CN103180368A - Ethyl oligo-silicates with strong acid heterogenous polymeric catalysts - Google Patents
Ethyl oligo-silicates with strong acid heterogenous polymeric catalysts Download PDFInfo
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- CN103180368A CN103180368A CN2011800511938A CN201180051193A CN103180368A CN 103180368 A CN103180368 A CN 103180368A CN 2011800511938 A CN2011800511938 A CN 2011800511938A CN 201180051193 A CN201180051193 A CN 201180051193A CN 103180368 A CN103180368 A CN 103180368A
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/02—Polysilicates
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08F8/00—Chemical modification by after-treatment
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- C08F8/36—Sulfonation; Sulfation
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Abstract
The present invention provides a process for the synthesis of ethyl silicate with varying silica concentration, by hydrolysing ethyl silicate in varying water concentration in the presence of sulfonated catalysts having a styrene-divinyl benzene backbone. The present invention further relates to the preparation of beaded crosslinked polymers containing sulfonic acid moieties having an interconnected pore structure and surface area up to 400 m2 /g.
Description
Technical field
The present invention relates to use sulfonated polymer bead catalyzer hydrolyzing ethyl silicate, described sulfonated polymer bead catalyzer uses the High Internal Phase Emulsion methodology synthetic.The invention still further relates to the preparation of the crosslinked polymkeric substance of beading, described polymkeric substance has the aromatic ring that is present in polymer backbone, and uses the water-in-oil-in-water compositions technology synthetic, with its further modification to introduce sulfonic group on polymer backbone.
Background technology
Tetraethyl orthosilicate (EtO)
4Si has good thermostability and liquid behavior in wide temperature range.Tetraethyl silicate-32 are used as tackiness agent in paint and coating.It is used for making the linking agent sulfuration also as the room temperature silicone.Tetraethyl silicate-40 have stable and long shelf life.It mainly is used as tackiness agent in paint, coating, pottery and precision casting, and also as silicone self cure agent.Tetraethyl silicate-28 are used as tackiness agent in paint, coating, precision casting and pottery.The numeral explanation is present in the dioxide-containing silica in sample.Before forming silicon-dioxide, during the hydrolysis of tetraethyl silicate, form oxyethyl group derivative and the poly-silicic acid of intermediate silicic acid.This hydrolysis usable acid or base catalysis.With the reacting phase ratio of base catalysis, the speed of acid catalyzed hydrolysis is very fast, and due to the collosol and gel conversion, causes the more multi-linear polymkeric substance of generation.According to application, but selecting catalyst.For binder formulation, owing to promoting that stable silanol condensation product uses dilute hydrochloric acid or sulfuric acid.When preferably condensation more completely or gelation, preferred basic catalyst is as ammonia, volatile salt.
Be described in detail in hydrolysis acid and the lower tetraethyl silicate of basic catalyst existence, by changing reaction parameter (for example catalyst concn, water concentration, temperature of reaction and time), had the silicate hydrolyzate product of the hydrolysis of expected degree with production.
US4393230 has described the method with controlled process that is used for predetermined dioxide-containing silica.By silicon tetrachloride and ethanol synthesis, the preparation tetraethyl orthosilicate.If water is present in ethanol, it forms ethyl polysilicate, and if have excessive tetraethyl silicate, it forms polymerisate." silicon-dioxide (the SiO of predetermined amount
2) " referring to that water is the interior scope of reaction of one of reactant therein, its production contains the 28.8%SiO that has an appointment
2To as high as SiO
2The amount that is settled out from solution (about 53%SiO
2Content) product.Therefore, relate to (EtO)
4The stoichiometry of the complete hydrolysis of Si and the complete condensation of hydrolysate can be expressed as:
(EtO)
4Si+4HOH4EtOH+Si(OH)
4
Si(OH)
42HOH+SiO
2
(EtO)
4Si+2HOH4EtOH+SiO
2
(EtO) that this equation explanation complete hydrolysis is 1 mole
4Si needs the water of 2 moles.Hydrolysis reaction is random, makes the amount of the water that is equivalent to partial hydrolysis will obtain at first (EtO)
4Si, (EtO)
3SiOH, (EtO)
2Si (OH)
2, (EtO) Si (OH)
3And Si (OH)
4Distribution.
Along with the disappearance of water and the appearance of ethanol come monitoring reaction.
US4290811 described a kind of under strong acid ion exchange resin rather than conventional acid catalyst exist the method for hydrolyzing ethyl silicate.The acid of routine used is sulfuric acid and hydrochloric acid, but remaining acidity can produce tetraethyl silicate unstable and working life stability problem.Use heterogeneous catalyst to make finishing sequence minimize with the problem relevant to remove the sour vestige that stays in reaction mixture.Reported that conventional ion exchange resin such as Amberlyst15 (trade mark of Rohm and Hass Company) are used for hydrolyzing ethyl silicate.
The main drawback of the reaction that the use homogeneous catalyst carries out is pollution products due to the existence of catalyzer (for example sulfuric acid), and need the unit operation of other difficulty and costliness by remove catalyzer with salt (described salt may be crucial) processing during the application of processing and resin, dispose the refuse that produces by described processing.Use heterogeneous catalyst can evade this point, can easily remove heterogeneous catalyst and recyclingly repeatedly and not can lose catalyst activity by filtering after reaction.
The present invention relates to use highly porous polymerizing catalyst hydrolysis tetraethyl orthosilicate, compared with the Amberlyst-15 with SDVB skeleton, porousness is much higher.Use the crosslinked polymkeric substance of High Internal Phase Emulsion methodology resultant string pearl form.This polymkeric substance has the pore structure of interconnection, 100-400m
2The variable surface-area of/g scope, this depends on synthesis strategy, according to R.Kunin, E.A.Meitzner, J.A.Oline, S.A.Fischer, N.Frish (Ind.Eng.Chem.Prod.Res.Dev., 1962,1 (2), the 140-144 page) report, the surface-area of commercially available large mesh resin Amberlyst-15 is 42.5m
2/ g.With the aromatic ring modification on polymer backbone, to adhere to sulfonic acid group (moieties) thereon.The come-at-able sulfonic group in surface determines the catalytic efficiency of heterogeneous catalyst.Make the problem of reaction mixture charing by direct use strong acid by using heterogeneous acid catalyst to evade picture.The inventor is surprised to find that, uses catalyzer that effective hydrolysis of tetraethyl silicate for example is provided by the beading polymkeric substance that contains sulfonic acid group of High Internal Phase Emulsion polymer technology preparation, and therefore the catalyzer of dioxide-containing silica in the 32-40% scope be provided.
The beading polymkeric substance that contains sulfonic acid group can use suspension polymerization synthetic, to be used for chromatographic applications.Bead size, size distribution, surperficial come-at-able functional group, pore structure and porosity play important effect in the efficient of polymer application.The character of polymkeric substance depends on reaction parameter, as the reactive ratio of protective colloid type and character, stirring velocity, monomer and linking agent.Can be with the bead post-modification to introduce functional group, as sulfonic acid, amine, hydroxyl, the tertiary butyl, so that polymer support is hydrophobic or hydrophilic, to be used for chromatographic applications, for example ion-exchange, gel-filtration, absorption and affinity chromatography.US5863957 has described a kind of synthetic method with the cross linked porous polymerization microballon grain in the chamber that engages by interconnected pores, and wherein, at least some chambeies are connected with outside surface.
Goal of the invention
Main purpose of the present invention is to provide a kind of synthetic method with tetraethyl silicate of different silica concentrations.
An object of the present invention is to provide a kind of under the synthetic sulfonation catalyst of High Internal Phase Emulsion methodology exists the method for hydrolyzing ethyl silicate.
An object of the present invention is to provide a kind of under the crosslinked polymkeric substance of beading exists the method for hydrolyzing ethyl silicate, described polymkeric substance contains sulfonic acid group and uses the High Internal Phase Emulsion methodology synthetic and have a pore structure of interconnection.
A further object of the present invention is to provide the method for the crosslinked polymkeric substance of a kind of resultant string pearl, and described polymkeric substance has the pore structure of interconnection and surface-area up to 400m
2/ g.
A further object of the present invention is the crosslinked polymkeric substance of preparation beading, with its post-modification, so that sulfonic group to be provided in polymer backbone.
Summary of the invention
According to an aspect of the present invention, provide a kind of method of hydrolyzing ethyl silicate, the method comprises the following steps:
A) add in the container tetraethyl orthosilicate and weight at the water of the 0.5-5 of tetraethyl orthosilicate % by weight scope;
B) add surface-area at 100m in reaction mixture
2/ g-400m
2The sulfonated polymer bead of/g scope;
C) reaction mixture be heated to up to 60 ℃ and keep reaching 10 hours;
D) tetraethyl orthosilicate of analyze reaction mixture and ethanol;
E) measure the content of silicon-dioxide;
F) after completing, reaction removes the sulfonated polymer bead;
G) selectable described sulfonated polymer bead is recycled and reused for hydrolytic process.
According to a further aspect in the invention, provide a kind of prepare pore structure with interconnection on polymer backbone with the method for the polymerization bead of sulfonic acid group, the method comprises the following steps:
A) prepare oil-in-water phase emulsion by following steps:
I) merge the oil phase that contains vinylbenzene, linking agent, tensio-active agent, pore-creating agent and initiator as monomer;
Ii) under constant agitation, add moisture discontinuous phase in oil phase, to form water-in-oil emulsion;
B) under the constant agitation with the speed of 250-500 rev/min, add water-in-oil emulsion to the aqueous phase that contains protective colloid;
C) under comparatively high temps, under constant agitation, make the time of emulsion droplet polymerization up to 12 hours, to obtain surface-area up to 400m
2The polymerization bead of/g;
D) add sulfuric acid in the polymerization bead, and heat the time of 24 hours under 110 ℃, to obtain the sulfonated polymer bead.
Embodiment
The invention provides that a kind of to have controlled silica concentration in tetraethyl silicate (be SiO
2Content) method.Under sulfonated polymer bead catalyzer (the crosslinked polymkeric substance of beading that for example contains sulfonic acid group) exists, come hydrolyzing ethyl silicate by the water with aequum, realize this point.
Hydrolyzing ethyl silicate comprises the following steps:
A) add in the container tetraethyl orthosilicate and weight at the water of the 0.5-5 of tetraethyl orthosilicate % by weight scope;
B) add surface-area at 100m in reaction mixture
2/ g-400m
2The sulfonated polymer bead of/g scope;
C) reaction mixture be heated to up to 60 ℃ and keep reaching 10 hours;
D) tetraethyl orthosilicate of analyze reaction mixture and ethanol;
E) measure the content of silicon-dioxide;
F) after completing, reaction removes the sulfonated polymer bead;
G) selectable described sulfonated polymer bead is recycled and reused for described hydrolytic process.
In one embodiment of the invention, according to SiO required in product
2Amount, carry out the hydrolysis of tetraethyl orthosilicate by the concentration that changes water.
In another embodiment, be hydrolyzed under the change in concentration of water and sulfonated polymer bead catalyzer.
In another embodiment, under existing, used sulfonated polymer bead catalyzer is hydrolyzed.
The mol ratio of tetraethyl orthosilicate and water at 1:0.0065 to until the scope of 1:0.64.
The mol ratio of tetraethyl orthosilicate and sulfonated polymer bead catalyzer is 1:0.1.
The mol ratio of water and sulfonated polymer bead catalyzer at 1:0.15 to until the scope of 1:1.54.
The surface-area of the catalyzer that uses is at 100-400m
2/ g scope is preferably at 100-350m
2/ g scope.
The per-cent of hydrolysis and the dioxide-containing silica of hydrolysate depend on the water yield of using, and it is preferably in the 0.5-5% of tetraethyl orthosilicate scope.
The invention still further relates to the synthetic crosslinked porous polymer of beading with pore structure of interconnection.The method relates to by suspension polymerization technique makes the emulsion oil-in-water polymerization, to produce the polymkeric substance of beading form.
Described method was comprised of two steps.It is water-in-oil-in-water compositions, and namely inner most water is surrounded by oil phase, this oil phase and then surrounded by the foreign minister.In the first step, the preparation water-in-oil emulsion, in subordinate phase, the water-in-oil emulsion by hanging drop form in the reactor that contains protective colloid that stirs with constant rpm forms O/w emulsion.Therefore, subordinate phase forms O/w emulsion, therefore is polymerized to the system of water-in-oil-in-water type.
The method that preparation has the pore structure of interconnection and have a polymerization bead of sulfonic acid group on polymer backbone comprises the following steps:
A) prepare oil-in-water phase emulsion by following steps:
I) merge the oil phase that contains styrene monomer, linking agent, tensio-active agent, pore-creating agent and initiator;
Ii) under the constant agitation with the speed of 350-1400 rev/min, add moisture discontinuous phase in oil phase, form water-in-oil emulsion;
B) under the constant agitation with the speed of 300 rev/mins, add water-in-oil emulsion to the outer aqueous phase that contains protective colloid;
C) under comparatively high temps, under constant agitation, make the emulsion droplet polymerization reach the time of 12 hours, to obtain surface-area up to 400m
2The polymerization bead of/g;
D) add sulfuric acid in the polymerization bead, and heat the time of 24 hours under 110 ℃, to obtain the sulfonated polymer bead.
In the present invention, the monomer that uses is vinylbenzene.With respect to tensio-active agent and initiator, in oil phase, the concentration of monomer is 80%.
In the present invention, the linking agent that uses is selected from Vinylstyrene, Ethylene glycol dimethacrylate (having another name called ethylene glycol dimethacrylate).
Be used for the concentration of linking agent of the present invention from 0.05 times to 2.0 times variation of monomer concentration.
With respect to tensio-active agent and initiator, in oil phase, the concentration of monomer is 15 % by weight.
The initiator that uses is 2,2 '-Diisopropyl azodicarboxylate, and be 3 % by mole of monomer phase.
Being used for tensio-active agent of the present invention is the Span of Span20 to Span80 scope.
Be used for pore-creating agent of the present invention and be selected from chlorobenzene, toluene and heptane.
The ratio of monomer and pore-creating agent changes in the scope of 1:2 at 1:0.5 in the present invention.
Pore-creating agent concentration account for monomer 50% to as high as 200%.
The pore volume scope depends on the pore-creating agent that uses, and preferably at 0.2cm
3/ g-0.6cm
3The scope of/g.
The come-at-able functional group in surface is in 2.8-3.9 milliequivalent/gram scope.
Forming the water-in-oil phase time, with respect to monomer, water can be 5:1 to as high as 30:1, and during suspension polymerization, is 10 times-20 times of oil phase.
During the preparation oil-in-water phase emulsion, stirring velocity can the variation from 350 rev/mins to 1400 rev/mins.
During viscosity period of polymerization, protective colloid prevents that the polymerization bead is coalescent, and when reaction finishes, obtains the polymkeric substance of bead form.The alkaline functional of protective colloid improves the viscosity of water.Be used for protective colloid of the present invention and be selected from polyvinyl (pyrrolidone), poly-(vinyl alcohol), sodium-chlor or calcium chloride.
The concentration that is used for protective colloid of the present invention is from 0.5 % by weight of water to changing up to 2 % by weight.
The stirring velocity of the particle that suspends in the present invention can be from 250 rev/mins to as high as 500 rev/mins of variations.
Embodiment
Hereinafter with reference following examples are described method of the present invention, and these embodiment are only illustrative, and should not regard as by any way and to limit the scope of the invention.
Embodiment 1
In the plastic containers that clog with stopper, get tetraethyl orthosilicate and 0.05g (0.0028mol) water that 9.020g (0.0433mol) has 28% dioxide-containing silica.Add 1.032g to use the synthetic surface-area of High Internal Phase Emulsion polymerization process to be 330m in reaction mixture
2The sulfonation of/g gathers (styrene-divinylbenzene) catalyzer.Reaction mixture is heated the time of 10 hours under 60 ℃.Pass through subsequently tetraethyl orthosilicate and the ethanol of vapor-phase chromatography (GC) analyze reaction mixture.Subsequently reaction mixture is filtered, to remove heterogeneous catalyst, then distillation is to remove ethanol.With respect to tetraethyl silicate, realize 33.3% hydrolysis, by the gravimetric determination dioxide-containing silica, survey and be approximately 30%.
Embodiment 2
In the plastic containers that clog with stopper, get 9.020g (0.0433mol) tetraethyl orthosilicate and 0.100g (0.0056mol) water.Add 1.032g to use the High Internal Phase Emulsion polymerization process to learn synthetic sulfonation poly-(styrene-divinylbenzene) in reaction mixture.Reaction mixture is heated the time of 10 hours under 60 ℃.Pass through subsequently tetraethyl orthosilicate and the ethanol of vapor-phase chromatography (GC) analyze reaction mixture.Subsequently reaction mixture is filtered, to remove heterogeneous catalyst, then distillation is to remove ethanol.With respect to tetraethyl silicate, realize 46% hydrolysis, by the gravimetric determination dioxide-containing silica, survey and be approximately 32%.
Embodiment 3
In the plastic containers that clog with stopper, get 9.020g (0.0433mol) tetraethyl orthosilicate and 0.201g (0.0112mol) water.Add 1.032g to use the High Internal Phase Emulsion polymerization process to learn synthetic sulfonation poly-(styrene-divinylbenzene) in reaction mixture.Reaction mixture is heated the time of 10 hours under 60 ℃.Pass through subsequently tetraethyl orthosilicate and the ethanol of vapor-phase chromatography (GC) analyze reaction mixture.Subsequently reaction mixture is filtered, to remove heterogeneous catalyst, then distillation is to remove ethanol.With respect to tetraethyl silicate, realize 50% hydrolysis, by the gravimetric determination dioxide-containing silica, survey and be approximately 34%.
Embodiment 4
In the plastic containers that clog with stopper, get 9.020g (0.0433mol) tetraethyl orthosilicate and 0.502g (0.0279mol) water.Add 1.032g to use the High Internal Phase Emulsion polymerization process to learn synthetic sulfonation poly-(styrene-divinylbenzene) in reaction mixture.Reaction mixture is heated the time of 10 hours under 60 ℃.Pass through subsequently tetraethyl orthosilicate and the ethanol of vapor-phase chromatography (GC) analyze reaction mixture.Subsequently reaction mixture is filtered, to remove heterogeneous catalyst, then distillation is to remove ethanol.With respect to tetraethyl silicate, realize 87% hydrolysis, by the gravimetric determination dioxide-containing silica, survey and be approximately 37%.
Embodiment 5
The reaction that repeats as illustrate in embodiment 2 is to check the reusability of catalyzer.The concentration of ethanol and tetraethyl orthosilicate in use gc analysis reaction mixture, by the weight analysis determining dioxide-containing silica, result is as follows:
| Circulation | % ethanol | The % tetraethyl orthosilicate | The % dioxide-containing silica |
| 1 | 60.4 | 12.8 | 42 |
| 2 | 13.1 | 52.2 | 33 |
| 3 | 12.2 | 69.7 | 30 |
Dioxide-containing silica is 28% in initial tetraethyl orthosilicate.The water yield used is 0.1g (0.0056mol).
Embodiment 6
In the plastic containers that clog with stopper, get 9.020g (0.0433mol) tetraethyl orthosilicate and 0.05g (0.028mol) water.Add 0.516g to use the High Internal Phase Emulsion polymerization process to learn synthetic sulfonation poly-(styrene-divinylbenzene) in reaction mixture.Reaction mixture is heated the time of 10 hours under 60 ℃.Pass through subsequently tetraethyl orthosilicate and the ethanol of vapor-phase chromatography (GC) analyze reaction mixture.Subsequently reaction mixture is filtered, to remove heterogeneous catalyst, then distillation is to remove ethanol.By the gravimetric determination dioxide-containing silica, survey and be approximately 30%.
Embodiment 7
In the plastic containers that clog with stopper, get 9.020g (0.0433mol) tetraethyl orthosilicate and 0.05g (0.028mol) water.Add 1.548g to use the High Internal Phase Emulsion polymerization process to learn synthetic sulfonation poly-(styrene-divinylbenzene) in reaction mixture.Reaction mixture is heated the time of 10 hours under 60 ℃.Pass through subsequently tetraethyl orthosilicate and the ethanol of vapor-phase chromatography (GC) analyze reaction mixture.Subsequently reaction mixture is filtered, to remove heterogeneous catalyst, then distillation is to remove ethanol.By the gravimetric determination dioxide-containing silica, survey and be approximately 34%.
Embodiment 8
The reaction that repeats as illustrate in embodiment 2 wherein changes reaction times and temperature of reaction, and keeps other parameters identical.Analyze dioxide-containing silica by gravimetric analysis:
When reaction was carried out 2.5 hours, the dioxide-containing silica that obtains was 30%, and when reaction was carried out 5 hours, the dioxide-containing silica that obtains was 36%.
When reaction was carried out 10 hours under 40 ℃, the dioxide-containing silica that obtains was 38%, and when reaction was carried out 10 hours under 80 ℃, the dioxide-containing silica that obtains was 45%.
Embodiment 9
In the plastic containers that clog with stopper, get 9.020g (0.0433mol) tetraethyl orthosilicate and 0.05g (0.0028mol) water.Add 0.516g to use the High Internal Phase Emulsion polymerization process to learn synthetic sulfonation poly-(styrene-divinylbenzene) in reaction mixture.Reaction mixture is heated the time of 5 hours under 60 ℃.Pass through subsequently tetraethyl orthosilicate and the ethanol of vapor-phase chromatography (GC) analyze reaction mixture.Subsequently reaction mixture is filtered, to remove heterogeneous catalyst, then distillation is to remove ethanol.By the gravimetric determination dioxide-containing silica, survey and be approximately 32%.
Embodiment 10
In the plastic containers that clog with stopper, get 9.020g (0.0433mol) tetraethyl orthosilicate and 0.05g (0.0028mol) water.Add 0.516g to use the High Internal Phase Emulsion polymerization process to learn synthetic sulfonation poly-(styrene-divinylbenzene) in reaction mixture.Reaction mixture is heated the time of 5 hours under 40 ℃.Pass through subsequently tetraethyl orthosilicate and the ethanol of vapor-phase chromatography (GC) analyze reaction mixture.Subsequently reaction mixture is filtered, to remove heterogeneous catalyst, then distillation is to remove ethanol.By the gravimetric determination dioxide-containing silica, survey and be approximately 32%.
Embodiment 11
Preparation water-in-oil phase (HIPE): in container, get 1.65g (0.0158mol) styrene monomer, 2.07g (0.0158mol) linking agent Vinylstyrene, 0.818g Span80 tensio-active agent and 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate, 4.5mL chlorobenzene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 98.16mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 298m
2/ g.
The sulfonation of bead: all polymkeric substance experience post-modification reactions as synthetic in explanation in embodiment 1-5, to introduce sulfonic group on polymer backbone.
For poly-(styrene-divinylbenzene) bead of 8.96g (100%CLD), add 45mL (98%) sulfuric acid (0.449mol).Reaction mixture is heated the time of 24 hours under 110 ℃.After reaction is completed, reaction mixture is poured into water.Bead is filtered, wash with water for several times.With bead dried overnight in the vacuum drying oven of 80 ℃.
Embodiment 12
Preparation water-in-oil phase (HIPE): in container, get 1.65g (0.0158mol) styrene monomer, 2.07g (0.0158mol) linking agent Vinylstyrene, 0.818g Span80 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 4.5mL toluene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 98.16mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 293m
2/ g.
Adopt and carry out sulfonation procedure with the described identical mode of embodiment 11.
Embodiment 13
Preparation water-in-oil phase (HIPE): in container, get 1.65g (0.0158mol) styrene monomer, 2.07g (0.0158mol) linking agent Vinylstyrene, 0.818g Span80 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 4.5mL heptane are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 98.16mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 357m
2/ g.
Adopt and carry out sulfonation procedure with the described identical mode of embodiment 11.
Embodiment 14
Preparation water-in-oil phase (HIPE): in container, get 1.65g (0.0158mol) styrene monomer, 2.07g (0.0158mol) linking agent Vinylstyrene, 1.116g Span80 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 4.5mL chlorobenzene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 98.16mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 333m
2/ g.
Embodiment 15
Preparation water-in-oil phase (HIPE): in container, get 1.65g (0.0158mol) styrene monomer, 2.07g (0.0158mol) linking agent Vinylstyrene, 1.116g Span80 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 4.5mL toluene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 98.16mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 274m
2/ g.
Embodiment 16
Preparation water-in-oil phase (HIPE): in container, get 1.54g (0.0148mol) styrene monomer, 2.94g (0.0148mol) linking agent Ethylene glycol dimethacrylate, 0.982g Span80 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 5.4mL toluene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 116.3mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 114m
2/ g.
Embodiment 17
Preparation water-in-oil phase (HIPE): in container, get 1.54g (0.0148mol) styrene monomer, 2.94g (0.0148mol) linking agent Ethylene glycol dimethacrylate, 0.982g Span80 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 5.4mL chlorobenzene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 116.3mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 108m
2/ g.
Embodiment 18
Preparation water-in-oil phase (HIPE): in container, get 1.54g (0.0148mol) styrene monomer, 2.94g (0.0148mol) linking agent Ethylene glycol dimethacrylate, 1.346g Span80 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 5.4mL chlorobenzene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 116.3mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 133m
2/ g.
Embodiment 19
Preparation water-in-oil phase (HIPE): in container, get 1.65g (0.0158mol) styrene monomer, 2.07g (0.0158mol) linking agent Vinylstyrene, 0.818g Span20 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 4.5mL chlorobenzene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 98.16mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 275m
2/ g.
Embodiment 20
Preparation water-in-oil phase (HIPE): in container, get 1.65g (0.0158mol) styrene monomer, 2.07g (0.0158mol) linking agent Vinylstyrene, 0.818g Span20 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 4.5mL toluene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 98.16mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 1 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 250m
2/ g.
Embodiment 21
Preparation water-in-oil phase (HIPE): in container, get 1.65g (0.0158mol) styrene monomer, 2.07g (0.0158mol) linking agent Vinylstyrene, 0.818g Span80 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 4.5mL toluene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 98.16mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 2 % by weight protective colloids.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 275m
2/ g.
Embodiment 22
Preparation water-in-oil phase (HIPE): in container, get 1.65g (0.0158mol) styrene monomer, 2.07g (0.0158mol) linking agent Vinylstyrene, 0.818g Span80 tensio-active agent, 0.15g (9.34 * 10
-4Mol) Diisopropyl azodicarboxylate and 4.5mL chlorobenzene are as pore-creating agent (external phase).Under the constant agitation of 1400rpm, 98.16mL deionized water (discontinuous phase) is joined the maintenance time of 10 minutes in oil phase, to obtain water-in-oil emulsion.
The suspension polymerization of oil phase: under constant agitation, be equipped with condenser, nitrogen inlet and overhead remain on double-walled cylindrical glass reactor under steady temperature in carry out suspension polymerization.Under the constant agitation speed of 300 rev/mins, the water-in-oil emulsion for preparing is as mentioned above joined in the suspension reactor that comprises 200mL water and 0.5 % by weight protective colloid.Complete add water-in-oil mutually to outside aqueous phase after, the temperature of reactor is increased to up to 70 ℃, and keeps time of 12 hours.After this reaction times completes, the product of the bead form that obtains is cooling, filter, wash for several times subsequent drying with water.The surface-area of the bead that obtains is 290m
2/ g.
Claims (14)
1. the method for a hydrolyzing ethyl silicate, the method comprises the following steps:
A) add in the container tetraethyl orthosilicate and weight at the water of the 0.5-5 of tetraethyl orthosilicate % by weight scope;
B) add surface-area at 100m in reaction mixture
2/ g-400m
2The sulfonated polymer bead of/g scope;
C) reaction mixture be heated to up to 60 ℃ and keep reaching 10 hours;
D) tetraethyl orthosilicate of analyze reaction mixture and ethanol;
E) measure the content of silicon-dioxide;
F) after completing, reaction removes the sulfonated polymer bead;
G) selectable described sulfonated polymer bead is recycled and reused for hydrolytic process.
2. the method for hydrolyzing ethyl silicate according to claim 1, wherein, the mol ratio of tetraethyl orthosilicate and water at 1:0.0065 to until the scope of 1:0.64.
3. the method for hydrolyzing ethyl silicate according to claim 1, wherein, the mol ratio of tetraethyl orthosilicate and sulfonation catalyst is 1:0.1.
4. the method for hydrolyzing ethyl silicate according to claim 1, wherein, the mol ratio of water and sulfonation catalyst at 1:0.15 to until the scope of 1:1.54.
One kind prepare pore structure with interconnection on polymer backbone with the method for the polymerization bead of sulfonic acid group, the method comprises the following steps:
A) prepare oil-in-water phase emulsion by following steps:
I) merge the oil phase that contains vinylbenzene, linking agent, tensio-active agent, pore-creating agent and initiator as monomer;
Ii) under constant agitation, add moisture discontinuous phase in oil phase, to form water-in-oil emulsion;
B) under the constant agitation with the speed of 250-500 rev/min, add water-in-oil emulsion to the aqueous phase that contains protective colloid;
C) under comparatively high temps, under constant agitation, make the emulsion droplet polymerization reach the time of 12 hours, to obtain surface-area up to 400m
2The polymerization bead of/g;
D) add sulfuric acid in the polymerization bead, and heat the time of 24 hours under 110 ℃, to obtain the sulfonated polymer bead.
6. the method for preparing the polymerization bead according to claim 5, wherein, with respect to tensio-active agent and initiator, in oil phase, the concentration of styrene monomer is 80%.
7. the method for preparing the polymerization bead according to claim 5, wherein, described linking agent is selected from Vinylstyrene and Ethylene glycol dimethacrylate, and exists with the 0.05-2.0 scope doubly of monomer concentration.
8. the method for preparing the polymerization bead according to claim 5, wherein, the initiator that uses is 2,2 '-Diisopropyl azodicarboxylate, and be 3 % by mole of monomer phase.
9. the method for preparing the polymerization bead according to claim 5, wherein, the tensio-active agent that the present invention uses is Span20 to Span80.
10. the method for preparing the polymerization bead according to claim 5, wherein, described pore-creating agent is selected from chlorobenzene, toluene and heptane.
11. the method for preparing the polymerization bead according to claim 5, wherein, in the present invention, the ratio of monomer and pore-creating agent changes in the scope of 1:2 at 1:0.5.
12. the method for preparing the polymerization bead according to claim 5; wherein; the protective colloid that uses is selected from polyvinyl (pyrrolidone), poly-(vinyl alcohol), sodium-chlor or calcium chloride, and exists with the scope of 0.5 % by weight-2 % by weight of water.
13. the method for preparing the polymerization bead according to claim 5, wherein, the pore volume of polymerization bead is at 0.2cm
3/ g-0.6cm
3/ g scope.
14. the method for preparing the polymerization bead according to claim 5, wherein, in polymerization bead upper surface come-at-able functional group in 2.8-3.9 milliequivalent/gram scope.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN2538/DEL/2010 | 2010-10-25 | ||
| IN2538DE2010 | 2010-10-25 | ||
| IN2539DE2010 | 2010-10-25 | ||
| IN2539/DEL/2010 | 2010-10-25 | ||
| PCT/IB2011/002531 WO2012056290A1 (en) | 2010-10-25 | 2011-10-24 | Ethyl oligo-silicates with strong acid heterogenous polymeric catalysts |
Publications (2)
| Publication Number | Publication Date |
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| CN103180368A true CN103180368A (en) | 2013-06-26 |
| CN103180368B CN103180368B (en) | 2015-09-23 |
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| CN201180051193.8A Expired - Fee Related CN103180368B (en) | 2010-10-25 | 2011-10-24 | Use the low poly-tetraethyl silicate of strong acid heterophase polymerization catalyzer |
Country Status (6)
| Country | Link |
|---|---|
| KR (1) | KR101512580B1 (en) |
| CN (1) | CN103180368B (en) |
| AU (1) | AU2011322203B2 (en) |
| BR (1) | BR112013010055A2 (en) |
| IL (1) | IL225723A0 (en) |
| WO (1) | WO2012056290A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112135860A (en) * | 2018-11-27 | 2020-12-25 | 株式会社Lg化学 | Process for the synthesis of prehydrolyzed polysilicates |
| CN116948285A (en) * | 2023-07-21 | 2023-10-27 | 广州瑞远新材料股份有限公司 | Integrated polyethylene double-material hose and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289727B (en) * | 2014-06-11 | 2017-11-28 | 中国科学院大连化学物理研究所 | Sulfonate functional fluidized polymer phenyl ring hybridization silicon oxide composite Nano ball and preparation |
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| US4290811A (en) * | 1980-03-31 | 1981-09-22 | Rust-Oleum Corporation | Method of producing silicate binders and coatings |
| CN1150764A (en) * | 1994-06-06 | 1997-05-28 | 拜奥波尔公司 | Polymeric microbeads and method of preparation |
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| US4393230A (en) | 1981-09-25 | 1983-07-12 | Teledyne Industries, Inc. | Method of preparing ethyl silicate |
| US5328936A (en) * | 1993-02-01 | 1994-07-12 | Rohm And Haas Company | Polymerization process for making porous polymeric particles |
| JPH10147750A (en) * | 1996-11-20 | 1998-06-02 | Colcoat Kk | Preparation of partial condensate of alkyl silicate |
| US7301042B2 (en) * | 2002-04-23 | 2007-11-27 | Cruse Richard W | Blocked mercaptosilane hydrolyzates as coupling agents for mineral-filled elastomer compositions |
| DE102004006116A1 (en) * | 2004-02-06 | 2005-08-25 | Bayer Chemicals Ag | Process for the preparation of monodisperse porous ion exchangers |
| US7915368B2 (en) * | 2007-05-23 | 2011-03-29 | Bridgestone Corporation | Method for making alkoxy-modified silsesquioxanes |
| US20100151206A1 (en) | 2008-12-11 | 2010-06-17 | Air Products And Chemicals, Inc. | Method for Removal of Carbon From An Organosilicate Material |
-
2011
- 2011-10-24 KR KR1020137012929A patent/KR101512580B1/en not_active IP Right Cessation
- 2011-10-24 AU AU2011322203A patent/AU2011322203B2/en not_active Ceased
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- 2011-10-24 WO PCT/IB2011/002531 patent/WO2012056290A1/en active Application Filing
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4290811A (en) * | 1980-03-31 | 1981-09-22 | Rust-Oleum Corporation | Method of producing silicate binders and coatings |
| CN1150764A (en) * | 1994-06-06 | 1997-05-28 | 拜奥波尔公司 | Polymeric microbeads and method of preparation |
Non-Patent Citations (1)
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| FERNANDA M. B. COUTINHO等: "Characterization of sulfonated poly(styrene-divinylbenzene) and poly(divinylbenzene) and its application as catalysts in esterification reaction", 《JOURNAL OF APPLIED POLYMER SCIENCE》, vol. 102, 31 December 2006 (2006-12-31) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112135860A (en) * | 2018-11-27 | 2020-12-25 | 株式会社Lg化学 | Process for the synthesis of prehydrolyzed polysilicates |
| CN112135860B (en) * | 2018-11-27 | 2022-05-03 | 株式会社Lg化学 | Process for the synthesis of prehydrolyzed polysilicates |
| US11945915B2 (en) | 2018-11-27 | 2024-04-02 | Lg Chem, Ltd. | Method for synthesizing pre-hydrolyzed polysilicate |
| CN116948285A (en) * | 2023-07-21 | 2023-10-27 | 广州瑞远新材料股份有限公司 | Integrated polyethylene double-material hose and preparation method thereof |
| CN116948285B (en) * | 2023-07-21 | 2024-02-27 | 广州瑞远新材料股份有限公司 | Integrated polyethylene double-material hose and preparation method thereof |
Also Published As
| Publication number | Publication date |
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| KR101512580B1 (en) | 2015-04-15 |
| AU2011322203A1 (en) | 2013-05-02 |
| AU2011322203B2 (en) | 2015-02-26 |
| IL225723A0 (en) | 2013-06-27 |
| KR20130102086A (en) | 2013-09-16 |
| CN103180368B (en) | 2015-09-23 |
| WO2012056290A1 (en) | 2012-05-03 |
| BR112013010055A2 (en) | 2018-05-08 |
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