JPH02164842A - Dialkoxycarboxylic acid and salt thereof - Google Patents
Dialkoxycarboxylic acid and salt thereofInfo
- Publication number
- JPH02164842A JPH02164842A JP32004588A JP32004588A JPH02164842A JP H02164842 A JPH02164842 A JP H02164842A JP 32004588 A JP32004588 A JP 32004588A JP 32004588 A JP32004588 A JP 32004588A JP H02164842 A JPH02164842 A JP H02164842A
- Authority
- JP
- Japan
- Prior art keywords
- dialkoxycarboxylic
- acid ester
- acid
- alcohol
- formula
- 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.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 150000003839 salts Chemical class 0.000 title claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 150000007513 acids Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 14
- 150000002148 esters Chemical class 0.000 abstract description 12
- -1 3-butenoic acid ester Chemical class 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000004513 sizing Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N 3-Butenoic acid Natural products OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XJHNCGVHPLDMRK-UHFFFAOYSA-N 4,4-dimethoxybutanenitrile Chemical compound COC(OC)CCC#N XJHNCGVHPLDMRK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CFEYBLWMNFZOPB-UHFFFAOYSA-N pent-4-enenitrile Chemical compound C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ZYQXJBONHXBUKI-UHFFFAOYSA-N 4,4-dimethoxybutanoic acid Chemical group COC(OC)CCC(O)=O ZYQXJBONHXBUKI-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UNAQSRLBVVDYGP-UHFFFAOYSA-N hex-5-enenitrile Chemical compound C=CCCCC#N UNAQSRLBVVDYGP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- OXOUJUXDEZZIEF-UHFFFAOYSA-N oct-7-enenitrile Chemical compound C=CCCCCCC#N OXOUJUXDEZZIEF-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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、糊付剤、紙のサイズ剤として優れた性能を示
すポリビニルアルコールのアニオン変性体の変性剤とし
て有用なジアルコキシカルボン酸及びその塩に関する。Detailed Description of the Invention <Industrial Application Field> The present invention is directed to dialkoxycarboxylic acids and dialkoxycarboxylic acids useful as modifiers for anionically modified polyvinyl alcohols that exhibit excellent performance as sizing agents and paper sizing agents. Regarding salt.
〈従来の技術及び問題点〉
近年ポリビニルアルコールの′Ｓ機能化が行われている
。その中で、カルボキシル基による変性も盛んに行われ
ており、例えば、カルボキシル基の導入によりその優れ
た水溶性を生かした糊付剤をはじめ、エマルジョンの保
護剤、紙のサイズ剤等に優れた性能を発揮している。<Prior Art and Problems> In recent years, polyvinyl alcohol has been converted to 'S' functionality. Among these, modification with carboxyl groups is also actively being carried out, and for example, by introducing carboxyl groups, it has been used to make sizing agents that take advantage of their excellent water solubility, as well as emulsion protectants, paper sizing agents, etc. It is demonstrating its performance.
カルボキシル基による変性の方法としては、以下に示す
２つの方法が知られている。２１つは不飽和ｊ詰合を（
Ｓつカルボン酸誘啓ｊ、（、：と酢酸ビニルどを１−３
重合させた後ケン化を行う共重合変性であり、他の方法
は酢酸ビニルをＩｐ：合しケン化した後反応性基を導入
する後変性法である。共重合変性法については、アクリ
ル酸分゛の・塩〕１（酸及びそのエステルを用いた場合
ラクトン環が生成しカルボキシル基の導入は困難であり
、２塩基酸等を用いた研究が行われている。The following two methods are known as methods for modification with carboxyl groups. 21 is unsaturated j packing (
S carboxylic acid derivatives (,: and vinyl acetate etc. 1-3
This is a copolymerization modification method in which saponification is performed after polymerization, and another method is a post-modification method in which vinyl acetate is combined with Ip, saponified, and then a reactive group is introduced. Regarding the copolymerization modification method, research has been conducted using dibasic acids, etc., since it is difficult to introduce a carboxyl group because a lactone ring is generated when an acrylic acid component (salt) 1 (acid and its ester is used). ing.
一方、カルボキシル基をもつ化合物での後変性は、これ
までに余り知られていない。これは、ポリビニルアルコ
ールのヒドロキシル基と選択的に反応する基を一方に持
ち他方に反応性の高い置換基をもつ２官能性化合物がそ
れほど知られていない為である。On the other hand, post-modification with a compound having a carboxyl group is not well known so far. This is because bifunctional compounds having a group that selectively reacts with the hydroxyl group of polyvinyl alcohol on one side and a highly reactive substituent on the other are not so well known.
〈発明が解決しようとする課題〉
本発明の課題は、糊付剤等として有用な、水溶性に優れ
たポリビニルアルコールのカルボキシル基変性体を開発
する事にあり、ポリビニルアルコールのヒドロキシル基
と選択的に反応する置換基を一方に持ち他方にアニオン
性基を有する２官能性の化合物を提供することである。<Problems to be Solved by the Invention> An object of the present invention is to develop a carboxyl group-modified product of polyvinyl alcohol that is useful as a sizing agent and has excellent water solubility. The object of the present invention is to provide a bifunctional compound having a substituent that reacts with ion on one side and an anionic group on the other side.
〈課題を解決するための手段〉
本発明者らは、ポリビニルアルコールのヒドロキシル基
と選択的に反応する置換基を一方に持ち他方にアニオン
性基を有する２官能性の化合物ついて鋭意検討の結果、
一方にポリビニルアルコールのヒドロキシル基と選択的
に反応できるアセタール基をもち他方にカルボキシル基
を有する化合物であるジアルコキシカルボン酸を見いだ
した。<Means for Solving the Problems> As a result of intensive studies by the present inventors on bifunctional compounds having a substituent that selectively reacts with the hydroxyl group of polyvinyl alcohol on one side and an anionic group on the other side,
We have discovered dialkoxycarboxylic acids, which are compounds that have an acetal group that can selectively react with the hydroxyl group of polyvinyl alcohol on one side and a carboxyl group on the other.
これまでにジアルコキシカルボン酸ｍ導体とじてはジア
ルコキシカルボン酸エステル類が知られている。例えば
３．３−ジアルコキシプロピオン酸エステル、４．４−
ジアルコキシプロピオン酸エステル等が主に知られてい
る。しかし、これらのカルボン酸及びその塩については
報告されていない。また、これらの化合物は、次に示す
方法にて合成されている。アクリル酸エステル類のオキ
ソ反応、フランの電解酸化（Ｊ、Ｏｒｇ、Ｃｈｅｍ。So far, dialkoxycarboxylic acid esters have been known as dialkoxycarboxylic acid m-conductors. For example, 3,3-dialkoxypropionic acid ester, 4,4-
Dialkoxypropionate esters and the like are mainly known. However, these carboxylic acids and their salts have not been reported. Moreover, these compounds are synthesized by the method shown below. Oxo reaction of acrylic acid esters, electrolytic oxidation of furan (J, Org, Chem.
、支ユ ３７９９ （１９８２））、ニトロアルキ
ルカルボン酸のネフ反応（Ｔｅｔｒａｈｅｄｒｏｎ、４
４ １０１５ （１９８８））、アルケニルカルボ
ン酸エステルのオゾン酸化（Ｊ、 Ａｒｎ。, Support 3799 (1982)), Neff reaction of nitroalkyl carboxylic acids (Tetrahedron, 4
4 1015 (1988)), Ozone Oxidation of Alkenyl Carboxylic Esters (J, Arn.
Ｃｈｅｍ、Ｓｏｃ、、１０３ ５１６ （１９８１）
）等の方法である。しかし、これら何れの方法もジアル
コキシカルボン酸及びその塩を経由するものでは無い。Chem, Soc, 103 516 (1981)
) etc. However, none of these methods involve dialkoxycarboxylic acids and their salts.
ジアルコキシカルボン酸及びその塩は、アルケニルカル
ボン酸エステルのアルコール中でのオキソ反応によりジ
アルコキシカルボン酸エステルとした後加水分解するこ
とにより得ることが出来る。Dialkoxycarboxylic acids and salts thereof can be obtained by oxo-reacting alkenylcarboxylic esters in alcohol to form dialkoxycarboxylic esters, followed by hydrolysis.
ここで用いることの出来るアルケニルカルボン酸エステ
ルとしては、アクリル酸エステル、３−ブテン酸エステ
ル、４−ペンテン酸エステル、５ヘキセン酸エステル、
６−ヘプテン酸エステル、７−オクテン酸エステルが
挙げられ、アルコールとしては、炭素数１〜５の低級ア
ルコールが挙げられる。更に加水分解に用いるアルカリ
としては、Ｎａ等のアルカリ金属の水酸化物、または、
Ｃａ等のアルカリ土類金属の水酸化物が用いられる。Examples of alkenylcarboxylic esters that can be used here include acrylic esters, 3-butenoic esters, 4-pentenoic esters, 5-hexenoic esters,
Examples include 6-heptenoic acid ester and 7-octenoic acid ester, and examples of the alcohol include lower alcohols having 1 to 5 carbon atoms. Further, as the alkali used for hydrolysis, hydroxides of alkali metals such as Na, or
Hydroxides of alkaline earth metals such as Ca are used.
また、アルケノニトリルのアルコール中でのオキソ反応
（エル、６４ ２１４２ （１９６１））によりジアル
コキシアルキルニトリルにした後アルカリ加水分解を行
うことによりジアルコキシカルボン酸の塩を得ることが
でき、更に、酸で中和する事によりジアルコキシカルボ
ン酸を得ることが出来る。Further, a salt of a dialkoxycarboxylic acid can be obtained by converting an alkenonitrile into a dialkoxyalkyl nitrile through an oxo reaction in an alcohol (L, 64 2142 (1961)) and then performing alkaline hydrolysis. Dialkoxycarboxylic acid can be obtained by neutralizing with acid.
ここで用いることの出来るアルケノニトリルとしては、
アクリロニトリル、３−ブテノニトリル、４−ペンテノ
ニトリル、 ５−ヘキセノニトリル、６−へブテノニト
リル、 ７−オクテノニトリルが挙げられ、アルコール
としては、炭素数］〜５の低級アルコールが挙げら抗る
。更に加水分解に用いるアルカリとしては、Ｎａ等のア
ルカリ金属の水酸化物、または、Ｃａ等のアルカリ土類
金属の水酸化物が用いられる。Alkenonitriles that can be used here include:
Examples include acrylonitrile, 3-butenonitrile, 4-pentenonitrile, 5-hexenonitrile, 6-hebutenonitrile, and 7-octenonitrile, and examples of the alcohol include lower alcohols having 5 to 5 carbon atoms. Furthermore, as the alkali used for hydrolysis, hydroxides of alkali metals such as Na or hydroxides of alkaline earth metals such as Ca are used.
例えば、４．４−ジメトキシプロピオン酸ナトリウムは
、既知の方法（エル、６４． ２１４２（１９６１））
によりβ−シアノプロピオンアルデヒドジメチルアセタ
ールを得た後、水溶液中、当量の荷性ソーダを加え加熱
還流する事により収率よく得ることが出来る。For example, sodium 4,4-dimethoxypropionate can be prepared using known methods (El., 64. 2142 (1961)).
After obtaining β-cyanopropionaldehyde dimethyl acetal, it can be obtained in good yield by adding an equivalent amount of carrier soda to the aqueous solution and heating to reflux.
また、ポリビニルアルコールのジアルコキシカルボン酸
でのアセタール化変性は、極性溶媒中、酸触媒の存在下
加熱することにより行うことが出来る。以下実施例をも
って説明する。Moreover, acetalization modification of polyvinyl alcohol with a dialkoxycarboxylic acid can be carried out by heating in a polar solvent in the presence of an acid catalyst. This will be explained below using examples.
〈実施例〉
実施例１
β−シアノプロピオンアルデヒドジメチルアセタール９
９０ｇ、荷性ソーダ３２３ｇを９９０ｍ１のイオン交換
水に溶解し６時間３０分加熱還流した。水を減圧留去し
た後、加熱乾燥し１２７２ｇの生成物を得た（収率９８
％）。ＮＭＲｌＩ Ｒにより４．４−ジメトキシブタン
酸ナトリウム篇であることを確認した。<Example> Example 1 β-cyanopropionaldehyde dimethyl acetal 9
In 990 ml of ion-exchanged water, 90 g and 323 g of loaded soda were dissolved and heated under reflux for 6 hours and 30 minutes. After water was distilled off under reduced pressure, 1272 g of product was obtained by heating and drying (yield: 98
%). It was confirmed by NMRlIR that it was sodium 4,4-dimethoxybutanoate.
実施例２
４．４−ジメトキシブタン酸１５ｇをＤＭＳ○２５０ｇ
に溶解し、濃塩酸、完全ケン孔型ポリビニルアルコール
２２ ｇを加え９０℃で６時間加熱捜はんした。ＤＭＳ
Ｏを減圧留去した後、石油エーテルに注ぎ生じた沈澱を
濾別、乾燥しポリビニルアルコールの変性体を得た。Example 2 15g of 4.4-dimethoxybutanoic acid was added to 250g of DMS○
Concentrated hydrochloric acid and 22 g of completely pore-type polyvinyl alcohol were added to the mixture, followed by heating and stirring at 90°C for 6 hours. DMS
After O was distilled off under reduced pressure, the resulting precipitate was poured into petroleum ether and the resulting precipitate was filtered and dried to obtain a modified polyvinyl alcohol.
実施例３ 実施例２の化合物１ｇを室温で２０ｍ］の水に加えた。Example 3 1 g of the compound of Example 2 was added to 20 m of water at room temperature.
対照として完全ケン孔型ポリビニルアルコール１ｇを室
温で２０ｍ１の水に加えた。As a control, 1 g of fully pore-type polyvinyl alcohol was added to 20 ml of water at room temperature.
各々の室温での水に対する溶解性を比較した。The solubility of each in water at room temperature was compared.
その結果４．４−ジメトキシブタン酸で変性したポリビ
ニルアルコールは、未変性ポリビニルアルコールに比べ
水溶性に優れていた。As a result, polyvinyl alcohol modified with 4,4-dimethoxybutanoic acid had better water solubility than unmodified polyvinyl alcohol.
〈本発明の効果〉
実施例１−３に示したように、ジアルコキシカルボン酸
で変性したポリビニルアルコールは、未変性ポリビニル
アルコールに比べ水溶性に優れていた。<Effects of the Present Invention> As shown in Examples 1-3, polyvinyl alcohol modified with dialkoxycarboxylic acid had better water solubility than unmodified polyvinyl alcohol.
Claims (1)
、Ｍは、ＨまたはＮａ等のアルカリ金属、または、Ｃａ
等のアルカリ土類金属）で示されるジアルコキシカルボ
ン酸及びその塩。[Claims] 1) General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, n is 2 to 7, R is a lower alkyl group having 1 to 5 carbon atoms, M is H or Alkali metal or Ca
dialkoxycarboxylic acids and their salts represented by alkaline earth metals such as
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32004588A JPH02164842A (en) | 1988-12-19 | 1988-12-19 | Dialkoxycarboxylic acid and salt thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32004588A JPH02164842A (en) | 1988-12-19 | 1988-12-19 | Dialkoxycarboxylic acid and salt thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02164842A true JPH02164842A (en) | 1990-06-25 |
Family
ID=18117120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32004588A Pending JPH02164842A (en) | 1988-12-19 | 1988-12-19 | Dialkoxycarboxylic acid and salt thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02164842A (en) |
-
1988
- 1988-12-19 JP JP32004588A patent/JPH02164842A/en active Pending
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