JPH0411601A - Polyvinyl alcohol polymer and its production - Google Patents
Polyvinyl alcohol polymer and its productionInfo
- Publication number
- JPH0411601A JPH0411601A JP22322690A JP22322690A JPH0411601A JP H0411601 A JPH0411601 A JP H0411601A JP 22322690 A JP22322690 A JP 22322690A JP 22322690 A JP22322690 A JP 22322690A JP H0411601 A JPH0411601 A JP H0411601A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- group
- vinyl
- alcohol polymer
- polymerization
- 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.)
- Granted
Links
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 125000003277 amino group Chemical group 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical group CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001290 polyvinyl ester Polymers 0.000 claims description 8
- 229920001567 vinyl ester resin Polymers 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 150000003573 thiols Chemical group 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 4
- 239000004753 textile Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 78
- 239000004372 Polyvinyl alcohol Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 238000007127 saponification reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- -1 α-ethyl vinyl Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229950010765 pivalate Drugs 0.000 description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 2
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 2
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
A 産業上のl
本発明はポリビニルアルコール系重合体およびその製造
法に関する。DETAILED DESCRIPTION OF THE INVENTION A. Industrial Field The present invention relates to a polyvinyl alcohol polymer and a method for producing the same.
B 従来の技術
従来、ポリビニルアルコール系重合体は分散剤、界面活
性剤として広く用いられている。しかし界面活性能を向
上させるfコめに、けん化度を下げると、ポリビニルア
ルコール系重合体の分点現象のため満足な分散性能が得
られないという欠点かあった。したがって、従来はカチ
オン基またはアニオン基などを側鎖に導入することによ
り、分点を上昇させるという方法が用いられてきた。し
かし側鎖にカチオン基またはアニオン基を有するポリビ
ニルアルコール系重合体は、側鎖にカチオン基とかアニ
オン基を有さないポリビニルアルコール系重合体と比較
して、分散質への吸着状態が変化するためか、分点上昇
はみられるものの分散性能としては満足できるものでは
なかった。B. Prior Art Conventionally, polyvinyl alcohol polymers have been widely used as dispersants and surfactants. However, if the degree of saponification is lowered in order to improve the surfactant ability, there is a drawback that satisfactory dispersion performance cannot be obtained due to the equinox phenomenon of the polyvinyl alcohol polymer. Therefore, a method has conventionally been used in which the equinox point is raised by introducing a cationic group or anionic group into the side chain. However, polyvinyl alcohol-based polymers that have cationic or anionic groups in their side chains have different adsorption conditions on dispersoids compared to polyvinyl alcohol-based polymers that do not have cationic or anionic groups in their side chains. However, although an increase in the equinox point was observed, the dispersion performance was not satisfactory.
Cが 決しようとする課題
本発明の目的は、上記の問題点のない、新規なポリビニ
ルアルコール系重合体を提供することにある。Problems to be Solved by C An object of the present invention is to provide a novel polyvinyl alcohol polymer free from the above-mentioned problems.
D 課題を解決するための手段
本発明者らは、かかる現状に鑑み、よりすくれた分散性
能を有し、分点の高いポリビニルアルコール系重合体に
ついて鋭意検討した結果、ポリビニルアルコール単位を
50モル%以上含有し、重合度か3500以下で末端に
アミノ基、アンモニウム基またはスルホン酸基を含有す
るポリビニルアルコール系重合体を見いだし、本発明を
完成させるに到った。D. Means for Solving the Problems In view of the current situation, the inventors of the present invention have conducted intensive studies on polyvinyl alcohol polymers that have better dispersion performance and a higher equinox point. % or more, a polymerization degree of 3,500 or less, and an amino group, an ammonium group, or a sulfonic acid group at the end, and have completed the present invention.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のポリビニルアルコール系重合体は下記の構造単
位Aを50モル%以上含有し、重合度が3500以下で
末端にアミノ基、アンモニウム基またはスルホン酸基を
含有するポリビニルアルコール系重合体である。The polyvinyl alcohol polymer of the present invention contains 50 mol% or more of the following structural unit A, has a degree of polymerization of 3500 or less, and has an amino group, an ammonium group, or a sulfonic acid group at the terminal.
A : −(−CH,−CH→−
H
本発明のポリビニルアルコール系重合体が含有するビニ
ルアルコール単位(構造単位A)以外のアルコール単位
としてはα−メチルビニルアルコール、α−エチルビニ
ルアルコール、α−ブロビルビニルアルコール、α〜プ
チルビニルアルコール、α−ヘキンルビニルアルコール
からなる構造単位かあげられる。A: -(-CH, -CH→-H Alcohol units other than the vinyl alcohol unit (structural unit A) contained in the polyvinyl alcohol polymer of the present invention include α-methyl vinyl alcohol, α-ethyl vinyl alcohol, α -Structural units consisting of brobyl vinyl alcohol, α-butyl vinyl alcohol, and α-hexynruvinyl alcohol can be mentioned.
構造単位Aの含量は該重合体の分点、および分散性能の
点から50モル%以上であることが必要であり、好まし
くは60モル%以上、より好ましくは70モル%以上で
ある。The content of structural unit A needs to be 50 mol% or more from the point of view of the polymer's point and dispersion performance, preferably 60 mol% or more, more preferably 70 mol% or more.
本発明のポリビニルアルコール系重合体が含有する構造
単位Aおよび上記のアルコール単位以外の構造単位とし
ては特に制限はないが、該重合体の分点を低下させない
という点および分散性能の点からは、下記の構造単位B
が好ましい。There are no particular restrictions on the structural units other than the structural unit A and the above-mentioned alcohol units contained in the polyvinyl alcohol polymer of the present invention, but from the viewpoint of not lowering the equinox point of the polymer and dispersion performance, Structural unit B below
is preferred.
B : (−CH,−CH+−
0= C−R2
(ここてR1はHまたは炭素数1から20までの炭化水
素基をあられす。)
R1の炭素数が上記より大の場合には、疎水性か強くな
りすぎて、該重合体の分点が低下するので好ましくない
。B: (-CH, -CH+- 0=C-R2 (Here, R1 is H or a hydrocarbon group having 1 to 20 carbon atoms.) If the number of carbon atoms in R1 is larger than the above, it is hydrophobic. This is not preferable because the chemical properties become too strong and the equinox point of the polymer decreases.
構造単位Bとしては、ギ酸ビニル、酢酸ビニル、プロピ
オン酸ビニル、ピバリン酸ビニル、バーサチック酸ビニ
ル、ラウリン酸ビニル、ステアリン酸ビニルおよびこれ
らのα置換体からなる構造単位があげられ、なかても酢
酸ビニル単位およびピバリン酸ビニル単位が好ましい。Structural unit B includes structural units consisting of vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, and α-substituted products thereof, especially vinyl acetate. units and vinyl pivalate units are preferred.
構造単位Bの含量は、分散性能および分点の点から50
モル%未満であることが必要である。The content of structural unit B is 50% from the viewpoint of dispersion performance and equinox.
It is necessary that the amount is less than mol%.
本発明のポリビニルアルコール系重合体は、該重合体の
末端にアミノ基、アンモニウム基またはスルホン酸基を
含有することが必要である。分散性能の点からは該重合
体の片末端にのみアミノ基、アンモニウム基またはスル
ホン酸基を含有するのが好ましい。The polyvinyl alcohol polymer of the present invention must contain an amino group, an ammonium group, or a sulfonic acid group at the end of the polymer. From the viewpoint of dispersion performance, it is preferable that the polymer contains an amino group, an ammonium group, or a sulfonic acid group only at one end.
アミノ基をまたはアンモニウム基を含有する末端基の具
体例な例としては以下のものが挙げられる。Specific examples of terminal groups containing an amino group or an ammonium group include the following.
に゛
およびこの四級化物
基の窒素原子あるいは(I[I)式中の酸素原子とを連
結する基をそれぞれ示す。)
またスルホン酸基を含有する末端基の具体的な例として
は以下のものが挙げられる。and a group connecting the nitrogen atom of the quaternized group or the oxygen atom in the formula (I[I), respectively. ) Further, specific examples of the terminal group containing a sulfonic acid group include the following.
CH2CHCoo (CHz)n 503M
(V a)p!
およびこの四級化物
およびこの四級化物
p鵞
およびこの四級化物
(ここてnはO〜3、mは1〜10、R″、 R3,R
6,R7R8は水素原子またはメチル基、R’、 R5
は低級アルキル基(置換基を含んでもよい)、Xはアン
モニウム窒素と塩を形成する陰性の基、Lはアミノある
いはアンモニウム窒素原子と(1)式中のアミド(ここ
でR8は低級のアルキル基、R10,R11は水素原子
またはメチル基、nは2〜4、Mは水素原子、アルカリ
金属またはアンモニウムイオンをそれぞれ示す。)
R2−R11の炭素数、mおよびnか上記より大の場合
には疎水性が強くなりすぎて、該重合体の分点が低下す
るので好ましくない。CH2CHCoo (CHz)n 503M
(Va)p! and this quaternized product and this quaternized product P and this quaternized product (where n is O~3, m is 1~10, R'', R3, R
6, R7R8 is a hydrogen atom or a methyl group, R', R5
is a lower alkyl group (which may contain a substituent); X is a negative group that forms a salt with ammonium nitrogen; L is an amino or ammonium nitrogen atom; , R10 and R11 are hydrogen atoms or methyl groups, n is 2 to 4, M is a hydrogen atom, an alkali metal or an ammonium ion, respectively.) If the number of carbon atoms in R2-R11, m and n are larger than the above, This is not preferable because the hydrophobicity becomes too strong and the equinox point of the polymer decreases.
本発明のポリビニルアルコール系重合体は前記の構造単
位Aを含むことか必須であり、好ましくは構造単位Aお
よび構造単位Bを含むが、構造単位Aおよび構造単位B
以外の構造単位を含むことは何らさしつかえなく、Aの
含量が50モル%以上であれば他の構造単位の存在は何
ら問題ない。その池の構造単位としては、たとえばエチ
レン、プロピレン、イソブチン、アクリル酸、メタクリ
ル酸ま几はその塩あるいはこれらのアルキルエステル、
アクリロニトリル、メタクリロニトリル、アクリルアミ
ド、メタクリルアミド、エチルビニルエーテル、ブチル
ビニルエーテル、N−ビニルピロリドン、塩化ビニル、
臭化ビニル、フッ化ビニル、塩化ビニリデン、フッ化ビ
ニリデン、テトラフルオロエチレンなどからなる構造単
位かあげられる。It is essential that the polyvinyl alcohol polymer of the present invention contains the above-mentioned structural unit A, and preferably contains structural unit A and structural unit B.
There is no problem with the presence of other structural units as long as the content of A is 50 mol% or more. The structural units of the pond include, for example, ethylene, propylene, isobutyne, acrylic acid, methacrylic acid, their salts, or their alkyl esters,
Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, ethyl vinyl ether, butyl vinyl ether, N-vinylpyrrolidone, vinyl chloride,
Examples of structural units include vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene.
本発明のポリビニルアルコール系重合体の重合度につい
ては重合体の末端、好ましくは片末端にのみ存在するア
ミノ基、アンモニウム基またはスルホン酸基を有効に作
用させるという視点から、重合度3500以下、好まし
くは2000以下、さらに好ましくは1000以下であ
る。また該重合体の重合度の下限については特に制限は
ないが20以上、好ましくは40以上である。The degree of polymerization of the polyvinyl alcohol polymer of the present invention is preferably 3,500 or less, from the viewpoint of effectively allowing the amino group, ammonium group, or sulfonic acid group present only at one end of the polymer to act effectively. is 2000 or less, more preferably 1000 or less. The lower limit of the degree of polymerization of the polymer is not particularly limited, but is 20 or more, preferably 40 or more.
次に、本発明のポリビニルアルコール系重合体の製造法
について説明する。Next, a method for producing the polyvinyl alcohol polymer of the present invention will be explained.
ポリビニルアルコール系重合体の末端にアミノ基、アン
モニウム基、またはスルホン酸基を導入する方法として
大別して次の2つの方法が知られている。The following two methods are known as methods for introducing amino groups, ammonium groups, or sulfonic acid groups into the terminals of polyvinyl alcohol polymers.
第1の方法はアミノ基、アンモニウム基、またはスルホ
ン酸基を有するビニル系モノマーを共重合する方法であ
る。The first method is a method of copolymerizing a vinyl monomer having an amino group, an ammonium group, or a sulfonic acid group.
第2の方法は、いわゆる高分子反応により導入する方法
で、ポリビニルアルコール系重合体のアルコール部分に
アミノ基、アンモニウム基またはスルホン酸基を後変性
により導入する方法である。The second method is a so-called polymer reaction method, in which an amino group, an ammonium group, or a sulfonic acid group is introduced into the alcohol moiety of a polyvinyl alcohol polymer by post-modification.
しかしこれらの方法によって重合体中にアミノ基、アン
モニウム基まfこはスルホン酸基を導入することは可能
であるが、本発明の重合体の特徴である分子の末端にの
み選択的にアミノ基、アンモニウム基またはスルホン酸
基を導入することはできない。このような情勢の中で本
発明者らは分子の末端にのみ選択的にアミノ基、アンモ
ニウム基まf二はスルホン酸基を導入する方法について
検討した結果、アミノ基、アンモニウム基またはスルホ
ン酸基を有する連鎖移動剤の存在下にビニルエステル類
を重合することにより末端にのみアミノ基、アンモニウ
ム基またはスルホン酸基を有するポリビニルアルコール
系重合体が得られることを見出し、本発明の製造法を完
成させたものである。However, although it is possible to introduce amino groups, ammonium groups, or sulfonic acid groups into the polymer by these methods, it is possible to selectively introduce amino groups only at the terminals of the molecules, which is a feature of the polymer of the present invention. , ammonium groups or sulfonic acid groups cannot be introduced. Under these circumstances, the present inventors investigated methods for selectively introducing amino groups, ammonium groups, or sulfonic acid groups only at the terminal ends of molecules. discovered that polyvinyl alcohol-based polymers having amino groups, ammonium groups, or sulfonic acid groups only at the ends can be obtained by polymerizing vinyl esters in the presence of a chain transfer agent having This is what I did.
本発明の製造法の特徴はアミノ基、アンモニウム基また
はスルホン酸基を有する連鎖移動剤の存在下に酢酸ビニ
ル等のビニルエステル類モノマーを主体とするビニル系
モノマーを重合することにより、末端にアミノ基、アン
モニウム基、まにはスルホン酸基を有するポリビニルエ
ステル系重合体を製造する。次に、上記の方法により得
られた重合体をけん化することにより構造単位Aを含有
する重合体を得ることができる。The production method of the present invention is characterized by polymerizing vinyl monomers mainly composed of vinyl ester monomers such as vinyl acetate in the presence of a chain transfer agent having an amino group, an ammonium group, or a sulfonic acid group. A polyvinyl ester polymer having ammonium groups, ammonium groups, and sometimes sulfonic acid groups is produced. Next, a polymer containing structural unit A can be obtained by saponifying the polymer obtained by the above method.
本発明で使用されるビニルエステルはラジカル重合可能
なビニルエステルであれば使用できる。The vinyl ester used in the present invention can be any vinyl ester that can be radically polymerized.
例えばギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、
ピバリン酸ビニル、パーサティック酸ビニル、ラウリル
酸ビニル、ステアリン酸ビニル等があげられるが、なか
でも酢酸ビニルが最も重合性がよく好ましい。またこれ
らビニルエステルと共重合可能なモノマーを共存させ共
重合することもてきる。例えばエチレン、プロピレン、
イソブチレン、アクリル酸、メタクリル酸ま几はその塩
あるいはこれらのアルキルエステル、アクリロニトリル
、メタクリロニトリル、アクリルアミド、メタクリルア
ミド、エチルビニルエーテル、ブチルビニルエーテル、
N−ビニルピロリドン、塩化ビニル、臭化ビニル、フッ
化ビニル、塩化ビニリデン、フッ化ビニリデン、テトラ
フルオロエチレンなどがあげられる。For example, vinyl formate, vinyl acetate, vinyl propionate,
Examples include vinyl pivalate, vinyl persate, vinyl laurate, and vinyl stearate, among which vinyl acetate is preferred because it has the best polymerizability. Furthermore, monomers copolymerizable with these vinyl esters can be copolymerized. For example, ethylene, propylene,
Isobutylene, acrylic acid, methacrylic acid, their salts or alkyl esters thereof, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, ethyl vinyl ether, butyl vinyl ether,
Examples include N-vinylpyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene.
本発明において使用される連鎖移動剤としては、アミノ
基、アンモニウム基またはスルホン酸基を含有するもの
であれば、特に制限はないが、なかでも以下の連鎖移動
剤か好適に用いられる。The chain transfer agent used in the present invention is not particularly limited as long as it contains an amino group, an ammonium group, or a sulfonic acid group, but among them, the following chain transfer agents are preferably used.
アミノ基またはアンモニウム基を含有する連鎖移動剤の
具体例な例としては以下のものが挙げられる。Specific examples of chain transfer agents containing an amino group or an ammonium group include the following.
に゛
およびこの四級化物
バ
およびこの四級化物
るいはアンモニウム窒素原子と(1)式中のアミド基の
窒素原子あるいは(I[[)式中の酸素原子とを連結す
る基をそれぞれ示す。)
またスルホン酸基を含有する連鎖移動剤の具体的な例と
しては以下のものが挙げられる。and a group connecting the quaternized compound or ammonium nitrogen atom with the nitrogen atom of the amide group in the formula (1) or the oxygen atom in the formula (I[[), respectively. ) Specific examples of chain transfer agents containing sulfonic acid groups include the following.
R3CHz−CHCoo (Ct(−)n SO3
M (V’ b)およびこの四級化物
p!
およびこの四級化物
(ここてnは0〜3、mは1〜10. R’、 R3,
R6,R’R8は水素原子またはメチル基、R’、 R
5は低級アルキル基(置換基を含んでもよい)、xはア
ンモニウム窒素と塩を形成する陰性の基、Lはアミノあ
(ここでR11は低級のアルキル基、Rlo、 R1+
は水素原子またはメチル基、nは2〜4、Mは水素原子
、アルカリ金属またはアンモニウムイオンをそれぞれ示
す。)
本発明のアミノ基、アンモニウム基またはスルホン酸基
を有する連鎖移動剤の存在下の酢酸ビニル等のビニルエ
ステル類モノマーを主体とするビニル系モノマーの重合
はラジカル重合開始剤の存在下、塊状重合法、溶液重合
法、パール重合法、乳化重合法などいずれの方法でも行
なうことができるが、メタノールを溶媒とする溶液重合
法が工業的には最も有利である。重合中に存在させる連
鎖移動剤の重合系への添加量、添加方法には特に制限は
なく、目的とするポリビニルエステル系重合体の物性値
によって適宜決定されるべきものである。重合方法とし
ては回分式、半連続式、連続式等公知の方法を採用しう
る。R3CHz-CHCoo (Ct(-)n SO3
M (V′ b) and its quaternized product p! and its quaternized product (where n is 0 to 3, m is 1 to 10. R', R3,
R6, R'R8 are hydrogen atoms or methyl groups, R', R
5 is a lower alkyl group (which may contain a substituent), x is a negative group that forms a salt with ammonium nitrogen, L is amino (here, R11 is a lower alkyl group, Rlo, R1+
represents a hydrogen atom or a methyl group, n represents 2 to 4, and M represents a hydrogen atom, an alkali metal or an ammonium ion, respectively. ) The polymerization of vinyl monomers mainly composed of vinyl ester monomers such as vinyl acetate in the presence of a chain transfer agent having an amino group, an ammonium group, or a sulfonic acid group according to the present invention is carried out in the presence of a radical polymerization initiator, resulting in bulk polymerization. Although the polymerization can be carried out by any method such as legal polymerization, solution polymerization, pearl polymerization, or emulsion polymerization, solution polymerization using methanol as a solvent is industrially most advantageous. There are no particular limitations on the amount and method of addition of the chain transfer agent present in the polymerization system, and should be appropriately determined depending on the physical properties of the intended polyvinyl ester polymer. As the polymerization method, known methods such as batch, semi-continuous, and continuous methods can be employed.
ラジカル重合開始剤としては2.2′−アゾビスイソブ
チロニトリル、過酸化ベンゾイル、過酸化カーボネート
等公知のラジカル重合開始剤が使用できるが、2.2’
−アゾビスイソブチロニトリル等のアゾ系開始剤が取扱
いやすく好ましい。また放射線、電子線等も使用するこ
とができる。重合温度は使用する開始剤の種類により適
当な温度を採用することが望ましいが、通常30〜9a
℃の範囲から選ばれる。As the radical polymerization initiator, known radical polymerization initiators such as 2.2'-azobisisobutyronitrile, benzoyl peroxide, and carbonate peroxide can be used, but 2.2'
- Azo initiators such as azobisisobutyronitrile are preferred because they are easy to handle. Furthermore, radiation, electron beams, etc. can also be used. It is desirable to adopt an appropriate polymerization temperature depending on the type of initiator used, but it is usually 30-9a.
Selected from the range of °C.
所定時間重合した後未重合のビニルエステル類モノマー
を通常の方法で除去することにより末端にアミノ基、ア
ンモニウム基またはスルホン酸基を有するポリビニルエ
ステル系重合体かえられる。After polymerization for a predetermined period of time, unpolymerized vinyl ester monomers are removed by a conventional method to obtain a polyvinyl ester polymer having an amino group, an ammonium group, or a sulfonic acid group at the terminal end.
次に構造単位Aを有するポリビニルアルコール系重合体
を得るためには、このようにし−で得られたポリビニル
エステル系重合体を常法によりけん化することにより得
られるか、通常重合体をアルコール溶液とりわけメタノ
ール溶液とし実施するのが有利である。アルコールは無
水物のみならず少量の含水系のものも目的に応じて用い
られ、また酢酸メチル、酢酸エチルなどの有機溶媒を任
意に含有せしめてもよい。けん化温度は通常10〜70
℃の範囲から選ばれる。けん化触媒としては、水酸化ナ
トリウム、水酸化カリウム、ナトリウムメチラート、カ
リウムメチラート等のアルカリ性触媒が好ましく、該触
媒の使用量はけん化度の大小および水分量等により適宜
法められるが、ビニルエステル単位に対しモル比で0.
001以上、好ましくは0.002以上用いることが望
ましい。一方アルカリ量が多くなりすぎると残存アルカ
リをポリマー中より除去することが困難となり、ポリマ
ーが着色する等好ましくなく、モル比で0.2以下にす
ることが望ましい。但し、構造単位Bがピバリン酸ビニ
ルの場合にはモル比を高めにして酸素を除去してけん化
するのが好ましL)。なおポリビニルエステル系重合体
中にカルボキシル基やそのエステル基等アルカリ触媒と
反応し、アルカリを消費する成分が共重合含有されてい
る場合は、その分量を加えた量のアルカリ触媒を使用す
る必要がある。Next, in order to obtain a polyvinyl alcohol polymer having the structural unit A, the polyvinyl ester polymer thus obtained can be saponified by a conventional method, or the polyvinyl ester polymer can be obtained by saponifying the polyvinyl ester polymer having the structural unit A in an alcohol solution. Preferably, it is carried out as a methanol solution. Not only anhydrous alcohols but also those containing a small amount of water can be used depending on the purpose, and organic solvents such as methyl acetate and ethyl acetate may be optionally contained. Saponification temperature is usually 10-70
Selected from the range of °C. As the saponification catalyst, alkaline catalysts such as sodium hydroxide, potassium hydroxide, sodium methylate, and potassium methylate are preferable. 0. molar ratio to unit.
It is desirable to use 0.001 or more, preferably 0.002 or more. On the other hand, if the amount of alkali is too large, it will be difficult to remove the residual alkali from the polymer, and the polymer will be colored, which is undesirable, so it is desirable that the molar ratio is 0.2 or less. However, when the structural unit B is vinyl pivalate, it is preferable to increase the molar ratio and remove oxygen for saponification (L). In addition, if the polyvinyl ester polymer contains copolymerized components such as carboxyl groups and their ester groups that react with alkali catalysts and consume alkali, it is necessary to use the amount of alkali catalyst in addition to that amount. be.
けん化反応後、析出した重合体は例えばメタノールで洗
浄する等公知の方法で精製し、残存アルカリ、酢酸アル
カリ金属塩等の不純物を除去して乾燥することにより通
常白色粉末としてえることができる。After the saponification reaction, the precipitated polymer is purified by a known method, such as washing with methanol, to remove impurities such as residual alkali and alkali metal salts of acetate, and then dried to obtain a usually white powder.
Uエム
以下に実施例を挙げて本発明を具体的に説明するが本発
明はこれらによって同等限定されるものではない。The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to the same extent by these.
なお実施例中「部」および「%」は特にことわりのない
限り、いずれも重量基準を意味する。In the examples, "parts" and "%" are based on weight unless otherwise specified.
実施例1
酢酸ビニル(以下VAcと略記する) 2BoO部、メ
タ/−ル69D部および)l S +c Hz 井N
(CH−) 3CρD、 23部を反応容器にとり、内
部を充分に窒素置換した後、外温を65℃にあげ、内温
か60°Cに達したところで、2.2°−アゾヒスイソ
ブチロニトリル1.1部を含むメタノール10部を加え
た。直ちにH3BHth−N(CH3)3C45,を部
を含むメタノール50部を4時間にわたって均一に加え
た。4時間後の重合率は65%であった。4時間後に容
器を冷却し、減圧下に残留するVAcをメタノールとと
もに系外に追い出す操作をメタノールを追加しながら行
ない ポリ酢酸ビニル(以下PVA cと略記する)の
メタノール溶液(濃度70%)を得た。このメタノール
溶液の一部をとり、PVAc濃度30%、[NaO[/
C酢酸ビニル単位]= l)、01 (モル比)とな
るようにNaOHのメタノール溶液を加え、40 ℃て
けん化して、けん化度95モル%のポリビニルアルコー
ル(以下PVAと略記する)を得た。Example 1 Vinyl acetate (hereinafter abbreviated as VAc) 2 parts of BoO, 69 parts of methanol and )l S +c Hz well N
(CH-) 3CρD, 23 parts were placed in a reaction vessel, the inside was sufficiently purged with nitrogen, the external temperature was raised to 65°C, and when the internal temperature reached 60°C, 2.2°-Azohisisobutyronitrile was added. 10 parts of methanol containing 1.1 parts were added. Immediately, 50 parts of methanol containing 1 part of H3BHth-N(CH3)3C45 was added uniformly over 4 hours. The polymerization rate after 4 hours was 65%. After 4 hours, the container was cooled and the remaining VAc was expelled from the system together with methanol under reduced pressure while adding methanol to obtain a methanol solution (concentration 70%) of polyvinyl acetate (hereinafter abbreviated as PVA c). Ta. A portion of this methanol solution was taken, and the PVAc concentration was 30%, [NaO[/
C vinyl acetate units] = l), 01 (mole ratio), a methanol solution of NaOH was added and saponified at 40 °C to obtain polyvinyl alcohol (hereinafter abbreviated as PVA) with a saponification degree of 95 mol%. .
PVAの重合度をけん化後のPVAを精製後、再アセチ
ル化して得たPVAcのアセトン中の極限粘度「ηコよ
り中島式(中島章夫 高分子化学6451(1949)
)で計算する方法で測定したところ、重合度は305て
あった。The degree of polymerization of PVA is determined by the Nakajima formula (Akio Nakajima, Kobunshi Kagaku 6451 (1949)).
), the degree of polymerization was 305.
上記PVAを少量の水を含む酢酸メチルで還流下に洗浄
し、メタノールで48時間ソックスレー抽出による精製
を行なった後、重水に溶解し、核磁気共鳴分析(以下N
MRと略記する)を行なった。The PVA was washed under reflux with methyl acetate containing a small amount of water, purified by Soxhlet extraction with methanol for 48 hours, dissolved in heavy water, and subjected to nuclear magnetic resonance analysis (hereinafter referred to as N
(abbreviated as MR) was performed.
これにより、末端にアンモニウム基の存在が認められ、
重合機構も合せ考えると分子の片末端に5BH2丹N(
CH3)、CQのアンモニウ基を有するPVAであるこ
とが確認できた。This confirmed the presence of an ammonium group at the end,
Considering the polymerization mechanism, 5BH2N(
It was confirmed that the product was PVA having an ammonium group of CH3) and CQ.
上記PVAcを部分けん化し、けん化度72モル%のポ
リビニルアルコール系重合体を得た。この0.4%水溶
液の分点を目視により測定すると、58℃であった。The above PVAc was partially saponified to obtain a polyvinyl alcohol polymer with a saponification degree of 72 mol%. When the equinox point of this 0.4% aqueous solution was visually measured, it was 58°C.
実施例2
ピバリン酸ビニル2800部、メタノール690部およ
びH3−CH(CH3)−C00B)[2)2− SO
3Na O,07部を反応容器にとり、内部を充分に窒
素置換した後、外温を65℃にあげ、内温が60℃に達
したところで、2.2°−アゾヒスイソブチロニトリル
20部を含むメタノール10部を加えた。直ちに
)Is CH(CL)−COOBHt′+rSOJa
1.15wJを含ムメタノール50部を4時間にわた
って均一に加えた。4時間後の重合率は65%であった
。4時間後に容器を冷却し、減圧下に残留するピバリン
酸ビニルをメタノールとともに系外に追い出す操作をテ
トラヒドロフランを追加しながら行ない、ポリピバリン
酸ビニルのテトラヒドロフラン溶液(濃度15%)を得
た。このテトラヒドロフラン溶液の一部をとりポリピバ
リン酸ビニル濃度15%、[Na0)[]/ [ピバリ
ン酸ビニル単位]= 0.8 (モル比)となるように
NaOHのメタノール溶液を加え、40℃でけん化して
、けん化度98モル%のPVAを得た。Example 2 2800 parts of vinyl pivalate, 690 parts of methanol and H3-CH(CH3)-C00B) [2) 2-SO
After placing 0.7 parts of 3NaO in a reaction vessel and thoroughly purging the inside with nitrogen, the external temperature was raised to 65°C, and when the internal temperature reached 60°C, 20 parts of 2.2°-azohisisobutyronitrile was added. 10 parts of methanol were added. Immediately) Is CH(CL)-COOBHt'+rSOJa
50 parts of methanol containing 1.15 wJ was added uniformly over 4 hours. The polymerization rate after 4 hours was 65%. After 4 hours, the container was cooled and the remaining vinyl pivalate was expelled from the system together with methanol under reduced pressure while adding tetrahydrofuran to obtain a solution of polyvinyl pivalate in tetrahydrofuran (concentration 15%). A methanol solution of NaOH was added to a portion of this tetrahydrofuran solution so that the polyvinyl pivalate concentration was 15%, [Na0)[]/[vinyl pivalate unit] = 0.8 (molar ratio), and the solution was quenched at 40°C. PVA with a saponification degree of 98 mol% was obtained.
PVAの重合度を実施例1と同様の方法で測定したとこ
ろ、重合度は1000であった。When the degree of polymerization of PVA was measured in the same manner as in Example 1, the degree of polymerization was 1000.
上記PVAを少量の水を含む酢酸メチルで還流下に洗浄
し、メタノールで48時間ソックスレー抽出による精製
を行なった後、D、−DMSOに溶解し、NMR分析を
行なった。これにより、末端にスルホン酸基の存在か認
められ、重合機構ら合せ考えると分子の片末端に
−S −CH4−C)l 3) −C00e(:H2′
h−8O,teaのスルホン酸基を有するPVAである
ことか確認できた。The PVA was washed under reflux with methyl acetate containing a small amount of water, purified by Soxhlet extraction with methanol for 48 hours, and then dissolved in D,-DMSO and subjected to NMR analysis. As a result, the presence of a sulfonic acid group at the terminal was confirmed, and considering the polymerization mechanism, -S -CH4-C)l 3) -C00e(:H2'
It was confirmed that it was PVA having h-8O, tea sulfonic acid groups.
上記ポリピバリン酸ビニルを部分けん化し、けん化度6
2モル%のポリビニルアルコール系重合体を得た。この
04%水溶液の分点を目視により測定すると、65℃で
あっf二。The above polyvinyl pivalate was partially saponified, and the degree of saponification was 6.
A 2 mol % polyvinyl alcohol polymer was obtained. When the equinox of this 04% aqueous solution was visually measured, it was 65°C.
実施例3
パーサティック酸ビニル2800部、メタノール690
部およびHS (−CH、+rN (Cf(、) 3C
Q 0 、005 mを反応容器にとり、内部を充分に
窒素置換した後、外温を65°Cにあげ、内温か606
Cに達したところで、2.2−アゾビスイソブチロニト
リル185部を含むメタノール10部を加えた。直ちに
HS B H2’rrN (C)i 3 ) s C(
10,02部を含むメタノール20部を2時間にわたっ
て均一に加えた。2時間後の重合率は32%であった。Example 3 Vinyl persate 2800 parts, methanol 690
and HS (-CH, +rN (Cf(,) 3C
After placing Q 0 , 005 m in a reaction vessel and purging the inside sufficiently with nitrogen, the external temperature was raised to 65°C, and the internal temperature was 606°C.
When the temperature reached C, 10 parts of methanol containing 185 parts of 2,2-azobisisobutyronitrile was added. Immediately HS B H2'rrN (C)i 3 ) s C(
20 parts of methanol containing 10.02 parts were added uniformly over a period of 2 hours. The polymerization rate after 2 hours was 32%.
2時間後に容器を冷却し、減圧下に残留するメタノール
を系外に追い出す操作を行ない、ポリバーサチック酸ビ
ニルのメタノール溶液(濃度70%)を得た。このメタ
ノール溶液の一部をとりポリバーサチック酸ビニル濃度
30%、[NaOH]/ [バーサチック酸ビニル単位
]= 0.01 (モル比)となるようにNa0)1の
メタノール溶液を加え、4 D ’Cでけん化して、け
ん化度96モル%のPVAを得た。After 2 hours, the container was cooled and residual methanol was expelled from the system under reduced pressure to obtain a methanol solution (70% concentration) of vinyl polyversate. To a part of this methanol solution, add a methanol solution of Na0)1 so that the concentration of vinyl polyversatate is 30%, [NaOH] / [vinyl versatate unit] = 0.01 (molar ratio), and 4D It was saponified with 'C to obtain PVA with a saponification degree of 96 mol%.
PVAの重合度を実施例1と同様の方法で測定したとこ
ろ、重合度は2050であった。The degree of polymerization of PVA was measured in the same manner as in Example 1, and was found to be 2,050.
上記PVAを少量の水を含む酢酸メチルで還流下に洗浄
し、メタノールで48時間ソックスレー抽出による精製
を行なった後、重水に溶解し、NMR分析を行なった。The PVA was washed under reflux with methyl acetate containing a small amount of water, purified by Soxhlet extraction with methanol for 48 hours, then dissolved in heavy water and subjected to NMR analysis.
これにより、末端にアンモニウム基の存在が認められ、
重合機構も合せ考えると分子の片末端ニ5kHz′+r
N(CH3)3c((” 7 ンモニウム基を有するP
VAであることが確認できた。This confirmed the presence of an ammonium group at the end,
Considering the polymerization mechanism, one end of the molecule is 5kHz'+r.
N(CH3)3c((” 7 P with ammonium group
It was confirmed that it was VA.
上記ポリバーサチック酸ビニルを部分けん化し、けん化
度80モル%のポリビニルアルコール系重合体を得た。The above vinyl polyversatate was partially saponified to obtain a polyvinyl alcohol polymer with a saponification degree of 80 mol%.
この0.4%水溶液の分点を目視により測定すると83
℃であつ1こ。Visually measuring the equinox of this 0.4% aqueous solution, it was 83.
℃ and 1 piece.
実施例4〜■6
実施例1〜3と同様の方法で、種々の連鎖移動剤を用い
重合を行ない次いてsMR測定により、片末端にアミノ
基、アンモニウム基またはスルホン酸基が導入されてい
ることを確認しに。次にこれをけん化することによりポ
リビニルアルコール系重合体を得た。Examples 4 to 6 In the same manner as in Examples 1 to 3, an amino group, an ammonium group, or a sulfonic acid group was introduced at one end by polymerization using various chain transfer agents, and then by sMR measurement. To make sure. Next, this was saponified to obtain a polyvinyl alcohol polymer.
ざらにこれらの重合体の0.4%水溶液の分点を目視に
より測定した。結果を表1に示した。Roughly, the equinox points of 0.4% aqueous solutions of these polymers were visually measured. The results are shown in Table 1.
以下余白 実施例17 実施例1〜3と同様の方法で、 CH。Margin below Example 17 In the same manner as Examples 1 to 3, CH.
H3EHI)、C0NH−C−C)I、SO3NaH3
を連鎖移動剤に用いて酢酸ビニルの重合を用い、けん化
することにより、末端にスルホン酸基を有する重合度2
400、けん化度71モル%のポリビニルアルコール系
重合体を得た。H3EHI), C0NH-C-C)I, SO3NaH3 is used as a chain transfer agent to polymerize vinyl acetate, and by saponification, a polymerization degree of 2 with a sulfonic acid group at the terminal is obtained.
400, and a polyvinyl alcohol polymer having a saponification degree of 71 mol% was obtained.
得られたポリビニルアルコールをり、−DMSOに溶解
し、NMR分析を行ったところ末端にスルホン酸基の存
在か確認された。The obtained polyvinyl alcohol was dissolved in -DMSO and subjected to NMR analysis, which confirmed the presence of a sulfonic acid group at the end.
この重合体の濃度04%水溶液の曇点を目視により測定
したところ、85°Cてあった。The cloud point of a 04% aqueous solution of this polymer was visually measured and found to be 85°C.
以下余白
几−一魚ヱし乞勿」L
本発明のポリビニルアルコール系重合体は、曇点か高い
ために、均一な水溶液か得られ、分散性能も高く、工業
的な価値が極めて高い。さらに、本発明のポリビニルア
ルコール系重合体は、従来からの用途たとえば紙加工、
繊維加工等に用いてもその効果を充分に発揮する。Since the polyvinyl alcohol polymer of the present invention has a high clouding point, a uniform aqueous solution can be obtained and its dispersion performance is also high, so that it has extremely high industrial value. Furthermore, the polyvinyl alcohol polymer of the present invention can be used in conventional applications such as paper processing,
It fully exhibits its effects even when used in textile processing, etc.
実施例17におけるポリビニルアルコール系重合体のN
MRスペクトルを第1図に示す。
特許出願人 株式会社 り ラ しN of the polyvinyl alcohol polymer in Example 17
The MR spectrum is shown in FIG. Patent applicant RiRa Shi Co., Ltd.
Claims (7)
度が3500以下で末端にアミノ基、アンモニウム基ま
たはスルホン酸基を含有するポリビニルアルコール系重
合体。 A:▲数式、化学式、表等があります▼(1) A polyvinyl alcohol polymer containing 50 mol% or more of the following structural unit A, a degree of polymerization of 3500 or less, and an amino group, ammonium group, or sulfonic acid group at the end. A: ▲There are mathematical formulas, chemical formulas, tables, etc.▼
項1記載のポリビニルアルコール系重合体。 B:▲数式、化学式、表等があります▼ (ここでR^1はHまたは炭素数1から20までの炭化
水素基をあらわす。)(2) The polyvinyl alcohol polymer according to claim 1, which contains less than 50 mol% of the following structural unit B. B: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R^1 represents H or a hydrocarbon group with 1 to 20 carbon atoms.)
のポリビニルアルコール系重合体。(3) The polyvinyl alcohol polymer according to claim 2, wherein the structural unit B is a vinyl acetate unit.
2記載のポリビニルアルコール系重合体。(4) The polyvinyl alcohol polymer according to claim 2, wherein the structural unit B is a vinyl pivalate unit.
1または2記載のポリビニルアルコール系重合体。(5) The polyvinyl alcohol polymer according to claim 1 or 2, wherein the content of structural unit A is 70 mol% or more.
有する連鎖移動剤の存在下にビニルエステル類モノマー
を主体とするビニル系モノマーを重合して得たポリビニ
ルエステル系重合体をけん化することを特徴とする請求
項1または2記載のポリビニルアルコール系重合体の製
造法。(6) A polyvinyl ester polymer obtained by polymerizing vinyl monomers mainly consisting of vinyl ester monomers in the presence of a chain transfer agent having an amino group, an ammonium group, or a sulfonic acid group is saponified. The method for producing a polyvinyl alcohol polymer according to claim 1 or 2.
ルホン酸基を有するチオールである請求項6記載のポリ
ビニルアルコール系重合体の製造法。(7) The method for producing a polyvinyl alcohol polymer according to claim 6, wherein the chain transfer agent is a thiol having an amino group, an ammonium group, or a sulfonic acid group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2223226A JP2989644B2 (en) | 1990-04-04 | 1990-08-23 | Polyvinyl alcohol polymer and method for producing the same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9129590 | 1990-04-04 | ||
JP2-91295 | 1990-04-04 | ||
JP2223226A JP2989644B2 (en) | 1990-04-04 | 1990-08-23 | Polyvinyl alcohol polymer and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0411601A true JPH0411601A (en) | 1992-01-16 |
JP2989644B2 JP2989644B2 (en) | 1999-12-13 |
Family
ID=26432756
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Application Number | Title | Priority Date | Filing Date |
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JP2223226A Expired - Lifetime JP2989644B2 (en) | 1990-04-04 | 1990-08-23 | Polyvinyl alcohol polymer and method for producing the same |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1384730A1 (en) * | 2002-07-23 | 2004-01-28 | Kuraray Co., Ltd. | Polyvinyl acetal and its use |
EP1369439A4 (en) * | 2001-01-25 | 2005-04-06 | Sekisui Chemical Co Ltd | Polyvinyl acetal, polyvinyl acetal composition, ink, coating material, dispersant, heat-developable photosensitive material, ceramic green sheet, primer for plastic lens, recording agent for water-based ink, and adhesive for metal foil |
-
1990
- 1990-08-23 JP JP2223226A patent/JP2989644B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1369439A4 (en) * | 2001-01-25 | 2005-04-06 | Sekisui Chemical Co Ltd | Polyvinyl acetal, polyvinyl acetal composition, ink, coating material, dispersant, heat-developable photosensitive material, ceramic green sheet, primer for plastic lens, recording agent for water-based ink, and adhesive for metal foil |
EP1384730A1 (en) * | 2002-07-23 | 2004-01-28 | Kuraray Co., Ltd. | Polyvinyl acetal and its use |
Also Published As
Publication number | Publication date |
---|---|
JP2989644B2 (en) | 1999-12-13 |
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