JPH02153907A - Production of highly hygroscopic polymer - Google Patents
Production of highly hygroscopic polymerInfo
- Publication number
- JPH02153907A JPH02153907A JP30864288A JP30864288A JPH02153907A JP H02153907 A JPH02153907 A JP H02153907A JP 30864288 A JP30864288 A JP 30864288A JP 30864288 A JP30864288 A JP 30864288A JP H02153907 A JPH02153907 A JP H02153907A
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- polymer
- acid ester
- acrylic acid
- surfactant
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 title abstract description 42
- -1 sorbitan fatty acid ester Chemical class 0.000 claims abstract description 38
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 32
- 239000000194 fatty acid Substances 0.000 claims abstract description 32
- 229930195729 fatty acid Natural products 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 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 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 229930006000 Sucrose Natural products 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 5
- 229920000247 superabsorbent polymer Polymers 0.000 claims description 25
- 239000005720 sucrose Substances 0.000 claims description 19
- 239000007870 radical polymerization initiator Substances 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 235000013681 dietary sucrose Nutrition 0.000 abstract 2
- 229960004793 sucrose Drugs 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000010526 radical polymerization reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 238000010521 absorption reaction Methods 0.000 description 28
- 239000002245 particle Substances 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 9
- 239000001587 sorbitan monostearate Substances 0.000 description 9
- 235000011076 sorbitan monostearate Nutrition 0.000 description 9
- 229940035048 sorbitan monostearate Drugs 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002504 physiological saline solution Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004583 superabsorbent polymers (SAPs) Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000001589 sorbitan tristearate Substances 0.000 description 2
- 235000011078 sorbitan tristearate Nutrition 0.000 description 2
- 229960004129 sorbitan tristearate Drugs 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- PAFJZWHXMSQJKV-UQZRNVAESA-N (3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol;octadecanoic acid Chemical compound OC[C@@H](O)C1OC[C@H](O)[C@H]1O.OC[C@@H](O)C1OC[C@H](O)[C@H]1O.OC[C@@H](O)C1OC[C@H](O)[C@H]1O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O PAFJZWHXMSQJKV-UQZRNVAESA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000003084 food emulsifier Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の背景〕
産業上の利用分野
本発明は、高吸水性ポリマーの製造法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] Industrial Field of Application The present invention relates to a method for producing superabsorbent polymers.
本発明で得られる高吸水性ポリマーは、安全性が高く、
吸水諸性能に優れ、しかも大きな平均粒子径を有してい
る。さらに、製品としての流動性、搬送性が良好である
ので、各種の吸水材料に対して有利に使用することがで
きる。The superabsorbent polymer obtained by the present invention is highly safe,
It has excellent water absorption performance and has a large average particle size. Furthermore, since the product has good fluidity and transportability, it can be advantageously used for various water-absorbing materials.
従来技術
近年、高吸水性ポリマーは、生理用品や紙おむつ等の衛
生材料分野のみならず、止水材、結露防止材、さらに鮮
度保持材、溶剤脱水材等の産業用途、緑化、農園芸用途
等にも実用化されつつあり、今後、応用範囲はさらに拡
大されていくと思われる合成ポリマーである。Conventional technology In recent years, superabsorbent polymers have been used not only in the field of sanitary materials such as sanitary products and disposable diapers, but also in industrial applications such as water-stopping materials, anti-condensation materials, freshness preservation materials, solvent dehydration materials, greening, agricultural and horticultural applications, etc. It is a synthetic polymer that is now being put into practical use in the field, and its range of applications is expected to further expand in the future.
この種の高吸水性ポリマーとしては、澱粉−アクリロニ
トリルグラフト共重合体の加水分解物、カルボキシメチ
ルセルロース架橋体、ポリアクリル酸(塩)架橋体、ア
クリル酸(塩)−ビニルアルコール共重合体、ポリエチ
レンオキサイド架橋体等が知られている。Examples of this type of superabsorbent polymer include starch-acrylonitrile graft copolymer hydrolyzate, carboxymethyl cellulose crosslinked product, polyacrylic acid (salt) crosslinked product, acrylic acid (salt)-vinyl alcohol copolymer, and polyethylene oxide. Crosslinked products and the like are known.
しかし、これらの高吸水性ポリマーのいずれもが、吸水
能はほぼ満足しているものの、吸水速度、保水力等の吸
水諸性能を同時に満足しているとは言い難い。すなわち
、吸水能の高いポリマーは、−膜内に、吸水速度が遅く
、保水力に乏しいからである。However, although all of these highly water-absorbent polymers have almost satisfactory water absorption capacity, it is difficult to say that they simultaneously satisfy various water absorption properties such as water absorption rate and water retention capacity. That is, polymers with high water absorption ability have a slow water absorption rate and poor water retention ability into the membrane.
上記高吸水性ポリマーの吸水速度を向上させる方法とし
ては、親油性界面活性剤、非揮発性炭化水素またはステ
アリン酸カルシウム等の、所謂、滑剤を混合する方法、
ポリマー自体の架橋密度を高くして、ポリマーの親水性
を低下させる方法等が提案されている。しかし、前者の
方法は、単なる物理的混合であって滑剤がポリマーに化
学的に固定化されていないために、ごく初期においては
改善はみられるものの、その効果は永続きしないという
問題点がある。Methods for improving the water absorption rate of the superabsorbent polymer include a method of mixing a so-called lubricant such as a lipophilic surfactant, a non-volatile hydrocarbon, or calcium stearate;
A method has been proposed in which the hydrophilicity of the polymer is reduced by increasing the crosslinking density of the polymer itself. However, the former method involves mere physical mixing and the lubricant is not chemically immobilized on the polymer, so although an improvement can be seen in the very early stages, the problem is that the effect is not permanent. .
また、後者の方法には、ポリマーの吸水能自体を低下さ
せてしまうという問題点がある。Furthermore, the latter method has the problem of reducing the water absorbing ability of the polymer itself.
次に平均粒子径においては、特に、逆相懸濁重合法にお
いて合成された高吸水性ポリマーは、微粒子が多く、取
扱い上、困難なものが多い。Next, regarding the average particle size, particularly superabsorbent polymers synthesized by reverse-phase suspension polymerization have many fine particles and are often difficult to handle.
高吸水性ポリマーの平均粒子径の増大方法としては、モ
ノマー相に増粘剤を加えて重合させる方法、生成した微
粒子をバインダーを用いて造粒する方法等が一般的であ
る。しかし、前者はモノマー相の粘度を増大させるため
に、重合物粒子が相互に粘希し、全体または一部分が塊
状物となったりして良好な方法とは言い難い。又、後者
は、バインダーを使用するため、安全性、コストの面で
不利となる。Common methods for increasing the average particle size of superabsorbent polymers include a method in which a thickener is added to the monomer phase and polymerized, a method in which the produced fine particles are granulated using a binder, and the like. However, the former method is not a good method because it increases the viscosity of the monomer phase, which causes the polymer particles to become viscous with each other, resulting in all or part of the polymer particles becoming agglomerated. Furthermore, since the latter uses a binder, it is disadvantageous in terms of safety and cost.
その他にも、吸水諸性能のアップ又は平均粒子径のアッ
プを目的として、種々の界面活性剤を使用することが提
案されている。In addition, the use of various surfactants has been proposed for the purpose of improving water absorption performance or increasing the average particle size.
そのようなものとしては、例えば、
■ 特開昭56−131608号公報記載のHLB8〜
12の界面活性剤を用いる方法■ 特開昭57−1.5
8209号、特開昭57−158210号各公報記載の
セルロース系保護コロイド剤を用いる方法
■ 特開昭61−43606号公報記載のショ糖脂肪酸
エステルを用いる方法
■ 特開昭62−172006号公報記載のHLB2〜
16のポリグリセリン脂肪酸エステルを用いる方法
等が掲げられる。As such, for example, ■ HLB8~ described in JP-A-56-131608;
Method using 12 surfactants■ JP-A-57-1.5
8209 and JP-A No. 57-158210, a method using a cellulose-based protective colloid; ■ A method using a sucrose fatty acid ester, described in JP-A No. 61-43606; and JP-A No. 62-172,006. HLB2~
Examples include methods using 16 polyglycerin fatty acid esters.
しかし、前記■の方法は、得られたポリマーの平均粒子
径が改良され、微粒子は減るものの、重合時に重合槽器
壁へのポリマーの付着が激しくて、安定操業をする点に
於いて必ずしも満足できるものとは言えない。However, although method (2) improves the average particle diameter of the resulting polymer and reduces the number of fine particles, it is not always satisfactory in terms of stable operation because the polymer adheres to the walls of the polymerization tank during polymerization. I can't say it's possible.
又、■の方法は、セルロース系保護コロイド剤がポリマ
ー表面に少しでも残っていると、乾燥時に溶融し、ポリ
マーの一部分が塊状物となったり、流動性、搬送性に問
題が生じたりすることがあることから良好な方法とは言
い難い。In addition, in method (2), if even a small amount of cellulose-based protective colloid remains on the polymer surface, it will melt during drying, causing part of the polymer to form into lumps and causing problems with fluidity and transportability. It is difficult to say that it is a good method because of the following.
■の方法は、安全性が高く、比較的大粒径のポリマーが
得られるが、吸水性能、特に、吸水速度、保水力におい
て他の界面活性剤を使用した場合に比較して劣る傾向が
ある。Method (2) is highly safe and yields polymers with relatively large particle sizes, but it tends to be inferior in water absorption performance, especially in water absorption speed and water holding capacity, compared to when other surfactants are used. .
■の方法は、大粒径のポリマーを得るための製造条件の
許容範囲が非常に狭く、その条件をはずれると塊状重合
を起こし、工業的な安定生産を考慮した場合には、有利
なものとはLい難い。Method (2) has a very narrow tolerance range for manufacturing conditions to obtain polymers with large particle diameters, and if these conditions are exceeded, bulk polymerization occurs, so it is not advantageous when considering stable industrial production. It's hard.
従って、平均粒径が大きく、且つ、高吸水性ポリマーに
要求される吸水諸性能を充分に満足している高吸水性ポ
リマーは未だなく、その吸水速度、保水力等の吸水諸性
能及び平均粒子径さらには生産安定性をも考慮した場合
、まだ改善される余地は残されている。Therefore, there is still no superabsorbent polymer that has a large average particle diameter and fully satisfies the various water absorption properties required of a superabsorbent polymer. When considering the diameter and production stability, there is still room for improvement.
要旨
本発明は、安全性が高く、吸水諸性能に優れ、しかも大
きな平均粒子径を有し、製品としての流動性、搬送性が
良好な高吸水性ポリマーを容易に製造する方法を提供し
ようとするものである。Summary The present invention aims to provide a method for easily producing a superabsorbent polymer that is highly safe, has excellent water absorption performance, has a large average particle size, and has good fluidity and transportability as a product. It is something to do.
本発明者等は、前記の問題点を解決する目的で種々検討
を重ねた結果、上記逆相懸濁重合法において、界面活性
剤として、(イ)■少なくとも常温で固体状態の外観を
持ち且つ、■HLB値が1〜8の範囲にあるソルビタン
脂肪酸エステルと(ロ)HLB値が1〜6の範囲にある
ショ糖脂肪酸エステルとの混合界面活性剤を使用するこ
とにより、安全性が高く、吸水諸性能に優れ、しかも大
きな平均粒子径を有し、製品としての流動性、搬送性が
良好な高吸水性ポリマーが得られることを見出して、本
発明を完成するに至った。As a result of various studies aimed at solving the above-mentioned problems, the present inventors have found that, in the above-mentioned reverse phase suspension polymerization method, as a surfactant, (a) (i) has a solid appearance at least at room temperature; , ■ By using a mixed surfactant of sorbitan fatty acid ester with an HLB value in the range of 1 to 8 and (b) sucrose fatty acid ester with an HLB value in the range of 1 to 6, it is highly safe. The present invention was completed based on the discovery that a superabsorbent polymer having excellent water absorption performance, a large average particle diameter, and good fluidity and transportability as a product can be obtained.
即ち、本発明による高吸水性ポリマーの製造法は、アク
リル酸及び/又はメタクリル酸並びにそのアルカリ金属
塩よりなる群から選ばれるアクリル酸系モノマーを、架
橋剤の存在下に、ラジカル重合開始剤を用いて、炭化水
素溶媒中で逆相懸濁重合させる方法に於いて、逆相懸濁
重合に使用する界面活性剤が(イ)少なくとも常温で固
体状態の外観を持ち且つ、HLB値が1〜8の範囲にあ
るソルビタン脂肪酸エステルと(ロ)HLB値が1〜6
の範囲にあるショ糖脂肪酸エステルとの混合界面活性剤
であること、を特徴とするものである。That is, the method for producing a superabsorbent polymer according to the present invention involves adding a radical polymerization initiator to an acrylic acid monomer selected from the group consisting of acrylic acid and/or methacrylic acid and alkali metal salts thereof in the presence of a crosslinking agent. In the method of reverse-phase suspension polymerization in a hydrocarbon solvent, the surfactant used in the reverse-phase suspension polymerization (a) has the appearance of a solid state at least at room temperature and has an HLB value of 1 to 1. Sorbitan fatty acid ester in the range of 8 and (b) HLB value of 1 to 6
It is characterized by being a mixed surfactant with a sucrose fatty acid ester within the range of .
効果
本発明によって製造される高吸水性ポリマーは、吸水能
、吸水速度、保水力等の吸水諸性能に優れたものである
。しかも大きな平均粒子径を持ち、製品としての、流動
性、搬送性も良好である。Effects The superabsorbent polymer produced by the present invention has excellent water absorption properties such as water absorption capacity, water absorption rate, and water retention capacity. In addition, it has a large average particle diameter and has good fluidity and transportability as a product.
モノマー
本発明において重合させるべき七ツマ−としては、アク
リル酸及び/又はメタクリル酸並びにそのアルカリ金属
塩よりなる群から選ばれるアクリル酸系モノマーが用い
られる。ここで言うアルカリ金属塩とは、アクリル酸及
び/又はメタクリル酸のカルボキシル基を、例えば、水
酸化ナトリウム、水酸化カリウム、水酸化リチウム等の
アルカリ金属水酸化物、で中和させて得られた塩のこと
である。生成ポリマーの性能、価格等の面からいえば、
アクリル酸及び/又はメタクリル酸を水酸化ナトリウム
にて中和した塩が特に好ましく用もられる。アクリル酸
及び/又はメタクリル酸の中和度は、本発明に於ける高
吸水性ポリマーの性能面を考慮する場合に非常に重要な
因子の一つであり、生成高吸水性ポリマーの性能のトー
タルバランスを考える場合には、アクリル酸系モノマー
の全カルボキシル基の50〜95モル%が中和されてい
ることが望ましい。中和度が50モル%未満である場合
は、吸水能が劣る傾向にあり、性能をバランス良く保つ
のが困難となる。逆に95モル%を越えて中和すると、
重合速度が極端に遅くなるので中和のメリットは少ない
。Monomer As the monomer to be polymerized in the present invention, an acrylic acid monomer selected from the group consisting of acrylic acid and/or methacrylic acid and alkali metal salts thereof is used. The alkali metal salt referred to here is a salt obtained by neutralizing the carboxyl group of acrylic acid and/or methacrylic acid with an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. It's about salt. In terms of performance, price, etc. of the produced polymer,
Salts obtained by neutralizing acrylic acid and/or methacrylic acid with sodium hydroxide are particularly preferably used. The degree of neutralization of acrylic acid and/or methacrylic acid is one of the very important factors when considering the performance of the superabsorbent polymer in the present invention, and it When considering balance, it is desirable that 50 to 95 mol% of all carboxyl groups in the acrylic acid monomer be neutralized. If the degree of neutralization is less than 50 mol%, water absorption capacity tends to be poor, making it difficult to maintain well-balanced performance. Conversely, if more than 95 mol% is neutralized,
Since the polymerization rate becomes extremely slow, neutralization has little merit.
これらのアクリル酸系モノマーの溶液中での濃度は、2
0%以上、特に30%〜60%、であることが好ましい
。The concentration of these acrylic acid monomers in solution is 2
It is preferably 0% or more, particularly 30% to 60%.
また、本発明では、上述したアクリル酸系モノマー以外
にこれらと共重合可能な七ツマ−1例えばマレイン酸(
塩)、イタコン酸(塩)、アクリルアミド、2−アクリ
ルアミド−2−メチルプロパンスルホン酸、2− (メ
タ)アクリロイルエタンスルホン酸、2−ヒドロキシエ
チル(メタ)アクリレート等も吸水性ポリマーの吸水性
能を実質的に損なわない範囲で併用することも可能であ
る。In addition, in the present invention, in addition to the above-mentioned acrylic acid monomers, 7mers copolymerizable with these monomers, such as maleic acid (
Salt), itaconic acid (salt), acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2-(meth)acryloylethanesulfonic acid, 2-hydroxyethyl (meth)acrylate, etc. also substantially improve the water absorption performance of water-absorbing polymers. It is also possible to use them together as long as they do not damage the product.
架橋剤
上記アクリル酸系モノマーは、何ら架橋剤を使用しなく
ても、ある程度の自己架橋が生じて高吸水性ポリマーと
なるが、吸水諸性能をバランス良く保つためには、この
七ツマー水溶液に架橋剤成分を加える必要がある。架橋
剤成分としては、分子内に2個以上の重合性不飽和基を
有し、かつ前記アクリル酸系モノマーと共重合性を示す
水溶性化合物、例えばN、N’ −メチレンビスアク
リルアミド、N、N’ −メチレンビスメタクリルア
ミド等のビスアクリルアミド類が一般的であり、且つ好
ましい。Crosslinking agent The above acrylic acid monomer undergoes self-crosslinking to some extent and becomes a highly water-absorbing polymer even without the use of any crosslinking agent. It is necessary to add a crosslinker component. As the crosslinking agent component, a water-soluble compound having two or more polymerizable unsaturated groups in the molecule and exhibiting copolymerizability with the acrylic acid monomer, such as N,N'-methylenebisacrylamide, N, Bisacrylamides such as N'-methylenebismethacrylamide are common and preferred.
上記架橋剤成分は、通常、モノマー水溶液に対して、約
0.005〜0.5重量%、好ましくは約0.01〜0
.3重量%、の範囲で用いるのが適当である。The crosslinking agent component is usually about 0.005 to 0.5% by weight, preferably about 0.01 to 0.0% by weight, based on the monomer aqueous solution.
.. It is appropriate to use it in a range of 3% by weight.
ラジカル重合開始剤
本発明における逆相懸濁重合法においては予めモノマー
水溶液中に水溶性ラジカル重合開始剤を溶解させておく
ことがふつうである。ここで用いる水溶性ラジカル重合
開始剤としては、過硫酸カリウム、過硫酸アンモニウム
等の過硫酸塩や、アゾビス−(2−アミジノプロパン)
塩酸塩等のアゾ系開始剤等が代表的である。これらのラ
ジカル重合開始剤は、モノマー水溶液に対して、通常は
約0.001〜5.0重量%、好ましくは約0.01〜
1.0ff11%、の範囲で用いるのが適当である。Radical Polymerization Initiator In the reverse phase suspension polymerization method of the present invention, a water-soluble radical polymerization initiator is usually dissolved in advance in the monomer aqueous solution. Examples of water-soluble radical polymerization initiators used here include persulfates such as potassium persulfate and ammonium persulfate, and azobis-(2-amidinopropane).
Typical examples include azo initiators such as hydrochloride. These radical polymerization initiators are usually used in an amount of about 0.001 to 5.0% by weight, preferably about 0.01 to 5.0% by weight, based on the monomer aqueous solution.
It is appropriate to use it within the range of 1.0ff11%.
溶媒
本発明に使用する逆相懸濁重合の溶媒としては、脂肪族
炭化水素もしくは脂環式炭化水素が好ましい。具体的に
は、ノルマルペンタン、ノルマルヘキサン、ノルマルヘ
プタン、シクロヘキサン、リグロイン等が掲げられる。Solvent The solvent for reverse phase suspension polymerization used in the present invention is preferably an aliphatic hydrocarbon or an alicyclic hydrocarbon. Specific examples include normal pentane, normal hexane, normal heptane, cyclohexane, and ligroin.
このうち、特に、シクロへ牛サン、ノルマルへ牛サンは
、重合熱の除去および得られたポリマーの乾燥の観点か
らも好ましいものである。Among these, cyclohegyu-san and normal hegyo-san are particularly preferred from the viewpoint of removing polymerization heat and drying the obtained polymer.
界面活性剤
本発明に用いられる界面活性剤、即ち、ソルビタン脂肪
酸エステル及びショ糖脂肪酸エステルは、食品用乳化剤
として知られるように、食品添加物公定書の規格項目に
合致する安全なものであり、安全性の観点からも非常に
好ましい界面活性剤である。Surfactant The surfactant used in the present invention, that is, sorbitan fatty acid ester and sucrose fatty acid ester, is known as a food emulsifier and is safe, meeting the specifications of the Japanese Food Additives Standard. It is a very preferable surfactant from the viewpoint of safety.
これらの界面活性剤を混合して使用する際、ソルビタン
脂肪酸エステル(イ)は、■少なくとも常温で固体状態
の外観を持ち、且つ、■HLB値が1〜8の範囲にある
ことが必須の条件となる。When using a mixture of these surfactants, it is essential that the sorbitan fatty acid ester (a): ■ have a solid appearance at least at room temperature, and ■ have an HLB value in the range of 1 to 8. becomes.
■の条件を満たさないソルビタン脂肪酸エステルは、ポ
リマー表面に若干量でも残留すると、製品ポリマーの流
動性および搬送性が悪くなり、方、■の条件を満たさな
いソルビタン脂肪酸エステルは、平均粒子径及び性能を
低下させる傾向があるので好ましくない。If even a small amount of sorbitan fatty acid ester that does not meet the conditions (2) remains on the polymer surface, the fluidity and transportability of the product polymer will deteriorate. This is not preferable because it tends to lower the
もう一方のショ糖脂肪酸エステル(ロ)は、HLB値が
1〜6の範囲にあるものが好ましい。The other sucrose fatty acid ester (b) preferably has an HLB value in the range of 1 to 6.
HLB値が6を超過するショ糖脂肪酸エステルでは、生
成ポリマーの粒径が細かくなってしまう傾向がある。Sucrose fatty acid esters with an HLB value of more than 6 tend to have a fine particle size of the resulting polymer.
これらの界面活性剤の添加量は、両者を混合した状態で
、モノマーに対して通常0,1〜10重量%、好ましく
は0. 5〜5蚤量%、の範囲の門である。添加量が0
.1重量%未満であると目的とする分散の効果が得られ
ず、又、10重量%超過では、重合後のポリマーを乾燥
させた時にポリマーが凝集する傾向かあるので好ましく
ない。The amount of these surfactants added is usually 0.1 to 10% by weight, preferably 0.1 to 10% by weight, based on the monomer in a mixed state. This phylum ranges from 5 to 5% flea mass. Added amount is 0
.. If it is less than 1% by weight, the desired dispersion effect cannot be obtained, and if it exceeds 10% by weight, there is a tendency for the polymer to aggregate when it is dried after polymerization, which is not preferable.
これらの界面活性剤の混合割合は、吸水諸性能及び粒径
を成立させる点で非常に重要な因子であり、通常、ソル
ビタン脂肪酸エステル対ショ糖脂肪酸エステルを重量化
で80対20〜20対80、好ましくは60対40〜4
0対60、の範囲で混合する。The mixing ratio of these surfactants is a very important factor in establishing water absorption performance and particle size, and is usually 80:20 to 20:80 by weight of sorbitan fatty acid ester to sucrose fatty acid ester. , preferably 60:40-4
Mix in the range of 0:60.
代表的なソルビタン脂肪酸エステルの例としては、ソル
ビタンモノパルミテート(I(LB:6.7)ソルビタ
ンモノステアレート(HLB−4,7)、ソルビタンセ
スキステアレート(HLB−4,2) 、ソルビタント
リステアレート(HLB−2,1)等が掲げられる。Examples of representative sorbitan fatty acid esters include sorbitan monopalmitate (I (LB: 6.7)) sorbitan monostearate (HLB-4,7), sorbitan sesquistearate (HLB-4,2), and sorbitan tri. Stearate (HLB-2, 1), etc. are listed.
重合
前記した様に、本発明は、アクリル酸及び/又はメタク
リル酸並びにそのアルカリ金属塩よりなる群から選ばれ
るアクリル酸系モノマーを、架橋剤、ラジカル重合開始
剤及び二種の界面活性剤の存在下に、逆相懸濁重合法に
よって重合を行うものである。アクリル酸系モノマー、
架橋剤、ラジカル重合開始剤および界面活性剤の添加順
序、添加態様ないし重合操作は、本発明の目的に反しな
い限り任意である。例えば、(イ)架橋剤およびラジカ
ル重合開始剤を溶解させたアクリル酸系モノマー水溶液
を、界面活性剤を添加しておいた炭化水素溶媒に添加し
て懸濁させ、その後に加熱を行なって重合を行う方法、
(ロ)架橋剤およびラジカル重合開始剤を溶解させたア
クリル酸系モノマー水溶液に界面活性剤を添加し、これ
を炭化水素溶媒に添加して懸濁させ、加熱により重合を
iテう方法、(ハ)架橋剤およびラジカル重合開始剤を
溶解させたアクリル酸系モノマー水溶液を、炭化水素溶
媒に添加して懸濁させ、その後に界面活性剤を添加し、
加熱して重合を行う方法、などを例示することができる
。Polymerization As described above, the present invention is characterized in that an acrylic acid monomer selected from the group consisting of acrylic acid and/or methacrylic acid and its alkali metal salts is used in the presence of a crosslinking agent, a radical polymerization initiator, and two types of surfactants. Below, polymerization is carried out by a reversed phase suspension polymerization method. acrylic acid monomer,
The order of addition, mode of addition, and polymerization operation of the crosslinking agent, radical polymerization initiator, and surfactant are arbitrary as long as they do not contradict the purpose of the present invention. For example, (a) an aqueous acrylic acid monomer solution in which a crosslinking agent and a radical polymerization initiator are dissolved is added to a hydrocarbon solvent to which a surfactant has been added, suspended, and then heated to polymerize. how to do,
(b) A method in which a surfactant is added to an aqueous acrylic acid monomer solution in which a crosslinking agent and a radical polymerization initiator are dissolved, and this is added to a hydrocarbon solvent to suspend it and polymerize by heating. c) Adding an aqueous acrylic acid monomer solution in which a crosslinking agent and a radical polymerization initiator are dissolved to a hydrocarbon solvent to suspend it, and then adding a surfactant,
Examples include a method of polymerizing by heating.
重合温度は、40〜120℃、好ましくは60〜90℃
、が採用される。また、重合時間は、重合温度等によっ
て異なるが、−船釣には30分〜6時間程度、好ましく
は、1時間〜4時間、である。重合終了後、ポリマーを
炭化水素溶媒から分離し乾燥させれば、目的とする粉末
高吸水性ポリマーが得られる。Polymerization temperature is 40-120°C, preferably 60-90°C
, will be adopted. The polymerization time varies depending on the polymerization temperature, etc., but for boat fishing it is about 30 minutes to 6 hours, preferably 1 hour to 4 hours. After the polymerization is completed, the polymer is separated from the hydrocarbon solvent and dried to obtain the desired powdered superabsorbent polymer.
以下、実験例により本発明の詳細な説明する。 The present invention will be explained in detail below using experimental examples.
尚、高吸水性ポリマーの吸水諸性能とは、吸水能、吸水
速度(拡散速度)、保水力を表わし、次の様にして測定
した。又、平均粒子径の測定法も記した。The water absorption performance of the superabsorbent polymer refers to water absorption capacity, water absorption rate (diffusion rate), and water retention capacity, and was measured as follows. The method for measuring the average particle diameter is also described.
吸水能
高吸水性ポリマー1gを400メツシユのナイロン袋(
10cmxlOcmの大きさ)に入れ、1リツトルの0
.9%−生理食塩水に30分浸漬する。Water absorption capacity 1g of super absorbent polymer in a 400 mesh nylon bag (
(size: 10cm x lOcm) and 1 liter of 0
.. 9% - Soak in saline for 30 minutes.
30分後、ナイロン袋を引き上げ、15分水切り後、重
量測定をし、ブランク補正をして、高吸水性ポリマー1
gが吸収した0、9%生理食塩水の重量を吸水能とした
。After 30 minutes, pull up the nylon bag, drain it for 15 minutes, weigh it, make a blank correction, and add super absorbent polymer 1.
The weight of 0.9% physiological saline absorbed by g was defined as the water absorption capacity.
吸水速度(拡散速度)
第1図に示す装置を用いて’APE定した。高吸水性ポ
リマー1.0gを***のあいた支持板の上の不織布上に
おく。下面より0.9%−生理食塩水と接触させたとき
に高吸水性ポリマーが、0.9%生理食塩水を吸水する
量を測定した。開始後、10分間に吸水した0、 9
%生理食塩水の量をもって吸水速度(拡散速度)とした
。Water absorption rate (diffusion rate) 'APE was determined using the apparatus shown in FIG. 1.0 g of a superabsorbent polymer is placed on a nonwoven fabric on a support plate with small holes. When the superabsorbent polymer was brought into contact with 0.9% physiological saline from the lower surface, the amount of water absorbed by the superabsorbent polymer was measured. Water absorbed in 10 minutes after starting 0, 9
The amount of % physiological saline was defined as the water absorption rate (diffusion rate).
保水力
第1図に示した装置を用いて、高吸水性ポリマー1gに
0.9%−生理食塩水25m1を均一に吸水させる。こ
の吸水ゲルを400メツシユのナイロン袋(10cn+
X I C1eyn)に入れ、入口をシールする。この
サンプルの上下を濾紙(10cmX10cm)10枚ず
つではさみ、これに45g/cdの荷重を3分間かける
。濾紙に移った0、9%生理食塩水二を測定し、加圧前
後の吸水量より、保水力を求めた。Water Retention Capacity Using the apparatus shown in FIG. 1, 25 ml of 0.9% physiological saline is uniformly absorbed into 1 g of superabsorbent polymer. This water-absorbing gel is packed in a 400-mesh nylon bag (10cn+
X I Cleyn) and seal the entrance. This sample was sandwiched between 10 pieces of filter paper (10 cm x 10 cm) at the top and bottom, and a load of 45 g/cd was applied for 3 minutes. The amount of 0.9% physiological saline transferred to the filter paper was measured, and the water retention capacity was determined from the amount of water absorbed before and after pressurization.
甲均粒子径
JIS規格の標準フルイのうち、42.60.80.1
00.150.200.325メツシユのフルイを用い
て質量規準の粒径分布を求め、質量規準の50%粒子径
を平均粒子径とした。Among the standard sieves with average particle size of JIS standard, 42.60.80.1
A particle size distribution based on mass was determined using a sieve with a mesh size of 00.150.200.325, and the 50% particle size based on mass was taken as the average particle size.
実施例1
撹拌機、還流冷却器、温度計、窒素ガス導入管を付設し
た容量1リツトルの四つ目丸底フラスコに、シクロヘキ
サン282gを入れ、これにソルビタンモノステアレー
ト1.05sr及びショ糖脂肪酸エステル(第−工業製
薬株式会社製、商品名rDK−エステルF−10J)1
.05gを添加して溶解させた後、窒素ガスを吹込み、
溶存酸素を追い出した。Example 1 282 g of cyclohexane was placed in a 1 liter four-eye round bottom flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen gas inlet tube, and 1.05 sr of sorbitan monostearate and sucrose fatty acid were added to this. Ester (manufactured by Dai-Kogyo Seiyaku Co., Ltd., trade name rDK-Ester F-10J) 1
.. After adding and dissolving 05g, nitrogen gas was blown into the solution.
Dissolved oxygen was expelled.
別に、8量500mlのコニカルビーカー中で、アクリ
ル酸70gの外部より氷冷しながら、これに水185.
85gに溶解した28.6gの純度95%の水酸化ナト
リウムを加えて、全カルボキシル基の70モル%を中和
した。この場合の水に対する七ツマー濃度は30重量%
に相当する。次いで、これにN、 N’ −メチレ
ンビスアクリルアミド0.098g、過硫酸カリウム0
.243gを加えて溶解した後、窒素ガスを吹き込んで
溶存酸素を追い出した。Separately, in a 500 ml conical beaker, 70 g of acrylic acid was added to 185 g of water while cooling with ice from the outside.
28.6 g of 95% pure sodium hydroxide dissolved in 85 g was added to neutralize 70 mole % of the total carboxyl groups. In this case, the concentration of 7mer in water is 30% by weight
corresponds to Next, 0.098 g of N,N'-methylenebisacrylamide and 0.0 g of potassium persulfate were added to this.
.. After adding and dissolving 243 g, nitrogen gas was blown in to drive out dissolved oxygen.
前記の四つ口丸底フラスコの内容物に、この容ff15
00mlのコニカルビーカーの内容物を添加し、攪拌し
て分散させ、窒素ガスをバブリングさせなから油浴によ
りフラスコ内温を昇温させたところ、60℃付近に達し
たから内温か急激に上昇し、数十分後には75℃に達し
た。次いで、その内温を60〜65℃に保持し、且つ攪
拌しながら3時間反応させた。尚、攪拌は25Orpm
で行なった。Add this volume ff15 to the contents of the four-necked round bottom flask.
00 ml of the contents of the conical beaker was added, stirred to disperse, and the temperature inside the flask was raised in an oil bath without bubbling nitrogen gas.As it reached around 60°C, the internal temperature rose rapidly. After several tens of minutes, the temperature reached 75°C. Next, the internal temperature was maintained at 60 to 65° C. and the mixture was reacted for 3 hours with stirring. In addition, stirring is at 25 rpm.
I did it.
3時間反応させた後、攪拌を停止すると、湿潤ポリマー
粒子が丸底フラスコの底に沈降したので、デカンテーシ
ョンでシクロヘキサン相と容易に分離で1だ。分離した
湿潤ポリマーを減圧乾燥機に移し、80〜90℃に加熱
して付着したシクロヘキサン及び水を除去し、さらさら
とした粉末ポリマー約90gを得た。After reacting for 3 hours, stirring was stopped and the wet polymer particles settled to the bottom of the round bottom flask and were easily separated from the cyclohexane phase by decantation. The separated wet polymer was transferred to a vacuum dryer and heated to 80 to 90°C to remove adhering cyclohexane and water, yielding about 90 g of a smooth powdered polymer.
実施例2
実施例1において、界面活性剤として、ソルビタンモノ
ステアレート1゜75g及びショ糖脂肪酸エステル(D
K−エステルF−10)1.75gを用いた以外は同様
にして、粉末ポリマー約90gを得た。Example 2 In Example 1, 1.75 g of sorbitan monostearate and sucrose fatty acid ester (D
About 90 g of powdered polymer was obtained in the same manner except that 1.75 g of K-ester F-10) was used.
実施例3
実施例1において、界面活性剤として、ソルビタンモノ
ステアレート1.4Of及びショ糖脂肪酸エステル(D
K−エステルF−10)0.7gを用いた以外は同様に
して、粉末ポリマー約90gを得た。Example 3 In Example 1, sorbitan monostearate 1.4Of and sucrose fatty acid ester (D
About 90 g of powdered polymer was obtained in the same manner except that 0.7 g of K-ester F-10) was used.
実施例4
実施例1において、界面活性剤として、ソルビタンモノ
ステアレート1.05.及びショ糖脂肪酸エステル(第
−工業製薬株式会社製、商品名rDK−エステルF−2
0Jン1.05gを用いた以外は同様にして、粉末ポリ
マー約90gを得た。Example 4 In Example 1, sorbitan monostearate 1.05% was used as the surfactant. and sucrose fatty acid ester (manufactured by Dai-Kogyo Seiyaku Co., Ltd., trade name rDK-ester F-2
Approximately 90 g of powdered polymer was obtained in the same manner except that 1.05 g of OJ was used.
実施例5
実施例1において、界面活性剤として、ソルビタンモノ
ステアレート1.40g及びショ糖脂肪酸エステル(D
K−エステルF −20) 0. 7gを用いた以外は
同様にして、粉末ポリマー約90gを得た。Example 5 In Example 1, 1.40 g of sorbitan monostearate and sucrose fatty acid ester (D
K-ester F-20) 0. Approximately 90 g of powdered polymer was obtained in the same manner except that 7 g was used.
実施例6
実施例1において、界面活性剤として、ソルビタントリ
ステアレー)1. 05g−及びショ糖脂肪酸エステル
(DK−エステルF−10>1.05gを用いた以外は
同様にして、粉末ポリマー約90gを得た。Example 6 In Example 1, as a surfactant, sorbitan tristearate)1. Approximately 90 g of powdered polymer was obtained in the same manner except that DK-ester F-10 and 1.05 g of sucrose fatty acid ester (DK-ester F-10>1.05 g) were used.
実施例7
実施例1において、界面活性剤として、ソルビタントリ
ステアレート1.05g及びショ糖脂肪酸エステル(第
−工業製薬株式会社製、商品名rDK−エステルF−5
0J)1.05gを用いた以外は同様にして、粉末ポリ
マー約90gを得た。Example 7 In Example 1, 1.05 g of sorbitan tristearate and sucrose fatty acid ester (manufactured by Dai-Kogyo Seiyaku Co., Ltd., trade name rDK-ester F-5) were used as surfactants.
About 90 g of powdered polymer was obtained in the same manner except that 1.05 g of 0J) was used.
比較例1
実施例1において、界面活性剤として、ショ糖脂肪酸エ
ステル(DK−エステルF−10)2.1gを用いた以
外は同様にして、粉末ポリマー約90gを得た。Comparative Example 1 About 90 g of powdered polymer was obtained in the same manner as in Example 1, except that 2.1 g of sucrose fatty acid ester (DK-ester F-10) was used as the surfactant.
比較例2
実施例1において、界面活性剤として、ショ糖脂肪酸エ
ステル(DK−エステルF−20)2.1gを用いた以
外は同様にして、粉末ポリマー約90gを得た。Comparative Example 2 About 90 g of powdered polymer was obtained in the same manner as in Example 1, except that 2.1 g of sucrose fatty acid ester (DK-ester F-20) was used as the surfactant.
比較例3
実施例1において、界面活性剤として、ソルビタンモノ
ステアレー)2.1gを用いた以外は同様にして、粉末
ポリマー約90gを得た。Comparative Example 3 About 90 g of powdered polymer was obtained in the same manner as in Example 1 except that 2.1 g of sorbitan monostearate was used as the surfactant.
比較例4
実施例1において1.界面活性剤として、ソルビタンモ
ノステアレート1.89g及びショ糖脂肪酸エステル(
DK−エステルF −10)0.21gを用いた以外は
同様にして、粉末ポリマー約90gを得た。Comparative Example 4 In Example 1, 1. As surfactants, 1.89 g of sorbitan monostearate and sucrose fatty acid ester (
About 90 g of powdered polymer was obtained in the same manner except that 0.21 g of DK-ester F-10) was used.
比較例5
実施例1において、界面活性剤として、ソルビタンモノ
ステアレート0.21g及びショ糖脂肪酸エステル(D
K−エステルF −10)1.89gを用いた以外は同
様にして、粉末ポリマー約90gを得た。Comparative Example 5 In Example 1, 0.21 g of sorbitan monostearate and sucrose fatty acid ester (D
About 90 g of powdered polymer was obtained in the same manner except that 1.89 g of K-ester F-10) was used.
比較例6
実施例1において、モノマー相にヒドロキシエチルセル
ロース(フジケミカル社製、フジへツクA−5000)
を2.3g加えた以外は同様にして、粉末ポリマー約9
0gを得た。Comparative Example 6 In Example 1, hydroxyethylcellulose (manufactured by Fuji Chemical Co., Ltd., Fujihetsuku A-5000) was added to the monomer phase.
About 9 g of powdered polymer was added in the same manner except that 2.3 g of
Obtained 0g.
上記ポリマーの吸水諸性能、平均粒子径、及び流動性の
結果を下記第1表に示す。The results of the water absorption performance, average particle diameter, and fluidity of the above polymer are shown in Table 1 below.
第
表
な平均粒子径を持ち、流動性も良好であることがわかる
。It can be seen that the average particle diameter is as shown in the table below, and the fluidity is also good.
第1図は、高吸水性ポリマーの吸水速度および保水力を
測定するのに使用した装置の概略を示す図面である。
1・・・高吸水性ポリマー(Ig)、2・・・***のあ
いた支持板、3・・・不織布、4・・・0.9%食塩水
、5・・・ビューレット、6・・・ゴム栓、7,8・・
・バルブ、9・・・空気入口。FIG. 1 is a diagram schematically showing an apparatus used to measure the water absorption rate and water retention capacity of superabsorbent polymers. DESCRIPTION OF SYMBOLS 1... Super absorbent polymer (Ig), 2... Support plate with small holes, 3... Nonwoven fabric, 4... 0.9% saline, 5... Buret, 6... Rubber stopper, 7, 8...
・Valve, 9...Air inlet.
Claims (1)
金属塩よりなる群から選ばれるアクリル酸系モノマーを
、架橋剤の存在下に、ラジカル重合開始剤を用いて、炭
化水素溶媒中で逆相懸濁重合させる方法に於いて、逆相
懸濁重合に使用する界面活性剤が(イ)少なくとも常温
で固体状態の外観を持ち且つ、HLB値が1〜8の範囲
にあるソルビタン脂肪酸エステルと(ロ)HLB値が1
〜6の範囲にあるショ糖脂肪酸エステルとの混合界面活
性剤であることを特徴とする、高吸水性ポリマーの製造
法。An acrylic acid monomer selected from the group consisting of acrylic acid and/or methacrylic acid and alkali metal salts thereof is subjected to reverse phase suspension polymerization in a hydrocarbon solvent using a radical polymerization initiator in the presence of a crosslinking agent. In the method, the surfactant used in the reverse phase suspension polymerization is (a) a sorbitan fatty acid ester that has a solid appearance at least at room temperature and has an HLB value in the range of 1 to 8, and (b) an HLB value. is 1
A method for producing a superabsorbent polymer, characterized in that it is a mixed surfactant with a sucrose fatty acid ester in the range of .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30864288A JP2716485B2 (en) | 1988-12-06 | 1988-12-06 | Method for producing superabsorbent polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30864288A JP2716485B2 (en) | 1988-12-06 | 1988-12-06 | Method for producing superabsorbent polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02153907A true JPH02153907A (en) | 1990-06-13 |
JP2716485B2 JP2716485B2 (en) | 1998-02-18 |
Family
ID=17983518
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30864288A Expired - Lifetime JP2716485B2 (en) | 1988-12-06 | 1988-12-06 | Method for producing superabsorbent polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2716485B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007084656A (en) * | 2005-09-21 | 2007-04-05 | Dainippon Ink & Chem Inc | Method for producing liquid absorbing resin |
WO2012033025A1 (en) | 2010-09-06 | 2012-03-15 | 住友精化株式会社 | Water absorbent resin and method for producing same |
-
1988
- 1988-12-06 JP JP30864288A patent/JP2716485B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007084656A (en) * | 2005-09-21 | 2007-04-05 | Dainippon Ink & Chem Inc | Method for producing liquid absorbing resin |
WO2012033025A1 (en) | 2010-09-06 | 2012-03-15 | 住友精化株式会社 | Water absorbent resin and method for producing same |
Also Published As
Publication number | Publication date |
---|---|
JP2716485B2 (en) | 1998-02-18 |
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