JP3547788B2 - Method for stabilizing alkylene oxide polymer - Google Patents
Method for stabilizing alkylene oxide polymer Download PDFInfo
- Publication number
- JP3547788B2 JP3547788B2 JP07381494A JP7381494A JP3547788B2 JP 3547788 B2 JP3547788 B2 JP 3547788B2 JP 07381494 A JP07381494 A JP 07381494A JP 7381494 A JP7381494 A JP 7381494A JP 3547788 B2 JP3547788 B2 JP 3547788B2
- Authority
- JP
- Japan
- Prior art keywords
- alkylene oxide
- oxide polymer
- weight
- viscosity
- stabilizing
- 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 - Lifetime
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、アルキレンオキシド重合体の安定化方法に関する。
【０００２】
【従来の技術】
アルキレンオキシド重合体は、例えば、エチレンオキシド重合体が抄紙用分散剤、凝集剤、水溶性フィルム、水溶性繊維、捺染用糊剤、可塑剤等種々の用途を有する等、極めて有用な水溶性高分子である。
【０００３】
上記アルキレンオキシド重合体は、例えば、エチレンオキシド重合体を和紙抄造用粘剤等として使用する場合、重合度が低いと、水溶液の粘度及び法線応力が低く、多量に使用する必要があり不経済となるばかりでなく、抄紙の地合が悪くなる等和紙抄造上好ましくない。この点、重合度が高いと、粘剤としての効果が大であるため使用量が少なくてよく好都合である。一般にアルキレンオキシド重合体は、重合度の高いものが要望され、商品価値も高い。しかし重合度の高いものは安定性が悪く、保存中に分子量が低下し、そのため使用に際し、これを溶解して得られる水溶液の粘度及び法線応力が低下するなど、重合体の性質が変化し、甚だしい場合には使用が不可能となる不都合がある。この傾向は、保存期間が長い程、保存温度が高い程著しく、また、重合度の大なるもの程、低下の程度が甚だしい。なお、法線応力とは水溶液の剪断力に対して垂直に働く力を指し、ワイセンベルグ効果により、回転する攪拌棒に沿って粘弾性液体が這い上がる現象として目にすることができる。
【０００４】
従来より、保存中における分子量の低下を防止するため、アルキレンオキシド重合体には、酸化防止剤等を安定剤として添加する技術が検討されており、例えば、没食子酸ｎ−プロピルを用いるものが特公昭３４−１０７８３号公報に、Ｎ−ニトロソジフェニルアミンを用いるものが特公昭３５−１８３４号公報に、第三ブチルヒドロキノンを用いるものが特公昭５７−５０８２２号公報に、それぞれ開示されている。
【０００５】
【発明が解決しようとする課題】
しかし、これらの酸化防止剤等を用いた場合、分子量の低下防止効果が充分でなかったり、水溶液とした場合着色する等の問題があった。本発明の目的は、これらに鑑み、アルキレンオキシド重合体を水溶液として粘度及び法線応力を測定した場合、それが当初の値に比べて低下することのない、アルキレンオキシド重合体の安定化方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者らは、上記アルキレンオキシド重合体の安定化をはかるため、種々の添加剤について鋭意検討を重ねた結果、重量平均分子量１００万〜１０００万のアルキレンオキシド重合体に脂肪族多価アルコールを添加した場合、長期間にわたって保存した後も、上記アルキレンオキシド重合体の分子量が低下することのない、すなわち保存後にそれを水溶液として、粘度及び粘弾性に寄与する法線応力を測定しても当初の値と殆ど変わらないことを見いだし、本発明を完成するにいたった。すなわち、本発明の要旨は、重量平均分子量１００万〜１０００万のアルキレンオキシド重合体の安定化方法を、アルキレンオキシド重合体１００重量部に、１〜４０重量部の脂肪族多価アルコールを添加して構成するところにある。
【０００７】
本発明が適用できるアルキレンオキシド重合体の分子量は特に限定されないが、通常は、重量平均分子量２万〜１０００万のもの、好ましくは１００万〜１０００万の高重合度のものに適用すると良い結果が得られる。本発明のアルキレンオキシド重合体は特に限定されないが、例えば、エチレンオキシドを１成分として含むものを挙げることができ、エチレンオキシドの単独重合体、エチレンオキシドと他のアルキレンオキシドとの共重合体等が挙げられる。上記他のアルキレンオキシドとしては、例えば、プロピレンオキシド、ブチレンオキシド、スチレンオキシド、エピクロルヒドリン等が挙げられる。
【０００８】
本発明で使用される脂肪族多価アルコールは、水酸基を２個以上有する脂肪族アルコールであれば特に限定されず、炭素数３〜７のものがよい。例えば、トリメチレングリコール、ジエチレングリコール、１，２，４−ブタントリオール、２，２−ジメチル−１，３−プロパンジオール、２−ヒドロキシメチル−２−メチル−１，３−プロパンジオール、ペンタエリスリトール、トリエチレングリコール、ソルビット、ヘプタンジオール等が挙げられる。なかでも炭素数５の脂肪族多価アルコール、例えば、２，２−ジメチル−１，３−プロパンジオール、２−ヒドロキシメチル−２−メチル−１，３−プロパンジオール、ペンタエリスリトール等が好適に用いられ、特にペンタエリスリトールが好ましい。
【０００９】
上記多価アルコールの添加量は、アルキレンオキシド重合体１００重量部に対して１〜４０重量部が適量である。添加量が１重量部未満であると、アルキレンオキシド重合体の分子量の低下防止効果が充分でなく、４０重量部を超えると、添加に伴なう効果はみられず、却って上記組成物中のアルキレンオキシド含量が少なくなり前記組成物を多量に用いないと目的とする粘度が得られないので、上記範囲に限定される。好ましくは３〜３５重量部であり、さらに好ましくは５〜２５重量部である。かくすることにより１０〜５０℃の条件下で、約１年間にわたって分子量を低下させることなくアルキレンオキシド重合体を安定して保存することが可能となる。
【００１０】
本発明においては、必要に応じてさらに既存の酸化防止剤、熱安定剤、紫外線吸収剤等を添加することもできる。
【００１１】
【実施例】
以下に実施例を挙げて本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
【００１２】
実施例１〜３
重量平均分子量４００万のポリエチレンオキシド１００重量部に、表１に示す添加量でペンタエリスリトールを添加混合し、ポリエチレン製の袋に密閉して４０℃にて所定の期間保存した。下記粘度及び法線応力は、脂肪族多価アルコールの添加にともないアルキレンオキシド重合体濃度が低下するため、アルキレンオキシド重合体の含有量が０．５重量％となるよう濃度を一定にして測定した。即ち分子量低下の尺度として、所定の経時日数におけるポリエチレンオキシド含有量が０．５重量％の水溶液を調製し、該水溶液の粘度及び法線応力を測定し、その経時変化率を求め、結果を表１に示した。経時変化率は、所定の経時日数における水溶液の粘度及び法線応力を、以下に示した方法により測定し、最初の粘度及び法線応力を１００としたときの変化率（％）で示した。水溶液には、いずれの場合も着色は認められなかった。
【００１３】
測定方法
（１）粘度の測定
本発明の脂肪族多価アルコールを含むアルキレンオキシド重合体組成物を、攪拌周速１ｍ／秒の条件下でイオン交換水に溶解し、上記０．５重量％水溶液を調製し、該水溶液の２５℃における粘度を、Ｂ形回転式粘度計により測定した。
（２）法線応力の測定
粘度測定で用いたのと同様の溶液を用いて、以下の条件下でレオペキシーアナライザー（岩本製作所製）により測定した。
比較例１
ペンタエリスリトールを添加しないこと以外は実施例１〜３と同様にして粘度及び法線応力の経時変化率を求め、結果を表１に示した。
【００１５】
【表１】
実施例４〜６
重量平均分子量７００万のポリエチレンオキシドを使用したこと以外は実施例１〜３と同様にして、所定の経時日数における粘度及び法線応力の経時変化率を求め、結果を表２に示した。
【００１７】
比較例２
ペンタエリスリトールを添加しないこと以外は実施例４〜６と同様にして粘度及び法線応力の経時変化率を求め、結果を表２に示した。
【００１８】
【表２】
これらの結果より、本発明の脂肪族多価アルコールを添加されたアルキレンオキシド重合体は、水溶液としてその粘度及び法線応力の経時変化を測定すると分子量低下の程度が少なく、保存安定性に優れたものであることが判明した。
【００２０】
【発明の効果】
本発明の脂肪族多価アルコールを添加されたアルキレンオキシド重合体は、水溶液としてその粘度及び法線応力の経時変化を測定すると、その程度が少なく、保存安定性に優れたものである。従って、保存による該重合体の分子量の低下、それによる粘度及び法線応力の低下を心配することなく、目的の用途に最適の使用量で使用することが可能となる。[0001]
[Industrial applications]
The present invention relates to a method for stabilizing an alkylene oxide polymer.
[0002]
[Prior art]
Alkylene oxide polymers are extremely useful water-soluble polymers, for example, ethylene oxide polymers have various uses such as dispersants for papermaking, flocculants, water-soluble films, water-soluble fibers, pastes for printing, plasticizers, etc. It is.
[0003]
The above-mentioned alkylene oxide polymer, for example, when using an ethylene oxide polymer as a Japanese papermaking adhesive, if the degree of polymerization is low, the viscosity of the aqueous solution and the normal stress are low, it is necessary to use a large amount, and it is uneconomical. In addition to the above, it is not preferable in terms of Japanese paper making, such as poor paper formation. In this regard, when the degree of polymerization is high, the effect as a thickener is large, so that the amount of use is small and it is convenient. In general, alkylene oxide polymers are desired to have a high degree of polymerization and have high commercial value. However, those with a high degree of polymerization have poor stability and the molecular weight decreases during storage, and when used, the properties of the polymer change, such as lowering the viscosity and normal stress of the aqueous solution obtained by dissolving it. However, in severe cases, there is a disadvantage that use is impossible. This tendency is more remarkable as the storage period is longer and the storage temperature is higher, and the degree of reduction is larger as the degree of polymerization is larger. The normal stress refers to a force acting perpendicular to the shear force of the aqueous solution, and can be seen as a phenomenon in which the viscoelastic liquid creeps up along the rotating stirring rod by the Weissenberg effect.
[0004]
Conventionally, a technique of adding an antioxidant or the like as a stabilizer to an alkylene oxide polymer has been studied in order to prevent a decrease in molecular weight during storage. For example, a technique using n-propyl gallate has been studied. Japanese Patent Publication No. 34-10783 discloses a method using N-nitrosodiphenylamine and Japanese Patent Publication No. 35-1834, and a method using tertiary butylhydroquinone is disclosed in Japanese Patent Publication No. 57-50822.
[0005]
[Problems to be solved by the invention]
However, when these antioxidants and the like are used, there are problems such as an insufficient effect of preventing a decrease in molecular weight and coloring when used as an aqueous solution. In view of the above, an object of the present invention is to provide a method for stabilizing an alkylene oxide polymer in which the viscosity and normal stress are not reduced as compared with the initial values when the viscosity and the normal stress are measured using the alkylene oxide polymer as an aqueous solution. To provide.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on various additives in order to stabilize the above-mentioned alkylene oxide polymer.As a result, an aliphatic polyhydric alcohol was added to the alkylene oxide polymer having a weight average molecular weight of 1,000,000 to 10,000,000. When added, even after storage for a long period of time, the molecular weight of the alkylene oxide polymer does not decrease, that is , even if it is used as an aqueous solution after storage and the normal stress contributing to viscosity and viscoelasticity is measured, Have been found to be almost the same as the above, and the present invention has been completed. That is, the gist of the present invention is to provide a method for stabilizing an alkylene oxide polymer having a weight average molecular weight of 1,000,000 to 10,000,000 by adding 1 to 40 parts by weight of an aliphatic polyhydric alcohol to 100 parts by weight of an alkylene oxide polymer. It is the place to be composed.
[0007]
The molecular weight of the alkylene oxide polymer to which the present invention can be applied is not particularly limited, but usually, a weight average molecular weight of 20,000 to 10,000,000, preferably 1,000,000 to 10,000,000, and a good result is obtained when applied to a polymer having a high degree of polymerization. can get. The alkylene oxide polymer of the present invention is not particularly limited, and examples thereof include those containing ethylene oxide as one component, and include a homopolymer of ethylene oxide and a copolymer of ethylene oxide and another alkylene oxide. Examples of the other alkylene oxide include propylene oxide, butylene oxide, styrene oxide, and epichlorohydrin.
[0008]
The aliphatic polyhydric alcohol used in the present invention is not particularly limited as long as it is an aliphatic alcohol having two or more hydroxyl groups, and preferably has 3 to 7 carbon atoms. For example, trimethylene glycol, diethylene glycol, 1,2,4-butanetriol, 2,2-dimethyl-1,3-propanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, pentaerythritol, Ethylene glycol, sorbit, heptanediol and the like can be mentioned. Among them, aliphatic polyhydric alcohols having 5 carbon atoms, for example, 2,2-dimethyl-1,3-propanediol, 2-hydroxymethyl-2-methyl-1,3-propanediol, pentaerythritol and the like are preferably used. Pentaerythritol is particularly preferred.
[0009]
The appropriate amount of the polyhydric alcohol to be added is 1 to 40 parts by weight based on 100 parts by weight of the alkylene oxide polymer. If the addition amount is less than 1 part by weight, the effect of preventing the decrease in the molecular weight of the alkylene oxide polymer is not sufficient, and if it exceeds 40 parts by weight, the effect accompanying the addition is not seen, but rather the composition in the composition If the content of the alkylene oxide is low and the composition is not used in a large amount, the desired viscosity cannot be obtained. Preferably it is 3 to 35 parts by weight, more preferably 5 to 25 parts by weight. Thus, the alkylene oxide polymer can be stably stored under the conditions of 10 to 50 ° C. for about one year without lowering the molecular weight.
[0010]
In the present invention, if necessary, an existing antioxidant, heat stabilizer, ultraviolet absorber and the like can be further added.
[0011]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[0012]
Examples 1-3
To 100 parts by weight of polyethylene oxide having a weight-average molecular weight of 4,000,000, pentaerythritol was added and mixed in the amount shown in Table 1 and sealed in a polyethylene bag and stored at 40 ° C for a predetermined period. The following viscosity and normal stress were measured by keeping the concentration of the alkylene oxide polymer constant at 0.5% by weight because the alkylene oxide polymer concentration decreased with the addition of the aliphatic polyhydric alcohol. . That is, as a measure of the decrease in molecular weight, an aqueous solution having a polyethylene oxide content of 0.5% by weight over a predetermined number of days was prepared, the viscosity and normal stress of the aqueous solution were measured, the rate of change over time was obtained, and the results were tabulated. 1 is shown. The rate of change over time was determined by measuring the viscosity and normal stress of the aqueous solution over a predetermined number of days by the following method, and was expressed as a rate of change (%) when the initial viscosity and normal stress were set to 100. No coloring was observed in any of the aqueous solutions.
[0013]
Measurement Method (1) Measurement of Viscosity The alkylene oxide polymer composition containing the aliphatic polyhydric alcohol of the present invention was dissolved in ion-exchanged water at a stirring peripheral speed of 1 m / sec. Was prepared, and the viscosity of the aqueous solution at 25 ° C. was measured with a B-type rotary viscometer.
(2) Measurement of normal stress Using a solution similar to that used in the viscosity measurement, it was measured by a rheopexy analyzer (manufactured by Iwamoto Seisakusho) under the following conditions.
Comparative Example 1
Except that pentaerythritol was not added, the time-dependent changes in viscosity and normal stress were determined in the same manner as in Examples 1 to 3, and the results are shown in Table 1.
[0015]
[Table 1]
Examples 4 to 6
Except that polyethylene oxide having a weight-average molecular weight of 7,000,000 was used, the rate of change of viscosity and normal stress over time over a predetermined number of days was determined in the same manner as in Examples 1 to 3, and the results are shown in Table 2.
[0017]
Comparative Example 2
Except that pentaerythritol was not added, the rate of change in viscosity and normal stress with time was determined in the same manner as in Examples 4 to 6, and the results are shown in Table 2.
[0018]
[Table 2]
From these results, the alkylene oxide polymer to which the aliphatic polyhydric alcohol of the present invention has been added has a small degree of decrease in molecular weight when measured over time in viscosity and normal stress as an aqueous solution, and has excellent storage stability. Turned out to be something.
[0020]
【The invention's effect】
When the viscosity and normal stress of the alkylene oxide polymer to which the aliphatic polyhydric alcohol is added as an aqueous solution are measured over time, the degree is small and the storage stability is excellent. Therefore, it is possible to use the polymer in an optimal amount for the intended use without worrying about a decrease in the molecular weight of the polymer due to storage and a decrease in the viscosity and normal stress due to the storage.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07381494A JP3547788B2 (en) | 1994-03-18 | 1994-03-18 | Method for stabilizing alkylene oxide polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07381494A JP3547788B2 (en) | 1994-03-18 | 1994-03-18 | Method for stabilizing alkylene oxide polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07258533A JPH07258533A (en) | 1995-10-09 |
| JP3547788B2 true JP3547788B2 (en) | 2004-07-28 |
Family
ID=13529011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07381494A Expired - Lifetime JP3547788B2 (en) | 1994-03-18 | 1994-03-18 | Method for stabilizing alkylene oxide polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3547788B2 (en) |
-
1994
- 1994-03-18 JP JP07381494A patent/JP3547788B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07258533A (en) | 1995-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4799962A (en) | Water-soluble polymer dispersion | |
| Smith et al. | Association reactions for poly (alkylene oxides) and polymeric poly (carboxylic acids) | |
| US4594108A (en) | Highly pseudoplastic polymer solutions | |
| CA1307258C (en) | Carboxymethyl hydrophobically modified hydroxyethylcellulose (cmhmhec) and use of cmhmhec in protective coating compositions | |
| SU1382403A3 (en) | Suspension for thickening water media | |
| EP0686683B1 (en) | Cross-linkable thixotropic wood adhesive gel | |
| CA2039098C (en) | Polymer/fatty acid fluid suspension | |
| IL135668A (en) | Fluidized polymer suspension of hydrophobically modified poly (acetal- or ketal-polyether), polyurethane and polyacrylate | |
| US5550177A (en) | Starch and poly (ethlene-co-acrylic acid) pastes and gels, and method for their making | |
| BRPI0515808B1 (en) | aqueous poly (acetal-polyether) dispersion, aqueous backing composition and method of incorporating said polymer into backing formulation | |
| EP0997502A1 (en) | Combinations of associative thickeners and aqueous protective coating compositions | |
| JP3547788B2 (en) | Method for stabilizing alkylene oxide polymer | |
| CA2035495A1 (en) | Stabilized polymer latex composition | |
| US10316178B2 (en) | Starch suspension for adhesive coatings | |
| JP2001527596A (en) | Aqueous dispersion of polyamide | |
| JP2002020614A (en) | Method for decreasing syneresis in aqueous composition | |
| EP1035134B1 (en) | Cellulose-based associative thickeners having a high ICI viscosity | |
| US5246490A (en) | Water soluble liquid alginate dispersions | |
| US20020086919A1 (en) | Gum slurries | |
| EP0373739B1 (en) | Improved adhesive emulsion composition and accompanying coated substrates, such as prepasted wall coverings | |
| JP3602866B2 (en) | Additive for earth pressure shield method | |
| JPS62112675A (en) | Synthetic rubber latex adhesive composition | |
| GB1589798A (en) | Adhesive compositions | |
| US3278468A (en) | Periodate oxidized polysaccharide urea resin dispersions | |
| CN113831551A (en) | Aqueous dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20040105 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040226 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20040316 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040409 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040415 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090423 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090423 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100423 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110423 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120423 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130423 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130423 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140423 Year of fee payment: 10 |
|
| EXPY | Cancellation because of completion of term |