Standard sample for detecting short-chain chlorinated paraffins in leather and preparation method thereof

Abstract

The present application provides a kind of standard sample for detecting short-chain chlorinated paraffin in leather and its preparation method.The standard sample includes: matrix, and rubber layer in contact with the matrix, the rubber layer is derived from rubber composition;Wherein, the rubber composition includes short-chain chlorinated paraffin, diisocyanate compound, macromolecular polyol, polypropylene alcohol and chain extender;The content of short-chain chlorinated paraffin is 0.025%-0.25% with the total mass of the matrix being 100%;The content of diisocyanate compound is 1%-2.6%;The content of macromolecular polyol is 3.5%-6.5%;The content of polypropylene alcohol is 0.05%-0.15%;The content of chain extender is 0.2%-0.6%.The standard sample of the present application can improve test uniformity, can be used as a standard reference, so as to improve the reliability of short-chain chlorinated paraffin detection in leather.

Description

TECHNICAL FIELD

[0001] The present application relates to a standard sample for detecting short chain chlorinated paraffins in leather and a preparation method thereof, and belongs to the field of chemical substance detection. BACKGROUND

[0002] Short chain chlorinated paraffins (SCCPs) mainly refer to straight-chain chlorinated carbon-hydrogen compounds with a carbon chain length of 10-13. Short chain chlorinated paraffins are formulaed polychlorinated paraffin industrial products, mainly used as flame retardants for textiles, rubber and plastic, leather processing aids, plasticizers for paints and other coatings. Short chain chlorinated paraffins are the most toxic component of chlorinated paraffins (CPs) and meet the characteristics of persistent organic pollutants (POPs). The results of toxicological animal tests show that short chain chlorinated paraffins have low acute toxicity to rodents, subacute toxicity to their immune systems, subchronic toxicity to multiple organs such as liver, and chronic toxicity effects on aquatic organisms. In addition, increasing the dose of short chain chlorinated paraffins can increase the incidence of adenoma and cancer of the liver, thyroid and kidney of rodents, and is related to reproductive development, etc.

[0003] Short chain chlorinated paraffins are listed in the Stockholm Convention on Persistent Organic Pollutants (POPs) by the United Nations Environment Programme as prohibited persistent organic pollutants, and are also listed as hazardous preparations for restricted use in the REACH regulation. The EU Directive 2002 / 45 / EC prohibits the use of short chain chlorinated paraffins in metal processing and leather finishing agents. In order to evaluate the safety of imported and exported leather products, especially for children's products, to cope with the technical trade barriers of the European Union, to improve the quality of Chinese leather and its products, and to promote the export of Chinese leather products, the accuracy and consistency of the detection of short chain chlorinated paraffins in leather are crucial. At present, the detection of short chain chlorinated paraffins in leather in China is relatively late, and there is a lack of standard sample materials suitable for GB / T 38405-2019 "Chemical Test for Leather and Fur - Determination of Short Chain Chlorinated Paraffins".

[0004] At present, the detection technology of short chain chlorinated paraffins in China mainly involves short chain chlorinated paraffins itself, and there is no related prior art for standard sample materials of short chain chlorinated paraffins in leather. Moreover, the existing detection technology of short chain chlorinated paraffins takes short chain chlorinated paraffin standard as the direct detection object, and cannot reflect the applicability and accuracy of leather product detection.

[0005] In addition, the short-chain chlorinated paraffin standard sample material in the leather should have good test uniformity and test stability. The existing conventional leather processing technology generally uses a rotating drum to add chemicals in a water bath to achieve the corresponding effect. The penetration of chemicals in the water phase to the inside of the leather is affected by many factors, and there may be insufficient penetration and uneven distribution, which is not conducive to meeting the requirements of standard sample material uniformity.

[0006] Therefore, it is a technical problem to be solved to study a short-chain chlorinated paraffin standard sample for detecting short-chain chlorinated paraffin in leather and a preparation method thereof, which has excellent test uniformity and test stability. SUMMARY

[0007] Problems to be solved by the invention

[0008] In view of the technical problems existing in the prior art, the present application mainly aims at the vacancy of short-chain chlorinated paraffin standard sample in the domestic leather detection industry, and solves a series of problems easily produced in the process of detecting short-chain chlorinated paraffin in leather, and proposes a standard sample containing short-chain chlorinated paraffin. The standard sample can improve the test uniformity, so that the standard sample can be used as a standard reference, thereby improving the reliability of the detection of short-chain chlorinated paraffin in leather.

[0009] Further, the present application further provides a preparation method of the standard sample containing short-chain chlorinated paraffin. The preparation method is simple and easy to operate, the raw materials are easy to obtain, and is suitable for mass production.

[0010] Solution for solving the problem

[0011] The present application provides a standard sample containing short-chain chlorinated paraffin, which comprises:

[0012] a substrate, and

[0013] a rubber layer in contact with the substrate, the rubber layer being derived from a rubber composition; wherein

[0014] The rubber composition comprises short-chain chlorinated paraffin, diisocyanate compound, macromolecular polyol, polypropylene glycol and chain extender.

[0015] The content of the short-chain chlorinated paraffin is 0.025%-0.25% based on the total mass of the substrate being 100%; the content of the diisocyanate compound is 1%-2.6%; the content of the macromolecular polyol is 3.5%-6.5%; the content of the polypropylene glycol is 0.05%-0.15%; and the content of the chain extender is 0.2%-0.6%.

[0016] The standard sample according to the present application, wherein the short-chain chlorinated paraffin includes one or a combination of two or more of a short-chain chlorinated paraffin with a chlorine content of 42%, a short-chain chlorinated paraffin with a chlorine content of 48%, a short-chain chlorinated paraffin with a chlorine content of 50-52%, and a short-chain chlorinated paraffin with a chlorine content of 65-70%.

[0017] The standard sample according to the present application, wherein the thickness of the standard sample is 0.10-0.15 mm; and / or,

[0018] The content of the short-chain chlorinated paraffin in the standard sample is 400-1200 mg / kg.

[0019] The standard sample according to the present application, wherein the diisocyanate compound includes toluene diisocyanate and / or diphenylmethane diisocyanate; and / or,

[0020] The macromolecular polyol includes polyhexanedioate-1,4-butanediol glycol and / or polycarbonate diol; and / or,

[0021] The chain extender includes one or a combination of two or more of butanediol, hexanediol, and sorbitol.

[0022] The standard sample according to the present application, wherein the rubber composition further includes a stabilizer and / or a catalyst; preferably, the content of the stabilizer is 0.01%-0.04% and the content of the catalyst is 0.0005%-0.002%, based on the total mass of the substrate being 100%.

[0023] The standard sample according to the present application, wherein the stabilizer includes carbodiimide; and / or, the catalyst includes triethylenediamine.

[0024] The present application also provides a preparation method of the standard sample containing short-chain chlorinated paraffin according to the present application, which includes the step of compounding the substrate and the rubber layer; preferably, the substrate and the rubber layer are compounded by calendering.

[0025] The preparation method according to the present application, wherein the preparation method includes:

[0026] After mixing and mixing the components of the rubber composition, a plasticized product is obtained;

[0027] The plasticized product is placed on the surface of the substrate for calendering to obtain the standard sample containing short-chain chlorinated paraffin.

[0028] The preparation method according to the present application, wherein the preparation method of the plasticized product includes the following steps:

[0029] The short-chain chlorinated paraffin, the diisocyanate compound and the chain extender are mixed and then densified to obtain a first mixture;

[0030] The macromolecular polyol, the polypropylene glycol, the optional catalyst and the optional stabilizer are mixed with the first mixture and then mixed and kneaded to obtain a second mixture;

[0031] The second mixture is extruded to obtain a plasticized product.

[0032] The present application also provides a use of the standard sample containing the short-chain chlorinated paraffin according to the present application for detecting the short-chain chlorinated paraffin in the leather.

[0033] Effects of the present application

[0034] The standard sample containing the short-chain chlorinated paraffin according to the present application can improve the test uniformity and can be used as a standard reference, thereby improving the reliability of the detection of the short-chain chlorinated paraffin in the leather.

[0035] Further, the preparation method of the standard sample containing the short-chain chlorinated paraffin according to the present application is simple and easy to operate, the raw materials are easy to obtain, and is suitable for mass production. DETAILED DESCRIPTION

[0036] Various exemplary embodiments, features, and aspects of the present application will be described in detail below. The word "exemplary" is used herein to mean "serving as an example, instance, or illustration." Any implementation described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other implementations.

[0037] In addition, for the purpose of better illustrating the present application, numerous specific details are set forth in the following detailed description. Those skilled in the art will appreciate that the present application can be practiced without some or all of the specific details. In other instances, well known methods, apparatuses, materials and steps have not been described in detail in order to avoid obscuring the present application.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The meaning of "a", "an", and "the" includes plural references unless otherwise indicated. The meaning of "in" includes "in" and "on" unless otherwise indicated. The numerical values of the present application appearing in the present application should be understood as including the systematic errors that are inevitable in industrial production.

[0039] In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0040] In the present specification, the "some specific / preferred embodiments", "other specific / preferred embodiments", "embodiments", and the like mean that the specific elements (for example, features, structures, properties, and / or characteristics) described in relation to the embodiments are included in at least one of the embodiments described herein, and can be present in other embodiments or can not be present in other embodiments. In addition, it should be understood that the elements can be combined in various embodiments in any suitable manner.

[0041] In the present specification, the numerical range represented by "numerical value A ~ numerical value B" means a range including the end point values A, B.

[0042] In the present specification, when "room temperature" is used, the temperature thereof can be 10-40°C.

[0043] <First aspect>

[0044] The first aspect of the present application provides a standard sample containing short-chain chlorinated paraffin, which comprises:

[0045] a base body, and

[0046] a rubber layer in contact with the base body, the rubber layer being derived from a rubber composition; wherein

[0047] the rubber composition includes short-chain chlorinated paraffin, a diisocyanate compound, a macromolecular polyol, a polypropylene glycol, and a chain extender;

[0048] The amount of the short-chain chlorinated paraffin is 0.025%-0.25% based on the total mass of the base body being 100%; the content of the diisocyanate compound is 1%-2.6%; the content of the macromolecular polyol is 3.5%-6.5%; the content of the polypropylene glycol is 0.05%-0.15%; and the content of the chain extender is 0.2%-0.6%.

[0049] Currently, the existing short-chain chlorinated paraffin detection technology takes short-chain chlorinated paraffin standard as the direct detection object, and cannot reflect the applicability and accuracy of leather product detection. The present application can provide support for ensuring the detection accuracy and consistency of short-chain chlorinated paraffin in leather, and fill the blank of standard sample materials suitable for GB / T 38405-2019 "Chemical Test of Leather and Fur Determination of Short-Chain Chlorinated Paraffin".

[0050] The standard sample containing short-chain chlorinated paraffin of the present application can improve the test uniformity, so that the standard sample can serve as a standard reference, thereby improving the reliability of the detection of short-chain chlorinated paraffin in leather.

[0051] In some specific embodiments, the standard sample containing short-chain chlorinated paraffin of the present application has a thickness of 0.10-0.15 mm, for example, 0.11 mm, 0.12 mm, 0.13 mm, 0.14 mm, etc. The standard sample of the present application is thin enough for easy detection.

[0052] In other specific embodiments, the standard sample containing short-chain chlorinated paraffin of the present application has a content of short-chain chlorinated paraffin of 400-1200 mg / kg, for example, 600 mg / kg, 800 mg / kg, 1000 mg / kg, etc. When the content of short-chain chlorinated paraffin is 400-1200 mg / kg, it can be used as a standard sample better.

[0053] <base>

[0054] The base material of the present application is not particularly limited and can be selected as needed. Preferably, leather is used as the base material. The kind of leather is also not particularly limited and can be selected as needed, for example, it can be natural leather, substitute leather, etc. For natural leather, it can be cowhide, sheepskin, pigskin, mixed leather, buffed leather, etc. For substitute leather, it can be regenerated leather, artificial leather, synthetic leather, PU leather, etc.

[0055] <rubber composition>

[0056] The present application uses a rubber composition to make the short-chain chlorinated paraffin uniformly dispersed in the standard sample. The rubber composition includes short-chain chlorinated paraffin, a diisocyanate compound, a macromolecular polyol, polypropylene glycol, and a chain extender. Specifically:

[0057] short-chain chlorinated paraffins

[0058] The short-chain chlorinated paraffin is a straight-chain chlorinated carbon-hydrogen compound with a chain length of C10 to C13. Specifically, the short-chain chlorinated paraffin can be divided into four types according to the chlorine content: 42%, 48%, 50-52%, and 65-70%. The first three types are light yellow viscous liquids, and the last type is a yellow viscous liquid.

[0059] In the present application, the short-chain chlorinated paraffin includes one or a combination of two or more of short-chain chlorinated paraffin with a chlorine content of 42%, short-chain chlorinated paraffin with a chlorine content of 48%, short-chain chlorinated paraffin with a chlorine content of 50-52%, and short-chain chlorinated paraffin with a chlorine content of 65-70%.

[0060] Specifically, in the present application, the content of the short-chain chlorinated paraffin is 0.025%-0.25%, for example: 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.18%, 0.2%, 0.22%, etc., based on the total mass of the substrate being 100%. When the content of the short-chain chlorinated paraffin is 0.025%-0.25%, the desired standard sample can be obtained.

[0061] diisocyanate compounds

[0062] In the present application, the purpose of using the diisocyanate compound is to react with the macromolecular polyol and the chain extender to form the rubber. The molecular structure of the rubber of the present application is alternately composed of rigid segments obtained by the reaction of the diisocyanate compound and the chain extender and flexible segments obtained by the reaction of the diisocyanate compound and the macromolecular polyol.

[0063] The present inventors found that by adding the short-chain chlorinated paraffin during the reaction of the diisocyanate compound with the macromolecular polyol and the chain extender, the short-chain chlorinated paraffin can be more uniformly dispersed without affecting the preparation of the rubber, and the standard sample containing the short-chain chlorinated paraffin can improve the testing uniformity.

[0064] Specifically, the diisocyanate compound includes toluene diisocyanate and / or diphenylmethane diisocyanate.

[0065] In some specific embodiments, the content of the diisocyanate compound is 1%-2.6%, for example: 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, etc., based on the total mass of the substrate being 100%. When the content of the diisocyanate compound is 1%-2.6%, the plasticized product has good calenderability on the surface of the substrate.

[0066] macromolecular polyols

[0067] In the present application, the purpose of using the macromolecular polyol is to react with the diisocyanate compound to obtain the flexible segment. In the present application, the macromolecular polyol used is not particularly limited as long as it can react with the diisocyanate compound to obtain the flexible segment.

[0068] Specifically, in the present application, the macromolecular polyol includes polyhexanedioic acid-1,4-butanediol ester diol and / or polycarbonate diol.

[0069] In the present application, the content of the macromolecular polyol is 3.5%-6.5%, for example: 3.8%, 4%, 4.2%, 4.5%, 4.8%, 5%, 5.2%, 5.5%, 5.8%, 6%, 6.2%, etc., based on the total mass of the matrix being 100%. When the content of the macromolecular polyol is 3.5%-6.5%, it can ensure that sufficient flexible segments are obtained.

[0070] polypropylene glycol

[0071] The present application can effectively improve the cross-linking property inside the rubber composition by adding polypropylene glycol.

[0072] In the present application, the content of the polypropylene glycol is 0.05%-0.15%, for example: 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, etc., based on the total mass of the matrix being 100%. When the content of the polypropylene glycol is 0.05%-0.15%, the obtained rubber composition has good calendering property on the surface of the matrix.

[0073] chain extender

[0074] In the present application, the purpose of using the chain extender is to react with the diisocyanate compound to form rigid segments. In the present application, the chain extender used is not particularly limited as long as it can react with the diisocyanate compound to obtain rigid segments.

[0075] Specifically, the chain extender includes one or a combination of two or more of butanediol, hexanediol, and sorbitol.

[0076] In the present application, the content of the chain extender is 0.2%-0.6%, for example: 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, etc., based on the total mass of the matrix being 100%. When the content of the chain extender is 0.2%-0.6%, the controllability of the reaction speed is better, and the required rigid segments can be obtained.

[0077] other components

[0078] In the present application, in order to prepare a standard sample with excellent performance, the rubber composition further includes a stabilizer and / or a catalyst.

[0079] The present application can make the chemical reaction stable during mixing by using a stabilizer. In the present application, the content of the stabilizer is 0.01%-0.04%, for example: 0.015%, 0.02%, 0.025%, 0.03%, 0.035%, etc., based on the total mass of the matrix being 100%.

[0080] The present application can reduce the activation energy required for the reaction, improve the reaction rate, and accelerate the reaction by using a catalyst. In the present application, the reaction can be orderly carried out by adding a small amount of catalyst. Specifically, in the present application, the content of the catalyst is 0.0005%-0.002%, for example: 0.0008%, 0.001%, 0.0012%, 0.0015%, 0.0018%, etc., based on the total mass of the matrix.

[0081] Specifically, the stabilizer includes carbodiimide; and / or, the catalyst includes triethylenediamine.

[0082] The standard sample of the present application has the following advantages: (1) prepared by using a standard substance, excellent traceability; (2) excellent uniformity of the sample; (3) excellent stability of the sample.

[0083] <Second aspect>

[0084] The second aspect of the present application provides a preparation method of a standard sample containing short-chain chlorinated paraffin according to the first aspect of the present application, comprising the step of compounding the matrix and the rubber layer; preferably, the matrix and the rubber layer are compounded by calendering.

[0085] The preparation method of the present application is simple and easy to operate, the raw materials are easy to obtain, and is suitable for mass production. The content of short-chain chlorinated paraffin in the prepared standard sample containing short-chain chlorinated paraffin is 400-1200 mg / kg.

[0086] In some specific embodiments, the preparation method comprises:

[0087] After mixing and mixing the components of the rubber composition, a plasticized product is obtained;

[0088] The plasticized product is placed on the surface of the matrix for calendering to obtain a standard sample containing short-chain chlorinated paraffin.

[0089] When calendering, the temperature of the calendering is 155-165℃, for example: 158℃, 160℃, 162℃, etc.; the pressure during calendering is 45-50 kg, for example: 46 kg, 47 kg, 48 kg, 49 kg, etc. The plasticized product can be attached to the surface of the matrix by calendering. Moreover, calendering can also make the standard sample form a thin film of 0.10-0.15 mm, which is convenient for subsequent detection.

[0090] In some specific embodiments, the preparation method of the plasticized product comprises the following steps:

[0091] The short-chain chlorinated paraffin, the diisocyanate compound and the chain extender are mixed and then mixed and kneaded to obtain a first mixture;

[0092] The macromolecular polyol, the polypropylene glycol, the optional catalyst and the optional stabilizer are mixed with the first mixture and then mixed and kneaded to obtain a second mixture;

[0093] The second mixture is extruded to obtain a plasticized product.

[0094] Specifically, in the preparation of the first mixture, the time for the kneading is 3-5 min, for example, 3.5 min, 4 min, 4.5 min, etc.; the temperature for the kneading is 40-60℃, for example, 42℃, 45℃, 48℃, etc.; and the rotating speed of the kneader is 20-30 rpm, for example, 22 rpm, 25 rpm, 28 rpm, etc.

[0095] In the preparation of the second mixture, the time for the mixing is 3-5 min, for example, 3.5 min, 4 min, 4.5 min, etc.; the temperature for the mixing is 140-160℃, for example, 142℃, 145℃, 148℃, 150℃, 152℃, 155℃, 158℃, etc.; and the rotating speed of the kneader is 20-30 rpm, for example, 22 rpm, 25 rpm, 28 rpm, etc.

[0096] Further, the plasticized mixture can be extruded by an extruder and then supplied to a calender by a transfer device for calendering.

[0097] Further, the obtained standard sample can be cut and mixed to obtain a standard sample with a desired size. Specifically, an automatic hydraulic cutting machine can be used to cut the standard sample by using a cutter mold with a desired size, and then the cut standard sample is mixed by a three-dimensional mixing machine for 60-90 min to obtain a standard sample with a desired size. The size of the standard sample is not particularly limited in the present application and can be selected as desired.

[0098] Finally, the standard sample is packed and collected in a clean and dry sealed bag for use.

[0099] The present application greatly improves the uniformity of the distribution of the short-chain chlorinated paraffin in the matrix by mixing and kneading the short-chain chlorinated paraffin and the rubber composition and finally calendering to the surface of the matrix, and the added short-chain chlorinated paraffin is fully integrated with the matrix, which also improves the utilization rate of the reagent compared with the traditional water bath processing method.

[0100] <Third aspect>

[0101] The third aspect of the present application provides a use of the standard sample containing short-chain chlorinated paraffin according to the first aspect of the present application for detecting short-chain chlorinated paraffin in leather.

[0102] The standard sample of the present application can be used in the following aspects:

[0103] (1) for calibrating instruments: the standard value provided by the standard sample is accurate and reliable. When the result obtained by measuring the standard sample with an instrument deviates from the original result of the standard sample and is beyond the uncertainty interval thereof, it can be determined that the instrument has a problem and measures should be taken to calibrate and correct it.

[0104] (2) for evaluating measurement methods: the standard sample can provide a basis for the development of new and high-tech measurement methods. The reliability of measurement methods is the most difficult and urgent problem to be solved in the field of professional measurement technology. Generally speaking, a measurement method includes measurement procedures, measurement instruments and auxiliary facilities, operators, sampling procedures, data processing and statistical analysis, and environmental conditions during measurement. Therefore, even if the measurement instrument is good, if any other element of the measurement method is problematic, the entire measurement result is unreliable. The generation of the standard sample provides a basis for comprehensively evaluating the reliability of the measurement method, that is, the measurement method can be comprehensively evaluated using the standard sample.

[0105] (3) to establish the traceability of measurement results.

[0106] (4) to determine the uncertainty of measurement results.

[0107] (5) to establish the comparability of measurement results obtained by interlaboratory tests.

[0108] (6) to assign values to materials.

[0109] (7) to evaluate the operation level of laboratory operators.

[0110] (8) for quality control on production lines.

[0111] Examples

[0112] The embodiments of the present application will be described in detail below with reference to the examples, but those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be regarded as limiting the scope of the present application. If the specific conditions are not specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are used. If the manufacturer of the reagent or instrument is not specified, it is a conventional product that can be obtained by purchase.

[0113] Example 1

[0114] (1) Mixing: 0.010% of short-chain chlorinated paraffin with a chlorine content of 42%, 0.015% of short-chain chlorinated paraffin with a chlorine content of 52%, 0.010% of short-chain chlorinated paraffin with a chlorine content of 65-70%, 1.5% of toluene diisocyanate, 0.2% of butanediol were weighed based on 100% of the total mass of the matrix, and were added to the internal mixer for mixing, the mixing time was 5 min, the mixing temperature was 60°C, and the mixer speed was 30 rpm; 4% of polycarbonate diol, 0.15% of polypropylene glycol, 0.001% of triethylene diamine, and 0.02% of carbodiimide were added based on 100% of the total mass of the matrix, and were mixed, the mixing time was 5 min, the mixing temperature was 160°C, the mixer speed was 20 rpm, and a rubber composition was obtained.

[0115] (2) Calendering: the rubber composition obtained after mixing was extruded through an extruder to obtain a plasticized product; the plasticized product was supplied to a calendering machine through a transfer device, and the plasticized product was extruded into a 0.10 mm film at 165°C using the calendering machine, and was attached to the surface of the leather under a pressure of 50 kg, and was naturally cooled to obtain a composite.

[0116] (3) Cutting and mixing: an automatic hydraulic cutting machine was used, and a cutter die of 4 mm x 4 mm was used to cut the composite obtained in (2) into small pieces of 4 mm x 4 mm, and then a three-dimensional mixing machine was used to mix for 90 min to obtain a standard sample for detecting short-chain chlorinated paraffin in leather, which had a light blue appearance and was a small piece of leather with a length and width of about 4 mm.

[0117] (4) Sub-packing: in order to avoid contamination, the samples were sub-packed in a double-layer packaging manner. Food-grade polypropylene (PP) bags were used for the inner bags, each bag contained about 1.0 g of samples, and the bag opening was fusion sealed. The outer packaging was a composite film aluminum foil bag which was fusion sealed twice to avoid the influence of external light on the stability of the samples. The sub-packed samples were stored at room temperature.

[0118] The average content of short-chain chlorinated paraffin in the obtained standard sample for detecting short-chain chlorinated paraffin in leather was 505 mg / kg.

[0119] uniformity detection

[0120] According to GB / T 38405-2019 "Chemical Test for Leather and Fur-Determination of Short-Chain Chlorinated Paraffin", 10 bags of samples were randomly selected, each bag of sample was detected twice, and F test method was used to judge the uniformity of the samples. The detection results are shown in Table 1.

[0121] Table 1

[0122]

[0123] As can be seen from Table 1, the uniformity of the standard sample for detecting short-chain chlorinated paraffins in leather according to the application is excellent.

[0124] stability detection

[0125] According to GB / T 38405-2019 Leather and Fur Chemical Test Determination of Short-Chain Chlorinated Paraffins, 3 bags of samples were taken at different time points, each bag of sample was detected twice, and the stability of the sample was judged by t test. The detection results are shown in Table 2 as follows:

[0126] Table 2

[0127]

[0128] As can be seen from Table 2, the stability of the standard sample for detecting short-chain chlorinated paraffins in leather according to the application is excellent.

[0129] Example 2

[0130] (1) Mixing: 0.050% of short-chain chlorinated paraffin with a chlorine content of 42%, 0.065% of short-chain chlorinated paraffin with a chlorine content of 52%, 0.025% of short-chain chlorinated paraffin with a chlorine content of 65-70%, 2.5% of toluene diisocyanate, 0.4% of butanediol were weighed based on 100% of the total mass of the matrix, and were added into the internal mixer for mixing, the mixing time was 5 min, the mixing temperature was 50°C, and the mixer speed was 20 rpm; 5.5% of polycarbonate diol, 0.05% of polypropylene glycol, 0.0005% of triethylenediamine, and 0.04% of carbodiimide were further added based on 100% of the total mass of the matrix, and were mixed, the mixing time was 5 min, the mixing temperature was 150°C, the mixer speed was 25 rpm, and a rubber composition was obtained.

[0131] (2) Calendering: the rubber composition obtained after mixing was extruded through an extruder to obtain a plasticized product; the plasticized product was supplied to a calendering machine through a transmission device, and the plasticized product was extruded into a 0.15 mm film using the calendering machine at 170°C, and was attached to the surface of the leather under a pressure of 50 kg, and was naturally cooled to obtain a composite.

[0132] (3) Cutting and mixing: an automatic hydraulic sample cutter was used, the cutter die was 4 mm x 4 mm, the composite obtained in (2) was cut into 4 mm x 4 mm pieces using the sample cutter, and then was mixed for 60 min using a three-dimensional mixing machine to obtain a standard sample for detecting short-chain chlorinated paraffins in leather, which had a light blue appearance and was a small piece of leather with a length and width of about 4 mm.

[0133] (4) Sub-packing: In order to avoid contamination, the sample is sub-packed by using double packaging. The inner bag uses food-grade polypropylene (PP) bag, about 1.0 g of sample is packed in each bag, and the bag opening is fusion sealed. The outer packaging uses a composite film aluminum foil bag for secondary fusion sealing to avoid the influence of external light on the stability of the sample. The sub-packed sample is stored at room temperature.

[0134] The average content of short-chain chlorinated paraffin in the obtained standard sample for detecting short-chain chlorinated paraffin in leather is 1097 mg / kg. This value is the average value of the homogeneity test.

[0135] uniformity detection

[0136] According to GB / T 38405-2019 Leather and Fur Chemical Test Determination of Short-Chain Chlorinated Paraffin, 10 bags of samples are randomly selected, each sample is detected twice, and F test is used to judge the homogeneity of the sample. The detection results are shown in Table 3 as follows:

[0137] Table 3

[0138]

[0139] As can be seen from Table 3, the homogeneity of the standard sample for detecting short-chain chlorinated paraffin in leather of the present application is excellent.

[0140] Stability test

[0141] According to GB / T 38405-2019 Leather and Fur Chemical Test Determination of Short-Chain Chlorinated Paraffin, 3 bags of samples are taken from different time points, each sample is detected twice, and t test is used to judge the stability of the sample. The detection results are shown in Table 4 as follows:

[0142] Table 4

[0143]

[0144] As can be seen from Table 4, the stability of the standard sample for detecting short-chain chlorinated paraffin in leather of the present application is excellent.

[0145] It should be noted that although the technical solutions of the present application are introduced by specific examples, those skilled in the art can understand that the present application should not be limited thereto.

[0146] Having described various embodiments of the application, it is to be understood that the above description is meant not to limit and not to encompass all of the possible embodiments covered by the claims. Many modifications and variations of this application can be apparent to those of ordinary skill in the art without departing from the spirit and scope of the described embodiments. It is intended that the scope of the application should only be limited by the appended claims.

Claims

1. A standard sample containing short-chain chlorinated paraffins, characterized in that, The standard sample comprises: a base body, and a rubber layer in contact with the base body, the rubber layer being derived from a rubber composition; wherein the rubber composition comprises a short-chain chlorinated paraffin, a diisocyanate compound, a macromolecular polyol, a polypropylene glycol, and a chain extender; the content of the short-chain chlorinated paraffin is 0.025%-0.25% based on the total mass of the base body; the content of the diisocyanate compound is 1%-2.6%; the content of the macromolecular polyol is 3.5%-6.5%; the content of the polypropylene glycol is 0.05%-0.15%; and the content of the chain extender is 0.2%-0.6%.

2. The standard sample of claim 1, wherein, The short-chain chlorinated paraffin comprises one or more than two combinations of a short-chain chlorinated paraffin with a chlorine content of 42%, a short-chain chlorinated paraffin with a chlorine content of 48%, a short-chain chlorinated paraffin with a chlorine content of 50-52%, and a short-chain chlorinated paraffin with a chlorine content of 65-70%.

3. The standard sample according to claim 1 or 2, characterized in that The standard sample has a thickness of 0.10-0.15 mm; and / or The content of the short-chain chlorinated paraffin in the standard sample is 400-1200 mg / kg.

4. The standard sample according to claim 1 or 2, characterized in that, The diisocyanate compound comprises toluene diisocyanate and / or methylene diphenyl diisocyanate; and / or The macromolecular polyol comprises polybutylene adipate glycol and / or polycarbonate diol; and / or The chain extender comprises one or more than two combinations of butanediol, hexanediol, and sorbitol.

5. The standard sample according to claim 1 or 2, characterized in that, The rubber composition further comprises a stabilizer and / or a catalyst.

6. The standard sample of claim 5, wherein, The content of the stabilizer is 0.01%-0.04% based on the total mass of the base body, and the content of the catalyst is 0.0005%-0.002% based on the total mass of the base body.

7. The standard sample of claim 5, wherein, The stabilizer comprises carbodiimide; and / or the catalyst comprises triethylenediamine.

8. A method for preparing a standard sample containing short-chain chlorinated paraffins according to any one of claims 1 to 7, characterized in that, The method comprises the step of compounding the base body and the rubber layer.

9. The production method according to claim 8, characterized by, The base body and the rubber layer are compounded by calendering.

10. The method of claim 9, wherein, The method comprises the steps of: mixing and mixing-compacting the components of the rubber composition to obtain a plasticized product; placing the plasticized product on the surface of the base body to obtain the standard sample containing the short-chain chlorinated paraffin by calendering.

11. The method of claim 10, wherein, The method for preparing the plasticized product comprises the steps of: mixing and mixing-compacting the short-chain chlorinated paraffin, the diisocyanate compound, and the chain extender to obtain a first mixture; mixing and mixing-compacting the macromolecular polyol, the polypropylene glycol, the catalyst, and the stabilizer with the first mixture to obtain a second mixture; extruding the second mixture to obtain the plasticized product.

12. Use of the standard sample containing the short-chain chlorinated paraffin according to any one of claims 1-7 for detecting short-chain chlorinated paraffin in leather.

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