Method for analyzing grafting rate of an amidoxime resin

Abstract

The application relates to an analysis method of grafting rate of an amidoxime resin, comprising the following steps: providing a polymer filling material and dried amidoxime resin particles, filling the polymer filling material into the interspace of the amidoxime resin particles to prepare a preform block; slicing the preform block and selecting a preform sheet with an amidoxime resin particle section; performing a gold spraying treatment on the preform sheet to obtain a test sheet; observing the surface morphology of the amidoxime resin particle section through a scanning electron microscope and performing EDS energy spectrum analysis to obtain the N element content; and calculating the amidoxime resin grafting rate through the N element content. The application calculates the amidoxime resin grafting rate through the N element content, has higher accuracy, does not need to add toxic and harmful chemical reagents such as acetone, is simple to operate, and is fast in analysis and determination.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high polymer materials, in particular to amidoxime resin. BACKGROUND

[0002] Gallium is a rare metal, mainly distributed in bauxite. Due to its special physical properties, it is listed as an important strategic resource and is widely used in semiconductor, photovoltaic material, magnetic material, chemical industry, medical treatment, national defense and other fields. At present, more than 90% of gallium is recovered from the seed mother liquor produced by alumina production, and resin adsorption method is mainly used in China. At present, the annual output of crude gallium in China is about 360 tons, and the resin consumption is about 10 tons per ton of gallium produced. The price of each ton of resin is 100,000 yuan, and the value of resin consumed annually is 360 million yuan. The quality of resin is one of the most important factors affecting the yield of gallium, and the adsorption capacity of resin for metal ions mainly depends on the number of characteristic functional groups and the binding capacity of metal ions.

[0003] Amidoxime resin is generally used for gallium extraction, which realizes the extraction and separation of gallium by forming coordination with gallium ions through amino and oxime groups. Amino and oxime groups are obtained by chemical grafting of cyano in acrylonitrile, and the higher the grafting rate of amino and oxime groups, the better the adsorption effect of gallium. Therefore, the grafting rate of amino and oxime groups is directly related to the adsorption capacity of gallium, and further affects the yield of gallium.

[0004] At present, the commonly known method for determining the grafting rate of amidoxime resin is weight method, that is, the percentage content of grafting is calculated by the weight difference before and after chemical grafting. However, the weight method is easily affected by the residues of impurities such as by-products, pore-forming agents, diluents and initiators, resulting in large measurement deviation. SUMMARY

[0005] The embodiment of the present application provides an analysis method for the grafting rate of amidoxime resin, so as to solve the technical problem of large deviation of the grafting rate determination method in the amidoxime resin.

[0006] The embodiment of the present application provides an analysis method for the grafting rate of amidoxime resin, which comprises the following steps:

[0007] A high polymer filler and dry amidoxime resin particles are provided, the high polymer filler is filled into the voids of the amidoxime resin particles, and a preform block is prepared;

[0008] The preform block is sliced, and a preform sheet with an amidoxime resin particle section is selected;

[0009] The preform sheet is subjected to gold spraying treatment to obtain a test sheet;

[0010] The surface morphology of the cross section of the amidoxime resin particles is observed by a scanning electron microscope, and EDS energy spectrum analysis is performed to obtain the content of N element;

[0011] The grafting rate of the amidoxime resin is calculated according to the content of N element.

[0012] In some embodiments of the present application, the grafting rate of the amidoxime resin is calculated according to the following formula:

[0013]

[0014] wherein, the N amidoxime is the weight content of N element of the amidoxime resin, and the N acrylonitrile is the weight content of N element of the acrylonitrile resin used for grafting to obtain the amidoxime resin.

[0015] In some embodiments of the present application, the high polymer filling material is a thermosetting resin.

[0016] In some embodiments of the present application, the high polymer filling material is an epoxy resin.

[0017] In some embodiments of the present application, the filling of the high polymer filling material into the interspace of the amidoxime resin particles comprises:

[0018] The high polymer filling material in powder form is provided and blended with the amidoxime resin particles to obtain a mixture;

[0019] The mixture is added into a mold, and hot pressing is performed at a predetermined temperature and a predetermined pressure.

[0020] In some embodiments of the present application, the predetermined temperature is not lower than the thermosetting temperature of the thermosetting resin; and / or,

[0021] The predetermined pressure is not lower than 10 MPa.

[0022] In some embodiments of the present application, the filling of the high polymer filling material into the interspace of the amidoxime resin particles comprises:

[0023] The amidoxime resin particles are added into a mold;

[0024] The high polymer filling material is added into the mold after being melted.

[0025] In some embodiments of the present application, one side of the pre-made sheet is polished before the pre-made sheet is subjected to the gold spraying treatment.

[0026] In some embodiments of the present application, the thickness of the pre-made sheet is 1-8 mm.

[0027] In some embodiments of the present application, the duration of the electroless plating process is 10-60 seconds.

[0028] The above technical solution provided by the embodiments of the present application has the following advantages compared with the prior art:

[0029] The analysis method for grafting rate of the amidoxime resin provided by the embodiments of the present application can measure the N element content of the amidoxime resin by EDS energy spectrum analysis, and can further calculate the grafting rate of the amidoxime resin by the N element content. The embodiments of the present application calculate the grafting rate of the amidoxime resin by the N element content, which has high accuracy, does not need to add toxic and harmful chemical reagents such as acetone, is simple to operate, and is fast in analysis and determination. BRIEF DESCRIPTION OF DRAWINGS

[0030] The accompanying drawings, which are incorporated into and form a part of the specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the application.

[0031] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced as follows. Obviously, for those skilled in the art, other drawings can also be obtained from these drawings without creative labor.

[0032] Figure 1 The electron microscope-energy spectrum of the amidoxime resin in the test piece provided for Embodiment 1 of the present application;

[0033] Figure 2 The electron microscope-energy spectrum of the amidoxime resin in the test piece provided for Embodiment 2 of the present application;

[0034] Figure 3 The electron microscope-energy spectrum of the amidoxime resin in the test piece provided for Embodiment 3 of the present application. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0036] Unless otherwise defined, all terms used in disclosing the application, including technical and scientific terms, have the meaning as commonly understood by one of ordinary skill in the art to which this application belongs. By means of non-limiting example, the terms "comprise", "comprising", "comprises" and "comprising" specify the presence of stated features, integers, steps, or components thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.

[0037] Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or prepared by existing methods.

[0038] The existing determination method of grafting rate of amidoxime resin has a technical problem of large deviation.

[0039] The technical scheme provided by the embodiments of the present application is to solve the above technical problems, and the general idea is as follows:

[0040] The embodiments of the present application provide an analysis method of grafting rate of amidoxime resin, which comprises the following steps:

[0041] S1: providing a high polymer filling material and dry amidoxime resin particles, filling the high polymer filling material into the voids of the amidoxime resin particles to make a preform block;

[0042] S2: slicing the preform block and selecting a preform sheet with a cross section of the amidoxime resin particles;

[0043] S3: gold spraying treatment is performed on the preform sheet to obtain a test sheet;

[0044] S4: the surface morphology of the cross section of the amidoxime resin particles is observed by scanning electron microscopy, and EDS energy spectrum analysis is performed to obtain the content of N element;

[0045] S5: the grafting rate of the amidoxime resin is calculated by the content of N element.

[0046] The present application analyzes the grafting rate of the prepared amidoxime resin. The amidoxime resin is generally in the form of particles.

[0047] The amidoxime resin particles generally have small particle size, which is not conducive to the preparation of a sheet material for SEM test. In the present application, the voids of the amidoxime resin particles are filled with a high polymer filling material, and the preform block is formed by solidification as a whole. The reason for choosing high polymer material as the filler is that the high polymer material has low hardness, which is beneficial to slicing.

[0048] The high polymer filling material described in the present application is any curable high polymer material. The curing methods include, but are not limited to, melt-cooling curing, thermal curing, curing by adhesion with an adhesive, light curing, and gelation. Therefore, the high polymer filling material described in the present application includes not only plastics and rubber materials in the conventional sense, but also gel materials. The form of the high polymer filling material before filling can be solid or liquid. As a preferred and easy-to-implement method, the melt-cooling curing or thermal curing method is generally selected in actual cases.

[0049] The amidoxime resin particles need to be dried before being made into a preform block, because the residual water molecules on the surface of the particles will interfere with the calculation of the element content, causing errors.

[0050] Since the preform sheet is a high polymer material, the electrical conductivity is generally poor, which is not conducive to scanning electron microscopy analysis, and therefore needs to be gold-sprayed.

[0051] The amidoxime resin grafting rate refers to the grafting rate of groups that can adsorb gallium ions. These groups have the common feature of containing N elements, and the N elements in the amidoxime resin are theoretically all present in these groups, so the N element content can be used to calculate the amidoxime resin grafting rate.

[0052] The present application can measure the N element content of the amidoxime resin by EDS energy spectrum analysis, and can further calculate the amidoxime resin grafting rate by the N element content, by preparing a high polymer filling material and amidoxime resin particles into a preform block, and then preparing a test piece for scanning electron microscopy testing. The present application has high accuracy in calculating the amidoxime resin grafting rate by the N element content, and does not need to add toxic and harmful chemical reagents such as acetone, is easy to operate, and is fast in analysis and determination.

[0053] In some embodiments of the present application, the amidoxime resin grafting rate is calculated by the N element content by the following formula:

[0054]

[0055] wherein the N amidoxime is the weight content of N elements in the amidoxime resin, and the N acrylonitrile is the weight content of N elements in the acrylonitrile resin used to graft to obtain the amidoxime resin.

[0056] As understood by those skilled in the art, the amidoxime resin is prepared by grafting an acrylonitrile resin.

[0057] In some embodiments of the present application, the high polymer filling material is a thermosetting resin.

[0058] Using a thermosetting resin as the high polymer filling material can more conveniently prepare a preform block from the high polymer filling material and the amidoxime resin particles by thermal curing.

[0059] In some embodiments of the present application, the polymer filling material is an epoxy resin.

[0060] It is understood by those skilled in the art that the epoxy resin is a common thermosetting resin. It is further noted that the selection of the epoxy resin as the polymer filling material does not mean that the polymer filling material must be cured by heat curing, for example, the polymer filling material can also be cured by melting-cooling.

[0061] In some embodiments of the present application, in step S1, the filling of the polymer filling material into the voids of the amidoxime resin particles comprises:

[0062] S111: providing the polymer filling material in powder form and blending with the amidoxime resin particles to obtain a mixture;

[0063] S112: adding the mixture into a mold and performing hot pressing at a predetermined temperature and a predetermined pressure.

[0064] The above steps S111 and S112 are the conventional way of preparing the preform block by heat curing. Those skilled in the art can select appropriate predetermined temperature and predetermined pressure according to actual conditions.

[0065] In some embodiments of the present application, the predetermined temperature is not lower than the heat curing temperature of the thermosetting resin.

[0066] The predetermined temperature is not lower than the heat curing temperature of the thermosetting resin, which enables the mixture to be well heat cured at the predetermined temperature.

[0067] In some embodiments of the present application, the predetermined pressure is not lower than 10 MPa.

[0068] The predetermined pressure is not lower than 10 MPa, which can ensure the heat curing effect.

[0069] In some embodiments of the present application, the filling of the polymer filling material into the voids of the amidoxime resin particles comprises:

[0070] S121: adding the amidoxime resin particles into a mold;

[0071] S122: adding the polymer filling material into the mold after melting.

[0072] The above steps S121 and S122 are the conventional operation method of the melting-cooling curing method. The polymer filling material is mixed with the amidoxime resin particles after melting, and the polymer filling material is cured after cooling to obtain the preform block.

[0073] In some embodiments of the present application, one side of the pre-made sheet is polished before the pre-made sheet is subjected to the gold spraying process.

[0074] As understood by those skilled in the art, the polished side is the observation surface for SEM testing.

[0075] Polishing one side of the pre-made sheet can make the surface of the test sheet more even and the element distribution more uniform.

[0076] In some embodiments of the present application, the pre-made sheet has a thickness of 1-8 mm.

[0077] As understood by those skilled in the art, 1-8 mm is a conventional sample thickness for SEM testing.

[0078] In some embodiments of the present application, the gold spraying process lasts for 10-60 s.

[0079] As understood by those skilled in the art, a gold spraying process lasting for 10-60 s can effectively improve the conductivity of the test sheet without causing excessively high gold spraying cost.

[0080] The present application is further described in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. The experimental methods in the following examples, if not otherwise specified, are generally determined according to national standards. If there is no corresponding national standard, the methods are determined according to the general international standards, conventional conditions, or the conditions suggested by the manufacturers.

[0081] Example 1

[0082] The present embodiment provides a method for analyzing the grafting rate of an amidoxime resin, which comprises the following steps:

[0083] Providing and drying the amidoxime resin particles, and adding the amidoxime resin particles into a mold;

[0084] After the epoxy resin is melted, it is added into the mold, and after cooling, the pre-made block is demolded;

[0085] The pre-made block is sliced, and a pre-made sheet having a cross section of the amidoxime resin particles is selected, and the obtained pre-made sheet has a thickness of 2 mm;

[0086] One side of the pre-made sheet is polished;

[0087] The unpolished side of the pre-made sheet is subjected to a 20 s gold spraying process to obtain a test sheet;

[0088] The surface morphology of the section of the amine oxime resin particle is observed by a scanning electron microscope, and EDS energy spectrum analysis is performed to obtain the N element content, wherein the scanning electron microscope parameter is set as: acceleration voltage 15 kV, scale 80 μm, picture width: 269 μm, detector: BSD Full.

[0089] The grafting rate of the amine oxime resin is calculated according to the N element content.

[0090] Please refer to Figure 1 , Figure 1 The electron microscope-energy spectrum of the amine oxime resin in the test piece obtained in the embodiment is shown, including the surface morphology information and element content information of the test piece. Figure 1 The middle green area is the area for EDS energy spectrum analysis. Figure 1 It is known that the atomic number content of N element is 21.95%, and the weight content is 23.03%.

[0091] The grafting rate of the amine oxime resin is calculated according to the N element content, including the following steps:

[0092]

[0093] Example 2

[0094] The embodiment provides an analysis method for the grafting rate of an amine oxime resin, and the analysis method for the grafting rate of the amine oxime resin comprises the following steps:

[0095] The dried amine oxime resin particles are provided, and the amine oxime resin particles are added to a mold;

[0096] The epoxy resin is added to the mold after being melted, and a preform block is obtained after cooling and demolding;

[0097] The preform block is sliced, and a preform sheet with a section of the amine oxime resin particle is selected, and the obtained preform sheet has a thickness of 4 mm;

[0098] One side of the preform sheet is polished;

[0099] The other side of the preform sheet is subjected to 30 s of gold spraying treatment to obtain a test piece;

[0100] The surface morphology of the section of the amine oxime resin particle is observed by a scanning electron microscope, and EDS energy spectrum analysis is performed to obtain the N element content, wherein the scanning electron microscope parameter is set as: acceleration voltage 15 kV, scale 80 μm, picture width: 269 μm, detector: BSD Full.

[0101] The grafting rate of the amine oxime resin is calculated according to the N element content.

[0102] Please refer to Figure 1 , Figure 1 The scanning electron microscope-energy spectrum of the amine oxime resin in the test piece obtained in the embodiment is shown, including the surface topography information and element content information of the test piece. Figure 1 The light green area is the area for EDS energy spectrum analysis. From Figure 1 It is known that the atomic number content of N element is 21.86%, and the weight content is 22.75%.

[0103] The grafting rate of the amine oxime resin is calculated by the N element content, including the following steps:

[0104]

[0105] Example 3

[0106] The embodiment provides an analysis method for the grafting rate of an amine oxime resin, which comprises the following steps:

[0107] The dried amine oxime resin particles are provided and added to a mold;

[0108] After the epoxy resin is melted, it is added to the mold, and after cooling, the preform block is demolded;

[0109] The preform block is sliced, and a preform sheet with an amine oxime resin particle section is selected, and the obtained preform sheet has a thickness of 6mm;

[0110] One side of the preform sheet is polished;

[0111] The unpolished side of the preform sheet is subjected to 40s gold spraying treatment to obtain a test piece;

[0112] The surface topography of the amine oxime resin particle section is observed by a scanning electron microscope, and EDS energy spectrum analysis is performed to obtain the N element content, wherein the scanning electron microscope parameter is set as: acceleration voltage 15kV, scale 80μm, picture width: 269μm, detector: BSD Full;

[0113] The grafting rate of the amine oxime resin is calculated by the N element content.

[0114] Please refer to Figure 1 , Figure 1 The scanning electron microscope-energy spectrum of the amine oxime resin in the test piece obtained in the embodiment is shown, including the surface topography information and element content information of the test piece. Figure 1 The light green area is the area for EDS energy spectrum analysis. From Figure 1 It is known that the atomic number content of N element is 22.66%, and the weight content is 23.85%.

[0115] calculating the grafting of the amidoxime resin by the N element content includes the steps of:

[0116]

[0117] Various embodiments of the application can exist in a range of forms; it should be understood that a range format is used herein only for convenience and brevity, and should not be construed as limiting the scope of the application to a broadest form; therefore, you should consider that the description of a range format has specifically disclosed all the possible sub-ranges as well as the individual numerical values within that range. For example, you should consider that the description of a range of from 1 to 6 has specifically disclosed the sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within the range, for example 1, 2, 3, 4, 5, and 6, regardless of the breadth of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integral) within the indicated range.

[0118] In this application, the positional words such as "upper" and "lower" are specifically the directions of the drawing surface in the drawings unless otherwise stated. In addition, in the description of the specification, the terms "comprise", "include" and the like mean "including but not limited to". Moreover, the terms "comprise", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus including a series of elements includes not only those elements but also other elements not explicitly listed or inherent to such a process, method, article or apparatus. Without more limitations, the elements defined by the statement "comprise" do not exclude the presence of other identical elements in the process, method, article or apparatus including the elements. In this text, the relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between the entities or operations. In this text, "and / or" describes the association relationship of the associated objects, which means that there can be three relationships, for example, A and / or B can represent the cases of A alone, A and B together, and B alone. For the association relationship of more than three associated objects described by "and / or", it means that any one of the three associated objects can exist alone, or any at least two of them exist together, for example, for A, and / or B, and / or C, it means that any one of A, B, and C exists alone, or any two of them exist together, or all three exist together. In this text, "at least one" means one or more, and "multiple" means two or more. "At least one", "at least one of the following" or the like means any combination of the items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can mean a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

[0119] The above description is only a specific embodiment of the present application, which enables those skilled in the art to understand or implement the present application. Various modifications of these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features applied herein.

Claims

1. A method for analyzing the grafting ratio of an amidoxime resin, characterized by, The analysis method of the grafting rate of the amidoxime resin comprises the following steps: The polymer filling material and the dried amidoxime resin particles are provided, the polymer filling material is filled into the voids of the amidoxime resin particles to make a preform, and the polymer filling material is a thermosetting resin; The preform is sliced, and a preform sheet with a cross section of the amidoxime resin particles is selected; The preform sheet is subjected to a gold spraying treatment to obtain a test sheet; The surface morphology of the cross section of the amidoxime resin particles is observed by a scanning electron microscope, and EDS energy spectrum analysis is performed to obtain the content of N element; The grafting rate of the amidoxime resin is calculated by the content of N element; The grafting rate of the amidoxime resin is the grafting rate of the group capable of adsorbing gallium ions; The grafting rate of the amidoxime resin is calculated by the content of N element, comprising the following steps: The grafting rate of the amidoxime resin is calculated by the content of N element by the following formula: Grafting rate = (N amidoxime - N acrylonitrile) / N acrylonitrile * 100%, Wherein, the N amidoxime is the weight content of N element of the amidoxime resin, and the N acrylonitrile is the weight content of N element of the acrylonitrile resin used for grafting to obtain the amidoxime resin; The polymer filling material is filled into the voids of the amidoxime resin particles, comprising: The polymer filling material in powder form is provided, and is blended with the amidoxime resin particles to obtain a mixture; The mixture is added to a mold, and hot pressing is performed at a predetermined temperature and a predetermined pressure, the predetermined temperature is not lower than the thermosetting temperature of the thermosetting resin, and the predetermined pressure is not lower than 10 MPa; The thickness of the preform sheet is 1-8 mm, and the duration of the gold spraying treatment is 10-60 s.

2. The method of claim 1, wherein the method is characterized by: The polymer filling material is an epoxy resin.

3. The method of claim 1, wherein the method is characterized by: The polymer filling material is filled into the voids of the amidoxime resin particles, comprising: The amidoxime resin particles are added to a mold; The polymer filling material is added to the mold after being melted.

4. The method of claim 1, wherein the method is characterized by: Before the preform sheet is subjected to the gold spraying treatment, one side of the preform sheet is polished.

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