CN105218724A - A kind of preparation method of strong-acid cation-exchange resin - Google Patents

Abstract

The invention discloses a kind of preparation method of strong-acid cation-exchange resin, comprise the steps: vinylbenzene, divinylbenzene, methenyl bromide, BDO, benzoyl peroxide to be mixed to get the first prefabricated material; Sodium lignosulfonate is sent in Reaktionsofen, heat up under nitrogen protection, insulation, cooling, grinding, add the chloro-2-propyl alcohol of 1,3-bis-, poly-alkylsiloxane, sodium hydroxide stirring, add hydrochloric acid and stir, filter, washing, dry and obtain the second prefabricated material; By water, polyvinyl alcohol, ethyl propenoate mixing, add methylene blue and stir, add the first prefabricated material and stir, it is swelling to add chloroform, add sulphuric acid soln, sulphur trioxide, the second prefabricated material stirring, boil off chloroform, cooling, adds water standing, remove water layer, washing, to neutral, add sodium hydroxide solution and stirs, filter, product washing is to neutral, and add water stirring, heating, insulation, filter, add dehydrated alcohol backflow, cooling, filter, washing, drying obtains strong-acid cation-exchange resin.

Description

A kind of preparation method of strong-acid cation-exchange resin

Technical field

The present invention relates to strong-acid cation-exchange resin technical field, particularly relate to a kind of preparation method of strong-acid cation-exchange resin.

Background technology

China has started produce and answer spent ion exchange resin since the 1950's.Through the development of over half a century, the Synthesis and applications technology of domestic conventional ion exchange resin is comparatively ripe, and level is with quite external.Along with oiler feed, tap water and electronic water etc. improve day by day to the purity requirement of ion-exchange water outlet, impel conventional ion exchange resin to produce and utilisation technology constantly perfect, expedited the emergence of many novel production technique simultaneously and continued to bring out.

Ion exchange resin is the reticular polymer compound of a class with active group.In its molecular structure, a part is the matrix skeleton of resin, and another part is the active group be made up of non diffusible ion and exchangable ion.Ion exchange resin has the functions such as exchange, selection, absorption and catalysis, and in recent years, water treatment spent ion exchange resin is from kind, structure or performance, all occurred very large change, and it is produced and application is also obtained for very large development.

Strong-acid cation-exchange resin not only can be used for the organic chemical reactionses such as etherificate, esterification, hydration, ether solution and hydrolysis, is also more and more widely used in pure water preparation field at present.The principal element of decision ion exchange resin performance is specific surface area and pore structure, and current pure water preparation Zeo-karb specific surface area, thermostability and ion-exchange speed can't meet the particular requirement of pure water preparation to strong-acid cation-exchange resin.

Summary of the invention

The present invention proposes a kind of preparation method of strong-acid cation-exchange resin, goods specific surface area is large, and Heat stability is good, ion-exchange speed is fast.

The preparation method of a kind of strong-acid cation-exchange resin that the present invention proposes, comprises the steps:

S1, vinylbenzene, divinylbenzene, methenyl bromide, BDO, benzoyl peroxide are uniformly mixed, whipping temp is 40-60 DEG C, obtains the first prefabricated material;

S2, sodium lignosulfonate is sent in Reaktionsofen, heat up under nitrogen protection, insulation, cooling, grinding, adds the chloro-2-propyl alcohol of 1,3-bis-, poly-alkylsiloxane, sodium hydroxide stirs, whipping temp is 80-95 DEG C, add hydrochloric acid to stir, filter, deionized water wash, dry, obtain the second prefabricated material;

S3, Jiang Shui, polyvinyl alcohol, ethyl propenoate mix, and add methylene blue and are stirred to dissolving completely, add the first prefabricated material, heat up and stir, obtain the 3rd prefabricated material;

S4, in the 3rd prefabricated material, add chloroform swelling, and add sulphuric acid soln, sulphur trioxide, the second prefabricated material, heat up and stir, boil off chloroform, be cooled to room temperature, add water standing, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, add sodium hydroxide solution stir in the 4th prefabricated material, filter, product washing is to neutral, and add water stirrings, heats, insulation, filters, refluxes, be cooled to room temperature under adding absolute ethyl alcohol and stirring state, filter, product washing is to neutral, dry, obtains strong-acid cation-exchange resin.

Preferably, in S1, the weight ratio of vinylbenzene, divinylbenzene and methenyl bromide is 20-50:2-8:0.1-0.4.

Preferably, in S2, the weight ratio of sodium lignosulfonate, 1,3-bis-chloro-2-propyl alcohol and poly-alkylsiloxane is 30-50:1-3:40-60.

Preferably, in S4, the weight ratio of sulphuric acid soln, sulphur trioxide and the second prefabricated material is 30-60:2-10:15-40; Wherein the concentration of sulphuric acid soln is 40-60wt%.

Preferably, in S1, by weight by 20-50 part vinylbenzene, 2-8 part divinylbenzene, 0.1-0.4 part methenyl bromide, 1-5 part 1,4-butyleneglycol, 0.1-0.8 part benzoyl peroxide stir, churning time is 15-40min, and whipping temp is 40-60 DEG C, obtains the first prefabricated material.

Preferably, in S2,30-50 part sodium lignosulfonate will be taken by weight and send in Reaktionsofen, under nitrogen protection, be warming up to 100-120 DEG C, insulation 20-50mmin, be warming up to 165-170 DEG C, insulation 15-30min, be cooled to 155-160 DEG C, insulation 10-20min, be warming up to 170-175 DEG C, insulation 20-30min, be cooled to room temperature, grinding, add 1-3 part 1, the chloro-2-propyl alcohol of 3-bis-, 40-60 part gathers alkylsiloxane, 10-15 part sodium hydroxide stirs, whipping temp is 80-95 DEG C, churning time is 20-50min, add the hydrochloric acid stirring 10-30min that 10-20 part concentration is 4-5mol/L, whipping temp is 45-55 DEG C, filter, add the hydrochloric acid stirring 5-15min that 20-40 part concentration is 5.5-6.32mol/L, whipping temp is 35-45 DEG C, filter, add the hydrochloric acid stirring 40-60min that 20-40 part concentration is 6.5-7mol/L, filter, adopt deionized water wash 2-5 time, send in 90-95 DEG C of baking oven and dry, obtain the second prefabricated material.

Preferably, in S3, by weight 20-30 part water, 1-4 part polyvinyl alcohol, 2-8 part ethyl propenoate are mixed, add 0.2-0.6 part methylene blue and be stirred to dissolving completely, add the prefabricated material of 10-16 part first, DEG C stirring 20-50h from room temperature to 40-50, be warming up to 60-69 DEG C and stir 15-40min, be warming up to 75-79 DEG C and stir 20-50min, be cooled to 68-72 DEG C and stir 5-15min, be warming up to 92-96 DEG C and stir 20-50min, be cooled to 50-55 DEG C and stir 50-100min, obtain the 3rd prefabricated material.

Preferably, in S4, the swelling 20-50min of 40-70 part chloroform is added by weight in the prefabricated material of 20-50 part the 3rd, add sulphuric acid soln, 2-10 part sulphur trioxide, the prefabricated material of 15-40 part second that 30-60 part concentration is 40-60wt%, DEG C stirring 20-50min from room temperature to 50-60, be increased to 64-68 DEG C and stir 40-60min, be warming up to 75-80 DEG C and stir 30-50min, boil off chloroform, be cooled to room temperature, add 100 parts of water, leave standstill 3-7h, remove water layer, product washing, to neutral, obtains the 4th prefabricated material.

Preferably, in S5, the sodium hydroxide solution stirring 20-50min that 20-40 part concentration is 0.5-2.5wt% is added by weight in the prefabricated material of 5-15 part the 4th, whipping temp is 55-65 DEG C, filter, product washing, to neutral, add 50-80 part water and is heated with stirring to 90-96 DEG C, insulation 1-4h, filter, add 40-70 part dehydrated alcohol, reflux under whipped state 20-60min, is cooled to room temperature, filter, product washing, to neutral, put into the 80-90 DEG C of dry 30-50min of baking oven, is obtained the preparation method of strong-acid cation-exchange resin.

Preferably, the preparation method of described strong-acid cation-exchange resin, comprises the steps:

S1, by weight by 30-36 part vinylbenzene, 4-5 part divinylbenzene, 0.2-0.24 part methenyl bromide, 2-4 part 1,4-butyleneglycol, 0.2-0.6 part benzoyl peroxide stir, churning time is 20-26min, and whipping temp is 50-55 DEG C, obtains the first prefabricated material;

S2,40-44 part sodium lignosulfonate will be taken by weight and send in Reaktionsofen, be warming up to 110-115 DEG C under nitrogen protection, insulation 40-42mmin, be warming up to 166-168 DEG C, insulation 20-24min, be cooled to 156-158 DEG C, insulation 12-15min, be warming up to 172-174 DEG C, insulation 26-28min, be cooled to room temperature, grinding, add 2-2.4 part 1, the chloro-2-propyl alcohol of 3-bis-, 50-55 part gathers alkylsiloxane, 11-13 part sodium hydroxide stirs, whipping temp is 90-94 DEG C, churning time is 40-44min, add the hydrochloric acid stirring 20-23min that 15-17 part concentration is 4.2-4.5mol/L, whipping temp is 50-52 DEG C, filter, add the hydrochloric acid stirring 6-10min that 30-34 part concentration is 6-6.2mol/L, whipping temp is 40-42 DEG C, filter, add the hydrochloric acid stirring 50-54min that 30-36 part concentration is 6.6-6.8mol/L, filter, adopt deionized water wash 3-4 time, send in 92-94 DEG C of baking oven and dry, obtain the second prefabricated material,

S3, by weight 24-26 part water, 2-2.6 part polyvinyl alcohol, 4-6 part ethyl propenoate to be mixed, add 0.2-0.3 part methylene blue and be stirred to dissolving completely, add the prefabricated material of 14-15 part first, DEG C stirring 30-34h from room temperature to 44-46, be warming up to 64-66 DEG C and stir 30-34min, be warming up to 76-78 DEG C and stir 30-34min, be cooled to 69-70 DEG C and stir 10-12min, be warming up to 94-95 DEG C and stir 30-34min, be cooled to 52-53 DEG C and stir 60-70min, obtain the 3rd prefabricated material;

S4, in the prefabricated material of 40-44 part the 3rd, add the swelling 40-46min of 60-65 part chloroform by weight, add sulphuric acid soln, 4-6 part sulphur trioxide, the prefabricated material of 20-26 part second that 50-55 part concentration is 45-50wt%, from room temperature to 52-55, DEG C stirring 30-36min, is increased to 65-66 DEG C and stirs 50-54min, be warming up to 76-78 DEG C and stir 40-44min, boil off chloroform, be cooled to room temperature, add 100 parts of water, leave standstill 4-5h, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, by weight add in the prefabricated material of 10-12 part the 4th 30-36 part concentration be 2-2.3wt% sodium hydroxide solution stir 40-46min, whipping temp is 60-62 DEG C, filter, product washing is to neutral, add 70-76 part water and be heated with stirring to 92-94 DEG C, insulation 2-3.5h, filter, add 60-65 part dehydrated alcohol, reflux under whipped state 40-50min, is cooled to room temperature, filter, product washing, to neutral, put into the 84-86 DEG C of dry 40-45min of baking oven, is obtained the preparation method of strong-acid cation-exchange resin.

In the present invention, with vinylbenzene, divinylbenzene is polymerization major ingredient, add benzoyl peroxide near as initiation, add 1 successively, 4-butyleneglycol, polyvinyl alcohol, methylene blue, and conservative control each material add-on and each processing parameter, goods specific surface area is large, ion-exchange speed is fast, the sodium lignosulfonate side-chain structure fracture wherein added, produce small molecules, add 1, the chloro-2-propyl alcohol of 3-bis-, poly-alkylsiloxane synergy, in generation molecule, intermolecular cross-linking reaction, produce a large amount of sulfonic group, a large amount of active group such as carboxyl and hydroxyl, and methenyl bromide must add, the bromine atoms on it can be made to introduce resin matrix molecule chain end, active bromine can react with the follow-up ethyl propenoate added, grafting one deck 2-methacrylate ion on goods, by conservative control sodium lignosulfonate, 1, the chloro-2-propyl alcohol of 3-bis-, poly-alkylsiloxane, methenyl bromide, the add-on of ethyl propenoate, comprehensive action, article hydrophilic is fabulous, the goods size obtained and aperture are all very excellent, goods specific surface area is large, ion-exchange speed is fast, the sulphuric acid soln added, sulphur trioxide synergy sulfonation system, sulfonation efficiency is high, goods specific surface area is very excellent.

Embodiment

Below, by specific embodiment, technical scheme of the present invention is described in detail.

Embodiment 1

A preparation method for strong-acid cation-exchange resin, comprises the steps:

S1, vinylbenzene, divinylbenzene, methenyl bromide, BDO, benzoyl peroxide are uniformly mixed, whipping temp is 44 DEG C, obtains the first prefabricated material;

S2, sodium lignosulfonate is sent in Reaktionsofen, heat up under nitrogen protection, insulation, cooling, grinding, adds the chloro-2-propyl alcohol of 1,3-bis-, poly-alkylsiloxane, sodium hydroxide stirs, whipping temp is 92 DEG C, add hydrochloric acid to stir, filter, deionized water wash, dry, obtain the second prefabricated material;

S3, Jiang Shui, polyvinyl alcohol, ethyl propenoate mix, and add methylene blue and are stirred to dissolving completely, add the first prefabricated material, heat up and stir, obtain the 3rd prefabricated material;

S4, in the 3rd prefabricated material, add chloroform swelling, and add sulphuric acid soln, sulphur trioxide, the second prefabricated material, heat up and stir, boil off chloroform, be cooled to room temperature, add water standing, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, add sodium hydroxide solution stir in the 4th prefabricated material, filter, product washing is to neutral, and add water stirrings, heats, insulation, filters, refluxes, be cooled to room temperature under adding absolute ethyl alcohol and stirring state, filter, product washing is to neutral, dry, obtains strong-acid cation-exchange resin.

Embodiment 2

A preparation method for strong-acid cation-exchange resin, comprises the steps:

S1,30 parts of vinylbenzene, 5 parts of divinylbenzenes, 0.2 part of methenyl bromide, 4 parts of BDOs, 0.2 part of benzoyl peroxide are stirred by weight, churning time is 26min, and whipping temp is 50 DEG C, obtains the first prefabricated material;

S2,44 parts of sodium lignosulfonates will be taken by weight and send in Reaktionsofens, be warming up to 110 DEG C under nitrogen protection, insulation 42mmin, be warming up to 166 DEG C, insulation 24min, be cooled to 156 DEG C, insulation 15min, be warming up to 172 DEG C, insulation 28min, be cooled to room temperature, grinding, add 2 part 1, the chloro-2-propyl alcohol of 3-bis-, 55 parts of poly-alkylsiloxanes, 11 parts of sodium hydroxide stir, whipping temp is 94 DEG C, churning time is 40min, add the hydrochloric acid stirring 23min that 17 parts of concentration are 4.2mol/L, whipping temp is 50 DEG C, filter, add the hydrochloric acid stirring 10min that 34 parts of concentration are 6mol/L, whipping temp is 40 DEG C, filter, add the hydrochloric acid stirring 54min that 36 parts of concentration are 6.6mol/L, filter, adopt deionized water wash 3 times, send in 94 DEG C of baking ovens and dry, obtain the second prefabricated material,

S3, by weight 24 parts of water, 2.6 parts of polyvinyl alcohol, 4 parts of ethyl propenoates to be mixed, add 0.3 part of methylene blue and be stirred to dissolving completely, add 14 part of first prefabricated material, stir 30h from room temperature to 46 DEG C, be warming up to 66 DEG C and stir 30min, be warming up to 78 DEG C and stir 30min, be cooled to 70 DEG C and stir 10min, be warming up to 95 DEG C and stir 30min, be cooled to 53 DEG C and stir 60min, obtain the 3rd prefabricated material;

S4, in 44 part of the 3rd prefabricated material, add 60 parts of swelling 46min of chloroform by weight, add the sulphuric acid soln that 50 parts of concentration are 50wt%, 4 parts of sulphur trioxides, 26 part of second prefabricated material, stir 36min from room temperature to 52 DEG C, be increased to 65 DEG C and stir 54min, be warming up to 76 DEG C and stir 44min, boil off chloroform, be cooled to room temperature, add 100 parts of water, leave standstill 4h, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, by weight add in 12 part of the 4th prefabricated material 30 parts of concentration be 2.3wt% sodium hydroxide solution stir 40min, whipping temp is 62 DEG C, filter, product washing, to neutral, add 70 parts of water and is heated with stirring to 94 DEG C, insulation 2h, filter, add 65 parts of dehydrated alcohols, reflux under whipped state 40min, is cooled to room temperature, filter, product washing, to neutral, put into 86 DEG C of dry 40min of baking oven, is obtained the preparation method of strong-acid cation-exchange resin.

Embodiment 3

A preparation method for strong-acid cation-exchange resin, comprises the steps:

S1,36 parts of vinylbenzene, 4 parts of divinylbenzenes, 0.24 part of methenyl bromide, 2 parts of BDOs, 0.6 part of benzoyl peroxide are stirred by weight, churning time is 20min, and whipping temp is 55 DEG C, obtains the first prefabricated material;

S2,40 parts of sodium lignosulfonates will be taken by weight and send in Reaktionsofens, be warming up to 115 DEG C under nitrogen protection, insulation 40mmin, be warming up to 168 DEG C, insulation 20min, be cooled to 158 DEG C, insulation 12min, be warming up to 174 DEG C, insulation 26min, be cooled to room temperature, grinding, add 2.4 part 1, the chloro-2-propyl alcohol of 3-bis-, 50 parts of poly-alkylsiloxanes, 13 parts of sodium hydroxide stir, whipping temp is 90 DEG C, churning time is 44min, add the hydrochloric acid stirring 20min that 15 parts of concentration are 4.5mol/L, whipping temp is 52 DEG C, filter, add the hydrochloric acid stirring 6min that 30 parts of concentration are 6.2mol/L, whipping temp is 42 DEG C, filter, add the hydrochloric acid stirring 50min that 30 parts of concentration are 6.8mol/L, filter, adopt deionized water wash 4 times, send in 92 DEG C of baking ovens and dry, obtain the second prefabricated material,

S3, by weight 26 parts of water, 2 parts of polyvinyl alcohol, 6 parts of ethyl propenoates to be mixed, add 0.2 part of methylene blue and be stirred to dissolving completely, add 15 part of first prefabricated material, stir 34h from room temperature to 44 DEG C, be warming up to 64 DEG C and stir 34min, be warming up to 76 DEG C and stir 34min, be cooled to 69 DEG C and stir 12min, be warming up to 94 DEG C and stir 34min, be cooled to 52 DEG C and stir 70min, obtain the 3rd prefabricated material;

S4, in 40 part of the 3rd prefabricated material, add 65 parts of swelling 40min of chloroform by weight, add the sulphuric acid soln that 55 parts of concentration are 45wt%, 6 parts of sulphur trioxides, 20 part of second prefabricated material, stir 30min from room temperature to 55 DEG C, be increased to 66 DEG C and stir 50min, be warming up to 78 DEG C and stir 40min, boil off chloroform, be cooled to room temperature, add 100 parts of water, leave standstill 5h, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, by weight add in 10 part of the 4th prefabricated material 36 parts of concentration be 2wt% sodium hydroxide solution stir 46min, whipping temp is 60 DEG C, filter, product washing, to neutral, add 76 parts of water and is heated with stirring to 92 DEG C, insulation 3.5h, filter, add 60 parts of dehydrated alcohols, reflux under whipped state 50min, is cooled to room temperature, filter, product washing, to neutral, put into 84 DEG C of dry 45min of baking oven, is obtained the preparation method of strong-acid cation-exchange resin.

Embodiment 4

A preparation method for strong-acid cation-exchange resin, comprises the steps:

S1,20 parts of vinylbenzene, 8 parts of divinylbenzenes, 0.1 part of methenyl bromide, 5 parts of BDOs, 0.1 part of benzoyl peroxide are stirred by weight, churning time is 40min, and whipping temp is 40 DEG C, obtains the first prefabricated material;

S2,50 parts of sodium lignosulfonates will be taken by weight and send in Reaktionsofens, be warming up to 100 DEG C under nitrogen protection, insulation 50mmin, be warming up to 165 DEG C, insulation 30min, be cooled to 155 DEG C, insulation 20min, be warming up to 170 DEG C, insulation 30min, be cooled to room temperature, grinding, add 1 part 1, the chloro-2-propyl alcohol of 3-bis-, 60 parts of poly-alkylsiloxanes, 10 parts of sodium hydroxide stir, whipping temp is 95 DEG C, churning time is 20min, add the hydrochloric acid stirring 30min that 20 parts of concentration are 4mol/L, whipping temp is 45 DEG C, filter, add the hydrochloric acid stirring 15min that 40 parts of concentration are 5.5mol/L, whipping temp is 35 DEG C, filter, add the hydrochloric acid stirring 60min that 40 parts of concentration are 6.5mol/L, filter, adopt deionized water wash 2 times, send in 95 DEG C of baking ovens and dry, obtain the second prefabricated material,

S3, by weight 20 parts of water, 4 parts of polyvinyl alcohol, 2 parts of ethyl propenoates to be mixed, add 0.6 part of methylene blue and be stirred to dissolving completely, add 10 part of first prefabricated material, stir 20h from room temperature to 50 DEG C, be warming up to 69 DEG C and stir 15min, be warming up to 79 DEG C and stir 20min, be cooled to 72 DEG C and stir 5min, be warming up to 96 DEG C and stir 20min, be cooled to 55 DEG C and stir 50min, obtain the 3rd prefabricated material;

S4, in 50 part of the 3rd prefabricated material, add 40 parts of swelling 50min of chloroform by weight, add the sulphuric acid soln that 30 parts of concentration are 60wt%, 2 parts of sulphur trioxides, 40 part of second prefabricated material, stir 50min from room temperature to 50 DEG C, be increased to 64 DEG C and stir 60min, be warming up to 75 DEG C and stir 50min, boil off chloroform, be cooled to room temperature, add 100 parts of water, leave standstill 3h, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, by weight add in 15 part of the 4th prefabricated material 20 parts of concentration be 2.5wt% sodium hydroxide solution stir 20min, whipping temp is 65 DEG C, filter, product washing, to neutral, add 50 parts of water and is heated with stirring to 96 DEG C, insulation 1h, filter, add 70 parts of dehydrated alcohols, reflux under whipped state 20min, is cooled to room temperature, filter, product washing, to neutral, put into 90 DEG C of dry 30min of baking oven, is obtained the preparation method of strong-acid cation-exchange resin.

Embodiment 5

A preparation method for strong-acid cation-exchange resin, comprises the steps:

S1,50 parts of vinylbenzene, 2 parts of divinylbenzenes, 0.4 part of methenyl bromide, 1 part of BDO, 0.8 part of benzoyl peroxide are stirred by weight, churning time is 15min, and whipping temp is 60 DEG C, obtains the first prefabricated material;

S2,30 parts of sodium lignosulfonates will be taken by weight and send in Reaktionsofens, be warming up to 120 DEG C under nitrogen protection, insulation 20mmin, be warming up to 170 DEG C, insulation 15min, be cooled to 160 DEG C, insulation 10min, be warming up to 175 DEG C, insulation 20min, be cooled to room temperature, grinding, add 3 part 1, the chloro-2-propyl alcohol of 3-bis-, 40 parts of poly-alkylsiloxanes, 15 parts of sodium hydroxide stir, whipping temp is 80 DEG C, churning time is 50min, add the hydrochloric acid stirring 10min that 10 parts of concentration are 5mol/L, whipping temp is 55 DEG C, filter, add the hydrochloric acid stirring 5min that 20 parts of concentration are 6.32mol/L, whipping temp is 45 DEG C, filter, add the hydrochloric acid stirring 40min that 20 parts of concentration are 7mol/L, filter, adopt deionized water wash 5 times, send in 90 DEG C of baking ovens and dry, obtain the second prefabricated material,

S3, by weight 30 parts of water, 1 part of polyvinyl alcohol, 8 parts of ethyl propenoates to be mixed, add 0.2 part of methylene blue and be stirred to dissolving completely, add 16 part of first prefabricated material, stir 50h from room temperature to 40 DEG C, be warming up to 60 DEG C and stir 40min, be warming up to 75 DEG C and stir 50min, be cooled to 68 DEG C and stir 15min, be warming up to 92 DEG C and stir 50min, be cooled to 50 DEG C and stir 100min, obtain the 3rd prefabricated material;

S4, in 20 part of the 3rd prefabricated material, add 70 parts of swelling 20min of chloroform by weight, add the sulphuric acid soln that 60 parts of concentration are 40wt%, 10 parts of sulphur trioxides, 15 part of second prefabricated material, stir 20min from room temperature to 60 DEG C, be increased to 68 DEG C and stir 40min, be warming up to 80 DEG C and stir 30min, boil off chloroform, be cooled to room temperature, add 100 parts of water, leave standstill 7h, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, by weight add in 5 part of the 4th prefabricated material 40 parts of concentration be 0.5wt% sodium hydroxide solution stir 50min, whipping temp is 55 DEG C, filter, product washing, to neutral, add 80 parts of water and is heated with stirring to 90 DEG C, insulation 4h, filter, add 40 parts of dehydrated alcohols, reflux under whipped state 60min, is cooled to room temperature, filter, product washing, to neutral, put into 80 DEG C of dry 50min of baking oven, is obtained the preparation method of strong-acid cation-exchange resin.

Embodiment 6

A preparation method for strong-acid cation-exchange resin, comprises the steps:

S1,36 parts of vinylbenzene, 6 parts of divinylbenzenes, 0.3 part of methenyl bromide, 2.6 parts of BDOs, 0.5 part of benzoyl peroxide are stirred by weight, churning time is 30min, and whipping temp is 55 DEG C, obtains the first prefabricated material;

S2,42 parts of sodium lignosulfonates will be taken by weight and send in Reaktionsofens, be warming up to 115 DEG C under nitrogen protection, insulation 35mmin, be warming up to 168 DEG C, insulation 18min, be cooled to 158 DEG C, insulation 16min, be warming up to 173 DEG C, insulation 24min, be cooled to room temperature, grinding, add 2.4 part 1, the chloro-2-propyl alcohol of 3-bis-, 55 parts of poly-alkylsiloxanes, 12 parts of sodium hydroxide stir, whipping temp is 91 DEG C, churning time is 36min, add the hydrochloric acid stirring 20min that 16 parts of concentration are 4.5mol/L, whipping temp is 51 DEG C, filter, add the hydrochloric acid stirring 10min that 36 parts of concentration are 6.2mol/L, whipping temp is 42 DEG C, filter, add the hydrochloric acid stirring 55min that 36 parts of concentration are 6.8mol/L, filter, adopt deionized water wash 3 times, send in 92 DEG C of baking ovens and dry, obtain the second prefabricated material,

S3, by weight 24 parts of water, 2.4 parts of polyvinyl alcohol, 6 parts of ethyl propenoates to be mixed, add 0.45 part of methylene blue and be stirred to dissolving completely, add 14 part of first prefabricated material, stir 32h from room temperature to 46 DEG C, be warming up to 65 DEG C and stir 32min, be warming up to 77 DEG C and stir 30min, be cooled to 70 DEG C and stir 12min, be warming up to 95 DEG C and stir 42min, be cooled to 53 DEG C and stir 80min, obtain the 3rd prefabricated material;

S4, in 42 part of the 3rd prefabricated material, add 61 parts of swelling 42min of chloroform by weight, add the sulphuric acid soln that 55 parts of concentration are 52wt%, 6 parts of sulphur trioxides, 32 part of second prefabricated material, stir 35min from room temperature to 56 DEG C, be increased to 66 DEG C and stir 52min, be warming up to 78 DEG C and stir 45min, boil off chloroform, be cooled to room temperature, add 100 parts of water, leave standstill 5h, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, by weight add in 12 part of the 4th prefabricated material 35 parts of concentration be 2.1wt% sodium hydroxide solution stir 34min, whipping temp is 61 DEG C, filter, product washing, to neutral, add 66 parts of water and is heated with stirring to 94 DEG C, insulation 2h, filter, add 50 parts of dehydrated alcohols, reflux under whipped state 25min, is cooled to room temperature, filter, product washing, to neutral, put into 88 DEG C of dry 35min of baking oven, is obtained the preparation method of strong-acid cation-exchange resin.

Carry out performance test to above-mentioned strong-acid cation-exchange resin, test result is as follows:

Test event	Average test result	Conventional ion exchange resin
			Water content (%)	44	40
Quality complete exchange capacity (mmol/g)	4.8	4.3
			Volume complete exchange capacity (mmol/ml)	2.6	2.1
Granularity (0.315-1.25mm)	99％	95％
			Specific surface area (m2/g)	335	210

The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.

Claims (10)

1. a preparation method for strong-acid cation-exchange resin, is characterized in that, comprises the steps:

S1, vinylbenzene, divinylbenzene, methenyl bromide, BDO, benzoyl peroxide are uniformly mixed, whipping temp is 40-60 DEG C, obtains the first prefabricated material;

S2, sodium lignosulfonate is sent in Reaktionsofen, heat up under nitrogen protection, insulation, cooling, grinding, adds the chloro-2-propyl alcohol of 1,3-bis-, poly-alkylsiloxane, sodium hydroxide stirs, whipping temp is 80-95 DEG C, add hydrochloric acid to stir, filter, deionized water wash, dry, obtain the second prefabricated material;

S3, Jiang Shui, polyvinyl alcohol, ethyl propenoate mix, and add methylene blue and are stirred to dissolving completely, add the first prefabricated material, heat up and stir, obtain the 3rd prefabricated material;

S4, in the 3rd prefabricated material, add chloroform swelling, and add sulphuric acid soln, sulphur trioxide, the second prefabricated material, heat up and stir, boil off chloroform, be cooled to room temperature, add water standing, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, add sodium hydroxide solution stir in the 4th prefabricated material, filter, product washing is to neutral, and add water stirrings, heats, insulation, filters, refluxes, be cooled to room temperature under adding absolute ethyl alcohol and stirring state, filter, product washing is to neutral, dry, obtains strong-acid cation-exchange resin.

2. the preparation method of strong-acid cation-exchange resin according to claim 1, is characterized in that, in S1, the weight ratio of vinylbenzene, divinylbenzene and methenyl bromide is 20-50:2-8:0.1-0.4.

3. the preparation method of strong-acid cation-exchange resin according to claim 1 and 2, is characterized in that, in S2, the weight ratio of sodium lignosulfonate, 1,3-bis-chloro-2-propyl alcohol and poly-alkylsiloxane is 30-50:1-3:40-60.

4. the preparation method of the strong-acid cation-exchange resin according to any one of claim 1-3, is characterized in that, in S4, the weight ratio of sulphuric acid soln, sulphur trioxide and the second prefabricated material is 30-60:2-10:15-40; Wherein the concentration of sulphuric acid soln is 40-60wt%.

5. the preparation method of the strong-acid cation-exchange resin according to any one of claim 1-4, it is characterized in that, in S1, by weight by 20-50 part vinylbenzene, 2-8 part divinylbenzene, 0.1-0.4 part methenyl bromide, 1-5 part 1,4-butyleneglycol, 0.1-0.8 part benzoyl peroxide stir, churning time is 15-40min, and whipping temp is 40-60 DEG C, obtains the first prefabricated material.

6. the preparation method of the strong-acid cation-exchange resin according to any one of claim 1-5, it is characterized in that, in S2,30-50 part sodium lignosulfonate will be taken by weight and send in Reaktionsofen, 100-120 DEG C is warming up to, insulation 20-50mmin under nitrogen protection, be warming up to 165-170 DEG C, insulation 15-30min, be cooled to 155-160 DEG C, insulation 10-20min, be warming up to 170-175 DEG C, insulation 20-30min, be cooled to room temperature, grinding, add 1-3 part 1, the chloro-2-propyl alcohol of 3-bis-, 40-60 part gathers alkylsiloxane, 10-15 part sodium hydroxide stirs, whipping temp is 80-95 DEG C, churning time is 20-50min, add the hydrochloric acid stirring 10-30min that 10-20 part concentration is 4-5mol/L, whipping temp is 45-55 DEG C, filter, add the hydrochloric acid stirring 5-15min that 20-40 part concentration is 5.5-6.32mol/L, whipping temp is 35-45 DEG C, filter, add the hydrochloric acid stirring 40-60min that 20-40 part concentration is 6.5-7mol/L, filter, adopt deionized water wash 2-5 time, send in 90-95 DEG C of baking oven and dry, obtain the second prefabricated material.

7. the preparation method of the strong-acid cation-exchange resin according to any one of claim 1-6, it is characterized in that, in S3, by weight by 20-30 part water, 1-4 part polyvinyl alcohol, 2-8 part ethyl propenoate mixes, add 0.2-0.6 part methylene blue and be stirred to dissolving completely, add the prefabricated material of 10-16 part first, DEG C stirring 20-50h from room temperature to 40-50, be warming up to 60-69 DEG C and stir 15-40min, be warming up to 75-79 DEG C and stir 20-50min, be cooled to 68-72 DEG C and stir 5-15min, be warming up to 92-96 DEG C and stir 20-50min, be cooled to 50-55 DEG C and stir 50-100min, obtain the 3rd prefabricated material.

8. the preparation method of the strong-acid cation-exchange resin according to any one of claim 1-7, it is characterized in that, in S4, the swelling 20-50min of 40-70 part chloroform is added by weight in the prefabricated material of 20-50 part the 3rd, adding 30-60 part concentration is the sulphuric acid soln of 40-60wt%, 2-10 part sulphur trioxide, the prefabricated material of 15-40 part second, DEG C stirring 20-50min from room temperature to 50-60, be increased to 64-68 DEG C and stir 40-60min, be warming up to 75-80 DEG C and stir 30-50min, boil off chloroform, be cooled to room temperature, add 100 parts of water, leave standstill 3-7h, remove water layer, product washing is to neutral, obtain the 4th prefabricated material.

9. the preparation method of the strong-acid cation-exchange resin according to any one of claim 1-8, it is characterized in that, in S5, the sodium hydroxide solution stirring 20-50min that 20-40 part concentration is 0.5-2.5wt% is added by weight in the prefabricated material of 5-15 part the 4th, whipping temp is 55-65 DEG C, filter, product washing is to neutral, add 50-80 part water and be heated with stirring to 90-96 DEG C, insulation 1-4h, filter, add 40-70 part dehydrated alcohol, reflux under whipped state 20-60min, be cooled to room temperature, filter, product washing is to neutral, put into the 80-90 DEG C of dry 30-50min of baking oven, obtain the preparation method of strong-acid cation-exchange resin.

10. the preparation method of the strong-acid cation-exchange resin according to any one of claim 1-9, is characterized in that, comprises the steps:

S1, by weight by 30-36 part vinylbenzene, 4-5 part divinylbenzene, 0.2-0.24 part methenyl bromide, 2-4 part 1,4-butyleneglycol, 0.2-0.6 part benzoyl peroxide stir, churning time is 20-26min, and whipping temp is 50-55 DEG C, obtains the first prefabricated material;

S2,40-44 part sodium lignosulfonate will be taken by weight and send in Reaktionsofen, be warming up to 110-115 DEG C under nitrogen protection, insulation 40-42mmin, be warming up to 166-168 DEG C, insulation 20-24min, be cooled to 156-158 DEG C, insulation 12-15min, be warming up to 172-174 DEG C, insulation 26-28min, be cooled to room temperature, grinding, add 2-2.4 part 1, the chloro-2-propyl alcohol of 3-bis-, 50-55 part gathers alkylsiloxane, 11-13 part sodium hydroxide stirs, whipping temp is 90-94 DEG C, churning time is 40-44min, add the hydrochloric acid stirring 20-23min that 15-17 part concentration is 4.2-4.5mol/L, whipping temp is 50-52 DEG C, filter, add the hydrochloric acid stirring 6-10min that 30-34 part concentration is 6-6.2mol/L, whipping temp is 40-42 DEG C, filter, add the hydrochloric acid stirring 50-54min that 30-36 part concentration is 6.6-6.8mol/L, filter, adopt deionized water wash 3-4 time, send in 92-94 DEG C of baking oven and dry, obtain the second prefabricated material,

S3, by weight 24-26 part water, 2-2.6 part polyvinyl alcohol, 4-6 part ethyl propenoate to be mixed, add 0.2-0.3 part methylene blue and be stirred to dissolving completely, add the prefabricated material of 14-15 part first, DEG C stirring 30-34h from room temperature to 44-46, be warming up to 64-66 DEG C and stir 30-34min, be warming up to 76-78 DEG C and stir 30-34min, be cooled to 69-70 DEG C and stir 10-12min, be warming up to 94-95 DEG C and stir 30-34min, be cooled to 52-53 DEG C and stir 60-70min, obtain the 3rd prefabricated material;

S4, in the prefabricated material of 40-44 part the 3rd, add the swelling 40-46min of 60-65 part chloroform by weight, add sulphuric acid soln, 4-6 part sulphur trioxide, the prefabricated material of 20-26 part second that 50-55 part concentration is 45-50wt%, from room temperature to 52-55, DEG C stirring 30-36min, is increased to 65-66 DEG C and stirs 50-54min, be warming up to 76-78 DEG C and stir 40-44min, boil off chloroform, be cooled to room temperature, add 100 parts of water, leave standstill 4-5h, remove water layer, product washing, to neutral, obtains the 4th prefabricated material;

S5, by weight add in the prefabricated material of 10-12 part the 4th 30-36 part concentration be 2-2.3wt% sodium hydroxide solution stir 40-46min, whipping temp is 60-62 DEG C, filter, product washing is to neutral, add 70-76 part water and be heated with stirring to 92-94 DEG C, insulation 2-3.5h, filter, add 60-65 part dehydrated alcohol, reflux under whipped state 40-50min, is cooled to room temperature, filter, product washing, to neutral, put into the 84-86 DEG C of dry 40-45min of baking oven, is obtained the preparation method of strong-acid cation-exchange resin.