CN109929215A - A kind of phenolic aldehyde-polyacrylic mutually passes through high mechanical strength anion exchange resin of structure and preparation method thereof - Google Patents
A kind of phenolic aldehyde-polyacrylic mutually passes through high mechanical strength anion exchange resin of structure and preparation method thereof Download PDFInfo
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- CN109929215A CN109929215A CN201910226501.4A CN201910226501A CN109929215A CN 109929215 A CN109929215 A CN 109929215A CN 201910226501 A CN201910226501 A CN 201910226501A CN 109929215 A CN109929215 A CN 109929215A
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- Prior art keywords
- resin
- anion exchange
- exchange resin
- polyacrylic
- aldehyde
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- 239000003957 anion exchange resin Substances 0.000 title claims abstract description 64
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 114
- 229920005989 resin Polymers 0.000 claims abstract description 114
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 24
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 24
- -1 aldehyde compound Chemical class 0.000 claims abstract description 22
- 150000002989 phenols Chemical class 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000005349 anion exchange Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 12
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000010775 animal oil Substances 0.000 claims description 7
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 7
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 7
- 239000008158 vegetable oil Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 150000001896 cresols Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 3
- 150000004996 alkyl benzenes Chemical group 0.000 claims 2
- 125000005526 alkyl sulfate group Chemical group 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 150000004665 fatty acids Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 1
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 20
- 235000019441 ethanol Nutrition 0.000 description 19
- 230000035484 reaction time Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 208000012826 adjustment disease Diseases 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000008051 alkyl sulfates Chemical group 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PCNMALATRPXTKX-UHFFFAOYSA-N 1,4-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CCC(C)(O)C=C1 PCNMALATRPXTKX-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- SIKFEKGWQGBLRP-UHFFFAOYSA-N tert-butylbenzene;phenol Chemical compound OC1=CC=CC=C1.CC(C)(C)C1=CC=CC=C1 SIKFEKGWQGBLRP-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to resin material fields, and in particular to a kind of phenolic aldehyde-polyacrylic mutually passes through high mechanical strength anion exchange resin of structure and preparation method thereof.Wherein, preparation method is the following steps are included: phenolic compound, aldehyde compound and polyacrylic acid series anion exchange resin are uniformly mixed by (1)；(2) resin in the mixed liquor that step (1) obtains is isolated, after being mixed with dispersion, surfactant and acid or basic catalyst is added, is reacted at 35 ~ 105 DEG C；(3) resin that step (2) obtains is cleaned to neutrality, then is mixed with dispersion, basic catalyst is added, is reacted at 35 ~ 105 DEG C, to after the reaction was completed, isolate resin, cleaning to neutrality to get.Resin mechanical strength prepared by the present invention significantly improves, and rate of small round spheres can reach 99.9% after mill, and the resin has biggish strong alkali anion exchange capacity, can be used for the removal of anionic pollutant in actual waste water.
Description
Technical field
The invention belongs to resin material fields, and in particular to a kind of height that phenolic aldehyde-polyacrylic mutually passes through structure is mechanical strong
Spend anion exchange resin and preparation method thereof.
Background technique
Resin material is used extensively because its structure is controllable, adsorption capacity is high, selectivity is strong and the advantages such as easy desorption and regeneration
In water process.Polyacrylic resin and polystyrene resin are two resinoids being most widely used at present, but for parent
Aqueous stronger organic pollutant, polyacrylic based resin are better than polystyrene resin in absorption and regenerability.It is magnetic
The further exploitation of polyacrylic resin, the exchange of the magnetic acrylic acid series strongly basic anion as disclosed in patent CN101781437A are micro-
Pelletized resin, which makes to be easier to be separated in practical water process because having magnetism, thus in water process
Full-mixing type contact chamber technology generations are realized in technique for fixed-bed process, and then reduce water process operating cost.The resinoid energy
Organic matter in water body is effectively enough removed by ion exchange, the anion such as disinfection by-products and nitrate, sulfate radical,
So that it also has relatively broad application in drinking water treatment.
But either magnetic or nonmagnetic polyacrylic resin, the synthesis of the resinoid are needed using acrylic acid
Ester or glycidyl acrylate are as monomer, to cause the resin mechanical strength after synthesis poor, so that it is in water process
The resin suspended particulate for contacting with each other and generating 5-10 μm in friction process, leads to the secondary pollution of resin loss and water body.Mesh
Before, some researchers are such as adjusted and are handed over using different synthetic method and technique to improve the mechanical strength of polyacrylic resin
Join agent type and content, optimize the proportion of monomer and change experiment condition etc., but the mechanical strength of polyacrylic resin improves simultaneously
It is unobvious.Although some researchers by by inorganic nanoparticles introduce polyacrylic resin particle to change its mechanical strength,
Magnetic-particle is introduced into polyacrylic resin using in-situ method as disclosed in patent CN107754867A, it is then even using silane
Join agent coated magnetic polyacrylic resin, obtains the higher magnetic polyacrylic acid resin of mechanical strength, but this method synthesizes
Resin afterwards can also have the obscission of inorganic magnetic particle to a certain degree, thus after influencing processing in water treatment procedure
Water quality.In addition, patent CN1470541A and patent CN1050882A are disclosed and are used cation exchange resin as catalyst
The method for preparing phenolic resinoid, but the height machinery of structure is mutually passed through by force with a kind of phenolic aldehyde polyacrylic disclosed in this patent
It spends anion exchange resin and preparation method is different.
Summary of the invention
The height for mutually passing through structure the purpose of the present invention is on the basis of existing technology, providing a kind of phenolic aldehyde-polyacrylic
Mechanical strength anion exchange resin.
It is a further object of the present invention to provide a kind of above-mentioned phenolic aldehyde-polyacrylic mutually pass through the high mechanical strength yin of structure from
The preparation method of sub-exchange resin.
Technical scheme is as follows:
A kind of phenolic aldehyde-polyacrylic mutually passes through the high mechanical strength anion exchange resin of structure, it is made of following steps
:
(1) phenolic compound, aldehyde compound and polyacrylic acid series anion exchange resin are uniformly mixed；
(2) resin in the mixed liquor that step (1) obtains is isolated, after mixing with dispersion, surfactant and acidity is added
Or basic catalyst, it is reacted at 35 ~ 105 DEG C；
(3) resin that step (2) obtains is cleaned to neutrality, then is mixed with dispersion, basic catalyst is added, at 35 ~ 105 DEG C
Reacted, to after the reaction was completed, isolate resin, cleaning to neutrality to get.
In a preferred embodiment, resin provided by the invention tests (national standard GB/T 12598- by rate of small round spheres after mill
2001) rate of small round spheres is 80.0 ~ 99.9% after, grinding；Exchange capacity is 2.5 ~ 4.8 mmol/g；Moisture content is 30 ~ 85%.
A kind of phenolic aldehyde-polyacrylic mutually passes through the preparation method of the high mechanical strength anion exchange resin of structure, it is wrapped
Include following steps:
(1) phenolic compound, aldehyde compound and polyacrylic acid series anion exchange resin are uniformly mixed；
(2) resin in the mixed liquor that step (1) obtains is isolated, after mixing with dispersion, surfactant and acidity is added
Or basic catalyst, it is reacted at 35 ~ 105 DEG C；
(3) resin that step (2) obtains is cleaned to neutrality, then is mixed with dispersion, basic catalyst is added, at 35 ~ 105 DEG C
Reacted, to after the reaction was completed, isolate resin, cleaning to neutrality to get.
In a preferred embodiment, in step (1), the quality of polyacrylic acid series anion exchange resin and phenols chemical combination
The ratio of object and aldehyde compound total volume is 1:2 ~ 1:65g/mL；In the case where not influencing effect of the present invention, preferably 1:5 ~
1:45g/mL；Further preferably 1:6 ~ 1:25g/mL.
In a kind of more preferable scheme, in step (1), the volume ratio of phenolic compound and aldehyde compound be 1:0.3 ~
1:8；Preferably 1:0.5 ~ 5.5；Further preferably 1:1.5 ~ 3.5.
In step (1), the phenolic compound referred to is phenol, resorcinol, tertiary butyl phenol, cresols, xylenol to the present invention
Or one or more of bisphenol-A.For example, phenol, resorcinol, o-tert-butylphenol, p-tert-butylphenol, tert-butyl benzene
Phenol, ortho-methyl phenol, p-methyl phenol, m-methyl phenol, 2,3- xylenol, 2,4- xylenol, 2,5- dimethyl
Phenol or bisphenol-A.
The polyacrylic acid series anion exchange resin that the present invention uses is polyacrylic strong basic anion-exchange resin, example
Such as, D213 (in domestic polyacrylic anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.).Further
, aldehyde compound can with but be not limited to, one or more of formaldehyde, paraformaldehyde, acetaldehyde or furfural.
In a preferred embodiment, in step (2), the quality of surfactant is polyacrylic anion exchange tree
The 0.01 of lipid amount ~ 10.00 ‰；It can be more preferably 0.05 ~ 1.00%.For example, in step (2), the surface that refers to
Activating agent is one or more of alkylbenzene sulfonate, secondary alkyl sulfate, fatty acid salt, aliphatic ester or enuatrol.Its
In, used alkylbenzene sulfonate is not limited to sodium alkyl benzene sulfonate, for example, neopelex, used secondary
Alkyl sulfate is not limited to Teepol, and used fatty acid salt is not limited to sodium soap, used fat
Acid esters is not limited to fatty glyceride.
In a preferred embodiment, in step (2), acidic catalyst is one of hydrochloric acid, sulfuric acid, nitric acid or oxalic acid
Or it is several.
Further, in step (2), surfactant and acid or basic catalyst is added, is carried out at 35 ~ 105 DEG C
The time of reaction is 0.5 ~ 10 hour.
In a kind of more preferable scheme, the quality of acidic catalyst and the mass ratio of polyacrylic acid series anion exchange resin
For 1:0.2 ~ 1:90；Preferably 1:0.5 ~ 1:10.5；More preferably 1:2.0 ~ 1:5.5.
Further, the mass fraction of acidic catalyst is 5.0 ~ 37.0%；Preferably 20.0 ~ 37.0%.
In a preferred embodiment, in step (2) and step (3), basic catalyst is ammonium hydroxide, sodium hydroxide, hydrogen-oxygen
Change one or more of potassium, calcium hydroxide, diethylenetriamine, triethylene tetramine, tetraethylenepentamine or ethylenediamine.
In a kind of more preferable scheme, the quality of basic catalyst and the mass ratio of polyacrylic acid series anion exchange resin
For 1:0.2 ~ 1:50；Preferably 1:0.5 ~ 1:10.5；More preferably 1:2.0 ~ 1:5.5.
Further, the mass fraction of acidic catalyst is 5.0 ~ 40.0%；Preferably 5.0 ~ 20.0%.
In step (2) and step (3), the dispersed phase that the present invention uses is atoleine, diethyl phthalate, plant
One or more of object oil or animal oil.
Further, in step (3), basic catalyst is added, is 0.5 ~ 10 in the time that 35 ~ 105 DEG C are reacted
Hour.
Using technical solution of the present invention, advantage is as follows:
The present invention provides high mechanical strength anion exchange resin and its preparations that a kind of phenolic aldehyde-polyacrylic mutually passes through structure
Method, by rate of small round spheres test (national standard GB/T 12598-2001) after mill, rate of small round spheres is 80.0 ~ 99.9% after mill；Exchange is held
Amount is 2.5 ~ 4.8 mmol/g；Moisture content is 30 ~ 85%.
Rate of small round spheres country testing standard after being ground by resin, phenolic aldehyde-polyacrylic of the method according to the invention preparation
The resin mechanical strength for mutually passing through structure is significantly improved, and rate of small round spheres can reach 90% or more after resin mill, is higher than tradition
Acrylic acid type anion exchange resin (rate of small round spheres is 55.0 ~ 75.0% after mill) and phenolic resin, for example, patent CN1470541A
With phenolic resin of the cation exchange resin as catalyst preparation is used disclosed in patent CN1050882A.In addition, synthesis
Resin exchange capacity afterwards is not affected.Resin prepared by the present invention, be crushed in water treatment procedure it is less, can be long-term
It is recycled, to reduce cost of water treatment.
Specific embodiment
The high mechanical strength anion exchange of structure is mutually passed through to phenolic aldehyde-polyacrylic of the invention by following embodiment
Resin is further described, but these embodiments do not form any restrictions to the present invention.
Embodiment 1:
20.0mL phenol and 36.5mL formalin are mixed, 10.0g anion exchange resin D213 (China is added thereto
Produce polyacrylic acid series anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.), uniform stirring 1.0h at room temperature,
After being drained after resin in mixed solution is pulled out, resin is transferred in the flask equipped with 50 mL atoleines, into flask
The hydrochloric acid that 0.010g enuatrol and 5.0mL mass fraction are 37.0% is added, adjustment reaction temperature is 80 DEG C, and the reaction time is
1.0h.After reaction, resin is separated with mixed solution, is cleaned resin to neutrality, then by resin using first alcohol and water
It is transferred in new 50mL atoleine, the ammonia spirit that 5mL mass fraction is 37.5% is added thereto, adjusts reaction temperature
To 80 DEG C, reaction time 1.0h.After the reaction was completed, resin is cleaned to neutrality using first alcohol and water.Circle after being ground by resin
Ball rate country testing standard, rate of small round spheres is after the anion exchange resin that phenolic aldehyde-polyacrylic after synthesis mutually passes through structure is ground
99.9%, exchange capacity is 3.8 mmol/g, moisture content 45%.
Embodiment 2:
20.0mL phenol and 49.5mL paraformaldehyde solution are mixed, be added thereto 15.0g anion exchange resin D213 (in
Domestic polyacrylic acid series anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.), uniform stirring at room temperature
Resin after draining after pulling the resin in mixed solution out, is transferred to the burning equipped with 50 mL diethyl phthalates by 1.0h
In bottle, the sulfuric acid that 0.015g neopelex and 7.5mL mass fraction are 35.0%, adjustment reaction are added into flask
Temperature is 105 DEG C, reaction time 0.5h.After reaction, resin is separated with mixed solution, using second alcohol and water by resin
Then resin is transferred in new 50mL diethyl phthalate to neutrality, 4.0mL mass fraction is added thereto by cleaning
For 40.0% sodium hydroxide solution, reaction temperature is adjusted to 85 DEG C, reaction time 1.0h.After the reaction was completed, using ethyl alcohol and
Water cleans resin to neutrality.Rate of small round spheres country testing standard after being ground by resin, phenolic aldehyde-polyacrylic after synthesis mutually pass through
Rate of small round spheres is 98.1% after the anion exchange resin mill of structure, and exchange capacity is 4.0 mmol/g, moisture content 50%.
Embodiment 3:
20.0mL phenol and 55.5mL acetaldehyde solution are mixed, be added thereto 8.0g anion exchange resin D213 (in it is domestic
Polyacrylic acid series anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.), uniform stirring 1.0h, is incited somebody to action at room temperature
After resin in mixed solution drains after pulling out, resin is transferred in the flask equipped with 50 mL vegetable oil, is added into flask
The nitric acid that 0.001g Teepol and 3.5mL mass fraction are 25.0%, adjustment reaction temperature is 90 DEG C, and the reaction time is
5.0h.After reaction, resin is separated with mixed solution, is cleaned resin to neutrality, then by resin using second alcohol and water
It is transferred in new 50mL vegetable oil, the potassium hydroxide solution that 2.5mL mass fraction is 10.0%, adjustment reaction is added thereto
Temperature is to 90 DEG C, reaction time 10.5h.After the reaction was completed, resin is cleaned to neutrality using second alcohol and water.It is ground by resin
Rate of small round spheres country testing standard afterwards, ball after the anion exchange resin that phenolic aldehyde-polyacrylic after synthesis mutually passes through structure is ground
Rate is 96.8%, and exchange capacity is 4.2 mmol/g, moisture content 62%.
Embodiment 4:
20.0mL phenol and 82.1mL furfuryl aldehyde solution are mixed, be added thereto 4.5g anion exchange resin D213 (in it is domestic
Polyacrylic acid series anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.), uniform stirring 1.0h, is incited somebody to action at room temperature
After resin in mixed solution drains after pulling out, resin is transferred in the flask equipped with 50 mL animal oil, is added into flask
The oxalic acid that 0.023g fatty glyceride and 1.5mL mass fraction are 30.0%, adjustment reaction temperature is 70 DEG C, and the reaction time is
10.5h.After reaction, resin is separated with mixed solution, is cleaned resin to neutrality, then by resin using first alcohol and water
It is transferred in new 50mL animal oil, the calcium hydroxide solution that 3.5mL mass fraction is 15.0%, adjustment reaction is added thereto
Device temperature is to 65 DEG C, reaction time 3.5h.After the reaction was completed, resin is cleaned to neutrality using first alcohol and water.Pass through resin
Rate of small round spheres country testing standard after mill, circle after the anion exchange resin that phenolic aldehyde-polyacrylic after synthesis mutually passes through structure is ground
Ball rate is 93.4%, and exchange capacity is 4.8 mmol/g, moisture content 85%.
Embodiment 5:
20.0mL resorcinol and 110.0mL formalin are mixed, be added thereto 3.0g anion exchange resin D213 (in
Domestic polyacrylic acid series anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.), uniform stirring at room temperature
After draining after pulling the resin in mixed solution out, resin is transferred in the flask equipped with 50 mL atoleines by 1.0h, to
The ammonium hydroxide that 0.002g enuatrol and 5.0mL mass fraction are 20.5% is added in flask, adjustment reaction temperature is 80 DEG C, when reaction
Between be 5.5h.After reaction, resin is separated with mixed solution, resin is cleaned to neutrality using first alcohol and water, then will
Resin is transferred in new 50mL atoleine, and the ammonia spirit that 2.5mL mass fraction is 30.0% is added thereto, and adjustment is anti-
Answer temperature to 35 DEG C, reaction time 0.5h.After the reaction was completed, resin is cleaned to neutrality using first alcohol and water.Pass through resin
Rate of small round spheres country testing standard after mill, circle after the anion exchange resin that phenolic aldehyde-polyacrylic after synthesis mutually passes through structure is ground
Ball rate is 90.5%, and exchange capacity is 4.6 mmol/g；Moisture content is 82%.
Embodiment 6:
20.0mL o-tert-butylphenol and 25.5mL formalin are mixed, 2.0g anion exchange resin D213 is added thereto
(in domestic polyacrylic anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.), at room temperature uniform stirring
After draining after pulling the resin in mixed solution out, resin is transferred in the flask equipped with 50 mL atoleines by 1.0h, to
The hydrochloric acid that 0.003g neopelex and 0.5mL mass fraction are 5.0% is added in flask, adjustment reaction temperature is 70
DEG C, reaction time 8.5h.After reaction, resin is separated with mixed solution, is cleaned resin into using second alcohol and water
Property, then resin is transferred in new 50mL diethyl phthalate, it is 5.0% that 1.0mL mass fraction is added thereto
Sodium hydroxide solution, adjustment reaction temperature is to 105 DEG C, reaction time 6.0h.After the reaction was completed, using first alcohol and water by resin
It cleans to neutrality.Rate of small round spheres country testing standard after being ground by resin, phenolic aldehyde-polyacrylic after synthesis mutually pass through the yin of structure
Rate of small round spheres is 90.5% after ion exchange resin mill, and exchange capacity is 4.2 mmol/g；Moisture content is 75%.
Embodiment 7:
20.0mL p-methyl phenol and 10.0mL formalin are mixed, 1.0g anion exchange resin D213 is added thereto
(in domestic polyacrylic anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.), at room temperature uniform stirring
Resin after draining after pulling the resin in mixed solution out, is transferred to the burning equipped with 50 mL diethyl phthalates by 1.0h
In bottle, the sodium hydroxide that 0.001g Teepol and 0.5mL mass fraction are 20.0%, adjustment reaction are added into flask
Temperature is 35 DEG C, reaction time 4.5h.After reaction, resin is separated with mixed solution, using second alcohol and water by resin
Then resin is transferred in new 50mL atoleine, it is 35.5% that 0.5mL mass fraction is added thereto by cleaning to neutrality
Potassium hydroxide solution, adjustment reaction temperature is to 80 DEG C, reaction time 3.5h.After the reaction was completed, it will be set using second alcohol and water
Rouge is cleaned to neutrality.Rate of small round spheres country testing standard after being ground by resin, phenolic aldehyde-polyacrylic after synthesis mutually pass through structure
Rate of small round spheres is 92.5% after anion exchange resin mill, and exchange capacity is 4.3 mmol/g；Moisture content is 84%.
Embodiment 8:
By 20.0mL 2,10.0g anion exchange resin is added in 4- xylenol and the mixing of 40.5mL formalin thereto
D213 (in domestic polyacrylic anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.), at room temperature uniformly
1.0h is stirred, after draining after the resin in mixed solution is pulled out, resin is transferred to the flask equipped with 50 mL atoleines
In, the hydrochloric acid that 0.010g fatty glyceride and 7.5mL mass fraction are 10.0% is added into flask, adjustment reaction temperature is
75 DEG C, reaction time 7.5h.After reaction, resin is separated with mixed solution, using first alcohol and water by resin clean to
Then resin is transferred in new 50mL vegetable oil by neutrality, four ethylene that 8.0mL mass fraction is 25.5% are added thereto
Five amine aqueous solutions, adjustment reaction temperature is to 55 DEG C, reaction time 0.5h.After the reaction was completed, resin is cleaned using second alcohol and water
To neutrality.Rate of small round spheres country testing standard after being ground by resin, phenolic aldehyde-polyacrylic after synthesis mutually pass through the anion of structure
Rate of small round spheres is 95.6% after exchanger resin mill, and exchange capacity is 2.8 mmol/g；Moisture content is 80%.
Embodiment 9:
20.0mL bisphenol-A and 45.5mL formalin are mixed, be added thereto 9.5g anion exchange resin D213 (in it is domestic
Polyacrylic acid series anion exchange resin D213, Jiangsu Jin Kai resin Chemical Co., Ltd.), uniform stirring 1.0h, is incited somebody to action at room temperature
After resin in mixed solution drains after pulling out, resin is transferred in the flask equipped with 50 mL vegetable oil, is added into flask
The nitric acid that 0.009g enuatrol and 8.5mL mass fraction are 35.0%, adjustment reaction temperature are 90 DEG C, reaction time 3.5h.Instead
After answering, resin is separated with mixed solution, resin is cleaned to neutrality using second alcohol and water, is then transferred to resin newly
50mL vegetable oil in, thereto be added 6.5mL mass fraction be 25.5% ammonia spirit, adjust reaction temperature to 90 DEG C, instead
It is 6.5h between seasonable.After the reaction was completed, resin is cleaned to neutrality using second alcohol and water.Rate of small round spheres country surveys after being ground by resin
Test-object is quasi-, and rate of small round spheres is 98.2% after the anion exchange resin that phenolic aldehyde-polyacrylic after synthesis mutually passes through structure is ground, exchange
Capacity is 2.5 mmol/g, moisture content 35%.
Embodiment 10:
20.0mL resorcinol and 35.5mL acetaldehyde solution are mixed, 8.5g anion exchange resin D213, room are added thereto
The lower uniform stirring 1.0h of temperature, after draining after the resin in mixed solution is pulled out, resin is transferred to equipped with 50 mL animal oil
In flask, the sulfuric acid that 0.007g neopelex and 5.0mL mass fraction are 30.0% is added into flask, adjustment is anti-
Answering temperature is 70 DEG C, reaction time 3.5h.After reaction, resin is separated with mixed solution, will be set using second alcohol and water
Rouge is cleaned to neutrality, is then transferred to resin in new 50mL animal oil, and it is 15.5% that 5.5mL mass fraction is added thereto
Sodium hydroxide solution, adjustment reaction temperature is to 60 DEG C, reaction time 2.5h.After the reaction was completed, it will be set using second alcohol and water
Rouge is cleaned to neutrality.Rate of small round spheres country testing standard after being ground by resin, phenolic aldehyde-polyacrylic after synthesis mutually pass through structure
Rate of small round spheres is 97.8% after anion exchange resin mill, and exchange capacity is 2.7 mmol/g, moisture content 30%.
Claims (10)
1. the high mechanical strength anion exchange resin that a kind of phenolic aldehyde-polyacrylic mutually passes through structure, which is characterized in that it be by
Made of following steps:
(1) phenolic compound, aldehyde compound and polyacrylic acid series anion exchange resin are uniformly mixed；
(2) resin in the mixed liquor that step (1) obtains is isolated, after mixing with dispersion, surfactant and acidity is added
Or basic catalyst, it is reacted at 35 ~ 105 DEG C；
(3) resin that step (2) obtains is cleaned to neutrality, then is mixed with dispersion, basic catalyst is added, at 35 ~ 105 DEG C
Reacted, to after the reaction was completed, isolate resin to get.
2. phenolic aldehyde-polyacrylic according to claim 1 mutually passes through the high mechanical strength anion exchange resin of structure,
It is characterized in that, rate of small round spheres is 80.0 ~ 99.9% after the resin mill；Exchange capacity is 2.5 ~ 4.8 mmol/g；Moisture content be 30 ~
85%。
3. phenolic aldehyde-polyacrylic according to claim 1 mutually passes through the high mechanical strength anion exchange resin of structure,
It is characterized in that, in step (1), the quality and phenolic compound and aldehyde compound of polyacrylic acid series anion exchange resin are total
The ratio of volume is 1:2 ~ 1:65g/mL；Preferably 1:5 ~ 1:45g/mL；More preferably 1:6 ~ 1:25g/mL；Phenolic compound and aldehyde
The volume ratio of class compound is 1:0.3 ~ 1:8；Preferably 1:0.5 ~ 5.5；More preferably 1:1.5 ~ 3.5.
4. phenolic aldehyde-polyacrylic according to claim 3 mutually passes through the high mechanical strength anion exchange resin of structure,
It is characterized in that, in step (1), the phenolic compound is phenol, resorcinol, tertiary butyl phenol, cresols, xylenol or bisphenol-A
One or more of；The aldehyde compound is one or more of formaldehyde, paraformaldehyde, acetaldehyde or furfural.
5. the high mechanical strength anion exchange tree that phenolic aldehyde-polyacrylic according to claim 3 or 4 mutually passes through structure
Rouge, which is characterized in that in step (2), the quality of the surfactant is the polyacrylic acid series anion exchange resin
The 0.01 of quality ~ 10.00 ‰；Preferably 0.05 ~ 1.00%.
6. phenolic aldehyde-polyacrylic according to claim 5 mutually passes through the high mechanical strength anion exchange resin of structure,
It is characterized in that, in step (2), the surfactant is alkylbenzene sulfonate, secondary alkyl sulfate, fatty acid salt, fat
One or more of acid esters or enuatrol；The acidic catalyst is one of hydrochloric acid, sulfuric acid, nitric acid or oxalic acid or several
Kind；The mass ratio of the quality of the acidic catalyst and the polyacrylic acid series anion exchange resin is 1:0.2 ~ 1:90；It is excellent
It is selected as 1:0.5 ~ 1:10.5；More preferably 1:2.0 ~ 1:5.5；The mass fraction of the acidic catalyst is 5.0 ~ 37.0%；It is excellent
It is selected as 20.0 ~ 37.0%.
7. phenolic aldehyde-polyacrylic according to claim 6 mutually passes through the high mechanical strength anion exchange resin of structure,
It is characterized in that, in step (2) and step (3), the basic catalyst is ammonium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide
One or more of calcium, diethylenetriamine, triethylene tetramine, tetraethylenepentamine or ethylenediamine；The matter of the basic catalyst
The mass ratio of amount and the polyacrylic acid series anion exchange resin is 1:0.2 ~ 1:50；Preferably 1:0.5 ~ 1:10.5；It is more excellent
It is selected as 1:2.0 ~ 1:5.5；The mass fraction of the acidic catalyst is 5.0 ~ 40.0%；Preferably 5.0 ~ 20.0%.
8. phenolic aldehyde-polyacrylic according to claim 1 mutually passes through the high mechanical strength anion exchange resin of structure,
Be characterized in that, in step (2) and step (3), the dispersed phase be atoleine, diethyl phthalate, vegetable oil or
One or more of animal oil.
9. a kind of phenolic aldehyde-polyacrylic described in claim 1 mutually passes through the high mechanical strength anion exchange resin of structure
Preparation method, which is characterized in that it the following steps are included:
(1) phenolic compound, aldehyde compound and polyacrylic acid series anion exchange resin are uniformly mixed；
(2) resin in the mixed liquor that step (1) obtains is isolated, after mixing with dispersion, surfactant and acidity is added
Or basic catalyst, it is reacted at 35 ~ 105 DEG C；
(3) resin that step (2) obtains is cleaned to neutrality, then is mixed with dispersion, basic catalyst is added, at 35 ~ 105 DEG C
Reacted, to after the reaction was completed, isolate resin, cleaning to neutrality to get.
10. phenolic aldehyde-polyacrylic according to claim 9 mutually passes through the high mechanical strength anion exchange resin of structure
Preparation method, which is characterized in that
In step (1), the quality of polyacrylic acid series anion exchange resin and phenolic compound and aldehyde compound total volume
Than for 1:2 ~ 1:65g/mL；Preferably 1:5 ~ 1:45g/mL；More preferably 1:6 ~ 1:25g/mL；Phenolic compound and aldehydes chemical combination
The volume ratio of object is 1:0.3 ~ 1:8；Preferably 1:0.5 ~ 5.5；More preferably 1:1.5 ~ 3.5；The phenolic compound be phenol,
One or more of resorcinol, tertiary butyl phenol, cresols, xylenol or bisphenol-A；The aldehyde compound is formaldehyde, poly first
One or more of aldehyde, acetaldehyde or furfural；
In step (2), the quality of the surfactant be the polyacrylic acid series anion exchange resin quality 0.01 ~
10.00 ‰；Preferably 0.05 ~ 1.00%；The surfactant is alkylbenzene sulfonate, secondary alkyl sulfate, fatty acid
One or more of salt, aliphatic ester or enuatrol；The acidic catalyst is one in hydrochloric acid, sulfuric acid, nitric acid or oxalic acid
Kind is several；The mass ratio of the quality of the acidic catalyst and the polyacrylic acid series anion exchange resin is 1:0.2 ~ 1:
90；Preferably 1:0.5 ~ 1:10.5；More preferably 1:2.0 ~ 1:5.5；The mass fraction of the acidic catalyst be 5.0 ~
37.0%；Preferably 20.0 ~ 37.0%；
In step (2) and step (3), the basic catalyst is ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, diethyl
One or more of alkene triamine, triethylene tetramine, tetraethylenepentamine or ethylenediamine；The quality of the basic catalyst with it is described
The mass ratio of polyacrylic acid series anion exchange resin is 1:0.2 ~ 1:50；Preferably 1:0.5 ~ 1:10.5；More preferably 1:2.0
~1:5.5；The mass fraction of the acidic catalyst is 5.0 ~ 40.0%；Preferably 5.0 ~ 20.0%；The dispersed phase is liquid
One or more of paraffin, diethyl phthalate, vegetable oil or animal oil.
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