JPS6233241B2 - - Google Patents
Info
- Publication number
- JPS6233241B2 JPS6233241B2 JP14860479A JP14860479A JPS6233241B2 JP S6233241 B2 JPS6233241 B2 JP S6233241B2 JP 14860479 A JP14860479 A JP 14860479A JP 14860479 A JP14860479 A JP 14860479A JP S6233241 B2 JPS6233241 B2 JP S6233241B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- parts
- polymerization
- alcohol
- vinyl
- 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
Links
- 229920001577 copolymer Polymers 0.000 claims description 54
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 22
- 229920001567 vinyl ester resin Polymers 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229910052783 alkali metal Chemical group 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 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 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000001340 alkali metals Chemical group 0.000 claims description 7
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000007870 radical polymerization initiator Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 120
- 238000006116 polymerization reaction Methods 0.000 description 34
- 239000000243 solution Substances 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000007127 saponification reaction Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 125000001174 sulfone group Chemical group 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- -1 Olefin sulfonic acid salts Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BWFJQOYMXHEGNQ-UHFFFAOYSA-M potassium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C BWFJQOYMXHEGNQ-UHFFFAOYSA-M 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical group [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 2
- ZLHDYZWYTZWPOO-UHFFFAOYSA-M sodium;butane-2-sulfonate Chemical compound [Na+].CCC(C)S([O-])(=O)=O ZLHDYZWYTZWPOO-UHFFFAOYSA-M 0.000 description 2
- VSSGDAWBDKMCMI-UHFFFAOYSA-N 2-methyl-2-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)NC(C)(C)CS(O)(=O)=O VSSGDAWBDKMCMI-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- DMLOUIGSRNIVFO-UHFFFAOYSA-N 3-(prop-2-enoylamino)butane-2-sulfonic acid Chemical compound OS(=O)(=O)C(C)C(C)NC(=O)C=C DMLOUIGSRNIVFO-UHFFFAOYSA-N 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VPNMZHXSIDMXTM-UHFFFAOYSA-N C(CC)S(=O)(=O)OC.[Na] Chemical compound C(CC)S(=O)(=O)OC.[Na] VPNMZHXSIDMXTM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- VXJPCEOTZNHHOA-UHFFFAOYSA-N [K].OC Chemical compound [K].OC VXJPCEOTZNHHOA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- NONFLFDSOSZQHR-CQOLUAMGSA-N d4-trimethyl silyl propionic acid Chemical compound OC(=O)C([2H])([2H])C([2H])([2H])[Si](C)(C)C NONFLFDSOSZQHR-CQOLUAMGSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 102000035118 modified proteins Human genes 0.000 description 1
- 108091005573 modified proteins Proteins 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- VYXIHUMXWWDVQH-UHFFFAOYSA-M potassium;butane-2-sulfonate Chemical compound [K+].CCC(C)S([O-])(=O)=O VYXIHUMXWWDVQH-UHFFFAOYSA-M 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- MKAXISKDFRQLBH-UHFFFAOYSA-M sodium;2-methylpropane-1-sulfonate Chemical compound [Na+].CC(C)CS([O-])(=O)=O MKAXISKDFRQLBH-UHFFFAOYSA-M 0.000 description 1
- SQSAJLXDUSFNKX-UHFFFAOYSA-M sodium;3-(prop-2-enoylamino)butane-2-sulfonate Chemical group [Na+].[O-]S(=O)(=O)C(C)C(C)NC(=O)C=C SQSAJLXDUSFNKX-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
Description
【発明の詳細な説明】
本発明は新規なポリビニルアルコール系共重合
体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel polyvinyl alcohol copolymer.
更に詳しくはビニルエステルと次式（）で示
される重合性単量体をアルコールの存在下でラジ
カル重合開始剤を用いて共重合させ、しかる後に
該共重合体のアルコール溶液にアルカリあるいは
酸触媒を作用させて共重合体中のビニルエステル
単位を部分的にあるいは高度にケン化せしめビニ
ルアルコール単位とすることを特徴とする新規な
ポリビニルアルコール系共重合体の製造方法に関
する。 More specifically, vinyl ester and a polymerizable monomer represented by the following formula () are copolymerized using a radical polymerization initiator in the presence of alcohol, and then an alkali or acid catalyst is added to the alcohol solution of the copolymer. The present invention relates to a method for producing a novel polyvinyl alcohol copolymer, which is characterized by partially or highly saponifying the vinyl ester units in the copolymer to convert them into vinyl alcohol units.
（ここで、R1は水素原子または低級アルキル
基、R2はアルキル基、R3、R4、R5は水素原子ま
たはアルキル基、Ｍは水素またはアルカリ金属を
それぞれ意味している。）
ポリビニルアルコール（以下PVAと略記す
る）は従来より代表的な合成高分子として知ら
れ、合成繊維ビニロン原料としてあるいは糊剤と
して広範囲な工業的用途で用いられている。その
中で製紙工業においては表面サイジングなどのク
リヤーコーテイング、あるいは顔料コーテイング
におけるバインダーなどの紙のコーテイング剤と
して使用されており、PVAは強度および造膜性
においては他の糊剤の追随を許さぬ優れた性能を
有することが広く知られている。しかるに一方、
PVAをコーテイング剤に用いて製造した塗工紙
において、しばしばパターンとも称する塗工むら
が発生することがある。この欠点は高速度で塗工
したとき、PVAの濃度が高いとき、あるいはク
レーなどの顔料が共存するときなどに顕著に現わ
れ、高い剪断力下における糊液の流動性に関係が
あると考えられるが、その発生機構の詳細はよく
わかつていない。この欠点に対する対策として、
糊剤に流動性を改善する各種の添加剤が検討され
たが充分な性能を与えるものはなく、また特公昭
44―5331号、特公昭46―7605号あるいは特公昭46
―7606号において、PVAの分子中にカルボキシ
ル基あるいはアミド基を導入せしめることにより
流動性を改良した紙用コーテイング剤の技術が開
示されているが実用的にはその効果はなお充分で
なく、流動性に関係したかかる欠点を改良し前述
したPVA本来の優れた性能を利用したいという
強い工業的要望がある。 (Here, R 1 is a hydrogen atom or a lower alkyl group, R 2 is an alkyl group, R 3 , R 4 and R 5 are a hydrogen atom or an alkyl group, and M is hydrogen or an alkali metal.) Polyvinyl Alcohol (hereinafter abbreviated as PVA) has been known as a typical synthetic polymer, and is used in a wide range of industrial applications as a raw material for vinylon synthetic fibers or as a sizing agent. In the paper manufacturing industry, it is used as a coating agent for paper, such as clear coatings for surface sizing, or binders for pigment coatings, and PVA has superior strength and film-forming properties that are unrivaled by other adhesives. It is widely known that it has excellent performance. However, on the other hand,
In coated paper manufactured using PVA as a coating agent, coating unevenness, also called a pattern, sometimes occurs. This drawback becomes more noticeable when coating at high speeds, when the concentration of PVA is high, or when pigments such as clay coexist, and is thought to be related to the fluidity of the size solution under high shear forces. However, the details of its mechanism of occurrence are not well understood. As a countermeasure to this shortcoming,
Various additives have been investigated to improve the fluidity of adhesives, but none have provided sufficient performance.
No. 44-5331, Special Publication No. 7605 or Special Publication No. 1973
- No. 7606 discloses a technology for a paper coating agent that improves fluidity by introducing a carboxyl group or an amide group into the PVA molecule, but the effect is still insufficient for practical use. There is a strong industrial desire to improve upon such disadvantages related to the properties of PVA and to take advantage of the above-mentioned excellent properties inherent in PVA.
本発明者はかかる欠点を改良すべく鋭意研究し
た結果、分子中にスルホン基を導入せしめた変性
PVAを紙用コーテイング剤として用いるときは
該変性PVAを含む塗工液による塗工状態は従来
のPVA系と比較し顕著に改良され得るという事
実を見出した。この知見は従来全く知られていな
い新規なものであつたが、当初採用したスルホン
基の導入法は性能に不満があるかまたは製造コス
トが高価で工業的には実際的ではなかつた。従来
より知られているPVAのスルホン化方法として
はPVAと濃硫酸を反応させる方法、PVAを臭
素、ヨウ素等で酸化処理した後に酸性亜硫酸ソー
ダ水溶液と反応させる方法、あるいはPVAとス
ルホン基を有するアルデヒド化合物を酸触媒下で
反応させスルホアセタール化する方法など後変性
の方法が知られているが、これらは実験室では可
能であるが工業的には工程が複雑で高価であり実
用的でない。また、エチレンスルホン酸、アリル
スルホン酸、メタリルスルホン酸等のオレフイン
スルホン酸またはその塩と酢酸ビニルとを共重合
せしめた後、ケン化反応によりスルホン基を含有
した変性PVAを製造し得ることも知られてお
り、こうして得られた変性PVAも流動性改良効
果が見られるが、次の点で性能および経済性に難
点がある。(1)オレフインスルホン酸の塩はアルコ
ールおよび酢酸ビニルに対する溶解度が低く溶液
重合を好条件で実施することが困難である。(2)オ
レフインスルホン酸あるいはその塩と酢酸ビニル
との共重合速度が極めて遅くまた重合度が低下す
る傾向が強く、経済性、物性上好ましくない。(3)
オレフインスルホン酸が高価である。また、別の
スルホン基含有単量体としてスルホアルキル（メ
タ）アクリル酸エステルやスルホアルキルマレイ
ン酸エステルなども知られているが、これらは酢
酸ビニルとの共重合は可能であるがその共重合体
をケン化する時はスルホン基含有単量体中のエス
テル結合も同時にケン化され、生成したPVA中
にスルホン基を含有せしめることができない。 As a result of intensive research to improve this drawback, the present inventor has developed a modified protein that introduces a sulfone group into the molecule.
It has been found that when PVA is used as a coating agent for paper, the coating condition of a coating liquid containing the modified PVA can be significantly improved compared to conventional PVA systems. This finding was completely new and previously unknown, but the method of introducing sulfone groups that was initially adopted was either unsatisfactory in performance or expensive to produce, and was not industrially practical. Conventionally known methods for sulfonating PVA include reacting PVA with concentrated sulfuric acid, oxidizing PVA with bromine, iodine, etc. and then reacting it with an acidic sodium sulfite aqueous solution, or reacting PVA with an aldehyde having a sulfonic group. Post-modification methods are known, such as a method in which a compound is reacted in the presence of an acid catalyst to form a sulfoacetal, but although these methods are possible in the laboratory, they are complicated and expensive and are not practical for industrial use. Furthermore, after copolymerizing olefin sulfonic acid or its salt such as ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, and vinyl acetate, a modified PVA containing a sulfonic group can be produced by a saponification reaction. Although the modified PVA obtained in this way has the effect of improving fluidity, it has the following drawbacks in terms of performance and economy. (1) Olefin sulfonic acid salts have low solubility in alcohol and vinyl acetate, making it difficult to perform solution polymerization under favorable conditions. (2) The copolymerization rate of olefin sulfonic acid or its salt and vinyl acetate is extremely slow, and the degree of polymerization tends to decrease, which is unfavorable from an economic standpoint and physical properties. (3)
Olefin sulfonic acid is expensive. In addition, sulfoalkyl (meth)acrylic acid esters and sulfoalkyl maleic esters are known as other sulfonic group-containing monomers, but although these can be copolymerized with vinyl acetate, their copolymers are When saponifying PVA, the ester bonds in the sulfonic group-containing monomer are also saponified at the same time, making it impossible to contain sulfonic groups in the resulting PVA.
こうしてPVAに工業的有利にスルホン基を導
入することは予想以上に困難であり末だ工業的有
利な方法は見出されていなかつた。本発明者らは
このような状況を踏まえ、安定かつ有効にPVA
にスルホン基を導入せしめる工業的に安価な製造
方法を確立することを目的として探究した結果、
本発明を完成したものであり、本発明に示された
変性PVAである共重合体は従来未知の新規な化
合物である。即ち、本発明の目的はビニルアルコ
ール単位とスルホン基を含む有用かつ製造工業的
実用性を有する共重合体を得ることにある。 Thus, it was more difficult than expected to introduce a sulfone group into PVA in an industrially advantageous manner, and no industrially advantageous method had yet been found. Based on this situation, the present inventors have developed a stable and effective PVA system.
As a result of our research aimed at establishing an industrially inexpensive manufacturing method for introducing sulfone groups into
The present invention has been completed, and the modified PVA copolymer shown in the present invention is a novel compound that was previously unknown. That is, an object of the present invention is to obtain a copolymer containing a vinyl alcohol unit and a sulfone group that is useful and has industrial practicality.
本発明の新規なPVA共重合体は、ビニルエス
テルと次式（）
（ここで、R1は水素原子または低級アルキル
基、R2はアルキル基、R3、R4、R5は水素原子ま
たはアルキル基、Ｍは水素またはアルカリ金属を
それぞれ意味している。）
で示される重合性単量体とをアルコールの存在下
でラジカル重合開始剤を用いて共重合させ、しか
る後に該共重合体のアルコール溶液にアルカリあ
るいは酸触媒を作用させて該共重合体中のビニル
エステル単位を部分的にあるいは高度にケン化せ
しめてビニルアルコール単位とすることにより製
造される。 The novel PVA copolymer of the present invention is composed of vinyl ester and the following formula () (Here, R 1 is a hydrogen atom or a lower alkyl group, R 2 is an alkyl group, R 3 , R 4 and R 5 are a hydrogen atom or an alkyl group, and M is hydrogen or an alkali metal, respectively.) The shown polymerizable monomers are copolymerized using a radical polymerization initiator in the presence of alcohol, and then an alkali or acid catalyst is applied to the alcohol solution of the copolymer to form the vinyl in the copolymer. It is produced by partially or highly saponifying ester units to form vinyl alcohol units.
本発明のPVA系共重合体を製造する際に使用
し得るビニルエステルとしては、酢酸ビニル、プ
ロピオン酸ビニル、ギ酸ビニル等があげられるが
経済的に見て酢酸ビニルが好ましい。また、本発
明で用いられるスルホン基を含有した重合性単量
体は上述した一般式（）で示される。R1は水
素原子または低級アルキル基であるが、通常水素
原子またはメチル基が好ましく、更に、共重合反
応における重合速度が大である点で水素原子であ
ることが特に好ましい。R2はアルキル基である
ことが必要であるが、その理由はアミド結合の安
定性が高く、共重合体のケン化反応において結合
が切れないこと、およびこの形の単量体はその合
成が経済的に有利であることの二点にある。
R2、R3が共に水素原子である単量体はアミド結
合の安定性が低く、ケン化時に結合が切れ易いた
め本発明の対象に含まれない。R3、R4、R5は水
素原子またはアルキル基であるが、このうちR3
は水素原子でなくアルキル基であることがアミド
結合の安定性が高いので好ましい。Ｍは水素また
はアルカリ金属すなわちNa、Ｋ、Liあるいは類
似物としてのNH4を示している。Ｍが水素である
場合、すなわちスルホン基が酸の状態でもビニル
エステルとの共重合は可能であるが、共重合系内
のPHが低下しビニルエステルが分解する傾向が大
となるため、一般的にはスルホン基を部分的ある
いは完全にアルカリにより中和してアルカリ金属
塩としてビニルエステルとの共重合を実施するこ
とが好ましい。アルカリ金属塩の形ではスルホン
基含有単量体のアルコールに対する溶解度が向上
する点も有利である。アルカリ金属のうちNaあ
るいはＫが経済性および性能の上から特に好まし
い。上記のスルホン基を含有する重合性単量体を
重合系に仕込む方法としてアルコール溶液として
仕込むことが実用上有利であるが、この場合の仕
込液の調製方法としては、単量体のアルカリ金属
塩をアルコールに溶解してもよく、あるいは酸形
の単量体を中和当量あるいは部分中和量の水酸化
ナトリウムまたは水酸化カリウムと共にアルコー
ルに溶解する方法も採用され得る。 Vinyl esters that can be used in producing the PVA copolymer of the present invention include vinyl acetate, vinyl propionate, vinyl formate, etc., but vinyl acetate is preferred from an economical standpoint. Moreover, the polymerizable monomer containing a sulfone group used in the present invention is represented by the above-mentioned general formula (). Although R 1 is a hydrogen atom or a lower alkyl group, a hydrogen atom or a methyl group is generally preferred, and a hydrogen atom is particularly preferred since the polymerization rate in the copolymerization reaction is high. R 2 must be an alkyl group because the amide bond is highly stable and the bond does not break during the saponification reaction of the copolymer, and this type of monomer is difficult to synthesize. There are two points: it is economically advantageous.
Monomers in which both R 2 and R 3 are hydrogen atoms are not included in the scope of the present invention because the stability of the amide bond is low and the bond is easily broken during saponification. R 3 , R 4 , and R 5 are hydrogen atoms or alkyl groups, and among these, R 3
is preferably an alkyl group rather than a hydrogen atom because the stability of the amide bond is high. M represents hydrogen or NH 4 as an alkali metal such as Na, K, Li or similar. When M is hydrogen, that is, even when the sulfone group is in an acid state, copolymerization with vinyl ester is possible, but the PH in the copolymerization system decreases and the vinyl ester tends to decompose, so it is generally not possible to copolymerize with vinyl ester. In this case, it is preferable to partially or completely neutralize the sulfonic group with an alkali and copolymerize the alkali metal salt with the vinyl ester. The alkali metal salt form is also advantageous in that the solubility of the sulfonic group-containing monomer in alcohol is improved. Among the alkali metals, Na or K is particularly preferred from the viewpoint of economy and performance. It is practically advantageous to introduce the above-mentioned polymerizable monomer containing a sulfonic group into the polymerization system as an alcohol solution. Alternatively, a method may be adopted in which the acid form monomer is dissolved in alcohol together with a neutralizing equivalent or partially neutralizing amount of sodium hydroxide or potassium hydroxide.
以上述べた構造上の特徴を満足し本発明の目的
に叶つた代表的なスルホン基含有単量体の具体例
として次のものが挙げられる。 The following are specific examples of representative sulfone group-containing monomers that satisfy the above-mentioned structural characteristics and achieve the purpose of the present invention.
２―アクリルアミド―２―メチルプロパンスル
ホン酸またはそのアルカリ金属塩
２―アクリルアミド―１―メチルプロパンスル
ホン酸またはそのアルカリ金属塩
２―メタクリルアミド―２―メチルプロパンス
ルホン酸またはそのアルカリ金属塩
このうち２―アクリルアミド―２―メチルプロ
パンスルホン酸またはそのアルカリ金属塩は工業
的製造が比較的安価であること、ビニルエステル
ことに酢酸ビニルとの共重合速度が速くまた高重
合度の共重合体の合成が可能であること、アミド
結合の安定性がとりわけ高いこと、さらにケン化
せしめた水溶性共重合体の目的とした性能が高い
ことなど特に本発明の目的に合致して好ましい。 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salt 2-acrylamido-1-methylpropanesulfonic acid or its alkali metal salt 2-methacrylamido-2-methylpropanesulfonic acid or its alkali metal salt Among these, 2-acrylamido-2-methylpropanesulfonic acid or its alkali metal salt is relatively inexpensive to produce industrially, has a high copolymerization rate with vinyl ester, especially vinyl acetate, and is a copolymer with a high degree of polymerization. It is preferable because it is particularly suitable for the purpose of the present invention, such as being able to synthesize , the stability of the amide bond is particularly high, and the desired performance of the saponified water-soluble copolymer is high.
この単量体は米国特許第2983712号、
同3332904号、同3547899号あるいは同3709816号
などで公知であり酢酸ビニルなどのビニルエステ
ルを含めた多くの単量体との共重合体について実
施例あるいは提案が示されているが、ビニルエス
テルとの共重合体をケン化することにより得られ
る共重合体、すなわちビニルアルコールとの共重
合体については知られておらず、本発明に示され
ているような工業的に重要な優れた性能を有する
共重合体については全く知られていなかつた。 This monomer is known in U.S. Patent Nos. 2983712, 3332904, 3547899, and 3709816. Although proposals have been made, copolymers obtained by saponifying copolymers with vinyl esters, i.e. copolymers with vinyl alcohol, are not known and are presented in the present invention. No copolymers with such industrially important and excellent performance were known.
上述したスルホン基含有単量体とビニルエステ
ル、とりわけ酢酸ビニルとの共重合はアルコール
の存在下で溶液重合で実施することが好ましい。
アルコールは通常メタノール、エタノールなど低
級アルコールが工業的に望ましい。重合は回分方
式、連続方式のいずれにても実施可能である。回
分方式の場合、共重合反応性比（r1、r2）に従つ
て重合率と共に単量体組成が変動していくことは
よく知られているが、単量体組成が一定となるよ
うに一方もしくは両方の単量体を添加していく所
謂半回分方式を採用することが均一な共重合組成
を有する共重合体を得るためには望ましい。 The copolymerization of the above-mentioned sulfone group-containing monomer and vinyl ester, especially vinyl acetate, is preferably carried out by solution polymerization in the presence of alcohol.
As the alcohol, lower alcohols such as methanol and ethanol are usually preferred industrially. Polymerization can be carried out either batchwise or continuously. In the case of a batch method, it is well known that the monomer composition changes with the polymerization rate according to the copolymerization reactivity ratio (r 1 , r 2 ), but in order to keep the monomer composition constant, In order to obtain a copolymer having a uniform copolymerization composition, it is desirable to adopt a so-called semi-batch method in which one or both monomers are added to the copolymer.
この場合の添加量の算出方法の一例としては
R.J.HannaがIndustrial and Engineering
Chemistry，Vol49，No.２ 208―209（1957）に
提出している式が挙げられる。多塔式の連続共重
合の場合にも同様の理由で、各塔内の単量体組成
が一定となるように２塔以後の塔に単量体を添加
することが望ましい。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、過酸化アセチル、ジメチル―２，2′―アゾ
ビスイソブチレート等公知のラジカル重合用開始
剤が使用され得る。重合反応温度は通常50℃〜重
合系の沸点の範囲から選ばれる。単量体の反応率
は、経済性、重合度の調節など目的に応じて適宜
決められる。共重合体中のスルホン基含有単量体
の量は用途に応じて適宜選択され特に制限はな
く、任意の組成の共重合体を合成し得る。また共
重合体の重合度は溶媒のアルコールの種類と量に
より調節し得る。重合度に関する制限はなく、い
ずれの重合度の共重合体も本発明に含まれる。共
重合を完了した後、反応液中にビニルエステルが
残存している場合には蒸留などにより分離除去す
る必要がある。スルホン基含有単量体は除去して
もよく、また少量であれば残存させたままでも一
般的目的には支障がない。 An example of how to calculate the amount added in this case is
RJ Hanna works in Industrial and Engineering
The formula presented in Chemistry, Vol. 49, No. 2, 208-209 (1957) is mentioned. In the case of continuous multi-column copolymerization, for the same reason, it is desirable to add monomers to the second and subsequent columns so that the monomer composition in each column is constant. As a polymerization initiator, 2,
Known radical polymerization initiators such as 2'-azobisisobutyronitrile, benzoyl peroxide, acetyl peroxide, and dimethyl-2,2'-azobisisobutyrate may be used. The polymerization reaction temperature is usually selected from the range of 50°C to the boiling point of the polymerization system. The reaction rate of the monomers is appropriately determined depending on the purpose, such as economical efficiency and adjustment of the degree of polymerization. The amount of the sulfonic group-containing monomer in the copolymer is appropriately selected depending on the application and is not particularly limited, and a copolymer having an arbitrary composition can be synthesized. Further, the degree of polymerization of the copolymer can be controlled by the type and amount of alcohol in the solvent. There is no restriction regarding the degree of polymerization, and copolymers having any degree of polymerization are included in the present invention. After the copolymerization is completed, if vinyl ester remains in the reaction solution, it is necessary to separate and remove it by distillation or the like. The sulfonic group-containing monomer may be removed, or may be left in a small amount without hindering the general purpose.
こうして得られた共重合体は次いでビニルエス
テル部分がケン化される。ケン化反応は通常共重
合体をアルコール溶液として実施し、アルコリシ
スにより反応を行わしめるのが有利である。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。ケン化触媒としては、水酸化ナトリウム、水
酸化カリウム等のアルカリ金属の水酸化物、ナト
リウムメチラート、カリウムメチラートなどのア
ルコラートあるいはアンモニアなどのアルカリ性
触媒が用いられ、また塩酸、硫酸などの酸触媒も
また用いられ得る。このうち工業的には水酸化ナ
トリウムが経済的に有利である。ケン化温度は通
常10〜50℃の範囲から選ばれる。強アルカリ性、
あるいは強酸性の条件下で100℃以上の高温に長
時間放置すると徐々にアミド結合の分解が進行す
るので望ましくないが、通常そのような条件下に
おく必要はなく、本発明の共重合体の場合、ケン
化時にアミド結合は分解することなく安定に保た
れる。ケン化反応によりビニルエステル単位は部
分的にあるいは高度にケン化されてビニルアルコ
ール単位に転換されるが、この転化率つまりケン
化度は該共重合体の使用目的に応じて任意の値と
することができるが、工業的に有利に製造できる
ケン化度の範囲は通常60〜100モル％である。本
発明の共重合体は一般のPVAと同様に、粉体で
保存、輸送が可能であり、使用時に水に分散後、
撹拌しながら加温することにより均一な糊液を得
ることができる。 The vinyl ester portion of the copolymer thus obtained is then saponified. The saponification reaction is usually carried out in the form of an alcohol solution of the copolymer, and it is advantageous to carry out the reaction by alcoholysis. 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. As saponification catalysts, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alcoholates such as sodium methylate and potassium methylate, or alkaline catalysts such as ammonia are used, and acid catalysts such as hydrochloric acid and sulfuric acid are used. may also be used. Among these, sodium hydroxide is economically advantageous from an industrial standpoint. The saponification temperature is usually selected from the range of 10 to 50°C. strong alkaline,
Alternatively, it is undesirable to leave the copolymer of the present invention under strongly acidic conditions at a high temperature of 100°C or higher for a long period of time because the decomposition of the amide bond will gradually proceed. In this case, the amide bond remains stable without decomposition during saponification. Through the saponification reaction, vinyl ester units are partially or highly saponified and converted into vinyl alcohol units, but this conversion rate, or degree of saponification, can be set to any value depending on the purpose of use of the copolymer. However, the degree of saponification that can be produced industrially advantageously is usually 60 to 100 mol%. The copolymer of the present invention, like general PVA, can be stored and transported in powder form, and when used, after being dispersed in water,
A uniform paste solution can be obtained by heating while stirring.
前述したように本発明で得られた新規な共重合
体は紙用コーテイング剤として優れた性能を有す
るが、これ以外にも水酸基、ビニルエステル基の
有する性能とスルホン基の機能を生かした様々な
用途が考えられる。例えば、繊維の経糸サイジン
グ用糊剤、静電記録紙、電子写真紙などの導電
剤、高分子凝集剤、脱水剤、原油の二次回収剤、
イオン交換樹脂、アミノ樹脂系接着剤の改良剤、
エマルジヨン重合用乳化安定剤、マイクロカプセ
ル用壁剤、家庭用糊料、繊維状物のバインダー、
化粧品添加剤、分散剤、接着剤、フイルムなどの
成型物などである。 As mentioned above, the new copolymer obtained by the present invention has excellent performance as a coating agent for paper, but it can also be used in various ways that take advantage of the performance of the hydroxyl group and vinyl ester group and the function of the sulfone group. Possible uses. For example, sizing agents for warp sizing of fibers, conductive agents for electrostatic recording paper and electrophotographic paper, polymer flocculants, dehydrating agents, secondary recovery agents for crude oil,
Improving agent for ion exchange resins and amino resin adhesives,
Emulsion stabilizer for emulsion polymerization, wall material for microcapsules, household glue, binder for fibrous materials,
These include cosmetic additives, dispersants, adhesives, and molded products such as films.
以下、実施例によつて本発明を具体的に説明す
るが、これらの実施例は本願発明を何等限定する
ものではない。また、特に断りない限り、部ある
いは％は重量基準を意味するものとする。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but these Examples are not intended to limit the present invention in any way. Furthermore, unless otherwise specified, parts and percentages are based on weight.
実施例 １
撹拌後、温度計、滴下ロートおよび還流冷却器
を付した反応容器中に酢酸ビニル500部、メタノ
ール83部、２―アクリルアミド―２―メチルプロ
パンスルホン酸ナトリウム塩５部を仕込み恒温槽
内に据えて撹拌しながら系内を窒素置換した後、
内温を60℃まで上げた。この系に２，2′―アゾビ
スイソブチロニトリル0.4部を含むメタノール溶
液41部を添加し重合を開始した。重合時間１時間
55分の間に２―アクリルアミド―２―メチルプロ
パンスルホン酸ナトリウム塩19部を含むメタノー
ル溶液76部を重合系の固型分濃度の測定値に応じ
て系に滴下した。重合停止時の系内の固型分濃度
は20.5％であつた。メタノール蒸気の導入によ
り、未反応の酢酸ビニル単量体を追出した後、共
重合体の35％メタノール溶液を得た。この共重合
体は２―アクリルアミド―２―メチルプロパンス
ルホン酸ナトリウム単位を6.1モル％と酢酸ビニ
ル単位を93.9モル％含有することが該磁気共鳴分
析により確認された。この共重合体のメタノール
溶液100部を40℃で撹拌しながらこの中に2Nの苛
性ソーダメタノール溶液を８部添加して、よく混
合後放置した。得られた白色のゲルを粉砕器にて
粉砕し、メタノールで洗浄精製後、乾燥し白色の
重合体粉末を得た。この共重合体は水溶性良好
で、その４％水溶液の20℃におけるブルツクフイ
ールド粘度は35センチポイズであつた。この共重
合体の重水溶液のプロトン核磁気共鳴スペクトル
を第１図に示した。3.4PPMの吸収は２―アクリ
ルアミド―２―メチルプロパンスルホン酸ナトリ
ウム単位中のイオウ原子に結合したメチレン基の
プロトンに帰属され、その吸収強度から２―アク
リルアミド―２―メチルプロパンスルホン酸ナト
リウム単位は6.1モル％含有されると分析され
た。また、酢酸ビニル単位のケン化度は99.9モル
％と求められた。つまり、得られた共重合体は実
質的に２―アクリルアミド―２―メチルプロパン
スルホン酸ナトリウム―ビニルアルコール共重合
体である。Example 1 After stirring, 500 parts of vinyl acetate, 83 parts of methanol, and 5 parts of 2-acrylamide-2-methylpropanesulfonic acid sodium salt were placed in a reaction vessel equipped with a thermometer, a dropping funnel, and a reflux condenser, and the mixture was placed in a constant temperature bath. After replacing the system with nitrogen while stirring,
The internal temperature was raised to 60℃. To this system, 41 parts of a methanol solution containing 0.4 parts of 2,2'-azobisisobutyronitrile was added to initiate polymerization. Polymerization time 1 hour
Over a period of 55 minutes, 76 parts of a methanol solution containing 19 parts of 2-acrylamide-2-methylpropanesulfonic acid sodium salt was dripped into the system according to the measured value of the solid content concentration of the polymerization system. The solid content concentration in the system at the time of termination of polymerization was 20.5%. After expelling unreacted vinyl acetate monomer by introducing methanol vapor, a 35% methanol solution of the copolymer was obtained. It was confirmed by the magnetic resonance analysis that this copolymer contained 6.1 mol% of sodium 2-acrylamido-2-methylpropanesulfonate units and 93.9 mol% of vinyl acetate units. To 100 parts of a methanol solution of this copolymer was added 8 parts of a 2N caustic soda methanol solution while stirring at 40°C, and after thorough mixing, the mixture was allowed to stand. The obtained white gel was pulverized using a pulverizer, washed and purified with methanol, and then dried to obtain a white polymer powder. This copolymer had good water solubility, and a 4% aqueous solution thereof had a Bruckfield viscosity of 35 centipoise at 20°C. The proton nuclear magnetic resonance spectrum of a heavy aqueous solution of this copolymer is shown in FIG. The absorption of 3.4PPM is attributed to the proton of the methylene group bonded to the sulfur atom in the sodium 2-acrylamide-2-methylpropanesulfonate unit, and from the absorption intensity, the sodium 2-acrylamide-2-methylpropanesulfonate unit is 6.1 It was analyzed that it contained mol%. Furthermore, the degree of saponification of vinyl acetate units was determined to be 99.9 mol%. In other words, the obtained copolymer is essentially a sodium 2-acrylamide-2-methylpropanesulfonate-vinyl alcohol copolymer.
実施例 ２
実施例１と同様の反応容器中に酢酸ビニル1500
部、メタノール300部、２―アクリルアミド―２
―メチルプロパンスルホン酸ナトリウム塩８部を
仕込み、恒温槽内に据えて撹拌しながら系内を窒
素置換した後、内温を60℃まで上げた。この系に
ジメチル―２，2′―アゾビスイソブチレート2.3
部を含むメタノール溶液75部を添加して重合を開
始した。重合時間２時間５分の間に、２―アクリ
ルアミド―２―メチルプロパンスルホン酸ナトリ
ウム塩46部を含むメタノール溶液90部を重合系の
固形分濃度の測定値に応じて系に滴下した。重合
停止時の系内の固形分濃度は33.0％であつた。メ
タノール蒸気の導入により、未反応の酢酸ビニル
単量体を追出した後、共重合体の40％メタノール
溶液を得た。この共重合体は２―アクリルアミド
―２―メチルプロパンスルホン酸ナトリウム単位
を3.0モル％と酢酸ビニル単位を97モル％含有す
ることが核磁気共鳴分析により確認された。この
共重合体のメタノール溶液200部を40℃で撹拌し
ながらこの中に1Nの苛性ソーダメタノール溶液
を3.4部添加してよく混合後放置した。得られた
白色ゲルを粉砕し、メタノールで洗浄精製後、乾
燥して白色の重合体粉末を得た。この共重合体は
水溶性良好で、その４％水溶液の20℃におけるブ
ルツクフイールド粘度は40センチポイズであつ
た。この共重合体の重水溶液のプロトン核磁気共
鳴スペクトルを第２図に示した。２―アクリルア
ミド―２―メチルプロパンスルホン酸ナトリウム
単位が3.0モル％含有し、酢酸ビニル単位のケン
化度は88.0モル％である共重合体であると分析さ
れた。得られた共重合体は２―アクリルアミド―
２―メチルプロパンスルホン酸ナトリウム―ビニ
ルアルコール―酢酸ビニル３元共重合体である。Example 2 In a reaction vessel similar to Example 1, 1500 mg of vinyl acetate was added.
parts, 300 parts of methanol, 2-acrylamide-2
- 8 parts of sodium methylpropanesulfonate was charged, placed in a constant temperature bath, and the system was replaced with nitrogen while stirring, and the internal temperature was raised to 60°C. In this system, dimethyl-2,2'-azobisisobutyrate 2.3
Polymerization was initiated by adding 75 parts of a methanol solution containing 1. During a polymerization time of 2 hours and 5 minutes, 90 parts of a methanol solution containing 46 parts of 2-acrylamide-2-methylpropanesulfonic acid sodium salt was dropped into the system according to the measured solid content concentration of the polymerization system. The solid content concentration in the system at the time of termination of polymerization was 33.0%. After expelling unreacted vinyl acetate monomer by introducing methanol vapor, a 40% methanol solution of the copolymer was obtained. It was confirmed by nuclear magnetic resonance analysis that this copolymer contained 3.0 mol% of sodium 2-acrylamido-2-methylpropanesulfonate units and 97 mol% of vinyl acetate units. While stirring 200 parts of a methanol solution of this copolymer at 40°C, 3.4 parts of a 1N caustic soda methanol solution was added thereto, mixed well, and then allowed to stand. The obtained white gel was crushed, washed with methanol, purified, and dried to obtain a white polymer powder. This copolymer had good water solubility, and a 4% aqueous solution thereof had a Bruckfield viscosity of 40 centipoise at 20°C. The proton nuclear magnetic resonance spectrum of a heavy aqueous solution of this copolymer is shown in FIG. It was analyzed to be a copolymer containing 3.0 mol% of sodium 2-acrylamide-2-methylpropanesulfonate units and having a saponification degree of 88.0 mol% of vinyl acetate units. The obtained copolymer is 2-acrylamide-
It is a terpolymer of sodium 2-methylpropanesulfonate-vinyl alcohol-vinyl acetate.
実施例 ３
実施例１と同様の反応器中に酢酸ビニル1800
部、メタノール2000部、２―アクリルアミド―２
―メチルプロパンスルホン酸カリウム塩１部を仕
込み、恒温槽内に据えて撹拌しながら系内を窒素
置換した後、内温を60℃まで上げた。この系にジ
メチル―２，2′―アゾビスイソブチレート24部を
メタノール110部と共に添加して重合を開始し
た。重合時間１時間40分の間に、２―アクリルア
ミド―２―メチルプロパンスルホン酸カリウム塩
11部を含むメタノール溶液35部を重合系の固形分
温度の測定値に応じて系に滴下した。重合停止時
の系内の固形分濃度は32.9％であつた。メタノー
ル蒸気の導入により、未反応の酢酸ビニル単量体
を追出した後、共重合体の66％メタノール溶液を
得た。この溶液528部にメタノール67部と酢酸メ
チル105部を加えて良く混合後40℃で撹拌しなが
ら2Nの苛性カリメタノール溶液を14部添加し
て、よく混合後放置した。得られた白色ゲルを粉
砕器にて粉砕し、メタノールで洗浄精製後乾燥し
て、白色の重合体粉末を得た。この共重合体は水
溶性良好でその４％水溶液の20℃におけるブルツ
クフイールド粘度は8.2センチポイズであつた。
この共重合体は２―アクリルアミド―２―メチル
プロパンスルホン酸カリウム単位を0.3モル％含
有し、酢酸ビニル単位のケン化度は69.0モル％で
あると分析された。Example 3 In a reactor similar to Example 1, vinyl acetate 1800
parts, 2000 parts of methanol, 2-acrylamide-2
- 1 part of methylpropane sulfonic acid potassium salt was charged, placed in a constant temperature bath, and the system was purged with nitrogen while stirring, and the internal temperature was raised to 60°C. 24 parts of dimethyl-2,2'-azobisisobutyrate and 110 parts of methanol were added to this system to initiate polymerization. During the polymerization time of 1 hour and 40 minutes, 2-acrylamido-2-methylpropanesulfonic acid potassium salt
35 parts of a methanol solution containing 11 parts was added dropwise to the system according to the measured solid content temperature of the polymerization system. The solid content concentration in the system at the time of termination of polymerization was 32.9%. After expelling unreacted vinyl acetate monomer by introducing methanol vapor, a 66% methanol solution of the copolymer was obtained. To 528 parts of this solution, 67 parts of methanol and 105 parts of methyl acetate were added and mixed well, and then 14 parts of a 2N caustic potassium methanol solution was added while stirring at 40°C, and after thorough mixing, the mixture was allowed to stand. The obtained white gel was pulverized using a pulverizer, washed with methanol, purified, and dried to obtain a white polymer powder. This copolymer had good water solubility, and the Bruckfield viscosity of a 4% aqueous solution at 20°C was 8.2 centipoise.
This copolymer contained 0.3 mol% of potassium 2-acrylamido-2-methylpropanesulfonate units, and the degree of saponification of vinyl acetate units was analyzed to be 69.0 mol%.
実施例 ４
実施例１と同様の反応器中に酢酸ビニル1800
部、メタノール1100部、２―アクリルアミド―１
―メチルプロパンスルホン酸ナトリウム塩16部を
仕込み、恒温槽内に据えて撹拌しながら系内を窒
素置換した後、内温を60℃まで上げた。この系に
２，2′―アゾビスイソブチロニトリル６部を含む
メタノール溶液100部を添加して重合を開始し
た。重合時間２時間の間に２―アクリルアミド―
１―メチルプロパンスルホン酸ナトリウム塩144
部を含むメタノール溶液288部を重合系の固形分
濃度の測定値に応じて系に滴下した。重合停止時
の系内の固形分濃度は38％であつた。メタノール
蒸気の導入により未反応の酢酸ビニル単量体を追
出した後、共重合体の45％メタノール溶液を得
た。この溶液363部に酢酸メチル64部を加えてよ
く混合後40℃で撹拌しながら2Nの苛性ソーダメ
タノール溶液を5.3部加えてよく混合後放置し
た。得られた白色ゲルを粉砕器にて粉砕し、メタ
ノールで洗浄精製後乾燥して白色の重合体粉末を
得た。この共重合体は水溶性良好でその４％水溶
液の20℃におけるブルツクフイールド粘度は14.0
センチポイズであつた。この共重合体は２―アク
リルアミド―１―メチルプロパンスルホン酸ナト
リウム単位を５モル％含有し、酢酸ビニル単位の
ケン化度は75モル％であると分析された。Example 4 In a reactor similar to Example 1, vinyl acetate 1800
part, methanol 1100 parts, 2-acrylamide-1
- 16 parts of methylpropanesulfonic acid sodium salt was charged, placed in a constant temperature bath, and the system was replaced with nitrogen while stirring, and the internal temperature was raised to 60°C. Polymerization was initiated by adding 100 parts of a methanol solution containing 6 parts of 2,2'-azobisisobutyronitrile to this system. 2-acrylamide- during the polymerization time of 2 hours.
1-Methylpropanesulfonic acid sodium salt 144
288 parts of a methanol solution containing 288 parts of methanol solution was added dropwise to the polymerization system according to the measured solid content concentration of the polymerization system. The solid content concentration in the system at the time of termination of polymerization was 38%. After expelling unreacted vinyl acetate monomer by introducing methanol vapor, a 45% methanol solution of the copolymer was obtained. After adding 64 parts of methyl acetate to 363 parts of this solution and mixing well, 5.3 parts of 2N caustic soda methanol solution was added while stirring at 40°C, and after mixing well, the mixture was allowed to stand. The obtained white gel was pulverized using a pulverizer, washed with methanol, purified, and dried to obtain a white polymer powder. This copolymer has good water solubility, and the Bruckfield viscosity of a 4% aqueous solution at 20°C is 14.0.
It was centipoise hot. This copolymer contained 5 mol% of sodium 2-acrylamido-1-methylpropanesulfonate units, and the degree of saponification of vinyl acetate units was analyzed to be 75 mol%.
実施例 ５
実施例１と同様の反応器中に酢酸ビニル1500
部、メタノール2686部、２―メタクリルアミド―
２―メチルプロパンスルホン酸ナトリウム塩３部
を仕込み、恒温槽内に据えて撹拌しながら系内を
窒素置換した後、内温を60℃まで上げた。この系
に２，2′―アゾビスイソブチロニトリル18部をメ
タノール100部と共に添加して重合を開始した。
重合時間５時間20分の間に２―メタクリルアミド
―２―メチルプロパンスルホン酸トナリウム塩27
部を含むメタノール溶液54部を重合系の固形分濃
度に応じて系に滴下した。重合停止時の系内の固
形分濃度は24％であつた。メタノール蒸気の導入
により未反応の酢酸ビニル単量体を追出した後、
共重合体の52％メタノール溶液を得た。この溶液
250部を40℃で撹拌しながら2Nの苛性ソーダメタ
ノール溶液を30部添加してよく混合後放置した。
得られた白色ゲルを粉砕器にて粉砕し、メタノー
ルで洗浄精製後乾燥して、白色の重合体粉末を得
た。この共重合体は水溶性良好で、その４％水溶
液の20℃におけるブルツクフイールド粘度は7.1
センチポイズであつた。この共重合体は２―メタ
クリルアミド―２―メチルスルホン酸ナトリウム
単位を1.0モル％含有し、酢酸ビニル単位のケン
化度は99.9モル％と分析された。Example 5 In a reactor similar to Example 1, 1500 mg of vinyl acetate was added.
parts, methanol 2686 parts, 2-methacrylamide-
Three parts of 2-methylpropanesulfonic acid sodium salt was charged, and the system was placed in a constant temperature bath and the system was replaced with nitrogen while stirring, and the internal temperature was raised to 60°C. 18 parts of 2,2'-azobisisobutyronitrile and 100 parts of methanol were added to this system to initiate polymerization.
2-Methacrylamide-2-methylpropanesulfonic acid tonalium salt 27 during polymerization time of 5 hours and 20 minutes.
54 parts of methanol solution containing 54 parts of methanol solution was added dropwise to the polymerization system depending on the solid content concentration of the polymerization system. The solid content concentration in the system at the time of termination of polymerization was 24%. After expelling unreacted vinyl acetate monomer by introducing methanol vapor,
A 52% methanol solution of the copolymer was obtained. This solution
While stirring 250 parts at 40°C, 30 parts of 2N caustic soda methanol solution was added, mixed well, and then left to stand.
The obtained white gel was pulverized using a pulverizer, washed with methanol, purified, and dried to obtain a white polymer powder. This copolymer has good water solubility, and the Bruckfield viscosity of a 4% aqueous solution at 20°C is 7.1.
It was centipoise hot. This copolymer contained 1.0 mol% of sodium 2-methacrylamido-2-methylsulfonate units, and the degree of saponification of vinyl acetate units was analyzed to be 99.9 mol%.
第１図および第２図は主周波数90MHzのプロト
ン核磁気共鳴スペクトル（VARIAN社、EM―
390）であり、いずれも本発明の共重合体の５％
重水溶液を測定したものである。第１図は２―ア
クリルアミド―２―メチル―プロパンスルホン酸
ナトリウム―ビニルアルコール共重合体であり、
第２図は２―アクリルアミド―２―メチルプロパ
ンスルホン酸ナトリウム―ビニルアルコール―酢
酸ビニル共重合体のスペクトル図である。各図
中、横軸は試料溶液中に共存させた基準物質（ト
リメチルシリルプロピオン酸―d4―ナトリウム
塩）からの化学シフトをPPMで示してある。
Figures 1 and 2 are proton nuclear magnetic resonance spectra (VARIAN, EM-
390), both of which are 5% of the copolymer of the present invention.
This is a measurement of a heavy aqueous solution. Figure 1 shows a sodium 2-acrylamide-2-methyl-propanesulfonate-vinyl alcohol copolymer,
FIG. 2 is a spectrum diagram of sodium 2-acrylamide-2-methylpropanesulfonate-vinyl alcohol-vinyl acetate copolymer. In each figure, the horizontal axis indicates the chemical shift in PPM from a reference substance (trimethylsilylpropionic acid-d 4 -sodium salt) coexisting in the sample solution.
Claims (1)
性単量体をアルコールの存在下でラジカル重合開
始剤を用いて共重合させ、しかる後に該共重合体
のアルコール溶液にアルカリあるいは酸触媒を作
用させて共重合体中のビニルエステル単位を部分
的にあるいは高度にケン化せしめビニルアルコー
ル単位とすることを特徴とする新規なポリビニル
アルコール系共重合体の製造方法。 （ここで、R1は水素原子または低級アルキル
基、R2はアルキル基、R3、R4、R5は水素原子ま
たはアルキル基、Ｍは水素またはアルカリ金属を
それぞれ意味している。） ２ ビニルエステルが酢酸ビニルである特許請求
の範囲第１項記載の製造方法。 ３ （）式においてR1、R4、R5が水素原子、
R2、R3がメチル基である特許請求の範囲第１項
記載の製造方法。 ４ （）式においてＭがナトリウムまたはカリ
ウムである特許請求の範囲第１項記載の製造方
法。[Claims] 1. A vinyl ester and a polymerizable monomer represented by the following formula () are copolymerized using a radical polymerization initiator in the presence of alcohol, and then an alcohol solution of the copolymer is added to an alkali solution. Alternatively, a novel method for producing a polyvinyl alcohol copolymer, characterized in that vinyl ester units in the copolymer are partially or highly saponified to vinyl alcohol units by the action of an acid catalyst. (Here, R 1 is a hydrogen atom or a lower alkyl group, R 2 is an alkyl group, R 3 , R 4 and R 5 are a hydrogen atom or an alkyl group, and M is hydrogen or an alkali metal, respectively.) 2 The manufacturing method according to claim 1, wherein the vinyl ester is vinyl acetate. 3 In formula (), R 1 , R 4 , R 5 are hydrogen atoms,
The manufacturing method according to claim 1, wherein R 2 and R 3 are methyl groups. 4. The manufacturing method according to claim 1, wherein M in formula () is sodium or potassium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14860479A JPS5672006A (en) | 1979-11-15 | 1979-11-15 | Novel copolymer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14860479A JPS5672006A (en) | 1979-11-15 | 1979-11-15 | Novel copolymer and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5672006A JPS5672006A (en) | 1981-06-16 |
| JPS6233241B2 true JPS6233241B2 (en) | 1987-07-20 |
Family
ID=15456480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14860479A Granted JPS5672006A (en) | 1979-11-15 | 1979-11-15 | Novel copolymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5672006A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS581702A (en) * | 1981-06-25 | 1983-01-07 | Kuraray Co Ltd | Emulsion polymerization of vinyl ester |
| JPH0627205B2 (en) * | 1986-12-27 | 1994-04-13 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for packaging alkaline substances |
| EP0769369B1 (en) | 1995-10-09 | 2004-07-14 | Kyodo Shiko Co., Ltd. | Laminated film, method for production thereof, bag and package using the laminated film, and method for separation thereof |
| JP3756937B2 (en) * | 1997-03-26 | 2006-03-22 | 共同紙工株式会社 | LAMINATED FILM, PROCESS FOR PRODUCING THE SAME, AND PACKAGE BODY AND PACKAGING BODY USING THE SAME |
| US6440508B1 (en) | 1997-11-13 | 2002-08-27 | Kyodo Shiko Co. | Laminated film, method for production thereof, bag and package using the laminated film, and method for separation thereof |
| JP6691641B2 (en) | 2018-02-14 | 2020-04-28 | 株式会社クラレ | Modified vinyl alcohol polymer and method for producing the same |
-
1979
- 1979-11-15 JP JP14860479A patent/JPS5672006A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5672006A (en) | 1981-06-16 |
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