JP2734072B2 - Method for producing amphoteric copolymer - Google Patents
Method for producing amphoteric copolymerInfo
- Publication number
- JP2734072B2 JP2734072B2 JP1069291A JP6929189A JP2734072B2 JP 2734072 B2 JP2734072 B2 JP 2734072B2 JP 1069291 A JP1069291 A JP 1069291A JP 6929189 A JP6929189 A JP 6929189A JP 2734072 B2 JP2734072 B2 JP 2734072B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- copolymer
- maleic anhydride
- added
- maleic acid
- 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
Links
- 229920001577 copolymer Polymers 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 15
- 239000011976 maleic acid Substances 0.000 claims description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 15
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical class C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000178 monomer Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XCENPWBBAXQVCG-UHFFFAOYSA-N 4-phenylpiperidine-4-carbaldehyde Chemical compound C=1C=CC=CC=1C1(C=O)CCNCC1 XCENPWBBAXQVCG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
- C08F226/04—Diallylamine
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、第４級アンモニウム塩型ジアリルアミン誘
導体と、マレイン酸又は無水マレイン酸を共重合してな
る両性共重合体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing an amphoteric copolymer obtained by copolymerizing a quaternary ammonium salt type diallylamine derivative with maleic acid or maleic anhydride.
〈従来の技術及びその課題〉 ジアリルアミン誘導体は、周知のようにその分子内に
アリル基を有する為、いわゆるアリル型破壊的連鎖移動
を起こし、必ずしも重合活性は高くない。一方マレイン
酸及び無水マレイン酸を単独に重合させても高分子量の
ポリカルボン酸が得られないことも周知である。<Conventional Technology and its Problems> As is well known, diallylamine derivatives have an allyl group in the molecule, so cause so-called allyl-type destructive chain transfer, and do not always have high polymerization activity. On the other hand, it is also well known that a high molecular weight polycarboxylic acid cannot be obtained even when maleic acid and maleic anhydride are polymerized singly.
このことは、ジアリルアミン誘導体とマレイン酸又は
無水マレイン酸の共重合においても例外では無く、例え
ばラジカル開始剤による水溶液重合では高分子量の共重
合体を製造することは困難とされてきた。This is no exception in the copolymerization of a diallylamine derivative with maleic acid or maleic anhydride. For example, it has been considered difficult to produce a high molecular weight copolymer by aqueous solution polymerization using a radical initiator.
ジアリルアミン誘導体とマレイン酸又は無水マレイン
酸の高分子量の共重合体を製造する方法としては特許88
6374号によって公知であるが、この方法はジアリルアミ
ン誘導体及びマレイン酸又は無水マレイン酸の溶液状又
はスラリー状混合物に光増感剤の存在下又は非存在下に
おいて200〜500nmの波長を含む光を照射して共重合体を
得る製造方法であり、工業的に大量の共重合体を製造す
る方法としては優れた方法とは言い難い。又、この製造
方法によって得られる共重合体は、いずれも固体状であ
り使用に際しては、共重合体を粉砕し更に水等の溶媒に
溶解せねばならないという不便さがある。Patent No. 88 discloses a method for producing a high molecular weight copolymer of a diallylamine derivative and maleic acid or maleic anhydride.
No. 6374, this method involves irradiating a solution or slurry mixture of a diallylamine derivative and maleic acid or maleic anhydride with light having a wavelength of 200 to 500 nm in the presence or absence of a photosensitizer. This is a production method for obtaining a copolymer by the above method, and is not an excellent method for industrially producing a large amount of a copolymer. Further, the copolymers obtained by this production method are all in a solid state, and when used, there is the inconvenience that the copolymers must be ground and further dissolved in a solvent such as water.
〈課題を解決する為の手段〉 本発明者らは、このように従来かかえていた課題を解
決すべく、鋭意研究した結果、本発明を完成した。<Means for Solving the Problems> The inventors of the present invention have made intensive studies to solve the problems that have been conventionally solved, and as a result, completed the present invention.
即ち、本発明は一般式（１） （式中、R1、R2は水素又はメチル基を表し、R3、R4はそ
れぞれ単独にメチル基、エチル基であり、X-は無機酸の
陰イオンを表す。）で表わされる第４級アンモニウム塩
型ジアリルアミン誘導体と、アニオン成分としてのマレ
イン酸又は無水マレイン酸とを、水中でラジカル開始剤
を触媒として共重合させるに際し、重合液にアルカリ剤
を添加してpHを13以上とすることを特徴とする両性共重
合体の製造方法を提供するものである。That is, the present invention relates to the general formula (1) (Wherein, R 1 and R 2 represent hydrogen or a methyl group, R 3 and R 4 each independently represent a methyl group or an ethyl group, and X − represents an anion of an inorganic acid.) When copolymerizing a quaternary ammonium salt type diallylamine derivative and maleic acid or maleic anhydride as an anionic component in water with a radical initiator as a catalyst, an alkali agent is added to the polymerization solution to adjust the pH to 13 or more. It is another object of the present invention to provide a method for producing an amphoteric copolymer.
本発明の一般式（１）で表わされる第４級アンモニウ
ム塩型ジアリルアミン誘導体のうち、主なものを例示す
れば以下の通りである。Among the quaternary ammonium salt type diallylamine derivatives represented by the general formula (1) of the present invention, the main ones are as follows.
ジメチルジアリルアンモニウムクロライド、ジエチル
ジアリルアンモニウムクロライド、メチルエチルジアリ
ルアンモニウムクロライド、ジメチルジアリルマアンモ
ニウムブロマイド、ジエチルジアリルアンモニウムブロ
マイド。Dimethyldiallylammonium chloride, diethyldiallylammonium chloride, methylethyldiallylammonium chloride, dimethyldiallylammonium bromide, diethyldiallylammonium bromide.
ジアリルミン誘導体であっても、ジアリルアミン塩酸
塩の如き２級アミンの塩、メチルジアリルアミン塩酸塩
の如き３級アミンの塩には、本発明の方法を適用する事
はできない。Even if it is a diallylamine derivative, the method of the present invention cannot be applied to a salt of a secondary amine such as diallylamine hydrochloride or a salt of a tertiary amine such as methyldiallylamine hydrochloride.
本発明において重合液のpHを13以上とするために、重
合系に添加されるアルカリ剤のうち主なものを例示すれ
ば、水酸化ナトリウム，水酸化カリウムなどのアルカリ
金属水酸化物，炭酸ナトリウム，炭酸カリウムなどのア
ルカリ金属炭酸塩などが挙げられる。In order to adjust the pH of the polymerization solution to 13 or more in the present invention, examples of the main alkaline agents added to the polymerization system include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and sodium carbonate. And alkali metal carbonates such as potassium carbonate.
本発明の共重合体の製造方法を実施するにあたって、
通常一般式（１）の第４級アンモニウム塩型ジアリルア
ミン誘導体に、マレイン酸又は無水マレイン酸を添加、
混合し、これに水を加えて調整するか、又はあらかじめ
調整した一般式（１）のモノマー水溶液にマレイン酸又
は無水マレイン酸を加えて調整される。マレイン酸又は
無水マレイン酸の仕込み量は、得られる共重合体の使用
目的に応じて任意に選ばれ、特に限定されないが多くの
場合、第４級アンモニウム塩型ジアリルアミン誘導体１
モルに対して0.01〜２モル、好ましくは0.1〜0.5モルの
範囲である。In carrying out the method for producing a copolymer of the present invention,
Usually, maleic acid or maleic anhydride is added to the quaternary ammonium salt type diallylamine derivative of the general formula (1),
It is adjusted by mixing and adding water thereto, or by adding maleic acid or maleic anhydride to the previously prepared aqueous monomer solution of the general formula (1). The amount of maleic acid or maleic anhydride to be charged is arbitrarily selected depending on the purpose of use of the obtained copolymer, and is not particularly limited. In many cases, the quaternary ammonium salt type diallylamine derivative 1
It is in the range of 0.01 to 2 mol, preferably 0.1 to 0.5 mol, per mol.
pH調整のために重合系に添加されるアルカリ剤の量
は、マレイン酸又は無水マレイン酸の仕込み量に対応し
て変わるが、いずれの場合も重合液のpHが13以上になる
ことが必要である。一般にアルカリ剤の添加量が多いほ
ど重合速度は大きくなる。The amount of the alkaline agent added to the polymerization system for pH adjustment varies depending on the charged amount of maleic acid or maleic anhydride, but in any case, the pH of the polymerization solution must be 13 or more. is there. Generally, the larger the amount of the alkali agent added, the higher the polymerization rate.
重合開始剤は、過硫酸アンモニウム、過硫酸カリウム
などの過硫酸塩、2,2′−アゾビス（２−アミジノプロ
パン）二塩酸塩などのアゾ化合物、また公知のレドック
ス系開始剤、例えば過硫酸カリウムと亜硫酸水素ナトリ
ウムとの組合せが例示できる。添加量はモノマーに対す
る重量で0.1〜５％、好ましくは１〜３％である。Polymerization initiators include persulfates such as ammonium persulfate and potassium persulfate, azo compounds such as 2,2'-azobis (2-amidinopropane) dihydrochloride, and known redox initiators such as potassium persulfate. A combination with sodium bisulfite can be exemplified. The addition amount is 0.1 to 5%, preferably 1 to 3% by weight based on the monomer.
重合温度は、20〜100℃、好ましくは30〜70°で行わ
れる。モノマー濃度には特に制限は無いが、通常20〜80
％である。The polymerization temperature is from 20 to 100 ° C, preferably from 30 to 70 °. There is no particular limitation on the monomer concentration, but usually 20 to 80
%.
重合は、空気中でも可能であるが、窒素ガスなどの不
活性ガスの雰囲気で行うことが好ましい。また本発明は
攪拌又は静置のいずれの重合方法にも適用可能である。The polymerization can be performed in air, but is preferably performed in an atmosphere of an inert gas such as nitrogen gas. Further, the present invention is applicable to any polymerization method of stirring or standing.
なお、重合後の共重合体は、アニオン成分であるカル
ボン酸が塩の形で存在しているので、必要に応じて塩酸
などの無機酸を重合液に添加する事によって遊離のカル
ボン酸に変換できる。In the copolymer after polymerization, the carboxylic acid, which is an anionic component, exists in the form of a salt.If necessary, the carboxylic acid is converted into a free carboxylic acid by adding an inorganic acid such as hydrochloric acid to the polymerization solution. it can.
以上説明したように、本発明は第４級アンモニウム塩
型ジアリルアミン誘導体とマレイン酸又は無水マレイン
酸を共重合させるに際し、重合液のpHを13以上とする事
により、共重合がきわめて容易となりその結果、高分子
量の両性共重合体を高収率で、しかも大量に製造できる
ことを、その本質とするものである。As described above, in the present invention, when a quaternary ammonium salt type diallylamine derivative is copolymerized with maleic acid or maleic anhydride, the pH of the polymerization solution is adjusted to 13 or more, so that the copolymerization becomes extremely easy, and as a result, The essential feature is that a high molecular weight amphoteric copolymer can be produced in high yield and in large quantities.
〈実施例〉 以下、実施例により本発明を更に詳細に説明するが、
本発明はこれら実施例のみに限定されるものではない。
なお実施例及び比較例中に記載の％は全て重量％を表
す。<Examples> Hereinafter, the present invention will be described in more detail by way of examples,
The present invention is not limited to only these examples.
The percentages described in Examples and Comparative Examples all represent% by weight.
実施例１〜３ 攪拌機、温度計、窒素吹き込み管、コンデンサーを備
えた反応器に65％ジメチルジアリルアンモニウムクロラ
イドと無水マレイン酸を第１表に示す割合で仕込み、さ
らに50％水酸化ナトリウムとイオン交換水を加えモノマ
ー濃度60％、pH14の液を調整した。次いで窒素ガスで充
分反応器内の空気を置換し酸素不含とした後、攪拌しな
がら内温を60℃に保ちつつ、モノマーに対して２％の過
硫酸アンモニウムを10回に分けて１時間おきに添加し
た。重合液は時間の経過とともに次第に粘稠となる。最
後の過硫酸アンモニウムを添加後、60℃で10時間保温し
重合反応を完結させた。重合終了後、冷却し、次に重合
時にpH調整用として添加した水酸化ナトリウムと等モル
の塩酸を加え中和した、次いで液の一部を採取しアセト
ンに注入し、生じた共重合体の沈澱を濾別し、減圧乾燥
し収率及び固有粘度を測定した。なお理論収率は無水マ
レイン酸が水を付加してマレイン酸に変換しているもの
として求めた。Examples 1 to 3 A reactor equipped with a stirrer, a thermometer, a nitrogen blowing tube, and a condenser was charged with 65% dimethyldiallylammonium chloride and maleic anhydride in the proportions shown in Table 1, and further ion-exchanged with 50% sodium hydroxide. Water was added to adjust a solution having a monomer concentration of 60% and a pH of 14. Next, the air in the reactor is sufficiently replaced with nitrogen gas to make it oxygen-free, and while maintaining the internal temperature at 60 ° C. while stirring, ammonium persulfate of 2% with respect to the monomer is divided into 10 portions, every one hour. Was added. The polymerization liquid gradually becomes viscous over time. After the last ammonium persulfate was added, the temperature was kept at 60 ° C. for 10 hours to complete the polymerization reaction. After completion of the polymerization, the mixture was cooled, and then neutralized by adding equimolar hydrochloric acid to sodium hydroxide added for pH adjustment at the time of polymerization, and then a part of the liquid was collected and poured into acetone to form a copolymer. The precipitate was separated by filtration, dried under reduced pressure, and the yield and the intrinsic viscosity were measured. The theoretical yield was determined assuming that maleic anhydride was converted to maleic acid by adding water.
また、この共重合体には微量の食塩が含まれている
為、共重合体を電気、炉中で600℃、２時間焼却し残査
すなわち食塩の量を求め収率を補正した。固有粘度は、
共重合体の0.5gを1/10N−食塩水100mlで溶解し、30℃恒
温水槽中でウベローデ粘度管（80秒計）を用いて測定し
た。結果を第１表に示す。Further, since this copolymer contained a trace amount of salt, the copolymer was incinerated in an electric furnace at 600 ° C. for 2 hours, and the residue, that is, the amount of salt was determined to correct the yield. The intrinsic viscosity is
0.5 g of the copolymer was dissolved in 100 ml of a 1 / 10N-brine solution, and measured in a constant temperature water bath at 30 ° C. using an Ubbelohde viscosity tube (80 second meter). The results are shown in Table 1.
得られた共重合体は、いずれも水及びメタノールに溶
解するがアセトンには不溶であり吸湿性が強い。またこ
れら共重合体の赤外線吸収スペクトルは、ジメチルジア
リルアンモニウムクロライドからの単独重合体の吸収を
示すほかに、1720cm-1付近にカルボニル基に基く吸収が
存在し、またこの吸収は無水マレイン酸の仕込み組成が
大きいほどの強度が増加している。これらの結果からこ
の重合体は次の構造を有する線状高分子両性電解質であ
ると考えられる。Each of the obtained copolymers is soluble in water and methanol, but is insoluble in acetone and has strong hygroscopicity. The infrared absorption spectra of these copolymers show the absorption of the homopolymer from dimethyldiallylammonium chloride, as well as the presence of a carbonyl-based absorption near 1720 cm -1. The strength increases as the composition increases. From these results, it is considered that this polymer is a linear polyampholyte having the following structure.
比較例１〜３ 攪拌機、温度計、窒素ガス吹き込み管、コンデンサー
を備えた反応器に65％ジメチルジアリルアンモニウムク
ロライドと無水マレイン酸を第２表に示す割合で仕込
み、さらにイオン交換水を加えモノマー濃度60％の液を
調整する。次いで窒素ガスで充分反応器内の空気を置換
し酸素不含とした後、攪拌しながら内温を60℃に保ちつ
つ、モノマーに対して２％の過硫酸アンモニウムを10回
に分けて１時間おきに添加した。最後の過硫酸アンモニ
ウムを添加後、60℃で10時間保温し重合反応を完結させ
た。重合終了後、冷却し重合液の一部を採取しアセトン
に注入し、生じた共重合体の沈澱を濾別し、減圧下60℃
で恒量になるまで乾燥し、収率及び固有粘度を測定し
た。なお、理論収率は無水マレイン酸が水を付加してマ
レイン酸に変換しているものとして求めた。固有粘度は
共重合体の0.5gを1/10N−食塩水100mlで溶解し、30℃恒
温水槽中でウベローデ粘度管（80秒計）を用いて測定し
た。結果を第２表に示す。得られた共重合体は、いずれ
も実施例１〜３に示した共重合体と同様の性質を有して
おり、赤外線吸収スペクトルも全く同一であった。 Comparative Examples 1 to 3 65% dimethyldiallylammonium chloride and maleic anhydride were charged into a reactor equipped with a stirrer, a thermometer, a nitrogen gas injection tube, and a condenser at the ratio shown in Table 2, and ion-exchanged water was added thereto to obtain a monomer concentration. Prepare 60% solution. Next, the air in the reactor is sufficiently replaced with nitrogen gas to make it oxygen-free, and while maintaining the internal temperature at 60 ° C. while stirring, ammonium persulfate of 2% with respect to the monomer is divided into 10 portions, every one hour. Was added. After the last ammonium persulfate was added, the temperature was kept at 60 ° C. for 10 hours to complete the polymerization reaction. After completion of the polymerization, the mixture was cooled, a part of the polymerization solution was collected, poured into acetone, and the resulting precipitate of the copolymer was separated by filtration.
And dried until constant weight was obtained, and the yield and the intrinsic viscosity were measured. The theoretical yield was determined assuming that maleic anhydride was converted to maleic acid by adding water. The intrinsic viscosity was measured by dissolving 0.5 g of the copolymer in 100 ml of 1 / 10N-brine and using a Ubbelohde viscometer (80 second meter) in a water bath at 30 ° C. The results are shown in Table 2. All of the obtained copolymers had the same properties as the copolymers shown in Examples 1 to 3, and the infrared absorption spectra were completely the same.
〈発明の効果〉 実施例と比較例の対比からもわかるように、本発明の
製造方法によれば、従来困難とされていた第４級アンモ
ニウム塩型ジアリルアミン誘導体とマレイン酸又は無水
マレイン酸とを効率よく共重合させ、高収率でより高分
子量の両性共重合体を製造できるようになる。 <Effects of the Invention> As can be seen from the comparison between Examples and Comparative Examples, according to the production method of the present invention, a quaternary ammonium salt type diallylamine derivative and maleic acid or maleic anhydride, which have been considered difficult, have been used. Copolymerization can be carried out efficiently, and a higher molecular weight amphoteric copolymer can be produced in high yield.
Claims (1)
れぞれ単独にメチル基、エチル基であり、X-は無機酸の
陰イオンを表す。）で表わされる第４級アンモニウム塩
型ジアリルアミン誘導体と、アニオン成分としてのマレ
イン酸又は無水マレイン酸とを、水中でラジカル開始剤
を触媒として共重合させるに際し、重合液にアルカリ剤
を添加してpHを13以上とすることを特徴とする両性共重
合体の製造方法。1. The general formula (1) (Wherein, R 1 and R 2 represent hydrogen or a methyl group, R 3 and R 4 each independently represent a methyl group or an ethyl group, and X − represents an anion of an inorganic acid.) When quaternary ammonium salt type diallylamine derivative and maleic acid or maleic anhydride as an anionic component are copolymerized in water with a radical initiator as a catalyst, an alkali agent is added to the polymerization solution to adjust the pH to 13 or more. A method for producing an amphoteric copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1069291A JP2734072B2 (en) | 1989-03-23 | 1989-03-23 | Method for producing amphoteric copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1069291A JP2734072B2 (en) | 1989-03-23 | 1989-03-23 | Method for producing amphoteric copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02248410A JPH02248410A (en) | 1990-10-04 |
| JP2734072B2 true JP2734072B2 (en) | 1998-03-30 |
Family
ID=13398336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1069291A Expired - Fee Related JP2734072B2 (en) | 1989-03-23 | 1989-03-23 | Method for producing amphoteric copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2734072B2 (en) |
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| JP5120566B2 (en) * | 2009-03-26 | 2013-01-16 | 日東紡績株式会社 | Method for producing a copolymer of diallyl compound and maleic acid |
| CN103965400B (en) * | 2014-05-26 | 2016-08-17 | 深圳天鼎精细化工制造有限公司 | A kind of formaldehyde-free color fixing agent and preparation method thereof |
| JP6972546B2 (en) * | 2016-12-27 | 2021-11-24 | 日東紡績株式会社 | Dye fixing agent for cellulosic fibers |
| WO2022091315A1 (en) * | 2020-10-29 | 2022-05-05 | 佐々木化学株式会社 | Hair cosmetic and method for producing same, and method for improving hair quality and method for hairstyling using same |
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1989
- 1989-03-23 JP JP1069291A patent/JP2734072B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02248410A (en) | 1990-10-04 |
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