CN113292664A - Adsorption resin and preparation method thereof - Google Patents

Adsorption resin and preparation method thereof Download PDF

Info

Publication number
CN113292664A
CN113292664A CN202110651162.1A CN202110651162A CN113292664A CN 113292664 A CN113292664 A CN 113292664A CN 202110651162 A CN202110651162 A CN 202110651162A CN 113292664 A CN113292664 A CN 113292664A
Authority
CN
China
Prior art keywords
adsorption resin
polystyrene
diethylamine
primary product
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202110651162.1A
Other languages
Chinese (zh)
Inventor
曹玲玲
宗冰
鲍守珍
蔡延国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qinghai Asia Silicon Silicon Material Engineering Technology Co Ltd
Asia Silicon Qinghai Co Ltd
Qinghai Asia Silicon Semiconductor Co Ltd
Original Assignee
Qinghai Asia Silicon Silicon Material Engineering Technology Co Ltd
Asia Silicon Qinghai Co Ltd
Qinghai Asia Silicon Semiconductor Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qinghai Asia Silicon Silicon Material Engineering Technology Co Ltd, Asia Silicon Qinghai Co Ltd, Qinghai Asia Silicon Semiconductor Co Ltd filed Critical Qinghai Asia Silicon Silicon Material Engineering Technology Co Ltd
Priority to CN202110651162.1A priority Critical patent/CN113292664A/en
Publication of CN113292664A publication Critical patent/CN113292664A/en
Priority to CN202210642428.0A priority patent/CN114989335A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/06—Oxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/10778—Purification
    • C01B33/10784—Purification by adsorption
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The application provides an adsorption resin and a preparation method thereof, and relates to the technical field of high polymer materials. The preparation method of the adsorption resin comprises the following steps: reacting chloroacetylated polystyrene with diethylamine to obtain a primary product, and reacting the primary product with an oxidant at the temperature of 20-80 ℃ to obtain the adsorption resin. The adsorption resin can simultaneously remove boron impurities and phosphorus impurities in chlorosilane, and has high removal rate.

Description

Adsorption resin and preparation method thereof
Technical Field
The application relates to the technical field of high polymer materials, in particular to adsorption resin and a preparation method thereof.
Background
With the rapid development of electronic information and solar photovoltaic industry, the market demand for polycrystalline silicon is increasing day by day, most polycrystalline silicon enterprises adopt the trichlorosilane hydrogen reduction process to produce solar grade polycrystalline silicon, the quality of the electronic grade polycrystalline silicon produced by the trichlorosilane hydrogen reduction process depends on the purity of chlorosilane to a great extent, the chlorosilane contains trace impurities, the impurities comprise metal chlorides, chlorides and hydrides containing boron and phosphorus, metal compounds and the like, and the impurities all have great influence on the quality of polycrystalline silicon products. Impurities in the chlorosilane can be removed by adopting an adsorption method, but in the prior art, the boron impurities and the phosphorus impurities in the chlorosilane are generally removed separately, and the boron impurities and the phosphorus impurities in the chlorosilane cannot be removed simultaneously.
Disclosure of Invention
The embodiment of the application aims to provide the adsorption resin and the preparation method thereof, the adsorption resin can simultaneously remove boron impurities and phosphorus impurities in chlorosilane, and the removal rate is high.
The embodiment of the application is realized as follows:
the embodiment of the application provides an adsorption resin, the structural formula of which is as follows:
Figure BDA0003111228070000011
the embodiment of the application also provides a preparation method of the adsorption resin, which comprises the following steps:
reacting chloroacetylated polystyrene with diethylamine to obtain a primary product, and reacting the primary product with an oxidant at the temperature of 20-80 ℃ to obtain the adsorption resin.
The adsorption resin and the preparation method thereof provided by the embodiment of the application at least have the following beneficial effects:
in the preparation method, chloracetyl polystyrene and diethylamine are subjected to cross-linking reaction to obtain an initial product, and tertiary amine compound modification is introduced on the chloracetyl polystyrene by a chemical modification method. The primary product reacts with an oxidant to oxidize tertiary amine so that the skeleton of the adsorption resin is provided with an oxidation group to obtain the adsorption resin
Figure BDA0003111228070000021
Thereby simultaneously adsorbing boron and phosphorus in chlorosilane.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is an infrared detection chart of an adsorbent resin according to example 1 of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Impurities in the chlorosilane can be removed by adopting an adsorption method, but in the prior art, the boron impurities and the phosphorus impurities in the chlorosilane are generally removed separately, and the boron impurities and the phosphorus impurities in the chlorosilane cannot be removed simultaneously.
The embodiment of the application provides an adsorption resin and a preparation method thereof, and the adsorption resin can simultaneously remove boron impurities and phosphorus impurities in chlorosilane.
The following is a detailed description of the adsorption resin and the preparation method thereof according to the embodiments of the present application:
the embodiment of the application provides an adsorption resin with a structural formula
Figure BDA0003111228070000031
The inventor of the application discovers in research that boron impurities and phosphorus impurities in chlorosilane are respectively Lewis acid and Lewis base, and the adsorption resin of the application
Figure BDA0003111228070000032
The adsorbent resin simultaneously contains Lewis acid and Lewis base groups, the Lewis acid groups in the adsorbent resin and phosphorus impurities are subjected to neutralization reaction to remove the phosphorus impurities in the chlorosilane, the Lewis base groups in the adsorbent resin and boron impurities are subjected to neutralization reaction to form complexes, the boron impurities in the chlorosilane are removed to form complexes, and then the adsorbent resin can simultaneously remove the boron impurities and the phosphorus impurities in the chlorosilane.
The adsorption resin of the embodiment of the application has the following mechanism for adsorbing boron impurities and phosphorus impurities:
Figure BDA0003111228070000041
the embodiment of the present application further provides a preparation method of the adsorption resin, which includes:
performing cross-linking reaction on chloroacetylated polystyrene and diethylamine to obtain a primary product, and reacting the primary product with an oxidant at the temperature of 20-80 ℃ to obtain the adsorption resin.
In the preparation method, chloracetyl polystyrene and diethylamine are subjected to cross-linking reaction to obtain an initial product, and tertiary amine compound modification is introduced to the chloracetyl polystyrene by a chemical modification method, wherein the reaction mechanism is as follows:
Figure BDA0003111228070000042
then the primary product reacts with an oxidant to oxidize tertiary amine so that the framework of the adsorption resin is provided with an oxidation group to obtain the adsorption resin
Figure BDA0003111228070000043
Thereby can adsorb boron and phosphorus in chlorosilane simultaneously, and the adsorption capacity is stronger.
Illustratively, the reaction temperature of the primary product with the oxidizing agent is 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃.
Optionally, the reaction time of the primary product and the oxidant is 0.5-8 h, which is favorable for the sufficient reaction of the primary product and the oxidant, and optionally, the reaction time of the primary product and the oxidant is 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8 h.
In some possible embodiments, the oxidizing agent comprises any one or more of hydrogen peroxide, ketone peroxide, and peroxyacid.
The hydrogen peroxide, the ketone peroxide and the peroxy acid can oxidize tertiary amine on the primary product to enable the adsorption resin skeleton to have an oxidizing group.
Illustratively, the volume concentration of the oxidizing agent is 5 to 30%, such as 5%, 10%, 15%, 20%, or 30%.
In some possible embodiments, the mass ratio of chloroacetylated polystyrene to diethylamine is 5 to 20: 100.
the research of the inventor of the application shows that the reaction of the chloracetyl polystyrene and the diethylamine in the mass ratio can ensure that the crosslinking reaction degree of the chloracetyl polystyrene and the diethylamine is higher. Illustratively, the mass ratio of chloroacetylated polystyrene to diethylamine is 5:100, 10:100, 15:100, or 20: 100. Further optionally, the mass ratio of the chloracetyl polystyrene to the diethylamine is 5-10: 100.
illustratively, the reaction time of the chloracetyl polystyrene and the diethylamine is 2-8 h. This time frame is advantageous for the sufficient reaction of the chloroacetylated polystyrene with diethylamine. Alternatively, the reaction time of the chloroacetylated polystyrene with diethylamine is 2h, 3h, 4h, 5h, 6h, 7h or 8 h.
In one possible embodiment, the step of reacting chloroacetylated polystyrene with diethylamine comprises:
swelling microspheres of chloroacetylated polystyrene in an organic solvent, and then reacting with diethylamine at the temperature of 60-90 ℃.
The microsphere of the chloracetyl polystyrene can be subjected to a crosslinking reaction with diethylamine at 60-90 ℃ after being swelled, and the organic solvent can swell the microsphere of the chloracetyl polystyrene. Illustratively, the organic solvent includes any one of a tetrahydrofuran solution and toluene.
Alternatively, the reaction temperature is 60 ℃, 70 ℃, 80 ℃ or 90 ℃.
In other embodiments, the chloroacetylated polystyrene may also be mixed with a solution of diethylamine for reaction.
The characteristics and properties of the adsorbent resin of the present application and the method for preparing the same are further described in detail with reference to examples below.
Example 1
The embodiment provides an adsorbent resin, and a preparation method thereof comprises the following steps:
swelling the chloracetyl polystyrene microspheres in tetrahydrofuran, adding diethylamine, and reacting for 4h at 70 ℃ to obtain a primary product. Wherein the mass ratio of the chloracetyl polystyrene microspheres to the diethylamine is 1: 10.6.
Mixing the primary product with a hydrogen peroxide solution with the volume concentration of 30%, stirring and refluxing at the temperature of 60 ℃ for 2 hours to react to obtain adsorption resin, cooling and washing to be neutral, and drying in vacuum at the temperature of 80 ℃. Wherein the mass ratio of the primary product to the hydrogen peroxide solution is 1:10.
Example 2
The embodiment provides an adsorbent resin, and a preparation method thereof comprises the following steps:
swelling the chloracetyl polystyrene microspheres in tetrahydrofuran, adding diethylamine, and reacting for 2h at the temperature of 80 ℃ to obtain a primary product. Wherein the mass ratio of the chloracetyl polystyrene microspheres to the diethylamine is 1: 18.5.
Mixing the primary product with a hydrogen peroxide solution with the volume concentration of 10%, stirring and refluxing at the temperature of 40 ℃ for reaction for 4 hours to obtain adsorption resin, cooling and washing to be neutral, and drying in vacuum at the temperature of 80 ℃. Wherein the mass ratio of the primary product to the hydrogen peroxide solution is 1:10.
Example 3
The embodiment provides an adsorbent resin, and a preparation method thereof comprises the following steps:
swelling the chloracetyl polystyrene microspheres in tetrahydrofuran, adding diethylamine, and reacting for 3h at the temperature of 80 ℃ to obtain a primary product. Wherein the mass ratio of the chloracetyl polystyrene microspheres to the diethylamine is 1: 20.
mixing the primary product with a peroxy acid solution with the volume concentration of 15%, stirring and refluxing at the temperature of 70 ℃ for 2h to obtain an adsorption resin, cooling, washing to neutrality, and vacuum drying at the temperature of 80 ℃. Wherein the mass ratio of the primary product to the peroxy acid solution is 1: 12.
Example 4
The embodiment provides an adsorbent resin, and a preparation method thereof comprises the following steps:
swelling the chloracetyl polystyrene microspheres in tetrahydrofuran, adding diethylamine, and reacting for 2h at the temperature of 90 ℃ to obtain a primary product. Wherein the mass ratio of the chloracetyl polystyrene microspheres to the diethylamine is 1: 5.
mixing the primary product with a ketone peroxide solution with the volume concentration of 10%, stirring and refluxing at the temperature of 60 ℃ for reaction for 3 hours to obtain adsorption resin, cooling, washing to neutrality, and vacuum-drying at the temperature of 80 ℃. Wherein the mass ratio of the primary product to the ketone peroxide solution is 1: 15.
Experimental example 1
(1) 2g of the adsorption resins of example 1, example 3 and example 4 were weighed and respectively added into a PFA bottle containing 20mL of chlorosilane, and after soaking and standing for 1h, the filtration was performed, and the impurity content of the original sample and the filtered sample were respectively detected by ICP-OES, and the results are shown in Table 1.
(2) Dynamic experiment: the adsorption condition of the adsorption resin in the example 2 on impurities in trichlorosilane is observed when the flow rate of trichlorosilane is 5BV/h and the adsorption temperature is 40 ℃.
TABLE 1 boron adsorption and phosphorus adsorption
Figure BDA0003111228070000071
Figure BDA0003111228070000081
As can be seen from the results in Table 1, the adsorption resin of each example was high in both the boron adsorption rate and the phosphorus adsorption rate. The adsorption resin in the embodiment of the application can simultaneously adsorb boron impurities and phosphorus impurities in chlorosilane, and has good adsorption effect.
Test example 2
The results of infrared detection of the adsorbent resin of example 1 are shown in FIG. 1.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. An adsorbent resin having the structural formula:
Figure FDA0003111228060000011
2. a method of preparing the adsorbent resin of claim 1, comprising:
performing cross-linking reaction on chloroacetylated polystyrene and diethylamine to obtain a primary product, and reacting the primary product with an oxidant at the temperature of 20-80 ℃ to obtain the adsorption resin.
3. The method for preparing the adsorbent resin according to claim 2, wherein the step of reacting chloroacetylated polystyrene with diethylamine comprises:
swelling the microsphere of the chloracetyl polystyrene in an organic solvent, and then reacting with diethylamine at the temperature of 60-90 ℃.
4. The method according to claim 3, wherein the organic solvent comprises tetrahydrofuran.
5. The method for preparing the adsorption resin according to claim 2, wherein the oxidizing agent comprises any one or more of hydrogen peroxide, ketone peroxide and peroxy acid.
6. The method for preparing the adsorption resin according to claim 2 or 5, wherein the volume concentration of the oxidant is 5-30%.
7. The method for preparing the adsorption resin according to any one of claims 2 to 5, wherein the mass ratio of the chloroacetylated polystyrene to the diethylamine is 5 to 20: 100.
8. the method for preparing the adsorption resin according to claim 7, wherein the mass ratio of the chloroacetylated polystyrene to the diethylamine is 5-10: 100.
9. the method for preparing the adsorption resin according to any one of claims 2 to 5, wherein the reaction time of the chloroacetylated polystyrene and the diethylamine is 2 to 8 hours.
10. The method for preparing the adsorption resin according to any one of claims 2 to 5, wherein the reaction time of the primary product and the oxidant is 0.5 to 8 hours.
CN202110651162.1A 2021-06-10 2021-06-10 Adsorption resin and preparation method thereof Withdrawn CN113292664A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202110651162.1A CN113292664A (en) 2021-06-10 2021-06-10 Adsorption resin and preparation method thereof
CN202210642428.0A CN114989335A (en) 2021-06-10 2022-06-08 Adsorption resin and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110651162.1A CN113292664A (en) 2021-06-10 2021-06-10 Adsorption resin and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113292664A true CN113292664A (en) 2021-08-24

Family

ID=77327866

Family Applications (2)

Application Number Title Priority Date Filing Date
CN202110651162.1A Withdrawn CN113292664A (en) 2021-06-10 2021-06-10 Adsorption resin and preparation method thereof
CN202210642428.0A Pending CN114989335A (en) 2021-06-10 2022-06-08 Adsorption resin and preparation method thereof

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN202210642428.0A Pending CN114989335A (en) 2021-06-10 2022-06-08 Adsorption resin and preparation method thereof

Country Status (1)

Country Link
CN (2) CN113292664A (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5577637B2 (en) * 2008-07-18 2014-08-27 三菱化学株式会社 Amine oxide group-containing resin solution and hair cosmetic resin composition using the same
KR101321035B1 (en) * 2012-02-09 2013-10-23 주식회사 삼양사 Ion exchange resin and method for fabricating the same
CN104801354B (en) * 2015-04-09 2017-10-03 中国纺织科学研究院 The purification process of hydrogen-oxygen type tertiary amine oxide anion exchange resin, its preparation method and the NMMO aqueous solution
CN105153344A (en) * 2015-10-23 2015-12-16 蓝星（成都）新材料有限公司 Diethylamine anion exchange resin and preparation method thereof
CN105329902B (en) * 2015-11-24 2017-11-10 宜昌南玻硅材料有限公司 The adsorption-edulcoration technique of ppb levels boron and P elements impurity in a kind of trichlorosilane

Also Published As

Publication number Publication date
CN114989335A (en) 2022-09-02

Similar Documents

Publication Publication Date Title
Qu et al. Syntheses, characterization, and adsorption properties for metal ions of silica-gel functionalized by ester-and amino-terminated dendrimer-like polyamidoamine polymer
JP4962490B2 (en) Modified silica gel and use thereof
Jiang et al. Synthesis and selective adsorption behavior of Pd (II)-imprinted porous polymer particles
CN111116296B (en) Method for separating benzene and cyclohexane
Liu et al. Synthesis and characterization of poly (acrylaminophosphonic-carboxyl-hydrazide) chelating fibre
CN106700088B (en) A kind of preparation method and applications of Pd ion blotting silica gel absorber
Zhao et al. Development of novel adsorbent bearing aminocarbonylmethylglycine and its application to scandium separation
Salahchini Javanmardi et al. Pervaporation characteristics of PDMS/PMHS nanocomposite membranes inclusive multi-walled carbon nanotubes for improvement of acetic acid–methanol esterification reaction
CN108299652B (en) Graphene nano material with high chiral selectivity and preparation and application thereof
Milja et al. Synthesis, characterization and application of uranyl ion imprinted polymers of aniline and 8-hydroxy quinoline functionalized aniline
CN112979985A (en) Composite metal organic framework material and preparation method thereof
CN114044844B (en) Chelate resin and preparation method and application thereof
CN113292664A (en) Adsorption resin and preparation method thereof
CN111636145A (en) Polyester fiber film for adsorbing heavy metals and preparation method thereof
CN103638970A (en) Ion liquid catalyst and preparation method thereof as well as preparation method of cyclic carbonate
Rashid et al. An advanced Cr (III) selective nano-composite cation exchanger: synthesis, characterization and sorption characteristics
CN113402640A (en) Adsorption resin for impurity removal of chlorosilane and preparation method thereof
CN109550405B (en) Preparation method and application of ion selective polymer containing membrane
KR20020007772A (en) Synthesis Method of Mesoporous Silicas with Chelating Ligands for Heavy Metal Ion Removal in Aqueous Solutions
CN114181056B (en) Cage arene, and preparation method and application thereof
Jabli et al. [Copper (II)/cellulose-chitosan] microspheres complex for dye immobilization: isotherm, kinetic and thermodynamic analysis
CN114195981A (en) Biphenyl epoxy resin and synthetic method and application thereof
CN118108914A (en) COFs chemometric sub-metering controllable assembly and application thereof in gas adsorption separation
CN117209691A (en) Modified polystyrene and production process thereof
US3116976A (en) Process for recovering bromine

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20210824