JPH07119241B2 - Method for producing high degree of polymerization cellulose ether - Google Patents
Method for producing high degree of polymerization cellulose etherInfo
- Publication number
- JPH07119241B2 JPH07119241B2 JP28639989A JP28639989A JPH07119241B2 JP H07119241 B2 JPH07119241 B2 JP H07119241B2 JP 28639989 A JP28639989 A JP 28639989A JP 28639989 A JP28639989 A JP 28639989A JP H07119241 B2 JPH07119241 B2 JP H07119241B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- cellulose ether
- cellulose
- degree
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/38—Polysaccharides or derivatives thereof
- C04B24/383—Cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/193—Mixed ethers, i.e. ethers with two or more different etherifying groups
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、コンクリートおよびセメント質成形体の押出
成形用混和剤として好適な、高重合度セルロースエーテ
ルの製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a highly polymerized cellulose ether, which is suitable as an admixture for extrusion molding of concrete and cementitious moldings.
（従来の技術） 水溶性セルロースエーテルは比較的低い添加量で増粘効
果を発揮するため増粘剤、バインダーなどとして幅広い
分野に利用されている。工業的に生産されているセルロ
ースエーテルの重合度は、その２％水溶液の粘度で表し
て3cpsから100,000cpsと幅広く、使用目的に応じて適切
な添加量と粘度を有するものが選択されている。(Prior Art) Water-soluble cellulose ethers are used in a wide range of fields as thickeners, binders, etc., because they exhibit thickening effects with a relatively low amount added. The degree of polymerization of industrially produced cellulose ethers is wide, ranging from 3 cps to 100,000 cps in terms of the viscosity of its 2% aqueous solution, and one having an appropriate addition amount and viscosity is selected according to the purpose of use.
一方、最近になって検討され実用化されつつある用途と
して、補強繊維としてアスベストを含まないセメント質
成形体の押出成形物と、粘稠性を付与したコンクリート
とを中心とした土木分野がある。On the other hand, as applications that have been recently studied and put into practical use, there are civil engineering fields centering on extruded products of cementitious molded articles that do not contain asbestos as reinforcing fibers and concrete to which viscosity is imparted.
両製品共、混和剤の重合度が高いほど、すなわちその水
溶液粘度が高いほど、少ない添加量で有効なことが確認
されており、より安価でより重合度の高いセルロースエ
ーテルが要求されている。とりわけ、セルロースをハロ
ゲン化アルキルでエーテル化して得られる高重合度のア
ルキルセルロースエーテルが、優れた増粘性を付与する
セメント系の混和剤として好まれている。For both products, it has been confirmed that the higher the degree of polymerization of the admixture, that is, the higher the viscosity of the aqueous solution thereof, the smaller the addition amount of the admixture, and the more inexpensive and higher the degree of polymerization of cellulose ether is required. In particular, an alkyl cellulose ether having a high degree of polymerization obtained by etherifying cellulose with an alkyl halide is preferred as a cement-based admixture that imparts an excellent thickening property.
（発明が解決しようとする課題） ところで、セルロースおよびその誘導体は一般に熱、酸
化、機械的な力、酸、アルカリ、バクテリア等、種々の
要因によって解重合を受け易い物質で、セルロース関連
工業では如何にして目的の重合度まで下げるか、または
如何にして重合度低下を抑制するかが常に技術的に重要
な課題となっている。(Problems to be Solved by the Invention) By the way, cellulose and its derivatives are substances that are easily susceptible to depolymerization due to various factors such as heat, oxidation, mechanical force, acid, alkali, bacteria, etc. It is always a technically important issue how to reduce the polymerization degree to a desired level or how to suppress the decrease in the polymerization degree.
この高重合度セルロースエーテルを製造する手段は次の
２つに集約される。Means for producing this high degree of polymerization cellulose ether are summarized in the following two.
１）高重合度セルロース原料を使用する。1) Use a high degree of polymerization cellulose raw material.
２）重合度低下を抑制する条件でエーテル化を行なう。2) Etherification is carried out under the condition that the decrease in the degree of polymerization is suppressed.
現在、前者のために入手可能なセルロース原料は精製コ
ットンリンターである。これから作られたリンターパル
プの重合度は通常銅アンモニア溶液の粘度（A.C.S法、
2.5％落球式）で表わされ、従来は粘度として3,000から
4,500秒、重合度として2,500〜3,000程度のものであっ
たが、最近のリンター精製技術の進歩により粘度として
10,000〜130,000秒、重合度として5,000程度のものが入
手可能となり、当面はこのレベルが限界に近いといわれ
ている。勿論、実験室的には原料である粗リンターのま
まの重合度を保った精製リンターを得ることも可能であ
るが、工業的には採算が合わず実行不可能である。Currently, the cellulose raw material available for the former is refined cotton linter. The degree of polymerization of linter pulp made from this is usually the viscosity of the copper ammonia solution (ACS method,
2.5% falling ball formula)
It had a polymerization degree of 4,500 seconds and a polymerization degree of 2,500-3,000, but due to recent advances in linter refining technology
It becomes possible to obtain 10,000 to 130,000 seconds and a polymerization degree of about 5,000, and it is said that this level is near the limit for the time being. Of course, in the laboratory, it is possible to obtain a refined linter that maintains the degree of polymerization of the raw linter as it is, but it is industrially unprofitable and not feasible.
後者については、酸素不存在下でセルロースをアルカリ
化およびエーテル化することによって、重合度低下を極
力抑制する技術が確立している。とりわけ、セルロース
に対するアルカリ添加量によってエーテル化度が規定さ
れるハロゲン化アルキルを用いて製造されるアルキルセ
ルロースエーテルでは、通常アルカリ添加量が多く、後
者の方法を取ることが高粘度のアルキルセルロースエー
テルを得るのに必須の条件となっている。しかし、これ
らの従来技術を使って得られるセルロースエーテルは、
高粘度のものであっても１％水溶液の20℃における測定
粘度で約20,000cps程度が限界である。Regarding the latter, a technique has been established in which the decrease in the degree of polymerization is suppressed as much as possible by alkalizing and etherifying cellulose in the absence of oxygen. In particular, alkyl cellulose ethers produced by using an alkyl halide whose degree of etherification is regulated by the amount of alkali added to cellulose usually have a large amount of alkali added, and the latter method can be used to obtain a highly viscous alkyl cellulose ether. It is an indispensable condition to obtain. However, the cellulose ethers obtained using these conventional techniques are
Even with high viscosity, the measured viscosity of a 1% aqueous solution at 20 ° C is about 20,000 cps.
本発明者らはかかる事実に対してセメントに対する混和
剤として充分使用に耐え１％水溶液の粘度が20,000cps
以上という高重合度のセルロースエーテルの安価な製造
方法について検討した結果、綿実から長毛繊維（リン
ト）を刈り取った後、さらに綿実の殻から分離して得ら
れる短毛繊維（粗リンター）を、そのままセルロース原
料として採用し、公知のアルキルセルロースエーテルの
製造方法でエーテル化すれば、１％水溶液の20℃におけ
る測定粘度で約20,000cps以上のアルキルセルロースエ
ーテルが製造できることを見出し、本発明に到達した。Against this fact, the present inventors have been able to withstand the use sufficiently as an admixture for cement and have a viscosity of 1% aqueous solution of 20,000 cps.
As a result of investigating the inexpensive production method of cellulose ether having a high degree of polymerization as described above, short hair fibers (coarse linters) obtained by cutting long hair fibers (lint) from cottonseed and then separating them from cottonseed shells were used. It was found that an alkyl cellulose ether having a measured viscosity of a 1% aqueous solution at 20 ° C. of about 20,000 cps or more can be produced by directly adopting it as a cellulose raw material and etherifying it by a known method for producing an alkyl cellulose ether. did.
すなわち、通常粗リンター中のαセルロース分は90％前
後であり、これを精製した後は約99％にまで純度が高め
られる。他方、天然状態におけるセルロースの重合度は
5,000程度であるといわれているが、希薄水酸化ナトリ
ウム水溶液による煮沸、その後の次亜塩素酸ナトリウム
等、塩素系漂白剤による漂白、酸による脱灰等の一連の
処理において連続的に解重合され、精製されたコットン
リンターの重合度は最高のもので、2,500程度にまで低
下する。そこで、本発明者らは天然状態の重合度を保っ
たままでエーテル化すれば最高の粘度を発現するセルロ
ースエーテルが得られる筈であることに着目し研究を進
めた。That is, the α-cellulose content in the crude linter is usually around 90%, and the purity can be increased to about 99% after purification. On the other hand, the degree of polymerization of cellulose in its natural state is
It is said to be about 5,000, but it is continuously depolymerized in a series of treatments such as boiling with a dilute aqueous solution of sodium hydroxide, bleaching with a chlorine-based bleaching agent such as sodium hypochlorite, and deashing with an acid. The degree of polymerization of the refined cotton linter is the highest and drops to about 2,500. Therefore, the present inventors have paid attention to the fact that if etherification is carried out while maintaining the degree of polymerization in the natural state, a cellulose ether exhibiting the highest viscosity should be obtained, and the research was advanced.
なお、粗リンター中にはペクチン質、蛋白質等の不純物
が１〜４％程度含まれている。これらの不純物の存在と
αセルロース分の少ないことから、製造時の収率の低
下、製品の着色等が懸念されたが、本発明者らは粗リン
ターパルプのコストが通常の精製リンターパルプの1/3
で、その収率の減少以上に本発明にはコストメリットが
あること、さらに製品の着色があっても、セメント製品
への混和剤の添加量が１％以下の少量であることから、
着色の影響が問題とならないことを見出し本発明を完成
した。The crude linter contains impurities such as pectin and protein in an amount of about 1 to 4%. Due to the presence of these impurities and the small amount of α-cellulose, there was a concern that the yield at the time of production might be reduced, the product might be colored, etc. / 3
Therefore, since the present invention has a cost advantage over the reduction of the yield, and the addition amount of the admixture to the cement product is 1% or less even if the product is colored,
The present invention has been completed by finding that the influence of coloring does not pose a problem.
（課題を解決するための手段） 本発明による高重合度セルロースエーテルの製造方法
は、無水粗リンター１重量部に対し、0.5〜1.5重量部の
塩基の存在下、ハロゲン化アルキル0.6〜1.9重量部とア
ルキレンオキサイド０〜１重量部を用いてエーテル化し
た後、熱水にて洗浄することを特徴とするものである。(Means for Solving the Problems) The method for producing a high-polymerization degree cellulose ether according to the present invention is carried out in the presence of 0.5 to 1.5 parts by weight of a base with respect to 1 part by weight of anhydrous crude linter, and an alkyl halide of 0.6 to 1.9 parts by weight. And etherification with 0 to 1 part by weight of alkylene oxide, followed by washing with hot water.
これらをさらに詳細に説明すると、本発明において原料
として使用する粗リンターとは、綿実から長毛繊維（リ
ント）を刈り取った後、さらに綿実の殻から分離して得
られる短毛繊維（粗リンター）であって、従来のように
アルカリ溶液や塩素系漂白剤などで精製されてない、そ
のままのものが採用される。Explaining these in more detail, coarse linters used as a raw material in the present invention means short-hair fibers (coarse linters) obtained by cutting long-haired fibers (lint) from cottonseed and then separating them from the shells of cottonseed. ), Which has not been purified with an alkaline solution or a chlorine-based bleaching agent as in the past, is used as it is.
セルロースエーテルの製造に際して使用される塩基は、
セルロースの結晶性を崩すのに必要であり、反応終了
後、未反応の塩基を残すことなく反応し、塩基と空気中
の酸素による老成重合度の低下を少なくすることが必要
である。そのため一般には、使用するハロゲン化アルキ
ル量の90モル％以下程度の使用が好ましく、本発明では
無水粗リンター１重量部に対して、0.5〜1.5重量部の割
合で使用される。The base used in the production of cellulose ether,
It is necessary to destroy the crystallinity of cellulose, and after the reaction is completed, it is necessary to react without leaving unreacted base to reduce the deterioration of the degree of aging polymerization due to the base and oxygen in the air. Therefore, in general, it is preferably used in an amount of about 90 mol% or less of the amount of the alkyl halide used, and in the present invention, it is used in a ratio of 0.5 to 1.5 parts by weight to 1 part by weight of the crude anhydrous linter.
本発明はセルロースをハロゲン化アルキルエーテル化剤
とほぼ等モルの塩基の存在下に反応させる（１）式と、
セルロースのヒドロキシ基と直接反応し得る活性化反応
成分（アルキレンオキサイド）を触媒量の塩基の存在下
で反応させる（２）式とにおいて、（１）式または
（１）式を基本とする塩基量下で、（１）（２）式の両
方を行なう（３）式によるものである。The present invention comprises formula (1) in which cellulose is reacted with a halogenated alkyl etherifying agent in the presence of an approximately equimolar base, and
The amount of a base based on the formula (1) or the formula (1) in the formula (2) in which an activation reaction component (alkylene oxide) capable of directly reacting with a hydroxy group of cellulose is reacted in the presence of a catalytic amount of the base. This is due to the equation (3) which performs both the equations (1) and (2) below.
Cell-OH・BOH＋Hal-R1→Cell-O-R1＋H2Ｏ＋BHal …
（１） ここにBOH:アルカリ金属水酸化物、 アルカリ土類金属水酸化物 または第４級アンモニウム塩の ような塩基類 Hal :塩素または臭素原子 R1 :アルキル基 R2、R3：水素原子またはアルキル基 （１）（２）を両方行なう反応 …（３） （２）のみの反応生成物は熱水にも溶解し反応物の精製
に熱水以外の有機溶剤の使用が不可欠となり、安価な製
造ができなくなる。Cell-OH ・ BOH ＋ Hal-R 1 → Cell-OR 1 ＋ H 2 O ＋ BHal…
(1) Here, BOH: alkali metal hydroxide, alkaline earth metal hydroxide or base such as quaternary ammonium salt Hal: chlorine or bromine atom R 1 : alkyl group R 2, R 3: a hydrogen atom or an alkyl group (1) (2) performing both reactions (3) (2) the reaction product of only organic purification other than hydrothermal reaction was dissolved in hot water The use of a solvent becomes indispensable, and it becomes impossible to manufacture inexpensively.
本発明で使用するハロゲン化アルキルとしてはクロロメ
チルもしくはクロロエチルのいずれか、または両方であ
る。炭素原子数がこれ以上のハロゲン化アルキルもエー
テル化剤となり得るが、炭素原子数が多くなると水溶性
になりにくくなり、セメント等に使用するセルロースエ
ーテルとして不適当になる。The alkyl halide used in the present invention is either chloromethyl or chloroethyl, or both. Alkyl halides having more carbon atoms can also serve as etherifying agents, but if the number of carbon atoms increases, they become less water-soluble and are unsuitable as cellulose ethers used for cement and the like.
ハロゲン化アルキルの添加量は無水粗リンター１重量部
に対して0.6〜1.9重量部である。これが0.6重量部未満
では反応により生成するセルロースエーテル中にセルロ
ースの結晶が残り水に溶けにくくなって粘性が得られ
ず、また、1.9重量部を超えると、逆にセルロースエー
テルが疎水性になり易く、これもまた水に溶けにくくな
って粘性の発現が悪くなる。The amount of the alkyl halide added is 0.6 to 1.9 parts by weight with respect to 1 part by weight of the crude anhydrous linter. If this is less than 0.6 parts by weight, crystals of cellulose remain in the cellulose ether produced by the reaction and it becomes difficult to dissolve in water and viscosity is not obtained, and if it exceeds 1.9 parts by weight, the cellulose ether tends to become conversely hydrophobic. However, this also becomes less soluble in water and the expression of viscosity becomes worse.
本発明ではハロゲン化アルキルに加えてアルキレンオキ
サイドを添加してエーテル化反応を行うことができる。
アルキレンオキサイドの導入により、さらに水溶解性が
増進される利点がある。In the present invention, an etherification reaction can be carried out by adding an alkylene oxide in addition to the alkyl halide.
The introduction of alkylene oxide has the advantage of further improving water solubility.
アルキレンオキサイドとしてはプロピレンオキサイド、
エチレンオキサイドが使用できる。これよりも炭素原子
数の多いアルキレンオキサイドでもエーテル化できる
が、得られるセルロースエーテルが疎水性になりやすく
水溶性になりにくい。Propylene oxide as the alkylene oxide,
Ethylene oxide can be used. Although alkylene oxides having a larger number of carbon atoms can be etherified, the obtained cellulose ether is likely to be hydrophobic and less likely to be water-soluble.
この添加量としてはエーテル化したものの水溶性が充分
助長される範囲であればよく、粗リンター１重量部当り
０〜１重量部であって、これ以上添加しても水溶性増進
の効果が殆どない。The amount added may be within the range that the water solubility of the etherified product is sufficiently promoted, and it is 0 to 1 part by weight per 1 part by weight of the rough linter. Absent.
本発明による反応は耐圧容器内に粗リンターを仕込み、
高真空にして攪拌しながら塩基成分を添加し、ついで真
空下にハロゲン化アルキルとアルキレンオキサイドとを
仕込み、室温〜100℃で数時間かけて反応を進める。な
お、この反応の際、ジメチルエーテル等の不活性な溶媒
を添加して反応させてもよい。In the reaction according to the present invention, a crude linter is charged in a pressure vessel,
The base component is added under high vacuum with stirring, then the alkyl halide and alkylene oxide are charged under vacuum, and the reaction proceeds at room temperature to 100 ° C. for several hours. At the time of this reaction, an inert solvent such as dimethyl ether may be added and reacted.
反応を終了した生成物は、精製したセルロースエーテル
が溶解するのを防ぐために、80℃以上の高い温度で洗浄
した後、乾燥して適当な粉砕装置で粉砕するか、そのま
ま水に溶解して使用することのできる製品とする。The product after the reaction is washed at a high temperature of 80 ° C or higher to prevent the purified cellulose ether from being dissolved, and then dried and ground with an appropriate grinding device, or dissolved in water as it is and used. It is a product that can
（実施例） 以下、本発明の具体的態様を実施例により説明するが、
本発明はこの実施例に限定されるものではない。(Examples) Hereinafter, specific embodiments of the present invention will be described with reference to Examples.
The invention is not limited to this example.
実施例 １〜2.および比較例１〜3. 次表に示す組成比になるように、まず粗リンターをオー
トクレーブに仕込み、真空後、NaOH水溶液を酸素分子が
入らないように仕込み、内部を攪拌した後、メチルクロ
ライドまたはエチルクロライドとプロピレンオキサイド
またはエチレンオキサイドを仕込んだ。Examples 1 to 2 and Comparative Examples 1 to 3. First, a crude linter was charged into an autoclave so that the composition ratios shown in the following table were obtained, and after vacuuming, a NaOH aqueous solution was charged so that oxygen molecules did not enter, and the inside was stirred. After that, methyl chloride or ethyl chloride and propylene oxide or ethylene oxide were charged.
50℃で５時間攪拌しながら反応させた後、80℃で２時
間、さらに90℃で１時間攪拌しながら反応させ、得られ
た反応生成物を80℃以上の過剰の熱水中で洗浄し、水分
を分離後、105℃で乾燥した。After reacting with stirring at 50 ° C for 5 hours, the mixture was reacted at 80 ° C for 2 hours and further with stirring at 90 ° C for 1 hour, and the obtained reaction product was washed with excess hot water of 80 ° C or more. After separating the water content, it was dried at 105 ° C.
得られた製品について１％水溶液を調製し、20℃で粘度
を測定し、その結果を次表に併記した。A 1% aqueous solution of the obtained product was prepared and the viscosity was measured at 20 ° C., and the results are also shown in the following table.
表中、 通常リンターパルプ：αセルロース分98.5％、 粗リンターパルプ ：αセルロース分89.0％を使用。 In the table, normal linter pulp: α cellulose content 98.5%, coarse linter pulp: α cellulose content 89.0% are used.
実施例１で得られたセルロースエーテルの粗リンターパ
ルプに対する収率（Q1）と、比較例３で得られたセルロ
ースエーテルの通常リンターパルプに対する収率（Q2）
との比、Q2/Q1は0.95であった。Yield of cellulose ether obtained in Example 1 to crude linter pulp (Q1) and yield of cellulose ether obtained in Comparative Example 3 to ordinary linter pulp (Q2)
Q2 / Q1 was 0.95.
また、添加したエーテル化剤の反応効率は実施例１と比
較例３とには差が認められなかった。In addition, the reaction efficiency of the added etherifying agent was not different between Example 1 and Comparative Example 3.
実施例１および２で使用した粗リンターパルプのコスト
は、比較例３で使用した通常リンターパルプに対して1/
3であり、十分にメリットのあることが判る。The cost of the crude linter pulp used in Examples 1 and 2 is 1 / the cost of the normal linter pulp used in Comparative Example 3.
It is 3 and it turns out that there is sufficient merit.
（発明の効果） 本発明によれば、高重合度で高い粘性を発現する水溶性
セルロースエーテルを安価に提供できる。(Effect of the Invention) According to the present invention, a water-soluble cellulose ether that exhibits a high degree of polymerization and a high viscosity can be provided at low cost.
Claims (1)
重量部の塩基の存在下、ハロゲン化アルキル0.6〜1.9重
量部とアルキレンオキサイド０〜１重量部を用いてエー
テル化した後、熱水にて洗浄することを特徴とする高重
合度セルロースエーテルの製造方法。1. 0.5 to 1.5 per part by weight of anhydrous crude linter
Production of a high degree of polymerization cellulose ether characterized by being etherified with 0.6 to 1.9 parts by weight of an alkyl halide and 0 to 1 part by weight of an alkylene oxide in the presence of parts by weight of a base, followed by washing with hot water. Method.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28639989A JPH07119241B2 (en) | 1989-11-02 | 1989-11-02 | Method for producing high degree of polymerization cellulose ether |
| DE19904034709 DE4034709A1 (en) | 1989-11-02 | 1990-11-01 | Cellulose ether prods. with high degree of polymerisation - prepd. by etherifying raw cotton linters with alkyl halide and opt. alkylene oxide, useful thickening agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28639989A JPH07119241B2 (en) | 1989-11-02 | 1989-11-02 | Method for producing high degree of polymerization cellulose ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03146501A JPH03146501A (en) | 1991-06-21 |
| JPH07119241B2 true JPH07119241B2 (en) | 1995-12-20 |
Family
ID=17703900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28639989A Expired - Fee Related JPH07119241B2 (en) | 1989-11-02 | 1989-11-02 | Method for producing high degree of polymerization cellulose ether |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH07119241B2 (en) |
| DE (1) | DE4034709A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1652860A1 (en) | 2004-11-02 | 2006-05-03 | Shin-Etsu Chemical Co., Ltd. | Method of separating water-soluble cellulose ether |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19746264A1 (en) * | 1997-10-20 | 1999-04-29 | Wolff Walsrode Ag | Cellulose ether with low salt content |
| SE520715C2 (en) * | 2001-12-03 | 2003-08-12 | Akzo Nobel Nv | Process for the preparation of methyl cellulose ethers |
| US8173799B2 (en) | 2004-04-13 | 2012-05-08 | Hercules Incorporated | Raw cotton linters composition, method of making, and uses thereof |
| EP1758834A1 (en) * | 2004-04-27 | 2007-03-07 | Hercules Incorporated | Cement-based plasters using water rentention agents prepared from raw cotton linters |
| EP1740513A1 (en) * | 2004-04-27 | 2007-01-10 | Hercules Incorporated | Tile cement mortars using water retention agents |
| EP1740514A1 (en) * | 2004-04-27 | 2007-01-10 | Hercules Incorporated | Gypsum-based mortars using water retention agents prepared from raw cotton linters |
| WO2005105702A1 (en) * | 2004-04-27 | 2005-11-10 | Hercules Incorporated | Cement-based systems using water retention agents prepared from raw cotton linters |
| US7066996B2 (en) * | 2004-04-27 | 2006-06-27 | Hercules Incorporated | Joint compounds using thickeners prepared from raw cotton linters |
| US20050241543A1 (en) * | 2004-04-27 | 2005-11-03 | Wolfgang Hagen | Cement-based systems using plastification/extrusion auxiliaries prepared from raw cotton linters |
| JP5084719B2 (en) * | 2005-04-04 | 2012-11-28 | ハーキュリーズ・インコーポレーテッド | Improved raw cotton linter compositions, methods for their production and use |
| WO2007056070A2 (en) | 2005-11-04 | 2007-05-18 | Hercules Incorporated | Ether derivatives of raw cotton linters for water-borne coatings |
| CN101389729B (en) | 2006-02-23 | 2015-12-09 | 赫尔克里士公司 | For the raw cotton linter of the ethoxylation of well finishing liquid and workover fluid |
| JP5412191B2 (en) * | 2009-06-29 | 2014-02-12 | 富士フイルム株式会社 | Cellulose resin composition, molded body, and casing for electrical and electronic equipment |
| CN101906167B (en) * | 2010-06-07 | 2012-05-02 | 新疆大学 | Method for preparing concrete water reducing agent by utilizing waste cellulose deposited in pulping black liquor |
-
1989
- 1989-11-02 JP JP28639989A patent/JPH07119241B2/en not_active Expired - Fee Related
-
1990
- 1990-11-01 DE DE19904034709 patent/DE4034709A1/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1652860A1 (en) | 2004-11-02 | 2006-05-03 | Shin-Etsu Chemical Co., Ltd. | Method of separating water-soluble cellulose ether |
| US8324377B2 (en) | 2004-11-02 | 2012-12-04 | Shin-Etsu Chemical Co., Ltd. | Method of separating water-soluble cellulose ether |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03146501A (en) | 1991-06-21 |
| DE4034709A1 (en) | 1991-05-08 |
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