CN106008800B - 一种抗酸碱性能强的高分子吸水树脂的制备方法 - Google Patents
一种抗酸碱性能强的高分子吸水树脂的制备方法 Download PDFInfo
- Publication number
- CN106008800B CN106008800B CN201610355955.8A CN201610355955A CN106008800B CN 106008800 B CN106008800 B CN 106008800B CN 201610355955 A CN201610355955 A CN 201610355955A CN 106008800 B CN106008800 B CN 106008800B
- Authority
- CN
- China
- Prior art keywords
- water
- weight
- parts
- resin
- strong
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000011347 resin Substances 0.000 title claims abstract description 87
- 229920005989 resin Polymers 0.000 title claims abstract description 87
- 239000003513 alkali Substances 0.000 title claims abstract description 22
- 230000001458 anti-acid effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 238000007664 blowing Methods 0.000 claims abstract description 14
- 239000000872 buffer Substances 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 14
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000297 Rayon Polymers 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 239000001103 potassium chloride Substances 0.000 claims abstract description 3
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 81
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- FPNCFEPWJLGURZ-UHFFFAOYSA-L iron(2+);sulfite Chemical compound [Fe+2].[O-]S([O-])=O FPNCFEPWJLGURZ-UHFFFAOYSA-L 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000008363 phosphate buffer Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 239000007979 citrate buffer Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 27
- 239000007853 buffer solution Substances 0.000 abstract description 4
- 239000002250 absorbent Substances 0.000 description 42
- 230000002745 absorbent Effects 0.000 description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 14
- 238000005213 imbibition Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 238000013019 agitation Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000003926 acrylamides Chemical class 0.000 description 4
- 235000012216 bentonite Nutrition 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012966 redox initiator Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical class CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000009288 screen filtration Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 229920000247 superabsorbent polymer Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/20—Vinyl polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Absorbent Articles And Supports Therefor (AREA)
Abstract
本发明提供一种抗酸碱性能强的高分子吸水树脂的制备方法，步骤是将丙烯酸和等量碳酸钾，经中和反应生成丙烯酸钾盐，再加入丙烯酰胺；完全溶解后加入交联剂、缓冲剂、致孔剂搅拌均匀；加入亚硫酸钠，搅拌均匀，然后加入交联剂；在0‑30℃条件下吹氮气除氧到体系含氧量≤0.1mg/L；降温至10℃，加入引发剂，继续吹氮气至发粘，聚合2小时后成聚合物胶块；经挤压造粒，烘干，粉碎，筛分，成为不同粒径的产品。本发明吸水树脂在缓冲溶液体系中进行聚合，具有抗酸碱性能强，吸水速度快等优点。
Description
技术领域
本发明涉及一种抗酸碱性能强的高分子吸水树脂的制备方法，属于化工领域。
背景技术
吸水树脂(Super Absorbent Polymer，SAP)是一种新型功能高分子材料。它具有吸收比自身重几百到几千倍水的高吸水功能，并且保水性能优良，一旦吸水膨胀成为水凝胶时，即使加压也很难把水分离出来。高吸水性树脂是一种带有大量亲水基团的功能性高分子材料。以其高吸液能力、高吸液速度和高保液能力，广泛应用于生理卫生用品，如妇女卫生巾、纸尿裤、成人多功能护理垫、吸水纸、宠物垫等。使得此类产品大大轻度化、小型化、舒适化，给人们带来了福音，是卫生用品领域不可替代的理想产品。
用于农业与园艺方面的高吸水性树脂又称为保水剂和土壤改良剂。我国是世界上缺水较严重的国家，因此，保水剂的应用就显得越来越重要，目前国内已有十几家科研院所的研制高吸水性树脂产品用于粮、棉、油、糖、烟、果、菜、林等60多种植物上进行应用试验，推广面积超过7万多公顷，并在西北、内蒙等地利用高吸水性树脂进行大面积防砂绿化造林。用于这方面的高吸水性树脂主要是淀粉接枝丙烯酸盐聚合交联物和丙烯酰胺-丙烯酸盐共聚交联物，其中盐已由钠型转向钾型。使用的方法主要有拌种、喷撤、穴施、或用水调成糊状后浸泡植物根部。同时，还可以利用高吸水性树脂对化肥进行包衣后施肥，充分发挥化肥的利用率，防止浪费和污染。
然而，目前高吸水树脂在农业应用中存在一定困难，如，产品成本较高；吸水树脂本身存在的问题“架桥堆积”、结块及吸水倍数易受土壤酸碱度的影响等问题亟待解决。
发明内容
本发明旨在提供一种抗酸碱性能强的高分子吸水树脂的制备方法，该吸水树脂在缓冲溶液体系中进行聚合，具有抗酸碱性能强，吸水速度快等优点。
本发明采用技术方案如下，一种抗酸碱性能强的高分子吸水树脂的制备方法，包括如下步骤：
(1)在300重量份的水中，加入30-50重量份的丙烯酸和等重量份的碳酸钾，经中和反应生成丙烯酸钾盐，再加入50-70重量份的丙烯酰胺，完全溶解后测PH值为7.0±0.1；
(2)加入交联剂0.04-0.06重量份，然后加缓冲剂2.3-2.7重量份，待完全溶解后形成一个缓冲溶液体系，在搅拌下加入致孔剂3-5重量份，搅拌均匀；
(4)加入0.02重量份的亚硫酸钠，搅拌均匀，然后加入0.02重量份的交联剂；
(5)在0-30℃条件下吹氮气除氧到体系含氧量≤0.1mg/L；
(6)降温至10℃，加入0.03-0.07重量份的引发剂，聚合2小时后成聚合物胶块；
(7)上述胶块经挤压造粒，烘干，粉碎，筛分，成为不同粒径的产品。
所述致孔剂为碳酸钙、氢氧化铝、膨润土、淀粉中的任意一种或几种；
所述引发剂为过硫酸铵和硫酸亚铁按照1:1-1:2的混合；
所述交联剂为：六亚甲基四胺；
所述缓冲剂为pH 6.2-7.8磷酸盐缓冲剂或pH 6.2-7.8柠檬酸盐缓冲剂。
优选地，所述步骤(1)中加入丙烯酰胺，完全溶解后，降温至10℃。
所述步骤(5)如测定体系的含氧量未达到≤0.01mg/L，再加入0.02重量份的亚硫酸钠进一步吸收溶解氧，直至体系含氧量≤0.01mg/L；
所述步骤(7)烘干温度为120℃。
本发明具有以下关键技术点：1、选择磷酸盐或柠檬酸作为缓冲液；2、加入致孔剂：碳酸钙、氢氧化铝、膨润土、淀粉等；3、采用合适的聚合条件：温度，酸碱性(PH值)，除溶解氧(吹氮气)时间；4、优选引发剂的加量和种类。
本发明方法制备的吸水树脂，主要有如下两个方面的优点：
一、抗酸碱性能强。在作为土壤保水树脂时，由于土质的不同或水源的差别，土壤环境会显弱酸性或弱碱性。而酸碱性的不同会影响树脂的吸水倍数。试验证明，吸水树脂在pH为7左右时吸水能力最大，为了保证其吸水能力，就要保证所吸水分为中性，因此本发明采用了加入缓冲剂的方法。由于缓冲剂的存在，可以使外部环境pH值在一定变化范围内变化时，保持体系内部PH值基本不变。因此，当颗粒进入呈弱酸/碱性的水时，颗粒中的缓冲剂会使其瞬间变为中性体系，从而达到一定抗酸碱能力。虽然加入缓冲剂可有多种选择，但是如何选择恰当的缓冲剂，是问题的关键。因为所要选择缓冲剂，既要在加工过程中不影响产品性能，无毒无害。又要在烘干后能保留在产品中，这是目前面临的主要问题。因而本发明人经过长期研究发现以磷酸盐或柠檬酸作为缓冲剂制备吸水树脂可行，试验证明能起到很好的抗酸碱的效果。
二、吸水速度提高。加快吸水速度，可以使树脂一旦遇水迅速吸收，有效防止水流失。本发明在制备时加入致孔剂，使吸水速率提高至2倍以上。为了提高吸水树脂的吸水速率，本发明在聚合制备过程中，加入了水不溶的微颗粒，例如，碳酸钙、氢氧化铝、膨润土等物质作为致孔剂。经过试验证明加入该类物质后，吸水速度大有提高，其原理应是，树脂细颗粒接触水时，致孔剂微粒瞬间从树脂表面游离进入水中，在树脂表面形成蜂窝状，微粒不断游离，微孔也不断深入，水就可以较快速的进入。最终结果是大大加快了吸水速率。
附图说明
图1为本发明吸水树脂与普通吸水树脂吸水倍率与pH之间的关系。
图2为本发明吸水树脂与普通吸水树脂吸水速率。
图3为本发明吸水树脂在不同的吸液介质中的吸水性能。
图4为普通吸水树脂在不同的吸液介质中的吸水性能。
具体实施方式
为使本发明更加容易理解，下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明，而不用于限制本发明的范围。
实施例1.一种抗酸碱性能强的高分子吸水树脂的制备方法，步骤如下，
将50g丙烯酸放入盛有300g水的500ml反应瓶中，在搅拌下加入50g碳酸钾(K2CO3)中和反应完成后pH值达到6.8-7.2，然后加入70g丙烯酰胺，搅拌均匀完全溶解后，测pH值应为7.0±0.1。在搅拌下加入0.06g交联剂六亚甲基四胺，然后加磷酸盐缓冲剂2.38g(磷酸二氢钾2.04g、氢氧化钠0.34g)，再加入3g碳酸钙，搅拌均匀。加入0.02g的亚硫酸钠，搅拌均匀，然后加入0.02g交联剂。在0-30℃条件下吹氮气0.5小时除去溶解氧，测定体系的溶解氧≤0.01mg/L。如达不到，可加入0.02g的亚硫酸钠进一步吸收溶解氧。10分钟后加入过硫酸钾0.02g,亚硫酸铁0.03g形成氧化还原引发体系，停止吹氮气静止聚合2小时，温度升至约95-98℃，形成胶块造粒。120℃烘干至含水量10％±1时再粉碎，用分样筛筛至≤20目。用20目的产品测试，pH为7时吸水倍数≥600倍。
实施例2.一种抗酸碱性能强的高分子吸水树脂的制备方法，步骤如下，
将30g丙烯酸放入盛有300g水的500ml反应瓶中，在搅拌下加入30g碳酸钾(K2CO3)中和反应完成后pH值达到6.8-7.2，然后加入50g丙烯酰胺，搅拌均匀完全溶解后，测pH值应为7.0±0.1。在搅拌下加入0.04g交联剂六亚甲基四胺，然后加磷酸盐缓冲剂2.38g(磷酸二氢钾2.04g、氢氧化钠0.34g)，再加入4g淀粉，搅拌均匀。加入0.02g的亚硫酸钠，搅拌均匀，然后加入0.02g交联剂。在0-30℃条件下吹氮气0.5小时除去溶解氧，测定体系的溶解氧≤0.01mg/L。如达不到，可加入0.02g的亚硫酸钠进一步吸收溶解氧。10分钟后加入过硫酸钾0.01g,亚硫酸铁0.03g形成氧化还原引发体系，停止吹氮气静止聚合2小时，温度升至约95-98℃，形成胶块造粒。150℃烘干至含水量10％±1时再粉碎，用分样筛筛至≤20目。用20目的产品测试，pH为7时吸水倍数≥600倍。
实施例3.一种抗酸碱性能强的高分子吸水树脂的制备方法，步骤如下，
将40g丙烯酸放入盛有300g水的500ml反应瓶中，在搅拌下加入40g碳酸钾(K2CO3)中和反应完成后pH值达到6.8-7.2，然后加入60g丙烯酰胺，搅拌均匀完全溶解后，测pH值应为7.0±0.1。在搅拌下加入0.05g交联剂六亚甲基四胺，然后加柠檬酸缓冲剂2.68g(柠檬酸0.33g，磷酸氢二钠2.35g)，再加入5g膨润土，搅拌均匀。加入0.02g的亚硫酸钠，搅拌均匀，然后加入0.02g交联剂。在0-30℃条件下吹氮气0.5小时除去溶解氧，测定体系的溶解氧≤0.01mg/L。如达不到，可加入0.02g的亚硫酸钠进一步吸收溶解氧。10分钟后加入过硫酸钾0.02g,亚硫酸铁0.02g形成氧化还原引发体系，停止吹氮气静止聚合2小时，温度升至约95-98℃，形成胶块造粒。150℃烘干至含水量10％±1时再粉碎，用分样筛筛至≤20目。用20目的产品测试，pH为7时吸水倍数≥600倍。
实施例4.一种抗酸碱性能强的高分子吸水树脂的制备方法，步骤如下，
将35g丙烯酸放入盛有300g水的500ml反应瓶中，在搅拌下加入35g碳酸钾(K2CO3)中和反应完成后pH值达到6.8-7.2，然后加入60g丙烯酰胺，搅拌均匀完全溶解后，测pH值应为7.0±0.1。在搅拌下加入0.06g交联剂六亚甲基四胺，然后加柠檬酸缓冲剂2.68g(柠檬酸0.33g，磷酸氢二钠2.35g)，再加入4.5g氢氧化铝，搅拌均匀。加入0.02g的亚硫酸钠，搅拌均匀，然后加入0.02g交联剂。在0-30℃条件下吹氮气0.5小时除去溶解氧，测定体系的溶解氧≤0.01mg/L。如达不到，可加入0.02g的亚硫酸钠进一步吸收溶解氧。10分钟后加入过硫酸钾0.02g,亚硫酸铁0.05g形成氧化还原引发体系，停止吹氮气静止聚合2小时，温度升至约95-98℃，形成胶块造粒。150℃烘干至含水量10％±1时再粉碎，用分样筛筛至≤20目。用20目的产品测试，pH为7时吸水倍数≥600倍。
试验例1本发明吸水树脂与普通吸水树脂抗酸碱性比较
采用网筛过滤法：称取一定粒径范围的吸水树脂200mg放入500mL烧杯中，加入一定量的去离子水(或预先配置好的不同pH值的水溶液)，静置吸液一段时间，采用自然过滤法，滤去多余的水，按照下式计算吸水倍率(Y).
式中：m1-滤网与干树脂的总质量(g)；m2-凝胶与滤网的总质量(g)；m0-干树脂质量。
试验选取20目的实施例1的吸水树脂，与20目普通市售吸水树脂，烘干后，在完全相同的条件下，同时进行吸水率试验：吸水树脂200mg，加水量为480g,室温25℃。试验分为5组，每组分别用本发明吸水树脂与市售普通吸水树脂进行对比，加水pH值分别为5.8、6.5、7.0、7.8、8.5，按照上式计算吸水倍率。结果如表1和图1所示。
表1.本发明吸水树脂与市售普通吸水树脂抗酸碱性能比较
表1和图1直观的显示了吸水树脂吸水倍率与pH之间的关系，从图1中可以看出，无论是本发明吸水树脂还是对照组市售普通吸水树脂，有相似的变化趋势，即在pH为7附近的水溶液中，吸水树脂的吸水倍率最大。当pH小于7时，吸水倍率随着pH的降低而降低，当pH大于7时，吸水倍率随着pH的增加而降低。pH＜6或pH＞8时，吸水树脂的吸水能力显著下降。
而与普通市售树脂随pH变化吸水倍率急剧变化不同的是，虽然在pH7.0的水中，本发明吸水树脂与市售普通吸水树脂的吸水倍数相差较少，但本发明吸水树脂在pH5.8-pH8.5的范围内，吸水倍率与pH7.0相比降低较少。市售普通吸水树脂在pH5.8时，吸水倍率较pH7.0下降36％，在pH8.5时，吸水倍率较pH7.0下降34.3％。本发明吸水树脂在pH5.8时，吸水倍率较pH7.0下降16％，在pH8.5时，吸水倍率较pH7.0下降16.5％。说明在偏酸或者偏碱性的条件下，本发明吸水树脂的吸水倍数明显高于普通吸水树脂。表明本发明吸水树脂具有很好的抗酸碱性能，更适合常规的弱酸或弱碱性环境。
试验例2.本发明吸水树脂与普通吸水树脂吸水速率比较
吸液速率为单位质量的吸水树脂在单位时间内吸收的吸液质量。瞬时吸水速率可反映吸水树脂随着条件变化而变化的规律，采用与上述同样的方法，根据样品的吸液倍率与吸液时间的吸液曲线，求导，得出瞬时吸液速率(见表2、图2)
表2本发明吸水树脂与市售普通吸水树脂吸水速率比较
在水的pH为7.0条件下，测本发明吸水树脂与普通吸水树脂吸水速率，从表2和图2可以看到，本发明吸水树脂在吸水15分钟达到吸水倍率最高值，而普通吸水树脂要在20-30分钟达到吸水倍率最高值，说明本发明吸水树脂吸水速度远远快于普通市售树脂。
试验例3.不同吸水介质对吸水性能影响比较
以实施例2制备的吸水树脂和普通市售吸水树脂，用不同的吸液介质：纯水、0.1％氯化钠溶液、0.9％氯化钠溶液参照试验例1的方法分别进行吸水试验。结果如表3、表4、图3、图4所示。
表3不同吸液介质对本发明吸水树脂吸水性能的影响
表4不同吸液介质对普通吸水树脂吸水性能的影响
由表3、表4、图3、图4可以看出不同吸液介质与SAP吸水倍率之间的关系。随着溶液中氯化钠浓度的增大，曲线斜率变小，吸水树脂的吸水倍率与吸水速率减小。可以看出本发明吸水树脂在0.1％氯化钠溶液吸液介质中虽然吸水速率降低了，但是吸水倍率降低较少。而普通吸水树脂在0.1％氯化钠溶液，中表现出吸水速率和吸水倍率的显著降低。本发明吸水树脂在较高浓度0.9％氯化钠溶液的吸液介质中，吸水速率和吸水倍率的下降也比普通市售树脂要低。说明本发明可以在一定的有渗透压的环境中保持较好的吸水性能。这将大大拓展本发明的应用范围。
Claims (4)
1.一种抗酸碱性能强的高分子吸水树脂的制备方法，其特征是，包括如下步骤：
(1)在300重量份的水中，加入30-50重量份的丙烯酸和等重量份的碳酸钾，经中和反应生成丙烯酸钾盐，再加入50-70重量份的丙烯酰胺，完全溶解后测PH值为7.0±0.1；
(2)加入交联剂0.04-0.06重量份，然后加缓冲剂2.3-2.7重量份，待完全溶解后，在搅拌下加入致孔剂3-5重量份，搅拌均匀；
(4)加入0.02重量份的亚硫酸钠，搅拌均匀，然后加入0.02重量份的交联剂；
(5)在0-30℃条件下吹氮气除氧到体系含氧量≤0.1mg/L；
(6)降温至10℃，加入0.03-0.07重量份的引发剂，继续吹氮气至发粘，聚合2小时后成聚合物胶块；
(7)胶块经挤压造粒，烘干，粉碎，筛分，成为不同粒径的产品；
所述引发剂为过硫酸钾和亚硫酸铁按照1:1-1:2的混合；
所述缓冲剂为pH 6.2-7.8磷酸盐缓冲剂或pH 6.2-7.8柠檬酸盐缓冲剂。
2.如权利要求1所述抗酸碱性能强的高分子吸水树脂的制备方法，其特征是，所述致孔剂为碳酸钙、氢氧化铝、膨润土、淀粉中的任意一种或几种。
3.如权利要求1所述抗酸碱性能强的高分子吸水树脂的制备方法，其特征是，所述步骤(1)中加入丙烯酰胺，完全溶解后，降温至10℃。
4.如权利要求1所述抗酸碱性能强的高分子吸水树脂的制备方法，其特征是，所述步骤(5)如测定体系的含氧量未达到≤0.01mg/L，再加入0.02重量份的亚硫酸钠进一步吸收溶解氧，直至体系含氧量≤0.01mg/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610355955.8A CN106008800B (zh) | 2016-05-26 | 2016-05-26 | 一种抗酸碱性能强的高分子吸水树脂的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610355955.8A CN106008800B (zh) | 2016-05-26 | 2016-05-26 | 一种抗酸碱性能强的高分子吸水树脂的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106008800A CN106008800A (zh) | 2016-10-12 |
| CN106008800B true CN106008800B (zh) | 2018-04-13 |
Family
ID=57093406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610355955.8A Expired - Fee Related CN106008800B (zh) | 2016-05-26 | 2016-05-26 | 一种抗酸碱性能强的高分子吸水树脂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106008800B (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5408019A (en) * | 1990-05-11 | 1995-04-18 | Chemische Fabrik Stockhausen Gmbh | Cross-linked, water-absorbing polymer and its use in the production of hygiene items |
| CN101171272A (zh) * | 2005-05-07 | 2008-04-30 | 基奥霍姆斯国际研究开发有限责任和两合公司 | 含有无机添加剂的水可溶胀杂化材料及其生产方法 |
| CN102584422A (zh) * | 2012-01-04 | 2012-07-18 | 中国水稻研究所 | 一种无土水稻盘育秧基质及育秧方法 |
| CN103224635A (zh) * | 2013-05-15 | 2013-07-31 | 南京林业大学 | 一种复合型淀粉改性高吸水树脂的制备方法 |
| CN103361069A (zh) * | 2012-03-30 | 2013-10-23 | 赵建军 | 一种生态保水剂的制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005037875A1 (ja) * | 2003-10-16 | 2005-04-28 | Mitsubishi Chemical Corporation | レドックス重合法、吸水性樹脂複合体および吸収性物品 |
-
2016
- 2016-05-26 CN CN201610355955.8A patent/CN106008800B/zh not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5408019A (en) * | 1990-05-11 | 1995-04-18 | Chemische Fabrik Stockhausen Gmbh | Cross-linked, water-absorbing polymer and its use in the production of hygiene items |
| CN101171272A (zh) * | 2005-05-07 | 2008-04-30 | 基奥霍姆斯国际研究开发有限责任和两合公司 | 含有无机添加剂的水可溶胀杂化材料及其生产方法 |
| CN102584422A (zh) * | 2012-01-04 | 2012-07-18 | 中国水稻研究所 | 一种无土水稻盘育秧基质及育秧方法 |
| CN103361069A (zh) * | 2012-03-30 | 2013-10-23 | 赵建军 | 一种生态保水剂的制备方法 |
| CN103224635A (zh) * | 2013-05-15 | 2013-07-31 | 南京林业大学 | 一种复合型淀粉改性高吸水树脂的制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| 聚(丙烯酸-丙烯酰胺) /膨润土/淀粉吸水性复合材料的制备及其性能;张秀兰等;《信阳师范学院学报：自然科学版》;20091031;第22卷(第4期);568-571 * |
| 膨润土/丙烯酸/丙烯酰胺三元共聚物的合成与吸水性能研究;徐玉文等;《矿物学报》;20060630;第26卷(第2期);224-228 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106008800A (zh) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ZOHOURIAN et al. | Superabsorbent polymer materials: a review | |
| CN103665411B (zh) | 一种高耐盐高吸水倍率的高吸水树脂及其制备方法 | |
| JP6557721B2 (ja) | 粒子状吸水剤 | |
| ES2260863T3 (es) | Agente absorbente de agua, su procedimiento de produccion, y su uso. | |
| Xie et al. | Slow-release nitrogen and boron fertilizer from a functional superabsorbent formulation based on wheat straw and attapulgite | |
| EP2727953B1 (en) | Polyacrylic acid (salt) water-absorbent resin powder, and method for producing same | |
| US5340853A (en) | Polymer-based swelling and absorbing agents with an improved degradability and an improved absorption for water, aqueous solutions and body liquids and the use of said agents for the production of hygienic articles and for soil conditioning | |
| CN102838714B (zh) | 一种秸秆复合高吸水树脂的制备方法 | |
| CN110272314A (zh) | 一种制备包覆型秸秆纤维基保水缓释肥的方法 | |
| CN1087749C (zh) | 一种聚丙烯酸盐类高吸水树脂 | |
| CN101511916A (zh) | 聚胺涂覆的超吸收性聚合物 | |
| CN101111540A (zh) | 聚胺涂覆的超吸收性聚合物 | |
| NL8006622A (nl) | Werkwijze voor het bereiden van absorbentia op basis van met boorverbindingen behandelde polysacchariden, alsmede daaruit verkregen absorberende produkten. | |
| CN101638461B (zh) | 马铃薯淀粉磷酸酯接枝共聚合成含磷和氮高吸水树脂的方法 | |
| JPS58131133A (ja) | 吸収材料の製造方法 | |
| CN104072686A (zh) | 一种具有缓释氮磷肥功能的秸秆基高吸水树脂的制备方法 | |
| BR112013024775B1 (pt) | método para a produção de resina absorvente de água | |
| JPS63270741A (ja) | ポリアクリル酸系吸水性樹脂の製造方法 | |
| Meshram et al. | Super-absorbent polymer: a review on the characteristics and application | |
| Liao et al. | Review on super absorbent polymer application for improving fertilizer efficiency and controlling agricultural non-point source pollutions | |
| CN106008800B (zh) | 一种抗酸碱性能强的高分子吸水树脂的制备方法 | |
| CN106496382A (zh) | 一种高吸水性树脂及其制备方法和应用 | |
| CN110372833A (zh) | 一种用竹屑制备可降解高吸水树脂的方法 | |
| CN108610459A (zh) | 一种快速吸收型高吸水性树脂的制备方法 | |
| CN106117442B (zh) | 一种应用于尿不湿的吸水树脂及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180413 |