CN102351976A - Synthetic method of salt tolerant quadripolymer superabsorbent resin - Google Patents
Synthetic method of salt tolerant quadripolymer superabsorbent resin Download PDFInfo
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- CN102351976A CN102351976A CN2011102063247A CN201110206324A CN102351976A CN 102351976 A CN102351976 A CN 102351976A CN 2011102063247 A CN2011102063247 A CN 2011102063247A CN 201110206324 A CN201110206324 A CN 201110206324A CN 102351976 A CN102351976 A CN 102351976A
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Abstract
The invention relates to a synthetic method of a salt tolerant quadripolymer superabsorbent resin, comprising the following steps of: adding cyclohexane and a dispersant Span-80 into a 3-mouth flask, stirring and heating up to the temperature of 60-68 DEG C, dropwisely adding a hydrophilic cross-linking agent, an initiator and a comonomer by a constant-voltage titration tunnel, staying at constant temperature for 1 hour after the addition, heating up to the temperature of 70-75 DEG C and reacting for 2-3 hours, cooling to room temperature, pouring the obtained product into a beaker with enough methanol, fully depositing, followed by pumping filtration by a vacuum pump, repeatedly washing by the use of methanol, and drying in a vacuum chamber at the temperature of 80-90 DEG C to obtain a white powder, namely the salt tolerant quadripolymer superabsorbent resin. The invention has the following beneficial effects: the technology is simple; the requirement on equipment is low; the resin prepared by the synthetic method has strong water absorption, fast water absorption rate, excellent water retention, high strength in the superabsorbent state, good light and thermal stability as well as salt tolerance which is remarkably improved.
Description
Technical field
The invention belongs to functional high polymer material field, be specifically related to the synthesis method of the quarternary copolymerized High hydrophilous resin of a kind of salt tolerance, particularly aspect salt tolerance, promoted comprehensively, and can regulate the resin water-intake rate through regulating monomer ratio.
Background technology
Super absorbent resin (SAP) is a kind of new functional macromolecule material.It has the heavy hundreds of of specific absorption self to the high absorbent function of several thousand times of water, and water retention property is good, in case when water-swelling becomes hydrogel, even pressurization also is difficult to water sepn is come out.Super absorbent resin is a kind of functional high molecule material that has a large amount of hydrophilic radicals; With its high water-retaining capacity, high absorption speed and high water retention capacity; Be widely used in the physiological hygiene articles for use, like sanitary napkin, paper diaper, adult's multifunction nursing pad, thieving paper, pet pads etc.
High molecular material of high water absorption the earliest is at first to develop the researchist by USDA in 1974, and at first is used for water conservation and manufacturing paper diaper and sanitary napkin on the agricultural.At present super absorbent resin has been developed starch derivative series, derivatived cellulose series, chitin derivative is serial, polyacrylic acid is serial and polyvinyl alcohol series etc.Wherein, Natural polymers such as starch, Mierocrystalline cellulose, chitin are carried out the natural macromolecule modification super absorbent resin that structure of modification obtains; Be characterized in that production cost is low, material source is extensive, and product has biological degradability, do not cause secondary environmental pollution.But the physical strength of product is low, poor heat stability, and particularly the poor-performing after the suction can not be applied to such as occasions such as hygroscopicity fibre, fabric, films.The super absorbent resin of synthetic is characterized in clear in structure, steady quality, and suction back physical strength is higher, Heat stability is good.Like the resin of polyacrylic acid series, structurally with carboxylate groups as hydrophilic functional groups, polymkeric substance has ionic nature, water-retaining capacity is subjected in the water influence of salt concn bigger, salt concn is high more, maximum water regain descends big more.
Lin Jian etc. are monomer with vinylformic acid, and sodium alginate is a grafts, add kaolin, acrylamide, have prepared compound salt tolerant super absorbent resin through solution polymerization process, and the synthetic resin can partly be degraded, but the salt tolerance improvement is not obvious.It is raw material with vinylformic acid, starch and diatomite that Si Mayi makes every effort to overcome hot wood etc.; Use homemade uv photopolymerization device to synthesize compound anti salt super absorbent resin; This method has some improvement to the salt tolerance of polyacrylic water-absorbing resin; But need UV-irradiation; Experimentation is complicated, has relatively high expectations.
The water-retaining capacity of polyacrylic resin is strong, and good water-retentivity is arranged, and under height suction state, still has very high intensity, and has light, thermostability preferably.Prepare nano level sodium polyacrylate High hydrophilous resin through inverse suspension method and microemulsion polymerization method, select for use the oxidation-reduction quality initiator that water-absorbing resin is carried out hydrophobically modified, than other method of modifying, technology is simple and convenient, and equipment requirements is low.Improve the bonding force of water-absorbing resin and rubber after the modification, reduced turnover rate.Through comonomer is selected, the rate of water absorption and the water absorbent rate of the regulating and controlling water-absorbing resin of set of dispense ratio, the water-absorbing resin to preparation carries out thermotolerance and salt tolerance analysis simultaneously.Great majority adopt hexanaphthenes, normal hexanes to make dispersion agent at present relevant patent documentation, and its shortcoming is that price is high, and at the bottom of the burning-point of hexanaphthene, normal hexane, are prone to cause danger.
Summary of the invention
The synthesis method that the purpose of this invention is to provide the quarternary copolymerized super absorbent resin of a kind of salt tolerance, the salt tolerance that it has improved polyacrylic acid series water-absorbing resin can control its temperature of reaction preferably, and cost is low.
The present invention solves the problems of the technologies described above the scheme that is adopted: the synthetic method of the quarternary copolymerized super absorbent resin of salt tolerance; It is characterized in that including following steps: in there-necked flask, add cyclohexane and dispersant Span-80; Stirring is warming up to 60-68 ℃; Drip the mixed solution of hydrophilic crosslinker, initator and comonomer by constant voltage titration funnel; After dropwising; Constant temperature 1 hour; Cool to room temperature behind the reaction 2-3h under being warming up to 70-75 ℃; Products therefrom is poured in the beaker that capacity methyl alcohol is housed; Abundant post precipitation; Behind the vavuum pump suction filtration, use the methyl alcohol cyclic washing more repeatedly, 80-90 ℃ of following oven dry obtains white powder and is the quarternary copolymerized high hydroscopic resin of salt tolerance in vacuum tank again.
Press such scheme, described hydrophilic crosslinker is N,N methylene bis acrylamide (NMBA), N hydroxymethyl acrylamide (HAM), N,N-DMAA (DMAA) or N,N-dimethylacetamide (DMAC).
Regulate water-absorbing resin in water and the water-intake rate in the different concns salt solution through the proportioning that changes AA and AM among the present invention.
Press such scheme; Described comonomer is the mixture of vinylformic acid, acrylamide, 2-acrylamide-2-methyl propane sulfonic acid and cationic monomer, and its quality proportioning is: vinylformic acid: acrylamide: 2-acrylamide-2-methyl propane sulfonic acid: cationic monomer=1.9～2.1:0.3～0.6:1:0.3～0.5.
Press such scheme, described cationic monomer is dimethyl diallyl ammonium chloride (DMDAAC), acrylyl oxy-ethyl-trimethyl salmiac (DAC), methylacryoyloxyethyl trimethyl ammonium chloride (DMC) or N-acrylamide ammonium chloride (DBPMA).
Press such scheme, described initiator is Potassium Persulphate (KPS), ammonium persulphate, Diisopropyl azodicarboxylate (AIBN) or azo dicyano valeric acid (ACVA).
Press such scheme, described initiator amount is the 0.54wt.%～0.72wt.% of comonomer total amount, and dosage of crosslinking agent is the 0.06wt.%～0.1wt.% of comonomer total amount.
Be improved significantly with synthetic High hydrophilous resin salt tolerance of the present invention, and the water-intake rate in salt solution is had certain regulating effect.
The process of hydrophilic crosslinker role of the present invention is the process of an electrophilic addition; Two keyed jointings in the acrylic resin main chain are opened by proton (initiator); Carbonium ion appears; Carbonium ion is attacked another pair key again; The chainpropagation part of similar alkane photoresponse; Add linking agent (N when therein; The N-methylene-bisacrylamide; N hydroxymethyl acrylamide; N; The N-DMAA; N; N-N,N-DIMETHYLACETAMIDE etc.) time; Linking agent also can be attacked by carbonium ion, just brings out various electrophilic addition reactions afterwards, makes water-absorbing resin present spatial space reticulated structure.
With the AA that crosses, ionization goes out Na when contacting with water in by NaOH
+With-COO
-,-COO
-Be fixed on the molecular chain Na
+Be removable ion.Electrostatic repulsion between the former is expanded network structure, and in order to keep electric neutrality, Na
+Can not cause Na to outside solvent diffusion
+Inside and outside the resin network, have concentration difference, the osmotic pressure of Chan Shenging further infiltrates water molecules therefrom, so just can absorb a large amount of water.Because acrylamide is the non-ionic type hydrophilic monomer, it leans on the wetting ability of hydrophilic functional groups and water molecules to form hydrogen bond, thereby has water-retaining capacity.The .-CONH of non-ionic hydrophilic group
2With anionic hydrophilic group .-COO
-Na
+Produce synergy, weakened the common-ion effcet and the salt effect of suction (salt) process, suction (salt) rate is improved.Because acrylamide does not dissociate in the aqueous solution, its water absorbing properties is subjected to Na again
+Concentration affects is very little, and promptly the susceptibility to salt is low, so the salt tolerance that acrylamide monomer can improve water-absorbing resin is introduced in copolymerization.But when the amount of acrylamide was too much, water-intake rate and absorption salt ratio will descend, and this is because the water absorbing properties of amide group is far smaller than carboxyl.Amide group is many, and carboxyl is just few relatively, has only when amide group and carboxyl to constitute certain ratio, and the existing higher water-absorbent of water-absorbing resin ability have salt tolerance preferably again.
Cationic monomer of the present invention is a kind of water-soluble extremely strong positively charged ion ammonium salt, is used in the present invention preparing amphoteric ion type SAR, enriches hydrophilic radical, has synergistic effect between the multiple hydrophilic radical, can improve the water absorbent rate of SAR to a certain extent.But because the cationic monomer molecule volume is bigger, steric effect is big, and reactive behavior is low, and when feeding intake when too much, the polyreaction difficulty increases and possibly have influence on the molecular weight of SAR, causes SAR suction network structure imperfect.The cationic monomer molecular structure contains abundant hydrophobic alkyl in addition; Increase along with its content; The product hydrophilicity is reduced; Thereby cause the decrease to some degree of SAR water absorbing properties; But aspect salt tolerance, improve a lot; Admittedly will choose proper proportion, make resin reach ideal salt tolerance and maximum water regain.
Beneficial effect of the present invention is: prepare the method for water-absorbing resin than other, experimental article of the present invention is cheap, and technology is simple, and equipment requirements is low.The present invention has adopted vinylformic acid and other salt tolerance monomers to carry out copolymerization; Not only water-retaining capacity is strong for the polyacrylic water-absorbing resin that makes; Rate of water absorption is fast; Good water-retentivity is arranged; Under height suction state, still have very high intensity; And have light, thermostability preferably, and salt tolerance also is significantly improved, and is a kind of method of novel quarternary copolymerized production anti salt super absorbent resin.
Embodiment
Below in conjunction with embodiment the present invention is further specified:
Embodiment 1
In having the 250ml there-necked flask of agitator, prolong, thermometer; Add hexanaphthene 105ml; Span-80 2.5g; Stirring is warming up to 66 ° of C; Drip N through constant voltage titration funnel; N-methylene-bisacrylamide 0.01g; Potassium Persulphate (KPS) 0.08g; Vinylformic acid (AA) (using massfraction to be 40%NaOH 2.7789g neutralization) 7.1458g; Acrylamide (AM) 2.0417g, the mixing solutions of 2-acrylamide-2-methyl propane sulfonic acid (AMPS) 3.758g and dimethyl diallyl ammonium chloride (DMDAAC) 1.8g.After dropwising; Constant temperature 1 hour; Be warming up to 72 ℃ and react the 2h postcooling down to room temperature; Product is poured in the beaker that capacity methyl alcohol is housed; Abundant post precipitation; Behind the vacuum pump suction filtration, use the methyl alcohol repetitive scrubbing more repeatedly, oven dry obtains white powder and is quarternary copolymerized High hydrophilous resin under 80 ℃ in vacuum chamber.
Particle size analysis shows that the resin particle diameter is about 156nm, and acrylic acid degree of neutralization is 70%, and the mass ratio of vinylformic acid and acrylamide is 3.5:1, this quarternary copolymerized High hydrophilous resin in 20 ℃ of different time different concns NaCl solution water-intake rate (g/g) as follows:
This resin of table 1 in 20 ℃ of different time different concns NaCl solution water-intake rate
AA：AM=3.5:1
| Time/h | Distilled water | 0.90% | 2% | 5% |
| 1 | 465.5 | 136.2 | 79.45 | 39.01 |
| 2 | 478.5 | 143.25 | 89.75 | 43.65 |
| 3 | 498.45 | 150.75 | 100.95 | 44.32 |
| 4 | 484.05 | 145.23 | 95.06 | 49.41 |
| 5 | 442.25 | 132.05 | 88.95 | 42.65 |
| 6 | 417.35 | 128.98 | 88.35 | 41.75 |
Embodiment 2
In having the 250ml there-necked flask of agitator, prolong, thermometer; Add hexanaphthene 105ml; Span-80 2.5g; Stirring is warming up to 66 ℃, drips N hydroxymethyl acrylamide 0.015g, ammonium persulphate 0.08g through constant voltage titration funnel; Vinylformic acid (using massfraction to be 40%NaOH 2.858g neutralization) 7.35g; Acrylamide 1.8375g, 2-acrylamide-2-methyl propane sulfonic acid (AMPS) 3.758g, the mixing solutions of acrylyl oxy-ethyl-trimethyl salmiac (DAC) 1.5g.After dropwising; Constant temperature 1 hour; Be warming up to 72 ℃ and react the 1-2h postcooling down to room temperature; Product is poured in the beaker that capacity methyl alcohol is housed; Abundant post precipitation; Behind the vacuum pump suction filtration, use the methyl alcohol repetitive scrubbing more repeatedly, oven dry obtains white powder and is quarternary copolymerized High hydrophilous resin under 80 ℃ in vacuum chamber.
Particle size analysis shows that the resin particle diameter is about 156nm, and acrylic acid degree of neutralization is 70%, and the mass ratio of vinylformic acid and acrylamide is 4:1, this resin in 20 ℃ of different time different concns NaCl solution water-intake rate (g/g) as follows:
This resin of table 2 in 20 ℃ of different time different concns NaCl solution water-intake rate
AA：AM=4：1
| Time/h | Distilled water | 0.90% | 2% | 5% |
| 1 | 485.7 | 155.3 | 133.1 | 50.6 |
| 2 | 552.2 | 185.2 | 142.5 | 50.6 |
| 3 | 561.4 | 200.4 | 150.5 | 59.0 |
| 4 | 543.8 | 182.3 | 138.5 | 54.3 |
| 5 | 516.8 | 156.1 | 123.5 | 50.6 |
| 6 | 515.3 | 160.8 | 125.1 | 50.2 |
Embodiment 3
In having the 250ml there-necked flask of agitator, prolong, thermometer; Add hexanaphthene 110ml; Span-80 2.8g; Stirring is warming up to 66 ℃; Drip N through constant voltage titration funnel; N-DMAA 0.012g; Diisopropyl azodicarboxylate (AIBN) 0.085g; Vinylformic acid (using massfraction to be 40%NaOH 2.977g neutralization) 7.6562g; Acrylamide 1.5313g; 2-acrylamide-2-methyl propane sulfonic acid (AMPS) 3.758g, the mixing solutions of methylacryoyloxyethyl trimethyl ammonium chloride 1.4g.After dropwising; Constant temperature 1 hour; Be warming up to 72 ℃ and react the 1-2h postcooling down to room temperature; Product is poured in the beaker that capacity methyl alcohol is housed; Abundant post precipitation; Behind the vacuum pump suction filtration, use the methyl alcohol repetitive scrubbing more repeatedly, oven dry obtains white powder and is quarternary copolymerized High hydrophilous resin under 80 ℃ in vacuum chamber.
Particle size analysis shows that the resin particle diameter is about 156nm, and acrylic acid degree of neutralization is 70%, and the mass ratio of vinylformic acid and acrylamide is 5:1, this resin in 20 ℃ of different time different concns NaCl solution water-intake rate (g/g) as follows:
This resin of table 3 in 20 ℃ of different time different concns NaCl solution water-intake rate
AA：AM=5：1
| Time/h | Distilled water | 0.90% | 2% | 5% |
| 1 | 465.5 | 135.1 | 97.5 | 45.3 |
| 2 | 478.5 | 150.1 | 100.4 | 48.9 |
| 3 | 528.5 | 165.5 | 130.3 | 47.2 |
| 4 | 484.1 | 149.9 | 107.2 | 51.1 |
| 5 | 442.3 | 123.7 | 104.3 | 40.7 |
| 6 | 417.4 | 125.5 | 103.1 | 40.7 |
Embodiment 4
In having the 250ml there-necked flask of agitator, prolong, thermometer; Add hexanaphthene 115ml; Span-80 2.5g; Stirring is warming up to 66 ℃; Drip N through constant voltage titration funnel; N-N,N-DIMETHYLACETAMIDE 0.015g; Azo dicyano valeric acid (ACVA) 0.10g; Vinylformic acid (using massfraction to be 40%NaOH 2.3.062g neutralization) 7.875g; Acrylamide 1.3125g; 2-acrylamide-2-methyl propane sulfonic acid (AMPS) 3.758g, the mixing solutions of N-acrylamide ammonium chloride 1.2g.After dropwising; Constant temperature 1 hour; Be warming up to 72 ℃ and react the 1-2h postcooling down to room temperature; Product is poured in the beaker that capacity methyl alcohol is housed; Abundant post precipitation; Behind the vacuum pump suction filtration, use the methyl alcohol repetitive scrubbing more repeatedly, oven dry obtains white powder and is quarternary copolymerized High hydrophilous resin under 80 ℃ in vacuum chamber.
Particle size analysis shows that the resin particle diameter is about 156nm, and acrylic acid degree of neutralization is 70%, and the mass ratio of vinylformic acid and acrylamide is 6:1, this resin in 20 ℃ of different time different concns NaCl solution water-intake rate (g/g) as follows:
This resin of table 3 in 20 ℃ of different time different concns NaCl solution water-intake rate
AA：AM=6：1
| Time/h | Distilled water | 0.90% | 2% | 5% |
| 1 | 281.5 | 120.4 | 89.2 | 47.6 |
| 2 | 327.3 | 139.3 | 100.8 | 48.7 |
| 3 | 336.3 | 155.3 | 112.0 | 48.1 |
| 4 | 368.9 | 119.9 | 98.4 | 44.5 |
| 5 | 354.7 | 105.9 | 89.8 | 45.3 |
| 6 | 350.2 | 107.5 | 88.6 | 44.8 |
The mensuration of water absorbent rate
Accurately take by weighing W
0G (about 0.5 g) adds in the homemade nylon sandbag through the quarternary copolymerized High hydrophilous resin of thorough drying, and the note quality is W., immerse in the cut-and-dried beaker that distilled water and different concns (0.9%, 2%, 5%) salt solution be housed, then at a distance from one hour at t
1Constantly take out the nylon sandbag, squeeze out the moisture that is not absorbed by High hydrophilous resin in the sandbag rapidly, wipe out the water on sandbag surface and weigh, note water absorbent gel quality is W
1, more at interval after one hour promptly in t
2Constantly take out the nylon sandbag, squeeze out the water that is not absorbed by High hydrophilous resin in the sandbag equally rapidly, wipe out the moisture on sandbag surface and weigh, note water absorbent gel quality is W
2..., so repeat down.Remember that successively the water absorbent gel quality is W
3..., W
nInstantaneous mass water absorbent rate Q
n(n is 1,2,3,4,5,6) calculates by following formula:
……
Claims (6)
1. the synthetic method of the quarternary copolymerized super absorbent resin of salt tolerance; It is characterized in that including following steps: in there-necked flask, add cyclohexane and dispersant Span-80; Stirring is warming up to 60-68 ℃; Drip the mixed solution of hydrophilic crosslinker, initator and comonomer by constant voltage titration funnel; After dropwising; Constant temperature 1 hour; Cool to room temperature behind the reaction 2-3h under being warming up to 70-75 ℃; Products therefrom is poured in the beaker that capacity methyl alcohol is housed; Abundant post precipitation; Behind the vavuum pump suction filtration, use the methyl alcohol cyclic washing more repeatedly, 80-90 ℃ of following oven dry obtains white powder and is the quarternary copolymerized high hydroscopic resin of salt tolerance in vacuum tank again.
2. press the synthesis method of the quarternary copolymerized super absorbent resin of the described salt tolerance of claim 1; It is characterized in that described hydrophilic crosslinker is N; N-methylene-bisacrylamide, N hydroxymethyl acrylamide, N,N-DMAA or N,N-dimethylacetamide.
3. press the synthesis method of the quarternary copolymerized super absorbent resin of the described salt tolerance of claim 1; It is characterized in that described comonomer is the mixture of vinylformic acid, acrylamide, 2-acrylamide-2-methyl propane sulfonic acid and cationic monomer, its quality proportioning is: vinylformic acid: acrylamide: 2-acrylamide-2-methyl propane sulfonic acid: cationic monomer=1.9～2.1:0.3～0.6:1:0.3～0.5.
4. by the synthesis method of the quarternary copolymerized super absorbent resin of the described salt tolerance of claim 1, it is characterized in that described cationic monomer is dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, methylacryoyloxyethyl trimethyl ammonium chloride or N-acrylamide ammonium chloride.
5. by the synthesis method of the quarternary copolymerized super absorbent resin of the described salt tolerance of claim 1, it is characterized in that described initiator is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or azo dicyano valeric acid.
6. press the synthesis method of the quarternary copolymerized super absorbent resin of the described salt tolerance of claim 1; It is characterized in that described initiator amount is the 0.54wt.%～0.72wt.% of comonomer total amount, dosage of crosslinking agent is the 0.06wt.%～0.1wt.% of comonomer total amount.
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