CN110003391A - Collect polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object - Google Patents
Collect polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object Download PDFInfo
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- 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
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- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
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- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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Abstract
The present invention discloses a kind of collection polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, with olefin(e) acid salt, alkene acrylic monomer and and graft polymers be polymeric monomer intermixture, initiation system is that water-soluble oxidizers are compounded with natural goods reducing agent, it is placed in refrigerating plant and cools down to system, any chemical change will not still occur for system at this time, when preparation, suspension media and dispersing agent are added into reaction system, temperature is down to -15~-20 DEG C, the completion of initiated polymerization, isothermal reaction, polymerization is completed, the form spherical polymeric beads of generation fall to bottom, separation, which obtains polymer beads and is placed under room temperature, is melted, finally it is dehydrated with dehydrating agent, it is dry to obtain product.The present invention collects polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, realize that polymerization reaction, pore-forming and granulation are completed at the same time, it is reprocessed without subsequent pore-forming, the hole of the superelevation rate of water absorption polymer surfaces and internal uniformly continuous that are prepared, which has the absorption rate of liquid, significantly to be promoted.
Description
Technical field
The present invention relates to Functional polymer materials technology fields, and in particular to be collection polymerization, pore-forming, be granulated synchronous prepare
The method of high water absorption rate aggregation object.
Background technique
High water absorbency polymer is that develop rapidly in recent years a kind of contains strongly hydrophilic with three-dimensional net structure
The novel high molecular polymer of group can quickly absorb large quantity of moisture and be expanded to gelatinous resin, have high-hydroscopicity and
Water-retaining property.High water absorbency polymer is widely used to many fields such as health care, industry, agricultural and daily life, wherein
The medical and hygiene articles such as urinary incontinence mattress, infant's diaper and sanltary towel account for about 70% of the total market size or more.
Traditional high water absorbency polymer is Macromolecule blob of viscose, and microstructure lacks hole, therefore high-hydroscopicity
Polymer absorption path is only diffused from resin surface to three-dimensional net structure, and rate of water absorption is slower, this is current high water absorption
Property polymer research difficult point.Such as infant's diaper and sanltary towel imbibition ability it is low, usually occur urine in use
Or the liquid side leakage such as menstruation, night at least need replacing an amenities.Since high water absorbency polymer generallys use water
Polymerisation in solution preparation, the later period is crushed after long-time is dry, classification obtains superabsorbent polymeric particles shape product, subsequent work
Skill is cumbersome, while polymer is broken uneven, generates a large amount of powder products, " dough " phenomenon occurs in imbibition process, make high suction
The imbibition ability degradation of waterborne polymeric, has been lost a large amount of sold resin.
High water absorbency polymer comprising hole can significantly promote the rate of water absorption of high water absorbency polymer.Existing report
The hole creating technology of the high water absorbency polymer of road or industrialized production has the disadvantage that (1) freeze-drying and freezing
It lures phase detachment technique: being to carry out whole freezing comprehensively on the basis of being rich in the high molecular polymer gel of a large amount of water, then make again
The pressure of system is lower than the saturated vapor pressure of ice under cryogenic temperature, promotes crystallization ice cube integrally to distil and leaves hole inside gel
Gap.This method preparation process period is longer, and the pore-forming time is more than that for 24 hours, freezing needs just ice be made to distil in the environment of negative pressure,
System pressure is under 5~20kPa pressure for a long time, more demanding to Preparation equipment pressure resistance, whole gel often surface elder generation shape
At hole, be finally gel inside at hole, prepared porous water-absorbing polymer hole is uneven.(2) foam dispersion
Method: necessary condition is that system should have foaming agent, or the condensate such as salt (such as sodium carbonate, sodium bicarbonate) and acid generation bulk gas
System, the maximum bottleneck of the polymerization technique are the control of reaction system, and the liquid film in the foam gap that moment generates is as polymerization field
Institute, completing hole, there are gels to exist in the form of dispersed, does not have continuity, furthermore the removal of heat of polymerization and to foam size
Influence all there is complex relationships, therefore the bubble face gel piece of finished product also needs not remove at bore region, need to be with a large amount of molten
Agent removes the impurity such as foaming agent, and subsequent treatment process is complicated.(3) self-propagating FP technology: key point is to utilize conversion zone
The reaction heat of generation causes unreacted region, and the reaction heat with the region of stylish reaction promotes solvent in the gel of fully reacting
Gasification carries out hot pore-forming, therefore the control of heat of polymerization is the difficult point entirely polymerizeing, and reaction overheat causes hole uneven greatly, and polymerization is anti-
Answer temperature at 80~110 DEG C, the excessively high generation for leading to implode phenomenon of temperature；If polymerization temperature is lower, such as made using persulfate
When to cause system, temperature is lower than 60 DEG C, can occur " polymerization is extinguished " phenomenon suddenly, therefore the technology is only in laboratory at present
Conceptual phase, it is difficult to fast and effective prepare with scale porous water-absorbing polymer.
Summary of the invention
It is real the purpose of the present invention is to provide collection polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object
Existing polymerization reaction, pore-forming and granulation are completed at the same time, and are reprocessed without subsequent pore-forming, it is easy to accomplish pilot scale and large-scale production, contracting
The short preparation process of high water absorbency polymer, the superelevation rate of water absorption polymer surfaces being prepared and internal uniformly continuous
Hole, which has the absorption rate of liquid, significantly to be promoted.
In order to achieve the above objectives, solution of the invention is:
Collect polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, comprising the following steps:
Step 1, configuration aqueous phase reactions liquid:
By olefin(e) acid class salt, alkene acrylic monomer and graft polymers, water-soluble cross-linker, water-soluble oxidizers and deionized water
It is mixedly configured into aqueous phase reactions liquid, in the aqueous phase reactions liquid, the mass fraction of the olefin(e) acid class salt is 5~40%, described
The mass fraction of alkene acrylic monomer is 0~20%, and the mass fraction of the graft polymers is 0~20%, the water soluble crosslinkable
The mass fraction for joining agent is 0.1~0.5%, and the mass fraction of the water-soluble oxidizers is 0.5~5%, wherein by the alkene
The mass fraction for the polymeric monomer intermixture that acids salt, alkene acrylic monomer and graft polymers are constituted is controlled 10~50%；
Step 2, low temperature environment dispersion:
The aqueous phase reactions liquid of configuration is injected in reaction environment under the action of metering pump, is placed in freezing equipment
In, the temperature of reaction solution is reduced to 0~-5 DEG C；
Then natural goods reducing agent is added in aqueous phase reactions liquid, the additive amount of the natural goods reducing agent is the water
The 0.2~3.0% of phase reaction liquid mass fraction；
It selects hydrophobic organic solvent as suspension media, the aqueous phase reactions liquid for adding natural goods reducing agent is continuously being stirred
It is broken up in the state of mixing and constitutes suspension polymerization system in suspension media, stirring rate is 200~800r/min, is situated between wherein suspending
Matter and the volume ratio of aqueous phase reactions liquid are 5:1~1:1, and aqueous-phase suspending particle occurs in suspension polymerization system；
Bonding occurs in the course of the polymerization process to avoid aqueous-phase suspending particle for dispersing agent existing into suspension polymerization system simultaneously
As aqueous-phase suspending grain granulation being become spherical particle, the additive amount of the dispersing agent is the aqueous phase reactions liquid mass fraction
1~10%；
Step 3, low temperature environment polymerization: being down to -15~-20 DEG C from 0~-5 DEG C for the temperature of suspension polymerization system, causes poly-
Reaction is closed, 3~9h of isothermal reaction reaches polymerization terminal and completes reaction；
Step 4, post-processing: taking out the reaction system after terminating polymerization reaction, separates by standard machinery and obtains reaction life
At polymer beads, be placed under room temperature and melted, after the ice formation of composition granule to be polymerized is melted, is dehydrated with dehydrating agent
Cleaning, dry, acquisition finished product.
In step 1, the olefin(e) acid class salt is sodium acrylate (AANa), potassium acrylate (AAK), Sodium methacrylate
(MAANa), one or more of in methacrylic acid potassium (MAANa).
In step 1, the alkene acrylic monomer is acrylic acid (AA), methacrylic acid (MAA), maleic acid (MA), anti-
One or more of butene dioic acid (FA), methylene-succinic acid (MSA), 2- acrylamide-2-methylpro panesulfonic acid (AMPS).
In step 1, the graft polymers be starch (AM), sodium carboxymethylcellulose (CMCNa), chitosan (CTS), sea
One or more of mosanom (SNa), sodium humate (SHNa).
In step 1, the water-soluble cross-linker is N hydroxymethyl acrylamide (NMA), N, N '-methylene-bisacrylamide
(MBA), one of ethylene glycol (EG), glycerine (GG), polyethylene glycol (PEG), polypropylene glycol (PPG), propylene glycol (MPD) or
It is several.
In step 1, the water-soluble oxidizers are hydrogen peroxide (HP), ammonium persulfate (APS), potassium peroxydisulfate (KPS), over cure
One or more of sour sodium (SPS), potassium permanganate (PHG).
In step 2, the natural goods reducing agent is the organic substance with reproducibility extracted from natural goods, preferably
Vitamin C (VC) or tea polyphenols (PPH)；The dispersing agent is calcium carbonate (CC), magnesium sulfate (MS), calcium sulfate (MC), phosphoric acid
One or more of calcium (CPT), talcum powder (FC), kaolin (KL), preferably calcium carbonate (CC), calcium sulfate (MC), phosphoric acid
Calcium (CPT)；The suspension media is pentane (NPA), n-hexane (NHA), normal heptane (NHP), normal octane (NOA), gasoline
(GL), one or more of kerosene (KS), toluene (MBZ), petroleum ether (PE), carbon tetrachloride (CTC), preferably kerosene, four
The mixture of chlorination carbon and alkanes mixture, carbon tetrachloride and petroleum ether.
In step 3, temperature is down to -15~-20 DEG C of temperature-fall period control in 5~20min from 0~-5 DEG C.
In step 4, the dehydrating agent is one or more of ethyl alcohol (EA), methanol (ME), acetone (ACT).
After adopting the above technical scheme, the present invention collects polymerization, pore-forming, the side for being granulated synchronous preparation high water absorption rate aggregation object
Method, using olefin(e) acid salt, alkene acrylic monomer and and graft polymers as polymeric monomer intermixture, initiation system be water soluble oxidized
Agent is compounded with natural goods reducing agent, is placed in refrigerating plant and is cooled down to reaction system, and system will not still occur at this time
The temperature of reaction system when preparation, is down to -15~-20 DEG C, controls the reaction time by any chemical change, during this, reaction
The environment temperature of system reduces, and phenomenon of phase separation occurs for aqueous solvent, i.e., occurs a large amount of ice pellets formed by cooling, structure in system
At ice formation, it is in situ as pore former that solid phase ice pellets can not participate in reaction；Non- ice formation reactant concentration increases simultaneously, and activation energy is low
Redox initiation system still generate at a lower temperature and cause free radical, it is permanent thus the completion of initiated polymerization
After 3~9h of temperature reaction, polymerization is completed, and the form spherical polymeric beads of generation fall to bottom, is separated and is obtained by standard machinery
Polymer beads, which are placed under room temperature, to be melted, and leaves continuous state on the surface of polymer beads and inside after the thawing of ice formation
Hole, finally carry out simple dehydration, dry i.e. acquisition product with dehydrating agent.
Therefore, which is to utilize inverse suspension polymerization technology, alkene acrylic monomer and its grafting at low ambient temperatures
Copolymer causes polymerization under the action of reductant-oxidant, realize spherical particle ontology internal solvent be separated into hole, polymerization reaction,
Product is granulated while carrying out, and a step completes polymerization technique in the short time, and post-processing is simple, and product utilization rate is high.
The present invention collects polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, has below beneficial to effect
Fruit:
(1) granular superelevation rate of water absorption polymer can be efficiently prepared, the hole of polymer is by aqueous phase reactions liquid itself
The cooling of aqueous solvent at ice pellets caused by, can by polymerization, pore-forming, be granulated a step be completed at the same time operation, therefore preparation process efficiency
Height can promote large-scale production；
(2) innovation selects natural goods reducing agent to replace traditional reducing agent, in favor of alkene acrylic monomer in low temperature environment into
Row polymerization reaction, polymerization time shorten 1 times or more than existing low temperature polymerization technology, are completed in a short time polymerization reaction, polymerize
It is high-efficient；
(3) the finished product superelevation rate of water absorption polymer being prepared is rendered as spherical particle, particle size distribution 0.1
~2mm, polymer have the continuous hole from surface to inner open, and for pore-size at 10~80 μm, pore-forming technique is advanced can
Control；Guarantee to make water imbibition polymers reach water suction equilibrium state within the < 30sec time under the capillarity of hole.
To sum up, collect polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, realize polymerization reaction, pore-forming
It is completed at the same time with granulation, is reprocessed without subsequent pore-forming, it is easy to accomplish pilot scale and large-scale production shorten high-hydroscopicity polymerization
Absorption of the hole of the preparation process of object, the superelevation rate of water absorption polymer surfaces being prepared and internal uniformly continuous to liquid
Rate, which has, significantly to be promoted.
Specific embodiment
In order to further explain the technical solution of the present invention, being explained in detail below by specific embodiment the present invention
It states.
Embodiment 1
One, petrochemical material acrylic acid (AA) and its sodium salt (AANa) is selected to be used as main polymerisation chain growth monomer, acrylic acid
Sodium (AANa) a large amount of Na since side chain contains, macromolecule have very strong hydrophily, improve making for water absorbent polymer
With performance and cost of material is reduced, selects sodium carboxymethylcellulose (CMCNa) as graft polymers, under this preparation method
Prepare the polymer with superelevation rate of water absorption.
Collect polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, comprising the following steps:
Step 1, configuration CMCNa aqueous solution: in the state of magnetic agitation, taking CMCNa to be slowly dissolve into deionized water,
It is that 15%CMCNa aqueous solution is spare that formation, which is configured to mass fraction,；
Step 2, configuration aqueous phase reactions liquid:
By AANa, AA monomer, N, N '-methylene-bisacrylamide (MBA), sodium peroxydisulfate (SPS) are mixed with deionized water
It is configured to aqueous solution, in the state of magnetic agitation, the CMCNa aqueous solution of above-mentioned configuration is added to the aqueous solution, is formed and is stablized
Aqueous phase reactions liquid；
In aqueous phase reactions liquid, it is 4.8%, CMCNa that the mass fraction for controlling AANa, which is the mass fraction of 22%, AA monomer,
Mass fraction be 2.2%, MBA mass fraction be 0.15%, SPS mass fraction be 2.8%；At this point, reaction system
Temperature is room temperature, fails the activation energy temperature for reaching SPS decomposition, therefore any polymerization reaction will not occur for reaction system；
Step 2, low temperature environment dispersion:
1. being injected the aqueous phase reactions liquid of configuration in the reaction kettle with agitating device under the action of metering pump, it is placed in cold
Freeze in equipment, reduces the temperature of aqueous phase reactions liquid to -2 DEG C；
2. then vitamin C (VC) is added in aqueous phase reactions liquid, the additive amount of VC is aqueous phase reactions liquid mass fraction
1.5%；
3. selecting volume ratio is the carbon tetrachloride (CTC) of 1:1 and the mixture of pentane (NPA) as suspension media, drop
The temperature of low suspension media is to -5 DEG C；
4. the aqueous phase reactions liquid for adding VC is broken up in the state of continuously stirring and constitutes suspension polymerisation in suspension media
System, stirring rate are 380~400r/min, and wherein the volume ratio of suspension media and aqueous phase reactions liquid is 2.4:1, suspension polymerisation
There is the aqueous-phase suspending particle of uniform diameter in system, while adding calcium carbonate (CC) into suspension polymerization system, to avoid water phase
Suspended particulate occurs to be bonded phenomenon in the course of the polymerization process, under the action of mechanical stirring shearing force, by aqueous-phase suspending grain granulation
As spherical particle, the additive amount of calcium carbonate (CC) is the 2% of aqueous phase reactions liquid mass fraction；
Step 3, low temperature environment polymerization: the temperature of suspension polymerization system is down to -20 DEG C in 12min, is being suspended at this time
Aqueous solvent inside polymerization system initially forms ice pellets, while non-ice formation part reaction solution concentration increases, and SPS is aoxidized with VC
Reduction reaction maintains -20 DEG C of isothermal reaction 7h with the generation of this initiated polymerization, reaches polymerization terminal and completes reaction；
Step 4, post-processing: taking out the reaction system after terminating polymerization reaction, filters by standard machinery and obtains reaction life
At polymer beads, be placed under room temperature and melted, after the ice formation of composition granule to be polymerized is melted, carried out with acetone (ACT)
Dehydration is cleaned, dry in 60 DEG C of baking ovens, obtains finished product.
Two, prepared superelevation rate of water absorption polymer beads are regular, handle without subsequent reprocessing, and particle size range is
0.5~1.5mm, porosity 82%, 10~60 μm of pore diameter range, hole is continuously distributed in polymeric inner, passes through the superelevation
Rate of water absorption polymer determines its uptake and rate of water absorption to the study on monitoring of water, physiological saline adsorbance, as a result such as 1 institute of table
Show, the saturated extent of adsorption of deionized water is 1080g/g, and 8sec reaches adsorption equilibrium state, and the saturated extent of adsorption of physiological saline is
92g/g, 15sec reach adsorption equilibrium state, guarantee there is superelevation absorption rate while high adsorption capacity.
Embodiment 2
One, it selects sodium acrylate (AANa), methacrylic acid (MAA) to be used as main polymerisation chain growth monomer, selects de- second
The chitosan (CTS) that acyl degree is 90% is used as graft polymers, and preparation has the poly- of superelevation rate of water absorption under this preparation method
Close object.
Collect polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, comprising the following steps:
Step 1, configuration CTS acetic acid solution: in the state of magnetic agitation, CTS is taken to be dissolved in 2% glacial acetic acid, configured
Mass fraction is that 15%CTS acetic acid solution is spare；
Step 2, configuration aqueous phase reactions liquid: by AANa, MAA monomer, N, N '-methylene-bisacrylamide (MBA), permanganic acid
Potassium (PHG) and deionized water are mixedly configured into aqueous solution, in the state of magnetic agitation, add above-mentioned configuration to the aqueous solution
CTS acetic acid solution forms stable aqueous phase reactions liquid；
In aqueous phase reactions liquid, it is 4.1%, CTS's that the mass fraction for controlling AANa, which is the mass fraction of 18%, AA monomer,
The mass fraction that the mass fraction that mass fraction is 1.8%, MBA is 0.12%, PHG is 3.2%；At this point, the temperature of reaction system
Degree is room temperature, fails the activation energy temperature for reaching PHG decomposition, therefore any polymerization reaction will not occur for reaction system；
Step 2, low temperature environment dispersion:
1. being injected the aqueous phase reactions liquid of configuration in the reaction kettle with agitating device under the action of metering pump, it is placed in cold
Freeze in equipment, reduces the temperature of aqueous phase reactions liquid to -4 DEG C；
2. then vitamin C (VC) is added in aqueous phase reactions liquid, the additive amount of VC is aqueous phase reactions liquid mass fraction
1.7%；
3. selecting kerosene (KS) as suspension media, the temperature of suspension media is reduced to -3 DEG C；
4. the aqueous phase reactions liquid for adding VC is broken up in the state of continuously stirring and constitutes suspension polymerisation in suspension media
System, stirring rate are 500~520r/min, and wherein the volume ratio of suspension media and aqueous phase reactions liquid is 1.8:1, suspension polymerisation
There is the aqueous-phase suspending particle of uniform diameter in system, while adding calcium carbonate (CC) into suspension polymerization system, to avoid water phase
Suspended particulate occurs to be bonded phenomenon in the course of the polymerization process, under the action of mechanical stirring shearing force, by aqueous-phase suspending grain granulation
As spherical particle, the additive amount of calcium carbonate (CC) is the 4% of aqueous phase reactions liquid mass fraction；
Step 3, low temperature environment polymerization: the temperature of suspension polymerization system is down to -18 DEG C in 15min, is being suspended at this time
Aqueous solvent inside polymerization system initially forms ice pellets, while non-ice formation part reaction solution concentration increases, and PHG is aoxidized with VC
Reduction reaction maintains -18 DEG C of isothermal reaction 8h with the generation of this initiated polymerization, reaches polymerization terminal and completes reaction；
Step 4, post-processing: taking out the reaction system after terminating polymerization reaction, filters by standard machinery and obtains reaction life
At polymer beads, be placed under room temperature and melted, after the ice formation of composition granule to be polymerized is melted, with 100% ethyl alcohol (EA)
Carry out dehydration cleaning, dry, acquisition finished product in 60 DEG C of baking ovens.
Two, prepared superelevation rate of water absorption polymer beads are regular, handle without subsequent reprocessing, and particle size range is
0.4~1.2mm, porosity 87%, 10~80 μm of pore diameter range, hole is continuously distributed in polymeric inner, passes through the superelevation
Rate of water absorption polymer determines its uptake and rate of water absorption to the study on monitoring of water, physiological saline adsorbance, as a result such as 1 institute of table
Show, the saturated extent of adsorption of deionized water is 968g/g, and 9sec reaches adsorption equilibrium state, and the saturated extent of adsorption of physiological saline is 87g/
G, 18sec reach adsorption equilibrium state, guarantee there is superelevation absorption rate while high adsorption capacity.
Embodiment 3
It selects acrylic acid (AA) and its sodium salt (AANa) to be used as main polymerisation chain growth monomer, selects sodium alginate (SNa)
As graft polymers, preparation has the polymer of superelevation rate of water absorption under this preparation method.
Collect polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, comprising the following steps:
Step 1, configuration SNa aqueous solution: in the state of ultrasonic oscillation, SNa is taken to be dissolved in deionized water, configures matter
It is spare to measure the SNa aqueous solution that score is 10%；
Step 2, configuration aqueous phase reactions liquid: by AANa, AA monomer, N, N '-methylene-bisacrylamide (MBA), persulfuric acid
Potassium (KPS) and deionized water are mixedly configured into aqueous solution, in the state of magnetic agitation, add above-mentioned configuration to the aqueous solution
SNa aqueous solution forms stable aqueous phase reactions liquid；
In aqueous phase reactions liquid, it is 3.9%, SNa that the mass fraction for controlling AANa, which is the mass fraction of 20.5%, AA monomer,
Mass fraction be 3.2%, MBA mass fraction be 0.2%, KPS mass fraction be 3.5%；
At this point, the temperature of reaction system is room temperature, fail the activation energy temperature for reaching KPS decomposition, therefore reaction system will
Any polymerization reaction does not occur；
Step 2, low temperature environment dispersion:
1. being injected the aqueous phase reactions liquid of configuration in the reaction kettle with agitating device under the action of metering pump, it is placed in cold
Freeze in equipment, reduces the temperature of aqueous phase reactions liquid to -4 DEG C；
2. then tea polyphenols (PPH) are added in aqueous phase reactions liquid, the additive amount of PPH is aqueous phase reactions liquid mass fraction
2.1%；
4. selecting volume ratio is the carbon tetrachloride (CTC) of 1:1.2 and the mixture of n-hexane (NHA) as suspension media,
The temperature of suspension media is reduced to -4 DEG C；
4. the aqueous phase reactions liquid for adding PPH is broken up in the state of continuously stirring and constitutes suspension polymerisation in suspension media
System, stirring rate are 360~380r/min, and wherein the volume ratio of suspension media and aqueous phase reactions liquid is 1.9:1, suspension polymerisation
There is the aqueous-phase suspending particle of uniform diameter in system, while adding calcium carbonate (CC) into suspension polymerization system, to avoid water phase
Suspended particulate occurs to be bonded phenomenon in the course of the polymerization process, under the action of mechanical stirring shearing force, by aqueous-phase suspending grain granulation
As spherical particle, the additive amount of calcium carbonate (CC) is the 2% of aqueous phase reactions liquid mass fraction；
Step 3, low temperature environment polymerization: the temperature of suspension polymerization system is down to -20 DEG C in 15min, is being suspended at this time
Aqueous solvent inside polymerization system initially forms ice pellets, while non-ice formation part reaction solution concentration increases, and oxygen occurs for KPS and PPH
Change reduction reaction, with the generation of this initiated polymerization, maintain -20 DEG C of isothermal reaction 8h, reaches polymerization terminal and complete reaction；
Step 4, post-processing: taking out the reaction system after terminating polymerization reaction, filters by standard machinery and obtains reaction life
At polymer beads, be placed under room temperature and melted, after the ice formation of composition granule to be polymerized is melted, carried out with acetone (ACT)
Dehydration is cleaned, dry in 60 DEG C of baking ovens, obtains finished product.
Two, prepared superelevation rate of water absorption polymer beads are regular, handle without subsequent reprocessing, and particle size range is
0.5~1.8mm, porosity 76%, 10~70 μm of pore diameter range, hole is continuously distributed in polymeric inner, passes through the superelevation
Rate of water absorption polymer determines its uptake and rate of water absorption to the study on monitoring of water, physiological saline adsorbance, as a result such as 1 institute of table
Show, the saturated extent of adsorption of deionized water is 998g/g, and 10sec reaches adsorption equilibrium state, and the saturated extent of adsorption of physiological saline is
84g/g, 17sec reach adsorption equilibrium state, guarantee there is superelevation absorption rate while high adsorption capacity.
Embodiment 4
One, select Sodium methacrylate (MAANa), 2- acrylamide-2-methylpro panesulfonic acid (AMPS) as main poly-
Chain growth monomer is closed, selects sodium carboxymethylcellulose (CMCNa) as graft polymers, preparation has super under this preparation method
The polymer of high water absorption rate.
Collect polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, comprising the following steps:
Step 1, configuration CMCNa aqueous solution: in the state of magnetic agitation, taking CMCNa to be slowly dissolve into deionized water,
It is spare to be configured to the CMCNa aqueous solution that mass fraction is 15%；
Step 2, configuration aqueous phase reactions liquid: by MAANa, AMPS monomer, N, N '-methylene-bisacrylamide (MBA), over cure
Sour sodium (SPS) and deionized water are mixedly configured into aqueous solution, in the state of magnetic agitation, add above-mentioned configuration to the aqueous solution
CMCNa aqueous solution, form stable aqueous phase reactions liquid；
In aqueous phase reactions liquid, it is 4.5% that the mass fraction for controlling MAANa, which is the mass fraction of 24.5%, AMPS monomer,
The mass fraction that the mass fraction that the mass fraction of CMCNa is 3.0%, MBA is 0.18%, SPS is 3.6%；
At this point, the temperature of reaction system is room temperature, fail the activation energy temperature for reaching SPS decomposition, therefore reaction system will
Any polymerization reaction does not occur；
Step 2, low temperature environment dispersion:
1. being injected the aqueous phase reactions liquid of configuration in the reaction kettle with agitating device under the action of metering pump, it is placed in cold
Freeze in equipment, reduces the temperature of aqueous phase reactions liquid to -5 DEG C；
2. then tea polyphenols (PPH) are added in aqueous phase reactions liquid, the additive amount of PPH is aqueous phase reactions liquid mass fraction
1.8%；
3. selecting volume ratio is the carbon tetrachloride (CTC) of 1:1 and the mixture of petroleum ether (PE) as suspension media, reduce
The temperature of suspension media is to -5 DEG C；
4. the aqueous phase reactions liquid for adding PPH is broken up in the state of continuously stirring and constitutes suspension polymerisation in suspension media
System, stirring rate are 450~470r/min, and wherein the volume ratio of suspension media and aqueous phase reactions liquid is 2.2:1, suspension polymerisation
There is the aqueous-phase suspending particle of uniform diameter in system, while adding calcium carbonate (CC) into suspension polymerization system, to avoid water phase
Suspended particulate occurs to be bonded phenomenon in the course of the polymerization process, under the action of mechanical stirring shearing force, by aqueous-phase suspending grain granulation
As spherical particle, the additive amount of calcium carbonate (CC) is the 2.4% of aqueous phase reactions liquid mass fraction；
Step 3, low temperature environment polymerization: the temperature of suspension polymerization system is down to -20 DEG C in 10min, is being suspended at this time
Aqueous solvent inside polymerization system initially forms ice pellets, while non-ice formation part reaction solution concentration increases, and oxygen occurs for SPS and PPH
Change reduction reaction, with the generation of this initiated polymerization, maintain -20 DEG C of isothermal reaction 8.5h, reaches polymerization terminal and complete reaction；
Step 4, post-processing: taking out the reaction system after terminating polymerization reaction, filters by standard machinery and obtains reaction life
At polymer beads, be placed under room temperature and melted, after the ice formation of composition granule to be polymerized is melted, taken off with methanol (ME)
Water cleans, dry in 60 DEG C of baking ovens, obtains finished product.
Two, prepared superelevation rate of water absorption polymer beads are regular, handle without subsequent reprocessing, and particle size range is
0.2~1.6mm, porosity 75%, 10~70 μm of pore diameter range, hole is continuously distributed in polymeric inner, passes through the superelevation
Rate of water absorption polymer determines its uptake and rate of water absorption to the study on monitoring of water, physiological saline adsorbance, as a result such as 1 institute of table
Show, the saturated extent of adsorption of deionized water is 1125g/g, and 12sec reaches adsorption equilibrium state, and the saturated extent of adsorption of physiological saline is
96g/g, 23sec reach adsorption equilibrium state, guarantee there is superelevation absorption rate while high adsorption capacity.
1 superelevation rate of water absorption polymer orifices gauge structure of table and the study on monitoring result to water, physiological saline adsorbance
Above-described embodiment and non-limiting product form and style of the invention, the ordinary skill people of any technical field
The appropriate changes or modifications that member does it, all should be regarded as not departing from patent category of the invention.
Claims (9)
1. collecting polymerization, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, it is characterised in that: the following steps are included:
Step 1, configuration aqueous phase reactions liquid:
Olefin(e) acid class salt, alkene acrylic monomer and graft polymers, water-soluble cross-linker, water-soluble oxidizers are mixed with deionized water
It is configured to aqueous phase reactions liquid, in the aqueous phase reactions liquid, the mass fraction of the olefin(e) acid class salt is 5~40%, the olefin(e) acid
The mass fraction of class monomer is 0~20%, and the mass fraction of the graft polymers is 0~20%, the water-soluble cross-linker
Mass fraction be 0.1~0.5%, the mass fractions of the water-soluble oxidizers is 0.5~5%, wherein by the olefin(e) acid class
The mass fraction for the polymeric monomer intermixture that salt, alkene acrylic monomer and graft polymers are constituted is controlled 10~50%；
Step 2, low temperature environment dispersion:
The aqueous phase reactions liquid of configuration is injected in reaction environment under the action of metering pump, is placed in freezing equipment, is dropped
The temperature of low reaction liquid is to 0~-5 DEG C；
Then natural goods reducing agent is added in aqueous phase reactions liquid, the additive amount of the natural goods reducing agent is that the water phase is anti-
Answer the 0.2~3.0% of liquid mass fraction；
It selects hydrophobic organic solvent as suspension media, the aqueous phase reactions liquid that adds natural goods reducing agent is being continuously stirred
Broken up under state and constitute suspension polymerization system in suspension media, stirring rate be 200~800r/min, wherein suspension media with
The volume ratio of aqueous phase reactions liquid is 5:1~1:1, and aqueous-phase suspending particle occurs in suspension polymerization system；
Dispersing agent occurs to be bonded phenomenon to avoid aqueous-phase suspending particle in the course of the polymerization process into suspension polymerization system simultaneously, will
Aqueous-phase suspending grain granulation becomes spherical particle, the additive amount of the dispersing agent be the aqueous phase reactions liquid mass fraction 1~
10%；
Step 3, low temperature environment polymerization: the temperature of suspension polymerization system is down to -15~-20 DEG C from 0~-5 DEG C, it is anti-to cause polymerization
It should occur, 3~9h of isothermal reaction, reach polymerization terminal and complete reaction；
Step 4, post-processing: taking out the reaction system after terminating polymerization reaction, separates by standard machinery and obtains what reaction generated
Polymer beads are placed under room temperature and are melted, and after the ice formation of composition granule to be polymerized is melted, be dehydrated with dehydrating agent clear
It washes, dry, obtain finished product.
2. collection polymerization according to claim 1, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, special
Sign is: in step 1, the olefin(e) acid class salt is sodium acrylate, one in potassium acrylate, Sodium methacrylate, methacrylic acid potassium
Kind is several.
3. collection polymerization according to claim 1, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, special
Sign is: in step 1, the alkene acrylic monomer is acrylic acid, methacrylic acid, maleic acid, fumaric acid, methylene
One or more of succinic acid, 2- acrylamide-2-methylpro panesulfonic acid.
4. collection polymerization according to claim 1, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, special
Sign is: in step 1, the graft polymers is starch, in sodium carboxymethylcellulose, chitosan, sodium alginate, sodium humate
One or more.
5. collection polymerization according to claim 1, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, special
Sign is: in step 1, the water-soluble cross-linker is N hydroxymethyl acrylamide, N, N '-methylene-bisacrylamide, second two
One or more of alcohol, glycerine, polyethylene glycol, polypropylene glycol, propylene glycol.
6. collection polymerization according to claim 1, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, special
Sign is: in step 1, the water-soluble oxidizers are hydrogen peroxide, in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, potassium permanganate
One or more.
7. collection polymerization according to claim 1, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, special
Sign is: in step 2, the natural goods reducing agent is the organic substance with reproducibility extracted from natural goods, preferably
Vitamin C or tea polyphenols；The dispersing agent is calcium carbonate, magnesium sulfate, calcium sulfate, calcium phosphate, talcum powder, one in kaolin
Kind is several, preferably calcium carbonate, calcium sulfate, calcium phosphate；The suspension media is pentane, n-hexane, normal heptane, just pungent
One or more of alkane, gasoline, kerosene, toluene, petroleum ether, carbon tetrachloride, preferably kerosene, carbon tetrachloride and alkanes are mixed
Close the mixture of object, carbon tetrachloride and petroleum ether.
8. collection polymerization according to claim 1, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, special
Sign is: in step 3, temperature being down to -15~-20 DEG C of temperature-fall period control in 5~20min from 0~-5 DEG C.
9. collection polymerization according to claim 1, pore-forming, the method for being granulated synchronous preparation high water absorption rate aggregation object, special
Sign is: in step 4, the dehydrating agent is one or more of ethyl alcohol, methanol, acetone.
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| CN112553679A (en) * | 2020-11-03 | 2021-03-26 | 中国航发北京航空材料研究院 | Monomer separation method for harmful phase of isothermal forging die material for turbine disc |
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| CN112553679B (en) * | 2020-11-03 | 2024-02-09 | 中国航发北京航空材料研究院 | Method for separating harmful phase monomer from isothermal forging die material for turbine disk |
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