JPH02189314A - Material for water-absorptive resin - Google Patents
Material for water-absorptive resinInfo
- Publication number
- JPH02189314A JPH02189314A JP1084189A JP1084189A JPH02189314A JP H02189314 A JPH02189314 A JP H02189314A JP 1084189 A JP1084189 A JP 1084189A JP 1084189 A JP1084189 A JP 1084189A JP H02189314 A JPH02189314 A JP H02189314A
- Authority
- JP
- Japan
- Prior art keywords
- water
- copolymer
- maleic anhydride
- alternating copolymer
- resin
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 27
- 239000011347 resin Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 17
- 229920005603 alternating copolymer Polymers 0.000 claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- 238000004132 cross linking Methods 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 125000004018 acid anhydride group Chemical group 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 5
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 abstract description 5
- -1 isopropenylethyl ester Chemical class 0.000 abstract description 4
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 14
- 239000000203 mixture Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- HKKOVPPBQKFVNN-UHFFFAOYSA-N prop-1-en-2-yl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC(C)=C HKKOVPPBQKFVNN-UHFFFAOYSA-N 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- IBFVKFASESHLFP-UHFFFAOYSA-N C(CCCCCCCCCCC)(=O)OC(C)C(=C)C Chemical compound C(CCCCCCCCCCC)(=O)OC(C)C(=C)C IBFVKFASESHLFP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- VGMRJSWQULGOOO-UHFFFAOYSA-N prop-1-en-2-yl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC(C)=C VGMRJSWQULGOOO-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CWDYIYQRGPVXFN-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)(=O)OC(C)C(=C)C Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)OC(C)C(=C)C CWDYIYQRGPVXFN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000002747 voluntary effect Effects 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は新規な吸水性樹脂用素材に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a new material for water absorbent resin.
（従来の技術）
近年、自重の数１０倍から数１００倍もの蒸留水を吸収
しうる高吸水性樹脂が開発され、水と接触して短時間に
極めて多量の水を吸水する性質を生かして生理用品やお
むつ等の衛材、土壌改良剤などの用途に用いられている
。(Conventional technology) In recent years, super absorbent resins that can absorb distilled water tens to hundreds of times their own weight have been developed. It is used in hygiene products such as sanitary products and diapers, and as a soil conditioner.
このような高分子材料としてはポリエチレンオキシド、
ポリビニルアルコール、ポリビニルアルコール・ポリア
クリル酸ソーダブロック共重合物、デンプンまたはセル
ロース・ポリアクリロニトリルグラフト共重合物の加水
分解物、デンプン・ポリアクリル酸ソーダ・グラフト共
重合体、ポリアクリル酸ソーダ、カルボキシメチルセル
ロースなどの天然又は合成高分子が使用されているが、
ポリエチレンオキシド及び低ケン化度のポリビニルアル
コールを除けばいずれも熱可塑性を有しないため熔融成
形が不可能であり、水溶液からのキャストフィルム以外
は粉末又は顆粒状の形でしか吸水性樹脂が得られない。Examples of such polymer materials include polyethylene oxide,
Polyvinyl alcohol, polyvinyl alcohol/sodium polyacrylate block copolymer, hydrolyzate of starch or cellulose/polyacrylonitrile graft copolymer, starch/sodium polyacrylate graft copolymer, sodium polyacrylate, carboxymethyl cellulose, etc. natural or synthetic polymers have been used;
With the exception of polyethylene oxide and polyvinyl alcohol with a low degree of saponification, none of them have thermoplasticity and cannot be melt-molded, and water-absorbing resins can only be obtained in the form of powder or granules, except for cast films from aqueous solutions. do not have.
また熱可塑性のポリエチレンオキサイド、低ケン化度の
ポリビニルアルコールは非イオン性ゆえに充分な吸水性
を有しないという欠点がある。Furthermore, thermoplastic polyethylene oxide and polyvinyl alcohol with a low degree of saponification have the disadvantage that they do not have sufficient water absorbency because they are nonionic.
（発明が解決しようとする課題）
上記のような、吸水性樹脂の現状に鑑み、本発明の目的
は、熱可塑性を有するアニオン性の水溶性樹脂を吸水性
樹脂の素材として提供するものである。(Problems to be Solved by the Invention) In view of the current state of water-absorbing resins as described above, an object of the present invention is to provide an anionic water-soluble resin having thermoplasticity as a material for water-absorbing resins. .
（課題を解決するための手段） 本発明によれば、上記目的は、下記一般弐ＣＨ。(Means for solving problems) According to the present invention, the above object is the following general 2CH.
ＣＨｚ ＝ＣＣＨｚ ＣＨｚ ＯＣＲ（式中Ｒは炭
素数９〜１７の炭化水素基を表わす）で示される化合物
〔！〕 と無水マレイン酸（ＩＩ）との交互共重合体を
吸水性樹脂用素材に用いることで達成される。A compound represented by CHz = CCHz CHz OCR (in the formula, R represents a hydrocarbon group having 9 to 17 carbon atoms) [! This can be achieved by using an alternating copolymer of ] and maleic anhydride (II) as a material for a water-absorbing resin.
化合物Ｎ）を表わす上記−船人中Ｒは炭素数９〜１７の
炭化水素基を表わし、その例としてはデシ）Ｌ４、ドデ
シル基、テトラデシル基、ヘキサデシル基、ヘプタデシ
ル基等の直鎖状もしくは分岐状のアルキル基があげられ
る。In the above-mentioned compound N), R represents a hydrocarbon group having 9 to 17 carbon atoms, examples of which include linear or branched hydrocarbon groups such as deci)L4, dodecyl group, tetradecyl group, hexadecyl group, and heptadecyl group. Examples include alkyl groups such as
前記化合物（１）と無水マレイン酸（Ｉｔ）との交互共
重合体は、従来公知の方法にしたがって得ることができ
る。例えば、有機溶剤中でのアゾ系化合物や有機過酸化
物等の開始剤を用いたラジカル重合があげられる。交互
共重合体が得られたことは、共重合組成が各成分の混合
比に依らず１：１であること、元素分析値、赤外吸収ス
ペクトル、該磁気共鳴スペクトル等により確認される。The alternating copolymer of the compound (1) and maleic anhydride (It) can be obtained according to a conventionally known method. For example, radical polymerization using an initiator such as an azo compound or an organic peroxide in an organic solvent can be mentioned. The fact that an alternating copolymer was obtained was confirmed by the fact that the copolymer composition was 1:1 regardless of the mixing ratio of each component, elemental analysis values, infrared absorption spectra, magnetic resonance spectra, etc.
本発明で用いられる交互共重合体の熱溶融温度は一般式
中ＯＲの炭素により異なり、炭素数が９より小さいと溶
融温度が高すぎて成形が困難になり、一方Ｒの炭素数が
１７を超えると分子中の酸無水物基の存在割合が小さく
なり、充分な吸水性能を示さなくなるので、Ｒの炭素数
は９から１７の範囲内にあることが必要である。The thermal melting temperature of the alternating copolymer used in the present invention varies depending on the carbon in OR in the general formula; if the number of carbon atoms is less than 9, the melting temperature is too high and molding becomes difficult; If the number of carbon atoms in R exceeds 9, the proportion of acid anhydride groups in the molecule decreases and sufficient water absorption performance is not exhibited.
本発明で用いられる交互共重合体の平均重合度は、低す
ぎると得られる吸水性樹脂の強度および吸水性能が充分
でなく、一方高すぎると熔融粘度が高くなりすぎて成形
困難となるので、１００〜１０００の間にあることが望
ましい。If the average degree of polymerization of the alternating copolymer used in the present invention is too low, the resulting water-absorbing resin will not have sufficient strength and water absorption performance, while if it is too high, the melt viscosity will become too high, making molding difficult. It is desirable that it be between 100 and 1000.
次に、本発明の素材を用いて吸水性樹脂を作る具体的な
方法について以下に記す。Next, a specific method for producing a water-absorbing resin using the material of the present invention will be described below.
本発明を構成する交互共重合体は吸水性を付与するため
、分子中の酸無水物基をＮａＯＨ，ＮＨ８等のアルカリ
物質と反応させてＮａ塩、ＮＨ，塩等に変性させる必要
があり、さらに水不溶性とするために架橋剤を用いて３
次元架橋させなければならない。In order to impart water absorbency to the alternating copolymer constituting the present invention, it is necessary to react the acid anhydride group in the molecule with an alkaline substance such as NaOH or NH8 to modify it into Na salt, NH, salt, etc. Furthermore, in order to make it water-insoluble, 3
It must be dimensionally bridged.
酸無水物基を変性する方法として、（１）該共重合体を
直接ＮＨ３ガスと接触させる、（２）ＮａＯＨのエタノ
ール溶液に該共重合体を浸漬し、加熱撹拌してケン化を
行う、（３）ＮａＯＨまたはＮＨ，水に該共重合体を投
入、加熱溶解後蒸発乾固する、等があり、状況により選
択される。As a method for modifying acid anhydride groups, (1) the copolymer is brought into direct contact with NH3 gas, (2) the copolymer is immersed in an ethanol solution of NaOH and saponified by heating and stirring. (3) Adding the copolymer to NaOH, NH, or water, heating and dissolving it, and then evaporating to dryness, etc., which is selected depending on the situation.
前記目的に用いられる架橋剤は、酸無水物基またはカル
ボキシル基と交差結合しうる多官能性化合物であればよ
く、具体的には多価エポキシ化合物、多価アミン、多価
アルコール等があげられる。The crosslinking agent used for the above purpose may be any polyfunctional compound that can cross-link with an acid anhydride group or a carboxyl group, and specific examples thereof include polyvalent epoxy compounds, polyvalent amines, polyhydric alcohols, etc. .
架橋反応は、上記多官能性化合物を交互共重合体もしく
は該交互共重合体のＮａ塩、ＮＨ４塩等の変性物に混合
後、１００〜２００℃で１〜数時間熱処理することで達
成される。架橋剤の添加量は、少なすぎると架橋が充分
でなく、吸水状態でのゲル強度が極端に弱くなったり、
樹脂の一部が水へ溶解したりするので好ましくなく、一
方多すぎると架橋密度が太き（なりすぎて充分な吸水性
能が得られないので、交互共重合体もしくは交互共重合
体の変性物に対し０．１〜１０重量％の量であるのが好
ましい。The crosslinking reaction is achieved by mixing the above polyfunctional compound with the alternating copolymer or a modified product of the alternating copolymer such as Na salt or NH4 salt, and then heat-treating the mixture at 100 to 200°C for 1 to several hours. . If the amount of crosslinking agent added is too small, crosslinking will not be sufficient, and the gel strength in the water absorption state will become extremely weak.
Part of the resin dissolves in water, which is undesirable. On the other hand, if the resin is too large, the crosslinking density becomes too thick (too much, and sufficient water absorption performance cannot be obtained, so alternating copolymers or modified products of alternating copolymers The amount is preferably 0.1 to 10% by weight.
本発明を実施するにあたり交互共重合体のアルカリ物質
による変性度すなわち中和度は１０〜７０％の範囲にあ
ることが重要である。すなわち、中和度が１０％より小
さいと、得られる吸水性樹脂の吸水倍率が小さくなりす
ぎるし、一方７０％を越えると該共重合体変性物の熱可
塑性が極端に低下するので本発明の目的にそぐわない。In carrying out the present invention, it is important that the degree of modification of the alternating copolymer with an alkaline substance, that is, the degree of neutralization, is in the range of 10 to 70%. That is, if the degree of neutralization is less than 10%, the water absorption capacity of the resulting water-absorbing resin will be too low, while if it exceeds 70%, the thermoplasticity of the modified copolymer will be extremely reduced. Not fit for purpose.
本発明の素材を用いて吸水性樹脂を製造する場合、該共
重合体のアルカリ物質による変性を行った後に架橋剤を
加えて熱処理してもよいし、その逆に架橋剤を加えて熱
処理した後に、（１）ＮＨｓガスと接触させる、（２）
ＮａＯＨのエタノール溶液に浸漬してケン化を行う、等
の方法でアルカリ物質による変性を行うこともできる。When producing a water absorbent resin using the material of the present invention, a crosslinking agent may be added and heat treated after the copolymer is modified with an alkaline substance, or vice versa, a crosslinking agent may be added and heat treated. After that, (1) contact with NHs gas, (2)
Denaturation with an alkaline substance can also be carried out by a method such as saponification by immersion in an ethanol solution of NaOH.
さらに本発明の素材を用いて吸水性樹脂を製造するに際
し、他の熱可塑性樹脂、顔料１．染料、紫外線吸収剤、
酸化防止剤、防カビ剤、殺菌剤、香料、消臭剤等を含有
させることも可能である。Furthermore, when producing a water-absorbing resin using the material of the present invention, other thermoplastic resins, pigments 1. dyes, ultraviolet absorbers,
It is also possible to contain antioxidants, fungicides, bactericidal agents, fragrances, deodorants, and the like.
本発明の吸水性樹脂用素材は、熱可塑性を利用して各種
の形状に成形可能なので、用途に応じてフィルム状、塊
状、繊維状の吸水性樹脂が容易に得られ、脱水フィルタ
ー、止水用のシール材、バンキング材、結露防止材等の
用途に好適である。The material for water-absorbent resin of the present invention can be molded into various shapes using thermoplasticity, so water-absorbent resin in the form of a film, block, or fiber can be easily obtained depending on the application, and can be used as a dehydration filter, water stopper, etc. It is suitable for applications such as sealing materials, banking materials, and dew condensation prevention materials.
以下実施例によって本発明を具体的に説明するが、本発
明はそれらによって何ら限定されるものではない。The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.
実施例１
攪拌機のついた１１オートクレーブに酢酸エチル２００
ｇ、ラウリン酸イソプロペニルエチル８０．４ｇ（０，
３モル）、無水マレイン酸２９．４ ｇ（０，３モル）
およびアゾビスイソブチロニトリル０．４９ ｇ （０
，００３モル）を仕込み、３０分間攪拌して混合溶解お
よび窒素置換を行った後、６５℃に昇温して６時間重合
を行った。重合終了後内液を取り出してロータリーエバ
ポレータで溶媒を留去した後、４０℃で真空乾燥してポ
リマー１０３、１ ｇを得た。このポリマーのＧＰＣに
よる平均分子量は、ポリスチレン換算でＭｗ ＝６，８
００、Ｍｗ ／ Ｍｎ ＝ ２．５であり、溶融温度は
１３２℃であった。該ポリマーを元素分析して得られた
Ｃ１Ｈ％は各々６８．６７．９．２４であり、ラウリン
酸イソプロペニルエチルと無水マレイン酸の１＝１共重
合体の理論値６８．８２．９．３５に極めて近い値であ
った。又’ＩＩ−ＮＭＲの測定値に基づいて算出したラ
ウリン酸イソプロペニルと無水マレイン酸の共重合体組
成比はｓｏ、ｏ：ｓｏ、ｏであり、該ポリマーがラウリ
ン酸イソプロペニルと無水マレイン酸の交互共重合体で
あることを裏づけるものであった。Example 1 200 ml of ethyl acetate was placed in a 11 autoclave equipped with a stirrer.
g, isopropenylethyl laurate 80.4 g (0,
3 mol), maleic anhydride 29.4 g (0.3 mol)
and azobisisobutyronitrile 0.49 g (0
,003 mol) and stirred for 30 minutes to perform mixed dissolution and nitrogen substitution, and then the temperature was raised to 65° C. and polymerization was carried out for 6 hours. After the polymerization was completed, the internal solution was taken out and the solvent was distilled off using a rotary evaporator, followed by vacuum drying at 40°C to obtain 1 g of Polymer 103. The average molecular weight of this polymer by GPC is Mw = 6,8 in terms of polystyrene.
00, Mw/Mn = 2.5, and the melting temperature was 132 °C. The C1H% obtained by elemental analysis of the polymer was 68.67.9.24, respectively, and the theoretical value of a 1=1 copolymer of isopropenylethyl laurate and maleic anhydride was 68.82.9.35. The value was extremely close to . The copolymer composition ratio of isopropenyl laurate and maleic anhydride calculated based on the measured values of 'II-NMR is so, o: so, o, and the copolymer composition ratio of isopropenyl laurate and maleic anhydride is so, o: so, o. This confirmed that it was an alternating copolymer.
該交互共重合体粉末に分子１１２００のポリエチレンイ
ミドを該共重合体に対して１ｗｔ％添加してブラベンダ
ーで１５０℃で混練してコンパウンドを得た。このコン
パウンドを１５０°ｃｘｌＯｋｇ／ｃ！１１の条件で５
分間ヒートプレスし、厚み１■菖のシートを作成した。Polyethyleneimide having a molecular weight of 11,200 was added to the alternating copolymer powder in an amount of 1 wt% based on the copolymer, and the mixture was kneaded in a Brabender at 150° C. to obtain a compound. This compound is 150°cxlOkg/c! 5 with 11 conditions
Heat pressing was performed for a minute to create a sheet with a thickness of 1 inch.
得られたシートを１８０”ｃｘｌｈｒ熱処理後１ ｃｍ
Ｘ４ｃｍの短冊状に切ったもの５５．１ｇ（０，１５モ
ル）と水酸化ナトリウム７．２ｇ（０，１８モル）、エ
タノール２００ｇをオートクレーブに仕込み、８０’Ｃ
で６時間攪拌後、脱液乾燥して短冊状の吸水性樹脂を得
た。この短冊状の吸水性樹脂を常温の蒸留水中に１時間
浸漬して吸水倍率を測定したところ３６倍であった。The obtained sheet was heated to 180”cxlhr after 1 cm
55.1 g (0.15 mol) of the strips cut into 4 cm x 4 cm strips, 7.2 g (0.18 mol) of sodium hydroxide, and 200 g of ethanol were placed in an autoclave and heated at 80'C.
After stirring for 6 hours, the mixture was deliquified and dried to obtain a strip-shaped water-absorbing resin. When this strip-shaped water-absorbing resin was immersed in distilled water at room temperature for 1 hour and its water absorption capacity was measured, it was found to be 36 times.
実施例２
ラウリン酸イソプロペニルエチルの代わりにステアリン
酸イソプロペニルエチル７０．４ｇ（０，２ｍｏｒ）を
用い、さらに無水マレイン酸を１９．６ ｇ（０，２モ
ル）、アゾビスイソブチロニトリル０．３３ｇ（０，０
０２モル）用いて実施例１と同様にして重合を行い、ポ
リマー８２．５ ｇを得た。このポリマーのＧＰＣによ
る平均分子量はポリスチレン換算でＭｗ ＝５．８００
、Ｍｗ ／ Ｍｎ □ ＝ ２．４であり、溶融温度
は１０７℃であった。該ポリマーを元素分析して得られ
たＣ、Ｈ％は各々？ ２．０３．１０．３５であり、ス
テアリン酸イソプロペニルと無水マレイン酸の１：１共
重合体の理論値７１．９６．１０．２９に極めて近い値
であった。又’Ｈ−ＮＭＲの測定値に基づいて算出した
ステアリン酸イソプロペニルと無水マレイン酸の共重合
組成比は５０．１：４９．９であり、該ポリマーがラウ
リン酸イソプロペニルと無水マレイン酸の交互共重合体
であることを裏づけるものであった。Example 2 70.4 g (0.2 mol) of isopropenylethyl stearate was used instead of isopropenylethyl laurate, 19.6 g (0.2 mol) of maleic anhydride, and 0.0 g of azobisisobutyronitrile. .33g (0,0
Polymerization was carried out in the same manner as in Example 1 using 02 mol) to obtain 82.5 g of polymer. The average molecular weight of this polymer by GPC is Mw = 5.800 in terms of polystyrene.
, Mw/Mn □ = 2.4, and the melting temperature was 107°C. What are the C and H% obtained by elemental analysis of the polymer? 2.03.10.35, which is extremely close to the theoretical value of 71.96.10.29 for a 1:1 copolymer of isopropenyl stearate and maleic anhydride. Furthermore, the copolymer composition ratio of isopropenyl stearate and maleic anhydride calculated based on the measured values of 'H-NMR is 50.1:49.9, and the copolymer composition ratio of isopropenyl stearate and maleic anhydride is 50.1:49.9, and the copolymerization ratio of isopropenyl stearate and maleic anhydride is 50.1:49.9. This confirmed that it was a copolymer.
次にこの交互共重合体に対してエタノール苛性中でＮ＆
変性（中和度０．３）を行い、脱液乾燥して該交互共重
合体のＮａ塩粉末を得た。交互共重合体のＮａ塩粉末に
、テトラエチレンペンタミンを２ｗｔ％加えて１５０℃
で混練りし、コンパウンドを得た。このコンパウンドを
２００℃Ｘ５Ｑｋｇ／ｃＪＡの条件で５分間ヒートプレ
スして厚さ２１層のシートを作成した。得られたシート
を１８０℃×１時間熱処理して架橋反応を行った。得ら
れた吸水性シートの蒸留水での吸水倍率は１８倍であっ
た。This alternating copolymer was then treated with N&
Modification (degree of neutralization: 0.3) was carried out, followed by dehydration and drying to obtain Na salt powder of the alternating copolymer. Add 2 wt% of tetraethylenepentamine to the Na salt powder of the alternating copolymer and heat at 150°C.
The mixture was kneaded to obtain a compound. This compound was heat pressed for 5 minutes at 200°C and 5Qkg/cJA to form a sheet with a thickness of 21 layers. The obtained sheet was heat-treated at 180° C. for 1 hour to perform a crosslinking reaction. The water absorption capacity of the obtained water absorbent sheet in distilled water was 18 times.
実施例３
実施例２で得られたステアリン酸イソプロペニルエチル
と無水マレイン酸共重合体のＮａ変性物ｉｏｏ重量部に
ホットメルト型ポリビニルアルコール（ケン化度６０％
、重合度４５０）１００重置部を加え、ブラベンダーで
１２０°Ｃで混練りしてコンパウンドを得た。このコン
パウンドを１８０℃Ｘ５０ｋｇ／ＣｒＡの条件で５分間
ヒートプレスして厚さｌ ｘｍのシートを作成した。得
られたシートを１５０℃で２時間加熱処理して架橋反応
を行ったところ、蒸留水での吸水倍率は８倍であった。Example 3 Hot-melt polyvinyl alcohol (Saponification degree 60%
, polymerization degree 450) were added thereto and kneaded at 120°C in a Brabender to obtain a compound. This compound was heat pressed for 5 minutes at 180° C. and 50 kg/CrA to form a sheet with a thickness of 1×m. When the obtained sheet was heat-treated at 150° C. for 2 hours to perform a crosslinking reaction, the water absorption capacity with distilled water was 8 times.
（発明の効果）
本発明によって熱可塑性を有するアニオン性の水溶性樹
脂となりうる吸水性樹脂用素材が提供される。(Effects of the Invention) The present invention provides a material for a water-absorbing resin that can be an anionic water-soluble resin having thermoplasticity.
手続補正書（自発） １、事件の我示 特Ｉｊｉ乎１−１０８４１号 ２、発明の名称 吸水性樹脂用素材 ３、補正をする者 事件との関係 特許出願人 倉敷市酒津１６２１番地 （ｔｏ８）株式会社クラレ 代表取締役 中 村 尚 夫 ４、代 理 人 倉敷市酒津２０４５の１ 株式会社クラレ内 特許出願人 株式会社 り ラ しProcedural amendment (voluntary) 1. Revealing the incident Special number 1-10841 2. Name of the invention Material for water absorbent resin 3. Person who makes corrections Relationship to the case Patent applicant 1621 Sakazu, Kurashiki City (to8) Kuraray Co., Ltd. Representative Director Nao Nakamura 4. Deputy manager 2045-1, Sakazu, Kurashiki City Within Kuraray Co., Ltd. Patent applicant: RiRashi Co., Ltd.
Claims (1)
される化合物〔 I 〕と無水マレイン酸〔II〕との交互
共重合体からなる吸水性樹脂用素材。[Claims] A compound [I] represented by the following general formula ▲ Numerical formula, chemical formula, table, etc.▼ (in the formula, R represents a hydrocarbon group having 9 to 17 carbon atoms) and maleic anhydride [II] A water-absorbing resin material made of an alternating copolymer with
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1010841A JP2721532B2 (en) | 1989-01-18 | 1989-01-18 | Water absorbent resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1010841A JP2721532B2 (en) | 1989-01-18 | 1989-01-18 | Water absorbent resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02189314A true JPH02189314A (en) | 1990-07-25 |
| JP2721532B2 JP2721532B2 (en) | 1998-03-04 |
Family
ID=11761580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1010841A Expired - Fee Related JP2721532B2 (en) | 1989-01-18 | 1989-01-18 | Water absorbent resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2721532B2 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01131218A (en) * | 1987-08-03 | 1989-05-24 | Kuraray Co Ltd | Novel alternate copolymer |
-
1989
- 1989-01-18 JP JP1010841A patent/JP2721532B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01131218A (en) * | 1987-08-03 | 1989-05-24 | Kuraray Co Ltd | Novel alternate copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2721532B2 (en) | 1998-03-04 |
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