Aldehyde ketone solid standard substance and preparation method thereof

Abstract

The invention discloses an aldehyde ketone solid standard substance and a preparation method thereof, and belongs to the technical field of standard samples, the product takes bisphenol A type ether resin as an adsorption fixing component of an aldehyde ketone compound, so that the aldehyde ketone compound in the product can be ensured to have long-acting stability, the stability reaches the standard when the aldehyde ketone solid standard substance is used as the standard substance, and the aldehyde ketone solid standard substance can be used for adsorbing and fixing the aldehyde ketone compound. Meanwhile, the loading capacity is controllable, the application range is wide, and the method can be popularized on an industrial production line.

Description

Technical Field

[0001] The present invention relates to the technical field of standard samples, and in particular to an aldehyde or ketone solid standard substance and a preparation method thereof. Background Art

[0002] Aldehyde and ketone compounds are a class of volatile compounds containing aldehyde or ketone functional groups. These compounds are extremely easy to diffuse and spread in the air, thereby affecting human health. Therefore, the emission standards of aldehyde and ketone compounds are strictly controlled in various industries.

[0003] In the automotive and electrical industries, due to the large number of plastic parts used, these parts are prone to precipitating aldehydes and ketones during use and aging, especially parts such as instrument panels in enclosed vehicle compartments. Regular testing of aldehyde and ketone compound emissions and content is required in strict accordance with industry standards.

[0004] However, existing standard substances for the detection of aldehyde and ketone compounds are mainly liquid targets, that is, aldehyde and ketone compounds are dissolved in organic solvents to prepare standard substances. However, this type of standard substance not only has the defects of being difficult to transport and preserve, but also cannot intuitively simulate the dispersion and volatilization of aldehyde and ketone compounds in solid products, and the detection error is large; and the main aldehyde and ketone compound detection objects are currently mostly solids, and the corresponding detection cycle is long. When using liquid standard substances for instrument calibration, there are too many control factors and the operation is complicated.

[0005] To this end, attempts have been made to prepare solid aldehyde and ketone reference materials using plastics such as polypropylene as a matrix. However, due to the volatility and decomposition of aldehydes and ketones, complex processing techniques are generally required for product preparation. Furthermore, the loading capacity of aldehydes and ketones is limited, making industrialization difficult. Furthermore, these existing solid reference materials have a short shelf life, making them difficult to use for long-term testing and control on factory production lines. Summary of the Invention

[0006] Based on the defects of the existing technology, the purpose of the present invention is to provide a solid standard substance of aldehydes and ketones. The product uses bisphenol A ether resin as the adsorption and fixation component of aldehyde and ketone compounds, which can not only ensure that the aldehyde and ketone compounds in the product have long-term stability and meet the stability standards when used as a standard substance, but also has a controllable loading amount, a wide range of applications, and can be promoted on industrial production lines.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is:

[0008] An aldehyde and ketone solid standard substance comprises the following components in parts by weight:

[0009] 400-600 parts of polypropylene resin, 3-5 parts of antioxidant, 0.8-1.2 parts of aldehyde-ketone fixing resin, 0.0001-0.005 parts of aldehyde-ketone compound;

[0010] The aldehyde-ketone fixing resin includes bisphenol A ether resin.

[0011] Preferably, the bisphenol A ether resin includes at least one of phenylene ether epoxy resin and bisphenol A diglycidyl ether (DGEBA).

[0012] Traditional aldehyde-ketone standard substances are mainly liquid products prepared by compounding organic solvents with aldehyde-ketone compounds, and this product is difficult to transport and preserve, and cannot effectively match solid sample to be tested. And although prior art also has some solid aldehyde-ketone plastic standard substances, but the aldehyde-ketone compound loading of this type of material is relatively low at present, and controllable range is wide, once content is introduced and increased, due to the volatility and easy decomposition of aldehyde-ketone compounds, it is impossible to ensure the uniformity and stability of product, and use and preservation life are shorter, it is impossible to be applied in the middle of the product quality inspection of some continuous industrial production lines. For this reason, in technical solution of the present invention, in order to take into account the addition controllability of aldehyde-ketone compounds and its stability in polypropylene resin, the aldehyde-ketone fixed resin of specific species is synchronously introduced in product for fixing and compatible with aldehyde-ketone compounds, even if aldehyde-ketone compounds are still not separated out and decomposed in daily use and preservation process under more content, and then the detection accuracy of subject matter is affected.

[0013] However, as a key component, the type of aldehyde-ketone fixing resin cannot be arbitrary. If a type outside the limited range is selected, although better uniformity may still be achieved, the product may not achieve the required stability after being stored for a long time. At the same time, the amount of this component added cannot be too much or too little, otherwise it will also easily cause the product's uniformity to decrease.

[0014] Preferably, the aldehyde and ketone compounds include at least one of formaldehyde, acetaldehyde, acrolein, and acetone.

[0015] It should be noted that the target aldehyde and ketone compounds used to prepare standard substances described in the present invention are not limited to the above-mentioned types. Those skilled in the art can select the above-mentioned common aldehyde and ketone compounds as constant detection target objects according to actual detection needs or project requirements, or can select other types of aldehyde and ketone substances as target objects, as long as they do not exceed the range of aldehyde and ketone compounds known to those skilled in the art.

[0016] Preferably, the weight proportion of the polypropylene resin is 400 parts, 420 parts, 450 parts, 480 parts, 500 parts, 520 parts, 550 parts, 580 parts, 600 parts or any two of the range values; the weight proportion of the antioxidant is 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts or any two of the range values; the weight proportion of the aldehyde-ketone fixing resin is 0.8 parts, 0.85 parts, 0.90 parts, 1.00 parts, 2.00 parts, 3.00 parts, 4.00 parts, 5.00 parts, The weight proportions of the aldehyde and ketone compounds are in the range of 0.0001 part, 0.0005 part, 0.001 part, 0.0015 part, 0.002 part, 0.0025 part, 0.003 part, 0.0035 part, 0.004 part, 0.0045 part, 0.005 part or any two of the range values.

[0017] More preferably, the aldehyde and ketone solid standard substance comprises the following components in parts by weight:

[0018] 450-550 parts of polypropylene resin, 3.5-4.5 parts of antioxidant, 0.9-1.1 parts of aldehyde-ketone fixing resin, and 0.0003-0.0045 parts of aldehyde-ketone compound.

[0019] Preferably, the mass content of polypropylene resin in the aldehyde and ketone solid standard substance is ≥95%.

[0020] Preferably, the components of the aldehyde and ketone solid standard substance further include a curing agent, and the mass ratio of the curing agent to the aldehyde and ketone fixing resin is (0.5:9.5) to (1.5:8.5).

[0021] The aldehyde-ketone fixing resin defined in the present invention takes one of the bisphenol A diglycidyl ethers as an example. This resin has high chemical resistance and mechanical strength, and high viscosity, so it has good adhesion and compatibility when mixed with polypropylene resin and aldehyde-ketone compounds; at the same time, after the introduction of a curing agent, it can be cured at room temperature, and after curing, its fixing effect on the aldehyde-ketone compounds is still good, and the cured aldehyde-ketone fixing resin is easier to shear and stir, and the processing effect is higher. Therefore, in order to improve the production efficiency of the product, those skilled in the art can pre-mix the aldehyde-ketone compound with the aldehyde-ketone fixing resin during the preparation of the product, and then add an appropriate amount of curing agent to cure the mixture, and then crush and refine the cured material and add other components to prepare an aldehyde-ketone solid standard substance. The product obtained by this processing operation method has a similar uniformity effect as the traditional plastic solid standard substance processing operation method.

[0022] More preferably, the curing agent includes at least one of diethylenetriamine, fatty amine, and m-phenylenediamine.

[0023] More preferably, the aldehyde-ketone fixing resin is bisphenol A diglycidyl ether.

[0024] Research has shown that different aldehyde and ketone fixing resins have different fixing effects on aldehyde and ketone compounds in the product and their compatibility with various components. When bisphenol A diglycidyl ether is used, the compatibility of the various components of the product is better, the fixing effect on aldehyde and ketone compounds is more lasting, and the uniformity and long-term stability of the product are better.

[0025] Preferably, the antioxidant includes at least one of a hindered phenol antioxidant and a phosphite antioxidant.

[0026] More preferably, the antioxidant is a mixture of a hindered phenol antioxidant and a phosphite antioxidant.

[0027] More preferably, the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is (0.5-1.5):(0.5-1.5).

[0028] More preferably, the hindered phenol antioxidant includes at least one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 2,6-di-tert-butyl-4-methylphenol; and the phosphite antioxidant includes at least one of bis(2,4-di-tert-butylphenyl)pentaerythritol bisdiphosphite and tris(2,4-di-tert-butylphenyl)phosphite.

[0029] Preferably, the polypropylene resin has a melt flow rate of 10 to 35 g / 10 min at 230° C. and a load of 2.16 kg according to ISO 1133-2011.

[0030] In the technical solution of the present invention, there are no special requirements for the types of polypropylene resin and antioxidant. Based on the actual processing conditions and the compatibility of the types of the objects to be tested, those skilled in the art can select various common commercially available antioxidants and polypropylene resins to prepare the product of the present invention, without restriction as long as they do not affect the expected homogeneity and stability.

[0031] Preferably, the components of the aldehyde and ketone solid standard substance also include 0.01 to 2 parts of functional additives.

[0032] More preferably, the processing aid includes at least one of an antistatic agent, an antibacterial agent, and an anti-ultraviolet agent.

[0033] According to actual needs, those skilled in the art may add various functional additives without affecting the homogeneity and stability of the standard substance described in the present invention. For example, in order to prevent the product from being affected by static electricity during transportation and storage, those skilled in the art may add antistatic agents to the product; in order to make the product more resistant to ultraviolet radiation during storage, those skilled in the art may add anti-ultraviolet light agents to the product.

[0034] Another object of the present invention is to provide a method for preparing the aldehyde and ketone solid standard substance, comprising the following steps:

[0035] After the components are uniformly mixed, they are melt-extruded in a screw extruder to obtain the aldehyde and ketone solid standard substances.

[0036] Preferably, the aldehyde and ketone solid standard substances may be further subjected to shaping treatment after melt extrusion.

[0037] The aldehyde and ketone solid standard substances described in the present invention can be used in the form of particles based on the usage scenario, and can also be molded into shaped product samples for required testing scenarios, and there is no special restriction on the sample size.

[0038] Preferably, the temperature during the melt extrusion is 150-250° C., the screw speed is 120-170 r / min, and the screw aspect ratio is 25:1-30:1.

[0039] The preparation method of the aldehyde and ketone solid standard substance of the present invention has simple operation steps and can realize industrial-scale production.

[0040] The method for preparing the aldehyde and ketone solid standard substance of the present invention may further comprise the following steps:

[0041] Before the components are evenly mixed, the aldehyde-ketone fixing resin and the aldehyde-ketone compound are mixed, and then the curing agent is added and mixed and stirred at 40-60° C. for 15-30 minutes. The obtained mixture is crushed, and the obtained powder is then evenly mixed with the other components of the aldehyde-ketone solid standard substance and melt-extruded in a screw extruder.

[0042] As described above, when preparing the product of the present invention, based on the controllability of production efficiency, it is also possible to choose to introduce some curing agents into the product. Before the components are mixed and melted, the aldehyde-ketone fixing resin and the aldehyde-ketone compound are mixed in advance, and then solidified and crushed. The obtained granular powder is then mixed and melted with other ingredients. Such operation can further improve the mixing and melting efficiency of the components and reduce the difficulty of operation and energy consumption.

[0043] Another object of the present invention is to provide an application of the aldehyde and ketone solid standard substance in the detection of aldehyde and ketone content in solid samples and in the evaluation and calibration of sample aldehyde and ketone content testing equipment.

[0044] The aldehyde and ketone solid standard substance described in the present invention not only has uniformity and stability, but also has a wide and controllable loading range of aldehyde and ketone compounds, and is very convenient in preparation, transportation and application. At the same time, the product can still meet the application indicators at room temperature for 6 months and has a long shelf life. It is very suitable for aldehyde and ketone content detection of various solid samples, or for accuracy evaluation, verification and instrument calibration of corresponding test equipment.

[0045] The beneficial effect of the present invention is that the present invention provides an aldehyde and ketone solid standard substance. The product uses ether resin as the adsorption and fixing component of aldehyde and ketone compounds, which can not only ensure that the aldehyde and ketone compounds in the product have long-term stability and meet the stability standards when used as a standard substance, but also has a controllable loading amount, a wide range of applications, and can be promoted on industrial production lines. DETAILED DESCRIPTION

[0046] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments and comparative examples. Its purpose is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without making creative work premise all fall within the protection scope of the present invention. The experimental reagents and instruments involved in the implementation of the present invention are all conventional common reagents and instruments unless otherwise specified.

[0047] Examples 1 to 6

[0048] An embodiment of the aldehyde and ketone solid silicon standard substance and the preparation method thereof according to the present invention, the composition of the aldehyde and ketone solid standard substance is shown in Table 1.

[0049] The preparation method of the aldehyde and ketone solid standard substance comprises the following steps:

[0050] After the components are uniformly mixed, they are melt-extruded in a sealed screw extruder to obtain the aldehyde and ketone solid standard substances.

[0051] During the melt extrusion, the temperature of the screw extruder is set to: zone 1: 150-170°C, zone 2: 180-190°C, zone 3: 190-200°C, zone 4: 200-210°C, zone 5: 210-220°C, zone 6: 220-230°C, zone 7: 230-240°C, zone 8: 220-230°C, zone 9: 200-210°C, zone 10: 185-200°C; the screw speed is 150 r / min, and the screw aspect ratio is 28:1.

[0052] Example 7

[0053] An embodiment of the aldehyde and ketone solid silicon standard substance and the preparation method thereof according to the present invention, the composition of the aldehyde and ketone solid standard substance is shown in Table 1.

[0054] The preparation method of the aldehyde and ketone solid standard substance comprises the following steps:

[0055] The aldehyde-ketone fixed resin and the aldehyde-ketone compound are mixed, and then a curing agent is added and mixed. The mixture is stirred at 60°C in a sealed environment for 30 minutes. The resulting solid is crushed into powder under the protection of liquid nitrogen, and then evenly mixed with other components of the aldehyde-ketone solid standard substance. The mixture is melt-extruded and granulated in a sealed screw extruder to obtain the aldehyde-ketone solid standard substance. The parameter settings during melt extrusion in the screw extruder are the same as those in Examples 1 to 6.

[0056] Comparative Examples 1 to 4

[0057] The difference between the comparative examples and the examples is only in the types and proportions of the components, as shown in Table 2.

[0058] Among the components described in each embodiment and comparative example,

[0059] The polypropylene resin 1 is PP150 produced by Sinopec, and has a melt flow rate of 15 g / 10 min at 230° C. and a load of 2.16 kg;

[0060] The polypropylene resin 2 is PP 320 powder produced by Sinopec Yanshan, with a melt flow rate of 28 g / 10 min at 230° C. and a load of 2.16 kg;

[0061] The antioxidant 1 is commercially available antioxidant 1010, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, a hindered phenol antioxidant;

[0062] The antioxidant 2 is commercially available antioxidant 168, tris[2,4-di-tert-butylphenyl]phosphite, a phosphite antioxidant;

[0063] The aldehyde-ketone fixing resin 1 is bisphenol A diglycidyl ether produced by Merck;

[0064] The aldehyde-ketone fixing resin 2 is DER332 (bisphenol A epoxy resin, CAS 25085-99-8, phenylene ether epoxy resin) produced by Dow Chemical (DOW).

[0065] The aldehyde-ketone fixing resin 3 is JP-H26 (organic silicon modified epoxy resin) produced by Shenzhen Jipeng Silicon Fluorine Materials Co., Ltd.

[0066] The fixed substance is 200 mesh activated carbon produced by Macklin, activated carbon, 200 mesh;

[0067] The curing agent is commercially available diethylenetriamine;

[0068] The aldehyde and ketone compound 1 is formaldehyde, which is added with a commercially available formaldehyde aqueous solution during the preparation of the product, with a solution mass concentration of 50%;

[0069] The aldehyde and ketone compound 2 is acetaldehyde, which is added with a commercially available acetaldehyde aqueous solution during the preparation of the product, with a solution mass concentration of 40%;

[0070] The aldehyde and ketone compound 3 is commercially available analytically pure acrolein;

[0071] The aldehyde and ketone compound 4 is commercially available analytically pure acetone.

[0072] Unless otherwise specified, the components and raw materials used in the examples and comparative examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all of the same kind.

[0073] Table 1

[0074] Component weight parts Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Polypropylene resin 1 500 550 500 500 500 500 Polypropylene resin 2 450 Antioxidant 1 2 1.5 2 2 2 2 2 Antioxidant 2 2 2 2 2 2 2 2 Aldehyde and Ketone Fixation Resin 1 1 0.9 1.1 1 0.5 1 Aldehyde and Ketone Fixed Resin 2 1 0.5 curing agent 0.1 Aldehyde and ketone compounds 1 0.0001 0.0002 0.0005 0.001 0.001 0.001 0.001 Aldehyde and ketone compounds 2 0.0001 0.0002 0.0005 0.001 0.001 0.001 0.001 Aldehyde and ketone compounds 3 0.0001 0.0002 0.0005 0.001 0.001 0.001 0.001 Aldehyde and ketone compounds 4 0.0001 0.0002 0.0005 0.001 0.001 0.001 0.001

[0075] Table 2

[0076]

[0077]

[0078] In order to verify the performance of the products of the present invention, the products prepared in each embodiment and comparative example were subjected to the following performance tests. The specific steps are as follows:

[0079] (1) Establishment of a standard curve: Standard solutions of commercially available formaldehyde aqueous solution (50%), commercially available acetaldehyde aqueous solution (40%), analytical grade acrolein, and analytical grade acetone were prepared at concentrations of 10 ppb to 500 ppb, respectively, and a standard curve was established by high performance liquid chromatography;

[0080] (2) Uniformity test: According to ISO 12219-2:2012; test temperature: 65℃; test time: 2h; flow rate: 100mL / min, test method: 10L bag method; during the test, the mass M1 of the product is measured by weighing method, and the concentration C is read on the instrument of the bag method test. The volume of elution solvent V2, the volume of gas extracted from the bag V3, and the total volume of gas released from the bag V4 during the test process are recorded. The concentration of aldehyde and ketone compounds in the sample is obtained by calculation using the formula: (C*V2 / V3*V4) / M1;

[0081] Ten groups of samples were randomly selected from each parallel batch of the products prepared in each embodiment and comparative example. Each group of samples was tested twice, and a total of 20 test results were obtained. The uniformity verification was carried out using the "single-factor variance analysis method". According to the degree of freedom and the significance level, the critical value F 0.05 (9, 10) = 3.02, if the statistical value F 0.05 (9, 10)≤3.02, it means that the product has reached the uniformity index;

[0082] (3) Stability test: The same method as step (2) is used, but 6 samples are randomly selected from parallel batches at the initial, room temperature and 1 month and 6 months points, respectively. Each sample is tested twice in parallel, and the t value of the test data is calculated to find the critical value t 0.05 (11)=1.796, if t <t 0.05 (11), it means that the product is stable; where t is calculated according to the following formula:

[0083]

[0084] Where: - Average value of n measurements:

[0085] μ-standard value / reference value:

[0086] n - number of measurements:

[0087] The standard deviation of Sn measurements.

[0088] n≥6; if t<significance level a (usually a=0.05) and the degrees of freedom is n-1, the critical value t a (n-1), there is no significant difference between the mean value and the standard value / reference value;

[0089] The test results are shown in Tables 3 and 4.

[0090] Table 3

[0091]

[0092]

[0093] Table 4

[0094]

[0095]

[0096] It can be clearly seen from the test results that the aldehyde-ketone solid standard material of the present invention can reach the critical value standard when conducting uniformity and stability tests, indicating that the uniformity of the product is up to standard. In contrast, the product of Comparative Example 1 does not introduce an aldehyde-ketone fixed resin, and the uniformity of the product is not high. The F values ​​of the four aldehyde-ketone compounds all exceed the standard. Comparative Example 3 uses a conventional organosilicon epoxy resin, and the stability of the product is improved to a certain extent, but there is still an unqualified acetone index, and the uniformity is not fully up to standard. Comparative Example 4 uses activated carbon with an adsorption effect as a fixture of the aldehyde-ketone compound, and it is obvious that it is not possible to achieve the uniformity and long-term stability of the product, and can only adapt to some aldehyde-ketone compounds. However, even if a suitable aldehyde-ketone fixed resin is selected, if its addition amount is too much, the fixing effect will deteriorate due to the dispersion uniformity problem. As shown in Comparative Example 2, the uniformity of the product cannot be up to standard.

[0097] Furthermore, when bisphenol A ether resin is selected, the use effect of bisphenol A diglycidyl ether is better, and the prepared product has higher uniformity.

[0098] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An aldehyde or ketone solid standard substance, characterized in that: The composition comprises the following components in parts by weight: 400-600 parts of polypropylene resin, 3-5 parts of antioxidant, 0.8-1.2 parts of aldehyde-ketone fixing resin, 0.0001-0.005 parts of aldehyde-ketone compound; The aldehyde-ketone fixing resin includes bisphenol A ether resin.

2. The aldehyde and ketone solid standard substance according to claim 1, wherein The aldehyde and ketone compounds include at least one of formaldehyde, acetaldehyde, acrolein, and acetone.

3. The aldehyde and ketone solid standard substance according to claim 1, wherein The components of the aldehyde and ketone solid standard substance also include a curing agent, and the mass ratio of the curing agent to the aldehyde and ketone fixing resin is (0.5:9.5) to (1.5:8.5).

4. The aldehyde and ketone solid standard substance according to claim 1, wherein The antioxidant includes at least one of a hindered phenol antioxidant and a phosphite antioxidant.

5. The aldehyde and ketone solid standard substance according to claim 1, wherein The polypropylene resin has a melt flow rate of 10 to 35 g / 10 min at 230° C. and a load of 2.16 kg.

6. The method for preparing the aldehyde and ketone solid standard substance according to any one of claims 1 to 5, characterized in that: The following steps are involved: After the components are uniformly mixed, they are melt-extruded in a screw extruder to obtain the aldehyde and ketone solid standard substances.

7. Use of the aldehyde and ketone solid standard substance according to any one of claims 1 to 5 in detecting the aldehyde and ketone content of solid samples and in evaluating and calibrating equipment for testing the aldehyde and ketone content of samples.

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