile phase. The concentration gradients are 0.01 g / L, 0.05 g / L, 0.1 g / L, 0.25 g / L, and 0.5 g / L respectively.

[0071] Under the optimal elution program determined in Example 4, draw the standard curve as Figure 5 shown. Through data regression analysis, there is a good linear relationship between the logarithmic function of the mass concentration of butylene oxide self-polymer HPLC standard (PBG) in the range of 0.05 g / L - 1 g / L and the chromatographic peak area. Take the logarithm of the peak area A of the butylene oxide self-polymerization by-product standard (PBG) and the mass m of the butylene oxide self-polymer standard (PBG) in the solution. Use lgA as the y-axis and lgm as the x-axis to draw the standard curve. According to the drawn standard curve, obtain the mass m of the butylene oxide self-polymerization by-product 1 , then the content ω of the butylene oxide self-polymerization by-product in the sample is expressed as a mass fraction and calculated according to the formula:

[0072]

[0073] In the formula: m1 - the mass (g) of the butylene oxide self-polymerization by-product in the sample; m 0 - the total mass (g) of the sample weighed. The detailed data is shown in Table 1.

[0074] Table 1 Calculation data for each concentration gradient

[0075]

[0076] The accuracy R of the experimental values and the fitted values 2 = 0.9998, with good accuracy, proving that this standard curve can be used for the quantitative calculation of by-products in the butylene oxide addition reaction. Among them, the self-made ABO synthesized in the laboratory 2 Using the above standard curve to test, the mass fraction of the by-product is obtained as 7%. On this basis, the recovery rate of standard addition is verified based on 7%; at the same time, the content of 7% is also within the range of by-products of industrial production of alkoxylated products.

[0077] As Figure 6As shown, the content of by-products in ABO was tested using the HPLC standard of epoxybutane homopolymer (PBG) as the standard, and the content of by-products was 7%. The peaks corresponding to this retention time were all based on the standard of epoxybutane homopolymer by-products (PBG). Then, a spike test was carried out on the basis of 7%. The enlarged views of by-product PBG corresponding to 8 - 15 min are shown in (a) and (b) of 2 respectively. Figure 6

[0078]

Example 6

[0079] Reliability Test of HPLC Analysis Method Established Based on HPLC Standard

[0080] To verify the accuracy and precision of this analytical method and this standard curve, we carried out verification of the spike recovery rate and RSD. Using ABO 2 as the blank sample, the spike recovery rate solution was prepared and tested. Based on the mass fraction of by-products measured in Example 4 being 7%, the spike recovery rate was verified; before and after spiking, the peak area of by-product PBG in ABO 2 changed significantly. After calculation, the results of the spike recovery rate and precision test are shown in Table 2. As can be seen from Table 2, the average recovery rate of the HPLC standard was 91.75% - 98%, and the relative standard deviation was 1.58% - 3.03% (n = 9); indicating that the precision of this method is good, accurate and reliable.

[0081] Table 2 Results of spike recovery and precision tests

[0082]

[0083] ​

Claims

1. A high performance liquid chromatography standard product, used for the analysis of by-products in the synthesis of polyether polyols using butylene oxide as a monomer, characterized in that: The structural formula is: Wherein, n is a positive integer between 2 and 30; The method for preparing the high performance liquid chromatography standard comprises the following steps: (1) mixing the catalyst, butanediol and the first part of butylene oxide, reacting them at 150-180° C. at a stirring rate of 500-600 r / min under inert gas protection conditions, reacting for 30 minutes, adding the second part of butylene oxide to the reaction system and continuing the reaction until the reaction is completed; (2) The reaction product obtained in step (1) is subjected to molecular distillation and reduced pressure distillation in sequence to obtain a high performance liquid chromatography standard product with a purity of not less than 98%.

2. The high performance liquid chromatography standard according to claim 1, characterized in that The mass ratio of the first part of butylene oxide to the second part of butylene oxide is 1:5-30.

3. The high performance liquid chromatography standard according to claim 1, characterized in that The molecular distillation and reduced pressure distillation treatment process is to first remove the initiator residue and a small amount of low molecular weight impurities in the product by molecular distillation at a temperature of 90-100°C and a vacuum degree of 0.001-0.01 kPa; and then remove the low addition number products in the product by reduced pressure distillation at a temperature of 100-300°C and a pressure of 2.67 kPa.

4. A high performance liquid chromatography method for analyzing byproducts of a reaction in which butylene oxide is used as a monomer to synthesize polyether polyols, characterized in that: 1) using the HPLC standard substance described in claims 1 to 3, firstly preparing a standard stock solution with the HPLC standard substance, and then using the standard stock solution to prepare a series of standard solutions with concentration gradients of 0.01 g / L, 0.05 g / L, 0.1 g / L, 0.25 g / L, 0.5 g / L, and 1 g / L; 2) using high performance liquid chromatography to measure the peak areas of the series of standard solutions, respectively, and draw a peak area-mass standard curve; 3) preparing a sample solution from a reaction product of a reaction for synthesizing polyether polyols using butylene oxide as a monomer, and determining a peak area of ​​a by-product in the sample solution by high performance liquid chromatography; 4) According to the external standard method, using the peak area-concentration standard curve obtained in step 2), the peak area of ​​the by-product in the sample solution is recorded to obtain the content value of the by-product component in the sample.

5. The high performance liquid chromatography analysis method for analyzing byproducts of the reaction of synthesizing polyether polyols using butylene oxide as a monomer as claimed in claim 4, characterized in that: The detection conditions of the high performance liquid chromatography analysis are as follows: Mobile phase: water is used as mobile phase A, and methanol solution is used as mobile phase B; the mobile phase A and mobile phase B flow in pump A and pump B respectively; gradient elution is adopted, and the gradient elution procedure is as follows: The chromatographic column is Agilent ZORBAX SB-C18 column; specifications: 4.6×250mm, 5μm; The detector used was ELSD 6000 evaporative light scattering detector; The column temperature is 25-35°C; The flow rate range is 0.5ml / min~1.0ml / min.

6. The high performance liquid chromatography analysis method for analyzing byproducts of the reaction of synthesizing polyether polyols using butylene oxide as a monomer as claimed in claim 5, characterized in that: The column temperature was 25°C.

7. The high performance liquid chromatography analysis method for analyzing byproducts of the reaction of synthesizing polyether polyols using butylene oxide as a monomer as claimed in claim 5, characterized in that: The flow rate of mobile phase A and mobile phase B was 0.8 ml / min.

8. The high performance liquid chromatography analysis method for analyzing byproducts of the reaction of synthesizing polyether polyols using butylene oxide as a monomer as claimed in claim 5, characterized in that: Mobile phase A and mobile phase B were injected simultaneously, and the injection volume was 20 μL each.

9. The high performance liquid chromatography analysis method for analyzing byproducts of the reaction of synthesizing polyether polyols using butylene oxide as a monomer as claimed in claim 4, characterized in that: The concentration gradient range of the standard solution is 0.05g / L to 1g / L.

10. The high performance liquid chromatography analysis method for analyzing byproducts of the reaction of synthesizing polyether polyols using butylene oxide as a monomer as claimed in claim 4, characterized in that: The specific process of obtaining the content value of the by-product component in the sample is to first calculate the logarithm of the peak area A of the HPLC standard and the mass m of the HPLC standard in the solution, and draw a standard curve with lgA as the y-axis and lgm as the x-axis; then, the mass m1 of the butylene oxide self-polymerization by-product in the sample is obtained according to the prepared standard curve, and the content ω of the butylene oxide self-polymerization by-product in the sample is expressed as a mass fraction and calculated according to the formula: In the formula: m1 is the mass of butylene oxide self-polymerization by-product in the sample (g); m0 is the total mass of the sample in grams (g).

Images