JP2012167050A - Water soluble crosslinking agent - Google Patents
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本発明は、水溶性架橋剤に関する。 The present invention relates to a water-soluble crosslinking agent.
逆相懸濁重合及び水溶液重合等の水系の重合条件で架橋重合体を製造するために用いられる水溶性架橋剤としては、Ｎ，Ｎ’−メチレンビスアクリルアミド、エチレングリコールジメタクリレート、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジメタクリレート、ポリエチレングリコールジグリシジルエーテル等の化合物が広く使用されている。これらの水溶性架橋剤により架橋された架橋重合体は、オムツ及び衛生材料等に使用される吸水性樹脂をはじめとして、種々の産業分野における添加剤として用いられている。 Examples of water-soluble crosslinking agents used for producing a crosslinked polymer under aqueous polymerization conditions such as reverse phase suspension polymerization and aqueous solution polymerization include N, N′-methylenebisacrylamide, ethylene glycol dimethacrylate, ethylene glycol diglycidyl. Compounds such as ether, polyethylene glycol dimethacrylate, and polyethylene glycol diglycidyl ether are widely used. Crosslinked polymers crosslinked with these water-soluble crosslinking agents are used as additives in various industrial fields including water-absorbing resins used in diapers and sanitary materials.
一方、化粧料、トイレタリー等の分野では、長年実績があり、安全性の高い油溶性のショ糖アリルエーテル（アリルスクロース）及びペンタエリスリトールトリアリルエーテル（アリルペンタエリスリトール）等の油溶性架橋剤により架橋された、カルボキシル基を有する親水性の架橋重合体が用いられている（特許文献１）。この親水性の架橋重合体としては、カルボキシルビニルポリマーが代表的である。カルボキシル基を有する親水性の架橋重合体は、少量の使用量で優れた増粘性を示すことから、化粧品、トイレタリー等の分野で増粘、分散および乳化安定剤等の添加剤として広く使用されている。 On the other hand, in fields such as cosmetics and toiletries, it has been used for many years and is crosslinked with oil-soluble crosslinking agents such as highly safe oil-soluble sucrose allyl ether (allyl sucrose) and pentaerythritol triallyl ether (allyl pentaerythritol). A hydrophilic cross-linked polymer having a carboxyl group is used (Patent Document 1). A typical example of the hydrophilic crosslinked polymer is a carboxyl vinyl polymer. A hydrophilic cross-linked polymer having a carboxyl group exhibits excellent thickening with a small amount of use, and is therefore widely used as an additive for thickening, dispersion, and emulsion stabilizers in cosmetics, toiletries and other fields. Yes.
カルボキシル基を有する親水性の架橋重合体は、例えば、アクリル酸と、重合性不飽和基を有する油溶性架橋剤と、特定の有機溶媒とを用いた沈殿重合法により製造される。 The hydrophilic crosslinked polymer having a carboxyl group is produced, for example, by a precipitation polymerization method using acrylic acid, an oil-soluble crosslinking agent having a polymerizable unsaturated group, and a specific organic solvent.
一般に、親水性の架橋重合体からなるポリマー粒子の増粘特性等の特性は、粒子のサイズ及び形状、並びに架橋重合体の架橋度及び分子量等の性状と密接に関連している。したがって、所望の特性を得るためには、これらの性状を精密に制御することが必要とされる。 In general, properties such as thickening properties of polymer particles made of a hydrophilic cross-linked polymer are closely related to particle size and shape, and properties such as cross-linking degree and molecular weight of the cross-linked polymer. Therefore, in order to obtain desired characteristics, it is necessary to precisely control these properties.
しかし、沈殿重合法では、得られるポリマー粒子の性状が有機溶媒に対するポリマーの溶解性の影響を大きく受けることから、これを任意に制御することは非常に困難である。そのため、沈殿重合法により製造される従来の親水性の架橋重合体を用いた親水性増粘剤の場合、増粘特性等の性能を、要求特性の異なる多様な用途それぞれに応じて適正化する上で制約が多いという問題があった。 However, in the precipitation polymerization method, since the properties of the polymer particles obtained are greatly affected by the solubility of the polymer in the organic solvent, it is very difficult to arbitrarily control this. Therefore, in the case of a hydrophilic thickener using a conventional hydrophilic cross-linked polymer produced by a precipitation polymerization method, the performance such as the thickening property is optimized according to each of various uses with different required properties. There was a problem that there were many restrictions.
一方、逆相懸濁重合等の水系の重合条件によれば、攪拌速度等の重合条件を調整することにより、所望の粒子径、架橋度、分子量等の性状を有するポリマー粒子として架橋重合体を容易に得ることができる。したがって、架橋重合体の特性を各種の用途に適するように容易に調整することが可能である。 On the other hand, according to the aqueous polymerization conditions such as reverse phase suspension polymerization, by adjusting the polymerization conditions such as the stirring speed, the crosslinked polymer can be obtained as polymer particles having properties such as a desired particle diameter, degree of crosslinking, and molecular weight. Can be easily obtained. Therefore, it is possible to easily adjust the characteristics of the crosslinked polymer so as to be suitable for various applications.
ところが、水系の重合条件に用いることのできる水溶性架橋剤については、これまでに、化粧料、トイレタリー等の一部の分野において十分な使用実績のあるものがない。また、使用実績のある油溶性架橋剤を用いても、水系の重合条件では架橋反応が起こらないため、十分に架橋された架橋重合体を製造することができない。 However, water-soluble crosslinking agents that can be used for water-based polymerization conditions have not been used enough in some fields such as cosmetics and toiletries. Further, even when an oil-soluble crosslinking agent having a proven track record is used, a crosslinking reaction does not occur under aqueous polymerization conditions, so that a sufficiently crosslinked crosslinked polymer cannot be produced.
したがって、特定の分野においては、水溶性架橋剤を用いた水系の重合による方法は回避され、架橋重合体の製造方法は、油溶性架橋剤を用いた沈殿重合法に実質的に限られていた。 Therefore, in a specific field, a method based on water-based polymerization using a water-soluble crosslinking agent is avoided, and a method for producing a crosslinked polymer is substantially limited to a precipitation polymerization method using an oil-soluble crosslinking agent. .
そこで、本発明は、化粧料、トイレタリー等の分野で好適に用いることのできる親水性の架橋重合物を、逆相懸濁重合及び水溶液重合等の水系の重合条件で製造することを可能にする、新規な水溶性架橋剤の提供を目的とする。 Therefore, the present invention makes it possible to produce a hydrophilic crosslinked polymer that can be suitably used in the fields of cosmetics, toiletries, and the like, under aqueous polymerization conditions such as reverse phase suspension polymerization and aqueous solution polymerization. An object is to provide a novel water-soluble crosslinking agent.
本発明は、アリルエーテル基及び水酸基を有する水溶性ショ糖アリルエーテルを含む水溶性架橋剤に関する。 The present invention relates to a water-soluble crosslinking agent comprising a water-soluble sucrose allyl ether having an allyl ether group and a hydroxyl group.
本発明に係る水溶性架橋剤によれば、化粧料、トイレタリー等の分野で好適に用いることのできる親水性の架橋重合物を、逆相懸濁重合及び水溶液重合等の水系の重合条件で製造することができる。 According to the water-soluble cross-linking agent according to the present invention, a hydrophilic cross-linked polymer that can be suitably used in the fields of cosmetics, toiletries and the like is produced under aqueous polymerization conditions such as reverse phase suspension polymerization and aqueous solution polymerization. can do.
水溶性ショ糖アリルエーテルのエーテル化度は、好ましくは１．８〜４．０である。このエーテル化度は、水溶性ショ糖アリルエーテルに対する、当該水溶性ショ糖アリルエーテルが有するアリルエーテル基のモル比の平均値に相当する。エーテル化度が１．８〜４．０の範囲内にあるショ糖アリルエーテルは、良好な水溶性を維持しつつ、より効果的に架橋剤として機能する。 The degree of etherification of the water-soluble sucrose allyl ether is preferably 1.8 to 4.0. This degree of etherification corresponds to the average value of the molar ratio of the allyl ether group of the water-soluble sucrose allyl ether to the water-soluble sucrose allyl ether. Sucrose allyl ether having an etherification degree in the range of 1.8 to 4.0 functions as a crosslinking agent more effectively while maintaining good water solubility.
本発明に係る水溶性架橋剤によれば、化粧料、トイレタリー等の分野で好適に用いることのできる親水性の架橋重合物を、逆相懸濁重合及び水溶液重合等の水系の重合条件で製造することができる。本発明に係る水溶性架橋剤によれば、水系の重合条件で優れた増粘性を有する親水性の架橋重合体を得ることができる。 According to the water-soluble cross-linking agent according to the present invention, a hydrophilic cross-linked polymer that can be suitably used in the fields of cosmetics, toiletries and the like is produced under aqueous polymerization conditions such as reverse phase suspension polymerization and aqueous solution polymerization. can do. According to the water-soluble crosslinking agent according to the present invention, a hydrophilic crosslinked polymer having an excellent viscosity can be obtained under aqueous polymerization conditions.
化粧品、トイレタリー等の分野においては、使用実績のない材料の使用は回避される傾向があるが、ショ糖アリルエーテルであれば、化粧品、トイレタリー等の分野において十分な使用実績があることから、これらの分野でも実用化が容易である。 In the fields of cosmetics, toiletries, etc., there is a tendency to avoid the use of materials that have not been used, but sucrose allyl ether has been used sufficiently in the fields of cosmetics, toiletries, etc. It is easy to put it into practical use in this field.
以下、本発明の好適な実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
従来、親水性の架橋重合体を製造するための架橋剤として用いられている、アリルエーテル基及び水酸基を有するショ糖アリルエーテルは、主原料のショ糖（グラニュー糖）の水酸基を、臭化アリルとの反応により高度にエーテル化して得られる油溶性のものである。油溶性ショ糖アリルエーテルは、化粧料、トイレタリー等の分野において長年の使用実績があり、安全面での信頼性が高い。また、エーテル化度が高いことにより、油溶性ショ糖アリルエーテルは、有機溶媒への良好な溶解性を有するとともに、高い反応性も有する。油溶性ショ糖アリルエーテルは、一般に、５．０〜８．０の高いエーテル化度にまで高度に置換されている。油溶性ショ糖アリルエーテルは、水に実質的に不溶であり、ペンタエリスリトールトリアリルエーテル等と同様に、有機溶媒を使用した沈殿重合法による架橋重合体の製造に広く使用されている。 Conventionally, sucrose allyl ether having an allyl ether group and a hydroxyl group, which is used as a crosslinking agent for producing a hydrophilic cross-linked polymer, has a hydroxyl group of sucrose (granulated sugar) as a main raw material. It is oil-soluble and obtained by highly etherifying by the reaction. Oil-soluble sucrose allyl ether has a long track record of use in cosmetics, toiletries, and other fields, and is highly reliable in terms of safety. In addition, due to the high degree of etherification, oil-soluble sucrose allyl ether has good solubility in organic solvents and high reactivity. Oil-soluble sucrose allyl ethers are generally highly substituted to a high degree of etherification of 5.0 to 8.0. Oil-soluble sucrose allyl ether is substantially insoluble in water and is widely used in the production of a crosslinked polymer by precipitation polymerization using an organic solvent, like pentaerythritol triallyl ether.
これに対して、本実施形態に係るショ糖アリルエーテルは、エーテル化度を低く抑えることにより残存する水酸基の割合を多くして、水溶性が付与されたものである。本実施形態に係る水溶性ショ糖アリルエーテルの水溶液は、少なくとも、水溶液の質量を基準として１０質量％以下の濃度の範囲で、油分の分離のない単一相を維持することができる。このような良好な水溶性を有するショ糖アリルエーテルによれば、逆相懸濁重合及び水溶液重合等の水系の重合条件で親水性の架橋重合体を容易に製造することが可能である。 On the other hand, the sucrose allyl ether according to this embodiment is provided with water solubility by increasing the ratio of the remaining hydroxyl groups by keeping the degree of etherification low. The aqueous solution of the water-soluble sucrose allyl ether according to the present embodiment can maintain a single phase without oil separation in at least a concentration range of 10% by mass or less based on the mass of the aqueous solution. According to such sucrose allyl ether having good water solubility, it is possible to easily produce a hydrophilic crosslinked polymer under aqueous polymerization conditions such as reverse phase suspension polymerization and aqueous solution polymerization.
本実施形態に係る水溶性ショ糖アリルエーテルのエーテル化度は、１．８〜４．０程度の低置換度であることが好ましい。このエーテル化度は、水溶性ショ糖アリルエーテルに対する、当該水溶性ショ糖アリルエーテルが有するアリルエーテル基のモル比の平均値に相当する。エーテル化度（平均エーテル化度）は、例えば、ショ糖アリルエーテル中に残存する水酸基を、ピリジン中で無水酢酸と反応させ、このとき消費される無水酢酸の量から算出することができる。ショ糖アリルエーテルのエーテル化度は、その化学構造から最大で８．０である。 The degree of etherification of the water-soluble sucrose allyl ether according to this embodiment is preferably a low substitution degree of about 1.8 to 4.0. This degree of etherification corresponds to the average value of the molar ratio of the allyl ether group of the water-soluble sucrose allyl ether to the water-soluble sucrose allyl ether. The degree of etherification (average degree of etherification) can be calculated, for example, from the amount of acetic anhydride consumed by reacting the hydroxyl group remaining in sucrose allyl ether with acetic anhydride in pyridine. Due to its chemical structure, the maximum degree of etherification of sucrose allyl ether is 8.0.
水溶性ショ糖アリルエーテルのエーテル化度が低いと、架橋反応に関わる官能基であるアリル基が不足して、架橋反応が効果的に進行し難くなる傾向がある。水溶性ショ糖アリルエーテルのエーテル化度が高いと、水に対する溶解性が低下するため、水相中においてショ糖アリルエーテルと水溶性エチレン性不飽和単量体との架橋反応が進行し難くなる傾向がある。係る観点から、水溶性ショ糖アリルエーテルのエーテル化度は、より好ましくは２．０〜３．５、更に好ましくは２．２〜３．２である。 If the degree of etherification of the water-soluble sucrose allyl ether is low, the allyl group, which is a functional group involved in the cross-linking reaction, is insufficient, and the cross-linking reaction tends not to proceed effectively. If the degree of etherification of the water-soluble sucrose allyl ether is high, the solubility in water decreases, so that the cross-linking reaction between the sucrose allyl ether and the water-soluble ethylenically unsaturated monomer is difficult to proceed in the aqueous phase. Tend. From such a viewpoint, the degree of etherification of the water-soluble sucrose allyl ether is more preferably 2.0 to 3.5, and still more preferably 2.2 to 3.2.
水溶性ショ糖アリルエーテルは、例えば、ショ糖水溶液に触媒の水酸化ナトリウムを加え、ショ糖をアルカリショ糖に転化した後、臭化アリルを滴下してエーテル化を行う方法により得ることができる。このとき、臭化アリルの量を、ショ糖に対して２〜６倍モルの、好ましくは２〜５倍モルの範囲に調整することにより、効率的に水溶性ショ糖アリルエーテルを得ることができる。エーテル化の反応温度は、例えば８０℃程度である。通常、臭化アリルの滴下後３時間程度で反応が完結する。反応液から分離した水相にアルコールを添加し、析出する塩類を濾別した後、余分なアルコールと水分を留去させることにより、水溶性ショ糖アリルエーテルを回収することができる。 The water-soluble sucrose allyl ether can be obtained, for example, by a method in which sodium hydroxide as a catalyst is added to an aqueous sucrose solution to convert sucrose to alkaline sucrose and then etherified by dropwise addition of allyl bromide. . At this time, by adjusting the amount of allyl bromide in the range of 2 to 6 times mol, preferably 2 to 5 times mol of sucrose, water-soluble sucrose allyl ether can be obtained efficiently. it can. The etherification reaction temperature is, for example, about 80 ° C. Usually, the reaction is completed in about 3 hours after the addition of allyl bromide. Water-soluble sucrose allyl ether can be recovered by adding alcohol to the aqueous phase separated from the reaction solution, filtering out precipitated salts, and distilling off excess alcohol and water.
なお、油溶性のショ糖アリルエーテルは、通常、ショ糖に対して約１２〜１６倍モルの大過剰量の臭化アリルを用いて、できるだけ多くの水酸基がアリルエーテル化されるような条件で合成される。ショ糖１モル中が有する、臭化アリルと反応する水酸基は８当量である。すなわち、油溶性のショ糖アリルエーテルを合成する場合は、水酸基に対して１．５倍〜２倍モルの臭化アリルが使用される。 In addition, oil-soluble sucrose allyl ether is usually used under the condition that as many hydroxyl groups as possible are allyl-etherified using a large excess of allyl bromide of about 12 to 16 times mole relative to sucrose. Synthesized. One mole of sucrose has 8 equivalents of hydroxyl groups that react with allyl bromide. That is, when synthesizing oil-soluble sucrose allyl ether, 1.5 to 2 moles of allyl bromide are used with respect to the hydroxyl group.
有機溶媒を用いた沈殿重合法による従来の方法で親水性の架橋重合体を合成する場合、重合の進行に伴い高分子化したポリマーの析出が起こり、一旦、析出したポリマーに関しては、それ以上の重合反応は実質的に進行しないものと考えられている。そのため、架橋剤として用いるショ糖アリルエーテルの親油性を、エーテル化度をできるだけ高くすることにより高めて、ポリマーの有機溶媒に対する溶解性を保つとともに、より効果的に架橋反応を進行させる必要があった。すなわち、架橋剤として用いられるショ糖アリルエーテルのエーテル化度を低くするという発想は、これまでなかった。 When a hydrophilic cross-linked polymer is synthesized by a conventional method using a precipitation polymerization method using an organic solvent, a polymerized polymer is precipitated as the polymerization proceeds. It is believed that the polymerization reaction does not proceed substantially. Therefore, it is necessary to increase the lipophilicity of sucrose allyl ether used as a crosslinking agent by increasing the degree of etherification as much as possible to maintain the solubility of the polymer in an organic solvent, and to promote the crosslinking reaction more effectively. It was. That is, there has never been an idea to reduce the degree of etherification of sucrose allyl ether used as a crosslinking agent.
一方、水溶性架橋剤を用いる逆相懸濁重合及び水溶液重合等の水系の重合条件の場合、重合反応中に高分子化したポリマーの析出が起こることもなく、反応終了まで均一な状態が保たれる。このため、従来の油溶性ショ糖アリルエーテルに比べて架橋点の少ない、即ち、エーテル化度の低い水溶性ショ糖アリルエーテルであっても、効果的に架橋反応が進行して、十分に架橋された架橋重合体を製造することができると考えられる。 On the other hand, in the case of aqueous polymerization conditions such as reverse phase suspension polymerization and aqueous solution polymerization using a water-soluble crosslinking agent, the polymerized polymer does not precipitate during the polymerization reaction, and a uniform state is maintained until the end of the reaction. Be drunk. For this reason, even if it is a water-soluble sucrose allyl ether having fewer cross-linking points than the conventional oil-soluble sucrose allyl ether, that is, a low degree of etherification, the cross-linking reaction proceeds effectively and sufficient crosslinking is achieved. It is considered that a crosslinked polymer can be produced.
ペンタエリスリトールのアリルエーテルのエーテル化度は、その化学構造から最大４までになり得る。エーテル化度３のペンタエリスリトールトリアリルーテル、及びエーテル化度４のペンタエリスリトールテトラアリルエーテルが、油溶性ショ糖アリルエーテルと同様に、有機溶媒を用いる沈殿重合法等の架橋剤として使用されている。このペンタエリスリトールのアリルエーテルは、そのエーテル化度が２であっても油溶性である。そのため、ペンタエリスリトールのアリルエーテルを逆相懸濁重合及び水溶液重合等の水系の重合条件下で架橋剤として用いても、架橋反応を十分に進行させることは極めて困難である。 The degree of etherification of allyl ether of pentaerythritol can be up to 4 due to its chemical structure. Pentaerythritol triallyl ether having a degree of etherification of 3 and pentaerythritol tetraallyl ether having a degree of etherification of 4 are used as crosslinking agents for precipitation polymerization using an organic solvent, like oil-soluble sucrose allyl ether. . This allyl ether of pentaerythritol is oil-soluble even if its degree of etherification is 2. Therefore, it is extremely difficult to sufficiently advance the crosslinking reaction even when allyl ether of pentaerythritol is used as a crosslinking agent under aqueous polymerization conditions such as reverse phase suspension polymerization and aqueous solution polymerization.
本実施形態に係る水溶性架橋剤は、水溶性ショ糖アリルエーテルから構成される。この水溶性架橋剤は、水溶性エチレン性不飽和単量体の重合体の架橋剤として好適に用いられる。例えば、水溶性エチレン性不飽和単量体を、水溶性架橋剤の存在下で、逆相懸濁重合又は水溶液重合により重合させる工程を含む方法により架橋重合体を製造するために用いられる。逆相懸濁重合では、水溶性エチレン性不飽和単量体、水溶性架橋剤及び水を含む水相の液滴を疎水性溶媒中に分散させながら重合反応が行われる。 The water-soluble crosslinking agent according to this embodiment is composed of water-soluble sucrose allyl ether. This water-soluble crosslinking agent is suitably used as a crosslinking agent for a polymer of a water-soluble ethylenically unsaturated monomer. For example, it is used for producing a crosslinked polymer by a method comprising a step of polymerizing a water-soluble ethylenically unsaturated monomer by reverse phase suspension polymerization or aqueous solution polymerization in the presence of a water-soluble crosslinking agent. In reverse phase suspension polymerization, a polymerization reaction is carried out while dispersing aqueous phase droplets containing a water-soluble ethylenically unsaturated monomer, a water-soluble crosslinking agent and water in a hydrophobic solvent.
上記水溶性エチレン性不飽和単量体は、特に限定されるものではないが、好ましくは、アクリル酸及びその塩、メタクリル酸及びその塩、２−アクリルアミド−２メチルプロパンスルホン酸及びその塩、アクリルアミド、メタクリルアミド、並びに、Ｎ，Ｎ−ジメチルアクリルアミドからなる群より選ばれる少なくとも一種の化合物である。これらの中でも、水溶性エチレン性不飽和単量体は、十分な増粘性を得やすいこと等の観点から、カルボキシル基を有する単量体、すなわち、アクリル酸及びその塩、並びに、メタクリル酸及びその塩から選ばれる化合物を含むことが好ましい。カルボキシル基を有する単量体を用いることにより、カルボキシル基を有する親水性の架橋重合体を容易に得ることができる。 The water-soluble ethylenically unsaturated monomer is not particularly limited, but preferably acrylic acid and its salt, methacrylic acid and its salt, 2-acrylamido-2methylpropanesulfonic acid and its salt, acrylamide , Methacrylamide, and at least one compound selected from the group consisting of N, N-dimethylacrylamide. Among these, a water-soluble ethylenically unsaturated monomer is a monomer having a carboxyl group, that is, acrylic acid and its salt, and methacrylic acid and its It is preferable to include a compound selected from salts. By using a monomer having a carboxyl group, a hydrophilic crosslinked polymer having a carboxyl group can be easily obtained.
以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
エーテル化度の測定方法
ショ糖アリルエーテルのエーテル化度は、以下の手順で測定した。
（１）還流冷却管を取り付けた１００ｍＬのフラスコに、ショ糖アリルエーテルを０．６ｇ精秤する。
（２）精秤されたショ糖アリルエーテルを、無水酢酸：ピリジン（１：３容積比）の混合溶媒１０ｍＬに溶解させる。
（３）溶液を９０℃で４５分間加熱し、その後、蒸留水１０ｍＬを添加し、更に溶液を冷却する。
（３）溶液の冷却の後、２０ｍＬのｎ―ブタノールおよび２０ｍＬの蒸留水によりフラスコの内壁を洗浄する。
（４）得られた溶液を２００ｍＬのビーカーに移し、さらに２０ｍＬの蒸留水によりフラスコの内壁を洗浄する。洗浄液は、ビーカーに加える。
（５）１Ｎ−ＮａＯＨ標準溶液を用いた滴定を滴定装置により行い、サンプル滴定量を求める。
（６）ブランク滴定として、ショ糖アリルエーテルが添加されない無水酢酸：ピリジン（１：３容積比）の混合溶液１０ｍＬを同様に処理し、１Ｎ−ＮａＯＨ標準溶液を用いた滴定を滴定装置により行い、ブランク滴定量を求める。
（７）サンプル滴定量およびブランク滴定量の値を用いて、式１にしたがってショ糖アリルエーテルの残存ＯＨ基含量（％）を求める。次いで式２にしたがって、ショ糖中の８個の水酸基のうちアリルエーテル化された基により置換されたものの割合の平均値、即ちエーテル化度ｎを算出する。
ＯＨ基含量（％）＝（Ｂml−Ｓml）×ｆ×Ｎ×１７／（Ｓwt×１０）・・・式１
Ｂml：ブランク滴定量（ｍｌ）
Ｓml：サンプル滴定量（ｍｌ）
Ｓwt：サンプル量（ｇ）
ｆ：ファクター（１Ｎ−ＮａＯＨ標準溶液の濃度補正係数）
Ｎ：１（ＮａＯＨ標準溶液の規定数）
ＯＨ基含量（％）＝１７×（８−ｎ）×１００／（４０×ｎ＋３４２）・・・式２
ｎ：エーテル化度（ショ糖中の水酸基のうちアリルエーテル基の置換度）
Method of measuring degree of etherification The degree of etherification of sucrose allyl ether was measured by the following procedure.
(1) Into a 100 mL flask equipped with a reflux condenser, 0.6 g of sucrose allyl ether is precisely weighed.
(2) The weighed sucrose allyl ether is dissolved in 10 mL of a mixed solvent of acetic anhydride: pyridine (1: 3 volume ratio).
(3) Heat the solution at 90 ° C. for 45 minutes, then add 10 mL of distilled water and further cool the solution.
(3) After cooling the solution, wash the inner wall of the flask with 20 mL of n-butanol and 20 mL of distilled water.
(4) Transfer the obtained solution to a 200 mL beaker, and further wash the inner wall of the flask with 20 mL of distilled water. The cleaning solution is added to the beaker.
(5) Titration using a 1N-NaOH standard solution is performed with a titration apparatus, and a sample titer is determined.
(6) As blank titration, 10 mL of a mixed solution of acetic anhydride: pyridine (1: 3 volume ratio) to which sucrose allyl ether is not added is treated in the same manner, and titration using a 1N-NaOH standard solution is performed with a titration apparatus. Determine the blank titer.
(7) The residual OH group content (%) of sucrose allyl ether is determined according to Equation 1 using the sample titration value and the blank titration value. Next, an average value of the ratio of the eight hydroxyl groups in sucrose substituted with allyl etherified groups, that is, the degree of etherification n is calculated according to Formula 2.
OH group content (%) = (B ml −S ml ) × f × N × 17 / (S wt × 10) Formula 1
B ml : Blank titration (ml)
S ml : Sample titration (ml)
S wt : Sample amount (g)
f: Factor (concentration correction coefficient of 1N-NaOH standard solution)
N: 1 (specified number of NaOH standard solution)
OH group content (%) = 17 × (8−n) × 100 / (40 × n + 342) Equation 2
n: Degree of etherification (degree of substitution of allyl ether group among hydroxyl groups in sucrose)
粘度の測定方法
架橋重合体をそれぞれ水に溶解して、０．５質量％濃度の水溶液を調製する。この水溶液の粘度を、粘度計（芝浦システム株式会社製、ビスメトロンＶＳ−１Ｈ）を用いて、温度２５℃、ローターＮＯ．６（２０回転／分）の条件下で測定し、１分後の粘度の値を測定値として読み取った。
Method for Measuring Viscosity Each of the crosslinked polymers is dissolved in water to prepare an aqueous solution having a concentration of 0.5% by mass. The viscosity of this aqueous solution was measured using a viscometer (Bushimetron VS-1H, manufactured by Shibaura System Co., Ltd.) at a temperature of 25 ° C., rotor NO. It was measured under the condition of 6 (20 revolutions / minute), and the value of the viscosity after 1 minute was read as a measured value.
実施例１
撹拌機、還流冷却管、滴下ロートを取り付けた１Ｌの四つ口セパラブルフラスコにイオン交換水５０ｇと水酸化ナトリウム２４ｇ（０．６モル）を加え、水酸化ナトリウムをイオン交換水に溶解させた。さらにショ糖６８．４ｇ（０．２モル）を添加して、８０℃で９０分間、撹拌しながら反応させてアルカリショ糖水溶液を得た。このアルカリショ糖水溶液に対して、エーテル化反応に伴う急激な発熱を制御しながら、臭化アリル７３ｇ（０．６モル）を２時間かけて滴下した。その後、反応液を８０℃で３時間熟成してエーテル化反応を完結させた。冷却後、セパラブルフラスコから取り出した反応液にイオン交換水４００ｇを添加して不要な油分を分離し、水溶性の粗ショ糖アリルエーテル水溶液６６０ｇを得た。さらに塩酸を加えてｐＨを７に調整した後、ロータリーエバポレーターを用いてこの水溶液を約２００ｇまで濃縮した。複生成物の臭化ナトリウム等の塩類は、エタノール２００ｇを添加し、析出させてから濾別することで水溶液から除いた。次いでロータリーエバポレーターを用いて余分な水分およびエタノールを留去させることで、精製された水溶性ショ糖アリルエーテル８２ｇを取得した。この水溶性ショ糖アリルエーテルのエーテル化度は、２．４であった。
Example 1
Ion-exchanged water 50 g and sodium hydroxide 24 g (0.6 mol) were added to a 1 L four-necked separable flask equipped with a stirrer, reflux condenser, and dropping funnel to dissolve sodium hydroxide in ion-exchanged water. . Further, 68.4 g (0.2 mol) of sucrose was added and reacted with stirring at 80 ° C. for 90 minutes to obtain an aqueous alkaline sucrose solution. To this alkaline sucrose aqueous solution, 73 g (0.6 mol) of allyl bromide was added dropwise over 2 hours while controlling a rapid exotherm accompanying the etherification reaction. Thereafter, the reaction solution was aged at 80 ° C. for 3 hours to complete the etherification reaction. After cooling, 400 g of ion-exchanged water was added to the reaction solution taken out from the separable flask to separate unnecessary oil, thereby obtaining 660 g of a water-soluble crude sucrose allyl ether aqueous solution. Further, hydrochloric acid was added to adjust the pH to 7, and then the aqueous solution was concentrated to about 200 g using a rotary evaporator. Salts such as sodium bromide as a double product were removed from the aqueous solution by adding 200 g of ethanol and precipitating the solution. Next, 82 g of purified water-soluble sucrose allyl ether was obtained by distilling off excess water and ethanol using a rotary evaporator. The degree of etherification of this water-soluble sucrose allyl ether was 2.4.
実施例２
撹拌機、還流冷却管、滴下ロートを取り付けた１Ｌの四つ口セパラブルフラスコにイオン交換水７２ｇと水酸化ナトリウム３２ｇ（０．８モル）を加え、水酸化ナトリウムをイオン交換水に溶解させた。さらにショ糖６８．４ｇ（０．２モル）を添加して、８０℃で９０分間、撹拌しながら反応させてアルカリショ糖水溶液を得た。このアルカリショ糖水溶液に対して、エーテル化反応に伴う急激な発熱を制御しながら、臭化アリル９７ｇ（０．８モル）を２時間かけて滴下した。その後、反応液を８０℃で３時間熟成してエーテル化反応を完結させた。冷却後、セパラブルフラスコから取り出した反応液にイオン交換水４００ｇを添加して不要な油分を分離し、水溶性の粗ショ糖アリルエーテル水溶液６８５ｇを得た。さらに塩酸を加えてｐＨを７に調整した後、ロータリーエバポレーターを用いてこの水溶液を約２２５ｇまで濃縮した。副生成物の臭化ナトリウム等の塩類は、エタノール２００ｇを添加し、析出させてから濾別することで水溶液から除いた。次いでロータリーエバポレーターを用いて余分な水分およびエタノールを留去させることで、精製された水溶性ショ糖アリルエーテル８５ｇを取得した。この水溶性ショ糖アリルエーテルのエーテル化度は、２．６であった。
Example 2
72 g of ion-exchanged water and 32 g (0.8 mol) of sodium hydroxide were added to a 1 L four-necked separable flask equipped with a stirrer, a reflux condenser, and a dropping funnel, and sodium hydroxide was dissolved in the ion-exchanged water. . Further, 68.4 g (0.2 mol) of sucrose was added and reacted with stirring at 80 ° C. for 90 minutes to obtain an aqueous alkaline sucrose solution. To this alkaline sucrose aqueous solution, 97 g (0.8 mol) of allyl bromide was added dropwise over 2 hours while controlling the rapid exotherm accompanying the etherification reaction. Thereafter, the reaction solution was aged at 80 ° C. for 3 hours to complete the etherification reaction. After cooling, 400 g of ion-exchanged water was added to the reaction solution taken out from the separable flask to separate unnecessary oil, thereby obtaining 685 g of a water-soluble crude sucrose allyl ether aqueous solution. Further, hydrochloric acid was added to adjust the pH to 7, and then the aqueous solution was concentrated to about 225 g using a rotary evaporator. By-products such as sodium bromide were removed from the aqueous solution by adding 200 g of ethanol and precipitating the solution. Subsequently, 85 g of purified water-soluble sucrose allyl ether was obtained by distilling off excess water and ethanol using a rotary evaporator. The degree of etherification of this water-soluble sucrose allyl ether was 2.6.
実施例３
撹拌機、還流冷却管、滴下ロートを取り付けた１Ｌの四つ口セパラブルフラスコにイオン交換水８６ｇと水酸化ナトリウム４０ｇ（１．０モル）を加え、水酸化ナトリウムをイオン交換水に溶解させた。さらにショ糖６８．４ｇ（０．２モル）を添加して、８０℃で９０分間、撹拌しながら反応させてアルカリショ糖水溶液を得た。このアルカリショ糖水溶液に対して、エーテル化反応に伴う急激な発熱を制御しながら、臭化アリル１２１ｇ（１．０モル）を２時間かけて滴下した。その後、反応液を８０℃で３時間熟成してエーテル化反応を完結させた。冷却後、セパラブルフラスコから取り出した反応液にイオン交換水４００ｇを添加して不要な油分を分離し、水溶性の粗ショ糖アリルエーテル水溶液７００ｇを得た。さらに塩酸を加えてｐＨを７に調整した後、ロータリーエバポレーターを用いてこの水溶液を約２４０ｇまで濃縮した。副生成物の臭化ナトリウム等の塩類は、エタノール２００ｇを添加し、析出させてから濾別することで水溶液から除いた。次いでロータリーエバポレーターを用いて余分な水分およびエタノールを留去させることで、精製された水溶性ショ糖アリルエーテル８８ｇを取得した。この水溶性ショ糖アリルエーテルのエーテル化度は、２．８であった。
Example 3
86 g of ion exchange water and 40 g of sodium hydroxide (1.0 mol) were added to a 1 L four-necked separable flask equipped with a stirrer, a reflux condenser, and a dropping funnel, and sodium hydroxide was dissolved in the ion exchange water. . Further, 68.4 g (0.2 mol) of sucrose was added and reacted with stirring at 80 ° C. for 90 minutes to obtain an aqueous alkaline sucrose solution. To this alkaline sucrose aqueous solution, 121 g (1.0 mol) of allyl bromide was added dropwise over 2 hours while controlling a rapid exotherm accompanying the etherification reaction. Thereafter, the reaction solution was aged at 80 ° C. for 3 hours to complete the etherification reaction. After cooling, 400 g of ion-exchanged water was added to the reaction solution taken out from the separable flask to separate unnecessary oil, and 700 g of a water-soluble crude sucrose allyl ether aqueous solution was obtained. Further, hydrochloric acid was added to adjust the pH to 7, and then the aqueous solution was concentrated to about 240 g using a rotary evaporator. By-products such as sodium bromide were removed from the aqueous solution by adding 200 g of ethanol and precipitating the solution. Subsequently, 88 g of purified water-soluble sucrose allyl ether was obtained by distilling off excess water and ethanol using a rotary evaporator. The degree of etherification of this water-soluble sucrose allyl ether was 2.8.
比較例１
撹拌機、還流冷却管、滴下ロートを取り付けた１Ｌの四つ口セパラブルフラスコにイオン交換水１２０ｇと水酸化ナトリウム１２０ｇ（３．０モル）を加え、水酸化ナトリウムをイオン交換水に溶解させた。さらにショ糖６８．４ｇ（０．２モル）を添加して、８０℃で９０分間、撹拌しながら反応させてアルカリショ糖水溶液を得た。このアルカリショ糖水溶液に対して、エーテル化反応に伴う急激な発熱を制御しながら、臭化アリル３６３ｇ（３．０モル）を２時間かけて滴下した。その後、反応液を８０℃で３時間熟成してエーテル化反応を完結させた。冷却後、セパラブルフラスコから取り出した反応液にイオン交換水４００ｇを添加して不要な水溶性成分を油分から分離し、油溶性の粗ショ糖アリルエーテルを得た。次いでイオン交換水２５０ｇを加えて、ロータリーエバポレーターで加えた水と共に余分な揮発成分を留去させた。さらにｎ−ヘキサン１２０ｇとイオン交換水６０ｇを添加し、再度、水溶性の不純物を分液により取り除いた。分液した油相からｎ−ヘキサンをロータリーエバポレーターを用いて留去し、精製された油溶性ショ糖アリルエーテル１１２ｇを取得した。この油溶性ショ糖アリルエーテルのエーテル化度は、６．５であった。
Comparative Example 1
120 g of ion exchange water and 120 g of sodium hydroxide (3.0 mol) were added to a 1 L four-necked separable flask equipped with a stirrer, a reflux condenser, and a dropping funnel, and sodium hydroxide was dissolved in the ion exchange water. . Further, 68.4 g (0.2 mol) of sucrose was added and reacted with stirring at 80 ° C. for 90 minutes to obtain an aqueous alkaline sucrose solution. To this alkaline sucrose aqueous solution, 363 g (3.0 mol) of allyl bromide was added dropwise over 2 hours while controlling rapid heat generation accompanying the etherification reaction. Thereafter, the reaction solution was aged at 80 ° C. for 3 hours to complete the etherification reaction. After cooling, 400 g of ion-exchanged water was added to the reaction solution taken out from the separable flask to separate unnecessary water-soluble components from the oil, and oil-soluble crude sucrose allyl ether was obtained. Next, 250 g of ion-exchanged water was added, and excess volatile components were distilled off together with the water added by the rotary evaporator. Further, 120 g of n-hexane and 60 g of ion-exchanged water were added, and water-soluble impurities were again removed by liquid separation. N-Hexane was distilled off from the separated oil phase using a rotary evaporator to obtain 112 g of purified oil-soluble sucrose allyl ether. The degree of etherification of this oil-soluble sucrose allyl ether was 6.5.
実施例および比較例で調製したショ糖アリルエーテルを用いてカルボキシビニルポリマーを製造した結果を以下に示す。 The result of producing a carboxyvinyl polymer using the sucrose allyl ether prepared in Examples and Comparative Examples is shown below.
合成例１
５００ｍＬ三角フラスコに８０質量％のアクリル酸水溶液９０ｇを加え、外部よりフラスコを冷却しながら３０質量％の水酸化ナトリウム９４ｇを滴下して水溶液を中和した。さらにイオン交換水５６ｇ、架橋剤として実施例１で得られた低置換度の水溶性ショ糖アリルエーテル０．０９ｇ（アクリル酸水溶液に対して０．１質量％）、アゾ系開始剤である２，２’−アゾビス（２−メチルプロピオンアミジン）２塩酸塩（和光純薬工業株式会社製 Ｖ−５０）０．０６４ｇを加えて水溶性エチレン性不飽和単量体水溶液を調製した。これとは別に、撹拌機、還流冷却管、滴下ロート、窒素ガス導入管を取り付けた２Ｌの四つ口セパラブルフラスコにｎ−ヘプタン３３０ｇを加え、さらに界面活性剤としてソルビタンモノステアレート（日油株式会社製 ＳＰ−６０Ｒ）２．７ｇを分散及び溶解させた。そこに、先に調製した水溶性エチレン性不飽和単量体水溶液を加え、撹拌速度１０００回転／分で攪拌しながら、系内を窒素置換すると共に浴温を６０℃に保持して、１時間、重合を行った。重合終了後、水およびｎ−ヘプタンを留去して架橋重合物の粉体１０３ｇを得た。得られた架橋重合物の０．５質量％水溶液を調製したところ、曳糸性は認められなかった。この水溶液の粘度は１８５００ｍＰａ・ｓであった。
Synthesis example 1
To a 500 mL Erlenmeyer flask, 90 g of an 80% by mass acrylic acid aqueous solution was added, and 94 g of 30% by mass sodium hydroxide was added dropwise while cooling the flask from the outside to neutralize the aqueous solution. Furthermore, 56 g of ion-exchanged water, 0.09 g of water-soluble sucrose allyl ether having a low substitution degree obtained in Example 1 as a crosslinking agent (0.1% by mass with respect to an aqueous acrylic acid solution), 2 which is an azo-based initiator , 2'-azobis (2-methylpropionamidine) dihydrochloride (V-50 manufactured by Wako Pure Chemical Industries, Ltd.) (0.064 g) was added to prepare a water-soluble ethylenically unsaturated monomer aqueous solution. Separately, 330 g of n-heptane was added to a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube, and sorbitan monostearate (NOF) as a surfactant. 2.7 g of SP-60R manufactured by Co., Ltd. was dispersed and dissolved. The water-soluble ethylenically unsaturated monomer aqueous solution prepared previously was added thereto, and the system was purged with nitrogen while stirring at a stirring speed of 1000 revolutions / minute, and the bath temperature was maintained at 60 ° C. for 1 hour. Polymerization was performed. After completion of the polymerization, water and n-heptane were distilled off to obtain 103 g of a crosslinked polymer powder. When a 0.5 mass% aqueous solution of the obtained cross-linked polymer was prepared, no spinnability was observed. The viscosity of this aqueous solution was 18500 mPa · s.
合成例２
実施例１で得られた低置換度の水溶性ショ糖アリルエーテルの添加量を０．３５ｇ（アクリル酸水溶液に対して０．４質量％）に変更したこと以外は合成例１と同様の操作により、架橋重合物の粉体１０２ｇを得た。得られた架橋重合物０．５質量％水溶液を調製したところ、曳糸性は認められなかった。この水溶液の粘度は３００００ｍＰａ・ｓであった。
Synthesis example 2
Operation similar to Synthesis example 1 except having changed the addition amount of the water-soluble sucrose allyl ether of the low substitution degree obtained in Example 1 into 0.35g (0.4 mass% with respect to acrylic acid aqueous solution). As a result, 102 g of a powder of a crosslinked polymer was obtained. When a 0.5% by mass aqueous solution of the obtained cross-linked polymer was prepared, no spinnability was observed. The viscosity of this aqueous solution was 30000 mPa · s.
合成例３
実施例１で得られた低置換度の水溶性ショ糖アリルエーテルの添加量を０．７ｇ（アクリル酸水溶液に対して０．８質量％）に変更したこと以外は合成例１と同様の操作により、架橋重合物の粉体１００ｇを得た。得られた架橋重合物の０．５質量％水溶液を調製したところ、曳糸性は認められなかった。この水溶液の粘度は４２０００ｍＰａ・ｓであった。
Synthesis example 3
The same operation as in Synthesis Example 1 except that the amount of the low-substituted water-soluble sucrose allyl ether obtained in Example 1 was changed to 0.7 g (0.8% by mass with respect to the aqueous acrylic acid solution). As a result, 100 g of a crosslinked polymer powder was obtained. When a 0.5 mass% aqueous solution of the obtained cross-linked polymer was prepared, no spinnability was observed. The viscosity of this aqueous solution was 42000 mPa · s.
合成例４
架橋剤を実施例３で得られた低置換度の水溶性ショ糖アリルエーテル０．３５ｇ（アクリル酸水溶液に対して０．４質量％）に変更したこと以外は合成例１と同様の操作により、架橋重合物の粉体１００ｇを得た。得られた架橋重合物の０．５質量％水溶液を調製したところ、曳糸性は認められなかった。この水溶液の粘度は３２０００ｍＰａ・ｓであった。
Synthesis example 4
By the same operation as in Synthesis Example 1 except that the crosslinking agent was changed to 0.35 g of water-soluble sucrose allyl ether having a low substitution degree obtained in Example 3 (0.4% by mass with respect to the aqueous acrylic acid solution). 100 g of a crosslinked polymer powder was obtained. When a 0.5 mass% aqueous solution of the obtained cross-linked polymer was prepared, no spinnability was observed. The viscosity of this aqueous solution was 32000 mPa · s.
比較合成例１
５００ｍＬ三角フラスコに８０質量％のアクリル酸９０ｇを加え、外部よりフラスコを冷却しながら３０質量％の水酸化ナトリウム水溶液９４ｇを滴下して水溶液を中和した。さらにイオン交換水５６ｇ、および２，２’−アゾビス(２−メチルプロピオンアミジン)２塩酸塩（和光純薬工業株式会社製 Ｖ−５０）０．０６４ｇを加えて水溶性エチレン性不飽和単量体水溶液を調製した。これとは別に、撹拌機、還流冷却管、滴下ロート、窒素ガス導入管を取り付けた２Ｌの四つ口セパラブルフラスコにｎ−ヘプタン３３０ｇと、架橋剤として比較例１で合成した油溶性のショ糖アリルエーテル０．３５ｇ（アクリル酸水溶液に対して０．４質量％）を加え、さらに界面活性剤としてソルビタンモノステアレート（日油株式会社製 ＳＰ−６０Ｒ）２．７ｇを分散及び溶解させた。そこに、先に調製した水溶性エチレン性不飽和単量体水溶液を加え、撹拌速度１０００回転／分で攪拌しながら、系内を窒素置換すると共に浴温を６０度に保持して、１時間重合を行った。重合終了後、水およびｎ−ヘプタンを留去して、架橋重合体の粉体１０２ｇを得た。得られた架橋重合体の０．５質量％水溶液を調製したところ、曳糸性のある粘稠液となった。架橋反応が充分に進行しなかったためであると考えられる。この水溶液の粘度は４１００ｍＰａ・ｓであった。
Comparative Synthesis Example 1
90 g of 80% by mass acrylic acid was added to a 500 mL Erlenmeyer flask, and 94 g of 30% by mass sodium hydroxide aqueous solution was added dropwise while cooling the flask from the outside to neutralize the aqueous solution. Further, 56 g of ion-exchanged water and 0.064 g of 2,2′-azobis (2-methylpropionamidine) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto to add a water-soluble ethylenically unsaturated monomer. An aqueous solution was prepared. Separately, 330 g of n-heptane was added to a 2 L four-necked separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction pipe, and the oil-soluble starch synthesized in Comparative Example 1 as a crosslinking agent. 0.35 g of sugar allyl ether (0.4% by mass with respect to the aqueous acrylic acid solution) was added, and 2.7 g of sorbitan monostearate (SP-60R manufactured by NOF Corporation) was dispersed and dissolved as a surfactant. . The water-soluble ethylenically unsaturated monomer aqueous solution prepared previously was added thereto, and the system was purged with nitrogen while stirring at a stirring speed of 1000 revolutions / minute, and the bath temperature was maintained at 60 ° C. for 1 hour. Polymerization was performed. After completion of the polymerization, water and n-heptane were distilled off to obtain 102 g of a crosslinked polymer powder. When a 0.5 mass% aqueous solution of the obtained cross-linked polymer was prepared, a viscous liquid having a spinnability was obtained. This is probably because the crosslinking reaction did not proceed sufficiently. The viscosity of this aqueous solution was 4100 mPa · s.
以上の実験結果に示されるように、水溶性の低置換度のショ糖アリルエーテルを用いて、水系の逆相懸濁重合により十分に架橋されたカルボキシルビニルポリマーの架橋重合体を合成できることが確認された。更に、得られた架橋重合体は、少量の添加で水溶液を増粘させる優れた増粘性を示し、本発明の水溶性ショ糖アリルエーテルが水溶性架橋剤として効果的に反応することが確認された。 As shown in the above experimental results, it was confirmed that a cross-linked polymer of carboxyl vinyl polymer that was sufficiently cross-linked by aqueous reverse phase suspension polymerization could be synthesized using water-soluble low-substituted sucrose allyl ether It was done. Further, the obtained cross-linked polymer showed excellent thickening that thickens the aqueous solution with a small amount of addition, and it was confirmed that the water-soluble sucrose allyl ether of the present invention reacts effectively as a water-soluble cross-linking agent. It was.
一方、比較例１により調製された油溶性の高置換度のショ糖アリルエーテルの場合、逆相懸濁重合の条件では、十分な架橋が進行しなかった。その結果、得られた重合体を水に添加したときの増粘効果が少なく、得られる水溶液は曳糸性のある粘稠液となった。 On the other hand, in the case of the oil-soluble highly substituted sucrose allyl ether prepared in Comparative Example 1, sufficient crosslinking did not proceed under the conditions of reverse phase suspension polymerization. As a result, there was little thickening effect when the obtained polymer was added to water, and the resulting aqueous solution became a viscous liquid with spinnability.
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