CN105820282B - A kind of high stability hydrogen bonds are to receptor macroporous absorbent resin and its synthetic method - Google Patents
A kind of high stability hydrogen bonds are to receptor macroporous absorbent resin and its synthetic method Download PDFInfo
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- CN105820282B CN105820282B CN201610326490.3A CN201610326490A CN105820282B CN 105820282 B CN105820282 B CN 105820282B CN 201610326490 A CN201610326490 A CN 201610326490A CN 105820282 B CN105820282 B CN 105820282B
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- 229920005989 resin Polymers 0.000 title claims abstract description 152
- 239000011347 resin Substances 0.000 title claims abstract description 152
- 239000001257 hydrogen Substances 0.000 title claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 45
- 239000002250 absorbent Substances 0.000 title claims abstract description 21
- 230000002745 absorbent Effects 0.000 title claims abstract description 21
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 41
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 19
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000005917 acylation reaction Methods 0.000 claims abstract description 3
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 48
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 29
- 239000000460 chlorine Substances 0.000 claims description 29
- 229910052801 chlorine Inorganic materials 0.000 claims description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 25
- 235000005074 zinc chloride Nutrition 0.000 claims description 24
- 239000011592 zinc chloride Substances 0.000 claims description 24
- 239000005711 Benzoic acid Substances 0.000 claims description 22
- 235000010233 benzoic acid Nutrition 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims description 19
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 15
- 108010010803 Gelatin Proteins 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 12
- 239000008273 gelatin Substances 0.000 claims description 12
- 229920000159 gelatin Polymers 0.000 claims description 12
- 235000019322 gelatine Nutrition 0.000 claims description 12
- 235000011852 gelatine desserts Nutrition 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 9
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000012797 qualification Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- -1 benzene Acyl chlorides Chemical class 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000004900 laundering Methods 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 239000004760 aramid Substances 0.000 abstract description 2
- 229920003235 aromatic polyamide Polymers 0.000 abstract description 2
- 239000003365 glass fiber Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 241001566735 Archon Species 0.000 description 4
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 0 C*c1ccc(*)cc1 Chemical compound C*c1ccc(*)cc1 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
Abstract
The present invention provides a kind of high stability hydrogen bonds to the synthetic method of receptor macroporous absorbent resin; using suspension polymerization synthetic polystyrene resin macroreticular resin ball; ball containing carboxy resin is obtained by chloromethylation and potassium dichromate oxidation; acylation reaction is carried out using with thionyl chloride; COCl functional groups are introduced on the phenyl ring of styrene, then macroreticular resin of the hydrogen bonds to receptor is obtained by the reaction with p-phenylenediamine；Aromatic polyamide molecule chain rigidity increases in structure, thus its fibrous glass temperature, heat resistance and modulus are higher.
Description
【Technical field】
The invention belongs to macromolecule separation materials, are related to a kind of preparation method of macroporous absorbent resin, and in particular to Yi Zhonggao
Stability hydrogen bonds are to receptor macroporous absorbent resin and its synthetic method.
【Background technology】
Macroporous absorbent resin is the macromolecule separation material that six the seventies of last century grow up, as a kind of artificial conjunction
At material, compared with traditional material such as activated carbon, have the characteristics that adsorption capacity is big, easily parsing, intensity is high, with long service life.
In decades, prodigious achievement has been achieved to the research for adsorbing resin.Absorption resin also gradually expands to more using upper
Field.In the research to adsorbing resin, the target that the selectivity of absorption is always the unremitting pursuit of people how is improved.
It tentatively verifies, the mechanism of absorption is mainly by hydrophobic adsorbent, delocalizedπelectron absorption and Hydrogen Binding Adsorption, and adsorption mechanism is more single
One, adsorptive selectivity is higher.Since hydrogen bond is widespread in nature, people have been carried out a series of grind to Hydrogen Binding Adsorption
Study carefully, and has obtained some applications in practice.
(ion exchange and absorption, 2001,17 (6) such as Li Jiazheng：It 561-566.) proposes, usually presses hydrogen bond absorbing resin
It is divided into three classes according to the property of hydrogen-bond donor receptor, i.e., to build, receptor type and mixed type three classes.Common gives build Hydrogen Binding Adsorption
Resin has：Poly(4-hydroxystyrene), poly- polyhydroxy styrene, the PS-DVB of sulfonation；Receptor type hydrogen bond absorbing resin has：Polypropylene
Esters of gallic acid, polyamide-based, poly- p-nitrophenyl vinyl；The hydrogen bond absorbing resin of mixed type has：Polyamide-based, ureaformaldehyde condensation polymer,
The gelatin-compounded resin of polyvinyl alcohol-, polyamide-silica gel compound resin etc..
Following resin structure is referred in Nankai University's patent 200810153620.3：
The method is to utilize suspension polymerisation synthetic polystyrene-methyl acrylate matrix, then with partition diamine reactant, is generated
Structure as above, method synthesis is simple, and reaction efficiency is high.The resin of synthesis belongs to mixed type hydrogen bond absorbing resin, hydrogen bond functional groups
Belong to fatty polyamide structure, for aliphatic polyamide material, the maximum general character is good hydrophilic property, and resin can be long-term
It is used in water phase, but resin is when in use, common desorbed solution may be the acid-base solution of 1~4mol/L, and temperature highest can
To 90~100 DEG C, for a long time in these systems, it may occur that following reaction：
Cause the decline of resin adsorption performance.Currently, all commercially available acrylic acid series strongly basics, weak base resin, all have-
CONH- keys also have Hydrogen Binding Adsorption function, but the easy hydrolysis of amido bond is also to inhibit its use scope one of the main reasons.
【Invention content】
The object of the present invention is to provide a kind of high stability hydrogen bonds to receptor macroporous absorbent resin and its synthetic method, system
Standby macroporous absorbent resin has high temperature resistant, resistant to chemical etching, fatigue resistance.
To achieve the above object, the present invention uses following technical scheme：
A kind of high stability hydrogen bonds give receptor macroporous absorbent resin, structure as follows：
High stability hydrogen bonds to receptor macroporous absorbent resin synthetic method, using suspension polymerization synthetic polystyrene
Resin macroreticular resin ball obtains ball containing carboxy resin by chloromethylation and potassium dichromate oxidation, using with thionyl chloride into
Row acylation reaction, the introducing-COCl functional groups on the phenyl ring of styrene, then hydrogen bonds are obtained by the reaction to receptor with p-phenylenediamine
Macroreticular resin.
High stability hydrogen bonds are as follows to the synthetic method of receptor macroporous absorbent resin：
(1) synthetic polystyrene resin macroreticular resin ball
Water phase：Magnesium sulfate, gelatin, methylene blue are dissolved in the water as water phase under room temperature；
Oil phase：Polymerized monomer is styrene and divinylbenzene, and wherein divinylbenzene accounts for 6~10%, remaining is benzene second
Alkene will be oil phase after monomer and pore-foaming agent mixing, and pore-foaming agent is that gasoline and liquid are cured, gasoline and the cured mass ratio (1~3) of liquid：5,
Pore-foaming agent is the 50~100% of monomer mass；
In the reaction kettle equipped with water phase, by heated aqueous to 55 DEG C, reaction kettle, the body of water phase and oil phase is added in oil phase
Product is than being 3~4:1, so that oil phase is dispersed in water phase by stirring, control grain size is 0.3~1.0mm, is warming up to 70~80 DEG C,
3~5h is reacted, is continuously heating to 90 DEG C, reacts 3~5h, stops reaction, cooling, after being extracted with dimethoxym ethane, washing, boiling are done
It is dry, obtain polystyrene resin macroreticular resin ball；
(2) chloromethylation prepares chlorine ball
Raw material：Polystyrene resin macroreticular resin ball, chloromethyl ether；
Catalyst：Zinc chloride
The reaction kettle for cleaning drying is taken, polystyrene resin macroreticular resin ball and chloromethyl ether, polyphenyl are added into reaction kettle
The mass ratio of vinyl macroreticular resin ball and chloromethyl ether is 1:The mass ratio of (4~5), resin balls and zinc chloride be (2~
2.5):5, it is swollen 2h at 20-25 DEG C, after swelling, puts into 1/2 zinc chloride, is warming up to 45 DEG C, insulation reaction 2h, then
Then the zinc chloride of input 1/2 reacts 12~16h；
Sampling is qualification when measuring chlorinity >=18%, recycles chloromethyl ether mother liquor, spare after chlorine ball massive laundering；
(3) oxidation reaction prepares resin balls containing benzoic acid
Raw material：Chlorine ball, potassium bichromate, the sulfuric acid of 1mol/L
Chlorine ball, potassium bichromate, the sulfuric acid of 1mol/L, the mass ratio of potassium bichromate and 1mol/L sulfuric acid are added in a kettle
It is 1：10,1mol/L sulfuric acid and the mass ratio of chlorine ball are (1~1.5):1, it is warming up to reflux under stirring, reacts 3~4h；Discharging
After wash, after the HCl treatment of 1mol/L, pure water is washed till neutrality, drying, obtain adsorbent resin microballon containing carboxyl；
(4) preparation of the resin balls containing chlorobenzoyl chloride
Raw material：Resin microsphere containing benzoic acid
Resin microsphere containing benzoic acid is added in a kettle, thionyl chloride is added, wherein resin balls containing benzoic acid and dichloro
The mass ratio of sulfoxide is 1:(0.5~0.8) reacts 3~5h at 50~70 DEG C, and reaction terminates, and rotates thionyl chloride, generation contains
Chlorobenzoyl chloride resin balls；
(5) preparation of the hydrogen bonds to the resin of receptor
Benzoyl resin balls will be contained to be swollen with chloroform, p-phenylenediamine is added and is reacted, wherein tree containing chlorobenzoyl chloride
The mass ratio of fat ball, chloroform swelling and p-phenylenediamine is 1:0.5:(0.5~0.8) reacts 3~5h, mistake at 30~40 DEG C
It is washed after filter, drying is to get hydrogen bonds to the macroreticular resin of receptor.
Further, the polystyrene resin macroreticular resin ball ball degree of cross linking of synthesis is 6~10%.
Further, after the step (1) stops reaction, after resin balls after cooling are discharged, 90 DEG C or more hot water wash are used
After 5-10 times of resin volume dimethoxym ethane extraction, washing, boiling, 80~90 DEG C of dry 10h or more obtain polystyrene resin macropore
Resin balls.
Further, in water phase, gelatin concentration is 0.5~2%, magnesium sulfate concentration 10%.
Further, the step (4) rotates thionyl chloride at 70~85 DEG C after reaction, generates and contains chlorobenzoyl chloride
Resin balls.
The high stability hydrogen bonds of the present invention give receptor macroporous absorbent resin, and aromatic polyamide strand is rigid in structure
Property increase, thus its fibrous glass temperature, heat resistance and modulus are higher.Since there is stronger covalent bonds and weaker hydrogen
Key, and in amide groups, the electronics of oxygen atom and nitrogen-atoms will produce conjugation, and 9 can form greatly with benzene ring structure simultaneously
Conjugation there are the property such as high temperature resistant, resistant to chemical etching, antifatigue therefore compared with common fats polyamide structure.More
Importantly, in the structure, there is amide and primary amine structure, amide can be used as hydrogen bond as the receptor of hydrogen bond, primary amine
Give bodies, very effective in flavonoids, saponins, Polyphenols extraction, there play the role of on pigment separated to be special.
【Specific implementation mode】
With reference to specific embodiment, present invention is further described in detail, but not as a limitation of the invention.
The object of the present invention is to provide a kind of high stability hydrogen bonds to the synthetic method of receptor macroporous absorbent resin, prepares
Macroporous absorbent resin have high temperature resistant, resistant to chemical etching, fatigue resistance.
The structure of resin balls of the present invention is as follows：
The reaction equation for synthesizing the resin is as follows：
It is as follows：
(1) the polystyrene resin macroreticular resin ball that the degree of cross linking is 6~10% is aggregated into suspension polymerisation, then washed,
Pore-foaming agent and then drying are extracted, Archon is obtained.
(2) it by Archon chloromethylation, then washes, is dried to obtain chloromethylation Archon, control chlorinity >=18% or more；
(3) hydrochloric acid transition is added in chloromethylation Archon potassium dichromate oxidation, washing, obtains adsorbing resin balls containing carboxyl；
(4) it uses thionyl chloride and ball containing carboxy resin to react, rotates thionyl chloride, generate resin balls containing chlorobenzoyl chloride；
(5) using chloroform as solvent, after the swelling of chlorobenzoyl chloride resin balls will be contained, p-phenylenediamine is added, reacts to contain
The macroreticular resin of Qing Jian Give receptors.
Detailed step is as follows：
(1) synthetic polystyrene resin macroreticular resin ball
Water phase：Magnesium sulfate, gelatin, methylene blue are dissolved in the water as water phase under room temperature, gelatin concentration is 0.5~
2%, magnesium sulfate concentration 10%；
Oil phase：Polymerized monomer is styrene and divinylbenzene, and wherein divinylbenzene accounts for 6~10%, remaining is benzene second
Alkene will be oil phase after monomer and pore-foaming agent mixing, and pore-foaming agent is that gasoline and liquid are cured, gasoline and the cured mass ratio (1~3) of liquid：5,
Pore-foaming agent is the 50~100% of monomer mass；
In the reaction kettle equipped with water phase, by heated aqueous to 55 DEG C, reaction kettle, the body of water phase and oil phase is added in oil phase
Product is than being 3~4:1, so that oil phase is dispersed in water phase by stirring, control grain size is 0.3~1.0mm, is warming up to 70~80 DEG C,
3~5h is reacted, is continuously heating to 90 DEG C, reacts 3~5h, stops reaction, it is cooling；
After resin balls after cooling are discharged, 90 DEG C or more hot water wash are washed after being extracted with 5-10 times of resin volume dimethoxym ethane
It washs, boiling, 80~90 DEG C of dry 10h or more obtain polystyrene resin macroreticular resin ball；
(2) chloromethylation prepares chlorine ball
Raw material：Polystyrene resin macroreticular resin ball, chloromethyl ether；
Catalyst：Zinc chloride
The reaction kettle for cleaning drying is taken, polystyrene resin macroreticular resin ball and chloromethyl ether, polyphenyl are added into reaction kettle
The mass ratio of vinyl macroreticular resin ball and chloromethyl ether is 1:The mass ratio of (4~5), resin balls and zinc chloride be (2~
2.5):5, it is swollen 2h at 20-25 DEG C, after swelling, puts into 1/2 zinc chloride, is warming up to 45 DEG C, insulation reaction 2h, then
Then the zinc chloride of input 1/2 reacts 12~16h；
Sampling is qualification when measuring chlorinity >=18%, recycles chloromethyl ether mother liquor, spare after chlorine ball massive laundering；
(3) oxidation reaction prepares resin balls containing benzoic acid
Raw material：Chlorine ball, potassium bichromate, the sulfuric acid of 1mol/L
Chlorine ball, potassium bichromate, the sulfuric acid of 1mol/L, the mass ratio of potassium bichromate and 1mol/L sulfuric acid are added in a kettle
It is 1：10,1mol/L sulfuric acid and the mass ratio of chlorine ball are (1~1.5):1, it is warming up to reflux under stirring, reacts 3~4h；
It is washed after discharging, after the HCl treatment of 1mol/L, pure water is washed till neutrality, drying, obtains adsorbing resin containing carboxyl
Microballoon；
(4) preparation of the resin balls containing chlorobenzoyl chloride
Raw material：Resin microsphere containing benzoic acid
Resin microsphere containing benzoic acid is added in a kettle, thionyl chloride is added, reacts 3~5h at 50~70 DEG C.Reaction
Terminate, rotated at 70~85 DEG C, rotate thionyl chloride, generates resin balls containing chlorobenzoyl chloride.
(5) preparation of the hydrogen bonds to the resin of receptor
Benzoyl resin balls will be contained to be swollen with chloroform, be added p-phenylenediamine reacted, at 30~40 DEG C react 3~
5h is washed after filtering, and drying is to get hydrogen bonds to the macroreticular resin of receptor.
The present invention will be further described by the following examples.
Embodiment 1
1) synthetic polystyrene resin microsphere
It counts in parts by weight, proportioning is as follows：
Oil phase：
100 parts of styrene
10 parts of divinylbenzene
100 parts of pore-foaming agent
Water phase：
700 parts of distilled water
Magnesium sulfate, gelatin, methylene blue are dissolved in the water as water phase under room temperature, gelatin concentration is 0.5~2%, sulphur
Sour magnesium density is 10%；
First by water phase be added 2000ml reaction kettles in, be heated to 55 DEG C, will after oil phase mixing be added reaction kettle in, water phase and
The volume ratio of oil phase is 3:1, control grain size is 0.3-1.0mm, is warming up to 75 DEG C, after reacting 3h, is continuously heating to 90 DEG C, reaction
5h stops reaction, cooling, 90 DEG C or more hot water washings, after the dimethoxym ethane extraction of 5 times of resin volumes, washing, and boiling, 80~
90 DEG C of dry 10h or more, obtain polystyrene resin macroreticular resin ball；.
2) chloromethylation prepares chlorine ball
Polystyrene resin is added into reaction kettle and chloromethyl ether, the mass ratio of wherein polystyrene resin and chloromethyl ether are
1:4.After being swollen 2h at 25 DEG C, 1/2 zinc chloride is added, wherein zinc chloride and the mass ratio of polystyrene resin balls is 2.5:
After 5 DEG C of Isosorbide-5-Nitrae reaction 2h, 1/2 zinc chloride is added, the reaction was continued 12-16h, sampling is to close when measuring chlorinity >=18%
Lattice recycle chloromethyl ether mother liquor, are washed after filtering, and drying obtains chlorine ball.
3) oxidation prepares resin balls containing benzoic acid
The sulfuric acid of chlorine ball, potassium bichromate and 1mol/L is added in a kettle, wherein potassium bichromate and 1mol/L sulfuric acid
Mass ratio is 1：10,1mol/L sulfuric acid and the mass ratio of chlorine ball are 1:1, reflux is warming up under stirring, after reacting 3h, filtering,
It washs, after the HCl treatment of 1mol/L, pure water is washed till neutrality, drying.
4) resin balls containing chlorobenzoyl chloride are prepared
Resin balls containing benzoic acid and thionyl chloride are added in a kettle, wherein resin balls containing benzoic acid and thionyl chloride
Mass ratio is 1:0.5,70 DEG C of reaction 3h, rotates, washes, drying.
5) hydrogen bonds are prepared and give receptor resin balls
Resin balls containing chlorobenzoyl chloride are added in a kettle, p-phenylenediamine is added after being swollen with chloroform, wherein containing benzene
The mass ratio of formyl chloride resin balls, chloroform swelling and p-phenylenediamine is 1:0.5:5h is reacted at 0.5,40 DEG C, is filtered, is washed
It washs, after the HCl treatment of 1mol/L, pure water is washed till neutrality, drying.
Embodiment 2：
Other steps are identical with embodiment 1, and the addition of chloromethyl ether is different only in step 2.
2) chloromethylation prepares chlorine ball
Polystyrene resin is added into reaction kettle and chloromethyl ether, the mass ratio of wherein polystyrene resin and chloromethyl ether are
1:5.After being swollen 2h at 20 DEG C, 1/2 zinc chloride is added, wherein zinc chloride and the mass ratio of polystyrene resin balls is 2:1,
After 45 DEG C of reaction 2h, 1/2 zinc chloride is added, the reaction was continued 12-16h, sampling is qualification when measuring chlorinity >=18%,
Chloromethyl ether mother liquor is recycled, is washed after filtering, drying obtains chlorine ball.
Finally obtain resin of the hydrogen bonds to receptor.
Embodiment 3：
Other steps are identical with embodiment 1, and the addition of thionyl chloride is different only in step 4.
4) resin balls containing chlorobenzoyl chloride are prepared
Resin balls containing benzoic acid and thionyl chloride are added in a kettle, wherein resin balls containing benzoic acid and thionyl chloride
Mass ratio is 1:0.8,50 DEG C of reaction 3h, rotates, washes, drying.
Finally obtain resin of the hydrogen bonds to receptor.
Embodiment 4：
Other steps are identical with embodiment 1, and the addition of p-phenylenediamine is different only in step 5.
It prepares hydrogen bonds and gives receptor resin balls
Resin balls containing chlorobenzoyl chloride are added in a kettle, p-phenylenediamine is added after being swollen with chloroform, wherein containing benzene
The mass ratio of formyl chloride resin balls, chloroform swelling and p-phenylenediamine is 1:0.5:5h is reacted at 0.8,30 DEG C, is filtered, is washed
It washs, after the HCl treatment of 1mol/L, pure water is washed till neutrality, drying.
Embodiment 5：
1) synthetic polystyrene resin microsphere
It counts in parts by weight, proportioning is as follows：
Oil phase：
90 parts of styrene
10 parts of divinylbenzene
50 parts of pore-foaming agent
Water phase：
700 parts of distilled water
Magnesium sulfate, gelatin, methylene blue are dissolved in the water as water phase under room temperature, gelatin concentration is 0.5~2%, sulphur
Sour magnesium density is 10%；
First by water phase be added 2000ml reaction kettles in, be heated to 55 DEG C, will after oil phase mixing be added reaction kettle in, water phase and
The volume ratio of oil phase is 4:1, control grain size is 0.3-1.0mm, is warming up to 70 DEG C, after reacting 5h, is continuously heating to 90 DEG C, reaction
4h stops reaction, cooling, 90 DEG C or more hot water washings, after the dimethoxym ethane extraction of 10 times of resin volumes, washing, and boiling, 80~
90 DEG C of dry 10h or more obtain polystyrene resin macroreticular resin ball, the polystyrene resin macroreticular resin ball ball crosslinking of synthesis
Degree is 6~10%.
2) chloromethylation prepares chlorine ball
Polystyrene resin is added into reaction kettle and chloromethyl ether, the mass ratio of wherein polystyrene resin and chloromethyl ether are
1:4.5.After being swollen 2h at 22 DEG C, 1/2 zinc chloride is added, wherein zinc chloride and the mass ratio of polystyrene resin balls is
2.5:After 5 DEG C of Isosorbide-5-Nitrae reaction 2h, 1/2 zinc chloride is added, the reaction was continued 12-16h, when sampling measures chlorinity >=18% i.e.
For qualification, chloromethyl ether mother liquor is recycled, is washed after filtering, drying obtains chlorine ball.
3) oxidation prepares resin balls containing benzoic acid
The sulfuric acid of chlorine ball, potassium bichromate and 1mol/L is added in a kettle, wherein potassium bichromate and 1mol/L sulfuric acid
Mass ratio is 1：10,1mol/L sulfuric acid and the mass ratio of chlorine ball are 1.5:1, reflux is warming up under stirring, after reacting 4h, mistake
Filter is washed, and after the HCl treatment of 1mol/L, pure water is washed till neutrality, drying.
4) resin balls containing chlorobenzoyl chloride are prepared
Resin balls containing benzoic acid and thionyl chloride are added in a kettle, wherein resin balls containing benzoic acid and thionyl chloride
Mass ratio is 1:0.6,50 DEG C is reacted 5h, is rotated thionyl chloride at 70-85 DEG C, is washed, drying.
5) hydrogen bonds are prepared and give receptor resin balls
Resin balls containing chlorobenzoyl chloride are added in a kettle, p-phenylenediamine is added after being swollen with chloroform, wherein containing benzene
The mass ratio of formyl chloride resin balls, chloroform swelling and p-phenylenediamine is 1:0.5:3h is reacted at 0.5,35 DEG C, is filtered, is washed
It washs, after the HCl treatment of 1mol/L, pure water is washed till neutrality, drying.
Embodiment 6：
1) synthetic polystyrene resin microsphere
It counts in parts by weight, proportioning is as follows：
Oil phase：
94 parts of styrene
6 parts of divinylbenzene
75 parts of pore-foaming agent
Water phase：
700 parts of distilled water
Magnesium sulfate, gelatin, methylene blue are dissolved in the water as water phase under room temperature, gelatin concentration is 0.5~2%, sulphur
Sour magnesium density is 10%；
First by water phase be added 2000ml reaction kettles in, be heated to 55 DEG C, will after oil phase mixing be added reaction kettle in, water phase and
The volume ratio of oil phase is 3.5:1, control grain size is 0.3-1.0mm, is warming up to 80 DEG C, after reacting 4h, is continuously heating to 90 DEG C, instead
4.5h is answered, reaction is stopped, cooling, 90 DEG C or more hot water washings, after the dimethoxym ethane extraction of 8 times of resin volumes, washing, boiling,
80~90 DEG C of dry 10h or more obtain polystyrene resin macroreticular resin ball, the polystyrene resin macroreticular resin ball ball of synthesis
The degree of cross linking is 6~10%.
2) chloromethylation prepares chlorine ball
Polystyrene resin is added into reaction kettle and chloromethyl ether, the mass ratio of wherein polystyrene resin and chloromethyl ether are
1:4.5.After being swollen 2h at 22 DEG C, 1/2 zinc chloride is added, wherein zinc chloride and the mass ratio of polystyrene resin balls is
2.5:After 5 DEG C of Isosorbide-5-Nitrae reaction 2h, 1/2 zinc chloride is added, the reaction was continued 12-16h, when sampling measures chlorinity >=18% i.e.
For qualification, chloromethyl ether mother liquor is recycled, is washed after filtering, drying obtains chlorine ball.
3) oxidation prepares resin balls containing benzoic acid
The sulfuric acid of chlorine ball, potassium bichromate and 1mol/L is added in a kettle, wherein potassium bichromate and 1mol/L sulfuric acid
Mass ratio is 1：10,1mol/L sulfuric acid and the mass ratio of chlorine ball are 1.25:1, reflux is warming up under stirring, after reacting 3.5h,
Filtering is washed, and after the HCl treatment of 1mol/L, pure water is washed till neutrality, drying.
4) resin balls containing chlorobenzoyl chloride are prepared
Resin balls containing benzoic acid and thionyl chloride are added in a kettle, wherein resin balls containing benzoic acid and thionyl chloride
Mass ratio is 1:0.7,60 DEG C is reacted 4h, is rotated thionyl chloride at 70-85 DEG C, is washed, drying.
5) hydrogen bonds are prepared and give receptor resin balls
Resin balls containing chlorobenzoyl chloride are added in a kettle, p-phenylenediamine is added after being swollen with chloroform, wherein containing benzene
The mass ratio of formyl chloride resin balls, chloroform swelling and p-phenylenediamine is 1:0.5:3h is reacted at 0.7,35 DEG C, is filtered, is washed
It washs, after the HCl treatment of 1mol/L, pure water is washed till neutrality, drying.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
The specific implementation mode of the present invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
Under the premise of from present inventive concept, several simple deduction or replace can also be made, all shall be regarded as belonging to the present invention by institute
Claims of submission determine scope of patent protection.
Claims (7)
1. a kind of high stability hydrogen bonds give receptor macroporous absorbent resin, it is characterised in that structure is as follows：
2. a kind of claim 1 high stability hydrogen bonds are to the synthetic method of receptor macroporous absorbent resin, it is characterised in that：Using
Suspension polymerization synthetic polystyrene resin macroreticular resin ball obtains containing carboxy resin by chloromethylation and potassium dichromate oxidation
Ball, using with thionyl chloride carry out acylation reaction, the introducing-COCl functional groups on the phenyl ring of styrene, then with p-phenylenediamine
Macroreticular resin of the hydrogen bonds to receptor is obtained by the reaction.
3. high stability hydrogen bonds as claimed in claim 2 are to the synthetic method of receptor macroporous absorbent resin, it is characterised in that
It is as follows：
(1) synthetic polystyrene resin macroreticular resin ball
Water phase：Magnesium sulfate, gelatin, methylene blue are dissolved in the water as water phase under room temperature；
Oil phase：Polymerized monomer is styrene and divinylbenzene, and wherein divinylbenzene accounts for 6~10%, remaining is styrene, will
It is oil phase after monomer and pore-foaming agent mixing, pore-foaming agent is gasoline and liquid wax, the mass ratio (1~3) of gasoline and liquid wax：5, pore
Agent is the 50~100% of monomer mass；
In the reaction kettle equipped with water phase, by heated aqueous to 55 DEG C, reaction kettle, the volume ratio of water phase and oil phase is added in oil phase
It is 3~4:1, so that oil phase is dispersed in water phase by stirring, control grain size is 0.3~1.0mm, is warming up to 70~80 DEG C, reaction 3
~5h is continuously heating to 90 DEG C, reacts 3~5h, stops reaction, cooling, and after being extracted with dimethoxym ethane, washing, boiling are dry, obtain
To polystyrene resin macroreticular resin ball；
(2) chloromethylation prepares chlorine ball
Raw material：Polystyrene resin macroreticular resin ball, chloromethyl ether；
Catalyst：Zinc chloride
The reaction kettle for cleaning drying is taken, polystyrene resin macroreticular resin ball and chloromethyl ether, polystyrene are added into reaction kettle
The mass ratio of resin macroreticular resin ball and chloromethyl ether is 1:The mass ratio of (4~5), resin balls and zinc chloride is (2~2.5):5,
It is swollen 2h at 20-25 DEG C, after swelling, puts into 1/2 zinc chloride, is warming up to 45 DEG C, insulation reaction 2h, then put into 1/2
Zinc chloride, then react 12~16h；
Sampling is qualification when measuring chlorinity >=18%, recycles chloromethyl ether mother liquor, spare after chlorine ball massive laundering；
(3) oxidation reaction prepares resin balls containing benzoic acid
Raw material：Chlorine ball, potassium bichromate, the sulfuric acid of 1mol/L
The mass ratio of addition chlorine ball in a kettle, potassium bichromate, the sulfuric acid of 1mol/L, potassium bichromate and 1mol/L sulfuric acid is 1：
10,1mol/L sulfuric acid and the mass ratio of chlorine ball are (1~1.5):1, it is warming up to reflux under stirring, reacts 3~4h；
It is washed after discharging, after the HCl treatment of 1mol/L, pure water is washed till neutrality, and drying obtains adsorbent resin microballon containing carboxyl；
(4) preparation of the resin balls containing chlorobenzoyl chloride
Raw material：Resin microsphere containing benzoic acid
Resin microsphere containing benzoic acid is added in a kettle, thionyl chloride is added, wherein resin balls containing benzoic acid and thionyl chloride
Mass ratio be 1:(0.5~0.8) reacts 3~5h at 50~70 DEG C, and reaction terminates, and rotates thionyl chloride, generates first containing benzene
Acyl chlorides resin balls；
(5) preparation of the hydrogen bonds to the resin of receptor
Benzoyl resin balls will be contained first to be swollen with chloroform, p-phenylenediamine is added and reacted, wherein tree containing chlorobenzoyl chloride
The mass ratio of fat ball, chloroform and p-phenylenediamine is 1:0.5:(0.5~0.8) reacts 3~5h at 30~40 DEG C, after filtering
Washing, drying is to get hydrogen bonds to the macroreticular resin of receptor.
4. high stability hydrogen bonds as claimed in claim 2 are to the synthetic method of receptor macroporous absorbent resin, it is characterised in that：
The polystyrene resin macroreticular resin ball degree of cross linking of synthesis is 6~10%.
5. high stability hydrogen bonds as claimed in claim 3 are to the synthetic method of receptor macroporous absorbent resin, it is characterised in that：
After the step (1) stops reaction, after resin balls after cooling are discharged, 90 DEG C or more hot water wash, with 5-10 times of resin volume
After dimethoxym ethane extraction, washing, boiling, 80~90 DEG C of dry 10h or more obtain polystyrene resin macroreticular resin ball.
6. high stability hydrogen bonds as claimed in claim 3 are to the synthetic method of receptor macroporous absorbent resin, it is characterised in that：
In the water phase of step S1 synthetic polystyrene resin macroreticular resin balls, gelatin concentration is 0.5~2%, magnesium sulfate concentration 10%.
7. high stability hydrogen bonds as claimed in claim 3 are to the synthetic method of receptor macroporous absorbent resin, it is characterised in that：
The step (4) rotates thionyl chloride at 70~85 DEG C after reaction, generates resin balls containing chlorobenzoyl chloride.
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| CN111111791A (en) * | 2020-01-06 | 2020-05-08 | 凯瑞环保科技股份有限公司 | Methanesulfonic acid type cation exchange resin and preparation method thereof |
| CN111530432B (en) * | 2020-05-07 | 2022-06-14 | 西安蓝深新材料科技有限公司 | Preparation method of adsorbing material for blood perfusion |
| CN111533946A (en) * | 2020-05-19 | 2020-08-14 | 陕西蓝深特种树脂有限公司 | Hydrophilic polystyrene macroporous resin for streptomycin sulfate extraction and synthesis method thereof |
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