CN106366221A - Preparation method for amino-functionalized macroporous styrene resin with large specific surface - Google Patents
Preparation method for amino-functionalized macroporous styrene resin with large specific surface Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 41
- 229920005989 resin Polymers 0.000 title claims abstract description 41
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 235000011150 stannous chloride Nutrition 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000003643 water by type Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 239000001117 sulphuric acid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006396 nitration reaction Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 30
- 239000007787 solid Substances 0.000 abstract description 17
- 239000011148 porous material Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 15
- 238000004900 laundering Methods 0.000 description 9
- 230000003213 activating effect Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 150000003941 n-butylamines Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005815 base catalysis Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000007040 multi-step synthesis reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method for amino-functionalized macroporous styrene resin with a large specific surface, belonging to the technical field of material science. According to the invention, an amino-functionalized macroporous styrene resin material is successfully prepared by using a one-step method; an amino group is immobilized on the skeleton of the hydrophobic macroporous styrene resin material (XAD-4); and the material with abundant pore structures, a large specific surface area and the unique hydrophobic and lipophilic skeleton substantially overcomes problems caused by scarcity of pore structures of traditional solid alkali and hydrophilicity of skeletons in the prior art, and the excellent acid and alkali resistance of the polymer skeleton improves the stability of the material in catalytic process. The preparation method provided by the invention is of important theoretical research significance and practical application value to development of novel highly-efficient renewable solid alkali materials.
Description
Technical field
The invention belongs to materials science field is and in particular to the macropore benzene second of a kind of Large ratio surface, amino functional
The preparation method of vinyl resin.
Background technology
Base catalysiss have important application as the important catalytic process of a class in the field such as petrochemical industry and fine chemistry industry
It is worth.Industrial common acid catalysiss process mainly using sodium hydroxide, potassium hydroxide etc. be catalyst.Although it has excellent
Catalytic performance, but it has number of disadvantages such as: corrosivity are strong, reclaims difficult, ambient pressure leading to during use etc.
Greatly limit its extensive application industrially.Recent years, substitute traditional base catalyst using solid base and be applied to multiclass
Base catalyzed reactions become Green Chemistry recent years and the hot issue of sustainable chemistry research.Compared with conventional base catalysis agent
Relatively, to have corrosivity little for solid base, easily reclaims, during use the advantages of environmental protection.Common solid base mainly includes by force
Deacidite, alkali metal oxide, basic zeolite molecular sieve etc., although they overcome the difficulty of homogeneous base catalyst
The shortcomings of separation, corrosivity are strong.But its catalysis activity ratio is relatively low, main reason is that its deficient pore structure is limited with aperture
Factor, disadvantages mentioned above leads to most active center to be embedded in catalytic process, and then greatly reduces in course of reaction
The degrees of exposure of catalytic active center.
Bigger serface is fixed at base catalysiss center, wide-aperture porous material will largely overcome conventional solid acid hole
The shortcoming of structure scarcity, aperture restriction etc., is conducive to for the catalytic efficiency improving material.Here it is noted that mesh
The solid base of front research mainly based on the solid-acid material of inorganic skeleton, and solid base exist another problem is that inorganic bone
The active center that the hydrophilic at Jia Yujian center is led to hydrolyzes, is passivated etc., has had a strong impact on the catalytic efficiency of solid alkali material
With regeneration capacity (journal of catalysis 2010,271,52-58).
Content of the invention
For the problem overcoming above-mentioned solid alkali material to exist, amino is fixed on hydrophobic phenylethylene macropore by the present invention
On resin material (xad-4) skeleton, the hydrophobic oleophilic oil skeleton of pore structure, big specific surface area and uniqueness that this material enriches is big
Overcome greatly conventional solid alkali pore structure scarcity, hydrophilic the led to problem of skeleton, the excellent acid and alkali-resistance of polymer backbone simultaneously
Performance improves the stability in its catalytic process.The present invention for develop new, efficiently renewable solid alkali material have
Important theoretical significance and actual application value.
One-step method of the present invention achieves the preparation of the macropore styrene resin material of amino functional, preparation method letter
Single, with low cost, overcome the shortcomings of step complexity in conventional solid base material preparation process, high cost, pore structure scarcity, with
When solve basic zeolite to bulky molecular catalysis aperture restricted problem.In addition the unique mesoporous organic backbone of this material overcomes no
Machine skeleton mesoporous solid base material resistance to acids and bases is poor, the shortcoming of the aspect such as active center passivation that hydrophilic skeleton is led to, significantly
Improve the catalytic performance during material base catalyzed reactions and regeneration capacity.
To achieve these goals, the present invention provides a kind of preparation side of the macropore styrene resin of amino functional
Method, comprises the steps:
A., under room temperature condition, xad-4 macroporous resin is scattered in nitrification in concentrated sulphuric acid and the nitration mixture of concentrated nitric acid, nitrifies temperature
For 0～10 DEG C, the nitrification time is 12～72 hours, then product is scattered in a large amount of deionized waters, and filtering and washing is to neutrality
After be dried；
B. step a product is scattered in concentrated hydrochloric acid and the mixed aqueous solution of stannous chloride, under room temperature, stirring 12～72 is little
When step a product is reduced, be dried after product washing, step a product and concentrated hydrochloric acid (mass fraction 35～38%), chlorination
The mass ratio of stannous is 1:10～40:1～5；
C. step b product is scattered in common fatty amine (n-butylamine, the n-amylamine such as 2-aminopropane. (mass ratio is in 1:10～50)
Deng) in, stirring under room temperature is activated for 12～72 hours, sucking filtration post-drying；Press aforesaid operations again and will dry product activation 1～3
Secondary, sucking filtration post-drying obtains the macropore styrene resin (xad-4-nh of bigger serface, amino functional2).
In step a, xad-4 macroporous resin is 1:5～30, xad-4 macroporous resin and concentrated sulphuric acid with the mass ratio of concentrated nitric acid
Mass ratio be 1:15～60；The mass fraction of concentrated sulphuric acid is 95～98%, and the mass fraction of concentrated nitric acid is 30～40%；
The specific surface area of the xad-4 macroporous resin chosen in the present invention is 1000m2/ g, average pore size about 15nm, average grain
Footpath is about 640 μm.Different from concentration of nitric acid according to the nitrification time, the specific surface area of step c products therefrom is in 580～800m2/
Between g, aperture concentrates on 10～30nm, and pore volume is 0.8～1.13cm3/g.
The amino center content of the macropore styrene resin of amino functional of present invention preparation and acid strength are in synthesis
During can be with modulation, amino center content is adjustable between 1.2～3.8mmol/g, and optimal synthetic ratio amino center contains
Measure as 2.8mmol/g, can be by modulation nitric acid content in building-up process, nitrification, recovery time to be realized with nitrifying temperature.With
The increase of amino content, the specific surface area of material, pore volume accordingly decline.
The present invention is successfully prepared the macropore styrene resin material of amino functional, one-step synthesis gram using one-step method
The shortcoming having taken traditional preparation ammonification mesoporous polymer material multistep synthesis aspect.The present invention with business-like xad-4 resin is
Primary raw material, sulphuric acid, nitric acid nitration mixture make xad-4 resin nitrify, then through reduction, realize phenylethylene xad- under temperate condition
The ammonification of 4 resins, keeps the nano-porous structure that material enriches simultaneously, and then prepares the macromolecular scaffold with bigger serface
Catalyzed by solid base material.This is industrial extensive, low cost, simply prepare new, efficient catalyzed by solid base material and sharp
Substitute homogeneous base catalyst with it and there is important actual application value.
It is that above and other objects of the present invention, feature and advantage can be become apparent, below especially exemplified by preferred embodiment,
It is described in detail below.
Specific embodiment
Example is set forth below, the synthetic method of the macroporous resin catalysis material of amino functional in the present invention is described.
Embodiment 1:
Under room temperature condition, take 1.0 grams of xad-4 macroporous resins (sigma-aldrich company purchases, white spherical particle)
It is scattered in 30 grams of concentrated nitric acid solutions and 60 grams of concentrated sulfuric acid solutions, the mass fraction of concentrated nitric acid is 35%, and the quality of concentrated sulphuric acid is divided
Number is 98%, nitrifies 72 hours, then product is scattered in a large amount of deionized waters under the conditions of 10 DEG C, after filtering and washing to neutrality
It is dried, products therefrom quality is 1.5 grams.
The product (1.5 grams) being dried is scattered in mixing of 40 grams of concentrated hydrochloric acid (mass fraction 37.5%) and 5 grams of stannous chlorides
Under room temperature in Heshui solution, stirring reduction 72 hours, are dried after product massive laundering, and products therefrom quality is 1.46 grams.
1.46 grams of above-mentioned product is scattered in stirring under room temperature in 30 milliliters of n-butylamines activated within 72 hours, sucking filtration after bake
Do, then drying product is scattered in stirring under room temperature in 30 milliliters of n-butylamines and activated for 72 hours, sucking filtration post-drying is produced
The specific surface area of thing is 580m2/ g, pore volume reaches 0.8cm3/ g, aperture is 15.3 nanometers, and amino center content is 3.8mmol/g
(this result is obtained by elementary analysiss test).
Embodiment 2:
Take that 1.0 grams of xad-4 macroporous resins are scattered in 5 grams of concentrated nitric acid solutions (mass fraction be 35%) and 15 grams of concentrated sulphuric acids are molten
In liquid (mass fraction is 98%), nitrify 12 hours under the conditions of 0 DEG C, then product is scattered in a large amount of deionized waters, sucking filtration
Wash to neutrality and be dried, products therefrom quality is 1.53 grams.Then (quality is divided the product being dried to be scattered in 10 grams of concentrated hydrochloric acid
Number 37.5%) and the mixed aqueous solution of 1 gram of stannous chloride in room temperature reduce 12 hours, after product massive laundering be dried, gained produce
Amount of substance is 1.54 grams.It is then dispersed in 30 milliliters of n-butylamines activating 2 times (operating procedure is with embodiment 1), sucking filtration post-drying
The specific surface area obtaining product is 800m2/ g, pore volume reaches 1.13cm3/ g, aperture is 25.2 nanometers, amino center content
For 1.2mmol/g.
Embodiment 3:
1.0 grams of xad-4 macroporous resins are taken to be scattered in 15 grams of salpeter solutions (mass fraction is 35%) and 40 grams of sulfuric acid solutions
In (mass fraction is 98%), nitrifies 50 hours under the conditions of 5 DEG C, then product is scattered in a large amount of deionized waters, sucking filtration is washed
Wash to neutrality and be dried, products therefrom quality is 1.61 grams.Then the product being dried is scattered in 20 grams of concentrated hydrochloric acid (mass fractions
37.5%) in the mixed aqueous solution of and 2.5 grams of stannous chlorides, room temperature reduces 56 hours, is dried after product massive laundering, and gained produces
Amount of substance is 1.52 grams.It is then dispersed in activating 2 times in 30 milliliters of n-amylamines, sucking filtration post-drying obtains the specific surface of product
Amass as 710m2/ g, pore volume reaches 1.0cm3/ g, aperture is 20.2 nanometers, and amino center content is 2.8mmol/g.
Embodiment 4:
1.0 grams of xad-4 macroporous resins are taken to be scattered in 10 grams of salpeter solutions (mass fraction is 35%) and 30 grams of sulfuric acid solutions
In (mass fraction is 98%), nitrifies 72 hours under the conditions of 7 DEG C, then product is scattered in a large amount of deionized waters, sucking filtration is washed
Wash to neutrality and be dried, products therefrom quality is 1.55 grams.Then the product being dried is scattered in 20 grams of concentrated hydrochloric acid (mass fractions
37.5%) in the mixed aqueous solution of and 3 grams of stannous chlorides, room temperature reduces 48 hours, is dried, products therefrom after product massive laundering
Quality is 1.43 grams.It is then dispersed in activating 2 times in 30 milliliters of n-amylamines, sucking filtration post-drying obtains the specific surface area of product
For 630m2/ g, pore volume reaches 0.96cm3/ g, aperture is 19.4 nanometers, and amino center content is 3.0mmol/g.
Embodiment 5:
1.0 grams of xad-4 macroporous resins are taken to be scattered in 8 grams of salpeter solutions (mass fraction is 35%) and 27 grams of sulfuric acid solutions
In (mass fraction is 98%), nitrifies 36 hours under the conditions of 3 DEG C, then product is scattered in a large amount of deionized waters, sucking filtration is washed
Wash to neutrality and be dried, products therefrom quality is 1.55 grams.Then the product being dried is scattered in 18 grams of concentrated hydrochloric acid (mass fractions
37.5%) in the mixed aqueous solution of and 2.0 grams of stannous chlorides, room temperature reduces 40 hours, is dried after product massive laundering, and gained produces
Amount of substance is 1.32 grams.It is then dispersed in activating 2 times in 30 milliliters of n-amylamines, sucking filtration post-drying obtains the specific surface of product
Amass as 730m2/ g, pore volume reaches 1.05cm3/ g, aperture is 23.4 nanometers, and amino center content is 1.8mmol/g.
Embodiment 6:
1.0 grams of xad-4 macroporous resins are taken to be scattered in 22 grams of salpeter solutions (mass fraction is 35%) and 45 grams of sulfuric acid solutions
In (mass fraction is 98%), nitrifies 24 hours under the conditions of 2 DEG C, then product is scattered in a large amount of deionized waters, sucking filtration is washed
Wash to neutrality and be dried, products therefrom quality is 1.34 grams.Then the product being dried is scattered in 22 grams of concentrated hydrochloric acid (mass fractions
37.5%) in the mixed aqueous solution of and 1.6 grams of stannous chlorides, room temperature reduces 52 hours, is dried after product massive laundering, and gained produces
Amount of substance is 1.31 grams.It is then dispersed in activating 2 times in 30 milliliters of n-butylamines, sucking filtration post-drying obtains product.
Embodiment 7:
1.0 grams of xad-4 macroporous resins are taken to be scattered in 12 grams of salpeter solutions (mass fraction is 35%) and 22 grams of sulfuric acid solutions
In (mass fraction is 98%), nitrifies 16 hours under the conditions of 9 DEG C, then product is scattered in a large amount of deionized waters, sucking filtration is washed
Wash to neutrality and be dried, products therefrom quality is 1.46 grams.Then the product being dried is scattered in 18 grams of concentrated hydrochloric acid (mass fractions
37.5%) in the mixed aqueous solution of and 2.6 grams of stannous chlorides, room temperature reduces 68 hours, is dried after product massive laundering, and gained produces
Amount of substance is 1.42 grams.It is then dispersed in activating 2 times in 30 milliliters of n-butylamines, sucking filtration after bake dryed product.
Embodiment 8:
1.0 grams of xad-4 macroporous resins are taken to be scattered in 9 grams of salpeter solutions (mass fraction is 35%) and 21 grams of sulfuric acid solutions
In (mass fraction is 98%), nitrifies 14 hours under the conditions of 9 DEG C, then product is scattered in a large amount of deionized waters, sucking filtration is washed
Wash to neutrality and be dried, products therefrom quality is 1.28 grams.Then the product being dried is scattered in 15 grams of concentrated hydrochloric acid (mass fractions
37.5%) in the mixed aqueous solution of and 3.5 grams of stannous chlorides, room temperature reduces 15 hours, is dried after product massive laundering, and gained produces
Amount of substance is 1.26 grams.It is then dispersed in activating 2 times in 30 milliliters of n-butylamines, sucking filtration after bake dryed product.
Embodiment 9:
1.0 grams of xad-4 macroporous resins are taken to be scattered in 31 grams of salpeter solutions (mass fraction is 35%) and 58 grams of sulfuric acid solutions
In (mass fraction is 98%), nitrifies 56 hours under the conditions of 1 DEG C, then product is scattered in a large amount of deionized waters, sucking filtration is washed
Wash to neutrality and be dried, products therefrom quality is 1.35 grams.Then the product being dried is scattered in 23 grams of concentrated hydrochloric acid (mass fractions
37.5%) room temperature reductase 12 8 hours in the mixed aqueous solution of and 4.6 grams of stannous chlorides, are dried after product massive laundering, and gained produces
Amount of substance is 1.33 grams.It is then dispersed in activating 2 times in 30 milliliters of n-butylamines, sucking filtration after bake dryed product.
In sum, the present invention is successfully prepared the phenylethylene macroporous resin material of amino functional using a step nitrification process
Material, one-step synthesis overcome the shortcoming of tradition preparation ammonification mesoporous polymer material multistep synthesis aspect, simply effectively, low cost
Honest and clean；Unique hydrophobic framework overcome conventional solid alkali by hydrophilic led to active center be passivated the shortcomings of, this material
Invent the functionalization research in terms of base catalysiss for nano-porous polymer material and provide method.The amino content of material, ratio
Surface area can carry out modulation by controlling reaction condition.Material preparation method is simple, low cost, the macropore tree greatly enriching
The functionalization research of fat.
Large ratio surface that the present invention obtains, the macropore styrene resin of amino functional are in the promise Culture Revolution reaction of catalysis section
(1 mM of benzaldehyde, 1 mM of Cyanoacetyl-Cyacetazid, the macropore styrene resin of 0.05 gram of present invention preparation, anti-under the conditions of 60 degree
Answer 2 hours and terminate) excellent catalytic performance and reproducibility (providing in table 1) are provided, this is to industrial low cost development
New and effective mesoporous solid alkali is simultaneously applied to base catalysiss field and has important using value.
Although the present invention is disclosed above by preferred embodiment, but be not limited to the present invention, any know this skill
Skill person, without departing from the spirit and scope of the present invention, can make a little change and retouching, therefore protection scope of the present invention is worked as
It is defined depending on claims scope required for protection.
Table 1: the xad-4-nh of embodiment 1 gained2In section's promise Culture Revolution condensation reaction performance data
| Sample | Products collection efficiency (%) | |
| 1 | xad-4-nh2 | >99.5 |
| 2 | Xad-4-nh2 recycles 5 times | 98.8 |
Reaction equation is as follows:
Claims (5)
1. the preparation method of the macropore styrene resin of a kind of Large ratio surface, amino functional, its step is as follows:
A. under room temperature condition, xad-4 macroporous resin is scattered in nitrification in concentrated sulphuric acid and the nitration mixture of concentrated nitric acid, nitrification temperature is 0
～10 DEG C, the nitrification time is 12～72 hours, then product is scattered in a large amount of deionized waters, dry after filtering and washing to neutrality
Dry；
B. step a product is scattered in concentrated hydrochloric acid and the mixed aqueous solution of stannous chloride, under room temperature stirring 12～72 hours right
Step a product is reduced, and is dried after product washing；
C. step b product is scattered in 2-aminopropane., stirring under room temperature is activated for 12～72 hours, sucking filtration post-drying；Press again
Aforesaid operations will dry product activation 1～3 time, and sucking filtration post-drying obtains the macropore benzene second of bigger serface, amino functional
Vinyl resin.
2. the preparation method of the macropore styrene resin of a kind of Large ratio surface, amino functional as claimed in claim 1, its
It is characterised by: in step a, xad-4 macroporous resin is 1:5～30, xad-4 macroporous resin and concentrated sulphuric acid with the mass ratio of concentrated nitric acid
Mass ratio be 1:15～60；The mass fraction of concentrated sulphuric acid is 95～98%, and the mass fraction of concentrated nitric acid is 30～40%.
3. the preparation method of the macropore styrene resin of a kind of Large ratio surface, amino functional as claimed in claim 1, its
It is characterised by: in step b, step a product is 1:10～40:1～5 with the mass ratio of concentrated hydrochloric acid, stannous chloride；The matter of concentrated hydrochloric acid
Amount fraction 35～38%.
4. the preparation method of the macropore styrene resin of a kind of Large ratio surface, amino functional as claimed in claim 1, its
It is characterised by: in step c, step b product is 1:10～50 with the mass ratio of 2-aminopropane..
5. the preparation method of the macropore styrene resin of a kind of Large ratio surface, amino functional as claimed in claim 1, its
It is characterised by: in step c, 2-aminopropane. is n-butylamine or n-amylamine.
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Citations (4)
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|---|---|---|---|---|
| CN102259029A (en) * | 2010-05-24 | 2011-11-30 | 江苏圣奥化学科技有限公司 | Solid alkali catalyst |
| CN104437632A (en) * | 2014-11-03 | 2015-03-25 | 江苏大学 | Macro-porous acid-base dual-functional organic solid catalyst as well as preparation method and application thereof |
| CN105037602A (en) * | 2015-08-20 | 2015-11-11 | 天津博纳艾杰尔科技有限公司 | Surface phenolic hydroxyl modified resin and preparation method thereof |
| CN105153344A (en) * | 2015-10-23 | 2015-12-16 | 蓝星（成都）新材料有限公司 | Diethylamine anion exchange resin and preparation method thereof |
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2016
- 2016-08-07 CN CN201610639451.9A patent/CN106366221A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259029A (en) * | 2010-05-24 | 2011-11-30 | 江苏圣奥化学科技有限公司 | Solid alkali catalyst |
| CN104437632A (en) * | 2014-11-03 | 2015-03-25 | 江苏大学 | Macro-porous acid-base dual-functional organic solid catalyst as well as preparation method and application thereof |
| CN105037602A (en) * | 2015-08-20 | 2015-11-11 | 天津博纳艾杰尔科技有限公司 | Surface phenolic hydroxyl modified resin and preparation method thereof |
| CN105153344A (en) * | 2015-10-23 | 2015-12-16 | 蓝星（成都）新材料有限公司 | Diethylamine anion exchange resin and preparation method thereof |
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