CN103122046A - Production method of acrylic polymer resin and products produced thereby - Google Patents
Production method of acrylic polymer resin and products produced thereby Download PDFInfo
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- CN103122046A CN103122046A CN2011103668073A CN201110366807A CN103122046A CN 103122046 A CN103122046 A CN 103122046A CN 2011103668073 A CN2011103668073 A CN 2011103668073A CN 201110366807 A CN201110366807 A CN 201110366807A CN 103122046 A CN103122046 A CN 103122046A
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Abstract
The invention discloses a production method of acrylic polymer resin. The production method includes the steps of forming bulky hydrogel of acrylic polymer, granulating and drying. The production method is characterized in that by weight of the bulky hydrogel of acrylic polymer, 6-7% of initiator solution is added to obtain gel granules 15-25mm in diameter; the drying step includes two drying stages, drying in the first stage is at 50-110 DEG C for the duration of 5-20 minutes, and drying the second stage is at 110-180 DEG C for the duration of 10-30 minutes. The invention further discloses products produced by the production method and applications thereof.
Description
Technical field
The present invention relates to a kind of method for preparing low Acrylic Acid Monomer residual volume, super absorbent resin, the high-absorbable resin made by the inventive method is particularly useful for for example sanitary napkin, baby paper diaper, adult-incontinence articles, the disposable mattress of hospital etc. health field.
Technical background
High absorptive resin in acrylic acid type is the macromolecular material of a kind of safety, environmental protection, and because its water-absorbent is high, water-retentivity is strong, so it has been subject to application widely at health field.
At present at health field widespread use high absorptive resin in acrylic acid type such as sanitary napkin, baby paper diaper, adult-incontinence articles, the disposable mattresses of hospital.While being used due to these products and the human skin intimate contact, therefore to the content requirement of residual acrylic monomer in super absorbent resin (SAP) product and strict.At present to the super absorbent resin for health field, in the world the control of residual acrylic monomer content is commonly lower than 500ppm, if single residual content is higher, acrylic acid acidic character can produce to skin the uncomfortable symptoms such as itch, erythema, allergy, therefore, more low better to the vinylformic acid single residual content requirement of one of super absorbent resin product performance index.
The preparation method of super absorbent resin obtains final finished after being included under certain conditions of mixture ratios and raw material being prepared to polymerization single polymerization monomer solution, monomer polymerization, the resulting polymeric gel thing of dry polyreaction, pulverizing sub-sieve, particle surface processing.
With regard to acrylic type high-absorbable resin, in polymerization process, the height of acroleic acid polymerization monomer conversion directly affects the content of residual acrylic monomer in the finished product.In addition, the existence of dimer in the acroleic acid polymerization monomer (DAA) also has influence on the content of residual acrylic monomer in the finished product, its reason is that the acroleic acid polymerization monomer is undersaturated olefin(e) compound, physical property is more active, easily generate acrylic acid dimer or other oligopolymer, in the polymerization process for preparing the high-absorbable resin, dimeric pair of key opened on the main chain that can be attached to polymkeric substance, under the drying and the high-temperature situation in solid particles surface crosslinking Treatment process of follow-up high-absorbable resin gel particle, the dimer of polymerization produces the Michael reversed reaction and generates Acrylic Acid Monomer, thereby cause the increase of remaining acrylic acid content in product.
Prior art has proposed the method for multiple minimizing acrylic acid oligomer.For example, Chinese patent CN1723223A discloses a kind of method that reduces the oligopolymer such as acrylic acid dimer and trimer in raw material, and it is, before the high water-base resin of preparation, raw material propylene acid is carried out to the purpose that crystallization reaches the purifying propenoic acid raw material.But this method makes troubles to suitability for industrialized production on the one hand, using and storing also and have higher requirement raw material propylene acid on the other hand.
Chinese patent CN1628146A discloses a kind of method that reduces vinylformic acid residual monomer content in product, and it is included in the epomine solution that sprays into high molecular in the surface-crosslinked process of super absorbent resin.Although this method can reduce the residual acrylic monomer content in product to a certain extent, due to what add, be pluronic polymer, therefore, soltion viscosity is higher on the one hand, easy plug nozzle in commercial process, thus bring difficulty to production; Color due to high molecular polymer can cause the product colour of preparation to increase the weight of on the other hand, and this is that the sanitary material user does not wish to see.
Therefore, still need to develop a kind of high-absorbable resin with low residual monomer content.
Summary of the invention
A goal of the invention of the present invention is to provide a kind of super absorbent resin of low residual monomer content.
Another goal of the invention of the present invention is to provide a kind of manufacture method of super absorbent resin of low residual monomer content.
Therefore, one aspect of the present invention relates to a kind of manufacture method of acrylic polymer resins, and it comprises block water gel, granulation and the drying step that forms acrylic polymers, it is characterized in that:
In described granulation process, press the weighing scale of the block water gel of acrylic polymers, add the initiator solution of 4-8%, obtain the gel particle that diameter is 15-25mm;
Described drying step carries out successively in two dryer section:
The temperature of the first dryer section is that 50-110 ℃, the residence time are 5-20 minute;
The temperature of the second dryer section is for being greater than 110 to 180 ℃, and the residence time is 10-30 minute.
Another aspect of the present invention relates to a kind of acrylic polymer resins, and its number-average molecular weight is 500,000～1,200,000 dalton, weight-average molecular weight is 500,000～1,200,000 dalton, water-absorbent is 300～800g/g, and the content of remaining acrylic monomer is less than 100ppm.
Embodiment
In the present invention, term " acrylic polymers " refers to a kind of polymkeric substance that formed by acrylic monomer or that mainly formed by acrylic monomer.
In the present invention, term " mainly formed by acrylic monomer polymkeric substance " refers to a kind of like this polymkeric substance, the amount that wherein is derived from the monomeric unit of acrylic monomer account for 70 % by weight or more than, better 80 % by weight or more than, better 90 % by weight or more than.
In described " mainly formed by acrylic monomer polymkeric substance ", with the monomer of described acrylic monomer copolymerization can be any ethylene linkage unsaturated monomer known in the art, its indefiniteness example has, for example C
2-C
5straight or branched alkene (such as ethene, propylene, n-butene etc.), vinylbenzene etc.
In the present invention, term " acrylic monomer " comprises (methyl) vinylformic acid C
1-8two or more mixture of alkane ester, (methyl) acrylamide, (methyl) vinyl cyanide, (methyl) vinylformic acid or its.
In the present invention, term " (methyl) " adds another term, and for example " acrylate " or " acrylamide " and so on, both meaned respectively acrylate or acrylamide, means again methacrylic ester or Methacrylamide.
The present invention relates to a kind of manufacture method of acrylic polymer resins, it comprises block water gel, granulation and the drying step that forms acrylic polymers.
i. form the block water gel of acrylic polymers
In the present invention, form in the method for acrylic polymer resins, the method for the block water gel of formation acrylic polymers is without particular limitation, can be any ordinary method known in the art.
In an example of the present invention, the method for the block water gel of described formation acrylic polymers comprises the steps:
(1) for example, when acrylic monomer is acid monomer (vinylformic acid or methacrylic ester), need to be neutralized it.In an example of the present invention, described acrylic monomer is (methyl) vinylformic acid, and described method comprises that take the ratio that the mol ratio of acrylic monomer and alkali is 1: 0.6 to 1: 0.9 mixes acrylic compounds in liquid medium mutually with alkali:
Applicable alkali is without particular limitation, can be this area alkali commonly used, for example alkali metal hydroxide, alkaline earth metal hydroxides, there is alkaline transition metal hydroxide etc.The indefiniteness example of described alkali has, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, aluminium hydroxide, ammoniacal liquor, sodium carbonate, salt of wormwood, sodium bicarbonate etc.
Described liquid medium is without particular limitation, as long as it does not affect polyreaction subsequently.In a better example of the present invention, described liquid medium is deionized water.
(2) by the weighing scale of described acrylic monomer, add the linking agent of 0.30-1.0% and the initiator of 0.1-0.6%, form polymerization single polymerization monomer solution:
Suitable linking agent is without particular limitation, can be any conventional linking agent known in the art.The indefiniteness example of applicable linking agent has, and such as oxyethyl group glycerol tri-acrylate, polyethyleneglycol diacrylate, Viscoat 295 etc. has the compound of two or above unsaturated functional group.
Suitable initiator (below be called polymerization starter) is without particular limitation, can be any normal starter known in the art.The indefiniteness example of applicable initiator has, for example, and the mixture that the thermolysis type initiator such as persulphate (as ammonium persulphate, Potassium Persulphate), Diisopropyl azodicarboxylate and two or more above-mentioned initiators form with arbitrary proportion.
In the methods of the invention, by the weighing scale of described acrylic monomer, the amount of contained linking agent preferably 0.3-0.80%, 0.4-0.6%, preferably 0.42% more preferably in the polymerization single polymerization monomer solution formed.
In the methods of the invention, by the weighing scale of described acrylic monomer, the amount of the contained polymerization starter that forms polymkeric substance for polyreaction preferably 0.2-0.5%, more preferably 0.25-0.4% in the polymerization single polymerization monomer solution formed.In a better example of the present invention, by the weighing scale of described acrylic monomer, in the polymerization single polymerization monomer solution formed, the amount of the contained initiator that is used to form polymkeric substance is 0.26%.
(3) polymerization single polymerization monomer solution obtained is made to the hydrogel of large block acrylic polymers under microwave radiation by the high temperature static polymerization;
Polymeric reaction condition of the present invention is without particular limitation, can be any polymeric reaction condition known in the art.In an example of the present invention, the polymerization of acrylic monomer is carried out under microwave radiation, and microwave power and microwave radiation amount are without particular limitation, can be the amount of any routine known in the art.For example the polymerization single polymerization monomer solution made above can be placed to 5-2 minute under the microwave of 2000-4000W power, obtain the hydrogel of large block acrylic polymers.
In a better example of the present invention, the polymerization liquid (being polymerization single polymerization monomer solution) of the acrylic monomer of formation is placed to 3 minutes under the microwave of 2500W power.
ii. granulation
For acquisition has the acrylic polymers of suitable particles particle diameter, the hydrogel of the large block acrylic polymers that need to make above-mentioned polyreaction carries out granulation step.In granulation step of the present invention, press the weighing scale of the block water gel of acrylic polymers, add the initiator solution (for ease of describing, below being referred to as dry initiator) of 4-8%, obtain the gel particle that diameter is 15-25mm:
Described dry initiator is without particular limitation, can be this area polypropylene acids monomer initiator commonly used.It is identical or different for polymerization starter that described dry initiator is used in the time of can be with aforesaid propylene acids monomer polymerization, better adopts identical initiator.The indefiniteness example of described dry initiator has, thermolysis type initiators such as persulphate (as ammonium persulphate, Potassium Persulphate), Diisopropyl azodicarboxylate or the mixture that also can use two or more above-mentioned initiator to form with arbitrary proportion.
The prilling process of the block water gel of described acrylic polymers is without particular limitation, can be the prilling process of any routine known in the art.At one preferably in example of the present invention, described prilling process comprises stripping and slicing, separates broken two steps.
In a better example of the present invention, described prilling process comprise will make the first slitting of gel after stripping and slicing, make the gel lumpy material of 1000 * 500mm.With 25-29kg/hr speed, add screw rod machine for decomposing and smashing (RY-8 (S) model, purchased from positive element precision optical machinery company limited) to be separated broken granulation block gel masses, spray into the dry initiator of 0.5-5wt% concentration simultaneously in gel surface with the 1-2.5kg/hr flow, the 4-8wt% that the add-on that makes initiator is gel weight, obtaining diameter is the hydrogel particle that 15-25mm left and right, water content are 40-60%.
In granulation step of the present invention, press the weighing scale of the block water gel of acrylic polymers, the add-on of described dry initiator is 4.5-7.5% preferably, and more preferably the 5-7 % by weight, be preferably 6.0-6.5%.
iii. dry
Drying step of the present invention carries out successively in two dryer section:
A) temperature of the first dryer section is that 50-110 ℃, the residence time are 5-20 minute;
The temperature of the first dryer section is 60-100 ℃ preferably, and more preferably 65-95 ℃, be preferably 70-90 ℃; The residence time is 6-18 minute, and preferably 8-16 minute, be preferably 10-14 minute.
In an example of the present invention, described the first dryer section adopts the warm air drying method, and the air quantity of its heating hot blast is 55-85m
3/ hour, 60-80m preferably
3/ hour, 65-75m more preferably
3/ hour.
After the first dryer section processing treatment, the water content of gel particle of the present invention is generally the 35-50 % by weight, preferably 40-45 % by weight, more preferably 42-43 % by weight.
The first dryer section makes the residual acrylic monomer in gel particle carry out Raolical polymerizable under certain water content environment, reach and reduce remaining acrylic acid purpose.
B) temperature of the second dryer section is for being greater than 110 to 180 ℃, and the residence time is 10-30 minute.
The temperature of the second dryer section is 120-160 ℃ preferably, and more preferably 130-150 ℃, be preferably 135-145 ℃; The residence time is 12-25 minute, and preferably 16-22 minute, be preferably 18-20 minute.
In an example of the present invention, described the second dryer section adopts the warm air drying method, and the air quantity of its heating hot blast is 650-800m
3/ hour, 700-780m preferably
3/ hour, 720-750m more preferably
3/ hour.
After the second dryer section processing treatment, the water content of gel particle of the present invention is generally the 5-10 % by weight, preferably 5.5-8 % by weight, more preferably 6-7 % by weight.
Described the second dryer section adopts Wind Volume and the high characteristics of Heating temperature, and the water of the existence in flocculated particle is evaporated in the short period of time, reaches quick-drying purpose.
C) cooling processing sections
In the methods of the invention, also optionally comprise a cooling working zone after the second dryer section.The purpose of setting up the cooling working zone is to reach the purpose of cooling when gel particle is further dewatered.
The temperature of described cooling working zone is generally 65-85 ℃, and the residence time is 3-7 minute.
In a better example of the present invention, the temperature of described cooling working zone is 70-80 ℃, preferably 72-78 ℃, more preferably 74-76 ℃; The residence time is 4-6 minute, 4.5-5.5 minute preferably.
The present invention's working zone of lowering the temperature adopts the warm air drying method, and air quantity of its heating hot blast is 650-800m
3/ hour, 700-780m preferably
3/ hour, 720-750m more preferably
3/ hour.
After described cooling working zone processing treatment, the water content of gel particle of the present invention is generally the 1-4.5 % by weight, preferably 2-4 % by weight, more preferably 2.5-3.0 % by weight.
The present invention in drying process for example, by taking stage by stage different technical parameters with the water content in controlling the different steps desiccant gel (, water content when the first drying stage starts is the 40-60 % by weight, water content when subordinate phase starts is the 30-50 % by weight, water content when the cooling processing sections starts is the 5-10 % by weight), realize reducing residual acrylic monomer content and efficient by the dual purpose of aqueous gel drying in drying process.
Simple, the applicable suitability for industrialized production of production technique of the present invention.Add appropriate dry initiator solution in the polymeric gel granulation process, hydrogel particle is evenly distributed on the drying machine hot-plate of hot air circulation form heating, drying process by three phases is controlled, and makes drying stage realize dehydrating and falling the purpose of low-residue single, optimizing product performance.
It is to make the abundant polymerization of remaining monomer when guaranteeing drying efficiency that the present invention sets up the main purpose of two drying zones and an optional cooling processing district, to reduce the remaining quantity of unreacted monomer.
In the present invention, the first drying zone is by the control to temperature, hot air flow, make the gel water content in this stage at 40-60%, preferably 42～45%, in the situation that water content is higher, by controlling the residence time, in this stage makes gel, Raolical polymerizable comparatively fully occurs in remaining Acrylic Acid Monomer, reaches the target that reduces remaining acrylic acid content; The second drying zone adopts Wind Volume and the high characteristics of Heating temperature, and the water existed in flocculated particle is evaporated in the short period of time, reaches quick-drying purpose; And the cooling processing district reaches the purpose of cooling when gel particle is further dewatered.
The inventive method drying efficiency is high, and dried particles, through pulverizing, surface-crosslinked, finally makes the super absorbent resin product of excellent performance.
The inventive method provides a kind of new drying technique of super absorbent resin polymeric gel particle, it is main raw material that this hydrogel be take vinylformic acid, sodium hydroxide, in the situation that polymerization starter, linking agent exist through microwave radiation, making water content by cross-linking polymerization is 40-60%, for example 50%, hydrogel.The drying of hydrogel is to carry out under such condition: the residual acrylic monomer of the first dryer section in making gel particle carries out Raolical polymerizable under the existence at dry initiator, reaches and reduce remaining acrylic acid purpose under certain water content environment; The second dryer section is issued to gel particle fast dewatering and dry purpose in the situation of high air quantity heating hot blast, high-temperature; The cooling processing sections makes gel particle further dewater, reach simultaneously the effect of cooling.Through this drying process, dried particles through pulverizing, aftertreatment, the characteristics such as the super absorbent resin product residual monomer content made is low, and other performances are as high as pick up, rate of liquid aspiration is fast.
At one preferably in example of the present invention, the inventive method comprises vinylformic acid, 32% aqueous sodium hydroxide solution and a certain amount of deionized water, in the situation that continuously stirring adds a certain amount of linking agent, bridging agent, polymerization starter solution, prepared polymerization single polymerization monomer solution is under the condition of microwave radiation, make by the high temperature static polymerization the large bulk polymer hydrogel that 5000mm is wide, 20mm is thick, block hydrogel is carried out to the gel granulation, add dry initiator solution in the gel granulation process.The gel particle that the diameter that will obtain through above-mentioned granulation is 20mm carries out drying, in drying process, by taking stage by stage different technical parameters with the water content in controlling the different steps desiccant gel, realize reducing residual acrylic monomer content and efficient by the dual purpose of aqueous gel drying in drying process.
It is fast that drying process provided by the invention has characteristics, drying efficiency that polymeric gel is further reacted residual acrylic monomer in drying process, by residual monomer content in the prepared super absorbent resin product of this technique lower than 100ppm, the product good combination property, be applicable to suitability for industrialized production fully.
Further illustrate the present invention below in conjunction with embodiment.
Embodiment
1. measure the water content of gel
Get that 10.0g is to be measured has separated broken absorption capacity of superabsorbent gel particles, be placed in the small beaker (W0) of having weighed, weighing is accurate to 0.1g, take both gross weight W1, this beaker that sample is housed is put into to electric drying oven with forced convection, be dried to example weight (W2) and no longer change under 150 ℃, take weight now.
Result is calculated:
In formula: W0---the weight of small beaker
The gross weight of W1---small beaker and wet gel particle
The gross weight of W2---small beaker and desiccant gel
The difference of five results of replicate(determination) must not be greater than 3%, and the arithmetical av of getting its three replicate(determination) results is measurement result.
2. the mensuration of residual monomer content
At the 250ml beaker that magnetic stir bar is housed, be put on magnetic stirrer, taking 0.9% NaCl aqueous solution 100g pours in beaker, the super absorbent resin that accurately takes 0.5g (being accurate to 0.1g) drying adds in the NaCl aqueous solution under magnetic agitation, adding a cover stirring with film took out and filters after 1 hour, collect weighing filtrate, and filtrate is carried out to liquid-phase chromatographic analysis, thereby obtain residual monomer content in absorbent resin (ppm by weight/with respect to absorbent resin).
3. the water absorption test of resin
Accurately take 1.000g (being accurate to 0.001g) absorbent resin pack into one weigh (W0) be of a size of in 23 * 32cm, 400 purpose nylon net bags, tighten opening.The mesh bag of dress sample is immersed in 25 ℃ of distilled water, after all infiltrating, keep submerged state 30 minutes, then mesh bag is taken out, allow it drain 60 minutes, remove after too much distilled water weigh (W1).
By the absorbent resin in this mesh bag, pour out clean subsequently, after oven dry, weigh, the error of its weight and former weight W0 should be no more than 1% (otherwise relaunder and dry), by this, blank mesh bag immerses in 25 ℃ of distilled water subsequently, after all infiltrating, keep submerged state 30 minutes, then mesh bag is taken out, allow it drain 60 minutes, remove after too much distilled water weigh (W2).
Result is calculated:
Absorbing pure water multiplying power (g/g)=W1-W2-1.0
In formula: W1---sample and mesh bag absorb distilled water and drain after weight;
W2---the weight of wet nylon net bag;
The difference of five results of replicate(determination) must not be greater than 5%, and the arithmetical av of getting its five replicate(determination) results is measurement result.
embodiment 1
the preparation of gel
At 1m
3reactor in add 283 kilograms of aqueous sodium hydroxide solutions (32wt%), 351 kilograms of deionized waters, open the stirring of reactor, slowly drip 225 kilograms of vinylformic acid, keeping temperature of reaction kettle is 25 ℃, vinylformic acid drips and finishes, add 0.5 kilogram of linking agent polyethyleneglycol diacrylate and 0.45 kilogram of linking agent oxyethyl group glycerol tri-acrylate, then add 0.6 kilogram of ammonium persulphate as polymerization starter, continue to stir, reactor is carried out to inflated with nitrogen, continue to keep 25 ℃ of temperature of reaction kettle, above-mentioned material is entered to a long 6000mm continuously with the flow of 34.5kg/hr, on the continuous conveyor of wide 500mm, two microwave generator (W-8512 models through polymerization travelling belt ingress, purchased from precious microwave products company limited of Chinese Guangdong Foshan Fuji) radiation (radiation power 1250W) carries out polyreaction, the temperature of this travelling belt is controlled at 70 ℃, reaction time is 60 minutes, can obtain the high water absorbency polymer gel, the gel water content is 50%.
the solution of gel is broken
By the above-mentioned gel made, first carry out slitting, stripping and slicing, make the gel lumpy material of 1000 * 500mm.With 27.6kg/hr speed, add screw rod machine for decomposing and smashing (RY-8 (S) model, purchased from positive element precision optical machinery company limited) to be separated broken granulation block gel masses, opening auxiliary agent adds valve, adjust flux meter to the 1.66kg/hr flow, spray into the dry initiator ammonium persulfate aqueous solution of 1wt% concentration in gel surface, the 6wt% that the ammonium persulfate aqueous solution added is gel weight, obtaining diameter is the hydrogel particle of 20mm left and right.
the drying of gel particle
Carry out drying by separating the broken hydrogel particle obtained.The dry hot air circulation mode that adopts is carried out, and specifically is divided into three phases: dry reaction district, rapid drying district and cooling area.
1) the first step: dry reaction district
Be introduced into dry reactor and carry out vinylformic acid residual monomer Raolical polymerizable and dehydrating through separating broken gel particle of coming, this stage drying temperature is 80 ℃, and heating hot blast air quantity is 72m
3/ h, drying residencing time is 20 minutes, after the first step drying, the water content of material is 42.5 % by weight.
2) second step: rapid drying district
The gel particle of drying reaction zone drying enters the quick dewatering drying that dry subordinate phase rapid drying district carries out hydrogel particle, and this stage drying temperature is 168 ℃, and heating hot blast air quantity is 720m
3/ h, drying residencing time is 25 minutes, after the second step drying, the moisture of material is 6.8 % by weight.
3) the 3rd step: cooling area
Solid particulate behind the rapid drying district enters the cooling that cooling area carries out dried material, and this section temperature is 75 ℃, and the cooling air air quantity is 720m
3/ h, this period residence time is 5 minutes, after the 3rd step is cooling, the water ratio of dried particles is 3 % by weight.
By top described method, measured, the number-average molecular weight of the super absorbent resin that result makes is that 1,100,000 dalton, weight-average molecular weight are that 1,100,000 dalton, water-absorbent are that 450g/g, the residual list of vinylformic acid are 70ppm.
comparative Examples 1
Broken same embodiment 1 is conciliate in the preparation of gel, difference is to adopt a step desiccating method in drying process, dry reaction district temperature is 140 ℃, other Drying Technology Parameters are with embodiment 1, by top described method, measured, the water-absorbent of the super absorbent resin that result makes is that 400g/g, the residual list of vinylformic acid are 150ppm.
comparative Examples 2
Broken same embodiment 1 is conciliate in the preparation of gel, and difference is to adopt a step desiccating method in drying process, and dry reaction district temperature is 140 ℃, and heating hot blast air quantity is 432m
3/ h, other Drying Technology Parameters, with embodiment 1, are measured by top described method, and the water-absorbent of the super absorbent resin that result makes is that 380g/g, the residual list of vinylformic acid are 235ppm.
comparative Examples 3
Broken same embodiment 1 is conciliate in the preparation of gel, and difference is to adopt a step desiccating method in drying process, and dry reaction district temperature is 140 ℃, and heating hot blast air quantity is 720m
3/ h, other Drying Technology Parameters, with embodiment 1, are measured by top described method, and the water-absorbent of the super absorbent resin that result makes is that 330g/g, the residual list of vinylformic acid are 458ppm.
comparative Examples 4
Broken same embodiment 1 is conciliate in the preparation of gel, and difference is to adopt a step desiccating method in drying process, and dry reaction district temperature is 160 ℃, and heating hot blast air quantity is 720m
3/ h, other Drying Technology Parameters, with embodiment 1, are measured by top described method, and the water-absorbent of the super absorbent resin that result makes is that 315g/g, vinylformic acid are residual singly at 635ppm.
comparative Examples 5
The preparation of gel is with embodiment 1, difference is not add ammonium persulphate class initiator solution in separating broken process, drying process is with embodiment 1, by top described method, measured, the water-absorbent of the super absorbent resin that result makes is 420g/g, the single residual content in product is at 1126ppm after tested.
The product performance of table 1 embodiment 1 and Comparative Examples 1～5
In preparing the process of super absorbent resin, by in the broken process of gel solution, adding quantitative initiator solution, by processing parameter, drying process is carried out to control by stages in the gel particle drying process simultaneously, reach the control of different steps gel water content, make to remain in the Raolical polymerizable that in hydrogel, residual acrylic monomer carries out again and form polymkeric substance, reach the content that reduces residual monomer in the super absorbent resin product.
The residual list of super absorbent resin product that adopts drying process of the present invention to prepare is low, good combination property, and its water-absorbent is substantially unaffected simultaneously.On the contrary, in the broken process of gel solution, do not add initiator solution, or the dry reaction district of drying process do not carry out control and the adjusting of drying temperature and hot blast air quantity, can cause that single residual content in the finished product obviously increases, water-retaining capacity descends.
embodiment 2
the preparation of gel
At 1m
3reactor in add 283 kilograms of aqueous sodium hydroxide solutions (32wt%), 351 kilograms of deionized waters, open the stirring of reactor, slowly drip 225 kilograms of vinylformic acid, keeping temperature of reaction kettle is 25 ℃, vinylformic acid drips and finishes, add 0.5 kilogram of linking agent polyethyleneglycol diacrylate and 0.45 kilogram of linking agent oxyethyl group glycerol tri-acrylate, then add 0.6 kilogram of polymerization starter ammonium persulphate, continue to stir, reactor is carried out to inflated with nitrogen, continue to keep 25 ℃ of temperature of reaction kettle, above-mentioned material is entered to a long 6000mm continuously with the flow of 34.5kg/hr, on the continuous conveyor of wide 500mm, two microwave generator (W-8512 models through polymerization travelling belt ingress, purchased from precious microwave products company limited of Chinese Guangdong Foshan Fuji) radiation (radiation power 1250W) carries out polyreaction, the temperature of this travelling belt is controlled at 70 ℃, reaction time is 60 minutes, can obtain the high water absorbency polymer gel, the gel water content is 50%.
the solution of gel is broken
By the above-mentioned gel made, first carry out slitting, stripping and slicing, make the gel lumpy material of 1000 * 500mm.With 27.6kg/hr speed, add screw rod machine for decomposing and smashing (RY-8 (S) model, purchased from positive element precision optical machinery company limited) to be separated broken granulation block gel masses, opening auxiliary agent adds valve, adjust flux meter to the 1.93kg/hr flow, spray into the ammonium persulfate aqueous solution of 1wt% concentration as dry initiator in gel surface, the 7wt% that the ammonium persulfate aqueous solution added is gel weight, obtaining diameter is the hydrogel particle of 20mm left and right.
the drying of gel particle
Carry out drying by separating the broken hydrogel particle obtained.The dry hot air circulation mode that adopts is carried out, and specifically is divided into three phases: dry reaction district, rapid drying district and cooling area.
1) the first step: dry reaction district
Be introduced into dry reactor and carry out vinylformic acid residual monomer Raolical polymerizable and dehydrating through separating broken gel particle of coming, this stage drying temperature is 90 ℃, and heating hot blast air quantity is 82m
3/ h, drying residencing time is 18 minutes, after the first step drying, the water content of material is 41 % by weight.
2) second step: rapid drying district
The gel particle of drying reaction zone drying enters the quick dewatering drying that dry subordinate phase rapid drying district carries out hydrogel particle, and this stage drying temperature is 150 ℃, and heating hot blast air quantity is 650m
3/ h, drying residencing time is 20 minutes, after the second step drying, the moisture of material is 6.0 % by weight.
3) the 3rd step: cooling area
Solid particulate behind the rapid drying district enters the cooling that cooling area carries out dried material, and this section temperature is 70 ℃, and the cooling air air quantity is 750m
3/ h, this period residence time is 6 minutes, after the 3rd step is cooling, the water ratio of dried particles is 2.8 % by weight.
By top described method, measured, the number-average molecular weight of the super absorbent resin that result makes is that 1,000,000 dalton, weight-average molecular weight are that 1,000,000 dalton, water-absorbent are that 442g/g, the residual list of vinylformic acid are 71ppm.
embodiment 3
the preparation of gel
At 1m
3reactor in add 283 kilograms of aqueous sodium hydroxide solutions (32wt%), 276 kilograms of deionized waters, open the stirring of reactor, slowly drip 225 kilograms of vinylformic acid, keeping temperature of reaction kettle is 25 ℃, vinylformic acid drips and finishes, add 0.5 kilogram of linking agent polyethyleneglycol diacrylate and 0.45 kilogram of linking agent oxyethyl group glycerol tri-acrylate, then add 0.6 kilogram of polymerization starter ammonium persulphate, continue to stir, reactor is carried out to inflated with nitrogen, continue to keep 25 ℃ of temperature of reaction kettle, above-mentioned material is entered to a long 6000mm continuously with the flow of 34.5kg/hr, on the continuous conveyor of wide 500mm, two microwave generator (W-8512 models through polymerization travelling belt ingress, purchased from precious microwave products company limited of Chinese Guangdong Foshan Fuji) radiation (radiation power 1250W) carries out polyreaction, the temperature of this travelling belt is controlled at 70 ℃, reaction time is 60 minutes, can obtain the high water absorbency polymer gel, the gel water content is 50%.
the solution of gel is broken
By the above-mentioned gel made, first carry out slitting, stripping and slicing, make the gel lumpy material of 1000 * 500mm.With 27.6kg/hr speed, add screw rod machine for decomposing and smashing (RY-8 (S) model, purchased from positive element precision optical machinery company limited) to be separated broken granulation block gel masses, opening auxiliary agent adds valve, adjust flux meter to the 1.93kg/hr flow, spray into the ethanolic soln of the dry initiator Diisopropyl azodicarboxylate of conduct of 2wt% concentration in gel surface, the 7wt% that the Diisopropyl azodicarboxylate alcoholic solution added is gel weight, obtaining diameter is the hydrogel particle of 20mm left and right.
the drying of gel particle
Carry out drying by separating the broken hydrogel particle obtained.The dry hot air circulation mode that adopts is carried out, and specifically is divided into three phases: dry reaction district, rapid drying district and cooling area.
1) the first step: dry reaction district
Be introduced into dry reactor and carry out vinylformic acid residual monomer Raolical polymerizable and dehydrating through separating broken gel particle of coming, this stage drying temperature is 70 ℃, and heating hot blast air quantity is 61m
3/ h, drying residencing time is 18 minutes, after the first step drying, the water content of material is 40 % by weight.
2) second step: rapid drying district
The gel particle of drying reaction zone drying enters the quick dewatering drying that dry subordinate phase rapid drying district carries out hydrogel particle, and this stage drying temperature is 127 ℃, and heating hot blast air quantity is 680m
3/ h, drying residencing time is 15 minutes, after the second step drying, the moisture of material is 6.2 % by weight.
3) the 3rd step: cooling area
Solid particulate behind the rapid drying district enters the cooling that cooling area carries out dried material, and this section temperature is 70 ℃, and the cooling air air quantity is 650m
3/ h, this period residence time is 6 minutes, after the 3rd step is cooling, the water ratio of dried particles is 2.7 % by weight.
By top described method, measured, the number-average molecular weight of the super absorbent resin that result makes is that 1,000,000 dalton, weight-average molecular weight are that 1,000,000 dalton, water-absorbent are that 467g/g, the residual list of vinylformic acid are 65ppm.
The invention effect
The high water absorbency polymer gel adds a certain amount of initiator solution in the gel granulation process, the gel particle obtained through the granulation of interpolation initiator carries out different technical parameters stage by stage in drying process and controls, by the control to drying stage dried material water content, the vinylformic acid residual monomer that makes to remain in gel carries out further Raolical polymerizable, reach the vinylformic acid residual monomer content reduced in super absorbent resin, the water-absorbent of the super absorbent resin simultaneously made does not change substantially, it is low that the high water absorbency polymer product prepared through this technique has a residual acrylic monomer content, the characteristics of every good product performance, reach the sanitary material requirement fully.This technological operation is simple, need not add extra equipment in production process, is applicable to suitability for industrialized production fully.
Claims (10)
1. the manufacture method of an acrylic polymer resins, it comprises block water gel, granulation and the drying step that forms acrylic polymers, it is characterized in that:
In described granulation process, press the weighing scale of the block water gel of acrylic polymers, add the initiator of 4-8%, obtain the gel particle that diameter is 15-25mm;
Described drying step carries out successively in two dryer section:
The temperature of the first dryer section is that 50-110 ℃, the residence time are 5-20 minute;
The temperature of the second dryer section is for being greater than 110 to 180 ℃, and the residence time is 10-30 minute.
2. the method for claim 1, is characterized in that, after described drying step, described method also comprises the cooling algorithm, and the temperature that described cooling algorithm adopts is 65-85 ℃, and the residence time is 3-7 minute.
3. method as claimed in claim 1 or 2, the temperature that it is characterized in that the second dryer section is 120-160 ℃, more preferably 130-150 ℃, be preferably 135-145 ℃; The residence time is 12-25 minute, and preferably 16-22 minute, be preferably 18-20 minute.
4. method as described as any one in claim 1-3, is characterized in that described the second dryer section adopts the warm air drying method, and the air quantity of its heating hot blast is 650-800m
3/ hour, 700-780m preferably
3/ hour, 720-750m more preferably
3/ hour.
5. method as described as any one in claim 1-4, the temperature that it is characterized in that described the first dryer section is 60-100 ℃, more preferably 65-95 ℃, be preferably 70-90 ℃; The residence time is 6-18 minute, and preferably 8-16 minute, be preferably 10-14 minute.
6. method as described as any one in claim 1-5, is characterized in that described the first dryer section adopts the warm air drying method, and the air quantity of its heating hot blast is 55-85m
3/ hour, 60-80m preferably
3/ hour, 65-75m more preferably
3/ hour.
7. method as described as any one in claim 2-6, the temperature that it is characterized in that described cooling algorithm is 70-80 ℃, preferably 72-78 ℃, more preferably 74-76 ℃; The residence time is 4-6 minute, 4.5-5.5 minute preferably.
8. method as described as any one in claim 2-7, is characterized in that described cooling algorithm adopts the warm air drying method, and the air quantity of its heating hot blast is 650-800m
3/ hour, 700-780m preferably
3/ hour, 720-750m more preferably
3/ hour; After described cooling working zone processing treatment, the water content of described gel particle is the 1-4.5 % by weight, preferably 2-4 % by weight, more preferably 2.5-3.0 % by weight.
9. method as described as any one in claim 1-8, is characterized in that described aftertreatment initiator is selected from two or more mixture of persulphate (for example ammonium persulphate, Potassium Persulphate), Diisopropyl azodicarboxylate or its.
10. an acrylic polymer resins, its number-average molecular weight is 500,000～1,200,000 dalton, weight-average molecular weight is 500,000～1,200,000 dalton, water-absorbent is 300～800g/g, and the content of remaining acrylic monomer is less than 100ppm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105884974A (en) * | 2016-06-14 | 2016-08-24 | 四川省农业科学院生物技术核技术研究所 | Segmented drying method for starch system water-absorbent resin |
| CN109280185A (en) * | 2018-08-16 | 2019-01-29 | 仲恺农业工程学院 | A kind of high hydroscopic resin superfine powder surface modifying method and modification liquid |
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| CN101333261A (en) * | 2007-06-29 | 2008-12-31 | 台湾塑胶工业股份有限公司 | Method for making high water absorption resin |
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| CN109280185A (en) * | 2018-08-16 | 2019-01-29 | 仲恺农业工程学院 | A kind of high hydroscopic resin superfine powder surface modifying method and modification liquid |
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